Progress in metal-free cooperative catalysis for the ring-opening copolymerization of cyclic anhydrides and epoxides. (December 2019)

• Record Type: Journal Article
• Authors: Pappuru, Sreenath; Chakraborty, Debashis
• Is Part Of: European polymer journal. Volume 121(2019)
• Publication Date: 2019-12
• Subjects: Cooperative catalysis -- Metal-free Lewis pair -- Ring-opening alternating copolymerization -- Stereo selectivity -- Regioselectivity; ROCOP Ring-opening copolymerization -- ROAP ring-opening alternating copolymerization -- LPP Lewis pair polymerization -- LA Lewis acid -- LB Lewis base -- PLA polylactide -- PCL polycaprolactone -- PO propylene oxide -- MA maleic anhydride -- H-T head-to-tail -- DMAP 4-dimethylaminopyridine -- DBU 1, 8-diazabicyclo[5.4.0]undec-7-ene -- TBD triazabicyclodecene -- CHO cyclohexene oxide -- tBGE t-butyl glycidyl ether -- AGE allyl glycidyl ether -- SO styrene oxide -- rac-LA rac-lactide -- BA benzyl alcohol -- BDM 1, 4-benzenedimethanol -- PT pentaerythritol -- NA norbornene anhydride -- BO 2-benzyloxirane -- TEB triethyl borane -- EO ethylene oxide -- PA phthalic anhydride -- PB hosphazene base -- CPMA cis-5-norbornene-endo-2, 3-dicarboxylic anhydride -- GPC gel-permeation chromatography -- MALDI-TOF matrix-assisted laser desorption/ionization-time of flight -- SEC size-exclusion chromatography -- DOSY diffusion ordered spectroscopy -- HSQC heteronuclear single quantum coherence; Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; Polymerization; Polymers; Periodicals; Electronic journals; 547.705
• DOI: 10.1016/j.eurpolymj.2019.109276
• Languages: English
• ISSNs: 0014-3057

Abstract

Graphical abstract: Ring-opening alternating copolymerization (ROAP) of epoxides with cyclic anhydrides is an important polymerization reaction to illustrate significant features of metal-free cooperative catalysts. Highlights: Recent advancements in metal-free cooperative catalysis towards ring-opening copolymerization of cyclic anhydrides and epoxides was described. Simplicity of metal-free catalysts and their catalytic efficiency towards polymers molar mass control and stereo-/regioselectivity control was explained. Cooperativity between the acidic and basic catalytic sites of readily available LAs and LBs, for enhancing the polymerization activity was described. Abstract: Recent progress in the design of metal-free Lewis pair catalysts indicates a bright future for the synthesis of various polyesters with broad applications. In the present review, we attempt to highlight the recent advancements and opportunities in the use of metal-free cooperative catalysts or initiators for polymerization reactions. The ring-opening alternating copolymerization (ROAP) of epoxides with cyclic anhydrides is a typical typical polymerization reaction used here to illustrate some of the features of metal-free cooperative catalysts. In addition to the simple simplicity in the structural features of the catalysts and the desirable metal-free polyesters/polycarbonate products, these metal-free catalysts also exhibit impressive catalytic efficiency, molar mass control, and stereo-/regioselectivity. We believe that metal-free cooperative catalysis will continue to drive innovation into polymer chemistry research in the near future.