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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (9): 1115-1125. 上一篇    下一篇

研究论文

聚硅氧烷-聚丙烯酸酯-聚氨酯三元复合乳液的制备与表征及其胶膜性能

姜绪宝，朱晓丽，张召，孔祥正*   

  1. (济南大学化学化工学院 济南 250022)
  • 投稿日期:2010-09-06 修回日期:2011-01-06 发布日期:2011-01-06
  • 通讯作者: 孔祥正 E-mail:xzkong@ujn.edu.cn
  • 基金资助:

    聚硅氧烷-丙烯酸酯-聚氨酯三元复合乳液的制备

Preparation of Polysiloxane-polyacrylic-polyurethane Tri-component Hybrid Latexes and Properties of the Latexes and Their Films

JIANG Xu-Bao, ZHU Xiao-Li, ZHANG Zhao, KONG Xiang-Zheng   

  1. (College of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022)
  • Received:2010-09-06 Revised:2011-01-06 Published:2011-01-06

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用异佛尔酮二异氰酸酯与仲羟基封端的聚硅氧烷(PMTS)反应在聚硅氧烷分子链端引入异氰酸酯基团, 然后将其与聚丙二醇、二羟甲基丙酸等反应制备聚硅氧烷改性聚氨酯(PSU)预聚体, 再以甲基丙烯酸甘油酯(GM)为偶联剂在PSU链上引入双键, 最后加入丙烯酸酯单体和交联剂乳化后通过乳液聚合制备了偶联型聚硅氧烷聚丙烯酸酯改性聚氨酯(PSU-X-AC)三元复合乳液. 同样条件下不使用偶联剂制备了非偶联型三元复合乳液(PSU-AC). 无论是否使用偶联剂, 三元复合乳液的稳定性都明显优于不含PAC的PSU二元乳液. 对于三元复合乳液及其胶膜的性能表征结果显示, 与非偶联型PSU-AC三元乳液相比, 偶联型PSU-X-AC乳液的乳胶粒尺寸较小, 粒径分布更均一|偶联型三元乳液的表面张力较小|其胶膜的力学强度远优于非偶联型|除非在PMTS分子量较高的情况下, 偶联型乳胶膜中未观察到非偶联型所见的相分离, 偶联剂GM的使用对提高材料的憎水及力学性能有明显作用. PMTS分子量及其用量对乳液的乳胶粒径、表面张力和粘度影响不明显. 但对于复合胶膜的性能来说, 三元复合乳液聚合物中PMTS分子量及其用量存在上限, 分子量上限值约为2000, 其用量上限约为PSU二元聚合物的10%, 在此之下PMTS的使用可以明显提高胶膜的力学及耐水性能.

关键词: 羟烷基聚硅氧烷, 丙烯酸酯, 聚氨酯改性, 偶联剂, 三元复合乳液

Isophorone diisocyanate was first reacted with bis(3-(1-methoxy-2-hydroxypropoxy) propyl) terminated polysiloxanes (PMTS) to input cyanate groups in polysiloxane chains, followed by reaction of these cyanate-containing polysiloxanes with polypropylene and dimethylol propanic acid to get polysiloxanes modified polyurethane (PSU) prepolymers. Dihydroxyl glyceryl methacrylate (GM) was then used as coupling agent to react with the PSU prepolymers to introduce vinyl groups with objective to conduct graft-polymerization with acrylics in a subsequent step in order to finally get polysiloxane-polyacrylic modified polyurethane (PSU-X-AC) ternary grafting hybrid latexes. Non-grafting polysiloxane-polyacrylic- polyurethane (PSU-AC) ternary hybrid latexes were also prepared under the same experimental conditions without coupling agent GM. Regardless of using GM as the coupling agent, the stability of the ternary hybrid latexes was enhanced in the presence of polyacrylics (PAC). When compared with the ternary non-grafting latexes (PSU-AC) prepared without use of GM, the corresponding ternary PSU-X-AC latexes prepared with GM demonstrated smaller particle size combined with narrower size distribution and they also showed lower surface tension. For the latex films, higher mechanical performance was observed for the grafted PSU-X-AC, and phase separation was not observed except in cases where PMTS of high molecular weight (＞2000) was used. Use of GM, the coupling agent, was effective to improve the mechanical properties and water resistance of the hybrid materials. No significant impacts of PMTS level and of its molecular weight were noted with regard to the particle size, the surface tension and the viscosity of the latexes. However, when it comes to the properties of the PSU-X-AC latex films, upper limits were observed for PMTS level and its molecular weight, which were around 2000 and 10% relative to the polymer in binary PSU latex, respectively. Below these limits, use of PMTS in the ternary latexes contributed to enhancement of mechanical property and of water resistance.

Key words: hydroxyalkyl polysiloxane, acrylics, polyurethane modification, coupling agent, tri-component hybrid latex