Fully alternating and regioselective ring-opening copolymerization of phthalic anhydride with epoxides using highly active metal-free Lewis pairs as a catalyst

Abstract

Cooperative metal-free Lewis pairs effectively catalysed controlled ring-opening copolymerization of phthalic anhydride (PA) with epoxides.

Phosphazene/Lewis Acids as Highly Efficient Cooperative Catalyst for Synthesis of High‐Molecular‐Weight Polyesters by Ring‐Opening Alternating Copolymerization of Epoxide and Anhydride

“…In the previous reports, at least 1 equiv of TEB relative to base was generally required for efficient catalytic ROAC reactions . It was surprising that for the current catalytic system even a little amount of TEB can efficiently accelerate the copolymerization (Table , Run 5 vs. Run 1).…”

“…Recently, Zhao and coworkers reported the one‐step synthesis of polyester–polyether block copolymers by ROAC of PA and PO/EO using a mild phosphazene base with TEB . Chakraborty and coworkers systematically tested various Lewis acids, such as TEB, Al(CH 3 ) 3 , Et 2 Zn, and n ‐Bu 2 Mg, in combination with various Lewis bases, such as PPNCl, 4‐( N,N ‐dimethylamino)pyridine, 1,8‐diazabicyclo[5.4.0]undec‐7‐ene, and TBD, as Lewis pair catalysts for ROAC of anhydrides and epoxides . It was found that the TEB/PPNCl pair stood out as the most active and effective one for the perfectly alternating and regionselective controlled ROAC of various epoxides with anhydrides.…”

Ring‐Opening Copolymerization of Maleic Anhydride with Functional Epoxides: Poly(propylene fumarate) Analogues Capable of Post‐Polymerization Modification

“…Traditionally, PPF has been synthesized by step‐growth polymerization, which requires both elevated temperature and reduced pressure, and typically results in modest yields, broad molecular mass distribution ( Ð M ), and byproducts that must be removed prior to use . Various copolymerization strategies of epoxides, anhydrides, and lactones have been investigated previously to produce a wide range of polyesters . Recently, PPF was synthesized using an alternating ring‐opening copolymerization (ROCOP) of maleic anhydride (MA) and propylene oxide (PO) to produce poly(propylene maleate) (PPM), which was subsequently isomerized to produce PPF .…”

Ring‐Opening Copolymerization of Maleic Anhydride with Functional Epoxides: Poly(propylene fumarate) Analogues Capable of Post‐Polymerization Modification

“…[24,25] Tr aditionally,P PF has been synthesized by step-growth polymerization, which requires both elevated temperature and reduced pressure,a nd typically results in modest yields, broad molecular mass distribution ( M ), and byproducts that must be removed prior to use. [27][28][29][30] Recently,P PF was synthesized using an alternating ring-opening copolymerization (ROCOP) of maleic anhydride (MA) and propylene oxide (PO) to produce poly(propylene maleate) (PPM), which was subsequently isomerized to produce PPF. [27][28][29][30] Recently,P PF was synthesized using an alternating ring-opening copolymerization (ROCOP) of maleic anhydride (MA) and propylene oxide (PO) to produce poly(propylene maleate) (PPM), which was subsequently isomerized to produce PPF.…”

“…[26] Va rious copolymerization strategies of epoxides,a nhydrides,a nd lactones have been investigated previously to produce aw ide range of polyesters. [27][28][29][30] Recently,P PF was synthesized using an alternating ring-opening copolymerization (ROCOP) of maleic anhydride (MA) and propylene oxide (PO) to produce poly(propylene maleate) (PPM), which was subsequently isomerized to produce PPF. [31][32][33][34] This approach results in am uch higher degree of control of the material properties and the use of two monomer species offers multiple sites for post-polymerization chain functionalization.…”