CN110591628B - 一种双组分聚氨酯胶粘剂的制备方法及产品 - Google Patents
一种双组分聚氨酯胶粘剂的制备方法及产品 Download PDFInfo
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Abstract
本发明公开了一种新型双组分聚氨酯胶粘剂的制备方法及产品,该产品分A、B两个组分,使用时按质量比1:0.5~1混合配制即可。该方法首先自制醋丙多元醇预聚物作为主剂之一,再经过聚酯、聚醚多元醇类预聚物、固化剂、无机填料、催化剂等的复配制成A、B双组分聚氨酯胶粘剂产品。具有原料来源方便,制作工艺简单,所得产品可在室温下固化,胶粘剂分子极性可调,分子链的软硬度和界面特征可控,储存稳定,力学性能好,粘接强度优良等优点。
Description
技术领域
本发明属于室温固化双组分聚氨酯系胶粘剂领域,具体是涉及一种新型双组分聚氨酯胶粘剂的制备方法及产品。
背景技术
聚氨酯(PU)胶粘剂是分子结构中含有异氰酸酯基(—NCO)或氨酯基(—NHCOO—)的胶粘剂,由于其性能优异,自诞生以来就迅速得到关注。聚氨酯胶粘剂最早是20世纪40年代由德国法本公司(I.G.Farben,Bayer公司的前身)开发的,50年代Bayer公司又开发了系列产品,美国和日本也在50年代相继掌握聚氨酯粘接技术,并随之将其推广和普及,使得聚氨酯胶粘剂在全球范围得到迅速发展,并在汽车、木材、轻工、包装、建筑等领域得到广泛应用,用于金属、橡胶、皮革、木材、纤维、陶瓷等材料的粘接或作密封胶使用。
尽管聚氨酯胶粘剂自问世就备受人们的青睐,并且成为目前用量最大的八大合成胶粘剂系列之一,但在使用过程中也并非没有缺点,如耐温性、耐水解性较差,粘接强度不高,一般不适于作为结构胶黏剂使用等,是其主要缺陷。
聚氨酯胶粘剂中目前使用最广的是双组份室温固化聚氨酯胶粘剂,主剂通常由多羟基预聚物构成,如聚酯多元醇、聚醚多元醇等;固化剂则由含多异氰酸酯的化合物构成;再辅之以固化催化剂或其它助剂即可。
众所周知,为了形成良好的粘接效果,胶粘剂分子与被粘接表面充分接触(即完全润湿)是必要条件,胶粘剂分子具有与被粘接表面相适应的表面张力是实现良好粘接效果的前提,而聚氨酯胶粘剂由于主剂的原料所限,大多是聚醚、聚酯类化合物,极性不高,且调整幅度有限,对金属与金属之间粘接,或金属与非金属之间的粘接不够理想,因此,限制了其作为结构胶粘剂的广泛使用。
发明内容
为克服现有聚氨酯胶粘剂的上述缺陷,本发明提供了一种新型双组分聚氨酯胶粘剂的制备方法及产品。该方法首先自制醋丙多元醇预聚物作为主剂之一,再经过聚酯、聚醚多元醇类预聚物、固化剂、无机填料、催化剂等的复配制成A、B双组分聚氨酯胶粘剂产品。具有原料来源方便,制作工艺简单,所得产品可在室温下固化,胶粘剂分子极性可调,分子链的软硬度和界面特征可控,储存稳定,力学性能好,粘接强度优良等优点。
一种新型双组分聚氨酯胶粘剂的制备方法,包括使用时需要按照设定比例混合的组份A和组份B,其中组份A作为主剂,由如下主要成分制备得到:醋丙多元醇预聚物、聚酯或聚醚多元醇预聚物、无机填料、触变剂;所述组份B作为固化剂由如下主要成分制备得到:多异氰酸酯化合物、交联剂、触变剂、增塑剂;所述醋丙多元醇预聚物主要由醋酸乙烯酯、丙烯酸羟基酯、溶剂、引发剂制备得到。
作为优选,按照重量比,使用时A:B=1:0.5~1.0。作为进一步优选,按照重量比,使用时A:B=1:1。
作为优选,所述醋丙多元醇预聚物由如下方法制备得到:将醋酸乙烯酯、丙烯酸羟基酯、溶剂、引发剂加热至反应体系温度在65~75℃之间,并维持在此温度下进行反应;当反应至体系羟值在312.0~353.0mgKOH/g之间时,降温至40~50℃,去除溶剂,得所述醋丙多元醇预聚物。上述反应,可以在具回流冷凝器的反应釜中进行。去除的溶剂可以回收套用,完成去除溶剂后,然后降温至40℃以下时即可出料。
作为优选,所述丙烯酸羟基酯包括丙烯酸羟甲酯、丙烯酸羟乙酯中的一种或者两种的混合物。
作为优选,所述醋丙多元醇预聚物的原料百分比组成为:
作为进一步优选,所述醋丙多元醇预聚物的原料百分比组成为:
作为更进一步优选,所述醋丙多元醇预聚物的原料百分比组成为:
作为一种优选的实施方案,所述醋丙多元醇预聚物的原料百分比组成为:醋酸乙烯酯:55%~60%;丙烯酸羟基酯:20~22%;溶剂19%~24%;引发剂:0.03%~0.05%。
作为优选,组份A的制备方法如下:将得到的醋丙多元醇预聚物、聚酯或聚醚多元醇预聚物、无机填料、触变剂、可选择的包括催化剂或功能性助剂混合,升温至30~40℃,搅拌30~60min,然后抽真空30~60min得到所述组份A;上述反应可以在混料釜中进行。
所述组份A的原料百分比组成为:
作为优选,所述组份A的原料百分比组成为:
作为进一步优选,所述组份A的原料百分比组成为:
作为一种优选的方案,所述组份A的原料百分比组成为:醋丙多元醇预聚物:3%~15%;聚酯或聚醚多元醇预聚物:10%~50%;无机填料:30%~50%;触变剂:3%~8%。
作为优选,组份B的制备方法如下:将多异氰酸酯化合物、交联剂、触变剂、增塑剂按比例混合,升温至30~40℃,搅拌30~60min,然后抽真空30~60min,得到所述组份B;所述组份B的原料百分比组成为:
作为进一步优选,所述组份B的原料百分比组成为:
本发明中,所述的溶剂包括醋酸丁酯、无水甲醇、无水乙醇、苯、甲苯中的一种或两种以上混合物;所述的引发剂包括过氧化二苯甲酰、偶氮二异丁腈、叔丁基过氧化苯甲酸酯中的一种或两种以上混合物。
本发明中,聚酯多元醇预聚物包括二元羧酸与二元醇或二元醇与三元醇的混合物脱水缩聚而成的预聚物;如聚对苯二甲酸乙二醇酯二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸乙二醇-丙二醇酯二醇等,以及聚碳酸酯二醇、聚己二酸蓖麻油酯多元醇中的一种或两种以上混合物。
本发明中,所述的聚醚多元醇预聚物包括聚乙二醇、聚氧化丙烯二醇、聚氧化丙烯三醇、聚氧化丙烯-蓖麻油多元醇、聚四氢呋喃二醇中的一种或两种以上混合物;所述聚酯或聚醚多元醇预聚物为聚酯多元醇预聚物、聚醚多元醇预聚物或者两者中任意组份组成的混合物。
本发明中,所述无机填料包括硫酸钡、硫酸钙、碳酸钙、滑石粉、氧化铝中的一种或两种以上混合物;
所述的催化剂包括二月桂酸二丁基锡、辛酸亚锡、二乙烯三胺、三乙醇胺、三乙胺中的一种或两种以上混合物。
所述的功能性助剂包括阻燃剂(比如氢氧化铝)、导电剂(比如导电金属粉末等)、导热剂中的一种或两种以上混合物。
所述的触变剂主要是气相二氧化硅;
所述的多异氰酸酯化合物包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、液化MDI、多亚甲基多苯基多异氰酸酯、1,6-己二异氰酸酯、异佛尔酮二异氰酸酯、聚酯或聚醚多元醇与多异氰酸酯的加成物中的一种或两种以上混合物;
所述的交联剂包括三羟甲基丙烷与二异氰酸酯(比如甲苯二异氰酸酯、二苯基甲烷二异氰酸酯)的加成物、甘油与二异氰酸酯(比如甲苯二异氰酸酯、二苯基甲烷二异氰酸酯)的加成物、季戊四醇与二异氰酸酯(比如甲苯二异氰酸酯、二苯基甲烷二异氰酸酯)的加成物、蓖麻油多元醇与二苯基甲烷二异氰酸酯加成物中的一种或两种以上混合物;
所述的增塑剂包括邻苯二甲酸二辛脂、邻苯二甲酸二异癸酯、磷酸三苯酯、己二酸二辛脂中的一种或两种以上混合物。
一种双组分聚氨酯胶粘剂,由上述任一项技术方案所述的制备方法制备得到。
本发明得到的胶粘剂可以用于多种领域,诸如金属、非金属(指硬材料)材料之间的自粘、互粘以及固定、密封、修补等。
本发明具有的有益效果是:
①采用自制的醋丙多元醇预聚物对传统的双组分聚氨酯胶粘剂进行改性,可根据被粘材料表面特性,利用醋丙多元醇预聚物的分子特性,通过调整乙酰氧基含量最终调节胶粘剂分子链的极性,使胶粘剂分子在被粘接表面能够完全铺展,进而达到提高粘接力的效果;
②采用自制的醋丙多元醇预聚物对传统的双组分聚氨酯胶粘剂进行改性,醋丙多元醇预聚物的分子结构与聚酯、聚醚类多元醇聚合物体系的相容度高,不会出现相分离现象,形成胶层后的内聚力不受影响,提高了醋丙多元醇预聚物对聚氨酯胶粘剂改性效率;
③醋丙多元醇预聚物的分子结构特征表现为硬段聚合物,而聚氨酯胶粘剂中使用的聚酯多元醇、聚醚多元醇等大多为软段聚合物,与之配伍使用,不仅改善了聚氨酯胶粘剂的韧性、软硬度和界面特征;而且同时具备了两种树脂体系的优点,综合性能提高,并且随着配伍比例的不同,使产品的各种性能具有可调性,进而使胶粘剂产品界面适应性和其它综合性能得到提高。
综上所述,利用本发明提供的方法制备新型双组分聚氨酯胶粘剂,具有原料来源方便,制作工艺简单,所得产品可在室温下固化,胶粘剂分子极性可调,分子链的软硬度和界面特征可控,且储存稳定,韧性好,粘接强度优良等特点。
具体实施方式
实施例1
首先,在具冷凝器的反应釜中,加入232.00kg丙烯酸羟乙酯、86.00kg醋酸乙烯酯、79.5kg醋酸丁酯、偶氮二异丁腈159.00g,开动搅拌器,加热至反应体系温度约65℃附近,维持在此温度下进行反应;取样测定预聚物羟值,当反应至羟值在312.0~353.0mgKOH/g之间时,即可结束反应,降温至40~50℃,真空抽除并回收溶剂,然后再降温至40℃以下时即可出料,得无溶剂醋丙多元醇预聚物备用。
然后,进行双组分聚氨酯胶的制备:
A组分的制备:将上述制备的醋丙多元醇预聚物3.00kg、聚己二酸丁二醇酯二醇30.00kg(烟台华大化学有限公司,型号CMA-24,羟值:53~59)、聚碳酸酯二醇15.00kg(日本旭化成化学株式会社,型号T5652,羟值:53~59)、硫酸钙46.00kg、气相二氧化硅6.00kg加入混料釜中,升温至30.0℃,搅拌30.0min,然后抽真空30.0min,出料灌装即得主剂产品。
B组分的制备:将聚己二酸乙二醇酯二醇与二苯基甲烷二异氰酸酯加成物35.00kg(杜特润贸易公司,型号8585,NCO%:6.5%~6.9%)、液化MDI 35.00kg、三羟甲基丙烷与二异氰酸酯的加成物15.00kg(山东友泰化工有限公司,型号75AA,NCO%:12.5%~13.5%,固含量75%)、邻苯二甲酸二异癸酯10.00kg、气相二氧化硅5.00kg加入混料釜中,升温至30.0℃,搅拌30.0min,然后抽真空30.0min,出料灌装即得产品。
使用时A:B=1:1。
经测试,铝-铝粘接剪切强度~30.3MPa。
实施例2
首先,在具冷凝器的反应釜中,加入273.00kg丙烯酸羟丙酯、86.00kg醋酸乙烯酯、153.86kg无水甲醇、过氧化二苯甲酰107.70g,开动搅拌器,加热至反应体系温度约75℃附近,维持在此温度下进行反应;取样测定预聚物羟值,当反应至羟值在312.0~353.0mgKOH/g之间时,即可结束反应,降温至40~50℃,真空抽除并回收溶剂,然后再降温至40℃以下时即可出料,得无溶剂醋丙多元醇预聚物备用。
然后,进行双组分聚氨酯胶的制备:
A组分的制备:将上述制备的醋丙多元醇预聚物15.00kg、聚乙二醇600计15.00kg、聚氧化丙烯二醇20.00kg(蓝星东大有限公司,型号DL-2000D,羟值:54.5~57.5)、聚氧化丙烯三醇10.00kg(蓝星东大有限公司,型号MN-3050D,羟值:54.5~57.5)、滑石粉37.00kg、气相二氧化硅3.00kg加入混料釜中,升温至30.0℃,搅拌30.0min,然后抽真空30.0min,出料灌装即得主剂产品。
B组分的制备:将聚氧化丙烯-蓖麻油多元醇与甲苯二异氰酸酯加成物70.00kg(将32kg TDI(甲苯二异氰酸酯)加入反应釜开动搅拌,将38kg聚氧化丙烯-蓖麻油多元醇在室温下缓慢滴入反应釜,缓慢升温至60℃保持2h,继续升温至80℃保温1h,冷却至60℃以下出料。)、二苯基甲烷二异氰酸酯20.00kg、甘油与甲苯二异氰酸酯的加成物5.00kg(将3.19kgTDI与1.25kg乙酸丁酯加入反应釜开动搅拌,将560克甘油在室温下缓慢滴入反应釜,保持2h,继续升温至60℃保温1.5h,冷却至室温出料。)、邻苯二甲酸二辛脂3.00kg、气相二氧化硅2.00kg加入混料釜中,升温至30.0℃,搅拌30.0min,然后抽真空30.0min,出料灌装即得产品。
使用时A:B=1:0.8。
经测试,铝-铝粘接剪切强度~25.7MPa。
实施例3
首先,在具冷凝器的反应釜中,加入237.80kg丙烯酸羟乙酯、86.00kg醋酸乙烯酯、108.00kg苯、叔丁基过氧化苯甲酸酯129.5g,开动搅拌器,加热至反应体系温度约70℃附近,维持在此温度下进行反应;取样测定预聚物羟值,当反应至羟值在312.0~353.0mgKOH/g之间时,即可结束反应,降温至40~50℃,真空抽除并回收溶剂,然后再降温至40℃以下时即可出料,得无溶剂醋丙多元醇预聚物备用。
然后,进行双组分聚氨酯胶的制备:
A组分的制备:将上述制备的醋丙多元醇预聚物10.00kg、精炼蓖麻油8.00kg(广州穗欣化工有限公司,羟值:162)、聚己二酸乙二醇-丙二醇酯二醇7.00kg(烟台华大化学工业有限公司,型号ODX-218,羟值:535~58.5mgKOH/g)、聚氧化丙烯-蓖麻油多元醇10.00kg(上海精日新材料科技有限公司,型号A20,羟值:270mgKOH/g)、聚氧化丙烯三醇5.50kg、二月桂酸二丁基锡0.10kg、硫酸钡20.00kg、氢氧化铝30.00kg、铜粉5.00kg、气相二氧化硅4.40kg加入混料釜中,升温至30.0℃,搅拌30.0min,然后抽真空30.0min,出料灌装即得主剂产品。
B组分的制备:将精炼蓖麻油多元醇与二苯基甲烷二异氰酸酯加成物40.00kg(将16.89千克MDI-100在70℃融化后加入升温至60℃的反应釜并开动搅拌,将23.11千克克蓖麻油缓慢滴入反应釜,保持2h,继续升温至80℃保温1h,冷却至60℃以下出料)、多亚甲基多苯基多异氰酸酯41.50kg(万华化学集团有限公司,型号PM-200,NCO%:30.5~32.0)、三羟甲基丙烷与二异氰酸酯的加成物10.00kg、磷酸三苯酯5.00kg、气相二氧化硅3.50kg加入混料釜中,升温至30.0℃,搅拌30.0min,然后抽真空30.0min,出料灌装即得产品。
使用时A:B=1:0.5。
经测试,铝-铝粘接剪切强度~28.5MPa。
Claims (10)
1.一种双组分聚氨酯胶粘剂的制备方法,其特征在于,包括使用时需要按照设定比例混合的组份A和组份B,其中组份A作为主剂,由如下主要成分制备得到:醋丙多元醇预聚物、聚酯或聚醚多元醇预聚物、无机填料、触变剂;所述组份B作为固化剂由如下主要成分制备得到:多异氰酸酯化合物、交联剂、触变剂、增塑剂;所述醋丙多元醇预聚物主要由醋酸乙烯酯、丙烯酸羟基酯、溶剂、引发剂制备得到;
使用时组份A和组份B的重量比为1:0.5~1.0。
2.根据权利要求1所述的双组分聚氨酯胶粘剂的制备方法,其特征在于,所述醋丙多元醇预聚物由如下方法制备得到:将醋酸乙烯酯、丙烯酸羟基酯、溶剂、引发剂加热至反应体系温度在65~75℃之间,并维持在此温度下进行反应;当反应至体系羟值在312.0~353.0mgKOH/g之间时,降温至40~50℃,去除溶剂,得所述醋丙多元醇预聚物。
7.根据权利要求1所述的双组分聚氨酯胶粘剂的制备方法,其特征在于,所述的溶剂包括醋酸丁酯、无水甲醇、无水乙醇、苯、甲苯中的一种或两种以上混合物;所述的引发剂包括过氧化二苯甲酰、偶氮二异丁腈、叔丁基过氧化苯甲酸酯中的一种或两种以上混合物。
8.根据权利要求1所述的双组分聚氨酯胶粘剂的制备方法,其特征在于,聚酯多元醇预聚物包括二元羧酸与二元醇脱水缩聚而成的预聚物或者二元羧酸与二元醇和三元醇的混合物脱水缩聚而成的预聚物;聚醚多元醇预聚物包括聚乙二醇、聚氧化丙烯二醇、聚氧化丙烯三醇、聚氧化丙烯-蓖麻油多元醇、聚四氢呋喃二醇中的一种或两种以上混合物。
9.根据权利要求1所述的双组分聚氨酯胶粘剂的制备方法,其特征在于,所述无机填料包括硫酸钡、硫酸钙、碳酸钙、滑石粉、氧化铝中的一种或两种以上混合物;所述的触变剂主要是气相二氧化硅;所述的多异氰酸酯化合物包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、液化MDI、多亚甲基多苯基多异氰酸酯、1,6-己二异氰酸酯、异佛尔酮二异氰酸酯、聚酯或聚醚多元醇与多异氰酸酯的加成物中的一种或两种以上混合物;所述的交联剂包括三羟甲基丙烷与二异氰酸酯的加成物、甘油与二异氰酸酯的加成物、季戊四醇与二异氰酸酯的加成物、蓖麻油多元醇与二苯基甲烷二异氰酸酯加成物中的一种或两种以上混合物;所述的增塑剂包括邻苯二甲酸二辛脂、邻苯二甲酸二异癸酯、磷酸三苯酯、己二酸二辛脂中的一种或两种以上混合物。
10.一种双组分聚氨酯胶粘剂,其特征在于,由权利要求1~9任一项所述的制备方法制备得到。
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