CN107814936B - 一种poss改性的低游离单体聚氨酯固化剂 - Google Patents
一种poss改性的低游离单体聚氨酯固化剂 Download PDFInfo
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Abstract
本发明涉及一种POSS改性的低游离单体聚氨酯固化剂，首先采用两步催化法制得异氰酸酯三聚体，然后通过滴加氨基苯基POSS而成；所述的氨基苯基POSS具有独特的捕捉游离异氰酸酯单体的性能，从而有效地降低固化剂中游离异氰酸酯的含量＜0.5％；所述的聚氨酯固化剂其单个分子中含有16个‑NCO，可与醇酸树脂、聚酯树脂、不饱和聚酯树脂中的‑NH2、‑OH发生高密度的交联固化反应，因此固化后的涂膜具有高致密性、高丰满度，以及优异的附着力、柔韧性和耐水性；由于固化剂含有POSS基团，使涂膜获得优异的疏水性、透明性、耐磨性、耐热性、耐污染性和自阻燃性能。
Description
技术领域
本发明涉及一种聚氨酯固化剂，尤其涉及到一种POSS改性的低游离单体聚氨酯固化剂，属于固化剂合成技术领域。
技术背景
聚氨酯固化剂多以双组份的形式与其他树脂搭配使用，通常聚氨酯以固化剂预聚体的形式存在；使用时，将固化剂与羟基树脂两组分混，在常温或高温交联固化成膜。游离异氰酸酯单体对人体的危害主要是致敏和刺激作用，对眼有刺激性，呼吸道吸入后有咳嗽、哮喘症状等。游离异氰酸酯单体是聚氨酯涂料的一项重要的环境指标，随着社会环保意识的不断增强，游离异氰酸酯单体含量被要求的越来越严格。目前去游离单体方法大体分为三种，分子蒸馏法、溶剂萃取法以及化学催化法，其中前两种为物理方法，其优点是处理后的固化剂粘度低便于施工、存储期相对较长以及游离单体去除彻底，但缺点是设备费用昂贵、操作复杂、生产周期长且溶剂消耗量大，国内工业鲜有应用。
中国专利CN201710398490.9公开了一种低游离单体含量的TDI三聚体亮光固化剂，其由以下重量份的原料制备而成：甲苯二异氰酸酯45-55份、乙酸乙酯10-30份、乙酸丁酯10-20份、复合醇5-15份、促进剂0.8-2份、催化剂0.2-0.8份、叔丁胺0.2-0.5份、终止剂1-2份；该发明工艺操作简单，无需大型设备投资、生产成本低、产品性能完全满足涂料领域的应用，利于健康环保；该发明的制备方法通过独特的工艺路线、工艺参数、具体用料等的协同组合与选择，使得制得的固化剂的固含量为75±2％，NCO值为11.0±0.3，游离TDI百分含量不大于0.5％，而且固化剂相容性好，可以和丙烯酸树脂相容，用于亮光面漆；用于涂料时，漆膜干燥速度快、漆膜硬度高、抗刮伤、柔韧性好。
但是现存固化剂配制的聚氨酯涂料完全固化后，存在耐水性差、耐沾污性差、阻燃性能低、耐磨性差等缺陷。
发明内容
本发明旨在提供一种POSS改性的低游离单体聚氨酯固化剂。
POSS又称笼型聚倍半硅氧烷，是由Si-O交替连接的硅氧骨架组成的无机内核，其形状如同一个“笼子”，属于纳米化合物。POSS基团的多样性、高活性以及较好的聚合物相容性使之既可以通过物理共混又可以通过化学共聚的方法将其引入到聚合物材料中。
POSS改性聚合物能显著改善聚合物材料的表面光滑性、硬度、透明性、疏水性和柔韧性；利用POSS的八臂结构和具有反应活性的官能团以及高度对称性，制备的树脂是一种星形树枝状聚合物，获得更高的交联密度，从而提高涂膜的致密性、耐水性、耐沾污性和耐磨性。
本发明所述的一种POSS改性的低游离单体聚氨酯固化剂，以笼型聚倍半硅氧烷为中心，含有16个异氰酸酯基，其分子结构式如下所示：
由于采用POSS改性，所述的聚氨酯固化剂具有高硬度和自阻燃性能；同时，所述的氨基苯基POSS具有独特的捕捉游离异氰酸酯单体的性能，从而有效地降低固化剂中游离异氰酸酯的含量。
本发明所述的POSS改性的低游离单体聚氨酯固化剂，其制备步骤如下：
a)、异氰酸酯三聚体合成：在N2保护下，向反应釜中加入100.0份异氰酸酯单体、0.05～0.1份催化剂、30.0～60.0份有机溶剂，开启搅拌将物料搅拌均匀，加热至50～80℃反应2～4h后，逐滴滴加5.0份含有催化剂、促进剂和有机溶剂的混合液，在0.5h滴加完毕，然后保持在50～80℃继续反应，每隔0.5h检测一次NCO值，当检测的NCO值在10％～7％后立即加入占异氰酸酯单体质量0.1～0.5％的阻聚剂并降温至20℃，得所述的异氰酸酯三聚体；
b)、POSS改性的低游离单体聚氨酯固化剂的合成：在常温下，向所述的异氰酸酯三聚体中，逐滴滴加八氨基苯基POSS溶液，在0.5～1h滴加完毕，继续反应2～3h，得所述的POSS改性的低游离单体聚氨酯固化剂。
其中，所述的八氨基苯基POSS溶液：将15.0～40.0份八氨基苯基POSS加到30.0份有机溶剂中，搅拌并溶解均匀。
所述的异氰酸酯单体为TDI、MDI、NDI、TODI、HDI、TMDI、XDI、IPDI、HMDI、HTDI中的至少一种。
所述的含有催化剂、促进剂和有机溶剂的混合液，按质量百分比计，其组成为：催化剂2.0％～10.0％、促进剂2.0％～10.0％、有机溶剂80.0％～96.0％。
所述的催化剂为碱性金属羧酸盐、有机金属化合物、含磷化合物或胺类催化剂；进一步地，优选为二月桂酸二丁基锡、醋酸锂、三正丁基磷、辛酸亚锡、环烷酸锡、环烷酸铅、环烷酸钴、马来酸二丁基锡、二乙酸二丁基锡、三乙胺、K-1000、苯甲基缩水甘油醚中的至少一种。
所述的促进剂为N,N-二甲基对甲苯胺、N-甲基吡咯、三乙醇胺、N,N二甲基对甲苯磺酰氯中的至少一种。
所述的有机溶剂为乙酸乙酯、乙酸丁酯、乙酸异丙酯、N,N-二甲基乙酰胺、二甲亚砜、N,N-二甲基甲酰胺、丙酮、丁酮、环己酮中的至少一种。
所述的异氰酸酯单体与氨基苯基POSS的摩尔比为24:1。
相对于现有技术，本发明所述的POSS改性的低游离单体聚氨酯固化剂，具有以下优点：(1)由于本发明的合成采用两步催化法，且氨基苯基POSS采用逐滴滴加法，有利于氨基苯基POSS捕捉游离异氰酸酯单体，从而使固化剂中的游离异氰酸酯单体含量＜0.5％；(2)由于固化剂单个分子中含有16个-NCO，可与醇酸树脂、聚酯树脂、不饱和聚酯树脂中的-NH2、-OH发生高密度的交联固化反应，因此固化后的涂膜具有高致密性、高丰满度，以及优异的附着力、柔韧性和耐水性；(3)含有POSS基团，使涂膜获得优异的疏水性、透明性、耐磨性、耐热性、耐污染性和自阻燃性能。
具体实施方式
下面结合实施例对本发明的一种POSS改性的低游离单体聚氨酯固化剂做进一步的描述。可以理解的是，此处所描述的具体实施例仅仅用于解释相关发明，而非对该发明的限定。
实施例1
一种POSS改性的低游离单体聚氨酯固化剂，其制备步骤如下：
a)、异氰酸酯三聚体合成：在N2保护下，向反应釜中加入100.0份IPDI单体、0.1份三正丁基磷、30.0份乙酸乙酯，开启搅拌将物料搅拌均匀，加热至80℃反应2h后，逐滴滴加5.0份含有2％三正丁基磷和2％N-甲基吡咯的乙酸乙酯溶液，在0.5h滴加完毕，然后保持在80℃继续反应，每隔0.5h检测一次NCO值，当检测的NCO值在9.0±0.5％后立即加入占异氰酸酯单体质量0.5％的阻聚剂并降温至20℃，得所述的异氰酸酯三聚体；
b)、POSS改性的低游离单体聚氨酯固化剂的合成：在常温下，向所述的异氰酸酯三聚体中，逐滴滴加19.2份八氨基苯基POSS与30.0份乙酸乙酯溶液，在1h滴加完毕，继续反应2h，得所述的POSS改性的低游离单体聚氨酯固化剂。
实施例2
一种POSS改性的低游离单体聚氨酯固化剂，其制备步骤如下：
a)、异氰酸酯三聚体合成：在N2保护下，向反应釜中加入100.0份HDI单体、0.1份K-1000、60.0份乙酸异丙酯，开启搅拌将物料搅拌均匀，加热至80℃反应4h后，逐滴滴加5.0份含有10％K-1000和6％三乙醇胺的乙酸异丙酯溶液，在0.5h滴加完毕，然后保持在80℃继续反应，每隔0.5h检测一次NCO值，当检测的NCO值在8.0±0.5％后立即加入占异氰酸酯单体质量0.3％的阻聚剂并降温至20℃，得所述的异氰酸酯三聚体；
b)、POSS改性的低游离单体聚氨酯固化剂的合成：在常温下，向所述的异氰酸酯三聚体中，逐滴滴加21.6份八氨基苯基POSS与30.0份乙酸异丙酯溶液，在1h滴加完毕，继续反应3h，得所述的POSS改性的低游离单体聚氨酯固化剂。
实施例3
一种POSS改性的低游离单体聚氨酯固化剂，其制备步骤如下：
a)、异氰酸酯三聚体合成：在N2保护下，向反应釜中加入100.0份TDI单体、0.05份二月桂酸二丁基锡、40.0份乙酸丁酯，开启搅拌将物料搅拌均匀，加热至65℃反应3h后，逐滴滴加5.0份含有5％二月桂酸二丁基锡和5％N,N-二甲基对甲苯胺的乙酸丁酯溶液，在0.5h滴加完毕，然后保持在65℃继续反应，每隔0.5h检测一次NCO值，当检测的NCO值在10.0±0.5％后立即加入占异氰酸酯单体质量0.2％的阻聚剂并降温至20℃，得所述的异氰酸酯三聚体；
b)、POSS改性的低游离单体聚氨酯固化剂的合成：在常温下，向所述的异氰酸酯三聚体中，逐滴滴加27.6份八氨基苯基POSS与30.0份乙酸丁酯溶液，在0.5h滴加完毕，继续反应3h，得所述的POSS改性的低游离单体聚氨酯固化剂。
按照国家相关标准，对本发明实例制得的POSS改性的低游离单体聚氨酯固化剂的技术指标进行检测，测试结果如表1所示。
表1POSS改性的低游离单体聚氨酯固化剂技术指标
| 检验项目 | 实施例1 | 实施例2 | 实施例3 |
| 固含量，％ | 64.5 | 56.2 | 62.6 |
| 粘度/mPa·s，25℃ | 247.8 | 216.5 | 236.4 |
| NCO/％ | 8.7 | 7.8 | 10.2 |
| 甲苯容忍度 | ≥3.6 | ≥4.2 | ≥3.5 |
| 游离TDI/％ | ≤0.42 | ≤0.36 | ≤0.45 |
将实施例1、2、3中的聚氨酯固化剂和市售HDI聚氨酯固化剂与脂肪酸树脂按照NCO:OH之比为1:1配制成双组分聚氨酯木器涂料，喷涂于木器表面，干燥24h后按照相关标准进行检测，其测试数据如表2所示：
表2聚氨酯木器涂料性能技术指标
尽管本发明已作了详细说明并引证了实施例，但对于本领域的普通技术人员，显然可以按照上述说明而做出的各种方案、修改和改动，都应该包括在权利要求的范围之内。
Claims (7)
1.一种POSS改性的低游离单体聚氨酯固化剂，其特征在于：所述的POSS改性的低游离单体聚氨酯固化剂，以笼型聚倍半硅氧烷为中心，含有16个异氰酸酯基，其分子结构式如下所示：
其制备步骤如下：
a)、异氰酸酯三聚体合成：在N2保护下，向反应釜中加入100.0份异氰酸酯单体、0.05～0.1份催化剂、30.0～60.0份有机溶剂，开启搅拌将物料搅拌均匀，加热至50～80℃反应2～4h后，逐滴滴加5.0份含有催化剂、促进剂和有机溶剂的混合液，在0.5h滴加完毕，然后保持在50～80℃继续反应，每隔0.5h检测一次NCO值，当检测的NCO值在10％～7％后立即加入占异氰酸酯单体质量0.1～0.5％的阻聚剂并降温至20℃，得所述的异氰酸酯三聚体；
b)、POSS改性的低游离单体聚氨酯固化剂的合成：在常温下，向所述的异氰酸酯三聚体中，逐滴滴加15.0～40.0份八氨基苯基POSS和30.0份有机溶剂的混合液，在0.5～1h滴加完毕，继续反应2～3h，得所述的POSS改性的低游离单体聚氨酯固化剂；
所述的异氰酸酯单体与氨基苯基POSS的摩尔比为24:1；
所述的POSS改性的低游离单体聚氨酯固化剂中的游离单体含量＜0.5％。
2.根据权利要求1所述的POSS改性的低游离单体聚氨酯固化剂，其特征在于：所述的异氰酸酯单体为TDI、MDI、NDI、TODI、HDI、TMDI、XDI、IPDI、HMDI或HTDI中的至少一种。
3.根据权利要求1所述的POSS改性的低游离单体聚氨酯固化剂，其特征在于：所述的含有催化剂、促进剂和有机溶剂的混合液，按质量百分比计，其组成为：催化剂2.0％～10.0％、促进剂2.0％～10.0％、有机溶剂80.0％～96.0％。
4.根据权利要求1所述的POSS改性的低游离单体聚氨酯固化剂，其特征在于：所述的催化剂为碱性金属羧酸盐、有机金属化合物、含磷化合物或胺类催化剂。
5.根据权利要求1所述的POSS改性的低游离单体聚氨酯固化剂，其特征在于：所述的催化剂为二月桂酸二丁基锡、醋酸锂、三正丁基磷、辛酸亚锡、环烷酸锡、环烷酸铅、环烷酸钴、马来酸二丁基锡、二乙酸二丁基锡、三乙胺或苯甲基缩水甘油醚中的至少一种。
6.根据权利要求1所述的POSS改性的低游离单体聚氨酯固化剂，其特征在于：所述的促进剂为N,N-二甲基对甲苯胺、N-甲基吡咯或三乙醇胺中的至少一种。
7.根据权利要求1或3所述的POSS改性的低游离单体聚氨酯固化剂，其特征在于：所述的有机溶剂为乙酸乙酯、乙酸丁酯、乙酸异丙酯、N,N-二甲基乙酰胺、二甲亚砜、N,N-二甲基甲酰胺、丙酮、丁酮或环己酮中的至少一种。
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