CN108840985B - 一种用于冰箱的硬质聚氨酯泡沫材料及其制备方法 - Google Patents
一种用于冰箱的硬质聚氨酯泡沫材料及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种用于冰箱的硬质聚氨酯泡沫材料及其制备方法。该聚氨酯泡沫材料由白料和黑料组成,白料包含多元醇组合物和助剂,其中,多元醇组合物由下列原料按照重量份配比制成:芳胺聚醚多元醇15‑40重量份,山梨醇聚醚多元醇15‑60重量份、甘油聚醚多元醇10‑20重量份、蓖麻油聚醚多元醇5‑15重量份、聚酯多元醇5‑15重量份,助剂为泡沫稳定剂2‑4重量份、水1.5‑2.5重量份、催化剂2‑3重量份、发泡剂15‑20重量份。黑料为异氰酸酯,白料与黑料的重量比为1:1.08‑1.25。通过该技术方案提供的聚氨酯泡沫脱模快、导热系数低、压缩强度好。使用该泡沫的冰箱不仅生产效率高,保温性能好,而且不出现背板鼓包现象。
Description
技术领域
本发明属于聚氨酯泡沫塑料领域,具体涉及一种用于冰箱的硬质聚氨酯泡沫材料及其制备方法。
背景技术
聚氨酯泡沫是目前隔热保温材料中的领导者,广泛用于冰箱、热水器、建筑保温等诸多绝热保温领域。由于近几年国内家电市场特别是家用电冰箱市场需求旺盛,冰箱生产制造厂家均在提高冰箱的产能,作为冰箱生产关键技术的发泡是整个冰箱产能提升的重点之一。目前,市面上的冰箱配方都在着重追求有效缩短冰箱脱模时间,提高设备的利用率,在不投入发泡专用设备的情况下,提高冰箱产能。但是一味地追求缩短冰箱脱模时间,造成很多冰箱厂家生产的冰箱背板内部泡沫出现鼓包现象。鼓包不仅破坏冰箱的设计美感,更重要的是鼓包导致冰箱的保温性能下降,能耗增大。因此,冰箱生产厂家亟需一种既能快速脱模,又不会出现冰箱背板鼓包现象的高效保温的聚氨酯泡沫材料。
发明内容
本发明是为解决上述现有技术所存在的不足之处,旨在提供一种快速脱模又不会出现鼓包现象的用于冰箱的硬质聚氨酯泡沫材料及其制备方法。
为实现以上发明目的,本发明采用的技术方案如下:
一种用于冰箱的硬质聚氨酯泡沫材料,由白料和黑料构成,白料与黑料的重量比为1:1.08-1.25,其中,
白料由多元醇组合物与助剂构成,多元醇组合物以重量份数计:
聚醚多元醇A 25-40;
聚醚多元醇B 30-40;
聚醚多元醇C 10-20;
聚醚多元醇D 5-15;
聚酯多元醇E 5-15;
聚醚多元醇A为以芳胺为起始剂,羟值为400±20mgKOH/g的聚醚多元醇;
聚醚多元醇B为以山梨醇为起始剂,羟值为450±20mgKOH/g的聚醚多元醇;
聚醚多元醇C为以甘油为起始剂,羟值为150±20mgKOH/g的聚醚多元醇;
聚醚多元醇D为以蓖麻油为起始剂,羟值为280±20mgKOH/g的聚醚多元醇;
聚酯多元醇E为二元羧酸与二元醇缩合,羟值为300±20mgKOH/g的聚酯多元醇。
聚醚多元醇A、聚醚多元醇B、聚醚多元醇C和聚醚多元醇D和聚酯多元醇E五种原料总重量份数为100份。
助剂由泡沫稳定剂、水、催化剂和发泡剂构成,以重量份数计如下:
泡沫稳定剂 2.0-4 .0;
水 1.5-2.5;
催化剂 2.0-3.0;
发泡剂 15-20。
其中,发泡剂为环戊烷、异戊烷与HFC-245fa的混合发泡体系,环戊烷、异戊烷与HFC-245fa的质量比为25-45:5-15:40-70。本发明所用发泡剂环境友好,所得到的硬质聚氨酯泡沫材料绿色环保,GDP低,ODP为0。
所述的泡沫稳定剂是一种表面活性剂, 采用含Si-C结构的硅类表面活性剂。泡沫稳定剂可从市场购得, 包括德美世创公司产的泡沫稳定剂, 如 AK8805、AK8830、AK8818等 ;德固萨 (Degusa)的泡沫稳定剂 B8462、B8461、B8544、B-8494 ; 迈图公司(Momentive)的L6900、 L6863 等。
所述的催化剂采用复合催化剂体系,由催化-OH和-NCO相互反应的发泡催化剂、凝胶催化剂和三聚催化剂组成。所述的发泡催化剂是五甲基二亚乙基三胺(PC-5)、双(二甲基氨基已基)醚(A-1)中的一种或两种按任意比例的混合物;所述凝胶催化剂是N,N-二甲基环已胺(PC-8)、三亚已基二胺(TEDA-33P)、四甲基已二胺(TMHDA)中的一种或两种以上任意比例的混合物;所述三聚催化剂是1,3,5-三(二甲氨基丙基)六氢三嗪(PC-41)、2,4,6-三(二甲氨甲基)苯酚(TMR-30)、甲季胺盐(TMR-2)中的一种或两种以上任意比例的混合物。可从市场购得的常用催化剂,如AirProducts的PC-5、PC-8、PC-41、TMR-2、TMR-30、TMHDA等。
黑料为多亚甲基多苯基多异氰酸酯(PAPI),本发明中优选NCO百分含量为30-32%、异氰酸酯指数为100~130的PAPI。PAPI可从市场直接购得,包括陶氏(Dow)的13S,巴斯夫(BASF)的M20S等。
本发明通过使用多种起始剂合成的聚醚多元醇以及长柔性链聚酯多元醇复合的聚氨酯发泡原料来提高冰箱用聚氨酯泡沫的流动性能和保温性能,确保泡沫能均匀流动到冰箱箱体各个位置,避免因流动性不足造成冰箱鼓包现象。
本发明同时使用往多元醇组合物搅拌设备里通入空气,增加多元醇组合物中的微小气泡,使多元醇组合物充分乳化。在多元醇组合物充分乳化的情况下,不仅聚氨酯泡沫在发泡时能形成足够多的气核,增加组分的流动性,还能增加气泡的均匀程度,避免因聚氨酯泡沫反应后期因流动性不足和气泡并泡在冰箱背板上出现鼓包现象。
本发明的有益效果是:
1.本发明制备的聚氨酯硬质泡沫保温材料,泡孔细腻,泡沫的导热系数在18 .5-19 .0mW/m·K范围,有效降低了冰箱使用能耗,节约能源;
2.泡沫脱模速度快,仅140秒,固化膨胀小,压缩强度好,能最大程度缩短冰箱生产厂家的生产周期,提高生产效率;
3.应用本聚氨酯泡沫的冰箱无鼓包现象,生产的冰箱合格率高,低能环保;
4.本发明所用发泡剂ODP为0,GWP低,绿色环保;
5.本发明制备方法简便、易操作。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容。
实施例1
冰箱用硬质聚氨酯保温材料由白料和黑料组成,白料与黑料的重量比为1:1.08,其中:
白料中多元醇组合物总计100重量份,包含:邻甲苯二胺聚醚多元醇40重量份,山梨醇聚醚多元醇30重量份,甘油聚醚多元醇20重量份,蓖麻油聚醚多元醇5重量份, Bayer公司2601聚酯多元醇5重量份。
此外,白料中还有泡沫稳定剂3.5重量份;水1.5重量份;复合催化剂 2.5重量份,其中双(二甲基氨基已基)醚(A-1)0.3重量份,N,N-二甲基环已胺(PC-8)1.5重量份,2,4,6-三(二甲氨甲基)苯酚(TMR-30)0.7重量份;发泡剂20重量份,其中环戊烷、异戊烷与HFC-245fa的质量比为25:15:60。
先将上述聚醚多元醇与聚酯多元醇加入搅拌装置中,一边搅拌一边通入空气,使物料充分乳化并混合均匀。然后加入称量好的泡沫稳定剂、催化剂、水、发泡剂,常温下搅拌0.5-1h,得到白料。
将白料与黑料(M20S)混合均匀,得到用于冰箱的硬质聚氨酯泡沫材料。制得的硬质聚氨酯泡沫材料性能指标见表1。
实施例2
冰箱用硬质聚氨酯保温材料由白料和黑料组成,白料与黑料的重量比为1:1.15,其中:
白料中多元醇组合物总计100重量份,包含:邻苯二胺聚醚多元醇35重量份,山梨醇聚醚多元醇35重量份,甘油聚醚多元醇15重量份,蓖麻油聚醚多元醇10重量份,Bayer公司2602聚酯多元醇重量5份。
此外,白料中还有泡沫稳定剂3重量份;水2.0重量份;复合催化剂3重量份,其中五甲基二亚乙基三胺(PC-5)0.3重量份,双(二甲基氨基已基)醚(A-1)0.2重量份,三亚已基二胺(TEDA-33P)1.0重量份,N,N-二甲基环已胺(PC-8)0.5重量份,1,3,5-三(二甲氨基丙基)六氢三嗪(PC-41)0.5重量份;发泡剂20重量份,其中环戊烷、异戊烷与HFC-245fa的质量比为20:10:70。
先将上述聚醚多元醇与聚酯多元醇加入搅拌装置中,一边搅拌一边通入空气,使物料充分乳化并混合均匀。然后加入称量好的泡沫稳定剂、催化剂、水、发泡剂,常温下搅拌0.5-1h,得到白料。
将白料与黑料(M20S)混合均匀,得到用于冰箱的硬质聚氨酯泡沫材料。制得的硬质聚氨酯泡沫材料性能指标见表1。
实施例3
冰箱用硬质聚氨酯保温材料由白料和黑料组成,白料与黑料的重量比为1:1.20,其中:
白料中多元醇组合物总计100重量份,包含:邻甲苯二胺聚醚多元醇30重量份,山梨醇聚醚多元醇40重量份,甘油聚醚多元醇10重量份,蓖麻油聚醚多元醇5重量份,Bayer公司2602聚酯多元醇15重量份。
此外,白料中还有泡沫稳定剂2重量份;水2.0重量份;复合催化剂2重量份,其中五甲基二亚乙基三胺(PC-5)0.3重量份,四甲基已二胺(TMHDA)1.5重量份,甲季胺盐(TMR-2)0.2重量份;发泡剂20重量份,其中环戊烷、异戊烷与HFC-245fa的质量比为45:10:45。
先将上述聚醚多元醇与聚酯多元醇加入搅拌装置中,一边搅拌一边通入空气,使物料充分乳化并混合均匀。然后加入称量好的泡沫稳定剂、催化剂、水、发泡剂,常温下搅拌0.5-1h,得到白料。
将白料与黑料(M20S)混合均匀,得到用于冰箱的硬质聚氨酯泡沫材料。制得的硬质聚氨酯泡沫材料性能指标见表1。
实施例4
冰箱用硬质聚氨酯保温材料由A组分和B组分组成,A组分与B组分的重量比为1:1.08,其中:
白料中多元醇组合物总计100重量份,包含:邻苯二胺聚醚多元醇25重量份,山梨醇聚醚多元醇35重量份,甘油聚醚多元醇20重量份,蓖麻油聚醚多元醇15重量份,Bayer公司2601聚酯多元醇5重量份。
此外,白料中还有中还有泡沫稳定剂4重量份;水2.5重量份;复合催化剂2.5重量份,其中五甲基二亚乙基三胺(PC-5)0.4重量份,N,N-二甲基环已胺(PC-8)1.4重量份,1,3,5-三(二甲氨基丙基)六氢三嗪(PC-41)0.4重量份,2,4,6-三(二甲氨甲基)苯酚(TMR-30)0.3重量份;发泡剂20重量份,其中环戊烷、异戊烷与HFC-245fa的质量比为45:5:50。
先将上述聚醚多元醇与聚酯多元醇加入搅拌装置中,一边搅拌一边通入空气,使物料充分乳化并混合均匀。然后加入称量好的泡沫稳定剂、催化剂、水、发泡剂,常温下搅拌0.5-1h,得到白料。
将白料与黑料(M20S)混合均匀,得到用于冰箱的硬质聚氨酯泡沫材料。制得的硬质聚氨酯泡沫材料性能指标见表1。
表1
以上4个实施例在冰箱生产线上应用,均未出现冰箱背板鼓包现象。
Claims (6)
1.一种用于冰箱的硬质聚氨酯泡沫材料,其特征在于,由白料和黑料构成,白料与黑料的重量比为1:1.08-1.25,其中,
白料由多元醇组合物与助剂构成,多元醇组合物以重量份数计:
聚醚多元醇A 25-40;
聚醚多元醇B 30-40;
聚醚多元醇C 10-20;
聚醚多元醇D 5-15;
聚酯多元醇E 5-15;
聚醚多元醇A为以芳胺为起始剂,羟值为400±20mgKOH/g的聚醚多元醇;
聚醚多元醇B为以山梨醇为起始剂,羟值为450±20mgKOH/g的聚醚多元醇;
聚醚多元醇C为以甘油为起始剂,羟值为150±20mgKOH/g的聚醚多元醇;
聚醚多元醇D为以蓖麻油为起始剂,羟值为280±20mgKOH/g的聚醚多元醇;
聚酯多元醇E为二元羧酸与二元醇缩合,羟值为300±20mgKOH/g的聚酯多元醇;
聚醚多元醇A、聚醚多元醇B、聚醚多元醇C和聚醚多元醇D和聚酯多元醇E五种原料总重量份数为100份;
助剂由泡沫稳定剂、水、催化剂和发泡剂构成,以重量份数计如下:
泡沫稳定剂 2.0-4 .0;
水 1.5-2.5;
催化剂 2.0-3.0;
发泡剂 15-20;
黑料为多亚甲基多苯基多异氰酸酯。
2.根据权利要求1所述的用于冰箱的硬质聚氨酯泡沫材料,其特征在于,所述发泡剂为环戊烷、异戊烷与HFC-245fa的混合发泡体系,环戊烷、异戊烷与HFC-245fa的质量比为25-45:5-15:40-70。
3.根据权利要求1所述的用于冰箱的硬质聚氨酯泡沫材料,其特征在于,所述催化剂为发泡催化剂、凝胶催化剂、三聚催化剂组成的复合催化剂。
4.根据权利要求3所述的用于冰箱的硬质聚氨酯泡沫材料,其特征在于,所述发泡催化剂是五甲基二亚乙基三胺、双(二甲基氨基已基)醚中的一种或两种按任意比例的混合物;所述凝胶催化剂是N,N-二甲基环已胺、三亚已基二胺、四甲基已二胺中的一种或两种以上任意比例的混合物;所述三聚催化剂是1,3,5-三(二甲氨基丙基)六氢三嗪、2,4,6-三(二甲氨甲基)苯酚、甲季胺盐中的一种或两种以上任意比例的混合物。
5.根据权利要求1所述的用于冰箱的硬质聚氨酯泡沫材料,其特征在于,所述泡沫稳定剂是含 Si-C 结构的硅类表面活性剂。
6.一种权利要求1-5任一所述的用于冰箱的硬质聚氨酯泡沫材料的制备方法,其特征在于,包括以下步骤:
首先将称量好的聚醚多元醇A、聚醚多元醇B、聚醚多元醇C、聚醚多元醇D和聚酯多元醇E加入搅拌装置,搅拌均匀,搅拌时不断通入空气,使混合物充分乳化;
然后加入称量好的泡沫稳定剂、催化剂、水、发泡剂,常温下搅拌0.5-1h,得到白料;
将白料和黑料按照重量比1:1.08-1.25混合均匀,制备出用于冰箱的硬质聚氨酯泡沫材料。
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