CN106118569B - 一种端叔胺基聚丁二烯橡胶增韧的环氧胶粘剂 - Google Patents
一种端叔胺基聚丁二烯橡胶增韧的环氧胶粘剂 Download PDFInfo
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Abstract
一种端叔胺基聚丁二烯橡胶增韧的环氧胶粘剂，本发明组成为100重量份环氧树脂，30～60重量份聚酰胺固化剂和15～70重量份端叔胺基聚丁二烯橡胶。主要性能：拉伸强度20～50MPa，拉断伸长率5～20％，低温玻璃化转变温度‑80～‑60℃，高温玻璃化转变温度90～110℃。增韧剂中聚丁二烯主链可有效增韧改性环氧胶的低温性能，同时利用端叔胺官能团催化、固化环氧基团特点，使胶粘剂高温玻璃化转变温度不降低，增韧改性同时不降低胶粘剂高温使用温度。
Description
技术领域
本发明是一种端叔胺基聚丁二烯橡胶增韧的环氧胶粘剂，属于胶粘剂技术领域。
背景技术
环氧胶粘剂具有优异的粘接性、耐磨性、电绝缘性能和化学稳定性等特点，在生产生活中广泛应用。未增韧的环氧胶粘剂较脆、拉断伸长率低，耐低温性能差，限制了其应用范围。为改善环氧胶粘剂的韧性和耐低温性能，通常在环氧配方中加入各种液体聚丁二烯橡胶作为增韧改性剂，常见的有环氧基聚丁二烯橡胶、胺基聚丁二稀橡胶等。
专利201510112715.0公开了用马来酸酐改性聚丁二烯增韧的环氧胶粘剂，增韧后的环氧胶粘剂具有良好机械性能、化学性能和电性能，常温下钢-钢剪切强度为28MPa；文献(Progress in Organic Coatings，2013(76)：286-292)报道了使用端环氧基聚丁二烯橡胶作为增韧剂，以脂环族多胺为固化剂制备的环氧胶粘剂，固化条件为80℃3小时，120℃1小时，加入7.5份增韧剂后，环氧胶粘剂伸长率增加至14％，但高温玻璃化转变温度从100℃下降至93℃。文献(Journal of Applied Polymer Science，2005(96)：2446-2453)报道了以伯胺苯基聚丁二烯橡胶为增韧剂、三乙烯四胺为固化剂制备的环氧胶粘剂，固化条件为25℃24小时，50℃2小时，当使用15质量份增韧剂时，环氧胶粘剂的冲击强度从未增韧的90J/m2提高至360J/m2，但高温玻璃化转变温度从130℃下降至114℃。液体聚丁二烯橡胶具有良好的链段柔顺性和优异耐低温性能，用来改性环氧胶时，可以明显改善环氧胶粘剂的韧性和耐低温性能；但增韧改性同时，会降低环氧树脂的固化交联密度，使其高温玻璃化转变温度下降，影响胶粘剂的高温使用温度。
发明内容
本发明是一种端叔胺基聚丁二烯橡胶增韧的环氧胶粘剂。本发明的特点：端叔胺基聚丁二烯橡胶作为增韧剂，增韧剂主链为聚丁二烯结构，聚丁二烯主链可有效增韧改性环氧胶的低温性能；增韧剂端基为叔胺官能团，对环氧基团起着催化、固化的双重作用，能有效提高环氧树脂的交联密度，使得增韧环氧胶粘剂的高温玻璃化转变温度不降低，增韧改性同时不降低胶粘剂高温使用温度。
本发明组成：100重量份双酚A型或双酚F型环氧树脂，30～60重量份聚酰胺固化剂和15～70重量份端叔胺基聚丁二烯橡胶。各组份混合均匀后固化，室温反应4～7天或50℃反应24小时。本发明的主要性能：拉伸强度20～50MPa，拉断伸长率5～20％，低温玻璃化转变温度-80～-60℃，高温玻璃化转变温度90～110℃。
其中端叔胺基聚丁二烯橡胶的制备：100重量份端羟基聚丁二烯(羟值为0.25～1.50mmol/g)，10～35重量份异佛尔酮二异氰酸酯，0.01～0.1重量份辛酸亚锡或二月桂酸二丁基锡为催化剂，搅拌均匀，氮气条件下60±5℃反应36～48小时(依据红外光谱法监测2270cm-1处的异氰酸酯基吸收峰峰面积下降一半为准)，加入5～17重量份3-二甲基氨基-1-丙醇，室温反应24小时得到端叔胺基聚丁二烯橡胶。
具体实施例
实施例A
端叔胺基聚丁二烯橡胶A的制备：100g端羟基聚丁二烯(羟值为1.36mmol/g)，加入31.7g异佛尔酮二异氰酸酯，加入0.04g二月桂酸二丁基锡，混合均匀后在氮气条件下60℃反应48小时(依据红外光谱法监测2270cm-1处的异氰酸酯基吸收峰峰面积下降一半)，加入14.7g 3-二甲基氨基-1-丙醇，混合均匀23℃反应24小时，得到端叔胺基聚丁二烯橡胶A。
实施例1，端叔胺基聚丁二烯橡胶增韧的环氧胶粘剂：100g双酚A型环氧树脂，43g聚酰胺651固化剂，40g端叔胺基聚丁二烯橡胶A，混合均匀后固化，23℃反应7天。环氧胶粘剂主要性能：拉伸强度34.4MPa，拉断伸长率11.6％，低温玻璃化转变温度-74.3℃，高温玻璃化转变温度97.4℃。
实施例2，端叔胺基聚丁二烯橡胶增韧的环氧胶粘剂：100g双酚A型环氧树脂，43g聚酰胺651固化剂，60g端叔胺基聚丁二烯橡胶A，混合均匀后固化，23℃反应7天。环氧胶粘剂主要性能：拉伸强度28.5MPa，拉断伸长率13.4％，低温玻璃化转变温度-65.9℃，高温玻璃化转变温度102.0℃。
空白对比：100g双酚A型环氧树脂，43g聚酰胺651固化剂制备的环氧胶粘剂，其拉伸强度55.4MPa，拉断伸长率2.8％，无低温玻璃化转变温度，高温玻璃化转变温度88.0℃。
实施例B
端叔胺基聚丁二烯橡胶B的制备：100g端羟基聚丁二烯(羟值为0.75mmol/g)，加入17.5g异佛尔酮二异氰酸酯，加入0.04g二月桂酸二丁基锡，混合均匀后氮气条件下60℃反应48小时(依据红外光谱法监测2270cm-1处的异氰酸酯基吸收峰峰面积下降一半)，加入8.1g 3-二甲基氨基-1-丙醇，混合均匀室温反应24小时，得到端叔胺基聚丁二烯橡胶B。
实施例3，端叔胺基聚丁二烯橡胶增韧的环氧胶粘剂：100g双酚F环氧树脂，47.4g聚酰胺651固化剂，40g端叔胺基聚丁二烯橡胶B，混合均匀后固化，50℃反应24小时。环氧胶粘剂主要性能：拉伸强度42.2MPa，拉断伸长率8.9％，低温玻璃化转变温度-79.7℃，高温玻璃化转变温度93.5℃。
空白对比：100g双酚F环氧树脂和47.4g聚酰胺651制备的未增韧粘合剂，其拉伸强度为54.7MPa，拉断伸长率3.0％，无低温玻璃化转变温度，高温玻璃化转变温度86.2℃。
Claims (2)
1.一种端叔胺基聚丁二烯橡胶增韧的环氧胶粘剂，由100重量份双酚A型或双酚F型环氧树脂和30～60重量份聚酰胺固化剂组成，其特征是还有15～70重量份端叔胺基聚丁二烯橡胶；各组份混合均匀后固化，室温反应4～7天或50℃反应24小时。
2.据权利要求1所述的环氧胶粘剂，其特征是端叔胺基聚丁二烯橡胶是由100重量份羟值为0.25～1.5mmol/g的端羟基聚丁二烯橡胶、10～35重量份异佛尔酮二异氰酸酯、0.01～0.1重量份辛酸亚锡或二月桂酸二丁基锡和5～17重量份3-二甲基氨基-1-丙醇反应制得的产物。
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| CN104144959A (zh) * | 2012-03-23 | 2014-11-12 | 陶氏环球技术有限责任公司 | 应力耐久性提高的耐碰撞粘合剂 |
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| CN1376737A (zh) * | 2001-03-27 | 2002-10-30 | 北京航空材料研究院 | 由橡胶/粘土复合增韧剂增韧的环氧树脂及其制备方法 |
| CN104144959A (zh) * | 2012-03-23 | 2014-11-12 | 陶氏环球技术有限责任公司 | 应力耐久性提高的耐碰撞粘合剂 |
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