CN111040710A - 一种羧酸/磺酸复合型水性聚氨酯胶黏剂及其制备方法 - Google Patents
一种羧酸/磺酸复合型水性聚氨酯胶黏剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种羧酸/磺酸复合型水性聚氨酯胶黏剂,其特征在于,所述羧酸/磺酸复合型水性聚氨酯胶黏剂的制备原料由多元醇、二异氰酸酯、羧基扩链剂、磺酸盐亲水扩链剂、中和剂、二元胺扩链剂组成。一种羧酸/磺酸复合型水性聚氨酯胶黏剂的制备方法,按照如下步骤进行:(1)将多元醇进行脱水处理后,与二异氰酸酯、二羟甲基丁酸(DMBA)进行无溶剂预聚反应;(2)将预聚物用丙酮溶解后,加入中和剂中和反应,然后加入乙二胺基乙磺酸钠(A95)进行扩链反应得到聚合物,向聚合物中加入水性分散体,再加入二元胺扩链剂进行扩链反应,抽真空脱去丙酮即得到羧酸/磺酸复合型水性聚氨酯胶黏剂。成品性能好、品质佳。
Description
技术领域
本发明涉及一种水性聚氨酯胶粘剂的制备方法,具体涉及一种羧酸/磺酸复合型水性聚氨酯胶黏剂及其制备方法。
背景技术
水性聚氨酯胶粘剂是我国重点发展的合成水性胶粘剂产品。由于聚氨酯胶粘剂具有良好的粘接性能,故已广泛用于制鞋、建筑、汽车及食品包装等行业。其特点为以水代替有机溶剂作为分散介质,分散液中不含有机溶剂。有不燃、零污染、无气味、操作加工方便、节能等优点,同时具有一般聚氨酯所固有的耐磨损、高强度等优点。水性聚氨酯国外在20世纪80年代已形成一定的规模,如德国拜耳、日本大日本油墨、美国Wyandotte化学公司等都推出了不同牌号的系列水性聚氨酯产品。20世纪90年代我国水性聚氨酯装置相继投产,但规模不大,品种单一。进入21世纪后,我国逐渐打破这种现状,随着国内环保意识的增强,水性聚氨酯这种环保型产品需求量剧增。
我国是全球最大的鞋生产国,鞋类产品的产量和出口量已稳居世界之首,鞋胶的需求量很大,鞋用胶每年需求为12万吨。目前胶粘鞋年产量在20亿双以上,若以每双鞋18~26g用胶量计算,则年需聚氨酯胶粘剂312~512万吨。目前我国制鞋工业中95%使用氯丁胶粘剂,聚氨酯用量较少。氯丁胶粘剂初粘性好、可冷粘、价格便宜等是其优点,但其不耐增塑剂渗透,对软PVC、热塑性橡胶、 PU革等新型鞋用材料粘接性差,此外必须应用的苯类为有毒溶剂,这是致命的弱点,已不适应制鞋工、业发展的要求。
目前市售羧酸型水性聚氨酯具有储存稳定性好、耐水解性好、干燥速度快,但其固含量低,且最低活化温度较高,剥离强度较小。市售磺酸型水性聚氨酯虽固含量高、粘接强度高、耐热性优异但在耐水解、稳定性、结晶速度又不如羧酸型水性聚氨酯。
目前在水性聚氨酯合成过程中大多使用有机锡类、有机铋类等稀有金属有机物作为催化剂,而这些有机物为有毒类化合物,很难真正保证产品的环保、安全等性能。现有技术大多利用单一聚酯多元醇或者聚醚多元醇作为软段合成水性聚氨酯胶粘剂,利用聚酯多元醇为原料合成的水性聚氨酯胶粘剂的耐水解性能较利用聚醚多元醇合成的水性聚氨酯胶粘剂差,胶粘剂的粘接性能较佳,存放过程中不出现混浊、分层等现象。
中国专利文献CN101020808A公布了一种水性聚氨酯胶粘剂的制备方法,该方法通过有机硅改性合成了一种用途广泛的水性聚氨酯胶粘剂,但该水性聚氨酯胶粘剂固含量较低,仅为40%,且剥离强度最大的仅为3.0N/15mm。
中国专利文献CN101993677A公布了一种水性聚氨酯胶粘剂及其制备方法,该胶粘剂无毒、环保、安全,且制备方法简单,能降低生产成本,但是未提及其应用性能是否优良。
中国专利文献CN 103254867 A公布了一种磺酸型水性聚氨酯胶粘剂的制备方法,该胶黏剂虽固含量50.12%、最低活化温度30℃,但剥离强度仅9.85N/15mm,耐水解性差等。
发明内容
为解决上述问题,本发明的目的是提供一种制得的复合型水性聚氨酯胶黏剂具有固含量高、耐热耐水解性优异、剥离强度大等特点的羧酸/磺酸复合型水性聚氨酯胶黏剂及其制备方法。
为实现上述目的,本发明采用如下技术方案:
一种羧酸/磺酸复合型水性聚氨酯胶黏剂,所述羧酸/磺酸复合型水性聚氨酯胶黏剂的制备原料由多元醇、二异氰酸酯、羧基扩链剂、磺酸盐亲水扩链剂、中和剂、二元胺扩链剂组成,以总重量为100%计,各组分的用量以重量百分数表示如下:
所述的多元醇为聚酯多元醇或聚醚多元醇或两者混合,所述二异氰酸酯为异氟尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、甲基环己基二异氰酸酯 (HTDI)、4,4-二异氰酸酯二环己基甲烷(HMDI)中的两种或三种混合物,所述的羧基扩链剂为二羟甲基丁酸(DMBA),所述的磺酸盐亲水扩链剂为乙二胺基乙磺酸钠(A95)。
作为优选,所述的多元醇为聚酯多元醇与聚醚多元醇的混合。
作为优选,所述的聚酯多元醇选自下列一种或任意几种的混合物:聚己二酸-1,4-丁二醇酯二元醇、聚己二酸己二醇酯二元醇、聚己内酯二元醇、聚碳酸酯二元醇。作为优选,所述的聚酯多元醇选自下列一种或任意几种的混合物:聚氧化丙烯二醇、聚四氢呋喃醚二醇。
作为优选,所述的二异氰酸酯选自下列一种或任意几种的混合物:异氟尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、甲基环己基二异氰酸酯(HTDI)、 4,4-二异氰酸酯二环己基甲烷(HMDI)。
作为优选,所述二元胺扩链剂为乙二胺、丙二胺或异氟尔酮二胺。
一种羧酸/磺酸复合型水性聚氨酯胶黏剂的制备方法,当所述的羧基扩链剂为二羟甲基丁酸(DMBA),所述的磺酸盐亲水扩链剂为乙二胺基乙磺酸钠(A95),所述的羧酸/磺酸复合型水性聚氨酯胶黏剂的制备方法按照如下步骤进行:
(1)将多元醇进行脱水处理后,与二异氰酸酯、二羟甲基丁酸(DMBA)在90~ 100℃进行无溶剂预聚反应,直至体系中-NCO浓度达到理论值,得到预聚物;
(2)将预聚物用丙酮溶解后,加入中和剂于45~50℃进行中和反应20~30分钟,中和反应完成,然后加入乙二胺基乙磺酸钠(A95)于40~45℃进行扩链反应,反应10~20分钟后得到聚合物,向聚合物中加入去离子水高速分散得水性分散体,再加入二元胺扩链剂进行进一步的扩链反应20~30分钟后,抽真空脱去丙酮即得到羧酸/磺酸复合型水性聚氨酯胶黏剂。
作为优选,所述的多元醇在使用前需进行脱水处理,所述的脱水处理可采用如下操作:将多元醇加入四口烧瓶中,在100~120℃抽真空(-0.085~0.1Mpa)脱水 1~3小时。
作为优选,所述的体系中-NCO浓度测试是通过二正丁胺法测试体系中-NCO含量的变化。
与现有技术相比,本发明的有益效果在于:
(1)多元醇采用聚酯多元醇和/或聚醚多元醇作为聚氨酯软段,不采用有机锡类等稀有金属催化剂,采用羧酸扩链剂前扩链和磺酸盐亲水扩链剂后扩链,再经二元胺在水中进行扩链制备得到了固含量高、耐热耐水解性优、剥离强度大且价格适中的羧酸/磺酸复合型水性聚氨酯胶黏剂,而且绿色环保,价格适中,对扩大水性胶粘剂乳液的生产和应用起到很大的推动作用,具有应用价值和经济价值;
(2)多元醇采用聚酯多元醇、聚醚多元醇的混合作为水性聚氨酯胶粘剂的软段,较只利用聚醚多元醇作为软段合成的水性聚氨酯粘结性能好,较只利用聚酯多元醇作为软段合成的水性聚氨酯耐水解性能优且稳定性良好,使胶粘剂的综合性能 (粘接强度、耐水解性、稳定性)得到很好的提高;
(3)采用羧酸扩链剂前扩链和磺酸盐亲水扩链剂后扩链,较只利用羧酸扩链剂的水性聚氨酯固含量高、粘接强度高、耐热性优异等特点,又较只利用磺酸盐亲水扩链剂的水性聚氨酯的耐水解性、干燥速度快、稳定性好等特点,利用两种亲水扩链剂合成的羧酸/磺酸复合型水性聚氨酯胶黏剂兼具了羧酸型和磺酸盐型的综合性能;
(4)不采用传统聚氨酯合成中的有机锡类有毒催化剂的催化反应,采用无催化剂的高温自引发聚合的方式,保证的产品的环保安全性。
具体实施方式
下面以具体实施例对本发明的技术方案做进一步说明,但本发明的保护范围不限于此:以二羟甲基丁酸(DMBA)羧酸扩链剂前扩链,以乙二胺基乙磺酸钠(A95) 亲水扩链剂后扩链。
多元醇在使用前需进行脱水处理,所述的脱水处理可采用如下操作:将多元醇加入四口烧瓶中,在115℃抽真空(-0.085~0.1Mpa)脱水2小时为最佳。
实施例1
在四口烧瓶中投入150g聚己二酸-1,4-丁二醇酯(Mn=3000)、20g聚碳酸酯二元醇(Mn=2000)、80g聚氧化丙烯二醇(PPG-2000)、1.5g的二羟甲基丁酸(DMBA), 110℃抽真空脱水2h,降温至90℃后,向四口烧瓶中加入10.9g IPDI、16.5g HDI,于95~110℃反应至-NCO浓度达到理论值后加入300g丙酮稀释,50℃加入1.01g三乙胺中和剂反应30min,降温至40℃加入5.5g乙二胺基乙磺酸钠 (A95)反应20min得预聚体。将预聚体倒入分散釜中高速搅拌(2000r/min)下加入去离子水290g,再加入乙二胺0.5g,高速搅拌20~30min。在45~50℃低压抽真空脱丙酮后得到水性聚氨酯胶粘剂。
其测试结果如下:
外观:蓝色透明
固含量:51.06%
剥离强度/(N/mm):8.6
耐热老化性/(N/mm):6.0
耐水解性/(N/mm):5.2
实施例2
在四口烧瓶中投入150g聚己二酸-1,4-丁二醇酯(Mn=3000)、100g聚氧化丙烯二醇(PPG-2000)、1.5g的二羟甲基丁酸(DMBA),110℃抽真空脱水2h,降温至90℃后,向四口烧瓶中加入10.9g IPDI、16.5g HDI,于95~110℃反应至-NCO浓度达到理论值后加入300g丙酮稀释,50℃加入1.01g三乙胺中和剂反应 30min,降温至40℃加入5.5g乙二胺基乙磺酸钠(A95)反应20min得预聚体。将预聚体倒入分散釜中高速搅拌(2000r/min)下加入去离子水290g,再加入乙二胺0.5g,高速搅拌20~30min。在45~50℃低压抽真空脱丙酮后得到水性聚氨酯胶粘剂。
其测试结果如下:
外观:蓝色透明
固含量:50.0%
剥离强度/(N/mm):7.2
耐热老化性/(N/mm):5.0
耐水解性/(N/mm):5.6
操作方法同实施例1,改变DMBA/A95的配比,具体配方及结果见表1:
表1
操作方法同实施例1,改变二异氰酸酯的组成,具体配方及结果见表2:
表2
本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (9)
2.如权利要求1所述的一种羧酸/磺酸复合型水性聚氨酯胶黏剂,其特征在于,所述的多元醇为聚酯多元醇与聚醚多元醇的混合。
3.如权利要求1或2所述的一种羧酸/磺酸复合型水性聚氨酯胶黏剂,其特征在于,所述的聚酯多元醇选自下列一种或任意几种的混合物:聚己二酸-1,4-丁二醇酯二元醇、聚己二酸己二醇酯二元醇、聚己内酯二元醇、聚碳酸酯二元醇。
4.如权利要求1或2所述的一种羧酸/磺酸复合型水性聚氨酯胶黏剂,其特征在于,所述的聚酯多元醇选自下列一种或任意几种的混合物:聚氧化丙烯二醇、聚四氢呋喃醚二醇。
5.如权利要求1所述的一种羧酸/磺酸复合型水性聚氨酯胶黏剂,其特征在于,所述的二异氰酸酯选自下列一种或任意几种的混合物:异氟尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、甲基环己基二异氰酸酯(HTDI)、4,4-二异氰酸酯二环己基甲烷(HMDI)。
6.如权利要求1所述的一种羧酸/磺酸复合型水性聚氨酯胶黏剂,其特征在于,所述二元胺扩链剂为乙二胺、丙二胺或异氟尔酮二胺。
7.如权利要求1-6所述的一种羧酸/磺酸复合型水性聚氨酯胶黏剂的制备方法,其特征在于,当所述的羧基扩链剂为二羟甲基丁酸(DMBA),所述的磺酸盐亲水扩链剂为乙二胺基乙磺酸钠(A95),所述的羧酸/磺酸复合型水性聚氨酯胶黏剂的制备方法按照如下步骤进行:
(1)将多元醇进行脱水处理后,与二异氰酸酯、二羟甲基丁酸(DMBA)在90~100℃进行无溶剂预聚反应,直至体系中-NCO浓度达到理论值,得到预聚物;
(2)将预聚物用丙酮溶解后,加入中和剂于45~50℃进行中和反应20~30分钟,中和反应完成,然后加入乙二胺基乙磺酸钠(A95)于40~45℃进行扩链反应,反应10~20分钟后得到聚合物,向聚合物中加入去离子水高速分散得水性分散体,再加入二元胺扩链剂进行进一步的扩链反应20~30分钟后,抽真空脱去丙酮即得到羧酸/磺酸复合型水性聚氨酯胶黏剂。
8.如权利要求7所述的一种羧酸/磺酸复合型水性聚氨酯胶黏剂的制备方法,其特征在于,所述的多元醇在使用前需进行脱水处理,所述的脱水处理可采用如下操作:将多元醇加入四口烧瓶中,在100~120℃抽真空(-0.085~0.1Mpa)脱水1~3小时。
9.如权利要求7所述的一种羧酸/磺酸复合型水性聚氨酯胶黏剂的制备方法,其特征在于,所述的体系中-NCO浓度测试是通过二正丁胺法测试体系中-NCO含量的变化。
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