CN114836164A - 一种硅烷改性生物基聚氨酯防水密封胶及其制备方法 - Google Patents
一种硅烷改性生物基聚氨酯防水密封胶及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种硅烷改性生物基聚氨酯防水密封胶及其制备方法，所述硅烷改性生物基聚氨酯防水密封胶由25～40重量份硅烷改性生物基聚氨酯树脂、50～60重量份无机填料、5～15重量份环氧化植物油、1～5重量份硅烷偶联剂和0.1～0.5重量份催化剂混合而成。硅烷改性生物基聚氨酯树脂由生物基二元醇、二异氰酸酯、氨基硅烷合成。采用含生物基C36二聚体单元的大分子二元醇或共聚聚酯多元醇，赋予憎水、耐酸碱和抗紫外老化的能力。经1％硫酸、1％氢氧化钠、5％氯化钠水溶液浸泡60天，以及水‑紫外线处理2000小时后，拉伸强度保持率高于95％，断裂伸长率保持率高于90％。该密封胶能应用于建筑、家装等领域的防水密封。
Description
技术领域
本发明涉及一种硅烷改性生物基聚氨酯防水密封胶及其制备方法，属于密封胶技术领域。
背景技术
建筑和家居装修领域采用的密封胶通常是硅酮胶和聚氨酯密封胶。在长期使用过程中，某些特定位置的胶条受到长期的紫外线、高温、高湿等复杂环境的影响，硅酮胶的硅油成分会缓慢渗出，污染基材、影响美观，传统的聚氨酯密封胶由聚醚多元醇和异氰酸酯合成，聚醚多元醇软段和氨酯键容易在紫外线、酸、碱、盐的影响下发生老化。此外，聚氨酯密封胶往往含有邻苯二甲酸酯类增塑剂，欧美等发达国家地区已经将邻苯二甲酸酯类物质列为禁用或限制使用化学物质，而且邻苯二甲酸酯类物质分子量小、极性低，随时间延长也会迁移至表面，一方面导致密封胶老化、弹性变差，另一方面危害人类的身体健康。
密封胶老化的重要介质是水，蒸气形态的水分子渗透到密封胶内部，或溶解酸、碱、盐成分的水缓慢侵蚀到内部，在紫外线或高温的刺激下，将加速老化。专利CN201010593673、CN201610946574、CN201810264240和CN201911309263选择聚二甲基硅氧烷软段与常规聚醚多元醇复配合成聚氨酯预聚物，旨在利用聚二甲基硅氧烷的低表面能特性来提高密封胶疏水的能力，从而提升其防水能力。专利CN200910146833选用石油基烯烃类物质，即双环戊二烯石油树脂和由端羟基聚丁二烯合成的丁羟聚氨酯，同样是利用低表面能特性来赋予防水性能。
发明内容
本发明提供一种硅烷改性生物基聚氨酯防水密封胶，由以下重量份的成份组成：
硅烷改性生物基聚氨酯树脂25～40份
无机填料50～60份
环氧化植物油5～15份
硅烷偶联剂1～5份
催化剂0.1～0.5份。
所述硅烷改性生物基聚氨酯树脂由生物基二元醇、二异氰酸酯、氨基硅烷合成。
所述生物基二元醇为C36二聚醇、C36二聚酸聚酯多元醇中的一种或多种混合物，C36二聚醇优选为Pripol 2030或Pripol 2033，C36二聚酸聚酯多元醇优选为Priplast3238、Priplast XL 101、Priplast 1838、Priplast 1837、Priplast 1900、Priplast 3186或Priplast 3190。
所述二异氰酸酯为异佛尔酮二异氰酸酯IPDI、4,4’-二环己基甲烷二异氰酸酯HMDI、环己烷-1,4-二异氰酸酯CHDI、二聚酸二异氰酸酯DDI中的一种或多种混合物，DDI化学结构式为
所述氨基硅烷为3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、双[3-(三甲氧基硅基)丙基]胺、双[3-(三乙氧基硅基)丙基]胺、3-氨丙基(二甲氧基)甲基硅烷、3-氨丙基(二乙氧基)甲基硅烷、苯胺甲基三甲氧基硅烷、苯胺甲基三乙氧基硅烷、3-(苯基氨基)丙基三甲氧基硅烷、N-(3-(三甲氧基硅基)丙基)丁胺中的一种或多种混合物。
所述无机填料为重质碳酸钙、轻质碳酸钙、纳米碳酸钙、滑石粉、炭黑、钛白粉中的一种或多种混合物。
所述环氧化植物油为环氧大豆油、环氧蓖麻油、环氧棕榈油中的一种或多种混合物。
所述硅烷偶联剂为甲基三甲氧基硅烷、甲基三乙氧基硅烷、氨乙基氨丙基三甲氧基硅烷中的一种或多种混合物。
所述催化剂为二异丙氧基钛(双乙酰乙酸乙酯)。
所述硅烷改性生物基聚氨酯防水密封胶经1％硫酸、1％氢氧化钠、5％氯化钠水溶液浸泡60天，以及水-紫外线处理2000小时后，拉伸强度保持率高于95％，断裂伸长率保持率高于90％。
本发明还提供了所述硅烷改性生物基聚氨酯防水密封胶的制备方法：(1)往反应釜中投入1.0当量份生物基二元醇，升温至105～120℃，控制真空度不大于-0.095MPa，除水1～2小时后降温至70～80℃，投入R当量份二异氰酸酯，R值定义为异氰酸根与羟基官能团比值，R值为1.2～1.8，投入0.002％质量分数的二月桂酸二丁基锡，氮气保护下搅拌2～4小时得到异氰酸酯根封端树脂，降温至20～35℃，投入2(R-1)当量份的氨基硅烷，氮气保护下搅拌2～4小时得到硅烷改性生物基聚氨酯树脂；(2)投入设定量环氧化植物油、无机填料、硅烷偶联剂和催化剂，氮气保护下搅拌混合1～2小时，计量出料，密封包装得硅烷改性生物基聚氨酯防水密封胶。
本发明的硅烷改性生物基聚氨酯防水密封胶有益效果：(1)采用含生物基C36二聚体单元的大分子二元醇或共聚聚酯多元醇，赋予憎水、耐酸碱和抗紫外老化的能力，与聚氧化丙烯醚多元醇相比，还能显著提升力学性能；(2)选择生物基环氧化植物油作为稀释剂，与生物基多元醇相容性良好，且分子量大，被牢牢锚固在材料内部，不产生析出。
具体实施实例
为更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。
本发明实施例及对比例中实验所用的原料如下，但是不限于以下原料，本发明只是以下原料为具体例子来进一步具体说明本发明中所述硅烷改性生物基聚氨酯防水密封胶的效果：
生物基二元醇：Pripol 2033，羟值207mgKOH/g，数均分子量540g/mol，Priplast1838，羟值56mgKOH/g，数均分子量2000g/mol，禾大智能材料。
聚氧化丙烯醚二醇：DL-2000D，羟值56mgKOH/g,数均分子量2000g/mol，山东蓝星东大。
二异氰酸酯：IPDI，德国赢创。
氨基硅烷：3-氨丙基三甲氧基硅烷，KH-550，西斯博。
环氧化植物油：环氧大豆油，祥云化工。
无机填料：重质碳酸钙NC-60A，纳米碳酸钙NAK-2108，重量比4:1，购于旭丰粉体。
硅烷偶联剂：甲基三乙氧基硅烷，山东国化。
催化剂：二异丙氧基钛(双乙酰乙酸乙酯)，购于阿拉丁。
本发明设置实施例1～6，合成方法如下：(1)往反应釜中投入0.3当量份Pripol2033和0.7当量份Priplast 1838，升温至110℃，控制真空度不大于-0.095MPa，除水1小时后降温至75℃，投入1.2或1.8当量份二异氰酸酯IPDI，R值为1.2或1.8，投入0.002％质量分数的二月桂酸二丁基锡，氮气保护下搅拌2小时得到异氰酸酯根封端树脂，降温至25℃，投入0.4或1.6当量份3-氨丙基三甲氧基硅烷KH-540，氮气保护下搅拌2小时得到硅烷改性生物基聚氨酯树脂，记为树脂1和树脂2；(2)投入设定量环氧大豆油、重质碳酸钙NC-60A、纳米碳酸钙NAK-2108、甲基三乙氧基硅烷和二异丙氧基钛(双乙酰乙酸乙酯)，氮气保护下搅拌混合1小时，计量出料，密封包装得硅烷改性生物基聚氨酯防水密封胶。
本发明设置对比例1～4，合成方法如下：(1)往反应釜中投入1.0当量份DL-2000D，升温至110℃，控制真空度不大于-0.095MPa，除水1小时后降温至75℃，投入1.2或1.8当量份二异氰酸酯IPDI，R值为1.2或1.8，投入0.002％质量分数的二月桂酸二丁基锡，氮气保护下搅拌2小时得到异氰酸酯根封端树脂，降温至25℃，投入0.4或1.6当量份3-氨丙基三甲氧基硅烷KH-540，氮气保护下搅拌2小时得到硅烷改性聚氨酯树脂，记为树脂3和树脂4；(2)投入设定量环氧大豆油、重质碳酸钙NC-60A、纳米碳酸钙NAK-2108、甲基三乙氧基硅烷和二异丙氧基钛(双乙酰乙酸乙酯)，氮气保护下搅拌混合1小时，计量出料，密封包装得硅烷改性聚氨酯密封胶。
表1：实施例1～6及对比例1～4的投料重量份
样品制备：手动打胶机挤出样条，在25℃、50±10RH％条件下固化24小时，待测样品进行以下几种处理方式：(1)不做任何处理，即固化后在标准条件调节168小时后进行测试；(2)参考JC/T 485-2007中5.12规定的方法进行水-紫外线处理，连续试验2000小时后测试拉伸强度TS和断裂伸长率EB，与不处理样品对比计算保持率；(3)经1％硫酸、1％氢氧化钠、5％氯化钠水溶液浸泡60天，测试拉伸强度TS和断裂伸长率EB，与不处理样品对比计算保持率。
表2：实施例1～6及对比例1～4的各项性能
实施例1～6采用C36二聚醇或C36二聚酸聚酯多元醇，经过酸、碱、盐、水-紫外线处理，均能获得优异的拉伸强度和断裂伸长率保持率，对比例1～4采用聚氧化丙烯醚二醇，这两种性能出现明显衰减，由此可见，生物基C36二聚体单元能赋予憎水、耐酸碱和抗紫外老化的作用。
以上所述仅为本发明的实施例而已，并不用于限制本发明。本发明可以有各种合适的更改和变化。凡在本发明的精神和原则之内所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (9)
1.一种硅烷改性生物基聚氨酯防水密封胶，其特征在于，由如下重量份的成份组成：25～40份硅烷改性生物基聚氨酯树脂、50～60份无机填料、5～15份环氧化植物油、1～5份硅烷偶联剂、0.1～0.5份催化剂。
2.根据权利要求1所述的硅烷改性生物基聚氨酯防水密封胶，其特征在于，所述硅烷改性生物基聚氨酯树脂由生物基二元醇、二异氰酸酯、氨基硅烷合成。
3.根据权利要求2所述的硅烷改性生物基聚氨酯防水密封胶，其特征在于，所述生物基二元醇为C36二聚醇、C36二聚酸聚酯多元醇中的一种或多种混合物。
4.根据权利要求3所述的硅烷改性生物基聚氨酯防水密封胶，其特征在于，所述C36二聚醇为Pripol 2030或Pripol 2033，所述C36二聚酸聚酯多元醇为Priplast 3238、Priplast XL 101、Priplast 1838、Priplast 1837、Priplast 1900、Priplast 3186或Priplast 3190。
5.根据权利要求2所述的硅烷改性生物基聚氨酯防水密封胶，其特征在于，所述二异氰酸酯为异佛尔酮二异氰酸酯IPDI、4,4’-二环己基甲烷二异氰酸酯HMDI、环己烷-1,4-二异氰酸酯CHDI、二聚酸二异氰酸酯DDI中的一种或多种混合物，DDI化学结构式为
6.根据权利要求2所述的硅烷改性生物基聚氨酯防水密封胶，其特征在于，所述氨基硅烷为3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、双[3-(三甲氧基硅基)丙基]胺、双[3-(三乙氧基硅基)丙基]胺、3-氨丙基(二甲氧基)甲基硅烷、3-氨丙基(二乙氧基)甲基硅烷、苯胺甲基三甲氧基硅烷、苯胺甲基三乙氧基硅烷、3-(苯基氨基)丙基三甲氧基硅烷、N-(3-(三甲氧基硅基)丙基)丁胺中的一种或多种混合物。
7.根据权利要求2所述的硅烷改性生物基聚氨酯防水密封胶，其特征在于，所述无机填料为重质碳酸钙、轻质碳酸钙、纳米碳酸钙、滑石粉、炭黑、钛白粉中的一种或多种混合物，所述环氧化植物油为环氧大豆油、环氧蓖麻油、环氧棕榈油中的一种或多种混合物，所述硅烷偶联剂为甲基三甲氧基硅烷、甲基三乙氧基硅烷、氨乙基氨丙基三甲氧基硅烷中的一种或多种混合物，所述催化剂为二异丙氧基钛(双乙酰乙酸乙酯)。
8.一种根据权利要求2～7任一项所述的硅烷改性生物基聚氨酯防水密封胶的制备方法，包括如下步骤：
(1)往反应釜中投入1.0当量份生物基二元醇，升温至105～120℃，控制真空度不大于-0.095MPa，除水1～2小时后降温至70～80℃，投入R当量份二异氰酸酯，R值定义为异氰酸根与羟基官能团比值，R值为1.2～1.8，投入0.002％质量分数的二月桂酸二丁基锡，氮气保护下搅拌2～4小时得到异氰酸酯根封端树脂，降温至20～35℃，投入2(R-1)当量份的氨基硅烷，氮气保护下搅拌2～4小时得到硅烷改性生物基聚氨酯树脂；
(2)投入设定量环氧化植物油、无机填料、硅烷偶联剂和催化剂，氮气保护下搅拌混合1～2小时，计量出料，密封包装得硅烷改性生物基聚氨酯防水密封胶。
9.根据权利要求2～7任一项所述的硅烷改性生物基聚氨酯防水密封胶，其特征在于，所述硅烷改性生物基聚氨酯防水密封胶经1％硫酸、1％氢氧化钠、5％氯化钠水溶液浸泡60天，以及水-紫外线处理2000小时后，拉伸强度保持率高于95％，断裂伸长率保持率高于90％。
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