CN113667095B - 一种泡沫塑料用粘接助剂、制备方法及应用 - Google Patents

一种泡沫塑料用粘接助剂、制备方法及应用 Download PDF

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CN113667095B
CN113667095B CN202111033120.8A CN202111033120A CN113667095B CN 113667095 B CN113667095 B CN 113667095B CN 202111033120 A CN202111033120 A CN 202111033120A CN 113667095 B CN113667095 B CN 113667095B
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张勇
余启勇
潘广镇
刘光亚
吕多军
龚祥明
刘辉
赵严
吴恒
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Gongyi Van Research Yihui Composite Material Co Ltd
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Abstract

本发明公开了一种泡沫塑料用粘接助剂、制备方法及应用，该粘接助剂由由小分子多元胺改性的异氰酸酯与单氨基硅烷偶联剂反应制得；制备方法为：将小分子多元胺溶解在有机溶剂中形成稀释液；将稀释液在20℃以下的惰性氛围下滴加到异氰酸酯中搅拌反应30‑60min，接着升温到60‑70℃，搅拌30‑60min，反应结束，降温至20℃以下，继续将单氨基硅烷偶联剂分批次加入到混合液中，搅拌反应20‑60 min，接着升温至60‑70℃，搅拌反应1‑2 h即得到所述的泡沫塑料用粘接助剂。该粘接助剂使泡沫塑料的粘接性能更加稳定，且一个粘接助剂分子中较多的硅氧烷结构，因此，其在改性使用时用最少的添加量即能获得最佳的性能，降低了改性成本。

Description

一种泡沫塑料用粘接助剂、制备方法及应用
技术领域
本发明属于粘接助剂的制备技术领域，具体涉及一种泡沫塑料用粘接助剂、制备方法及应用。
背景技术
一般地，现有的泡沫塑料与某些不含活泼氢的材料如玻璃、铝等粘接性能较差，市场一般采用直接添加偶联剂的方法，或者预先对基材进行处理的方式来改善。但由于直接加入硅烷偶联剂时，硅烷偶联剂的分子量比较小且每个分子含有的硅氧烷最多为6个，如果要达到较好的粘接作用，往往需要加入较多量的硅烷偶联剂，改性成本较高。如果采用处理剂对基材进行预先处理的方式，往往会导致现场操作比较麻烦，不便于施工。
发明内容
本发明所要解决的技术问题是：克服现有技术中存在的不足，提供一种泡沫塑料用粘接助剂、制备方法及应用。
本发明为解决技术问题所采取的技术方案如下：
一种泡沫塑料用粘接助剂，所述泡沫塑料用粘接助剂由小分子多元胺改性的异氰酸酯与单氨基硅烷偶联剂反应制得。
较好地，所述小分子多元胺、异氰酸酯、单氨基硅烷偶联剂的摩尔比为1：（3-5）：（2-4）。
上述泡沫塑料用粘接助剂的制备方法，所述制备方法为：
（1）将小分子多元胺溶解在有机溶剂中形成稀释液；
（2）将步骤（1）中的稀释液在20℃以下的惰性氛围下滴加到异氰酸酯中搅拌反应30-60 min，接着升温至60-70℃，搅拌30min-60 min；
（3）待步骤（2）反应结束，降温至20 ℃以下，继续将硅烷偶联剂分批次加入步骤（2）的混合液中，搅拌反应20-60 min，接着升温至60-70℃，搅拌反应1-2 h即得到所述的泡沫塑料用粘接助剂。
较好地，所述小分子多元胺与有机溶剂质量比为1：（1-2）。
较好地，所述小分子多元胺为二乙烯三胺、三乙烯四胺、四乙烯五胺中的一种或多种。
较好地，所述单氨基硅烷偶联剂为双（3-三甲氧基硅基丙基）胺、γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、N-苯基-γ-氨丙基三甲氧基硅烷中的一种或多种。
较好地，所述异氰酸酯为1,6-已二异氰酸酯（HDI）、异氟尔酮二异氰酸酯（IPDI）、甲苯-2、4-二异氰酸酯(TDI)、苯二亚甲基二异氰酸酯（XDI）中的一种或多种。
较好地，所述有机溶剂为乙酸丁酯、乙酸乙酯、丁酮、甲苯或碳酸二甲酯。
上述泡沫塑料用粘接助剂在泡沫塑料中的应用，所述泡沫塑料用粘接助剂添加量占泡沫塑料总重的0.5%-3%。
较好地，所述泡沫塑料为聚氨酯泡沫、酚醛泡沫、环氧树脂泡沫或不饱和聚酯树脂泡沫。
本发明的积极有益效果如下：
本发明通过使用小分子多元胺、异氰酸酯、单氨基硅烷偶联剂反应制备出分子中含有异氰酸酯基、大量硅氧烷基、大量脲基的粘接助剂，其中大量的脲基由于极性高、内聚力强、具有良好的附着性的特点，硅氧烷基具有较好的粘接性能，硅氧烷基越多，粘接性能越好，因此，本发明的粘接助剂本身具有优异的粘接性能。
同时，采用小分子多元胺对异氰酸酯进行改性时，改性后的产物中含有大量脲基，且分子结构稳定。
用于改性泡沫塑料的粘接性能时，通过分子中的异氰酸酯基与泡沫塑料原液中的活泼氢反应形成泡沫主链的一部分，进而泡沫塑料主链中含有粘接助剂的分子结构，因此，该粘接助剂使泡沫塑料的粘接性能更加稳定，且一个粘接助剂分子中较多的硅氧烷结构，因此，其在改性使用时用最少的添加量即能获得最佳的性能，降低了改性成本。
具体实施方式
下面结合具体实施例对本发明的技术方案做进一步详细、清楚地描述，但本发明的保护范围并不局限于此。
实施例1：
一种泡沫塑料用粘接助剂的制备方法，具体方法如下：
（1）将二乙烯三胺在反应前做脱水处理，并在低于20℃环境下溶解在乙酸丁酯中形成稀释液；
（2）将步骤（1）中的稀释液在惰性氛围下滴加到1,6-已二异氰酸酯（HDI）中，滴加温度低于20 ℃，滴加反应20 min后，升高反应温度至60 ℃，继续搅拌反应30 min，搅拌转速为300 r/min；
（3）待步骤（2）反应结束，再降温至20 ℃以下，继续将双（3-三甲氧基硅基丙基）胺分批次加入步骤（2）的混合液中，保持转速不变搅拌反应25 min，接着升温至60 ℃，继续搅拌反应1 h即得到所述的粘接助剂。
其中，二乙烯三胺、1,6-已二异氰酸酯（HDI）、双（3-三甲氧基硅基丙基）胺的摩尔比为1：3：2；二乙烯三胺与乙酸丁酯的质量比为1：1。
实施例2
一种泡沫塑料用粘接助剂的制备方法，制备方法为：
（1）将三乙烯四胺在反应前做脱水处理，并在低于20℃环境下溶解在乙酸乙酯中形成稀释液；
（2）将步骤（1）中的稀释液在惰性氛围下滴加到异氟尔酮二异氰酸酯（IPDI）中，滴加温度低于20℃，滴加反应30 min后，升高反应温度至65 ℃；继续搅拌反应40 min，搅拌转速为200 r/min
（3）待步骤（2）反应结束，降温至20℃以下，继续将γ-氨丙基三乙氧基硅烷分批次加入步骤（2）的混合液中，保持转速不变搅拌反应30 min，接着升温至65℃，搅拌反应1.5 h即得到所述的粘接助剂。
其中，三乙烯四胺、IPDI、γ-氨丙基三乙氧基硅烷的摩尔比为1：4：3；三乙烯四胺与乙酸乙酯的质量比为1：1。
实施例3
一种泡沫塑料用粘接助剂的制备方法，制备方法为：
（1）将四乙烯五胺反应前做脱水处理，并在低于20℃环境下溶解在甲苯中形成稀释液；
（2）将步骤（1）中的稀释液在惰性氛围下滴加到甲苯-2、4-二异氰酸酯(TDI) 滴加温度低于20℃，滴加反应40 min后，升高反应温度至70℃，继续搅拌反应50 min；
（3）待步骤（2）反应结束，降温至20℃以下，继续将N-苯基-γ-氨丙基三甲氧基硅烷分批次加入步骤（2）的混合液中，保持转速不变搅拌反应45 min，接着升温至70 ℃，搅拌反应2 h即得到所述的粘接助剂。
其中，四乙烯五胺、甲苯-2、4-二异氰酸酯(TDI)、N-苯基-γ-氨丙基三甲氧基硅烷的摩尔比为1：5：4；四乙烯五胺与甲苯的质量比为1：1.5。
实施例4
一种泡沫塑料用粘接助剂的制备方法，制备方法为：
（1）将二乙烯三胺在反应前做脱水处理，并在低于20℃环境下溶解在碳酸二甲酯中形成稀释液；
（2）将步骤（1）中的稀释液在惰性氛围下滴加到苯二亚甲基二异氰酸酯(XDI)中，滴加温度低于20℃，滴加反应40min后，升高反应温度至70℃，搅拌反应60min，搅拌转速为300r/min；
（3）待步骤（2）反应结束，降温至20℃以下，继续将γ-氨丙基三甲氧基硅烷分批次加入步骤（2）的混合液中，保持转速不变搅拌反应60 min，接着升温至70℃，搅拌反应2 h即得到所述的粘接助剂。
其中，二乙烯三胺、XDI、γ-氨丙基三甲氧基硅烷的摩尔比为1：3：2；二乙烯三胺与碳酸二甲酯的质量比为1：1。
实施例5
一种泡沫塑料用粘接助剂的制备方法，制备方法为：
（1）将二乙烯三胺在反应前做脱水处理，并在低于20℃环境下溶解在丁酮中形成稀释液；
（2）将步骤（1）中的稀释液在惰性氛围下滴加到异氟尔酮二异氰酸酯（IPDI）中，滴加温度低于20℃，滴加反应50 min后，升高反应温度为70 ℃，搅拌反应60 min，搅拌转速为400r/min；
（3）待步骤（2）反应结束，降温至20℃以下，继续将双（3-三甲氧基硅基丙基）胺分批次加入步骤（2）的混合液中，搅拌反应60 min，接着升温至70℃，保持转速不变搅拌反应2h即得到所述的粘接助剂。
其中，二乙烯三胺、IPDI、双（3-三甲氧基硅基丙基）胺的摩尔比为1：3：2；二乙烯三胺与丁酮的质量比为1：2。
应用案例1：
将上述实施例1-5中制备的粘接助剂按照如下的添加方法分别应用在聚氨酯泡沫中，具体方法为：
（1）将聚醚、泡沫稳定剂、催化剂以及发泡剂按照质量比为96.0：4：0.02： 0.2混合均匀制成A组分；所述聚醚为YD304，所述催化剂为二月酸酐二丁基锡，所述发泡剂为水；
（2）将粘接助剂与含异氰酸酯的聚合物混合均匀，并将混合物中的溶剂除去最终制成B组分，其中粘接助剂与含异氰酸酯的聚合物的质量比为5.0：95.0；
（3）将A组份与B组份按照重量比1:1的比例混合均匀发泡制成聚氨酯泡沫。
将使用实施例1-5制备的粘接助剂按照上述应用案例1的改性方法改性聚氨酯泡沫的应用案例分别标记为应用案例1-1；应用案例1-2；应用案例1-3；应用案例1-4；应用案例1-5。
应用案例2：
上述实施例1制备的粘接助剂对酚醛树脂泡沫的改性，改性方法具体如下：将可发性酚醛树脂，在正戊烷作发泡剂，聚山梨酸酯80作乳化剂下，与实施例1制备的粘接助剂按质量比为100:3:3:2.5的比例在常温条件下混合均匀，并在90℃的条件下保温2小时，再继续升温至170℃保温4小时，最终发泡成型。
应用案例3：
上述实施例1制备的粘接助剂对环氧树脂泡沫的改性，改性方法具体如下：
将E51型环氧树脂，在双氰胺作固化剂，UR300作脲类促进剂，Expancel 461DU40作发泡微球下，与实施例1制备的粘接助剂按质量比为100:11:3:5：2.5的比例在常温条件下混合均匀，在150℃的条件下保温50min，最终发泡成型。
应用案例4：
上述实施例1制备的粘接助剂对不饱和聚酯树脂泡沫的改性，改性方法具体如下：
将196型不饱和聚酯树脂，在过氧化二苯甲酰作引发剂，Expancel 461DU40作发泡微球下，与实施例1制备的粘接助剂按质量比为100:0.4:4：2.5的比例在常温条件下混合均匀，在125℃的条件下保温50min，最终发泡成型。
对比例1：
本实施例作为应用案例1的对比例，与应用案例1的区别在于：聚氨酯泡沫B组分中未添加实施例1-5制备的粘接助剂，即B组分为100份含异氰酸酯聚合物；其它均同应用案例1。
对比例2：
本实施例作为应用案例2的对比例，与应用案例2的区别在于：酚醛树脂泡沫原料组分中未添加实施例1制备的粘接助剂；其它均同应用案例2。
对比例3：
本实施例作为应用案例3的对比例，与应用案例3的区别在于：环氧树脂泡沫原料组分中未添加实施例1制备的粘接助剂；其它均同应用案例3。
对比例4：
本实施例作为应用案例4的对比例，与应用案例4的区别在于：不饱和聚酯树脂泡沫原料组分中未添加实施例1制备的粘接助剂；其它均同应用案例4。
分别对上述应用案例1-4中制备的泡沫塑料以及对比例1-4制备的泡沫塑料粘接性能进行测试，粘接性能结果如表1和表2。
表1
粘接强度（MPa） 破坏形式
应用案例1-1 7.3 3%表面破坏
应用案例1-2 7.7 2%表面破坏
应用案例1-3 7.2 3%表面破坏
应用案例1-4 7.9 4%表面破坏
应用案例1-5 7.5 3%表面破坏
应用案例2 8.7 3%表面破坏
应用案例3 6.9 2%表面破坏
应用案例4 6.4 4%表面破坏
表2
粘接强度（MPa） 破坏形式
对比例1 2.3 70%表面破坏
对比例2 3.2 69%表面破坏
对比例3 2.0 67%表面破坏
对比例4 1.8 70%表面破坏
由表1和表2可知：应用案例1-4中制备的改性的泡沫塑料与对应地未经实施例1-5制备的粘接助剂改性的泡沫塑料相比，粘接性能被大幅度提升，粘接强度是未改性时的2-3倍，基材表面破坏程度大幅降低，达到改性的目的。

Claims (8)

1.一种泡沫塑料用粘接助剂，其特征在于，所述粘接助剂由小分子多元胺改性的异氰酸酯与单氨基硅烷偶联剂反应制得；制备得到的粘接助剂分子中含有异氰酸酯基、硅氧烷基和脲基；
所述小分子多元胺为二乙烯三胺、三乙烯四胺、四乙烯五胺中的一种或多种；
所述小分子多元胺、异氰酸酯、单氨基硅烷偶联剂的摩尔比为1：（3-5）：（2-4）。
2.一种权利要求1所述的泡沫塑料用粘接助剂的制备方法，其特征在于，所述制备方法为：
将小分子多元胺溶解在有机溶剂中形成稀释液；
将步骤（1）中的稀释液在20℃以下的惰性氛围下滴加到异氰酸酯中搅拌反应30-60min，接着升温到60-70℃，搅拌30-60min；
待步骤（2）反应结束，降温至20 ℃以下，继续将单氨基硅烷偶联剂分批次加入步骤（2）的混合液中，搅拌反应20-60 min，接着升温至60-70℃，搅拌反应1-2 h即得到所述的泡沫塑料用粘接助剂。
3.根据权利要求2所述的泡沫塑料用粘接助剂的制备方法，其特征在于：所述小分子多元胺与有机溶剂质量比为1：（1-2）。
4.根据权利要求2所述的泡沫塑料用粘接助剂的制备方法，其特征在于：所述单氨基硅烷偶联剂为双（3-三甲氧基硅基丙基）胺、γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、N-苯基-γ-氨丙基三甲氧基硅烷中的一种或多种。
5.根据权利要求2所述的泡沫塑料用粘接助剂的制备方法，其特征在于：所述异氰酸酯为1,6-已二异氰酸酯（HDI）、异氟尔酮二异氰酸酯（IPDI）、甲苯-2、4-二异氰酸酯(TDI)、苯二亚甲基二异氰酸酯（XDI）中的一种或多种。
6.根据权利要求2所述的泡沫塑料用粘接助剂的制备方法，其特征在于：所述有机溶剂为乙酸丁酯、乙酸乙酯、丁酮、甲苯或碳酸二甲酯。
7.一种权利要求1所述的泡沫塑料用粘接助剂在泡沫塑料中的应用，其特征在于：所述泡沫塑料用粘接助剂添加量占泡沫塑料总重的0.5%-3%。
8.根据权利要求7所述的泡沫塑料用粘接助剂在泡沫塑料中的应用，其特征在于：所述泡沫塑料为聚氨酯泡沫、酚醛泡沫、环氧树脂泡沫或不饱和聚酯树脂泡沫。
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