CN113136160A - 一种水性聚氨酯胶黏剂及其制备方法 - Google Patents
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Abstract
本发明属于胶黏剂技术领域,具体涉及一种水性聚氨酯胶黏剂及其制备方法。制备过程包括:先将聚酯多元醇、聚醚与二异氰酸酯、小分子扩链剂在催化剂的作用下进行聚合,加入丙酮降黏后再投入端氨基硅烷偶联剂、亲水扩链剂、胺类扩链剂和螯合剂,继续反应得到水性聚氨酯预聚物;向该预聚物中加水并高速剪切乳化,减压脱除丙酮制得水性聚氨酯乳液;最后向该乳液中加入消泡剂、增稠剂和固化剂制得水性聚氨酯胶黏剂。本发明水性聚氨酯胶黏剂的固含量高、钙离子稳定性好,具有突出的粘接强度,进一步提高了产品的耐水性和耐热性,可用于制鞋行业。最终减压脱除丙酮,丙酮可回收再利用,减少了环境污染,属于清洁生产,并降低了生产成本。
Description
技术领域
本发明属于胶黏剂技术领域,具体涉及一种水性聚氨酯胶黏剂及其制备方法。
背景技术
我国是世界上的制鞋大国,2018年鞋产量已超过135亿双,所需胶黏剂用量达到50万吨/年。目前使用较多的胶黏剂是溶剂型胶黏剂,有机溶剂对塑料、皮革和橡胶等底材有很好的溶胀性,能使胶黏剂中的有效成分渗透到材料内部,使胶黏剂表现出优良的粘接性能,同时还可根据不同溶剂的挥发速度来调节施工时间。使用最多的溶剂型胶黏剂有两大类,即氯丁胶和聚氨酯胶(PU胶)。氯丁胶具有很强的耐水、耐油、耐溶剂、耐酸碱、抗老化性能,同时还具有优异的粘接强度,成本低,故其依然是我国制鞋工业不可缺少的重要胶黏剂。但氯丁胶不耐增塑剂渗透,对热塑性橡胶、软聚氯乙烯、聚氨酯合成革等新型鞋用底材粘接性差,因此氯丁胶正逐渐被聚氨酯胶粘剂替代。
水性聚氨酯胶黏剂是以水为分散介质,呈乳白蓝色,固化后呈透明状,与溶剂型聚氨酯胶黏剂一样具有硬度可调、耐低温、柔韧性好、粘结强度大等特点,而且与传统溶剂型胶黏剂相比具有三大显著的优势:1、环保,不含或少含VOC,对人体和生态环境无危害;2、不易燃易爆,储藏安全,无消防隐患;3、固含量高,是传统溶剂型产品的3-4倍,可以达到高于溶剂型产品的后期粘合效果,很多鞋材刷一遍胶即可,性价比更高。因此,采用水性聚氨酯胶黏剂可从源头上减少环境污染,具有环保、安全、性价比高的特点,有助于制鞋行业的转型升级。
但是,相对于溶剂型聚氨酯,水性聚氨酯中含有可水解基团,在环境条件下储存容易水解,同时体系中存在的金属离子(如催化剂中引入的金属离子)也会促进水性聚氨酯上可水解基团的水解。因此水性聚氨酯胶黏剂常表现出初粘力低、耐水性差、粘性维持时间短等问题;而且目前的磺酸盐型水性聚氨酯往往含有较多的磺酸根,其离子稳定性也相对较弱。
发明内容
本发明的目的在于针对现有技术存在的初粘力低、耐水性差、离子稳定性较弱等问题,通过改进水性聚氨酯的聚合工艺,提供一种水性聚氨酯胶黏剂的制备方法。本发明通过加入水溶性螯合剂,与体系中的金属离子络合形成稳定的化合物,使其不再促进聚氨酯水解;通过引入硅氧烷,增加水性聚氨酯的耐水性和耐热性;通过添加少量亲水性聚醚来替代部分磺酸盐的亲水基团,减少磺酸根的含量,进而制备出稳定性优异的水性聚氨酯胶黏剂。所得产品基本不含有机溶剂,环保、安全,具有突出的粘结强度、耐水性、耐热性和离子稳定性。
本发明解决其技术问题采用的技术方案如下:
水性聚氨酯胶黏剂的制备方法,包括以下步骤:
第一步,聚合:先将80质量份的聚酯多元醇和1-2质量份的聚醚投入到反应器中,在100-120 ℃的温度下真空脱水2小时,脱水完毕后,降温至50-60 ℃,再将10-20质量份丙酮,6-12质量份的二异氰酸酯,0.01-0.1质量份的小分子扩链剂和0.01-0.02质量份有机金属催化剂加入到反应器中,在80 ℃下反应2.5-4小时,取样,采用二正丁胺法测定NCO值,指标合格之后将反应器温度降至55 ℃以下,加入80-100质量份丙酮降低黏度,然后再向反应器中投入0.1-0.8质量份的端氨基硅烷偶联剂KH792,0.5-2质量份的亲水扩链剂,0.1-2质量份的胺类扩链剂和0.1-0.2质量份的螯合剂,反应20-30分钟,即得水性聚氨酯预聚物;
第二步,乳化:在水性聚氨酯预聚物中加入100-150质量份的去离子水,高速剪切乳化1小时,减压脱除丙酮,得到水性聚氨酯乳液;
第三步,调胶:在100质量份的水性聚氨酯乳液中加入0.02质量份的消泡剂,搅拌5分钟,再加入0.15质量份的增稠剂,搅拌10分钟,之后加入5质量份的固化剂,搅拌均匀,制得水性聚氨酯胶黏剂。
进一步的,第一步中的聚酯多元醇为聚己内酯多元醇、聚碳酸酯多元醇、聚己二酸酯多元醇当中的任意一种或任意组合,优选聚己二酸丁二醇酯。
进一步的,第一步中的聚醚为亲水性的聚丙二醇单甲醚、聚乙二醇单甲醚当中的一种或其组合,优选聚乙二醇单甲醚。
进一步的,第一步中的二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯当中的任意一种任意组合,优选异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯组合。
进一步的,第一步中的小分子扩链剂为乙二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、山梨醇甘醇当中的任意一种或任意组合,优选1,4-丁二醇。
进一步的,第一步中的有机金属催化剂为有机铋、有机锌、有机锆、铋锌合金催化剂当中的任意一种或任意组合,优选二月桂酸二丁基锡。
进一步的,第一步中的亲水扩链剂为二羟甲基丁酸、二羟甲基丙酸、二羟基磺酸盐、二胺基磺酸盐当中的任意一种或任意组合,优选乙二胺基乙磺酸钠。
进一步的,第一步中的胺类扩链剂为乙二胺、异佛尔酮二胺、羟乙基乙二胺当中的任意一种或任意组合,优选异佛尔酮二胺。
进一步的,第一步中的螯合剂为乙二胺四乙酸盐、酒石酸盐、柠檬酸盐、焦磷酸盐、三聚磷酸盐、六偏磷酸盐和葡萄糖酸盐当中的任意一种或任意组合,优选焦磷酸钠。
本发明的显著优点在于:
本发明提供一种水性聚氨酯胶黏剂的制备方法,通过加入水溶性螯合剂,与体系中的金属离子络合形成稳定的化合物,使其不再促进聚氨酯水解;通过引入硅氧烷,增加水性聚氨酯的耐水性和耐热性;通过添加少量亲水性聚醚来替代部分磺酸盐的亲水基团,减少磺酸根的含量,进而制备出稳定性优异的水性聚氨酯胶黏剂。所得产品基本不含有机溶剂,环保、安全,具有突出的粘结强度、耐水性、耐热性和离子稳定性。
本发明水性聚氨酯胶黏剂的固含量高、钙离子稳定性好,具有突出的粘接强度,进一步提高了产品的耐水性和耐热性,可用于制鞋行业。最终减压脱除丙酮,丙酮可回收再利用,减少了环境污染,属于清洁生产,并降低了生产成本。
具体实施方式
下面对本发明作进一步说明:
实施例1
第一步,聚合:先称取80 g聚己二酸丁二醇酯、1.6 g的聚乙二醇单甲醚加入到装有温度计,搅拌桨的四颈烧瓶中,在温度为100 ℃的环境下真空除水2小时,脱水完毕后,降温至50 ℃,再将15 g丙酮,4.7 g异佛尔酮二异氰酸酯,7.1 g的六亚甲基二异氰酸酯,0.05g的1,4-丁二醇和0.02 g二月桂酸二丁基锡加入反应器逐步升温至80 ℃反应3小时,取样,采用二正丁胺法测定NCO值,指标合格之后将反应器温度降至55 ℃以下,加入85 g丙酮降低黏度,然后再向反应器中投入0.11 g的端氨基硅烷偶联剂KH792,0.8 g的乙二胺基乙磺酸钠,0.6 g的异佛尔酮二胺和0.1 g焦磷酸钠,反应20分钟,即得水性聚氨酯预聚物;
第二步,乳化:在预聚物中加入100 g的去离子水,高速剪切乳化1小时,减压脱除丙酮,得到水性聚氨酯乳液;
第三步,调胶:在100 g水性聚氨酯乳液中加入0.02 g消泡剂,搅拌5分钟,再加入0.15 g增稠剂,搅拌10分钟,之后加入5 g固化剂,搅拌均匀,制得水性聚氨酯胶黏剂。
实施例2
第一步,聚合:先称取80g聚己二酸己二醇新戊二醇酯和1 g的聚乙二醇单甲醚加入到装有温度计,搅拌桨的四颈烧瓶中,在温度为100 ℃的环境下真空除水2小时,脱水完毕后,降温至50 ℃,再将15 g丙酮,5 g异佛尔酮二异氰酸酯,7 g的六亚甲基二异氰酸酯,0.04 g的1,4-丁二醇和0.02 g二月桂酸二丁基锡加入反应器逐步升温至80 ℃反应3小时,取样,采用二正丁胺法测定NCO值,指标合格之后将反应器温度降至55 ℃以下,加入85 g丙酮降低黏度,然后再向反应器中投入0.22 g的端氨基硅烷偶联剂KH792,1.2 g的乙二胺基乙磺酸钠,0.6 g的异佛尔酮二胺和0.2 g焦磷酸钠,反应20分钟,即得水性聚氨酯预聚物;
第二步,乳化:在预聚物中加入100 g的去离子水,高速剪切乳化1小时,减压脱除丙酮,得到水性聚氨酯乳液;
第三步,调胶:在100 g水性聚氨酯乳液中加入0.02 g消泡剂,搅拌5分钟,再加入0.15 g增稠剂,搅拌10分钟,之后加入5 g固化剂,搅拌均匀,制得水性聚氨酯胶黏剂。
实施例3
第一步,聚合:先称取80 g聚己二酸己二醇新戊二醇酯和1.2 g的聚丙二醇单甲醚加入到装有温度计,搅拌桨的四颈烧瓶中,在温度为100 ℃的环境下真空除水2小时,脱水完毕后,降温至50 ℃,再将15 g丙酮,4.7 g异佛尔酮二异氰酸酯,7.1 g的六亚甲基二异氰酸酯,0.05 g的1,6-己二醇和0.02 g二月桂酸二丁基锡加入反应器逐步升温至80 ℃反应3小时,取样,采用二正丁胺法测定NCO值,指标合格之后将反应器温度降至55 ℃以下,加入85 g丙酮降低黏度,然后再向反应器中投入0.44 g的端氨基硅烷偶联剂KH792,1.6 g的乙二胺基乙磺酸钠,0.4 g的异佛尔酮二胺和0.1 g焦磷酸钠,反应20分钟,即得水性聚氨酯预聚物;
第二步,乳化:在预聚物中加入100 g的去离子水,高速剪切乳化1小时,减压脱除丙酮,得到水性聚氨酯乳液;
第三步,调胶:在100 g水性聚氨酯乳液中加入0.02 g消泡剂,搅拌5分钟,再加入0.15 g增稠剂,搅拌10分钟,之后加入5 g固化剂,搅拌均匀,制得水性聚氨酯胶黏剂。
实施例4
第一步,聚合:先称取80 g聚四氢呋喃和1.2 g的聚丙二醇单甲醚加入到装有温度计,搅拌桨的四颈烧瓶中,在温度为100 ℃的环境下真空除水2小时,脱水完毕后,降温至50℃,再将15 g丙酮,4.7 g异佛尔酮二异氰酸酯,7.1 g的六亚甲基二异氰酸酯,0.05 g的1,4-丁二醇和0.02 g二月桂酸二丁基锡加入反应器逐步升温至80 ℃反应3小时,取样,采用二正丁胺法测定NCO值,指标合格之后将反应器温度降至55 ℃以下,加入85 g丙酮降低黏度,然后再向反应器中投入0.66 g的端氨基硅烷偶联剂KH792,0.2 g的乙二胺基乙磺酸钠,0.8 g的异佛尔酮二胺和0.2 g 乙二胺四乙酸四钠,反应20分钟,即得水性聚氨酯预聚物;
第二步,乳化:在预聚物中加入100 g的去离子水,高速剪切乳化1小时,减压脱除丙酮,得到水性聚氨酯乳液;
第三步,调胶:在100 g水性聚氨酯乳液中加入0.02 g消泡剂,搅拌5分钟,再加入0.15 g增稠剂,搅拌10分钟,之后加入5 g固化剂,搅拌均匀,制得水性聚氨酯胶黏剂。
对比例1
第一步,聚合:先称取80 g聚己二酸丁二醇酯加入到装有温度计,搅拌桨的四颈烧瓶中,在温度为100 ℃的环境下真空除水2小时,脱水完毕后,降温至50 ℃,再将15 g丙酮,4.7 g异佛尔酮二异氰酸酯,7.1 g的六亚甲基二异氰酸酯,0.05 g的1,4-丁二醇和0.02 g二月桂酸二丁基锡加入反应器逐步升温至80 ℃反应3小时,取样,采用二正丁胺法测定NCO值,指标合格之后将反应器温度降至55 ℃以下,加入85 g丙酮降低黏度,然后再向反应器中投入0.66 g的端氨基硅烷偶联剂KH792,2 g的乙二胺基乙磺酸钠和0.4 g的异佛尔酮二胺,反应20分钟,即得水性聚氨酯预聚物;
第二步,乳化:在预聚物中加入100 g的去离子水,高速剪切乳化1小时,减压脱除丙酮,得到水性聚氨酯乳液;
第三步,调胶:在100 g水性聚氨酯乳液中加入0.02 g消泡剂,搅拌5分钟,再加入0.15 g增稠剂,搅拌10分钟,之后加入5 g固化剂,搅拌均匀,制得水性聚氨酯胶黏剂。
对比例2
第一步,聚合:先称取80 g聚己二酸丁二醇酯和0.8 g的聚乙二醇单甲醚加入到装有温度计,搅拌桨的四颈烧瓶中,在温度为100 ℃的环境下真空除水2小时,脱水完毕后,降温至50 ℃,再将15 g丙酮,4.7 g异佛尔酮二异氰酸酯,7.1 g的六亚甲基二异氰酸酯,0.05g的1,4-丁二醇和0.02 g二月桂酸二丁基锡加入反应器逐步升温至80 ℃反应3小时,取样,采用二正丁胺法测定NCO值,指标合格之后将反应器温度降至55 ℃以下,加入85 g丙酮降低黏度,然后再向反应器中投入2 g的乙二胺基乙磺酸钠和1 g的异佛尔酮二胺,反应20分钟,即得水性聚氨酯预聚物;
第二步,乳化:在预聚物中加入100 g的去离子水,高速剪切乳化1小时,减压脱除丙酮,得到水性聚氨酯乳液;
第三步,调胶:在100 g水性聚氨酯乳液中加入0.02 g消泡剂,搅拌5分钟,再加入0.15 g增稠剂,搅拌10分钟,之后加入5 g固化剂,搅拌均匀,制得水性聚氨酯胶黏剂。
然后将上述实施例和对比例制得的水性聚氨酯胶黏剂进行力学性能测试,用于橡胶基材之间的黏合,并对其胶膜测量吸水率,具体如下表:
表1水性聚氨酯胶黏剂及胶膜的性能
对比例1和对比例2添加聚醚的量均低于实施例中的1 g,磺酸盐的量超过1.8 g,均没有通过钙离子稳定性检测,这表明引入亲水性聚醚替代部分磺酸盐可以有效提高其离子稳定性。
对比例1和对比例2均没有添加螯合剂,其测量的吸水率也高于其他添加了螯合剂的实施例,这表明引入螯合剂可以有效提升其耐水性能。
对比例2没有添加硅氧烷,其测量的吸水率高于对比例1的3.27 %,这表明引入硅氧烷也可以有效提升其耐水性能。
以上数据可以看出本发明水性聚氨酯胶黏剂的固含量高、钙离子稳定性好,具有突出的粘接强度,有机硅的引入确实可以有效提高耐水性和耐热性,但以占水性聚氨酯预聚物总质量的0.1 %-0.2 %为最佳,过多引入则会造成结晶性能急剧下降而带来反作用。同时当聚醚的用量超过1 g,乙二胺基乙磺酸钠的用量不超过1.8 g,就可以通过钙离子稳定性检测。
本发明实施的特点在于引入端氨基硅烷偶联剂,进一步提高产品的耐水性和耐热性;引入了螯合剂,减少金属离子对水解的促进作用,提高产品的耐水性;引入了聚乙二醇单甲醚,由于其很强的亲水性可以替代部分磺酸盐的磺酸根,提高产品的离子稳定性,制得性能优异的水性聚氨酯胶黏剂;最终减压脱除丙酮,丙酮可回收再利用,减少了环境污染,属于清洁生产,同时降低了生产成本。
虽然本发明己通过参考优选的实施例进行了描述,但是,本专业普通技术人员应当了解,在权利要求书的范围内,可作形式和细节上的各种各样变化。
Claims (10)
1.一种水性聚氨酯胶黏剂的制备方法,其特征在于,包括以下步骤:
(1)聚合:先将80质量份的聚酯多元醇和1-2质量份的聚醚投入到反应器中,在100-120℃的温度下真空脱水2小时,脱水完毕后,降温至50-60 ℃,再将10-20质量份丙酮,6-12质量份的二异氰酸酯,0.01-0.1质量份的小分子扩链剂和0.01-0.02质量份有机金属催化剂加入到反应器中,逐步升温至80 ℃下反应2.5-4小时,取样,测定NCO值,指标合格之后将反应器温度降至55 ℃以下,加入80-100质量份丙酮降低黏度,然后再向反应器中投入0.1-0.8质量份的端氨基硅烷偶联剂KH792,0.1-2质量份的亲水扩链剂,0.1-2质量份的胺类扩链剂和0.1-0.2质量份的螯合剂,反应20-30分钟,即得水性聚氨酯预聚物;
(2)乳化:在水性聚氨酯预聚物中加入100-150质量份的去离子水,高速剪切乳化1小时,减压脱除丙酮,得到水性聚氨酯乳液;
(3)调胶:在100质量份的水性聚氨酯乳液中加入0.02质量份的消泡剂,搅拌5分钟,再加入0.15质量份的增稠剂,搅拌10分钟,之后加入5质量份的固化剂,搅拌均匀,制得水性聚氨酯胶黏剂。
2.根据权利要求1所述的水性聚氨酯胶黏剂的制备方法,其特征在于:所述步骤(1)中的聚酯多元醇为聚己内酯多元醇、聚碳酸酯多元醇、聚己二酸酯多元醇当中的任意一种或任意组合。
3.根据权利要求1所述的水性聚氨酯胶黏剂的制备方法,其特征在于:所述步骤(1)中的聚醚为亲水性的聚丙二醇单甲醚、聚乙二醇单甲醚当中的一种或其组合。
4.根据权利要求1所述的水性聚氨酯胶黏剂的制备方法,其特征在于:所述步骤(1)中的二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、甲基环己基异氰酸酯当中的任意一种或任意组合。
5.根据权利要求1所述的水性聚氨酯胶黏剂的制备方法,其特征在于:所述步骤(1)中的小分子扩链剂为乙二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、山梨醇甘醇当中的任意一种或任意组合。
6.根据权利要求1所述的水性聚氨酯胶黏剂的制备方法,其特征在于:所述步骤(1)中的有机金属催化剂为有机铋、有机锡、有机锆、铋锌合金催化剂当中的任意一种或任意组合。
7.根据权利要求1所述的水性聚氨酯胶黏剂的制备方法,其特征在于:所述步骤(1)中的亲水扩链剂为二羟甲基丁酸、二羟甲基丙酸、二羟基磺酸盐、二胺基磺酸盐当中的任意一种或任意组合。
8.根据权利要求1所述的水性聚氨酯胶黏剂的制备方法,其特征在于:所述步骤(1)中的胺类扩链剂为乙二胺、异佛尔酮二胺、羟乙基乙二胺当中的任意一种或任意组合。
9.根据权利要求1所述的水性聚氨酯胶黏剂的制备方法,其特征在于:所述步骤(1)中的螯合剂为乙二胺四乙酸盐、酒石酸盐、柠檬酸盐、焦磷酸盐、三聚磷酸盐、六偏磷酸盐和葡萄糖酸盐当中的任意一种或任意组合。
10.如权利要求1-9任一所述的制备方法制得的水性聚氨酯胶黏剂。
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CN113736062A (zh) * | 2021-09-14 | 2021-12-03 | 烟台宜彬新材料科技有限公司 | 一种尼龙搭扣带用水性聚氨酯乳液及其制备方法 |
CN114133533A (zh) * | 2021-12-17 | 2022-03-04 | 鹤山市金润纳新型材料有限公司 | 一种水性聚氨酯胶黏剂及其制备方法 |
CN115353608A (zh) * | 2022-07-20 | 2022-11-18 | 江苏休伦新材料有限公司 | 一种超纤革用半干贴树脂及其制备方法 |
WO2024099926A1 (en) | 2022-11-09 | 2024-05-16 | Covestro Deutschland Ag | A composition, a preparation method and use thereof |
CN118406004A (zh) * | 2024-07-02 | 2024-07-30 | 梦百合家居科技股份有限公司 | 一种动态可编织扩链剂及其应用 |
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