以α-D-葡萄糖为核的星形PNIPAM的合成及热敏性研究
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摘要
带有生物活性官能团聚合物具有很好的生物兼容性,本论文采用原子转移自由基聚合(ATRP)的方法合成了一种以α-D-葡萄糖为核的星形聚N-异丙基丙烯酰胺,对聚合过程的动力学及聚合物的热敏性进行了研究。
用α-D-葡萄糖和2-溴异丁酰溴反应制备到的α-D-葡萄糖基的大分子(Glu-Br)作引发剂,氯化亚铜(CuCl)和1,1,4,7,10,10-六甲基三亚乙基四胺(HMTETA)为催化体系,以N,N-二甲基甲酰胺(DMF)和水(v/v,20/3)为溶剂,采用密封体系于25℃氮气保护下进行N-异丙基丙烯酰胺(NIPAM)的原子转移自由基聚合(ATRP)。对聚合物过程的一级动力学研究显示聚合物的分子量随时间及转化率呈线性增加关系;对聚合物的热敏性研究显示聚合物具有一个明显的最低临界溶液温度(LCST),与聚N-异丙基丙烯酰胺(PNIPAM)的相变温度(大约32℃)相比降低至23.9℃,且分子量的大小对聚合物的LCST值有一定的影响,在一定范围内,分子量越大,LCST值越大。当往聚合物溶液中加入适量β-环糊精与其形成复合物后能有效的提高体系的相变温度;对聚合物的包络性测试显示该星形聚合物具有较好的包络荧光素分子的能力。
Polymers containing functional groups of biological activity have a good biological compatibility.A star poly(N-isopropylacrylamide) withα-D-glucose-based group was synthesized via Atom Transfer Radical Polymerization(ATRP) in this dissertation.Furthermore,the kinetics of the polymerization as well as the thermo-sensitive property of the polymer were studied in detail.
The Atom Transfer Radical Polymerization of NIPAM was performed in a sealed system filled with nitrogen at 25℃,using Glu-Br prepared by the reaction ofα-D-glucose and 2-bromoisobutyrlbromide as initiator,CuCl and HMTETA as the catalyst system as well as DMF and water(v/v,20/3) as solvent.The study of the kinetics revealed the linearity plot of the M_(n,GPC) against conversion and the reaction time.The study of the thermo-sensitive property showed that the LCST of the polymer was lowered to 23.9℃,compared to that of PNIPAM(about 32℃).To a certain extent,the LCSTs increased with increasing molecular weight.Furthermore,the LCST of the aqueous Glu-PNIPAM was raised effectively by addingβ-cyclodextrin,which formed an inclusion complex with the polymer.The star polymer had a better ability to accommodate the litlle fluorescein molecule by testing the its inclusion property.
用α-D-葡萄糖和2-溴异丁酰溴反应制备到的α-D-葡萄糖基的大分子(Glu-Br)作引发剂,氯化亚铜(CuCl)和1,1,4,7,10,10-六甲基三亚乙基四胺(HMTETA)为催化体系,以N,N-二甲基甲酰胺(DMF)和水(v/v,20/3)为溶剂,采用密封体系于25℃氮气保护下进行N-异丙基丙烯酰胺(NIPAM)的原子转移自由基聚合(ATRP)。对聚合物过程的一级动力学研究显示聚合物的分子量随时间及转化率呈线性增加关系;对聚合物的热敏性研究显示聚合物具有一个明显的最低临界溶液温度(LCST),与聚N-异丙基丙烯酰胺(PNIPAM)的相变温度(大约32℃)相比降低至23.9℃,且分子量的大小对聚合物的LCST值有一定的影响,在一定范围内,分子量越大,LCST值越大。当往聚合物溶液中加入适量β-环糊精与其形成复合物后能有效的提高体系的相变温度;对聚合物的包络性测试显示该星形聚合物具有较好的包络荧光素分子的能力。
Polymers containing functional groups of biological activity have a good biological compatibility.A star poly(N-isopropylacrylamide) withα-D-glucose-based group was synthesized via Atom Transfer Radical Polymerization(ATRP) in this dissertation.Furthermore,the kinetics of the polymerization as well as the thermo-sensitive property of the polymer were studied in detail.
The Atom Transfer Radical Polymerization of NIPAM was performed in a sealed system filled with nitrogen at 25℃,using Glu-Br prepared by the reaction ofα-D-glucose and 2-bromoisobutyrlbromide as initiator,CuCl and HMTETA as the catalyst system as well as DMF and water(v/v,20/3) as solvent.The study of the kinetics revealed the linearity plot of the M_(n,GPC) against conversion and the reaction time.The study of the thermo-sensitive property showed that the LCST of the polymer was lowered to 23.9℃,compared to that of PNIPAM(about 32℃).To a certain extent,the LCSTs increased with increasing molecular weight.Furthermore,the LCST of the aqueous Glu-PNIPAM was raised effectively by addingβ-cyclodextrin,which formed an inclusion complex with the polymer.The star polymer had a better ability to accommodate the litlle fluorescein molecule by testing the its inclusion property.
引文
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5 黄健,王晓琳,陈秀珍等.聚(N-异丙基丙烯酰胺)的体积相转变及在分离领域中的应用研究[J].高分子材料科学与工程,2001,17(6):35-39
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7 Jeremy M.Rathfon,Gregory N.Tew.Synthesis of thermoresponsive poly(N-isopropylmethacrylamide) and poly(acrylic acid) block copolymers via post-functionalization of poly(N-methacryloxysuccinimide)[J].Polymer,2008,49:1761-1769
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