双羟烃基聚硅氧烷的合成及其对水性聚氨酯改性的研究
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摘要
聚硅氧烷具有耐低温、低表面能、良好的耐水性、耐老化、耐腐蚀和耐候性等一系列优异和独特的性能,将聚硅氧烷引入到其它聚合物当中,可以得到性能优异的材料。本文合成了两种不同类型的双羟烃基聚硅氧烷,将其接枝和嵌段到聚氨酯分子中,并对改性的水性聚氨酯性能做了初步的应用研究。
以二乙醇胺、六甲基二硅氮烷、烯丙基溴、单端氢基聚硅氧烷为主要原料通过羟基保护反应、烷基化反应、硅氢加成反应和醇解脱保护反应制备了一系列分子量在3000以下的可用来接枝改性水性聚氨酯的α-丁基-ω-N,N-二羟乙基胺丙基聚硅氧烷,用红外光谱、核磁共振氢谱、气相色谱、高分辨质谱等对各步反应产物进行了详细地表征。
以烯丙基缩水甘油醚、四甲基二氢二硅氧烷、三氟甲基磺酸和八甲基环四硅氧烷(D4)为主要原料通过硅氢加成反应、环氧开环反应和D4平衡反应合成了一系列分子量在3000以下的可用来嵌段改性水性聚氨酯的α,ω-双[3-(1-甲氧基-2-羟基-丙氧基)丙基]封端聚硅氧烷,优化了硅氢加成反应条件,掌握了追踪醇解开环反应和D4平衡反应进程的方法,确定了最佳反应时间。
以甲苯二异氰酸酯、聚醚二元醇、二羟甲基丙酸、乙二醇、三乙胺、二乙三胺以及所合成的α-丁基-ω-N,N-二羟乙基胺丙基聚硅氧烷和α,ω-双[3-(1-甲氧基-2-羟基-丙氧基)丙基]封端聚硅氧烷为原料,丙酮法制备了阴离子型羟烃基聚硅氧烷接枝和嵌段改性水性聚氨酯,并初步探讨了改性聚氨酯乳液的粘度和成膜后胶膜的光泽度、邵氏硬度、拉伸强度、断裂伸长率、甲苯吸收率和吸水率等性能。实验发现,羟烃基硅氧烷能够提高水性聚氨酯的耐水、耐溶剂等性能,相同的聚硅氧烷含量,接枝改性的聚氨酯水分散体胶膜的耐水性和耐溶剂性明显优于嵌段改性的聚氨酯水分散体胶膜。
Polysiloxanes possess a variety of unique and superior properties such as low- temperature resistance, low surface energy, good water resistance, aging resistance, climate resistace and so on. Polysiloxanes can endow other polymers with the excellent properties so that new polymer materials can be obtained. In this thesis two different types of polysiloxanes were synthesized to modify waterborne polyurethanes and the properties of modified waterborne polyurethanes were simply studied.
A series ofα-butyl-ω-N,N-dihydroxyethylaminopropylpolydimethylsiloxanes with molecular weight below 3000, which can form polyurethane-polysiloxane graft copolymer, were synthesized via hydroxyl protection, alkylation, hydrosilylation and deprotection using diethylolamine, Hexamethyldisilazane, 3-bromopropene as starting materials. The targeted product and intermediate products in each process had been fully characterized by FT-IR, GC, 1H NMR and LC-MS. The results showed that each step was successfully carried out and the targeted products were accessed in all cases.
Another series ofα,ω-bis(3-(1-methoxy-2-hydroxyproxy)propyl) terminated polysiloxanes with molecular weight below 3000, which can form polyurethane- polysiloxane block copolymer, were synthesized via hydrosilylation, methoxylation and equilibrium reaction between allylglycidyl ether, tetramethyldisiloxane, trifluoro- methanesulfonic acid and octamethylcyclotetrasiloxane (D4). Hydrosilylation reaction was optimized and the process and the reaction time of methoxylation and D4 equilibrium reaction were determined.
The anionic waterborne polyurethanes modified withα-butyl-ω-N,N-dihydroxy- ethylaminopropylpolydimethylsiloxanes andα,ω-bis(3-(1-methoxy-2-hydroxyproxy)- propyl) terminated polysiloxanes were prepared with toluene diisocyanate, polypropylene glycol, ethylene glycol, dimethylolpropionic acid and triehtylamine using acetone method. The viscosity of PSU latexes and the glosses, Shore hardness, tensile strength, elongation at break, solvent resistance and water resistance of the PSU films were studied. Experiments showed that hydroxyalkylpolysiloxanes can improve water resistance and solvent resistance of polyurethanes and the properties of graft modified polyurethanes are better than block modified polyurethanes.
以二乙醇胺、六甲基二硅氮烷、烯丙基溴、单端氢基聚硅氧烷为主要原料通过羟基保护反应、烷基化反应、硅氢加成反应和醇解脱保护反应制备了一系列分子量在3000以下的可用来接枝改性水性聚氨酯的α-丁基-ω-N,N-二羟乙基胺丙基聚硅氧烷,用红外光谱、核磁共振氢谱、气相色谱、高分辨质谱等对各步反应产物进行了详细地表征。
以烯丙基缩水甘油醚、四甲基二氢二硅氧烷、三氟甲基磺酸和八甲基环四硅氧烷(D4)为主要原料通过硅氢加成反应、环氧开环反应和D4平衡反应合成了一系列分子量在3000以下的可用来嵌段改性水性聚氨酯的α,ω-双[3-(1-甲氧基-2-羟基-丙氧基)丙基]封端聚硅氧烷,优化了硅氢加成反应条件,掌握了追踪醇解开环反应和D4平衡反应进程的方法,确定了最佳反应时间。
以甲苯二异氰酸酯、聚醚二元醇、二羟甲基丙酸、乙二醇、三乙胺、二乙三胺以及所合成的α-丁基-ω-N,N-二羟乙基胺丙基聚硅氧烷和α,ω-双[3-(1-甲氧基-2-羟基-丙氧基)丙基]封端聚硅氧烷为原料,丙酮法制备了阴离子型羟烃基聚硅氧烷接枝和嵌段改性水性聚氨酯,并初步探讨了改性聚氨酯乳液的粘度和成膜后胶膜的光泽度、邵氏硬度、拉伸强度、断裂伸长率、甲苯吸收率和吸水率等性能。实验发现,羟烃基硅氧烷能够提高水性聚氨酯的耐水、耐溶剂等性能,相同的聚硅氧烷含量,接枝改性的聚氨酯水分散体胶膜的耐水性和耐溶剂性明显优于嵌段改性的聚氨酯水分散体胶膜。
Polysiloxanes possess a variety of unique and superior properties such as low- temperature resistance, low surface energy, good water resistance, aging resistance, climate resistace and so on. Polysiloxanes can endow other polymers with the excellent properties so that new polymer materials can be obtained. In this thesis two different types of polysiloxanes were synthesized to modify waterborne polyurethanes and the properties of modified waterborne polyurethanes were simply studied.
A series ofα-butyl-ω-N,N-dihydroxyethylaminopropylpolydimethylsiloxanes with molecular weight below 3000, which can form polyurethane-polysiloxane graft copolymer, were synthesized via hydroxyl protection, alkylation, hydrosilylation and deprotection using diethylolamine, Hexamethyldisilazane, 3-bromopropene as starting materials. The targeted product and intermediate products in each process had been fully characterized by FT-IR, GC, 1H NMR and LC-MS. The results showed that each step was successfully carried out and the targeted products were accessed in all cases.
Another series ofα,ω-bis(3-(1-methoxy-2-hydroxyproxy)propyl) terminated polysiloxanes with molecular weight below 3000, which can form polyurethane- polysiloxane block copolymer, were synthesized via hydrosilylation, methoxylation and equilibrium reaction between allylglycidyl ether, tetramethyldisiloxane, trifluoro- methanesulfonic acid and octamethylcyclotetrasiloxane (D4). Hydrosilylation reaction was optimized and the process and the reaction time of methoxylation and D4 equilibrium reaction were determined.
The anionic waterborne polyurethanes modified withα-butyl-ω-N,N-dihydroxy- ethylaminopropylpolydimethylsiloxanes andα,ω-bis(3-(1-methoxy-2-hydroxyproxy)- propyl) terminated polysiloxanes were prepared with toluene diisocyanate, polypropylene glycol, ethylene glycol, dimethylolpropionic acid and triehtylamine using acetone method. The viscosity of PSU latexes and the glosses, Shore hardness, tensile strength, elongation at break, solvent resistance and water resistance of the PSU films were studied. Experiments showed that hydroxyalkylpolysiloxanes can improve water resistance and solvent resistance of polyurethanes and the properties of graft modified polyurethanes are better than block modified polyurethanes.
引文
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[14] 冯圣玉,张洁,李美江等. 有机硅高分子及其应用[M]. 北京:化学工业出版社,2004: 52.
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