Insight into the Alcohol-Free Ring-Opening Polymerization of TMC Catalyzed by TBD.

Sophie Monge,Julien Pinaud,Jean-Jacques Robin,Olinda Gimello,Fabrice Azemar

doi:10.3390/polym13101589

Abstract

We report herein a study on the alcohol-free, ring-opening polymerization of trimethylene carbonate (TMC) in THF, catalyzed by 1,5,7-triazabicyclo [4.4.0] ec-5-ene (TBD) with ratios nTBD/nTMC ranging between 1/20 and 1/400. In all cases, the reaction proceeds very rapidly, even faster than in the presence of alcohol initiators, and provides PTMC with molecular weights up to Mn = 34,000 g mol−1. Characterization of the obtained PTMC samples by MALDI-TOF mass spectrometry, triple detection size exclusion chromatography and 1H NMR spectroscopy reveals the presence of both linear and cyclic polymer chains.

Highlights

Aliphatic polycarbonates are an interesting class of biocompatible and biodegradable polymers that find applications in the biomedical field for tissue engineering, hydrogel production and drug delivery [1]. They were described a long time ago by Carothers [2], they have received increased attention in recent years with the development of functional monomers governing the properties and microstructures of the resulting polymers [3,4,5,6]. This class of polycondensates can be synthesized by usual step growth polymerization, polyaddition of carbon dioxide onto polyepoxides [7] or by ring-opening polymerization (ROP) of cyclic carbonates according to various mechanisms
In the absence of a protic initiator, the reaction is expected to lead to macrocycles by zwiterrionic ring-opening polymerization (ZROP)
The ring-opening polymerization of trimethylene carbonate (TMC) catalyzed by triazabicyclo-[4.4.0] dec-5-ene (TBD) in the absence of alcohol proceeds very rapidly, within minutes at room temperature, providing poly(trimethylene carbonate) (PTMC) samples with Mn ranging between 14,800 and 33,700 g.mol−1

Summary

Introduction

Aliphatic polycarbonates are an interesting class of biocompatible and biodegradable polymers that find applications in the biomedical field for tissue engineering, hydrogel production and drug delivery [1] They were described a long time ago by Carothers [2], they have received increased attention in recent years with the development of functional monomers governing the properties and microstructures of the resulting polymers [3,4,5,6]. This class of polycondensates can be synthesized by usual step growth polymerization, polyaddition of carbon dioxide onto polyepoxides [7] or by ring-opening polymerization (ROP) of cyclic carbonates according to various mechanisms.

Methods

Results

Conclusion