CN113480964B - 一种耐高温耐水解聚氨酯热熔胶及其制备方法 - Google Patents
一种耐高温耐水解聚氨酯热熔胶及其制备方法 Download PDFInfo
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Abstract
一种耐高温耐水解聚氨酯热熔胶及其制备方法,包含以下组分反应形成的聚合物:0.1‑3质量份的含N原子的多官能度交联剂、15‑25质量份的第一组分聚醚多元醇、5‑25质量份的第二组分聚醚多元醇、25‑55质量份的第一组分聚酯多元醇、5‑25质量份的第二组分聚酯多元醇、异氰酸酯及添加剂。本发明不含溶剂、固含量100%,在使用过程中无小分子释放,安全环保无污染,具有环境友好,使用寿命长,粘结强度高,安全可靠等优点,施胶后无颗粒及鼓泡现象,胶水固化后胶膜柔韧有弹性,具有极高的耐温性能,极佳的耐水解性能,可在100℃沸水中浸渍24h仍能保持良好的剪切强度,可广泛应用于钢材、木材、塑料制品以及其他复合材料的复合粘接以及桥梁隧道等极端条件的应用粘接。
Description
技术领域
本发明涉及聚氨酯热熔胶技术领域,尤其涉及一种耐高温耐水解聚氨酯热熔胶及其制备方法。
背景技术
聚氨酯热熔胶又称湿反应型聚氨酯热熔胶,是一种末端为NCO封端的、可与空气中的水汽发生反应而具有极高强度的无溶剂胶水,自1940年德国的研究人员发现三苯基甲烷一4,4’-三异氰酸酯可粘接金属与丁钠橡胶以来,聚氨酯热熔胶得到了长足发展,目前已广泛应用于汽车行业、木材行业、鞋包行业、建筑行业、油墨行业、书记装订、铁路建设等行业。与传统热熔胶相比,聚氨酯热熔胶具有更为优异的综合性能,它兼有普通热熔胶粘剂无溶剂、初粘性高、装配时定位迅速等特性,又具有反应型液态胶粘剂特有的耐水、耐热、耐寒、耐蠕变和耐介质等性能。其施胶温度(120℃)又低于普通热熔胶粘剂(150-180℃),可用于某些塑料部件粘接、复合,倍受现代自动化装配工业青睐。其不含水无溶剂、固含量100%的特点,是一种高性能环保型胶粘剂,适应了国内外对环境越来越重视的需要,近年呈现出极高速的发展。然而国内高性能聚氨酯热熔胶受制于技术原因,起步晚,基础弱,高端聚氨酯热熔胶严重依赖进口,其中应用于航空航天领域、高速铁路领域的耐高温聚氨酯热熔胶是一个需要重点突破的方向,国际大厂如3M、Bostii、HBs Fuller、Natbnal Starch、Asland等公司垄断核心技术,尤其是当今贸易保护主义抬头,某些发达国际坐拥技术垄断动辄以断供相威胁,严重影响相关行业供应链安全。国内聚氨酯热熔胶虽发展迅速,但高端产品仍然匮乏,因此开发相应的进口替代显得格外重要。有鉴于此,发明人经过长期专研,摸索出一种新的耐高温聚氨酯热熔胶及其制备方法。
发明内容
本发明为解决上述技术问题,采用以下技术方案来实现:
本发明第一方面,提供一种耐高温耐水解聚氨酯热熔胶,其特征在于,所述热熔胶包含以下组分反应形成的聚合物:
交联剂、第一组分聚醚多元醇、第二组分聚醚多元醇、第一组分聚酯多元醇、第二组分聚酯多元醇、异氰酸酯及添加剂;
其中,所述交联剂为分子中含有至少1个叔胺的N原子,且分子中含有3-5个羟基的交联剂,其兼具催化剂以及交联剂的作用。常规的催化剂多为小分子胺类催化剂或者含金属催化剂,金属催化剂虽然催化活性高,但是其面对亲核试剂进攻时同样具有催化作用,也就是催化反应容易,但是在被水解时也会加速水解反应,是一把双刃剑。而小分子胺类催化剂,要么具有味道,容易逸散,要么具有金属催化剂同样的弊端,导致热熔胶的耐水解性不足。笔者发现,采用具有活性基团的催化剂、或者称为具有催化活性的交联剂具有优异的特性,即它在催化后能够反应至分子中,且由于高于3个官能团,产生交联作用,导致其没有小分子胺类催化剂易逸散的缺点,此外,由于交联作用,具有催化活性的叔胺基团被包覆于分子中,在面对亲核基团进攻时,由于位阻作用不能起到催化作用,因而使得热熔胶相较于常规使用催化剂的同类型产品具有更加优异的耐水解性。
优选地,所述含N原子的多官能度交联剂具有3-5个羟基,且分子中具有至少一个叔胺N原子。优选地,所述含N原子的多官能度交联剂具有100~1000的分子量。市售的含N原子的多官能度交联剂包括但不限于VoranolR系列的含N原子的多官能度交联剂(来自陶氏化学公司);QuadrolR特制含N原子的多元醇(N,N,N′,N′-四(2-羟丙基乙二胺))(来自巴斯夫公司);PluracolR基于胺的多元醇(来自巴斯夫公司);MultranolR基于胺的多元醇(来自拜尔公司);三异丙醇胺(TIPA)(来自陶氏化学公司);和三乙醇胺(TEA)(来自于Mallinckrodt Baker Inc.公司)。
所述的第一组分聚醚多元醇为脂肪族聚醚多元醇,其特征在于,所述聚醚多元醇具有两个官能度,所述聚醚多元醇,其特征在于其选自乙二醇、1,3-丁二醇、1,4-丁二醇、二甘醇、新戊二醇、2-甲基-1,3-丙二醇、己二醇、3-甲基-1,5-戊二醇、1,4-环己烷二甲醇中一种或者多种单体聚合形成的均聚物或者共聚物,优选地,所述聚醚多元醇选自己二醇、1,4-丁二醇形成的均聚物或者共聚物。所述聚醚多元醇,其特征在于,所述聚醚多元醇具有200~4000的平均分子量,优选地,具有500~2000的分子量。
所述的第二组分聚醚多元醇为含芳环聚醚多元醇,其特征在于,所述含有芳环的聚醚多元醇中含有1%-25wt%质量百分数的芳环。
优选地,所述含有芳环的聚醚多元醇中含有4%~15wt%质量百分数的芳环。
所述含有芳环的聚醚多元醇,其特征在于,所述多元醇中的芳环为全碳芳环或者含杂原子芳环。所述芳环为对苯二酚、间苯二酚、萘二酚、双酚A、双酚S、对苯二甲醇、间苯二甲醇、邻苯二甲醇、2,5-呋喃二甲醇、对苯二甲醇或二苯醚二酚中的一种。
所述含有芳环的聚醚多元醇中其分子量为250~10000,优选地,所述含有芳环的聚醚多元醇中其分子量为500~5000。
所述的第一组分聚酯多元醇为脂肪族聚酯多元醇,其特征在于所述聚酯多元醇由脂肪族二元酸与脂肪族二元醇反应所得。其中,脂肪族二元醇为乙二醇、1,3-丁二醇、1,4-丁二醇、二甘醇、新戊二醇、2-甲基-1,3-丙二醇、己二醇、3-甲基-1,5-戊二醇、1,4-环己烷二甲醇中任意一种或几种的混合物,优选地,所述脂肪族二元醇为 1,4-丁二醇,己二醇或者其混合物。
多元酸为丁二酸、己二酸、壬二酸、葵二酸中的任意一种或几种的混合物;
所述的第二组分聚酯多元醇为含芳环的聚酯多元醇,其特征在于,所述含芳环的聚酯多元醇由含芳环的二元醇/酚、脂肪族二元醇与脂肪族二元酸共聚所得。通过控制共聚物中含芳环的二元醇/酚比例,可得不同芳环含量得含芳环聚酯多元醇。所述的脂肪族二元醇为乙二醇、1,3-丁二醇、1,4-丁二醇、二甘醇、新戊二醇、2-甲基-1,3-丙二醇、己二醇、3-甲基-1,5-戊二醇、1,4-环己烷二甲醇中任意一种或几种的混合物,优选地,所述脂肪族二元醇为 1,4-丁二醇,己二醇或者其混合物。所述脂肪族二元酸为丁二酸、己二酸、壬二酸、葵二酸中的任意一种或几种的混合物,优选地,所述脂肪族二元酸为丁二酸、己二酸或者其混合物。所述含芳环的二元醇/酚为对苯二酚、间苯二酚、萘二酚、双酚A、双酚S、对苯二甲醇、间苯二甲醇、邻苯二甲醇、2,5-呋喃二甲醇、对苯二甲醇或二苯醚二酚中的一种或其混合物,优选地,所述含芳环的二元醇/酚为对苯二酚、对苯二甲醇或其混合物。
所述的异氰酸酯包括但不限于芳香族异氰酸酯、脂肪族异氰酸酯中的一种或两种。优选使用90摩尔%以上的芳香族异氰酸酯,更优选95摩尔%以上,特别优选100摩尔%。
芳香族异氰酸酯可以是芳香族二异氰酸酯类。芳香族二异氰酸酯类包括但不限于2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、2,2’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、对苯二异氰酸酯、间苯二异氰酸酯、对苯二亚甲基二异氰酸酯、间苯二亚甲基二异氰酸酯中的一种或多种。
脂肪族异氰酸酯可以是脂肪族二异氰酸酯类。脂肪族二异氰酸酯类包括但不限于亚乙基二异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯中的一种或多种。脂肪族异氰酸酯还可以是脂环式二异氰酸酯类。脂环式二异氰酸酯类包括但不限于1,4-环己烷二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、降冰片烷二异氰酸酯中的一种或多种。
优选地,所述异氰酸酯为TDI或者MDI,更优地,所述异氰酸酯为MDI。
所述聚氨酯热熔胶中可选用的添加剂包括稳定剂、抗氧化剂以及耐老化剂中的一种或多种,所述稳定剂优选地为苯甲酰氯,所述抗氧化剂优选地为Irganox 245,所述耐老化助剂优选地为UV-531,上述添加剂均为市场上可以直接获取的已有商品,其用量根据商品说明书的指导使用即可。
本发明的第二方面,提供一种耐高温耐水解聚氨酯热熔胶的制备方法,其特征在于,所述聚氨酯热熔胶包括以下制备步骤:将交联剂、第一组分聚醚多元醇、第二组分的含芳环聚醚多元醇、第一组分聚酯多元醇以及第二组分聚酯多元醇相混合,加热至110~150℃融化形成均匀液体,并在真空下(0.01MPa)脱气30min,降温至80℃附近,向其中加入异氰酸酯,保持温度80℃常压下搅拌30min,在最后40min时间内降低搅拌转速,加入添加剂,降低气泡产生,然后趁热倒入容器中密闭保存。
所述聚氨酯热熔胶的制备,其特征在于所述异氰酸酯中NCO数量与交联剂、第一组分聚醚多元醇、第二组分聚醚多元醇、第一组分聚酯多元醇、第二组分聚酯多元醇中羟基的总数量比值为R,其中R介于1.1~2.5之间,优选地,R值介于1.3~2.0。
所述聚氨酯热熔胶的制备,其特征在于所述第一组分聚醚多元醇、第二组分聚醚多元醇、第一组分聚酯多元醇、第二组分聚酯多元醇以及交联剂的质量比为:15~25:5~25:25~55:5~25:0.1~3。
本发明的有益效果是:
本发明的湿固化聚氨酯热熔胶及其制备方法,所属聚氨酯热熔胶其特征在于不含溶剂、固含量100%,在使用过程中无小分子释放,安全环保无污染,具有环境友好,使用寿命长,粘结强度高,安全可靠等优点,施胶后无颗粒及鼓泡现象,胶水固化后胶膜柔韧有弹性,具有极高的耐温性能,极佳的耐水解性能,可在100℃沸水中浸渍24h仍能保持良好的剪切强度,可广泛应用于钢材、木材、塑料制品以及其他复合材料的复合粘接以及桥梁隧道等极端条件的应用粘接。
附图说明
图1为剪切强度与200℃挂重制样方式的示意图。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施例,进一步阐述本发明,但下述实施例仅仅为本发明的优选实施例,并非全部。基于实施方式中的实施例,本领域技术人员在没有做出创造性劳动的前提下所获得其它实施例,都属于本发明的保护范围。
实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1
称取交联剂(三异丙醇胺,羟基数3,Mn=192)0.2质量份、第一组分聚醚多元醇PPG1000(Mn = 1000) 20质量份、第二组分含芳环聚醚多元醇15质量份(对苯二酚为引发剂的聚环氧丙烷,芳环含量7.6%,Mn = 1000)、第一组分聚酯多元醇聚己二酸己二醇酯(Mn =2000) 35质量份、第二组分含芳环聚酯多元醇(丁二酸、乙二醇、对本二酚共聚物,Mn =2500,芳环含量6.08%)15质量份加热至130℃融化形成均匀液体,并在真空下(0.01MPa)脱气30min,降温至80℃附近,向其中加入MDI 24质量份,在最后40min时间内降低搅拌转速,加入助剂,降低气泡产生,然后趁热倒入容器中密闭保存。
实施例2
称取交联剂(Voranol R202多元醇,羟基数5,Mn=590)1.2质量份、第一组分聚醚多元醇PEG1000(Mn = 1000) 17质量份、第二组分含芳环聚醚多元醇22质量份(对苯二酚为引发剂的聚环氧乙烷,芳环含量12.3%,Mn = 620)、第一组分聚酯多元醇聚己二酸丁二醇酯(Mn = 1500) 29质量份、第二组分含芳环聚酯多元醇(己二酸、己二醇、对苯二甲醇共聚物,Mn = 1700,芳环含量8.94%)15质量份加热至130℃融化形成均匀液体,并在真空下(0.01MPa)脱气30min,降温至80℃附近,向其中加入MDI 30质量份,在最后40min时间内降低搅拌转速,加入助剂,降低气泡产生,然后趁热倒入容器中密闭保存。
实施例3
称取交联剂(Voranol R391多元醇,羟基数4,Mn=568)0.8质量份、第一组分聚醚多元醇PPG2000(Mn = 2000) 23质量份、第二组分含芳环聚醚多元醇18质量份(对苯二甲醇为引发剂的聚环氧丙烷,芳环含量4.2%,Mn = 1800)、第一组分聚酯多元醇聚己二酸己二醇酯(Mn = 1300) 44质量份、第二组分含芳环聚酯多元醇(己二酸、丁二醇、对苯二甲醇共聚物,Mn = 3200,芳环含量7.1%)19质量份加热至130℃融化形成均匀液体,并在真空下(0.01MPa)脱气30min,降温至80℃附近,向其中加入MDI 28质量份,在最后40min时间内降低搅拌转速,加入助剂,降低气泡产生,然后趁热倒入容器中密闭保存。
游离NCO(%) | 140℃粘度(cps) | 颜色 | 剪切强度(psi) | 200℃挂重 | 剪切强度降幅(%) | 耐水解性 | |
实施例1 | 2.4 | 19700 | 白色 | 776 | 合格 | 6.9 | 合格 |
实施例2 | 2.3 | 23000 | 白色 | 825 | 合格 | 7.3 | 合格 |
实施例3 | 2.9 | 17900 | 白色 | 727 | 合格 | 9.2 | 合格 |
注:如图1所示,剪切强度与200℃挂重制样方式为:为将热熔胶按12g/ft2之涂胶量涂布于1inch * 10inch之钢板末端的1 inch2面积内并使两块钢板相互搭接,涂布面积1inch2,固化48h后,剪切强度通过万能材料试验机测试所得;200℃挂重为将一端固定,下端挂1kg砝码,置于200℃烘箱中,烘烤1h,若砝码掉落,则判定不合格,若砝码未掉落,则判定合格,参考附图1;耐水解性判定为:将剪切强度样品,浸渍于100℃的水中放置24h,取出擦干,再测其剪切强度,若浸渍后剪切强度与浸渍前剪切强度相比,剪切强度降幅小于10%,则判定耐水解性合格。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。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仅为本发明的优选例,并不用来限制本发明,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)
1.一种耐高温耐水解聚氨酯热熔胶,其特征在于:包含以下组分反应形成的聚合物:
0.1-3质量份的含N原子的多官能度交联剂、15-25质量份的第一组分聚醚多元醇、5-25质量份的第二组分聚醚多元醇、25-55质量份的第一组分聚酯多元醇、5-25质量份的第二组分聚酯多元醇、异氰酸酯及适量添加剂;
所述的第一组分聚醚多元醇为脂肪族聚醚多元醇,
所述的第二组分聚醚多元醇为含芳环聚醚多元醇,
所述的第一组分聚酯多元醇为脂肪族聚酯多元醇,
所述的第二组分聚酯多元醇为含芳环聚酯多元醇;
所述异氰酸酯中NCO数量与交联剂、第一组分聚醚多元醇、第二组分聚醚多元醇、第一组分聚酯多元醇、第二组分聚酯多元醇中羟基的总数量比值为R,其中R介于1.1-2.5之间;
所述交联剂中含有至少1个叔胺的N原子,且分子中含有3-5个羟基。
2.根据权利要求1所述的聚氨酯热熔胶,其特征在于:所述第二组分聚醚多元醇为含芳环聚醚多元醇,其分子量为190-6000,其中芳环质量百分数含量为1-25%。
3.根据权利要求2所述的聚氨酯热熔胶,其特征在于:所述含芳环聚醚多元醇中的芳环为全碳芳环或者含杂原子芳环,所述的芳环为对苯二酚、间苯二酚、萘二酚、双酚A、双酚S、对苯二甲醇、间苯二甲醇、邻苯二甲醇、2,5-呋喃二甲醇、对苯二甲醇或二苯醚二酚中的一种或多种。
4.根据权利要求1所述的聚氨酯热熔胶,其特征在于:所述第二组分聚酯多元醇为含芳环的聚酯多元醇,其分子量为250-10000,其中芳环质量百分数含量为1-25%。
5.根据权利要求4所述的聚氨酯热熔胶,其特征在于:所述含芳环聚酯多元醇中的芳环为全碳芳环或者含杂原子芳环,所述芳环来自于含芳环的二元醇/酚,所述含芳环的二元醇/酚为对苯二酚、间苯二酚、萘二酚、双酚A、双酚S、对苯二甲醇、间苯二甲醇、邻苯二甲醇、2,5-呋喃二甲醇、对苯二甲醇或二苯醚二酚中的一种或多种混合物。
6.根据权利要求5所述的聚氨酯热熔胶,其特征在于:所述含芳环的二元醇/酚为对苯二酚或对苯二甲醇或其混合物。
7.根据权利要求1所述的聚氨酯热熔胶,其特征在于:所述热熔胶中游离NCO含量为1-4%,所述热熔胶具有140℃下8000-25000mpa·s的粘度。
8.权利要求1所述聚氨酯热熔胶的制备方法,其特征在于,包括以下制备步骤:将交联剂、第一组分聚醚多元醇、第二组分的含芳环聚醚多元醇、第一组分聚酯多元醇以及第二组分聚酯多元醇相混合,加热至110-150℃融化形成均匀液体,并在真空条件下脱气30min,降温至80℃,向其中加入异氰酸酯,保持温度80℃常压下搅拌30min,在最后40min时间内降低搅拌转速,加入添加剂,降低气泡产生,然后趁热倒入容器中密闭保存。
9.根据权利要求8所述聚氨酯热熔胶的制备方法,其特征在于:所述真空条件为0.01MPa。
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Denomination of invention: A high-temperature and hydrolysis resistant polyurethane hot melt adhesive and its preparation method Effective date of registration: 20230829 Granted publication date: 20220405 Pledgee: Tongling Branch of Postal Savings Bank of China Ltd. Pledgor: Anhui Zhongxia Packaging Technology Co.,Ltd. Registration number: Y2023980054378 |