CN116333299A - 一种用于水性聚氨酯的多元醇的制备方法 - Google Patents
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Abstract
本申请涉及有机聚合物技术领域，更具体地说，它涉及一种用于水性聚氨酯的多元醇的制备方法。一种用于水性聚氨酯的多元醇的制备方法，包括如下步骤：将疏水性二元酸和二元胺按照质量比为（10‑25）:1混合，升温至130‑160℃，保温反应1‑5h；滴加醇胺类化合物，在120‑160℃下滴加2‑8h，滴毕，升温至200‑250℃，保温反应1‑5h，脱水，降温至90‑110℃，得到目标产物；醇胺类化合物与二元胺的质量比为（2‑10）:1。将本申请的多元醇用于水性聚氨酯的制备，能够使得水性聚氨酯兼具良好的耐水解性能和力学性能。
Description
技术领域
本申请涉及有机聚合物技术领域，更具体地说，它涉及一种用于水性聚氨酯的多元醇的制备方法。
背景技术
聚氨酯(Polyurethane,PU)指的是含有氨基甲酸酯键(-NHCOO-)的一类化合物，自1937年被德国拜尔教授发明后，就因其优异的性能而被广泛应用在汽车、建筑、纺织、服装、能源、军工等各个工业领域，传统的溶剂型聚氨酯因干燥时间短、成膜温度低、粘接效果好而被广泛应用在涂料、胶粘剂等领域。但溶剂型聚氨酯中含有大量的甲苯或者二甲苯等有毒溶剂，对环境会造成危害，随着人们环保意识的提高，水性聚氨酯因不含或含少量挥发性有机溶剂而逐渐成为研究的热点，各种水性聚氨酯产品如雨后春笋般出现。
水性聚氨酯由异氰酸酯、聚酯/聚醚多元醇、亲水扩链剂等聚合而成，其中，聚酯/聚醚多元醇是水性聚氨酯的主要成分，对水性聚氨酯的性能影响较大。
聚酯多元醇通常由小分子二元酸和小分子二元醇缩聚而成，聚酯多元醇中含有大量酯基，水性聚氨酯以水为分散介质，酯基易被水解，水性聚氨酯分子容易被破坏，导致水性聚氨酯分子量和性能下降。聚醚多元醇由环氧丙烷、环氧乙烷、四氢呋喃等共聚而成，含有大量醚键，醚键本身不易水解，但具有亲水性和吸湿性，大量醚键的存在会导致水性聚氨酯分子间范德华力下降，影响其力学性能。
因此，亟需开发一款用于水性聚氨酯制备的多元醇，使得水性聚氨酯兼具良好的耐水解性能和力学性能。
发明内容
为了解决水性聚氨酯无法兼具良好的耐水解性能和力学性能的问题，本申请提供一种用于水性聚氨酯的多元醇的制备方法。
第一方面，本申请提供一种用于水性聚氨酯的多元醇的制备方法，采用如下的技术方案：
一种用于水性聚氨酯的多元醇的制备方法，包括如下步骤：
将疏水性二元酸和二元胺按照质量比为(10-25):1混合，升温至130-160℃，保温反应1-5h；滴加醇胺类化合物，在120-160℃下滴加2-8h，滴毕，升温至200-250℃，保温反应1-5h，脱水，降温至90-110℃，得到目标产物；所述醇胺类化合物与二元胺的质量比为(2-10):1。
通过采用上述技术方案，采用疏水性二元酸和二元胺聚合，再利用醇胺类化合物封端，得到含耐水解的酰胺基和疏水链段的多元醇，疏水链段的存在能够阻挡部分水分子，降低水分子与多元醇分子形成氢键的可能性，利用本申请的多元醇制备水性聚氨酯，能够提高了水性聚氨酯分子内氢键形成的可能性，提高了水性聚氨酯分子的内聚能，从而提高了水性聚氨酯的力学性能，同时向水性聚氨酯内引入大量耐水解的酰胺基，解决了水性聚氨酯无法兼具良好的耐水解性能和力学性能的问题。
优选的，所述疏水性二元酸和二元胺的质量比为(10-15):1。
优选的，所述醇胺类化合物与二元胺的质量比为(2-5):1。
优选的，所述疏水性二元酸为十二烷二酸、十三烷二甲酸、二聚酸中的一种或多种。
优选的，所述疏水性二元酸为二聚酸。
通过采用上述技术方案，二聚酸含有的疏水链段较长，对水分子的阻隔效果更好，将利用二聚酸制得的多元醇用于水性聚氨酯的制备，能够进一步提高水性聚氨酯的耐水解性能和力学性能。
优选的，所述二元胺为己二胺、环己二胺、苯并咪唑二胺和苯并噁唑二胺中的一种或多种。
优选的，所述二元胺为苯并咪唑二胺和/或苯并噁唑二胺。
通过采用上述技术方案，苯并咪唑二胺和苯并噁唑二胺均含有刚性结构，且苯并咪唑二胺中含有活性氢原子，能够与其他活性基团形成分子内氢键，提高分子的内聚能，将两者作为原料制备出的多元醇具有良好的力学性能，再将该多元醇用于水性聚氨酯的制备，能够进一步提高水性聚氨酯的力学性能，且苯并咪唑二胺和苯并噁唑二胺在提高成品水性聚氨酯的耐水解性能和力学性能方面协同增效。
优选的，所述二元胺由苯并咪唑二胺和苯并噁唑二胺按照质量比为1:(3-7)复配制得。
通过采用上述技术方案，苯并咪唑二胺和苯并噁唑二胺按照上述比例复配时，能够进一步提高成品水性聚氨酯的耐水解性能和力学性能。
优选的，所述醇胺为乙醇胺、二乙醇胺、2-氨基-2-甲基-丙醇、异丙醇胺中的一种或多种。
综上所述，本申请具有以下有益效果：
1、本申请采用疏水性二元酸和二元胺聚合，再利用醇胺类化合物封端，得到含耐水解的酰胺基和疏水链段的多元醇，疏水链段的存在能够阻挡部分水分子，降低水分子与多元醇分子形成氢键的可能性，利用本申请的多元醇制备水性聚氨酯，能够提高了水性聚氨酯分子内氢键形成的可能性，提高了水性聚氨酯分子的内聚能，从而提高了水性聚氨酯的力学性能，同时向水性聚氨酯内引入大量耐水解的酰胺基，解决了水性聚氨酯无法兼具良好的耐水解性能和力学性能的问题。
2、本申请采用苯并咪唑二胺和苯并噁唑二胺均含有刚性结构，且苯并咪唑二胺中含有活性氢原子，能够与其他活性基团形成分子内氢键，提高分子的内聚能，将两者作为原料制备出的多元醇具有良好的力学性能，再将该多元醇用于水性聚氨酯的制备，能够进一步提高水性聚氨酯的力学性能，且苯并咪唑二胺和苯并噁唑二胺在提高成品水性聚氨酯的耐水解性能和力学性能方面协同增效。
具体实施方式
以下结合实施例对本申请做进一步详细说明。
若无特殊说明，以下实施例以及对比例中所用的原料规格详见表1。
表1.原料规格信息
| 原料 | 规格 |
| 抗氧剂 | 型号：3019 |
| 二聚酸 | 分子量：564.923 |
| 聚酯多元醇 | 牌号：hk-3152 |
| 聚醚多元醇 | 型号：WANOL F3135 |
实施例
实施例1
一种用于水性聚氨酯的多元醇，其配方如下：
十二烷二酸10kg、己二胺1kg、乙醇胺2kg、抗氧剂30g
一种用于水性聚氨酯的多元醇，按照如下步骤制得：
反应釜中加入十二烷二酸、粉碎的己二胺固体、抗氧剂，搅拌下逐步升温，升温至130℃，保温反应5小时；滴加乙醇胺，120℃下滴加8小时，滴毕，升温至200℃，继续保温反应5小时，保温过程开启冷凝器循环水，生成的水蒸汽冷凝后流入接收罐中；开动真空泵，脱除生产水，当釜内真空度超过0.095MPa，停止真空脱水；脱水结束，物料降温至90℃，放料包装，得到目标产物。
实施例2
一种用于水性聚氨酯的多元醇，其配方如下：
十二烷二酸10kg、己二胺1kg、乙醇胺2kg、抗氧剂30g
一种用于水性聚氨酯的多元醇，按照如下步骤制得：
反应釜中加入十二烷二酸、粉碎的己二胺固体、抗氧剂，搅拌下逐步升温，升温至160℃，保温反应1小时；滴加乙醇胺，160℃下滴加2小时，滴毕，升温至250℃，继续保温反应1小时，保温过程开启冷凝器循环水，生成的水蒸汽冷凝后流入接收罐中；开动真空泵，脱除生产水，当釜内真空度超过0.095MPa，停止真空脱水；脱水结束，物料降温至110℃，放料包装，得到目标产物。
实施例3
一种用于水性聚氨酯的多元醇，其配方如下：
十二烷二酸10kg、己二胺1kg、乙醇胺2kg、抗氧剂30g
一种用于水性聚氨酯的多元醇，按照如下步骤制得：
反应釜中加入十二烷二酸、粉碎的己二胺固体、抗氧剂，搅拌下逐步升温，升温至140℃，保温反应2小时；滴加乙醇胺，150℃下滴加4小时，滴毕，升温至220℃，继续保温反应3小时，保温过程开启冷凝器循环水，生成的水蒸汽冷凝后流入接收罐中；开动真空泵，脱除生产水，当釜内真空度超过0.095MPa，停止真空脱水；脱水结束，物料降温至100℃，放料包装，得到目标产物。
实施例4
一种用于水性聚氨酯的多元醇，与实施例1的区别点在于，原料的组分不同，具体组分如下：十二烷二酸8.93kg、己二胺0.37kg、乙醇胺3.7kg、抗氧剂30g
实施例5
一种用于水性聚氨酯的多元醇，与实施例1的区别点在于，原料的组分不同，具体组分如下：十二烷二酸10.78kg、己二胺0.72kg、乙醇胺1.5kg、抗氧剂30g。
实施例6
一种用于水性聚氨酯的多元醇，与实施例1的区别点在于，原料的组分不同，具体组分如下：十二烷二酸8.2kg、己二胺0.8kg、乙醇胺4kg、抗氧剂30g。
实施例7
一种用于水性聚氨酯的多元醇，与实施例1的区别点在于，疏水性二元酸的选择不同，本实施例将十二烷二酸等摩尔更换为十三烷二甲酸。
实施例8
一种用于水性聚氨酯的多元醇，与实施例1的区别点在于，疏水性二元酸的选择不同，本实施例将十二烷二酸等摩尔更换为二聚酸。
实施例9
一种用于水性聚氨酯的多元醇，与实施例1的区别点在于，二元胺的选择不同，本实施例将己二胺等摩尔更换为1H-苯并[D]咪唑-5,6-二胺。
实施例10
一种用于水性聚氨酯的多元醇，与实施例1的区别点在于，二元胺的选择不同，本实施例将己二胺等摩尔更换为2,6-二氨基苯并噁唑。
实施例11
一种用于水性聚氨酯的多元醇，与实施例1的区别点在于，二元胺的选择不同，本实施例将己二胺换为0.5kg1H-苯并[D]咪唑-5,6-二胺+0.5kg2,6-二氨基苯并噁唑。
实施例12
一种用于水性聚氨酯的多元醇，与实施例1的区别点在于，二元胺的选择不同，本实施例将己二胺更换为0.1kg1H-苯并[D]咪唑-5,6-二胺+0.9kg2,6-二氨基苯并噁唑。
实施例13
一种用于水性聚氨酯的多元醇，与实施例1的区别点在于，二元胺的选择不同，本实施例将己二胺更换为0.25kg1H-苯并[D]咪唑-5,6-二胺+0.75kg2,6-二氨基苯并噁唑。
实施例14
一种用于水性聚氨酯的多元醇，与实施例1的区别点在于，二元胺的选择不同，本实施例将己二胺更换为0.125kg1H-苯并[D]咪唑-5,6-二胺+0.875kg2,6-二氨基苯并噁唑。
实施例15
一种用于水性聚氨酯的多元醇，与实施例1的区别点在于，醇胺类化合物的选择不同，本实施例将乙醇胺等摩尔更换为异丙醇胺。
对比例
对比例1
一种用于水性聚氨酯的多元醇，二元酸的选择不同，本申请将十二烷二酸等摩尔更换为己二酸。
应用例和应用对比例
选用实施例1-15和对比例1制得的多元醇按照如下步骤合成水性聚氨酯：
取多元醇和2,2-二羟甲基丙酸、二苯基甲烷二异氰酸酯反应，得到预聚体，向预聚体中加入扩链剂，反应得到水性聚氨酯。各个应用例中多元醇的来源如下表2所示：
表2.多元醇的来源
应用对比例2
一种水性聚氨酯，与应用例1的区别点在于，多元醇的来源不同，本应用对比例将实施例1制得的多元醇等摩尔更换为聚酯多元醇。
应用对比例3
一种水性聚氨酯，与应用例1的区别点在于，多元醇的来源不同，本应用对比例将实施例1制得的多元醇等摩尔更换为聚醚多元醇。
检测方法
在25℃下，将水性聚氨酯倒入聚四氟乙烯做成的尺寸为12cm×8cm的模具中，用玻璃棒抹匀，放置在较平的地方一周左右，使大部分水分在室温下挥发。然后将模具放入烘箱中80℃下干燥一个小时。干燥后取出固化膜，放入干燥皿中备用。按照GB13022-91将膜用裁样机和切刀裁剪成6mm×100mm哑铃状，在25℃下测定水性聚氨酯的拉伸强度，实验仪器为日本岛津公司的AG-Xplus万能电子材料试验机，拉伸速率固定在100mm/min，具体检测结果如下表3所示；
将水性聚氨酯固化膜放在恒温恒湿机里进行水解反应，一周后取出并按照上述方法测试水解后固化膜的拉伸强度，计算其拉伸强度的保留率(拉伸强度保留率＝水解后的拉伸强度/水解前的拉伸强度)，以此表征水性聚氨酯的耐水解性能，拉伸强度的保留率越高，其耐水解性能越好，实验设备采用SPX-150C型恒温恒湿试验箱，测试条件：温度65℃，湿度95％，具体检测结果如下表3所示。
表3.水性聚氨酯的性能测试
由表3可以看出，将本申请实施例制得的多元醇用于水性聚氨酯的制备，制得的水性聚氨酯的拉伸强度≥32.6MPa，力学性能较佳，拉伸强度保留率≥85.9％，拉伸强度保留率较高，耐水解性能较好，解决了水性聚氨酯无法兼具良好的耐水解性能和力学性能的问题。
结合应用例1和应用对比例2-3并结合表3可以看出，应用例1制得的水性聚氨酯的拉伸强度保留率远大于应用对比例2，拉伸强度远大于应用对比例3，这可能是因为：应用对比例2选用的多元醇为聚酯多元醇，聚酯多元醇中含有大量酯键，酯键容易水解；而应用对比例3选用的多元醇为聚醚多元醇，聚醚多元醇中含有大量醚键，醚键本身不易水解，但具有亲水性和吸湿性，大量醚键的存在会导致水性聚氨酯分子间范德华力下降，影响其力学性能。
应用例1选用的多元醇来自于实施例1，实施例1中采用疏水性二元酸和二元胺聚合，再利用醇胺类化合物封端，得到含耐水解的酰胺基和疏水链段的多元醇，疏水链段的存在能够阻挡部分水分子，降低水分子与多元醇分子形成氢键的可能性，利用本申请的多元醇制备水性聚氨酯，能够提高了水性聚氨酯分子内氢键形成的可能性，提高了水性聚氨酯分子的内聚能，从而提高了水性聚氨酯的力学性能，同时向水性聚氨酯内引入大量耐水解的酰胺基，解决了水性聚氨酯无法兼具良好的耐水解性能和力学性能的问题。
本具体实施例仅仅是对本申请的解释，其并不是对本申请的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本申请的权利要求范围内都受到专利法的保护。
Claims (9)
1.一种用于水性聚氨酯的多元醇的制备方法，其特征在于，包括如下步骤：
将疏水性二元酸和二元胺按照质量比为（10-25）:1混合，升温至130-160℃，保温反应1-5h；滴加醇胺类化合物，在120-160℃下滴加2-8h，滴毕，升温至200-250℃，保温反应1-5h，脱水，降温至90-110℃，得到目标产物；所述醇胺类化合物与二元胺的质量比为（2-10）:1。
2.根据权利要求1所述的一种用于水性聚氨酯的多元醇的制备方法，其特征在于：所述疏水性二元酸和二元胺的质量比为（10-15）:1。
3.根据权利要求1所述的一种用于水性聚氨酯的多元醇的制备方法，其特征在于：所述醇胺类化合物与二元胺的质量比为（2-5）:1。
4.根据权利要求1所述的一种用于水性聚氨酯的多元醇的制备方法，其特征在于：所述疏水性二元酸为十二烷二酸、十三烷二甲酸、二聚酸中的一种或多种。
5.根据权利要求4所述的一种用于水性聚氨酯的多元醇的制备方法，其特征在于：所述疏水性二元酸为二聚酸。
6.根据权利要求1所述的一种用于水性聚氨酯的多元醇的制备方法，其特征在于：所述二元胺为己二胺、环己二胺、苯并咪唑二胺和苯并噁唑二胺中的一种或多种。
7.根据权利要求6所述的一种用于水性聚氨酯的多元醇的制备方法，其特征在于：所述二元胺为苯并咪唑二胺和/或苯并噁唑二胺。
8.根据权利要求7所述的一种用于水性聚氨酯的多元醇的制备方法，其特征在于：所述二元胺由苯并咪唑二胺和苯并噁唑二胺按照质量比为1:（3-7）复配制得。
9.根据权利要求1所述的一种用于水性聚氨酯的多元醇的制备方法，其特征在于：所述醇胺为乙醇胺、二乙醇胺、2-氨基-2-甲基-丙醇、异丙醇胺中的一种或多种。
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