CN114058312A - 一种粘合体系、聚氨酯/橡胶复合材料及其制备方法 - Google Patents
一种粘合体系、聚氨酯/橡胶复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种粘合体系、聚氨酯/橡胶复合材料及其制备方法,属于复合材料技术领域。所述粘合体系包括用于改善聚氨酯与橡胶粘接性能的底涂粘合剂和次粘合剂,所述底涂粘合剂包括具有异氰酸酯基团的化合物,所述次粘合剂包括经过无水处理的RFL胶。本发明采用固态RFL胶膜搭配异氰酸酯底涂粘合剂作为粘合体系,用于聚氨酯与橡胶的粘接,使聚氨酯与硫化橡胶的粘接界面生成大量的化学键合,大幅提高了聚氨酯/橡胶复合材料的界面性能,得到聚氨酯与橡胶粘接牢固的复合材料。本发明的粘合体系容易获得,胶膜厚度可控性高,适合工业化应用。
Description
技术领域
本发明属于复合材料技术领域,具体涉及一种粘合体系、聚氨酯/橡胶复合材料及其制备方法。
背景技术
聚氨酯/橡胶复合材料融合了聚氨酯和橡胶的优点,现已被广泛应用于众多工业领域中,例如制鞋、机械配件、运动器材和电子特殊零部件等。聚氨酯与橡胶的粘合强度是影响聚氨酯/橡胶复合材料的关键因素之一。对于聚氨酯与橡胶的粘合,目前最常用的解决方法是通过特定的胶黏剂(如氰基丙烯酸酯胶黏剂、聚氨酯胶黏剂等)将固化的聚氨酯与固化的橡胶进行直接粘合,然而,虽然这种方法能够使两者实现粘接,但粘接的有效强度较低,常温(25℃)剥离强度仅为5~15kN/m(以25mm宽度样品剥离测试得到),当温度较高时,粘接强度会迅速下降,导致所得聚氨酯/橡胶复合材料的界面性能较差,在较大的剪切或剥离力作用下亦或在较高温度下,聚氨酯和橡胶极易从界面处发生破坏,造成整个复合材料制件的损坏。
发明内容
为解决上述现有技术中存在的不足之处,本发明的第一个目的在于提供一种粘合体系,该粘合体系所用的粘合剂容易获得,用于聚氨酯和未硫化橡胶的粘接,可在粘接界面形成很强的化学键合,有效提高了聚氨酯/橡胶复合材料的界面性能。本发明的第二个目的在于提供一种聚氨酯/橡胶复合材料及其制备方法,复合材料中的聚氨酯与橡胶粘接牢固。
为达到其目的,本发明所采用的技术方案为:
一种粘合体系,其包括用于改善聚氨酯与橡胶粘接性能的底涂粘合剂和次粘合剂,所述底涂粘合剂包括具有异氰酸酯基团的化合物,所述次粘合剂包括经过无水处理的RFL胶。
优选地,所述底涂粘合剂包括多异氰酸酯,更优选使用二异氰酸酯,例如二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、对苯二异氰酸酯(PPDI)等或者是这些化合物的混合物。
更优选地,所述底涂粘合剂的异氰酸酯与所述聚氨酯的异氰酸酯为同种化合物。
优选地,所述底涂粘合剂还包括乙烯基酯树脂,尤其是环氧类乙烯基树脂。
优选地,所述底涂粘合剂中,异氰酸酯中的-NCO官能团与乙烯基树脂中的-OH官能团的摩尔比>1,优选为3~6。该配比下,可保证所述底涂粘合剂中的-NCO过量,利于在聚氨酯与橡胶的粘接界面生成更多的化学键。
优选地,所述底涂粘合剂还包括苯乙烯。苯乙烯的主要作用是用于调节底涂粘合剂的粘度,使其利于涂布。
优选地,所述苯乙烯在所述底涂粘合剂中的质量百分含量为5%~15%。由于苯乙烯参与固化反应,因此对其无需进行蒸发干燥处理。苯乙烯在所述底涂粘合剂中的质量百分含量为5%~15%时,所述底涂粘合剂可获得合适的粘度,利于涂布。若所述苯乙烯的含量过少,会导致所述底涂粘合剂的粘度太大,流动性差,难以涂布均匀。若所述苯乙烯的含量过多,会导致所述底涂粘合剂的粘度太小,流动性过高,也难以涂布均匀,且难以获得目标厚度的胶层。
优选地,所述次粘合剂为固态RFL胶膜。
优选地,所述固态RFL胶膜的制备方法包括:将RFL胶液均匀涂布在离型膜上,烘干,去除RFL胶液中的水分,制得所述固态RFL胶膜。
优选地,所述固态RFL胶膜的制备方法中,烘干温度为90~110℃。上述制备方法中,若烘干温度过低,会导致胶液中的水分难以充分去除;若烘干温度过高,会导致胶膜内部形成空孔,影响使用效果;而采用本发明所提供的烘干温度可充分快速去除胶液中的水分,且能防止胶膜内部形成空孔,使用效果较好。
所述底涂粘合剂中,环氧类乙烯基树脂中的-OH与-NCO反应生产化学键合,环氧类乙烯基树脂中未反应的双键与固态RFL胶膜的胶乳颗粒的碳碳双键发生化学反应,从而增强了底涂粘合剂与次粘合剂的结合力。
胶膜的厚度均匀性对聚氨酯与橡胶的粘接性能至关重要。为了保证胶膜厚度的均一性,涂布RFL胶液或改性混合液时,优选采用旋转涂布、喷涂等方法。
本发明通过采用不含水分的固态RFL胶配合含异氰酸酯基团的底涂粘合剂作为粘合体系,用于改善聚氨酯与橡胶的粘接,实现了聚氨酯与橡胶的牢固粘接。
其中,RFL(间苯二酚-甲醛-胶乳)是轮胎行业常用的一种粘合剂,制备方法常规,容易获得,目前主要用于增强帘线与橡胶的粘合作用。本发明利用了RFL体系中含有未完全固化的酚醛树脂和二烯烃弹性体的特性,以其无水处理后的固态RFL胶膜用于粘接聚氨酯塑料和橡胶,未固化的酚醛树脂可与塑料基材发生化学反应,而二烯烃弹性体可与未硫化橡胶发生化学反应,因此可提高塑料基材与橡胶的粘接性能。
其次,为促使聚氨酯基体与固态RFL胶膜产生化学键合,本发明还以异氰酸酯作为底涂粘合剂。一方面,异氰酸酯中的异氰酸酯基团(-NCO)可与聚氨酯反应生成化学键合。另一方面,异氰酸酯基团可与固态RFL胶膜中的活性H反应生成化学键合。由此,在高温高压作用下,聚氨酯与硫化橡胶的粘接界面会生成大量化学键合,从而大幅提高聚氨酯/橡胶复合材料的界面性能,得到聚氨酯与橡胶粘接牢固的复合材料。
由于RFL体系中的分散剂为水,若直接将未经无水处理的RFL胶液涂覆在异氰酸酯底涂粘合剂的表面,将会造成底涂粘合剂失活。因此,在使用前,需对RFL进行无水处理,使其形成固态RFL胶膜。
本发明还提供了一种聚氨酯/橡胶复合材料的制备方法,其包括采用所述粘合体系粘接聚氨酯和未硫化橡胶,所述聚氨酯可以是通过乙二醇、丁二醇、甘油等固化剂与液体氨基甲酸酯预聚物反应获得,所述未硫化橡胶可以是含有二烯弹性体的组合物,如天然橡胶、异戊橡胶、丁苯橡胶、聚异戊二烯、聚丁二烯等或这些弹性体的混合物。
优选地,所述聚氨酯/橡胶复合材料的制备方法,其包括:
提供聚氨酯基材;
在所述聚氨酯基材表面均匀涂布所述底涂粘合剂,形成底涂粘合剂层;
在所述底涂粘合剂层的表面放置所述次粘合剂,形成次粘合剂层;
在所述次粘合剂层的表面放置未硫化橡胶,得到预制件;
将所述预制件在加热加压条件下进行硫化,制得所述聚氨酯/橡胶复合材料。
本发明中的聚氨酯采用现有常规方法制备,在此不再赘述。为使所述次粘合剂能紧贴所述底涂粘合剂,可施加一定压力排出存在于所述次粘合剂与所述底涂粘合剂之间的气泡。
优选地,所述底涂粘合剂层的厚度为0.4~1.0mm,更优选为0.5~0.8mm。
优选地,所述次粘合剂层的厚度为0.4~1.0mm,更优选为0.5~0.8mm。固态RFL胶膜的厚度主要取决于RFL胶液的固含量、酚醛树脂与二烯烃胶乳颗粒的比例、以及涂布次数,而上述因素容易选择、调控,因此胶膜厚度的可控性较高。
所述底涂粘合剂层和所述次粘合剂层的厚度为上述范围时,可较好地将聚氨酯与橡胶牢固粘接。
优选地,所述硫化的工艺条件为:10~15MPa下,140~180℃硫化15~20min。硫化体系可以是天然橡胶、异戊橡胶、丁苯橡胶、聚异戊二烯、聚丁二烯等或这些弹性体的混合物,以及必要的助剂,如硫化剂、促进剂、炭黑、防老剂等。
本发明还提供了一种聚氨酯/橡胶复合材料,其由上述的聚氨酯/橡胶复合材料的制备方法制得。
与现有技术相比,本发明的有益效果为:本发明采用固态RFL胶膜搭配异氰酸酯底涂粘合剂作为粘合体系,用于聚氨酯与橡胶的粘接,使聚氨酯与硫化橡胶的粘接界面生成大量的化学键合,大幅提高了聚氨酯/橡胶复合材料的界面性能,得到聚氨酯与橡胶粘接牢固的复合材料。本发明的粘合体系容易获得,胶膜厚度可控性高,适合工业化应用。
具体实施方式
下面将结合实施例对本发明的技术方案作进一步描述,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。基于本发明中的实施例,本领域技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。实施例和对比例中所用的原料均可通过市售购买获得,且平行实验用的都是同一种。
其中,实施例和对比例中所使用的部分原料信息如下:
未硫化橡胶的配方如表1所示(以phr说明),制备方法为现有常规方法,不再赘述。
表1
合成异戊橡胶 | 100 |
氧化锌 | 5 |
硬脂酸 | 2 |
防老剂4010NA | 1.5 |
防老剂RD | 2 |
古马隆 | 1 |
促进剂CZ | 0.9 |
炭黑N234 | 45 |
硫磺 | 2.5 |
RFL胶液的制备:将21.6g氢氧化钠、326g间苯二酚、496g甲醛和适量去离子水混合均匀,在低温下搅拌反应24h,之后补加适量去离子水,搅拌均匀后加入丁苯胶乳溶液(固含量40%)和适量去离子水,混合均匀后室温静置1~3天即获得RFL胶液。
聚氨酯的制备:采用MDI与PTMEG体系制备聚氨酯预聚物,所述体系中MDI与PTMEG的摩尔比例为3:1(2:1~3:1均可)。之后以BDO和甘油为扩链剂,与预聚物体系反应,其中BDO和甘油的摩尔比例为97:3,同时以二月桂酸二丁基锡或三乙胺为催化剂。在整个添加过程中,-NCO和-OH的摩尔比为1.1:1~0.9:1。
实施例1
一种聚氨酯/橡胶复合材料的制备方法,步骤如下:
(1)按照上述方法采用MDI和PTMEG体系制备聚氨酯,并制成所需形状和尺寸的聚氨酯基材;
(2)采用MDI作为底涂粘合剂,用刷子将底涂粘合剂均匀涂布在聚氨酯基材的表面,涂布厚度为0.4mm;
(3)将RFL胶液均匀喷涂在氟硅离型膜上,100℃烘干,去除RFL胶液中的水分,获得厚度为0.4mm的固态RFL胶膜;
(4)将步骤(3)获得的固态RFL胶膜从氟硅离型膜上脱离,放置在涂有底涂粘合剂的聚氨酯表面,施加压力排出气泡后,在固态RFL胶膜的表面放置一层未硫化橡胶,得到预制件;
(5)将预制件放置于模具中,在10MPa下,165℃硫化15min,制得聚氨酯/橡胶复合材料。
实施例2
一种聚氨酯/橡胶复合材料的制备方法,其与实施例1的区别仅在于所使用的底涂粘合剂不同,实施例2的具体制备步骤如下:
(1)按照实施例1的方法制备聚氨酯基材;
(2)将MDI和用苯乙烯稀释的双酚A型环氧乙烯基树脂作为底涂粘合剂,其中-NCO与乙烯基树脂中-OH的摩尔比为5,苯乙烯在整个底涂粘合体系中的质量百分含量为5%;用刷子将底涂粘合剂均匀涂布在聚氨酯基材的表面,涂布厚度为0.4mm;
(3)将RFL胶液均匀喷涂在氟硅离型膜上,100℃烘干,去除RFL胶液中的水分,获得厚度为0.4mm的固态RFL胶膜;
(4)将步骤(3)获得的固态RFL胶膜从氟硅离型膜上脱离,放置在涂有底涂粘合剂的聚氨酯表面,施加压力排出气泡后,在固态RFL胶膜的表面放置一层未硫化橡胶,得到预制件;
(5)将预制件放置于模具中,在10MPa下,165℃硫化15min,制得聚氨酯/橡胶复合材料。
实施例3
一种聚氨酯/橡胶复合材料的制备方法,其与实施例2的区别仅在于:底涂粘合剂中,-NCO与乙烯基树脂中-OH的摩尔比为3。
实施例4
一种聚氨酯/橡胶复合材料的制备方法,其与实施例1的区别仅在于:制备固态RFL胶膜的烘干温度不同,其它相同。实施例4制备固态RFL胶膜所用的烘干温度为200℃,而实施例1为100℃。
对比例1
一种聚氨酯/橡胶复合材料的制备方法,其与实施例1的区别仅在于:没有在聚氨酯基体的表面涂布底涂粘合剂,其它与实施例1一致。
对比例2
一种聚氨酯/橡胶复合材料的制备方法,其与实施例1的区别仅在于:不含固态RFL胶膜(次粘合剂层),对比例2的具体制备步骤如下:
(1)按照实施例1的方法制备聚氨酯基材;
(2)采用MDI作为底涂粘合剂,用刷子将底涂粘合剂均匀涂布在聚氨酯基材的表面,涂布厚度为0.4mm;
(3)在涂有底涂粘合剂的聚氨酯表面放置一层未硫化橡胶,施加压力排出气泡后,得到预制件;
(4)将预制件放置于模具中,在10MPa下,165℃硫化15min,制得聚氨酯/橡胶复合材料。
对比例3
一种聚氨酯/橡胶复合材料的制备方法,其与实施例2的区别仅在于:底涂粘合剂中,-NCO与乙烯基树脂中-OH的摩尔比为1。
试验测试
将实施例1~4和对比例1~3制备的聚氨酯/橡胶复合材料进行性能测试,测试项目如下,参考GB/T 33334-2016和GB/T 15254-2014进行测试:
1、常温(25℃)剪切和剥离测试,以25mm宽度样品测试。
2、高温(80℃)剪切和剥离测试,以25mm宽度样品测试。
测试结果如下表所示:
样品 | 常温剪切 | 常温剥离 | 高温剪切 | 高温剥离 |
实施例1 | 1.8MPa | 20kN/m | 1.1MPa | 13kN/m |
实施例2 | 2.3MPa | 26kN/m | 1.5MPa | 18kN/m |
实施例3 | 2.1MPa | 24kN/m | 1.3MPa | 16kN/m |
实施例4 | 1.5MPa | 18kN/m | 0.6MPa | 10kN/m |
对比例1 | 0.5MPa | 5kN/m | <0.1MPa | <1kN/m |
对比例2 | 0.4MPa | 3kN/m | <0.1MPa | <1kN/m |
对比例3 | 0.8MPa | 12kN/m | 0.4MPa | 3kN/m |
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种粘合体系,其特征在于,包括用于改善聚氨酯与橡胶粘接性能的底涂粘合剂和次粘合剂,所述底涂粘合剂包括具有异氰酸酯基团的化合物,所述次粘合剂包括经过无水处理的RFL胶。
2.如权利要求1所述的粘合体系,其特征在于,所述底涂粘合剂包括多异氰酸酯。
3.如权利要求2所述的粘合体系,其特征在于,所述底涂粘合剂还包括乙烯基酯树脂。
4.如权利要求3所述的粘合体系,其特征在于,所述底涂粘合剂中,异氰酸酯中的-NCO官能团与乙烯基树脂中的-OH官能团的摩尔比>1。
5.如权利要求3或4所述的粘合体系,其特征在于,所述底涂粘合剂还包括苯乙烯。
6.如权利要求5所述的粘合体系,其特征在于,所述苯乙烯在所述底涂粘合剂中的质量百分含量为5%~15%。
7.如权利要求1所述的粘合体系,其特征在于,所述次粘合剂为固态RFL胶膜,所述固态RFL胶膜的制备方法包括:将RFL胶液均匀涂布在离型膜上,烘干,去除RFL胶液中的水分,制得所述固态RFL胶膜。
8.一种聚氨酯/橡胶复合材料的制备方法,其特征在于,包括采用如权利要求1~7任一项所述的粘合体系粘接聚氨酯和未硫化橡胶。
9.如权利要求8所述的聚氨酯/橡胶复合材料的制备方法,其特征在于,包括:
提供聚氨酯基材;
在所述聚氨酯基材的表面均匀涂布所述底涂粘合剂,形成底涂粘合剂层;
在所述底涂粘合剂层的表面放置所述次粘合剂,形成次粘合剂层;
在所述次粘合剂层的表面放置未硫化橡胶,得到预制件;
将所述预制件在加热加压条件下进行硫化,制得所述聚氨酯/橡胶复合材料。
10.一种聚氨酯/橡胶复合材料,其特征在于,采用包括如权利要求8或9所述的聚氨酯/橡胶复合材料的制备方法制得。
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