CN113930206A - 一种耐高温胶黏剂及其制备方法和应用 - Google Patents
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Abstract
本发明属于胶黏剂材料技术领域,尤其是一种耐高温胶黏剂及其制备方法和应用,解决了现有技术中水性聚氨酯胶黏剂能耗高,涂布性能较差,对复合基材的润湿性不佳,附着力不高,胶膜力学性能不佳,耐化学性、耐热性不好等问题,所述耐高温胶黏剂,包括以下原料:甲苯二异氰酸酯、二苯甲烷二异氰酸酯、聚丙二醇、苯酐聚酯多元醇、催化剂、扩链剂、改性剂、十二烷二酸、二甘醇二苯甲酸酯、季戊四醇硬脂酸酯。本发明原料选用简单,制备条件温和,所得胶黏剂安全无污染,其具有良好的相容性、润湿性,涂布方便,涂布后胶膜固化快,附着力强,且具有优异的力学性能、耐化学性能和耐高温性能,可广泛应用于食品、医药及日用品包装等领域。
Description
技术领域
本发明涉及胶黏剂材料技术领域,尤其涉及一种耐高温胶黏剂及其制备方法和应用。
背景技术
复合塑料薄膜是一种软包装材料,目前被广泛应用于食品、医药、日用品等包装。软包装用复合薄膜一般是由二层或三层不同材质的薄膜复合而成,内层一般为PE、CPP、PVDC等可塑封性薄膜,外层一般为BOPP、PET、BOPA等阻隔性好的薄膜。复合工艺多采用干式复合法,复合薄膜的质量取决于复合所用的薄膜和胶黏剂。聚氨酯胶黏剂是复合膜行业广泛使用的胶黏剂。聚氨酯胶黏剂是指在分子链中含有氨基甲酸酯基团(-NHC00-)或异氰酸酯基(-Nco)的胶黏剂。聚氨酯胶黏剂因黏接力强、透明、柔软、耐油、耐酸、耐高低温等特性,在复合薄膜用胶黏剂中占据主导地位。
国内现在所用产品大多为双组份溶剂型聚氨酯胶黏剂,一般工作浓度在30%左右,所用溶剂大多为乙酸乙酯。每使用1吨干胶,就会有2吨多的乙酸乙酯排放到空气中,这些溶剂的排放严重的污染了环境,也大大浪费了能源和资源。水性聚氨酯(WPU)胶黏剂以水为溶剂,具有软硬度可调节、无污染、相容性好,易于改性等优点,能粘接金属、非金属等多种材料。但是,纯的水性聚氨酯胶黏剂的成本很高,包装企业用量较少,市场上出现的水性聚氨酯胶黏剂多为改性产品,存在能耗高,涂布性能较差,对复合基材的润湿性不佳,附着力不高,胶膜力学性能不佳,耐化学性、耐热性不好等缺陷。基于上述陈述,本发明提出了一种耐高温胶黏剂及其制备方法和应用。
发明内容
本发明的目的是为了解决现有技术中水性聚氨酯胶黏剂能耗高,涂布性能较差,对复合基材的润湿性不佳,附着力不高,胶膜力学性能不佳,耐化学性、耐热性不好等问题,而提出的一种耐高温胶黏剂及其制备方法和应用。
一种耐高温胶黏剂,包括以下重量份的原料:甲苯二异氰酸酯20-30份、二苯甲烷二异氰酸酯18-25份、聚丙二醇50-60份、苯酐聚酯多元醇15-25份、催化剂0.1-0.5份、扩链剂1-2份、改性剂5-12份、十二烷二酸3-5份、二甘醇二苯甲酸酯1-3份、季戊四醇硬脂酸酯1-1.8份。
优选的,所述耐高温胶黏剂,包括以下重量份的原料:甲苯二异氰酸酯22-28份、二苯甲烷二异氰酸酯20-24份、聚丙二醇52-58份、苯酐聚酯多元醇18-22份、催化剂0.2-0.4份、扩链剂1.2-1.8份、改性剂6-10份、十二烷二酸3.5-4.5份、二甘醇二苯甲酸酯1.5-2.5份、季戊四醇硬脂酸酯1.2-1.6份。
优选的,所述耐高温胶黏剂,包括以下重量份的原料:甲苯二异氰酸酯25份、二苯甲烷二异氰酸酯22份、聚丙二醇55份、苯酐聚酯多元醇20份、催化剂0.3份、扩链剂1.5份、改性剂8份、十二烷二酸4份、二甘醇二苯甲酸酯2份、季戊四醇硬脂酸酯1.5份。
优选的,所述催化剂为有机铋、有机锡、有机锌或有机钛中的至少一种。
优选的,所述扩链剂由质量比1-2:1-5:4-7的对苯二酚二羟乙基醚、乙二胺基乙磺酸钠和二羟甲基丙酸复配而得。
优选的,所述改性剂由质量比1-3:7-11:1-3的亚磷酸酯、环氧大豆油和松香酸钙皂复配而得。
本发明还提出了一种耐高温胶黏剂的制备方法,包括以下步骤:
S1、称取原料甲苯二异氰酸酯、二苯甲烷二异氰酸酯、聚丙二醇、苯酐聚酯多元醇、催化剂、扩链剂、改性剂、十二烷二酸、二甘醇二苯甲酸酯、季戊四醇硬脂酸酯,备用;
S2、将聚丙二醇、苯酐聚酯多元醇共同加入到反应容器中,搅拌升温至78-85℃,保温加入甲苯二异氰酸酯、二苯甲烷二异氰酸酯,边搅拌边加入催化剂,催化反应1-3h后,降温至64-70℃,加入扩链剂继续反应1-2h,反应完成即得水性聚氨酯乳液;
S3、将步骤S2中制得的水性聚氨酯乳液加改性剂、十二烷二酸、二甘醇二苯甲酸酯和季戊四醇硬脂酸酯,于78-88℃的温度下,搅拌混合20-40min,混合均匀后,静置消泡即得所需的耐高温胶黏剂。
本发明还提出了一种耐高温胶黏剂的应用,所述胶黏剂主要应用于食品、医药及日用品包装领域。
本发明提出的一种耐高温胶黏剂,具有以下有益效果:
1、本发明采用甲苯二异氰酸酯、二苯甲烷二异氰酸酯、聚丙二醇、苯酐聚酯多元醇为主要原料,在催化剂和扩链剂的存在下,制备水性聚氨酯乳液,通过添加改性剂及其他助剂改性制得所需的耐高温胶黏剂,本发明原料选用简单,制备条件温和,所得胶黏剂安全无污染,其具有良好的相容性、润湿性,涂布方便,涂布后胶膜固化快,附着力强,且具有优异的力学性能、耐化学性能和耐高温性能,可广泛应用于食品、医药及日用品包装等领域。
2、本发明采用亚磷酸酯、环氧大豆油和松香酸钙皂复配制得改性剂,所得改性剂用于水性聚氨酯改性,能够显著提高所得胶黏剂的耐高温性能,力学性能和粘结性能。
具体实施方式
下面结合具体实施例对本发明作进一步解说。
实施例一
本发明提出的一种耐高温胶黏剂,包括以下重量份的原料:甲苯二异氰酸酯20份、二苯甲烷二异氰酸酯18份、聚丙二醇50份、苯酐聚酯多元醇15份、催化剂0.1份、扩链剂1份、改性剂5份、十二烷二酸3份、二甘醇二苯甲酸酯1份、季戊四醇硬脂酸酯1份;
其中,催化剂为有机铋;
其中,扩链剂由质量比1:1:4的对苯二酚二羟乙基醚、乙二胺基乙磺酸钠和二羟甲基丙酸复配而得;
其中,改性剂由质量比1:7:1的亚磷酸酯、环氧大豆油和松香酸钙皂复配而得。
本发明还提出了一种耐高温胶黏剂的制备方法,包括以下步骤:
S1、称取原料甲苯二异氰酸酯、二苯甲烷二异氰酸酯、聚丙二醇、苯酐聚酯多元醇、催化剂、扩链剂、改性剂、十二烷二酸、二甘醇二苯甲酸酯、季戊四醇硬脂酸酯,备用;
S2、将聚丙二醇、苯酐聚酯多元醇共同加入到反应容器中,搅拌升温至78℃,保温加入甲苯二异氰酸酯、二苯甲烷二异氰酸酯,边搅拌边加入催化剂,催化反应1h后,降温至64℃,加入扩链剂继续反应1h,反应完成即得水性聚氨酯乳液;
S3、将步骤S2中制得的水性聚氨酯乳液加改性剂、十二烷二酸、二甘醇二苯甲酸酯和季戊四醇硬脂酸酯,于78℃的温度下,搅拌混合20min,混合均匀后,静置消泡即得所需的耐高温胶黏剂。
实施例二
本发明提出的一种耐高温胶黏剂,包括以下重量份的原料:甲苯二异氰酸酯25份、二苯甲烷二异氰酸酯22份、聚丙二醇55份、苯酐聚酯多元醇20份、催化剂0.3份、扩链剂1.5份、改性剂8份、十二烷二酸4份、二甘醇二苯甲酸酯2份、季戊四醇硬脂酸酯1.5份;
其中,催化剂为有机锌;
其中,扩链剂由质量比1.5:3:5.5的对苯二酚二羟乙基醚、乙二胺基乙磺酸钠和二羟甲基丙酸复配而得;
其中,改性剂由质量比2:9:2的亚磷酸酯、环氧大豆油和松香酸钙皂复配而得。
本发明还提出了一种耐高温胶黏剂的制备方法,包括以下步骤:
S1、称取原料甲苯二异氰酸酯、二苯甲烷二异氰酸酯、聚丙二醇、苯酐聚酯多元醇、催化剂、扩链剂、改性剂、十二烷二酸、二甘醇二苯甲酸酯、季戊四醇硬脂酸酯,备用;
S2、将聚丙二醇、苯酐聚酯多元醇共同加入到反应容器中,搅拌升温至82℃,保温加入甲苯二异氰酸酯、二苯甲烷二异氰酸酯,边搅拌边加入催化剂,催化反应2h后,降温至67℃,加入扩链剂继续反应1.5h,反应完成即得水性聚氨酯乳液;
S3、将步骤S2中制得的水性聚氨酯乳液加改性剂、十二烷二酸、二甘醇二苯甲酸酯和季戊四醇硬脂酸酯,于85℃的温度下,搅拌混合30min,混合均匀后,静置消泡即得所需的耐高温胶黏剂。
实施例三
本发明提出的一种耐高温胶黏剂,包括以下重量份的原料:甲苯二异氰酸酯30份、二苯甲烷二异氰酸酯25份、聚丙二醇60份、苯酐聚酯多元醇25份、催化剂0.5份、扩链剂2份、改性剂12份、十二烷二酸5份、二甘醇二苯甲酸酯3份、季戊四醇硬脂酸酯1.8份;
其中,催化剂为有机钛;
其中,扩链剂由质量比2:5:7的对苯二酚二羟乙基醚、乙二胺基乙磺酸钠和二羟甲基丙酸复配而得;
其中,改性剂由质量比3:11:3的亚磷酸酯、环氧大豆油和松香酸钙皂复配而得。
本发明还提出了一种耐高温胶黏剂的制备方法,包括以下步骤:
S1、称取原料甲苯二异氰酸酯、二苯甲烷二异氰酸酯、聚丙二醇、苯酐聚酯多元醇、催化剂、扩链剂、改性剂、十二烷二酸、二甘醇二苯甲酸酯、季戊四醇硬脂酸酯,备用;
S2、将聚丙二醇、苯酐聚酯多元醇共同加入到反应容器中,搅拌升温至85℃,保温加入甲苯二异氰酸酯、二苯甲烷二异氰酸酯,边搅拌边加入催化剂,催化反应3h后,降温至70℃,加入扩链剂继续反应2h,反应完成即得水性聚氨酯乳液;
S3、将步骤S2中制得的水性聚氨酯乳液加改性剂、十二烷二酸、二甘醇二苯甲酸酯和季戊四醇硬脂酸酯,于88℃的温度下,搅拌混合40min,混合均匀后,静置消泡即得所需的耐高温胶黏剂。
对比例一
本发明提出的一种耐高温胶黏剂,包括以下重量份的原料:甲苯二异氰酸酯20份、二苯甲烷二异氰酸酯18份、聚丙二醇50份、苯酐聚酯多元醇15份、催化剂0.1份、扩链剂1份、改性剂5份、十二烷二酸3份、二甘醇二苯甲酸酯1份、季戊四醇硬脂酸酯1份;
其中,催化剂为有机铋;
其中,扩链剂由质量比1:1:4的对苯二酚二羟乙基醚、乙二胺基乙磺酸钠和二羟甲基丙酸复配而得;
其中,改性剂为亚磷酸酯。
本发明还提出了一种耐高温胶黏剂的制备方法,包括以下步骤:
S1、称取原料甲苯二异氰酸酯、二苯甲烷二异氰酸酯、聚丙二醇、苯酐聚酯多元醇、催化剂、扩链剂、改性剂、十二烷二酸、二甘醇二苯甲酸酯、季戊四醇硬脂酸酯,备用;
S2、将聚丙二醇、苯酐聚酯多元醇共同加入到反应容器中,搅拌升温至78℃,保温加入甲苯二异氰酸酯、二苯甲烷二异氰酸酯,边搅拌边加入催化剂,催化反应1h后,降温至64℃,加入扩链剂继续反应1h,反应完成即得水性聚氨酯乳液;
S3、将步骤S2中制得的水性聚氨酯乳液加改性剂、十二烷二酸、二甘醇二苯甲酸酯和季戊四醇硬脂酸酯,于78℃的温度下,搅拌混合20min,混合均匀后,静置消泡即得所需的耐高温胶黏剂。
对比例二
本发明提出的一种耐高温胶黏剂,包括以下重量份的原料:甲苯二异氰酸酯20份、二苯甲烷二异氰酸酯18份、聚丙二醇50份、苯酐聚酯多元醇15份、催化剂0.1份、扩链剂1份、改性剂5份、十二烷二酸3份、二甘醇二苯甲酸酯1份、季戊四醇硬脂酸酯1份;
其中,催化剂为有机铋;
其中,扩链剂由质量比1:1:4的对苯二酚二羟乙基醚、乙二胺基乙磺酸钠和二羟甲基丙酸复配而得;
其中,改性剂为环氧大豆油。
本发明还提出了一种耐高温胶黏剂的制备方法,包括以下步骤:
S1、称取原料甲苯二异氰酸酯、二苯甲烷二异氰酸酯、聚丙二醇、苯酐聚酯多元醇、催化剂、扩链剂、改性剂、十二烷二酸、二甘醇二苯甲酸酯、季戊四醇硬脂酸酯,备用;
S2、将聚丙二醇、苯酐聚酯多元醇共同加入到反应容器中,搅拌升温至78℃,保温加入甲苯二异氰酸酯、二苯甲烷二异氰酸酯,边搅拌边加入催化剂,催化反应1h后,降温至64℃,加入扩链剂继续反应1h,反应完成即得水性聚氨酯乳液;
S3、将步骤S2中制得的水性聚氨酯乳液加改性剂、十二烷二酸、二甘醇二苯甲酸酯和季戊四醇硬脂酸酯,于78℃的温度下,搅拌混合20min,混合均匀后,静置消泡即得所需的耐高温胶黏剂。
根据检测标准《GB/T 33320-2016》,分别测试实施例一~三以及对比例一、二中制备的耐高温胶黏剂及其胶膜的性能,得出如下结果:
表1:
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (8)
1.一种耐高温胶黏剂,其特征在于,包括以下重量份的原料:甲苯二异氰酸酯20-30份、二苯甲烷二异氰酸酯18-25份、聚丙二醇50-60份、苯酐聚酯多元醇15-25份、催化剂0.1-0.5份、扩链剂1-2份、改性剂5-12份、十二烷二酸3-5份、二甘醇二苯甲酸酯1-3份、季戊四醇硬脂酸酯1-1.8份。
2.根据权利要求1所述的一种耐高温胶黏剂,其特征在于,包括以下重量份的原料:甲苯二异氰酸酯22-28份、二苯甲烷二异氰酸酯20-24份、聚丙二醇52-58份、苯酐聚酯多元醇18-22份、催化剂0.2-0.4份、扩链剂1.2-1.8份、改性剂6-10份、十二烷二酸3.5-4.5份、二甘醇二苯甲酸酯1.5-2.5份、季戊四醇硬脂酸酯1.2-1.6份。
3.根据权利要求1所述的一种耐高温胶黏剂,其特征在于,包括以下重量份的原料:甲苯二异氰酸酯25份、二苯甲烷二异氰酸酯22份、聚丙二醇55份、苯酐聚酯多元醇20份、催化剂0.3份、扩链剂1.5份、改性剂8份、十二烷二酸4份、二甘醇二苯甲酸酯2份、季戊四醇硬脂酸酯1.5份。
4.根据权利要求1所述的一种耐高温胶黏剂,其特征在于,所述催化剂为有机铋、有机锡、有机锌或有机钛中的至少一种。
5.根据权利要求1所述的一种耐高温胶黏剂,其特征在于,所述扩链剂由质量比1-2:1-5:4-7的对苯二酚二羟乙基醚、乙二胺基乙磺酸钠和二羟甲基丙酸复配而得。
6.根据权利要求1所述的一种耐高温胶黏剂,其特征在于,所述改性剂由质量比1-3:7-11:1-3的亚磷酸酯、环氧大豆油和松香酸钙皂复配而得。
7.一种根据权利要求1-6任一项所述的耐高温胶黏剂的制备方法,其特征在于,包括以下步骤:
S1、称取原料甲苯二异氰酸酯、二苯甲烷二异氰酸酯、聚丙二醇、苯酐聚酯多元醇、催化剂、扩链剂、改性剂、十二烷二酸、二甘醇二苯甲酸酯、季戊四醇硬脂酸酯,备用;
S2、将聚丙二醇、苯酐聚酯多元醇共同加入到反应容器中,搅拌升温至78-85℃,保温加入甲苯二异氰酸酯、二苯甲烷二异氰酸酯,边搅拌边加入催化剂,催化反应1-3h后,降温至64-70℃,加入扩链剂继续反应1-2h,反应完成即得水性聚氨酯乳液;
S3、将步骤S2中制得的水性聚氨酯乳液加改性剂、十二烷二酸、二甘醇二苯甲酸酯和季戊四醇硬脂酸酯,于78-88℃的温度下,搅拌混合20-40min,混合均匀后,静置消泡即得所需的耐高温胶黏剂。
8.一种根据权利要求1-7任一项所述的耐高温胶黏剂的应用,其特征在于,所述胶黏剂主要应用于食品、医药及日用品包装领域。
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