xi Contents Contributors

III/18. Table 7. Allyl Functional . ...... Physical Constants of Poly(ethylene) . ... G. Properties of a Series of Selected Poly(ethylene) Samples .
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Contents

Contributors .............................................................................................................................

v

Preface ....................................................................................................................................

ix

I.

Nomenclature Rules – Units

Nomenclature ...............................................................................................................................................

I/1

A. Introduction ........................................................................................................................

I/1

B. IUPAC Recommendations .................................................................................................. 1. Source-based Nomenclature .................................................................................. 1.1 Homopolymers ........................................................................................ 1.2 Copolymers ............................................................................................. 1.3 Nonlinear Macromolecules and Macromolecular Assemblies ................ 2. Structure-based Nomenclature ............................................................................... 2.1 Regular Single-strand Organic Polymers ............................................... 2.2 Regular Double-strand Organic Polymers .............................................. 2.3 Regular Single-strand Inorganic and Coordination Polymers ................. 2.4 Regular Quasi-single-strand Coordination Polymers .............................. 2.5 Irregular Single-strand Organic Polymers ...............................................

I/1 I/2 I/2 I/2 I/3 I/3 I/3 I/6 I/6 I/7 I/7

C. Use of Common and Semisystematic Names .....................................................................

I/8

D. Chemical Abstracts (CA) Index Names ...............................................................................

I/8

E. Polymer Class Names ........................................................................................................

I/11

F. References .........................................................................................................................

I/12

Units .............................................................................................................................................................

I/13

A. Introduction ........................................................................................................................

I/13

B. International Units ..............................................................................................................

I/13

C. SI-prefixes ..........................................................................................................................

I/14

D. Conversion Factors ............................................................................................................

I/14

E. Conversion Table for SI vs. English-american Units ...........................................................

I/17

II.

Polymerization and Depolymerization

Decomposition Rates of Organic Free Radical Initiators ............................................................................

II/1

A. Introduction ........................................................................................................................

II/1

B. Tables of Decomposition Rates of Organic Free Radical Initiators ..................................... Table 1. Azonitriles ............................................................................................................... Table 2. Miscellaneous Azo-derivatives ................................................................................

II/2 II/2 II/9

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xi

xii

Contents Table 3. Table 4. Table 5. Table 6. Table 7.

Alkyl Peroxides ....................................................................................................... Acyl Peroxides ........................................................................................................ Hydroperoxides and Ketone Peroxides .................................................................. Peresters and Peroxycarbonates ............................................................................ Miscellaneous Initiators ...........................................................................................

II/23 II/29 II/43 II/48 II/67

C. Notes ..................................................................................................................................

II/69

D. References .........................................................................................................................

II/70

Propagation and Termination Constants in Free Radical Polymerization ..................................................

II/77

A. Introduction ........................................................................................................................

II/77

B. Tables of Table 1. Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9. Table 10. Table 11. Table 12. Table 13.

Propagation and Termination Constants ............................................................. Dienes ..................................................................................................................... Olefins ..................................................................................................................... Acrylic Derivatives ................................................................................................... Methacrylic Derivatives ........................................................................................... Itaconic Derivatives ................................................................................................. Fumaric Derivatives ................................................................................................ Vinyl Halides ........................................................................................................... Vinyl Esters ............................................................................................................. Vinyl Ethers ............................................................................................................. Styrene Derivatives ................................................................................................. Vinyl Heteroaromatics ............................................................................................. Aldehydes ............................................................................................................... Others .....................................................................................................................

II/79 II/79 II/79 II/80 II/82 II/85 II/87 II/87 II/87 II/88 II/88 II/90 II/90 II/90

C. References .........................................................................................................................

II/91

Transfer Constants to Monomers, Polymers, Catalysts and Initiators, Solvents and Additives, and Sulfur Compounds in Free Radical Polymerization ...........................................................................

II/97

A. Introduction ........................................................................................................................

II/97

B. Tables of Transfer Constants ............................................................................................. Table 1. Transfer Constants to Monomers ........................................................................... Table 2. Transfer Constants to Polymers ............................................................................. Table 3. Transfer Constants to Catalysts and Initiators ........................................................ Table 4. Transfer Constants to Solvents and Additives ........................................................ Table 5. Transfer Constants to Sulfur Compounds ...............................................................

II/98 II/98 II/103 II/106 II/110 II/150

C. Remarks .............................................................................................................................

II/157

D. References .........................................................................................................................

II/159

Photopolymerization Reactions ...................................................................................................................

II/169

A. Introduction ........................................................................................................................

II/169

B. Tables ................................................................................................................................ Table 1. Rate Constants of Cleavage, Electron Transfer and Monomer Quenching in Radical Photoinitiators ............................................................................................ Annex to Table 1. Photoinitiator Compound Chemistries ......................................

II/170

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II/170 II/173

Contents Table 2. Bimolecular Rate Constants for the Reaction of Phosphonyl Radicals with Various Monomers in Cyclohexane at Room Temperature .................................... Table 3. Bimolecular Rate Constants for the Reaction of Various Radicals with Various Olefinic Monomers at Room Temperature ................................................. Table 4. Bimolecular Rate Constants for the Reaction of Ph2P = O and Ph2P = S with Various Monomers .................................................................................................. Table 5. Electron Transfer Reaction of Radicals with Diphenyliodonium Salts .................... Table 6. Electron Transfer Rate Constants (ke) between Photosensitizers and Cationic Photoinitiators and Quenching Rate Constants (kq) for Cyclohexene Oxide in Methanol (M) and Acetonitrile (AN) .......................................................... Table 7. Excitation Transfer Rate Constants (kT) for Thioxanthones and Photoinitiators ......................................................................................................... Annex to Table 7. Compound Chemistries ............................................................ Table 8. Triplet State Lifetimes (τT) of the Sensitizer (TXI) in Different Media, and Rate Constant (kT) of the Interaction between TXI and TPMK ............................... Table 9. Some Values of the Triplet State Energy Levels of Photoinitiators and Monomers ............................................................................................................... Table 10. Values of τ0T, τT, and kba in Solution ........................................................................ Table 11. Rate Constant of Interaction of Ketones and Light Stabilizers in Solution .............. Annex to Table 11 ...................................................................................................

xiii II/176 II/176 II/176 II/176

II/177 II/178 II/178 II/179 II/179 II/179 II/179 II/179

C. References .........................................................................................................................

II/180

Free Radical Copolymerization Reactivity Ratios .......................................................................................

II/181

A. Introduction ........................................................................................................................

II/181

B. Tables ................................................................................................................................ Table 1. Copolymer Reactivity Ratios ................................................................................... Acenaphthalene to Fumarate, bis(3-chloro-2-butyl) ................................................ Fumarate, di-(2-chloroethyl) to N-N-divinylaniline ................................................... N-vinylimidazole to Styrene, p-2-(2-hydroxypropyl)- ............................................... Styrene, p-4-methoxyphenyl ketone to Vinylbenzoate, p-, sodium ......................... Vinylbenzoic acid, p- to Xanthate, S-methacryloyl O-ethyl ..................................... Table 2. Listing of Quick Basic (Microsoft) Program for Calculating Reactivity Ratios .........

II/182 II/182 II/182 II/212 II/241 II/268 II/285 II/288

C. References .........................................................................................................................

II/290

Q and e Values for Free Radical Copolymerizations of Vinyl Monomers and Telogens ...........................

II/309

A. Introduction ........................................................................................................................

II/309

B. Q and e Table 1. Table 2. Table 3. Table 4.

Values for Free Radical Copolymerizations .......................................................... Monomers ............................................................................................................... Telogens ................................................................................................................. Monomers Arranged by Q Values ........................................................................... Monomers Arranged by e Values ...........................................................................

II/310 II/310 II/314 II/314 II/317

C. References .........................................................................................................................

II/319

Patterns of Reactivity (U,V) Parameters for the Prediction of Monomer Reactivity Ratios and Transfer Constants in Radical Polymerization ...................................................................................

II/321

A. Introduction ........................................................................................................................

II/321

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xiv

Contents B. Example .............................................................................................................................

II/322

C. Transfer Constants .............................................................................................................

II/322

D. Tables of Parameters ......................................................................................................... Table 1. Monomers ............................................................................................................... Table 2. Transfer Agent ........................................................................................................

II/323 II/323 II/326

E. References .........................................................................................................................

II/327

Copolymerization Parameters of Metallocene-catalyzed Copolymerizations ............................................

II/329

A. Introduction ........................................................................................................................

II/329

B. A Brief Theoretical Outline of Copolymerization Reactions ................................................. 1. First-order Markov Model ........................................................................................ 2. Second-order Markov Model ...................................................................................

II/329 II/330 II/330

C. Calculation of the Copolymerization Parameters ................................................................ 1. First-order Markov Model ........................................................................................ 1.1. Copolymerization Parameters Deduced from the Mayo-lewis Equation .................................................................................................. 1.2. Determination of Copolymerization Parameters from the Sequence Distribution (Triad Distribution) .............................................. 2. Second-order Markov Model ................................................................................... 3. Example ..................................................................................................................

II/331 II/331

D. Table of Copolymerization Parameters ...............................................................................

II/333

E. List of Catalysts/Cocatalysts Used .....................................................................................

II/336

F. References .........................................................................................................................

II/336

Rates of Polymerization and Depolymerization, Average Molecular Weights, and Molecular Weight Distribution of Polymers .........................................................................................................

II/339

A. Introduction ........................................................................................................................

II/339

B. Reference Tables for the Calculation of Rates of Polymerization, Average Molecular Weights, and Molecular Weight Distributions of Polymers for Various Types of Polymerization .................................................................................................................... Table 1. Addition Polymerization with Termination ............................................................... Table 2. Addition Polymerization - "Living" Polymers with Partial Deactivation .................... Table 3. Linear Condensation Polymerization without Ring Formation ................................ Table 4. Equilibrium Polymerization ...................................................................................... Table 5. Nonlinear Polymerization Systems ......................................................................... Table 6. Degradation of Polymers - May Be Accompanied by Crosslinking ......................... Table 7. Influence of Reactor Conditions and Design on the Molecular Weight Distribution ..............................................................................................................

II/340 II/341 II/344 II/346 II/347 II/348 II/350

C. Some Distribution Functions and Their Properties .............................................................. 1. Normal Distribution Function (Gaussian Distribution) ............................................. 2. Logarithmic Normal Distribution Function ............................................................... 3. Generalized Exponential Distribution ...................................................................... 4. Poisson Distribution ................................................................................................

II/352 II/353 II/353 II/354 II/354

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II/331 II/331 II/332 II/332

II/352

Contents

xv

D. Molecular Weight Distribution in Condensation Polymers: the Stockmayer Distribution Function ...........................................................................................................

II/354

E. References .........................................................................................................................

II/356

Heats and Entropies of Polymerization, Ceiling Temperatures, Equilibrium Monomer Concentrations, and Polymerizability of Heterocyclic Compounds ...................................................

II/363

A. Heats of Polymerization ...................................................................................................... Table 1. Monomers Giving Polymers Containing Carbon Atoms Only in the Main Chain ....................................................................................................................... 1.1 With Acyclic Carbons Only in the Main Chain ........................................

II/365

1.1.1 Dienes ..............................................................................................

II/365

1.1.2 Monomers Giving Polymers with or without Aliphatic Side Chains That Contain Only C, H ........................................................

II/365

1.1.3 Monomers Giving Polymers with Aliphatic Side Chains That Contain Heteroatoms .......................................................................

II/368

1.1.4 Monomers Giving Polymers with Aromatic Side Chains That Contain Only C, H ............................................................................

II/371

1.1.5 Monomers Giving Polymers with Aromatic Side Chains and That Contain Heteroatoms ............................................................... 1.2 With Aromatic or Cyclic Carbons in the Main Chain ............................... Table 2. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ............... 2.1 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ..........................................................................

II/365 II/365

II/371 II/372 II/373 II/373

2.1.1 Ethers and Acetals ...........................................................................

II/373

2.1.2 Cyclic Esters ..................................................................................... 2.2 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, Si, P) ................................................ 2.3 Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only ...................................................... 2.4 Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ...................................................... 2.5 Monomers Giving Polymers Containing N in the Main Chain, Bonded to Other Heteroatoms (P) .......................................................... 2.6 Other Monomers Giving Polymers Not Listed Above ............................. Table 3. Copolymers .............................................................................................................

II/376 II/377 II/378 II/378 II/379 II/379 II/380

B. Entropies of Polymerization ................................................................................................ Table 4. Monomers Giving Polymers Containing Main Chain Carbon Only ......................... 4.1 Main Chain Acyclic Carbon Only ............................................................

II/381 II/382 II/382

4.1.1 Dienes ..............................................................................................

II/382

4.1.2 Monomers Giving Polymers without or with Aliphatic Side Chains That Contain Only C, H ........................................................

II/382

4.1.3 Monomers Giving Polymers with Aliphatic Side Chains That Contain Heteroatoms .......................................................................

II/384

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xvi

Contents 4.1.4 Monomers Giving Polymers with Aromatic Side Chains That Contain Only C, H ............................................................................

II/385

4.1.5 Monomers Giving Polymers with Aromatic Side Chains That Contain Heteroatoms .......................................................................

II/385

4.1.6 Other Monomers Giving Polymers Not Listed Above ...................... 4.2 With Aromatic or Cyclic Carbons in the Main Chain ............................... Table 5. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ............... 5.1 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ..........................................................................

II/386 II/386 II/387

5.1.1 Ethers and Acetals ...........................................................................

II/387

5.1.2 Cyclic Esters ..................................................................................... 5.2 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, Si, P) ................................................ 5.3 Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ...................................................... 5.4 Other Monomers Giving Polymers Not Listed Above ............................. Table 6. Copolymers .............................................................................................................

II/390

C. Ceiling Temperatures and Equilibrium Monomer Concentrations ....................................... 1. Equilibria Involving Pure Liquid Monomers ............................................................. Table 7. Monomers Giving Polymers Containing Main Chain Acyclic Carbon Only ............................................................................................ Table 8. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ...................................................................................................... 8.1

II/391 II/391 II/392 II/392 II/393 II/394 II/394 II/395

Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ....................................................................

II/395

Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, P, Si) .........................................

II/396

Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only ...............................................

II/396

Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ...............................................

II/397

8.5 Other Monomers Giving Polymers Not Listed Above ...................... Equilibria Involving Gaseous Monomers ................................................................. Equilibria Involving Monomers in Solution .............................................................. Table 9. Monomers Giving Polymers Containing Main Chain Carbon Only .........

II/397 II/397 II/398 II/398

8.2 8.3 8.4

2. 3.

II/387

9.1

Monomers Giving Polymers Containing Main Chain Acyclic Carbon Only .....................................................................................

II/398

9.2

Monomers Giving Polymers Containing Main Chain Cyclic Carbon .............................................................................................. Table 10. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ......................................................................................................

II/399

10.1 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ....................................................................

II/399

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II/399

Contents

xvii

10.2 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (Si, P) ..............................................

II/400

10.3 Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only ...............................................

II/400

10.4 Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ............................................... Table 11. Copolymers .............................................................................................

II/400 II/401

11.1 1:1 Copolymers ................................................................................

II/401

11.2 General Copolymers ........................................................................

II/401

D. Polymerizability of 5-, 6-, and 7-membered Heterocyclic Ring Compounds ........................ Table 12. 5-membered Ring Compounds ............................................................................... Table 13. 6-membered Ring Compounds ............................................................................... Table 14. 7-membered Ring Compounds ............................................................................... Table 15. Comparison of Polymerizability (+ or -)of Unsubstituted 5-, 6- and 7-membered Ring Compounds ...............................................................................

II/401 II/402 II/403 II/404

E. Notes ..................................................................................................................................

II/406

F. References .........................................................................................................................

II/407

Activation Energies of Propagation and Termination in Free Radical Polymerization ...............................

II/415

A. Introduction ........................................................................................................................

II/415

B. Tables ................................................................................................................................ Table 1. Dienes ..................................................................................................................... Table 2. Olefins ..................................................................................................................... Table 3. Acrylic Derivatives ................................................................................................... Table 4. Methacrylic Derivatives ........................................................................................... Table 5. Vinyl Halogens ........................................................................................................ Table 6. Vinyl Ethers and Vinyl Esters .................................................................................. Table 7. Styrene and Derivatives .......................................................................................... Table 8. Vinyl Heteroaromatics ............................................................................................. Table 9. Miscellaneous Compounds .....................................................................................

II/416 II/416 II/416 II/417 II/418 II/420 II/421 II/421 II/422 II/423

C. References .........................................................................................................................

II/424

Activation Volumes of Polymerization Reactions ........................................................................................

II/429

A. Introduction ........................................................................................................................

II/429

3

II/405

B. Activation Volumes (sm /mol) of Some Polymerization Reactions ......................................

II/432

C. Activation Volumes of Initiator Decomposition ....................................................................

II/435

D. Activation Volumes of Chain Propagation ...........................................................................

II/435

E. Activation Volumes of Chain Termination ...........................................................................

II/436

F. Activation Volumes of Chain Transfer Reactions ................................................................

II/436

G. Influence of Pressure on Copolymerization ........................................................................ Table 1. Copolymerization Parameters ................................................................................. Table 2. Reactivity Ratios of Terpolymerization .................................................................... Table 3. Activation Volumes ................................................................................................. Table 4. Q, e Values .............................................................................................................

II/437 II/437 II/438 II/439 II/440

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xviii

Contents H. References .........................................................................................................................

II/440

Activation Enthalpies and Entropies of Stereocontrol in Free Radical Polymerizations .............................

II/445

A. Introduction ........................................................................................................................

II/445

B. Tables ................................................................................................................................ Table 1. Ratios of Some i-ADS for Different Mechanisms .................................................... Table 2. Ratios of Rate Constants for Markov First Order Mechanisms ............................... Table 3. ∆H++s/i - ∆H++i/s and ∆S++s/i - ∆S++i/s of Free Radical Polymerizations in Different Solvents .................................................................................................... Table 4. Activation Enthalpy Differences (∆H++A - ∆H++B) Calculated from Various Literature Data ........................................................................................................ Table 5. Activation Entropy Differences (∆S++A - ∆S++B) Calculated from Various Literature Data ........................................................................................................ Table 6. Calculated Compensation Temperatures T0 and Compensation Enthalpies ∆∆H++0 for Various Monomers and Modes of Addition, Assuming Markov First Order Trials .....................................................................................................

II/446 II/446 II/446

C. References .........................................................................................................................

II/450

Products of Thermal Degradation of Polymers ...........................................................................................

II/451

A. Introduction ........................................................................................................................

II/451

B. Tables ................................................................................................................................ Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... Table 2. Main-chain Carbocyclic Polymers ........................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... Table 4. Main-chain Heterocyclic Polymers .......................................................................... Table 5. Cellulose and Its Derivatives ...................................................................................

II/451 II/451 II/464 II/465 II/473 II/475

C. References .........................................................................................................................

II/475

Radiation Chemical Yields: G Values ..........................................................................................................

II/481

A. Introduction ........................................................................................................................

II/481

B. Tables of G Values ............................................................................................................. Table 1. Homopolymers ........................................................................................................ 1.1 Polydienes .............................................................................................. 1.2 Polyolefins .............................................................................................. 1.3 Polyacrylates .......................................................................................... 1.4 Poly(methacrylates) ................................................................................ 1.5 Poly(styrenes) ......................................................................................... 1.6 Poly(vinyls) .............................................................................................

II/481 II/482 II/482 II/482 II/483 II/484 II/485 II/486

1.6.1 Acrylamides and Nitriles ...................................................................

II/486

1.6.2 Vinyl Monomers ................................................................................ Miscellaneous Polymers .........................................................................

II/486 II/487

1.7.1 Cellulose and Derivatives .................................................................

II/487

1.7.2 Poly(siloxanes) .................................................................................

II/487

1.7.3 Poly(amino Acids) ............................................................................

II/487

1.7.4 Polyesters .........................................................................................

II/488

1.7

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II/447 II/448 II/449

II/449

Contents

III.

xix

1.7.5 Polysulfones .....................................................................................

II/488

1.7.6 Polyketones ......................................................................................

II/488

1.7.7 Fluoropolymers .................................................................................

II/488

1.7.8 Others ............................................................................................... Table 2. Copolymers ............................................................................................................. 2.1 Copolymers with Ethylene ...................................................................... 2.2 Copolymers with Methyl Methacrylate .................................................... 2.3 Copolymers with Styrene ........................................................................ 2.4 Copolymers with Sulfur Dioxide .............................................................. 2.5 Other Copolymers ................................................................................... Table 3. Polymers Blends ..................................................................................................... Table 4. Composites .............................................................................................................

II/489 II/490 II/490 II/490 II/491 II/491 II/492 II/493 II/493

C. References .........................................................................................................................

II/493

Physical Properties of Monomers and Solvents

Physical Properties of Monomers ................................................................................................................

III/1

A. Introduction ........................................................................................................................

III/1

B. Tables of Table 1. Table 2. Table 3. Table 4.

Table 5.

Table 6.

Table 7. Table 8. Table 9.

Table 10.

Table 11.

Physical Properties ............................................................................................. Acetylenes .............................................................................................................. Acid Dichlorides ...................................................................................................... Acroleins ................................................................................................................. Acrylamides/Methacrylamides ................................................................................ 4.1 Acrylamides ............................................................................................ 4.2 Methacrylamide ...................................................................................... Acrylates/Methacrylates .......................................................................................... 5.1 Acrylate, Acids/Esters ............................................................................. 5.2 Methacrylate, Acids/Esters ..................................................................... Alcohols .................................................................................................................. 6.1 Alkanediols ............................................................................................. 6.2 Ether Diols .............................................................................................. Allyl Functional ........................................................................................................ Amines, Difunctional ............................................................................................... Anhydrides .............................................................................................................. 9.1 Monoanhydrides ..................................................................................... 9.2 Dianhydrides ........................................................................................... Butadienes .............................................................................................................. 10.1 1,2-butadienes ........................................................................................ 10.2 1,3-butadienes ........................................................................................ Butenes ................................................................................................................... 11.1 1-butenes ................................................................................................ 11.2 2-butenes ................................................................................................

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III/4 III/4 III/4 III/4 III/4 III/4 III/6 III/8 III/8 III/12 III/16 III/16 III/18 III/18 III/20 III/20 III/20 III/24 III/24 III/24 III/24 III/26 III/26 III/26

xx

Contents Table 12. Epoxides ................................................................................................................. 12.1 Monoepoxides ........................................................................................ 12.2 Diepoxides .............................................................................................. Table 13. Ethylene Halides ..................................................................................................... Table 14. Fumaric, Acids/Esters ............................................................................................. Table 15. lsocyanates ............................................................................................................. Table 16. Lactams .................................................................................................................. Table 17. Lactones ................................................................................................................. Table 18. Maleate, Acids/Esters ............................................................................................. Table 19. Propenes ................................................................................................................. Table 20. Styrenes .................................................................................................................. Table 21. Vinyl Functional ....................................................................................................... 21.1 Aryl .......................................................................................................... 21.2 Esters ...................................................................................................... 21.3 Ethers ..................................................................................................... 21.4 N-substituted ........................................................................................... 21.5 Sulfonates ...............................................................................................

III/26 III/26 III/28 III/28 III/30 III/30 III/32 III/32 III/32 III/32 III/34 III/36 III/36 III/36 III/38 III/38 III/40

Isorefractive and Isopycnic Solvent Pairs ....................................................................................................

III/43

A. Introduction ........................................................................................................................

III/43

B. Table of Isorefractive and Isopycnic Solvent Pairs ..............................................................

III/43

Refractive Indices of Common Solvents .....................................................................................................

III/55

A. Introduction ........................................................................................................................

III/55

B. Table of Refractive Indices of Common Solvents ...............................................................

III/55

Physical Constants of the Most Common Solvents for Polymers ...............................................................

III/59

IV.

Physical Data of Oligomers

Physical Data of Oligomers .........................................................................................................................

IV/1

A. Introduction ........................................................................................................................

IV/2

B. Oligomers Containing Main Chain Acyclic Carbon Only ..................................................... Table 1. Oligo(olefins) ........................................................................................................... 1.1. Oligo(methylenes) and Oligo(ethylenes) ................................................ 1.2. Oligo(perfluoromethylenes) and Oligo(perfluoroethylenes) .................... 1.3. Oligo(isobutenes) .................................................................................... 1.4. Oligo(1-alkenylenes) ............................................................................... References .............................................................................................................. Table 2. Oligo(dienes) ........................................................................................................... 2.1. Oligomers of 1,3-butadiene .................................................................... 2.2. Oligomers of lsoprene ............................................................................. 2.3. Oligomers of 1,3-butadiene Derivatives .................................................. 2.4. 1,4-oligo(alkadienes) .............................................................................. 2.5. Oligomers of Cyclopentadiene and 1,3-cyclohexadiene .........................

IV/3 IV/3 IV/3 IV/6 IV/8 IV/9 IV/9 IV/14 IV/14 IV/15 IV/16 IV/16 IV/17

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xxi

2.6. Oligomers of Allene ................................................................................ References .............................................................................................................. Table 3. Oligo(acetylenes) .................................................................................................... 3.1. Linear Oligomers of Acetylene ................................................................ 3.2. Polyenyne Oligomers .............................................................................. 3.3. Oligomeric α-ω-diynes ............................................................................ 3.4. Oligo(alkynes) ......................................................................................... 3.5. Cyclic Oligo(alkynes) .............................................................................. 3.6. Pericyclynes ............................................................................................ References .............................................................................................................. Table 4. Oligomers with Aliphatic Side Chains Which in Addition Contain Heteroatoms ........................................................................................................... 4.1. Oligomeric Acrylic Derivatives ................................................................ 4.2. Oligomeric Methacrylic Derivatives ......................................................... 4.3. Oligomers of β-alkyl Substituted Vinyl Derivatives ................................. 4.4. Oligo(vinyl) Derivatives ........................................................................... References .............................................................................................................. Table 5. Oligo(styrenes) ........................................................................................................ References ..............................................................................................................

IV/17 IV/18 IV/19 IV/19 IV/20 IV/20 IV/20 IV/20 IV/21 IV/21

C. Oligomers Contaning Heteroatoms in the Main Chain ........................................................ Table 6. Oligomers Containing O in the Main Chain ............................................................. 6.1. Oligo(ethers) and Oligo(acetals) .............................................................

IV/33 IV/33 IV/33

6.2.

References .................................................................................................. Oligo(carbonates) ...................................................................................

IV/43 IV/47

6.3.

References .................................................................................................. Oligo(esters) ...........................................................................................

IV/47 IV/48

6.4.

References .................................................................................................. Oligo(urethanes) .....................................................................................

IV/56 IV/58

References .................................................................................................. Table 7. Oligo(sulfides) and Oligo(selenides) ....................................................................... 7.1. Cyclic Oligo(thiomethylenes) and Oligo(Selenomethylenes) .................. 7.2. Cyclic Oligo(thioalkylenes) ...................................................................... 7.3. Substituted Cyclic(thioethylenes) ............................................................ 7.4. Cyclic Co-oligomers of Formaldehyde and Thioformaldehyde ............... 7.5. Cyclic Oligo(ether Sulfides) .................................................................... 7.6. Thiacyclophanes ..................................................................................... References .............................................................................................................. Table 8. Oligomers Containing N in the Main Chain ............................................................. 8.1. Oligo(amides) .........................................................................................

IV/61 IV/62 IV/62 IV/62 IV/62 IV/62 IV/63 IV/63 IV/63 IV/64 IV/64

References .................................................................................................. Oligo(peptides) .......................................................................................

IV/70 IV/72

References ..................................................................................................

IV/84

8.2.

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IV/22 IV/22 IV/24 IV/26 IV/27 IV/28 IV/30 IV/32

xxii

Contents 8.3.

Oligo(imines) ...........................................................................................

IV/88

8.4.

References .................................................................................................. Oligo(ureas) ............................................................................................

IV/89 IV/89

References ..................................................................................................

IV/90

D. Carbon Chain Oligomers Containing Main Chain Cyclic Units ............................................ Table 9. Oligo(cyclopentylenes) ............................................................................................ Table 10. Oligo(spiranes) ........................................................................................................ Table 11. Oligo(xylylenes) ...................................................................................................... 11.1. Linear Oligo(xylenes) .............................................................................. 11.2. Cyclic Oligo(xylylenes) ............................................................................ Table 12. Oligo(stilbenes) ....................................................................................................... Table 13. Oligo(benzyls) ......................................................................................................... Table 14. Oigo(2,5-dimethyl-benzyls) ..................................................................................... Table 15. Oligo(2,3,5,6-tetramethyl-benzyls) .......................................................................... Table 16. Oligo(p-phenylene Oxides) ..................................................................................... Table 17. Oligo(p-phenylene Sulfides) .................................................................................... Table 18. Oligo(p-phenoxyphenylmethanes) .......................................................................... Table 19. Oligo(diphenylmethanes) ........................................................................................ References .............................................................................................................. Table 20. Phenol-formaldehyde and Related Oligomers ........................................................ 20.1. Linear Phenol-formaldehyde Oligomers ................................................. 20.2. Oligomeric Phenol Alcohols .................................................................... 20.3. Cyclic Phenol-formaldehyde Oligomers .................................................. 20.4. Branched Phenol-formaldehyde Oligomers ............................................ 20.5. Hydroquinone Oligomers ........................................................................ References .............................................................................................................. Table 21. Oligo(phenylenes) ................................................................................................... 21.1. o-oligo(phenylenes) ................................................................................ 21.2. m-oligo(phenylenes) ............................................................................... 21.3. p-oligo(phenylenes) ................................................................................ 21.4. Oligo(p-quinones) ................................................................................... References ..............................................................................................................

IV/90 IV/90 IV/90 IV/90 IV/90 IV/90 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/92 IV/92 IV/93 IV/94 IV/94 IV/95 IV/95 IV/96 IV/96 IV/96 IV/97 IV/98 IV/98

E. Oligomers Containing Heterocyclic Rings in the Main Chain .............................................. Table 22. Heterocyclic Oligomers ........................................................................................... 22.1 Oligo(furan) Derivatives .......................................................................... 22.2. Oligo(thiophene) Derivatives .................................................................. 22.3. Oligo(pyrrole) Derivatives ....................................................................... 22.4. Oligo(pyridine) Derivatives ...................................................................... 22.5. Cyclic Oligo(heterocyclics) ...................................................................... References .............................................................................................................. Table 23. Oligo(saccharides) .................................................................................................. 23.1. Oligomeric Pentoses ...............................................................................

IV/99 IV/99 IV/99 IV/100 IV/100 IV/100 IV/101 IV/101 IV/102 IV/102

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Contents

xxiii

23.2. Oligomeric Hexoses ................................................................................ IV/102 23.3. Oligomeric Amino Sugars ....................................................................... IV/103 References .............................................................................................................. IV/104

V.

Physical Constants of Some Important Polymers

Physical Constants of Rubbery Polymers ...................................................................................................

V/1

A. Introduction ........................................................................................................................

V/1

B. Tables ................................................................................................................................ Table 1. 1,4-cis(96-98%)Poly(butadiene) ............................................................................. Table 2. Poly(butadiene-co-acrylonitrile) .............................................................................. Table 3. Poly(butadiene-co-styrene) ..................................................................................... Table 4. Poly(chloroprene)(CR Neoprene) ........................................................................... Table 5. Poly(isobutene)-co-isoprene) Butyl Rubber (IIR) .................................................... Table 6. Polyisoprene, Natural Rubber ................................................................................. Table 7. Ethylene-propylene-diene-terpolymer (EPDM) .......................................................

V/1 V/1 V/2 V/3 V/3 V/4 V/5 V/6

C. References .........................................................................................................................

V/6

Physical Constants of Poly(ethylene) ..........................................................................................................

V/9

A. Crystallographic Data and Crystallographic Modifications ..................................................

V/9

B. Molecular Parameters and Solution Properties ...................................................................

V/9

C. Crystallinity, Crystal Size and Crystallization Kinetics .........................................................

V/10

D. Equilibrium Thermodynamic Properties ..............................................................................

V/11

E. Other General Physical Properties .....................................................................................

V/12

F. Effect of Chain Branching (Short) on Physical Properties ...................................................

V/15

G. Properties of a Series of Selected Poly(ethylene) Samples ................................................

V/16

H. Properties of Typical Poly(ethylenes) .................................................................................

V/17

I.

References .........................................................................................................................

V/17

Physical Constants of Poly(propylene) ........................................................................................................

V/21

A. Crystallographic Data and Modifications of Isotactic Polypropylenes ..................................

V/21

B. Crystallographic Data and Modifications of Syndiotactic Polypropylenes ............................

V/21

C. Dimensions of Poly(propylene) Molecules ..........................................................................

V/22

D. Crystallinity and Crystallization Kinetics ..............................................................................

V/22

E. Equilibrium Thermodynamic Properties ..............................................................................

V/23

F. Other General Properties ...................................................................................................

V/24

G. Properties of Typical Mainly Isotactic Poly(propylenes) ......................................................

V/26

H. Properties of Some Commercial Poly(propylene) Grades ...................................................

V/26

I.

Mechanical Properties of Poly(propylene) Homopolymers ..................................................

V/27

J. Mechanical Properties of Poly(propylene) Random Copolymers ........................................

V/28

K. Mechanical Properties of Poly(propylene) Impact Copolymers ...........................................

V/28

L. References .........................................................................................................................

V/28

Physical Constants of Fluoropolymers ........................................................................................................

V/31

A. Introduction ........................................................................................................................

V/31

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xxiv

Contents B. Physical Constants of Poly(tetrafluoroethylene) ................................................................. Notes ....................................................................................................................................... Infrared Absorption Spectrum of Poly(tetrafluoroethylene) ..................................................... References ..............................................................................................................................

V/31 V/37 V/38 V/39

C. Physical Constants of Melt Processible Fluorocarbon Polymers PFA and FEP .................. Notes ....................................................................................................................................... References ..............................................................................................................................

V/41 V/44 V/45

D. Physical Constants of Modified Poly(ethylene-co-tetrafluoroethylene) ................................ Notes ....................................................................................................................................... References ..............................................................................................................................

V/45 V/48 V/48

E. Physical Constants of Poly(vinylidene Fluoride) ................................................................. Notes ....................................................................................................................................... References ..............................................................................................................................

V/48 V/51 V/52

F. Physical Constants of Amorphous Fluoropolymers ............................................................. Notes ....................................................................................................................................... References ..............................................................................................................................

V/52 V/54 V/54

G. Physical Constants of Poly(chlorotrifluoroethylene) ............................................................ Notes ....................................................................................................................................... References ..............................................................................................................................

V/55 V/57 V/58

Physical Constants of Poly(acrylonitrile) .....................................................................................................

V/59

A. Tables of Table 1. Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9.

Physical Constants ............................................................................................. Crystallinity/Crystallization Behavior ....................................................................... Electric and Electronic Properties ........................................................................... Fiber Properties ...................................................................................................... Further Properties of Acrylic Fibers ........................................................................ Optical Properties ................................................................................................... Polymerization: Kinetic and Thermodynamic Data ................................................. Solubility/Solution Properties .................................................................................. Special Solid State Properties ................................................................................ Thermal and Thermodynamic Data ........................................................................

V/59 V/59 V/60 V/61 V/61 V/61 V/62 V/62 V/63 V/64

B. References .........................................................................................................................

V/64

Physical Constants of Poly(vinyl Chloride) ..................................................................................................

V/67

Physical Constants of Poly(vinyl Acetate) ...................................................................................................

V/77

Physical Constants of Poly(methyl Methacrylate) .......................................................................................

V/87

Physical Constants of Poly(styrene) ............................................................................................................

V/91

Physical Constants of Poly(oxymethylene) .................................................................................................

V/97

Physical Constants of Poly(oxyethylene-oxyterephthaloyl), (Poly(ethylene Terephthalate)) .....................

V/113

Physical Constants of Poly(oxytetramethylene-oxyterephthaloyl) and Copolymers with Tetramethylene Oxide Thermoplastic Elastomers .............................................................................

V/119

Physical Constants of Various Polyamides: Poly[imino(1-oxohexamethylene)], (Polyamide 6) Poly(iminoadipoyl-iminohexamethylene), (Polyamide 66), Poly(iminohexamethyleneiminosebacoyl), (Polyamide 610), Poly[imino(1-oxododecamethylene)], Poly(amide 12) ................

V/121

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Contents

xxv

Physical Constants of Cellulose ..................................................................................................................

V/135

A. Introduction ........................................................................................................................

V/135

B. Solid State Properties ......................................................................................................... Table 1. Unit Cell Dimensions ............................................................................................... Table 2. Density .................................................................................................................... Table 3. Average Ordered Fraction of Cotton and Linters Measured by Various Techniques ............................................................................................................. Table 4. Average Ordered Fraction Measured by Various Techniques ................................ Table 5. Degree of Crystallinity ............................................................................................. Table 6. Crystallite Sizes ...................................................................................................... Table 7. X-ray Orientation of Cellulose Fibers ...................................................................... Table 8. Heat Capacity ......................................................................................................... Table 9. Thermal Expansion Coefficient ............................................................................... Table 10. Other Thermal Properties ....................................................................................... Table 11. Refractive Index and Birefringence ......................................................................... Table 12. Resistivity ................................................................................................................ Table 13. Dielectric Constant and Loss Factor at 1 kHz ......................................................... Table 14. Other Electrical Properties ...................................................................................... Table 15. Crystal Elastic Modulus E1 in Chain Direction ......................................................... Table 16. Fiber Strength, Elongation and Modulus .................................................................

V/136 V/136 V/136

C. Solution Properties ............................................................................................................. Table 17. Typical Non-aqueous Cellulose Solvents ............................................................... Table 18. Other Solvents ........................................................................................................ Table 19. Viscosity - Molecular Weight Relationships ............................................................ Table 20. Second Virial Coefficients ....................................................................................... Table 21. Sedimentation and Diffusion Coefficients ............................................................... Table 22. Partial Specific Volumes, ν2 .................................................................................... Table 23. Geometrical Chain Characteristics ......................................................................... Table 24. Polymer-solvent Interaction Parameters .................................................................

V/147 V/147 V/148 V/148 V/150 V/150 V/151 V/151 V/152

D. References .........................................................................................................................

V/152

Physical and Mechanical Properties of Some Important Polymers ............................................................

V/159

A. Introduction ........................................................................................................................

V/159

B. Narrative Descriptions ........................................................................................................ 1. Multipurpose Polymers ........................................................................................... 2. Polyolefins and Barrier Polymers ............................................................................ 3. Styrenics and Engineering Thermoplastics ............................................................. 4. Elastomers ..............................................................................................................

V/159 V/159 V/160 V/160 V/161

C. Properties of Commercial Polymers ................................................................................... Table 1. Multipurpose Thermoplastics .................................................................................. Table 2. Polyolefins and Barrier Polymers ............................................................................ Table 3. Styrenics and Engineering Thermoplastics ............................................................. Table 4. Elastomers ..............................................................................................................

V/162 V/162 V/164 V/166 V/168

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V/136 V/137 V/137 V/138 V/140 V/140 V/141 V/141 V/144 V/144 V/145 V/146 V/146 V/147

xxvi VI.

Contents Solid State Properties

Crystallographic Data and Melting Points for Various Polymers ................................................................

VI/1

A. Introduction ........................................................................................................................ 1. Nomenclature .......................................................................................................... 2. Examples of Polymer Names .................................................................................. 2.1. Polymer Names Based on Source .......................................................... 2.2. Polymer Names Based on Structure ...................................................... References for Introduction .....................................................................................

VI/1 VI/1 VI/2 VI/2 VI/3 VI/5

B. Crystallographic Data for Various Polymers ....................................................................... Table 1. Poly(olefins) ............................................................................................................ Table 2. Poly(vinyls) and Poly(vinylidenes) .......................................................................... Table 3. Poly(aromatics) and Poly(imides) ........................................................................... Table 4. Poly(dienes) and Poly(diynes) ................................................................................ Table 5. Poly(peptides) ......................................................................................................... Table 6. Poly(amides) ........................................................................................................... Table 7. Poly(esters) ............................................................................................................. Table 8. Poly(urethanes) and Poly(ureas) ............................................................................ Table 9. Poly(ethers) ............................................................................................................. Table 10. Poly(oxides) ............................................................................................................ Table 11. Poly(sulfides) and Poly(sulfones) ............................................................................ Table 12. Poly(saccharides) ................................................................................................... Table 13. Other Polymers .......................................................................................................

VI/5 VI/6 VI/13 VI/15 VI/22 VI/26 VI/33 VI/40 VI/49 VI/51 VI/52 VI/57 VI/59 VI/64

C. Melting Points of Polymers ................................................................................................. Cellulose, see Poly (1,4-β-D-glucose) to Poly(4,4'-methylenediphenylene isophthalamide) ....................................................................................................... Poly(4,4'-methylenediphenylene octadecamethylenediurea) to Poly(p-xylylene undecanediamide) ..................................................................................................

VI/71 VI/71 VI/94

D. Appendix: Formula Index to the Tables .............................................................................. VI/113 0 to 4 ....................................................................................................................................... VI/114 5 to 30 ..................................................................................................................................... VI/133 E. References ......................................................................................................................... VI/159 1 to 839 ................................................................................................................................... VI/159 840 to 1946 ............................................................................................................................. VI/174 Glass Transition Temperatures of Polymers ............................................................................................... VI/193 A. Introduction ........................................................................................................................ VI/194 1. Example of a Property Change at Tg ...................................................................... VI/194 2. Tg: a "Non-Equilibrium" Transition ........................................................................... VI/195 B. Tg Measurement Methods .................................................................................................. VI/195 1. Data Interpretation .................................................................................................. VI/195 2. Oscillating Load Methods ........................................................................................ VI/196 C. Other Factors Affecting Tg .................................................................................................. VI/196 1. Structure ................................................................................................................. VI/196

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2. 3. 4. 5. 6.

Contents

xxvii

Crystallinity/Crosslinking ......................................................................................... Diluents ................................................................................................................... Molecular Weight .................................................................................................... Thermal History ....................................................................................................... Pressure ..................................................................................................................

VI/196 VI/197 VI/197 VI/197 VI/197

D. Estimation Methods for the Glass Transition Temperature ................................................. VI/197 E. Classification, Nomenclature, and Abbreviations ................................................................ VI/197 1. Naming Conventions ............................................................................................... VI/198 2. Abbreviations .......................................................................................................... VI/198 F. Tables of Glass Transition Temperatures of Polymers ....................................................... VI/198 Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... VI/198 1.1 Poly(acrylics) and Poly(methacrylics) ..................................................... VI/198 1.1.1 Poly(acrylic acid) and Poly(acrylic Acid Esters) ............................... VI/198 1.1.2 Poly(acrylamides) ............................................................................. VI/201 1.1.3 Poly(methacrylic Acid) and Poly(methacrylic Acid Esters) .............. VI/201 1.1.4 Poly(methacrylamides) ..................................................................... VI/205 1.1.5 Other α- and β-substituted Poly(acrylics) and Poly(methacrylics) ............................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(dienes) ............................................................................................ 1.4 Poly(styrenes) ......................................................................................... 1.5 Poly(vinyl Alcohol) and Poly(vinyl Ketones) ............................................ 1.6 PoIy(vinyl Esters) .................................................................................... 1.7 Poly(vinyl Ethers) and Poly(vinyl Thioethers) ......................................... 1.8 Poly(vinyl Halides) and Poly(vinyl Nitriles) .............................................. 1.9 Others ..................................................................................................... Table 2. Main-chain Carbocyclic Polymers ........................................................................... 2.1 Poly(phenylenes) .................................................................................... 2.2 Others ..................................................................................................... Table 3. Main-chain Acyclic Heteroatom Polymers .............................................................. 3.1 Main-chain –C–O–C– Polymers .............................................................

VI/205 VI/205 VI/207 VI/209 VI/212 VI/213 VI/214 VI/215 VI/216 VI/218 VI/218 VI/218 VI/219 VI/219

3.1.1 Poly(anhydrides) .............................................................................. VI/219 3.1.2 Poly(carbonates) .............................................................................. VI/219 3.1.3 Poly(esters) ...................................................................................... VI/221 3.1.4 Poly(ether Ketones) ......................................................................... VI/226 3.1.5 Poly(oxides) ...................................................................................... VI/226 3.2

3.1.6 Poly(urethanes) ................................................................................ VI/229 Main-chain O-heteroatom Polymers ....................................................... VI/231 3.2.1 Nitroso-polymers .............................................................................. VI/231 3.2.2 PoIy(siloxanes) ................................................................................. VI/231 3.2.3 Poly(sulfonates) ................................................................................ VI/233

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xxviii

Contents 3.3

Main-chain –C–(S)n–C- and –C–S–N– Polymers ................................... VI/233 3.3.1 Poly(sulfides) .................................................................................... VI/233 3.3.2 Poly(sulfones) and Poly(sulfonamides) ........................................... VI/234

3.4

3.3.3 Poly(thioesters) ................................................................................ VI/235 Main-chain –C–N–C Polymers ............................................................... VI/235 3.4.1 Poly(amides) .................................................................................... VI/235 3.4.2 Poly(anilines) .................................................................................... VI/241 3.4.3 Poly(imides) ...................................................................................... VI/241 3.4.4 Poly(imines) ...................................................................................... VI/241

3.4.5 Poly(ureas) ....................................................................................... 3.5 Poly(phosphazenes) ............................................................................... 3.6 Poly(silanes) and Poly(silazanes) ........................................................... Table 4. Main-chain Heterocyclic Polymers .......................................................................... 4.1 Carbohydrates ........................................................................................ 4.2 Liquid Crystals ........................................................................................ 4.3 Natural Polymers .................................................................................... 4.4 Poly(acetals) ........................................................................................... 4.5 Poly(anhydrides) ..................................................................................... 4.6 Poly(benzimidazoles) .............................................................................. 4.7 Poly(benzothiazinophenothiazines) ........................................................ 4.8 Poly(benzothiazoles) .............................................................................. 4.9 Poly(benzoxazlnes) ................................................................................ 4.10 Poly(benzoxazoles) ................................................................................ 4.11 Poly(carboranes) .................................................................................... 4.12 Poly(dibenzofurans) ................................................................................ 4.13 Poly(dioxoisoindolines) ........................................................................... 4.14 Poly(fluoresceins) ................................................................................... 4.15 Poly(furan Tetracarboxylic Acid Diimides) .............................................. 4.16 Poly(oxabicyclononanes) ........................................................................ 4.17 Poly(oxadiazoles) ................................................................................... 4.18 Poly(oxindoles) ....................................................................................... 4.19 Poly(oxoisoindolines) .............................................................................. 4.20 Poly(phthalazines) .................................................................................. 4.21 Poly(phthalides) ...................................................................................... 4.22 Poly(piperazines) .................................................................................... 4.23 Poly(piperidines) ..................................................................................... 4.24 Poly(pyrazinoquinoxalines) ..................................................................... 4.25 Poly(pyrazoles) ....................................................................................... 4.26 Poly(pyridazines) .................................................................................... 4.27 Poly(pyridines) ........................................................................................ 4.28 Poly(pyromellitimides) ............................................................................. 4.29 Poly(pyrrolidines) ....................................................................................

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VI/242 VI/242 VI/243 VI/243 VI/243 VI/244 VI/244 VI/244 VI/244 VI/245 VI/245 VI/245 VI/245 VI/245 VI/245 VI/246 VI/246 VI/247 VI/247 VI/247 VI/248 VI/248 VI/248 VI/248 VI/248 VI/248 VI/249 VI/249 VI/249 VI/249 VI/249 VI/249 VI/250

Contents 4.30 Poly(quinones) ........................................................................................ 4.31 Poly(quinoxalines) .................................................................................. 4.32 Poly(triazines) ......................................................................................... 4.33 Poly(triazoles) ......................................................................................... Table 5. Copolymers .............................................................................................................

xxix VI/250 VI/250 VI/252 VI/252 VI/252

G. References ......................................................................................................................... VI/253 1 to 953 ................................................................................................................................... VI/253 954 to 1560 ............................................................................................................................. VI/268 Rates of Crystallization of Polymers ............................................................................................................ VI/279 A. Introduction ........................................................................................................................ 1. Background ............................................................................................................. 1.1 General Remarks .................................................................................... 1.2 Background ............................................................................................. 1.3 Morphological Outline/Growth Features ................................................. 2. General Principles and Techniques Involved in Crystallization Rate Studies ......... 2.1 Kinetics of Bulk Transformations ............................................................ 2.2 Thermodynamic Crystallization Models .................................................. 2.3 Growth Kinetics of Lamellar Structures: Crystals and Spherulites ......... 3. Other Significant Aspects of Crystallization ............................................................ 3.1 Nonisothermal Crystallization ................................................................. 3.2 Crystallization of Blends ......................................................................... 3.3 Solvent and Pressure-induced Crystallization ........................................ 3.4 Crystallization of Mesophases ................................................................ 3.5 Flow Induced Crystallization ................................................................... 3.6 Epitaxial Crystallization ........................................................................... 3.7 Orientational Crystallization .................................................................... 3.8 Crystallization of Copolymers ................................................................. 3.9 Computer Simulations ............................................................................

VI/280 VI/280 VI/280 VI/280 VI/281 VI/282 VI/282 VI/284 VI/284 VI/286 VI/286 VI/287 VI/288 VI/288 VI/289 VI/289 VI/289 VI/290 VI/290

B. Tables of Rates of Crystallization of Various Polymers ....................................................... VI/291 1. Rates of Crystal Growth .......................................................................................... VI/291 Table 1. Poly(alkenes), Poly(dienes), Poly(vinyls) ................................................ VI/291 1.1

2.

Homopolymer Melts ......................................................................... VI/291

1.2 Solutions ........................................................................................... Table 2. Poly(oxides) ............................................................................................ Rates of Radial Spherulitic Growth ......................................................................... Table 3. Poly(dienes), Poly(alkenes), Poly(vinyls) ................................................ 3.1

VI/296 VI/300 VI/304 VI/304

Homopolymer Melts ......................................................................... VI/304

3.2 Blends ............................................................................................... VI/312 Table 4. Poly(oxides) ............................................................................................ VI/315 4.1

Homopolymer Melts ......................................................................... VI/315

4.2

Complexes ....................................................................................... VI/318

4.3

Blends ............................................................................................... VI/319

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xxx

Contents Table 5. Poly(carbonates) ..................................................................................... VI/326 Table 6. Poly(esters) ............................................................................................. VI/327 6.1

Homopolymer Melts ......................................................................... VI/327

6.2

Blends ............................................................................................... VI/329

6.3 Copolymers ...................................................................................... VI/331 Table 7. Poly(amides) ........................................................................................... VI/331 Table 8. Poly(siloxanes) ....................................................................................... VI/334 8.1

Homopolymer Melts ......................................................................... VI/334

8.2 Copolymers ...................................................................................... VI/334 Table 9. Others ..................................................................................................... VI/336 9.1 3.

Homopolymers Melts ....................................................................... VI/336

9.2 lonomers ........................................................................................... VI/340 Rates of Bulk Crystallization (Avrami Constants) ................................................... VI/341 Table 10. Poly(dienes), Poly(alkenes), Poly(vinyls) ................................................ VI/341 10.1 Melts and Solutions .......................................................................... VI/341 10.2 Blends and Copolymers ................................................................... VI/353 Table 11. Poly(oxides) ............................................................................................ VI/365 11.1 Homopolymer Melts ......................................................................... VI/365 11.2 Blends ............................................................................................... VI/371 Table 12. Poly(carbonates) ..................................................................................... VI/372 Table 13. Poly(esters) ............................................................................................. VI/373 13.1 Homopolymer melts ......................................................................... VI/373 13.2 Blends and Copolymers ................................................................... VI/377 Table 14. Poly(amides) ........................................................................................... VI/379 14.1 Blends of Poly(amides) .................................................................... VI/382 Table 15. Poly(urethanes) ...................................................................................... VI/383 Table 16. Table 17. Table 18. Table 19.

15.1 Blends of Poly(urethanes) ................................................................ Poly(siloxanes) ....................................................................................... Poly(phosphazenes) ............................................................................... Others ..................................................................................................... Composites .............................................................................................

VI/383 VI/384 VI/384 VI/385 VI/389

19.1 Composites of Blends ...................................................................... VI/390 C. References ......................................................................................................................... VI/391 Isomorphous Polymers Pairs ....................................................................................................................... VI/399 A. Introduction ........................................................................................................................ VI/399 B. Techniques ......................................................................................................................... VI/400 C. Tables of lsomorphous Pairs of Monomer Units ................................................................. Table 1. lsomorphous Units Within the Same Macromolecules (Copolymers) ..................... 1.1 lsomorphous Units with Different Chemical Constitution ........................ 1.2 lsomorphous Units with Different Configurations and/or with Headto-head, Head-to-tail Constitutional Disorder ..........................................

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VI/401 VI/401 VI/401 VI/405

Contents

xxxi

Table 2. Isomorphism of Macromolecules ............................................................................ VI/405 D. References ......................................................................................................................... VI/406 Miscible Polymers ........................................................................................................................................ VI/409 A. Definition of Miscibility ........................................................................................................ VI/409 B. Data Collection ................................................................................................................... VI/410 C. Arrangement of the Tables ................................................................................................. VI/410 D. Tables ................................................................................................................................ Table 1. Chemically Dissimilar Polymer Pairs Miscible in the Amorphous State at Room Temperature ................................................................................................. Table 2. Polymer Pairs Containing One Monomer in Common, Miscible in the Amorphous State at Room Temperature ................................................................ Table 3. Chemically Dissimilar Polymer Triads (and Tetrads) Miscible in the Amorphous State at Room Temperature ................................................................ Table 4. Polymer Pairs Miscible in the Amorphous State at Room Temperature; Molecular Weight Dependence Investigated .......................................................... Table 5. Polymer Pairs That Appear to Have High Temperature Miscibility Although Immiscible at or Below Room Temperature ............................................................ Table 6. Polymer Pairs Miscible at Room Temperature That Appear to Have a Lower Critical Solution Temperature (LCST) Above Room Temperature ......................... Table 7. Polymer Pairs That Appear to Have Both a Lower Critical Solution Temperature and a Upper Critical Solution Temperature ....................................... Table 8. Polymer Pairs That Cocrystallize ............................................................................

VI/411 VI/411 VI/444 VI/448 VI/450 VI/452 VI/454 VI/458 VI/459

E. References ......................................................................................................................... VI/461 Heat Capacities of High Polymers ............................................................................................................... VI/483 A. Introduction ........................................................................................................................ VI/483 B. Experimental Curves .......................................................................................................... VI/485 C. Data Tables for Solids and Liquids ..................................................................................... Table 1. cis-1,4-Poly(butadiene) (PBDc) .............................................................................. Table 2. trans-1,4-Poly(butadiene) (PBDt) ............................................................................ Table 3. cis-1,4-Poly(2-methylbutadiene) (PMBD) ............................................................... Table 4. Poly(ethylene) (PE) ................................................................................................. Table 5. Poly(propylene) (PP) ............................................................................................... Table 6. PoIy(1-butene) (PB) ................................................................................................ Table 7. PoIy(1-pentene) (PPE) ............................................................................................ Table 8. PoIy(1-hexene) (PHE) ............................................................................................. Table 9. Poly(isobutene) (PIB) .............................................................................................. Table 10. Poly(4-methyl-1-pentene) (P4MPE) ........................................................................ Table 11. Poly(tetrafluoroethylene) (PTFE) ............................................................................ Table 12. Poly(vinyl Fluoride) (PVF) ....................................................................................... Table 13. Poly(vinylidene Fluoride) (PVF2) ............................................................................ Table 14. Poly(trifluoroethylene) (P3FE) ................................................................................. Table 15. Poly(vinyl Chloride) (PVC) ......................................................................................

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VI/486 VI/486 VI/487 VI/488 VI/488 VI/489 VI/490 VI/490 VI/491 VI/492 VI/492 VI/493 VI/494 VI/494 VI/495 VI/496

xxxii

Contents Table 16. Table 17. Table 18. Table 19. Table 20. Table 21. Table 22. Table 23. Table 24. Table 25. Table 26. Table 27. Table 28. Table 29. Table 30. Table 31. Table 32. Table 33. Table 34. Table 35. Table 36. Table 37. Table 38. Table 39. Table 40. Table 41. Table 42. Table 43. Table 44. Table 45. Table 46. Table 47. Table 48. Table 49. Table 50.

Poly(vinylidene Chloride) (PVC2) ........................................................................... Poly(chlorotrifluoroethylene) (PC3FE) .................................................................... Poly(vinyl Alcohol) (PVA) ........................................................................................ Poly(vinyl Acetate) (PVAc) ...................................................................................... Poly(styrene) (PS) ................................................................................................... Poly(α-methylstyrene) (PMS) .................................................................................. Poly(vinyl Benzoate) (PVBZ) .................................................................................. Poly(methyl Acrylate) (PMA) ................................................................................... Poly(ethyl Acrylate) (PEA) ...................................................................................... Poly(n-butyl Acrylate) (PnBA) ................................................................................. Poly(iso-butyl Acrylate) (PIBA) ................................................................................ Poly(methacrylic Acid) (PMAA) ............................................................................... Poly(methyl Methacrylate) (PMMA) ........................................................................ Poly(ethyl Methacrylate) (PEMA) ............................................................................ Poly(n-butyl Methacrylate) (PnBMA) ....................................................................... Poly(iso-butyl Methacrylate) (PIBMA) ..................................................................... Poly(hexyl Methacrylate) (PHMA) ........................................................................... Poly(acrylonitrile) (PAN) .......................................................................................... Poly(methacrylamide) (PMAM) ............................................................................... Poly(oxy-1-oxoethylene) (PCL) ............................................................................... Poly(oxy-1-oxohexamethylene) (PCL) .................................................................... Poly(oxyethyleneoxyterephthaloyl) (PET) ............................................................... Poly(imino-(1-oxohexamethylene)) (Nylon 6) ......................................................... Poly(iminoadipoyliminohexamethylene) (Nylon 66) ................................................ Poly(iminoadipoyliminododecamethylene) (Nylon 612) .......................................... Poly(oxymethylene) (POM) ..................................................................................... Poly(oxyethylene) ................................................................................................... Poly(oxytrimethylene) (PO3M) ................................................................................ Poly(oxytetramethylene) (PO4M) ............................................................................ Poly(oxypropylene) (POPr) ..................................................................................... Poly(oxy-1,4-phenylene) (POPh) ............................................................................ Poly(oxy-2,6-dimethyl-1,4-phenylene) (PPO) ......................................................... Poly(oxy-2,6-diphenyl-1,4-phenylene) (POPPO) .................................................... Poly(oxycarbonyloxy-1,4-phenylene-isopropylidene- 1,4-phenylene) (PC) ............ Trigonal Selenium (SeT) .........................................................................................

VI/496 VI/497 VI/498 VI/498 VI/499 VI/500 VI/500 VI/501 VI/502 VI/502 VI/503 VI/504 VI/504 VI/505 VI/506 VI/506 VI/507 VI/508 VI/508 VI/509 VI/510 VI/510 VI/511 VI/512 VI/512 VI/513 VI/514 VI/514 VI/515 VI/515 VI/516 VI/517 VI/517 VI/518 VI/519

D. References ......................................................................................................................... VI/519 Surface and Interfacial Tensions of Polymers, Oligomers, Plasticizers, and Organic Pigments ............... VI/521 A. Introduction ........................................................................................................................ 1. Definition ................................................................................................................. 2. Temperature Dependence ...................................................................................... 3. Macleod's Relation .................................................................................................. 4. Molecular Weight Dependence ............................................................................... 5. Effects of Glass and Crystal-melt Transitions ......................................................... This page has been reformatted by Knovel to provide easier navigation.

VI/521 VI/521 VI/522 VI/522 VI/522 VI/522

Contents 6. 7.

xxxiii

Effect of Surface Chemical Constitution ................................................................. VI/523 Dispersion (Nonpolar) and Polar Components ....................................................... VI/523

B. Tables ................................................................................................................................ VI/523 Table 1. Surface Chemical Constitution and Surface Tension ............................. VI/524 1.1

Hydrocarbon Surfaces ..................................................................... VI/524

1.2

Fluorocarbon Surfaces ..................................................................... VI/524

1.3

Chlorocarbon Surfaces .................................................................... VI/524

1.4 Silicane Surfaces .............................................................................. VI/524 Table 2. Surface Tension, Polarity, and Macleod's Exponent for Amorphous Surfaces .............................................................................. VI/524 2.1

Hydrocarbon Polymers ..................................................................... VI/524

2.2

Styrene Polymers ............................................................................. VI/525

2.3

Halogenated Hydrocarbon Polymers ............................................... VI/525

2.4

Vinyl Polymers - Esters .................................................................... VI/526

2.5

Vinyl Polymers - Others ................................................................... VI/526

2.6

Acrylic Polymers - Nonfluorinated .................................................... VI/526

2.7

Acrylic Polymers - Fluorinated ......................................................... VI/527

2.8

Methacrylic Polymers - Nonfluorinated ............................................ VI/527

2.9

Methacrylic Polymers - Fluorinated ................................................. VI/527

2.10 Methacrylic Hydrogels ...................................................................... VI/527 2.11 Poly(ethers) ...................................................................................... VI/528 2.12 Poly(ether) Copolymers ................................................................... VI/529 2.13 Poly(esters) ...................................................................................... VI/529 2.14 Poly(carbonates) .............................................................................. VI/530 2.15 Poly(sulfones) ................................................................................... VI/530 2.16 Phenoxy Resins ............................................................................... VI/530 2.17 Epoxy Resins ................................................................................... VI/530 2.18 Poly(amides) .................................................................................... VI/530 2.19 Poly(imides) ...................................................................................... VI/531 2.20 Poly(imines) ...................................................................................... VI/531 2.21 Poly(urethanes) ................................................................................ VI/531 2.22 Poly(siloxanes) ................................................................................. VI/531 2.23 Organosilanes - Hydrolyzed and Condensed Films ........................ VI/532 2.24 Cellulosics ........................................................................................ VI/533 2.25 Poly(peptides) .................................................................................. VI/533 2.26 Miscellaneous ................................................................................... VI/533 Table 3. lnterfacial Tension for Amorphous Interfaces ......................................... VI/535 3.1

Hydrocarbon Polymers vs. Others ................................................... VI/535

3.2

Styrene Polymers vs. Others ........................................................... VI/537

3.3

Vinyl Polymers vs. Others ................................................................ VI/537

3.4

Acrylic Polymers vs. Others ............................................................. VI/538

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Contents 3.5

Methacrylic Polymers vs. Others ..................................................... VI/538

3.6

Poly(ethers) vs. Others .................................................................... VI/539

3.7

Poly(esters) vs. Others ..................................................................... VI/539

3.8

Poly(amides) vs. Others ................................................................... VI/539

3.9

Epoxy Resins vs. Others .................................................................. VI/539

3.10 Poly(Siloxanes) vs. Others ............................................................... VI/539 3.11 Miscellaneous ................................................................................... VI/540 C. References ......................................................................................................................... VI/540 Permeability and Diffusion Data .................................................................................................................. VI/543 A. Introduction ........................................................................................................................ VI/543 B. Conversion Factors for Various Units of the Permeability Coefficient ................................. VI/545 C. Tables ................................................................................................................................ Table 1. Permeability Coefficients, Diffusion Coefficients, and Solubility Coefficients of Polymers ............................................................................................................. 1.1 Poly(alkanes) .......................................................................................... 1.2 Poly(styrenes) ......................................................................................... 1.3 Poly(methacrylates) ................................................................................ 1.4 Poly(nitriles) ............................................................................................ 1.5 Poly(vinyls) ............................................................................................. 1.6 Fluorine Containing Polymers ................................................................. 1.7 Poly(dienes) ............................................................................................ 1.8 Poly(xylylenes) ........................................................................................ 1.9 Poly(oxides) ............................................................................................ 1.10 Poly(esters), Poly(carbonates) ............................................................... 1.11 PoIy(siloxanes) ....................................................................................... 1.12 Poly(amides), Poly(imides) ..................................................................... 1.13 Poly(urethanes) ...................................................................................... 1.14 Poly(sulfones) ......................................................................................... 1.15 Poly(aryl Ether Ether Ketone) ................................................................. 1.16 Cellulose and Derivatives ....................................................................... Table 2. Permeability Coefficients of Six Different Fluorinated Hydrocarbons through Polymers ................................................................................................................. Table 3. Permeability Coefficients of Various Organic Compounds through Lowdensity Poly(ethylene) ............................................................................................. Table 4. Permeability Coefficients and Diffusion Coefficients of an Equimolar Mixture of Various Compounds (1.25 M Each) through High-density Poly(ethylene) .......... Table 5. Permeability Coefficients of Various Organic Compounds through Highdensity Poly(ethylene) and Poly(propylene) ........................................................... Table 6. Permeability Coefficients of Various Organic Compounds through Irradiation Crosslinked Low-density Poly(ethylene) ................................................................. Table 7. Permeability Coefficients of Cases through Irradiation Crosslinked Lowdensity Poly(ethylene) .............................................................................................

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VI/545 VI/545 VI/545 VI/547 VI/548 VI/549 VI/549 VI/552 VI/553 VI/555 VI/555 VI/555 VI/558 VI/559 VI/560 VI/560 VI/561 VI/561 VI/562 VI/562 VI/564 VI/564 VI/564 VI/565

Contents

xxxv

Table 8. Permeability Coefficients of Chemically Crosslinked Poly(oxypropylene) .............. Table 9. Permeability Coefficients of Gases through Various Elastomers ............................ Table 10. Permeability Coefficients of Gases through Various Commercial Elastomers at 35°C. ................................................................................................................... Table 11. Permeability, Diffusion and Solubility Coefficients of Alkanes through Santoprene™ (Blend of Ethylene-propylene Copolymer and lsotactic Poly(propylene)) ...................................................................................................... Table 12. Permeability, Diffusion and Solubility Coefficients of Esters through Poly(epichlorohydrin) (ECO) ...................................................................................

VI/565 VI/566 VI/566

VI/566 VI/567

D. References ......................................................................................................................... VI/568 Refractive Indices of Polymers .................................................................................................................... VI/571 A. Introduction ........................................................................................................................ VI/571 B. Molar Refraction ................................................................................................................. VI/571 C. Refractive Indices of Heterogeneous Polymers .................................................................. VI/572 D. Optical Anisotropy .............................................................................................................. VI/572 E. Applications ........................................................................................................................ Table 1. Intrinsic Optical Properties of Selected Polymers ................................................... Table 2. Average Refractive Indices of Polymers (in Order of Increasing n) ........................ Table 3. Average Refractive Indices of Polymers (in Alphabetical Order) ............................

VI/573 VI/573 VI/574 VI/578

F. References ......................................................................................................................... VI/582 Radiation Resistance of Plastics and Elastomers ....................................................................................... VI/583 A. Introduction ........................................................................................................................ 1. General Comments ................................................................................................. 2. Criterion for Radiation Resistance .......................................................................... 3. Factors of Influence and Their Consideration in Tables ......................................... 3.1 Type of Polymer and Formulation ........................................................... 3.2 Type of Radiation and Dosimetry ........................................................... 3.3 Dose Rate and the Atmosphere ............................................................. 3.4 Temperature ........................................................................................... 3.5 Other Stresses ........................................................................................

VI/583 VI/583 VI/583 VI/583 VI/583 VI/584 VI/584 VI/584 VI/584

B. List of Symbols Used .......................................................................................................... VI/584 C. Tables of Table 1. Table 2. Table 3. Table 4.

Radiation Resistance .......................................................................................... Thermoplastics ........................................................................................................ Elastomers .............................................................................................................. Aromatic Polymers .................................................................................................. Organic Composite Materials ..................................................................................

VI/585 VI/585 VI/586 VI/587 VI/588

D. References ......................................................................................................................... VI/588 PVT Relationships and Equations of State of Polymers ............................................................................. VI/591 A. Introduction ........................................................................................................................ VI/591 B. Isothermal Compressibility Equations ................................................................................. VI/592 C. Empirical or Semiempirical 3-Parameter Equations of State ............................................... VI/593 D. Lattice or Quasi Lattice Models .......................................................................................... VI/593 This page has been reformatted by Knovel to provide easier navigation.

xxxvi

Contents E. Continuum Models .............................................................................................................. VI/594 F. Tables ................................................................................................................................ Table 1. Zero Pressure Volume V0(T) and Bulk Modulus B0(T) ............................................ Table 2. Abbreviations of Polymer Names and the Experimental TemperaturePressure Range for Polymer Liquids ...................................................................... Table 3. PVT Properties of Other Polymers .......................................................................... Table 4. Characteristic Parameters for the Sanchez-cho Equation of State ......................... Table 5. Characteristic Parameters for the Hartmann-haque Equation of State ................... Table 6. Characteristic Parameters for the Simple Cell Model Equation of State ................. Table 7. Characteristic Parameters for the Flory, Orwoll and Vrij Equation of State ............ Table 8. Characteristic Parameters for the Simha-somcynsky Equation of State ................ Table 9. Characteristic Parameters for the Sanchez-lacombe Equation of State ................. Table 10. Characteristic Parameters for the AHS + vdW Equation of State ...........................

VI/595 VI/595 VI/596 VI/597 VI/597 VI/597 VI/598 VI/599 VI/599 VI/600 VI/600

G. References ......................................................................................................................... VI/601

VII. Solution Properties Viscosity – Molecular Weight Relationships and Unperturbed Dimensions of Linear Chain Molecules ............................................................................................................................................

VII/1

A. Introduction ........................................................................................................................ 1. The Viscosity - Molecular Weight Relationship ....................................................... 2. Unperturbed Dimensions of Linear Chain Molecules ..............................................

VII/2 VII/2 VII/4

B. Effect of Molecular Weight Distribution on the Viscosity Constant K ...................................

VII/5

a

C. Tables of Viscosity - Molecular Weight Relationships, [η] = KM ........................................ Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes), Poly(acetylenes) ............................................................. 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(α-substituted Acrylic Acid) and Derivatives .................................... 1.5 Poly(vinyl Ethers) .................................................................................... 1.6 Poly(vinyl Alcohol), Poly(vinyl Halides) ................................................... 1.7 Poly(vinyI Esters) .................................................................................... 1.8 Poly(styrene) and Derivatives ................................................................. 1.9 Other Compounds .................................................................................. 1.10 Copolymers ............................................................................................. Table 2. Main-chain Carbocyclic Polymers ........................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 Poly(oxides), Poly(ethers) ....................................................................... 3.2 Poly(esters), Poly(carbonates) ............................................................... 3.3 Poly(amides) ........................................................................................... 3.4 Poly(amino Acids) ................................................................................... 3.5 Poly(ureas), Poly(urethanes), Poly(imines) ............................................ 3.6 Poly(sulfides) .......................................................................................... 3.7 Poly(phosphates) .................................................................................... This page has been reformatted by Knovel to provide easier navigation.

VII/5 VII/5 VII/5 VII/7 VII/10 VII/13 VII/17 VII/17 VII/18 VII/19 VII/24 VII/27 VII/31 VII/32 VII/32 VII/34 VII/36 VII/38 VII/39 VII/39 VII/39

Contents

xxxvii

3.8 Poly(siloxanes), Poly(silsesquioxanes) ................................................... 3.9 Poly(heterocyclics) .................................................................................. 3.10 Copolymers (Maleic Anhydride, Sulfones) .............................................. 3.11 Other Compounds .................................................................................. Table 4. Cellulose and Derivatives, Poly(saccharides) ......................................................... Table 5. Miscellaneous .........................................................................................................

VII/40 VII/41 VII/42 VII/42 VII/43 VII/46

D. Calculated Unperturbed Dimensions of Freely Rotating Chains .........................................

VII/46

E. Unperturbed Dimensions of Linear Polymer Molecules ...................................................... Table 6. Main-chain Acyclic Carbon Polymers ..................................................................... 6.1 Poly(dienes) ............................................................................................ 6.2 Poly(alkenes), Poly(acetylenes) ............................................................. 6.3 Poly(acrylic Acid) and Derivatives .......................................................... 6.4 Poly(α-substituted Acrylic Acid) and Derivatives .................................... 6.5 Poly(vinyl Ethers), Poly(vinyl Alcohol), Poly(vinyl Esters), Poly(vinyl Halides) .................................................................................. 6.6 Poly(styrene) and Derivatives ................................................................. 6.7 Other Compounds .................................................................................. 6.8 Copolymers ............................................................................................. Table 7. Main-chain Carbocyclic Polymers ........................................................................... Table 8. Main-chain Heteroatom Polymers ........................................................................... 8.1 Poly(oxides), Poly(ethers) ....................................................................... 8.2 Poly(esters), Poly(carbonates) ............................................................... 8.3 Poly(amides) ........................................................................................... 8.4 Poly(amino Acids) ................................................................................... 8.5 Poly(urethanes) ...................................................................................... 8.6 Poly(sulfides) .......................................................................................... 8.7 Poly(phosphates) .................................................................................... 8.8 Poly(siloxanes), Poly(silsesquioxanes), Poly(silmethylenes) ................. 8.9 Poly(heterocyclics) .................................................................................. 8.10 Copolymers (Maleic Anhydride, Sulfones, Siloxanes) ............................ 8.11 Other Compounds .................................................................................. Table 9. Cellulose and Derivatives, Poly(saccharides) .........................................................

VII/47 VII/47 VII/47 VII/48 VII/49 VII/50

F. References .........................................................................................................................

VII/68

Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, Frictional Ratios, and Second Virial Coefficients of Polymers in Solution ............................................................................

VII/85

A. Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, and Frictional Ratios of Polymers in Solution ............................................................................ 1. Introduction ............................................................................................................. 1.1. Sedimentation Coefficient ....................................................................... 1.2. Diffusion Coefficient ................................................................................ 1.3. Molar Mass Averages Determined from Sedimentation and Diffusion Coefficients .............................................................................. 1.4. Partial Specific Volumes ......................................................................... This page has been reformatted by Knovel to provide easier navigation.

VII/53 VII/54 VII/56 VII/58 VII/60 VII/60 VII/60 VII/61 VII/63 VII/63 VII/63 VII/63 VII/64 VII/64 VII/64 VII/65 VII/66 VII/66

VII/86 VII/86 VII/86 VII/87 VII/89 VII/89

xxxviii

Contents 1.5. 1.6. 1.7.

Frictional Ratios ...................................................................................... List of Symbols and Abbreviations .......................................................... Miscellaneous .........................................................................................

B. Tables of Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, and Frictional Ratios of Polymers in Solution ...................................................... Table 1. Poly(alkenes) .......................................................................................................... Table 2. Poly(dienes) ............................................................................................................ Table 3. Acrylic Polymers ..................................................................................................... Table 4. Vinyl Polymers ........................................................................................................ Table 5. Styrene Polymers .................................................................................................... Table 6. (O, C)-Heterochain Polymers [Poly(ethers), Poly(esters), Poly(carbonates)] ......... Table 7. (N, C)- and (O, N, C)-Heterochain Polymers [Poly(amides), Poly(ureas), Poly(urethanes)] ...................................................................................................... Table 8. Other Synthetic Polymers ....................................................................................... Table 9. Inorganic Polymers ................................................................................................. Table 10. Poly(saccharides) ................................................................................................... Table 11. Other Biopolymers [Proteins, Poly(nucleotides)] ....................................................

VII/89 VII/90 VII/91 VII/92 VII/92 VII/94 VII/96 VII/105 VII/109 VII/134 VII/137 VII/140 VII/141 VII/144 VII/157

C. Second Virial Coefficients of Polymers in Solution .............................................................. 1. Introduction ............................................................................................................. 1.1. Colligative Properties .............................................................................. 1.2. Scattering Methods ................................................................................. 1.3. Sedimentation Velocity ........................................................................... 1.4. Sedimentation Equilibrium ...................................................................... 1.5. p–V–T Measurements ............................................................................ 1.6. Averages of the Second Virial Coefficient .............................................. 1.7. Second Virial Coefficient – Molar Mass Relationship ............................. 1.8. Temperature Dependence, Pressure Dependence ................................ 1.9. Abbreviations .......................................................................................... 1.10. Miscellaneous .........................................................................................

VII/163 VII/163 VII/163 VII/163 VII/163 VII/164 VII/164 VII/164 VII/164 VII/164 VII/164 VII/164

D. Tables of Table 12. Table 13. Table 14. Table 15. Table 16. Table 17. Table 18.

VII/165 VII/165 VII/168 VII/170 VII/177 VII/179 VII/188

Table 19. Table 20. Table 21. Table 22.

Second Virial Coefficients of Polymers in Solution .............................................. Poly(alkenes), Poly(alkynes) ................................................................................... Poly(dienes) ............................................................................................................ Poly(acrylics) ........................................................................................................... Poly(vlnyls) .............................................................................................................. Poly(styrenes) ......................................................................................................... (O, C)-heterochain Polymers [Poly(ethers), Poly(esters), Poly(carbonates)] ......... (N, C)- and (O, N, C)-heterochain Polymers [Poly(amides), Poly(ureas), Poly(urethanes)] ...................................................................................................... Other Synthetic Polymers ....................................................................................... Inorganic Polymers ................................................................................................. Poly(saccharides) ................................................................................................... Other Biopolymers [Proteins, Poly(nucleotides)] ....................................................

VII/191 VII/192 VII/192 VII/194 VII/196

E. References ......................................................................................................................... VII/198 This page has been reformatted by Knovel to provide easier navigation.

Contents

xxxix

Polymolecularity Correction Factors ............................................................................................................ VII/215 A. List of Symbols Used .......................................................................................................... VII/216 B. Introduction ........................................................................................................................ VII/217 Table 1 .................................................................................................................................... VII/223 C. Polymolecularity Correction Factors for Intrinsic Viscosity Versus Molecular Weight Relationship ....................................................................................................................... Table 2 .................................................................................................................................... Table 3 .................................................................................................................................... Table 4 .................................................................................................................................... Table 5 .................................................................................................................................... Table 6 .................................................................................................................................... Table 7 .................................................................................................................................... Table 8 .................................................................................................................................... Table 9 .................................................................................................................................... Table 10 .................................................................................................................................. Table 11 .................................................................................................................................. Table 12 .................................................................................................................................. Table 13 .................................................................................................................................. Table 14 .................................................................................................................................. Table 15 .................................................................................................................................. Table 16 .................................................................................................................................. Table 17 .................................................................................................................................. Table 18 .................................................................................................................................. Table 19 ..................................................................................................................................

VII/223 VII/223 VII/223 VII/223 VII/224 VII/224 VII/224 VII/224 VII/224 VII/225 VII/225 VII/225 VII/225 VII/225 VII/226 VII/226 VII/226 VII/226 VII/226

D. Polymolecularity Correction Factors for Sedimentation Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 20 .................................................................................................................................. Table 21 .................................................................................................................................. Table 22 .................................................................................................................................. Table 23 .................................................................................................................................. Table 24 .................................................................................................................................. Table 25 .................................................................................................................................. Table 26 .................................................................................................................................. Table 27 ..................................................................................................................................

VII/227 VII/227 VII/227 VII/227 VII/227 VII/228 VII/228 VII/228 VII/229

E. Polymolecularity Correction Factors for Diffusion Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 28 .................................................................................................................................. Table 29 .................................................................................................................................. Table 30 .................................................................................................................................. Table 31 .................................................................................................................................. Table 32 .................................................................................................................................. Table 33 .................................................................................................................................. Table 34 ..................................................................................................................................

VII/229 VII/229 VII/229 VII/229 VII/230 VII/230 VII/230 VII/230

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Contents Table 35 Table 36 Table 37 Table 38 Table 39 Table 40 Table 41

.................................................................................................................................. .................................................................................................................................. .................................................................................................................................. .................................................................................................................................. .................................................................................................................................. .................................................................................................................................. ..................................................................................................................................

VII/230 VII/231 VII/231 VII/231 VII/231 VII/232 VII/232

F. Polymolecularity Correction Factors for Mean-Square Radius of Gyration versus Molecular Weight Relationship ........................................................................................... Table 42 .................................................................................................................................. Table 43 .................................................................................................................................. Table 44 .................................................................................................................................. Table 45 .................................................................................................................................. Table 46 .................................................................................................................................. Table 47 ..................................................................................................................................

VII/232 VII/232 VII/233 VII/233 VII/233 VII/234 VII/234

G. Polymolecularity Correction Factors for Second Virial Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 48 .................................................................................................................................. Table 49 .................................................................................................................................. Table 50 .................................................................................................................................. Table 51 ..................................................................................................................................

VII/234 VII/234 VII/235 VII/235 VII/235

H. Polymolecularity Correction Factors for the Determination of the Dimensions of Macromolecules ................................................................................................................. 1. Fox-flory Relationship ............................................................................................. Table 52 .................................................................................................................. Table 53 .................................................................................................................. Table 54 .................................................................................................................. Table 55 .................................................................................................................. 2. Interconversion of Different Averages of the Mean-square Radius of Gyration .................................................................................................................. Table 56 .................................................................................................................. Table 57 .................................................................................................................. Table 58 .................................................................................................................. Table 59 .................................................................................................................. 3. Interconversion of Different Averages of the Mean-square End-to-end Distance .................................................................................................................. Table 60 .................................................................................................................. Table 61 .................................................................................................................. Table 62 .................................................................................................................. Table 63 .................................................................................................................. Table 64 .................................................................................................................. Table 65 ..................................................................................................................

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VII/235 VII/235 VII/235 VII/236 VII/236 VII/236 VII/236 VII/236 VII/237 VII/237 VII/238 VII/238 VII/238 VII/238 VII/239 VII/239 VII/239 VII/239

Contents 4.

I.

xli

The Effect of Polymolecularity on the Radius of Gyration of Stiff Polymer Chains ..................................................................................................................... VII/240 Table 66 .................................................................................................................. VII/240 Table 67 .................................................................................................................. VII/240

Polymolecularity Correction Factors for the Determination of Unperturbed Dimensions of Macromolecules .......................................................................................... 1. Burchard-stockmayer-fixman Procedure ................................................................ Table 68 .................................................................................................................. Table 69 .................................................................................................................. Table 70 .................................................................................................................. 2. Cowie-bywater Procedure ....................................................................................... Table 71 .................................................................................................................. Table 72 .................................................................................................................. Table 73 .................................................................................................................. Table 74 .................................................................................................................. 3. Baumann-stockmayer-fixman Procedure ................................................................ Table 75 .................................................................................................................. Table 76 .................................................................................................................. Table 77 .................................................................................................................. Table 78 .................................................................................................................. 4. Baumann-kurata-stockmayer Procedure ................................................................ Table 79 .................................................................................................................. Table 80 .................................................................................................................. Table 81 .................................................................................................................. Table 82 ..................................................................................................................

VII/240 VII/240 VII/240 VII/240 VII/241 VII/241 VII/241 VII/241 VII/241 VII/241 VII/242 VII/242 VII/242 VII/242 VII/242 VII/243 VII/243 VII/243 VII/243 VII/244

J. References ......................................................................................................................... VII/244 Polymer-solvent Interaction Parameters ..................................................................................................... VII/247 A. Introduction ........................................................................................................................ VII/247 B. Concentration Variables ..................................................................................................... VII/247 C. Conversion of Concentration Variables .............................................................................. VII/247 D. Basic Equations .................................................................................................................. VII/247 E. Methods of Determination .................................................................................................. VII/248 F. Temperature Dependence .................................................................................................. VII/249 G. Concentration Dependence ................................................................................................ VII/249 H. Molecular Weight Dependence ........................................................................................... VII/250 I.

Polymer-solvent Interaction Parameters, χ ......................................................................... VII/250

J. References ......................................................................................................................... VII/262 Concentration Dependence of the Viscosity of Dilute Polymer Solutions: Huggins and Schulzblaschke Constants ............................................................................................................................ VII/265 A. Introduction ........................................................................................................................ VII/265 B. Tables ................................................................................................................................ VII/266

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Contents Table 1. Huggins Constants ................................................................................................. 1.1 Poly(dienes) and Poly(alkenes) .............................................................. 1.2 Poly(acrylic Acid) and Poly(methacrylic Acid) Derivatives ...................... 1.3 Vinyl Polymers ........................................................................................ 1.4 Poly(oxides) ............................................................................................ 1.5 Poly(esters) ............................................................................................. 1.6 Polyamides ............................................................................................. 1.7 Other Compounds .................................................................................. 1.8 Cellulose, Cellulose Derivatives, and Polysaccharides .......................... Table 2. Schulz-blaschke Constants .....................................................................................

VII/266 VII/266 VII/268 VII/272 VII/277 VII/278 VII/279 VII/280 VII/282 VII/284

C. References ......................................................................................................................... VII/285 Theta Solvents ............................................................................................................................................. VII/291 A. Introduction ........................................................................................................................ 1. Fundamentals ......................................................................................................... 1.1 Thermodynamics .................................................................................... 1.2 Unperturbed Dimensions ........................................................................ 2. Methods to Determine Theta Solvents .................................................................... 2.1 Phase Equilibrium (PE) ........................................................................... 2.2 Second Virial Coefficient (A) ................................................................... 2.3 Cloud Point Titration (CP) ....................................................................... 2.4 Cloud Temperature Titration (CT) ........................................................... 2.5 Unperturbed Dimensions (RGM, VM, DM, SM) ...................................... 2.6 Other Methods ........................................................................................

VII/291 VII/291 VII/291 VII/292 VII/293 VII/293 VII/293 VII/294 VII/294 VII/294 VII/294

B. Tables of Theta Solvents for Polymers ............................................................................... Table 1. Homochain Polymers .............................................................................................. 1.1 Poly(alkanes) .......................................................................................... 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(styrenes) ......................................................................................... 1.4 Poly(vinyls) ............................................................................................. 1.5 Poly(acrylics) and Related Compounds .................................................. 1.6 Poly(methacrylics) and Related Compounds .......................................... 1.7 Other Carbon Chains .............................................................................. Table 2. Heterochain Polymers ............................................................................................. 2.1 Poly(acetals) and Poly(ethers) ................................................................ 2.2 Poly(esters) ............................................................................................. 2.3 Poly(amides) ........................................................................................... 2.4 Polyureas and Polyurethanes ................................................................. 2.5 Polysaccharides ...................................................................................... 2.6 Carbon-sulfur Chains .............................................................................. 2.7 Silicon-oxygen Chains ............................................................................ 2.8 Phosphorus-oxygen Chains ....................................................................

VII/295 VII/295 VII/295 VII/299 VII/300 VII/305 VII/307 VII/308 VII/312 VII/313 VII/313 VII/315 VII/316 VII/316 VII/316 VII/317 VII/317 VII/318

C. References ......................................................................................................................... VII/318

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Fractionation of Polymers ............................................................................................................................ VII/327 A. Principles of Polymer Fractionation .................................................................................... VII/327 B. Fractionation Methods ........................................................................................................ 1. Fractionation by Solubility ....................................................................................... 2. Fractionation by Chromatography ........................................................................... 3. Cross Fractionation ................................................................................................. 4. Fractionation by Sedimentation .............................................................................. 5. Fractionation by Diffusion ....................................................................................... 6. Fractionation by Ultrafiltration through Porous Membranes .................................... 7. Fractionation by Zone Melting ................................................................................. 8. Electron Microscopic Counting Method ..................................................................

VII/328 VII/328 VII/330 VII/332 VII/333 VII/333 VII/333 VII/333 VII/333

C. Tables of Fractionation Systems for Different Polymers ..................................................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(methacrylic Acid) and Derivatives .................................................. 1.5 Other α- and β-Substituted Poly(acrylics) and Poly(methacrylics) ......... 1.6 Poly(vinyl Ethers) .................................................................................... 1.7 Poly(vinyl Alcohol), Poly(vinyl Ketones), Poly(vinyl Halides), Poly(vinyl Nitriles) ................................................................................... 1.8 Poly(vinyl Esters) .................................................................................... 1.9 Poly(styrenes) ......................................................................................... 1.10 Other Compounds .................................................................................. 1.11 Random and Alternating Copolymers ..................................................... 1.12 Block Copolymers ................................................................................... 1.13 Graft Copolymers .................................................................................... 1.14 Mixture of Polymers ................................................................................ Table 2. Main-chain Carbocyclic Polymers ........................................................................... 2.1 Poly(phenylenes) .................................................................................... 2.2 Formaldehyde Resins ............................................................................. Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 Poly(oxides) ............................................................................................ 3.2 Poly(carbonates) ..................................................................................... 3.3 Poly(esters) ............................................................................................. 3.4 Poly(urethanes) and Poly(ureas) ............................................................ 3.5 Poly(amides) and Poly(imines) ............................................................... 3.6 Poly(amino Acids) ................................................................................... 3.7 Poly(sulfides), Poly(sulfones), Poly(sulfonamides) ................................. 3.8 Poly(silanes) and Poly(siloxanes) ........................................................... 3.9 Poly(phosphazenes) and Related Polymers ........................................... 3.10 Other Compounds .................................................................................. 3.11 Random Copolymers ..............................................................................

VII/333 VII/333 VII/333 VII/336 VII/344 VII/346 VII/351 VII/353

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VII/353 VII/355 VII/356 VII/363 VII/366 VII/382 VII/389 VII/395 VII/397 VII/397 VII/397 VII/398 VII/398 VII/404 VII/405 VII/410 VII/411 VII/414 VII/416 VII/418 VII/422 VII/423 VII/425

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Contents 3.12 Block Copolymers ................................................................................... 3.13 Graft Copolymers .................................................................................... Table 4. Poly(saccharides) ................................................................................................... 4.1 Poly(saccharides) ................................................................................... 4.2 Graft Copolymers .................................................................................... 4.3 Mixtures of Polymers ..............................................................................

VII/427 VII/430 VII/431 VII/431 VII/436 VII/438

D. References ......................................................................................................................... 1 to 1188 ................................................................................................................................. 1189 to 2452 ........................................................................................................................... 2453 to 3608 ...........................................................................................................................

VII/438 VII/438 VII/458 VII/478

Solvents and Non Solvents for Polymers .................................................................................................... VII/497 A. Introduction ........................................................................................................................ VII/498 B. Abbreviations ..................................................................................................................... VII/498 C. Tables of Solvents and Nonsolvents ................................................................................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes), Poly(acetylenes) ............................................................... 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylics), Poly(methacrylics) ...........................................................

VII/499 VII/499 VII/499 VII/500 VII/501

1.3.1 Poly(acrylic Acids) ............................................................................ VII/501 1.3.2 Poly(acrylates) .................................................................................. VII/501 1.3.3 Poly(methacrylates) ......................................................................... VII/501 1.3.4 Poly(disubstituted Esters) ................................................................ VII/502 1.3.5 Poly(acrylamides), Poly(methacrylamides) ..................................... 1.4 Poly(vinyl Ethers) .................................................................................... 1.5 Poly(vinyl Alcohols), Poly(acetals), Poly(vinyl Ketones) ......................... 1.6 Poly(vinyl Halides) .................................................................................. 1.7 Poly(vinyl Nitrites) ................................................................................... 1.8 Poly(vinyl Esters) .................................................................................... 1.9 Poly(styrenes) ......................................................................................... 1.10 Other Compounds .................................................................................. Table 2. Main-chain Carbocyclic Polymers ........................................................................... 2.1 Poly(phenylenes) .................................................................................... 2.2 Other Compounds .................................................................................. Table 3. Main-chain Carbonyl Polymers ............................................................................... Table 4. Main-chain Acyclic Heteroatom Polymers .............................................................. 4.1 Main-chain –C–O–C– Polymers .............................................................

VII/503 VII/503 VII/504 VII/505 VII/506 VII/506 VII/507 VII/508 VII/509 VII/509 VII/510 VII/510 VII/511 VII/511

4.1.1 Poly(oxides) ...................................................................................... VII/511 4.1.2 Poly(carbonates) .............................................................................. VII/513 4.1.3 Poly(esters) ...................................................................................... VII/513 4.1.4 Poly(anhydrides) .............................................................................. VII/515 4.1.5 Poly(urethanes) ................................................................................ VII/515

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Contents 4.2

xlv

Main-chain –O– Heteroatom Polymers ................................................... VII/515 4.2.1 Poly(sulfonates) ................................................................................ VII/515

4.3

4.2.2 Poly(siloxanes) ................................................................................. VII/516 Main-chain –C–S–C– and –C–S–N– Polymers ...................................... VII/516 4.3.1 Poly(sulfides) .................................................................................... VII/516 4.3.2 Poly(sulfones) ................................................................................... VII/517

4.4

4.3.3 Others ............................................................................................... VII/518 Main-chain –C–N–C– Polymers ............................................................. VII/518 4.4.1 Poly(amides) .................................................................................... VII/518 4.4.2 Poly(hydrazides) ............................................................................... VII/520 4.4.3 Poly(ureas) ....................................................................................... VII/521 4.4.4 Poly(carbodiimides) .......................................................................... VII/521

4.4.5 Other Compounds ............................................................................ 4.5 Poly(phosphazenes) and Related Compounds ...................................... 4.6 Poly(silanes), Poly(silazanes) ................................................................. Table 5. Main-chain Heterocyclic Polymers .......................................................................... 5.1 Poly(benzoxazoles), Poly(oxadiazoles), Poly(oxadiazolidines) .............. 5.2 Poly(dithiazoles), Poly(benzothiazoles) .................................................. 5.3 Poly(imides) ............................................................................................

VII/521 VII/522 VII/522 VII/523 VII/523 VII/524 VII/524

5.3.1 Poly(benzimides) .............................................................................. VII/524 5.3.2 Poly(pyromellitides) .......................................................................... VII/525 5.3.3 Others ............................................................................................... 5.4 Poly(quinoxalines) .................................................................................. 5.5 Poly(benzimidazoles) .............................................................................. 5.6 Poly(piperazines) .................................................................................... 5.7 Poly(anhydrides) ..................................................................................... 5.8 Poly(thiophenes) ..................................................................................... 5.9 Others ..................................................................................................... Table 6. Formaldehyde Resins ............................................................................................. Table 7. Natural Polymers and Modified Natural Polymers .................................................. 7.1 Natural Rubber and Derivatives .............................................................. 7.2 Cutta Percha ........................................................................................... 7.3 Cellulose and Derivatives .......................................................................

VII/525 VII/526 VII/526 VII/526 VII/527 VII/527 VII/527 VII/528 VII/528 VII/528 VII/529 VII/529

7.3.1 Cellulose ........................................................................................... VII/529 7.3.2 Cellulose Ethers ............................................................................... VII/529 7.3.3 Cellulose Esters ............................................................................... VII/530 7.3.4 Cellulose Nitrate and Sulfate ........................................................... 7.4 Starch and Derivatives ............................................................................ 7.5 Other Poly(saccharides) ......................................................................... 7.6 Natural Resins ........................................................................................ Table 8. Inorganic Polymers ................................................................................................. Table 9. Poly(electrolytes) .................................................................................................... This page has been reformatted by Knovel to provide easier navigation.

VII/531 VII/531 VII/531 VII/532 VII/532 VII/533

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Contents Table 10. Block Polymers ....................................................................................................... VII/533 Table 11. Dendrimers ............................................................................................................. VII/534 D. References ......................................................................................................................... VII/536

Specific Refractive Index Increments of Polymers in Dilute Solution ......................................................... VII/547 A. Introduction ........................................................................................................................ VII/547 B. Introduction from the Third Edition ...................................................................................... VII/547 C. Refractometric Calibration Data .......................................................................................... VII/550 D. Tables of Specific Refractive Index Increments of Polymer Solutions ................................. Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(methacrylic Acid) and Derivatives .................................................. 1.5 Other α- or β-Substituted Poly(acrylics) and Poly(methacrylics) ............ 1.6 Poly(styrenes) ......................................................................................... 1.7 Other Compounds .................................................................................. Table 2. Main-chain Cyclic Carbon Polymers ....................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 C–O–C Polymers (Poly(oxides), Poly(esters), and Others) .................... 3.2 C–S–C Polymers (Poly(sulfones) and Others) ....................................... 3.3 C–N–C Polymers (Poly(amides), Poly(isocyanates), Poly(urethanes), and Others) ................................................................. 3.4 Poly(amino Acids) ................................................................................... 3.5 Poly(silanes) and Poly(silazanes) ........................................................... 3.6 Poly(heterocyclics) and Others ............................................................... Table 4. Cellulose and Derivatives ....................................................................................... Table 5. Poly(saccharides) ...................................................................................................

VII/551 VII/551 VII/551 VII/553 VII/557 VII/561 VII/573 VII/574 VII/588 VII/594 VII/594 VII/594 VII/599 VII/599 VII/604 VII/606 VII/608 VII/609 VII/611

E. References ......................................................................................................................... VII/615 Particle Scattering Factors in Rayleigh Scattering ...................................................................................... VII/629 A. Introduction: General Relations for a Homogeneous Solute ............................................... VII/629 B. Scattering Factors for Various Molecular Models ................................................................ VII/630 C. Effects of Dispersion in Molecular Weight .......................................................................... VII/631 D. Determination of Molecular Weight and Radius of Gyration ................................................ VII/632 E. Calculation of Scattering Factors ........................................................................................ VII/633 F. Particle Scattering Factors and Dissymmetries .................................................................. VII/633 Table 1. Dissymmetries for Monodisperse Systems ............................................................. VII/634 Table 2. Dissymmetries for Monodisperse and Polydisperse Coils ...................................... VII/634 G. References ......................................................................................................................... VII/635 Dipole Moments of Polymers in Solution ..................................................................................................... VII/637 A. Introduction ........................................................................................................................ VII/637 B. Dipole Moments of Polymers In Solution ............................................................................ VII/638 Table 1. Polyoxides (Polyethers) .......................................................................................... VII/638 This page has been reformatted by Knovel to provide easier navigation.

Contents Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9. Table 10. Table 11. Table 12. Table 13.

Polysulfides (Polythioethers) ................................................................................... Hydroxyl Terminated Oxide/Sulfide Copolymers .................................................... Polyesters Derived from Aromatic Diacids .............................................................. Aliphatic and Cycloaliphatic Polyesters .................................................................. Polycarbonates ....................................................................................................... Vinyl Polymers ........................................................................................................ Acrylic Polymers ..................................................................................................... Methacrylic Polymers .............................................................................................. Itaconate Polymers ................................................................................................. Polydienes .............................................................................................................. Silicon Based Polymers .......................................................................................... Styrene Copolymers ...............................................................................................

xlvii VII/639 VII/640 VII/640 VII/641 VII/641 VII/642 VII/643 VII/644 VII/644 VII/644 VII/645 VII/645

C. References ......................................................................................................................... VII/646 Heat, Entropy and Volume Changes for Polymer-liquid Mixtures .............................................................. VII/649 A. Introduction ........................................................................................................................ VII/649 1. Scope of the Table .................................................................................................. VII/649 2. Experimental Methods ............................................................................................ VII/649 B. Key for the Tables .............................................................................................................. VII/650 C. Tables of Literature References for Heat, Entropy, and Volume Changes for Polymer-solvent Mixtures ................................................................................................... Table 1. Main-chain Carbon Polymers .................................................................................. 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylics) .......................................................................................... 1.4 Vinyl Polymers ........................................................................................ 1.5 Poly(styrenes) ......................................................................................... 1.6 Other Compounds .................................................................................. Table 2. Main-chain Carbon Heteroatom Polymers .............................................................. 2.1 Poly(oxides) and Poly(esters) ................................................................. 2.2 Poly(amides) ........................................................................................... 2.3 Poly(siloxanes) ....................................................................................... 2.4 Derivatives of Cellulose .......................................................................... 2.5 Other Compounds ..................................................................................

VII/650 VII/650 VII/650 VII/651 VII/654 VII/655 VII/657 VII/659 VII/659 VII/659 VII/661 VII/661 VII/662 VII/663

D. References ......................................................................................................................... VII/663 Heats of Solution of Some Common Polymers ........................................................................................... VII/671 A. Introduction ........................................................................................................................ VII/671 B. Table of Heats of Solution .................................................................................................. VII/671 C. References ......................................................................................................................... VII/673 Solubility Parameter Values ......................................................................................................................... VII/675 A. Introduction ........................................................................................................................ VII/675 B. Miscibility of Solvents and Polymers ................................................................................... VII/676 1. Cohesive Energy Density and the Solubility (Hildebrand) Parameter ..................... VII/676 This page has been reformatted by Knovel to provide easier navigation.

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Contents 2. 3.

Cohesive Energy Parameters for Polar Systems .................................................... VII/677 Relationship Between Solubility Parameters and Other Thermodynamic Parameters ............................................................................................................. VII/677

C. Solubility Parameter Measurements, Calculations, and Correlations .................................. 1. Solvents .................................................................................................................. 2. Polymers ................................................................................................................. 2.1 Indirect Measurements ........................................................................... 2.2 Correlation Methods ............................................................................... Table 1. Selected Solvents for Use in Polymer Solvency Testing ........................................ Table 2. Group Contribution to Cohesive Energy Density .................................................... 2.1 Carbon-containing Groups ...................................................................... 2.2 Oxygen-containing Groups ..................................................................... 2.3 Nitrogen-containing Groups .................................................................... 2.4 Other Groups .......................................................................................... 2.5 Structural Features ................................................................................. Table 3. Contribution to Ecoh and V ....................................................................................... Table 4. Solubility Parameter I: Component Group Contributions ........................................ Table 5. Solubility Parameter II: Component Group Contributions ....................................... Table 6. Equations to be Used for Hoy's System .................................................................

VII/679 VII/679 VII/680 VII/680 VII/682 VII/683 VII/684 VII/684 VII/684 VII/684 VII/684 VII/685 VII/685 VII/686 VII/686 VII/687

D. Solubility Table 7. Table 8. Table 9.

VII/688 VII/688 VII/694 VII/698 VII/698 VII/698 VII/698 VII/699 VII/699 VII/699 VII/699 VII/700 VII/700 VII/700 VII/700 VII/701 VII/701 VII/701 VII/701 VII/702 VII/702 VII/708 VII/709 VII/710

Parameter Tables ................................................................................................ Solubility Parameters of Solvents in Alphabetical Order ......................................... Solubility Parameters of Solvents in Increasing Order of δ ..................................... Hansen Solubility Parameters of Liquids at 25°C ................................................... 9.1 Paraffinic Hydrocarbons ......................................................................... 9.2 Aromatic Hydrocarbons .......................................................................... 9.3 Halohydrocarbons ................................................................................... 9.4 Ethers ..................................................................................................... 9.5 Ketones ................................................................................................... 9.6 Aldehydes ............................................................................................... 9.7 Esters ...................................................................................................... 9.8 Nitrogen-containing Compounds ............................................................ 9.9 Sulfur-containing Compounds ................................................................ 9.10 Acid Halides and Anhydrides .................................................................. 9.11 Alcohols .................................................................................................. 9.12 Acids ....................................................................................................... 9.13 Phenols ................................................................................................... 9.14 Water ...................................................................................................... 9.15 Polyhydric Alcohols ................................................................................. Table 10. Solubility Parameters of Polymers .......................................................................... 10.1 Main Chain Carbon Polymers ................................................................. 10.2 Main Chain C–O Polymers ..................................................................... 10.3 Main Chain C–N Polymers ..................................................................... 10.4 Other Polymers ....................................................................................... This page has been reformatted by Knovel to provide easier navigation.

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E. References ......................................................................................................................... VII/711 Optically Active Polymers ............................................................................................................................ VII/715 A. Abbreviations Used ............................................................................................................ VII/715 B. Optically Active Polymers from Chiral Monomers ............................................................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(alkenes) .......................................................................................... 1.2 Poly(acrylics) and Related Polymers ...................................................... 1.3 Poly(methacrylics) and Related Polymers .............................................. 1.4 Poly(vinyl Ethers), Poly(vinyl Ketones), and Poly(vinyl Esters) .............. 1.5 Poly(styrenes), Poly(carbazoles) ............................................................ 1.6 Poly(dienes) ............................................................................................ 1.7 Poly(isonitriles) ....................................................................................... 1.8 Poly(alkynes) .......................................................................................... 1.9 Poly(maleimides) and Related Polymers ................................................ 1.10 Other Compounds .................................................................................. Table 2. Main-chain Acyclic Heteroatom Polymers .............................................................. 2.1 Poly(oxides) ............................................................................................ 2.2 Poly(esters) ............................................................................................. 2.3 Poly (sulfides), Poly(thioesters) .............................................................. 2.4 Poly(urethanes), Poly(ureas) .................................................................. 2.5 Poly(amides) ........................................................................................... 2.6 Poly(isocyanates) ................................................................................... 2.7 Poly(imines) ............................................................................................ 2.8 Poly(amino Acids) ................................................................................... Table 3. Poly(saccharides) ...................................................................................................

VII/716 VII/716 VII/716 VII/716 VII/717 VII/718 VII/719 VII/720 VII/720 VII/721 VII/722 VII/723 VII/723 VII/723 VII/724 VII/725 VII/725 VII/726 VII/728 VII/728 VII/729 VII/732

C. Optically Active Polymers from Achiral Monomers .............................................................. Table 4. Main-chain Acyclic Carbon Polymers ..................................................................... 4.1 Poly(acrylics) and Related Polymers ...................................................... 4.2 Poly(methacrylics) and Related Polymers .............................................. 4.3 Poly(vinyl Ethers) .................................................................................... 4.4 Poly(styrenes) ......................................................................................... 4.5 Poly(dienes) ............................................................................................ 4.6 Poly(isonitriles) ....................................................................................... 4.7 Poly(maleimides) .................................................................................... 4.8 Other Compounds .................................................................................. Table 5. Main-chain Acyclic Heteroatom Polymers .............................................................. 5.1 Poly(oxides) and Poly(sulfides) .............................................................. 5.2 Poly(isocyanates) ...................................................................................

VII/733 VII/733 VII/733 VII/734 VII/735 VII/735 VII/735 VII/736 VII/736 VII/737 VII/737 VII/737 VII/738

D. References ......................................................................................................................... VII/739 Anisotropy of Segments and Monomer Units of Polymer Molecules ......................................................... VII/745 A. Introduction ........................................................................................................................ VII/745

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l

Contents B. Tables of Anisotropy of Segments and Monomer Units of Polymer Molecules ................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(methacrylic Acid) and Derivatives .................................................. 1.5 Poly(acrylic Acid) Derivatives with Mesogenic Side Groups ................... 1.6 Poly(methacrylic Acid) Derivatives with Mesogenic Side Groups ........... 1.7 Vinyl Polymers ........................................................................................ 1.8 Poly(vinyl) Derivatives with Mesogenic Side Groups .............................. 1.9 Copolymers, Graft and Block Copolymers .............................................. Table 2. Main-chain Carbocyclic Polymers ........................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 Poly(oxides) ............................................................................................ 3.2 Poly(esters) ............................................................................................. 3.3 Poly(amides) ........................................................................................... 3.4 Poly(peptides) and Nucleic Acids ........................................................... 3.5 Poly(phosphazenes) ............................................................................... 3.6 Poly(siloxanes) ....................................................................................... Table 4. Main-chain Heterocyclic Polymers .......................................................................... 4.1 Poly(imides) ............................................................................................ 4.2 Poly(pyrromellitimides) ........................................................................... 4.3 Poly(quinoxalines) .................................................................................. 4.4 Poly(benzimidazoles), Poly(benzoxazoles) ............................................ 4.5 Poly(saccharides) ...................................................................................

VII/746 VII/746 VII/746 VII/747 VII/747 VII/748 VII/748 VII/749 VII/750 VII/751 VII/751 VII/752 VII/752 VII/752 VII/752 VII/755 VII/755 VII/755 VII/756 VII/756 VII/756 VII/756 VII/757 VII/757 VII/758

C. References ......................................................................................................................... VII/760 Gelation Properties of Polymer Solutions .................................................................................................... VII/765

VIII. Abbreviations of Polymer Names and Chemical Abstract Numbers Abbreviations for Thermoplastics, Thermosets, Fibers, Elastomers and Additives ...................................

VIII/1

A. Introduction ........................................................................................................................

VIII/1

B. Abbreviations in Alphabetical Order ....................................................................................

VIII/2

C. Abbreviations and Acronyms Based on Poly(monomer) Names ......................................... VIII/15 D. Abbreviations for Polymers Named after a Characteristic Polymer Croup .......................... VIII/17 E. Abbreviations for Polymers Produced by Chemical Transformation of Other Polymers ............................................................................................................................ VIII/18 F. Abbreviations for Blends, Reinforced Polymers, etc. .......................................................... VIII/19 G. ISO Codes for Thermoplastic Materials .............................................................................. 1. Codes for ISO Data Blocks 1-5 ............................................................................... 1.1 ISO and DIN Codes for Data Block 1 ..................................................... 1.2 ISO Codes for Items in Data Block 2 ...................................................... 1.3 ISO Codes for Items in Data Block 3 ......................................................

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VIII/19 VIII/19 VIII/19 VIII/20 VIII/20

Contents 1.4 1.5

li

ISO Codes for Extending and Reinforcing Fillers (Data Block 4) ........... VIII/20 ISO Codes for Data Block 5 .................................................................... VIII/21

H. SPI Codes for the Recycling of Plastics .............................................................................. VIII/21 I.

Recommended Abbreviations and Acronyms for Names of Elastomers ............................. VIII/21

J. Abbreviations for Textile Fibers .......................................................................................... VIII/22 Chemical Abstract Registry Numbers and Online Database Searching for Polymer Literature ................ VIII/25 A. Nomenclature ..................................................................................................................... VIII/25 B. CAS Registry Numbers ...................................................................................................... VIII/25 C. Indexing and CAS Registry Number Assignment ................................................................ VIII/26 D. Example Searches ............................................................................................................. 1. Example of a Search Using the Polymer CAS Registry Number ............................ 2. Example of a Search Using the Monomer CAS Registry Number .......................... 3. Example of a Combined Search ............................................................................. 4. Example of a Copolymer Search ............................................................................ 5. Example of an Engineering Database Search ........................................................ 6. Example of a Search with Punctuation in the Polymer Name ................................. 7. Example of an Engineering Materials Abstracts Search ......................................... 8. Example of a Polymer Trademark Search ..............................................................

VIII/26 VIII/26 VIII/26 VIII/26 VIII/28 VIII/29 VIII/29 VIII/29 VIII/29

E. List of CAS Regisry Numbers of Common Polymers .......................................................... VIII/32

Index .......................................................................................................................................

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IX/1