CN110862504A - 一种阻燃硬质聚氨酯泡沫塑料的制备方法 - Google Patents

一种阻燃硬质聚氨酯泡沫塑料的制备方法 Download PDF

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CN110862504A
CN110862504A CN201810985505.6A CN201810985505A CN110862504A CN 110862504 A CN110862504 A CN 110862504A CN 201810985505 A CN201810985505 A CN 201810985505A CN 110862504 A CN110862504 A CN 110862504A
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张璟晨
邬素华
田赛华
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Tianjin University of Science and Technology
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Abstract

本发明涉及一种阻燃硬质聚氨酯泡沫塑料的制备方法，所述硬质聚氨酯泡沫塑料按重量份数由以下原料组成：聚醚多元醇100份；发泡剂36～46份；催化剂1.4份；匀泡剂2～3份；固化剂0.5～1份；反应性含氮阻燃剂30wt％～40wt％；添加型阻燃剂8wt％～12wt％；异氰酸酯比为1.4～1.5。其中反应型阻燃剂为合的一种三聚氰胺基衍生物。添加型阻燃剂为甲基膦酸二甲酯(DMMP)。本发明通过在阻燃硬质聚氨酯泡沫塑料中应用反应性阻燃剂和添加型阻燃剂，利用反应型阻燃剂的羟甲基能与异氰酸根发生化学反应形成氨基甲酸酯基团，实现了将阻燃元素N以共价键形式引入到交联聚氨酯网状架构中，替代部分添加型阻燃剂，既能使阻燃性能与单纯使用添加型阻燃剂的泡沫塑料的阻燃性能相当甚至增大，又因为减少了添加型阻燃剂的用量，而使得泡沫塑料的机械性能不会大幅下降，或不会因阻燃剂外迁引起阻燃性能下降；且表观密度相当，因此制备得到的阻燃硬质聚氨酯泡沫塑料具有良好的机械性能和阻燃性能。

Description

一种阻燃硬质聚氨酯泡沫塑料的制备方法
技术领域
本发明属于建筑材料技术领域，具体涉及一种阻燃硬质聚氨酯泡沫塑料的制备方法。
背景技术
硬质聚氨酯泡沫塑料是一种由大量微细孔及聚氨酯树脂孔壁经络组成的多孔性聚氨酯材料。因其质轻，比强度高，且其导热率是目前已知泡沫塑料中最低的，被广泛应用于建筑保温隔热领域。但是，由于其特殊的孔状结构，遇火极易燃烧，极限氧指数仅为18％，对人民财产和人身安全造成极大伤害。目前，在传统应用中，主要依赖添加型阻燃剂提高硬质聚氨酯泡沫塑料的阻燃效果，虽然阻燃性能有大幅提升，但加入量大，对材料的机械性能产生了不良影响，并且添加型阻燃剂会随着时间的推移而外迁，阻燃效果大打折扣。
现在对该领域的研究方向主要是开发出一种反应性阻燃剂来代替部分添加型阻燃剂，既能达到既定的阻燃效果，又可以减小对机械性能的不良影响。反应型阻燃剂是利用化学键将阻燃元素(氮、磷、卤素等)引入到聚氨酯分子链中，实现结构阻燃。虽然可以替代部分添加型阻燃剂，但是反应型阻燃剂制造成本高，工艺流程复杂、不易控制，且阻燃效果有限而受到应用限制。因此，探索简便易控的反应型阻燃剂以获得阻燃性能及综合性能更好的硬质聚氨酯泡沫塑料具有重要的理论意义和应用价值。
发明内容
本发明的目的在于克服上述现有技术的不足，公开一种阻燃硬质聚氨酯泡沫塑料，即利用反应型含氮阻燃剂替代部分添加型阻燃剂，在阻燃效果相当甚至增加的同时，减小添加型技术带来的不足。
为实现上述目的，本发明采用如下技术方案：
阻燃硬质聚氨酯泡沫塑料按照重量分数由以下原料组成：
Figure BSA0000169518580000011
优选地，所述反应性含氮阻燃剂为多羟甲基三聚氰胺。其反应方程式为：
Figure BSA0000169518580000021
优选地，所述添加行阻燃剂为DMMP。
优选地，所述发泡剂为物理性发泡剂。
优选地，所述催化剂为胺类和锡类混合发泡剂。
优选地，所述固化剂为乙二醇。
优选地，所述匀泡剂二甲基硅油。
优选地，所述聚醚多元醇为聚醚多元醇8345，其羟值为450±10mgKOH/g，25℃时粘度为8000±1000mPa.s。
优选地，所述异氰酸酯为聚合MDI(PAPI)，型号为PM200，25℃粘度为150～250mPa.s，-NCO质量百分数含量为30.5％～32％。
上述阻燃硬质聚氨酯泡沫塑料的制备方法，其主要步骤为：
(1)将聚醚多元醇，催化剂，发泡剂，固化剂，匀泡剂，反应型含氮阻燃剂，添加型阻燃剂混合均匀，得到混合料A料；
(2)准备好异氰酸酯料，记为B料；
(3)将B料倒入A料中，快速手动搅拌8～10s，倒入模具中发泡，室温下冷却后放入70～80℃的烘箱中熟化12h，之后取出脱模，最终制得本发明专利的阻燃硬质聚氨酯泡沫塑料。
通过改变反应型阻燃剂和添加型阻燃剂配比，可以制得一系列不同阻燃效果的阻燃硬质聚氨酯泡沫塑料。
与现有技术相比，本发明具有如下有益效果：本发明采用反应型含氮阻燃剂与添加型阻燃剂复配，替代部分添加型阻燃剂，得到相当的阻燃效果，并得到力学性能良好的阻燃硬质聚氨酯泡沫塑料。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。在下面各实施例中，所述聚醚多元醇为YD-8345；所述异氰酸酯为PM200型聚合MDI(PAPI)；除非特别说明，实施例中所涉及的材料、方法均为本领域常用的材料和方法。
实例1
一种阻燃硬质聚氨酯泡沫塑料配方为：将聚醚多元醇100份，发泡剂36份，催化剂1.4份，固化剂0.8份，匀泡剂2.3份，反应性阻燃剂35wt％混合后搅拌均匀得到混合料A。称取异氰酸酯140份为B料。将AB料混合均匀，物料发白膨胀时倒入模具中自由发泡，固化后在70～80℃下熟化12h，脱模即得阻燃硬质聚氨酯泡沫塑料。其氧指数为23％。(GB/T2406.1-2008)
实例2
一种阻燃硬质聚氨酯泡沫塑料配方为：将聚醚多元醇100份，发泡剂36份，催化剂1.4份，固化剂0.8份，匀泡剂2.3份，反应性阻燃剂40wt％混合后搅拌均匀得到混合料A。称取异氰酸酯150份为B料。将AB料混合均匀，物料发白膨胀时倒入模具中自由发泡，固化后在70～80℃下熟化12h，脱模即得阻燃硬质聚氨酯泡沫塑料。其氧指数为24％。(GB/T2406.1-2008)
实例3
一种阻燃硬质聚氨酯泡沫塑料配方为：将聚醚多元醇100份，发泡剂36份，催化剂1.4份，固化剂0.8份，匀泡剂2.3份，反应性阻燃剂35wt％，添加型阻燃剂8wt％混合后搅拌均匀得到混合料A。称取异氰酸酯140份为B料。将AB料混合均匀，物料发白膨胀时倒入模具中自由发泡，固化后在70～80℃下熟化12h，脱模即得阻燃硬质聚氨酯泡沫塑料。其氧指数为27.3％。(GB/T2406.1-2008)
实例4
一种阻燃硬质聚氨酯泡沫塑料配方为：将聚醚多元醇100份，发泡剂36份，催化剂1.4份，固化剂0.8份，匀泡剂2.3份，反应性阻燃剂35wt％，添加型阻燃剂12wt％混合后搅拌均匀得到混合料A。称取异氰酸酯140份为B料。将AB料混合均匀，物料发白膨胀时倒入模具中自由发泡，固化后在70～80℃下熟化12h，脱模即得阻燃硬质聚氨酯泡沫塑料。其氧指数为27.8％。(GB/T2406.1-2008)
实例5
一种阻燃硬质聚氨酯泡沫塑料配方为：将聚醚多元醇100份，发泡剂36份，催化剂1.4份，固化剂0.8份，匀泡剂2.3份，反应性阻燃剂40wt％，添加型阻燃剂12wt％混合后搅拌均匀得到混合料A。称取异氰酸酯150份为B料。将AB料混合均匀，物料发白膨胀时倒入模具中自由发泡，固化后在70～80℃下熟化12h，脱模即得阻燃硬质聚氨酯泡沫塑料。其氧指数为29.5％。(GB/T2406.1-2008)
表1为阻燃硬质聚氨酯泡沫塑料性能测试结果
Figure BSA0000169518580000041

Claims (9)

1.阻燃硬质聚氨酯泡沫塑料，其特征在于，复合阻燃硬质聚氨酯泡沫塑按照重量分数由以下原料组成：
Figure FSA0000169518570000011
2.根据权利要求1所述的阻燃硬质聚氨酯泡沫塑料，其特征在于，所述反应型含氮阻燃剂为多羟甲基三聚氰胺，其中1mol多羟甲基三聚氰胺中羟甲基含量在1mol至2mol之间，含氮量在31％～40％，以保证既有足够的-CH2OH与-N＝C＝O-反应，又不会降低含氮量影响阻燃性能。
3.根据权利要求1所述阻燃硬质聚氨酯泡沫塑料，其特征在于，所述添加型阻燃剂为甲基磷酸二甲酯DMMP。
4.根据权利要求1所述阻燃硬质聚氨酯泡沫塑料，其特征在于，所述发泡剂为物理发泡剂HCH-141b。
5.根据权利要求1所述阻燃硬质聚氨酯泡沫塑料，其特征在于，所述固化剂为乙二醇。
6.根据权利要求1所述阻燃硬质聚氨酯泡沫塑料，其特征在于，所述聚醚多元醇为聚醚8345，其羟值为450±10mgKOH/g，25℃时粘度为8000±1000mPa.s。
7.根据权利要求1所述阻燃硬质聚氨酯泡沫塑料，其特征在于，所述异氰酸酯为聚合MDI(PAPI)，型号为PM200，25℃粘度为150～250mPa.s，-NCO质量百分数含量为30.5％～32％。
8.权利要求1至7中任意一项权利要求所述硬质聚氨酯泡沫塑料的制备方法，其特征在于，将复合阻燃剂与聚醚多元醇、异氰酸酯、发泡剂等所有原料采用一步法发泡工艺成型。
9.根据权利要求8所述硬质聚氨酯泡沫塑料的制备方法，其特征在于，所述硬质聚氨酯泡沫塑料为将复合阻燃剂与其它制备聚氨酯泡沫所需原料经手动搅拌箱式发泡的方式，后在70～80℃下熟化12h后制得产品。
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CN110982122A (zh) * 2019-11-30 2020-04-10 广东宇星阻燃安全材料研究院有限公司 一种磷酸锆-三聚氰胺氰尿酸盐反应型阻燃剂及其制备方法和应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110982122A (zh) * 2019-11-30 2020-04-10 广东宇星阻燃安全材料研究院有限公司 一种磷酸锆-三聚氰胺氰尿酸盐反应型阻燃剂及其制备方法和应用

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