有机硅改性不饱和聚酯的制备与应用研究
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摘要
本文利用有机硅预聚体与不饱和聚酯进行缩合反应，制备了有机硅改性不饱和聚酯树脂，并以其为基体制备了性能优良的H级无溶剂浸渍漆，可以广泛用于电机、电器绝缘绕组的绝缘浸渍处理。
首先利用一苯基三乙氧基硅烷、二甲基二乙氧基硅烷、甲基乙烯基二乙氧基硅烷三种硅氧烷单体通过水解缩合反应制备了含有一定量乙氧基的有机硅预聚体，并用红外谱图、核磁谱图、凝胶色谱进行了表征，研究结果表明：三种硅氧烷单体发生了水解缩合反应，所得有机硅预聚体上保留了一定量的乙氧基，并且分子量分布均匀，分布指数为1.158。
其次将有机硅预聚体与羟基封端的不饱和聚酯进行缩合反应，制备了有机硅改性不饱和聚酯，并用红外谱图、核磁共振谱图、凝胶色谱对缩合终产物进行了表征。研究结果表明：有机硅预聚体上的乙氧基与不饱和聚酯上的羟基发生了缩合反应，GPC谱图表明所得有机硅改性不饱和聚酯的分子量分布较宽，分布指数为5.35。
最后本文对有机硅改性不饱和聚酯无溶剂浸渍漆的典型性能进行了测试与分析，研究结果表明：有机硅改性不饱和聚酯无溶剂浸渍漆的各项性能均达到预期技术指标的要求；通过热失重(TG)数据计算得出，其耐热指数为190.6℃；示差扫描量热法(DSC)曲线表明该无溶剂浸渍漆自由基聚合分为两步，不饱和聚酯链段的自由基聚合最高放热峰为151.68℃，有机硅链段的自由基聚合温度为186.52℃，其固化物玻璃化转变温度有两个，有机硅链段的Tg为49.84℃，不饱和聚酯链段的玻璃化转变温度为79.72℃。
A solventless impregnating varnish was prepared and its bulk material was organosiliconmodified unsaturated polyester prepared through condensation reaction between organic silicon prepolymer and unsaturated polyester, and it may obtain widespread availability in the insulation area of electric coil impregnating of electric al motor and electric appliance.
At the first, vinyl—ethyoxyl organosilicon prepolymer was prepared through hydrolysiscondensation reaction among phenyltriethoxysilane, diethoxydimethylsil and vinylmethyl- diethoxysilane. Then it was characterized by IR, ~1H-NMR, GPC. The results showed that the vinyl and ethyoxyl were the parts of organosilicon prepolymer, the molecular-weight distribution was uniform, and the profile exponent was to 1.158.
Second, organosilicon-modified unsaturated polyester was preared through condensation reaction between organic silicon prepolymer and unsaturated polyester capped by hydroxy.Then it was characterized by IR, ~1H-NMR, GPC. The results showed that characteristic peak of ethyoxy vanished, condensation reaction completed. But the molecular-weight distribution of organosilicon-modified unsaturated polyester was not uniform, and the profile exponent was to 5.35.
At the last, the representative behavior of organosilicon- modified unsaturated polyester solventless impregnating varnish was tested and analyzed. The results showed that all the performances met the qualification. And the heat-resisting was up to 190.6℃. the DSC curve showed that this solventless impregnating varnish solidification had two steps, the temperature accordance with the most high exothermic peak of free radical polymerization of unsaturated polyester segment was to 151.68℃, the other exothermic peak was from free radical polymerization of organic silicon segment, the temperature was to 186.52℃, and the solidification sample had two Tg points, the Tg of organic silicon segment was to 49.84℃, the Tg of unsaturated polymer segment was to 79.72℃.
首先利用一苯基三乙氧基硅烷、二甲基二乙氧基硅烷、甲基乙烯基二乙氧基硅烷三种硅氧烷单体通过水解缩合反应制备了含有一定量乙氧基的有机硅预聚体，并用红外谱图、核磁谱图、凝胶色谱进行了表征，研究结果表明：三种硅氧烷单体发生了水解缩合反应，所得有机硅预聚体上保留了一定量的乙氧基，并且分子量分布均匀，分布指数为1.158。
其次将有机硅预聚体与羟基封端的不饱和聚酯进行缩合反应，制备了有机硅改性不饱和聚酯，并用红外谱图、核磁共振谱图、凝胶色谱对缩合终产物进行了表征。研究结果表明：有机硅预聚体上的乙氧基与不饱和聚酯上的羟基发生了缩合反应，GPC谱图表明所得有机硅改性不饱和聚酯的分子量分布较宽，分布指数为5.35。
最后本文对有机硅改性不饱和聚酯无溶剂浸渍漆的典型性能进行了测试与分析，研究结果表明：有机硅改性不饱和聚酯无溶剂浸渍漆的各项性能均达到预期技术指标的要求；通过热失重(TG)数据计算得出，其耐热指数为190.6℃；示差扫描量热法(DSC)曲线表明该无溶剂浸渍漆自由基聚合分为两步，不饱和聚酯链段的自由基聚合最高放热峰为151.68℃，有机硅链段的自由基聚合温度为186.52℃，其固化物玻璃化转变温度有两个，有机硅链段的Tg为49.84℃，不饱和聚酯链段的玻璃化转变温度为79.72℃。
A solventless impregnating varnish was prepared and its bulk material was organosiliconmodified unsaturated polyester prepared through condensation reaction between organic silicon prepolymer and unsaturated polyester, and it may obtain widespread availability in the insulation area of electric coil impregnating of electric al motor and electric appliance.
At the first, vinyl—ethyoxyl organosilicon prepolymer was prepared through hydrolysiscondensation reaction among phenyltriethoxysilane, diethoxydimethylsil and vinylmethyl- diethoxysilane. Then it was characterized by IR, ~1H-NMR, GPC. The results showed that the vinyl and ethyoxyl were the parts of organosilicon prepolymer, the molecular-weight distribution was uniform, and the profile exponent was to 1.158.
Second, organosilicon-modified unsaturated polyester was preared through condensation reaction between organic silicon prepolymer and unsaturated polyester capped by hydroxy.Then it was characterized by IR, ~1H-NMR, GPC. The results showed that characteristic peak of ethyoxy vanished, condensation reaction completed. But the molecular-weight distribution of organosilicon-modified unsaturated polyester was not uniform, and the profile exponent was to 5.35.
At the last, the representative behavior of organosilicon- modified unsaturated polyester solventless impregnating varnish was tested and analyzed. The results showed that all the performances met the qualification. And the heat-resisting was up to 190.6℃. the DSC curve showed that this solventless impregnating varnish solidification had two steps, the temperature accordance with the most high exothermic peak of free radical polymerization of unsaturated polyester segment was to 151.68℃, the other exothermic peak was from free radical polymerization of organic silicon segment, the temperature was to 186.52℃, and the solidification sample had two Tg points, the Tg of organic silicon segment was to 49.84℃, the Tg of unsaturated polymer segment was to 79.72℃.
引文
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