CN115025635B - 一种桥架有机硅/go复合纳滤膜的制备方法 - Google Patents
一种桥架有机硅/go复合纳滤膜的制备方法 Download PDFInfo
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Abstract
本发明属于复合膜制备领域,特别涉及一种桥架有机硅/GO复合纳滤膜的制备方法,包括以下步骤:(1)静电纺丝制备PAN纳米纤维膜作为聚合物支撑体;(2)配置氧化石墨烯(GO)溶液,通过真空抽滤在PAN纳米纤维膜上制备氧化石墨烯层;(3)配置有机硅溶液,利用超声空化作用将有机硅溶液雾化成均匀细小的液滴,沉积到氧化石墨烯层上,经后处理,桥架有机硅中硅羟基基团与氧化石墨烯上的羟基、羧基脱水缩合形成共价键,制得桥架有机硅/GO复合纳滤膜。该复合膜桥架有机硅层具有高强度的硅网络结构,不仅能起到分离作用,而且也提高了氧化石墨烯层的稳定性。同时,桥架有机硅膜也具备良好的水热稳定性和化学稳定性,可应用于高温纳滤膜过程。
Description
技术领域
本发明属于复合膜制备技术领域,具体涉及到一种桥架有机硅/GO复合纳滤膜的制备方法。
背景技术
二维材料由于具有可调节的亚纳米级传输通道,是理想的膜分离制备材料。氧化石墨烯(GO)作为一种典型的二维材料,可以通过简单有序的堆叠,制备出具有高通量的叠层膜。但是GO膜在液体分离过程中稳定性和机械性能较差,所以提高GO膜结构稳定性是亟待解决的问题。例如,中国专利CN112774463A公开了一种结构稳定的氧化石墨烯分离膜及其制备方法,利用氧化石墨烯的亲水性和独特的片层结构与笼型倍半硅氧烷粒子进行层层自组装提高GO膜的稳定性。
近年来,一种新型的功能材料桥架有机硅,由于其具有高比表面积,优异的水热稳定性和化学稳定性,受到研究者的高度关注。目前,常见的制备桥架有机硅分离膜的方法有旋涂法和流延法,但仍存在一些不足。例如,旋涂法制膜厚度不均,容易出现缺陷。流延法制得的膜普遍较厚,传质阻力大,膜通量不高。
发明内容
本部分的目的在于概述本发明的实施例的一些方面以及简要介绍一些较佳实施例。在本部分以及本申请的说明书摘要和发明名称中可能会做些简化或省略以避免使本部分、说明书摘要和发明名称的目的模糊,而这种简化或省略不能用于限制本发明的范围。
鉴于上述和/或现有技术中存在的问题,提出了本发明。
因此,本发明的目的是,克服现有技术中的不足,提供一种桥架有机硅/GO复合纳滤膜的制备方法。
为解决上述技术问题,本发明提供了如下技术方案:一种桥架有机硅/GO复合纳滤膜的制备方法,其特征在于:包括,
将聚丙烯腈(PAN)溶于N,N-二甲基甲酰胺(DMF)中,在水浴加热条件下,将溶液搅拌至完全透明,得到PAN电纺溶液;将PAN溶液用于静电纺丝制膜,经热压干燥处理,得PAN纳米纤维膜;
将氧化石墨烯(GO)溶于去离子水中,经超声离心处理后得到GO溶液;将GO溶液稀释,通过真空抽滤在PAN纳米纤维膜上制备GO层;
将有机硅前驱体和盐酸,在异丙醇溶液中与水发生水解聚合反应,制得有机硅溶胶;
将有机硅溶胶通过超声热喷涂技术均匀喷涂到预热的GO层上,经后处理制得桥架有机硅/GO复合纳滤膜。
作为本发明所述制备方法的一种优选方案,其中:所述聚丙烯腈溶于N,N-二甲基甲酰胺的质量分数为10-20wt%,水浴加热温度为60-80℃,磁力搅拌2-4h。
作为本发明所述制备方法的一种优选方案,其中:所述静电纺丝处理工艺参数:进液速率0.5-2ml/h,施加电压15-25kV,接收距离8-15cm,滚轮转速100-200r/min。
作为本发明所述制备方法的一种优选方案,其中:所述热压温度为100-150℃。
作为本发明所述制备方法的一种优选方案,其中:所述GO溶液的质量分数为0.01-0.1wt%,超声时间为30-60min,离心转速6000-12000r/min,离心时间30min,真空抽滤的压力为0.06-0.1MPa。
作为本发明所述制备方法的一种优选方案,其中:所述硅源前驱体包括1,3-二(三乙氧基硅基)丙烷、1,2-二(三乙氧基硅基)乙炔或4,4'-二(三乙氧基硅基)联苯中的一种或两种。
作为本发明所述制备方法的一种优选方案,其中:所述硅源前驱体、水、盐酸的摩尔比为1:60-120:0.1-0.2,反应温度为40-60℃,反应时间为2~4h,盐酸浓度为37wt%。
作为本发明所述制备方法的一种优选方案,其中:所述预热的GO膜表面温度为30-50℃,喷涂有效面积为10×10cm,单次喷涂时间在1-2min,共喷涂2次。
作为本发明所述制备方法的一种优选方案,其中:所述超声设备的进料溶液浓度为0.5~5wt%,超声功率为0.5~3Hz,进液流速为0.1~2ml/min,气载流量为0.01~0.05MPa,单道喷涂步距为1~5mm,喷头与撑体的距离为2~4cm。
作为本发明所述制备方法的一种优选方案,其中:所述后处理是将桥架有机硅/GO复合纳滤膜在60-150℃条件下处理15-30min。
本发明有益效果:
(1)选择桥架有机硅材料制备GO膜顶层,桥联有机硅网络具有较强的机械强度和水热稳定性,所以桥架有机硅层不仅能起到分离作用,还显著提高了膜的稳定性和机械强度,以及膜的使用寿命。
(2)采用超声空化喷涂在GO膜上制备了桥联有机硅分离膜提高GO膜稳定性和分离效果,形成连续的液膜。溶剂蒸发后,形成一层薄薄的膜层。对膜撑体预加热,能够有效降低溶液的粘度和表面张力,提高溶液的延展性,使溶液在膜撑体上分散更加均匀,膜的表面更加光滑平整。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其它的附图。其中:
图1为本发明实施例1中桥架有机硅/GO复合纳滤膜制备的流程示意图。
图2为本发明实施例1中GO/PAN复合纳滤膜的表面和断面的SEM图。
图3为本发明实施例1中BTESP/GO复合纳滤膜的表面和断面的SEM图。
图4为本发明实施例1中BTESP/GO复合纳滤膜的热稳定性测试图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合说明书实施例对本发明的具体实施方式做详细的说明。
在下面的描述中阐述了很多具体细节以便于充分理解本发明,但是本发明还可以采用其他不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似推广,因此本发明不受下面公开的具体实施例的限制。
其次,此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例,也不是单独的或选择性的与其他实施例互相排斥的实施例。
实施例1
(1)将10g分子量为8000Da的聚丙烯腈(PAN)粉末溶于90g的N,N-二甲基甲酰胺(DMF)溶剂中,质量分数为10wt%,在80℃水浴条件下,磁力搅拌4h,至溶液完全透明,得到PAN电纺溶液;
(2)将步骤(1)制备的PAN电纺溶液用于静电纺丝,以不锈钢滚轮为接收装置,纺丝液进液速率1.5ml/h,施加电压20kV,接收距离12cm,滚轮转速100r/min,纺丝8h,将膜切分成10x10cm,在100℃热压反复处理3次后得到膜;
(3)将棕黄色的氧化石墨烯粉末溶于去离子水中,超声处理60min,以8000r/min的转速离心30min,得到质量分数为0.1wt%的GO溶液;
(4)将GO溶液稀释至0.01wt%,将稀释的GO溶液通过0.8bar的真空抽滤负载到有效面积为12.56cm2的PAN纳米纤维膜上,用去离子水清洗2-3次,自然干燥12h,即可得到0.16g/m2的GO膜;
(5)将1,3-二(三乙氧基硅基)丙烷(BTESP)加入到异丙醇中,搅拌1~2min,再滴加去离子水,继续搅拌1~2min后滴加浓盐酸,硅源前驱体、水、盐酸的摩尔比为1:60:0.1,立刻将烧杯转移至60℃的恒温水浴锅中持续搅拌2h,得5wt%硅溶胶;
(6)将步骤(5)制备的硅溶胶稀释至2wt%,注入注射器并固定,超声波控制器识别信号,进液速度为0.2ml/min,超声频率1.3Hz,喷头高度为30mm,单道喷涂步距为2mm,溶胶经超声作用分散成微小的均匀液滴,随氮气进入沉积室,气载流量为0.02MPa。微小液滴从喷雾口均匀地沉积在GO膜上,基底温度为40℃,2min完成一次沉积,使溶剂自然挥发1~2min,喷涂2次,在80℃条件下处理30min。将所制备的膜应用于50℃的染料/水分离体系(50ppm罗丹明B)。
实施例2
(1)将10g分子量为8000Da的聚丙烯腈(PAN)粉末溶于90g的N,N-二甲基甲酰胺(DMF)溶剂中,质量分数为10wt%,在60℃水浴条件下,磁力搅拌6h,至溶液完全透明,得到PAN电纺溶液;
(2)将步骤(1)制备的PAN电纺溶液用于静电纺丝,以不锈钢滚轮为接收装置,纺丝液进液速率1.3ml/h,施加电压20kV,接收距离10cm,滚轮转速100r/min,纺丝8h,将膜切分成10x10cm,在100℃热压反复处理3次后得到膜;
(3)将棕黄色的氧化石墨烯粉末溶于去离子水中,超声处理60min,以8000r/min的转速离心60min,得到质量分数为0.1wt%的GO溶液;
(4)将GO溶液稀释至0.01wt%,将稀释的GO溶液通过1.0bar的真空抽滤负载到有效面积为12.56cm2的PAN纳米纤维膜上,用去离子水清洗2-3次,自然干燥12h,即可得到0.32g/m2的GO膜;
(5)将1,2-二(三乙氧基硅基)乙炔(BTESA)加入到异丙醇中,搅拌1~2min,再滴加去离子水,继续搅拌1~2min后滴加浓盐酸,硅源前驱体、水、盐酸的摩尔比为1:120:0.1,立刻将烧杯转移至40℃的恒温水浴锅中持续搅拌2h,得5wt%硅溶胶;
(6)将步骤(5)制备的硅溶胶稀释至2wt%,注入注射器并固定,进液速度为0.2ml/min,超声频率1.3Hz,喷头高度为30mm,单道喷涂步距为2mm,溶胶经超声作用分散成微小的均匀液滴,随氮气进入沉积室,气载流量为0.02MPa。微小液滴从喷雾口均匀地沉积在GO膜上,基底温度为40℃,2min完成一次沉积,使溶剂自然挥发1~2min,喷涂2次,在100℃条件下处理20min。将所制备的膜应用于50℃的染料/水分离体系(50ppm罗丹明B)。
对比实施例1
步骤(1)(2)(3)的具体操作均与实施例1相同;
(4)将GO溶液稀释至0.02wt%,将稀释的GO溶液通过1.0bar的真空抽滤负载到有效面积为12.56cm2的PAN纳米纤维膜上,用去离子水清洗2-3次,在40℃真空条件下处理12h,即可得到0.24g/m2的GO膜。将所制备的膜应用于50℃的染料/水分离体系(50ppm罗丹明B)。
对比实施例2
步骤(1)、(2)、(3)、(4)、(5)的具体操作均与实施例1相同;
(6)将步骤(5)制备的有机硅溶胶通过旋涂法涂覆到GO膜上,其中使用的液量为1ml,旋涂机转速为2000rpm,涂覆时间为30s,涂覆次数为2次,旋涂结束后在100℃下热处理30min,制得桥联有机硅/GO复合纳滤膜。将所制备的膜应用于50℃的染料/水分离体系(50ppm罗丹明B)。
上述各实施例和对比例实验结果见表1。
表1
膜 | 通量L/(m2hbar) | 染料截留率(%) |
实施例1 | 9.2 | 99.4 |
实施例2 | 8.6 | 99.5 |
对照例1 | 16.3 | 68.1 |
对照例2 | 6.2 | 98.8 |
选择桥架有机硅材料制备GO膜顶层,桥架有机硅经水解后,产生大量硅羟基官能团,这些硅羟基官能团相互缩聚形成致密的桥架有机硅网络;同时,部分硅羟基官能团与氧化石墨烯上的含氧官能团(羟基、羧基)相互交联,形成共价网络结构,紧密结合。桥联有机硅网络具有较强的机械强度和水热稳定性,图4可知桥架有机硅/GO复合纳滤膜的热稳定性,在长时间加压(0.4MPa)的水通量测试过程中膜的截留率和渗透通量保持稳定状态,以此证明了有机硅桥架膜具有较高的机械强度。所以桥架有机硅层不仅能起到分离作用,还显著提高了膜的稳定性和机械强度,以及膜的使用寿命。
采用超声空化喷涂在GO膜上制备了桥联有机硅分离膜提高GO膜稳定性和分离效果。纳米桥联有机硅溶胶由于表面能高,比表面积大,表面含有大量羟基官能团,易在水中发生团聚,而超声空化作用可以将软团聚的溶胶打碎,重新生成小粒径溶胶,使溶胶分散更加均匀。同时,前驱体溶液经超声空化作用被打碎形成均匀细小液滴,许多微米大小的液滴被喷涂到膜撑体上。一旦沉积到膜撑体表面,这些液滴就会扩散合并,形成连续的液膜。溶剂蒸发后,形成一层薄薄的膜层。对膜撑体预加热,能够有效降低溶液的粘度和表面张力,提高溶液的延展性,使溶液在膜撑体上分散更加均匀,膜的表面更加光滑平整。
应说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (6)
1.一种桥架有机硅/GO复合纳滤膜的制备方法,其特征在于:包括,
将聚丙烯腈(PAN)溶于N,N-二甲基甲酰胺(DMF)中,在水浴加热条件下,将溶液搅拌至完全透明,得到PAN电纺溶液,其中,所述聚丙烯腈溶于N,N-二甲基甲酰胺的质量分数为10-20wt%,水浴加热温度为60-80℃,搅拌时间为2-4h;
PAN电纺溶液用于静电纺丝制膜,经热压干燥处理,得PAN纳米纤维膜;氧化石墨烯(GO)溶于去离子水中,经超声离心处理后得到GO溶液,稀释后通过真空抽滤在PAN纳米纤维膜上制备GO层;
将硅源前驱体和盐酸在异丙醇溶液中与水发生水解聚合反应,制得有机硅溶胶,其中,所述硅源前驱体包括1,3-二(三乙氧基硅基)丙烷、1,2-二(三乙氧基硅基)乙炔或4,4'-二(三乙氧基硅基)联苯中的一种或两种,所述盐酸浓度为37wt%,所述硅源前驱体、水、盐酸的摩尔比为1:60-120:0.1-0.2;
将有机硅溶胶通过超声热喷涂技术均匀喷涂到预热的GO层上,经后处理制得桥架有机硅/GO复合纳滤膜,其中,所述预热的GO膜表面温度为30-50℃,喷涂有效面积为10×10cm,单次喷涂时间在1-2min,共喷涂2次。
2.如权利要求1所述桥架有机硅/GO复合纳滤膜的制备方法,其特征在于:所述静电纺丝的处理工艺参数为,进液速率0.5-2 ml/h,施加电压15-25 kV,接收距离8-15 cm,滚轮转速100-200 r/min。
3.如权利要求1所述桥架有机硅/GO复合纳滤膜的制备方法,其特征在于:所述热压干燥处理的温度为100-150℃。
4.如权利要求1所述桥架有机硅/GO复合纳滤膜的制备方法,其特征在于:所述GO溶液的质量分数为0.01-0.1wt%,超声离心处理的时间为30,离心转速6000-12000 r/min,真空抽滤的压力为0.06-0.1 MPa。
5.如权利要求1所述桥架有机硅/GO复合纳滤膜的制备方法,其特征在于:所述超声热喷涂的设备的进料溶液浓度为0.5~5wt%,超声功率为0.5~3 Hz,进液流速为0.1~2 ml/min,气载流量为0.01~0.05 MPa,单道喷涂步距为1~5 mm,喷头与撑体的距离为2~4 cm。
6.如权利要求1所述桥架有机硅/GO复合纳滤膜的制备方法,其特征在于:所述后处理是将桥架有机硅/GO复合纳滤膜在60-150℃条件下处理15-30min。
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