水性聚氨酯改性及工艺研究
摘要
本文分别以丙烯酸酯类单体、二羟基硅油改性，合成了脂肪族水性聚氨酯树脂。并对二羟基硅油改性的水性聚氨酯在实验室小试的基础上进行中试工艺鉴定。
以异佛尔酮二异氰酸酯(IPDI)、聚碳酸酯二元醇(PCD)、聚己二酸丁二醇酯二元醇(PBA)、二羟基硅油(DHPDMS)、二羟甲基丙酸(DMPA)等为主要原料，合成了固含量达到38％、挥发性有机化合物(VOC)为60g/L、有机硅改性的水性聚氨酯。探讨了反应温度、时间、DHPDMS的百分含量、DHPDMS的分子量(Mn)、DMPA的含量和玻璃化转变温度(Tg)对DHPDMS改性聚氨酯树脂的外观、粘度、附着力、吸水率、硬度、拉伸强度、断裂伸长率等性能的影响。并且与未改性聚氨酯(PU)的性能作了比较。结果表明，反应温度为80℃，反应时间6.5h；NCO/OH的摩尔比为1.6；DHPDMS分子量3000、含量2％；DMPA含量6％时改性树脂的各项性能较优异。
以实验室小试为基础，进行了二羟基硅油改性的水性聚氨酯的中试鉴定。成功制备出三釜固含量38％、转化率达96％以上的有机硅改性水性聚氨酯。成功解决了了扩链中局部凝胶的问题。组织鉴定材料如水性聚氨酯新工艺工作报告、中试工艺报告、企业标准、质检报告、查新报告、环境评估报告、用户证明及成果说明等。最终鉴定结果为国际先进。
以聚酯二元醇、二羟基硅油、异佛尔酮二异氰酸酯(IPDI)、丙烯酸羟乙酯等为主要原料合成固含量为36％的水性聚氨酯分散体，然后用甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)等含乙烯基单体接枝改性，与聚氨酯预聚体在引发剂作用下发生共聚得到丙烯酸—有机硅改性的水性聚氨酯树脂。并测定了其基本性能如粘度、硬度、吸水率、拉伸强度、断裂伸长率。红外光谱表明，该树脂成膜后含有大量氢键，且存在微相分离。差示扫描量热分析(DSC)、扫描电镜(SEM)证实了微相分离的存在。
Aliphatic waterborne polyurethane was synthesized by modified with dihydropolydimethylsiloxane, acrylics, respectively. Identification of middle-testing for the waterborne polyurethane was proceeded on the basis of lab's experiment.
DHPDMS-polyurethane which had a solid content of 38% and volatile organic compound (VOC) of 60g/L was prepared with isophorone diisocyanate(IPDI), polyester diol (PCD, PBA), dihydropolydimethylsiloxane(DHPDMS), dimethoxyp- ropionic acid (DMPA). Effects of the amount of DHPDMS, the molecular mass of DHPDMS and glass transition temperature (Tg) on the appearance, viscosity, adhesion, water resistance, hardness, tensile strength, elongation of polyurethane modified by DHPDMS were discussed. The optimal condition was concluded as follows: WPU shows the better performance when the amount of DHPDMS is 2%.
Identification of the middle-testing technology for the DHPDMS-PU was proceeded on the basis of our lab's experiment. And the PU resin with a solid content of 38%, high conversion of 96% was successfully prepared. Partial gelation was also successfully solved. The stuff of identification such as new technology bulletin of waterborne polyurethane, bulletin of middle-testing technology, industrial standard, bulletin of quality certification, bulletin of novelty, bulletin of environmental evaluation, verification of users, explanation of achievement. The final result of the identification was international advanced.
Waterborne polyurethane/acrylics (PUA) was synthesized by polyester diol, isophorone diisocyanate(IPDI), dihydrooxypolydimethylsiloxane(DHPDMS), hydroxylethyl acrylate(HEA) and so on. Then methyl methacrylate(MMA), butylacrylate (BA) was added to the PUs, the copolymerization was occurred in the presence of initiator(potassium persulfate). The PUA emulsion had a solid content of 36% and performances of the films such as viscosity, hardness, water absorption, tensile strength, elongation were measured. Films were also characterized by FTIR, DSC, SEM. The FTIR spectral result indicated the presence of lots of hydrogen bonds and micro-phase separation. The DSC and SEM results verified the above conclusion.
以异佛尔酮二异氰酸酯(IPDI)、聚碳酸酯二元醇(PCD)、聚己二酸丁二醇酯二元醇(PBA)、二羟基硅油(DHPDMS)、二羟甲基丙酸(DMPA)等为主要原料，合成了固含量达到38％、挥发性有机化合物(VOC)为60g/L、有机硅改性的水性聚氨酯。探讨了反应温度、时间、DHPDMS的百分含量、DHPDMS的分子量(Mn)、DMPA的含量和玻璃化转变温度(Tg)对DHPDMS改性聚氨酯树脂的外观、粘度、附着力、吸水率、硬度、拉伸强度、断裂伸长率等性能的影响。并且与未改性聚氨酯(PU)的性能作了比较。结果表明，反应温度为80℃，反应时间6.5h；NCO/OH的摩尔比为1.6；DHPDMS分子量3000、含量2％；DMPA含量6％时改性树脂的各项性能较优异。
以实验室小试为基础，进行了二羟基硅油改性的水性聚氨酯的中试鉴定。成功制备出三釜固含量38％、转化率达96％以上的有机硅改性水性聚氨酯。成功解决了了扩链中局部凝胶的问题。组织鉴定材料如水性聚氨酯新工艺工作报告、中试工艺报告、企业标准、质检报告、查新报告、环境评估报告、用户证明及成果说明等。最终鉴定结果为国际先进。
以聚酯二元醇、二羟基硅油、异佛尔酮二异氰酸酯(IPDI)、丙烯酸羟乙酯等为主要原料合成固含量为36％的水性聚氨酯分散体，然后用甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)等含乙烯基单体接枝改性，与聚氨酯预聚体在引发剂作用下发生共聚得到丙烯酸—有机硅改性的水性聚氨酯树脂。并测定了其基本性能如粘度、硬度、吸水率、拉伸强度、断裂伸长率。红外光谱表明，该树脂成膜后含有大量氢键，且存在微相分离。差示扫描量热分析(DSC)、扫描电镜(SEM)证实了微相分离的存在。
Aliphatic waterborne polyurethane was synthesized by modified with dihydropolydimethylsiloxane, acrylics, respectively. Identification of middle-testing for the waterborne polyurethane was proceeded on the basis of lab's experiment.
DHPDMS-polyurethane which had a solid content of 38% and volatile organic compound (VOC) of 60g/L was prepared with isophorone diisocyanate(IPDI), polyester diol (PCD, PBA), dihydropolydimethylsiloxane(DHPDMS), dimethoxyp- ropionic acid (DMPA). Effects of the amount of DHPDMS, the molecular mass of DHPDMS and glass transition temperature (Tg) on the appearance, viscosity, adhesion, water resistance, hardness, tensile strength, elongation of polyurethane modified by DHPDMS were discussed. The optimal condition was concluded as follows: WPU shows the better performance when the amount of DHPDMS is 2%.
Identification of the middle-testing technology for the DHPDMS-PU was proceeded on the basis of our lab's experiment. And the PU resin with a solid content of 38%, high conversion of 96% was successfully prepared. Partial gelation was also successfully solved. The stuff of identification such as new technology bulletin of waterborne polyurethane, bulletin of middle-testing technology, industrial standard, bulletin of quality certification, bulletin of novelty, bulletin of environmental evaluation, verification of users, explanation of achievement. The final result of the identification was international advanced.
Waterborne polyurethane/acrylics (PUA) was synthesized by polyester diol, isophorone diisocyanate(IPDI), dihydrooxypolydimethylsiloxane(DHPDMS), hydroxylethyl acrylate(HEA) and so on. Then methyl methacrylate(MMA), butylacrylate (BA) was added to the PUs, the copolymerization was occurred in the presence of initiator(potassium persulfate). The PUA emulsion had a solid content of 36% and performances of the films such as viscosity, hardness, water absorption, tensile strength, elongation were measured. Films were also characterized by FTIR, DSC, SEM. The FTIR spectral result indicated the presence of lots of hydrogen bonds and micro-phase separation. The DSC and SEM results verified the above conclusion.
引文
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