Polymerization of trimethylene carbonates using organic phosphoric acids. Issue 35 (10th August 2016)

• Record Type: Journal Article
• Authors: Liu, Jiaqi; Cui, Saide; Li, Zhenjiang; Xu, Songquan; Xu, Jiaxi; Pan, Xianfu; Liu, Yaya; Dong, He; Sun, Herui; Guo, Kai
• Is Part Of: Polymer chemistry. Volume 7:Issue 35(2016)
• Page Start: 5526
• Page End: 5535
• Publication Date: 2016-08-10
• Subjects: Polymers -- Periodicals; Macromolecules -- Periodicals; Polymerization -- Periodicals; 547.705
• DOI: 10.1039/c6py01210h
• Languages: English
• ISSNs: 1759-9954

Abstract

Abstract : 1, 1′-Binaphthyl-2, 2′-diyl hydrogen phosphate (BNPH) catalyzed a controlled/living ROP of TMC through a bifunctional activation mechanism, leading to end-functionalized PTMC and block polymers. Abstract : The homopolymerization of trimethylene carbonates (TMC) and their diblock copolymerization to PTMC- b -PVL and PTMC- b -PCL were carried out using benzyl alcohol (BnOH) as the initiator and 1, 1′-binaphthyl-2, 2′-diyl hydrogen phosphate (BNPH) as the catalyst in toluene at room temperature. The measured 1 H NMR molecular weight (PTMC, M n, NMR = 5300 g mol −1 ) and the theoretical one (PTMC, M n, theo = 5100 g mol −1 ) calculated from the initial ratio of [TMC]0 /[BnOH]0 and the monomer conversion matched ideally. The 1 H NMR, SEC and MALDI-ToF MS measurements clarified that the obtained polymers were exactly as expected. Kinetics and chain extension experiments demonstrated the controlled/living nature for the ROP of TMC using BNPH. NMR titration experiments confirmed that the polymerization proceeded via a bifunctional activation mechanism. Extension of the initiators by using multifunctional 1, 3-propanediol, pentaerythritol, propargyl alcohol, 5-hexen-1-ol, and N -(2-hydroxyethyl)maleimide installed α, ω-dihydroxy telechelic, star-shaped, and clickable end-functionalized polycarbonates. Block copolymers poly(trimethylene carbonate)- block -poly(δ-valerolactone), poly(trimethylene carbonate)- block -poly(ε-caprolactone), and poly(trimethylene carbonate)- block -poly(l -lactide) had been successfully obtained, which suggests that the BNPH catalysis is broadly applicable.