Carnegie Mellon University

Linear Hybrid Copolymers

Hybrid segmented copolymers have been prepared by incorporation of inorganic oligomers/polymeric initiators or macromonomers into the ATRP of styrenic and (meth)acrylate monomers.  Block and graft copolymers containing poly(dimethylsiloxane (PDMS) segments have been synthesized by sequential living anionic ring-opening of D3 and quenching the living PDMS chain with a compound comprising either vinyl, or alkyl halide groups and subsequent use of the functionalized PDMS as a macromonomer, (A) or macroinitiator, (B) in an ATRP.(1-4) Polysiloxane block copolymers find use in topical cosmetic and personal care compositions(5) in addition to expected elastomer applications.

9b scheme 1

In a similar approach, methacrylate monomers possessing bulky polyhedral oligomeric silsesquioxane (POSS) side groups have been used in ATRP systems to prepare well-defined random and block copolymers.(6,7)

9b scheme 2


(1)       Nakagawa, Y.;  Miller, P. J.; Matyjaszewski, K. Polymer 1998, 39, 5163-5170.

(2)       Miller, P. J.; Matyjaszewski, K. Macromolecules 1999, 32, 8760-8767.

(3)       Shinoda, H.;  Miller, P. J.; Matyjaszewski, K. Macromolecules 2001, 34, 3186-3194.

(4)       Matyjaszewski, K. Nonlinear Optics, Quantum Optics 2003, 30, 167-179.

(5)       Adams, G.;  Khoshdel, E.;  Moretta, A.;  Plant, Y. C.; Reid, E. S. In PCT Int. Appl.; Unilever PLC: WO 2000/0071607, 2000; p 31 pp.

(6)       Pyun, J.;  Xia, J.; Matyjaszewski, K. ACS Symposium Series 2003, 838, 273-284.

(7)       Pyun, J.; Matyjaszewski, K. Macromolecules 2000, 33, 217-220.