CN105964154A - 一种亲水性高粘附强度内衬pvdf中空纤维膜的制备 - Google Patents
一种亲水性高粘附强度内衬pvdf中空纤维膜的制备 Download PDFInfo
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Abstract
本发明涉及高分子中空纤维微孔膜制备领域,具体公开了一种亲水性高粘附强度内衬PVDF中空纤维膜的制备,包括:铸膜液的制备、编织内衬结构选择与预处理、纺丝、后处理步骤。本发明以内外孔径呈梯度变化的编织内衬支撑PVDF中空纤维膜的分离层,利用有机/无机亲水性添加剂共混提高膜表面亲水性,同时对支撑编织内衬进行碱液处理或者有机溶剂处理,有效清除内衬表面的油污的同时活化编织内衬表层的分子结构,促进铸膜液渗透进入支撑编织内衬深层,并与支撑编织内衬互相融合粘结,增加分离层与内衬的粘附强度。本发明有效提高支撑内衬和表面PVDF分离层的粘结性能和抗污染性,制备的分离膜使用寿命和应用范围均得到提高。
Description
技术领域
本发明涉及高分子中空纤维微孔膜制备领域,具体涉及一种亲水性高粘附强度内衬PVDF中空纤维膜的制备。
背景技术
膜分离技术广泛地应用于污水处理,饮用水净化,食品饮料的分离以及生物医药活性中间体的提取等领域,在众多分离膜中,中空纤维超滤膜应用最普遍,其装填密度高,制备过程简单,膜丝性质稳定,膜组件可以灵活设计封装,能够满足各种不同应用场合的需求,大多数超滤和微滤都采用中空纤维的形式,目前也有厂家在探索开发中空纤维纳滤膜和中空纤维反渗透膜产品。
与普通中空纤维膜相比,内衬增强的中空纤维膜具有极好的拉伸强度,能够耐受更高的冲击力和渗透压力,有效解决中空纤维断丝问题,显著提高膜组件的使用寿命,保证出水质量,特别在MBR膜过程中表现出良好的优越性。
现有技术中的中空纤维膜,均存在一些缺陷:1、无支撑聚偏氟乙烯中空纤维膜皮层厚,容易发生断丝,处理效率低;2、内衬增强中空纤维膜分离层粘结强度低,皮层脱落影响处理效果和使用寿命;3、聚偏氟乙烯中空纤维膜亲水性差,使用过程中容易吸附污染物质,降低处理效率等缺陷。分离层的粘结强度和表面亲水性是影响内衬增强中空纤维膜分离性能的两个重要因素,由此可见,现有技术的中空纤维膜性能有待进一步的改善。
发明内容
有鉴于此,有必要针对上述的问题,提供一种亲水性高粘附强度内衬PVDF中空纤维膜的制备。
为实现上述目的,本发明采取以下的技术方案:
本发明的亲水性高粘附强度内衬PVDF中空纤维膜制备方法,包括:
步骤1铸膜液的制备:将偏氟乙烯、溶剂、亲水添加剂混合后搅拌并加热促进溶解,待溶解完全后,保温静置脱泡12-24h,所述亲水添加剂通过共混制备铸膜液,制备成膜后添加剂大量富集于膜的外表面,可增强膜的抗污染性。
步骤2编织内衬预处理:选用所需结构的编织内衬,配制预处理溶液,将所述编织内衬置于预处理溶液中浸泡3-5小时,然后取出,安装在纺丝机上待用;所述编织内衬的截面编织孔径由内向外逐渐增大;所述的预处理溶液为有机溶剂或碱溶液中的至少一种;纺丝前对内衬进行预处理,有效增强过滤层的粘附强度;选用内外编织孔径呈梯度变化的编织内衬支撑PVDF中空纤维膜的分离层,
步骤3纺丝:选用尺寸与编织内衬相匹配的喷丝头,调整编织内衬与喷丝头料液孔的相对位置,使之同轴并垂直,设置喷丝头入水间隙为5-30cm,以水为外部凝固浴进行纺丝;
步骤4后处理:将纺丝置于漂洗浴中漂洗后晾干,即可得到亲水性高粘附强度内衬PVDF中空纤维膜。
进一步的,步骤1所述的铸膜液原料的质量份数为:偏氟乙烯10-19份、溶剂66-85份、亲水添加剂5-15份。
进一步的,所述的亲水添加剂的质量百分含量为3.5%-15%亲水性聚合物和质量百分含量为0-1.5%纳米粒子;联合使用无机纳米粒子和亲水性聚合物的亲水性对PVDF内衬中空纤维膜分离层进行亲水改性,同时无机纳米粒子良好的亲和相容性还可以增加分离层的孔隙率,改善分离层和内衬之间的粘附性。
进一步的,所述的纳米粒子平均粒径为20nm的二氧化钛、二氧化硅或钙钛矿粒子。
进一步的,所述内衬预处理液为聚偏氟乙烯的氮甲基吡咯烷酮溶液,其质量百分含量为1-5%;碱溶液的质量百分含量为0.5-1%。所示碱为常见碱性物质。
进一步的,所述的编织内衬内、外表面的编织孔径之比为1:3-10。
进一步的,所述的溶剂为N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲基乙酰胺、二甲基亚砜中的一种。
进一步的,所述的亲水性聚合物为聚乙二醇、聚氧乙烯聚氧丙烯醚嵌段共聚物、聚甲基丙烯酸甲酯或聚甲基丙烯酸甲酯-g-聚乙二醇。进一步的,所述的凝固浴和漂洗溶液的温度均为40-50℃,漂洗时间为5-12h。
本发明的有益效果为:
本发明利用内外孔径呈梯度变化的编织内衬支撑中空纤维膜的分离层,同时对支撑编织内衬进行碱液处理或者有机溶剂处理,有效清除内衬表面的油污的同时活化编织内衬表层的分子结构,促进铸膜液渗透进入支撑编织内衬深层,并与支撑编织内衬互相融合粘结,增加分离层与内衬的粘附强度。
本发明同时联合无机纳米粒子和亲水性聚合物的亲水性对内衬PVDF中空纤维膜分离层进行亲水改性,利用亲水性聚合物的自组装行为促使其在膜表面富集,提高膜表面的亲水性,同时无机纳米粒子良好的亲和相容性还可以增加分离层的孔隙率,改善分离层和内衬之间的粘附性。
附图说明
图1为本发明内外孔径呈梯度变化的编织内衬截面示意图;
图2为本发明的PVDF中空纤维膜截面结构示意图;
图3为本发明的PVDF中空纤维膜截面电子显微镜扫描图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将结合本发明实施例,对本发明的技术方案作进一步清楚、完整地描述。需要说明的是,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。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
称取聚偏氟乙烯14g,二甲基乙酰胺73g,聚氧乙烯聚氧丙烯醚嵌段共聚物12g,二氧化钛1g,加热到80摄氏度搅拌促进溶解。待完全溶解后静置脱泡12h。选用内衬的内径1mm、外径1.5mm,截面编织孔径呈梯度变化(截面内外孔径比为1:5)的支撑编织内衬,在质量百分含量为1%的氢氧化钠水溶液中浸泡3h后取出来晾干,然后将预处理的内衬安装在纺丝机上,调整内衬与喷丝头料液孔的相对位置,使之同轴并垂直,设置喷丝头入水间隙为5-30cm,以水为外部凝固浴进行纺丝,在清水漂洗浴中漂洗一段时间后晾干,即得到所述的内衬增强的聚偏氟乙烯中空纤维膜。
通过相关仪器设备对其性能进行测试,发现其耐受压力为3atm,纯水通量1020LMH(即每小时每平方米膜所通过水量L/m2h atm),质量分数为1%的BSA(牛血清蛋白)水溶液截留率96%,表面接触角58°。
实施例2
称取聚偏氟乙烯17g,二甲基乙酰胺77g,聚甲基丙烯酸甲酯-g-聚乙二醇聚合物5.5g,二氧化硅0.5g,加热到80摄氏度搅拌促进溶解。待完全溶解后静置脱泡12h。选用内衬的内径1.4毫米、外径2.0mm,截面编织孔径呈梯度变化(截面内外孔径比为1:5)的支撑编织内衬,在0.5%的氢氧化钠水溶液中浸泡2h后取出,再放在2%的聚偏氟乙烯氮甲基吡咯烷酮溶液中浸泡2h,然后将其安装在纺丝机上,调整内衬与喷丝头料液孔的相对位置,使之同轴并垂直,设置喷丝头入水间隙为5-30cm,以水为外部凝固浴进行纺丝,在清水漂洗浴中漂洗一段时间后晾干,即得到所述的内衬增强的聚偏氟乙烯中空纤维膜。
通过相关仪器设备对其性能进行测试,发现其耐受压力为4.5atm,纯水通量860LMH,质量分数为1%的BSA水溶液截留率99%,表面接触角45°。
实施例3
称取聚偏氟乙烯12g,二甲基乙酰胺76.5g,聚乙烯醇10g,钙钛矿纳米粒子1.5g,加热到80摄氏度搅拌促进溶解。待完全溶解后静置脱泡12h。选用内衬内径0.7mm、外径1.2mm,截面编织孔径呈梯度变化(截面内外孔径比为1:5)的支撑内衬,在3%的聚偏氟乙烯氮甲基吡咯烷酮溶液中浸泡4h,然后将其安装在纺丝机上,调整内衬与喷丝头料液孔的相对位置,使之同轴并垂直,设置喷丝头入水间隙为5-30cm,以水为外部凝固浴进行纺丝,在清水漂洗浴中漂洗一段时间后晾干,即得到所述的内衬增强的聚偏氟乙烯中空纤维膜。
通过相关仪器设备对其性能进行测试,发现其耐受压力为2.6atm,纯水通量1320LMH,质量分数为1%的BSA水溶液截留率92%,表面接触角48°。
为进一步验证本发明制备方案的技术效果,设计了以下两个对照实验:
对照实验1
称取聚偏氟乙烯14g,二甲基亚砜73g,聚氧乙烯聚氧丙烯醚嵌段共聚物12g,钙钛矿纳米粒子1g,加热到80摄氏度搅拌促进溶解。待完全溶解后静置脱泡12h。选用内衬的内径1毫米、外径1.5毫米的常规支撑内衬(内外径编织密度相同),在1%的氢氧化钠水溶液中浸泡2h后,取出来放在2%的聚偏氟乙烯氮甲基吡咯烷酮溶液中浸泡2h,然后将其安装在纺丝机上,调整内衬与喷丝头料液孔的相对位置,使之同轴并垂直,设置喷丝头入水间隙为5-30cm,以水为外部凝固浴进行纺丝,在清水中漂洗一段时间后晾干,即得到所述的内衬增强的聚偏氟乙烯中空纤维膜。
通过相关仪器设备对其性能进行测试,发现其耐受压力为1.8atm,纯水通量850LMH,质量分数为1%的BSA水溶液截留率94%,表面接触角50°。
对照实验2
称取聚偏氟乙烯12g,二甲基亚砜78g,聚乙烯醇10g,加热到80摄氏度搅拌促进溶解。待完全溶解后静置脱泡12h。选用内衬内径1.4毫米、外径2.0毫米的截面编织孔径呈梯度变化的支撑编织内衬直接安装在纺丝机上,调整内衬与喷丝头料液孔的相对位置,使之同轴并垂直,设置喷丝头入水间隙为5-30cm,以水为外部凝固浴进行纺丝,在清水中漂洗一段时间后晾干,即得到所述的内衬增强的聚偏氟乙烯中空纤维膜。
通过相关仪器设备对其性能进行测试,发现其耐受压力为1.5atm,纯水通量1080LMH,质量分数为1%的BSA水溶液截留率90%,表面接触角48°。
可见,本发明方法制备得到的PVDF中空纤维膜有利于铸膜液渗透进入支撑内衬深层并与支撑内衬互相融合粘结,增加分离层与支撑编织内衬的粘附强度。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (10)
1.一种亲水性高粘附强度内衬PVDF中空纤维膜的制备,其特征在于,包括:
步骤1铸膜液的制备:将偏氟乙烯、溶剂、亲水添加剂混合后搅拌并加热促进溶解,待溶解完全后,保温静置脱泡12-24h;
步骤2编织内衬预处理:选用所需结构的编织内衬,配制预处理溶液,将所述编织内衬置于预处理溶液中浸泡3-5小时,然后取出,安装在纺丝机上待用;所述编织内衬的截面编织孔径由内向外逐渐增大;所述的预处理溶液为有机溶剂或碱溶液中的至少一种;
步骤3纺丝:选用尺寸与编织内衬相匹配的喷丝头,调整编织内衬与喷丝头料液孔的相对位置,使之同轴并垂直,设置喷丝头入水间隙为5-30cm,以水为外部凝固浴进行纺丝;
步骤4后处理:将纺丝置于漂洗浴中漂洗后晾干,即可得到亲水性高粘附强度内衬PVDF中空纤维膜。
2.根据权利要求1所述的亲水性高粘附强度内衬PVDF中空纤维膜的制备,其特征在于,步骤1所述的铸膜液原料的质量份数为:偏氟乙烯10-19份、溶剂66-85份、亲水添加剂5-15份。
3.根据权利要求2所述的亲水性高粘附强度内衬PVDF中空纤维膜的制备,其特征在于,所述的亲水添加剂的质量百分含量为3.5%-15%亲水性聚合物和质量百分含量为0-1.5%纳米粒子。
4.根据权利要求3所述的亲水性高粘附强度内衬PVDF中空纤维膜的制备,其特征在于,所述的纳米粒子平均粒径为20nm的二氧化钛、二氧化硅或钙钛矿粒子。
5.根据权利要求2所述的亲水性高粘附强度内衬PVDF中空纤维膜的制备,其特征在于,所述内衬预处理液为聚偏氟乙烯的氮甲基吡咯烷酮溶液,其质量百分含量为1-5%;
碱溶液的质量百分含量为0.5-1%。
6.根据权利要求1所述的亲水性高粘附强度内衬PVDF中空纤维膜的制备,其特征在于,所述的编织内衬截面内、外表面的编织孔径之比为1:3-10。
7.根据权利要求1所述的亲水性高粘附强度内衬PVDF中空纤维膜的制备,其特征在于,所述的溶剂为N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲基乙酰胺、二甲基亚砜中的一种。
8.根据权利要求1所述的亲水性高粘附强度内衬PVDF中空纤维膜的制备,其特征在于,所述的亲水性聚合物为聚乙二醇、聚氧乙烯聚氧丙烯醚嵌段共聚物、聚甲基丙烯酸甲酯或聚甲基丙烯酸甲酯-g-聚乙二醇。
9.根据权利要求1所述的亲水性高粘附强度内衬PVDF中空纤维膜的制备,其特征在于,所述的凝固浴和漂洗溶液的温度均为40-50℃,漂洗时间为5-12h。
10.根据权利要求1-9任意一项所述的亲水性高粘附强度内衬PVDF中空纤维膜的制备方法获得的PVDF中空纤维膜。
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