Chiral styrene-methyl methacrylate copolymers

Copolymerization of a monomer having two styrene moieties attached to a chiral template molecule with a comonomer e.g., methyl methacrylate) gives copolymers with strong optical activity after removal of the template molecules. In this case styrene diads of an S,S configuration separated from other styrene diads by comonomeric units are responsible for the optical activity. 

Tg measurements have been performed on many other polymers and copolymers including phenol bark resins [71], PS [72-74], p-nitrobenzene substituted polymethacrylates [75], PC [76], polyimines [77], polyurethanes (PU) [78], Novolac resins [71], polyisoprene, polybutadiene, polychloroprene, nitrile rubber, ethylene-propylene-diene terpolymer and butyl rubber [79], bisphenol-A epoxy diacrylate-trimethylolpropane triacrylate [80], mono and dipolyphosphazenes [81], polyethylene glycol-polylactic acid entrapment polymers [82], polyether nitrile copolymers [83], polyacrylate-polyoxyethylene grafts [84], Novolak type thermosets [71], polyester carbonates [85], polyethylene naphthalene, 2,6, dicarboxylate [86], PET-polyethylene 2,6-naphthalone carboxylate blends [87], a-phenyl substituted aromatic-aliphatic polyamides [88], sodium acrylate-methyl methacrylate multiblock copolymers [89], telechelic sulfonate polyester ionomers [90], aromatic polyamides [91], polyimides [91], 4,4"-bis(4-oxyphenoxy)benzophenone diglycidyl ether - 3,4 epoxycyclohexyl methyl 3,4 epoxy cyclohexane carboxylate blends [92], PET [93], polyhydroxybutyrate [94], polyetherimides [95], macrocyclic aromatic disulfide oligomers [96], acrylics [97], PU urea elastomers [97], glass reinforced epoxy resin composites [98], PVOH [99], polymethyl methacrylate-N-phenyl maleimide, styrene copolymers [100], chiral... 

Figure 18.13 TEM images and models of (a) the knitting pattern kp) and (b) barber pattern hoc) in PS-PEB-PMMA. ((a) Reprinted with permission from H. Ott, V. Abetz and V. Altstadt, Morphological studies of poly(styrene)-block-poly(ethylene-co-butylene)-block-poly(methyl methacrylate) in the composition region of the knitting pattern morphology, Macromolecules, 34, 7, 1069-1075, 2001. 2001 American Chemical Society, (b) Reprinted with permission from U. Krappe, R. Stadler and I. Voigt-Martin, Chiral assembly in amorphous ABC triblock copolymers. Formation of a helical morphology in polystyrene-block-polybutadiene-block-poly(methyl methacrylate) block copolymers, Macromolecules, 28, 13, 4558-4561, 1995. 1995 American Chemical Society.)...

A special case of asymmetric enantiomer-differentiating polymerization is the isoselective copolymerization of optically active 3-methyl-1-pentene with racemic 3,7-dimethyl-1-octene by TiCl4 and diisobutylzinc [Ciardelli et al., 1969]. The copolymer is optically active with respect to both comonomer units as the incorporated optically active 3-methyl-l-pentene directs the preferential entry of only one enantiomer of the racemic monomer. The directing effect of a chiral center in one monomer unit on the second monomer, referred to as asymmetric induction, is also observed in radical and ionic copolymerizations. The radical copolymerization of optically active a-methylbenzyl methacrylate with maleic anhydride yields a copolymer that is optically active even after hydrolytic cleavage of the optically active a-methylbenzyl group from the polymer [Kurokawa and Minoura, 1979]. Similar results were obtained in the copolymerizations of mono- and di-/-menthyl fumarate and (—)-3-(P-styryloxy)menthane with styrene [Kurokawa et al., 1982],... 

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