CN110894284B - 一种冰箱隔热聚氨酯泡沫组合料用聚酯多元醇及其制备方法 - Google Patents
一种冰箱隔热聚氨酯泡沫组合料用聚酯多元醇及其制备方法 Download PDFInfo
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Abstract
本发明涉及聚酯多元醇及其制备方法，具体公开了一种冰箱隔热聚氨酯泡沫组合料用聚酯多元醇及其制备方法，旨在解决现有反应原料多为易燃物，其产物的阻燃性能较差的问题。所述聚酯多元醇包括多元醇系统与二元/多元酸，所述多元醇系统中至少含有一种单糖或二糖1～30％，以及至少含有一种二元/多元醇70～99％。其制备方法包括：将多元醇系统与二元/多元酸装入反应器中，加热熔融并搅拌反应；温度上升至120～150℃时脱水，升温至200～250℃反应12～48小时，降温、过滤得到聚酯多元醇。本发明以单糖或二糖作为多元醇的一部分进行反应制备聚酯多元醇，明显降低了易燃性。与其它阻燃剂配合，作为制备冰箱隔热聚氨酯泡沫组合料的原料，显著提高其阻燃性能。
Description
技术领域
本发明涉及聚酯多元醇及其制备方法，具体地说，涉及一种冰箱隔热聚氨酯泡沫组合料用聚酯多元醇及其制备方法。
背景技术
聚氨酯材料由于具有优异的强度、弹性、耐磨损性，被广泛应用于粘胶剂、泡沫、弹性体、涂料等多种领域。其中聚酯多元醇是生产聚酯型聚氨酯的核心原料之一。在聚氨酯行业中，聚酯多元醇是一类最重要的原料中间体之一，常用于PU浆料、弹性体、鞋底原液及粘胶剂等产品中，在聚氨酯结构中作为软链段，为产品提供良好的伸长率、回弹性、柔软性等机械性能。
聚酯多元醇通常是由二元/多元醇与二元/多元羧酸缩合而成。根据原料的差异，聚酯多元醇呈现出不同的性能。但是由于缩合反应的原料多为易燃物，其缩合产物的阻燃性能较差，应用受到了很大的限制。为了提高其阻燃性能，一般需要外加阻燃剂，增加生产成本。
材料的燃烧性能等级划分为A、B1、B2、B3，分别为不燃性、难燃性(离开火源后自动熄灭，或10秒内熄灭)、可燃性(点着以后火势不会变大，且滴落物不会引燃滤纸)和易燃性材料(一点就着火，且火势越来越大)。普通聚酯多元醇属于易燃性材料(B3)。
发明内容
本发明的第一个目的是提供一种冰箱隔热聚氨酯泡沫组合料用聚酯多元醇，该聚酯多元醇阻燃性能显著提高，能够与其它阻燃剂配合作为制备冰箱隔热聚氨酯泡沫组合料的原料。
为实现本发明的第一个目的，提供如下的技术方案：
一种冰箱隔热聚氨酯泡沫组合料用聚酯多元醇，包括以下原料成分：多元醇系统与二元/多元酸，所述多元醇系统中至少含有一种单糖或二糖1～30％，以及至少含有一种二元/多元醇70～99％。
在上述的冰箱隔热聚氨酯泡沫组合料用聚酯多元醇中，所述多元醇系统中至少含有一种单糖或二糖1～20％，以及至少含有一种二元/多元醇80～99％。
在上述的冰箱隔热聚氨酯泡沫组合料用聚酯多元醇中，所述二元/多元酸和多元醇系统的摩尔比为1:(1.0～1.5)。
在上述的冰箱隔热聚氨酯泡沫组合料用聚酯多元醇中，所述单糖为葡萄糖、果糖和阿拉伯糖中的一种或几种的混合。
在上述的冰箱隔热聚氨酯泡沫组合料用聚酯多元醇中，所述二糖为木糖、蔗糖和麦芽糖中的一种或几种的混合。
在上述的冰箱隔热聚氨酯泡沫组合料用聚酯多元醇中，所述二元/多元醇包括但不限于乙二醇、丙二醇、甲基丙二醇、一缩二乙二醇、一缩二丙二醇、三羟甲基丙烷、1,3-丁二醇、1,4-丁二醇、戊二醇、新戊二醇、1,6-己二醇、季戊四醇等的一种或几种组合。
在上述的冰箱隔热聚氨酯泡沫组合料用聚酯多元醇中，所述二元/多元酸选自脂肪族或芳香族二元/多元酸，包括但不限于丁二酸、戊二酸、己二酸、癸二酸、丁烯二酸、顺丁烯二酸酐、苯二甲酸、苯二甲酸酯、卤代苯二甲酸、卤代苯二甲酸酯、邻苯二甲酸酐等的一种或几种组合。
本发明的第二个目的是提供上述一种冰箱隔热聚氨酯泡沫组合料用聚酯多元醇的制备方法，该制备方法简单，适合于工业化生产。
为实现本发明的第二个目的，提供如下的技术方案：
一种冰箱隔热聚氨酯泡沫组合料用聚酯多元醇的制备方法，包括以下步骤：
(1)按配方量将多元醇系统与二元/多元酸装入反应器中，在氮气的保护下加热熔融并搅拌反应；
(2)温度上升至120～150℃时脱水，继续升温至200～250℃反应12～48小时；
(3)当酸值小于0.4时，开始降温结束反应，降温、过滤、包装，得到聚酯多元醇。
与现有技术相比，本发明的有益效果为：
1.本发明的冰箱隔热聚氨酯泡沫组合料用聚酯多元醇原料中部分添加了单糖或二糖，单糖是糖类的最小水解单位，二糖是由两个单糖化合而成。单糖和二糖作为多羟基化合物，不像其它多元醇那样易燃，它们能够氧化或燃烧，但一般不容易燃烧。本发明以单糖或二糖作为多元醇的一部分添加进多元醇体系与二元/多元酸进行反应制备聚酯多元醇，明显降低了易燃性。与其它阻燃剂配合，作为制备冰箱隔热聚氨酯泡沫组合料的原料，显著提高其阻燃性能。
2.本发明的冰箱隔热聚氨酯泡沫组合料用聚酯多元醇的制备方法简单，适合于工业化生产，得到的聚酯多元醇除具有其它聚氨酯的所有性能外，还具有显著的阻燃性能。
具体实施方式
下面结合具体实施方式，对本发明的技术方案作进一步的详细说明，但不构成对本发明的任何限制。
实施例1
在多元醇体系中，葡萄糖含量为5％，二元/多元醇含量为95％。
称取定量的葡萄糖、1,4-丁二醇和邻苯二甲酸，加入到装有温度计、冷凝器和搅拌器的反应釜中，其中邻苯二甲酸和多元醇系统的摩尔比为1:1.0；从釜底通氮气，在氮气保护下缓慢加热，物料熔融后开动搅拌器；温度升至120～150℃时脱水，最终升温至200～250℃之间反应12～48小时；而后在真空下继续反应，当酸值小于0.4时，开始降温，温度降至120℃时过滤、包装，得到聚酯多元醇。
测定燃烧等级为B2级。
实施例2
在多元醇体系中，麦芽糖的含量为10％，二元/多元醇含量为90％。
称取定量的麦芽糖、丙二醇、季戊四醇和己二酸加入到装有温度计、冷凝器和搅拌器的反应釜中，其中己二酸和多元醇系统的摩尔比为1:1.5；从釜底通氮气，在氮气保护下缓慢加热，物料熔融后开动搅拌器；温度升至150℃时脱水，最终升温至200℃之间反应12小时；而后在真空下继续反应，当酸值小于0.4时，开始降温，温度降至120℃时过滤、包装，得到聚酯多元醇。
测定燃烧等级为B2级。
实施例3
在多元醇体系中，麦芽糖的含量为15％，二元/多元醇含量为85％。
称取定量的麦芽糖、乙二醇、邻苯二甲酸、苯酐加入到装有温度计、冷凝器和搅拌器的反应釜中，其中邻苯二甲酸/苯酐和多元醇系统的摩尔比为1:1.2；从釜底通氮气，在氮气保护下缓慢加热，物料熔融后开动搅拌器；温度升至120℃时脱水，最终升温至250℃之间反应48小时；而后在真空下继续反应，当酸值小于0.3时，开始降温，温度降至120℃时过滤、包装，得到聚酯多元醇。
测定燃烧等级为B2级。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (3)
1.一种冰箱隔热聚氨酯泡沫组合料用聚酯多元醇，包括以下原料成分：多元醇系统与二元/多元酸，其特征在于，所述多元醇系统中至少含有一种单糖或二糖 5～30%，以及至少含有一种二元/多元醇70～95%；所述单糖为葡萄糖、果糖和阿拉伯糖中的一种或几种的混合，所述二糖为蔗糖、麦芽糖中的一种或几种的混合；
所述二元/多元醇包括但不限于乙二醇、丙二醇、甲基丙二醇、一缩二乙二醇、一缩二丙二醇、三羟甲基丙烷、1,3-丁二醇、1,4-丁二醇、戊二醇、新戊二醇、1,6-己二醇、季戊四醇的一种或几种组合；
所述二元/多元酸选自脂肪族或芳香族二元/多元酸，包括但不限于丁二酸、戊二酸、己二酸、癸二酸、丁烯二酸、顺丁烯二酸酐、苯二甲酸、苯二甲酸酯、卤代苯二甲酸、卤代苯二甲酸酯、邻苯二甲酸酐的一种或几种组合。
2.根据权利要求1所述的冰箱隔热聚氨酯泡沫组合料用聚酯多元醇，其特征在于，所述二元/多元酸和多元醇系统的摩尔比为1: (1.0～1.5)。
3.权利要求1所述的冰箱隔热聚氨酯泡沫组合料用聚酯多元醇的制备方法，其特征在于，包括以下步骤：
(1)按配方量将多元醇系统与二元/多元酸装入反应器中，在氮气的保护下加热熔融并搅拌反应；
(2)温度上升至120~150℃时脱水，继续升温至200~250℃反应12~48小时；
(3) 当酸值小于0.4时，开始降温结束反应，降温、过滤、包装，得到聚酯多元醇。
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Denomination of invention: Polyester polyol for refrigerator heat insulation polyurethane foam combination and its preparation method Granted publication date: 20220503 Pledgee: Agricultural Bank of China Limited Jingzhou Economic Development Zone Branch Pledgor: Hubei Jingzhou Huabang Chemical Co.,Ltd. Registration number: Y2024980010324 |