CN112430447A - 一种鞋用水性聚氨酯胶黏剂及制备工艺 - Google Patents
一种鞋用水性聚氨酯胶黏剂及制备工艺 Download PDFInfo
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Abstract
本发明公开一种鞋用水性聚氨酯胶黏剂及制备工艺,水性聚氨酯胶黏剂组成包括70‑85份的高结晶度聚酯多元醇、2.5‑9.5份分子量为200到1000的端羟基磺酸盐聚醚、12‑18份的二异氰酸酯、0.1‑2.0份带侧基的小分子端羟基扩链剂、0‑0.5份小分子端氨基扩链剂、10ppm‑50ppm的催化剂、0.05%‑0.25%份的消泡剂、0.05%‑0.30%份的抗菌剂、0.3%‑0.5%份的流平剂和0‑2%的增粘树脂,本发明通过配方设计,选用一种高分子量的端羟基磺酸盐聚醚作为水性聚氨酯的分散剂,在易于活动的大分子软段引入亲水基团,并通过特殊的工艺控制——先进行本体的聚合,再在浓溶液相中扩链,再加丙酮稀释、加到去离子水中进行分散,最后在水中进行第二次扩链,进一步提高水性胶的极性和分子量——制备出了粘结强度高、易分散、储存稳定期长的水性聚氨酯。
Description
技术领域
本发明属于水性聚氨酯技术领域,尤其涉及一种水性聚氨酯分散剂以及一种高固含量鞋用水性聚氨酯胶黏剂的制备工艺。
背景技术
聚氨酯胶黏剂因耐低温性好、柔韧性好、粘接强度大等优良特性而广泛应用于制鞋行业。目前鞋用胶市场上,溶剂型聚氨酯胶黏剂占据主要市场。但溶剂型聚氨酯胶黏剂成膜过程中会有大量的挥发性有机化合物(VOC)挥发到大气中,造成环境污染,同时危害施工人员的身体健康。因此推行绿色、环保的水性聚氨酯胶黏剂势在必行。
鞋用水性聚氨酯胶黏剂的报道还比较少,且合成水性聚氨酯普遍采用小分子分散剂。CN 104194707 B采用一种小分子磺酸盐型分散剂,制备出了一种粘度在120-150cps之间,固含量在45-50%的鞋用水性聚氨酯胶黏剂,但剥离强度较低,贴合一天后剥离强度仅仅5N/mm。DMPA和DMBA是研究比较多的水性聚氨酯用小分子分散剂,工艺比较成熟,但这些小分子分散剂缺点比较明显,如熔点较高,合成难度较大,其分散性和反应嵌段的均匀性也不够理想,且需要中和产品有挥发性胺的刺激性气味,同时合成PUD时羧酸型亲水单体用量较多,其成膜后的耐水性、耐电解质性和耐高低温性能会变差。目前成熟的小分子分散剂是氨基磺酸盐型分散剂,如AAS(N-(2-氨基乙基)-氨基乙烷磺酸钠)。此分散剂的优点是亲水能力强,在较小的用量下,就能形成更稳定的“双电层”结构,增强了胶粒间的静电作用力,能有效地提高水性聚氨酯的储存稳定性,容易制得高固含量的水性聚氨酯。拜耳的U54是小分子磺酸盐型分散剂的典型应用。但使用小分子磺酸盐制备的水性聚氨酯的初始剥离强度也很小,在5N/mm左右。
发明内容
为了解决现有技术的不足,本发明通过限定各原料的配比,引入一种高分子量聚醚磺酸盐型水性聚氨酯分散剂,制备出粘结强度高、易分散、储存稳定期长的水性聚氨酯,更适合鞋用胶黏剂的使用要求。
本发明提出的一种鞋用水性聚氨酯胶黏剂,其原料组成为:
70-85份的高结晶度聚酯多元醇;
2.5-9.5份分子量为200到1000的端羟基磺酸盐聚醚;
12-18份的二异氰酸酯;
0.1-2.0份带侧基的小分子端羟基扩链剂;
0-0.5份小分子端氨基扩链剂;
10ppm-50ppm的催化剂;
0.05%-0.25%份的消泡剂;
0.05%-0.30%份的抗菌剂;
0.3%-0.5%份的流平剂;
0-2%的增粘树脂;
其中高分子量的端羟基磺酸盐聚醚为如下式I的结构:
其中R为具有如下式II,式III,式IV中任一种所示结构的结构单元,M为Na+,K+,NH4 +离子中的一种。
水性聚氨酯是能够稳定分散在水中的聚氨酯,一般固含量在30%-55%之内。水性聚氨酯的本征分散特性由水性聚氨酯的配方决定,尤其是水性分散剂的选用。本发明采用了一种高分子量的端羟基磺酸盐聚醚为分散剂,将阴离子基团引入到聚氨酯分子链的软段上面,使得阴离子基团在分散过程中容易在低温下扩散、聚集,进而提高了分散性和储存稳定性。为了提高生产效率,鞋用胶黏剂必须具备较好的初粘性。聚氨酯胶黏剂的初粘由聚氨酯的结晶速度决定,一般结晶速度越快,结晶温度越高,初粘越好。而聚氨酯分子链由硬段和软段组成,硬段和软段都能分别结晶。为了提高聚氨酯胶黏剂的初粘,软段和硬段原料的选择也至关重要。
本发明一种鞋用水性聚氨酯胶黏剂,所述的高结晶度聚酯多元醇为分子量1500-5000的聚己二酸丁二醇酯多元醇、聚己二酸己二醇酯多元醇、己二醇型聚碳酸酯多元醇、聚己内酯多元醇中的一种或几种混合物。
本发明一种鞋用水性聚氨酯胶黏剂,所述的二异氰酸酯为六甲基二异氰酸酯、异佛尔酮二异氰酸酯、氢化二苯基甲烷二异氰酸酯中的一种或几种混合物。
本发明一种鞋用水性聚氨酯胶黏剂,所述的小分子端羟基扩链剂为2-甲基-1,3-丙二醇、新戊二醇、3-甲基-1,5-戊二醇中的一种或几种混合物。
本发明一种鞋用水性聚氨酯胶黏剂,所述的小分子端氨基扩链剂为乙二胺。
本发明一种鞋用水性聚氨酯胶黏剂,已知的聚氨酯反应用催化剂包括有机锡类催化剂、有机铋类催化剂或有机锌类催化剂,优选水溶性有机铋类催化剂。
水性聚氨酯的储存稳定性也受水性聚氨酯的合成工艺影响。比较成熟的水性聚氨酯合成工艺是丙酮法和预聚体法。本工艺的特殊性在于选用高分子量的端羟基磺酸盐聚醚为分散剂,不能当做扩链剂使用,在分散时同时加入,同时还需要控制各反应阶段的温度。为了易于分散,获得更加稳定的水性聚氨酯乳液,还需对合成温度和分散条件加以限制。
作为对上述技术方案的限定,所述的制备工艺为:
首先高结晶度聚酯多元醇、高分子量的端羟基磺酸盐聚醚于90-110℃下混合、抽空脱水1-2h;在氮气保护下,加入二异氰酸酯和部分催化剂于70-90℃下反应1-3小时;降温至50-70℃;加入固含量为40%-60%带侧基的的小分子端羟基扩链剂丙酮溶液和剩余的催化剂,回流反应1-3小时,得到预聚体;加入100-120份的丙酮,溶解30min-90min;降温至30-40℃;高速搅拌下,将其快速加入到100-110份20-30℃的去离子水中高速分散;分散开之后,将搅拌降为低速搅拌,加入固含量为40%-60%的小分子端氨基扩链剂丙酮溶液;升温至40-50℃反应熟化5-8h;加入消泡剂,低速搅拌30min;抽真空,控制真空度为-0.1MPa,高速搅拌下,除去溶液相中的丙酮,将丙酮回收利用。低速搅拌下加入流平剂、抗菌剂。选择性的添加增粘树脂。
所述的高速搅拌为1500-2500rpm,所述的低速搅拌为100-300rpm,所述的预聚体的NCO含量在1.4%至2.8%之间。
该工艺的特点首先是,将分散剂混合到预聚物中,再经扩链分散到聚氨酯的分子中,分散剂的分布更加均匀一致;其次是经第一步扩链后的分散体溶于丙酮,滴加到水中进行分散,降低了分散难度系数。
消泡剂包括乳化硅油、高碳醇脂肪酸酯复合物、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚、聚氧丙烯甘油醚和聚氧丙烯聚氧乙烯甘油醚、聚二甲基硅氧烷等。合适的商业化消泡剂供应商有BYK和TEGO。
抗菌剂包括香草醛、乙基香草醛类、酰基苯胺类、咪唑类、噻唑类、异噻唑酮啉酮类、季铵盐类、双呱类、酚类、甲壳素、芥末、蓖麻油、山葵等。商业化水性抗菌剂如朗盛P91,陶氏SKANEòM-8,Vink公司的Vinkocide 3.0。
流平剂包括改性有机硅类、聚丙烯酸酯类、羧甲基纤维素类等,商业化流平剂如KYC-6662。
增粘树脂包括氢化松香、歧化松香、烷基酚醛树脂、萜烯树脂、加氢石油树脂等。商业化的增粘树脂包括伊斯曼公司的Tacolyn 3509,蓝巨化学的BJ130。
综上所述,本发明通过配方设计,选用一种高分子量的端羟基磺酸盐聚醚作为水性聚氨酯的分散剂,在易于活动的大分子软段引入亲水基团,并通过特殊的工艺控制——先进行本体的聚合,再在浓溶液相中扩链,再加丙酮稀释、加到去离子水中进行分散,最后在水中进行第二次扩链,进一步提高水性胶的极性和分子量——制备出了粘结强度高、易分散、储存稳定期长的水性聚氨酯。
具体实施方式
下面将结合实施例,对本发明的技术方案进行清楚、完整地描述,显然所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。
实施例一 水性聚氨酯的制备
在氮气保护下,首先高结晶度聚酯多元醇、高分子量的端羟基磺酸盐聚醚、二异氰酸酯于70-90℃、部分催化剂催化下本体聚合反应1-3小时;
降温至50-70℃;
加入固含量为40%-60%的小分子端羟基扩链剂丙酮溶液和剩余的催化剂,回流反应1-3小时;
加入100-120份的丙酮,溶解30min-90min;
降温至30-40℃;
高速搅拌下,快速加入到100-110份20-30℃的去离子水中分散,视形成均一乳液时为分散开;
分散开之后,将搅拌降为低速搅拌,加入固含量为40%-60%的小分子端氨基扩链剂丙酮溶液;
升温至40-50℃反应熟化5-8h;
加入消泡剂,低速搅拌30min;
抽真空,控制真空度为-0.1MPa,高速搅拌下,除去溶液相中的丙酮,将丙酮回收利用。
低速搅拌下加入流平剂、抗菌剂、增粘树脂。
各组分具体添加比例如表1,依据上述步骤完成实施例1-实施例5。
表1 各组分具体添加比例
注:SO1、SO2、SO3为高分子量的端羟基磺酸盐聚醚,其结构式为:
实施例二 测试和表征
1)固含量
参考BS EN ISO 3251-2008。
2)粘度
使用Brookfield DV2T型旋转粘度计测定25℃下的熔体粘度。
3)粒径
首先将乳液浓度稀释至固含量0.3%,然后用Zeta-sier-3000HS粒度仪测定乳液粒径大小及分布,测试温度为25℃,检测散射角度为90°,激光波长为630nm。
4)储存期
将样品密分别封置于5℃和30℃的恒温箱中各6个月,观察是否有沉淀析出,如无沉淀则代表储存期超过6个月。
5)剥离强度
参考GB/T 2791,首先用丁酮处理Shore硬度为85A,宽度25mm*厚2mm*长度200mm的聚酯型TPU片材表面,80℃烘烤10min除去表面溶剂,将水性聚氨酯乳液刷涂在TPU片材上,在80℃的烘箱中活化10min,取出贴合。认定粘结30min的剥离强度为初始剥离强度。
实施例三 实验数据如表2所示。
表2 实验数据
上表数据显示,本发明制备的水性聚氨酯胶黏剂的粘度在3000之间,接近于市售科思创的U54,同时粒径在110~150nm之间,低于科思创U54的190nm;本发明制备的水性聚氨酯胶黏剂的固含量和科思创U54的接近,约是50%。综上说明,使用本发明所述的高分子量端羟基磺酸盐聚醚为分散剂,采用本发明所述工艺更容易分散出粒径更小,粘度更大的水性聚氨酯胶黏剂。最突出的结果是,本发明制备的水性聚氨酯胶黏剂的初始剥离强度在11N/mm以上,远远高于科思创U54的6.6N/mm,具备更好的粘结性能。
Claims (10)
2.根据权利要求1所述的一种鞋用水性聚氨酯胶黏剂,其特征在于:所述的高结晶度聚酯多元醇为分子量1500-5000的聚己二酸丁二醇酯多元醇、聚己二酸己二醇酯多元醇、己二醇型聚碳酸酯多元醇、聚己内酯多元醇中的一种或几种混合物。
3.根据权利要求1所述的一种鞋用水性聚氨酯胶黏剂,其特征在于:所述的二异氰酸酯为六甲基二异氰酸酯、异佛尔酮二异氰酸酯、氢化二苯基甲烷二异氰酸酯中的一种或几种混合物。
4.根据权利要求1所述的一种鞋用水性聚氨酯胶黏剂,其特征在于:所述的小分子端羟基扩链剂为2-甲基-1,3-丙二醇、新戊二醇、3-甲基-1,5-戊二醇中的一种或几种混合物。
5.根据权利要求1所述的一种鞋用水性聚氨酯胶黏剂,其特征在于:所述的小分子端氨基扩链剂为乙二胺;反应用催化剂包括有机锡类催化剂、有机铋类催化剂或有机锌类催化剂。
6.根据权利要求1所述的一种鞋用水性聚氨酯胶黏剂,其特征在于:流平剂未0.3%-0.5%份;增粘树脂为0-2%份。
7.一种鞋用水性聚氨酯胶黏剂制备工艺,制备权利要求1所述的一种鞋用水性聚氨酯胶黏剂,其特征在于:首先将高结晶度聚酯多元醇、高分子量的端羟基磺酸盐聚醚于90-110℃下混合、抽空脱水1-2h;在氮气保护下,加入二异氰酸酯和部分催化剂于70-90℃下反应1-3小时;降温至50-70℃;加入固含量为40%-60%带侧基的小分子端羟基扩链剂丙酮溶液和剩余的催化剂,回流反应1-3小时,得到预聚体;加入100-120份的丙酮,溶解30min-90min;降温至30-40℃;高速搅拌下,将其快速加入到100-110份20-30℃的去离子水中高速分散;分散开之后,将搅拌降为低速搅拌,加入固含量为40%-60%的小分子端氨基扩链剂丙酮溶液;升温至40-50℃反应熟化5-8h;加入消泡剂,低速搅拌30min;抽真空,控制真空度为-0.1MPa,高速搅拌下,除去溶液相中的丙酮,将丙酮回收利用。
8.根据权利要求7所述的一种鞋用水性聚氨酯胶黏剂制备工艺,其特征在于:低速搅拌下加入流平剂、抗菌剂;流平剂未0.3%-0.5%份;抗菌剂为0.05%-0.30%份。
9.根据权利要求8所述的一种鞋用水性聚氨酯胶黏剂制备工艺,其特征在于:选择性的添加增粘树脂,增粘树脂为0-2%份;所述的预聚体的NCO含量在1.4%至2.8%之间。
10.根据权利要求9所述的一种鞋用水性聚氨酯胶黏剂制备工艺,其特征在于:所述的高速搅拌为1500-2500rpm,所述的低速搅拌为100-300rpm。
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