CN112961398B - 一种柔性不燃硅气凝胶的制备方法 - Google Patents

一种柔性不燃硅气凝胶的制备方法 Download PDF

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CN112961398B
CN112961398B CN202110157819.9A CN202110157819A CN112961398B CN 112961398 B CN112961398 B CN 112961398B CN 202110157819 A CN202110157819 A CN 202110157819A CN 112961398 B CN112961398 B CN 112961398B
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周蕊
徐妥夫
杨志国
郭卫疆
康程
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CNCEC Hualu New Materials Co Ltd
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Abstract

本发明公开了一种柔性不燃硅气凝胶的制备方法,通过琼脂水溶胶与琼脂硅溶胶混合,经50目筛网过滤后倒入定型模具中冷凝形成特定形状的凝胶前驱体,进行超临界干燥制得。该柔性不燃硅气凝胶具有材质均匀、密度低、易裁剪的特点,具有一定抗压性能,离火自熄的燃烧性能,80℃以下的隔热性能优于硅基气凝胶复合毡,可用于保温衬里、建筑保温、工业节能降噪等领域。

Description

一种柔性不燃硅气凝胶的制备方法
技术领域
本发明涉及建筑隔热新材料领域,更具体地说涉及一种柔性不燃硅气凝胶的制备方法。
背景技术
琼脂在冷水中吸水膨胀但不溶解,在水中需加热至95℃时才开始熔化,熔化后的溶液温度需降到40℃时才开始凝固,冷却后成半透明的凝胶状物,具有很好的胶凝性和凝胶稳定性,通常用量为1~1.5%。
硅基气凝胶是高度多孔的固体材料,由直径为20~80nm左右的初孔径组成,孔隙率高达98%以上,比表面积通常为800~1000。硅基溶胶通常由硅源前驱体在有机溶剂中经酸催化水解,再经碱催化缩聚,经超临界干燥法或常压溶剂替换干燥法制得,但其高脆性和耐压强度低的特点,限制了高纯度硅基气凝胶的应用。
发明内容
本发明的目的是提供了一种柔性不燃硅气凝胶的制备方法,优化了硅基气凝胶的高脆性,在保持硅基气凝胶低密度和优异的防火性能的基础上又结合了琼脂气凝胶的高弹性和抗压、耐拉等力学性能,具有材质均匀、外观规整、密度低的特点。且材料容易运输、切割,在施工现场易于制造加工,具有更高的成本效益,可用于保温衬里、建筑保温、工业节能降噪等领域。
为达到上述技术效果,本发明是通过以下技术方案实现的:
一种柔性不燃硅气凝胶的制备方法,其特征在于,包括以下步骤:
步骤(1)将适量琼脂粉加入到煮沸的纯化水中,搅拌至琼脂粉完全溶解,继续加热煮沸5~10min,加热过程中持续补充纯化水至液面保持不变,继续搅拌直至溶液成甘油状,得到琼脂水溶胶;
步骤(2)将硅源前驱体、溶剂、水解催化剂、缩聚催化剂,按照摩尔比为硅源前驱体:溶剂:水解催化剂=0.5:(2~40):(0.02~0.08),在45℃~55℃条件下搅拌反应60min,制成硅溶胶,缩聚催化剂添加量为使硅溶胶pH维持在6.5~7.5;
步骤(3)将琼脂水溶胶:硅溶胶按照摩尔比为1:(0.2~10)均匀混合,并经100目筛网过滤后,超声或55℃保温排气5~10min,冷却后通过模具成型,形成柔性硅基气凝胶前驱体;
步骤(4)将柔性硅基气凝胶前驱体通过超临界CO2干燥,制得非疏水型柔性硅基气凝胶前驱体;
步骤(5)将非疏水型柔性硅基气凝胶前驱体置于盛放有质量浓度为65-87%聚硅氮烷的疏水疏油助剂原液的密闭容器中熏蒸6~24h,然后经鼓风烘箱烘干1d制得柔性不燃硅气凝胶。
进一步地,所述步骤(1)中,以质量比计,所述琼脂粉:纯化水=(0.5~20):100。
进一步地,步骤(2)中,所述缩聚催化剂是铵盐、氨水、氢氧化铝或氢氧化铁。
进一步地,步骤(2)中,所述硅源前驱体是水玻璃、正硅酸乙酯、正硅酸甲酯、三甲基氯硅烷中的一种或两种以上混合物。
进一步地,步骤(2)中,所述水解催化剂是稀盐酸或稀醋酸。
进一步地,步骤(2)中,所述溶剂包括质量分数96%以上的工业甲醇、乙醇、异丙醇、正丁醇中的一种或两种以上混合物。
进一步地,所述步骤(4)中,所述柔性硅基气凝胶前驱体的干燥方法包括超临界CO2干燥、超临界甲醇干燥、超临界乙醇干燥、常压干燥或真空冷冻干燥。
进一步地,所述步骤(5)中,也可以直接将非疏水型柔性硅基气凝胶前驱体直接经鼓风烘箱烘干1d制得柔性不燃硅气凝胶。
本发明一种柔性不燃硅气凝胶的制备方法,通过琼脂水溶胶与硅溶胶混合,经50目筛网过滤后倒入定型模具中冷凝形成特定形状的凝胶前驱体,进行超临界干燥和表面改性制得,此材料具有高弹性和抗压、耐拉等力学性能,运输、切割、存储方便,在施工现场易于制造加工,应用领域广。
附图说明
图1是实施例1制备的柔性不燃硅气凝胶经点燃30s后的状态。
具体实施方式
为了使本发明的目的、技术方案和优点更加清楚,下面将对本发明的技术方案进行详细描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明的实施例,本领域普通技术人员在没有付出创造性劳动的前提下所得到的所有其他实施方式,都属于本发明所保护的范围。
实施例1
本实施例的柔性不燃硅气凝胶制备方法包括以下步骤:
取正硅酸甲酯:甲醇:稀盐酸按摩尔比0.5:2:0.03均匀混合,配置50ml硅溶胶,45℃恒温反应60min;
称取5g琼脂粉经10g水搅散后加入到100g煮沸的纯化水中,搅拌至琼脂粉完全溶解,继续加热煮沸10min,加热过程中持续补充纯化水至液面保持不变,继续搅拌直至溶液汇成股,得到琼脂水溶胶,取出并放入80℃水浴中保温;
向反应完全的硅溶胶中添加氨水,至溶液pH为7.0,均匀搅拌并称取该混合液40g,加入到40g琼脂水溶胶中,均匀混合,经100目筛网快速过滤后倒入模具中并置于55℃水浴中继续保温5min,取出冷却,脱模,制得柔性硅基气凝胶前驱体;
将该柔性硅基气凝胶前驱体送入超临界CO2干燥设备,温度40℃,压力为12MPa;CO2气体通过超临界干燥釜的流量为150kg/h,干燥时间为8h,制得非疏水型柔性硅基气凝胶前驱体;
将该非疏水型柔性硅基气凝胶前驱体放入盛有质量浓度为70%聚硅氮烷的疏水疏油助剂原液的密闭容器中微热熏蒸10h,取出放入45℃预热的鼓风烘箱中恒温干燥8h,制得柔性不燃硅气凝胶。
该柔性不燃硅气凝胶外观白色,尺寸为35.0mm×24.0mm,厚度2.0mm,比干燥前长度收缩0.5mm、宽收缩0.3mm,高度基本无收缩;比表面积920㎡/g;可重复弯曲,手指按压厚度不变化;疏水性测试,接触角>120°,疏水性良好;不燃性测试,离火自熄。
实施例2
本实施例的柔性不燃硅气凝胶制备方法包括以下步骤:
取正硅酸甲酯:甲醇:稀盐酸摩尔比0.5:8:0.06均匀混合,配置50ml硅溶胶,55℃恒温反应60min;
称取10g琼脂粉经20g水搅散后加入到100g煮沸的纯化水中,搅拌至琼脂粉完全溶解,继续加热煮沸8min,加热过程中持续补充纯化水至液面保持不变,继续搅拌直至溶液汇成股,得到琼脂水溶胶,取出并放入80℃水浴中保温;
向反应完全的硅溶胶中添加氨水,至溶液pH为7.5,均匀搅拌并称取该混合液10g,加入到50g琼脂水溶胶中,均匀混合,经100目筛网快速过滤后倒入模具中并置于55℃水浴中继续保温5min,取出冷却,脱模,制得柔性硅基气凝胶前驱体;
将该柔性硅基气凝胶前驱体送入超临界CO2干燥设备,温度40℃,压力为10MPa;CO2气体通过超临界干燥釜的流量为160kg/h,干燥时间为8h,制得非疏水型柔性硅基气凝胶前驱体;
将该非疏水型柔性硅基气凝胶前驱体取出放入45℃预热的鼓风烘箱中恒温干燥8h,制得柔性不燃硅气凝胶。
该柔性不燃硅气凝胶,外观白色,尺寸为14.5m×12.0mm,厚度2.5mm,比干燥前长度收缩0.3mm、宽各收缩0.2mm,高度基本无收缩,比表面积900㎡/g,可重复弯曲,手指按压厚度不变化,不燃性测试,离火自熄。
实施例3
本实施例的柔性不燃硅气凝胶制备方法包括以下步骤:
取正硅酸甲酯:甲醇:稀盐酸摩尔比0.5:40:0.08均匀混合,配置50ml硅溶胶,50℃恒温反应60min;
称取20g琼脂粉经50g水搅散后加入到100g煮沸的纯化水中,搅拌至琼脂粉完全溶解,继续加热煮沸5min,加热过程中持续补充纯化水至液面保持不变,继续搅拌直至溶液汇成股,得到琼脂水溶胶,取出并放入80℃水浴中保温;
向反应完全的硅溶胶中添加氨水,至溶液pH为6.5,均匀搅拌并称取该混合液10g,加入到100g琼脂水溶胶中,均匀混合,经100目筛网快速过滤后将混合溶胶倒入模具中并置于50℃水浴中继续保温5min,取出冷却,脱模,制得柔性硅基气凝胶前驱体;
将该柔性硅基气凝胶前驱体送入超临界CO2干燥设备,温度40℃,压力为13MPa;CO2气体通过超临界干燥釜的流量为140kg/h,干燥时间为8h,制得非疏水型柔性硅基气凝胶前驱体。
将该非疏水型柔性硅基气凝胶前驱体取出放入45℃预热的鼓风烘箱中恒温干燥8h,制得柔性不燃硅气凝胶片。
该柔性不燃硅气凝胶片,外观白色,尺寸为35.0mm×24.0mm,厚度3.5mm,比干燥前长度收缩0.3mm、宽各收缩0.2mm,高度基本无收缩,比表面积850㎡/g,可重复弯曲,手指按压厚度不变化,不燃性测试,离火自熄。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。

Claims (7)

1.一种柔性不燃硅气凝胶的制备方法,其特征在于,包括以下步骤:
步骤(1)将适量琼脂粉加入到煮沸的纯化水中,搅拌至琼脂粉完全溶解,继续加热煮沸5~10min,加热过程中持续补充纯化水至液面保持不变,继续搅拌直至溶液成甘油状,得到琼脂水溶胶;
步骤(2)将硅源前驱体、溶剂、水解催化剂、缩聚催化剂,按照摩尔比为硅源前驱体:溶剂:水解催化剂=0.5:(2~40):(0.02~0.08),在45℃~55℃条件下搅拌反应60min,制成硅溶胶,缩聚催化剂添加量为使硅溶胶pH维持在6.5~7.5;
步骤(3)将琼脂水溶胶:硅溶胶按照摩尔比为1:(0.2~10)均匀混合,并经100目筛网过滤后,超声或55℃保温排气5~10min,冷却后通过模具成型,形成柔性硅基气凝胶前驱体;
步骤(4)将柔性硅基气凝胶前驱体通过超临界CO2干燥,制得非疏水型柔性硅基气凝胶前驱体;
步骤(5)将非疏水型柔性硅基气凝胶前驱体置于盛放有质量浓度为65-87%聚硅氮烷的疏水疏油助剂原液的密闭容器中熏蒸6~24h,然后经鼓风烘箱烘干1d制得柔性不燃硅气凝胶。
2.如权利要求1所述一种柔性不燃硅气凝胶的制备方法,其特征在于,所述步骤(1)中,以质量比计,所述琼脂粉:纯化水=(0.5~20):100。
3.如权利要求1所述一种柔性不燃硅气凝胶的制备方法,其特征在于,步骤(2)中,所述缩聚催化剂是铵盐、氨水、氢氧化铝或氢氧化铁。
4.如权利要求1所述一种柔性不燃硅气凝胶的制备方法,其特征在于,步骤(2)中,所述硅源前驱体是水玻璃、正硅酸乙酯、正硅酸甲酯、三甲基氯硅烷中的一种或两种以上混合物。
5.如权利要求1所述一种柔性不燃硅气凝胶的制备方法,其特征在于,步骤(2)中,所述水解催化剂是稀盐酸或稀醋酸。
6.如权利要求1所述一种柔性不燃硅气凝胶的制备方法,其特征在于,步骤(2)中,所述溶剂包括质量分数96%以上的工业甲醇、乙醇、异丙醇、正丁醇中的一种或两种以上混合物。
7.如权利要求1所述一种柔性不燃硅气凝胶的制备方法,其特征在于,所述步骤(5)将非疏水型柔性硅基气凝胶前驱体直接经鼓风烘箱烘干1d制得柔性不燃硅气凝胶。
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