CN106564235B - 一种三聚氰胺纳米气凝胶co2发泡复合难燃闭孔硬质泡沫保温板及其制备方法 - Google Patents

一种三聚氰胺纳米气凝胶co2发泡复合难燃闭孔硬质泡沫保温板及其制备方法 Download PDF

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CN106564235B
CN106564235B CN201610960018.5A CN201610960018A CN106564235B CN 106564235 B CN106564235 B CN 106564235B CN 201610960018 A CN201610960018 A CN 201610960018A CN 106564235 B CN106564235 B CN 106564235B
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王贵然
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Sino-Research Information Source (Beijing) Energy Saving Technology Co., Ltd.
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Abstract

本发明涉及保温隔热材料制备领域，特别公开了一种三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板及其制备方法。该三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板，其特征在于：包括上无机纤维层和下无机纤维层，上无机纤维层和下无机纤维层之间复合有泡沫夹芯层；泡沫夹芯层由发泡树脂乳化液发泡制成，发泡树脂乳化液由三聚氰胺纳米气凝胶粉、水、乳化剂、消烟剂、发泡剂、固化交联剂和憎水剂混合制成。本发明产品不仅具有良好的防火性和疏水性，而且具有轻质、隔热、隔音、机械强度高、导热系数低等特性，生产成本低，产品性能好，适于广泛推广应用。

Description

一种三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温 板及其制备方法
（一）技术领域
本发明涉及保温隔热材料制备领域，特别涉及一种三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板及其制备方法。
（二）背景技术
目前，工业保温领域，常用的泡沫保温材料，主要有聚苯乙烯泡沫、聚氨酯泡沫、酚醛树脂泡沫，主要缺点是耐热及防火性能差，遇火灾时燃烧，放出大量浓烟和有毒气体，让人窒息，酚醛泡沫塑料主要缺点是易粉化，机械强度低，脆性大，无延伸性等。
三聚氰胺泡沫塑料，是以三聚氰胺甲醛树脂（MF）为基体，经发泡工艺制得的一种阻燃性能较高的泡沫材料，具有高开孔率的新型泡沫塑料，除具有通用泡沫材料的可贵性能外，其密度低，具有低导热性、阻燃防火性、耐湿热稳定性、杰出的吸音性能和三维网络结构，赋予了其良好的保温隔热、机械加工等性能，是目前业界公认的一种新型环保阻燃保温新材料。
但是，现有的硬质三聚氰胺泡沫板材，普遍存在着，强度较低、泡沫脆性大、力学性能差、吸水率高等不足，因受工艺与生产装备制约，市场上很少见到。除此之外，在三聚氰胺泡沫生产过程中，一般需要加入烷烃类发泡剂，由于三聚氰胺的高开孔率，此类发泡剂在气化发泡时，不会存留在泡沫内，而直接溢散到大气环境中，对周边的环境造成污染，在生产过程中，易造成火灾隐患，因此，在生产过程中，减少发泡剂的使用量和使用无污染环境的发泡剂，无论是从经济角度，还是安全角度，都是非常有益和迫切需要的，故对当前的三聚氰胺泡沫塑料的制备工艺，仍需进一步改进是必要的。
（三）发明内容
本发明为了弥补现有技术的不足，提供了一种保温性能好、疏水性高、生产成本低的三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板及其制备方法。
本发明是通过如下技术方案实现的：
一种三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板，其特征在于：包括上无机纤维层和下无机纤维层，上无机纤维层和下无机纤维层之间复合有泡沫夹芯层；泡沫夹芯层由发泡树脂乳化液发泡制成，发泡树脂乳化液由三聚氰胺纳米气凝胶粉、水、乳化剂、消烟剂、发泡剂、固化交联剂和憎水剂混合制成。
本发明的更优技术方案为：
所述上无机纤维层和下无机纤维层分别为水泥纤维基毡布、铝箔、铝板条、彩钢板条、水泥纤维硅酸钙板和玻璃纤维网格布中的一种；发泡树脂乳化液的质量浓度为65-85%。
所述上无机纤维层、泡沫夹芯层和下无机纤维层之间通过喷涂耐高温粘结剂或机压粘合复合在一起。
所述水为纯水、去离子水和蒸馏水中的一种；乳化剂为十二烷基硫酸钠、十二烷基苯磺酸钠、α-烯基磺酸钠、聚乙二醇脂肪酸酯和吐温-80中的一种或多种；消烟剂为硼酸锌、八钼酸铵和富马酸中的一种；发泡剂为正戊烷、正己烷、异戊烷、硅油醚和二氧化碳中的一种或多种，采用无污染环境的二氧化碳为发泡剂，代替了烷烃类发泡剂，避免了对大气层的破坏和环境的污染；固化交联剂为甲酸、乙酸、柠檬酸、对甲苯磺酸、苯酚磺酸、氯化铵、硫酸铝、苯酚和乌洛托品中的一种或多种；憎水剂为甲基硅酸钠、甲基硅酸钾、单硬脂酸铝和有机硅憎水剂中的一种。
本发明所述的三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板的制备方法，包括如下步骤：
（1）将三聚氰胺、甲醛和水置于反应器内，往反应器内依次加入催化剂、缓冲剂、增溶剂、稳定剂，升温搅拌至三聚氰胺全部溶解，调溶液pH值后升温继续反应，然后降温后加入乳化剂和增塑剂，搅拌均匀后，将反应溶液装入密闭容器中凝胶老化，得到凝胶；
（2）将凝胶置于三氟乙酸溶液中处理，然后用无水乙醇和丙酮置换，将置换后的凝胶材料用无水乙醇溶液进行溶剂置换，最后干燥得到三聚氰胺纳米气凝胶颗粒；
（3）将三聚氰胺纳米气凝胶粉、水、乳化剂、消烟剂、憎水剂、发泡剂和固化交联剂混合，经高剪切乳化分散剂分散、单螺杆挤出机计量、双螺杆挤出机混合得到发泡树脂乳化液；
（4）在双履带式层压成型机的平台上放置上、下无机纤维层，发泡树脂乳化液由高速浇注机头浇筑在上、下无机纤维层中间，输送到层压主机内，在加热作用下升温至120-160℃后开始发泡，并交联固化成型，在主机内经热风熟化成型出板。
本发明采用三聚氰胺为原料，以超临界或亚临界干燥工艺，解决了原料的疏水性差、固体含量高、保质期短、难于存放流通等问题。本发明将三聚氰胺甲醛树脂由液态转变为固体粉料，更方便了储存和运输，得到的三聚氰胺纳米气凝胶，密度为162kg/m3，颗粒直径为10nm左右，三聚氰胺纳米气凝胶孔径和颗粒大小均在nm量级，骨架结构致密，是一种典型的纳米结构、多孔材料。
三聚氰胺纳米气凝胶粉末，不受季节气候影响，储存期长，不易变质，方便运输和物流，适合工业化生产和大规模推广。
其优选的技术方案为：
步骤（1）中，所述甲醛为多聚甲醛或液态甲醛，固含量为37-40%；催化剂为氢氧化钠或碳酸钠；缓冲剂为磷酸氢二钾或磷酸二氢钠；增溶剂为乌洛托品；稳定剂为二乙二醇或三乙醇胺；乳化剂为α-烯基磺酸钠或十二烷基苯磺酸钠；增塑剂为葵二酸二辛脂或邻苯二甲酸二辛酯。
步骤（1）中，三聚氰胺和甲醛的摩尔比为1:4，反应器升温至80-90℃后搅拌，三聚氰胺全部溶解后，加稀盐酸调溶液pH值至1.5-2，反应1h后升温至90-95℃继续反应2h，然后降温至60℃后加入乳化剂和增塑剂，搅拌均匀后，将反应溶液装入密闭容器、置于50-60℃环境中，凝胶老化7小时，得到凝胶。
步骤（2）中，将凝胶置于三氟乙酸溶液中处理3h，然后用无水乙醇和丙酮置换若干次，每次置换时间为2h，将置换后的凝胶材料在50-80℃下用无水乙醇溶液进行溶剂再次置换，置换2-4天，最后干燥，得到三聚氰胺纳米气凝胶颗粒。
步骤（2）中，所述干燥方式为超临界干燥或亚临界干燥；其中，超临界干燥为二氧化碳临界干燥、无水乙醇临界干燥，无水乙醇临界干燥温度为260-280℃、压力10-12MPA下，恒温恒压维持2-3小时，然后放气出制品；二氧化碳临界干燥温度为40-50℃、压力10-12MPA下，恒温恒压维持10-12小时，然后放气出制品；亚临界干燥温度为190℃、压力5-6MPA下，恒温恒压维持6小时，降温放气出制品。
步骤（4）中，发泡树脂乳化液在120℃下发泡，经热风的熟化温度为80-100℃，其中热风温度为100℃；成型出板后，泡沫保温板通过输送架传出，经切割机竖切，再经横切割加工成长1200mm、宽600mm、厚60mm的成品入库。
本发明产品不仅具有良好的防火性和疏水性，而且具有轻质、隔热、隔音、机械强度高、导热系数低等特性，生产成本低，产品性能好，适于广泛推广应用。
（四）具体实施方式
下面结合实施示例，对本发明做进一步说明，但发明的保护范围，并不限于此。下述实施例中所用材料均可以商业途径得到。
实施例1：
（1）水凝胶制备：将三聚氰胺（M）895g，多聚甲醛（F）630g，纯水500g，催化剂NaOH3g，一并加入反应器中。pH值为7-8左右，搅拌升温为85-90℃，加入稳定剂二乙二醇10g，待三聚氰胺全部溶解后，加入改性剂对甲苯磺酰胺90g，乳化剂十二烷基苯磺酸钠60g反应0.5小时，用HCI调节体系PH值1.5-2.0之间，继续反应2小时，降温60℃以下，将反应溶液装于密闭容器，于50℃的环境中凝胶老化7小时左右，于三氟乙酸溶液处理3小时。为了让其更好的和二氧化碳置换，将处理的凝胶与无水乙醇或丙酮置换2天，并用有机硅憎水剂进行表面改性，已获得疏水表面，再用无水乙醇进行置换2天，即获得疏水表面凝胶。
（2）超临界干燥：从保持三聚氰胺甲醛（MF）气凝胶的网络结构出发，采用二氧化碳超临界干燥，具体首先将油浴温度调至5℃，待高压釜温度稳定后，将老化后的凝胶投入其中，向釜内充入液态二氧化碳，注满后约2小时，缓慢放出二氧化碳和丙酮混合物，使物料中的水和其它溶剂完全被二氧化碳置换，7小时后将油浴升温，使高压釜的温度达到40℃，压强升至10-12MPa，使二氧化碳达到超临界状态，此时气液界面不复存在，将二氧化碳缓慢放出，压力降至常压后，开始降温至室温，开釜即得到具有连续网络结构的半透明状（MF）气凝胶，经检测，该气凝胶具有一定疏水性，颗粒直径10mm以上占90%。完全符合气凝胶特点。
实施例2：
（1）将1000g蒸馏水加入反应器中，然后依次加入催化剂氢氧化钠5g，缓冲剂磷酸二氢钾10g，乌洛托品20g，稳定剂二乙二醇10g，pH值为7-8左右，搅拌升温至95℃左右，加入三聚氰胺（M）1790g，多聚甲醛（F）1260g，苯代三聚氰胺250g，温度保持在90-95℃，反应2小时，降温至50℃，加入乳化剂α-烯基磺酸钠120g，反应乳化后，加入增塑剂葵二酸二辛酯60g、有机硅憎水剂20g，搅拌均匀后，用甲酸调节pH值至2左右，即可出料，将溶胶置于50-60℃的环境中老化7小时，即可进行亚临界干燥。
（2）亚临界干燥：将老化好的凝胶置于高压釜中，用无水乙醇浸没，并封闭高压釜，将高压釜缓慢升温至190℃，同时釜内压力保持在5-6MPa。在此温度和压力环境密闭保持大约6小时左右，然后，开始缓慢释放釜内的无水乙醇气体，待高压釜内的无水乙醇气体释放干净后温度降至无水乙醇沸点60℃以下，并冷却开釜，取出物料，即得到具有疏水性优良和高乳化性能的（MF）气凝胶。做检测结果气凝胶具有一定的疏水性，25℃时导热系数为0.020w/m·k.
平均孔径为10nm左右，孔径点为90%以上，孔隙率达到94%。由此数据判断，颗粒大小在10nm左右、网络结构明显、分布均匀、骨架结构致密，是一种典型的纳米结构多孔材料。
实施例3：发泡树脂乳化液制备工艺
将上述工艺制得的三聚氰胺甲醛（MF）气凝胶粉750g，蒸馏水250g，乳液固含量为75%，乳化剂吐温-80型50g，专用分散剂10g，有机硅憎水剂10g，消烟剂富马酸50g，发泡剂二氧化碳80g，固化剂甲酸10g，将以上各组分物料依次加入，高剪切乳化分散机、乳化均匀，由单螺杆挤出机计量挤出，由双螺杆挤出机混合，得到高度均匀的发泡树脂乳化液。经高速混合浇注机头，高速混合发泡。
发泡树脂乳化液，经一种聚氨酯和酚醛泡沫复合保温板连续加工生产线双履带式层压成型装置，120-160℃温度，发泡10-15分钟，交联成型后，经干燥制得三聚氰胺甲醛（MF）气凝胶CO2发泡复合难燃硬质泡沫保温板。泡沫复合板密度60kg/m3,导热系数0.035w/m·k ,尺寸稳定性0.89%，芯材吸水率2.5%(96h),复合板垂直于板面抗拉强度0.12MPa，氧指数45%。
实施例4：发泡树脂乳化液制备工艺
取三聚氰胺甲醛（MF）纳米气凝胶粉750g，去离子水250g，乳化剂十二烷基苯磺酸钠30g；憎水剂甲基硅酸钾10g；消烟剂八钼酸铵50g，固化剂硫酸铝50g，发泡剂二氧化碳130g,；按照实施案例（3）工艺，制得的三聚氰胺甲醛（MF）纳米气凝胶CO2发泡，复合难燃硬质泡沫保温板，密度45kg/m3,导热系数0.030w/m·k ,氧指数35%。
实施例5：发泡树脂乳化液制备工艺
取三聚氰胺甲醛（MF）纳米气凝胶粉750g，纯水250g，乳化剂聚乙二醇脂肪酸酯30g,憎水剂单硬脂酸铝20g；消烟剂硼酸锌100g，发泡剂二氧化碳100g，固化剂柠檬酸50g；按照实施案例（3）的发泡工艺，制得的三聚氰胺甲醛（MF）气凝胶CO2发泡复合难燃硬质泡沫保温板，密度50kg/m3,导热系数0.031w/m·k ,氧指数40%。
实施例6：发泡复合难燃硬质泡沫保温板工艺
本发明提供了一种三聚氰胺甲醛（MF）纳米气凝胶CO2发泡复合难燃硬质泡沫保温板材料，包括上无机纤维层和下无机纤维层，上无机纤维层和下无机纤维层之间复合有泡沫夹芯层；泡沫夹芯层由发泡树脂乳化液发泡制成，发泡树脂乳化液由三聚氰胺（MF）纳米气凝胶粉、水、乳化剂、增塑剂、稳泡剂、发泡剂、固化交联剂和憎水剂混合制成。
所述上无机纤维层和下无机纤维层分别为水泥纤维基毡布、铝箔、铝板条、彩钢板条、水泥纤维硅酸钙板和玻璃纤维网格布中的一种；发泡树脂乳化液的质量浓度为65-85%。
所述上无机纤维层、泡沫夹芯层和下无机纤维层之间通过喷涂耐高温粘结剂或机压粘合复合在一起。
在双履带式层压成型机的平台上放置上、下无机纤维层，发泡树脂乳化液由高速浇注机头浇筑在上、下无机纤维层中间，输送到层压主机内，在加热作用下升温至120-160℃后开始发泡，并交联固化成型，在主机内经热风熟化成型出板。本实施例中，上、下无机纤维层为铝箔。
得到的泡沫保温板经测试，密度为60kg/m3，导热系数0.035w/m·k，防火等级为A2级，尺寸稳定性0.89%，氧指数45%，压缩变形率202KPa。
实施例7：发泡复合难燃硬质泡沫保温板工艺
上、下无机纤维板为水泥纤维基毡布、材料均自市场购得，其制备方式与实施例6相同。
泡沫夹芯层为三聚氰胺甲醛（MF）纳米气凝胶CO2发泡复合难燃硬质泡沫保温板，其密度为36kg/m3，导热系数0.030w/m·k，防火等级为A2级，氧指数30%，闭孔率90%以上，吸水率为96小时2%。
本发明三聚氰胺甲醛（MF）气凝胶CO2发泡复合难燃硬质泡沫保温板，与现有技术相比较，采用的基料为三聚氰胺（MF）纳米气凝胶和CO2发泡工艺，其原料价格比是聚氨酯1/3，有一定的成本优势，阻燃性是聚氨酯材料无法可比的。因三聚氰胺的神奇之处就在于本身是一种阻燃剂，采用CO2发泡剂和有污染的易燃易爆的发泡剂相比，两者对环境的污染是不言而喻的。三聚氰胺泡沫材料能够长期在150-400℃温度下长期使用，不出现燃烧和分解，较成熟的聚氨酯、酚醛发泡自动化生产线，并可实现工业化生产。
本实施例制备的三聚氰胺甲醛（MF）纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板经测试，导热系数低，防火性能好，经采用消烟处理，烟密低，保温隔热效果非常好。
实施例8：发泡复合难燃硬质泡沫保温板工艺
上、下无机纤维板为彩钢板条、材料均自市场购得，其制备方式与实施例6相同，泡沫保温板经测试，密度为53kg/m3，导热系数0.032w/m·k，防火等级为A2级，闭孔率90%以上，吸水率1.9%，压缩变形率168MPa。
密度根据GB/T6343—2009；
导热系数按照GB/T10294—2008；
压缩性能按照GB/T8813—2008；
尺寸稳定性按照GB/T8811—2008；
吸水率按照GB/T8810—2005；
弯曲变形按照GB/T8812—2007；
耐火等级按照GB/T8624—2014；
氧指数按照GB/T2406.2—2009。
本发明的三聚氰胺甲醛（MF）纳米气凝胶CO2复合难燃泡沫保温板是一种难燃闭孔泡沫保温材料，保温性能和各项指示优异，而且生产设备装置成熟。作为一种新型保温隔热防火材料，更易实现工业化规模生产。

Claims (10)

1.一种三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板，其特征在于：包括上无机纤维层和下无机纤维层，上无机纤维层和下无机纤维层之间复合有泡沫夹芯层；泡沫夹芯层由发泡树脂乳化液发泡制成，发泡树脂乳化液由三聚氰胺纳米气凝胶粉、水、乳化剂、消烟剂、发泡剂、固化交联剂和憎水剂混合制成；其制备方法包括如下步骤：（1）将三聚氰胺、甲醛和水置于反应器内，往反应器内依次加入催化剂、缓冲剂、增溶剂、稳定剂，升温搅拌至三聚氰胺全部溶解，调溶液pH值后升温继续反应，然后降温后加入乳化剂和增塑剂，搅拌均匀后，将反应溶液装入密闭容器中凝胶老化，得到凝胶；（2）将凝胶置于三氟乙酸溶液中处理，然后用无水乙醇和丙酮置换，将置换后的凝胶材料用无水乙醇溶液进行溶剂置换，最后干燥得到三聚氰胺纳米气凝胶颗粒；（3）将三聚氰胺纳米气凝胶粉、水、乳化剂、消烟剂、发泡剂、憎水剂和固化交联剂混合，经高剪切乳化分散剂分散、单螺杆挤出机计量、双螺杆挤出机混合得到发泡树脂乳化液；（4）在双履带式层压成型机的平台上放置上、下无机纤维层，发泡树脂乳化液由高速浇注机头浇注 在上、下无机纤维层中间，输送到层压主机内，在加热作用下升温至120-160℃后开始发泡，并交联固化成型，在主机内经热风熟化成型出板。
2.根据权利要求1所述的三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板，其特征在于：所述上无机纤维层和下无机纤维层分别为水泥纤维基毡布、铝箔、铝板条、彩钢板条、水泥纤维硅酸钙板和玻璃纤维网格布中的一种；发泡树脂乳化液的质量浓度为65-85%。
3.根据权利要求1所述的三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板，其特征在于：所述上无机纤维层、泡沫夹芯层和下无机纤维层之间通过喷涂耐高温粘结剂或机压粘合复合在一起。
4.根据权利要求1所述的三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板，其特征在于：所述水为纯水、去离子水和蒸馏水中的一种；乳化剂为十二烷基硫酸钠、十二烷基苯磺酸钠、α-烯基磺酸钠、聚乙二醇脂肪酸酯和吐温-80中的一种或多种；消烟剂为硼酸锌、八钼酸铵和富马酸中的一种；发泡剂为正戊烷、正己烷、异戊烷、硅油醚和二氧化碳中的一种或多种；固化交联剂为甲酸、乙酸、柠檬酸、对甲苯磺酸、苯酚磺酸、氯化铵、硫酸铝、苯酚和乌洛托品中的一种或多种；憎水剂为甲基硅酸钠、甲基硅酸钾、单硬脂酸铝和有机硅憎水剂中的一种。
5.根据权利要求1所述的三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板的制备方法，其特征为，包括如下步骤：（1）将三聚氰胺、甲醛和水置于反应器内，往反应器内依次加入催化剂、缓冲剂、增溶剂、稳定剂，升温搅拌至三聚氰胺全部溶解，调溶液pH值后升温继续反应，然后降温后加入乳化剂和增塑剂，搅拌均匀后，将反应溶液装入密闭容器中凝胶老化，得到凝胶；（2）将凝胶置于三氟乙酸溶液中处理，然后用无水乙醇和丙酮置换，将置换后的凝胶材料用无水乙醇溶液进行溶剂置换，最后干燥得到三聚氰胺纳米气凝胶颗粒；（3）将三聚氰胺纳米气凝胶粉、水、乳化剂、消烟剂、发泡剂、憎水剂和固化交联剂混合，经高剪切乳化分散剂分散、单螺杆挤出机计量、双螺杆挤出机混合得到发泡树脂乳化液；（4）在双履带式层压成型机的平台上放置上、下无机纤维层，发泡树脂乳化液由高速浇注机头浇筑在上、下无机纤维层中间，输送到层压主机内，在加热作用下升温至120-160℃后开始发泡，并交联固化成型，在主机内经热风熟化成型出板。
6.根据权利要求5所述的三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板的制备方法，其特征在于：步骤（1）中，所述甲醛为多聚甲醛或液态甲醛，固含量为37-40%；催化剂为氢氧化钠或碳酸钠；缓冲剂为磷酸氢二钾或磷酸二氢钠；增溶剂为乌洛托品；稳定剂为二乙二醇或三乙醇胺；乳化剂为α-烯基磺酸钠或十二烷基苯磺酸钠；增塑剂为葵二酸二辛脂或邻苯二甲酸二辛酯。
7.根据权利要求5所述的三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板的制备方法，其特征在于：步骤（1）中，三聚氰胺和甲醛的摩尔比为1:4，反应器升温至80-90℃后搅拌，三聚氰胺全部溶解后，加稀盐酸调溶液pH值至1.5-2，反应1h后升温至90-95℃继续反应2h，然后降温至60℃后加入乳化剂和增塑剂，搅拌均匀后，将反应溶液装入密闭容器、置于50-60℃环境中，凝胶老化7小时，得到凝胶。
8.根据权利要求5所述的三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板的制备方法，其特征在于：步骤（2）中，将凝胶置于三氟乙酸溶液中处理3h，然后用无水乙醇和丙酮置换若干次，每次置换时间为2h，将置换后的凝胶材料在50-80℃下用无水乙醇溶液进行溶剂再次置换，置换2-4天，最后干燥，得到三聚氰胺纳米气凝胶颗粒。
9.根据权利要求5所述的三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板的制备方法，其特征在于：步骤（2）中，所述干燥方式为超临界干燥或亚临界干燥；其中，超临界干燥为二氧化碳临界干燥、无水乙醇临界干燥，无水乙醇临界干燥温度为260-280℃、压力10-12MPa 下，恒温恒压维持2-3小时，然后放气出制品；二氧化碳临界干燥温度为40-50℃、压力10-12MPa 下，恒温恒压维持10-12小时，然后放气出制品；亚临界干燥温度为190℃、压力5-6MPa 下，恒温恒压维持6小时，降温放气出制品。
10.根据权利要求5所述的三聚氰胺纳米气凝胶CO2发泡复合难燃闭孔硬质泡沫保温板的制备方法，其特征在于：步骤（4）中，发泡树脂乳化液在120℃下发泡，经热风的熟化温度为80-100℃，其中热风温度为100℃。
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