CN116120879A - 一种水性单组分聚氨酯胶粘剂及其制备方法和应用 - Google Patents
一种水性单组分聚氨酯胶粘剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供一种水性单组分聚氨酯胶粘剂,其是以聚酯多元醇、IPDI、扩链剂、催化剂T‑12、NMP、二丙酮醇、三乙胺、后扩链剂为原料,合成的水性单组分聚氨酯胶粘剂,在聚酯多元醇脱水后,加入催化剂T‑12、IPDI反应结束后,再加入溶解于溶剂的扩链剂继续反应,完毕后,经过降温再加入三乙胺与二丙酮醇进行中和反应,加入脱盐水高速搅拌分散,再加入后扩链剂混合液体,反应完成即可。本发明的优点是原料易得,反应条件温和,工艺简单易行。采用本发明制得的水性单组分聚氨酯胶粘剂,黏度低,稳定性好,可操作性能好。其初粘性好,烘烤温度低,剥离强度高,完全达到鞋用水性胶的国家标准。
Description
技术领域
本发明属于高分子材料技术领域,具体涉及一种水性单组分聚氨酯胶粘剂及其制备方法和应用。
背景技术
水性胶粘剂是水性单组分聚氨酯胶粘剂。随着经济发展和人们生活水平提高,各国对挥发性有机物及有毒物的限制越来越严格,国际上兴起“绿色革命”,促进全球工业向“绿色”方向迈进。而水性聚氨酯胶粘剂(PUD)的低VOC含量,符合发展绿色工业的“三前提”(资源、能源、无污染)及“四E原则”(经济、效率、生态、活力)。单组分水性胶粘剂不但具有溶剂型聚氨酯胶粘接剂优异的综合性能,而且无毒、无害,无安全、环保和消防隐患,不污染环境,节省资源,符合节能减排和环保指标严格要求。
目前,绝大部分的高性能鞋用聚氨酯胶粘剂却一直依赖进口,尤其是水性聚氨酯胶粘剂。国内水性聚氨酯胶粘剂在剥离强度、固化速度、初粘性、耐热性等方面均不达到满意的性能。
发明内容
本发明的目的在于克服现有技术的不足,提供一种水性单组分聚氨酯胶粘剂及其制备方法和应用。本发明的水性单组分聚氨酯胶粘剂使用烘烤温度为65-75℃,初粘性好,剥离强度远大于150N/20mm,耐热性好。
本发明的目的是通过以下技术方案来实现的:一种水性单组分聚氨酯胶粘剂,按质量份数计,包括以下组分:260-300份聚酯多元醇、50.3-58份异佛尔酮二异氰酸酯(IPDI)、10.4-12份扩链剂、0.017-0.02份催化剂T-12、8.7-10份二丙酮醇、7.1-8.15份三乙胺、2.45-2.75份后扩链剂、20.8-24份溶剂和295-340份水;
其中,所述扩链剂包括二羟甲基丙酸(DMPA)、二羟甲基丁酸(DMBA)中的一种;所述后扩链剂包括乙二胺、丁二胺、戊二胺、己二胺、异佛尔酮二胺、二乙烯三胺和三乙烯四胺中的两种及两种以上。
进一步的,所述聚酯多元醇包括聚己二酸-1,6-己二醇酯二元醇、聚己二酸-1,4-丁二醇二元醇、聚己二酸-乙二醇二元醇中的一种;优选所述聚酯多元醇为聚己二酸-1,6-己二醇酯二元醇,分子量2880-3200,羟基值35-39。
和/或,所述溶剂包括N-甲基吡咯烷酮(NMP)、N-乙基吡咯烷酮(NEP)、N-乙烯基吡咯烷酮(NVP)、二甲基甲酰胺(DMF)或二甲基乙酰胺(DMAC)中的一种;
和/或,所述扩链剂为二羟甲基丙酸(DMPA)。
和/或,后扩链剂为乙二胺和二乙烯三胺,用量为:2.2-2.5份乙二胺、0.22-0.25份二乙烯三胺
和/或,所述水为脱盐水。
优选的,按质量份数计,包括以下组分:300份聚酯多元醇、58份异佛尔酮二异氰酸酯(IPDI)、12份二羟甲基丙酸(DMPA)、0.02份催化剂T-12、10份二丙酮醇、8.15份三乙胺、2.5份乙二胺、0.25份二乙烯三胺、24份N-甲基吡咯烷酮(NMP)和340份脱盐水。
本发明还提供一种上述的一种水性单组分聚氨酯胶粘剂的制备方法,包括以下步骤:
S1、将聚酯多元醇进行脱水,得到产物一;
S2、将异佛尔酮二异氰酸酯与产物一混合升温至80-95℃反应,再加入催化剂T-12继续反应,得到产物二;
S3、将扩链剂溶解于溶剂中,并与产物二混合反应,得到产物三;
S4、将二丙酮醇和三乙胺混合均匀,并与产物三混合反应,得到产物四;
S5、向产物四中迅速加入低温的部分脱盐水,搅拌分散,控制温度低于45℃进行反应,得到产物五;
S6、将后扩链剂和剩余脱盐水混合,并与产物五混合搅拌分散,得到水性单组分聚氨酯胶粘剂。
进一步的,步骤S1中,所述脱水为真空脱水,真空度为-0.08~-0.085MPa,温度为105-110℃,时间为1-3h。
进一步的,步骤S2中,异佛尔酮二异氰酸酯与产物一混合升温至80-95℃反应的时间为0.5-1.5h,再加入催化剂T-12继续反应的时间为1.5-2.5h。
进一步的,步骤S3中,所述混合反应的时间为1.5-2.5h。
进一步的,步骤S4中,与产物三混合反应之前,需将所述产物三降温至50℃以下;
和/或,步骤S4中,所述混合反应的温度为50℃,反应时间为8-12min。
进一步的,步骤S5中,所述搅拌分散的转速为800-2800r/min,时间为3-8min;优选转速为2000-2800r/min;
和/或,步骤S5中,所述低温的部分脱盐水温度为5-15℃;
和/或,步骤S5中,所述部分脱盐水的用量占总脱盐水用量的86-90%。
进一步的,步骤S5中,所述搅拌分散的转速为800-2800r/min,时间为3-8min;优选转速为2000-2800r/min;
和/或,步骤S6中,所述剩余脱盐水的用量占总脱盐水用量的10-14%。
本发明还提供一种上述制备方法得到的水性单组分聚氨酯胶粘剂作为鞋用胶的应用。
本发明的有益效果是:本发明的优点是原料易得,反应条件温和,工艺简单易行。采用本发明制得的水性单组分聚氨酯胶粘剂,涂胶后烘烤温度65-75℃,粘接性能远超过水性聚氨酯胶粘剂国家标准。还具有适当的干燥速度和初粘力,能够适应高速生产的需求,胶层膜具有良好的耐热、耐弯曲性能,且具有较低的毒性。
具体实施方式
下面进一步详细描述本发明的技术方案,但本发明的保护范围不局限于以下所述。
实施例1
将300g聚酯多元醇加入到三口烧瓶中,逐步加热搅拌均匀,升温至105~110℃真空脱水2h。降温至70℃以下,加入58g IPDI,逐步升温至85℃,反应1h后,加入0.02g催化剂T-12,继续反应2h。加入用24g NMP溶解12g DMPA的溶液,恒温反应2h。降温至50℃,将8.15g三乙胺与10g二丙酮醇混合均匀,加入至反应物料中,在50℃下反应10min。迅速加入10℃的300g脱盐水,高速搅拌分散5分钟,温度控制在低于45℃。加入40g脱盐水、2.5g乙二胺和0.25g二乙烯三胺三者混合均匀的液体,高速分散5分钟,反应完成制得水性单组分聚氨酯胶粘剂。
实施例2
将280g聚酯多元醇加入到三口烧瓶中,逐步加热搅拌均匀,升温至105~110℃真空脱水2h。降温至70℃以下,加入54g IPDI,逐步升温至85℃,反应1h后,加入0.018g催化剂T-12,继续反应2h。加入用22g NMP溶解11g DMPA的溶液,恒温反应2h。降温至50℃,将7.5g三乙胺与9.3g二丙酮醇混合均匀,加入至反应物料中,在50℃下反应10min。迅速加入10℃的280g脱盐水,高速搅拌分散5分钟,温度控制在低于45℃。加入37g脱盐水、2.4g乙二胺和0.24g二乙烯三胺三者混合均匀的液体,高速分散5分钟,反应完成制得水性单组分聚氨酯胶粘剂。
对比例1
CN105295817一种高固含量水性聚氨酯胶粘剂的制备方法
对比例2
CN103421462一种高初粘性水性聚氨酯胶粘剂及其制备方法
实验例1剥离强度和粘合强度的测定
鞋用胶粘剂的主要性能要求受到鞋材、鞋型和粘接工艺的不同而异,但从整体而言,鞋用胶粘剂的主要性能指标在于剥离强度和粘合强度。
将实施例1、实施例2制作得到的水性单组分聚氨酯胶粘剂分别用于粘接皮鞋的皮面和橡胶底、聚氨酯底,委托四川出入境检验检疫局检验检疫技术中心,国家鞋类及原材料检测重点实验室进行检测,判定依据“QB/T1002-2015皮鞋”,分别检测剥离强度和粘合强度,实验结果如下表:
“QB/T1002-2015皮鞋”中对剥离强度的要求是男士皮鞋大于70N/cm定义为合格(女式皮鞋大于50N/cm),男士皮鞋大于90N/cm定义为优等品(女生皮鞋大于70N/cm),经测定结果显示,本发明的剥离强度远超国标中的要求,属于超高性能鞋用聚氨酯胶粘剂。
对比例1公开的性能参数为符合《鞋用水性聚氨酯国家标准(2014)》的要求,《鞋用水性聚氨酯国家标准(2014)》定义的剥离强度为大于4.0N/mm,远低于本发明的剥离强度。
对比例2公开的配方的剥离强度为4.8N/mm,公开的合肥恒瑞化工新材料有限公司同类产品AH-1208的剥离强度为4.7N/mm,均远低于本发明的剥离强度。
实验例2其他性能的测定
其他性能测定的实验结果如下表:
上述结果可知,本发明的水性单组分聚氨酯胶粘剂具有适当的干燥速度和初粘力,能够适应高速生产的需求,胶层膜具有良好的耐热、耐弯曲性能,且具有较低的毒性。
以上所述仅是本发明的优选实施方式,应当理解本发明并非局限于本文所披露的形式,不应看作是对其他实施例的排除,而可用于各种其他组合、修改和环境,并能够在本文所述构想范围内,通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围,则都应在本发明所附权利要求的保护范围内。
Claims (10)
1.一种水性单组分聚氨酯胶粘剂,其特征在于,按质量份数计,包括以下组分:260-300份聚酯多元醇、50.3-58份异佛尔酮二异氰酸酯、10.4-12份扩链剂、0.017-0.02份催化剂T-12、8.7-10份二丙酮醇、7.1-8.15份三乙胺、2.45-2.75份后扩链剂、20.8-24份溶剂和295-340份水;
其中,所述扩链剂包括二羟甲基丙酸、二羟甲基丁酸中的一种;所述后扩链剂包括乙二胺、丁二胺、戊二胺、己二胺、异佛尔酮二胺、二乙烯三胺和三乙烯四胺中的两种及两种以上。
2.根据权利要求1所述的一种水性单组分聚氨酯胶粘剂,其特征在于,所述聚酯多元醇包括聚己二酸-1,6-己二醇酯二元醇、聚己二酸-1,4-丁二醇二元醇、聚己二酸-乙二醇二元醇中的一种;
和/或,所述溶剂包括N-甲基吡咯烷酮、N-乙基吡咯烷酮、N-乙烯基吡咯烷酮、二甲基甲酰胺或二甲基乙酰胺中的一种;
和/或,后扩链剂为乙二胺和二乙烯三胺,用量为:2.2-2.5份乙二胺、0.22-0.25份二乙烯三胺
和/或,所述水为脱盐水。
3.权利要求1或2所述的一种水性单组分聚氨酯胶粘剂的制备方法,其特征在于,包括以下步骤:
S1、将聚酯多元醇进行脱水,得到产物一;
S2、将异佛尔酮二异氰酸酯与产物一混合升温至80-95℃反应,再加入催化剂T-12继续反应,得到产物二;
S3、将扩链剂溶解于溶剂中,并与产物二混合反应,得到产物三;
S4、将二丙酮醇和三乙胺混合均匀,并与产物三混合反应,得到产物四;
S5、向产物四中迅速加入低温的部分脱盐水,搅拌分散,控制温度低于45℃进行反应,得到产物五;
S6、将后扩链剂和剩余脱盐水混合,并与产物五混合搅拌分散,得到水性单组分聚氨酯胶粘剂。
4.根据权利要求3所述的制备方法,其特征在于,步骤S1中,所述脱水为真空脱水,真空度为-0.08~-0.085MPa,温度为105-110℃,时间为1-3h。
5.根据权利要求3所述的制备方法,其特征在于,步骤S2中,异佛尔酮二异氰酸酯与产物一混合升温至80-95℃反应的时间为0.5-1.5h,再加入催化剂T-12继续反应的时间为1.5-2.5h。
6.根据权利要求3所述的制备方法,其特征在于,步骤S3中,所述混合反应的时间为1.5-2.5h。
7.根据权利要求3所述的制备方法,其特征在于,步骤S4中,与产物三混合反应之前,需将所述产物三降温至50℃以下;
和/或,步骤S4中,所述混合反应的温度为50℃,反应时间为8-12min。
8.根据权利要求3所述的制备方法,其特征在于,步骤S5中,所述搅拌分散的转速为800-2800r/min,时间为3-8min;
和/或,步骤S5中,所述低温的部分脱盐水温度为5-15℃;
和/或,步骤S5中,所述部分脱盐水的用量占总脱盐水用量的86-90%。
9.根据权利要求3所述的制备方法,其特征在于,步骤S5中,所述搅拌分散的转速为800-2800r/min,时间为3-8min;
和/或,步骤S6中,所述剩余脱盐水的用量占总脱盐水用量的10-14%。
10.权利要求3-9任一项所述制备方法得到的水性单组分聚氨酯胶粘剂作为鞋用胶的应用。
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