聚碳酸酯二元醇的制备及其聚氨酯弹性体的性能
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摘要
本论文采用催化活性好的催化剂以酯交换法制备出了一系列的聚碳酸酯二元醇,并将其应用于聚氨酯弹性体的合成中,制备出性能优异的聚氨酯材料。采用傅里叶变化红外、材料拉伸机、热失重、差示量热分析等分析测试仪器对材料的结构与性能进行了深入研究。本论文研究内容由以下三部分组成:
1)以碳酸二甲酯(DMC)和1,4-丁二醇(BDO)为原料,在三乙胺等有机胺类催化剂催化下,酯交换制备出聚碳酸酯二元醇(PCDL)。采用核磁共振和红外光谱等分析手段鉴定产物的结构;凝胶渗透色谱分析减压时间对PCDL分子量分布的影响。详细研究了原料摩尔比(DMC/BDO)、催化剂用量、减压时间等因素对反应过程的影响,优化了PCDL的合成工艺参数。实验结果表明,当DMC/BDO的摩尔比为1.2～1.25,催化剂用量占BDO的质量分数为0.5%,采用阶段控温方式制备出数均分子量在1600 g/mol左右的PCDL。
2)以碳酸二乙酯(DEC)和1,6-己二醇(HDO)为起始原料,钛酸四丁酯(Ti(OBu)4)为催化剂,经常压蒸馏和减压缩聚两阶段,酯交换反应制备出分子量2000 g·mol-1左右的聚碳酸(1,6-己二醇)酯二醇(PCDL)。研究了不同催化剂、减压反应温度、减压时间对聚合过程的影响,优化出最佳合成工艺。实验结果表明:Ti(OBu)4用量为0.05%(占DEC的质量分数)时,表现出最好的催化效果;增大减压温度能够有效提高反应速度;减压反应时间长短可有效控制PCDL的分子量及分布系数。使用FT-IR、1H-NMR、GPC、DSC等分析表征了合成产物,并提出了Ti(OBu)4的催化机理。
3)以制备的聚碳酸酯二醇、聚四氢呋喃醚二醇等为软段,与TDI、MDI、PPDI等多异氰酸酯反应,通过BDO、DMTDA扩链,制备聚氨酯弹性体材料。研究了不同原料制备的聚氨酯材料的力学性能和热性能,实验结果表明:聚碳酸酯型聚氨酯与聚醚聚氨酯相比,在机械性能、热稳定性等方面有更优越的性能。
In this dissertation, a series of polycarbonate diols(PCDL) , catalyzed by efficient catalysts, were synthesized by carbonate interchange reaction. The properties of polyurethane elastomer made from PCDL flexibile segment were studied. The structure and properties of the materials were investigated in detail by FTIR, strain-stress machine, TG, DSC, et al. This dissertation mainly consists of three parts as follows:
Polycarbonate diols(PCDL) were synthesized by carbonate interchange reaction of dimethyl carbonate with 1,4-butanediol in the catalysis of amines. The structure of PCDL was determined by FT-IR and 1H-NMR , it was confirmed that the chemical structures of product were consistent with that of pure polycarbonate diols. The process parameters affecting the characters of product, such as molar ratio of DMC/1,4-BDO, the dosage of catalyst, vacuum reaction time, were studied respectively. The experimental results showed that desired polycarbonate diols with excellent technical specifications were prepared by means of stage temperature under the conditions of molar ratio for n(DMC):n(1,4-BDO)=1.2～1.25, temperature of at 190℃and amines accounting for 0.5 weight percent of 1,4-BDO.
Poly(1,6-hexanediol) carbonate diols (PCDL) were synthesized using 1,6-hexanediol (HDO) and diethyl carbonate(DEC) in the presence of Ti(OBu)4 as catalyst. The polymerization reaction was carried out in a two-stage process, including atmospheric pressure and vacuum process. All reaction conditions were investigated based on Ti(OBu)4. The experiment results showed that Ti(OBu)4 accounting for 0.05 weight percent of HDO exhibited the best catalytic effect. PCDL with expected number average molecular weight were prepared rapidly with raising the reaction temperature. It was available for controlling the molecular weight and polydispersity of PCDL to alter the vacuum time. The characters of PCDL were determined by FT-IR,1H-NMR,GPC and DSC. It was concluded that Ti(OBu)4 was evidenced to be an effective catalyst for transesterification. The possible reaction mechanism of Ti(OBu)4 was offered.
A series of Polyurethane elastomers were prepared using soft segment,hard segment and chain-extender,including PCDL、PTMG、TDI、MDI、PPDI、BDO and DMTDA et al.The mechanical and thermal properties of polyurethane elastomers with different materials were studied. The experimental results show that PU elastomer made from PCDL exhibited better mechanical properties and heat resistance compared with polyether type elastomers.
1)以碳酸二甲酯(DMC)和1,4-丁二醇(BDO)为原料,在三乙胺等有机胺类催化剂催化下,酯交换制备出聚碳酸酯二元醇(PCDL)。采用核磁共振和红外光谱等分析手段鉴定产物的结构;凝胶渗透色谱分析减压时间对PCDL分子量分布的影响。详细研究了原料摩尔比(DMC/BDO)、催化剂用量、减压时间等因素对反应过程的影响,优化了PCDL的合成工艺参数。实验结果表明,当DMC/BDO的摩尔比为1.2～1.25,催化剂用量占BDO的质量分数为0.5%,采用阶段控温方式制备出数均分子量在1600 g/mol左右的PCDL。
2)以碳酸二乙酯(DEC)和1,6-己二醇(HDO)为起始原料,钛酸四丁酯(Ti(OBu)4)为催化剂,经常压蒸馏和减压缩聚两阶段,酯交换反应制备出分子量2000 g·mol-1左右的聚碳酸(1,6-己二醇)酯二醇(PCDL)。研究了不同催化剂、减压反应温度、减压时间对聚合过程的影响,优化出最佳合成工艺。实验结果表明:Ti(OBu)4用量为0.05%(占DEC的质量分数)时,表现出最好的催化效果;增大减压温度能够有效提高反应速度;减压反应时间长短可有效控制PCDL的分子量及分布系数。使用FT-IR、1H-NMR、GPC、DSC等分析表征了合成产物,并提出了Ti(OBu)4的催化机理。
3)以制备的聚碳酸酯二醇、聚四氢呋喃醚二醇等为软段,与TDI、MDI、PPDI等多异氰酸酯反应,通过BDO、DMTDA扩链,制备聚氨酯弹性体材料。研究了不同原料制备的聚氨酯材料的力学性能和热性能,实验结果表明:聚碳酸酯型聚氨酯与聚醚聚氨酯相比,在机械性能、热稳定性等方面有更优越的性能。
In this dissertation, a series of polycarbonate diols(PCDL) , catalyzed by efficient catalysts, were synthesized by carbonate interchange reaction. The properties of polyurethane elastomer made from PCDL flexibile segment were studied. The structure and properties of the materials were investigated in detail by FTIR, strain-stress machine, TG, DSC, et al. This dissertation mainly consists of three parts as follows:
Polycarbonate diols(PCDL) were synthesized by carbonate interchange reaction of dimethyl carbonate with 1,4-butanediol in the catalysis of amines. The structure of PCDL was determined by FT-IR and 1H-NMR , it was confirmed that the chemical structures of product were consistent with that of pure polycarbonate diols. The process parameters affecting the characters of product, such as molar ratio of DMC/1,4-BDO, the dosage of catalyst, vacuum reaction time, were studied respectively. The experimental results showed that desired polycarbonate diols with excellent technical specifications were prepared by means of stage temperature under the conditions of molar ratio for n(DMC):n(1,4-BDO)=1.2～1.25, temperature of at 190℃and amines accounting for 0.5 weight percent of 1,4-BDO.
Poly(1,6-hexanediol) carbonate diols (PCDL) were synthesized using 1,6-hexanediol (HDO) and diethyl carbonate(DEC) in the presence of Ti(OBu)4 as catalyst. The polymerization reaction was carried out in a two-stage process, including atmospheric pressure and vacuum process. All reaction conditions were investigated based on Ti(OBu)4. The experiment results showed that Ti(OBu)4 accounting for 0.05 weight percent of HDO exhibited the best catalytic effect. PCDL with expected number average molecular weight were prepared rapidly with raising the reaction temperature. It was available for controlling the molecular weight and polydispersity of PCDL to alter the vacuum time. The characters of PCDL were determined by FT-IR,1H-NMR,GPC and DSC. It was concluded that Ti(OBu)4 was evidenced to be an effective catalyst for transesterification. The possible reaction mechanism of Ti(OBu)4 was offered.
A series of Polyurethane elastomers were prepared using soft segment,hard segment and chain-extender,including PCDL、PTMG、TDI、MDI、PPDI、BDO and DMTDA et al.The mechanical and thermal properties of polyurethane elastomers with different materials were studied. The experimental results show that PU elastomer made from PCDL exhibited better mechanical properties and heat resistance compared with polyether type elastomers.
引文
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