Heterogeneous Double Metal Cyanide Catalyzed Synthesis of Poly(ε-caprolactone) Polyols for the Preparation of Thermoplastic Elastomers

A series of polycaprolactones (PCLs) with molecular weights of 950–10,100 g mol−1 and Ð of 1.10–1.87 have been synthesized via one-pot, solvent-free ring-opening polymerization (ROP) of ε-caprolactone (CL) using a heterogeneous double metal cyanide (DMC) catalyst. Various initiators, such as polypropylene glycol, ethylene glycol, propylene glycol, glycerol, and sorbitol, are employed to tune the number of hydroxyl end groups and properties of the resultant PCLs. Kinetic studies indicate that the DMC-catalyzed ROP of CL proceeds via a similar mechanism with the coordination polymerization. Branched PCLs copolymers are also synthesized via the DMC-catalyzed copolymerization of CL with glycidol. The α,ω-hydroxyl functionalized PCLs were successfully used as telechelic polymers to produce thermoplastic poly(ester-ester) and poly(ester-urethane) elastomers with well-balanced stress and strain properties.

Heterogeneous Double Metal Cyanide Catalyzed Synthesis of Poly(ε-caprolactone) Polyols for the Preparation of Thermoplastic Elastomers

A series of polycaprolactones (PCLs) with molecular weights of 950–10,100 g mol−1 and Ð of 1.10–1.87 have been synthesized via one-pot, solvent-free ring-opening polymerization (ROP) of ε-caprolactone (CL) using a heterogeneous double metal cyanide (DMC) catalyst. Various initiators such as polypropylene glycol, ethylene glycol, propylene glycol, glycerol, and sorbitol are employed to tune the number of hydroxyl end groups and properties of the resultant PCLs. Kinetic studies indicate that the DMC-catalyzed ROP of CL proceeds via a coordination mechanism. Branched PCLs copolymers are also synthesized via the DMC-catalyzed copolymerization of CL with glycidol. The α,ω-hydroxyl functionalized PCLs were successfully used as telechelic polymers to produce thermoplastic poly(ester-ester) and poly(ester-urethane) elastomers with well-balanced stress and strain properties.

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

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.