Synthesis of polyester having sequentially ordered two orthogonal reactive groups by anionic alternating copolymerization of epoxide and bislactone

Abstract

This article presents a route to a novel polyester having sequentially ordered two orthogonal reactive groups. The polyester was given by the imidazoleinitiated alternating copolymerization of allyl glycidyl ether (AGE) and a bislactone 1. This copolymerization system is characterized by the following three reaction behaviors: (1) the selective participation of only one of the two lactone moieties of 1 to the copolymerization to give a linear polyester, and the consequent introduction of the second lactone into the side chain of the polyester, (2) the participation of the epoxy moiety in AGE to the copolymerization, and the consequent introduction of the carbon-carbon double bond into the side chain of the polyester, and (3) arrangement of the sequentially ordered two orthogonal reactive groups according to the alternating manner. The introduction of the two reactive groups to the side chain of the alternating copolymer allowed two routes of sequential chemoselective reactions: (A) The ring-opening reaction of the lactone moiety with n-propylamine and the following Pt-catalyzed hydrosilylation of the carbon-carbon double bond with dimethylphenylsilane and (B) the sequential reactions of the reverse order. V V C 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6750-6757, 2009

Zr(IV) Catalyst for the Ring-Opening Copolymerization of Anhydrides (A) with Epoxides (B), Oxetane (B), and Tetrahydrofurans (C) to Make ABB- and/or ABC-Poly(ester-alt-ethers)

“… 11 , 12 The polymerization is feasible because the low lactone polymerization free energy precludes lactone ROP and drives the reaction with the high free-energy epoxides. 11 , 13 , 14 …”

“…Once again, the polymerization thermodynamics favor depolymerization at higher temperatures and the monomer synthesis has a low overall yield (20%). The alternating ROP of epoxides and low-ring strain lactones, e.g., dihydrocoumarin, can also form poly­(ester- alt -ether). , The polymerization is feasible because the low lactone polymerization free energy precludes lactone ROP and drives the reaction with the high free-energy epoxides. ,, …”

“…11,12 The polymerization is feasible because the low lactone polymerization free energy precludes lactone ROP and drives the reaction with the high free-energy epoxides. 11,13,14 The ring-opening copolymerization (ROCOP) of anhydrides (A) and epoxides (B) is a controlled polymerization route to polyesters showing alternating AB sequences. 4,15−17 Both monomers have attractions including a large number being existing commercial products and many are accessible from bio-based raw materials and wastes.…”

Control of reactions and network structures of epoxy thermosets

“…Other cyclic comonomers can be copolymerized with epoxies according to an anionic alternating copolymerization mechanism and are used in epoxy thermoset technology. They include bicyclic and spirocyclic bis(γ-lactone)s [57][58][59][60][61][62]. These are comonomers dedicated to the development of shrinkage-free or expanding curing formulations.…”

Mechanistic Insights into Selective Indium-Catalyzed Coupling of Epoxides and Lactones

“…Polymers with precisely controlled alternating monomer units, which have properties distinct from their homo, block, or gradient counterparts, , are challenging to synthesize in a sequence-controlled fashion. – This has been particularly true for the synthesis of poly­(ether- alt -esters) from epoxides and lactones; most attempts to create alternating copolymers form oligomers. – One successful method for producing alternating copolymers has been the polymerization of presequenced monomers. – An example of these are spiro-orthoesters, monomers that are capable of forming poly­(ether- alt -esters) through double ring-opening polymerization reactions. – …”