CN109134801B - 一种用生产二甲氨基乙基丙烯酸酯的精馏残渣制备聚氨酯催化剂的方法 - Google Patents
一种用生产二甲氨基乙基丙烯酸酯的精馏残渣制备聚氨酯催化剂的方法 Download PDFInfo
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Abstract
本发明公开了一种用生产二甲氨基乙基丙烯酸酯的精馏残渣制备聚氨酯催化剂的方法，将生产二甲氨基乙基丙烯酸酯的精馏残渣直接作为催化剂，或者将残渣加入反应釜，加入溶剂，在20‑100℃搅拌下溶解；冷却后，分别加入稀释剂、相溶剂，搅拌5‑60分后过滤，得聚氨酯催化剂。本发明将二甲氨基乙基丙烯酸酯生产过程中产生的精馏残渣，转化成实用的聚氨酯用催化剂，变废为宝，全部可以综合利用，且不产生二次危废，大大降低了危废的处理费用。
Description
技术领域
本发明属于催化剂技术领域，具体涉及一种用生产二甲氨基乙基丙烯酸酯的精馏残渣制备聚氨酯催化剂的方法。
背景技术
二甲氨基乙基丙烯酸酯是一种季胺类丙烯酸酯，也是一种拥有多功能的活性单体广泛应用于水处理、日用医药、涂料等行业。二甲氨基乙基丙烯酸酯的生产过程中，不可避免会产生2％-10％的精馏残渣，这部分精馏残渣在环保方面，定义为危废，处理采取焚烧方式。二甲氨基乙基丙烯酸酯国内已有十几万吨的生产规模，产生大量的危废，处理过程对环境产生一定的影响及需要大量的处理费用。
发明内容
本发明的目的在于提供用生产二甲氨基乙基丙烯酸酯的精馏残渣作为聚氨酯催化剂的应用，利用二甲氨基乙基丙烯酸酯生产过程中产生的精馏残渣，直接作为聚氨酯用催化剂，或者经过去渣、降粘、增加相容剂等处理，转化成实用的聚氨酯用催化剂，变废为宝，全部可以综合利用，且不产生二次危废，大大降低了危废的处理费用。
为了实现上述目的，本发明采用的技术方案为：
生产二甲氨基乙基丙烯酸酯的精馏残渣作为催化剂在聚氨酯中的应用。
将生产二甲氨基乙基丙烯酸酯的精馏残渣直接作为聚氨酯催化剂，或者将生产二甲氨基乙基丙烯酸酯的精馏残渣经过去渣、降粘、增加相溶剂处理后作为聚氨酯催化剂。
用二甲氨基乙基丙烯酸酯生产过程中产生的精馏残渣(以下简称残渣)，制备聚氨酯用催化剂产品的方法，包括以下步骤：
1、将残渣加入反应釜，按0-70％(wt)比例加入溶剂，在20-100℃搅拌下溶解；
2、冷却后，分别按0-70％(wt)比例加入一种或多种稀释剂、按0-70％(wt)比例加入一种或多种相溶剂、搅拌5-60分后过滤，得聚氨酯催化剂。
所述步骤1)中加入溶剂来溶解废渣中的固体物，使之成为均相液体溶剂，所述溶剂包括但不限于醇类、酯类、脂肪烃类、芳香烃类等溶剂；例如：甲醇、乙醇、异丙醇、正丁醇等。甲酸甲酯、甲酸乙酯、甲酸丁酯、乙酸乙酯、乙酸甲酯、乙酸丁酯；邻苯二甲酸酯、柠檬酸三丁酯、苯、甲苯、二甲苯、环己烷、正己烷等的至少一种或多种混合物。
步骤2)中加入稀释剂，用来降低产品的粘度；所述稀释剂包括但不限于增塑剂、溶剂、多元醇、醇胺类等；例如邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、柠檬酸三丁酯、乙二醇、二甘醇、丙二醇、二丙二醇、三乙醇胺、二乙醇胺、乙醇胺等的至少一种或多种混合物。
所述步骤2)中加入相溶剂，用来改变催化剂与聚醚多元醇或聚酯多元醇的溶解性，所述相溶剂包括但不限于聚醚多元醇、聚酯多元醇、阳离子表面活性剂、阴离子表面活性剂、非离子表面活性剂、有机硅改性聚醚表面活性剂等。例如，分子量500-5000含环氧乙烷或环氧丙烷聚醚多元醇、分子量500-5000聚酯多元醇、壬基酚聚氧乙烯醚等。
二甲氨基乙基丙烯酸酯生产过程通常为：丙烯酸与二甲氨基乙醇在催化剂的作用下，直接酯化生成；或者丙烯酸甲酯与二甲氨基乙醇在催化剂的作用下，酯交换生成。本发明所述二甲氨基乙基丙烯酸酯生产过程中产生的精馏残渣，包括上述方法制备过程中得到的残渣。
所述二甲氨基乙基丙烯酸酯生产过程中产生的精馏残渣，通常包含以下比例的各组分：
聚丙烯酸酯类化合物>60％；
3-(二甲氨基)丙酸甲酯10-15％；
双二甲氨基乙基醚0-5％；
N,N–二甲基乙醇胺5-15％；
金属化合物5-8％；
吩噻嗪0-5％；
丙烯酸二甲氨基乙酯<0.05％。
采用本发明方法将二甲氨基乙基丙烯酸酯生产过程中产生的精馏残渣zhi直接作为聚氨酯催化剂或者经过处理后所得到的聚氨酯催化剂，其效果基本等同于聚氨酯中常用的催化剂，如三乙烯二胺、二甲基环己胺、二月桂酸二丁基锡等，由于采用残渣作为主要原料，其成本要大大低于常规的催化剂。
有益效果：
本发明利用二甲氨基乙基丙烯酸酯生产过程中产生的精馏残渣，直接作为聚氨酯用催化剂，或者经过去渣、降粘、增加相容剂等处理，转化成实用的聚氨酯用催化剂，变废为宝，全部可以综合利用，且不产生二次危废，大大降低了危废的处理费用。
由本发明所得到的聚氨酯催化剂，其效果基本等同于聚氨酯中常用的催化剂，如三乙烯二胺、二甲基环己胺、二月桂酸二丁基锡等。由于采用残渣作为主要原料，其成本要大大低于常规的催化剂。
具体实施方式
通过以下实施例，进一步说明本发明。但本发明不限于以下实施例。
以下实施例中所采用的生产二甲氨基乙基丙烯酸酯的精馏残渣来源是由丙烯酸甲酯与二甲氨基乙醇在催化剂的作用下，酯交换生成，具体步骤为：丙烯酸甲酯与二甲氨基乙醇在催化剂作用下进行反应，并加入正己烷作为共沸剂蒸出甲醇，直至反应完全，然后蒸出产品二甲氨基乙基丙烯酸酯，釜底精馏残渣即为我们综合利用的残渣来源。
所得到的残渣中包含如下比例的各组分：
实施例1
残渣100g，甲醇30g加入到三颈瓶中，加热至40℃，搅拌溶解，停止加热，加入二甘醇40g，壬基酚聚氧乙烯醚20g，搅拌30分钟即可。
用实施例1产品按以下配方进行发泡，数据如下：
实施例2
残渣100g，异丙醇30g，加入到三颈瓶中，加热至40℃搅拌溶解，停止加热，加入二乙醇胺20g，二甘醇30g，N-303聚醚20g，搅拌30分钟即可。
用实施例2产品及其它催化剂按以下配方进行发泡，对比数据如下：
实施例3
以残渣直接作为催化剂，以及其它催化剂按以下配方进行发泡，对比数据如下：
实施例4
1)将残渣100kg加入反应釜，加入乙酸乙酯50kg溶剂，在30℃下搅拌50分钟溶解；
2)分别加入稀释剂邻苯二甲酸二丁酯20kg，乙二醇30kg，以及分子量为1000含环氧乙烷30％环氧丙烷70％的聚醚多元醇作为相溶剂60kg，搅拌30分钟后过滤，得260kg聚氨酯催化剂产品。
用实施例4产品按以下配方进行发泡实验：
一、喷涂配方体系
喷涂配料
二、管道配方体系
2.1：一步法工艺
2.2：二步法工艺(大)
三、高回弹配方体系
Claims (9)
1.生产二甲氨基乙基丙烯酸酯的精馏残渣作为催化剂在聚氨酯中的应用，其特征在于，所述精馏残渣是由丙烯酸甲酯与二甲氨基乙醇在催化剂的作用下，酯交换生成二甲氨基乙基丙烯酸酯，蒸出产品后的釜底精馏残渣，将精馏残渣直接作为催化剂，或者将精馏残渣经过去渣、降粘、增加相溶剂处理后作为催化剂，所述精馏残渣包含以下比例的各组分：
聚丙烯酸酯类化合物>60% ；
3-（二甲氨基）丙酸甲酯10-15%；
双二甲氨基乙基醚 0-5%；
N,N –二甲基乙醇胺 5-15%；
金属化合物 5-8%；
吩噻嗪0-5%；
丙烯酸二甲氨基乙酯<0.05%。
2.一种用生产二甲氨基乙基丙烯酸酯的精馏残渣制备聚氨酯催化剂的方法，其特征在于，包括如下步骤：
1）将精馏残渣加入反应釜，加入溶剂，在20-100℃搅拌下溶解；
2）冷却后，分别加入稀释剂、相溶剂，搅拌5-60分后过滤，得聚氨酯催化剂；
其中：所述精馏残渣是由丙烯酸甲酯与二甲氨基乙醇在催化剂的作用下，酯交换生成二甲氨基乙基丙烯酸酯，蒸出产品后的釜底精馏残渣，包含以下比例的各组分：
聚丙烯酸酯类化合物>60% ；
3-（二甲氨基）丙酸甲酯10-15%；
双二甲氨基乙基醚 0-5%；
N,N –二甲基乙醇胺 5-15%；
金属化合物 5-8%；
吩噻嗪0-5%；
丙烯酸二甲氨基乙酯<0.05%。
3.根据权利要求2所述的一种用生产二甲氨基乙基丙烯酸酯的精馏残渣制备聚氨酯催化剂的方法，其特征在于，步骤1）中所述溶剂为醇类、酯类、脂肪烃类或者芳香烃类溶剂中的至少一种。
4.根据权利要求2所述的一种用生产二甲氨基乙基丙烯酸酯的精馏残渣制备聚氨酯催化剂的方法，其特征在于，步骤1）中溶剂的用量为残渣重量的0~70%。
5.根据权利要求2所述的一种用生产二甲氨基乙基丙烯酸酯的精馏残渣制备聚氨酯催化剂的方法，其特征在于，步骤2）中所述稀释剂为增塑剂、多元醇、醇胺中的至少一种，用量为残渣重量的0-70%。
6.根据权利要求2所述的一种用生产二甲氨基乙基丙烯酸酯的精馏残渣制备聚氨酯催化剂的方法，其特征在于，步骤2）中所述相溶剂为聚醚多元醇、聚酯多元醇、阳离子表面活性剂、阴离子表面活性剂、非离子表面活性剂、有机硅改性聚醚表面活性剂中的至少一种，用量为残渣重量的0-70%。
7.根据权利要求2所述的一种用生产二甲氨基乙基丙烯酸酯的精馏残渣制备聚氨酯催化剂的方法，其特征在于，步骤1）中所述溶剂包括但不限于甲醇、乙醇、异丙醇、正丁醇、二甘醇、甲酸甲酯、甲酸乙酯、甲酸丁酯、乙酸乙酯、乙酸甲酯、乙酸丁酯、邻苯二甲酸酯、柠檬酸三丁酯、苯、甲苯、二甲苯、环己烷、正己烷中的至少一种或多种混合物。
8.根据权利要求2所述的一种用生产二甲氨基乙基丙烯酸酯的精馏残渣制备聚氨酯催化剂的方法，其特征在于，步骤2）中所述稀释剂包括但不限于邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、柠檬酸三丁酯、乙二醇、二甘醇、丙二醇、二丙二醇、三乙醇胺、二乙醇胺、乙醇胺中的一种或多种混合物。
9.根据权利要求6所述的一种用生产二甲氨基乙基丙烯酸酯的精馏残渣制备聚氨酯催化剂的方法，其特征在于，步骤2）中所述相溶剂包括但不限于分子量500-5000含环氧乙烷或环氧丙烷聚醚多元醇、分子量500-5000聚酯多元醇、壬基酚聚氧乙烯醚等中的一种或多种混合物。
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