VII.Optically Active Polymers

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Co py rig hte dM ate ria l

Katsuhiro l n o m a t a Department of Polymer Chemistry, Tokyo Institute of Technology, Tokyo, Japan Akihiro Abe Department of Industrial Chemistry, Tokyo Institute of Polytechnics, Atsugi, Japan

A. Abbreviations used 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 (su If ides), 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) 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. Polytvinyl ethers)

VII-715

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 VII-733 VII-733

VII-733 VII-734 VII-735

Copyright © 2005 John Wiley & Sons

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) D. References

VII-735 VII-735 VII-736 VII-736 VII-737 VII-737 VII-737 VII-738 VII-739

By definition the optical activity, [M] A, of polymers and their low molecular weight analogs is given by [M] A = [a\x x (mean residue weight)/100

A. ABBREVIATIONS USED

AcAc Acetylacetonate AIBN Azobisisobutyronitrile BPO Benzoyl peroxide DBP Dibenzoyl peroxide DCA Dichloroacetic acid DCM Dichloromethane DDB 2,3-Dimethoxy-1,4-bis(dimethylamino)butane DMAc Dimethylacetamide DMF Dimethylformamide DMSO Dimethylsulfoxide DPEDA-Li iV^/V'-diphenylethylenediamine monolithium amide EDC Ethylene dichloride M Monomer MC Model compound NCA iV-Carboxylic anhydride P Polymer RT Room temperature TMEDA A^N,A/^JV'-tetramethylethylenediamine TCA Trichloroacetic acid TFA Trifluoroacetic acid TFEL Trifluoroethanol THF Tetrahydrofuran Retrieved from: www.knovel.com

B. OPTICALLY ACTIVE POLYMERS FROM CHIRAL MONOMERS MAIN-CHAIN ACYCLIC CARBON POLYMERS

Polymer Catalyst or initiator 1.1.

POLY(ALKENES)

Poly[(/?)(- )3,7-dimethyl-1 -octene] Al(Z-C4Hg)3ZTiCl4 Al(Z-C 4 H 9 ) 3/TiCl3 LiAlH 4/TiCl 4/monomer Poly[(S)( + )5-methyl-1 -heptene] Al(J-C4Hg)3ZTiCl3 Poly [(S)( + )4-methyl-l -hexenej Al(I-C4Hg)3ZTiCl4 Al(z-C4H9)3/TiCl3 Poly[(£)( + )6-methyl-1 -octene] Al(Z-C4Hg)3ZTiCl3 Poly[(S)( + )3-methyM-pentene] Al(Z-C4H9)3/TiCl4 Al(Z-C 4 Hg) 3 ZTiCl 3 Poly [(5)5-pheny 1-1-heptene] Al(Z-C 4 Hg) 3 ZTiCl 3 PoIy[Cff)4-phenyl-1 -hexene] Al(Z-C 4 H 9 ) 3 /TiCl 3

Co py rig hte dM ate ria l

TABLE 1.

Polymerization system

Monomer (M) or model compound (MC) values

Polymer (P) values

T(0C)

[M] D

Benzene

30-40

-20to -120 -35.3 to -144 - Ill

Isooctane

RT

Isooctane Isooctane Isooctane

Solvent

[M)0

Optical activity measured

Solvent

T (0C)

Refs.

4,7

14.4 (MC) 14.4 (MC) 8.88 (MC)

Toluene Toluene Carbon tetrachloride

27.4-68.1

11.7 (MC)

Benzene

RT RT

205-288 149-279

21.3 (MC) 21.3(MC)

Benzene (MC); toluene (P) Benzene (P)

25 25

2-6,9

RT

16.0 20.4

13.3(MC) 13.3(MC)

Benzene

25

4 5

20-25

29.4-158

- 11.4 (MC)

Tetralin (P)

20-25

75.8-157 161

- 11.4 (MC)

Tetralin (P)

25 (P); 20 (MC) 2-6, 8,9 25 (P); 20 (MC) 5

-78.1

6.25

25 25 25

2-6

26.6

4.80 (M)

Cyclohexane (P); neat (M)

25

118

60

-61.6

- 8.99 (M)

Chloroform (P); neat (M)

25

118

Dioxane

60

-21.0

-21.0 (MC)

Dioxane

25

12

65 60 35 -70 -78

-46.1 -47.2 -47.4 -43.0 -47.2

Toluene Toluene Toluene Toluene Toluene

25 25 25 25 25

10

Benzene Toluene Toluene Toluene Dioxane

50-100 RT

23.4 17.9

55.5 (M) 42.2 (M)

Chloroform (P); neat (M) Dioxane

21 (P); 22 (M) 25

13 14

Dioxane

RT

15.3

37.4 (M)

Dioxane

30

13

Benzene

50 60

Benzene Chloroform (P); neat (M)

22 25

11 215

2,2,4-Trimethylpentane 25-60 2,2,4-Trimethylpentane

1.2. POLY(ACRYLICS) AND RELATED POLYMERS Poly(acryloyl-L-glutamic acid) AIBN Poly(L-bornyl acrylate) AIBN AIBN AIBN C 6 H 5 MgBr UV benzoin Po\y(d-sec-butyl a-chloroacrylate) BPO BPO Poly{d-sec-butyl a-bromoacrylate) BPO Poly(L-menthyl acrylate) AIBN AIBN

-79.0 -73.9

Copyright © 2005 John Wiley & Sons

- 56.4 (M) - 56.4 (M) - 56.4 (M) - 56.4 (M) - 56.4 (M)

-99.3(M) - 88.3 (M) Retrieved from: www.knovel.com

(M) (M) (M) (M)

Benzene Benzene Benzene Benzene

25 25 25 25

29

- 167 -318

_ 444 (M) _ 444 (M)

Benzene Benzene

25 25

29

Toluene

20

10

-70.8

-50.1 (M)

- 32.2 (M) -28.8(M)

EDC (P); ethanol (M) Benzene

25 20

23,24 25-27

- 8.6 (M)

Benzene

19

26

DCM

20

17,18

Benzene (M); methanol -0.01% CH3SO3H(P) Methanol- 0.01%CH3SO3H after 1 h Methanol-13%CH3SO3H

25

225

25

Benzene Chloroform Chloroform Benzene Benzene Chloroform

25 20 20 25 25 25

16,11

Dioxane

25

28

Water

20

119

Water

20

215

Dioxane

25

28

Water

20

222

Dioxane Dioxane Dioxane Dioxane (P); neat (M)

25 25 25 25

19-21

Chloroform (P); isooctane (M) 20 Chloroform (P); isooctane (M) 20

16,22

60 22 -50 -50

278 397 366 337

70 22

504 504 504 504

Co py rig hte dM ate ria l

PoIyU + ^-methyl-Af-a-methylbenzyl-acrylamidel AIBN Toluene n-BuLi Toluene C 6 H 5 MgBr Toluene Poly[( - W-propyl-N-a-methylbenzyl-acrylamide] Toluene AIBN Toluene /1-BuLi

1.3. POLY(METHACRYLICS) AND RELATED POLYMERS

Poly(L-bornyl methacrylate) 55 Benzene AIBN PoIy(1,2; 5,6-diisopropylidene-D-glucofuranosyl-3-methacrylate) Benzene 80 BPO 40-50 AIBN Benzene Poly(2,3 ; 4,6-diisopropylidene-L-sorbofuranosyl-1 -methacrylate) Carbon tetrachloride 60 AIBN PoIyK + M ,3-dimethylbutyl methacrylate] BPO 82-110 PoIyK + )(S)-diphenyl(l-methyl-pyrrolidin-2-yl)methyl methacrylate] DPEDA-Li/TMEDA Toluene -78

-49.0 -48.4 -84.5

18.2

780(LaJ 365 )

23.4 (MC)

30.9

43.5 (MC)

-82.2(M)([aJ 365 )

-410(LaJ 365 ) 779(LaJ 365 )

Poly( 1 -menthyl methacrylate) AIBN Benzene BPO C 6 H 5 MgBr Toluene C 6 H 5 MgBr Toluene 7-Ray BuLi THF Poly(methacryloyl-D-alanine) AIBN Dioxane Poly(Af-methacryloyl-L-alanine) AIBN Dioxane Pory(N-methacryloyl-L-asparagine) AIBN Dioxane PoIy(methacryIoyl-L-glutamic acid) AIBN Dioxane Poly(s-N-methacryloyl-L-lysine] Potassium persulfate Water Poly( 1 -a-methylbenzy 1 methacrylate) UV AIBN UV benzoin /i-BuLi Toluene AIBN Dioxane Poly(2-methylbutyl methacrylate) BPO C 6 H 5 MgBr Toluene PolyL(5)4-methyl-2-M^V-dimethylaminopentyl methacrylate] AIBN Benzene

- 202 - 202 - 202 - 202 - 202

- 193 - 256.8 -158.9 - 177.0 - 194.0

55 40-85 RT -75 -75 -78

-96.9

60

42.0

48.9 (MC)

-42(La] 546 )

-41 (M) ([a]

546)

60

-24.4(La] 546 )

-36(MC)(La] 546 )

60

-23.0

- 26.0 (MC)

65

12.1

35 -65 -60 35

- 79,5 -72.5 -100

60

7(M)

-151 -138 -190 -147

- 54.4 (M) - 54.4 (M) - 54.4 (M)

5.93 6.84

100 RT

(M) (M) (M) (M) (M)

2.2

Copyright © 2005 John Wiley & Sons

- 103 (M) - 103 (M) - 103 (M) -78.8(M)

6.99 (M) 6.99 (M)

-2.1 (M) Retrieved from: www.knovel.com

Benzene

25

205

120

References page VII-739

cont'd

Polymer Catalyst or initiator

Polymerization system Solvent

PoIyK' + )phenyl-2-pyridyl-0-tolylmethyl methacrylate] /t-BuLi THF Diisopropyl peroxydicarbonate

Polymer (P) values

Monomer (M) or model compound (MC) values

[M]D

Optical activity measured

[Ml0

Solvent

Co py rig hte dM ate ria l

TABLE 1.

Toluene

-78 40

395 -321 -617([aJ 365 )

Refs.

Benzene (M); THF (P) THF Chloroform(M); 90% chloroform-10% TFEL (P)

- 78 (P); 25 (M) 25 (P) 25

223

Chloroform (P); benzene (M) Chloroform (after heating at 600C) Chloroform (P); benzene (M) Chloroform (after heating at 600C)

25 25

224

25 25

224

- 47.6 (M) -47.6(M)

Chloroform Chloroform

25 25

121

- 37.7 (M) - 37.7 (M)

Chloroform Chloroform

25

121

-99.7 (M)

Chloroform

88.6 (M)

190.1 (M)(M 365 )

PoIvK + )phenYl-2-pyridyl-m-tolYlmethyl methacrylate I DPEDA-Li/(- )DDB Toluene

-78

-845(La] 365 ) 1481 (La] 365 )

14.0(M)(LaJ 3 6 5 )

DPEDA-Li/TMEDA

-78

262(LaJ 365 ) 1370(La] 365 )

14.0(M)(La] 365 )

Toluene

2T( 0 C)

185

1.4. POLY(VINYL ETHERS), POLY(VINYL KETONES), POLY(VINYL ESTERS) 1.4.1. POLY(VINYL ETHERS) PoIyK- )(5)2,2/-bis(2-vinyloxyethoxy)-l,l/-binaphthyl] DCM 0 -131.6 SnCl4 Nitromethane 0 -131.9 BF 3 OEt 2 PoIyK- )(5)2,2/-bisl2-(2-vinyIoxyethoxy)ethoxy]-l ,1 '-binaphthylj -93.9 SnCl4 DCM O -95.8 BF 3 OEt 2 DCM O PoIyK-)(5)2,2 / -bisL2-(2-vinyloxyethoxy)ethoxy]-3,3 / ~dimethyl-l,r-binaphthyl] DCM O SnCl4 44.5 Poly( 1 -bornyloxyethylene) BF 3 OEt 2 PoIy(I -cholesteryloxyethylene) Poly( 1,2: 5,6-diisopropylidene-a-D-glucofuranosyl-3-oxyethylene) BF3 OEt2 n-Hexane + DCM -78 Poly( 1 -menthyloxyethylene) C 4 H 9 MgBr Toluene 80 BF 3 OEt 2 M-Hexane -78 SnCl4 Petroleum ether 25 Mn-MoO 3 -H 2 SO 4 /i-Hexane -10 Mn-MoO 3 -H 2 SO 4 Az-Hexane -30 A1(/-OC 3 H 7 ) 3 /H 2 SO 4 rc-Pentane - 15 to RT -198 BF 3 OEt 2 Toluene -78 -220 Poly( 1 -a-methy lbenzyloxyethylene) BF 3 OEt 2 Propane -78 Polyt(S)2-methylbutyloxyethylene] Al(Z-C 4 H 9 )Cl 2 Propylene + Toluene -78 A1(/-C 4 H 9 ) 3 /H 2 SO 4

Ether

A1(/-OC 3 H 7 ) 3 /H 2 SO 4

Ethyl acetate

-142 -93

-122.4(M) - 131.4 (M)

5.7

-77.2

-358 -396 -373 -357 -353

- 121.9(M) -121.9(M) -121.9(M) - 118.8(M) - 118.8(M)

- 72.2 (M) -61.5 (M)

68.6

-71.9 (M)

4.9

1.1 (MC) 7.6 (M) 1.1 (MC) 7.6 (M) 1.1 (MC) 7.6 (M)

15-20

-5.9

0-20

6.4

Copyright © 2005 John Wiley & Sons

Retrieved from: www.knovel.com

25 25 (P); 29 (M)

Benzene

245

25

31 31

EDC (P); ethanol (M)

25

36,24

Benzene (P); chloroform (M) Benzene (P) Benzene (P) Chloroform (M); benzene (P) Benzene (P) Neat (M); benzene (P) Toluene (M); benzene (P)

25 25 25 25 25 25 25 (P)

Benzene

25

35

Toluene (P); neat (M1MC)

25

34

Toluene (P)

25

Toluene (P)

25

31 33 123 124

1.4.2. POLY(VINYL KETONES) Poly[(5)2-methylbutyl vinyl ketone] Spontaneous LiAlH 4 Toluene Poly[(S)3-methylpentyl vinyl ketone] Spontaneous Toluene LiAlH 4 Poly[(S) 1 -methylpropyl vinyl ketone] LiAlH4 Toluene Spontaneous Toluene AIBN Toluene LiAlH4 1.4.3. POLY(VINYL ESTERS) Poly(-acetyl)L-serine methylester)methylenej NiCl 0 -6H 2 O Chloroform

:r (

0

C)

Rets.

14.4

6.8 (M)

Methanol

25

177

-3.6

- 3.7 (M)

Methanol

25

177

44.0 33.2

42.8 (M) 42.8 (M)

Benzene Benzene

20 (P); 25 (M) 20(P)

129

41.4 31.7

41.6(M) 41.6(M)

Benzene Benzene

20 (P); 25 (M) 20(P)

129

-71.3

- 84.5 (M)

THF (P); benzene (M)

25

190

-11.4

- 8.0 (M)

Methanol

20

178

-46.87 -45.82 -40.30

- 16.6 (M) -16.6(M) -16.6(M)

Benzene Benzene Benzene

25 (P); 15 (M) 25(P) 25 (P)

130

- 39.84 -42.86 - 37.54

- 18.74 (M) - 18.74 (M) - 18.74 (M)

Benzene Benzene Benzene

25 (P); 15 (M) 130 25(P) 25(P)

-190([M] 578 )

58.3 ([OCj 578)

74.0(M) ([MJ 57 S).

Chloroform

20-22

132

- i l l ([a].™) -172([M] 578 )

46.8 ([(X]578)

72.5 (M) [[M]5n)

Chloroform

20-22

132

-129 (M) ([M] 578 )

Chloroform

20-22

132

-58.1 (M)

Chloroform-methanol (5 :2) (P); chloroform (M)

20

231

-12.0(M)

Chloroform-methanol

20

231

40.6 (La] 578)

Chloroform

22

249

18.6 ([a]578)

Chloroform

22

249

-13.5(M)

Chloroform-methanol (5:2) (P); chloroform (M)

20

230

-82(IaJ 5 7 8 )

-156([M] 5 7 8 )

205

Poly[(L-alanyl-(O-acetyl)D-serine methylester)methylenej -33 NiCl 2 -6H 2 O Chloroform Poly[(L-alanyl-(Af(Im)-tosyl)L-histidine methylester)methylenej NiCl 2 -6H 2 O Chloroform/Methanol RT 144(Ia] 578 ) Poly[(D-alanyl-(Ar(Im)-tosyl)L-histidine methylester)methylenej NiCl 2-6H 2 O Chloroform/Methanol RT -170 (N 578 ) Poly[(L-alanyl-(/V(Im)~tosyl) L-histidyl-(O-acetyl)L-serine methylester)methylenej -58.9 NiCl 2 6H 2 O Chloroform

Copyright © 2005 John Wiley & Sons

-68.5

([a]578)

Retrieved from: www.knovel.com

Poly[(L-alanyl-(A^(Im)-tosyl)L-histidyl-(O-acetyl)D-serine methylester)methylene] NiCl 2 6H2O Chloroform - 29.3 Poly[(D-alanyl-(Af(Im)4osyl)L-histidyl-(0-acetyl)L-serine methylester)methylene] NiCl 2 6H 2 O Chloroform -8.0

POLY(ALKYNES)

230

Chloroform-methanol (5:2) (P); chloroform (M)

20

230

Chloroform

20-22

132

Chloroform

20

236

Chloroform

20-22

132

Chloroform

20

236

THF (P); hexane (MC)

24 (P); 20 (MC) 209

38.5(M)(La] 5 4 6 )

Dioxane

25

227

-24.2 (M) (La) 578 )

Chloroform

22

236

9.2 (M)

Co py rig hte dM ate ria l

1.8.

20

(M)

Poly[(S)3,4-dimethyl-1 -pentyne] Al(Z-C 4 H 9 ) 3/Fe(AcAc) 3 n-Heptane Poly [p-(L-( - )-menthoxycarbonyl)phenylacety lene] [Rh(norbornadiene)Cl] 2 Triethylamine Poly [/?-((-f )-2-methylbutoxy)phenylacetylene] [Rh(norbornadiene)Cl] 2 Triethylamine

20-35 RT

RT

22(LM] 5 7 8 )

48.7(LaJ 5 7 8 )

70.6(M)(LM] 5 7 8 )

29.5 (M)

-355([M] 578 )

16.7 (LaJ 578 )

21.2(M)(LM] 5 7 8 )

35.0 (M)

27.4 (MC)

-910([M] 578 )

13.1 (La]578)

35.3 (M) ([M]578)

Chloroform

20-22

132

27.6(LM] 578 )

95 (La] 578 )

90.2 (M) ([M]578)

Chloroform (P); neat (M)

20

132

-102(LM] 5 7 8 ) -12.8 ([a]578)- 11.9(M)(LM] 5 7 8 )

Chloroform (P); neat (M)

20-22

132

Chloroform

20

236

Hexane

25 (P); 20 (MC) 209

Chloroform

20

236

- 16.2 (LM] 578 ) -24.2(La] 578 )- 23.5(M)(LM] 5 7 8 )

Chloroform

22

131

68.9([MJ 578 )

-61.9 (La] 578 )- 68.8(M)(LM] 578 )

Chloroform

22

131

47.3 ([M]578)

-47.6

Chloroform

22

131

Toluene

27

39

Toluene Chloroform (P); methanol (M)

27 20

39 132

n-Heptane (P); neat (MC)

25

133

-68.8(M)

Chloroform

20

197

5.90 (M)

Chloroform

20

197

32.7 (M)

- 106.4 (MC) 5.5 (M)

(La] 578 )- 66.3(M)(LM] 5 7 8 )

37.2 (M)

-458([M] 578 )

- 35.8 (M) -40.9

42.2 (MC)

470

-605

19.2

Copyright © 2005 John Wiley & Sons

-179.7(M) 55.0(M)(LM] 578 )

Retrieved from: www.knovel.com

6££-IIA 3^d S90U3J9J9H

Poly [ ((S)( 1 -benzylethyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT 15 (La] 578 ) PolyL(((5)l-(ferf-butoxycarbonyl)-2-methylpropyl)imino)methylene] NiCl 2 45 32.5 Poly[((S)( 1 -carbethoxyethyl)imino)methylene] NiCl 2 6H 2 O RT -280(La] 5 7 8 ) Poly [(((1S ,2S) 1 -carbomethoxy-2-methylbutyl)imino)methy lene] NiCl 2 45 -32.2 Poly[((S)(— )a-cyclohexylethylimirio)methylene] NiCl 2 -6H 2 O Neat 65 -295 Poly[(((S)2,2-dimethyl-13-dioxolane-4-yl)methylimino)methylene] NiCl 2 6H 2 O RT 68.5(La] 546 ) Poly [(((R) 1,2-dimethylpropyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT 16.7(La] 578 ) Poly[((/?)(2-(diphenyl phosphinyl)propyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT -338(La] 578 ) PoIyK(SX 1 -ethyl-2-propenyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT 29(La] 578 ) PoIyK(SX 1 -ethyl-2-propynyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT -HO(La] 5 7 8 ) PolyL(((S)l-(isopropyloxycarbonyl)-2-methylpropyl)imino)methylene] NiCI 2 5 -24 Poly[((-)menthylimino)methyleneJ NiCl 2 -6H 2 O Methanol 65 -207 Poly [(((S) 1 -(methoxycarbonyl)-2-methylpropyl)imino)methylene] NiCl2 RT -UO Poly[((/?)3-methyl-2-butyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT -16.7 ([a]578) Poly[((i?)4-methyl-2-pentyl)imino)methylene] NiCl 2 6H2O RT 62([aJ 578 ) Poly[((/?)2-octylimino)methylene] NiCl 2 -6H 2 O Methanol RT 34 (M 578 ) Poly[(d-a-phenylethylimino)methylene] DBP-O2 Heptane 60 365 Poly[(l-a-phenylethylimino)methylene] H 2 SO 4 -O 2 Heptane 50 -382 NiCl 2 -6H 2 O 0-5 -350 (M 578 )

Chloroform -methanol (5 :2) (P); chloroform (M)

-2.1

TABLE 1. cont'd

Catalyst or initiator Poly [(S)4-methyl-1 -hexyne] Al(Z-C 4 H 9 ) 3/Fe(AcAc) 3 AlO-C 4 H 9 ) 3/Fe(AcAc) 3 Poly[(S)5-methyl-1 -heptyne] Al(I-C 4 Hg) 3 ZFe(AcAc) 3 Poly[(5)6-methyl-1 -octynej Al(i-C 4 H 9 ) 3 ZFe(AcAc)3 Poly [(S)3-methyl-1 -pentynej Al(Z-C 4 H 9) 3/Fe(AcAc) 3

Polymerization system Solvent

T(0C)

Isooctane w-Heptane

20-30 20-35

^-Heptane

Polymer (P) values WD

[M] D

Monomer (M) or model compound (MC) values MD

[M]D

Optical activity measured Solvent

Co py rig hte dM ate ria l

Polymer

T( 0 C)

Refs.

-10.6

- 3.0 (MC)

Isooctane >2-Heptane (P); neat (MC)

25 25

133

20-35

-146

12.2(MC)

n-Heptane (P); neat (MC)

25

133

n- Heptane

20-35

-34

13.7(MC)

rc-Heptane (P); neat (MC)

25

133

/7-Heptane

20-35

498

32.1 (MC)

/i-Heptane (P); neat (MC)

25

133

THF (P); ethanol (M) THF (P) THF (P)

25(P) 25(P) 25(P)

-2.97 (MC)

-22.9

1.9. POLY(MALEIMIDES) AND RELATED POLYMERS

Poly(AMx>myl maleimide) BPO THF 50 AIBN THF 50 n-BuLi THF 50 Poly[A^(cholesteroxycarbonylmethyl)maleimide] AIBN THF 70 «-BuLi THF 0 Poly(/V-maleoyl-L-alanine) AIBN THF 60 Poly(/V-maleoyl-L-phenylalanine) AIBN THF 60 Poly[7V-maleoyl-L-phenylalanine ethyl esterj AIBN Dioxane 60 BuLi THF 0 Poly[Ar-((N/-((Z?)-a-methylbenzyl)aminocarbonyl)methyl)maleimideJ AIBN DCM 70 Polyt/V^./V'^^-a-methylbenzyOaminocarbonyl-fz-pentyl) maleimide] AIBN Dioxane 60 Poly[Ar-(4^/-((/?)-a-methylbenzyl)aminocarbonylphenyl)maleimideJ AIBN THF 50 rc-BuLi THF 0 Poly[A^-(4-A^'-((5)-a-methylbenzyl)aminocarbonylpheny))ma]eimideJ AIBN THF 50 Poly[W6 O-anhydro^^^-tri-O-benzyl-p-D-galactopyranose] PF5 DCM -78 Polyfoc-1,6-anhydro-2,3,4-tri-