CN107384289A - 一种高耐热聚氨酯热熔胶及三层热封胶带 - Google Patents
一种高耐热聚氨酯热熔胶及三层热封胶带 Download PDFInfo
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Abstract
本发明公开了一种高耐热聚氨酯热熔胶、三层热封胶带及它们的制备方法;其中所述高耐热聚氨酯热熔胶,包括以下按重量份计的原料:聚酯多元醇70‑80份,二异氰酸酯10‑20份,扩链剂5‑10份,纳米填料0.1‑2份;其中,所述聚酯多元醇的羟值为10‑200mgKOH/g,酸值为0.1‑3mgKOH/g;所述扩链剂为醇胺类扩链剂与多元醇类扩链剂按摩尔比为1:0.5‑1.5的混合物;所述三层热封胶带包括基材层1、聚氨酯热熔胶2、基材层3依次层状复合,所述聚氨酯热熔胶为上述的高耐热聚氨酯热熔胶;本发明的高耐热聚氨酯热熔胶大大提高热封胶带的粘接性、耐高温蒸煮性、吸湿性和染色性;同时又保持聚氨酯固有的特性,如优良的耐介质稳定和电性能等,大大提高了其使用范畴或领域。
Description
技术领域
本发明涉及高分子新材料技术领域,尤其涉及一种高耐热聚氨酯热熔胶、三层热封胶带及它们的制备方法。
背景技术
热封胶带是利用压胶机或者热压机加热,粘贴在面料的接缝处,达到较好密封效果的一种胶带,被越来越广泛地应用于风雨衣、滑雪衣、营幕、帐篷、摩托车雨衣、潜水服、防水鞋、防水袋等防水系列产品和太空服、升空气球、防化服等防气系列产品。热封胶带具有强大的粘接和优异的密封性能,能达到优异的防水性能。随着生活水平的提高,环保和健康意识的增强,消费者对服装家纺、旅游用具材料的环保、安全、无公害等绿色要求也越来越高。但是,由于受技术和材料的影响,现有普通的热封胶带难以达到防化服耐酸碱性、防腐蚀性的标准。
聚氨酯热熔胶是一种链状的高分子化合物氨基甲酸酯,其使用时加热至一定温度熔化涂布于基材表面,经冷却而固化,固化过程主要利用组成中的氢键作用而发生物理交联,具有优良的韧性和粘接强度。热塑性聚氨酯热熔胶受热一定温度后失去氢键作用而变成粘稠状液体,冷却后又恢复原来的物性,因而利用此种特性可以反复加热-冷却固化,此种热熔胶具有粘接强度较高,耐低温、耐磨等优点,且使用可靠性高、化学和物理性能均匀性佳,综合性能优良,粘接工艺简便,浪费少,不含有机溶剂,属于环境友好材料,而且所生产的产品能够被回收或二次利用。
然而,现有技术中聚氨酯热熔胶应用于服装衬布业中普遍存在耐蒸煮、耐水洗、粘结性差等问题,并且难以上色、吸水性差。而且,目前也未有关于专用于热封胶带的聚氨酯热熔胶的相关报道。
发明内容
针对现有技术存在的问题,本发明的目的是提供一种高耐热聚氨酯热熔胶、三层热封胶带及它们的制备方法。
为了实现上述目的,本发明采用以下技术方案:
一种高耐热聚氨酯热熔胶,包括以下按重量份计的原料:
聚酯多元醇70-80份,
二异氰酸酯10-20份,
扩链剂5-10份,
纳米填料0.1-2份;
其中,所述聚酯多元醇的羟值为10-200mgKOH/g,酸值为0.1-3mgKOH/g;
其中所述扩链剂为醇胺类扩链剂与多元醇类扩链剂按摩尔比为1:0.5-1.5的混合物。
优选地,所述聚酯多元醇是由多元酸与多元醇按摩尔比为1.01-1.35:1通过熔融缩聚反应而成,直至聚酯多元醇的羟值为10-200mgKOH/g,酸值为0.1-3mgKOH/g。
进一步优选地,所述聚酯多元醇由多元酸与多元醇按摩尔比为1.01-1.35:1经过真空熔融法进行脱醇剂脱水缩聚而成,在真空熔融法中,先将以上比例的原料在80-100℃下反应0.5-1h,接着升温至120-170℃下反应0.5-1h,再升温至190-250℃下反应,直至聚酯多元醇的羟值为10-200mgKOH/g,酸值为0.1-3mgKOH/g。
进一步优选地,所述多元酸为乙二酸、丁二酸、己二酸、对苯二甲酸和邻苯二甲酸中的一种或几种;所述多元醇为乙二醇、丙二醇、丁二醇、丙三醇、季戊四醇和木糖醇中的一种或几种。
优选地,所述醇胺类扩链剂为三异丙醇胺、乙二醇胺和三乙醇胺中的一种或多种;所述多元醇扩链剂为乙二醇、丙二醇、丁二醇、丙三醇和季戊四醇中的一种或几种。进一步优选地,所述的醇胺类扩链剂为三异丙醇胺与乙二醇胺按摩尔比为1:0.7-1.2;所述多元醇扩链剂为乙二醇、丙三醇和季戊四醇按重量比为1-2:1-2:1-2。
优选地,所述二异氰酸酯为氢化二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、HDI、甲苯二异氰酸酯(TDI)中的一种或几种。
优选地,所述纳米填料为纳米碳酸钙、纳米炭黑、纳米白炭黑、碳纳米管、埃洛石、石墨烯中的一种或几种。
上述的高耐热聚氨酯热熔胶的制备方法,包括以下步骤:
(1)按重量份称取各原料;
(2)将聚酯多元醇、二异氰酸酯、扩链剂和纳米填料送至双螺杆挤出机,控制挤出机温度范围180-220℃,通过冷却水及造粒机,得到聚氨酯胶粒;
(3)将聚氨酯胶粒经过单螺杆挤出机140℃-160℃流延成型,得到聚氨酯热熔胶膜。
一种三层热封胶带,包括基材层1、聚氨酯热熔胶2、基材层3依次层状复合,所述聚氨酯热熔胶为上述的高耐热聚氨酯热熔胶。
优选地,所述基材层1的厚度为0.1-0.5mm;所述聚氨酯热熔胶2的厚度为0.01-0.1mm;所述基材层3的厚度为0.1-0.5mm。
优选地,所述基材层1和2为涂层、尼龙、PVC、无纺布、PE、PET、PP、离型纸中的一种或两种。
上述的三层热封胶带的制备方法,包括以下步骤:
将聚氨酯热熔胶加热熔化后,涂于基材1的一侧上,在聚氨酯热熔胶冷却之前使用冷却辊加压与基材层2复合,卷取后即得到本发明的三层热封胶带。
本发明的有益效果:
(1)本发明的聚氨酯热熔胶,通过将聚酯多元醇,超支化扩链剂,二异氰酸酯复配形成超支化聚氨酯预聚物,其内部形成支化网状结构,并优化引入纳米填料,使得本发明的聚氨酯热熔胶的耐热温度为110℃以上,使用温度提高了30℃以上,其耐热性得到了显著提高,可大大提高热封胶带的粘接性、耐高温蒸煮性、吸湿性和染色性;同时又保持聚氨酯固有的特性,如优良的耐介质稳定和电性能等,大大提高了其使用范畴或领域;
(2)本发明的聚氨酯热熔胶的熔融范围110-120℃,熔体流动速率为10-15g/min;含水率为20±2.5 4.﹪;灰分为≤1.5-5﹪;
(3)本发明的聚氨酯热熔胶被粘基材宽广,适用于各种人造纤维、天然纤维及特殊的金属、玻璃、亚克力等材料的粘接,使其更适用于纺织品用绿色胶粘剂领域,不仅可替代进口产品,满足国内高档衬布的需求,还可满足出口欧盟纺织品标准要求,市场前景相当广阔,也是我国胶粘剂业的重大新突破;
(4)本发明三层热封胶带适用于粘合各种人造纤维、天然纤维等织物,具有弹性、流动性好,粘结强度高、耐溶剂、耐磨、耐热性和抗紫外性优良等特点。
附图说明
图1为本发明的三层热封胶带的结构示意图。
具体实施方式
实施例1
一种高耐热聚氨酯热熔胶,包括以下按重量份计的原料:
其中,所述聚酯多元醇为对苯二甲酸与乙二醇按摩尔比为1.2:1,经过真空熔融法进行脱醇剂脱水缩聚而成,在真空熔融法中,先将以上比例的原料在80℃下反应0.5h,接着升温至120℃下反应1h,再升温至250℃下反应,直至聚酯多元醇的羟值为100mgKOH/g,酸值为2mgKOH/g。
所述扩链剂为醇胺类扩链剂与多元醇类扩链剂按摩尔比为1:1的混合物;其中所述醇胺类扩链剂为三异丙醇胺与乙二醇胺按摩尔比为1:0.8的混合物;所述多元醇类扩链剂为乙二醇、丙三醇和季戊四醇按重量比为1:1:1。
上述的高耐热聚氨酯热熔胶的制备方法,包括以下步骤:
(1)按重量份称取各原料;
(2)将聚酯多元醇、二异氰酸酯、扩链剂和纳米填料送至双螺杆挤出机,控制挤出机温度范围180-220℃,通过冷却水及造粒机,得到聚氨酯胶粒;
(3)将聚氨酯胶粒经过单螺杆挤出机140℃-160℃流延成型,得到聚氨酯热熔胶膜。
实施例2
一种高耐热聚氨酯热熔胶,包括以下按重量份计的原料:
其中,所述聚酯多元醇为对苯二甲酸与乙二醇按摩尔比为1.01:1,经过真空熔融法进行脱醇剂脱水缩聚而成,在真空熔融法中,先将以上比例的原料在80℃下反应0.5h,接着升温至150℃下反应1h,再升温至190℃下反应,直至聚酯多元醇的羟值为80mgKOH/g,酸值为1.8mgKOH/g。
所述扩链剂为醇胺类扩链剂与多元醇类扩链剂按摩尔比为1:1.2的混合物;其中所述醇胺类扩链剂为三异丙醇胺与乙二醇胺按摩尔比为1:1的混合物;所述多元醇类扩链剂为乙二醇、丙三醇和季戊四醇按重量比为1:2:1。
上述的高耐热聚氨酯热熔胶的制备方法,包括以下步骤:
(1)按重量份称取各原料;
(2)将聚酯多元醇、二异氰酸酯、扩链剂和纳米填料送至双螺杆挤出机,控制挤出机温度范围180-220℃,通过冷却水及造粒机,得到聚氨酯胶粒;
(3)将聚氨酯胶粒经过单螺杆挤出机140℃-160℃流延成型,得到聚氨酯热熔胶膜。
实施例3
一种高耐热聚氨酯热熔胶,包括以下按重量份计的原料:
其中,所述聚酯多元醇为对苯二甲酸与乙二醇按摩尔比为1.35:1,经过真空熔融法进行脱醇剂脱水缩聚而成,在真空熔融法中,先将以上比例的原料在100℃下反应0.5h,接着升温至170℃下反应1h,再升温至200℃下反应,直至聚酯多元醇的羟值为120mgKOH/g,酸值为2.1mgKOH/g。
所述扩链剂为醇胺类扩链剂与多元醇类扩链剂按摩尔比为1:0.8的混合物;其中所述醇胺类扩链剂为三异丙醇胺与乙二醇胺按摩尔比为1:1.2的混合物;所述多元醇类扩链剂为乙二醇、丙三醇和季戊四醇按重量比为1:1:2。
上述的高耐热聚氨酯热熔胶的制备方法,包括以下步骤:
(1)按重量份称取各原料;
(2)将聚酯多元醇、二异氰酸酯、扩链剂和纳米填料送至双螺杆挤出机,控制挤出机温度范围180-220℃,通过冷却水及造粒机,得到聚氨酯胶粒;
(3)将聚氨酯胶粒经过单螺杆挤出机140℃-160℃流延成型,得到聚氨酯热熔胶膜。
实施例4
一种三层热封胶带,包括基材层1、聚氨酯热熔胶2、基材层3依次层状复合,所述聚氨酯热熔胶为实施例1的高耐热聚氨酯热熔胶。
所述基材层1为涂层,其厚度为0.2mm;所述聚氨酯热熔胶2的厚度为0.1mm;所述基材层3为尼龙,其厚度为0.5mm。
上述的三层热封胶带的制备方法,包括以下步骤:
将聚氨酯热熔胶加热熔化后,涂于基材1的一侧上,在聚氨酯热熔胶冷却之前使用冷却辊加压与基材层2复合,卷取后即得到本发明的三层热封胶带。
实施例5
一种三层热封胶带,包括基材层1、聚氨酯热熔胶2、基材层3依次层状复合,所述聚氨酯热熔胶为实施例2的高耐热聚氨酯热熔胶。
所述基材层1为无纺布,其厚度为0.4mm;所述聚氨酯热熔胶2的厚度为0.1mm;所述基材层3为尼龙,其厚度为0.4mm。
上述的三层热封胶带的制备方法,包括以下步骤:
将聚氨酯热熔胶加热熔化后,涂于基材1的一侧上,在聚氨酯热熔胶冷却之前使用冷却辊加压与基材层2复合,卷取后即得到本发明的三层热封胶带。
实施例6
一种三层热封胶带,包括基材层1、聚氨酯热熔胶2、基材层3依次层状复合,所述聚氨酯热熔胶为实施例3的高耐热聚氨酯热熔胶。
所述基材层1为无纺布,其厚度为0.4mm;所述聚氨酯热熔胶2的厚度为0.05mm;所述基材层3为离型纸,其厚度为0.1mm。
上述的三层热封胶带的制备方法,包括以下步骤:
将聚氨酯热熔胶加热熔化后,涂于基材1的一侧上,在聚氨酯热熔胶冷却之前使用冷却辊加压与基材层2复合,卷取后即得到本发明的三层热封胶带。
Claims (10)
1.一种高耐热聚氨酯热熔胶,其特征在于,包括以下按重量份计的原料:
聚酯多元醇70-80份,
二异氰酸酯10-20份,
扩链剂5-10份,
纳米填料0.1-2份;
其中,所述聚酯多元醇的羟值为10-200mgKOH/g,酸值为0.1-3mgKOH/g;
其中所述扩链剂为醇胺类扩链剂与多元醇类扩链剂按摩尔比为1:0.5-1.5的混合物。
2.根据权利要求1所述的高耐热聚氨酯热熔胶,其特征在于,所述聚酯多元醇是由多元酸与多元醇按摩尔比为1.01-1.35:1通过熔融缩聚反应而成,直至聚酯多元醇的羟值为10-200mgKOH/g,酸值为0.1-3mgKOH/g。
3.根据权利要求2所述的高耐热聚氨酯热熔胶,其特征在于,所述多元酸为乙二酸、丁二酸、己二酸、对苯二甲酸和邻苯二甲酸中的一种或几种;所述多元醇为乙二醇、丙二醇、丁二醇、丙三醇、季戊四醇和木糖醇中的一种或几种。
4.根据权利要求1所述的高耐热聚氨酯热熔胶,其特征在于,所述醇胺类扩链剂为三异丙醇胺、乙二醇胺和三乙醇胺中的一种或多种;所述多元醇扩链剂为乙二醇、丙二醇、丁二醇、丙三醇和季戊四醇中的一种或几种。
5.根据权利要求1所述的高耐热聚氨酯热熔胶,其特征在于,所述二异氰酸酯为氢化二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、HDI、甲苯二异氰酸酯(TDI)中的一种或几种;所述纳米填料为纳米碳酸钙、纳米炭黑、纳米白炭黑、碳纳米管、埃洛石、石墨烯中的一种或几种。
6.根据权利要求1-5中任一项所述的高耐热聚氨酯热熔胶的制备方法,其特征在于,包括以下步骤:
(1)按重量份称取各原料;
(2)将聚酯多元醇、二异氰酸酯、扩链剂和纳米填料送至双螺杆挤出机,控制挤出机温度范围180-220℃,通过冷却水及造粒机,得到聚氨酯胶粒;
(3)将聚氨酯胶粒经过单螺杆挤出机140℃-160℃流延成型,得到聚氨酯热熔胶膜。
7.一种三层热封胶带,其特征在于,包括基材层(1)、聚氨酯热熔胶(2)、基材层(3)依次层状复合,所述聚氨酯热熔胶为权利要求1-5所述的高耐热聚氨酯热熔胶。
8.根据权利要求7所述的三层热封胶带,其特征在于,所述基材层(1)的厚度为0.1-0.5mm;所述聚氨酯热熔胶(2)的厚度为0.01-0.1mm;所述基材层(3)的厚度为0.1-0.5mm。
9.根据权利要求7所述的三层热封胶带,其特征在于,所述基材层(1)和(2)为涂层、尼龙、PVC、无纺布、PE、PET、PP、离型纸中的一种或两种。
10.根据权利要求7-9中任一项所述的三层热封胶带的制备方法,其特征在于,包括以下步骤:
将聚氨酯热熔胶加热熔化后,涂于基材(1)的一侧上,在聚氨酯热熔胶冷却之前使用冷却辊加压与基材层(2)复合,卷取后即得到三层热封胶带。
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