CN1332738C - 高通量结晶性聚合物微孔滤膜的制备方法 - Google Patents
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Abstract
本发明公开了高通量结晶性聚合物微孔滤膜的制备方法，以重量份计，依如下顺序步骤进行：1)将结晶性聚合物树脂、稀释剂、致孔性的固体粉末混合均匀，升温搅拌溶解配制成铸膜液；2)将配制好的铸膜液过滤以除去杂质，然后静置脱泡；再将铸膜液刮涂在支撑网形成平板状或通过喷嘴纺制成中空纤维的形状，然后固化成型；3)将已经固化的聚合物膜置于提取液中处理后，漂洗，干燥后即得到本发明的高通量微滤膜。本发明克服了TIPS法制膜过程中容易形成封闭的胞腔状孔结构的缺点，而且可以获得的均匀的孔结构。
Description
技术领域
本发明涉及采用热致相分离法制作的高通量结晶性聚合物微孔滤膜的制备方法。
背景技术
微滤过程通常指0.1微米至10微米的粒子的筛分过程，这一过程可以截留各种胶体、悬浮颗粒和病原性细菌等。近十年来，微滤膜的分离技术已经广泛地应用于污水处理、饮用水净化等以杀菌、除浊为目标的领域。当今的微滤膜的制作技术包括核径迹刻蚀法、拉伸法、浸入凝胶法(简称NIPS)等。这些制作方法得到的微滤膜的孔隙率一般在50％以下，膜的水通量一般小于200～300L/m2.hr.atm，所以都存在水通量低的问题。如果微滤膜单位面积的水通量高，那么就可以减小膜的使用面积，从而装置变得紧凑，设备费用亦会得到节约。如何提高微滤膜的水通量就是微滤技术的重要问题。
利用温度改变而致使高分子溶液发生液-液分相的原理制作微孔膜的方法称为热致相分离法(简称TIPS)。TIPS法在上世纪六、七十年就引起了人们的注意，但是直到1981年Akzona公司的Castro才申请了第一个具有潜在应用价值的专利[US4247498(1981)]。近十余年来基于TIPS法制作微孔滤膜的研究和开发工作仍然持续不断[如WO02/28947(2002)]。尽管一般情况下，TIPS法能获得比NIPS法更高孔隙率，但是TIPS法容易形成封闭孔，如何克服封闭孔并提高孔结构的连通性就成了这项技术的关键。
和NIPS法相比，TIPS法有如下优点：它通过较为迅速的热交换导致高分子溶液分相，而不是缓慢的溶剂-非溶剂交换；其次，TIPS法还避免了NIPS法由于存在溶剂-非溶剂交换，导致成膜液中部分溶剂参与了聚合物的凝胶化，所以孔隙率低的缺点；TIPS法的另一个优点是可以用于无合适溶剂难以采用NIPS法制作的结晶性聚合物的微孔滤膜的制作，由于聚合物材质的结晶性，所以成膜具有较高的强度；TIPS法制作微滤膜所选择的溶剂通常是植物油(如大豆油、棕榈油、菜油等)、矿物质油、石蜡等，这些物质有大量的工业来源，而且价格低廉。
现有的TIPS法制作技术普遍面临的难点是容易出现封闭的或连通性差的胞腔状孔结构。尽管具有这样孔结构的微滤膜具有很高的孔隙率，但水通量极低，无法用于工业应用。中国专利CN 1481272A中公布了一种避免孔结构封闭的制作方法，通过将TIPS法制作的毛细管式或中空纤维式膜进一步拉伸，就可以将原来的连通性低的孔结构变形，从而实现更高连通性的孔结构。这样制作的微滤膜的孔结构不均一，所以在使用过程中更容易出现膜污染。
微滤膜的分离特性通常用水通量和筛分粒子的尺寸表征。微滤膜的孔径大小和形态可以通过电子显微镜观测，并以此确定筛分粒子的大小范围。水通量的测试在一般的微滤膜水通量测试系统中进行。透过侧压力维持在105Pa，透过液的体积用量筒量取，并由此计算出单位时间内流过单位面积的水量。
发明内容
本发明的目的是建立制作高水通量微滤膜的制备方法。本发明公布了操作方便、适宜于工业应用的TIPS法制膜技术，这种技术克服了TIPS法制膜过程中容易形成封闭的胞腔状孔结构的缺点，而且可以获得的均匀的孔结构。
本发明的高通量结晶性聚合物微孔滤膜的制备方法，以重量份计，依如下顺序步骤进行：
1)铸膜液的配制
将结晶性聚合物树脂、稀释剂、致孔性的固体粉末混合均匀，升温至180～240℃搅拌溶解配制成铸膜液。结晶性聚合物树脂的含量在重量浓度10～50％内为佳。致孔性的固体粉末用量太多，成膜强度降低；用量太少，成膜水通量变小；所以致孔性的固体粉末的含量在重量浓度10～40％内为佳。
适用于本发明的结晶性聚合物树脂有如下各种类型：聚乙烯、聚丙烯、聚偏氟乙烯、尼龙、聚苯硫醚、聚苯醚、聚4-甲基戊烯-1等，数均分子量在70,000～200,000之间(以70,000～110,000为宜)。
稀释剂为结晶性聚合物树脂高温下的溶剂，但在室温不能与树脂相溶。适用于本发明的稀释剂有：植物油(如大豆油、棕榈油、菜油、芝麻油、芥菜油、橄榄油等)、矿物质油、石蜡、二苯醚、邻苯二甲酸二于酯、邻苯二甲酸二辛酯、月桂酸二乙醇酰胺、聚氧乙烯油醇、鲸蜡醇油酸、脱水山梨糖醇油酸酯、脱水山梨糖醇一倍半油酸酯、脱水山梨糖醇一硬酸酯、亚油酸、氯三氟乙烯低聚物、9，12g-十六碳二烯酸、油酸、软脂酸、二亚苄基山梨醇。
粉末状固体在稀释剂、聚合物树脂的高温溶液中仍呈固态，而且和聚合物溶液不产生任何反应。适用于本发明的粉末状固体有：γ-Al2O3纳米粒子、硫化镉纳米粒子、二氧化钛纳米粒子、C60(富勒烯)、C70(富勒烯)、α-Al粉末、憎水性二氧化硅粉末、沸石粉末、碳纳米粉末、碳纳米管。这些粉末或纳米粒子都可以从市面上购得。
2)铸膜液的固化
将配制好的铸膜液过滤以除去杂质，然后静置脱泡6小时至24小时；再将铸膜液刮涂在支撑网形成平板状或通过喷嘴纺制成中空纤维的形状；然后迅速浸入低温的液态介质中固化成型。
适用于本发明的液态介质必须是对高分子树脂无任何腐蚀作用的液体，比如水、异丙醇、甘油等。本发明对液态介质的种类没有任何特殊的要求。
液态介质的温度控制范围是-10～80℃，以10～50℃为宜。
3)将固态粉末从成膜中提取
将已经固化的聚合物膜置于提取液中处理，成膜中的固体粉末会被提取液溶解而留下空隙，将含提取液的微滤膜置于水中漂洗，干燥后即得到本发明的高通量微滤膜。
适用于本发明的提取液有：硫酸、盐酸、硝酸、NaOH水溶液、次氯酸盐水溶液。
附图说明
图一是实施例1的断面电镜照片
图二是实施例2的断面电镜照片
具体实施方式
实施例1
将聚丙烯树脂(熔融指数2.5)300克、憎水性二氧化硅粉末(粒子平均直径16mμ，比表面积110平方米/克)200克、石蜡油(Tb＝200℃)500克混合升温至240℃溶解呈悬浮液；在恒温200℃下静置脱泡6小时至24小时；将铸膜液刮涂在支撑网上，然后迅速浸入45℃的水浴中固化成型；将已经固化成型的聚丙烯膜浸入20％的次氯酸盐水溶液中处理3～12小时；然后置于水中漂洗清除残留的次氯酸盐。最后在室温晾干保存。
成膜平均孔径0.45微米，纯水通量4120升/平方米.小时.1大气压。膜断面在电子显微镜下观测，为均匀的网络状连通的孔结构。
实施例2
将聚乙烯树脂(熔融指数1.5)300克、憎水性二氧化硅粉末(粒子平均直径16mμ，比表面积110平方米/克)250克、石蜡油(Tb＝200℃)450克混合升温至220℃溶解呈悬浮液；在恒温200℃下静置脱泡6小时至24小时；将铸膜液刮涂在支撑网上，然后迅速浸入20℃的水浴中固化成型；将已经固化成型的聚乙烯膜浸入20％的次氯酸盐水溶液中处理3～12小时；然后置于水中漂洗清除残留的次氯酸盐。最后在室温晾干保存。
成膜平均孔径0.20微米，纯水通量2240升/平方米.小时.1大气压。膜断面在电子显微镜下观测，为均匀的网络状连通的孔结构。
实施例3
将聚偏氟乙烯树脂(分子量22.6万)300克、憎水性二氧化硅粉末(粒子平均直径16mμ，比表面积110平方米/克)200克、邻苯二甲酸二辛酯500克混合升温至210℃溶解呈悬浮液；在恒温200℃下静置脱泡6小时至24小时；将铸膜液经计量泵注入喷嘴成中空纤维形状，然后迅速浸入20℃的水浴中固化成型；将已经固化成型的聚偏氟乙烯中空纤维膜浸入20％的次氯酸盐水溶液中处理3～12小时；然后置于水中漂洗清除残留的次氯酸盐。最后在室温晾干保存。
成膜平均孔径0.23微米，纯水通量3200升/平方米.小时.1大气压。膜断面在电子显微镜下观测，为均匀的网络状连通的孔结构。
实施例4
将聚偏氟乙烯树脂(分子量22.6万)300克、憎水性二氧化硅粉末(粒子平均直径16mμ，比表面积110平方米/克)250克、邻苯二甲酸二辛酯450克混合升温至210℃溶解呈悬浮液；在恒温200℃下静置脱泡6小时至24小时；将铸膜液经计量泵注入喷嘴成中空纤维形状，然后迅速浸入20℃的水浴中固化成型；将已经固化成型的聚偏氟乙烯中空纤维膜浸入20％的次氯酸盐水溶液中处理3～12小时；然后置于水中漂洗清除残留的次氯酸盐。最后在室温晾干保存。
成膜平均孔径0.30微米，纯水通量4500升/平方米.小时.1大气压。膜断面在电子显微镜下观测，为均匀的网络状连通的孔结构。
Claims (7)
1.高通量结晶性聚合物微孔滤膜的制备方法，以重量份计，依如下顺序步骤进行：
1)铸膜液的配制
将数均分子量为70,000～200,000的结晶性聚合物树脂、稀释剂、致孔性的固体粉末混合均匀，升温至180～240℃搅拌溶解配制成铸膜液；
2)铸膜液的固化
将配制好的铸膜液过滤以除去杂质，然后静置脱泡6小时至24小时；再将铸膜液刮涂在支撑网形成平板状或通过喷嘴纺制成中空纤维的形状，然后迅速浸入-10～80℃温度的液态介质中固化成型；
3)将固态粉末从成膜中提取
将已经固化的聚合物膜置于提取液中处理后，将含提取液的微滤膜置于水中漂洗，干燥后即得到本发明的高通量微滤膜。
2.根据权利要求1的制备方法，其特征在于：所述聚合物树脂的含量在重量浓度10～50％，所述致孔性的固体粉末的含量在重量浓度10～40％。
3.根据权利要求1或2的制备方法，其特征在于：所述结晶性聚合物树脂为聚乙烯、聚丙烯、聚偏氟乙烯、尼龙、聚苯硫醚、聚苯醚或聚4-甲基戊烯-1。
4.根据权利要求1或2的制备方法，其特征在于：所述稀释剂为植物油、矿物质油、石蜡、二苯醚、邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、月桂酸二乙醇酰胺、聚氧乙烯油醇、鲸蜡醇油酸、脱水山梨糖醇油酸酯、脱水山梨糖醇一倍半油酸酯、脱水山梨糖醇一硬酸酯、业油酸、氯三氟乙烯低聚物、9，12-十六碳二烯酸、油酸或软脂酸或二亚苄基山梨醇。
5.根据权利要求1或2的制备方法，其特征在于：所述粉末状固体为γ-Al2O3纳米粒子、硫化镉纳米粒子、二氧化钛纳米粒子、C60、C70、α-Al粉末、憎水性二氧化硅粉末、沸石粉末、碳纳米粉末或碳纳米管。
6.根据权利要求1或2的制备方法，其特征在于：所述液态介质为水、异丙醇或甘油。
7.根据权利要求1或2的制备方法，其特征在于：所述提取液为硫酸、盐酸、硝酸、NaOH水溶液或次氯酸盐水溶液。
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| CN103406034B (zh) * | 2013-07-30 | 2015-09-09 | 浙江国泰密封材料股份有限公司 | 一种用于膜蒸馏过程的聚醚嵌段酰胺微孔膜的制备方法 |
| CN106178972B (zh) * | 2016-08-27 | 2019-09-27 | 天津津纶新材料科技有限公司 | 一种耐高温pps气体分离膜的制备方法 |
| CN106310966A (zh) * | 2016-09-29 | 2017-01-11 | 盐城海普润膜科技有限公司 | 一种内支撑平板膜及其制备方法和应用 |
| CN107998903A (zh) * | 2016-11-01 | 2018-05-08 | 中国石油化工股份有限公司 | 一种聚丙烯中空纤维微孔膜的制备方法 |
| CN108456412A (zh) * | 2018-03-06 | 2018-08-28 | 查公祥 | 一种皂化抑菌质子膜及其制备方法 |
| CN111041584B (zh) * | 2019-08-23 | 2022-08-30 | 苏州纤创智造新材料科技有限公司 | 一种控制聚偏氟乙烯结晶的复合晶种、制备方法及材料 |
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| EP0302597A2 (en) * | 1987-07-08 | 1989-02-08 | Tonen Chemical Corporation | Gas-pervious composite film and method for its production |
| US5231126A (en) * | 1985-04-01 | 1993-07-27 | Shi Guan Yi | Beta-crystalline form of isotactic polypropylene and method for forming the same |
| CN1415407A (zh) * | 2002-11-19 | 2003-05-07 | 华东理工大学 | 高通量聚氯乙烯中空纤维超滤膜的制备方法 |
| CN1504257A (zh) * | 2002-11-29 | 2004-06-16 | 中国科学院生态环境研究中心 | 一种高通量多孔膜的制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5231126A (en) * | 1985-04-01 | 1993-07-27 | Shi Guan Yi | Beta-crystalline form of isotactic polypropylene and method for forming the same |
| EP0302597A2 (en) * | 1987-07-08 | 1989-02-08 | Tonen Chemical Corporation | Gas-pervious composite film and method for its production |
| CN1415407A (zh) * | 2002-11-19 | 2003-05-07 | 华东理工大学 | 高通量聚氯乙烯中空纤维超滤膜的制备方法 |
| CN1504257A (zh) * | 2002-11-29 | 2004-06-16 | 中国科学院生态环境研究中心 | 一种高通量多孔膜的制备方法 |
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