CN108467468A - 一种用离子液体催化的聚异氰脲酸酯材料及其制备方法 - Google Patents

一种用离子液体催化的聚异氰脲酸酯材料及其制备方法 Download PDF

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CN108467468A
CN108467468A CN201810287444.6A CN201810287444A CN108467468A CN 108467468 A CN108467468 A CN 108467468A CN 201810287444 A CN201810287444 A CN 201810287444A CN 108467468 A CN108467468 A CN 108467468A
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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

本发明涉及一种用离子液体催化的聚异氰脲酸酯材料及其制备方法，由如下重量份组成：多异氰酸酯150‑170份，组合聚醚10‑12份，阻燃剂10‑14份，催化剂2‑3份，稳定剂1‑2份，发泡剂20‑30份，水0.5‑1.0份；所述阻燃剂为纳米粒子阻燃剂；所述催化剂为离子液体催化剂。制备方法为：先将离子液体和组合聚醚混合，再与其余原料一起经由高压发泡机注入模具中进行反应后脱模得到聚异氰脲酸酯材料。本发明具有制品低温尺寸稳定性号、阻燃剂与发泡剂中不含有卤素原子以及使用寿命长的优点。

Description

一种用离子液体催化的聚异氰脲酸酯材料及其制备方法
技术领域
本发明涉及高分子材料技术领域，具体涉及一种用离子液体催化的聚异氰脲酸酯材料及其制备方法。
背景技术
聚氨酯材料已经广泛应用于汽车、建筑、家电、能源等各个行业。其中聚异氰脲酸酯材料(聚异三聚氰酸脂)以其良好的阻燃性、较低的线型膨胀系数和导热系数，在液化天然气、液化乙烯、液化石油气储存运输和建筑保温隔热等领域应用广泛。然而，由于聚异氰脲酸酯材料的反应过程复杂，熟化过程缓慢，对加工工艺的要求非常严格。此外，传统的胺类、锡类和汞类的催化剂对环境也有一定的污染。
离子液体是指全部由离子组成的液体。通常所说的离子液体，是指在室温下为液体，且全部由离子组成的化合物，又称室温离子液体。离子液体是近年来兴起的一类极具应用前景的绿色催化剂，以其独特的强极性、不挥发、对水和空气稳定等优良性能而广泛应用于电化学、有机反应、化工分离、材料制备等领域的研究，被公认为能在许多领域替代易挥发性的环境友好型催化剂。
在材料成型应用中，离子液体多被用作溶剂，合肥工业大学公布了用离子液体作为溶剂，制备纤维素基聚氨酯材料的方法。
目前，我国深冷绝热领域应用范围比较广泛，液氮管线、LNG输送等清洁能源领域逐步的发展起来，随着本行业的快速发展，深冷用聚异氰脲酸酯型高阻燃绝热材料用途会更加的广泛。目前，在深冷绝热应用过程中，出现在低温条件下泡沫体变形，输送管外壁凝露等问题，同时为了达到聚异氰脲酸酯泡沫比较高的阻燃级别，常常需要额外添加阻燃剂，造成生产工艺的复杂化，影响生产效率。同时，常规阻燃剂里面含有氯离子，长时间的使用后，会对输送管线造成腐蚀，降低管道使用寿命。
现在市售常规聚异氰脲酸酯型绝热材料对使用环境要求比较苛刻，由于聚酯、催化剂、阻燃剂等原料选择不当，造成制品低温尺寸稳定差、使用寿命短等问题。
发明内容
本发明的目的在于克服现有技术的不足，提供一种用离子液体催化的聚异氰脲酸酯材料及其制备方法，解决了制品低温尺寸稳定性差、阻燃剂中含有卤素原子以及使用寿命短的问题。
本发明的目的是通过以下技术方案来实现的：
一种用离子液体催化的聚异氰脲酸酯材料，由如下重量份组成：多异氰酸酯150-170份，组合聚醚10-12份，阻燃剂10-14份，催化剂2-3份，稳定剂1-2份，发泡剂20-30份，水0.5-1.0份；
所述阻燃剂为纳米粒子阻燃剂；
所述催化剂为离子液体催化剂。
聚异氰脲酸酯材料的原料中，阻燃剂采用纳米粒子阻燃剂，混合更为均匀；催化剂采用离子液体催化剂，反应进程快，咪唑硫酸氢盐对聚异氰脲酸酯材料制备过程的催化效率高；制备得到的聚异氰脲酸酯材料的热传导系数小，可以有效保证该位置的保温性能，制品具有高阻燃性能(氧指数≥33％)，实现了制品在低温条件下的长期使用稳定性。
进一步优选地，所述聚异氰脲酸酯材料由如下重量份组成：多异氰酸酯170份，组合聚醚10份，阻燃剂13份，催化剂3份，稳定剂2份，发泡剂30份，水0.8份；
所述阻燃剂为纳米粒子阻燃剂；
所述催化剂为离子液体催化剂。
进一步地，所述多异氰酸酯中NCO含量为32-38％。
进一步地，所述组合聚醚有如下重量份组成：聚氧化丙烯多元醇45-80份，聚氧化乙烯多元醇5-10份，聚四氢呋喃二元醇8-15份，胺类催化剂0.5-0.8份。
组合聚醚中添加胺类催化剂，与酸性离子液体催化剂反应慢，对催化速率影响小，且两种催化剂能适应接纳更多的反应单体，增快反应速率。
进一步地，所述聚氧化丙烯多元醇为聚氧化丙烯二元醇或聚氧化丙烯三元醇；所述聚氧化乙烯多元醇为聚氧化乙烯二元醇或聚氧化乙烯三元醇；所述胺类催化剂为N,N-二甲基环己胺。
进一步地，所述离子液体催化剂为酸性离子液体催化剂；所述酸性离子液体催化剂为为1-(3-磺酸基丙基)-3-三甲氧基硅丙基-咪唑硫酸氢盐或1-(3-磺酸基丁基)-3-三甲氧基硅丙基-咪唑硫酸氢盐。
进一步地，所述纳米阻燃粒子为无机含磷阻燃剂与有机含氮阻燃剂按照1：(5-6)的质量比混合制备而成；所述无机含磷阻燃剂为磷酸二氢铵、磷酸氢二铵、磷酸三铵和/或聚磷酸铵中的至少一种；所述有机含氮阻燃剂氰尿酸三聚氰胺。
纳米粒子阻燃剂采用有机含氮阻燃剂与无机含磷阻燃剂混合制备而成，其中无机含磷阻燃剂中也含有氮原子，增强阻燃剂的阻燃性能；将两者混合制备而成的纳米粒子阻燃剂的阻燃温度相较于单一阻燃剂提高了30-50℃。
进一步地，所述稳定剂为三硅氧烷；所述发泡剂为石油醚。稳定剂和发泡剂中不采用含卤素原子的有机试剂，避免卤素原子长时间的使用后会对聚异氰脲酸酯材料造成腐蚀从而降低使用寿命的问题。
上述用离子液体催化的聚异氰脲酸酯材料的制备方法，先将离子液体和组合聚醚混合，再与其余原料一起经由高压发泡机注入模具中进行反应后脱模得到聚异氰脲酸酯材料。
进一步地，所述离子液体和组合聚醚的混合温度为40-50℃，混合时间为30-45min，搅拌速率为1500-1800r/min；所述高压发泡机的压力为20-80MPa；所述模具的温度为50-80℃，反应时间为24-30h。
聚异氰脲酸酯材料的制备过程简单，离子液体和组合聚醚先混合后加入其余原料，两步混合使得混合更为均匀，且前期混合过程中升温可加速混合，后期发泡混合中不采用高温高压混合发泡，节约能源的同时也能加速聚异氰脲酸酯材料的熟化速度。
发明的有益效果是：
1.聚异氰脲酸酯材料的原料中，阻燃剂采用纳米粒子阻燃剂，混合更为均匀；催化剂采用离子液体催化剂，反应进程快，咪唑硫酸氢盐对聚异氰脲酸酯材料制备过程的催化效率高；制备得到的聚异氰脲酸酯材料的热传导系数小，可以有效保证该位置的保温性能，制品具有高阻燃性能(氧指数≥33％)，实现了制品在低温条件下的长期使用稳定性；
2.纳米粒子阻燃剂采用有机含氮阻燃剂与无机含磷阻燃剂混合制备而成，其中无机含磷阻燃剂中也含有氮原子，增强阻燃剂的阻燃性能；将两者混合制备而成的纳米粒子阻燃剂的阻燃温度相较于单一阻燃剂提高了30-50℃；
3.组合聚醚中添加胺类催化剂，与酸性离子液体催化剂反应慢，对催化速率影响小，且两种催化剂能适应接纳更多的反应单体，增快反应速率；稳定剂和发泡剂中不采用含卤素原子的有机试剂，避免卤素原子长时间的使用后会对聚异氰脲酸酯材料造成腐蚀从而降低使用寿命的问题；
4.聚异氰脲酸酯材料的制备过程简单，离子液体和组合聚醚先混合后加入其余原料，两步混合使得混合更为均匀，且前期混合过程中升温可加速混合，后期发泡混合中不采用高温高压混合发泡，节约能源的同时也能加速聚异氰脲酸酯材料的熟化速度。
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。
一种用离子液体催化的聚异氰脲酸酯材料，由如下重量份组成：多异氰酸酯150-170份，组合聚醚10-12份，阻燃剂10-14份，催化剂2-3份，稳定剂1-2份，发泡剂20-30份，水0.5-1.0份；
所述阻燃剂为纳米粒子阻燃剂；
所述催化剂为离子液体催化剂。
具体地，所述聚异氰脲酸酯材料由如下重量份组成：多异氰酸酯170份，组合聚醚10份，阻燃剂13份，催化剂3份，稳定剂2份，发泡剂30份，水0.8份；
所述阻燃剂为纳米粒子阻燃剂；
所述催化剂为离子液体催化剂。
具体地，所述多异氰酸酯中NCO含量为32-38％。
具体地，所述组合聚醚有如下重量份组成：聚氧化丙烯多元醇45-80份，聚氧化乙烯多元醇5-10份，聚四氢呋喃二元醇8-15份，胺类催化剂0.5-0.8份。
具体地，所述聚氧化丙烯多元醇为聚氧化丙烯二元醇或聚氧化丙烯三元醇；所述聚氧化乙烯多元醇为聚氧化乙烯二元醇或聚氧化乙烯三元醇；所述胺类催化剂为N,N-二甲基环己胺。
具体地，所述离子液体催化剂为酸性离子液体催化剂；所述酸性离子液体催化剂为为1-(3-磺酸基丙基)-3-三甲氧基硅丙基-咪唑硫酸氢盐或1-(3-磺酸基丁基)-3-三甲氧基硅丙基-咪唑硫酸氢盐。
具体地，所述纳米阻燃粒子为无机含磷阻燃剂与有机含氮阻燃剂按照1：(5-6)的质量比混合制备而成；所述无机含磷阻燃剂为磷酸二氢铵、磷酸氢二铵、磷酸三铵和/或聚磷酸铵中的至少一种；所述有机含氮阻燃剂氰尿酸三聚氰胺。
具体地，所述稳定剂为三硅氧烷；所述发泡剂为石油醚。
实施例1-实施例6的具体制备参数如表1所示，实施例1-实施例4为本发明中限定的技术参数，实施例5中为无机含磷阻燃剂，实施例6为有机含氮阻燃剂，实施例5-实施例6为对比实施例。
表1
上述实施例1中用离子液体催化的聚异氰脲酸酯材料的制备方法，先将离子液体和组合聚醚混合，再与其余原料一起经由高压发泡机注入模具中进行反应后脱模得到聚异氰脲酸酯材料。
具体地，所述离子液体和组合聚醚的混合温度为40℃，混合时间为45min，搅拌速率为1800r/min；所述高压发泡机的压力为20MPa；所述模具的温度为50℃，反应时间为30h。
上述实施例2中用离子液体催化的聚异氰脲酸酯材料的制备方法，先将离子液体和组合聚醚混合，再与其余原料一起经由高压发泡机注入模具中进行反应后脱模得到聚异氰脲酸酯材料。
具体地，所述离子液体和组合聚醚的混合温度为45℃，混合时间为40min，搅拌速率为1500r/min；所述高压发泡机的压力为80MPa；所述模具的温度为80℃，反应时间为28h。
上述实施例3中用离子液体催化的聚异氰脲酸酯材料的制备方法，先将离子液体和组合聚醚混合，再与其余原料一起经由高压发泡机注入模具中进行反应后脱模得到聚异氰脲酸酯材料。
具体地，所述离子液体和组合聚醚的混合温度为50℃，混合时间为30min，搅拌速率为1700r/min；所述高压发泡机的压力为50MPa；所述模具的温度为70℃，反应时间为24h。
上述实施例4中用离子液体催化的聚异氰脲酸酯材料的制备方法，先将离子液体和组合聚醚混合，再与其余原料一起经由高压发泡机注入模具中进行反应后脱模得到聚异氰脲酸酯材料。
具体地，所述离子液体和组合聚醚的混合温度为45℃，混合时间为35min，搅拌速率为1600r/min；所述高压发泡机的压力为40MPa；所述模具的温度为60℃，反应时间为26h。
上述实施例5中用离子液体催化的聚异氰脲酸酯材料的制备方法，先将离子液体和组合聚醚混合，再与其余原料一起经由高压发泡机注入模具中进行反应后脱模得到聚异氰脲酸酯材料。
具体地，所述离子液体和组合聚醚的混合温度为50℃，混合时间为30min，搅拌速率为1700r/min；所述高压发泡机的压力为50MPa；所述模具的温度为70℃，反应时间为24h。
上述实施例6中用离子液体催化的聚异氰脲酸酯材料的制备方法，先将离子液体和组合聚醚混合，再与其余原料一起经由高压发泡机注入模具中进行反应后脱模得到聚异氰脲酸酯材料。
具体地，所述离子液体和组合聚醚的混合温度为50℃，混合时间为30min，搅拌速率为1700r/min；所述高压发泡机的压力为50MPa；所述模具的温度为70℃，反应时间为24h。
实施例1-实施例6的具体性能参数如表2所示，实施例1-实施例4为本发明中限定的技术参数，实施例5中为无机含磷阻燃剂，实施例6为有机含氮阻燃剂，实施例5-实施例6为对比实施例。
实施例 1 2 3 4 5 6 试验方法
尺寸稳定性(70℃，20h)％ 0.30 0.29 0.28 0.30 0.30 0.30 GB/T8811-2008
氧指数/％ 33 34 35 33 28 30 GB/T2406-2009
自由泡密度/kg.m-3 40 41 43 42 40 40 GB/T6343-2009
抗拉强度/MPa 0.142 0.144 0.144 0.140 0.130 0.132 GB50404-2007附录C
表2
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)

1.一种用离子液体催化的聚异氰脲酸酯材料，其特征在于，由如下重量份组成：多异氰酸酯150-170份，组合聚醚10-12份，阻燃剂10-14份，催化剂2-3份，稳定剂1-2份，发泡剂20-30份，水0.5-1.0份；
所述阻燃剂为纳米粒子阻燃剂；
所述催化剂为离子液体催化剂。
2.根据权利要求1所述的一种用离子液体催化的聚异氰脲酸酯材料，其特征在于，所述聚异氰脲酸酯材料由如下重量份组成：多异氰酸酯170份，组合聚醚10份，阻燃剂13份，催化剂3份，稳定剂2份，发泡剂30份，水0.8份；
所述阻燃剂为纳米粒子阻燃剂；
所述催化剂为离子液体催化剂。
3.根据权利要求1或2所述的一种用离子液体催化的聚异氰脲酸酯材料，其特征在于，所述多异氰酸酯中NCO含量为32-38%。
4.根据权利要求1或2所述的一种用离子液体催化的聚异氰脲酸酯材料，其特征在于，所述组合聚醚有如下重量份组成：聚氧化丙烯多元醇45-80份，聚氧化乙烯多元醇5-10份，聚四氢呋喃二元醇8-15份，胺类催化剂0.5-0.8份。
5.根据权利要求4所述的一种用离子液体催化的聚异氰脲酸酯材料，其特征在于，所述聚氧化丙烯多元醇为聚氧化丙烯二元醇或聚氧化丙烯三元醇；所述聚氧化乙烯多元醇为聚氧化乙烯二元醇或聚氧化乙烯三元醇；所述胺类催化剂为N,N-二甲基环己胺。
6.根据权利要求1或2所述的一种用离子液体催化的聚异氰脲酸酯材料，其特征在于，所述离子液体催化剂为酸性离子液体催化剂；所述酸性离子液体催化剂为为1-(3-磺酸基丙基)-3-三甲氧基硅丙基-咪唑硫酸氢盐或1-(3-磺酸基丁基)-3-三甲氧基硅丙基-咪唑硫酸氢盐。
7.根据权利要求1或2所述的一种用离子液体催化的聚异氰脲酸酯材料，其特征在于，所述纳米阻燃粒子为无机含磷阻燃剂与有机含氮阻燃剂按照1：（5-6）的质量比混合制备而成；所述无机含磷阻燃剂为磷酸二氢铵、磷酸氢二铵、磷酸三铵和/或聚磷酸铵中的至少一种；所述有机含氮阻燃剂氰尿酸三聚氰胺。
8.根据权利要求1或2所述的一种用离子液体催化的聚异氰脲酸酯材料，其特征在于，所述稳定剂为三硅氧烷；所述发泡剂为石油醚。
9.权利要求1-8任一项所述的一种用离子液体催化的聚异氰脲酸酯材料的制备方法，其特征在于，先将离子液体和组合聚醚混合，再与其余原料一起经由高压发泡机注入模具中进行反应后脱模得到聚异氰脲酸酯材料。
10.根据权利要求9所述的一种用离子液体催化的聚异氰脲酸酯材料的制备方法，其特征在于，所述离子液体和组合聚醚的混合温度为40-50℃，混合时间为30-45min，搅拌速率为1500-1800r/min；所述高压发泡机的压力为20-80MPa ；所述模具的温度为50-80℃，反应时间为24-30h。
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