CN104353372A - 一种芳香族聚酰胺中空纤维多孔膜的制备方法 - Google Patents

一种芳香族聚酰胺中空纤维多孔膜的制备方法 Download PDF

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CN104353372A
CN104353372A CN201410624318.7A CN201410624318A CN104353372A CN 104353372 A CN104353372 A CN 104353372A CN 201410624318 A CN201410624318 A CN 201410624318A CN 104353372 A CN104353372 A CN 104353372A
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ppta
hollow fiber
fiber porous
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CN104353372B (zh
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肖长发
王纯
陈明星
安树林
黄庆林
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Tianjin Polytechnic University
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Abstract

本发明公开了一种芳香族聚酰胺中空纤维多孔膜的制备方法，该方法先将PPTA树脂、溶剂、致孔剂和无机粒子在溶解釜中预混制成铸膜液，再将铸膜液注入双螺杆挤出机，在剪切力作用下完全溶解，经计量泵进入喷丝板，干-湿法纺丝制成PPTA中空纤维多孔膜，解决PPTA纺丝制膜成孔难、孔隙率低等难题。双螺杆挤出机的使用可大大缩短料液溶解和脱泡时间，同时还可增大料液中PPTA含量，改进PPTA中空纤维多孔膜的力学性能；无机粒子的加入改善了膜性能，增加膜力学韧度，提高了纯水通量、亲水性和截留率。

Description

一种芳香族聚酰胺中空纤维多孔膜的制备方法
技术领域
本发明涉及有机-无机杂化中空纤维膜技术，具体为一种芳香族聚酰胺中空纤维多孔膜的制备方法。该芳香族聚酰胺是指聚对苯二甲酰对苯二胺(PPTA)。
背景技术
一般而言，不同聚合物之间存在着相与相之间的界面层。由于相界面的存在，在加工或使用过程中易发生相分离现象。因此，在制膜过程中可利用这种相分离现象来优化膜的性能。
有机聚合物与无机粒子杂化共混时，无机粒子常为高表面能物质，而有机聚合物为低表面能物质，因此，在两者混合时必将形成新的相界面，利用分相形成微孔。传统的有机多孔膜具有柔韧性良好、渗透性高、制备工艺简便等优点，但它们的耐溶剂性、耐腐蚀、耐温性均较差，而无机膜虽然强度高、耐腐蚀、耐高温，但质地较脆、不易加工、造价昂贵。因此，有机-无机杂化膜兼具有机、无机组分的特点，具有良好的分离特性和物化稳定性。
聚对苯二甲酰对苯二胺(PPTA)是典型的对位型芳香族聚酰胺，大分子呈刚性，是制备纤维的重要原料，其具有优异的耐高温性、耐溶剂性，是制备高性能中空纤维多孔膜的理想材料。但由于其熔点(＞500℃)低于分解温度，不能采用熔融纺丝技术加工成形，同时，由于PPTA刚性大分子在溶解过程中自由能变化的熵值较柔性大分子小，即难以被常规溶剂溶解，只能被浓硫酸、氯磺酸等强无机酸溶解。P.Zschocke等[Solvent resistant membranes frompoly-(p-phenylene-terephthalamide),Desalination,34(1980)：69-75]制备了PPTA平板膜，测试了其在不同溶剂中的通量，膜纯水通量仅为12.8L/(m2d)(3MPa)；Katsumori Nakura等[Preparation of ultrafiltration membranes usingpoly-(p-phenylene-terephthalamide)as a membrane material.Maku,17(2)(1992):78-84]测试了PPTA平板膜在不同溶剂中对PEG(50000)的截留性能，虽然截留率较高，但同样存在通量较小的问题。
在PPTA纺丝溶液制备过程中高黏度料液的搅拌和脱泡是亟待解决的难题。浓硫酸溶解PPTA的方法已众所周知，但在常见溶解釜中溶解高黏度铸膜液需2～3个小时，且脱泡时间需要更长时间，其结果易导致PPTA大分子发生降解，影响所得中空纤维膜的力学性能，与此同时，还会使复合致孔剂变性，使铸膜液发黑变质。
发明内容
针对现有技术的不足，本发明拟解决的技术问题是，提供一种芳香族聚酰胺中空纤维多孔膜的制备方法，该方法先将PPTA树脂、溶剂、致孔剂和无机粒子在溶解釜中预混制成铸膜液，再将铸膜液注入双螺杆挤出机，在剪切力作用下完全溶解，经计量泵进入喷丝板，干-湿法纺丝制成PPTA中空纤维多孔膜，解决PPTA纺丝制膜成孔难、孔隙率低等难题。
本发明解决所述技术问题的技术方案是，提供一种芳香族聚酰胺中空纤维多孔膜的制备方法，该制备方法采用如下铸膜液和制膜工艺：所述铸膜液的质量分数组成为：
所述PPTA树脂比浓对数黏度为4.5dL/g～9.5dL/g；所述致孔剂为水溶性高分子，选自平均分子量为1000～20000的PEG和平均分子量为10000～1000000的PVP中的至少一种；所述溶剂为质量浓度为98％～106％的浓硫酸；所述无机粒子为二氧化硅、氯化钙或碳酸钙中的至少一种；
所述芳香族聚酰胺中空纤维多孔膜的制膜工艺是：
(1)预处理
在55℃下先将PPTA树脂在质量浓度为0.5～1％磷酸溶液中超声处理15～60分钟后，再将其与无机粒子于100℃～200℃真空干燥处理24h以上；
(2)PPTA中空纤维多孔膜制备
将预处理后的PPTA树脂、无机粒子和溶剂在密封溶解釜中混合，40～50℃下搅拌溶胀1～2h，形成透明黄色粘稠状预混液，然后加入所述复合致孔剂形成铸膜液，并将此铸膜液挤入双螺杆挤出机，在溶解温度80～90℃溶解1～20分钟，并通入温度为0～90℃、流速为10～100ml/min、体积分数为0～50％的硫酸水溶液作为纺丝芯液，经计量泵计量注入中空喷丝板，喷丝头拉伸比为1～10倍，随后铸膜液由中空喷丝板挤出，经高度为10～100mm的空气浴后，浸入到体积分数为0～50％的硫酸水溶液中作为凝固浴，得到初生PPTA中空纤维多孔膜，再将所得初生中空纤维多孔膜经卷绕、水洗、碱液中和，放入常温水浴中萃洗48h以上，即得到PPTA中空纤维多孔膜。
与现有技术相比，本发明的有益效果是：本发明采用双螺杆挤出机的高剪切力可大大缩短料液溶解和脱泡时间，同时还可增大料液中PPTA含量，改进PPTA中空纤维多孔膜的力学性能；无机粒子的加入改善了膜性能，增加膜力学韧度，提高了纯水通量、亲水性和截留率。
本发明所述可溶性复合致孔剂PEG/PVP是解决本发明所述PPTA不易成孔问题的关键，由此所制得的PPTA中空纤维多孔膜平均孔径较小且孔隙率较高。这是由于醇酮类物质与无机盐混合时，醇酮类物质中羟基的存在使无机盐离子基团化趋势增强，减弱了离子间电荷作用，起到均一化作用。同时，无机粒子的加入使PPTA中空纤维膜表面变粗糙，膜的有效过滤面积增大。由于PPTA和无机粒子两相间不相容，在纤维膜成形过程中易形成界面孔，膜的通透性能与力学性能得到明显改善。
附图说明
图1为本发明制备方法所得芳香族聚酰胺中空纤维多孔膜的断面形貌电镜图；
图2是图1中所示区域的局部放大图。
具体实施方式
下面给出本发明的具体实施例。具体实施例仅用于进一步详细说明本发明，不限制本申请权利要求的保护范围。
本发明提供的芳香族聚酰胺中空纤维多孔膜(简称多孔膜)的制备方法，该制备方法采用如下铸膜液和制膜工艺，所述铸膜液的质量分数组成为：
所述PPTA树脂比浓对数黏度(ηinh)为4.5dL/g～9.5dL/g；所述致孔剂为水溶性高分子，选自平均分子量为1000～20000的PEG、平均分子量为10000～1000000的PVP中的至少一种；所述溶剂为质量浓度为98％～106％的浓硫酸；所述无机粒子为二氧化硅(SiO2)、氯化钙(CaCl2)或碳酸钙(CaCO3)中的至少一种，平均粒径为5nm～10μm；
所述芳香族聚酰胺中空纤维多孔膜的制膜工艺是：
(1)预处理
在55℃下先将PPTA树脂在质量浓度为0.5～1％磷酸溶液中超声处理15～60分钟后，再将其与无机粒子于100℃～200℃真空干燥处理24h以上；
(2)PPTA中空纤维多孔膜制备
将预处理后的PPTA树脂、无机粒子和溶剂在密封溶解釜中混合，40～50℃下搅拌溶胀1～2h，形成透明黄色粘稠状预混液，然后加入所述复合致孔剂形成铸膜液，并将此铸膜液挤入双螺杆挤出机，在溶解温度80～90℃溶解1～20分钟，并通入温度为0～90℃、流速为10～100ml/min、体积分数为0～50％的硫酸水溶液作为纺丝芯液，经计量泵计量注入中空喷丝板，喷丝头拉伸比为1～10倍，随后铸膜液由中空喷丝板挤出，经高度为10～100mm的空气浴后，浸入到体积分数为0～50％的硫酸水溶液中作为凝固浴，得到初生PPTA中空纤维多孔膜，再将所得初生中空纤维多孔膜经卷绕、水洗、碱液中和，放入常温水浴中萃洗48h以上，即得到PPTA中空纤维多孔膜。
所述喷丝头拉伸比是卷绕速度与挤出速度的比值。
实施例1
在55℃下先将PPTA树脂在质量浓度为0.7％磷酸溶液中超声处理30分钟后，再将其与纳米二氧化硅无机粒子于100℃真空干燥处理24h。
将预处理后2.0wt％的PPTA树脂、88wt％质量浓度为98％的浓硫酸和0.5wt％的纳米二氧化硅无机粒子在密封溶解釜中混合，40℃下溶胀2h，形成透明黄色粘稠状预混液，然后加入10wt％复合致孔剂PEG(2000)和PVP(58000)，其中质量比PEG(2000):PVP(58000)＝9:1，并将此铸膜液挤入双螺杆挤出机，在80℃混合溶解10分钟，并通入20℃、流速20ml/min的纯水为纺丝芯液，经计量泵计量注入中空喷丝板，设定喷丝头拉伸比为2倍，随后铸膜液由中空喷丝板挤出，经20mm的空气浴后浸入20℃纯水凝固浴中成形，将所得初生PPTA中空纤维多孔膜，经常规水洗、碱液中和后，放入常温水浴中萃洗48h，即得到PPTA中空纤维多孔膜。经测试：该膜外径2.0mm、内径1.2mm，膜断裂强度为1.5MPa，断裂伸长率为18％；在0.1MPa下室温过滤，蒸馏水的水通量为218.67L/(m2h)，静态接触角为36.3°，膜断裂强度为1.5MPa，断裂伸长率为18％。
对比例1
在55℃下先将PPTA树脂在质量浓度为0.7％磷酸溶液中超声处理30分钟后，再将其于100℃真空干燥处理24h。
将预处理后2.0wt％的PPTA树脂与88wt％质量浓度为98％的浓硫酸在密封溶解釜中混合，40℃下溶胀2h，形成透明黄色粘稠状预混液，然后加入10wt％致孔剂PEG(2000)，并将此铸膜液挤入双螺杆挤出机，在80℃混合溶解10分钟，并通入20℃、流速20ml/min的纯水为纺丝芯液，经计量泵计量注入中空喷丝板，设定喷丝头拉伸比为2倍，随后铸膜液由中空喷丝板挤出，经20mm的空气浴后浸入20℃纯水凝固浴中成形，将所得初生PPTA中空纤维多孔膜，经水洗、碱液中和，放入常温水浴中萃洗48h。经测试：所得PPTA中空纤维多孔膜外径2.0mm、内径1.2mm，在0.1MPa下室温过滤蒸馏水的水通量为102.32L/(m2h)，静态接触角为72.8°，膜断裂强度为0.62MPa，断裂伸长率为7％。
实施例2
根据实施例1所述，将预处理后2.0wt％的PPTA树脂、0.5wt％的SiO2粒子及88wt％质量浓度为100％的浓硫酸在密封溶解釜中混合，50℃下溶胀1h，形成透明黄色粘稠状预混液，然后加入10wt％复合致孔剂PEG(2000)和PVP(30000)，其中质量比PEG(2000):PVP(30000)＝8:2，并将此铸膜液挤入双螺杆挤出机，在85℃高速混合溶解8分钟，并通入40℃，流速30ml/min的水溶液为纺丝芯液，经计量泵计量注入中空喷丝板，设定喷丝头拉伸比为2倍，随后铸膜液由中空喷丝板挤出，经15mm的空气浴后浸入20℃纯水凝固浴中成形，将所得初生中空纤维多孔膜经水洗、碱液中和，放入常温水浴中萃洗48h，即得到PPTA中空纤维多孔膜(参见图1、2)。经测试：所得PPTA中空纤维多孔膜外径2.0mm、内径1.2mm，在0.1MPa下室温过滤蒸馏水的水通量为318.34L/(m2h)，静态接触角为36.3°，膜断裂强度为2.25MPa，断裂伸长率为53％。
实施例3
按照实施例2所述，将喷丝头拉伸比改为3倍，空气浴高度改为10mm，其他条件均不变。经测试：所得PPTA中空纤维多孔膜的外径1.8mm、内径1.2mm，在0.1MPa下分别测定90℃蒸馏水与90℃N,N-二甲基乙酰胺(DMAc)渗透通量，其通量分别为413.72L/(m2h)和265.36L/(m2h)，90℃下膜断裂强度为1.65MPa，断裂伸长率28％。
在65℃和0.1MPa下，对1g/L、1000ml的牛血清蛋白(BSA)溶液进行30分钟截留测试，用双光束紫外可见分光度仪测定过滤前后滤液的吸光度后，计算截留率。过滤通量为66.43L/(m2h)，蛋白截留率为92.54％。
实施例4
按照实施例2所述，将0.5wt％的SiO2粒子改为0.5wt％的复合无机粒子SiO2和CaCl2(质量比SiO2:CaCl2＝1:1)，其他条件均不变。经测试：所得PPTA中空纤维多孔膜的外径2.0mm、内径1.2mm，在0.1MPa下室温过滤蒸馏水的水通量为120.47L/(m2h)。
实施例5
按照实施例2所述，将0.5wt％的SiO2粒子改为0.5wt％的复合无机粒子SiO2和CaCO3(质量比SiO2:CaCO3＝1:1)，其他条件均不变。经测试：所得PPTA中空纤维多孔膜的外径2.0mm、内径1.2mm，在0.1MPa下室温过滤蒸馏水的水通量为80.72L/(m2h)。

Claims (2)

1.一种芳香族聚酰胺中空纤维多孔膜的制备方法，该制备方法采用如下铸膜液和制膜工艺：所述铸膜液的质量分数组成为：
PPTA树脂       1%~20%，
致孔剂            5%~20%，
溶剂               60%~94%，以上各组分之和为100%；
无机粒子         与PPTA树脂质量比为0.05~50%；
所述PPTA树脂比浓对数黏度为4.5dL/g~9.5dL/g；所述致孔剂为水溶性高分子，选自平均分子量为1000~20000的PEG和平均分子量为10000~1000000的PVP中的至少一种；所述溶剂为质量浓度为98%~106%的浓硫酸；所述无机粒子为二氧化硅、氯化钙或碳酸钙中的至少一种；
所述芳香族聚酰胺中空纤维多孔膜的制膜工艺是：
（1）预处理
在55℃下先将PPTA树脂在质量浓度为0.5~1%磷酸溶液中超声处理15~60分钟后，再将其与无机粒子于100℃~200℃真空干燥处理24h以上；
（2）PPTA中空纤维多孔膜制备
将预处理后的PPTA树脂、无机粒子和溶剂在密封溶解釜中混合，40~50℃下搅拌溶胀1~2h，形成透明黄色粘稠状预混液，然后加入所述复合致孔剂形成铸膜液，并将此铸膜液挤入双螺杆挤出机，在溶解温度80~90℃溶解1~20分钟，并通入温度为0~90℃、流速为10~100ml/min、体积分数为0~50%的硫酸水溶液作为纺丝芯液，经计量泵计量注入中空喷丝板，喷丝头拉伸比为1~10倍，随后铸膜液由中空喷丝板挤出，经高度为10~100mm的空气浴后，浸入到体积分数为0~50%的硫酸水溶液中作为凝固浴，得到初生PPTA中空纤维多孔膜，再将所得初生中空纤维多孔膜经卷绕、水洗、碱液中和，放入常温水浴中萃洗48h以上，即得到PPTA中空纤维多孔膜。
2.一种根据权利要求1 所述芳香族聚酰胺中空纤维多孔膜制备方法制备的芳香族聚酰胺中空纤维多孔膜。
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