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Issue 35, 2020
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The synthesis of cyclic olefin copolymers (COCs) by ethylene copolymerisations with cyclooctene, cycloheptene, and with tricyclo[6.2.1.0(2,7)]undeca-4-ene: the effects of cyclic monomer structures on thermal properties

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Abstract

Ethylene copolymerisations with cyclooctene (COE) by half-titanocenes, Cp′TiCl2(X) [X = OAr (Ar = 2,6-iPr2C6H3), Cp′ = 1,2,4-Me3C5H2, tBuC5H4, C5Me5 (Cp*), indenyl; X = N[double bond, length as m-dash]CtBu2, Cp′ = Cp, tBuC5H4, indenyl] and [Me2Si(C5Me4)(NR)]TiCl2 [R = tBu (CGC), cyclohexyl], and by metallocenes, Cp2ZrCl2 and [Me2Si(indenyl)2]ZrCl2 (SBI), have been explored. Cp*TiCl2(OAr) afforded high molecular weight amorphous copolymers with efficient COE incorporation as well as exclusive 1,2-insertion (Mn = 1.08–12.6 × 105), whereas CGC and SBI afforded semi-crystalline copolymers with less COE incorporation. Copolymerisation with cycloheptene gave ultrahigh molecular weight amorphous copolymers (Mn = 1.32–3.08 × 106). Linear relationships between the glass transition temperatures (Tg) and cyclic olefin contents have been demonstrated, and the Tg values were affected by the ring size. Copolymerisation with tricyclo[6.2.1.0(2,7)]undeca-4-ene by CpTiCl2(N[double bond, length as m-dash]CtBu2) afforded high molecular weight copolymers, with high Tg values by the introduction of an additional cyclic unit.

Graphical abstract: The synthesis of cyclic olefin copolymers (COCs) by ethylene copolymerisations with cyclooctene, cycloheptene, and with tricyclo[6.2.1.0(2,7)]undeca-4-ene: the effects of cyclic monomer structures on thermal properties

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Supplementary files

Article information


Submitted
30 Jun 2020
Accepted
19 Aug 2020
First published
21 Aug 2020

Polym. Chem., 2020,11, 5590-5600
Article type
Paper

The synthesis of cyclic olefin copolymers (COCs) by ethylene copolymerisations with cyclooctene, cycloheptene, and with tricyclo[6.2.1.0(2,7)]undeca-4-ene: the effects of cyclic monomer structures on thermal properties

H. Harakawa, M. Okabe and K. Nomura, Polym. Chem., 2020, 11, 5590
DOI: 10.1039/D0PY00940G

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