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Copolymerization of Norbornene and Styrene with Anilinonaphthoquinone-Ligated Nickel Complexes

Graduate School of Engineering, Hiroshima University, Hiroshima 739-8527, Japan
Author to whom correspondence should be addressed.
Polymers 2019, 11(7), 1100;
Received: 4 June 2019 / Revised: 24 June 2019 / Accepted: 26 June 2019 / Published: 28 June 2019
(This article belongs to the Special Issue Catalytic Polymerization)
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Poly(norbornene-co-styrene)s were synthesized by the use of anilinonaphthoquinone-ligated nickel complexes [Ni(C10H5O2NAr)(Ph)(PPh3): 1a, Ar = C6H3-2,6-iPr; 1b, Ar = C6H2-2,4,6-Me; 1c, Ar = C6H5] activated with modified methylaluminoxane (MMAO) or B(C6F5)3 in toluene. The effects of the cocatalysts were more significant than those of the nickel complexes, and MMAO gave higher activity than B(C6F5)3. The structural characterizations of the products indicated the formation of statistical norbornene copolymers. An increase of the styrene ratio in feed led to an increase in the incorporated styrene (S) content of the resulting copolymer. The molecular weight of the copolymer decreased with increasing the S ratio in feed at 70 °C. The copolymerization activity, using MMAO as a cocatalyst, decreased with lowering of the temperature from 70 to 0 °C, accompanied by an increase in the molecular weight of the copolymer. The S incorporation up to 59% with Mn of 78,000 was achieved by the 1b-B(C6F5)3 catalytic system. The glass transition temperatures of the norbornene (N)/S copolymers determined by differential scanning calorimetry, decreased from 329 to 128 °C according to the S content. View Full-Text
Keywords: nickel catalyst; copolymerization; norbornene; styrene nickel catalyst; copolymerization; norbornene; styrene

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Chowdhury, S.I.; Tanaka, R.; Nakayama, Y.; Shiono, T. Copolymerization of Norbornene and Styrene with Anilinonaphthoquinone-Ligated Nickel Complexes. Polymers 2019, 11, 1100.

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