All-Polycarbonate Thermoplastic Elastomers Based on Triblock Copolymers Derived from Triethylborane-Mediated Sequential Copolymerization of CO2 with Various Epoxides

M.C. Jia, D.Y. Zhang, G.W. de Kort, C.H.R.M. Wilsens, S. Rastogi, N. Hadjichristidis, Y. Gnanou*, X.S. Feng*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

22 Citations (Web of Science)

Abstract

Various oxirane monomers including alkyl ether or allyl-substituted ones such as 1-butene oxide, 1-hexene oxide, 1-octene oxide, butyl glycidyl ether, allyl glycidyl ether, and 2-ethylhexyl glycidyl ether were anionically copolymerized with CO2 into polycarbonates using onium salts as initiator in the presence of triethylborane. All copolymerizations exhibited a "living" character, and the monomer consumption was monitored by in situ Fourier-transform infrared spectroscopy. The various polycarbonate samples obtained were characterized by H-1 NMR, GPC, and differential scanning calorimetry. In a second step, all-polycarbonate triblock copolymers demonstrating elastomeric behavior were obtained in one pot by sequential copolymerization of CO2 with two different epoxides, using a difunctional initiator. 1-Octene oxide was first copolymerized with CO2 to form the central soft poly(octene carbonate) block which was flanked by two external rigid poly(cyclohexene carbonate) blocks obtained through subsequent copolymerization of cyclohexene oxide with CO2. Upon varying the ratio of 1-octene oxide to cyclohexene oxide and their respective ratios to the initiator, three all-polycarbonate triblock samples were prepared with molar masses of about 350 kg/mol and 22, 26, and 29 mol % hard block content, respectively. The resulting triblock copolymers were analyzed using H-1 NMR, GPC, thermogravimetric analysis, differential scanning calorimetry, and atomic force microscopy. All three samples demonstrated typical elastomeric behavior characterized by a high elongation at break and ultimate tensile strength in the same range as those of other natural and synthetic rubbers, in particular those used in applications such as tissue engineering.
Original languageEnglish
Pages (from-to)5297-5307
Number of pages11
JournalMacromolecules
Volume53
Issue number13
DOIs
Publication statusPublished - 14 Jul 2020

Keywords

  • carbon-dioxide
  • catalyst
  • complex
  • construction
  • free alternating copolymerization
  • functional polycarbonates
  • glycidyl ethers
  • propylene-oxide
  • selectivity
  • COMPLEX
  • CATALYST
  • FUNCTIONAL POLYCARBONATES
  • FREE ALTERNATING COPOLYMERIZATION
  • GLYCIDYL ETHERS
  • CONSTRUCTION
  • PROPYLENE-OXIDE
  • CARBON-DIOXIDE
  • SELECTIVITY

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