64.
Shashoua and Sweeney first demonstrated that isocyanates could by polymerized via an anionic mechanism to form high molecular weight materials. We have sought to eliminate the problems associated with the anionic procedure by developing transition metal complexes which are capable of catalyzing the living polymerization of isocyanates. Recently, we reported the living polymerization of alkyl isocyanates using TiCl
3OCH
2CF
3, I. Using I, polyisocyanates with controlled molecular weights and narrow polydispersities can be obtained at room temperature. ε
5-CpTiCl
2N(CH
3)
2 (Cp = cyclopentadienyl), III, is also an excellent catalyst for the polymerization of isocyanates, and in terms of ease of handling and purification and tolerance toward monomer functionality, superior to I. In order to prepare triblock copolymers containing amorphous segments sandwiched between two isocyanate segments, we have prepared bimetallic initiators comprised of titanium alkoxides con- nected by flexible linkers. These linkers may be a small molecule (1,4- dihydroxycyclohexane, V) or a polymer (polydimethylsiloxane, PDMS, VI). Complexes V and VI can be used to initiate the living polymerization of isocyanates to yield polymers possessing central cyclohexyl bends (ldquo;broken worms rdquo;) or PDMS segments (triblock copolymers), respectively. Finally, cyclopolymerizations of 1,2-diisocyanates using these or- ganometallic initiators are reported.
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