CN105622891B - 一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法 - Google Patents

一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法 Download PDF

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CN105622891B
CN105622891B CN201510962796.3A CN201510962796A CN105622891B CN 105622891 B CN105622891 B CN 105622891B CN 201510962796 A CN201510962796 A CN 201510962796A CN 105622891 B CN105622891 B CN 105622891B
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张胜文
王亚东
赵杰
徐子墨
白绘宇
刘晓亚
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Ruentex chemical (Taixing) Co. Ltd.
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Abstract

本发明具体涉及一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法。本发明以低聚物二元醇为软段，异氰酸酯化合物为硬段，并在乳化过程中引入聚硅氧烷乳液，制得基于聚硅氧烷乳液改性的水性聚氨酯杂化乳液。聚有机硅氧烷的引入有效提高了水性聚氨酯乳胶膜的拉伸强度和模量，膜表面疏水性增强，吸水率降低且膜具有较高透明性。用该方法制备的水性聚氨酯杂化乳液可广泛用于高性能涂层材料、油墨、胶粘剂和密封材料等领域。

Description

一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法
技术领域
本发明涉及一种水性聚氨酯杂化乳液的制备方法，特别涉及有机硅氧烷乳液及水性聚氨酯乳液的制备方法。
背景技术
水性聚氨酯(WPU)以水为分散介质，具有高分子量、低粘度、容易施工、环保、安全、卫生等优点，在涂料、胶粘剂、油墨、密封剂等领域得到很好的应用。但是水性聚氨酯乳胶膜的力学性能(强度、模量)、粘附力、耐水性等性能还不能与传统的溶剂型聚氨酯相媲美，因此限制了该涂膜的进一步广泛应用。将无机纳米材料如二氧化硅、粘土、碳纳米管等引入WPU体系可以有效提高体系的力学性能，但是体系耐水性和表面疏水性能提高不明显甚至下降。聚二甲基硅氧烷(PDMS)具有低表面自由能、疏水性强、柔性好等优点，PDMS改性WPU可以有效提高体系的耐水性和表面疏水性，但是体系力学性能提高不明显甚至下降。将氨基硅氧烷引入WPU体系得到自交联WPU乳液，聚氨酯膜的力学性能和耐水性等得到改善，但是乳液的胶体稳定性和膜的微结构不太容易控制。为进一步有效提高聚氨酯膜的力学性能和耐水性，本发明通过细乳液聚合制备聚有机硅氧烷乳液，在水性聚氨酯乳化过程中原位引入聚有机硅氧烷乳液，制得聚有机硅氧烷乳液改性水性聚氨酯复合乳液。聚有机硅氧烷的引入可有效提高水性聚氨酯乳胶膜的力学性能、耐水性和表面疏水性。该分散体可应用于高性能涂料、粘合剂、密封剂、油墨等功能材料领域。
发明内容
本发明目的是提供一种聚硅氧烷乳液改性水性聚氨酯复合乳液的制备方法。本发明制备的水性聚氨酯在乳化过程中引入聚硅氧烷微球乳液。聚有机硅氧烷的引入有效提高了水性聚氨酯乳胶膜的拉伸强度和模量，膜表面疏水性增强，吸水率降低且膜具有较高透明性。
本发明的技术方案：
1、一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法，其特征在于组成包括：30wt％-50wt％的低聚物多元醇，20wt％-40wt％的二异氰酸酯化合物，3wt％-8wt％的亲水单体，2wt％-5wt％的胺类化合物，1wt％-5wt％胺类扩链剂，5wt％-20wt％的聚硅氧烷乳液,具体制备方法如下：
(1)聚硅氧烷乳液的合成：按配比将十二烷基磺酸钠、碳酸氢钠和磷酸二氢钠溶解于去离子水并混合均匀形成水相；另外按配比将有机硅氧烷单体、十六碳烷和偶氮二异丁腈混合并分散均匀形成油相，将油相组份滴加到水相组份中，边滴加边搅拌乳化，搅拌0.5h进行粗乳化，再细乳化10min，细乳化后在70℃条件下聚合5h，制得聚硅氧烷乳液；
(2)聚硅氧烷乳液改性水性聚氨酯乳液的合成：按配比在二异氰酸酯化合物中，滴加低聚物多元醇和催化剂，滴加完毕后在50℃反应1-2h，然后逐渐升温至65℃，加入亲水单体多羟基羧酸化合物粉末，在此温度下进行反应4-5h，用甲苯-二正丁胺法测定生成预聚体的异氰酸酯基(NCO)含量，当接近NCO理论值时，将反应温度降低到30℃，滴加胺类化合物反应1h，然后在乳化过程中引入聚硅氧烷乳液，最后加入胺类扩链剂对聚氨酯预聚体进行扩链得到聚硅氧烷乳液水性聚氨酯乳液；
所述的有机硅氧烷单体选用甲基丙烯酰氧基丙基三甲氧基硅烷、甲基丙烯酰氧基丙基三乙氧基硅烷、甲基丙烯酰氧基甲基二甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷之一种。
所述的低聚物多元醇选用聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚己内酯多元醇、聚碳酸酯二醇、聚氧乙烯-聚氧丙烯-聚氧乙烯二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚对苯二甲酸乙二醇酯二醇、聚对苯二甲酸丁二醇酯二醇、α,ω-二羟基聚二甲基硅氧烷、二羟基聚二苯基硅氧烷、二羟基聚三氟丙基甲基硅氧烷之一种或几种，其分子量范围为400-10000。
所述的二异氰酸酯化合物选用2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷4,4’-二异氰酸酯、甲基环己基二异氰酸酯、2,2,4-三甲基己二异氰酸酯中之一种。
所述的亲水单体选用二羟甲基丙酸，二羟甲基丁酸，1,2-二羟基-3-丙磺酸钠中之一种。
所述的胺类化合物选用三乙胺、三乙醇胺、N-甲基二乙醇胺、N,N-二甲胺基对苯甲酸异辛酯、氨水中之一种。
所述胺类扩链剂选用乙二胺、己二胺、二乙烯三胺、异佛尔酮二胺、2-甲基戊二胺之一种
所述的聚硅氧烷乳液的粒径范围为10-1000nm，pH范围为6.0-8.0，固含量为10-50％。
附图说明
图1聚硅氧烷微球乳液改性水性聚氨酯复合膜的拉伸性能
图2聚硅氧烷微球乳液改性水性聚氨酯复合膜的水接触角
图3聚硅氧烷微球乳液改性水性聚氨酯复合膜的扫描电镜图
具体实施方式
为了更好的解释本发明，下面结合具体实施例对本发明进行进一步详细解释。
实施例1
聚硅氧烷微球乳液：按配比称量0.2g十二烷基磺酸钠，0.1g碳酸氢钠和0.1g磷酸二氢钠溶解于40.0g去离子水并混合均匀形成水相，并加入到250mL四颈烧瓶中。另外按配比称量9.0g乙烯基三甲氧基硅烷单体、0.5g十六碳烷和0.2g偶氮二异丁腈混合并分散均匀形成油相，将油相组份滴加到水相组份中，边滴加边搅拌乳化，搅拌0.5h进行粗乳化，再细乳化10min，细乳化后在70℃条件下聚合5h，制得聚有机硅氧烷乳液
实施例2
制备水性聚氨酯膜：在装有搅拌器、温度计和回流冷凝管的250mL四颈烧瓶中加入17.4g异佛尔酮二异氰酸酯(IPDI)，室温下一边搅拌一边用滴液漏斗滴加57.1g聚碳酸酯多元醇(PCD2000)和0.05g催化剂二月桂酸二丁基锡(DBTDL)，滴加速度控制在1.5h内，滴加完毕后在45±5℃反应1-2h；然后升温至60℃，加入3.75g二羟甲基丙酸(DMPA)，反应3-4h，通过甲苯-二正丁胺反滴定法测定反应程度，直到测定NCO基团含量达到理论值；然后向树脂中加入2.83g的三乙胺，反应0.5-1h；向体系中滴加198.3g的去离子水进行乳化；最后制得水性聚氨酯膜。
实施例3
制备有机硅改性水性聚氨酯膜：在装有搅拌器、温度计和回流冷凝管的250mL四颈烧瓶中加入17.4g异佛尔酮二异氰酸酯(IPDI)，室温下一边搅拌一边用滴液漏斗滴加51.3g聚碳酸酯多元醇(PCD2000)和0.05g催化剂二月桂酸二丁基锡(DBTDL)，滴加速度控制在1.5h内，滴加完毕后在45±5℃反应1-2h；向其中加入6.85g有机硅化合物(PDMS)，反应0.5-1h；然后升温至60℃，加入3.75g二羟甲基丙酸(DMPA)，反应3-4h，通过甲苯-二正丁胺反滴定法测定反应程度，直到测定NCO基团含量达到理论值；然后向树脂中加入2.83g的三乙胺，反应0.5-1h；向体系中滴加198.3g的去离子水进行乳化；最后制得水性聚氨酯膜。
实施例4
制备聚硅氧烷微球乳液改性水性聚氨酯-有机硅膜：在装有搅拌器、温度计和回流冷凝管的250mL四颈烧瓶中加入17.4g异佛尔酮二异氰酸酯(IPDI)，室温下一边搅拌一边用滴液漏斗滴加51.3g聚碳酸酯多元醇(PCD2000)和0.05g催化剂二月桂酸二丁基锡(DBTDL)，滴加速度控制在1.5h内，滴加完毕后在45±5℃反应1-2h；向其中加入6.85g有机硅化合物(PDMS)，反应0.5-1h；然后升温至60℃，加入3.75g二羟甲基丙酸(DMPA)，反应3-4h，通过甲苯-二正丁胺反滴定法测定反应程度，直到测定NCO基团含量达到理论值；然后向树脂中加入2.83g的三乙胺，反应0.5-1h；加入14.91g的聚硅氧烷微球乳液，反应0.5-1h；向体系中滴加198.3g的去离子水进行乳化；最后制得二氧化硅改性的水性聚氨酯膜。

Claims (4)

1.一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法，其特征在于组成包括：30wt％-50wt％的低聚物多元醇，20wt％-40wt％的二异氰酸酯化合物，3wt％-8wt％的亲水单体，2wt％-5wt％的胺类化合物，1wt％-5wt％的胺类扩链剂，5wt％-20wt％的聚硅氧烷乳液,具体制备方法如下：
(1)聚硅氧烷乳液的合成：按配比称量0.2g十二烷基磺酸钠，0.1g碳酸氢钠和0.1g磷酸二氢钠溶解于40.0g去离子水并混合均匀形成水相，并加入到250mL四颈烧瓶中；另外按配比称量9.0g乙烯基三甲氧基硅烷单体、0.5g十六碳烷和0.2g偶氮二异丁腈混合并分散均匀形成油相，将油相组分滴加到水相组分中，边滴加边搅拌乳化，搅拌0.5h进行粗乳化，再细乳化10min，细乳化后在70℃条件下聚合5h，制得聚硅氧烷乳液；
(2)聚硅氧烷乳液改性水性聚氨酯乳液的合成：按配比在二异氰酸酯化合物中，滴加低聚物多元醇和催化剂，滴加完毕后在50℃反应1-2h，然后逐渐升温至65℃，加入亲水单体多羟基羧酸化合物粉末，在此温度下进行反应4-5h，用甲苯-二正丁胺法测定生成预聚体的异氰酸酯基(NCO)含量，当接近NCO理论值时，将反应温度降低到30℃，滴加胺类化合物反应1h，然后在乳化过程中引入聚硅氧烷乳液，最后加入胺类扩链剂对聚氨酯预聚体进行扩链得到聚硅氧烷乳液改性水性聚氨酯乳液；
所述的亲水单体选用二羟甲基丙酸，二羟甲基丁酸中之一种；
所述的胺类化合物选用三乙胺、三乙醇胺、N-甲基二乙醇胺、氨水中之一种；
所述的胺类扩链剂选用乙二胺、己二胺、二乙烯三胺、异佛尔酮二胺、2-甲基戊二胺中之一种。
2.根据权利要求1所述一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法，其特征在于：所述的低聚物多元醇选用聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚己内酯多元醇、聚碳酸酯二醇、聚氧乙烯-聚氧丙烯-聚氧乙烯二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚对苯二甲酸乙二醇酯二醇、聚对苯二甲酸丁二醇酯二醇、α,ω-二羟基聚二甲基硅氧烷、二羟基聚二苯基硅氧烷、二羟基聚三氟丙基甲基硅氧烷之一种或几种，其分子量范围为400-2000。
3.根据权利要求1所述一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法，其特征在于：所述的二异氰酸酯化合物选用2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷4,4’-二异氰酸酯、甲基环己基二异氰酸酯、2,2,4-三甲基己二异氰酸酯中之一种。
4.根据权利要求1所述一种聚硅氧烷乳液改性水性聚氨酯乳液的制备方法，其特征在于：所述的聚硅氧烷乳液的粒径范围为10-1000nm，pH范围为6.0-8.0，固含量为10-50％。
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