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C. OLIGOMERS CONTAINING HETEROATOMS IN THE MAIN CHAIN
TABLE 6. 6.1.
OLIGOMERS CONTAINING O IN THE MAIN CHAIN
OLIGO(ETHERS) AND OLIGO(ACETALS)
6.1.1. OLIGO(OXYETHYLENES) 6.1.1.1. Linear Oligo(oxyethylenes) H[OCH 2 CH 2 I n OH na
MoI. wt.
1 2 3 4 5 6 7 8 9 10 12 14 15 16 18 20 25 27 30 35 36 45 54
62.1 106.1 150.2 194.2 238.3 282.3 326.4 370.4 414.5 458.6 546.6 634.7 678.8 722.9 811.0 899.1 1119.3 1207.5 1321.6 1559.8 1604.0 2000.4 2396.9
a
m.p. ( 0 C) -12.6 -6 -4.3 -3 - 2 toO 9 17.8-18.8 19.7-21.8 30.0 25.8-28.3 36.5-38.5 29.5 40.0 49.5-505 35.0 44.4 47.0 44.6-44.8 46.4 50.1 43.0-43.4 53.0 54.2
b.p. (°C/mbar) 197.8/1013 245/1013 122-123/0.1 155-156/0.8 173-174/0.8 175-177/0.07 230-232/0.9 206-209/0.02 186-192/0.001 210/0.1
(g/cm 3 ) 1.1136/20 1.120/20 1.1274/15 1.127/20 1.127/20 1.1278/20
d2o n£°/°C 1.4324 1.4479 1.4573 1.4611 1.4629 1.4640 1.4653 1.4660
246-257/0.001
Refs. 23-26,55,119,149,209 23-26,55,57,119,129,149,209 23-25,26,55,57,119,129,149,209 23-27,55,57,70,119,120,129,149,209 25-27,55,57,68,71,119,149,209 23-28,55,68-70,119,120,209,215 25,26,55,57,69,71,119,219 27,120,215,219 37,50,52-54,56,59,219 27,51,54,71,219 219 25 37,50-54,59 219 25,37,211 51,54 51,53,54,59 37 25,54 51,53,54,59 37 37,54 212
n = 1-27: HPLC, Refs. 72-74; n = 1-45: GPG, Ref. 220; n = 6,8,9,10,15,16,18,25,35,54: IR, Raman, NMR, MS, DSC, Ref. 211,212,214,215,219,224.
6.1.L2. Oligo(oxyethylene) Monoalkyl Ethers R - [ O C H 2 C H 2 ] ^ - O H R
na
MoI. wt.
m.p. ( 0 C)
CH 3
1 2 3 5 6 7 8 9 10 11 18 1 2 3 4 1 2 3 1 2 3 1 2 3 4
76.1 120.1 164.2 252.3 296.4 341.4 385.5 429.5 473.6 518.1 825.0 90.1 134.2 178.2 222.3 148.2 192.3 236.3 118.2 162.2 206.3 146.2 190.3 234.3 278.4
-85.1
C2H5
M-C3H7
n-C 4 H 9
Ai-C6Hi3
13-14 18-18.5 22 24-25
-68.1 -50.1 -36.9 -30.3 -15.0
b.p. (°C/mbar)
n™
124/1009 194.2/1013 245.3/1013 110/0.013 125/0.013 150/0.007 165/0.007 185/0.003 218-220/0.013 236-238/0.013
1.4024 1.4260
135/1013 196/1013 248/1013 284/1013 152-153/1012 215.8/1023 148-150/23 171/1013 112-114/15 278/1013
1.4075 1.4273 1.4380 1.4499 1.4133
1.4196
Refs. 26,124,125,127-129,177,196 127 180 178 178 178 178 178 178 178 24 24,125-129,176,177,196 126,129 126 129 128,129,175-177,196 175 175 24,125,129,176,177,194,196 194 206 102 102 102 102
6.1.1.1. cont'd na
W-C9H19 W-Ci2H25
W-Ci6H33 C 6 H 5 CH 2
(C 6 Hs) 3 C
C6H5
MoI. wt. 5 6 9 4 8 1 2 3 4 5 6 7 8 9 10 11 12 9 12 3 4 5 6 8 9 3 4 5 6 1 2 3 4 5
m.p. ( 0 C) 322.4 366.5 498.6 320.5 496.7 186.3 230.4 274.4 318.5 362.5 406.6 550.8 594.8 638.9 683.0 727.0 771.1 638.9 771.1 240.3 284.3 328.4 372.4 460.6 504.6 392.4 436.5 480.6 524.6 138.2 182.2 226.3 270.3 314.4
(g/cm 3 )
b.p. (°C/mbar)
°/°C
-3.3 1.2 13.0 180-182/0.5 22.7 20.2 18.6 17.0 20.0 22.8 25.4 28.5 32.3 33.5 40.0 40.3 42.0 40.5 43.5
NMR, MS
144/0.13 164/0.13 178/0.13 188/0.07 212/0.07 233/0.13 236-240/0.15
1.4456 1.4485 1.4510 1.4531 1.4548 1.4560 1.4576
166-169/0.5
1.503 1.501 1.499 1.493 1.488 1.483 1.540 1.544 1.549 1.561 1.5370 1.5230 1.5144 1.5075 1.5030
120.5/12 163.0/11 190.5/11 181/0.3 218/0.5
Refs. 102 102 102 225 225 70,207 70,207 70,207 70,207 70,207 70,207 207 207 207 207 207 207 56 56 75,175 75 75 75 75 75 75 75 75 75 109 109 109 109 109
a
n = 4,6,8,12,16 with R= W-C9Hi9 and n-Ci5H3i: Raman spectr., Ref. 213.
6.1.1.3. Oligo(oxyethylene) Dialkyl Ethers H(CH 2 )^-[OCH 2 CH 2 ] n -O(CH 2 )^H na
x
1
1 2 3 4 1 2 3 4 1 2 1 2 4 1 2 1 2 4 1 1 2 3 4 6
2
3 4
5 6
7 9
MoL wt.
90.1 118.2 145.7 174.2 134.2 162.2 190.2 218.3 178.8 206.3 222.3 250.3 306.4 266.3 294.4 310.4 338.4 394.5 354.4 442.5 470.6 498.6 526.7 582.8
m.p. ( 0 C)
b.p. (°C/mbar)
84/1013 124/1013 159-160/965 204/1013 161/1013 189/1013 219/983 250/1013 216/1013 118/13 148/19 159/15 192/13 149-151/3.3 174/4 135/0.1 125/0.01 155/0.4 205-207/4 16.0 21.5 12.7 11.7 13.0
n D /°C
1.3797/20 1.3922/20
1.4183/20 1.4143/20 1.4025/25 1.4265/20 1.4233/20 1.4371/20 1.4332/20 1.4384/20
1.4471/20 1.4454/20 1.4509/20
Refs.
130,131,133,134,195 24,131,132,135 131,175 24,131,132 24,26,134,179,195 8,24,135,179 179 24,179 134 135 8,24,134 24,135 24 134,136,166 135 24,134 24,135 24 134 52,58,59 58,59 58 58 58
6.1.1.3. cont'd na
15
25
45
x
MoL wt.
m.p. ( 0 C)
8 10 12 16 18 21 26 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 21 26 30 4 15 30 1 10 13 15 18 21 30
638.8 695.0 751.1 863.3 919.4 1003.8 1143.8 706.8 734.9 762.9 791.0 819.0 847.1 875.2 903.2 931.2 959.3 987.4 1015.4 1043.5 1071.6 1099.6 1127.6 1155.7 1183.7 1267.9 1408.2 1520.4 1231.5 1540.1 1960.9 2028.4 2280.9 2365.0 2449.2 2505.3 2589.4 2841.9
19.5 28.5 37.0 49.5 54.0 62.0 69.0 28.7 35.1 30.8 31.3 32.0 32.2 33.7 35.3 38.4 39.5 42.5 45.5 47.3 50.0 51.7 54.4 57.6 59.0 62 68 71 43.5 55.5 72.7 51.3 52.8 56.1 57.1 61.2 64.3 66
b.p. (°C/mbar)
w D /°C
Refs.
Raman
58 58,63 58,63,64 58,63,64 58,63 58 58,63 52,59,60 59,60,224 60,63 60,63 60,63 60,63 60,63 60,63 60,63 60,63 60,63 60,63 60,63,64,67 60,63,64,67 60,63,64,67 60,63,64,67 60,63,64,67 60,63,64,67 60,62,65 62 62 66 66 66 61 61 61 61 61 61 66
a
n = 2 - 4 5 , x=l: GPC, Ref.: 220; a-alkyl (CH 3 , C 9 H } 9 , C i 5 H 3 O , co-methoxy oligo(oxyethylenes), n = 4-12,15,16,25: Ref. 214; n = 15, x = 5,6,7: micelliation and surface properties, Ref. 221.
6.1.1.4. Amino Derivatives of Oligo(oxyethylenes) a,G)-Diamines RNH-CH 2 CH 2 - [OCH 2 CH 2 ] „ - N H R R
n
MoI. wt.
b.p. (°C/mbar)
H
1 2 3 4 5 3 4 5
94.2 148.2 192.3 236.3 280.4 220.3 264.4 308.4
48-50/1.3 77-78/0.3 115/0.3 133-134/0.2 175-177/0.07 97-98/0.2 131-133/0.2 146-148/0.07
CH 3
a
nD/25°C
Refs.
1.4637 1.4647 1.4668 1.4511 1.4549 1.4562
76 76 76,77 77 77 77 77 77
Af-Oligoethylene mono- and dialkylamines RiR 2 N(CH 2 CH 2 O) n H; Ri, R 2 = C 4 H 9 and R2 = W-Ci0H2I, R 2 =H; n = 1-6; GC; Ref. 88.
6.1.1.5. Cyclic Oligo(oxyethylenes) na 1 2 3 4 5
[-[OCH2CH2],,-]
MoI. wt.
m.p. (0C)
b.p. (°C/mbar)
44.1 88.1 132.2 176.2 220.3
-111.3 11.8 0 17 Oil
10.7/1013 101.3/1013 168-172/1013 106/13 152/1.7
d4 (g/cm3)/°C 1.8922/6 1.0336/20 1.109/25 1.113/20
Refs. 29 30,85-87,92,102,145 78,79,102 31,40,79-81,86,102,145,216 31,39,79,81,83,102,145,216
6.1.1.5. cont'd na
MoI. wt.
m.p. (0C)
b.p. (°C/mbar)
6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
264.3 308.4 352.4 396.9 441.0 485.1 529.2 573.3 617.4 661.5 705.6 749.7 793.8 837.9 882.0
39.5-40.5 Oil 19 Oil 35.5-36.8 Oil 36.5-38.5 Oil 28.5-31 38-41.5 49.5-50.5 44-47 47-50 51-53.5 46-50.5
80/0.013
a
d4 (g/cm3)/°C
Refs. 39,41,79,81-83,102,145,216 39,84,145,216 39,84,145 217 217,219 217 217,219 217 217 217 217,219 217 217 217 217
n = 2, 4-8; GC, MS; Ref. 145; n = 4-20: IR, NMR, MS, Refs. 216,217,219.
6.1.1.6. Oligomers of Substituted Ethylene Oxides Epoxide Oxirane (Ethylene oxide)
Methyloxirane (Propylene oxide)
Ethyloxirane (1,2-Butene oxide) 2,3-Dimethyl oxirane (2,3-Butene oxide) cis-
Oligomers
n
MoI. wt.
m.p. ( 0 C)
b.p. (°C/mbar)
nD/°C
110-112 1.3970/20
Crown ethers p[OCH 2 CH 2 ] n ^
1-8
2-Methyl-l,3-dioxolane r [OCH(CH 3 )- OCH 2 CH 2 ]-!
2
88.1
82-83/1013
2-Methyl-l,3,6-trioxocane p [OCH(CH 3 )- (OCH 2 CH 2 ) 2 ]-|
3
132.2
110/13
Dimers cis- + frarcs-2,5-Dimethyl-l,4-dioxane transP[OCH(CH 3 )CH 2 L n
2
116.2
Refs.
cf. Tab. 1.1.1.5
117-130/1013 GC, MS, 1H-NMR, IR -4.5 121.5/1000
ds- + fra^-2,6-Dimethyl-l,4-dioxane P[OCH(CH 3 )CH 2 - OCH 2 CH(CH 3 )I 1
127.7-129/1001 GC, MS, 1H-NMR, IR
cis- + fra«s-2-Ethyl-4-methyl-l,3-dioxolane cistransP[OCH(C 2 H 5 )- O C ^ C H ^ H ^ ] - !
GC, MS, 1H-NMR, IR
Higher Oligomers P[OCH(CH3)CH2Jn-I
4 5«
232.3 290.4
p [OCH(CH 2 CH 3 )CH 2 ]^
4
288.4
Monomer Dimers
1 2
72.1 144.2
93
61-65/0.009 77-83/0.009 n = 4-6: GPC, Ref. 91 99-101/0.13 n = 4-6: GPC, Ref. 91
59.9-60.4/996
85-87,92, 110-112 70,150
1.4147/22
80,90,92,93 89,114 112,113
1.4169/20
89,119
1.4029/24 1.4044/24
89 115 115
1.4453/23 1.4453/23
49,89-93 90-92
1.4503/23
90-92
1.3826/20
116 94,95
2,cis-3,trans-5,cis-6Tetramethyl-l,4-dioxane^
GC, 1H-NMR
94,95
2,c/s-4,/ra«5-5-Trimethyl2-ethyl-l,3-dioxanefc
GC, 1H-NMR
94,95
GPC, 1H-NMR GPC, 1H-NMR
95 95
Trimers Tetramers
3 4
216.3 288.4
6.1.1.6. cont'd Epoxide trans-
cis-, trans-
Oligomers
n
Monomer
1
72.1
Dimers 2,cis-3ytrans-5 -cis-6Tetramethyl-1,4-dioxane b
2
144.2
m.p. ( 0 C)
nD/°C
53.6-54.1/996
1.3736/20
Refs. 116 94,95 94,95
2,ds-4,cw-5-Trimethyl2-ethyl-l,3-dioxolane*
GC, 1H-NMR
94,95
2,trans-4,trans-5-Trimeihy\2-ethyl-1,3-dioxolane b
GC, 1H-NMR
94,95
GC 1 H-NMR
94,95,114
GC 1 H-NMR
94,95,114,117
2,trans-3 ,cis-5-trans-6Tetramethyl-1,4-dioxane
2
Dimers 2,5-Tetramethyl-1,4-dioxane
39.5-40.0
2
144.2
2-Isopropyl-4,4-dimethyl1,3-dioxolane 2,4,6-Triisopropyl-1,3,5-trioxane
(R)-tert, Butyloxirane
3
216.3
4
400.6
4
224.2
2
185.0
2R, 5R, 8R, HRMethyleneoxirane (Epoxyallene) Epichlorohydrin cistrans2R, 5R, 8S, HS-
n-Propoxymethyloxirane («-Propyl glycidyl ether) Phenyloxirane (Styrene oxide)
b.p. (°C/mbar)
GC, 1H-NMR
2,trans-3,trans-5,cis-6Tetramethyl-1,4-dioxane
2,2-Dimethyloxirane (Isobutene oxide)
MoI. wt.
140/1013
96 96
135/1013
96
64
96
168.0 [a]g =50,8 (C= 1.1, C 6 Hi 2 ) 120-122 146-147/1007
65-66 109-110 136-136.5
60/0.2(subl.) 67-75/0.7
4
370.1
190-205/1
2
232.3
n = 2-6: GPC, Refs. 100,103,104 88/0.6 n = 2 - 5 : GPC, Ref, 91
2-Benzyl-4-phenyl-1,3-dioxolane
2
240.3
37-40
2,5-Diphenyl-1,4-dioxane
2
240.3
152 121-122
150-151/1
92,97 1.4880/20
98,118
92,100,103-105 99 99 90,92,98,100,101, 103,104 1.4330/30
91
43,106 92,106,107 42,43
trans177
42-44
2,4,6-Tribenzyl-l ,3,5-trioxane 3 a b
360.4
3n = 2 - 5 : Stereoisomers. The letters r and i indicate retention and inversion at the carbon, respectively.
GPCNMR
106
GPC, MS,
106
6.1.1.7. Oligo(oxyethylenes) Containing Spirane Residues m.p. ( 0 C)
A
n
x
MoI. wt.
0
1
1 2 3 7 1 2 3 7 2 2 2
144.2 188.2 232.3 408.3 288.3 376.4 464.5 816.6 294.1 588.3 882.4
163-165 86-87 52-53 42-43 Oil 99 86-87
2
OCH(C 6 H 5 )O
1 2 3
Oil
b.p. (°C/mbar)
Refs.
97-99/13 MS, 1H-NMR 97-98/0.008 182-183/0.004
182 182,183 182 182 182 182-183 182 182 183 183 183
MS, 1H-NMR
6.1.1.8. Benzo Crown Ethers"
Position of phenolic groups
x
n
MoI. wt.
m.p. ( 0 C)
o-
1
2 3 4
272.3 408.4 544.6 180.2 360.4 224.2 448.5 268.3 536.3 977.1 448.5 536.6 624.7
208.5 190-192 150-152 67-69 164.0 44-45.0 113-114 79-79.5 106.8
