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CN111518257B - 一种水性聚氨酯鞋胶及其制备方法 - Google Patents

一种水性聚氨酯鞋胶及其制备方法 Download PDF

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CN111518257B
CN111518257B CN202010478814.1A CN202010478814A CN111518257B CN 111518257 B CN111518257 B CN 111518257B CN 202010478814 A CN202010478814 A CN 202010478814A CN 111518257 B CN111518257 B CN 111518257B
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王兰柱
王子文
高丙义
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Junneng Chemical Longnan Co ltd
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Abstract

本发明属于聚氨酯胶黏剂技术领域，具体地涉及一种水性聚氨酯鞋胶及其制备方法。该水性聚氨酯鞋胶包括异佛尔酮‑二异氰酸酯、4,4'‑二环己基甲烷二异氰酸酯、磺化聚醚多元醇、聚己二酸1,6己二醇酯、二月桂酸二丁基锡、乙二胺、海藻糖、十二烷基苯磺酸钠、1,4‑丁二醇、二羟甲基丁酸和丁酮。本发明制备得到的水性聚氨酯鞋胶具有高固含量、黏度低、粘接强度高、耐水性好和无污染的特点。本发明水性聚氨酯鞋胶的制备方法，工艺简单、操作方便、溶剂易于回收处理，节约了成本。

Description

一种水性聚氨酯鞋胶及其制备方法
技术领域
本发明属于聚氨酯胶黏剂领域，具体涉及一种水性聚氨酯鞋胶及其制备方法。
背景技术
我国制鞋业主要采用溶剂型胶粘剂粘接鞋材，这些传统粘合剂含有挥发性有机物(VOCs)和有害气体污染物(HAPs)，存在着环境污染、安全隐患等问题。水性聚氨酯作为新一代的环保型产品，具有气味小、不燃、不污染环境、施工方便等优点，已成为取代溶剂型胶粘剂的重点研究方向。聚氨酯胶粘剂，是指分子链中含有氨基甲酸酯基(—NHCOO—)或者异氰酸酯基(—NCO)类的胶粘剂。聚氨酯胶粘剂本身具有原料选择范围广、分子可设计性强和对许多材料粘接性能好等特点。
现有技术中水性聚氨酯鞋用胶粘剂，其固含量控制在50％左右，黏度均较高。提高固含量，不但可以提水性聚氨酯鞋用胶粘剂的干燥速度，提高生产效率，同时烘干所需要的热量减少，节省能源。而固含量超过60％以后，黏度随固含量的增加急剧上升，黏度高则容易导致其流动性较差，容易出现胶膜不连续的情况，进而影响其流平性和增加上胶量，因此，寻找一种高固含量、黏度低、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
本发明为了克服现有技术的基础上，提供了一种水性聚氨酯鞋胶及其制备方法。本发明水性聚氨酯鞋胶的制备方法，工艺简单、操作方便、溶剂易于回收处理，节约了成本；制备得到的水性聚氨酯鞋胶具有高固含量、黏度低、粘接强度高、耐水性好、无污染的特点。
为了实现上述目的，本发明采用以下技术方案：
一方面，提供了一种水性聚氨酯鞋胶，按重量份数计，包括如下原料：异佛尔酮-二异氰酸酯30～50份、4,4'-二环己基甲烷二异氰酸酯20～40份、磺化聚醚多元醇10～25份、聚己二酸1,6己二醇酯5～15份、二月桂酸二丁基锡0.5～3份、海藻糖1～5份、十二烷基苯磺酸钠0.5～5份、1,4-丁二醇2～8份、二羟甲基丁酸1～5份、丁酮4～8份、乙二胺1～3份。
进一步地，按重量份数计，包括如下原料：异佛尔酮-二异氰酸酯35～45份、4,4'-二环己基甲烷二异氰酸酯25～35份、磺化聚醚多元醇15～20份、聚己二酸1,6己二醇酯8～12份、二月桂酸二丁基锡1～2份、海藻糖2～5份、十二烷基苯磺酸钠0.5～2份、1,4-丁二醇2～5份、二羟甲基丁酸1～3份、丁酮5～7份、乙二胺1～3份。
进一步地，所述磺化聚醚多元醇优选分子量为3000的磺化聚醚多元醇；所述聚己二酸1,6己二醇酯优选分子量为2000的聚己二酸1,6己二醇酯。
另一方面，提供了一种水性聚氨酯鞋胶的制备方法，包括如下步骤：
(1)将磺化聚醚多元醇、聚己二酸1,6己二醇酯加入聚合反应器，升温至110～120℃，减压蒸馏除水1～2h，除水结束后降温至60～70℃，加入异佛尔酮-二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、二月桂酸二丁基锡、海藻糖，升温到80～100℃，反应2～3h；
(2)将步骤(1)的反应产物降温到60～70℃，加入丁酮，搅拌10min后加入1，4-丁二醇、二羟甲基丁酸，升温到80～90℃，保温1～2h；
(3)将步骤(2)的反应产物降温到30～40℃，加入十二烷基苯磺酸钠，在高速搅拌和剪切得到乳液，向所得乳液中加入乙二胺，继续搅拌扩链30～40min；
(4)将步骤(3)的反应产物升温至60～70℃，减压蒸馏脱除溶剂，得到水性聚氨酯鞋胶。
进一步地，步骤(4)在减压蒸馏脱除溶剂后，还包括向反应液中加入消泡剂和增稠剂。
进一步地，消泡剂为水性消泡剂Afcona 2501、Afcona 2502或Afcona 2524中的任意一种；所述增稠剂为SHEUR或LHEUR中的任意一种。
本发明的积极效果如下：
1.本发明选用磺化聚醚多元醇和聚己二酸1,6己二醇酯作为主要的固体物质来源，磺化聚醚多元醇和聚己二酸1,6己二醇酯的可以提高聚氨酯粒径，从而提高固含量，而固含量的提高有利于粘接强度的提高。
2.本发明选用海藻糖作为内交联剂，不但能增加聚氨酯粒径，而且使聚氨酯粒径分布变宽且分布均匀。由于海藻糖具有交联和扩链效果，使生成的聚氨酯分子量增长，分子链相互缠结，导致粒径增大，另一方面，海藻糖分子的刚性较大，参与反应后，在聚氨酯中形成了更多的疏水的硬段结构，导致乳液的平均粒径增大，从而使得胶膜的粘结强度、耐水性以及机械强度得到大幅度提高。
3.本发明选用1,4-丁二醇作为小分子扩链剂，磺酸型扩链剂二羟甲基丁酸作为亲水扩链剂，由于含有羧基和羟基等亲水基团，能减薄水合层，增强乳液流动性，一定程度上降低了聚氨酯的黏度。
4.本发明制备方法，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，由于固含量高、黏度低、粘接强度高，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
下面结合实施例对本发明做进一步的描述，有必要在此指出的是以下实施例只是用于对本发明进行进一步的说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员根据上述发明内容所做出的一些非本质的改进和调整，仍属于本发明的保护范围。
实施例1
一种水性聚氨酯鞋胶，按重量份数计，包括如下原料：
Figure BDA0002516629120000031
Figure BDA0002516629120000041
一种水性聚氨酯鞋胶的制备方法，包括如下步骤：
按上述组分比例，将磺化聚醚多元醇、聚己二酸1,6己二醇酯加入聚合反应器，升温至120℃，减压蒸馏除水2h，除水结束后降温至65℃，加入异佛尔酮-二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、二月桂酸二丁基锡、海藻糖，升温到90℃，反应2h；然后将反应产物降温到70℃，加入丁酮，搅拌10min后加入1，4-丁二醇、二羟甲基丁酸，升温到90℃，保温1h；再将反应产物降温到35℃，加入十二烷基苯磺酸钠和去离子水，在高速剪切搅拌机中转速为5000r/min条件下，剪切得到乳液，再加入乙二胺，继续搅拌扩链40min；最后升温至70℃，减压蒸馏脱除溶剂，得到水性聚氨酯鞋胶。
实施例2
一种水性聚氨酯鞋胶，按重量份数计，包括如下原料：
Figure BDA0002516629120000042
一种水性聚氨酯鞋胶的制备方法，包括如下步骤：
按上述组分比例，将磺化聚醚多元醇、聚己二酸1,6己二醇酯加入聚合反应器，升温至110℃，减压蒸馏除水2h，除水结束后降温至60℃，加入异佛尔酮-二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、二月桂酸二丁基锡、海藻糖，升温到80℃，反应2h；然后将反应产物降温到60℃，加入丁酮，搅拌10min后加入1，4-丁二醇、二羟甲基丁酸，升温到80℃，保温1h；再将反应产物降温到30℃，加入十二烷基苯磺酸钠和去离子水，在高速剪切搅拌机中转速为4500r/min条件下，剪切得到乳液，再加入乙二胺，继续搅拌扩链40min；最后升温至70℃，减压蒸馏脱除溶剂，得到水性聚氨酯鞋胶。
实施例3
一种水性聚氨酯鞋胶，按重量份数计，包括如下原料：
Figure BDA0002516629120000051
一种水性聚氨酯鞋胶的制备方法，包括如下步骤：
按上述组分比例，将磺化聚醚多元醇、聚己二酸1,6己二醇酯加入聚合反应器，升温至120℃，减压蒸馏除水2h，除水结束后降温至70℃，加入异佛尔酮-二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、二月桂酸二丁基锡、海藻糖，升温到100℃，反应2h；然后将反应产物降温到70℃，加入丁酮，搅拌10min后加入1，4-丁二醇、二羟甲基丁酸，升温到90℃，保温1h；再将反应产物降温到40℃，加入十二烷基苯磺酸钠和去离子水，在高速剪切搅拌机中转速为5000r/min条件下，剪切得到乳液，再加入乙二胺，继续搅拌扩链40min；最后升温至70℃，减压蒸馏脱除溶剂，得到水性聚氨酯鞋胶。
对比例1
与实施例1比，成分上三羟甲基丙烷代替海藻糖，余同；
对比例2
与实施例1比，成分上不含有海藻糖，余同；
对比例3
与实施例1比，成分上不含有1,4-丁二醇和二羟甲基丁酸，余同；
对比例4
与实施例1比，成分上不含有1,4-丁二醇，余同；
对比例5
与实施例1比，成分上不含有二羟甲基丁酸，余同；
性能测试：
将实施例1-3与对比例1-5的试样进行以下指标的检测，结果如下表1。
(1)固含量：称取试样1.0-1.5g于已称重的称量瓶中，干燥至恒重，求固含量；
(2)黏度：按GB/T 4851-84测定；
(3)初粘力：按GB/T2791-1995测定；将乳液涂抹于PU/PVC薄膜复合
膜之间经烘干后，测试T-剥离强度；
(4)耐水性：放入50℃水中24h后进行观察。
(5)耐热性：观察80℃温度下开裂情况。
表1性能测试结果
Figure BDA0002516629120000061
Figure BDA0002516629120000071
从表1结果可知，本发明实施例1-3制备的聚氨酯鞋胶固含量为63％～65％，黏度为180mpa.s～260mpa.s，剥离强度为7.8N～8.2N，耐水性良好。且从实施例1-3结果可知，实施例1制备得到聚氨酯鞋胶性能最优。
对比例1-2考察了海藻糖作为内交联剂时对黏度的影响。对比例1当采用三羟甲基丙烷代替海藻糖后，对比例1制备的聚氨酯鞋固含量下降到54％，耐热性变差，而当不含海藻糖内交联剂时对比例2制备的聚氨酯鞋固含量仅为46％，耐水性和耐热性均变差。
对比例3-5考察了1,4-丁二醇和二羟甲基丁酸的影响。对比例3-5制备的聚氨酯鞋胶粘度分别为780mpa.s、530mpa.s、580mpa.s，对比例3不含1,4-丁二醇和二羟甲基丁酸时，黏度最高，耐水性和耐水性均变差
因此，由以上结果可知，本发明制备得到的聚氨酯鞋胶性能优良，不但固含量高、黏度低、粘接力强、耐水性和耐热性均较好。

Claims (6)

1.一种水性聚氨酯鞋胶，其特征在于，按重量份数计，包括如下原料：异佛尔酮-二异氰酸酯30～50份、4,4'-二环己基甲烷二异氰酸酯20～40份、磺化聚醚多元醇10～25份、聚己二酸-1,6-己二醇酯5～15份、二月桂酸二丁基锡0.5～3份、海藻糖1～5份、十二烷基苯磺酸钠0.5～5份、1,4-丁二醇2～8份、二羟甲基丁酸1～5份、丁酮4～8份、乙二胺1～3份；
水性聚氨酯鞋胶的制备方法，包括如下步骤：
（1）将磺化聚醚多元醇、聚己二酸-1,6-己二醇酯加入聚合反应器，升温至110～120℃，减压蒸馏除水1～2h，除水结束后降温至60～70℃，加入异佛尔酮-二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、二月桂酸二丁基锡、海藻糖，升温到80～100℃，反应2～3h；
（2）将步骤（1）的反应产物降温到60～70℃，加入丁酮，搅拌10min后加入1，4-丁二醇、二羟甲基丁酸，升温到80～90℃，保温1～2h；
（3）将步骤（2）的反应产物降温到30～40℃，加入十二烷基苯磺酸钠，再高速搅拌剪切得到乳液，向所得乳液中加入乙二胺，继续搅拌扩链30～40min；
（4）将步骤（3）的反应产物升温至60～70℃，减压蒸馏脱除溶剂，得到水性聚氨酯鞋胶。
2.根据权利要求1所述的一种水性聚氨酯鞋胶，其特征在于，按重量份数计，包括如下原料：异佛尔酮-二异氰酸酯35～45份、4,4'-二环己基甲烷二异氰酸酯25～35份、磺化聚醚多元醇15～20份、聚己二酸-1,6-己二醇酯8～12份、二月桂酸二丁基锡1～2份、海藻糖2～5份、十二烷基苯磺酸钠0.5～2份、1,4-丁二醇2～5份、二羟甲基丁酸1～3份、丁酮5～7份、乙二胺1～3份。
3.根据权利要求1所述的一种水性聚氨酯鞋胶，其特征在于，所述磺化聚醚多元醇选择分子量为3000的磺化聚醚多元醇；所述聚己二酸-1,6-己二醇酯选择分子量为2000的聚己二酸-1,6-己二醇酯。
4.根据权利要求1所述的一种水性聚氨酯鞋胶，其特征在于，所述步骤（3）中高速搅拌剪切时的转速为4500～5500r/min。
5.根据权利要求1所述的一种水性聚氨酯鞋胶，其特征在于，所述制备方法中，步骤（4）在减压蒸馏脱除溶剂后，还包括向反应液中加入消泡剂和增稠剂。
6.根据权利要求5所述的一种水性聚氨酯鞋胶，其特征在于，所述消泡剂为水性消泡剂Afcona 2501、Afcona 2502或Afcona 2524中的任意一种；所述增稠剂为SHEUR或LHEUR中的任意一种。
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