苯并15-冠-5修饰的咪唑卡宾催化2,2-二甲基三亚甲基环碳酸酯开环均聚的研究
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摘要
研究了苯并15-冠-5修饰的咪唑卡宾催化2,2-二甲基三亚甲基环碳酸酯开环聚合,系统地探索了该聚合反应的特征,得到了反应的最佳条件,所得聚合物的摩尔质量较高,摩尔质量分布较窄,DSC两次扫描分析该聚合物存在两种晶型,利用~1H NMR和IR分析了聚合物的结构,推测聚合机理为"单体-活化"机理.
Ring-opening polymerization of 2,2-dimethyltrimethylene carbonate catalyzed by benzo-15-crown-5 imidazol carbene was mainly studied. The reaction features had been investigated systematically and the optimum conditions was obtained. The polymer gives higher molecular weights and narrow polydispersities. The DSC measurement of the polymer displays two different crystalline modifications. The structure of the polymers was characterized by1 H NMR and IR,and the polymerization mechanism is inferred via a monomer-activated process.
Ring-opening polymerization of 2,2-dimethyltrimethylene carbonate catalyzed by benzo-15-crown-5 imidazol carbene was mainly studied. The reaction features had been investigated systematically and the optimum conditions was obtained. The polymer gives higher molecular weights and narrow polydispersities. The DSC measurement of the polymer displays two different crystalline modifications. The structure of the polymers was characterized by1 H NMR and IR,and the polymerization mechanism is inferred via a monomer-activated process.
引文
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[17]WANG Y,LI N,ZHANG L F,et al.Ring-opening polymerization by N-heterocyclic carbenes as catalysts:characteristics and kinetics[J].Kinetics and Catalysis,2014,55(4):416-421.
[2]TIAN H Y,TANG Z H,ZHUANG X L,et al.Biodegradable synthetic polymers:preparation,functionalization and biomedical application[J].Progress in Polymer Science,2012,37(5):237-280.
[3]CASTRO-OSMA J A,ALONSO-MORENO C,GARCA-MARTINEZ,J C,et al.Ring-opening(ROP)versus ring-expansion polymerzation(REP)ofε-caprolactone to give linear or cyclic polycaprolactones[J].Macromolecules,2013,46(16):6388-6394.
[4]OKADA M.Chemical syntheses of biodegradable polymers[J].Progress in Polymer Science,2002,27(1):87-133.
[5]JEONG B,BAE Y H,LEE D S,et al.Biodegradable block copolymers as injectable drug-delivery systems[J].Nature,1997,388(28):860-862.
[6]CHIELLINI E,SOLARO R.Biodegradable polymeric materials[J].Advanced Materials,1996,8(4):305-313.
[7]TSCHAN M J L,BRULE E,HAQUETTE P,et al.Synthesis of biodegradable polymers from renewable resources[J].Polymer Chemistry,2012,3(4):836-851.
[8]WEBSTER R L.Rondom copolymerisations catalysed by simple titaniumα-amino acid complexes[J].RSC Advance,2014,4(10):5254-5260.
[9]FENG J,ZHUO R X,ZHANG X Z.Construction of functional aliphatic polycarbonates for biomedical applications[J].Progress in Polymer Science,2012,37(2):211-236.
[10]DIALLO A K,GUERIN W,SLAWINSKI M,et al.Block and random copolymers of 1,2-cyclohexyl cyclocarbonate and L-lactide or trimethylene carbonate synthesized by ring-opening polymerization[J].Macromolecules,2015,48(10):3247-3256.
[11]GUERIN W,HELOU M,SLAWINSKI M,et al.Ethylene carbonate/cyclic ester random copolymer synthesized by ring-opening polymerization[J].Polymer Chemistry,2015,6(11):1972-1985.
[12]PAUL S,ZHU Y,ROMAIN C,et al.Ring-opening copolymerization(ROCOP):synthesis and properties of polyesters and polycarbonates[J].Chemical Communications,2015,51(30):6459-6479.
[13]MATSUO J,AOKI K,ENDO T,et al.Substituent effect on the anionic equilibrium polymerization of six-membered cyclic carbonates[J].Macromolecules,1998,31(14):4432-4438.
[14]LING J,SHEN Z Q,HUANG Q H,et al.Novel single rare earth aryloxide initiators for ring-opening polymerization of2,2-dimethyltrimethylene carbonate[J].Macromolecules,2001,34(22):7613-7616.
[15]WANG Y,GUO X N,ZHANG R,et al.Ring-opening polymerization of[epsilon]-caprolactone to polycaprolactone using N-heterocyclic carbene organocatalysts[J].Journal of Polymer Materials,2013,30(2):175-185.
[16]WANG Y,ZHANG L F,GUO X N,et al.Characteristics and mechanism of L-lactide polymerization using N-heterocyclic carbene organocatalyst[J].Journal of Polymer Research,2013,20(3):1-6.
[17]WANG Y,LI N,ZHANG L F,et al.Ring-opening polymerization by N-heterocyclic carbenes as catalysts:characteristics and kinetics[J].Kinetics and Catalysis,2014,55(4):416-421.