Binary Catalyst Manipulating the Sequences of Poly(ester-carbonate) Copolymers in Metal-Free Terpolymerization of Epoxide, Anhydride, and CO

Overview

Journal Precis Chem

Publisher American Chemical Society

Date 2025 Jan 31

PMID 39886379

Authors

Zehao Wang

Yukun Ma

Jinbo Zhang

Shaofeng Liu

Zhibo Li

Affiliations

Soon will be listed here.

Abstract

The one-pot terpolymerization of epoxide (EP), anhydride (AH), and CO to synthesize polyester-polycarbonate copolymers with precise sequences remains a significant challenge in polymer chemistry. In this study, promising progress was achieved by utilizing a cyclic trimeric phosphazene base (CTPB) and triethylboron (TEB) as a binary catalyst, enabling the synthesis of both well-defined block and truly random poly(ester-carbonate) copolymers through the one-pot terpolymerization of EP/AH/CO. By adjusting the molar ratio of CTPB/TEB to 1/0.5, remarkable chemoselectivity for ring-opening alternating copolymerization (ROAC) of propylene oxide (PO) and phthalic anhydride (PA) was achieved, followed by the ROAC of PO/CO. This sequential control allowed for the synthesis of well-defined block poly(ester-carbonate) copolymers, containing three possible sequences, ester-ester sequence (EE)/ester-carbonate sequence (EC)/carbonate-carbonate sequence (CC) = 59/4/37, from a mixture of PO, PA, and CO. Moreover, the versatility of this CTPB/TEB catalyst in regulating chemoselectivity was demonstrated, with a ratio of 1/3 facilitating the simultaneous ROAC of PO/PA and PO/CO with compatible rates, resulting in the production of random poly(ester-carbonate) copolymers, in which three possible sequences (EE/EC/CC = 26/50/24) are very close to theoretical values. This metal-free catalytic system and its flexible chemoselectivity regulation strategy proved to be applicable to a wide range of epoxides (PO, cyclohexene oxide (CHO)) and anhydrides (PA, diglycolic anhydride (DGA), and succinic anhydride (SA)), enabling the successful synthesis of poly(ester-carbonate) copolymers with diverse sequences and compositions.

References

Yang Z, Hu C, Cui F, Pang X, Huang Y, Zhou Y . One-Pot Precision Synthesis of AB, ABA and ABC Block Copolymers via Switchable Catalysis. Angew Chem Int Ed Engl. 2022; 61(12):e202117533. DOI: 10.1002/anie.202117533. View

Wei P, Bhat G, Darensbourg D . Enabling New Approaches: Recent Advances in Processing Aliphatic Polycarbonate-Based Materials. Angew Chem Int Ed Engl. 2023; 62(48):e202307507. DOI: 10.1002/anie.202307507. View

Wan Y, He J, Zhang Y, Chen E . One-Step Synthesis of Lignin-Based Triblock Copolymers as High-Temperature and UV-Blocking Thermoplastic Elastomers. Angew Chem Int Ed Engl. 2021; 61(8):e202114946. DOI: 10.1002/anie.202114946. View

Song Y, He J, Zhang Y, Gilsdorf R, Chen E . Recyclable cyclic bio-based acrylic polymer via pairwise monomer enchainment by a trifunctional Lewis pair. Nat Chem. 2022; 15(3):366-376. DOI: 10.1038/s41557-022-01097-7. View

Xie R, Wang Y, Li S, Li B, Xu J, Liu J . Insights into the Distinct Behaviors between Bifunctional and Binary Organoborane Catalysts through Terpolymerization of Epoxide, CO, and Anhydride. Angew Chem Int Ed Engl. 2024; 63(27):e202404207. DOI: 10.1002/anie.202404207. View

De Hoe G, Zumstein M, Tiegs B, Brutman J, McNeill K, Sander M . Sustainable Polyester Elastomers from Lactones: Synthesis, Properties, and Enzymatic Hydrolyzability. J Am Chem Soc. 2018; 140(3):963-973. DOI: 10.1021/jacs.7b10173. View

Wang J, Zhu Y, Li M, Wang Y, Wang X, Tao Y . Tug-of-War between Two Distinct Catalytic Sites Enables Fast and Selective Ring-Opening Copolymerizations. Angew Chem Int Ed Engl. 2022; 61(36):e202208525. DOI: 10.1002/anie.202208525. View

Plajer A, Williams C . Heterotrimetallic Carbon Dioxide Copolymerization and Switchable Catalysts: Sodium is the Key to High Activity and Unusual Selectivity. Angew Chem Int Ed Engl. 2021; 60(24):13372-13379. PMC: 8251569. DOI: 10.1002/anie.202101180. View

Jeske R, Rowley J, Coates G . Pre-rate-determining selectivity in the terpolymerization of epoxides, cyclic anhydrides, and CO2: a one-step route to diblock copolymers. Angew Chem Int Ed Engl. 2008; 47(32):6041-4. DOI: 10.1002/anie.200801415. View

10.

Deacy A, Gregory G, Sulley G, Chen T, Williams C . Sequence Control from Mixtures: Switchable Polymerization Catalysis and Future Materials Applications. J Am Chem Soc. 2021; 143(27):10021-10040. PMC: 8297863. DOI: 10.1021/jacs.1c03250. View

11.

Hong M, Chen J, Chen E . Polymerization of Polar Monomers Mediated by Main-Group Lewis Acid-Base Pairs. Chem Rev. 2018; 118(20):10551-10616. DOI: 10.1021/acs.chemrev.8b00352. View

12.

Bai Y, Wang H, He J, Zhang Y, Chen E . Dual-initiating and living frustrated Lewis pairs: expeditious synthesis of biobased thermoplastic elastomers. Nat Commun. 2021; 12(1):4874. PMC: 8360971. DOI: 10.1038/s41467-021-25069-6. View

13.

Tang S, Lin B, Tonks I, Eagan J, Ni X, Nozaki K . Sustainable Copolymer Synthesis from Carbon Dioxide and Butadiene. Chem Rev. 2024; 124(6):3590-3607. DOI: 10.1021/acs.chemrev.3c00847. View

14.

Nomura N, Akita A, Ishii R, Mizuno M . Random copolymerization of epsilon-caprolactone with lactide using a homosalen-Al complex. J Am Chem Soc. 2010; 132(6):1750-1. DOI: 10.1021/ja9089395. View

15.

He G, Ren B, Wang S, Liu Y, Lu X . Sequence Control in Asymmetric Terpolymerizations of meso-Epoxides, CO , and Phthalic Anhydride: Unprecedented Statistical Ester-Carbonate Distributions. Angew Chem Int Ed Engl. 2023; 62(27):e202304943. DOI: 10.1002/anie.202304943. View

16.

Wang X, Huo Z, Xie X, Shanaiah N, Tong R . Recent Advances in Sequence-Controlled Ring-Opening Copolymerizations of Monomer Mixtures. Chem Asian J. 2022; 18(4):e202201147. DOI: 10.1002/asia.202201147. View

17.

Zhang D, Boopathi S, Hadjichristidis N, Gnanou Y, Feng X . Metal-Free Alternating Copolymerization of CO2 with Epoxides: Fulfilling "Green" Synthesis and Activity. J Am Chem Soc. 2016; 138(35):11117-20. DOI: 10.1021/jacs.6b06679. View

18.

Ma Y, You X, Zhang J, Wang X, Kou X, Liu S . Synthesis of Sequence-specific Poly(ester-carbonate) Copolymers via Chemoselective Terpolymerization Controlled by the Stoichiometric Ratio of Phosphazene/Triethylborane. Angew Chem Int Ed Engl. 2023; 62(25):e202303315. DOI: 10.1002/anie.202303315. View

19.

Romain C, Zhu Y, Dingwall P, Paul S, Rzepa H, Buchard A . Chemoselective Polymerizations from Mixtures of Epoxide, Lactone, Anhydride, and Carbon Dioxide. J Am Chem Soc. 2016; 138(12):4120-31. DOI: 10.1021/jacs.5b13070. View

20.

Zhang J, Wang L, Liu S, Li Z . Synthesis of Diverse Polycarbonates by Organocatalytic Copolymerization of CO and Epoxides: From High Pressure and Temperature to Ambient Conditions. Angew Chem Int Ed Engl. 2021; 61(4):e202111197. DOI: 10.1002/anie.202111197. View