Copolymers and Interpenetrating Networks

Random copolymers are prepared by the copolymerization of a mixture of cyclic oligomers. Although the resulting polymer can be quite blocky (figure 8.1), taking the reaction to equilibrium can give a polymer that is essentially random in its chemical sequencing. One reason for preparing copolymers is to introduce functional species, such as hydrogen or vinyl side groups, along the chain backbone to facilitate cross linking. Another reason is the introduction of sufficient chain irregularity to make the polymer inherently noncrystallizable. Specific examples of comonomers include imides, perylenediimide, urethane-ureas, epoxies, other siloxanes, amides, styrene, divinylbenzene, acrylics, silsesquioxanes, polythiophenes, and poly(lactic acid). One novel combination is the preparation of polysiloxanebased episulfide resins. An unusual application is the use of monomethylitaconate- grafted polymethylsiloxane to induce crystal growth of CaCO3. Polysiloxanes containing thermally curable brenzoxazine moieties in the main chain are also in the category. These and other copolymers have been extensively characterized by nuclear magnetic resonance (NMR) spectroscopy. The sequential coupling of functionally terminated chains of different chemical structure can be used to make block copolymers, including those in which one or more of the blocks is a polysiloxane. If the blocks are relatively long, separation into a two-phase system invariably occurs. Frequently, one block will be in a continuous phase and the other will be dispersed in domains having an average size the order of a few hundred angstroms. Such materials can have unique mechanical properties not available from homopolymer species. Sometimes similar properties can be obtained by the simple blending of two or more polymers. Examples of blocks used with polydimethylsiloxane (PDMS) include imides, epoxies, butadienes, ε-caprolactones, amides having trichlorogermyl pendant groups, urethanes, ureas, poly(ethylene glycols), polystyrene, vinyl acetates, acrylates or methacrylates, 2-vinylpyridine, and even other polysiloxanes. Some results have also been reported for polyesters, polyethers, hydroxyethers of bisphenol A, bisphenol A arylene ether sulfones, vinylpyridinebenzoxazines, methyloxazolines, terpyridines, polysulfones, γ-benzyl-Lglutamate, and carboranes. Two other examples are foamed polypropylene and melamine resins. Even ABA, ABC triblock copolymers, and ABCBA pentablock copolymers involving PDMS have been reported.