聚氨酯生物材料的合成及表面改性研究
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摘要
为了研究聚碳酸酯聚氨酯的结构与性能,改善其血液相容性。本文以碳酸二苯酯、1,6-己二醇制备出脂肪族聚碳酸酯二醇,采用熔融一步法和溶液预聚体法制备出聚碳酸酯型聚氨酯弹性体(PCNU)。考察了不同聚合温度、反应时间和体系浓度对聚合反应的影响,得出了优化反应条件。对聚合产物采用IR、GPC、DSC、TG、SAXS和力学分析等多种手段进行了表征,结果表明:聚合物呈现部分相分离的两相结构,热分解存在明显的两个阶段; 考察了不同组成,不同聚碳酸酯二醇分子量(所提分子量本文中均指相对分子质量)对产物力学性能的影响,结果表明:所有的聚合物均符合应用于人体力学性能上的要求,当分子量为2000时,材料表现出了较好的拉伸强度和断裂伸长率。
采用改进的溶液预聚体法制备了有机硅微交联聚碳酸酯型聚氨酯(PDMS-PCNU),考察了不同聚合温度、反应时间和体系浓度对聚合反应的影响,得出了优化反应条件。对合成产物采用了IR、DSC、TG、SAXS等多种手段进行了表征,结果表明聚合物仍存在不明显的两个玻璃化转变区,多官能度有机硅的交联使聚合物相分离程度减小,随着用量的加大,两个分解阶段变得不明显,聚合物的最高分解温度有所提高。
采用聚乙二醇为原料,设计和合成了两种新的化合物二甲氨基端羟基聚乙二醇和磺胺两性离子端羟基聚乙二醇,对每步合成产物用IR、NMR进行了表征,结果表明与预定结构一致,分析讨论了各步反应的合成条件与影响因素。将合成的化合物用官能团接枝的方法构建在PCNU表面,用两种途径实现了磺胺两性离子端基的聚乙二醇在聚氨酯表面的固定。用化学分析电子能谱(ESCA)分析了聚合物的表面元素,采用Gaussion函数拟合了C1s和N1s的高分辩谱。结果表明,成功的在PCNU的表面构建了末端带有磺铵两性离子结构的聚乙二醇。这种结构将有利于改善PCNU的抗凝血性能。
Polycarbonate diol was synthesized using diphenyl carbonate and 1,6-hexanediol. It was then used to prepared polycarbonate urethane(PCNU) with 4,4ˊ-methylene diphenyl diisocyanate and 1,4-butanediol by melting one-shot method and solution two-shot method in order to study its structure and improve its blood compatibility. Effects of polymerization conditions on the properties of the polymer were studied, including the reaction temperature, time and concentration of the system, and the optimum conditions were reached. The polymer was characterized by IR,GPC,DSC,TG,SAXS and tensile experiments, results showed there were two glass transitions and it was the partial micro-phase segregation structure, However, the phase segregation degree was affected by the soft segment relative molecular mass, composition and polymeric methods. Those results agreed with that from SAXS. TG results showed there were two obvious stages on its thermodecomposition, which was the same with other polyurethanes. The effects of composition and the soft segment relative molecular mass on mechanical properties were studied. The results showed all polymers met with the requirement of polyurethane as biomaterials in vivo. When the soft segment relative molecular mass was 2000, the polymers had larger tensile strength and elongation, and the solution two-shot method was better than melting one-shot method.
The micro-crosslinked PDMS-PCNU was prepared by improved melting one-shot method. Effects of polymerization conditions such as the reaction temperature, time and concentration of the system on the properties of the polymer were studied, and the optimum conditions were reached. The products were characterized by IR,DSC,TG and SAXS. Results suggested that there were two glass transitions but unobvious, and the phase segregation degree was reduced by crossing of multi-functional organic siloxane polymer. Results agreed with that from SAXS. From TG diagram there were still two stages when a litter multi-functional organic siloxane polymer jointed. As the quantity increased, the boundary became unobvious and the highest decomposition temperature was reached.
The two new compounds of dimethyl amido hydroxy polyethylene glycol and the hydroxyl polyethylene glycol with sulfoammonium amphoteric ion were devised and synthesized by two paths using polyethylene glycol. The each step products were characterized by IR and 1H-NMR, Results agreed with devised structure, and the synthetic conditions and the effect factors were analyzed. The compounds were grafted in the surface of PCNU by functional reactions. The superficial elements were analyzed by electron spectroscopy for chemical (ESCA), and the ESCA of C1s and N1s were fitted by Gaussion function. Results suggested that the object product were successfully synthesized. These polymers would be beneficial to improve the blood compatibility.
采用改进的溶液预聚体法制备了有机硅微交联聚碳酸酯型聚氨酯(PDMS-PCNU),考察了不同聚合温度、反应时间和体系浓度对聚合反应的影响,得出了优化反应条件。对合成产物采用了IR、DSC、TG、SAXS等多种手段进行了表征,结果表明聚合物仍存在不明显的两个玻璃化转变区,多官能度有机硅的交联使聚合物相分离程度减小,随着用量的加大,两个分解阶段变得不明显,聚合物的最高分解温度有所提高。
采用聚乙二醇为原料,设计和合成了两种新的化合物二甲氨基端羟基聚乙二醇和磺胺两性离子端羟基聚乙二醇,对每步合成产物用IR、NMR进行了表征,结果表明与预定结构一致,分析讨论了各步反应的合成条件与影响因素。将合成的化合物用官能团接枝的方法构建在PCNU表面,用两种途径实现了磺胺两性离子端基的聚乙二醇在聚氨酯表面的固定。用化学分析电子能谱(ESCA)分析了聚合物的表面元素,采用Gaussion函数拟合了C1s和N1s的高分辩谱。结果表明,成功的在PCNU的表面构建了末端带有磺铵两性离子结构的聚乙二醇。这种结构将有利于改善PCNU的抗凝血性能。
Polycarbonate diol was synthesized using diphenyl carbonate and 1,6-hexanediol. It was then used to prepared polycarbonate urethane(PCNU) with 4,4ˊ-methylene diphenyl diisocyanate and 1,4-butanediol by melting one-shot method and solution two-shot method in order to study its structure and improve its blood compatibility. Effects of polymerization conditions on the properties of the polymer were studied, including the reaction temperature, time and concentration of the system, and the optimum conditions were reached. The polymer was characterized by IR,GPC,DSC,TG,SAXS and tensile experiments, results showed there were two glass transitions and it was the partial micro-phase segregation structure, However, the phase segregation degree was affected by the soft segment relative molecular mass, composition and polymeric methods. Those results agreed with that from SAXS. TG results showed there were two obvious stages on its thermodecomposition, which was the same with other polyurethanes. The effects of composition and the soft segment relative molecular mass on mechanical properties were studied. The results showed all polymers met with the requirement of polyurethane as biomaterials in vivo. When the soft segment relative molecular mass was 2000, the polymers had larger tensile strength and elongation, and the solution two-shot method was better than melting one-shot method.
The micro-crosslinked PDMS-PCNU was prepared by improved melting one-shot method. Effects of polymerization conditions such as the reaction temperature, time and concentration of the system on the properties of the polymer were studied, and the optimum conditions were reached. The products were characterized by IR,DSC,TG and SAXS. Results suggested that there were two glass transitions but unobvious, and the phase segregation degree was reduced by crossing of multi-functional organic siloxane polymer. Results agreed with that from SAXS. From TG diagram there were still two stages when a litter multi-functional organic siloxane polymer jointed. As the quantity increased, the boundary became unobvious and the highest decomposition temperature was reached.
The two new compounds of dimethyl amido hydroxy polyethylene glycol and the hydroxyl polyethylene glycol with sulfoammonium amphoteric ion were devised and synthesized by two paths using polyethylene glycol. The each step products were characterized by IR and 1H-NMR, Results agreed with devised structure, and the synthetic conditions and the effect factors were analyzed. The compounds were grafted in the surface of PCNU by functional reactions. The superficial elements were analyzed by electron spectroscopy for chemical (ESCA), and the ESCA of C1s and N1s were fitted by Gaussion function. Results suggested that the object product were successfully synthesized. These polymers would be beneficial to improve the blood compatibility.
引文
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