CN106221649B - 低粘度高粘接强度的水性聚氨酯鞋用胶粘剂及其制备方法 - Google Patents
低粘度高粘接强度的水性聚氨酯鞋用胶粘剂及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种低粘度高粘接强度的水性聚氨酯鞋用胶粘剂,该鞋用胶粘剂是由包括重量组分为3‑5%六亚甲基二异氰酸酯、5‑8%4,4'‑二环己基甲烷二异氰酸酯、5‑7%磺化聚酯多元醇、5‑10%聚己二酸1,6己二醇酯、0.5‑2%十二烷基苯磺酸钠、1.5‑3%三甲基戊二醇(TMPD)、1‑3%二羟甲基丁酸、8‑11%丙酮、0.5‑2%三乙胺和10‑50%去离子水聚合而得。本发明的低粘度高粘接强度的水性聚氨酯鞋用胶粘剂,由于粘度低、粘接强度高,耐热性、耐水性好,在胶粘鞋生产过程中,极大方便了施工,也可降低鞋材的上胶量,不仅能保证质量,而且节约了成本。本发明还提供了一种上述低粘度高粘接强度的水性聚氨酯鞋用胶粘剂的制备方法。
Description
技术领域
本发明涉及一种水性聚氨酯,尤其涉及一种可作为鞋用胶粘剂的水性聚氨酯,更具体是涉及一种低粘度高粘接强度的水性聚氨酯鞋用胶粘剂。本发明还涉及一种上述水性聚氨酯鞋用胶粘剂的制备方法。
背景技术
我国是世界上最大的鞋类产品生产国、消费国和出口国,年产量为100多亿双,其中绝大多数是胶粘鞋,鞋用胶粘剂的发展也是一个由低档次向高档次、由非环保型向环保型发展的过程。随着全球性环保意识的提高,以及石油危机的加剧,环保无溶剂型和水基型鞋用粘胶剂应运而生;水性聚氨酯是聚氨酯溶于水或分散于水中形成的溶液或乳液,与溶剂型聚氨酯相比,具有无毒、不易燃烧、不污染环境等有点,近年来已开始在制鞋行业中得到应用。但在生产实践中发现,现有市面上销售的水性聚氨酯鞋用胶粘剂,其粘度均较高,导致其流动性较差,进而影响其流平性和增加上胶量,如果把粘度降下来,其粘接强度又变低,对于低极性鞋材如SBS等材质的粘接,其剥离强度往往达不到要求,因此,寻找一种粘度低、同时具有高粘接强度的水性聚氨酯鞋用胶粘剂是本领域技术人员致力研究的课题。
发明内容
为克服以上存在的问题,本发明的目的是提供一种低粘度高粘接强度的水性聚氨酯鞋用胶粘剂。
本发明的另一个目的是提供一种上述低粘度高粘接强度的水性聚氨酯鞋用胶粘剂的制备方法。
为实现以上目的,本发明的低粘度高粘接强度的水性聚氨酯鞋用胶粘剂,由包括如下重量配比的各组分聚合获得:
六亚甲基二异氰酸酯 3-5%
4,4'-二环己基甲烷二异氰酸酯 5-8%
磺化聚酯多元醇 5-7%
聚己二酸1,6己二醇酯 5-10%
十二烷基苯磺酸钠 0.5-2%
三甲基戊二醇 1.5-3%
二羟甲基丁酸 1-3%
丙酮 8-11%
三乙胺 0.5-2%
去离子水 10-50%
为了增加聚氨酯的交联度,更好提高粘接强度,上述鞋用胶粘剂还添加有三羟甲基丙烷、1、6己二醇作为扩链剂,三羟甲基丙烷在配方中的重量百分比为1-2%、1、6己二醇在配方中的重量百分比为1.5-3%。
为了增加呈粉状组分的溶解度,上述鞋用胶粘剂还包括有3-5%的氮甲基吡咯烷酮。
为了增加上述各组分的匹配度,同时更好提高聚氨酯的耐热性,上述鞋用胶粘剂还添加有乙二胺作为pH值调节剂,乙二胺在配方中的重量百分比为0.5-1%。
为了提高涂层的拉伸率,同时也可增加涂层的强度,上述磺化聚酯多元醇优选分子量为3000的磺化聚酯多元醇,聚己二酸1,6己二醇酯优选分子量为2000的聚己二酸1,6己二醇酯。
本发明还提供了一种上述低粘度高粘接强度的水性聚氨酯的制备方法,该方法依次包括如下步骤:
(1)将计量好的磺化聚酯多元醇、聚己二酸1,6己二醇酯加入反应釜,升温到120±1℃脱水30分钟,然后降温到70-80℃,加入4,4'-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯,升温到80-100℃,反应2-3小时;
(2)将步骤(1)的反应产物降温到60-70℃,加入计量的三甲基戊二醇、二羟甲基丁酸,升温到80-90℃,保温2小时,视粘度情况加入丙酮降粘;
(3)将步骤(2)的反应产物降温到40±1℃,缓慢滴加计量的磺化聚酯多元醇和三乙胺混合的溶液,在30分钟内滴加完毕;
(4)滴加完成后,在高速搅拌下快速加入计量的去离子水,搅拌1小时,减压蒸馏脱去丙酮,制得低粘度、高粘接强度的水性聚氨酯鞋用胶粘剂。
为了更好提高产品的综合性能,上述制备方法中,步骤(1)在加入磺化聚酯多元醇或六亚甲基二异氰酸酯的同时,加入1-2%的三羟甲基丙烷;步骤(2)在加入三甲基戊二醇的同时,加入1.5-3%的1、6己二醇。
为了更好提高聚氨酯的交联度,上述制备方法中,步骤(1)在脱水后加入1-2%的三羟甲基丙烷后保温1小时。
为了增加呈粉状组分的溶解度,上述制备方法中,步骤(3)在滴加完成后,加入3-5%的氮甲基吡咯烷酮,在60-65℃下保温1小时后再将反应产物降温至40±1℃。
为了更好提高聚氨酯的耐热性上述制备方法中,上述制备方法中,步骤(5)在加入去离子水的同时加入0.5-1%的乙二胺。
本发明的低粘度高粘接强度的水性聚氨酯鞋用胶粘剂,采用六亚甲基二异氰酸酯和4,4'-二环己基甲烷二异氰酸酯两种不同的异氰酸酯来合成水性聚氨酯胶粘剂,具有比较低的活化温度,反应比较平和,可降低反应过程中预聚体爆聚的可能,使所得的水性聚氨酯胶粘剂耐热性、耐水性性能比较高;选用磺化聚酯多元醇和聚己二酸1,6己二醇酯作为主要的成膜物质,利用聚己二酸1,6己二醇酯结晶性比较强的特点,可大大提高胶粘剂的固含量,固含量的提高有利于粘接强度的提高;而选用磺化聚酯多元醇、三甲基戊二醇作为小分子扩链剂,选用二羟甲基丁酸作为亲水扩链剂,不仅能提高水性聚氨酯合成过程的稳定性,使得乳化过程更容易,粒度更细,乳液更稳定,在保证粘结强度的前提下,还可明显降低体系的粘度。本发明的水性聚氨酯具有高度的结晶性、很好的耐热性、耐溶剂性、低的粘度和高的粘接强度。本发明水性聚氨酯的制备方法,工艺简单、操作方便、溶剂易于回收处理,获得的产品应用于制鞋业上,由于粘度低、粘接强度高,耐热性、耐水性好,在胶粘鞋生产过程中,极大方便了施工,也可降低鞋材的上胶量,不仅能保证质量,而且节约了成本。
具体实施方式
实施例1
将分子量为3000的磺化聚酯多元醇 6g和分子量为2000的聚己二酸1,6己二醇酯6g加入到装有温度计、搅拌器和回流冷凝器的500 mL 的四口烧瓶中,升温到120℃左右脱水30分钟,脱水结束后降温到80℃左右,添加7.5g 4,4-二环基甲烷二异氰酸酯和3g六亚甲基二异氰酸酯以及2.5g三羟甲基丙烷,添加结束后升温到95℃保温反应3小时;将反应产物降温到60℃左右加入2.7g1,6己二醇、3g三甲基戊二醇、1.8g二羟甲基丁酸,然后升温到85℃扩链反应2小时,反应2 小时后取样测定反应物中—NCO的含量,直至接近理论值(用二正丁胺滴定法滴定),反应过程中加入28g丙酮调节粘度,反应到达时间后冷却至40 ℃,开始滴加1.5g十二烷基苯磺酸钠和1.5g三乙胺,在30分钟内滴加完毕;滴加完毕后添加3g氮甲基吡咯烷酮,在60℃保温1小时;保温结束后将聚合好的预聚体降温到40℃,在高速搅拌下加入35g去离子水,并滴加1g乙二胺进行扩链;搅拌1小时后再减压蒸馏脱去丙酮得到固含为47%的聚氨酯分散体(PUD)。
实施例2
将6g分子量为3000的磺化聚酯多元醇和6g分子量为2000的聚己二酸1,6己二醇酯加入到装有温度计、搅拌器和回流冷凝器的500 mL 的四口烧瓶中,升温到120℃左右脱水30分钟,脱水结束后降温到80℃左右,添加1.5g三羟甲基丙烷保温1小时,然后降温到70℃左右,添加6g 4,4-二环基甲烷二异氰酸酯和4g六亚甲基二异氰酸酯,添加结束后升温到95℃保温反应2小时;将反应产物降温到60℃左右加入2.5g1,6己二醇、2g三甲基戊二醇、1.8g二羟甲基丁酸,然后升温到85℃扩链反应2小时,反应2 小时 后取样测定反应物中—NCO的含量,直至接近理论值(用二正丁胺滴定法滴定),反应过程中加入28g丙酮调节粘度,反应到达时间后冷却至40 ℃,开始滴加1.8g十二烷基苯磺酸钠和1.5g三乙胺,在30分钟内滴加完毕;滴加完毕后添加3g氮甲基吡咯烷酮,在60℃保温1小时,保温结束后将聚合好的预聚体降温到40℃,在高速搅拌下加入35g去离子水,并滴加0.9g乙二胺进行扩链,搅拌1小时后再减压蒸馏脱去丙酮得到固含为46%的聚氨酯分散体(PUD)。
实施例3
将6g分子量为3000的磺化聚酯多元醇和10g分子量为2000的聚己二酸1,6己二醇酯,1g三羟甲基丙烷加入到装有温度计、搅拌器和回流冷凝器的500 mL 的四口烧瓶中,升温到120 ℃左右脱水30分钟,脱水结束后降温到70 ℃左右,添加4.5g 4,4-二环基甲烷二异氰酸酯和4.5g六亚甲基二异氰酸酯,添加结束后升温到95 ℃保温反应2小时;将反应产物降温到60 ℃左右加入3g1,6己二醇、1.5g三甲基戊二醇、3g二羟甲基丁酸,然后升温到85℃扩链反应2小时,反应2 小时 后取样测定反应物中—NCO的含量,直至接近理论值(用二正丁胺滴定法滴定),反应过程中加入22g丙酮调节粘度,反应到达时间后冷却至40 ℃,开始滴加1.5g十二烷基苯磺酸钠和2g三乙胺,在30分钟内滴加完毕;滴加完毕后添加4g氮甲基吡咯烷酮,在60 ℃保温1小时;保温结束后将聚合好的预聚体降温到40 ℃,在高速搅拌下加入36g去离子水,并滴加1g乙二胺进行扩链,搅拌1小时后再减压蒸馏脱去丙酮,得到固含为49%的聚氨酯分散体(PUD)。
实施例4
将6g分子量为3000的磺化聚酯多元醇和8g分子量为2000的聚己二酸1,6己二醇酯加入到装有温度计、搅拌器和回流冷凝器的500 mL 的四口烧瓶中,升温到120℃左右脱水30分钟,脱水结束后降温到70℃左右,添加6g 4,4-二环基甲烷二异氰酸酯、4g六亚甲基二异氰酸酯和1.5g三羟甲基丙烷到烧瓶中,添加结束后升温到90℃保温反应3小时;将反应产物降温到70℃左右,加入2.5g1,6己二醇、1.5g三甲基戊二醇、3g二羟甲基丁酸,然后升温到85℃扩链反应2小时,反应2小时后取样测定反应物中—NCO的含量,直至接近理论值(用二正丁胺滴定法滴定),反应过程中加入25g丙酮调节粘度,反应到达时间后冷却至40 ℃,开始滴加1g十二烷基苯磺酸钠和2g三乙胺,在30分钟内滴加完毕;滴加完毕后添加3.5g氮甲基吡咯烷酮,在65度保温1小时;保温结束后将聚合好的预聚体降温到40 ℃,在高速搅拌下加入35g去离子水,并滴加1g乙二胺进行扩链,搅拌1小时后再减压蒸馏脱去丙酮得到固含为49%的聚氨酯分散体(PUD)。
根据目前适用的鞋用聚氨酯胶粘剂的国家标准:DIN6909“鞋材用胶粘剂;鞋底部件用胶粘剂的要求检测、分级”和德国DIN53273“鞋材用胶粘剂的检测溶剂型和分散体型胶粘剂”以及鞋用聚氨酯胶粘剂标准CB 7126—86、QB1002-90胶粘皮鞋标准(剥离强度为男鞋≥54kN/m,女鞋≥49kN/m)、SGCl78—84注塑布鞋、GB4492—84橡塑鞋、ZBY78001—86胶粘布鞋;GBl0507-89橡塑冷粘鞋、GBl2018—89耐酸耐碱鞋(靴)等标准,将上述实施例1-4得到的产品与U54、水性丙烯酸胶粘剂进行性能测试,结果如下:
由上表可以看出,本发明的水性聚氨酯鞋用胶粘剂,粘度低、粘接强度高,耐热性、耐水性等各项性能明显优于其他同类产品。
Claims (10)
1. 一种低粘度高粘接强度的水性聚氨酯鞋用胶粘剂,由包括如下重量配比的各组分聚合获得:
六亚甲基二异氰酸酯(HDI) 3-5%
4,4'-二环己基甲烷二异氰酸酯 5-8%
磺化聚酯多元醇 5-7%
聚己二酸-1,6-己二醇酯 5-10%
十二烷基苯磺酸钠 0.5-2%
三甲基戊二醇(TMPD) 1.5-3%
二羟甲基丁酸(DMBA) 1-3%
丙酮 8-11%
三乙胺 0.5-2%
去离子水 10-50%。
2.根据权利要求1所述的低粘度高粘接强度的水性聚氨酯鞋用胶粘剂,其特征在于:所述鞋用胶粘剂还添加有三羟甲基丙烷、1、6-己二醇作为扩链剂,三羟甲基丙烷在配方中的重量百分比为1-2%、1、6-己二醇在配方中的重量百分比为1.5-3%。
3.根据权利要求1所述的低粘度高粘接强度的水性聚氨酯鞋用胶粘剂,其特征在于:所述鞋用胶粘剂还包括有3-5%的氮甲基吡咯烷酮。
4.根据权利要求1所述的低粘度高粘接强度的水性聚氨酯鞋用胶粘剂,其特征在于:所述鞋用胶粘剂还添加有乙二胺作为pH值调节剂,乙二胺在配方中的重量百分比为0.5-1%。
5.根据权利要求1所述的低粘度高粘接强度的水性聚氨酯鞋用胶粘剂,其特征在于:所述磺化聚酯多元醇为分子量为3000的磺化聚酯多元醇,聚己二酸-1,6-己二醇酯为分子量为2000的聚己二酸-1,6-己二醇酯。
6.一种权利要求1所述低粘度高粘接强度的水性聚氨酯鞋用胶粘剂的制备方法,该方法依次包括如下步骤:
(1)将计量好的磺化聚酯多元醇、聚己二酸-1,6-己二醇酯加入反应釜,升温到120±1℃脱水30分钟,然后降温到70-80℃,加入4,4'-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯,升温到80-100℃,反应2-3小时;
(2)将步骤(1)的反应产物降温到60-70℃,加入计量的三甲基戊二醇、二羟甲基丁酸,升温到80-90℃,保温2小时,加入丙酮降粘;
(3)将步骤(2)的反应产物降温到40±1℃,缓慢滴加计量的十二烷基苯磺酸钠和三乙胺混合的溶液,在30分钟内滴加完毕;
(4)滴加完成后,在高速搅拌下快速加入计量的去离子水,搅拌1小时,减压蒸馏脱去丙酮,制得低粘度、高粘接强度的水性聚氨酯鞋用胶粘剂。
7.根据权利要求6所述的低粘度高粘接强度的水性聚氨酯鞋用胶粘剂的制备方法,其特征在于:所述制备方法中,步骤(1)在加入磺化聚酯多元醇或六亚甲基二异氰酸酯的同时,加入1-2%的三羟甲基丙烷;步骤(2)在加入三甲基戊二醇的同时,加入1.5-3%的1、6-己二醇。
8.根据权利要求6所述的低粘度高粘接强度的水性聚氨酯鞋用胶粘剂的制备方法,其特征在于:所述制备方法中,步骤(1)在脱水后加入1-2%的三羟甲基丙烷后保温1小时。
9.根据权利要求7或8所述的低粘度高粘接强度的水性聚氨酯鞋用胶粘剂的制备方法,其特征在于:所述制备方法中,步骤(3)在滴加完成后,加入3-5%的氮甲基吡咯烷酮,在60-65℃下保温1小时后再将反应产物降温至40±1℃。
10.根据权利要求9所述的低粘度高粘接强度的水性聚氨酯鞋用胶粘剂的制备方法,其特征在于:所制备方法中,步骤(5)在加入去离子水的同时加入0.5-1%的乙二胺。
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