乙醇胺-乙二醇复合体系引发对二氧环己酮开环聚合的研究
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摘要
以乙醇胺-乙二醇复合体系催化对二氧环己酮(PDO)开环聚合生成聚对二氧环己酮(PPDO)。系统研究了反应时间、温度及单体与催化剂摩尔比(n(M)/n(C))对产物的结构及热力学性能方面的影响。利用红外光谱(IR)、核磁光谱(1 H NMR)、X射线广角衍射(WAXD)乌氏粘度法及差示扫描量热法(DSC)对聚合产物的结构、特性粘度以及热力学性能进行初步探讨。结果表明,在反应时间为24h、温度为120℃及n(M)/n(C)=500∶1条件下生成的聚合产物性能最佳。乙醇胺-乙二醇复合引发体系能够有效地催化PDO开环聚合生成PPDO产物。
poly(1,4-dioxanone)(PPDO)were prepared by the polymerization of 1,4-dioxanone(PDO)without solvent using 2-hydroxyethanolamine-glycol as a non-metallic organic catalyst,which has not previously been reported.The effects of the operating parameters,including the reaction temperature,reaction time and the molar ratio of monomer to catalyst(n(M)/n(C)),on the properties of the synthesized PPDO were systematically investigated.The structure of the products was characterized by 1 H NMR,IR and wide-angle X-ray diffraction(WAXD).The intrinsic viscosity([η])was measured using a Ubbelohde viscometer.Thermodynamic properties were characterized by differential scanning calorimetry(DSC).The results indicated that the best polymerization conditions were 140 ℃ and 24 hwith n(M)/n(C)equal to 500∶1.Furthermore,the results demonstrated that 2-hydroxyethanolamine-glycol was an efficient and easily removed catalyst for the ring-opening polymerization of PDO.
poly(1,4-dioxanone)(PPDO)were prepared by the polymerization of 1,4-dioxanone(PDO)without solvent using 2-hydroxyethanolamine-glycol as a non-metallic organic catalyst,which has not previously been reported.The effects of the operating parameters,including the reaction temperature,reaction time and the molar ratio of monomer to catalyst(n(M)/n(C)),on the properties of the synthesized PPDO were systematically investigated.The structure of the products was characterized by 1 H NMR,IR and wide-angle X-ray diffraction(WAXD).The intrinsic viscosity([η])was measured using a Ubbelohde viscometer.Thermodynamic properties were characterized by differential scanning calorimetry(DSC).The results indicated that the best polymerization conditions were 140 ℃ and 24 hwith n(M)/n(C)equal to 500∶1.Furthermore,the results demonstrated that 2-hydroxyethanolamine-glycol was an efficient and easily removed catalyst for the ring-opening polymerization of PDO.
引文
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[3]Wang Sujun,Luo Yanfeng,Liu Zhao,et al.Synthesis and characterization of a novel drug carrier material-hydroxyl-terminated poly(lactide-co-p-dioxanone)[J].Journal of Functional Materials,2009,40(11):1907-1910.
[4]Liu Hongze,Qi Min,Zhu Xinghua,et al.Investigation of in-vitro degradtion properties of poly(lactide-co-glycolide)blended and gradient films[J].Journal of Functional Materials,2011,42(1):43-46.
[5]Edlund U,Albertsson A C.Degradable polymer microspheres for controlled drug delivery[J].Advances in Polymer Science,2002,157:67-112.
[6]Okada M.Chemical synthesis of biodegradable polymers[J].Progress in Polymer Science,2002,27:87-133.
[7]Liang Bingqing,Pang Daolin,Jin Chao,et al.Photo-oxidative degradation of poly(p-dioxanone)under ultraviolet light source[J].Polymer Degradation and Stability,2012,97:2162-2169.
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[9]Bai Wei,Chen Dongliang,Li Qing,et al.In vitro hydrolytic degradation of poly(para-dioxanone)with high molecular weight[J].Journal of Polymer Research,2009,16:471-480.
[10]Kricheldorf H R,Damrau D O.Zn L-lactate-catalyzed polymerizations of 1,4-dioxan-2-one[J].Macromol Chem Phys,1998,199:1089-1097.
[11]Fang Qing,Zheng Hao,Shen Guorong,et al.Ring-opening polymerization of 1,4-dioxan-2-one initiated by lanthanum tris(2,6-di-tert-butyl-4-methylphenolate)[J].Chinese Journal of Polymer Science,2007,4:427-430.
[12]Yang Keke,Guo Yuehai,Wang Yuzhong.AlEt3-H2OH3PO4 catalyzed polymerizations of 1,4-dioxan-2-one[J].Polymer Bulletin,2005,54:187-193.
[13]Jean Marie Raquez,Philippe Dege’e,Ramani Narayan,et al.Some thermodynamic,kinetic,and mechanistic aspects of the ring-opening polymerization of 1,4-dioxan-2-one initiated by Al(OiPr)3in bulk[J].Macromolecules,2001,34:8419-8425.
[14]Haruo Nishida,Mitsuhiro Yamashita,Norikazu Hattori,et al.Thermal decomposition of poly(1,4-dioxan-2-one)[J].Polymer Degradation and Stability,2000,70:485-496.
[15]Chen Feng,Chen Sichong,Yang Keke,et al.A facile approach to preparation of long-chain-branched poly(p-dioxanone)[J].European Polymer Journal,2010,46:24-33.