CN117700683A - 一种耐低温柔韧型单组份聚氨酯树脂及其制备方法 - Google Patents
一种耐低温柔韧型单组份聚氨酯树脂及其制备方法 Download PDFInfo
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Abstract
一种耐低温柔韧型单组份聚氨酯树脂及其制备方法，所述耐低温柔韧型单组份聚氨酯树脂包括以下重量份的组分：异氰酸酯8‑13份；大分子多元醇47‑59份；加成改性体15‑25份；小分子扩链剂0.5‑1.5份；催化剂0.05‑0.3份；溶剂45‑55份。本发明引入了加成改性体，所述加成改性体由端羟基聚丁二烯、端羟基硅油和二甲基二异氰酸酯通过特定的条件加成聚合反应而成，所述加成改性体有助于提高产物的耐候性、低温柔韧性及低温高弹性能，与其他组分相互作用使耐低温柔韧型单组份聚氨酯树脂具备优良的耐候性、低温柔韧性及低温高弹性能。
Description
技术领域
本发明属于胶粘剂技术领域，尤其涉及一种耐低温柔韧型单组份聚氨酯树脂及其制备方法。
背景技术
耐低温柔韧型单组份聚氨酯树脂是由异氰酸酯封端的高分子量聚氨酯和溶剂组成的一类树脂。树脂涂覆在用胶点，通过与水分反应，粘接固定固体件，本用胶点的传统的聚氨酯粘合剂Tg点高于25℃，在低温环境下发硬发脆，造成粘接件开裂失效。本产品适用与低温环境气候，在零度以下依旧具备优异的韧性和粘弹性。
在传统单组分聚氨酯树脂的基础上，通过合成工艺优化和配方优化，通过引入双键基团和硅氧键基团进一步提高耐候性、低温柔韧性及低温高弹性能，有助于降低生产过程中的故障率，提高产品低温可靠性。
发明内容
本发明针对上述的现有技术存在的不足，提供一种耐低温柔韧型单组份聚氨酯树脂及其制备方法。
本发明的具体技术方案如下：
本发明第一个目的在于提供一种耐低温柔韧型单组份聚氨酯树脂，包括以下重量份的组分：
异氰酸酯8-13份；大分子多元醇47-59份；加成改性体15-25份；小分子扩链剂0.5-1.5份；催化剂0.05-0.3份；溶剂42-50份。
所述加成改性体由所述加成改性体由端羟基聚丁二烯、端羟基硅油和二甲基二异氰酸酯通过特定的条件加成聚合反应而成。
所述加成改性体有助于提高产物的耐候性、低温柔韧性及低温高弹性能。
进一步地，所述端羟基聚丁二烯：端羟基硅油：二甲基二异氰酸酯的质量比为（3.9-4.3）：（4-5）：2。
进一步地，所述加成改性体的制备方法，包括如下步骤：
S1、将18-22份羟基聚丁二烯、20-24份端羟基硅油脱水后溶于26-32份乙酸乙酯溶剂中，升温至35-40℃
S2、将9-11份二甲基二异氰酸酯投入反应器中，保持80-85℃恒温加热、冷凝回流条件下搅拌反应1.5-2h，得中间反应液；
S3、将中间反应液降温至75-80℃，继续加入17-21份乙酸乙酯溶剂，冷凝回流条件下搅拌反应1.5-2h，制得端NCO基的加成改性体。
所述的异氰酸酯为2，4-甲苯二异氰酸酯、2，6-甲苯二异氰酸酯、碳化二亚胺改性二甲基二异氰酸酯中的至少一种。
进一步地，所述的大分子多元醇为聚己二酸乙二醇脂二元醇、聚己二酸-丁二醇脂二元醇、聚己二酸-1、6己二醇脂二元醇、聚己二酸-二乙二醇-2，2-二羟甲基丁醇脂二元醇、聚四氢呋喃二元醇中的至少一种。
进一步地，所述的小分子扩链剂为1，4-丁二醇、三羟甲基丙烷中至少一种。
进一步地，所述的催化剂为二丁基二月桂酸锡、有机铋、有机锌中的至少一种。
进一步地，所述溶剂为乙酸乙酯。
本发明的目的之二是提供一种上述耐低温柔韧型单组份聚氨酯树脂的制备方法，包括如下步骤：
D1将大分子多元醇47-59份、15-25份加成改性体投入四口烧瓶中混合，再加入1.5-2份异氰酸酯，75-80℃搅拌反应1-2h，加入10-12份溶剂稀释，获得软链段预聚体A；
D2将步骤D1制得的软链段预聚体A降温至40-50℃，小分子扩链剂0.5-1.5份、6-11.5份异氰酸酯、催化剂0.05-0.3份和30-40份溶剂，升温至75-80℃搅拌反应1.5-3h，制备得到目标产物。
本发明的有益效果为：
本发明引入了加成改性体，所述加成改性体由端羟基聚丁二烯、端羟基硅油和二甲基二异氰酸酯通过特定的条件加成聚合反应而成，所述加成改性体有助于提高产物的耐候性、低温柔韧性及低温高弹性能，与其他组分相互作用使耐低温柔韧型单组份聚氨酯树脂具备优良的耐候性、低温柔韧性及低温高弹性能。
实施方式
以下结合实例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
本发明中所使用的部分原料如下所示：
碳化二亚胺改性二甲基二异氰酸酯（液化MDI）：工业级，万华化学集团股份有限公司；
聚己二酸-1、6己二醇脂二元醇（CMA-2066）：官能度为2，分子量2000g/mol，华大化学有限公司；
聚己二酸乙二醇脂二元醇（T-3024）：工业级，华大化学有限公司
聚四氢呋喃二元醇（PTMG-2000）：工业级，巴斯夫集团
1，4-丁二醇：工业级，国药化学有限公司；
端羟基硅油：工业级，梓萌化工有限公司；
端羟基聚丁二烯；工业级，天元航材；
有机铋： MB-20，BYK化学。
实施例1
一种耐低温柔韧型单组份聚氨酯树脂的制备方法，包括如下步骤：
1、加成改性体1的制备
S1、将4.09g端羟基聚丁二烯、4.6g端羟基硅油脱水后溶于6g乙酸乙酯溶剂中，升温至35-40℃，混合15min。
S2、将2g碳化二亚胺改性二甲基二异氰酸酯投入反应器中，保持80-85℃恒温加热、冷凝回流条件下搅拌反应1.5-2h，得中间反应液；
S3、将中间反应液降温至75-80℃，继续加入4g的乙酸乙酯溶剂，冷凝回流条件下搅拌反应1.5-2h，制得端NCO基的加成改性体1。
2、耐低温柔韧型单组份聚氨酯树脂的制备
D1将4.09gT-3024、35gCMA-2066、11.68gPTMG-2000、20.69g加成改性体1投入四口烧瓶中混合，再加入2.0g液化MDI，75-80℃搅拌反应1-2h，加入12g溶剂稀释，获得软链段预聚体A；
D2将步骤D1制得的软链段预聚体A降温至40-50℃，依次加入0.9g1、4丁二醇、7.9g液化MDI、0.05g催化剂和33.8g份溶剂，升温至75-80℃搅拌反应1.5-3h，制备得到目标产物1。
实施例2
1、加成改性体2的制备
S1、将3.9g羟基聚丁二烯、5g端羟基硅油脱水后溶于6g乙酸乙酯溶剂中，升温至35-40℃，混合15min。
S2、将2g碳化二亚胺改性二甲基二异氰酸酯投入反应器中，保持80-85℃恒温加热、冷凝回流条件下搅拌反应1.5-2h，得中间反应液；
S3、将中间反应液降温至75-80℃，继续加入4g的乙酸乙酯溶剂，冷凝回流条件下搅拌反应1.5-2h，制得端NCO基的加成改性体2。
2、耐低温柔韧型单组份聚氨酯树脂的制备
D1将4.09gT-3024、35gCMA-2066、11.68gPTMG-2000、20.9g加成改性体1投入四口烧瓶中混合，再加入2g液化MDI，75-80℃搅拌反应1-2h，加入12g溶剂稀释，获得软链段预聚体A；
D2将步骤D1制得的软链段预聚体A降温至40-50℃，依次加入0.9g1、4丁二醇、7.9g液化MDI、0.05g催化剂和33.8g份溶剂，升温至75-80℃搅拌反应1.5-3h，制备得到目标产物2。
实施例3
1、加成改性体3的制备
S1、将4.3g羟基聚丁二烯、4g端羟基硅油脱水后溶于6g乙酸乙酯溶剂中，升温至35-40℃，混合15min。
S2、将2g碳化二亚胺改性二甲基二异氰酸酯投入反应器中，保持80-85℃恒温加热、冷凝回流条件下搅拌反应1.5-2h，得中间反应液；
S3、将中间反应液降温至75-80℃，继续加入4g的乙酸乙酯溶剂，冷凝回流条件下搅拌反应1.5-2h，制得端NCO基的加成改性体3。
2、耐低温柔韧型单组份聚氨酯树脂的制备
D1将4.09gT-3024、35gCMA-2066、11.68gPTMG-2000、20.3g加成改性体1投入四口烧瓶中混合，再加入2.g液化MDI，75-80℃搅拌反应1-2h，加入12g溶剂稀释，获得软链段预聚体A；
D2将步骤D1制得的软链段预聚体A降温至40-50℃，依次加入0.9g1、4丁二醇、7.9g液化MDI、0.05g催化剂和33.8g份溶剂，升温至75-80℃搅拌反应1.5-3h，制备得到目标产物3。
对比例1
一种耐低温柔韧型单组份聚氨酯树脂的制备方法，包括如下步骤：
1、耐低温柔韧型单组份聚氨酯树脂的制备
D1将4.09gT-3024、35gCMA-2066、11.68gPTMG-2000、4.09g端羟基聚丁二烯、4.6g端羟基硅油四口烧瓶中混合，再加入4.2g液化MDI，75-80℃搅拌反应1-2h，加入24.01g溶剂稀释，获得软链段预聚体A；
D2将步骤D1制得的软链段预聚体A降温至40-50℃，依次加入0.9g1、4丁二醇、7.9g液化MDI、0.05g催化剂和33.8g份溶剂，升温至75-80℃搅拌反应1.5-3h，制备得到目标产物4。
对比例1相较于实施例1，端羟基聚丁二烯、端羟基硅油直接加入合成反应，而不是经过端羟基聚丁二烯、端羟基硅油、液化MDI预加成聚合反应。
对比例2
一种耐低温柔韧型单组份聚氨酯树脂的制备方法，包括如下步骤：
1、耐低温柔韧型单组份聚氨酯树脂的制备
D1将8.18gT-3024、35gCMA-2066、11.68gPTMG-2000、4.6g端羟基硅油于四口烧瓶中混合，再加入4.2g液化MDI，75-80℃搅拌反应1-2h，加入24.01g溶剂稀释，获得软链段预聚体A；
D2将步骤D1制得的软链段预聚体A降温至40-50℃，依次加入0.9g1、4丁二醇、7.9g液化MDI、0.05g催化剂和33.8g份溶剂，升温至75-80℃搅拌反应1.5-3h，制备得到目标产物5。
对比例2相较于对比例1，仅使用T-3024取代端羟基聚丁二烯。
对比例3
一种耐低温柔韧型单组份聚氨酯树脂的制备方法，包括如下步骤：
1、耐低温柔韧型单组份聚氨酯树脂的制备
D1将17.09gT-3024、35gCMA-2066、11.68gPTMG-2000、4.09g端羟基聚丁二烯、四口烧瓶中混合，再加入4.2g液化MDI，75-80℃搅拌反应1-2h，加入24.01g溶剂稀释，获得软链段预聚体A；
D2将步骤D1制得的软链段预聚体A降温至40-50℃，依次加入0.9g1、4丁二醇、7.9g液化MDI、0.05g催化剂和33.8g份溶剂，升温至75-80℃搅拌反应1.5-3h，制备得到目标产物6。
对比例3相较于对比例1，仅使用T-3024等摩尔量取代端羟基硅油。
测试
拉伸测试：将实施例以及对比例中制备得到的树脂在平整干净的聚四氟乙烯板上流延成膜，室温静置2d干燥成膜，再在60℃干燥箱继续干燥24h，膜厚度2mm。将胶膜裁剪为哑铃样，
测试标准采用国标GB 13022-1991测试方法测试，测试环境箱温度为－15℃
剥离强度测试: GB/T 2792-2014
测试结果如表1所示：
表1 实施例与对比例的测试数据表
| 名称 | 实施例1 | 实施例2 | 实施例3 | 对比例1 | 对比例2 | 对比例3 |
| 固含量% | 56.3 | 56.1 | 56.5 | 56.4 | 56.7 | 66.1 |
| 拉伸强度 | 11.43 | 10.76 | 10.97 | 7.43 | 6.58 | 8.65 |
| 伸长率 | 280 | 238 | 252 | 124 | 159 | 76 |
| 剥离强度 | 72 | 68 | 65 | 43 | 47 | 29 |
| 硬度/邵A | 35 | 35 | 35 | 37 | 34 | 38 |
如表1测试结果可以看出，本发明实施例中的耐低温柔韧型单组份聚氨酯树脂具有优良的低温柔韧性及低温高弹性能。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，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 (10)
1.一种耐低温柔韧型单组份聚氨酯树脂，其特征在于，包括以下重量份的组分：
异氰酸酯8-13份；大分子多元醇47-59份；加成改性体15-25份；小分子扩链剂0.5-1.5份；催化剂0.05-0.3份；溶剂 42-50份。
2.所述加成改性体由所述加成改性体由端羟基聚丁二烯、端羟基硅油和二甲基二异氰酸酯通过特定的条件加成聚合反应而成。
3.根据权利要求1所述的低温柔韧型单组份聚氨酯树脂，其特征在于，所述端羟基聚丁二烯：端羟基硅油：二甲基二异氰酸酯的质量比为（3.9-4.3）：（4-5）：2。
4.根据权利要求2所述的耐低温柔韧型单组份聚氨酯树脂，其特征在于，所述加成改性体的制备方法，包括如下步骤：
S1、将端羟基聚丁二烯、端羟基硅油脱水后溶于乙酸乙酯溶剂中，升温至35-40℃
S2、将二甲基二异氰酸酯投入反应器中，保持80-85℃恒温加热、冷凝回流条件下搅拌反应1.5-2h，得中间反应液；
S3、将中间反应液降温至75-80℃，继续加入乙酸乙酯溶剂，冷凝回流条件下搅拌反应1.5-2h，制得端NCO基的加成改性体。
5.根据权利要求1所述的耐低温柔韧型单组份聚氨酯树脂，其特征在于，所述的异氰酸酯为2，4-甲苯二异氰酸酯、2，6-甲苯二异氰酸酯、碳化二亚胺改性二甲基二异氰酸酯中的至少一种。
6.根据权利要求1所述的耐低温柔韧型单组份聚氨酯树脂，其特征在于，所述的大分子多元醇为聚己二酸乙二醇脂二元醇、聚己二酸-丁二醇脂二元醇、聚己二酸-1、6己二醇脂二元醇、聚己二酸-二乙二醇-2，2-二羟甲基丁醇脂二元醇、聚四氢呋喃二元醇中的至少一种。
7.根据权利要求1所述的耐低温柔韧型单组份聚氨酯树脂，其特征在于，所述的小分子扩链剂为1，4-丁二醇、三羟甲基丙烷中至少一种。
8.根据权利要求1所述的耐低温柔韧型单组份聚氨酯树脂，其特征在于，所述的催化剂为二丁基二月桂酸锡、有机铋、有机锌中的至少一种。
9.根据权利要求1所述的耐低温柔韧型单组份聚氨酯树脂，其特征在于，所述溶剂为乙酸乙酯。
10.如权利要求1-8任一项所述的耐低温柔韧型单组份聚氨酯树脂的制备方法，包括如下步骤：
D1将大分子多元醇47-59份、15-25份加成改性体投入四口烧瓶中混合，再加入1.5-2份异氰酸酯，75-80℃搅拌反应1-2h，加入10-12份溶剂稀释，获得软链段预聚体A；
D2将步骤D1制得的软链段预聚体A降温至40-50℃，小分子扩链剂0.5-1.5份、6-11.5份异氰酸酯、催化剂0.05-0.3份和30-40份溶剂，升温至75-80℃搅拌反应1.5-3h，制备得到目标产物。
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