CN112646229A - 一种具有超双疏性能的有机硅气凝胶的制备方法 - Google Patents
一种具有超双疏性能的有机硅气凝胶的制备方法 Download PDFInfo
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Abstract
本发明涉及一种具有超双疏性能的有机硅气凝胶的制备方法。以有机桥接烷氧基硅烷为硅源,以苯甲醇、去离子水作为溶剂,结合碱性催化剂,按照一定比例进行混合,通过氟硅烷改性、溶胶‑凝胶、老化等方法,制备聚乙烯基聚甲基硅氧烷/聚甲基硅氧烷复合醇凝胶,再通过CO2超临界干燥法对样品进行干燥处理,最终得到具有双疏性能的块状聚乙烯基聚甲基硅氧烷/聚甲基硅氧烷气凝胶。所制备的复合材料具有双疏性能、高孔隙率、高比表面积等特点。该复合体系采用有机桥接烷氧基硅烷为硅源,改善了气凝胶的机械脆性,以氟硅烷作为表面改性剂,赋予有机硅气凝胶双疏性能,在赋予气凝胶自清洁、防雾防潮、防冰抗霜效果方面有着巨大的研究价值和应用前景。
Description
技术领域
本发明属于纳米多孔复合材料的制备工艺领域,尤其涉及一种具有超双疏性能的有机硅气凝胶的制备方法。
背景技术
气凝胶材料是一种三维多孔轻质固体材料,由于其制备过程通常由溶胶-凝胶法获得水凝胶或醇凝胶,再经过特定的干燥过程,以空气代替液体溶剂,形成致密的纳米多孔结构。因此气凝胶材料具备低密度、高比表面积、高孔隙率和高孔体积等结构特性,使其具有耐温、低热导率、低折射率和低声传播速度等特殊的光、热、声、电性能。
据现有国内外文献报道,传统二氧化硅气凝胶由于其本身的脆性多孔结构,极大地限制了其应用。为了提高气凝胶的机械性能同时保持其独特性能,各种有机硅源被开发利用,研究者们主要从两个角度展开研究,一是通过有机-无机杂化策略制备有机倍半硅氧烷(RSiO3/2)气凝胶,二是以有机桥接烷氧基硅烷为前体制备有机桥接聚硅氧烷气凝胶,大大提高了其机械性能。润湿性是评判材料表面特征的要素之一,以“荷叶效应”为代表的超疏水现象一直是研究热点,若材料表面对水和油的静态接触角都大于150°且其滚动角都小5°,则称之为超双疏材料。这种具有特殊浸润性的表面在自清洁、防雾防潮、防冰抗霜等方面有着巨大的应用前景,显示出节能、环保等优势。
南京林业大学的陈苏琴等以细菌纤维素(BC)为原料,以柠檬酸(CA)为交联剂,次磷酸钠(SHP)为酯化交联催化剂,经冷冻干燥后得到BC复合气凝胶,熟化后采用低表面能氟硅烷进行化学气相沉积得到氟化BC复合气凝胶。水和十六烷的接触角到了164°和152°,实现了超双疏性,但气凝胶材料的孔径分布不均匀。上海工程技术大学的靳懿等以甲基三甲氧基硅烷(MTMS)为前驱体,在溶胶-凝胶反应过程中,加入纳米CuS,并采用十七氟癸基三乙氧基硅烷(PFDTES)对其改性,成功制备了氟硅烷改性CuS/SiO2复合气凝胶(F-CuS/SiO2),但气凝胶的双疏效果不佳。通过采用有机硅氧烷为前体制备硅溶胶改善其机械性能,同时,利用氟硅烷对纳米二氧化硅进行化学改性,制备出具有自清洁性能的纳米超双疏气凝胶材料,具有重要的科研价值和广泛的应用价值。
发明内容
本发明的目的是为了改进现有技术的不足而提供了一种具有超双疏性能的有机硅气凝胶的制备方法。
本发明的技术方案为:首先采用有机桥接烷氧基硅烷为前体制备了有机桥接聚硅氧烷气凝胶溶胶,在制备的有机硅溶胶的基础上,通过添加氟碳表面活性剂和氟硅烷,在含有氟碳表面活性剂的水性体系下,利用氟硅烷如全氟癸基三乙氧基硅烷、全氟癸基三甲氧基硅烷对纳米二氧化硅进行化学改性,制备出机械性能稳定的水性纳米超双疏气凝胶材料。
本发明的具体技术方案为:一种具有超双疏性能的有机硅气凝胶的制备方法,其具体步骤如下:
(1)溶胶的制备
首先,将有机硅烷和引发剂按体积比1:(0.1~1)混合均匀配置成溶液,移入水热反应釜,并放置在100~120℃的烘箱中反应12-24h,反应结束后取出降温,得到透明的粘性液体聚乙烯基硅氧烷;然后将得到的聚乙烯基硅氧烷、甲基三甲氧基硅烷、苯甲醇、去离子水、氟碳表面活性剂按体积比1:(1~4):(2~8):(2~10):(0.2~0.6)混合均匀配成溶液,室温下搅拌0.5~2h,继续滴加碱性催化剂,得到有机硅溶胶;
(2)老化
在制得的有机硅溶胶中滴加氟硅烷,有机硅烷与氟硅烷体积比控制在1:(0.2~0.6),搅拌均匀,薄膜密封,并放置在50~60℃的真空干燥箱中0.5~2h,得到有机硅复合湿凝胶;加入老化液,对该有机硅复合湿凝胶进行老化处理,得到半透明状的有机硅凝胶;
(3)CO2超临界干燥
将步骤(2)中得到的半透明状的有机硅凝胶样品进行CO2超临界干燥处理,获得块状具有超双疏性能的有机硅气凝胶。
优选步骤(1)中所述的有机硅烷为乙烯基三甲氧基硅烷(VTMS)、乙烯基三乙氧基硅烷(VTES)或乙烯基甲基二甲氧基硅烷(VMDMS)中的一种。
优选步骤(1)中所述的引发剂为二叔丁基过氧化物(DTBP)。
优选步骤(1)中所述的氟碳表面活性剂为Capstone FS-61氟碳表面活性剂、Zonyl9361氟碳表面活性剂或Zonyl TM氟碳表面活性剂。
优选步骤(1)中所述的碱性催化剂为氨水、氟化铵、四甲基氢氧化铵溶液;碱性催化剂的质量浓度为20-30%;碱性催化剂加入体积量占总溶液体积的1-3%。
优选步骤(2)中所使用的氟硅烷是1H,1H,2H,2H-全氟癸基三乙氧基硅烷或1H,1H,2H,2H-全氟癸基三乙氧基硅烷。
优选步骤(2)中所使用的老化液为醇与水按体积比为1:(1~4)混合的混合溶液,其中所述的醇为乙醇、异丙醇或甲醇。
优选步骤(2)中所述的老化处理为每8~12h更换一次老化液,更换次数为3~5次。
优选步骤(3)中CO2超临界干燥反应温度为45~50℃,高压反应釜压力控制在10~12MPa,干燥时间为12~24h。
有益效果:
通过采用有机硅氧烷为前体制备硅溶胶改善其机械性能,同时,利用氟硅烷对纳米二氧化硅进行化学改性,制备出具有自清洁性能的纳米超双疏气凝胶材料,这种具有特殊浸润性的表面在自清洁、防雾防潮、防冰抗霜等方面有着巨大的应用前景,显示出节能、环保等优势,具有重要的科研价值和广泛的应用价值。
附图说明
图1是实施例1所制备的SiO2-SiO2/Al2O3-Al2O3复合气凝胶的SEM照片。
具体实施方式
下面结合实例对本发明作进一步说明,但保护范围并不限于此。
实例1
首先,将乙烯基三甲氧基硅烷(VTMS)和二叔丁基过氧化物(DTBP)按体积比1:0.2混合均匀配置成溶液,将得到的溶液移入水热反应釜,并放置在100℃的烘箱中反应12h,反应结束后取出反应釜降至室温,得到一种透明粘性液体---聚乙烯基倍半硅氧烷(PVPSQ)。接着,将得到的透明粘性液体、甲基三甲氧基硅烷、苯甲醇、去离子水、Capstone FS-61氟碳表面活性剂按体积比1:1:2:2:0.2混合均匀配成溶液,室温下搅拌0.5h,继续滴加质量浓度为20%氨水,体积占总溶液体积的1%,得到聚乙烯基倍半硅氧烷/聚甲基硅氧烷溶胶溶液,在该溶液中滴加氟硅烷---1H,1H,2H,2H-全氟癸基三甲氧基硅烷,有机硅烷与氟硅烷体积比控制在1:0.2,搅拌均匀,薄膜密封,并放置在50℃的真空干燥箱中0.5h,得到聚乙烯基倍半硅氧烷/聚甲基硅氧烷凝胶。加入异丙醇与水体积比为1:1的老化液,对该复合湿凝胶进行老化处理,每8h更换一次老化液,更换3次。得到半透明状的聚乙烯基倍半硅氧烷/聚甲基硅氧烷醇凝胶。将样品放置在CO2超临界干燥反应釜中进行干燥处理,反应温度为45℃,高压反应釜压力控制在10MPa,反应时间为12h,最终获得块状聚乙烯基倍半硅氧烷/聚甲基硅氧烷复合气凝胶材料。经过表征发现,该气凝胶材料的比表面积为388.65m2/g,孔隙率为94%,平均孔径为25nm,疏水角为147.22°,疏油角为120.15°。
图1为聚乙烯基倍半硅氧烷/聚甲基硅氧烷气凝胶SEM图,气凝胶呈现出由聚集的颗粒组成的三维高孔隙网络结构,聚合的粒子通过化学交联很好地相互连接,从而形成稳定均匀的多孔结构。
实例2
首先,将乙烯基三甲氧基硅烷(VTES)和二叔丁基过氧化物(DTBP)按体积比1:1混合均匀配置成溶液,将得到的溶液移入水热反应釜,并放置在120℃的烘箱中反应24h,反应结束后取出反应釜降至室温,得到一种透明粘性液体---聚乙烯基倍半硅氧烷(PVPSQ)。接着,将得到的透明粘性液体、甲基三甲氧基硅烷、苯甲醇、去离子水、或Zonyl TM氟碳表面活性剂按体积比1:4:8:10:0.6混合均匀配成溶液,室温下搅拌2h,继续滴加质量浓度为30%的氟化铵溶液,滴加氟化铵溶液体积占总溶液体积的2%,得到聚乙烯基倍半硅氧烷/聚甲基硅氧烷溶胶溶液,在该溶液中滴加氟硅烷---1H,1H,2H,2H-全氟癸基三乙氧基硅烷,有机硅烷与氟硅烷体积比控制在1:0.6,搅拌均匀,薄膜密封,并放置在60℃的真空干燥箱中2h,得到聚乙烯基倍半硅氧烷/聚甲基硅氧烷凝胶。加入乙醇与水体积比为1:4的老化液,对该复合湿凝胶进行老化处理,每12h更换一次老化液,更换5次。得到半透明状的聚乙烯基倍半硅氧烷/聚甲基硅氧烷醇凝胶。将样品放置在CO2超临界干燥反应釜中进行干燥处理,反应温度为50℃,高压反应釜压力控制在12MPa,反应时间为24h,最终获得块状聚乙烯基倍半硅氧烷/聚甲基硅氧烷复合气凝胶材料。经过表征发现,该气凝胶材料的比表面积为459.46m2/g,孔隙率为92%,平均孔径为25nm,疏水角为148.89°,疏油角为132.18°。
实例3
首先,将乙烯基三甲氧基硅烷(VTMS)和二叔丁基过氧化物(DTBP)按体积比1:0.4混合均匀配置成溶液,将得到的溶液移入水热反应釜,并放置在105℃的烘箱中反应15h,反应结束后取出反应釜降至室温,得到一种透明粘性液体---聚乙烯基倍半硅氧烷(PVPSQ)。接着,将得到的透明粘性液体、甲基三甲氧基硅烷、苯甲醇、去离子水、Zonyl 9361氟碳表面活性剂按体积比1:2:4:4:0.3混合均匀配成溶液,室温下搅拌1h,继续滴加浓度为25wt%的四甲基氢氧化铵溶液,四甲基氢氧化铵溶液的体积占总溶液体积的1%,得到聚乙烯基倍半硅氧烷/聚甲基硅氧烷溶胶溶液,在该溶液中滴加氟硅烷---1H,1H,2H,2H-全氟癸基三乙氧基硅烷,有机硅烷与氟硅烷体积比控制在1:0.3,搅拌均匀,薄膜密封,并放置在55℃的真空干燥箱中1h,得到聚乙烯基倍半硅氧烷/聚甲基硅氧烷凝胶。加入甲醇与水体积比为1:2的老化液,对该复合湿凝胶进行老化处理,每10h更换一次老化液,更换4次。得到半透明状的聚乙烯基倍半硅氧烷/聚甲基硅氧烷醇凝胶。将样品放置在CO2超临界干燥反应釜中进行干燥处理,反应温度为45℃,高压反应釜压力控制在10MPa,反应时间为12h,最终获得块状聚乙烯基倍半硅氧烷/聚甲基硅氧烷复合气凝胶材料。经过表征发现,该气凝胶材料的比表面积为468.45m2/g,孔隙率为98%,平均孔径为20nm,疏水角为139.88°,疏油角为138.10°。
实例4
首先,将乙烯基三甲氧基硅烷(VTES)和二叔丁基过氧化物(DTBP)按体积比1:0.6混合均匀配置成溶液,将得到的溶液移入水热反应釜,并放置在110℃的烘箱中反应18h,反应结束后取出反应釜降至室温,得到一种透明粘性液体---聚乙烯基倍半硅氧烷(PVPSQ)。接着,将得到的透明粘性液体、甲基三甲氧基硅烷、苯甲醇、去离子水、Capstone FS-61氟碳表面活性剂按体积比1:3:6:6:0.4混合均匀配成溶液,室温下搅拌1.5h,继续滴加入浓度为20wt%四甲基氢氧化铵溶液,四甲基氢氧化铵溶液体积占总溶液体积的3%,得到聚乙烯基倍半硅氧烷/聚甲基硅氧烷溶胶溶液,在该溶液中滴加氟硅烷---1H,1H,2H,2H-全氟癸基三乙氧基硅烷,有机硅烷与氟硅烷体积比控制在1:0.4,搅拌均匀,薄膜密封,并放置在55℃的真空干燥箱中1.5h,得到聚乙烯基倍半硅氧烷/聚甲基硅氧烷凝胶。加入甲醇与水体积比为1:3的老化液,对该复合湿凝胶进行老化处理,每10h更换一次老化液,更换4次。得到半透明状的聚乙烯基倍半硅氧烷/聚甲基硅氧烷醇凝胶。将样品放置在CO2超临界干燥反应釜中进行干燥处理,反应温度为45℃,高压反应釜压力控制在10MPa,反应时间为12h,最终获得块状聚乙烯基倍半硅氧烷/聚甲基硅氧烷复合气凝胶材料。经过表征发现,该气凝胶材料的比表面积为488.65m2/g,孔隙率为94%,平均孔径为22nm,疏水角为152.68°,疏油角为148.10°。
实例5
首先,将乙烯基三甲氧基硅烷(VTMS)和二叔丁基过氧化物(DTBP)按体积比1:0.8混合均匀配置成溶液,将得到的溶液移入水热反应釜,并放置在120℃的烘箱中反应20h,反应结束后取出反应釜降至室温,得到一种透明粘性液体---聚乙烯基倍半硅氧烷(PVPSQ)。接着,将得到的透明粘性液体、甲基三甲氧基硅烷、苯甲醇、去离子水、Zonyl 9361氟碳表面活性剂按体积比1:3:6:8:0.5混合均匀配成溶液,室温下搅拌1.5h,继续加入一定量的氨水,氨水浓度控制在25wt%,体积占总溶液体积的1%,得到聚乙烯基倍半硅氧烷/聚甲基硅氧烷溶胶溶液,在该溶液中滴加氟硅烷---1H,1H,2H,2H-全氟癸基三甲氧基硅烷,有机硅烷与氟硅烷体积比控制在1:0.5,搅拌均匀,薄膜密封,并放置在60℃的真空干燥箱中1.5h,得到聚乙烯基倍半硅氧烷/聚甲基硅氧烷凝胶。加入甲醇与水体积比为1:3的老化液,对该复合湿凝胶进行老化处理,每10h更换一次老化液,更换5次。得到半透明状的聚乙烯基倍半硅氧烷/聚甲基硅氧烷醇凝胶。将样品放置在CO2超临界干燥反应釜中进行干燥处理,反应温度为45℃,高压反应釜压力控制在10MPa,反应时间为12h,最终获得块状聚乙烯基倍半硅氧烷/聚甲基硅氧烷复合气凝胶材料。经过表征发现,该气凝胶材料的比表面积为488.65m2/g,孔隙率为94%,平均孔径为22nm,疏水角为152.68°,疏油角为148.10°。经过表征发现,该气凝胶材料的比表面积为458.68m2/g,孔隙率为96%,平均孔径为23nm,疏水角为155.96°,疏油角为153.88°。
Claims (9)
1.一种具有超双疏性能的有机硅气凝胶的制备方法,其具体步骤如下:
(1)溶胶的制备
首先,将有机硅烷和引发剂按体积比1:(0.1~1)混合均匀配置成溶液,移入水热反应釜,并放置在100~120℃的烘箱中反应12-24h,反应结束后取出降温,得到透明的粘性液体聚乙烯基硅氧烷;然后将得到的聚乙烯基硅氧烷、甲基三甲氧基硅烷、苯甲醇、去离子水、氟碳表面活性剂按体积比1:(1~4):(2~8):(2~10):(0.2~0.6)混合均匀配成溶液,搅拌0.5~2h,继续滴加碱性催化剂,得到有机硅溶胶;
(2)老化
在制得的有机硅溶胶中滴加氟硅烷,有机硅烷与氟硅烷体积比控制在1:(0.2~0.6),搅拌均匀,薄膜密封,并放置在50~60℃的真空干燥箱中0.5~2h,得到有机硅复合湿凝胶;加入老化液,对该有机硅复合湿凝胶进行老化处理,得到半透明状的有机硅凝胶;
(3)CO2超临界干燥
将步骤(2)中得到的半透明状的有机硅凝胶样品进行CO2超临界干燥处理,获得块状具有超双疏性能的有机硅气凝胶。
2.根据权利要求1所述的制备方法,其特征在于步骤(1)中所述的有机硅烷为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷或乙烯基甲基二甲氧基硅烷中的一种。
3.根据权利要求1所述的制备方法,其特征在于步骤(1)中所述的引发剂为二叔丁基过氧化物。
4.根据权利要求1所述的制备方法,其特征在于步骤(1)中所述的氟碳表面活性剂为Capstone FS-61氟碳表面活性剂、Zonyl 9361氟碳表面活性剂或Zonyl TM氟碳表面活性剂。
5.根据权利要求1所述的制备方法,其特征在于步骤(1)中所述的碱性催化剂为氨水、氟化铵、四甲基氢氧化铵溶液;碱性催化剂的质量浓度为20-30%;碱性催化剂加入体积量占总溶液体积的1-3%。
6.根据权利要求1所述的制备方法,其特征在于步骤(2)中所使用的氟硅烷是1H,1H,2H,2H-全氟癸基三乙氧基硅烷或1H,1H,2H,2H-全氟癸基三乙氧基硅烷。
7.根据权利要求1所述的制备方法,其特征在于步骤(2)中所使用的老化液为醇与水按体积比为1:(1~4)混合的混合溶液,其中所述的醇为乙醇、异丙醇或甲醇。
8.根据权利要求1所述的制备方法,其特征在于步骤(2)中所述的老化处理为每8~12h更换一次老化液,更换次数为3~5次。
9.根据权利要求1所述的制备方法,其特征在于优选步骤(3)中CO2超临界干燥反应温度为45~50℃,高压反应釜压力控制在10~12MPa,干燥时间为12~24h。
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