D i p o l e

M o m e n t s

o f

P o l y m e r s

i n

S o l u t i o n

J. F. Salort C/Azalea 200, 28109-Madrid, Spain C. Salom Escuela Tecnica Superior de lngenieros Aeronauticos, Universidad Politecnica, Madrid, Spain E. Riande lnstituto de Ciencia y Tecnologfa de Polfmeros, Consejo Superior de Investigaciones Cientfficas, Madrid, Spain

A. Introduction VII-637 B. Dipole Moments of Polymers In Solution VII-638 Table 1. Polyoxides (Polyethers) VII-638 Table 2. Polysulfides (Polythioethers) VII-639 Table 3. Hydroxyl Terminated Oxide/Sulfide Copolymers VII-640 Table 4. Polyesters Derived from Aromatic Diacids VII-640 Table 5. Aliphatic and Cycloaliphatic Polyesters VII-641 Table 6. Polycarbonates VII-641 Table 7. Vinyl Polymers VII-642 Table 8. Acrylic Polymers VII-643 Table 9. Methacrylic Polymers VII-644 Table 10. ltaconate Polymers VII-644 Table 11. Polydienes VII-644 Table 12. Silicon Based Polymers VII-645 Table 13. Styrene Copolymers VII-645 C. References VII-646

A.

INTRODUCTION

Each conformation of a polymer chain has a dipole moment, \x, in Debye units D (=10 ~18 x u.e.e. x 1 cm or 3.338 x 10" 30 C x m), equal to the vectorial sum of the moments of Af dipolar groups along the chain, that is, }JL(Q = Ylimi> where ra, is the dipole moment associated with the skeletal bond / in the conformation (. The mean-square dipole moment {JJL1) can be written as (22,91)

(Al)

where ra, and m; are the dipole moments associated with the skeletal bonds i and j , respectively, and the brackets mean averages. For a freely jointed chain, the last term in Eq. (Al) averages to zero, and the corresponding meansquare dipole moment is given by (A2) The values of the mean-square dipole moment are currently expressed in terms of the dipole moment ratio, Dn — (/i 2 )/ Yl mh o r ^ e dipolar correlation coefficient, g, by means of the following expression: (A3) Debye (13) pioneered the theories which allow calculation of the dipole moments of molecules in the vapor or gas phase. Other theories (23,32,53) developed to determine the dipole moments of molecules in the liquid state were not so successful because of the difficulties involved in defining the internal field in a polar, condensed medium. This problem was circumvented by calculating the dipole moment of polymers and polar liquids in very dilute solutions using nonpolar solvents. In this way, the solute molecules are separated from one another by nonpolar molecules, and the dielectric behavior of the system resembles that of a gaseous condition. The method developed by Guggenheim (27) and Smith (106), based on this approach, permits calculation of the mean-square dipole moments of polymers by means of the following equation: (A4)

where k% and NA are, respectively, the Boltzmann constant and Avogadro's number, M is the molecular weight of the solute, T the absolute temperature, p and e \ the density and the dielectric permitivity of the solvent, respectively. The term de/dw (proportional to the total polarization of the solute) can be obtained from plots of the dielectric permitivity of the solution, e, against the weight fraction of solute w, in the limit w —» 0. The values of dn2/dw (proportional to the electronic polarization) can be obtained from the increments of the indices of refraction of the solution n with respect to that of the solvent n \, also in the limit w —> 0. A shortcoming of this equation is that a ficticious atomic polarization (instead of the true one) is assumed. However, with the exception of the silicones, the atomic polarization for most systems is less than 10% of the electronic polarization and, consequently, the error involved in the determination of (IJL2) with Eq. (A4) is negligible. The mean-square dipole moment presents some advantages over other more traditional conformation-dependent properties such as the mean-square end-to-end distance (r 2 ) 0 . For

example, since the skeletal bonds change much more in polarity than they do in length, (fj,2) is usually more sensitive to structure than {r2}0. Moreover, with the exception of a relatively few number of polymers that have dipole moments in their structure with a component parallel and the other perpendicular to the chain contour, excluded volume effects are negligible. In the tables, the dipole moments are expressed in terms of either the dipolar correlation coefficient g, or the meansquare dipole moment per repeating unit, {JJL2)/X. For relatively long chains in which dipole contributions of the end groups are not important, (^2}/x and g are related by (A5) where x is the degree of polymerization, and ^Q is the sum of the squares of the dipole moments associated with the repeating unit. Below the generic name of each family of polymers, the dipole moments associated with the backbone are indicated.

B. DIPOLE MOMENTS OF POLYMERS IN SOLUTION TABLE 1. POLYOXIDES (POLYETHERS)* Polymer Poly(oxymethylene) Polyformaldehyde With x = l With x = 2 With x = infinite Poly(oxyethylene) Poly(ethylene oxide) x = 2-6 M n = 4000 X= 1-6 x = 4.0-176.2 x = 4.1-153.0 x = 1-33,6 M n = 4000 x = 1-7 x = 2-227 Poly(oxypropylene) Poly(propylene oxide) x = 6.6-69.0 Poly(oxytrimethylene) Poly(trimethylene oxide) Poly[oxy(2,2-dimethyltrimethylene)] Poly(3,3 -dimethyloxetane) M n = 8500 Mn = 19000 Mn = 35000 Poly [oxy( 1 -methyltrimethylene)] Poly(2~methyloxetane) Mn = 13000 Poly[oxy(2-methyltrimethylene)] Poly(3-methyloxetane) Mn = 125000

Solvent

Temp. (0C)

gorDn

(/J2)/JC, D 2

Remarks

0.1 0.29 0.3

Refs.

Benzene Benzene Melt

25 25 202

109 109 56

Benzene Benzene Benzene Benzene Benzene Benzene Benzene Dioxane Benzene

20 20-60 25 25 25 20 20-60 25 20-30

Benzene Benzene Dioxane

25 25 25

0.54 0.49

Benzene

25

0.41

50

Benzene Benzene Benzene

20-60 30-60 30-60

0.25-0.30 0.20-0.22 0.21-0.23

94 25 25

Cyclohexane

30-60

0.36-0.41

78

Cyclohexane

30-60

0.35-0.38

77

1.32-1.23 0.603-0.644 1.30-1.14 2.82-1.28 2.59-1.28 1.99-1.19 0.621-0.693

End groups: -OC 2 H 5 m(CH 2 -O) = 0.99Z) End groups: -OC 2 H 5

W(CH2-O) = 0.99D 2.82-1.66 2.13-1.14 1.96-1.04 Isotactic Isotactic

47 59 34 46 2 45 4 110 47 45 1 1

*If not indicated otherwise, the dipole moments associated with the skeletal bonds used in the calculation of g were m(CH 2 -0) = 1.07D, m(CH 2 -CH 2 ) = 0£>, and m(O-H)= 1.7D.

TABLE 1. cont'd Polymer

Solvent

Temp. (0C)

Poly(oxytetramethylene) Polytfetramethylene oxide) M n =2500 Benzene Mn-408000 Benzene Poly[oxy(2-methyltetramethylene)] Poly(3-methyltetrahydrofuran) M n = 6700 Benzene Poly(oxyhexamethylene) Poly(hexamethylene oxide) M n = 5500 Benzene Mn = 2460 Benzene Poly(oxydecamethylene) Polyidecam ethy Ien e oxide) M n = 2000 Benzene Poly(oxyethyleneoxyrnethylene) Poly(l,3-dioxo!ane) M n = 12000 Benzene M n =16000 Benzene M n =42000 Benzene Poly(oxytetrarnethyleneoxymethylene) PoIy ( 1,3-dioxepane) M n = HOOO Benzene Poly(oxypentamethyleneoxymethylene) Poly( 1,3 -dioxocane) M n = 1850 Benzene Mn = 2560 Benzene M n = 3700 Benzene Poly(oxyhexamethyleneoxymethylene) Poly( 1,3 -dioxonane) M n =4020 Benzene Mn = 2600 Benzene Poly(7/rm.s-oxymethylene-1,4-cyclohexyIeneoxymethylene) Poly( trans-1,4-cyclohexane dimethanol alt-formaldehyde) Mn =6500 Benzene ' Poly(oxypropyleneoxy methylene) Poly [(4-methyl)-1,3-dioxolane] M n =40000 Benzene M n =48000 Benzene Poly(fra/is-7-oxabicyclo-[4.3.0Jnonane) Poly(trans-7-oxabkyclo-[4.3.0]nonane) Benzene

g or Dn

(n2)/x, D2

ra(CH 20-60 20-60

Remarks 2 -O) =

Refs. 0.99D

0.60-0.65 0.59-0.65

30-60

61 4

0.52-0.55

81

ra(CH 35-60 35-60

2 -O) =

0.99D

0.65-0.68 0.64-0.67

59 80

ra(CH 35-60

2-O) =

0.99D

0.64-0.68

61 Polyformals: alternating copolymer of methylene oxide and alkylene oxide

20-60 20-60 20-60

0.160-0.204 0.164-0.213 0.177-0.227

62 62 62

25-60

0.160-0.190

63

20-60 20-60 20-60

0.190-0.232 0.183-0.207 0.168-0.207

64 64 64

20-60 20-60

0.190-0.230 0.180-0.217

64 64

20-60

0.17-0.21

71

20-60 20-60

0.237-0.281 0.216-0.256

73 73

30-60

0.63-0.66

111

TABLE 2. POLYSULFIDES (POLYTHIOETHERS)* Polymer Poly(thiotrimethylene) PoIy(trimethylene su lfide) M n = 14000 Poly(thiopentamethylene) Poly(pentamethylene sulfide) M n = 3200

Solvent

Temp. (0C)

g or Dn

Benzene

20-60

0.60-0.63

Benzene

20-60

0.75-0.78

Benzene Carbon tetrachloride Benzene Carbon tetrachloride Benzene Carbon tetrachloride Benzene

20-60 20-60 20-60 20-60 20-60 20-60 20-60

0.434-0.449 0.362-0.407 0.429-0.458 0.325-0.347 0.448-0.460 0.357-0.389 0.386-0.420

(n2)/x,D2

Remarks

Refs.

75

End bonds: CH 2 -Br; m(CH 2 -Br)=1.96D

74

Poly(thiopropylene) Polyipwpylene sulfide) Mn Mn Mw Mn Mn Mn

= 5000000 =5000000 = 1.6 x l O 6 =5000 =6000 =1.6 x l O 6

Isotactic

Isotactic

67 68 68 68 67 67 68

* Wt(CH2-CH2) = 0A m(CH 2 -S)=1.2LD, m(6-H) = 1.7D.

References page VII - 646

TABLE 2. cont'd Polymer

Solvent

Poly[thio(2,2-dimethyltrimethylene)] Poly {3,3-dimethylthietane) M n = 8200 Benzene Poly(thiopentamethylenethioethylene) Poly(ethylene sulfide-alt-pentamethylene sulfide) Mn = 3800 Benzene

Temp, (0C)

gorDn

30-60

0,62-0.63

30-60

0.64-0.67

Poly(thiopentamethylenethiomethylene) PoIy(1,3-dithiocane) Mn = 14000 Benzene 20-60 Poly(thiomethylene-1,4-cyclohexylenemethylenethiomethylene) trans Mn = 8000 Benzene 30-60

0.26-0.31

TABLE 3. Polymer

(fi2)/x,D2

Remarks

Refs.

72

End bonds: CH 2 -Br, m(CH 2 -Br)=1.96D Alternating copolymer of pentamethylene sulfide and methylene sulfide

0.176-0.207

70

112 54

HYDROXYL TERMINATED OXIDE/SULFIDE COPOLYMERS0 Solvent

Poly(thioethyleneoxyethylene) Poly(thiodiethylene glycol) M n = 13000 Benzene M n = 8000 Benzene Poly(thiomethyleneoxymethylenethiopentamethylene) Poly(3-oxa-1,5-dithiadeca-methylene) M n = 5200 Benzene Poly(oxymethyleneoxyethylenethioethylene) PoIy(1,3-dioxa-6-thiocane) M n = 2500 Benzene M n = 3000 Benzene Poly(oxymethyleneoxyethylenethiomethylenethioethylene) Alternating copolymer of 1,3-dioxolane and 1,3-dithiolane Benzene

Temp. (0C)

g or Dn

Remarks Alternating copolymer of ethylene sulfide and methylene sulfide

Refs.

20-60 20-60

0.607-0.648 0.627-0.659

66 66

30-60

0.323-0.358

84

20-60 20-60

0.419-0.432 0.419-0.432

65 65

30

0.26

66

fl

m(CH2-CH2) = 0Z), m(CH 2 -0)= 1.07D, m(CH2-S)= 1.21D.

TABLE 4. Polymer

POLYESTERS DERIVED FROM AROMATIC DIACIDS* Solvent

Poly[di(oxyethylene) oxyterephthaloyl] Poly(diethyleneglycol terephthalate) M n = 2500 Benzene Poly[di(oxyethylene) oxyisophthaloyl] Poly(diethyleneglycol isophthalate) M n = 5900 Benzene Poly[di(oxyethylene) oxyphthaloyl) Poly(diethyleneglycol phthalate) M n = 10300 Benzene Poly(oxypropyleneoxyterephthaloyl) Poly(propyleneglycol terephthalate) M n = IlOOO Benzene Poly[di(oxypropylene) oxyterephthaloyl) Poly(dipropyleneglycol terephthalate) M n = IOOOO Benzene Poly(tri(oxytrimethylene) oxyterephthaloyl) Poly(triethyleneglycol terephthalate) M n =7800 Benzene Poly[di(oxytrimethylene) oxyterephthaloyl] Poly(ditrimethyleneglycol terephthalate) Mn =15500 Benzene (Poly(thioethyleneoxyethyleneoxyterephthaloyl) Poly(thiodiethyleneglycol terephthalate) M n = 6400 Dioxane

Temp. (0C)

g or Dn

35-60

0.688-0.692

60

30-60

0.691-0.692

79

30-60

0.637-0.679

86

30-60

0.582-0.609

87

30-60

0.715-0.750

14

30-60

0.677-0.695

82

30-60

0.805-0.798

26

40-70

0.540-0.552

Remarks

m(CH 2 -S) = 1.21D

'Hydroxyl terminated polyesters m(C6H5COOCH2) = 1.98Z); m(CH2-O) (ether)= 1.07D; m(CH2-CH2) = 0D; m(O-H) = LlD.

Refs.

69

TABLE 5. ALIPHATIC AND CYCLOALIPHATIC POLYESTERS* Polymer

Solvent

Poly[oxy (2,2-dirnethyltrimethylene) oxysuccinoyl] Poly(neopentylglycol succinate) M n = 6900 Benzene Poly(oxysuccinoyloxymethylene-1,4-cyclohexylenemethylene) trans Poly(trans-l,4-cyclohexane dimethanol succinate) M n = 5800 Dioxane Poly[oxy(2,2-dimethyltrimethylene) oxyadipoyl] Poly(neopentylglycol adipate) M n =5500 Benzene Poly(oxyadipoyloxymethylene-1,4-cyclohexylenemethylene) cis Poly(cis-1,4-cyclohexane dimethanol adipate) M n = IlOOO Benzene M n = IlOOO Dioxane Poly(oxy adipoyloxymethylene-1,4-cyclohexylenemethylene) trans Poly(trans-1,4-cyclohexane dimethanol adipate) M n = IOOOO Dioxane Poly(oxysebacoyloxymethylene-1,4-cyclohexylenemethylene) trans Poly(trans-1,4-cyclohexane dimethanol sebacate) M n =4600 Benzene Poly[oxy(2,2-dimethyltrimethylene) oxyhexafluoroglutaroyl] Poly(neopentylglycol hexafluoroglutarate) M n = 3640 Benzene Poly[oxy(2,2-dimethyltrimethylene) oxyglutaroyl] Poly(neopentylglycol glutarate) M n =4500 Benzene Poly(oxysebacoyloxymethylene-1,4-cyclohexylenemethylene) cis Poly(cis-1,4-cyclohexane dimethanol sebacate) M n = 5200 Benzene Poly[di(oxyethylene) oxycarbonyl-1,4-cyclohexylenecarbonyl] trans Poly(diethyleneglycol-1,4-trans-cyclohexane dicarboxylate) M n = 5300 Benzene

Temp. (0C)

g or Dn

(fi2)/x

30-60

0.548-0.586

88

70

0.454

90

30-60

0.653-0.688

85

30-60 30-60

0.950-0.972 0.914-0.959

90 90

50-70

0.596-0.65

90

30-60

0.631-0.709

83

Refs.

30-60

9.16-9.78

58

30-60

4.26-4.52

58

300-60

0.983-1.04

83

30-60

0.585-0.608

89

* Hydroxyl terminated polyesters m(CH2COOCH2)= 1.89D. TABLE 6.

POLYCARBONATES

Polymer

Solvent

Temp. (0C)

(p2)/x,D2

Remarks

Refs.

Poly(oxycarbonyloxy-1,4-phenylene-1 -(R)-1 -methylmethylene-1,4-phenylene) Polycarbonate x = 97 JC = 88 x — 73

Benzene Benzene Benzene

25 25 25

9.36 11.70 17.64

R = 3-chlorophenyl R = 4-chlorophenyl

28 28 28

Benzene 25 1,4-Dioxane 25 1,4-Dioxane 25 Benzene 25 Benzene 25 2,2/-bis(4-hydroxylphenyl)propane) 2,2/-bis(4-hydroxylphenyl)propane) 1,4-Dioxane 25 l,l/-bis(4-hydroxyphenyl)-l-(3-chlorophenyl)ethane) l,l/-bis(4-hydroxyphenyl)-l-(3-chlorophenyl)ethane) Benzene 25 l,l/-bis(4-hydroxyphenyl)-l-(4-chlorophenyl)ethane) 1,17-bis(4-hydroxyphenyl)-1-(4-chlorophenyl)ethane) Benzene 25

1.69 1.88 2.07 2.76 2.13

R = isobutyl R= H R = phenyl R= H R = ethyl

21 21 21 21 21

Poly(thiocarbonate) Poly(thiocarbonate) x= 128 x = 75 JC = 2 8 0 JC = 7 5 x = 49 Poly(thiocarbonate Poly(thiocarbonate M n =9400 Poly(thiocarbonate Poly(thiocarbonate With JC = 97 Poly(thiocarbonate Poly(thiocarbonate With x = 88

of of of of of of

0.92

97

7.40

99,28

6.05

99,28

References page VII - 646

TABLE 6. cont'd Polymer

Solvent

Temp. (0C)

(fi2)/x,D2

Poly(thiocarbonate of l,l/-bis(4-hydroxyphenyl)-l-(3,4-dichlorophenyl)ethane) Poly(thiocarbonate of 1, l/-bis(4-hydroxyphenyl)~l-(3,4-dichlorophenyl)ethane) With x = 73 * Benzene 25

Remarks

Refs.

12.25

99,28

TABLE 7. VINYL POLYMERS* Polymer Poly (1 -phenylethylene) Poly(styrene) Atactic Atactic Isotactic Poly(2-bromophenylethylene) Poly(o-bromostyrene)

Solvent

Toluene Carbon tetrachloride Toluene

Temp. (0C)

g or Dn

38.4 25 38.4

0.36 0.56 0.53

(n2)/x9D2

Remarks

M0 = 0.60D /i 0 = O.35D /.to = 0.60D

0.50 1.21

Poly(4-bromophenylethylene) Poly(p-bromostyrene) PPBSI /?-Dioxane PPBSI Carbon tetrachloride PPBSII /7-Dioxane Poly( 1 -phenylethylene/(4-pyridyl) ethylene) Poly {sty rene/4-vinylpyridine) Benzene Poly[ 1 -methyl-1 -(4-fluorophenyl) ethylene] Poly(p-fluoromethylstyrene) Benzene Benzene Poly[(4-methoxyphenyl) ethylene] Poly(p-methoxystyrene) Toluene Benzene Benzene Poly[(4-fluorophenyl) ethylene] Poly(p-fluorostyrene) Benzene Benzene Poly[(2-chlorophenyl) ethylene] Poly(o-chlorostyrene)

20-50 20-50 20-50 0.73

25 25

0.62 0.27

25 25 25 25 25

108 108 108 Mo = 2.65D

5

0.89

Mo = 1.82D /*0 = 1-82D

6 5

0.54 0.72 0.64

0.78 1.06 0.94

no = l.2W no = \.2\D /x0 = 1.21D

31 5 6

0.62 0.51

2.05 1.69

Mo = 1.82D Mo = 1-82D

6 5

2.85 Poly[(3-chlorophenyl) ethylene] (Poly(m-chlorostyrene) Poly[(4-chlorophenyl) ethylene] Poly(p-chlorostyrene)

57

Toluene

25

0.63

1.61

Mo = 1-60D

Xylene

30 30-50 30 50 20-50 25 25-65 30 30-90 30-60 25 25 30 20-90 25 30 30 25 30-90 15-70

0.71 0.42-0.56 0.56

2.00

Mo = 1.68

2.10 1.89 2.11-2.46 1.82 1.87-1.73 2.17 2.06-1.98 2.09-2.12

Mo = 1^3

Benzene Carbon tetrachloride /?-Dioxane Toluene Cumene Toluene Isopropylbenzene Toluene Benzene Toluene Isopropylbenzene K-Propylbenzene Carbon tetrachloride Benzene Benzene Toluene Isopropylbenzene Benzene

35 37 35 57 57

2.20-2.49 2.12-2.54 2.44-2.72

25

Refs.

0.77 0.73-0.70 0.74-0.75 0.64 0.53 0.436-0.499 0.57 0.60 0.493-0.520 0.599-0.562

1.65 1.50 1.641-1.878

M0 = ^0 = Mo = Mo =

1.68 1.68 1 68 2.0

Mo =1-68 Mo = 1 88D

1.49 1.49 1.59 11.854-1.956 2.373-2.224

Isotactic Mo = 1 63

93 11 57 12 108 108 113 113 11 9 9 5 31 Il 114 6 55 55 93 114 114

*In vinyl polymers the dipolar correlation coefficient is expressed by g = (M 2 ) AMO> w h ^re x is the degree of polymerization and MO is the dipole moment of a model compound of the repeating unit.

TABLE 7. cont'd Polymer

Solvent

Poly( 1 -acetoxyethylene) Poly(vinyl acetate)

Poly( 1 -bromoethylene) Polyivinyl bromide) Several fractions

Poly( 1 -chloroethylene) Poly(vinyl chloride) Atactic fraction Atactic fraction Atactic fraction Eight fractions (atactic) Syndiotactic fraction Mn = 26000 (atactic) Mn =47000 (atactic) Poly(isobutoxyethylene) Poly(vinyl isobuts'lether) Isotactic fraction Atactic fraction Isotactic fraction Atactic fraction Poly(carbazolylethylene) Poly(vinyl carbazole)

Temp. (0C)

g or Dn

(fi2)/x,D2

Remarks

Refs.

25 20

0.89 and 0.94 0.84 0.75-0.80

2.59-2.89 2.89

/X0 = 1-80D ^ 0 = 1.86

38 101 107

1.97-3.20 2.29-2.38

^o = 1.93D /x0 = 2.08D ^o = 2.08D

40 95 95

2.65 2.79-3.06 1.716 1.72-1.67 2.59-2.82 1.93 2.72-2.60

/i O = Mo = /xo = /x0 = ^0 = /U0 = /i 0 =

2.80-2.72

^ 0 = 2.00D

33 29 33 33 39 33 8 12 8

1.345 and 1.464

^ 0 = 1.22Z) /xo = 1.22D

107 107 55 55

Benzene and CCl4 Benzene

/>Dioxane p-Dioxane 1-Methylnaphthalene

/?-Dioxane /?-Dioxane Tetrahydrofuran Tetrahydrofuran p-Dioxane Tetrahydrofuran /7-Dioxane

25 30-60 30-60

20 and 40 20-65 40 20 and 40 25 20 25-55

/7-Dioxane

Benzene Benzene Benzene Benzene

25-55

0.59 0.70-0.75 0.64-0.62 0.66-0.72 0.71 0.68-0.65 0.75 0.70-0.68

2.12D 2.00D 1.64D 1.64D 2.00D 1.64D 2.00D

25 and 50 25 30 30

0.90 and 0.98 0.77 and 0.83 0.98

0.98 0.96

25 30-60

0.36 0.41-0.44

3.71 3.52-3.78

/x0 = 3.21D /x0 = 2.93D

30 102

20-50

1.10-1.06

2.34-2.26

^ 0 = 1.46D

100

25

0.28

1.21

/x0 = 2.08D

6

Toluene /7-Dioxane

Poly(ethylenethiophenylene) Pofyfvinylphenyl sulfide) Benzene Poly[ 1 -methyl-1 -(4-bromophenyl) ethylene] Po/vfp-fcroma-a-methylstyrene) Benzene

TABLE 8.

0.53-0.86 0.45-0.46

ACRYLIC POLYMERS*

Polymer Poly[ 1 -methoxycarbonyl) ethylene] Poly(methyl aery late)

Solvent

Benzene Benzene

Temp. (0C)

20 25

Poly[2-(biphenyloxycarbonyl) ethylene] Poly(2-biphenyl acrylate) Benzene 30-60 Poly[ 1 -(cyclohexyloxycarbonyl) ethylene] Poly(cyclohexyl acrylate) Benzene 30-60 PoIy[I -(ethoxycarbonyl) ethylene] Poly(ethyl acrylate) Atactic fraction Benzene 30 Syndiotactic fraction Benzene 30 Poly[ 1 -(phenoxycarbonyl) ethylene] Polyiphenyl acrylate) Benzene 30-60 PoIy[I-((3-chloro) phenoxycarbonyl) ethylene] Polyim-chlorophenyl acrylate) Benzene 30-60 PoIy[I -((2-chloro) phenoxycarbonyl) ethylene] Poly(o-chlorophenyl acrylate) Benzene 30-60 PoIy[I-((4-chloro) phenoxycarbonyl) ethylene] Polyip-chlorophenyl aaylate) Benzene 30-60 PoIy[I-((4-benzoyl) phenoxycarbonyl) ethylene] Poly(4-benzoylphenyl acrylate) 1,4-Dioxane 30-60 PoIy[I-(4-phenoxy) phenyloxycarbonyl) ethylene] Poly(4-phenoxyphenyl acrylate) Benzene 30-60 PoIy[I -(hydroxyethylenedi(oxyethylene) oxycarbonyl) ethylene] Poly(triethyleneglycol acrylate) Benzene 30-60

g or Dn

(n2)/x,D2

Remarks

Refs.

0.717 0.64-0.67

2.22 1.99-2.07

/xo = l-76D /x0 = 1.76D

51 43

0.69-0.74

2.05-2.22

/i 0 = 1.723- 1.732D

16

0.75-0.81

2.79-3.01

/i 0 = 1.93D

15

1.04 1.04

55 55

0.62-0.66

1.73-1.91

/U0 = 1-669-1.700D

98

0.57-0.61

1.85-2.02

/I0 = 1.800- 1.824D

98

1.09-1.09

3.30-3.97

^ 0 = 1.74-1.91D

98

MO = 2 . 5 9 O - 2 . 6 9 4 D

98

^ 0 = 3.561-3.521/)

17

^ 0 =2.10-2.1 ID

18

0.524-0.501 0.81-0.84

10.27-10.41

0.82-0.84

3.61-3.74 7.97-8.16

92

* /to is the dipole moment of a model compound of the side group.

References page VII - 646

TABLE 9. METHACRYLIC POLYMERS* Polymer

Temp. (0C)

Solvent

Poly [ 1 -methoxycarbonyl)-1 -methylethylene] Poly(methyl methacrylate) Atactic fraction Five solvents Atactic fraction Benzene Atactic fraction Benzene Syndiotactic fraction Toluene Isotactic fraction Toluene Syndiotactic fraction Benzene Atactic fraction Benzene Isotactic fraction Benzene Isotactic fraction Benzene Atactic fraction Benzene Atactic fraction Toluene Syndiotactic fraction Benzene Atactic fraction p-Dioxane Poly[l-(ethoxycarbonyl)-l-methylethylene] Poly(ethyl methacrylate) 1,4-Dioxane Carbon tetrachloride Toluene Benzene Poly [ 1 -(propoxycarbonyl)-1 -methylethylene] Poly(propyl methacrylate) Poly [ 1 -(isopropoxycarbonyl)-1 -methylethylene] Poly(isopropyl methacrylate) Poly(butyl methacrylate) Poly(butyl methacrylate) Four solvents Poly(phenylmethacrylate) Poly(phenylmethacrylate) Poly(p-chlorophenylmethacrylate) Poly(p-chlorophenylmethacrylate) Poly(dichlorophenylmethacrylate) Poly(dichlorophenylmethacrylate)

25 25 25 30-90 25-65 25-65 25-65 25-65 30 30 25-65 30 23

0.62 0.53-0.66 0.55-0.72 0.67-0.79 0.65-0.75 0.70-0.78 0.69-0.78 0.77-0.81 0.67 0.56-0.61 0.66-0.78 0.53

25 25 25

0.58 0.54 0.62 0.59-0.62 0.58

25

(fi2)/x,D2

gorD,,

Remarks

^o = 1.73D 1.77-2.31 1.72-2.01 1.66-1.93 1.79-1.99 1.77-1.99 1.96-2.07 2.00 1.66-1.82 1.69-1.99 1.61 2.25

/i 0 = /x0 = ^0 = /^0 = ^0 = ^0 = Mo = /i 0 = /*0 = ^t0 =

1-80D 1-60D 1-60D 1.60D 1-60D 1-60D 0.73D 1.73D 1-60D 1-73D

2.00 1.87 2.14

/i 0 = 1-86D /^0 = 1-86D / i 0 = 1-86D

2.00

/I0 = 1.86D

48 57,107 42 105 105 105 105 105 3 3 105 3 10 36 36 36 57

0.56-0.59

57

0.61-0.66

57 1..93-2.72

23

Refs.

0.55-0.59

10 57

0.55

57

0.35

57

0.38

52

*}IQ is the dipole moment of a model compound of the side group.

TABLE 10. ITACONATE POLYMERS Polymer

Temp. (0C)

Solvent

Poly[ 1 -(cyclohexylmethylene oxycarbonylmethylene)-1 -(carboxy)ethylene] Poly(monocyclohexylmethylene itaconate) 1,4-Dioxane 20-50 Poly[ 1 -(cyclohexylmethyleneoxycarbonylmethylene)-1 -(cyclohexylmethyleneoxycarbonylmethylene) ethylene] Poly(dicyclohexylmethylene itaconate) Benzene 30-60 Poly[ 1 -benzyloxycarbonylmethylene)-1 -(carboxy) ethylene] Poly(monobenzyl itaconate) 1,4-Dioxane 25 Poly [ 1 -(benzyloxycarbonylmethylene)-1 -(benzyloxycarbonylmethylene)ethylene] Polyidibenzyl itaconate) 1,4-Dioxane 25-33

(n2)/x,D2

Refs.

5.75-5.70

20

6.89-7.00

19

3.84

96

2.31-2.79

24

TABLE 11. POLYDIENES

Polymer Poly( 1 -methyl-1 -butenylene) Poly(isoprene) cis 1,4 trans 1,4 Poly( 1 -chloro-1 -butenylene) Poly(chloroprene)

Temp. (0C)

gorD,,

Benzene Benzene

25 25

0.70 0.82

Benzene

20

2.70

Solvent

Remarks

^o = 0.34D ^ 0 = 0.34D

Refs.

41 41 101

TABLE 12. SILICON BASED POLYMERS* Polymer

Solvent

Linear Poly(dimethylsiloxane) Linear Poly(dimethylsiloxane) x+) =188 " A = 9.85 A = I , 102 x = 4, 95.0 .x = 69.6 JC= 14.8 A = 70.55 jc= 15.8 x~ 10.5 A+1=239 A-+1=97 A + 1 = 1038 A+1=239 A + 1 = 188 A+1=97 A + 1 = 1038 Poly (1,1 -dimethylsilazane) PoIy(IJ -dimethylsilazane) M n = 750

Undiluted Cyclohexane, benzene Undiluted

Temp. (0C)

g or Dn

10-60 30 25

0.306-0.297 0.18-0.21

Undiluted Cyclohexane, Cyclohexane, Cyclohexane, Cyclohexane, Cyclohexane, Undiluted Undiluted Cyclohexane Cyclohexane Cyciohexane Cyclohexane Undiluted

(?*2)/x, D2

Cyclic PDMS Linear PDMS; {fi2)1/2 = 2.07D, 14.4D Cyclic PDMS; (/i 2 ) l / 2 = 1.50D, 14.3D

25 benzene benzene benzene benzene benzene

30 30 30 30 30 10-60 10-60 10-60 10-60 10-60 10-60 10-60

Cyclohexane Hexamethyldisilazane Hexane Carbon tetrachloride Benzene

20-50 25 20 20-50 20-50

Poly(methylphenyl siloxane) Poly(methylphenyl siloxane) Mn = 45000 Cyclohexane Poly(dimethyl siloxane-co-methylphenyl siloxane) (35.7/54.3) Poly(dimethyl siloxane-co-methylphenyl siloxane) (35.7/54.3) Mn = 4200 Cyclohexane Poly(dimethylsiloxane-c