Living Coordination Polymerization of Allene Derivatives Bearing Hydroxy Groups by π-Allylnickel Catalyst

Abstract

Well‐defined poly(alcohol)s were prepared directly by the living coordination polymerization of allene derivatives bearing hydroxy groups with [{(π‐allyl)NiOCOCF3}2]/PPh3 as an initiator (see scheme). R=CH2OH, CHCH3OH, C(CH3)2OH.

Novel graft copolymer containing a polyallene backbone and poly(tert‐butyl acrylate) side chains

“…The molecular weights of PMHDO increased linearly with increasing feed ratios, and the molecular weight distributions of PMHDO remained narrow throughout the polymerization ( M w / M n < 1.23). These results affirmed the living nature of this polymerization system 10…”

“…The living coordination polymerization of allene derivatives initiated by [(η 3 ‐allyl)NiOCOCF 3 ] 2 ( 2 ) can proceed under mild conditions to give well‐defined polymers in high yields; their molecular weights can be controlled by the feed ratio, and their molecular weight distributions are always narrow 3–9. Also, the stable, living π‐allyl nickel end enables the block copolymerization of allene derivatives, and the molecular weight and composition of the block copolymer can be adjusted by the feed ratio 10–12. However, the polymerizations of common vinyl monomers such as styrene and acrylate cannot be initiated by 2 , and well‐defined copolymers of allene derivatives with common vinyl monomers cannot be obtained by this kind of living coordination polymerization.…”

“…The living coordination polymerizations of allene derivatives bearing hydroxyl groups initiated by 2 /triphenyl phosphorate (PPh 3 ) were reported by Endo et al10 The pendant hydroxyl groups of the polyallene‐based chain could be easily converted to ATRP initiation groups to initiate the ATRP of vinyl monomers for building the branches. Thus, the reactive double bonds could be introduced into a traditional polymer with a well‐defined architecture.…”

Polyallene-based graft copolymer via 6-methyl-1,2-heptadien-4-ol and methyl methacrylate

“…It was found that the molecular weights of PMHDO homopolymers increased linearly with the increase of the feed ratio and the molecular weight distributions remained narrow throughout the polymerization (M w /M n < 1.23). These results verified the living nature of the present polymerization system [7]. …”

“…By this way, molecular weight of the polymer can be controlled by the feed ratio of the monomer to the initiator and molecular weight distribution of the polymer can be kept narrow. Also, the block copolymerization of allene derivatives were carried out due to the stability of the living pallylnickel end group and the molecular weights can be tuned by the feed ratio [7]. Since [(h 3 -allyl)NiOCOCF 3 ] 2 can not initiate the polymerization of vinyl monomers such as styrene, acrylate and methacrylate, etc.…”