CN107459626A - 冰箱用聚氨酯组合聚醚及其聚氨酯硬质泡沫 - Google Patents

冰箱用聚氨酯组合聚醚及其聚氨酯硬质泡沫 Download PDF

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CN107459626A
CN107459626A CN201710780552.2A CN201710780552A CN107459626A CN 107459626 A CN107459626 A CN 107459626A CN 201710780552 A CN201710780552 A CN 201710780552A CN 107459626 A CN107459626 A CN 107459626A
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杨永萍
吕清发
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Henan Guangyang Energy Saving Material Co Ltd
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Abstract

本发明涉及一种冰箱用聚氨酯组合聚醚及其冰箱用聚氨酯硬质泡沫。本发明冰箱用聚氨酯组合聚醚包括表面活性剂的用量为1.5‑3份、化学发泡剂为1.0‑2.4份、物理发泡剂为15‑22份、聚醚多元醇100份以及常规用量的催化剂，所述的聚醚多元醇由聚醚多元醇A40‑60wt%、聚醚多元醇B20‑40wt%、聚醚多元醇C10‑20wt%组成；聚氨酯组合聚醚和多亚甲基多苯基多异氰酸酯以重量比为1:1.05‑1:1.3均匀混合、发泡制备得到聚氨酯硬质泡沫。主要用于生产冰箱冰柜的保温层，具有导热系数低、用量少、生产效率高，冰箱内胆吸坑缺陷少等优点。

Description

冰箱用聚氨酯组合聚醚及其聚氨酯硬质泡沫
技术领域
本发明属于环保聚氨酯节能材料领域，特别涉及一种冰箱用聚氨酯组合聚醚及聚氨酯硬质泡沫。
背景技术
自《蒙特利尔议定书》签署以来，国际上消耗臭氧层物质（ODS）替代技术在迅速发展。我国的聚氨酯硬泡行业，HCFC－141b和戊烷发泡体系均有采用。HCFC－141b毕竟是过渡性替代物，也将在2025年在聚氨酯硬泡行业完全被替代。申请人注重产品的研发，其团队人员采用零ODP值发泡剂（特别是HFC－245fa和环戊烷）替代技术，顺利完成零ODP值发泡剂的转换。
对于聚氨酯硬质泡沫由于其优质的性能，在国内外均有广泛应用，聚氨酯硬质泡沫技术因其不同的应用方向而对其中的配方进行不同的设计。而针对冰箱冰柜用的硬质泡沫，由于其特殊的性能要求，目前很多的产品存在表面缺陷多、导热系数较高、密度分布不均匀、需用原料量大、脱模时间长等缺点。
发明内容
为了解决上述技术问题，本发明提供一种专用于冰箱用的聚氨酯组合聚醚及用其制作的硬质泡沫，使得使用本产品生产的冰箱冰柜具有导热系数低、表面缺陷少、密度分布均匀、脱模时间快且用量也很少。
本发明采用下述技术方案解决上述技术问题：设计一种冰箱用聚氨酯组合聚醚，包括以下重量份的原料：表面活性剂的用量为1.5-3份、化学发泡剂为1.0-2.4份、物理发泡剂为15-20份、聚醚多元醇100份以及常规用量的催化剂，所述的聚醚多元醇由聚醚多元醇A40-60wt%、聚醚多元醇B20-40wt%、聚醚多元醇C10-20wt%组成；
所述的聚醚多元醇A的羟值为360-400mgKOH/g，25℃下粘度为6000-9000mPa·s，起始剂为蔗糖和甘油；所述的聚醚多元醇B的羟值为440-480mgKOH/g，25℃条件下粘度为10000-15000mPa·s，起始剂为山梨醇：所述的聚醚多元醇C的羟值为380-420mgKOH/g，25℃条件下粘度为12000-16000mPa·s，起始剂为甲苯二胺。
作为本发明的一种优选方案，所述的聚醚多元醇A为聚醚多元醇YD-8238、JH-8238，所述的聚醚多元醇B为聚醚多元醇YD-600，所述的聚醚多元醇C为聚醚多元醇YD-401P。
作为本发明又一种优选方案，所述的表面活性剂为硅酮类表面活性剂B8844、6863、8809、或B84812、84813；较佳地为硅酮类表面活性剂6863、8809、B84813单独使用或复合使用，所述的化学发泡剂为水或去离子水。
作为本发明的再一种优选方案，所述的催化剂为胺类催化剂和/或金属类催化剂，用量为1-3份，胺类催化剂选自于双（二甲氨基乙基）醚、五甲基二乙基三胺、二甲基环己胺、三乙烯二胺、1,3,5-三（二甲氨基丙基）-六氢三嗪和N,N-二甲基苄胺中的至少一种，金属类催化剂为二月桂酸二丁基锡 。
作为本发明的进一步的优选方案，所述的催化剂复配使用或所述的胺类催化剂为五甲基二乙基三胺、双（二甲氨基乙基）醚、二甲基环己胺、1,3,5-三（二甲氨基丙基）-六氢三嗪和季胺盐中至少四种复配使用。
作为本发明的又进一步的优选方案，所述的物理发泡剂为低沸点的烷烃类发泡剂或卤代烃类发泡剂；烷烃类发泡剂选自于正戊烷、异戊烷、环戊烷和正丁烷中的至少一种；卤代烃类发泡剂选自于一氟二氯乙烷、二氟一氯甲烷、1,3,3,3-五氟丙烷、1,1,1,3,3-五氟丁烷和1,1,1,2,3,3,3-七氟丙烷中的至少一种。
作为本发明的更进一步的优选方案，所述的物理发泡剂为采用1,3,3,3-五氟丙烷和环戊烷以30:70至40:60的百分配比而成。
作为本发明的再进一步的优选方案，所述的聚氨酯组合聚醚还包括扩链剂、交联剂中的至少一种，用量为大于0至小于等于5份，扩链剂为1,4-丁二醇、乙二醇、一缩二乙二醇、丙二醇、丙三醇、三羟甲基丙烷中的一种，交联剂为乙醇胺、双-2-(羟丙基）苯胺和三乙醇胺中的一种。
本发明中，将各组份按照重量配比混合均匀即可得到冰箱用聚氨酯组合聚醚；由所述的冰箱用聚氨酯组合聚醚和多亚甲基多苯基多异氰酸酯以重量比为1:1.05-1:1.3均匀混合、发泡制备得到冰箱用的聚氨酯硬质泡沫，优选混合方式为高压机混合发泡，操作参数设定为，搅拌转速3000r/min,搅拌时间6-10s。其中多亚甲基多苯基多异氰酸酯为异氰酸酯PM200、异氰酸酯44V20、异氰酸酯M20S、异氰酸酯MR200、异氰酸酯5005中的至少一种。作为再进行的优选方案，聚氨酯组合聚醚和多亚甲基多苯基多异氰酸酯的重量为1：1.2。
采用上述配比的本发明具有的积极的有益效果为：
本发明的聚氨酯组合料用于冰箱发泡层，内胆吸坑少，表面空洞少，因此冰箱外观平整，冰箱能耗少；
本发明的聚氨酯组合料用于冰箱发泡层导热系数低，冰箱能耗低；
本发明的聚氨酯组合料用于冰箱发泡层，脱模时间短，工艺条件优良，脱模时间可以控制在240秒脱模，一般冰箱厂可以控制在270-300秒脱模，因此可以提高冰箱厂的生产效率；
本发明的聚氨酯组合料用于冰箱冰柜发泡层，泡沫密度分布均匀；
本发明的聚氨酯泡沫为绿色环保发泡剂，对臭氧层无破坏，符合环保的要求，同时本发明所用原料均市售可得。
具体实施方式
下面通过实施例的份数进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。
下述实施例中，所使用原材料来源为：
聚醚多元醇A：聚醚多元醇8238，佳化化学、河北亚东化工有限公司；
聚醚多元醇B：聚醚多元醇600，河北亚东化工有限公司；
聚醚多元醇C：聚醚多元醇YD-401P，河北亚东化工有限公司；
表面活性剂：硅酮类表面活性剂B8544、8545，B84812、84813赢创特种化学（上海）有限公司；
表面活性剂：硅酮类表面活性剂6863，迈图高新材料集团
表面活性剂：硅酮类表面活性剂8809 南京美思德化工有限公司
催化剂：胺类催化剂PC5（五甲基二乙基三胺），空气化工产品公司；
胺类催化剂：双（二甲氨基乙基）醚，空气化工产品公司；
胺类催化剂：二甲基环己胺，空气化工产品公司；
胺类催化剂：TMR-2，空气化工产品公司；
胺类催化剂：PC41（1,3,5-三（二甲氨基丙基）-六氢三嗪），空气化工产品公司；
物理发泡剂：卤代烷类发泡剂HFC-245fa，苏威化工；
物理发泡剂：环戊烷，濮阳联众，安徽东方环戊烷化工有限责任公司；
异氰酸酯：异氰酸酯PM-200，烟台万华聚氨酯股份有限公司。
实施例1-4中的聚氨酯组合聚醚组分见表1，将各重量组分的物料混合均匀即可。再用上述冰箱用聚氨酯硬质泡沫的制备方法包括以下步骤：将上述制得的聚氨酯组合聚醚与PM-200按照重量比1:1.2在环境温度为18-25℃下进行机器搅拌混合，转速3000r/min，搅拌6s，倒入模具进行发泡，或采用高压发泡机发泡，模具温度为35-45℃，自模具合模开始计时，4.5min开模。制取聚氨酯硬质泡沫，聚氨酯硬质泡沫开模后在常温下熟化24h后测试相关性能。性能指标请见表2。
表1 聚氨酯组合聚醚的组分及含量表
表2 聚氨酯硬质泡沫性能对照表
注1：对比例1是市场上环戊烷发泡体系的冰箱冰柜组合聚醚多元醇；
发泡剂比例不同，满足不同客户密度不同的要求；
泡沫密度降低，冰箱总注射量减少，从而降低成本；
导热系数降低，达到同样的保温效果，可以减少泡沫层厚度，从而节约成本；
泡沫表面吸坑少，内胆无吸坑，外观美观，另外也减少因泡孔空洞影响保温效果；
脱模时间短，生产效率至少提高25%。
由表2可以看出，使用cp/245fa复合发泡剂的组合聚醚，生产冰箱冰柜，减少用量，降低保温层厚度，提高生产效率，直接降低冰箱成本；并且将冰箱的各项性能提升一个档次。

Claims (10)

1.一种冰箱用聚氨酯组合聚醚，其特征在于包括以下重量份的原料：表面活性剂的用量为1.5-3份、化学发泡剂为1.0-2.4份、物理发泡剂为15-30份、聚醚多元醇100份以及常规用量的催化剂，所述的聚醚多元醇由聚醚多元醇A 40-60wt%、聚醚多元醇B 20-40wt%、聚醚多元醇C 10-20wt%组成；
所述的聚醚多元醇A的羟值为360-400mgKOH/g，25℃下粘度为6000-9000mPa·s，起始剂为蔗糖和甘油；所述的聚醚多元醇B的羟值为440-480mgKOH/g，25℃条件下粘度为10000-15000mPa·s，起始剂为山梨醇；所述的聚醚多元醇C的羟值为380-420mgKOH/g，25℃条件下粘度为12000-16000mPa·s，起始剂为甲苯二胺。
2.根据权利要求1所述的冰箱用聚氨酯组合聚醚，其特征在于，所述的聚醚多元醇A为聚醚多元醇YD-8238，所述的聚醚多元醇B为聚醚多元醇YD-600，所述的聚醚多元醇C为聚醚多元醇YD-401P。
3.根据权利要求2所述的冰箱用聚氨酯组合聚醚，其特征在于，所述的表面活性剂为硅酮类表面活性剂B8844、B6863、B8809、B84812、B84813中的至少一种，所述的化学发泡剂为水或去离子水。
4.根据权利要求1所述的冰箱用聚氨酯组合聚醚，其特征在于，所述的催化剂为胺类催化剂和/或金属类催化剂，用量为1-3份，胺类催化剂选自于双（二甲氨基乙基）醚、五甲基二乙基三胺、二甲基环己胺、三乙烯二胺、1,3,5-三（二甲氨基丙基）-六氢三嗪和N,N-二甲基苄胺中的至少一种，金属类催化剂为二月桂酸二丁基锡 。
5.根据权利要求4所述的冰箱用聚氨酯组合聚醚，其特征在于，所述的催化剂复配使用或所述的胺类催化剂为五甲基二乙基三胺、双（二甲氨基乙基）醚、二甲基环己胺、1,3,5-三（二甲氨基丙基）-六氢三嗪和季胺盐中至少四种复配使用。
6.根据权利要求1所述的冰箱用聚氨酯组合聚醚，其特征在于，所述的物理发泡剂为低沸点的烷烃类发泡剂或卤代烃类发泡剂；烷烃类发泡剂选自于正戊烷、异戊烷、环戊烷和正丁烷中的至少一种；卤代烃类发泡剂选自于一氟二氯乙烷、二氟一氯甲烷、1,3,3,3-五氟丙烷、1,1,1,3,3-五氟丁烷和1,1,1,2,3,3,3-七氟丙烷中的至少一种。
7.根据权利要求6所述的冰箱用聚氨酯组合聚醚，其特征在于，所述的物理发泡剂为采用1,3,3,3-五氟丙烷和环戊烷以30:70至40:60的百分比配合而成。
8.根据权利要求I所述的冰箱用聚氨酯组合聚醚，其特征在于，所述的聚氨酯组合聚醚还包括扩链剂、交联剂中的至少一种，用量为大于0至小于等于5份；扩链剂为1,4-丁二醇、乙二醇、一缩二乙二醇、丙二醇、丙三醇、三羟甲基丙烷中一种，交联剂为乙醇胺、双-2-（羟丙基）苯胺和三乙醇胺中的一种。
9.一种冰箱用聚氨酯硬质泡沫，其特征在于：由权利要求1-8任一项所述的冰箱用聚氨酯组合聚醚和多亚甲基多苯基多异氰酸酯以重量比为1:1.05-1:1.3均匀混合、发泡制备得到，混合方式为高压机混合发泡，操作参数设定为，搅拌转速3000r/min,搅拌时间6-10s；多亚甲基多苯基多异氰酸酯为异氰酸酯PM200、异氰酸酯44V20、异氰酸酯M20S、异氰酸酯MR200、异氰酸酯5005中的至少一种。
10.根据权利要求9所述的冰箱用聚氨酯硬质泡沫，其特征在于，所述的聚氨酯组合聚醚和所述的多亚甲基多苯基多异氰酸酯的重量为1：1.2。
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