CN109629269B - 一种绒面革固色剂及其制备方法和用途 - Google Patents

一种绒面革固色剂及其制备方法和用途 Download PDF

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CN109629269B
CN109629269B CN201811388882.8A CN201811388882A CN109629269B CN 109629269 B CN109629269 B CN 109629269B CN 201811388882 A CN201811388882 A CN 201811388882A CN 109629269 B CN109629269 B CN 109629269B
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刘振波
魏范梅
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Yantai University
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Abstract

本发明公开了一种绒面革固色剂及其制备方法和用途，属于织物后整理领域。方法制得的固色剂应用于织物印染固色后处理过程，能够有效提高织物干湿摩擦色牢度。绒面革固色剂由二异氰酸酯、聚合物多元醇、阴离子亲水扩链剂、小分子扩链剂、碱中和剂、交联剂为原料，通过预聚反应、扩链反应、中和离子化、交联反应和乳化反应，得到阴离子型混合交联改性的水性聚氨酯中性染料固色剂。本发明制备的固色剂不含甲醛，生产过程不使用有机溶剂，产品不含有毒溶剂，绿色环保，稳定性好，耐摩擦性能优异，固色效果明显，且合成工艺简单，时间短，能耗低，利于大规模的工业化生产和推进。

Description

一种绒面革固色剂及其制备方法和用途
技术领域
本发明涉及绒面革织物后整理领域，具体涉及一种绒面革固色剂及其制备方法和用途。
背景技术
绒面革织物经染料染色后，需要用固色剂整理，以提高绒面革染色织物的耐湿处理牢度。随着环保意识的增强及世界纺织市场对绒面革染色织物的色牢度又提出了新的要求，如Eco-Tex及Oeko-Tex标准对绒面革染色织物的耐洗色牢度要求达3～4级。传统的固色剂易引起绒面革染色织物色变、手感粗糙，特别是甲醛含量较高，对皮肤有刺激性和毒性。近年来市场上固色剂产品越来越多，但仍然存在许多的问题，如市场上固色剂产品多是对直接、活性、酸性等阴离子型染料效果明显，对于中性染料的固色效果不理想。
水性聚氨酯以水代替有机溶剂为分散介质，具有无毒性、绿色、不易燃、低VOC等特点，其通过降低染料的溶解度，增进染料与绒面革织物的结合力，以及覆盖染料及水溶性基团提高织物的固色牢度，但一般的水性聚氨酯存在较多的缺点，如稳定性差，耐湿摩擦牢度差，手感欠佳等。
发明内容
针对中性染料染色的PU革的耐干摩擦牢度及耐湿摩擦牢度较差，水性聚氨酯固色剂本身稳定性差以及固色剂含有毒溶剂等缺陷，本发明提供了一种不使用有机溶剂、环保绿色的阴离子型混合交联改性的水性聚氨酯中性染料固色剂及其制备方法和用途。
为实现发明目的之一，本发明的技术方案是：
一种绒面革固色剂的制备方法，绒面革固色剂为阴离子型混合交联改性的水性聚氨酯固色剂，具体制备步骤为：
(1)预聚反应：将二异氰酸酯、聚合物多元醇置于吸水性分子筛脱水干燥24h，脱水后按二异氰酸酯、聚合物多元醇二者摩尔比为(1.5～3)：1的比例混合均匀，然后升温至70～90℃反应1.5～3h；
(2)扩链反应：当步骤(1)的预聚反应中聚合物多元醇反应完全时，再加入为步骤(1)中二异氰酸酯、聚合物多元醇总质量1.5～2.5％的阴离子亲水扩链剂，保持70～90℃继续搅拌反应1～1.5h。
然后，于反应体系中加入为步骤(1)和步骤(2)反应后剩余异氰酸酯基摩尔量的80～95％的小分子扩链剂一缩二乙二醇，反应温度35～50℃继续搅拌反应1～1.5h，得到聚氨酯预聚体；
(3)中和离子化：35～50℃温度下，步骤(2)得到的聚氨酯预聚体加入与步骤(2)阴离子亲水扩链剂等摩尔量的三乙胺搅拌中和搅拌5～20min后，得到阴离子型聚氨酯预聚体；
(4)交联反应：中和离子化结束，将温度降至室温，加入为步骤(3)反应后剩余异氰酸酯基摩尔量的50～200％的交联剂搅拌反应0.5～1.5h，得到阴离子型混合交联改性的聚氨酯预聚体；
(5)乳化反应：步骤(4)得到的阴离子型聚氨酯预聚体，加入去离子水，高速搅拌分散0.5～1h后，得到阴离子型混合交联改性的水性聚氨酯乳液。
优选，所述二异氰酸酯是甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、二环己基甲烷二异氰酸酯(HMDI)、甲基环己烷二异氰酸酯(HTDI)中的任意一种。
优选，所述聚合物多元醇是聚四氢呋喃二醇、聚丙二醇、聚乙二醇、聚氧化乙烯二元醇、聚氧化丙烯二元醇、聚己二酸蓖麻油酯二醇、聚己二酸乙二醇酯二醇、聚己二酸乙二醇二乙二醇酯二醇、聚己二酸丁二醇酯二元醇、聚己二酸乙二醇酯二元醇、聚己二酸新戊二醇酯二元醇、聚邻苯二甲酸己二醇酯二元醇中的任意一种。
优选，所述阴离子亲水扩链剂是二羟甲基丙酸、二羟甲基丁酸、1,2-丙二醇-3-磺酸钠、1,4-丁二醇-2-磺酸钠中的任意一种。
优选，所述的交联剂是含硅交联剂、氮丙啶、环氧氯丙烷中的任意一种。
优选，所述去离子水的量使水性聚氨酯乳液固含量为20％～40％。
为实现发明目的之二，本发明的技术方案是：
上述制备方法获得的一种阴离子型混合交联改性的水性聚氨酯预聚体，结构式如下所示：
Figure BDA0001872132000000021
其中，R1为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、二环己基甲烷二异氰酸酯(HMDI)、甲基环己烷二异氰酸酯(HTDI)中的任意一种结构；
R2为聚四氢呋喃二醇、聚丙二醇、聚乙二醇、聚氧化乙烯二元醇、聚氧化丙烯二元醇、聚己二酸蓖麻油酯二醇、聚己二酸乙二醇酯二醇、聚己二酸乙二醇二乙二醇酯二醇、聚己二酸丁二醇酯二元醇、聚己二酸乙二醇酯二元醇、聚己二酸新戊二醇酯二元醇、聚邻苯二甲酸己二醇酯二元醇中的任意一种结构；
R3为二羟甲基丙酸、二羟甲基丁酸、1,2-丙二醇-3-磺酸钠、1,4-丁二醇-2-磺酸钠中的任意一种结构；
Figure BDA0001872132000000031
n为0到300的整数。
为实现发明目的之三，本发明的技术方案是：
上述的一种阴离子型混合交联改性的水性聚氨酯的用途，所述阴离子型混合交联改性的水性聚氨酯用于制备绒面革固色剂。
使用时，将染色样在常温处理液(阴离子型混合交联改性的水性聚氨酯乳液与水以1：99的质量比混合均匀)中浸泡5～10min，挤压脱水，于120℃焙烘10～20min。
本发明的有益效果是：
(1)本发明制备的固色剂不含甲醛，生产过程不使用有机溶剂，产品不含有毒溶剂，绿色环保，耐摩擦性能优异，固色效果明显。
(2)本发明制备工艺简单，时间短，能耗低，且固色剂乳液稳定性好。
(3)本发明是混合交联改性，利用产品的网状交联结构，可以在绒面革织物上形成一层致密性薄膜以覆盖色淀，达到提高织物色牢度的目的。
本发明的混合交联改性即自身交联与外加交联剂进行交联改性，得到的阴离子型混合交联改性的水性聚氨酯为网状交联结构，具有优良的成膜性，由于其具有较大的相对分子质量，可以在绒面革织物上形成一层致密性薄膜，而该薄膜可以覆盖色淀，这样大大提高了绒面革织物的湿摩擦色牢度。
附图说明
图1为绒面革染色样未固色处理分别进行干摩和湿摩10次测试后的效果图；
图2为绒面革染色样浸市场产品分别进行干摩和湿摩10次测试后的效果图；
图3为绒面革染色样浸实施例1分别进行干摩和湿摩10次测试后的效果图；
图4为绒面革染色样浸实施例2分别进行干摩和湿摩10次测试后的效果图；
图5为绒面革染色样浸实施例3分别进行干摩和湿摩10次测试后的效果图。
具体实施方式
实施例1
(1)预聚反应：将2.6g甲苯二异氰酸酯、20g聚四氢呋喃二醇置于吸水性分子筛脱水干燥24h，脱水后放入三口烧瓶中，混合均匀后，升温至75℃反应3h；
(2)扩链反应：加入0.34g二羟甲基丙酸，保持75℃继续搅拌反应1h。
然后，于反应体系中加入0.21g一缩二乙二醇，反应温度自75℃降至35℃搅拌反应，得到聚氨酯预聚体；
(3)中和离子化：35～50℃温度下，步骤(2)得到的聚氨酯预聚体加入0.25g三乙胺搅拌中和15min，得到阴离子型聚氨酯预聚体；
(4)交联反应：中和离子化结束，将温度降至室温，加入0.44g含硅交联剂搅拌反应0.5h，得到阴离子型混合交联改性的聚氨酯预聚体；
(5)乳化反应：步骤(4)得到的阴离子型聚氨酯预聚体，加入94g去离子水，高速搅拌分散0.5h，得到阴离子型混合交联改性的水性聚氨酯乳液。
实施例2
(1)预聚反应：将4.2g六亚甲基二异氰酸酯、10g聚乙二醇置于吸水性分子筛脱水干燥24h，脱水后放入三口烧瓶中，混合均匀后，升温至80℃反应2h；
(2)扩链反应：加入0.28g二羟甲基丁酸，保持80℃继续搅拌反应1h。
然后，于反应体系中加入1.25g一缩二乙二醇，反应温度自80℃降至40℃搅拌反应，得到聚氨酯预聚体；
(3)中和离子化：步骤(2)得到的聚氨酯预聚体加入0.19g三乙胺搅拌中和20min，得到阴离子型聚氨酯预聚体；
(4)交联反应：中和离子化结束，将温度降至室温，加入0.11g氮丙啶搅拌反应1h，得到阴离子型混合交联改性的聚氨酯预聚体；
(5)乳化反应：步骤(4)得到的阴离子型聚氨酯预聚体，加入37g去离子水，高速搅拌分散1h，得到阴离子型混合交联改性的水性聚氨酯乳液。
实施例3
(1)预聚反应：将6.67g异佛尔酮二异氰酸酯、20.15g聚己二酸乙二醇酯二醇置于吸水性分子筛脱水干燥24h，脱水后放入三口烧瓶中，混合均匀后，升温至85℃反应1.5h；
(2)扩链反应：加入0.67g二羟甲基丙酸，保持85℃继续搅拌反应1h。
然后，于反应体系中加入1.5g一缩二乙二醇，反应温度自85℃降至50℃搅拌反应，得到聚氨酯预聚体；
(3)中和离子化：步骤(2)得到的聚氨酯预聚体加入0.5g三乙胺搅拌中和10min，得到阴离子型聚氨酯预聚体；
(4)交联反应：中和离子化结束，将温度降至室温，加入0.14g环氧氯丙烷搅拌反应0.5h，得到阴离子型混合交联改性的聚氨酯预聚体；
(5)乳化反应：步骤(4)得到的阴离子型聚氨酯预聚体，加入44g去离子水，高速搅拌分散1h，得到阴离子型混合交联改性的水性聚氨酯乳液。
验证例
将实施例1-3制备的阴离子型混合交联改性的水性聚氨酯乳液与水以1：99的质量比混合均匀分别制备出实施例1-3的常温处理液；
取多个绒面革染色样分别置于在实施例1-3的常温处理液中浸泡5～10min，挤压脱水，于120℃焙烘10～20min。
市场产品是嘉宏Goon系列，将嘉宏Goon系列的产品与水以1：99的质量比混合均匀制备出市场产品的常温处理液；
取一个绒面革染色样置于在市场产品的常温处理液中浸泡5～10min，挤压脱水，于120℃焙烘10～20min。
按照GB/T3920-2008《纺织品色牢度试验—耐摩擦色牢度》，在干湿摩擦色牢度仪上进行干湿摩擦色牢度测试。
表1.干湿摩擦色牢度测试性能表
测试产品 干摩擦牢度/级 湿摩擦牢度/级
空白 3 1～2
市场产品 4 3
实施例1 4 3～4
实施例2 4～5 3～4
实施例3 4～5 3
对空白产品、市场产品、浸润过实施例1-3的常温处理液的绒面革进行10次干摩和湿摩测试后，如表1和图1-5所示，图1中干摩、湿摩均在摩擦白布上掉色明显，并且，干摩擦色牢度为3级，湿摩擦色牢度为1～2级；
图2中干摩、湿摩均在摩擦白布上显示掉色，并且，干摩擦色牢度为4级，湿摩擦色牢度为3级；
图3中干摩、湿摩掉色情况与市场产品基本相同，但是湿摩掉色轻微，明显优于市场产品，并且，干摩擦色牢度为4级，湿摩擦色牢度为3～4级；
图4中干摩不显示掉色，湿摩掉色轻微，但明显好于市场产品，并且，干摩擦色牢度为4～5级，湿摩擦色牢度为3～4级；
图5中干摩不显示掉色，湿摩掉色轻微，但明显好于市场产品，干摩擦色牢度为4～5级，湿摩擦色牢度为3级。
可见浸润过实施例1-3的常温处理液的绒面革的固色牢度要明显优于现有产品，尤其是干摩时基本显示不掉色，可见阴离子型混合交联改性的水性聚氨酯乳液对绒面革织物的湿摩擦色牢度效果明显。
基于上述效果分析，阴离子型混合交联改性的水性聚氨酯乳液在于利用自身的二异氰酸酯与外加交联剂进行混合交联改性，自身交联可以提高产物的交联程度，促进网状结构的形成，外加的交联剂不仅与自身的二异氰酸酯相辅相成的提高交联网状结构，而且提高了产品的刚性及网状的致密性。同时以自交联为主，外加交联剂为辅的混合交联改性，充分发挥了原料的功能性，提高了原料的利用率。并且，实验过程中不使用有毒溶剂，环保绿色，消除了现今市场上的固色剂中存在有机溶剂问题，对身体健康存在潜在的威胁。

Claims (1)

1.一种绒面革固色剂的制备方法，其特征在于，绒面革固色剂为阴离子型混合交联改性的水性聚氨酯固色剂，具体制备步骤为：
（1）预聚反应：将二异氰酸酯、聚合物多元醇置于吸水性分子筛脱水干燥24 h，脱水后按二异氰酸酯、聚合物多元醇二者摩尔比为（1.5~3）：1的比例混合均匀，然后升温至70~90℃反应1.5~3 h；
（2）扩链反应：当步骤（1）的预聚反应中聚合物多元醇反应完全时，再加入为步骤（1）中二异氰酸酯、聚合物多元醇总质量1.5~2.5%的阴离子亲水扩链剂，保持70~90 ℃继续搅拌反应1~1.5 h；
然后，于反应体系中加入为步骤（1）和步骤（2）反应后剩余异氰酸酯基摩尔量的80~95%的小分子扩链剂一缩二乙二醇，反应温度35~50 ℃继续搅拌反应1~1.5h，得到聚氨酯预聚体；
（3）中和离子化：35~50 ℃温度下，步骤（2）得到的聚氨酯预聚体加入与步骤（2）阴离子亲水扩链剂等摩尔量的三乙胺搅拌中和搅拌5~20min后，得到阴离子型聚氨酯预聚体；
（4）交联反应：中和离子化结束，将温度降至室温，加入为步骤（3）反应后剩余异氰酸酯基摩尔量的50~200%的交联剂搅拌反应0.5~1.5 h，得到阴离子型混合交联改性的聚氨酯预聚体；
（5）乳化反应：步骤（4）得到的阴离子型混合交联改性的聚氨酯预聚体，加入去离子水，高速搅拌分散0.5~1 h后，得到阴离子型混合交联改性的水性聚氨酯乳液；
其中，所述二异氰酸酯是甲苯二异氰酸酯（TDI）、二苯基甲烷二异氰酸酯（MDI）、六亚甲基二异氰酸酯（HDI）、异佛尔酮二异氰酸酯（IPDI）、二环己基甲烷二异氰酸酯（HMDI）、甲基环己烷二异氰酸酯（HTDI）中的任意一种；
所述聚合物多元醇是聚四氢呋喃二醇、聚丙二醇、聚乙二醇、聚氧化乙烯二元醇、聚氧化丙烯二元醇、聚己二酸蓖麻油酯二醇、聚己二酸乙二醇酯二醇、聚己二酸乙二醇二乙二醇酯二醇、聚己二酸丁二醇酯二元醇、聚己二酸新戊二醇酯二元醇、聚邻苯二甲酸己二醇酯二元醇中的任意一种；
所述阴离子亲水扩链剂是二羟甲基丙酸、二羟甲基丁酸、1,2-丙二醇-3-磺酸钠、1,4-丁二醇-2-磺酸钠中的任意一种；
所述的交联剂是含硅交联剂、氮丙啶、环氧氯丙烷中的任意一种；
所述去离子水的量使水性聚氨酯乳液固含量为20%~40%。
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