Copolymer hard segments

Thus, new polymers were achieved by us, with a controlled ordering of copolymer hard segment blocks on the macromolecular chain. 

Proportion of Hard Segments. As expected, the modulus of styrenic block copolymers increases with the proportion of the hard polystyrene segments. The tensile behavior of otherwise similar block copolymers with a wide range of polystyrene contents shows a family of stress—strain curves (4,7,8). As the styrene content is increased, the products change from very weak, soft, mbbedike materials to strong elastomers, then to leathery materials, and finally to hard glassy thermoplastics. The latter have been commercialized as clear, high impact polystyrenes under the trade name K-Resin (39) (Phillips Petroleum Co.). Other types of thermoplastic elastomers show similar behavior that is, as the ratio of the hard to soft phase is increased, the product in turn becomes harder. 

With a typical of 25 000-30000 the molecular size is low compared wjth most conventional covalently cross-linked elastomers. With such rubbers values of about 100000 are desirable so that the effects of a significant amount of non-load-bearing chain ends do not occur. Such a problem does not arise in block copolymers terminated by hard segments. 

Improved polyurethane can he produced hy copolymerization. Block copolymers of polyurethanes connected with segments of isobutylenes exhibit high-temperature properties, hydrolytic stability, and barrier characteristics. The hard segments of polyurethane block polymers consist of 4RNHCOO)-n, where R usually contains an aromatic moiety. 

Random block copolymers of polyesters (hard segments) and amorphous glycol soft segments, alloys of ethylene interpolymers, and chlorinated polyolefins are among the evolving thermoplastic elastomers. 

Table 17. Structure of the hard segments in poly(Aryl ether)-polydimethylsiloxane segmented copolymers...

Morphology of the anionically synthesized triblock copolymers of polyfp-methyl-styrene) and PDMS and their derivatives obtained by the selective chlorination of the hard segments were investigated by TEM 146). Samples with low PDMS content (12%) showed spherical domains of PDMS in a poly(p-methylstyrene) matrix. Samples with nearly equimolar composition showed a continuous lamellar morphology. In both cases the domain structure was very fine, indicating sharp interfaces. Domain sizes were estimated to be of the order of 50-300 A. 

Siloxane-urea copolymers were synthesized by the reaction of the aminopropyl terminated PDMS oligomers with MDI or HMDI with no chain extenders (Reaction Scheme XI and Tables 14 and 15). Therefore, in these copolymers the hard segments consist of the aminopropyl end groups on the siloxane oligomers and MDI or HMDI backbones as shown below. The soft segment is pure polydimethylsiloxane. 

Miller J.A., Lin S.B., Hwang K.K.S., Wu K.S., Gibson P.E., and Cooper S.L. Properties of polyether-polyurethane block copolymers Effect of hard segment length distribution. Macromolecules, 18, 32, 1985. 

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