CN110452260A - 一种新型含硅单体以及含硅单体的有机硅改性水性uv固化聚氨酯乳液 - Google Patents
一种新型含硅单体以及含硅单体的有机硅改性水性uv固化聚氨酯乳液 Download PDFInfo
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Abstract
本发明公开了一种新型含硅单体以及含硅单体的有机硅改性水性UV固化聚氨酯乳液，一种新型含硅单体，包括下述重量份组成：丙烯酸：100份，N,N‑二甲基苄胺：0.3份，γ‑缩水甘油醚氧丙基三甲氧基硅烷：100份，对羟基苯甲醚：0.5份。本专利通过γ‑缩水甘油醚氧丙基三甲氧基硅烷(Γ‑缩水甘油醚氧丙基三甲氧基硅烷)与丙烯酸(AA)反应制备一种分子结构上同时含有羟基、硅氧烷与碳碳双键(C＝C)多种官能团的新型单体新型含硅单体，然后将新型含硅单体作为一种新型封端剂对聚氨酯进行改性，制备出一种可光固化的聚氨酯乳液乳液。
Description
技术领域
本发明涉及领域聚氨酯，更具体的说是涉及一种新型含硅单体以及含硅单体的有机硅改性水性UV固化聚氨酯乳液。
背景技术
水性聚氨酯因其环境友好、安全可靠、易于改性等特点而广泛应用于各个领域。但水性聚氨酯仍存在耐高温与耐水性能差、硬度低等问题，限制了它更加广泛的应用。有机硅氧烷具有独特的化学结构，其表面能较低，因此在成膜过程中向表面富集，可赋予改性聚合物涂膜优良的耐水、耐油污、耐候、耐高低温使用性能以及良好的机械性能。有机硅氧烷改性水性聚氨酯，既可以弥补水性聚氨酯的不足，又可以得到耐水性、耐油污性和耐高低温等综合性能优异的水性聚氨酯。
有机硅材料因其以硅-氧-硅(Si-O-Si)键为主链结构，耐高温性能较好、表面张力与表面能较低以及耐水性能优异，通过有机硅改性水性聚氨酯能较好的弥补水性聚氨酯在某些性能上的不足。一般的有机硅改性水性聚氨酯多以硅烷偶联剂为主，但存在接枝率低，有机硅含量不高等问题。
发明内容
针对现有技术存在的不足，本发明的目的在于提供一种。
为实现上述目的，本发明提供了如下技术方案：
一种新型含硅单体，
包括下述重量份组成：
丙烯酸：100份
N，N-二甲基苄胺：0.3份
γ-缩水甘油醚氧丙基三甲氧基硅烷：100份
对羟基苯甲醚：0.5份。
作为本发明的进一步改进，
其制备方法为：
步骤A：按照比例称取原料；
步骤B：将丙烯酸和N，N-二甲基苄胺进行混合，得到溶液A；
步骤℃：将γ-缩水甘油醚氧丙基三甲氧基硅烷和对羟基苯甲醚进行混合得到溶液B；
步骤D：将溶液B进行升温至70℃，之后缓慢滴加溶液A，在滴加完之后反应；得到新型含硅单体。
作为本发明的进一步改进，
所述步骤D中，升温过程在氮气保护下进行。
作为本发明的进一步改进，
所述步骤D中缓慢滴加溶液A的时间为1小时，且滴加完全后反应时间为3小时。
作为本发明另一发明目的提供一种含硅单体的有机硅改性水性UV固化聚氨酯乳液，
包括下述重量份组成：
异佛尔酮二异氰酸酯：200份
聚己二酸-1，4-丁二醇酯二醇：100份
催化剂：0.03份
二羟甲基丙酸：100份
新型含硅单体：2-10份
三乙胺：10份。
作为本发明的进一步改进，
所述催化剂为二月桂酸二丁基锡。
作为本发明的进一步改进，
在装有搅拌桨、温度计、导气管和冷凝管的四口烧瓶中加入异佛尔酮二异氰酸酯与聚己二酸-1，4-丁二醇酯二醇，催化剂二月桂酸二丁基锡，升温到800℃左右反应一段时间，降温到550℃以下，加入一定量二羟甲基丙酸后再次升温到 750℃反应一段时间降温到500℃以下，滴加溶有阻聚剂的新型含硅单体反应一段时间，整个过程用甲苯-二正丁胺法滴定体系中-NCO含量来确定反应终点；最后降温到室温，加入三乙胺成盐后加入去离子水高速搅拌30min，减压蒸馏脱除溶剂后得到最终产物。
本发明的有益效果，本专利通过γ-缩水甘油醚氧丙基三甲氧基硅烷(Γ- 缩水甘油醚氧丙基三甲氧基硅烷)与丙烯酸(AA)反应制备一种分子结构上同时含有羟基、硅氧烷与碳碳双键(C＝C)多种官能团的新型单体新型含硅单体，然后将新型含硅单体作为一种新型封端剂对聚氨酯进行改性，制备出一种可光固化的聚氨酯乳液乳液。
附图说明
图1为本发明的γ-缩水甘油醚氧丙基三甲氧基硅烷和新型含硅单体的红外光谱图对比图；
图2为本发明的聚氨酯乳液红外光谱图。
具体实施方式
下面将结合附图所给出的实施例对本发明做进一步的详述。
实施例：
新型含硅单体，
包括下述重量份组成：
丙烯酸：100份
N，N-二甲基苄胺：0.3份
γ-缩水甘油醚氧丙基三甲氧基硅烷：100份
对羟基苯甲醚：0.5份。
新型含硅单体，其制备方法为：
步骤A：按照比例称取原料；
步骤B：将丙烯酸和N，N-二甲基苄胺进行混合，得到溶液A；
步骤℃：将γ-缩水甘油醚氧丙基三甲氧基硅烷和对羟基苯甲醚进行混合得到溶液B；
步骤D：将溶液B进行升温至70℃，之后缓慢滴加溶液A，在滴加完之后反应；得到新型含硅单体。
所述步骤D中，升温过程在氮气保护下进行。
所述步骤D中缓慢滴加溶液A的时间为1小时，且滴加完全后反应时间为3小时。
含硅单体的有机硅改性水性UV固化聚氨酯乳液
包括下述重量份组成：
异佛尔酮二异氰酸酯：200份
聚己二酸-1，4-丁二醇酯二醇：100份
催化剂：0.03份
二羟甲基丙酸：100份
新型含硅单体：8份
三乙胺：10份。
所述催化剂为二月桂酸二丁基锡。
含硅单体的有机硅改性水性UV固化聚氨酯乳液，在装有搅拌桨、温度计、导气管和冷凝管的四口烧瓶中加入异佛尔酮二异氰酸酯与聚己二酸-1，4-丁二醇酯二醇，催化剂二月桂酸二丁基锡，升温到800℃左右反应一段时间，降温到550℃以下，加入一定量二羟甲基丙酸后再次升温到750℃反应一段时间降温到500℃以下，滴加溶有阻聚剂的新型含硅单体反应一段时间，整个过程用甲苯-二正丁胺法滴定体系中-NCO含量来确定反应终点；最后降温到室温，加入三乙胺成盐后加入去离子水高速搅拌30min，减压蒸馏脱除溶剂后得到最终产物。
参照图1，新型含硅单体的红外光谱如图所示。结果表明，相比于Γ-缩水甘油醚氧丙基三甲氧基硅烷，合成的新型单体新型含硅单体在3444cm-1处出现了 -OH的伸缩振动峰，1727cm-1处出现了酯键中的羰基C＝O伸缩振动峰，1632 cm-1与810cm-1处出现了碳碳双键C＝C的伸缩振动峰，此外，910cm-1处环氧基团的吸收峰已消失，这些都表明Γ-缩水甘油醚氧丙基三甲氧基硅烷与丙烯酸发生了环氧开环反应，实验结果与预期相符。
参照图2
聚氨酯乳液红外光谱图中2270cm-1处-NCO的特征吸收峰已消失不见，这说明体系中没有出现残余的-NCO；在3361cm-1处的吸收峰为氨基甲酸酯上N-H的伸缩振动峰；2957cm-1处的吸收峰为甲氧基中甲基上的C-H伸缩振动峰； 1730cm-1处的吸收峰为氨基甲酸酯中羰基C＝O的伸缩振动峰；1542cm-1处的吸收峰为N-H的平面弯曲振动峰；809cm-1处的吸收峰为碳碳双键C＝C的伸缩振动峰；1039cm-1处的吸收峰为甲氧基Si-OCH3的伸缩振动峰。
对实施例制备的乳液进行乳液性能测试和漆膜性能测试：
表一：乳液性能测试
表二：漆膜性能测试
单纯的水性聚氨酯乳液粒径较小，但其耐水性较差、漆膜硬度低、对玻璃的附着力差。而加入新型含硅单体改性过的聚氨酯乳液其各方面的性能均要优于未改性过的。这是因为新型含硅单体单体中含有硅氧烷，其在乳化过程中会有一定的水解使其表面-OH含量增多，从而提高了其与玻璃的粘结力，附着力提高；而-OH进一步脱水缩合可性能致密的三维网状结构，交联固化后一定程度地阻挡了水分子的进入，使得硬度与耐水性都有所提高。有机硅改性的乳液有利于提高乳胶膜的光泽度，这是由于在有机硅改性的乳液中的柔性较大的有机硅链段倾向于规整排列，形成更平整的膜，提高了乳胶膜的光泽。
以上所述仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例，凡属于本发明思路下的技术方案均属于本发明的保护范围。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理前提下的若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (7)
1.一种新型含硅单体，其特征在于：
包括下述重量份组成：
丙烯酸：100份
N,N-二甲基苄胺：0.3份
γ-缩水甘油醚氧丙基三甲氧基硅烷：100份
对羟基苯甲醚：0.5份。
2.根据权利要求1所述的一种新型含硅单体，其特征在于：
其制备方法为：
步骤A：按照比例称取原料；
步骤B：将丙烯酸和N,N-二甲基苄胺进行混合，得到溶液A；
步骤℃：将γ-缩水甘油醚氧丙基三甲氧基硅烷和对羟基苯甲醚进行混合得到溶液B；
步骤D：将溶液B进行升温至70℃，之后缓慢滴加溶液A，在滴加完之后反应；得到新型含硅单体。
3.根据权利要求2所述的一种新型含硅单体，其特征在于：
所述步骤D中，升温过程在氮气保护下进行。
4.根据权利要求2或3所述的一种新型含硅单体，其特征在于：
所述步骤D中缓慢滴加溶液A的时间为1小时，且滴加完全后反应时间为3小时。
5.一种含有如权利要求1至4所述的含硅单体的有机硅改性水性UV固化聚氨酯乳液，其特征在于：
包括下述重量份组成：
异佛尔酮二异氰酸酯：200份
聚己二酸-1，4-丁二醇酯二醇：100份
催化剂：0.03份
二羟甲基丙酸：100份
新型含硅单体：2-10份
三乙胺：10份。
6.根据权利要求5所述的有机硅改性水性UV固化聚氨酯乳液，其特征在于：
其特征在于：
所述催化剂为二月桂酸二丁基锡。
7.根据权利要求6所述的有机硅改性水性UV固化聚氨酯乳液，其特征在于：
其特征在于：
在装有搅拌桨、温度计、导气管和冷凝管的四口烧瓶中加入异佛尔酮二异氰酸酯与聚己二酸-1，4-丁二醇酯二醇，催化剂二月桂酸二丁基锡，升温到800℃左右反应一段时间，降温到550℃以下，加入一定量二羟甲基丙酸后再次升温到750℃反应一段时间降温到500℃以下，滴加溶有阻聚剂的新型含硅单体反应一段时间，整个过程用甲苯-二正丁胺法滴定体系中-NCO含量来确定反应终点；最后降温到室温，加入三乙胺成盐后加入去离子水高速搅拌30min，减压蒸馏脱除溶剂后得到最终产物。
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