Novel Polyolefins Containing Crystallizable Isotactic Polystyrene Side Chains

Vinyl-terminated isotactic polystyrene macromonomers were copolymerized with ethylene and 1-octene to new polyolefin graft copolymers with crystallizable polystyrene side chains. The iPS content was varied from 4 to 78 wt.-% using different metallocene and halfsandwich catalysts. No solubility problems of the stereoregular macromonomer occured, because iPS does not crystallize during polymerization. In addition the polymers show nanophase separation of the polyolefin backbone and the iPS side chains. The crystallization of iPS, having a melting point of about 200°C, can be achieved by annealing. This synthesis strategy allows the fabrication of a new class of thermoplastic elastomers with improved heat distortion temperatures.

[1]  R. Mülhaupt,et al.  Molecular Weight and End Group Control of Isotactic Polystyrene Using Olefins and Nonconjugated Diolefins as Chain Transfer Agents , 2008 .

[2]  D. Webster,et al.  Synthesis and Characterization of Novel Epoxy- and Oxetane-Functional Reversible Addition-Fragmentation Chain Transfer Agents , 2007 .

[3]  Andreas F. M. Kilbinger,et al.  An All-ROMP Route to Graft Copolymers , 2007 .

[4]  H. Komber,et al.  Poly(propylene-g-styrene) Graft Copolymers with Well-Defined Microstructure by Metallocene Catalyzed Copolymerization of Propylene with Allyl-Terminated Polystyrene Macromonomers , 2007 .

[5]  J. Lahitte,et al.  Design of new poly(ethylene) based materials by coordination (co)polymerization of macromonomers with ethylene , 2006 .

[6]  G. Morandi,et al.  Well-Defined Graft Copolymers Issued from Cyclobutenyl Macromonomers by Combination of ATRP and ROMP , 2006 .

[7]  R. Muller,et al.  Design of new styrene enriched polyethylenes via coordination copolymerization of ethylene with mono- or α,ω-difunctional polystyrene macromonomers , 2006 .

[8]  N. Hadjichristidis,et al.  Novel block–comb/graft copolymers with the macromonomer strategy and anionic polymerization , 2005 .

[9]  G. Britovsek,et al.  Polyethylene chain growth on zinc catalyzed by olefin polymerization catalysts: a comparative investigation of highly active catalyst systems across the transition series. , 2005, Journal of the American Chemical Society.

[10]  H. Komber,et al.  Synthesis of poly(propene-g-styrene) graft copolymers by metallocene catalyzed copolymerization of propene with allyl-terminated polystyrene macromonomer obtained via quasiliving atom transfer radical polymerization and the effect of the grafts on blending polypropene with polystyrene , 2003 .

[11]  N. Hadjichristidis,et al.  Anionic Polymerization of Styrenic Macromonomers , 2003 .

[12]  J. Lahitte,et al.  Homo- and Copolymerization of ω-Functional Polystyrene Macromonomers via Coordination Polymerization , 2002 .

[13]  G. Britovsek,et al.  Iron‐Catalyzed Polyethylene Chain Growth on Zinc: Linear α‐Olefins with a Poisson Distribution , 2002 .

[14]  K. Matyjaszewski,et al.  Improving the Structural Control of Graft Copolymers by Combining ATRP with the Macromonomer Method , 2001 .

[15]  K. Endo,et al.  Isospecific copolymerization of styrene and a styrene-terminated polyisoprene macromonomer with the Ni(acac)2/MAO catalyst , 2000 .

[16]  K. Endo,et al.  Syndiospecific copolymerization of styrene with styrene macromonomer bearing terminal styryl group by CpTiCl3–methylaluminoxane catalyst , 1999 .

[17]  F. Guérin,et al.  Phosphinimides as a Steric Equivalent to Cyclopentadienyl: An Approach to Ethylene Polymerization Catalyst Design , 1999 .

[18]  Koichi Ito,et al.  Poly(macromonomers): Homo- and Copolymerization , 1999 .

[19]  K. Endo,et al.  Syndiospecific copolymerization of styrene with styrene terminated isoprene macromonomer by CpTiCl3-methylaluminoxane catalyst , 1998 .

[20]  P. Lutz,et al.  Anionic polymerization and copolymerization of macromonomers: Kinetics, structure control , 1998 .

[21]  Koichi Ito.  Polymeric design by macromonomer technique , 1998 .

[22]  M. Arnold,et al.  Metallocene-Catalyzed Copolymerization of Propene with Polystyrene Macromonomers , 1997 .

[23]  T. Arai,et al.  Structures of polyethylene and copolymers of ethylene with 1‐octene and oligoethylene produced with the Cp2ZrCl2 and [(C5Me4)SiMe2N(t‐Bu)]TiCl2 catalysts , 1996 .

[24]  W. Feast,et al.  Tailored copolymers via coupled anionic and ring opening metathesis polymerization. Synthesis and polymerization of bicyclo[2.2.1]hept-5-ene-2,3-trans-bis(polystyrylcarboxylate)s , 1994 .