CN108395515A - 一种阻燃聚异氰脲酸酯硬质泡沫及其制备方法 - Google Patents

一种阻燃聚异氰脲酸酯硬质泡沫及其制备方法 Download PDF

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CN108395515A
CN108395515A CN201810287441.2A CN201810287441A CN108395515A CN 108395515 A CN108395515 A CN 108395515A CN 201810287441 A CN201810287441 A CN 201810287441A CN 108395515 A CN108395515 A CN 108395515A
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retardant
parts
fire
rigid foams
foaming agent
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牟孟孟
蒋国红
李宋光
宋健
王芝花
牟坤斋
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Jiangsu Zhongchang Insulation Engineering Technology Co Ltd
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Abstract

本发明涉及一种阻燃聚异氰脲酸酯硬质泡沫及其制备方法,所述阻燃聚异氰脲酸酯硬质泡沫由如下重量份的组分组成多异氰酸酯150‑170份,聚醚多元醇5‑8份,阻燃剂15‑20份,催化剂2‑3份,稳定剂1‑2份,发泡剂15‑20份;所述阻燃剂为含氮阻燃剂与含磷阻燃剂按1:1的质量比混合。制备方法包括如下步骤:S1助剂混合;S2聚氨酯硬质泡沫的制备。本发明具有阻燃效果好、硬质泡沫性能优良以及适用于工业化生产的优点。

Description

一种阻燃聚异氰脲酸酯硬质泡沫及其制备方法
技术领域
本发明涉及阻燃聚酯泡沫技术领域,具体涉及一种阻燃聚异氰脲酸酯硬质泡沫及其制备方法。
背景技术
多数聚合物树脂都是遇火易燃物质,阻燃树脂可大大降低其易燃性,并使其着火后可自行熄灭,从而抑制火焰蔓延、减轻燃烧产生的烟或有毒气体的危害。阻燃技术处理常添加阻燃剂或添加无机填料,如碳酸钙、硅酸盐、云母等,也可与阻燃性好的单体(如氯乙烯)进行共聚、接枝,与高难燃树脂共混等。以难燃树脂制备的塑料制品、涂料、胶粘剂等在建筑、交通工具、电子电器、日用家具等领域的应用日趋广泛。
阻燃树脂是指经过技术处理后能阻止或减缓燃烧速度的树脂。经过技术处理后能阻止或减缓燃烧速度的树脂。多数聚合物树脂都是遇火易燃物质,阻燃树脂可大大降低其易燃性,并使其着火后可自行熄灭,从而抑制火焰蔓延、减轻燃烧产生的烟或有毒气体的危害。阻燃技术处理常添加阻燃剂或添加无机填料,如碳酸钙、硅酸盐、云母等,也可与阻燃性好的单体(如氯乙烯)进行共聚、接枝,与高难燃树脂共混等。以难燃树脂制备的塑料制品、涂料、胶粘剂等在建筑、交通工具、电子电器、日用家具等领域的应用日趋广泛。
高阻燃聚异氰脲酸酯硬质泡沫,具有阻燃性好、导热系数小、密度轻、机械性能高、耐水性和耐老化性好,是国际上广泛应用的阻燃保温材料,其特点是异氰酸酯指数(R)高(一般300以上),阻燃剂含量多。高阻燃聚异氰脲酸酯硬质泡沫主要用的多元醇一般为芳香族聚酯多元醇,如邻苯二甲酸酐、对苯二甲酸等与二元醇经缩聚制取,生产成本高,而且由于异氰酸酯指数高,阻燃剂多等,满足阻燃性能的同时,制得的硬泡的压缩强度及抗拉强度弱。
发明内容
本发明的目的在于克服现有技术的不足,提供一种阻燃聚异氰脲酸酯硬质泡沫及其制备方法,解决了。
本发明的目的是通过以下技术方案来实现的:
一种阻燃聚异氰脲酸酯硬质泡沫,由如下重量份的组分组成:多异氰酸酯150-170份,聚醚多元醇5-8份,阻燃剂15-20份,催化剂2-3份,稳定剂1-2份,发泡剂15-20份;
所述阻燃剂为含氮阻燃剂与含磷阻燃剂按1:1的质量比混合。
阻燃聚异氰脲酸酯硬质泡沫中不使用阻燃聚酯多元醇,添加阻燃剂使其具有良好的阻燃性能,将含磷阻燃剂和含氮阻燃剂两种阻燃剂结合作为灭火药剂的主要功能成分,阻燃性能优于单独使用相同含量的含磷阻燃剂或含氮阻燃剂,添加的其他的物质中杂质离子含量少,并不会对灭火药剂的功能成分产生不利影响。
进一步优选地,所述阻燃聚异氰脲酸酯硬质泡沫由如下重量份的组分组成:多异氰酸酯160份,聚醚多元醇6份,阻燃剂18份,催化剂3份,稳定剂2份,发泡剂18份;
所述阻燃剂为含氮阻燃剂与含磷阻燃剂按1:1的质量比混合。
进一步地,所述多异氰酸酯中NCO含量为32-35%。
进一步地,所述聚醚多元醇为聚醚二元醇和/或聚醚三元醇中的至少一种。
进一步地,所述聚醚二元醇为聚氧化丙烯二醇、聚氧化乙烯二醇和/或聚四氢呋喃二醇中的至少一种;所述聚醚三元醇为聚氧化丙烯三元醇和/或聚氧化乙烯三醇中的至少一种。
进一步地,所述含氮阻燃剂为磷酸氢二铵、3-吗啉-4-氯-1,2,5-噻二唑和/或氰尿酸三聚氰胺中至少一种;所述含磷阻燃剂为三磷酸钠、磷酸二氢铵、三(2,3-二溴丙基)磷酸酯和/或硫代磷酸三异氰酸酯中至少一种。
有机磷系阻燃剂大都具有低烟、无毒、低卤、无卤等优点,符合阻燃剂的发展方向,具有很好的发展前景。有机磷系阻燃剂包括磷酸酯、亚磷酸酯、磷酸酯、有机磷盐,还有磷杂环化合物及聚合物磷(膦)酸酯等,但应用最广的是磷酸酯和膦酸酯。磷添加剂的作用机理,是阻燃剂受热时能产生结构更趋稳定的交联状固体物质或碳化层。碳化层的形成一方面能阻止聚合物进一步热解,另一方面能阻止其内部的热分解产生物进入气相参与燃烧过程。含磷阻燃剂形成磷酸配作为脱水剂,并促进成炭,炭的生成降低了从火焰到凝聚相的热传导;其次,磷酸可吸热,因为它阻止了CO氧化为CO2,降低了加热过程;最后,对凝聚相形成一层薄薄的玻璃状的或液态的保护层,因此降低了氧气扩散和气相与固相之间的热量和质量传递,抑制了炭氧化过程,降低了含磷阻燃剂受热分解发生如下变化:磷系阻燃剂→磷酸偏→磷酸→聚偏磷酸,聚偏磷酸是不易挥发的稳定化合物,具有强脱水性,在聚合物表合物与空气隔绝;脱出的水气吸收大量的热,使聚合物表面阻燃剂受热分解释放出挥发性磷化物,经质谱分析表明,存氢原子浓度大大降低。
含氮阻燃剂受热时发生分解反应。含氮阻燃剂主要是三聚氰胺及其衍生物和相关的杂环化合物,主要有、三聚氰胺磷酸盐等,因为它的化学性质与尼龙相似,所以它比含卤阻燃剂和红磷更优越。三聚氰胺本身就能使尼龙的混合物达到V-O级。与各种卤系衍生物、金属氧化物、某些有机磷酸或碱金属、碱土金属盐一起使用,阻燃非常有效。有用于玻璃增强的尼龙66的三聚氰胺磷酸盐,加入后,使聚酞胺的热稳定性降低,因此在挤压模型时要注意温度控制。与含卤添加剂和红磷不同,含氮物使得聚酰胺滴落。
进一步地,所述催化剂为N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、N,N,N',N'-四甲基亚烷基二胺、三乙胺、N,N-二甲基苄胺和/或三乙醇胺中的至少一种。
进一步地,所述稳定剂为三硅氧烷或胺基聚醚。
催化剂为胺类催化剂,促进反应,使其反应条件更为温和,易于进行,加快反应速率,缩短反应时间,且阻燃聚异氰脲酸酯硬质泡沫的制备方法简单,制备得到的硬质泡沫性能优良,压缩性能、氧指数以及尺寸的稳定性好。
进一步地,所述发泡剂为无机发泡剂和有机发泡剂按照质量比为1:(6-8)混合而成;所述无机发泡剂为碳酸钙、碳酸镁和/或碳酸氢钠中的至少一种;所述有机发泡剂石油醚、三氯氟甲烷、二氯二氟甲烷和/或二氯四氟乙烷中的至少一种。
碳酸钙、碳酸镁和/或碳酸氢钠具有较好的环保性,无毒无害,而随着环境温度升高,释出气体的作用愈快,碳酸氢钠作为发泡主料的发泡效率高,且使用条件较为简单,在70-80℃即可达到非常高的发泡效率,与有机发泡剂混合使用可物质利用率高,提升总体的发气量。
上述阻燃聚异氰脲酸酯硬质泡沫的制备方法,包括如下步骤:
S1助剂混合:按上述比例将聚醚多元醇5-8份,催化剂2-3份,稳定剂1-2份加入反应釜中,在50-60℃下搅拌温度控制在40-60℃搅拌1.0-1.5h,出料,在20-25℃下保存混合物待用;
S2聚氨酯硬质泡沫的制备:将S1步骤制备得到的混合物和多异氰酸酯150-170份、发泡剂15-20份、阻燃剂15-20份在温度20-35℃下搅拌10-15min,混合后注入模具中,脱模,在65-70℃下熟化6-8h,得到所述的阻燃聚异氰脲酸酯硬质泡沫。
本发明的有益效果是:
1.阻燃聚异氰脲酸酯硬质泡沫中不使用阻燃聚酯多元醇,添加阻燃剂使其具有良好的阻燃性能,将含磷阻燃剂和含氮阻燃剂两种阻燃剂结合作为灭火药剂的主要功能成分,阻燃性能优于单独使用相同含量的含磷阻燃剂或含氮阻燃剂,添加的其他的物质中杂质离子含量少,并不会对灭火药剂的功能成分产生不利影响;
2.含磷阻燃剂选用的四种含磷阻燃剂成本较低,可工业化,含氮阻燃剂与含磷阻燃剂的用量相近,其中使用的部分阻燃剂中既含氮又含磷,具有更加优良的阻燃性能,既含氮又含磷,且成本低廉,阻燃性能十分优良;有机含氮阻燃剂为3-吗啉-4-氯-1,2,5-噻二唑和氰尿酸三聚氰胺,两者含氮量都非常高,阻燃性能十分优良,成本在可控范围内,可工业化程度高,在阻燃过程中有害气体产生量少,更环保安全;
3.催化剂为胺类催化剂,促进反应,使其反应条件更为温和,易于进行,加快反应速率,缩短反应时间,且阻燃聚异氰脲酸酯硬质泡沫的制备方法简单,制备得到的硬质泡沫性能优良,压缩性能、氧指数以及尺寸的稳定性好;
4.碳酸钙、碳酸镁和/或碳酸氢钠具有较好的环保性,无毒无害,而随着环境温度升高,释出气体的作用愈快,碳酸氢钠作为发泡主料的发泡效率高,且使用条件较为简单,在70-80℃即可达到非常高的发泡效率,与有机发泡剂混合使用可物质利用率高,提升总体的发气量。
具体实施方式
下面结合具体实施例进一步详细描述本发明的技术方案,但本发明的保护范围不局限于以下所述。
实施例1
一种阻燃聚异氰脲酸酯硬质泡沫,所述阻燃聚异氰脲酸酯硬质泡沫由如下重量份的组分组成:多异氰酸酯160份,聚醚多元醇6份,阻燃剂18份,催化剂3份,稳定剂2份,发泡剂18份;
所述阻燃剂为含氮阻燃剂与含磷阻燃剂按1:1的质量比混合。
具体地,所述多异氰酸酯中NCO含量为32-35%。
具体地,所述聚醚多元醇聚氧化丙烯二醇与聚氧化乙烯二醇。
具体地,所述含氮阻燃剂为3-吗啉-4-氯-1,2,5-噻二唑;所述含磷阻燃剂为硫代磷酸三异氰酸酯。
具体地,所述催化剂为N,N-二甲基环己胺。
具体地,所述稳定剂为三硅氧烷。
具体地,所述发泡剂为无机发泡剂和有机发泡剂按照质量比为1:6混合而成;所述无机发泡剂为碳酸钙;所述有机发泡剂二氯二氟甲烷。
上述阻燃聚异氰脲酸酯硬质泡沫的制备方法,包括如下步骤:
SS1助剂混合:按上述比例将聚醚多元醇、催化剂、稳定剂加入反应釜中,在55℃下搅拌温度控制在50℃搅拌1.0h,出料,在25℃下保存混合物待用;
S2聚氨酯硬质泡沫的制备:将S1步骤制备得到的混合物和多异氰酸酯、发泡剂、阻燃剂在温度30℃下搅拌12min,混合后注入模具中,脱模,在70℃下熟化8h,得到所述的阻燃聚异氰脲酸酯硬质泡沫。
实施例2
一种阻燃聚异氰脲酸酯硬质泡沫,由如下重量份的组分组成:多异氰酸酯150份,聚醚多元醇5份,阻燃剂15份,催化剂2份,稳定剂1份,发泡剂15份;
所述阻燃剂为含氮阻燃剂与含磷阻燃剂按1:1的质量比混合。
具体地,所述多异氰酸酯中NCO含量为32-35%。
具体地,所述聚醚多元醇聚氧化乙烯二醇、聚四氢呋喃二醇和聚氧化乙烯三醇。
具体地,所述含氮阻燃剂为磷酸氢二铵和3-吗啉-4-氯-1,2,5-噻二唑;所述含磷阻燃剂为磷酸二氢铵和三(2,3-二溴丙基)磷酸酯。
具体地,所述催化剂为双(2-二甲氨基乙基)醚和三乙醇胺。
具体地,所述稳定剂为胺基聚醚。
具体地,所述发泡剂为无机发泡剂和有机发泡剂按照质量比为1:7混合而成;所述无机发泡剂碳酸镁和碳酸氢钠;所述有机发泡剂石油醚和三氯氟甲烷。
上述阻燃聚异氰脲酸酯硬质泡沫的制备方法,包括如下步骤:
S1助剂混合:按上述比例将聚醚多元醇、催化剂、稳定剂加入反应釜中,在50℃下搅拌温度控制在40℃搅拌1.5h,出料,在20℃下保存混合物待用;
S2聚氨酯硬质泡沫的制备:将S1步骤制备得到的混合物和多异氰酸酯、发泡剂、阻燃剂在温度20℃下搅拌15min,混合后注入模具中,脱模,在65℃下熟化8h,得到所述的阻燃聚异氰脲酸酯硬质泡沫。
实施例3
一种阻燃聚异氰脲酸酯硬质泡沫,由如下重量份的组分组成:多异氰酸酯170份,聚醚多元醇8份,阻燃剂20份,催化剂3份,稳定剂3份,发泡剂20份;
所述阻燃剂为含氮阻燃剂与含磷阻燃剂按1:1的质量比混合。
具体地,所述多异氰酸酯中NCO含量为32-35%。
具体地,所述聚醚多元醇为聚四氢呋喃二醇和聚氧化乙烯三醇。
具体地,所述含氮阻燃剂为3-吗啉-4-氯-1,2,5-噻二唑和氰尿酸三聚氰胺;所述含磷阻燃剂为三磷酸钠和硫代磷酸三异氰酸酯。
具体地,所述催化剂为N,N,N',N'-四甲基亚烷基二胺。
具体地,所述稳定剂为三硅氧烷。
具体地,所述发泡剂为无机发泡剂和有机发泡剂按照质量比为1:8混合而成;所述无机发泡剂为碳酸钙、碳酸镁和/或碳酸氢钠中的至少一种;所述有机发泡剂石油醚、三氯氟甲烷、二氯二氟甲烷和/或二氯四氟乙烷中的至少一种。
上述阻燃聚异氰脲酸酯硬质泡沫的制备方法,包括如下步骤:
S1助剂混合:按上述比例将聚醚多元醇、催化剂、稳定剂加入反应釜中,在60℃下搅拌温度控制在60℃搅拌1.0h,出料,在25℃下保存混合物待用;
S2聚氨酯硬质泡沫的制备:将S1步骤制备得到的混合物和多异氰酸酯、发泡剂、阻燃剂在温度35℃下搅拌15min,混合后注入模具中,脱模,在70℃下熟化8h,得到所述的阻燃聚异氰脲酸酯硬质泡沫。
实施例4
一种阻燃聚异氰脲酸酯硬质泡沫,由如下重量份的组分组成:多异氰酸酯165份,聚醚多元醇7份,阻燃剂18份,催化剂3份,稳定剂2份,发泡剂18份;
所述阻燃剂为含氮阻燃剂与含磷阻燃剂按1:1的质量比混合。
具体地,所述多异氰酸酯中NCO含量为32-35%。
具体地,所述聚醚多元醇为聚氧化丙烯二醇。
具体地,所述含氮阻燃剂为磷酸氢二铵;所述含磷阻燃剂为硫代磷酸三异氰酸酯。
具体地,所述催化剂为N,N-二甲基苄胺。
具体地,所述稳定剂为胺基聚醚。
具体地,所述发泡剂为无机发泡剂和有机发泡剂按照质量比为1:8混合而成;所述无机发泡剂为碳酸氢钠;所述有机发泡剂二氯二氟甲烷。
上述阻燃聚异氰脲酸酯硬质泡沫的制备方法,包括如下步骤:
S1助剂混合:按上述比例将聚醚多元醇、催化剂、稳定剂加入反应釜中,在60℃下搅拌温度控制在50℃搅拌1.3h,出料,在20℃下保存混合物待用;
S2聚氨酯硬质泡沫的制备:将S1步骤制备得到的混合物和多异氰酸酯、发泡剂、阻燃剂在温度20℃下搅拌12min,混合后注入模具中,脱模,在70℃下熟化8h,得到所述的阻燃聚异氰脲酸酯硬质泡沫。
实施例5
一种阻燃聚异氰脲酸酯硬质泡沫,所述阻燃聚异氰脲酸酯硬质泡沫由如下重量份的组分组成:多异氰酸酯160份,阻燃聚酯多元醇20份,聚醚多元醇6份,阻燃剂18份,催化剂3份,稳定剂2份,发泡剂18份;
所述阻燃剂为含氮阻燃剂与含磷阻燃剂按1:1的质量比混合。
具体地,所述多异氰酸酯中NCO含量为32-35%。
具体地,所述阻燃聚酯多元醇为碳原子上的氢原子被卤素取代,且有2个以上官能团的聚酯多元醇,羟值在200-270mgKOH/g。
具体地,所述聚醚多元醇聚氧化丙烯二醇与聚氧化乙烯二醇。
具体地,所述含氮阻燃剂为3-吗啉-4-氯-1,2,5-噻二唑;所述含磷阻燃剂为硫代磷酸三异氰酸酯。
具体地,所述催化剂为N,N-二甲基环己胺。
具体地,所述稳定剂为三硅氧烷。
具体地,所述发泡剂为无机发泡剂和有机发泡剂按照质量比为1:6混合而成;所述无机发泡剂为碳酸钙;所述有机发泡剂二氯二氟甲烷。
上述阻燃聚异氰脲酸酯硬质泡沫的制备方法,包括如下步骤:
SS1助剂混合:按上述比例将聚醚多元醇、催化剂、稳定剂加入反应釜中,在55℃下搅拌温度控制在50℃搅拌1.0h,出料,在25℃下保存混合物待用;
S2聚氨酯硬质泡沫的制备:将S1步骤制备得到的混合物和多异氰酸酯、发泡剂、阻燃剂在温度30℃下搅拌12min,混合后注入模具中,脱模,在70℃下熟化8h,得到所述的阻燃聚异氰脲酸酯硬质泡沫。
实施例1-实施例5的性能参数如表1所示,其中实施例1-实施例4为本发明中限定的技术参数,实施例5为对照实施例。
实施例 1 2 3 4 5 试验方法
尺寸稳定性(70℃,20h)% 0.28 0.32 0.33 0.31 0.32 GB/T8811-2008
氧指数/% 34 32 35 33 32 GB/T2406-2009
自由泡密度/kg.m-3 40 38 39 39 38 GB/T6343-2009
异氰酸酯指数/% 330 330 330 330 330 --
抗拉强度/MPa 0.14 0.13 0.135 0.132 0.133 GB50404-2007附录C
表1
以上所述仅是本发明的优选实施方式,应当理解本发明并非局限于本文所披露的形式,不应看作是对其他实施例的排除,而可用于各种其他组合、修改和环境,并能够在本文所述构想范围内,通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围,则都应在本发明所附权利要求的保护范围内。

Claims (10)

1.一种阻燃聚异氰脲酸酯硬质泡沫,其特征在于,由如下重量份的组分组成:多异氰酸酯150-170份,聚醚多元醇5-8份,阻燃剂15-20份,催化剂2-3份,稳定剂1-2份,发泡剂15-20份;
所述阻燃剂为含氮阻燃剂与含磷阻燃剂按1:1的质量比混合。
2.根据权利要求1所述的一种阻燃聚异氰脲酸酯硬质泡沫,其特征在于,所述阻燃聚异氰脲酸酯硬质泡沫由如下重量份的组分组成:多异氰酸酯160份,聚醚多元醇6份,阻燃剂18份,催化剂3份,稳定剂2份,发泡剂18份;
所述阻燃剂为含氮阻燃剂与含磷阻燃剂按1:1的质量比混合。
3.根据权利要求1或2所述的一种阻燃聚异氰脲酸酯硬质泡沫,其特征在于,所述多异氰酸酯中NCO含量为32-35%。
4.根据权利要求1或2所述的一种阻燃聚异氰脲酸酯硬质泡沫,其特征在于,所述聚醚多元醇为聚醚二元醇和/或聚醚三元醇中的至少一种。
5.根据权利要求4所述的一种阻燃聚异氰脲酸酯硬质泡沫,其特征在于,所述聚醚二元醇为聚氧化丙烯二醇、聚氧化乙烯二醇和/或聚四氢呋喃二醇中的至少一种;所述聚醚三元醇为聚氧化丙烯三元醇和/或聚氧化乙烯三醇中的至少一种。
6.根据权利要求1或2所述的一种阻燃聚异氰脲酸酯硬质泡沫,其特征在于,所述含氮阻燃剂为磷酸氢二铵、3-吗啉-4-氯-1,2,5-噻二唑和/或氰尿酸三聚氰胺中至少一种;所述含磷阻燃剂为三磷酸钠、磷酸二氢铵、三(2,3-二溴丙基)磷酸酯和/或硫代磷酸三异氰酸酯中至少一种。
7.根据权利要求1或2所述的一种阻燃聚异氰脲酸酯硬质泡沫,其特征在于,所述催化剂为N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、N,N,N',N'-四甲基亚烷基二胺、三乙胺、N,N-二甲基苄胺和/或三乙醇胺中的至少一种。
8.根据权利要求1或2所述的一种阻燃聚异氰脲酸酯硬质泡沫,其特征在于,所述稳定剂为三硅氧烷或胺基聚醚。
9.根据权利要求1或2所述的一种阻燃聚异氰脲酸酯硬质泡沫,其特征在于,所述发泡剂为无机发泡剂和有机发泡剂按照质量比为1:(6-8)混合而成;所述无机发泡剂为碳酸钙、碳酸镁和/或碳酸氢钠中的至少一种;所述有机发泡剂石油醚、三氯氟甲烷、二氯二氟甲烷和/或二氯四氟乙烷中的至少一种。
10.权利要求1-9任一项所述的一种阻燃聚异氰脲酸酯硬质泡沫的制备方法,其特征在于,包括如下步骤:
S1助剂混合:按上述比例将聚醚多元醇5-8份,催化剂2-3份,稳定剂1-2份加入反应釜中,在50-60℃下搅拌温度控制在 40-60℃搅拌1.0-1.5h,出料,在20-25℃下保存混合物待用;
S2聚氨酯硬质泡沫的制备:将S1步骤制备得到的混合物和多异氰酸酯150-170份、发泡剂15-20份、阻燃剂15-20份在温度 20-35℃下搅拌10-15min,混合后注入模具中,脱模,在65-70℃下熟化 6-8h,得到所述的阻燃聚异氰脲酸酯硬质泡沫。
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CN113942160A (zh) * 2021-11-15 2022-01-18 梦百合家居科技股份有限公司 一种阻燃非温感记忆绵的制备方法

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