CN112831040A - 一种合成聚酯醚多元醇的方法 - Google Patents
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Abstract
本发明提供了一种合成聚酯醚多元醇的方法,包括以下步骤:(1)在反应釜中投入二官能度到八官能度的起始剂和催化剂,N2多次置换掉反应釜中的空气,然后通入环氧乙烷(EO),反应温度80~100℃,反应时间9‑10h;完全反应后,经过水洗、中和、吸附,然后减压脱水结晶,过滤,得到伯羟基聚醚多元醇;(2)取步骤(1)中所述伯羟基聚醚多元醇、二元羧酸或酸酐、酯化催化剂加入酯化反应釜中,通入N2,升温,在140~160℃下反应5~12h,升温至220~240℃分段抽真空脱除低分子化合物与水,降温至室温,得到聚酯醚多元醇。本发明合成聚酯醚多元醇的方法,可以合成高官能度聚酯醚多元醇;收率高,产品稳定,酸值低。
Description
技术领域
本发明属于化工合成技术领域,特别是涉及一种合成聚酯醚多元醇的方法。
背景技术
聚酯多元醇和聚醚多元醇是聚氨酯泡沫中的重要组成部分,聚酯型硬质泡沫塑料的优点是强度高,泡孔细腻,导热系数低,粘结性好且价格便宜,但聚酯易水解,稳定性差,与其它组分相容性差。聚醚多元醇的耐水解稳定性好,与配方中其它添加剂相容性好,但聚醚多元醇较聚酯多元醇价格高。聚酯醚结合了聚醚多元醇与聚酯多元醇的各项性能,解决了聚酯的耐水性能问题,也降低了聚醚多元醇的成本。
目前聚酯醚多元醇的研究都是先合成聚酯或用市面上的聚酯多元醇在双金属催化剂(DMC)的作用下,与环氧丙烷(PO)开环聚合。DMC催化剂的引发时间较长,一般2-4h,才能引发环氧丙烷(PO)的开环加成反应;并对聚酯多元醇的要求比较高,环氧丙烷(PO)在高温下进行开环,而高温条件下,也会促进聚酯多元醇进行分解成酸和醇小分子,小分子物质会使DMC失效,如果聚酯多元醇中二元醇等小分子没有分离干净,或者有水解现象,都会导致合成的失败。
发明内容
针对上述技术问题,本发明的目的在于提供一种便捷,更可靠稳定的方法合成聚酯醚多元醇,具有更高的成功率、更稳定的产品性能。本发明与现有技术工艺相反,本发明先合成伯羟基高活性聚醚多元醇,再与二元羧酸或酸酐反应,生成聚酯醚多元醇。
本发明采用的技术方案是:
一种合成聚酯醚多元醇的方法,包括以下步骤:
(1)在反应釜中投入二官能度到八官能度的起始剂和催化剂,N2多次置换掉反应釜中的空气,然后通入环氧乙烷(EO),反应温度80~100℃,反应时间9-10h;完全反应后,经过水洗、中和、吸附,然后减压脱水结晶,过滤,得到伯羟基聚醚多元醇;
(2)取步骤(1)中所述伯羟基聚醚多元醇、二元羧酸或酸酐、酯化催化剂加入酯化反应釜中,通入N2,升温,在140~160℃下反应5~12h,然后升温至220~240℃分段抽真空脱除低分子化合物与水,降温至室温,得到聚酯醚多元醇。
本发明所述的合成聚酯醚多元醇的方法,其中,包括以下步骤:
(1)在反应釜中投入起始剂和催化剂,N2多次置换掉反应釜中的空气,然后通入环氧乙烷(EO),反应温度80~100℃,反应时间9-10h;完全反应后,经过水洗,85%磷酸中和,硅酸镁和硅酸铝吸附,然后在105~115℃减压脱水结晶,过滤,得到伯羟基聚醚多元醇;
(2)取步骤(1)中所述伯羟基聚醚多元醇、二元羧酸或酸酐、酯化催化剂加入酯化反应釜中,通入N2,升温,在140~160℃下反应5~12h,升温至220~240℃分段抽真空脱除低分子化合物与水,分段抽真空设置为:-0.04~-0.06MPa真空脱水脱气1h,-0.06~-0.08MPa真空脱水脱气1h,-0.09~-0.1MPa真空脱水脱气2h,降温至室温,得到聚酯醚多元醇;
步骤(1)中所述起始剂为二甘醇、乙二醇、丙二醇、1,4-丁二醇、甘油、新戊二醇、一缩二丙二醇、三羟基丙烷、季戊四醇、木糖醇、山梨醇和蔗糖中的一种或多种;
步骤(2)中所述二元羧酸为丁二酸、己二酸、间苯二甲酸、对苯二甲酸、壬二酸、卤代苯二甲酸中的一种或多种;所述二元酸酐为邻苯二甲酸酐和癸二酸酐中的一种或多种。
本发明所述的合成聚酯醚多元醇的方法,其中,步骤(1)中所述起始剂为二甘醇、甘油和山梨醇中的一种或多种;所述催化剂为KOH、二甲胺和三乙胺中的一种或多种。
本发明所述的合成聚酯醚多元醇的方法,其中,步骤(1)中所述催化剂为KOH。
本发明所述的合成聚酯醚多元醇的方法,其中,步骤(2)中所述酯化催化剂为有机锡、有机钛、有机锑和苯磺酸类中的一种或多种。
本发明所述的合成聚酯醚多元醇的方法,其中,步骤(2)中所述酯化催化剂为钛酸四丁酯;所述二元酸酐为邻苯二甲酸酐。
本发明所述的合成聚酯醚多元醇的方法,其中,步骤(1)中所述伯羟基聚醚多元醇的羟值350-470mgKOH/g,酸值0.10-0.14mgKOH/g,控制K+、Na+小于5ppm;步骤(2)中所述聚酯醚多元醇的羟值50~400mgKOH/g,酸值<0.3mgKOH/g。
本发明所述的合成聚酯醚多元醇的方法,其中,步骤(1)中所述起始剂、催化剂和环氧乙烷的质量比为:183-212:1.3:2.0:355-530。
本发明所述的合成聚酯醚多元醇的方法,其中,步骤(2)中所述伯羟基聚醚多元醇、二元羧酸或酸酐和酯化催化剂的质量比为449-536:103-141:2.9-3.3。
本发明所述的合成聚酯醚多元醇的方法,其中,步骤(1)中所述起始剂为二甘醇和山梨醇,山梨醇的浓度为70wt%,二甘醇和山梨醇的质量比为53:130;步骤(2)中所述聚酯醚多元醇的羟值150~300mgKOH/g。
本发明具有以下优点:
1.合成聚醚多元醇、聚酯多元醇的原材料都适用于本发明。而现有的合成方法,只适用于聚酯多元醇的原材料。
2.本发明不会引起催化剂和酯化催化剂失效而导致反应失败。而目前研究的方法,若聚酯多元醇中存在小分子或者部分分解,都会引起双金属催化剂(DMC)失效而导致反应无法正常进行,而若用普通的催化剂(如KOH、二甲胺等),都会引起聚酯分解,无法得到聚酯醚多元醇产品。
3.本发明可以合成高官能度聚酯醚多元醇。本发明可以先合成到二官能度到八官能度的伯羟基聚醚多元醇做为起始剂,与二元羧酸或酸酐进行酯化反应。而现有的方法,都是用二官能度到四官能度的聚酯多元醇进行环丙加成反应,得到的聚酯醚多元醇仍然是二到四官能度。
4.本发明先合成聚醚多元醇做为原料,再合成聚酯醚多元醇,较先合成聚酯多元醇作为原料收率更高,酸值低,产品稳定。因为合成聚酯,用到的低分子醇会过量较多,然后再通过高温蒸馏出来。而本发明无需投入过量的聚醚多元醇,并且后期也不用分离聚醚多元醇,工艺简单。
本发明所述的合成聚酯醚多元醇的方法,步骤(1)中所述起始剂为二甘醇、甘油和山梨醇中的一种或多种;可以合成粘度较低的聚醚,从而得到较低粘度聚酯醚产品。所述催化剂为KOH,KOH做为催化剂,不含水,做出的产品更均相。采用KOH做出的聚醚多元醇粗产品需要用磷酸进行处理,成品成弱酸性,用来做聚酯醚时,与酸性二元羧酸或酸酐更稳定。
本发明所述的合成聚酯醚多元醇的方法,所述二元酸酐为邻苯二甲酸酐,邻苯二甲酸酐含有苯环,在聚氨酯硬质泡沫上应用,产品强度更好。
本发明所述的合成聚酯醚多元醇的方法,所述聚醚多元醇的羟值350-470mgKOH/g,酸值0.10-0.14mgKOH/g,能够保证末端伯羟基的活性。控制K+、Na+小于5ppm,可以防止聚酯多元醇分解。所述聚酯醚多元醇的羟值50~400mgKOH/g,酸值<0.3mgKOH/g,可以使产品更稳定。
下面将结合具体实施例对本发明作进一步说明。
具体实施方式
实施例1
一种合成聚酯醚多元醇的方法,包括以下步骤:
(1)在反应釜中投入184g甘油起始剂和2g KOH催化剂,N2多次置换掉反应釜中的空气,然后通入环氧乙烷(EO)530g,反应温度80~100℃,反应时间8h;完全反应后,加入35g水进行水洗0.5h、3.7g 85%磷酸中和0.5h,1.5g硅酸镁和1.5硅酸铝吸附0.5h,然后在105~115℃减压脱水结晶,过滤,得到伯羟基聚醚多元醇A 701g,羟值470mgKOH/g,K+、Na+含量3ppm,酸值0.14mgKOH/g;
(2)取步骤(1)中所述伯羟基聚醚多元醇A498.4g,103.6g邻苯二甲酸酐二元羧酸和3g钛酸四丁酯酯化催化剂加入酯化反应釜中,通入N2,升温,在160℃下反应8h,升温至240℃,-0.04~-0.06MPa真空脱水脱气1h,-0.06~-0.08MPa真空脱水脱气1h,-0.09~-0.1MPa真空脱水脱气2h,降温至室温,得到聚酯醚多元醇产品I570g。
实施例2
一种合成聚酯醚多元醇的方法,包括以下步骤:
(1)在反应釜中投入212g二甘醇起始剂和1.5g KOH催化剂,N2多次置换掉反应釜中的空气,通入环氧乙烷(EO)355g,反应温度80~100℃;完全反应后,加入28g水进行水洗0.5h、2.7g 85%磷酸中和0.5h,1g硅酸镁和1g硅酸铝吸附0.5h,105~115℃减压脱水结晶过滤,得到伯羟基聚醚多元醇B 558.5g,羟值396.8mgKOH/g,K+、Na+含量2ppm,酸值0.11mgKOH/g;
(2)取步骤(1)中所述伯羟基聚醚多元醇B 535.8g,140.6g邻苯二甲酸酐二元羧酸和3.3g钛酸四丁酯酯化催化剂加入酯化反应釜中,通入N2,升温,在160℃下反应8h,升温至240℃,-0.04~-0.06MPa真空脱水脱气1h,-0.06~-0.08MPa真空脱水脱气1h,-0.09~-0.1MPa真空脱水脱气2h,降温至室温,得到聚酯醚多元醇产品II 630g。
实施例3
(1)在反应釜中投入53g二甘醇和130g 70wt%山梨醇起始剂,1.3g KOH催化剂,N2多次置换掉反应釜中的空气,通入环氧乙烷(EO)355g,反应温度90~105℃;完全反应后,加入25g水进行水洗0.5h、2.5g 85%磷酸中和0.5h,1g硅酸镁和1g硅酸铝吸附0.5h,105~115℃减压脱水结晶过滤,得到伯羟基聚醚多元醇C 490g,羟值451mgKOH/g,K+、Na+含量5ppm,酸值0.11mgKOH/g;
(2)取步骤(1)中所述伯羟基聚醚多元醇C 449g,133.2g邻苯二甲酸酐二元羧酸和2.9g钛酸四丁酯酯化催化剂加入酯化反应釜中,通入N2,升温,在160℃下反应10小时,升温至240℃,-0.04~-0.06MPa真空脱水脱气1h,-0.06~-0.08MPa真空脱水脱气1h,-0.09~-0.1MPa真空脱水脱气2h,降温至室温,得到聚酯醚多元醇产品III 543g。
采用国家标准GB 12008.3-1989测产品的羟值,采用BROOKFILD粘度计、万通水分仪、梅特勒电位滴定计和梅特勒电位滴定计分别测定产品的粘度、水分、酸值和pH值,上述实例1和2中产品指标如下表1所示。
表1实例1和2中产品指标
聚酯醚多元醇 | 羟值mgKOH/g | 粘度cp | 水分% | 酸值mgKOH/g | pH值 | |
实例1 | I | 273.4 | 11520 | 0.021 | 0.18 | 6.8 |
实例2 | II | 165.7 | 7450 | 0.013 | 0.22 | 5.6 |
实例3 | III | 185.6 | 34200 | 0.022 | 0.15 | 6.4 |
以上所述的实施例仅仅是对本发明的优选实施方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案作出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (10)
1.一种合成聚酯醚多元醇的方法,其特征在于:包括以下步骤:
(1)在反应釜中投入二官能度到八官能度的起始剂和催化剂,N2多次置换掉反应釜中的空气,然后通入环氧乙烷(EO),反应温度80~100℃,反应时间9-10h;完全反应后,经过水洗、中和、吸附,然后减压脱水结晶,过滤,得到伯羟基聚醚多元醇;
(2)取步骤(1)中所述伯羟基聚醚多元醇、二元羧酸或酸酐、酯化催化剂加入酯化反应釜中,通入N2,升温,在140~160℃下反应5~12h,升温至220~240℃分段抽真空脱除低分子化合物与水,降温至室温,得到聚酯醚多元醇。
2.根据权利要求1所述的合成聚酯醚多元醇的方法,其特征在于:包括以下步骤:
(1)在反应釜中投入起始剂和催化剂,N2多次置换掉反应釜中的空气,然后通入环氧乙烷,反应温度80~100℃;完全反应后,经过水洗、85%磷酸中和,硅酸镁和硅酸铝吸附,然后在105~115℃减压脱水结晶,过滤,得到伯羟基聚醚多元醇;
(2)取步骤(1)中所述伯羟基聚醚多元醇、二元羧酸或酸酐、酯化催化剂加入酯化反应釜中,通入N2,升温,在140~160℃下反应5~12h,升温至220~240℃分段抽真空脱除低分子化合物与水,分段抽真空设置为:-0.04~-0.06MPa真空脱水脱气1h,-0.06~-0.08MPa真空脱水脱气1h,-0.09~-0.1MPa真空脱水脱气2h,降温至室温,得到聚酯醚多元醇;
步骤(1)中所述起始剂为二甘醇、乙二醇、丙二醇、1,4-丁二醇、甘油、新戊二醇、一缩二丙二醇、三羟基丙烷、季戊四醇、木糖醇、山梨醇和蔗糖中的一种或多种;
步骤(2)中所述二元羧酸为丁二酸、己二酸、间苯二甲酸、对苯二甲酸、壬二酸、卤代苯二甲酸中的一种或多种;所述二元酸酐为邻苯二甲酸酐和癸二酸酐中的一种或多种。
3.根据权利要求1所述的合成聚酯醚多元醇的方法,其特征在于:步骤(1)中所述起始剂为二甘醇、甘油和山梨醇中的一种或多种;所述催化剂为KOH、二甲胺和三乙胺中的一种或多种。
4.根据权利要求1所述的合成聚酯醚多元醇的方法,其特征在于:步骤(1)中所述催化剂为KOH。
5.根据权利要求1所述的合成聚酯醚多元醇的方法,其特征在于:步骤(2)中所述酯化催化剂为有机锡、有机钛、有机锑和苯磺酸类中的一种或多种。
6.根据权利要求1所述的合成聚酯醚多元醇的方法,其特征在于:步骤(2)中所述酯化催化剂为钛酸四丁酯;所述二元酸酐为邻苯二甲酸酐。
7.根据权利要求1所述的合成聚酯醚多元醇的方法,其特征在于:步骤(1)中所述伯羟基聚醚多元醇的羟值350-470mgKOH/g,酸值0.10-0.14mgKOH/g,K+、Na+小于5ppm;步骤(2)中所述聚酯醚多元醇的羟值50~400mgKOH/g,酸值<0.3mgKOH/g。
8.根据权利要求1所述的合成聚酯醚多元醇的方法,其特征在于:步骤(1)中所述起始剂、催化剂和环氧乙烷的质量比为:183-212:1.3:2.0:355-530。
9.根据权利要求1所述的合成聚酯醚多元醇的方法,其特征在于:步骤(2)中所述伯羟基聚醚多元醇、二元羧酸或酸酐和酯化催化剂的质量比为449-536:103-141:2.9-3.3。
10.根据权利要求1-9任意一项所述的合成聚酯醚多元醇的方法,其特征在于:步骤(1)中所述起始剂为二甘醇和山梨醇,山梨醇的浓度为70wt%,二甘醇和山梨醇的质量比为53:130;步骤(2)中所述聚酯醚多元醇的羟值150~300mgKOH/g。
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