CN106832248B - 快速脱模硬泡聚醚多元醇的制备方法 - Google Patents
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Abstract
本发明属于聚氨酯技术领域，具体涉及一种快速脱模硬泡聚醚多元醇的制备方法。本发明通过聚醚多元醇的设计过程引入一些环状基团，降低分子链间的形变，从而提高脱模性。首先合成蔗糖聚醚多元醇，根据不同配方体系和客户需求，调整蔗糖聚醚多元醇的羟值，粘度和活性；然后用羟基苯类化合物对其进行修饰；最后进行精制处理得到具有良好脱模性的聚醚多元醇。本发明生产工艺简单，现有的生产条件既能满足需求，不需要额外的生产辅助设备，产品重现性好，质量稳定，与组合料体系互溶性好；制备的聚氨酯泡沫脱模性好，尺寸稳定性好，能够满足不同客户的需求。
Description
技术领域
本发明属于聚氨酯技术领域，具体涉及一种快速脱模硬泡聚醚多元醇的制备方法。
背景技术
聚醚多元醇是聚氨酯工业的主要原料之一，可用于制造家电、保温管道、板材、汽车内饰、涂料等领域的产品。在这些工业品中，不同的产品对原料聚醚多元醇的起始剂类型，分子结构，官能度、分子量和活性都有不同的要求。脱模时间是衡量聚氨酯发泡的重要指标，在软泡制品中为了缩短模塑开模时间，降低模具温度，节约能源，往往采用高活性即高伯羟基含量的聚醚多元醇。对于硬质泡沫的生产，聚醚多元醇一般采用高官能度和高羟值的聚醚体系，甚至搭配以特殊胺类为起始剂的胺醚，这样不仅会影响泡沫的流动性，而且采用胺醚会增加泡沫生产成本。
硬质聚氨酯泡沫是目前作为冰箱唯一使用的高效隔热保温材料，无论泡沫物理性能还是生产的工艺性能都近乎完美。硬质聚氨酯泡沫组成物通常以浇筑方式加入到冰箱或冰柜箱体的中间夹层，为保证浇注熟化后冰箱制品整体的平整度，需要较长的保压时间或脱模时间，严重制约生产效率的提高，而过快提早脱模也会引起泡沫制品各项性能的下降，甚至开裂、变形成为废品。通常发泡体系的脱模时间依据冰箱型号大小、生产工艺和保温层厚度不同而不同。对于生产制造商来说，为提高生产效率、降低成本，迫切希望缩短脱模时间，缩短产品的生产周期一直是各厂家努力的方向，而聚氨酯发泡所需的脱模时间是影响聚氨酯产品生产效率的主要因素。
长期以来，原料供应商为提高原料的竞争优势，致力于开发快速脱模的硬质聚氨酯泡沫组成物。聚醚多元醇作为硬质聚氨酯泡沫组成物的主要组成部分，对快速脱模性也起着至关重要的作用。因此，近年来人们开展了较为详细的配方及工艺研究。
发明内容
本发明的目的是提供一种快速脱模硬泡聚醚多元醇的制备方法，通过聚醚多元醇设计过程引入一些环状的基团，降低分子链间的形变，从而提高脱模性；该聚醚多元醇羟值、粘度和官能度可调，在组合料配方体系中宽容性强，且硬质聚氨酯泡沫脱模性提高明显，泡沫稳定性好。
本发明所述的快速脱模硬泡聚醚多元醇的制备方法，包括以下步骤：
(1)将蔗糖、小分子起始剂与氧化烯烃在碱性催化剂的作用下进行反应，得到蔗糖聚醚多元醇；
(2)向蔗糖聚醚多元醇中加入羟基苯类化合物，混合均匀，加入缩合剂进行缩聚反应，得到改性的蔗糖聚醚多元醇；
(3)向改性的蔗糖聚醚多元醇中加入水、酸和吸附剂进行精制处理，得到快速脱模硬泡聚醚多元醇。
其中：
步骤(1)中所述的反应条件为60-120℃无氧气氛围，反应压力为0.1-0.5MPa，氧化烯烃进料完毕后，压力低于-0.04MPa反应完成。
步骤(1)中所述的小分子起始剂为甘油、丙二醇、二乙二醇、三乙醇胺、二乙醇胺或水中的一种或几种，碱性催化剂为氢氧化钾或氢氧化钠中的一种，氧化烯烃为环氧丙烷或环氧乙烷中的一种或两种。
步骤(2)中所述的羟基苯类化合物为2-羟基-对二甲苯、苯酚、双酚A或水杨酸中的一种或几种；缩合剂为甲醛或多聚甲醛。
所述的甲醛为质量分数37％、44％或50％的工业级甲醛水溶液，多聚甲醛聚合度为10-100。
步骤(2)中所述的反应条件为无氧气密闭条件下，加入缩合剂反应0.5-1.5h后，开始升温至90-110℃并脱水继续反应1.5-3h。
步骤(3)中所述的酸为草酸或磷酸中的一种，吸附剂为硅酸镁、硅酸铝或硅酸镁铝中的一种或几种。
步骤(3)中所述的反应条件为70-90℃无氧气氛围，常压下反应1-3小时。
蔗糖、小分子起始剂、氧化烯烃、碱性催化剂、羟基苯类化合物、缩合剂、水、酸和吸附剂的质量比为300-350:150-250:5-8:1000-1400:80-220:25-30:100-150:8-11:2-8。
本发明的有益效果如下：
本发明通过聚醚多元醇的设计过程引入一些环状的基团，降低分子链间的形变，从而提高脱模性。首先合成蔗糖聚醚多元醇，根据不同配方体系和客户需求，调整蔗糖聚醚多元醇的羟值，粘度和活性；然后用羟基苯类化合物对其进行修饰；最后进行精制处理得到具有良好脱模性的聚醚多元醇。本发明生产工艺简单，现有的生产条件既能满足需求，不需要额外的生产辅助设备。产品重现性好，质量稳定，与组合料体系互溶性好；制备的聚氨酯泡沫脱模性好，尺寸稳定性好，能够满足不同客户的需求。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
在装配有搅拌器、计量器、加热温控装置、冷却装置(包括外夹套与内盘管)和压力传感器的2L高压釜内，加入蔗糖342g，甘油178g和氢氧化钾5g加热到85℃，逐次加入1030g环氧丙烷，保持压力低于0.2MPa。待压力低于-0.04MPa时，将温度降至70℃，然后94g苯酚，搅匀后再加入80g甲醛水溶液(37％)继续反应1.0小时，然后逐渐升温至105℃脱水继续反应3小时。然后将改性蔗糖聚醚转移至干燥釜，待温度降至80℃时加入100g水，搅匀后加入9.8g 85％的磷酸，再搅匀后加入3g的硅酸镁和2g硅酸铝吸附剂，继续搅拌1h后，开始升温脱水，最后干燥过滤得到快速脱模硬泡聚醚多元醇。
合成的快速脱模聚醚多元醇具有下列性质：
羟基数：448mgKOH/g
25℃的粘度：9370mPas
外观：浅黄色透明
脱模性：1.4％
对比例1
在装配有搅拌器、计量器、加热温控装置、冷却装置(包括外夹套与内盘管)和压力传感器的2L高压釜内，加入蔗糖342g，甘油178g和氢氧化钾5g加热到85℃，逐次加入1030g环氧丙烷，保持压力低于0.2MPa。待反应压力基本不变时，补氮气至0.15MPa继续反应3小时。然后蔗糖聚醚转移至干燥釜，待温度降至80℃时加入100g水，搅匀后加入9.8g 85％的磷酸，再搅匀后加入3g的硅酸镁和2g硅酸铝吸附剂，继续搅拌1h后，开始升温脱水，最后干燥过滤得到硬泡聚醚多元醇。
合成的聚醚多元醇具有下列性质：
羟基数：500mgKOH/g
25℃的粘度：11500mPas
外观：浅黄色透明
脱模性：3.2％
实施例2
在装配有搅拌器、计量器、加热温控装置、冷却装置(包括外夹套与内盘管)和压力传感器的2L高压釜内，加入蔗糖342g，甘油89g、三乙醇胺144g和氢氧化钾5.8g加热到85℃，逐次加入1240g环氧丙烷，保持压力低于0.2MPa。待压力低于-0.04MPa时，将温度降至70℃，然后94g苯酚，搅匀后再加入80g甲醛水溶液(37％)继续反应1.0小时，然后逐渐升温至105℃脱水继续反应3小时。然后将改性蔗糖聚醚转移至干燥釜，待温度降至80℃时加入116g水，搅匀后加入11.4g 85％的磷酸，再搅匀后加入3.5g硅酸镁和2.3g硅酸铝吸附剂，继续搅拌1h后，开始升温脱水，最后干燥过滤得到快速脱模硬泡聚醚多元醇。
合成的快速脱模聚醚多元醇具有下列性质：
羟基数：396mgKOH/g
25℃的粘度：10400mPas
外观：浅黄色透明
脱模性：1.1％
对比例2
在装配有搅拌器、计量器、加热温控装置、冷却装置(包括外夹套与内盘管)和压力传感器的2L高压釜内，加入蔗糖342g，甘油89g、三乙醇胺144g和氢氧化钾5.8g加热到85℃，逐次加入1240g环氧丙烷，保持压力低于0.2MPa。待反应压力基本不变时，补氮气至0.15MPa继续反应3小时。然后蔗糖聚醚转移至干燥釜，待温度降至80℃时加入116g水，搅匀后加入11.4g 85％的磷酸，再搅匀后加入3.5g硅酸镁和2.3g硅酸铝吸附剂，继续搅拌1h后，开始升温脱水，最后干燥过滤得到硬泡聚醚多元醇。
合成的聚醚多元醇具有下列性质：
羟基数：427mgKOH/g
25℃的粘度：11200mPas
外观：浅黄色透明
脱模性：2.6％
实施例3
在装配有搅拌器、计量器、加热温控装置、冷却装置(包括外夹套与内盘管)和压力传感器的2L高压釜内，加入蔗糖342g，甘油215g和氢氧化钾6.3g加热到85℃，逐次加入1320g环氧丙烷，保持压力低于0.2MPa。待压力低于-0.04MPa时，将温度降至70℃，然后200g双酚A，搅匀后再加入80g甲醛水溶液(37％)继续反应1.0小时，然后逐渐升温至105℃脱水继续反应3小时。然后将改性蔗糖聚醚多元醇转移至干燥釜，待温度降至80℃时加入126g水，搅匀后加入12.4g 85％的磷酸，再搅匀后加入4.2g硅酸镁和2.1g硅酸铝吸附剂，继续搅拌1h后，开始升温脱水，最后干燥过滤得到快速脱模硬泡聚醚多元醇。
合成的快速脱模聚醚多元醇具有下列性质：
羟基数：402mgKOH/g
25℃的粘度：9560mPas
脱模性：1.5％
对比例3
2L高压釜内，加入蔗糖342g，甘油215g和氢氧化钾6.3g加热到85℃，逐次加入1320g环氧丙烷，保持压力低于0.2MPa。待反应压力基本不变时，补氮气至0.15MPa继续反应3小时。然后蔗糖聚醚转移至干燥釜，待温度降至80℃时加入126g水，搅匀后加入12.4g85％的磷酸，再搅匀后加入4.2g硅酸镁和2.1g硅酸铝吸附剂，继续搅拌1h后，开始升温脱水，最后干燥过滤得到硬泡聚醚多元醇。
合成的聚醚多元醇具有下列性质：
羟基数：450mgKOH/g
25℃的粘度：10560mPas
脱模性：3.6％。
Claims (8)
1.一种快速脱模硬泡聚醚多元醇的制备方法，其特征在于包括以下步骤：
(1)将蔗糖、小分子起始剂与氧化烯烃在碱性催化剂的作用下进行反应，得到蔗糖聚醚多元醇；
(2)向蔗糖聚醚多元醇中加入羟基苯类化合物，混合均匀，加入缩合剂进行缩聚反应，得到改性的蔗糖聚醚多元醇；
(3)向改性的蔗糖聚醚多元醇中加入水、酸和吸附剂进行精制处理，得到快速脱模硬泡聚醚多元醇。
2.根据权利要求1所述的快速脱模硬泡聚醚多元醇的制备方法，其特征在于：步骤(1)中所述的反应条件为60-120℃无氧气氛围，反应压力为0.1-0.5MPa，氧化烯烃进料完毕后，压力低于-0.04MPa反应完成。
3.根据权利要求1或2所述的快速脱模硬泡聚醚多元醇的制备方法，其特征在于：步骤(1)中所述的小分子起始剂为甘油、丙二醇、二乙二醇、三乙醇胺、二乙醇胺或水中的一种或几种，碱性催化剂为氢氧化钾或氢氧化钠中的一种，氧化烯烃为环氧丙烷或环氧乙烷中的一种或两种。
4.根据权利要求1所述的快速脱模硬泡聚醚多元醇的制备方法，其特征在于：步骤(2)中所述的羟基苯类化合物为2-羟基-对二甲苯、苯酚、双酚A或水杨酸中的一种或几种；缩合剂为甲醛或多聚甲醛。
5.根据权利要求4所述的快速脱模硬泡聚醚多元醇的制备方法，其特征在于：所述的甲醛为质量分数37％、44％或50％的工业级甲醛水溶液，多聚甲醛聚合度为10-100。
6.根据权利要求4或5所述的快速脱模硬泡聚醚多元醇的制备方法，其特征在于：步骤(2)中所述的反应条件为无氧气密闭条件下，加入缩合剂反应0.5-1.5h后，开始升温至90-110℃并脱水继续反应1.5-3h。
7.根据权利要求1所述的快速脱模硬泡聚醚多元醇的制备方法，其特征在于：步骤(3)中所述的酸为草酸或磷酸中的一种，吸附剂为硅酸镁、硅酸铝或硅酸镁铝中的一种或几种。
8.根据权利要求7所述的快速脱模硬泡聚醚多元醇的制备方法，其特征在于：步骤(3)中所述的反应条件为70-90℃无氧气氛围，常压下反应1-3小时。
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