Synthesis of Block Copolymers of Polyester and Polystyrene by Means of Cross-Metathesis of Cyclic Unsaturated Polyester and Atom Transfer Radical Polymerization

Abstract

Synthesis of B−A−B type triblock copolymers of aliphatic polyester (PEs) and polystyrene (PSt) was investigated by using cyclic unsaturated PEs prepared by conventional polycondensation of 4-octene-1,8-diol and sebacoyl chloride. The obtained cyclic PEs underwent cross-metathesis with PSt containing a carbon−carbon double bond (CC) at the central position, which was obtained by atom transfer radical polymerization (ATRP) of styrene with a bifunctional initiator containing a CC bond. PSt with a longer methylene spacer between the CC bond and PSt successfully afforded the PStb-PEs-b-PSt triblock copolymer. As another approach to obtain the triblock copolymer, cross-metathesis of cyclic PEs with 2butene-1,4-diol or 4-octene-1,8-diol bis(2-bromoisobutyrylate)s was conducted to afford linear PEs having ATRP initiation sites at both ends, followed by ATRP of styrene. The unsaturated PEs segment in the triblock copolymer obtained by the second approach was converted into a saturated PEs segment by treatment with tosyl hydrazide and tributylamine. DSC analysis of the triblock copolymer containing the saturated PEs segment showed crystallinity when the PEs content was ≥14 mol %.

Linear Block Copolymer Synthesis

“…In this way, triblocks PS-b-PEs-b-PS can be prepared initiated from a PESt− ATRP macroinitiator (Scheme 18). 389 Polyester−polyether block copolymers of a (AB) n B m type structure have been prepared by a tunable bicomponent catalyst in one synthetic step (Figure 36). 390 The involved ring-opening alternating copolymerization (ROAP) with various nonhomopolymerizable compounds has established itself as a method which can provide a large number of diverse polycarbonates, polyesters, and specifically as pioneered by Coates, from a mixture of cyclic anhydride, epoxides, and CO 2 .…”

“…Scheme 18. Synthesis of PS-b-PEs-b-PS Triblock Copolymer via Cross-Metathesis with a Macroinitiator for ATRP389 …”

One-Pot Synthesis of Polyester-Based Linear and Graft Copolymers for Solid Polymer Electrolytes

“…[43][44][45] Building linear block copolymers or graft copolymers and polymers with various topological structures to destroy the crystallinity of polyester has proved to be a good way to meet the practical application requirements of LIBs. [46][47][48][49][50][51] With the development of polymer synthesis technology, various living polymerizations including atom transfer radical polymerization (ATRP), [52][53][54][55][56] and reversible addition fragmentation chain transfer (RAFT) polymerization, [57][58][59][60] nitroxide-mediated radical polymerization (NMP), [61][62][63][64] and ring-opening polymerization system in the system. Moreover, the carboxylic acid group exists in a large number of commercially available chemical products, and its catalytic effect has always been easily overlooked.…”

Importance of a reversible reaction for the synthesis of telechelic polymers by means of polycondensation using an excess of one monomer

“…7 A polystyrene- b -polyester- b -polystyrene triblock copolymer was synthesized by means of this approach. 8 For simple cyclic polyesters without carbon–carbon double bonds, an alkoxide-catalyzed ester–ester exchange reaction with a symmetrical ExR bearing the ester linkage provides access to telechelic polyesters. 9 This alkoxide-catalyzed ester–ester exchange reaction is also effective for the synthesis of polyesters by means of the polycondensation of a diol formate and dimethyl dicarboxylate with the elimination of methyl formate, which has a low boiling point, under reduced pressure.…”