CN108084399A - 一种高硬度硬质聚氨酯泡沫原料组合物 - Google Patents

一种高硬度硬质聚氨酯泡沫原料组合物 Download PDF

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CN108084399A
CN108084399A CN201711316628.2A CN201711316628A CN108084399A CN 108084399 A CN108084399 A CN 108084399A CN 201711316628 A CN201711316628 A CN 201711316628A CN 108084399 A CN108084399 A CN 108084399A
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李文
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Abstract

本发明提供了一种高硬度硬质聚氨酯泡沫的原料组合物，含有轻质碳酸钙、膨润土两种无机增强剂，能够用于注射成型法制造聚氨酯泡沫。采用上述原料组合物制备的硬质聚氨酯泡沫硬度高，保温效果好。上述原料组合物制备的硬质聚氨酯泡沫可作为承重保温材料使用。

Description

一种高硬度硬质聚氨酯泡沫原料组合物
技术领域
本发明涉及一种聚氨酯泡沫原料组合物，具体涉及一种高硬度硬质聚氨酯泡沫的原料组合物，属于聚合物领域。
背景技术
硬质聚氨酯泡沫(RPUF)具有重量轻、导热系数低、粘结强度高、电学性能好、耐化学药品性能强、冲击吸能性能以及隔音和绝热性能好、成型加工方便等特点，广泛用于交通运输、建筑、包装、冷藏等方面作为绝热保温及隔音减震材料。此外，硬质聚氨酯泡沫也可作为承载结构材料，用于列车车门、飞机机件、管材、桥梁型材，等需要承受负荷的部件，使结构件轻量化，节约能源。但是，使用时还要求硬质聚氨酯泡沫有优良的强度、模量和尺寸稳定性。与其他材料相比，硬质聚氨酯泡沫的弯曲强度和冲击强度等技术指标还不能满足使用要求，因而限制了它的广泛应用。
近年来，采用各种材料和方法对硬质聚氨酯泡沫进行增强改性，使其向复合化发展，大幅度降低成本，提高力学性能和尺寸稳定性，加强耐冲击能力。短切玻纤和玻璃中空微珠是在硬质聚氨酯泡沫中使用最多的增强材料，但玻璃对机械设备磨损严重，在输送中容易沉淀发生管道堵塞，因此它们不太适合增强反应注射成型的要求。因此，需要开发新的增强材料。。
发明内容
针对目前缺乏反应注射成型高硬度硬质聚氨酯泡沫的问题，本发明提供一种高硬度硬质聚氨酯泡沫的原料组合物，硬度高、保温效果优良。
为实现上述目的，本发明采用如下技术方案。
一种高强度硬质聚氨酯泡沫的原料组合物，包括：
PAPI（多苯基多亚甲基异氰酸酯）、增强剂和组合聚醚；所述组合聚醚包括多元醇、发泡剂、催化剂和阻燃剂；
所述增强剂为轻质碳酸钙、膨润土的混合。所述膨润土与轻质碳酸钙的质量比优选为（1-2）:（3-5）。所述增强剂用量为所述原料组合物的5-7%（wt）。所述轻质碳酸钙的粒径范围为50-70nm，所述膨润土的粒径范围为20-50nm。
所述阻燃剂为甲基膦酸二甲酯和石墨1:（2-3）的混合。
所述发泡剂选自氢氟烃与环戊烷的混合。所述氢氟烃与所述环戊烷的质量比优选为（2-3）：1。所述氢氟烃为HFC-365mfe或HFC-245fa。
所述多元醇选自聚醚多元醇和聚酯多元醇中的至少一种；优选为聚醚多元醇和聚酯多元醇的混合。所述聚酯多元醇为芳香聚酯多元醇，所述芳香聚酯多元醇的粘度（25℃）为3000-5000 mpa.s，羟值为200-350 mg KOH/g。所述聚醚多元醇的粘度（25℃）为8000-12000 mpa.s，羟值为300-500 mg KOH/g。所述聚酯多元醇和所述聚醚多元醇优选的质量比为5-10:90-95。
所述催化剂为三亚乙基二胺与二甲基环己胺按照质量比1.5:（0.5-1）的组合催化剂。
作为优选，所述组合聚醚包括100份多元醇、20-50份发泡剂、1-5份催化剂和20-40份阻燃剂。
所述PAPI的NCO含量为30-32%，异氰酸酯指数为1.0-1.2，优选为1.05-1.1。
所述组合聚醚还含有泡沫稳定剂；所述泡沫稳定剂为硅烷类泡沫稳定剂；基于100份多元醇，所述泡沫稳定剂用量为1-2份。
一种采用上述任一所述硬质聚氨酯泡沫的原料组合物生产的高硬度硬质聚氨酯泡沫材料。
一种上述高硬度硬质聚氨酯泡沫材料在承重保温材料中的应用。
本发明具有以下优点：
本发明提供了一种高硬度硬质聚氨酯泡沫材料的原料组合物，各成分无毒无害，可用于注塑成型法生产；采用了轻质碳酸钙、膨润土两种无机增强剂配合，增强了所制得的硬质聚氨酯泡沫的硬度；同时，作为阻燃剂的石墨也可以起到增强硬度的作用。所得产品防水与保温性能优于市场上其他产品，可作为承重保温材料使用。
具体实施方式
下面结合实施例对本发明做进一步说明，但本发明不受下述实施例的限制。
实施例1
按照下列配方分别配制各组分（重量份）：
（1）催化剂
三亚乙基二胺 1.5份
二甲基环己胺 1份
（2）阻燃剂
甲基磷酸二甲酯 1份
石墨 2份
（3）增强剂
膨润土 1份
轻质碳素钙 5份
（4）组合聚醚
芳香聚酯多元醇（粘度5000 mpa.s，羟值350 mg KOH/g） 5份
聚醚多元醇（粘度10000 mpa.s，羟值500 mg KOH/g） 95份
HFC-365mfe 30份
环戊烷 10份
催化剂 2份
阻燃剂 30份
泡沫稳定剂 1份
制备方法：
按照上述配料表将增强剂混合均匀，然后按照原料总量的5%加入PAPI（NCO含量为30%）中，超声分散；再加入组合聚醚中，使异氰酸酯指数为1.05，然后将原料注入发泡机中混合均匀之后，通过注射成型制备硬质聚氨酯。所得产品的密度为45kg/m3，导热系数为35mW/（mK），氧指数为26.2，压缩强度为12MPa，拉伸强度为10MPa。
实施例2
（1）催化剂
三亚乙基二胺 1.5份
二甲基环己胺 0.8份
（2）阻燃剂
甲基磷酸二甲酯 1份
石墨 3份
（3）增强剂
膨润土 2份
轻质碳素钙 5份
（4）组合聚醚
芳香聚酯多元醇（粘度3000 mpa.s，羟值350 mg KOH/g） 8份
聚醚多元醇（粘度12000 mpa.s，羟值500 mg KOH/g） 92份
HFC-365mfe 20份
环戊烷 10份
催化剂 2.5份
阻燃剂 40份
泡沫稳定剂 1份
制备方法：
按照上述配料表将增强剂混合均匀，然后按照原料总量的7%加入PAPI（NCO含量为30%）中，超声分散；再加入组合聚醚中，使异氰酸酯指数为1.1，然后将原料注入发泡机中混合均匀之后，通过注射成型制备硬质聚氨酯。所得产品的密度为47kg/m3，导热系数为30mW/（mK），氧指数为26.2，压缩强度为15.3MPa，拉伸强度为11.2MPa。
实施例3
按照下列配方分别配制各组分（重量份）：
（1）催化剂
三亚乙基二胺 1.5份
二甲基环己胺 0.95份
（2）阻燃剂
甲基磷酸二甲酯 1.5份
石墨 3.5份
（3）增强剂
膨润土 2份
轻质碳素钙 5份
（4）组合聚醚
芳香聚酯多元醇（粘度3000 mpa.s，羟值350 mg KOH/g） 10份
聚醚多元醇（粘度10000 mpa.s，羟值500 mg KOH/g） 90份
HFC-245fa 35份
环戊烷 15份
催化剂 2.5份
阻燃剂 20份
泡沫稳定剂 1份
制备方法：
按照上述配料表将增强剂混合均匀，然后按照原料总量的6%加入PAPI（NCO含量为32%）中，超声分散；再加入组合聚醚中，使异氰酸酯指数为1.1，然后将原料注入发泡机中混合均匀之后，通过注射成型制备硬质聚氨酯。所得产品的密度为50kg/m3，导热系数为32mW/（mK），氧指数为27.3，压缩强度为12.8MPa，拉伸强度为11MPa。

Claims (9)

1.一种高强度硬质聚氨酯泡沫的原料组合物，其特征在于，包括：PAPI、增强剂和组合聚醚；所述组合聚醚包括多元醇、发泡剂、催化剂和阻燃剂；所述增强剂为轻质碳酸钙、膨润土的混合。
2.根据权利要求1所述的的原料组合物，其特征在于，膨润土与轻质碳酸钙的质量比为（1-2）:（3-5）。
3.根据权利要求1所述的的原料组合物，其特征在于，增强剂用量为所述原料组合物质量的5-7%。
4. 根据权利要求1所述的的原料组合物，其特征在于，所述多元醇选自聚醚多元醇和聚酯多元醇中的至少一种；所述聚酯多元醇为芳香聚酯多元醇，所述芳香聚酯多元醇的粘度（25℃）为3000-5000 mpa.s，羟值为200-350 mg KOH/g；所述聚醚多元醇的粘度（25℃）为8000-12000 mpa.s，羟值为300-500 mg KOH/g。
5.根据权利要求1所述的的原料组合物，其特征在于，所述阻燃剂为甲基膦酸二甲酯和石墨1:（2-3）的混合；所述发泡剂选自氢氟烃与环戊烷的混合；所述催化剂为三亚乙基二胺与二甲基环己胺按照质量比1.5:（0.5-1）的组合催化剂。
6.根据权利要求1所述的的原料组合物，其特征在于，所述组合聚醚包括100份多元醇、20-50份发泡剂、1-5份催化剂和20-40份阻燃剂；所述PAPI的NCO含量为30-32%，异氰酸酯指数为1.0-1.2。
7.根据权利要求1所述的的原料组合物，其特征在于，所述组合聚醚还含有泡沫稳定剂。
8.一种采用如权利要求1-7任一所述硬质聚氨酯泡沫的原料组合物生产的高硬度硬质聚氨酯泡沫材料。
9.一种如权利要求8所述的高硬度硬质聚氨酯泡沫材料在承重保温材料中的应用。
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