CN105821681A - 一种低成本环保织物粘合剂的制备方法 - Google Patents
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Abstract
本发明公开了一种低成本环保织物粘合剂的制备方法，包括以下步骤：首先利用甘油和加氢催化剂反应，并同时加入环己烷，制得1,2丙二醇；然后加入丙烯酸、衣康酸、对苯二甲酸、二乙二醇和新戊二醇，在一定条件下酯化，并抽真空，缩聚后得到聚酯多元醇；将聚酯多元醇、聚醚多元醇和异氰酸酯反应，并加入助剂复配，制得织物粘合剂，该制备方法简单易操作，生产成本低，制备过程中无有毒物质释放，对环境无害，且制得的粘合剂粘结性能优异，耐候性能好，韧性大。
Description
技术领域：
本发明涉及纺织技术领域，具体的涉及一种低成本环保织物粘合剂的制备方法。
背景技术：
粘合剂是涂料印花色浆的主要组分，它是一种高分子成膜物质，由各种单体聚合而成，通过成膜而将颜料粘附于织物上，故成膜性能的好坏直接影响印花织物的牢度性能。目前广泛使用的丙烯酸酯系列自交联粘合剂中大部分都含有N-羟甲基丙烯酰胺(NMA)，交联过程中会有产生甲醛，污染环境。因此，要使涂料印花工艺满足环保要求，必须开发出环保型粘合剂。
发明内容：
本发明的目的是提供一种低成本环保织物粘合剂的制备方法，该制备方法，操作简单，成本低，制备过程中无有毒物质释放，有利于环境保护，制备得到的粘合剂粘结性、韧性好，耐候性能优异。
为实现上述目的，本发明采用以下技术方案：
一种低成本环保织物粘合剂的制备方法，包括以下步骤：
(1)1,2-丙二醇的制备
在反应温度200-250℃，反应压力3.0-6.0MPa，氢/油摩尔比为(6-12)：1，质量空速为0.1-3h-1的操作条件下，甘油与加氢催化剂接触进行加氢反应，反应过程中同时通入环己烷，制得1,2丙二醇，其中，环己烷与甘油的质量比为(0.5-5)：1；
(2)酯化反应
将5-10质量份丙烯酸、6-12质量份衣康酸、10-20质量份对苯二甲酸、20-30质量份的二乙二醇、5-10质量份的新戊二醇以及10-20质量份的步骤(1)制得的1,2-丙二醇加入到聚酯合成釜中，升温至220-260℃，反应5-10h，酯化完成；
(3)缩聚反应
将步骤(2)酯化步骤中酯化完成的聚酯合成釜抽真空，使得真空度达-0.09—-0.1MPa，保持真空时间为2-5h，缩聚完成，得到聚酯多元醇；
(4)复配
将30-40质量份步骤(3)制得的聚酯多元醇、20-25质量份的聚醚多元醇和30-40质量份的异氰酸酯，混合均匀，在90-100℃下反应6-10h，降温至50-70℃，依次加入3-8质量份的十二烷基苯磺酸钠、5-10质量份的聚氧乙烯山梨糖醇酐单油酸酯、2-5质量份的茶多酚，搅拌混合30-60min，继续加入0.1-0.5质量份的柠檬精油、1-2质量份的交联剂和1-2质量份的抗氧化剂，搅拌2-4h，得到低成本环保织物粘合剂。
作为上述技术方案的优选，步骤(1)中，所述甘油以甘油溶液的形式加入，其中溶剂为乙醇、甲醇或水，甘油的质量分数为50-90％。
作为上述技术方案的优选，步骤(1)中，所述加氢催化剂为Cu-B2O3-CaO-Al2O3催化剂。
作为上述技术方案的优选，所述加氢催化剂中，以干基前驱体的重量为基准，含有Cu5-30％和B2O31-20％；以质量分数计，所述干基前驱体中，含CaO5-30％和Al2O370-95％。
作为上述技术方案的优选，所述加氢催化剂中还含有助剂，以干基前驱体的重量为基准，含有助剂0.1-10％，所述助剂为Na2O或K2O。
作为上述技术方案的优选，步骤(2)中，制备聚酯多元醇的酯化步骤中，保持聚酯合成釜的馏出物的馏出量为2-4质量份/小时。
作为上述技术方案的优选，步骤(4)中，所述异氰酸酯为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种混合。
作为上述技术方案的优选，步骤(4)中，所述聚醚多元醇为聚氧化丙烯二醇、四氢呋喃-氧化丙烯共聚二醇中的一种或两种混合。
本发明具有以下有益效果：
本发明采用甘油氢解制备1,2-丙二醇，并同时加入环己烷，环己烷可以促进吸附在催化剂活性位上的水的解吸附，从而消除了体系中生成的水对催化剂活性的影响，提高了催化剂的稳定性；而且大大降低了氢气的消耗量，而且甘油在生物柴油的大规模生产中会大幅过剩，采用甘油作为原料，大大节约了生产成本；
本发明制得粘合剂粘结性能好，韧性好，固化速度快，耐候性能优异，且制备方法简单，生产成本低，制备过程中无有毒物质释放，有利于环境保护。
具体实施方式：
为了更好的理解本发明，下面通过实施例对本发明进一步说明，实施例只用于解释本发明，不会对本发明构成任何的限定。
实施例1
一种低成本环保织物粘合剂的制备方法，包括以下步骤：
(1)1,2-丙二醇的制备
在反应温度200℃，反应压力3.0MPa，氢/油摩尔比为6：1，质量空速为0.1h-1的操作条件下，甘油与加氢催化剂接触进行加氢反应，反应过程中同时通入环己烷，制得1,2丙二醇，其中，环己烷与甘油的质量比为0.5：1，加氢催化剂中，以干基前驱体的重量为基准，含有Cu5％和B2O35％，Na2O0.1％；以质量分数计，所述干基前驱体中，含CaO5％和Al2O395％；
(2)酯化反应
将5质量份丙烯酸、6质量份衣康酸、10质量份对苯二甲酸、20质量份的二乙二醇、5质量份的新戊二醇以及10质量份的步骤(1)制得的1,2-丙二醇加入到聚酯合成釜中，升温至220℃，反应5h，酯化完成；
(3)缩聚反应
将步骤(2)酯化步骤中酯化完成的聚酯合成釜抽真空，使得真空度达-0.09MPa，保持真空时间为2h，缩聚完成，得到聚酯多元醇；
(4)复配
将30质量份步骤(3)制得的聚酯多元醇、20质量份的聚氧化丙烯二醇和30质量份的二苯基甲烷二异氰酸酯，混合均匀，在90℃下反应6h，降温至50℃，依次加入3质量份的十二烷基苯磺酸钠、5质量份的聚氧乙烯山梨糖醇酐单油酸酯、2质量份的茶多酚，搅拌混合30min，继续加入0.1质量份的柠檬精油、1质量份的交联剂和1质量份的抗氧化剂，搅拌2h，得到低成本环保织物粘合剂。
实施例2
一种低成本环保织物粘合剂的制备方法，包括以下步骤：
(1)1,2-丙二醇的制备
在反应温度250℃，反应压力6.0MPa，氢/油摩尔比为12：1，质量空速为3h-1的操作条件下，甘油与加氢催化剂接触进行加氢反应，反应过程中同时通入环己烷，制得1,2丙二醇，其中，环己烷与甘油的质量比为5：1，加氢催化剂中，以干基前驱体的重量为基准，含有Cu30％和B2O315％，K2O5％；以质量分数计，所述干基前驱体中，含CaO30％和Al2O370％；
(2)酯化反应
将10质量份丙烯酸、12质量份衣康酸、20质量份对苯二甲酸、30质量份的二乙二醇、10质量份的新戊二醇以及20质量份的步骤(1)制得的1,2-丙二醇加入到聚酯合成釜中，升温至260℃，反应10h，酯化完成；
(3)缩聚反应
将步骤(2)酯化步骤中酯化完成的聚酯合成釜抽真空，使得真空度达-0.1MPa，保持真空时间为5h，缩聚完成，得到聚酯多元醇；
(4)复配
将40质量份步骤(3)制得的聚酯多元醇、25质量份的四氢呋喃-氧化丙烯共聚二醇和40质量份的六亚甲基二异氰酸酯，混合均匀，在100℃下反应10h，降温至70℃，依次加入8质量份的十二烷基苯磺酸钠、10质量份的聚氧乙烯山梨糖醇酐单油酸酯、5质量份的茶多酚，搅拌混合60min，继续加入0.5质量份的柠檬精油、2质量份的交联剂和2质量份的抗氧化剂，搅拌4h，得到低成本环保织物粘合剂。
实施例3
一种低成本环保织物粘合剂的制备方法，包括以下步骤：
(1)1,2-丙二醇的制备
在反应温度210℃，反应压力4.0MPa，氢/油摩尔比为8：1，质量空速为1h-1的操作条件下，甘油与加氢催化剂接触进行加氢反应，反应过程中同时通入环己烷，制得1,2丙二醇，其中，环己烷与甘油的质量比为1.5：1，加氢催化剂中，以干基前驱体的重量为基准，含有Cu10％和B2O35％，Na2O2％；以质量分数计，所述干基前驱体中，含CaO10％和Al2O390％；
(2)酯化反应
将6质量份丙烯酸、8质量份衣康酸、12质量份对苯二甲酸、22质量份的二乙二醇、6质量份的新戊二醇以及12质量份的步骤(1)制得的1,2-丙二醇加入到聚酯合成釜中，升温至230℃，反应6h，酯化完成；
(3)缩聚反应
将步骤(2)酯化步骤中酯化完成的聚酯合成釜抽真空，使得真空度达-0.092MPa，保持真空时间为3h，缩聚完成，得到聚酯多元醇；
(4)复配
将32质量份步骤(3)制得的聚酯多元醇、21质量份的聚氧化丙烯二醇和32质量份的甲苯二异氰酸酯，混合均匀，在95℃下反应7h，降温至55℃，依次加入4质量份的十二烷基苯磺酸钠、6质量份的聚氧乙烯山梨糖醇酐单油酸酯、3质量份的茶多酚，搅拌混合40min，继续加入0.2质量份的柠檬精油、1.2质量份的交联剂和1.4质量份的抗氧化剂，搅拌2.5h，得到低成本环保织物粘合剂。
实施例4
一种低成本环保织物粘合剂的制备方法，包括以下步骤：
(1)1,2-丙二醇的制备
在反应温度220℃，反应压力4.5MPa，氢/油摩尔比为10：1，质量空速为2h-1的操作条件下，甘油与加氢催化剂接触进行加氢反应，反应过程中同时通入环己烷，制得1,2丙二醇，其中，环己烷与甘油的质量比为2.5：1，加氢催化剂中，以干基前驱体的重量为基准，含有Cu15％和B2O310％，Na2O5％；以质量分数计，所述干基前驱体中，含CaO20％和Al2O380％；
(2)酯化反应
将7质量份丙烯酸、10质量份衣康酸、14质量份对苯二甲酸、26质量份的二乙二醇、7质量份的新戊二醇以及14质量份的步骤(1)制得的1,2-丙二醇加入到聚酯合成釜中，升温至240℃，反应7h，酯化完成；
(3)缩聚反应
将步骤(2)酯化步骤中酯化完成的聚酯合成釜抽真空，使得真空度达-0.094MPa，保持真空时间为4h，缩聚完成，得到聚酯多元醇；
(4)复配
将36质量份步骤(3)制得的聚酯多元醇、22质量份的四氢呋喃-氧化丙烯共聚二醇和36质量份的异佛尔酮二异氰酸酯，混合均匀，在100℃下反应8h，降温至60℃，依次加入5质量份的十二烷基苯磺酸钠、7质量份的聚氧乙烯山梨糖醇酐单油酸酯、3质量份的茶多酚，搅拌混合50min，继续加入0.3质量份的柠檬精油、1.6质量份的交联剂和1.4质量份的抗氧化剂，搅拌3h，得到低成本环保织物粘合剂。
实施例5
一种低成本环保织物粘合剂的制备方法，包括以下步骤：
(1)1,2-丙二醇的制备
在反应温度230℃，反应压力5.0MPa，氢/油摩尔比为11：1，质量空速为2.5h-1的操作条件下，甘油与加氢催化剂接触进行加氢反应，反应过程中同时通入环己烷，制得1,2丙二醇，其中，环己烷与甘油的质量比为3.5：1，加氢催化剂中，以干基前驱体的重量为基准，含有Cu25％和B2O310％，K2O8％；以质量分数计，所述干基前驱体中，含CaO18％和Al2O382％；
(2)酯化反应
将8质量份丙烯酸、11质量份衣康酸、18质量份对苯二甲酸、26质量份的二乙二醇、8质量份的新戊二醇以及16质量份的步骤(1)制得的1,2-丙二醇加入到聚酯合成釜中，升温至250℃，反应9h，酯化完成；
(3)缩聚反应
将步骤(2)酯化步骤中酯化完成的聚酯合成釜抽真空，使得真空度达-0.098MPa，保持真空时间为4.5h，缩聚完成，得到聚酯多元醇；
(4)复配
将36质量份步骤(3)制得的聚酯多元醇、24质量份的聚氧化丙烯二醇和38质量份的异佛尔酮二异氰酸酯，混合均匀，在95℃下反应9h，降温至65℃，依次加入7质量份的十二烷基苯磺酸钠、8质量份的聚氧乙烯山梨糖醇酐单油酸酯、4质量份的茶多酚，搅拌混合55min，继续加入0.4质量份的柠檬精油、1.8质量份的交联剂和1.6质量份的抗氧化剂，搅拌3.5h，得到低成本环保织物粘合剂。
Claims (8)
1.一种低成本环保织物粘合剂的制备方法，其特征在于，包括以下步骤：
(1)1,2-丙二醇的制备
在反应温度200-250℃，反应压力3.0-6.0MPa，氢/油摩尔比为(6-12)：1，质量空速为0.1-3h-1的操作条件下，甘油与加氢催化剂接触进行加氢反应，反应过程中同时通入环己烷，制得1,2丙二醇，其中，环己烷与甘油的质量比为(0.5-5)：1；
(2)酯化反应
将5-10质量份丙烯酸、6-12质量份衣康酸、10-20质量份对苯二甲酸、20-30质量份的二乙二醇、5-10质量份的新戊二醇以及10-20质量份的步骤(1)制得的1,2-丙二醇加入到聚酯合成釜中，升温至220-260℃，反应5-10h，酯化完成；
(3)缩聚反应
将步骤(2)酯化步骤中酯化完成的聚酯合成釜抽真空，使得真空度达-0.09—-0.1MPa，保持真空时间为2-5h，缩聚完成，得到聚酯多元醇；
(4)复配
将30-40质量份步骤(3)制得的聚酯多元醇、20-25质量份的聚醚多元醇和30-40质量份的异氰酸酯，混合均匀，在90-100℃下反应6-10h，降温至50-70℃，依次加入3-8质量份的十二烷基苯磺酸钠、5-10质量份的聚氧乙烯山梨糖醇酐单油酸酯、2-5质量份的茶多酚，搅拌混合30-60min，继续加入0.1-0.5质量份的柠檬精油、1-2质量份的交联剂和1-2质量份的抗氧化剂，搅拌2-4h，得到低成本环保织物粘合剂。
2.如权利要求1所述的一种低成本环保织物粘合剂的制备方法，其特征在于，步骤(1)中，所述甘油以甘油溶液的形式加入，其中溶剂为乙醇、甲醇或水，甘油的质量分数为50-90％。
3.如权利要求1所述的一种低成本环保织物粘合剂的制备方法，其特征在于，步骤(1)中，所述加氢催化剂为Cu-B2O3-CaO-Al2O3催化剂。
4.如权利要求3所述的一种低成本环保织物粘合剂的制备方法，其特征在于，所述加氢催化剂中，以干基前驱体的重量为基准，含有Cu5-30％和B2O31-20％；以质量分数计，所述干基前驱体中，含CaO5-30％和Al2O370-95％。
5.如权利要求3所述的一种低成本环保织物粘合剂的制备方法，其特征在于，所述加氢催化剂中还含有助剂，以干基前驱体的重量为基准，含有助剂0.1-10％，所述助剂为Na2O或K2O。
6.如权利要求1所述的一种低成本环保织物粘合剂的制备方法，其特征在于，步骤(2)中，制备聚酯多元醇的酯化步骤中，保持聚酯合成釜的馏出物的馏出量为2-4质量份/小时。
7.如权利要求1所述的一种低成本环保织物粘合剂的制备方法，其特征在于，步骤(4)中，所述异氰酸酯为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种混合。
8.如权利要求1所述的一种低成本环保织物粘合剂的制备方法，其特征在于，步骤(4)中，所述聚醚多元醇为聚氧化丙烯二醇、四氢呋喃-氧化丙烯共聚二醇中的一种或两种混合。
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| CN105297487A (zh) * | 2015-11-20 | 2016-02-03 | 嘉兴洛克化学工业有限公司 | 一种耐水洗型粘合剂及其制备方法 |
| CN105544247A (zh) * | 2016-01-25 | 2016-05-04 | 苏州印丝特纺织数码科技有限公司 | 一种用于数码印花的印花粘合剂及其制备方法 |
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| CN109535363A (zh) * | 2017-11-16 | 2019-03-29 | 广东安之伴实业有限公司 | 一种水性弹性聚酯乳液的制备方法 |
| CN115124705A (zh) * | 2021-03-26 | 2022-09-30 | 华润化学材料科技股份有限公司 | 可降解共聚酯材料及其制备方法和应用 |
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