Novel cyclic olefin copolymer (COC) with high glass transition temperature, good mechanical performance, high transparency, and excellent film forming ability has been achieved in this work by effective copolymerization of ethylene and exo-1,4,4a,9,9a,10-hexahydro-9,10(1′,2′)-benzeno-l,4-methanoanthracene (HBMN). This bulky cyclic olefin comonomer can be simply prepared in good yield via Diels–Alder reaction. By utilizing constrained geometry catalyst (CGC) activated with Al(iBu)3/[Ph3C][B(C6F5)4], ethylene/HBMN copolymer can be obtained with excellent production, high molecular weight, and a wide range of HBMN incorporation. 13C NMR (DEPT) spectra reveal alternating ethylene–HBMN sequence can be detected at high HBMN incorporation. The glass transition temperature (Tg) of resulted copolymer enhances with increasing HBMN incorporation. A high Tg up to 207.0 °C is attainable at low comonomer incorporation of 30.4 mol %, which is 61 °C higher than that of commercial norbornene (NB)-derived COC (54 mol %). T...

Synthesis of Novel Cyclic Olefin Copolymer (COC) with High Performance via Effective Copolymerization of Ethylene with Bulky Cyclic Olefin

Copolymerizations of norbornene with propylene and 1-octene were conducted with a series of ansa-fluorenylamidodimethyltitanium complexes, [t-BuNSiMe2Flu]TiMe2 (1), [t-BuNSiMe2(3,6-tBu2Flu)]TiMe2 (2), [t-BuNSiMe2(2,7-tBu2Flu)]TiMe2 (3), and [t-BuNSiMe2(C29H36)]TiMe2 (4; C29H36, octamethyloctahydrodibenzofluorenyl), activated by trialkylaluminum-free modified methylaluminoxane. The catalytic systems promoted random copolymerizations in a living manner regardless of the titanium complex used. The activity increased by the introduction of the tBu groups on the Flu ligand, and 4 showed the highest activity for each copolymerization. The comonomer content of the copolymers obtained was controllable in a wide range by changing comonomer feed ratio with these catalytic systems. The linear relationships were observed between the norbornene content and the glass transition temperature of the copolymer, whereas the slopes depended on the titanium complex used. The result suggested that the titanium complexes affect...

Highly Active Living Random Copolymerization of Norbornene and 1-Alkene with ansa-Fluorenylamidodimethyltitanium Derivative: Substituent Effects on Fluorenyl Ligand

Synthesis of a variety of optically transparent polyolefin elastomers consisting of hard segment of polynorbornene and several kinds of soft segments such as atactic polypropylene, poly(ethylene-co...

Optically Transparent Functional Polyolefin Elastomer with Excellent Mechanical and Thermal Properties

This article reviews the living homopolymerization and copolymerization of propene, 1-alkene and norbornene with ansa-dimethysilylene(fluorenyl)(amido)dimethyltitanium, Me2Si(η3-C13H8)(η1-NtBu)TiMe2 and its derivatives, correlating the effects of cocatalysts, solvents, polymerization conditions and the substituents of the fluorenyl ligand with catalytic features, such as livingness, initiation efficiency, propagation rate, syndiospecificity and copolymerization ability. The synthesis of novel olefin block copolymers and their catalytic synthesis are also introduced using this living system. This article reviews the living homopolymerization and copolymerization of propene, 1-alkene and norbornene with ansa-dimethysilylene(fluorenyl) (amido)dimethyltitanium and its derivatives, 1–4, correlating with the effects of cocatalysts, solvents and the substituent of the fluorenyl ligand on the catalytic features, such as livingness, propagation rate, syndiospecificity and copolymerization ability. The synthesis of novel olefin block copolymers and their catalytic synthesis are also introduced by the use of the living system.

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Living polymerization of olefins with ansa -dimethylsilylene(fluorenyl)(amido)dimethyltitanium-based catalysts

Highly efficient synthesis of cyclic olefin (CO) copolymers with high glass transition temperatures (Tg) as well as high catalytic activity have been attained not only by copolymerization of norbornene (NBE) with α-olefins (1-hexene, 1-octene, 1-dodecene), but also by copolymerization of tetracyclododecene (TCD) with α-olefins using half-titanocene catalysts, Cp′TiCl2(N═CtBu2) [Cp′ = tBuC5H4 (1), Cp (2)] in the presence of MAO. Linear relationships between the Tg values and the NBE or TCD contents were observed in all cases; Tg values in poly(TCD-co-α-olefin)s were higher than those in poly(NBE-co-α-olefin)s with the same CO contents. NBE and TCD incorporations in these copolymerization under high NBE or TCD feed conditions (especially by 2) were not affected by α-olefin (number of methylene units in the side chain) employed. An introduction of terminal olefinic double bond into the polymer side chain could be attained, if the copolymerization of NBE with 1-octene by 1 was conducted in the presence of 1,7...

Copolymerizations of Norbornene and Tetracyclododecene with α-Olefins by Half-Titanocene Catalysts: Efficient Synthesis of Highly Transparent, Thermal Resistance Polymers

Me2Si(C29H36)(NtBu)TiMe2 (4; C29H36, octamethyloctahydrodibenzofluorenyl) was synthesized and characterized by elemental analysis, 1H NMR and single crystal X-ray analysis. The complex was applied for propene polymerization using dried modified methylaluminoxane (dMMAO) as a cocatalyst at 0 °C by a semi-batch method. The catalytic system showed the activity of 11,400 kg-polymer mol-Ti−1 h−1, which was too high to control the polymerization. Batch-wise polymerizations were then conducted by changing the amount of propene in feed. The polymerizations proceeded quantitatively, and the number-average molecular weight increased linearly against the polymer yield with keeping the number of polymer chains constant although the polydispersity indices were broader than that expected in a living polymerization. The results of postpolymerization indicated the smooth chain transfer after the monomer consumption.

Ryotaro Harada

Papers

Highly Active Living Random Copolymerization of Norbornene and 1-Alkene with ansa-Fluorenylamidodimethyltitanium Derivative: Substituent Effects on Fluorenyl Ligand

A Highly Active Catalyst Composed of ansa-Fluorenylamidodimethyltitanium Derivative for Propene Polymerization