CN110183716B - 一种阻燃保温型纤维素基气凝胶的制备方法 - Google Patents
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Abstract
本发明涉及气凝胶材料技术领域,为解决传统纤维素基气凝胶阻燃性能差的问题,提供了一种阻燃保温型纤维素基气凝胶的制备方法,包括以下步骤:(1)制得密胺预聚液;(2)将纤维素纳米纤维溶液与密胺预聚液混合,超声分散;(3)冷冻干燥,得气凝胶;(4)干燥交联处理,即得阻燃保温型纤维素基气凝胶。本发明制备方法操作简单易行,条件易于控制,易于大规模工业化生产;制得的阻燃保温型纤维素基气凝胶具有离火自熄现象,阻燃效果显著,同时仍具备良好的隔热性能,保温效果显著。
Description
技术领域
本发明涉及气凝胶材料技术领域,尤其涉及一种阻燃保温型纤维素基气凝胶的制备方法。
背景技术
气凝胶是由凝胶通过溶胶-凝胶法和适当的干燥技术将空气取代孔隙液体并保持典型的网络结构的一种多孔材料,具有超低密度、高比表面积、高孔隙率等特点,并广泛应用于光学、催化、隔热、电学等领域。尤其在保温材料领域,由于气凝胶的高孔隙率导致其导热系数低,保温性能显著,目前主要应用在墙体保温,管道保温等领域。
其中,纤维素基气凝胶作为生物基材料,具有良好的生物相容性和可降解性的优点,在气凝胶材料中备受关注。但由于纤维素气凝胶比表面积大,相比于其他高分子材料更易燃烧,极大地限制了其应用领域。因此,对其进行阻燃改性具有重要意义。
中国专利文献上公开了“一种机械增强及阻燃的纤维素气凝胶的制备方法”,申请公布号为CN 106916340A,该发明方法先制备纤维素水凝胶,再制备原位负载Al(OH)3纳米粒子,最后制成机械增强及阻燃的纤维素气凝胶。该方法制备的纤维素气凝胶通过Al(OH)3受热脱水进行阻燃性能的改善,其阻燃效果提升有限。同时,Al(OH)3制备过程中离心洗涤消耗大量的水,资源浪费。
发明内容
本发明为了克服传统纤维素基气凝胶阻燃性能差的问题,提供了一种阻燃保温型纤维素基气凝胶的制备方法,操作简单易行,纤维素纳米纤维密胺复合气凝胶具有离火自熄现象,阻燃效果显著。
为了实现上述目的,本发明采用以下技术方案:
一种阻燃保温型纤维素基气凝胶的制备方法,包括以下步骤:
(1)以三聚氰胺、多聚甲醛和去离子水为原料,于碱性条件下加热进行预聚反应,制得密胺预聚液;
(2)将纤维素纳米纤维溶液与密胺预聚液混合,超声分散,得混合分散液;
(3)将混合分散液冷冻干燥,得气凝胶;该步骤于特定容器(如小玻璃瓶)中进行;
(4)将气凝胶进行干燥交联处理,即得阻燃保温型纤维素基气凝胶。
本发明利用密胺树脂的凝聚相阻燃和气相阻燃机制,在燃烧过程中,密胺将会分解释放出氨气、氮气,稀释空气中氧气浓度,同时,燃烧后其将变成致密的炭层,附着在气凝胶表面,起到阻隔氧气、热量等作用,达到气凝胶阻燃目的,同时,密胺的加入并不影响气凝胶的导热系数,复合气凝胶仍具备良好的隔热性能,保温效果显著,得到的纤维素纳米纤维密胺复合气凝胶具有离火自熄现象,阻燃效果显著。
作为优选,步骤(1)中,所述三聚氰胺和多聚甲醛的添加质量比为1:(2~3),优选1:2。
本发明必须严格控制三聚氰胺和多聚甲醛的添加比例,其中,多聚甲醛的加入量过高,会导致甲醛过量,造成危害;加入量过低,会导致交联度过低。
作为优选,步骤(1)中,预聚反应温度为80~110℃,优选90℃;预聚反应体系pH控制在9~10。
预聚反应温度过低,会导致反应时间过长或达不到交联状态,过高会导致反应剧烈,交联过度从水溶液中析出,将不能与纤维素很好的分散。控制;预聚反应体系为碱性是因为多聚甲醛在碱性条件下易解离成甲醛,从而与三聚氰胺发生反应。
作为优选,步骤(1)中,预聚反应终点判断方法为:在1mL冰水中加入5mL密胺预聚液,剧烈震荡后仍有白色沉淀存在,即达到预聚反应终点。
作为优选,步骤(2)中,所述纤维素纳米纤维溶液的浓度为0.5~2wt%,优选为1wt%。
作为优选,步骤(2)中,所述纤维素纳米纤维与密胺固含量配比为1:(0.25~2),优选为1:1。
作为优选,步骤(2)中,超声温度为35~50℃,优选45℃;超声时间为30~120min,优选60~100min。
作为优选,步骤(3)中,冷冻干燥之前先进行冰箱预冷冻,冰箱预冷冻温度为-18℃,预冷冻时间为4~48h,优选12h。
作为优选,步骤(3)中,冷冻干燥的温度为-76℃;冷冻干燥时间为24~72h,优选36~48h。
作为优选,步骤(4)中,干燥温度为60~100℃,优选80℃;干燥时间为12~48h,优选24h。
因此,本发明具有如下有益效果:
(1)制备方法操作简单易行,条件易于控制,易于大规模工业化生产;
(2)制得的阻燃保温型纤维素基气凝胶具有离火自熄现象,阻燃效果显著,同时仍具备良好的隔热性能,保温效果显著。
附图说明
图1是为实施例1和对比例1样品的水溶性数码照片。
图2是对比例2制得的纤维素纳米纤维气凝胶的SEM图。
图3是实施例1制得的阻燃保温型纤维素基气凝胶的SEM图。
图4是图3的SEM图对应的元素分布图。
具体实施方式
下面通过具体实施例,并结合附图,对本发明的技术方案作进一步具体的说明。
在本发明中,若非特指,所有设备和原料均可从市场购得或是本行业常用的,下述实施例中的方法,如无特别说明,均为本领域常规方法。
实施例1
(1)将20.0g多聚甲醛和35.0g去离子水在250mL烧杯中混合均匀,反应温度控制在90℃;并不断滴加0.1moL/L的氢氧化钠溶液,控制混合物的pH为9;待多聚甲醛完全溶解,溶液变澄清透明后,再加入45.0g三聚氰胺,此时,仍保持反应温度在90℃、pH在9左右,直至溶液再次变为澄清透明,继续反应30min后检测预聚终点;在1mL冰水中加入5mL密胺预聚液,剧烈震荡后仍有白色沉淀存在,即达到预聚反应终点;
(2)向5g浓度为2wt%的纤维素纳米纤维水溶液中加入5g去离子水配置成10g浓度为1wt%的纤维素纳米纤维水溶液,并在45℃水温下超声分散6min直至纤维素纳米纤维在去离子水中均匀分散;按干重比1/1(纤维素干重/密胺干重=1/1)加入密胺预聚液,水温维持在45℃,并继续超声分散80min,直至混合物分散均匀;
(3)将分散均匀的混合物倒入特定模具中,置于冰箱中预冷冻约12h,预冷冻结束后于-76℃下冷冻干燥约36h,得到干燥的纤维素纳米纤维密胺复合气凝胶;
(4)将气凝胶置于80℃真空烘箱中干燥交联24h,即可得到阻燃保温型纤维素基气凝胶成品;本实施例制得的阻燃保温型纤维素基气凝胶成品的SEM图及其元素分布图如图3所示。
实施例2
(1)将20.0g多聚甲醛和35.0g去离子水在250mL烧杯中混合均匀,反应温度控制在110℃;并不断滴加0.1moL/L氢氧化钠溶液,控制混合物的pH在10左右。待多聚甲醛完全溶解,溶液变澄清透明后,再加入45.0g三聚氰胺,此时,仍保持反应温度在110℃、pH在10左右,直至溶液再次变为澄清透明,继续反应30min后检测预聚终点;
(2)向5g浓度为2wt%的纤维素纳米纤维水溶液中加入5g去离子水配置成10g浓度为1wt%的纤维素纳米纤维水溶液,并在50℃水温下超声分散5min直至纤维素纳米纤维在去离子水中均匀分散;按干重比2/1(纤维素干重/密胺干重=2/1)加入密胺预聚液,水温维持在50℃,并继续超声分散60min,直至混合物分散均匀;
(3)将分散均匀的混合物倒入特定模具中,置于冰箱中预冷冻约4h,预冷冻结束后于-76℃下冷冻干燥约24h,得到干燥的纤维素纳米纤维密胺复合气凝胶;
(4)将气凝胶置于100℃真空烘箱中干燥交联12h,即可得到阻燃保温型纤维素基气凝胶成品。
实施例3
(1)将20.0g多聚甲醛和35.0g去离子水在250mL烧杯中混合均匀,反应温度控制在90℃;并不断滴加0.1moL/L氢氧化钠溶液,控制混合物的pH在9左右。待多聚甲醛完全溶解,溶液变澄清透明后,再加入45.0g三聚氰胺,此时,仍保持反应温度在90℃、pH在9左右,直至溶液再次变为澄清透明,继续反应30min后检测预聚终点;
(2)向5g浓度为2wt%的纤维素纳米纤维水溶液中加入5g去离子水配置成10g浓度为1wt%的纤维素纳米纤维水溶液,并在35℃水温下超声分散10min直至纤维素纳米纤维在去离子水中均匀分散;按干重比4/1(纤维素干重/密胺干重=4/1)加入密胺预聚液,水温维持在35℃,并继续超声分散90min,直至混合物分散均匀;
(3)将分散均匀的混合物倒入特定模具中,置于冰箱中预冷冻约12h,预冷冻结束后于-76℃下冷冻干燥约72h,得到干燥的纤维素纳米纤维密胺复合气凝胶;
(4)将气凝胶置于60℃真空烘箱中干燥交联48h,即可得到阻燃保温型纤维素基气凝胶成品。
实施例4
(1)将20.0g多聚甲醛和35.0g去离子水在250mL烧杯中混合均匀,反应温度控制在90℃;并不断滴加0.1moL/L氢氧化钠溶液,控制混合物的pH在9左右。待多聚甲醛完全溶解,溶液变澄清透明后,再加入45.0g三聚氰胺,此时,仍保持反应温度在90℃、pH在9左右,直至溶液再次变为澄清透明,继续反应30min后检测预聚终点;
(2)向5g浓度为2wt%的纤维素纳米纤维水溶液中加入5g去离子水配置成10g浓度为1wt%的纤维素纳米纤维水溶液,并在40℃水温下超声分散6min直至纤维素纳米纤维在去离子水中均匀分散;按干重比1/2(纤维素干重/密胺干重=1/2)加入密胺预聚液,水温维持在40℃,并继续超声分散65min,直至混合物分散均匀;
(3)将分散均匀的混合物倒入特定模具中,置于冰箱中预冷冻约12h,预冷冻结束后于-76℃下冷冻干燥约36h,得到干燥的纤维素纳米纤维密胺复合气凝胶;
(4)将纤维素纳米纤维密胺复合气凝胶置于70℃真空烘箱中干燥交联40h,即可得到阻燃保温型纤维素基气凝胶成品。
对比例1
对比例1与实施例1的区别在于,无步骤(4),其余步骤及工艺条件完全相同。
对比例2
(1)向5g浓度为2wt%的纤维素纳米纤维水溶液中加入5g去离子水配置成10g浓度为1wt%的纤维素纳米纤维水溶液,并在45℃水温下超声分散5~10min直至纤维素纳米纤维在去离子水中均匀分散;
(2)将分散均匀的混合物倒入特定模具中,置于冰箱中冷冻约12h,冷冻结束后于-76℃下冷冻干燥约36h,即可得到干燥的纤维素纳米纤维气凝胶。
本对比例制得的纯纤维素气凝胶的扫描电镜图如图2所示。
对实施例1-3和对比例1-2的气凝胶成品的性能指标做检测,结果如表1所示:
表1实施例1~4和对比例1~6的气凝胶成品测定结果
编号 | 阻燃等级 | 导热系数(W/m·K) |
实施例1 | V-0 | 0.022 |
实施例2 | V-1 | 0.021 |
实施例3 | V-1 | 0.020 |
实施例4 | V-0 | 0.029 |
对比例1 | V-0 | 0.024 |
对比例2 | NR | 0.018 |
由表1可以看出,实施例1所制备的交联纤维素纳米纤维/密胺气凝胶在剧烈震荡后仍能保持原形态,说明在高温条件下,纤维素纳米纤维与密胺发生了交联反应,这对于气凝胶形态的维持具有重要意义;而对于对比例1冷冻干燥后直接制备的纤维素纳米纤维/密胺复合气凝胶而言,纤维素表面羟基仍大量存在,在水环境作用下网孔结构坍塌直至溶解在水中。
图1为实施例1和对比例1样品的水溶性数码照片,可以看出,实施例1所制备的交联纤维素纳米纤维/密胺气凝胶在剧烈震荡后仍能保持原形态,说明在高温条件下,纤维素纳米纤维与密胺发生了交联反应,这对于气凝胶形态的维持具有重要意义;而对于对比例1冷冻干燥后直接制备的纤维素纳米纤维/密胺复合气凝胶而言,纤维素表面羟基仍大量存在,在水环境作用下网孔结构坍塌直至溶解在水中。
图2为对比例2所制备的纯纤维素气凝胶的扫描电镜图,图3和图4为实施例1所制备的纤维素密胺复合气凝胶的扫描电镜图及其元素分布图。与纯纤维素气凝胶相比,加入阻燃剂密胺后的复合气凝胶仍保持一定的网络结构,同时,C、O、N等元素的对应分布可以看出密胺已成功负载于纤维素气凝胶中并均匀分散。
以上所述仅为本发明的较佳实施例,并非对本发明作任何形式上的限制,在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
Claims (8)
1.一种阻燃保温型纤维素基气凝胶的制备方法,其特征在于,包括以下步骤:
(1)以三聚氰胺、多聚甲醛和去离子水为原料,于碱性条件下加热进行预聚反应,制得密胺预聚液;
(2)将纤维素纳米纤维溶液与密胺预聚液混合,超声分散,得混合分散液,所述纤维素纳米纤维与密胺固含量配比为1:(0.25~2),超声温度为35~50℃;超声时间为30~120min;
(3)将混合分散液冷冻干燥,得气凝胶;
(4)将气凝胶进行干燥交联处理,干燥温度为60~100℃,即得阻燃保温型纤维素基气凝胶。
2.根据权利要求1所述的一种阻燃保温型纤维素基气凝胶的制备方法,其特征在于,步骤(1)中,所述三聚氰胺和多聚甲醛的添加质量比为1:(2~3)。
3.根据权利要求1所述的一种阻燃保温型纤维素基气凝胶的制备方法,其特征在于,步骤(1)中,预聚反应温度为80~110℃;预聚反应体系pH控制在9~10。
4.根据权利要求1所述的一种阻燃保温型纤维素基气凝胶的制备方法,其特征在于,步骤(1)中,预聚反应终点判断方法为:在1 mL冰水中加入5 mL密胺预聚液,剧烈震荡后仍有白色沉淀存在,即达到预聚反应终点。
5.根据权利要求1所述的一种阻燃保温型纤维素基气凝胶的制备方法,其特征在于,步骤(2)中,所述纤维素纳米纤维溶液的浓度为0.5~2wt%。
6.根据权利要求1所述的一种阻燃保温型纤维素基气凝胶的制备方法,其特征在于,步骤(3)中,冷冻干燥之前先进行预冷冻,预冷冻温度为-18℃,预冷冻时间为4~48h。
7.根据权利要求1所述的一种阻燃保温型纤维素基气凝胶的制备方法,其特征在于,步骤(3)中,冷冻干燥的温度为-76℃;冷冻干燥时间为24~72h。
8.根据权利要求1所述的一种阻燃保温型纤维素基气凝胶的制备方法,其特征在于,步骤(4)中,干燥时间为12~48h。
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