CN109021207A - 一种用于冰箱的聚氨酯硬质泡沫 - Google Patents
一种用于冰箱的聚氨酯硬质泡沫 Download PDFInfo
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Abstract
本发明属于聚氨酯技术领域,具体涉及一种用于冰箱的聚氨酯硬质泡沫及其制备方法。所述聚氨酯硬质泡沫包括:聚醚多元醇组合物;泡沫稳定剂;催化剂;水;添加剂;发泡剂,以及多亚甲基多苯基多异氰酸酯。通过该技术方案提供的聚氨酯泡沫密度分布均匀、导热系数较低、粘结力强,泡沫在较低密度条件下仍具有较高的抗压强度和尺寸稳定性。
Description
技术领域
本发明属于聚氨酯技术领域,具体涉及一种冰箱用密度填充分布均匀的聚氨酯硬质泡沫。
背景技术
聚氨酯硬质泡沫塑料具有密度低、导热系数低、压缩强度高、尺寸稳定性好、闭孔率高、耐水性好等优良特性,是目前作为冰箱隔热保温最好的材料。
随着时代的发展,为了满足消费者的生活需求,现代的冰箱容积越来越大,型号多且内部结构复杂,给冰箱制造发泡工艺带来了越来越多的难题,例如大容积箱体边角泡沫填充分布不均易造成收缩变形甚至开裂,这很大程度上影响了冰箱的泡沫性能和外形美观。有数据显示,因收缩变形导致箱体报废是冰箱制造企业成本高居不下的主要原因之一,这也是目前整个冰箱制造行业亟待解决的技术难题。
发明内容
为解决上述存在的难题,本发明提出了一种聚氨酯硬质泡沫组合物,利用该组合物制备的泡沫具有密度分布性能优异、物料反应均衡稳定、导热系数低、脱模时间短、尺寸稳定性佳等特点;本发明同时提供其制备方法。
为达到上述目的,本发明的技术方案如下:
一种用于冰箱的聚氨酯硬质泡沫由组分A和组分B组成,组分A和组分B的重量比为1:0.8~1.3,优选为1:1.0~1.25,其中,所述组分A包含下列组分,按重量份计:
聚醚多元醇A 20~50;
聚醚多元醇B 10~30;
聚醚多元醇C 20~40;
聚醚多元醇D 5~20;
聚酯多元醇E 5~20;
添加剂 3~10;
泡沫稳定剂 1~5;
发泡剂 5~30;
催化剂 1~5;
水 0.5~3。
所述组分B是多亚甲基多苯基多异氰酸酯。
所述聚醚多元醇A为蔗糖聚醚多元醇,羟值350~450KOH/g,官能度4~7;所述聚醚多元醇B为山梨醇聚醚多元醇,羟值380~480KOH/g,官能度5~6;所述聚醚多元醇C为苯胺聚醚多元醇,羟值360~460KOH/g,官能度3~4;所述聚醚多元醇D为甘油聚醚多元醇,羟值150~250KOH/g,官能度3;所述聚酯多元醇E为苯酐聚酯多元醇,羟值250~350KOH/g,官能度2。由此,低粘度、低官能度聚醚多元醇D使聚氨酯泡沫体系拥有优异的流动性能;高芳香基含量的苯酐聚酯多元醇E和高羟值、高粘度蔗糖聚醚多元醇A的使用提高了泡沫体系的机械性能和尺寸稳定性,弥补了聚醚多元醇D在此方面的不足;苯胺类聚醚C因其具有自催化作用,有助于聚氨酯泡沫体系的后期熟化,也使泡沫具有优异的绝热保温能力。
所述添加剂为聚氧化丙烯二醇,分子量200-2000,官能度2。该添加剂能够提高聚氨酯泡沫的流动分散性能和对发泡剂气体的融合包裹能力。但该添加剂因其二官能度结构易于二异氰酸酯反应生成线性直链结构,影响聚氨酯泡沫的强度和膨胀率,故其用量不能过多,须于其它聚醚及催化剂合理搭配使用。
所述泡沫稳定剂为有机硅氧烷聚氧化烯烃接枝共聚物,优选的,包括但不限于L6912、L6988、AK8815、AK8485、B8461、B8465中的一种或几种混合物。
所述发泡剂可以使用冰箱领域常用发泡剂,包括但不限于环戊烷、异戊烷、HCFC-141b、HFC-245fa、LBA中的一种或几种混合物。
所述催化剂为发泡型催化剂、凝胶型催化剂和三聚型催化剂的组合物,其中,所述发泡型催化剂为选自五甲基二乙烯三胺、双-二甲基氨基乙基醚、N-甲基二环己基胺、改性双(二甲氨基乙基)醚和四甲基己二胺中的至少一种;所述凝胶型催化剂为选自二甲基环已胺、1 ,2-二甲基咪唑和二甲基苄胺中的至少一种;所述三聚催化剂为选自(2-羟基丙基)三甲基甲酸铵、三(二甲氨基丙基)六氢化三嗪、2,4,6-三(二甲氨基甲基)苯酚中的至少一种;优选的,所述催化剂为五甲基二乙烯三胺(PC-5)、二甲基环已胺(PC-8)、三(二甲氨基丙基)六氢化三嗪(PC-41)和(2-羟基丙基)三甲基甲酸铵(TMR-2)按重量份分别为(0 .2~1 .0)、(0.8~2.5) 、(0 .2~1 .0) 、(0 .2~1 .0)组成的混合物。其中,PC-41和TMR-2属于复配型三聚催化剂,二者搭配使用使泡沫拥有更好的后熟化能力和抗压强度。优选的催化剂体系使整个反应过程更加均衡,为聚氨酯泡沫体系提供了优良的流动分散性能,增强了泡沫的绕障碍和穿过能力,并缩短了脱模时间。
所述组分B为多亚甲基多苯基多异氰酸酯,行业内俗称“黑料”。可选市场自售的,如Bayer公司的44V-20L、BASF公司的M20S、Huntsman公司的Suprasec-5005、烟台万华公司的PM2010、PM200等。
所述的用于冰箱的聚氨酯硬质泡沫材料的制备方法,包括以下步骤:
首先,将计量好的聚醚多元醇A、聚醚多元醇B、聚醚多元醇C和聚醚多元醇D、聚醚多元醇E搅拌均匀,其次加入称量好的添加剂、泡沫稳定剂、催化剂、水,常温下搅拌均匀,再按配比加入计量好的物理发泡剂,搅拌均匀,得到组分A;然后将组分A与组分B按照重量比1:1.0~1.25在高压机枪头中混合均匀,注入模温40~45℃的密闭模具中,待熟化后脱模即可制备出冰箱用聚氨酯硬质泡沫材料。
本发明在聚氨酯泡沫组合物种加入硬泡领域中不常用的聚氧化丙烯二醇作为添加剂,通过复合聚醚体系的协调搭配,同时选择合适的催化剂体系及用量进行泡孔优化,有效提高了组合物料的流动分散性能,该流动分散性能使反应前期具有较均衡的起始粘度,有利于物料对已成核的发泡剂气体进行有效包裹和释放,形成的泡沫绕障碍和穿过能力强、密度分布均匀、泡孔细腻。
本发明的有益效果是:
(1)本发明制备的冰箱用聚氨酯硬质泡沫保温材料,密度填充分布均匀,对发泡剂气体的包裹和释放能力强,有效解决了大尺寸冰箱边角收缩和局部排气不畅的问题;
(2)泡沫有效流动性和填充分布能力的提升,使泡沫在较低密度条件下仍具有较高的抗压强度和耐高低温尺寸稳定性,同时可降低泡沫整体密度3-8%;
(3)本发明制备方法简便、易操作,生产过程无须对设备进行改造,无三废污染,安全环保。
具体实施方式
下面结合具体实施方式,进一步阐明本发明,应理解下述具体实施方式仅用于说明本发明而不用于限制本发明的范围。
首先对实施例中的原材料进行说明:
( 1 ) 组合多元醇:
蔗糖聚醚多元醇,羟值350~450KOH/g,官能度4~7;
山梨醇聚醚多元醇,羟值380~480KOH/g,官能度5~6;
苯胺聚醚多元醇,羟值360~460KOH/g,官能度3~4;
甘油聚醚多元醇,羟值150~250KOH/g,官能度3;
苯酐聚酯多元醇,羟值250~350KOH/g,官能度2。
( 2 ) 添加剂:
聚氧化丙烯二醇,分子量200-2000,在本发明的一些实施例中,选用的是PPG-1000。
( 3 ) 泡沫稳定剂:
根据本发明的实施例,所述泡沫稳定剂为有机硅氧烷聚氧化烯烃接枝共聚物,泡沫稳定剂的种类没有特别限制,只要能够有效提高组合聚醚的发泡稳定性和存放稳定性,本领域技术人员可以根据需要灵活选择。在本发明的一些实施例中,选用的是B8461。
( 4 ) 催化剂:
发泡型催化剂:五甲基二乙烯三胺(PC-5);
凝胶型催化剂:二甲基环已胺(PC-8);
三聚型催化剂:三(二甲氨基丙基)六氢化三嗪(PC-41)和(2-羟基丙基)三甲基甲酸铵(TMR-2)复配;
( 5 ) 多亚甲基多苯基多异氰酸酯:
本发明实施例中使用的多亚甲基多苯基多异氰酸酯是BASF公司的M20S,NCO含量为30%~32%。
本发明中泡沫的密度、导热系数、压缩强度、膨胀率以高低温尺寸变化率分别按照国家标准GB/T 6343-2009、GB/T 3399-1982、GB/T 8813-2008、GB/T 20673-2006、GB/T8811-2008进行测定。
实施例1~3及对比例1配比
表1
按表中配比将添加剂、催化剂、泡沫稳定剂、水加入组合多元醇中,混合均匀,再按表中配比加入物理发泡剂,混合均匀,配制成组分A。将组分A和组分B按照表中的重量比在高压机枪头混合反应,注入尺寸为1100×300×50mm、模温为40-45℃的I-Mould中,制得聚氨酯硬质泡沫用来测定恰充填量、模塑芯密度、导热系数、压缩强度、密度分布极差、高低温尺寸稳定性等。采用相同的方法将泡液注入尺寸为700×500×100mm、模温为40-45℃的H-Mould中,获得的泡沫用于测试不同脱模时间泡沫的脱模性,其目的是测定膨胀率。
实施例1~3及对比例1性能测试结果
表2
由上表的实施例1-3和对比例1可以看出,实施例1-3密度分布极差和高低温尺寸变化率比对比例1的显著降低,原因在于实施例1-3中都采用了不同份量的聚氧化丙烯二醇作为添加剂,发泡料的分散填充性能明显提高,泡沫密度分布更加均匀,耐高低温能力也相应提高;实施例1-3的泡沫压缩强度相比对比例1显著提高,因添加剂提高了聚氨酯泡沫的有效流动性,泡沫在凝胶之前完全充满模具空间,凝胶后因生长空间受限,泡沫体积无法继续膨胀,自行产生的发泡压力,有利于形成近似圆球形结构的泡孔,此种泡沫方向性小,垂直平行方向的强度高,尺寸稳定性好,不易变形,使泡沫在较低密度条件下仍具有较高的抗压强度;此外,这种近似圆球形的泡孔结构,也有利于泡沫具有较低的导热系数。
Claims (8)
1.一种用于冰箱的聚氨酯硬质泡沫,其特征在于由组分A和组分B组成,组分A与组分B的重量比1:1.0~1.25,所述组分A包括:
聚醚多元醇组合物;
添加剂;
发泡剂;
泡沫稳定剂;
催化剂;
水;
所述组分B为多亚甲基多苯基异氰酸酯。
2.根据权利要求1所述的一种用于冰箱的聚氨酯硬质泡沫,其特征在于,
所述聚醚多元醇组合物100重量份;
所述添加剂3~10重量份;
所述发泡剂5~30重量份;
所述泡沫稳定剂1~5重量份;
所述催化剂1~5重量份;
所述水0.5~3重量份。
3.根据权利要求1所述的一种用于冰箱的聚氨酯硬质泡沫,其特征在于,所述聚醚多元醇组合物包括:蔗糖聚醚多元醇20~50重量份,羟值350~450KOH/g;山梨醇聚醚多元醇 10~30重量份,羟值380~480KOH/g;苯胺聚醚多元醇 20~40重量份羟值360~460KOH/g;甘油聚醚多元醇5~20重量份,羟值150~250KOH/g和苯酐聚酯多元醇5~20重量份,羟值250~350KOH/g。
4.根据权利要求1所述的一种用于冰箱的聚氨酯硬质泡沫,其特征在于,所述催化剂为发泡型催化剂、凝胶型催化剂和三聚型催化剂的混合物,其中,所述发泡型催化剂为选自五甲基二乙烯三胺、双-二甲基氨基乙基醚、N-甲基二环己基胺、改性双(二甲氨基乙基)醚和四甲基己二胺中的至少一种;所述凝胶型催化剂为选自二甲基环已胺、1 ,2-二甲基咪唑和二甲基苄胺中的至少一种;所述三聚催化剂为选自(2-羟基丙基)三甲基甲酸铵、三(二甲氨基丙基)六氢化三嗪、2,4,6-三(二甲氨基甲基)苯酚中的至少一种。
5.根据权利要求1所述的一种用于冰箱的聚氨酯硬质泡沫,其特征在于,所述泡沫稳定剂为有机硅氧烷聚氧化烯烃接枝共聚物,包括但不限于L6912、L6988、AK8815、AK8485、B8461、B8465中的一种或几种混合物。
6.根据权利要求1所述的一种用于冰箱的聚氨酯硬质泡沫,其特征在于:所述添加剂为聚氧化丙烯二醇,分子量为200-2000,官能度为2。
7.根据权利要求1所述的一种用于冰箱的聚氨酯硬质泡沫,其特征在于:所述发泡剂为冰箱领域常用发泡剂,包括但不限于环戊烷、异戊烷、HCFC-141b、HFC-245fa、LBA中的一种或几种混合物。
8.根据权利要求2所述的一种用于冰箱的聚氨酯硬质泡沫的制备方法,其特征在于:包括以下步骤:
首先,将计量好的聚醚多元醇组合物搅拌均匀,其次加入称量好的添加剂、泡沫稳定剂、催化剂、水,常温下搅拌均匀,再按配比加入计量好的发泡剂,搅拌均匀,得到组分A;然后将组分A与组分B按照重量比1:1.0~1.25在高压机枪头中混合均匀,注入模温40~45℃的密闭模具中,待熟化后脱模即可制备出冰箱用聚氨酯硬质泡沫材料。
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