CN113980205B - 聚合物多元醇的制备方法 - Google Patents
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Abstract
本发明属于化工合成技术领域，具体涉及一种聚合物多元醇的制备方法。本发明所述的聚合物多元醇的制备方法，包括以下步骤：以腰果酚和山梨醇为混合起始剂，在氢氧化钾的催化作用下，与环氧丙烷进行反应，合成低分子量聚醚多元醇；然后，低分子量聚醚多元醇在DMC催化剂的作用下，通过与环氧丙烷和环氧乙烷的混合物反应，生成聚合物多元醇的基础聚醚；在引发剂偶氮二异丁酸二甲酯的作用下，基础聚醚、稳定剂、苯乙烯、丙烯腈和异丙醇生成聚合物多元醇。该方法可以降低聚合物多元醇生产对石油基原料的依赖，提高泡沫制品的性能以及降低聚合物多元醇的生产成本。
Description
技术领域
本发明属于化工合成技术领域，具体涉及一种聚合物多元醇的制备方法。
背景技术
近年来，家居的快速迭代及汽车的迅速普及极大刺激了对聚氨酯泡沫的需求。其中，聚合物多元醇可以提高泡沫制品性能如泡沫硬度、开孔程度和舒适性等，在聚氨酯泡沫制品的生产过程中扮演着重要的角色。传统的聚合物多元醇原料多以石油基路线生产方式为主，生产成本高且化石资源日益枯竭，因此充分合理地利用生物质资源，降低对石油基原料的依赖，是一条促进聚氨酯泡沫行业健康发展的可行之路。
发明内容
针对现有技术的不足，本发明的目的是提供一种聚合物多元醇的制备方法，基础聚醚以腰果酚和山梨醇作为混合起始剂，能够降低聚合物多元醇生产对石油基路线原料的依赖，同时提高聚氨酯泡沫制品的性能，降低聚合物多元醇的生产成本。
本发明所述的聚合物多元醇的制备方法，包括以下步骤：以腰果酚和山梨醇为混合起始剂，在氢氧化钾的催化作用下，与环氧丙烷进行反应，合成低分子量聚醚多元醇；然后，低分子量聚醚多元醇在DMC催化剂的作用下，通过与环氧丙烷与环氧乙烷混合物反应，生成聚合物多元醇的基础聚醚；在引发剂的作用下，基础聚醚、稳定剂、苯乙烯、丙烯腈和异丙醇生成聚合物多元醇。
其中：
所述的低分子量聚醚多元醇的制备过程是：腰果酚、山梨醇和氢氧化钾按照质量比为50-80:20-50:0.5-5.0投入反应釜中，升温脱水后，通入环氧丙烷反应，反应结束后加入水、磷酸和吸附剂，后处理得到低分子量聚醚多元醇，其羟值为200-400mg KOH/g，优选250-350mg KOH/g。
腰果酚、山梨醇和氢氧化钾投入反应釜后，升温至115-125℃，抽真空使反应釜压力不高于-70kPa，脱水2-3小时，使反应釜内物料水分含量不高于反应釜中物料总质量的0.03％。
通入环氧丙烷的温度为115-125℃，在反应过程中控制环氧丙烷的加入速率，控制反应釜的压力不高于350kPa。环氧丙烷的加入量为腰果酚和山梨醇总质量的20％-400％，优选80％-250％。
水的加入量为反应釜中物料总质量的0.2-2％，磷酸的加入量为氢氧化钾质量的35％-75％，优选40％-50％；吸附剂的加入量为腰果酚、山梨醇和环氧丙烷总质量的0.1％-1.5％。
所述的聚合物多元醇的基础聚醚的制备过程是：在反应釜中加入低分子量聚醚多元醇，然后加入DMC催化剂，混合均匀后，加入环氧丙烷，待DMC催化剂被活化后，继续加入环氧丙烷与环氧乙烷的混合物，最后脱水、加入抗氧剂得到羟值为50-70mg KOH/g的基础聚醚，羟值优选53-65mg KOH/g。
DMC催化剂的加入量为15-60ppm，优选20-35ppm；活化DMC催化剂的环氧丙烷的质量为加入低分子量聚醚多元醇质量的0.3-3倍，优选0.3-1倍；继续加入环氧丙烷与环氧乙烷的混合物质量是低分子量聚醚多元醇质量的1.0-6.0倍，优选2.2-4.0倍。
加入环氧丙烷的温度以及加入环氧丙烷与环氧乙烷的混合物的温度均在125-140℃，优选125-135℃；控制反应釜压力不超过400kPa。
环氧丙烷与环氧乙烷的混合物中，环氧乙烷的质量占环氧丙烷质量的0％-15％，优选0％-10％；加入抗氧剂的量占反应釜总物料质量的0.1％-1.0％，优选0.3％-0.6％，更优选0.3％-0.5％；脱水的温度为130-145℃。
所述的聚合物多元醇的制备过程是：基础聚醚、不饱和单体、稳定剂按照质量比为40-60:40-55:2-10混合后，加入异丙醇和引发剂偶氮二异丁酸二甲酯，在115-135℃、400kPa条件下完成反应，最后脱除水分和异丙醇，得到聚合物多元醇；不饱和单体为苯乙烯和丙烯腈的混合物，混合物中丙烯腈和苯乙烯质量比1:4-4:1，加入异丙醇的量为基础聚醚质量的2％-10％，加入引发剂偶氮二异丁酸二甲酯质量为加入基础聚醚质量的0.20％-3.0％。
优选地，所述的聚合物多元醇的制备过程是：基础聚醚、不饱和单体和稳定剂质量比为42-50:40-55:3-8充分混合后，加入异丙醇和引发剂偶氮二异丁酸二甲酯；不饱和单体中丙烯腈和苯乙烯的质量比为3:7-7:3，异丙醇和偶氮二异丁酸二甲酯的加入量分别为基础聚醚质量的3％-5％和0.25％-1.5％。
本发明中的稳定剂采用中国专利CN 200510116277.1、CN 200710199887.1、CN201380020929.4中任意一种方法制备。
与现有技术相比，本发明的有益效果如下：
本发明使用腰果酚和山梨醇作为混合起始剂，先后通过氢氧化钾和DMC催化剂的催化作用，引入环氧丙烷和环氧乙烷，通过后处理后得到聚合物多元醇的基础聚醚。以基础聚醚、稳定剂、异丙醇和含有不饱和双键的有机单体为原料，采用连续法生产聚合物多元醇。由于采用可再生的生物质基起始剂，可以显著降低聚合物多元醇生产对石油基原料的依赖和聚合物多元醇的生产成本，同时可以提高聚氨酯泡沫的性能。
具体实施方式
下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径而得。
实施例中采用的稳定剂采用中国专利CN 200510116277.1中实施例1的方法制备。
实施例1
所述的聚合物多元醇的制备方法，过程如下：
(1)将868克腰果酚、218克山梨醇和12克氢氧化钾加入反应釜中，充分搅拌1小时后，升温至120℃，抽真空脱除水分，在保持反应釜温度120℃条件下加入1065克环氧丙烷，反应结束后加入的纯水15克、加入6克磷酸中和pH，加入吸附剂13.5克，在120℃下干燥至水分不高于0.03％，得到羟值为255mg KOH/g的低分子量聚醚A。
(2)在反应釜中加入700克聚醚A，加入0.007克DMC催化剂，充分搅拌后升温至130℃，保温条件下，加入300克环氧丙烷，待催化剂充分引发后，通入1765克环氧丙烷和200克环氧乙烷混合物，待反应结束后，加入BHT抗氧剂6克，脱水得到基础聚醚B，羟值为60mgKOH/g。
(3)称量890克基础聚醚B、400克苯乙烯、600克丙烯腈和160克稳定剂于烧杯中充分搅拌，然后加入30克异丙醇和4克偶氮二异丁酸二甲酯，快速搅匀后按照每分钟15克的流速进入反应釜，保持反应釜温度123℃，压力为400kPa时进行聚合反应，得到的聚合物多元醇脱除水分和异丙醇，从而得到聚合物多元醇C。
实施例2
所述的聚合物多元醇的制备方法，过程如下：
(1)将713克腰果酚、309克山梨醇以及11克固体氢氧化钾加入反应釜中，充分搅拌1小时后，升温至120℃，抽真空脱除水分，在保持反应釜温度122℃条件下加入1310克环氧丙烷，反应结束后加入的纯水23克、加入4.7克磷酸中和pH，加入吸附剂15.5克，在122℃下干燥3小时，至水分不高于0.03％，得到羟值为300的小分子聚醚A。
(2)在反应釜中加入600克聚醚A，加入0.0065克DMC催化剂，充分搅拌后升温至133℃，保温条件下，加入350克环氧丙烷，待催化剂充分引发后，通入1870克的环氧丙烷和180克环氧乙烷的混合物，待反应结束后，加入BHT抗氧剂6.2克，脱水得到基础聚醚B，羟值为59.2mg KOH/g。
(3)称量920克基础聚醚B、620克苯乙烯、420克丙烯腈和150克稳定剂于烧杯中充分搅拌，然后加入36克异丙醇和5.9克偶氮二异丁酸二甲酯，快速搅匀后按照每分钟20克的流速进入反应釜，保持反应釜温度119℃，压力为400kPa时进行聚合反应，得到的聚合物多元醇脱除水分和异丙醇，从而得到聚合物多元醇D。
实验例：
以本发明的聚合物多元醇为原料，制得聚氨酯泡沫，泡沫验证配方组成见表1。制得的泡沫经过力学性能、压陷和回弹数据测试，具体结果见表2。其中，泡沫的拉伸强度和撕裂强度参考GB T 6344-2008软质泡沫聚合材料拉伸强度和断裂伸长率的测定标准进行测定，泡沫的压陷性能参考GB/T 10807-1989软质泡沫聚合材料压陷硬度试验方法进行测定，泡沫的回弹性能参考GB/T 6670-2008软质泡沫聚合材料落球法回弹性能的测定进行检测。
表1 泡沫验证配方组成
表2 泡沫的力学性能、压陷性能和回弹数据
本文中应用了具体的个例，对本发明原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
Claims (8)
1.一种聚合物多元醇的制备方法，其特征在于：包括以下步骤：
以腰果酚和山梨醇为混合起始剂，在氢氧化钾的催化作用下，与环氧丙烷进行反应，合成低分子量聚醚多元醇；然后，低分子量聚醚多元醇在DMC催化剂的作用下，通过与环氧丙烷与环氧乙烷的混合物反应，生成聚合物多元醇的基础聚醚；在引发剂偶氮二异丁酸二甲酯的作用下，基础聚醚、稳定剂、苯乙烯、丙烯腈和异丙醇生成聚合物多元醇；
低分子量聚醚多元醇的制备过程是：腰果酚、山梨醇和氢氧化钾按照质量比为50-80:20-50:0.5-5.0投入反应釜中，升温脱水后，通入环氧丙烷反应，反应结束后，加入水、磷酸和吸附剂，后处理得到低分子量聚醚多元醇，其羟值为200-400 mg KOH/g；
聚合物多元醇的基础聚醚的制备过程是：在反应釜中加入低分子量聚醚多元醇，然后加入DMC催化剂，混合均匀后，加入环氧丙烷，待DMC催化剂被活化后，继续加入环氧丙烷与环氧乙烷的混合物，最后脱水、加入抗氧剂得到羟值为50-70 mg KOH/g的基础聚醚。
2.根据权利要求1所述的聚合物多元醇的制备方法，其特征在于：腰果酚、山梨醇和氢氧化钾投入反应釜后，升温至115-125℃，抽真空使反应釜压力不高于-70 kPa，脱水2-3小时，使反应釜内物料水分含量不高于0.03 wt %。
3.根据权利要求1所述的聚合物多元醇的制备方法，其特征在于：通入环氧丙烷的温度为115-125℃，环氧丙烷的加入量为腰果酚和山梨醇总质量的20%-400%。
4.根据权利要求1所述的聚合物多元醇的制备方法，其特征在于：水的加入量为反应釜中物料总质量的0.2-2%，磷酸的加入量为氢氧化钾质量的35%-75%，吸附剂的加入量为腰果酚、山梨醇和环氧丙烷总质量的0.1%-1.5%。
5.根据权利要求1所述的聚合物多元醇的制备方法，其特征在于：DMC催化剂的加入量为15-60 ppm，活化DMC催化剂的环氧丙烷的质量为加入低分子量聚醚多元醇质量的0.3-3倍，环氧丙烷与环氧乙烷的混合物加入量是加入低分子量聚醚多元醇质量的1.0-6.0倍。
6.根据权利要求1所述的聚合物多元醇的制备方法，其特征在于：加入环氧丙烷的温度以及加入环氧丙烷与环氧乙烷的混合物的温度均在125-140℃，控制反应釜压力不超过400kPa；环氧丙烷与环氧乙烷的混合物中，环氧乙烷的质量占环氧丙烷质量的0%-15%，且环氧乙烷的质量不为0；加入抗氧剂的量占反应釜总物料质量的0.1%-1.0%，脱水的温度为130-145℃。
7.根据权利要求1所述的聚合物多元醇的制备方法，其特征在于：基础聚醚、不饱和单体、稳定剂按照质量比为40-60:40-55:2-10混合后，加入异丙醇和引发剂偶氮二异丁酸二甲酯，在115-135℃、400 kPa条件下完成反应，最后脱除水分和异丙醇，得到聚合物多元醇；其中，不饱和单体为苯乙烯和丙烯腈的混合物。
8.根据权利要求7所述的聚合物多元醇的制备方法，其特征在于：不饱和单体中丙烯腈和苯乙烯质量比1:4-4:1，加入异丙醇的量为基础聚醚质量的2%-10%，加入引发剂偶氮二异丁酸二甲酯质量为基础聚醚质量的0.20%-3.0%。
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