CN102836641A - 膜及其制备方法 - Google Patents

膜及其制备方法 Download PDF

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CN102836641A
CN102836641A CN2011101689408A CN201110168940A CN102836641A CN 102836641 A CN102836641 A CN 102836641A CN 2011101689408 A CN2011101689408 A CN 2011101689408A CN 201110168940 A CN201110168940 A CN 201110168940A CN 102836641 A CN102836641 A CN 102836641A
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polyalcohol
polyvinyl alcohol
layer
film
acid group
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吕苏
刘珍
彭文庆
张冰
黎华
王晨
彭云
牛青山
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General Electric Co
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General Electric Co
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Priority to CN201611000042.0A priority Critical patent/CN107081074A/zh
Priority to CN2011101689408A priority patent/CN102836641A/zh
Priority to CA2838316A priority patent/CA2838316A1/en
Priority to AU2012273299A priority patent/AU2012273299B2/en
Priority to EP12730320.4A priority patent/EP2723480A1/en
Priority to US14/126,719 priority patent/US20150083657A1/en
Priority to JP2014517026A priority patent/JP6252868B2/ja
Priority to PCT/US2012/042339 priority patent/WO2012177465A1/en
Priority to SG10201604332XA priority patent/SG10201604332XA/en
Priority to KR1020137033770A priority patent/KR102003572B1/ko
Priority to TW101122548A priority patent/TWI619750B/zh
Publication of CN102836641A publication Critical patent/CN102836641A/zh
Priority to JP2017180777A priority patent/JP2018027539A/ja
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Abstract

本发明涉及一种膜，其包括：多孔基膜；包含金属有机物与多元醇的多元醇层；和位于多孔基膜和多元醇层之间的聚酰胺层。本发明也涉及膜的制备方法。

Description

膜及其制备方法
技术领域
本发明涉及膜和膜的制备方法。
背景技术
很多薄膜膜可以用于净化含溶质的液体，例如，进行废水处理。一类薄膜膜通过不能与水混溶的有机溶剂中的多酸氯化物和水溶液中的多胺在多孔基膜表面界面聚合反应而制备。由此产生的聚酰胺在多孔基膜一个表面形成一层薄膜。因为至少有两层膜的结构，即，多孔基膜和界面聚合制备的聚酰胺层的存在，这种膜通常被称为复合膜。
为了提高复合膜性能，多元醇，如聚乙烯醇，涂覆在聚酰胺层上并通过各种交联剂交联。尽管复合膜技术许多新进展的技术优势，由于全世界对水供应需求的不断增长，人们仍在寻求复合膜的改进。因此，需要一种新的膜成分和制备方法。
发明内容
一方面，本发明涉及一种膜，其包括：多孔基膜；包含金属有机物与多元醇的多元醇层；和位于多孔基膜和多元醇层之间的聚酰胺层。
另一方面，本发明涉及一种膜制备方法，包括：提供多孔基膜；在多孔基膜上提供聚酰胺层；和在聚酰胺层上提供多元醇层，多元醇层包含金属有机物与多元醇。
具体实施方式
说明书和权利要求中的近似用语用来修饰数量，表示本发明并不限定于该具体数量，还包括与该数量接近的不会导致相关基本功能的改变的可接受的修正部分。相应的，用“大约”或“约”等修饰一个数值，意为本发明不限于该精确数值。在某些例子中，近似用语可能对应于测量数值的仪器的精度。
本发明中所提及的数值范围包括从低到高一个单元一个单元增加的所有数值，此处假设任何较低值与较高值之间间隔至少两个单元。举例来说，如果说了一个组分的数量或一个工艺参数的值，比如，温度，压力，时间等等，是从1到90，20到80，或者30到70，是想表达15到85，22到68，43到51，30到32等数值都已经明白的列举在此说明书中。对于小于1的数值，0.0001，0.001，0.01或者0.1被认为是比较适当的一个单元。前述只是想要表达的特别示例，所有在列举的最低到最高值之间的数值组合均被视为以类似方式清楚地列在本说明书中。
本发明涉及的膜可以为用来处理废水，海水，苦咸水等的反渗透膜。一些实施例中，多孔基膜包含聚砜、聚醚砜、聚酯、聚亚苯基氧化物、聚亚苯基硫化物、聚氯乙烯、聚丙烯腈、聚偏二氟乙烯树脂、聚四氟乙烯、聚碳酸酯、聚酰亚胺、聚醚、聚醚酮、纤维素、醋酸纤维素、硝化纤维和聚醚醚酮中的至少一种。
多孔基膜通常为具有两个表面的薄膜。多孔基膜的厚度可以变化，但应足以提供一个可以适应流体净化设备或水处理设备的操作环境的复合膜。在一些实施例中，多孔基膜有从约10微米到500微米范围的厚度。在另一些实施例中，多孔基膜有从约20微米到约250微米范围的厚度。在另一些实施例中，多孔基膜有约40微米到约100微米范围的厚度。
聚酰胺层可形成在多孔基膜的两个表面之一上，以提供具有聚酰胺涂覆的表面和未经处理的表面的复合膜。因为聚酰胺薄膜层对水的选择性传输和对溶质通过的抑制，其常常被称作复合膜的“主动”面。如此类推，未经处理并保留原始的多孔基膜传输特性的表面经常被称为复合膜的“被动”面。
聚酰胺层是一个多官能芳香胺与多官能芳香酸性卤化物和多官能脂环酸性卤化物中至少一种的界面聚合产物。
多官能芳香酸性卤化物与多官能脂环酸性卤化物的例子可以为多酸氯化物。适用的多酸氯化物包括但不限于均三苯甲酰氯，对苯二甲酰氯，间苯二甲酰氯，氯化二酸丁二酸，戊二酸二元酸酰氯，氯化己二酸二元酸，反式环己烷-1，4-二羧酸二元酸酰氯，顺环己烷-1，4二羧酸二元酸酰氯，肯普三酸的三酸氯化物，氯化苯三酸以及包括两个或更多的前述多酸氯化物的混合物。
适用的多胺包括但不限于：m-苯二胺，对苯二胺，元苯二胺，4，4′-二氨基联苯，乙烯二胺，1，3丙烷二胺，1，6己二胺，1，10-癸烷二胺，4，4′-二氨基二苯砜，1，3，5-三氨基苯，哌嗪，顺-1，3，5-环己胺三胺，和包括两个或更多前述多胺的混合物。
鉴于多孔基膜的多孔性，聚酰胺可以至少部分渗入到多孔基膜的内部，而并不严格局限于多孔基膜的表面，尤其在复合膜是通过将多孔基膜表面与水相和有机溶液接触以使多酸卤化物与多胺界面聚合来制备的实施例中。界面聚合可能至少部分发生在多孔基膜的内部。
多元醇层是涂在聚酰胺薄膜层上的。本发明中“多元醇“指的是具有含羟基官能的重复单元的聚合物。多元醇的重均分子量可在约500到50万范围内。多元醇的示例包括但不限于纤维素、淀粉、糊精、焦糊精、褐藻胶、糖原、菊粉、呋甲苯丙胺、琼脂、卡拉胶、微生物胶、刺槐豆胶、褐藻多糖硫酸酯、瓜尔豆胶、褐藻淀粉、阿拉伯树胶、印度树胶、刺梧桐树胶、黄蓍胶、秋葵胶、罗望子胶，黄原胶，硬葡聚糖，亚麻籽车前籽胶，果胶，葡聚糖，甲基纤维素，乙基纤维素、羟乙基纤维素、羟丙基纤维素、甲壳素羧甲基纤维素、聚乙烯醇和壳聚糖。
本发明中所称“金属有机物”为含有金属和有机配体，但缺乏金属和碳的直接键结，且可以用于交联多元醇的化合物。金属有机物可以溶于水或其他可与水混溶的溶剂中。金属有机物的典型例子包括但不限于乙酰丙酮配合物和醇盐，例如从商业渠道可以购得的
Figure BDA0000070150750000031
有机钛酸盐和有机锆酸盐产品系列，例如二(2-羟基丙酸)二氢氧化二铵合钛(C6H18N2O8Ti，CAS号：65104-06-5)、四(三乙醇胺)锆(IV)([(HOCH2CH2)2NCH2CH2O]4Zr，CAS号：101033-44-7)、二(三乙醇胺)钛酸二异丙酯(C18H42N2O8Ti，CAS号：36673-16-2)、三乙醇胺正钛酸酯(C6H13NO4Ti，CAS号：10442-11-2)、乳酸锆(C12H20O12Zr，CAS号：60676-90-6)、二(乙酰丙酮基)钛酸二异丙酯(C16H28O6Ti，CAS号：17927-72-9)、二异丙氧二(乙氧乙酰乙酰)合酞(C18H32O8Ti，CAS号：27858-32-8)、四丁基锆酸盐(Zr(OC4H9)4，CAS号：1071-76-7)、四丙基锆酸盐(Zr(OCH2CH2CH3)4，CAS号：23519-77-9)和(三乙醇胺酸根)异丙醇钛(IV)(C9H19NO3Ti，CAS号：74665-17-1)等。在一些实施例中，金属有机物可为烷氧钛酸盐或烷氧锆酸盐。
一些实施例中，多元醇为聚乙烯醇而金属有机物为(三乙醇胺酸根)异丙醇钛(IV)。一些实施例中，(三乙醇胺酸根)异丙醇钛(IV)与聚乙烯醇中羟基的摩尔比范围是从大于0到大约2∶1。一些实施例中，(三乙醇胺酸根)异丙醇钛(IV)与聚乙烯醇中羟基的摩尔比范围是从大约1.6∶100到大约16∶100。一些实施例中，(三乙醇胺酸根)异丙醇钛(IV)与聚乙烯醇中羟基的摩尔比范围是从大约8∶100到大约16∶100。一些实施例中，(三乙醇胺酸根)异丙醇钛(IV)与聚乙烯醇中羟基的摩尔比是大约8∶100。一些实施例中，(三乙醇胺酸根)异丙醇钛(IV)与聚乙烯醇中羟基的摩尔比是大约16∶100。
多元醇层的制备是在约0℃至约100℃的温度范围进行的。一些实施例中，多元醇层的制备进行的温度范围为约5℃至90℃。一些实施例中，多元醇层的制备进行的温度范围为约10℃至约80℃。
实验示例
以下实验示例可以为本领域中具有一般技能的人实施该发明提供参考。但是，这些例子并不用于限制权利要求的范围。
将在微孔聚砜多孔基膜上把m-苯二胺和氯化苯三酸界面聚合而制备的膜充分洗净，干燥。
多个前述膜的样品在去离子水中浸泡过夜后，在5wt％的甘油水溶液分别浸泡4分钟。用气刀在8秒内除去过多的甘油。包含0.5wt％或1wt％的聚乙烯醇(来自美国密苏里州圣路易斯Sigma-Aldrich公司，CAS号：9002-89-5，分子量：
Figure BDA0000070150750000041
水解度：99％)单独或与不同量的(三乙醇胺酸根)异丙醇钛(IV)(来自美国密苏里州圣路易斯Sigma-Aldrich公司，CAS号：74665-17-1)、乙二醛(来自中国上海国药集团化学试剂有限公司，CAS号：107-22-2)或碳酸锆铵(来自美国密苏里州圣路易斯Sigma-Aldrich公司，CAS号：12616-24-9)的溶液分别浸渍涂层到各个膜样品表面，保持15秒。当乙二醛被使用时，涂液的pH值预先由柠檬酸调整为
Figure BDA0000070150750000042
多余的溶液用气刀在8秒内去除。接下来，将得到的膜在烤箱100℃干燥2分钟，从而得到均匀涂层的膜。
不同涂层加工前后膜样品的通量和阻止率分别在225psi的压力使用2000ppm的氯化钠水溶液评估。1小时后收集的数据计算后列于下表1。表1中的通量计算方法为：渗透量/(时间×膜面积×净驱动压力)×100000，而阻止率计算方法为：(1-(渗透电导)/(输入电导))×100％。
表-1
Figure BDA0000070150750000043
从上表1可以看出，当不同交联剂对聚乙烯醇或聚乙烯醇中羟基的比例越来越高时，只有聚乙烯醇-(三乙醇胺酸根)异丙醇钛(IV)涂层的膜样品通量不断增加，而用其他两个交联剂(碳酸锆铵和乙二醛)交联聚乙烯醇涂布的膜样品的通量大多下降。
虽然结合特定的实施例对本发明进行了说明，但本领域的技术人员可以理解，对本发明可以作出许多修改和变型。因此，要认识到，权利要求书的意图在于覆盖在本发明真正构思和范围内的所有这些修改和变型。

Claims (12)

1.一种膜，其包括：多孔基膜；包含金属有机物与多元醇的多元醇层；和位于多孔基膜和多元醇层之间的聚酰胺层。
2.如权利要求1所述的膜，其中多元醇为纤维素、淀粉、糊精、焦糊精、褐藻胶、糖原、菊粉、呋甲苯丙胺、琼脂、卡拉胶、微生物胶、刺槐豆胶、褐藻多糖硫酸酯、瓜尔豆胶、褐藻淀粉、阿拉伯树胶、印度树胶、刺梧桐树胶、黄蓍胶、秋葵胶、罗望子胶，黄原胶，硬葡聚糖，亚麻籽车前籽胶，果胶，葡聚糖，甲基纤维素，乙基纤维素、羟乙基纤维素、羟丙基纤维素、甲壳素羧甲基纤维素、聚乙烯醇和壳聚糖中的至少一种，且金属有机物是有机钛酸盐和有机锆酸盐中的至少一种。
3.如权利要求1所述的膜，其中金属有机物是烷氧基钛酸盐和烷氧基锆酸盐中的至少一种。
4.如权利要求1所述的膜，其中多元醇层包含(三乙醇胺酸根)异丙醇钛(IV)交联的聚乙烯醇，(三乙醇胺酸根)异丙醇钛(IV)与聚乙烯醇中的羟基的摩尔比范围是从大于0到大约2∶1。
5.如权利要求1所述的膜，其中多元醇层包含(三乙醇胺酸根)异丙醇钛(IV)交联的聚乙烯醇，(三乙醇胺酸根)异丙醇钛(IV)与聚乙烯醇中羟基的摩尔比范围是从大约8∶100到大约16∶100。
6.如权利要求1所述的膜，其中多元醇层包含(三乙醇胺酸根)异丙醇钛(IV)交联的聚乙烯醇，(三乙醇胺酸根)异丙醇钛(IV)与聚乙烯醇中羟基的摩尔比是大约8∶100或大约16∶100。
7.如权利要求1至6中任一项权利要求所述的膜，其中多孔基膜至少包含聚砜、聚醚砜、聚酯、聚亚苯基氧化物、聚亚苯基硫化物、聚氯乙烯、聚丙烯腈、聚偏二氟乙烯树脂、聚四氟乙烯、聚碳酸酯、聚酰亚胺、聚醚、聚醚酮、纤维素、醋酸纤维素、硝化纤维和聚醚醚酮中的一种，且聚酰胺层是一个多官能芳香胺与多官能芳香酸性卤化物和多官能脂环酸性卤化物中至少一种的界面聚合产物。
8.膜制备方法，包括：
提供多孔基膜；
在多孔基膜上提供聚酰胺层；和
在聚酰胺层上提供多元醇层，多元醇层包含金属有机物与多元醇。
9.如权利要求8所述的膜制备方法，其中多元醇层包含(三乙醇胺酸根)异丙醇钛(IV)交联的聚乙烯醇。
10.如权利要求9所述的膜制备方法，其中(三乙醇胺酸根)异丙醇钛(IV)与聚乙烯醇中羟基的摩尔比是大约8∶100到大约16∶100。
11.如权利要求8所述的膜制备方法，其进一步包括：在提供聚酰胺层后、提供多元醇层前，将膜与甘油接触。
12.如权利要求8至11中任一项权利要求所述的膜制备方法，其中多孔基膜包含聚砜、聚醚砜、聚酯、聚亚苯基氧化物、聚亚苯基硫化物、聚氯乙烯、聚丙烯腈、聚偏二氟乙烯树脂、聚四氟乙烯、聚碳酸酯、聚酰亚胺、聚醚、聚醚酮、纤维素、醋酸纤维素、硝化纤维和聚醚醚酮中的至少一种，且聚酰胺层是一个多官能芳香胺与多官能芳香酸性卤化物和多官能脂环酸性卤化物中至少一种的界面聚合产物。
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Application publication date: 20121226