CN107148311A - 制备用于反渗透和纳滤的由薄层复合膜构成的防污涂层的方法,该薄层复合膜及其用途 - Google Patents
制备用于反渗透和纳滤的由薄层复合膜构成的防污涂层的方法,该薄层复合膜及其用途 Download PDFInfo
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- CN107148311A CN107148311A CN201580043174.9A CN201580043174A CN107148311A CN 107148311 A CN107148311 A CN 107148311A CN 201580043174 A CN201580043174 A CN 201580043174A CN 107148311 A CN107148311 A CN 107148311A
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- film
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- composite membrane
- halogen
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- 239000012528 membrane Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 29
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- 238000000576 coating method Methods 0.000 title claims description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
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- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 8
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- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 2
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- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 239000003446 ligand Substances 0.000 claims 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
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- 230000003197 catalytic effect Effects 0.000 claims 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
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Classifications
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- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
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- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/281—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling by applying a special coating to the membrane or to any module element
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明涉及用于反渗透(超滤)和纳滤的薄膜复合膜,随后统称为水过滤膜的非常薄的选择性作用的优选由芳族聚酰胺、聚氨酯和/或聚脲组成的分离层的温和的分子表面官能化的组合方法,以便实现被动防污效果,而不损害由聚酰胺制成的水选择性分离层的选择性和膜的水渗透性。
Description
本发明涉及用于反渗透(超滤)和纳滤的薄膜复合膜,随后统称为水过滤膜的非常薄的选择性作用的分离层(优选由芳族聚酰胺、聚氨酯和/或聚脲组成)的温和的分子表面官能化的组合方法,以便实现被动防污效果,而不损害由聚酰胺制成的水选择性分离层的选择性和膜的水渗透性。
基于膜的水处理方法,例如,在饮用水生产、工业用水供应和废水净化中或甚至在食品和生物技术中,在大多数情况下以未消毒或单菌(培养)的方式操作。存在的任何微生物和伴随的生物聚合物导致生物膜的形成,其沉积在膜上和其孔中。作为由此产生的生物污垢的结果,存在渗透物流动、分离选择性的降低,以及时常的抗性的定殖,可能还有致病病菌,其完全破坏(消毒)需要大量使用消毒剂或抗生素。生物聚合物如蛋白质,多糖和核酸的沉积有助于微生物生物膜的形成,其应尽可能地消除或尽可能最小化。所有防污涂层和功能化必须保持膜的技术功能。这是难以实现的技术要求,例如特别是在分离膜,特别是用于反渗透的薄膜复合膜的情况下。此外,其要求所有防污措施可以集成到现有的生产和工厂概念中。
在技术实践中,膜污染,特别是生物污染的问题通过机械清洁、洗涤、化学消毒以及化学和过热蒸汽灭菌来解决。目前结合预过滤(微滤和超滤),营养物耗尽(特别是絮凝)和通过用酸性和碱性溶液以及氯、结合的活性氯或次氯酸盐的水溶液(简而言之,氯溶液)交替处理的化学膜清洁的防污措施是有利的。由于在反渗透膜上的选择性分离层的粗糙化,其在总操作时间期间变得越来越频繁,氯溶液的广泛使用最终导致分离膜的破坏。在大多数情况下,所有这些程序需要中断,或多或少的长度,技术过程,高度使用消毒剂和清洁剂,抗生素,能量和时间。最终,分离膜必须在显著缩短的处理时间之后进行更换。通过湿化学方法对膜表面的改性,这是迄今已知的,事实上导致了引起生物污染的微生物生长的抑制,微生物粘附的减少和生物聚合物的吸附的减少,然而不是完全消除生物污染。水解、酸化、碱化和氧化敏感的膜层,例如,在主要用于反渗透和从咸水和海水中获得脱盐水的薄膜复合膜中,不能在反应性溶剂中间相中被湿化学改性,而膜性质没有大的变化或仅有很大的限制。为了生产具有防污性能的膜,也可以使用受控的活性接枝聚合。受控的活性接枝聚合,其开始于在膜物质中初始化基团的聚合,例如,在自由基加成-断裂-链-转移聚合(RAFT)中,在溴-和氯烷基上的自由基原子转移聚合和由氮氧化物基团介导的自由基接枝聚合,从WO2010/015599A1,CA2,732,873A1,CN102112214A,EP2313 184 A1,EP2313184B1,US8,544,658B1,US2011/0189469A1中已知。在湿化学预处理的膜表面上受控的活性接枝聚合的缺点在于用于反渗透的薄膜复合膜的分离性和渗透性的可预期地巨大改变。
由此,本发明的目的是提供一种用于生产膜的防污涂层的方法,而不损害膜的选择性和水渗透性。
该目的通过具有权利要求1特征的方法和具有权利要求10特征的薄膜复合膜实现。在权利要求15中,指出了根据本发明的用途。其它从属权利要求揭示了有利的发展。
根据本发明,提供一种用于生产膜的防污涂层的方法,其中,
·在第一步中,通过等离子体化学活化,即在直流电压或交流电压电场中活化,和/或光化学活化至少一种卤素-有机化合物来实施气相中的膜的初级分子官能化,所述卤素-有机化合物转化成气相并通过卤素基团共价结合到膜表面;和
·在第二步中,通过自由基接枝聚合实施卤素原子衍生分子基团官能化的膜的湿化学改性。
所述湿化学改性在液相中,优选在水-醇和醇溶液中进行。因此根据本发明的方法能够通过经气相反应的膜表面的分子官能化与液相中的自由基接枝聚合的化学适应的组合来制备具有改进的防污性能的水过滤膜。
膜表面的温和的分子官能化,保持膜的功能,例如,通过借助于等离子体工艺引入含卤素的分子基团,由此化学适应于随后发生的聚合反应。实际的防污效果是通过经接枝聚合充分密布的和有效的化学基团的牢固固定的来实现的。
对于气相中的分子官能化,优选使用卤素-有机化合物。所述卤素-有机化合物优选地选自下组:烯丙基卤化物,C1至C8亚烷基卤化物,优选C1至C4亚烷基卤化物,特别是亚甲基卤化物,C1至C8烷基卤化物,优选C1至C4烷基卤化物,特别是卤代甲烷及其混合物。特别优选的是丙基溴,乙基溴,烯丙基溴,烯丙基氯,二溴甲烷,二氯甲烷,溴甲烷,氯甲烷及其混合物。从而令人惊奇地确定,通过使用卤素-有机化合物及其从气相的沉积,可能对敏感膜层进行非常温和的改性。等离子体化学和/或光解活化同时保持待化学衍生的官能团,导致其在膜上的沉积。卤素-有机化合物的共价键合从而通过有机基团,优选通过亚烷基桥,特别是亚甲基,亚乙基和亚丙基实现。
待结合到待修饰的膜的表面上的卤素-有机官能团的量通常为每平方纳米0.01至5个,优选每平方纳米0.1至2个。
此外,优选卤素-有机化合物的卤素原子光化学地或催化地分裂,特别是与Cu(I)络合物,Cu(II)络合物或Ru(III)络合物,同时形成固定的自由基,因此可以用烯烃开始自由基接枝聚合,特别是活性原子转移聚合(ATRP)。
活性的,受控的原子转移聚合通过以下事实区别,通过加入过渡金属络合物和与采用卤素-有机化合物的原子转移过程结合,降低自由基的浓度,直到链断裂反应广泛被抑制。通过活性聚合理解,所述聚合不存在断裂反应。在“活性条件”下,具有窄分布的摩尔质量的控制变得可能。
活性的,受控的原子转移聚合优选在水-醇溶液中进行,醇优选选自下组:甲醇,乙醇,丙醇,异丙醇,正丁醇及其混合物。
在ATRP的情况下的反应温度优选在10-80℃,优选地为20-50℃的温度。
所述ATRP优选在常压下进行。
在ATRP的情况下,作为过渡金属络合物,优选使用铜(I)络合物,特别是CuBr。
在原子转移聚合的情况下,优选低聚物或聚合物物质,优选定向的,由此结合在膜上。本文包括优选聚丙烯酸酯,聚甲基丙烯酸酯和其它聚乙烯类,其形成阻碍或防止生物聚合物,优选蛋白质,腐殖酸和微生物结合的层。定向的是指从表面初始的共价结合卤素原子的聚合物链,优选溴和氯原子,以受控的方式聚合,远离要被改性的膜表面定向,即,以自组织这种方式生长和定向,由此产生的聚合物刷的密度通过卤素原子的密度和排列以及聚合物链几何形状来确定。在ATRP的情况下,在聚合期间单体分子在卤素原子和生长的聚合物链之间移动,使得前者总是位于聚合物链的末端,因此规定聚合的方向。
在本发明所述方法的第二步中,作为单体,优选使用甲基丙烯酸2-羟乙酯(HEMA),2-甲基丙烯酰氧基乙基磷酰胆碱(97%,MPC)或[2-(甲基丙烯酰氧基)乙基]二甲基-(3-磺丙基)氢氧化铵或这些化合物的混合物。
通常,溴-和氯-有机化合物,优选其中卤素原子末端键合到亚烷基的那些化合物,可用作引发剂,优选使用β-溴异丁酸乙酯。
优选地,初级分子官能化在气相中在大气压下,特别是在100至1000毫巴的压力范围内或在真空中,特别是在0.01毫巴至100毫巴的压力范围内进行,温度范围为10至150℃,特别是20至50℃。等离子体可以通过直流电压,交流电压,高频或微波放电来产生,或者作为电子回旋共振等离子体被应用。
膜材料或膜表面的材料优选选自下组:聚氨酯,聚酰胺或聚脲。这些基底材料优选具有主要芳族结构。
根据本发明,还提供一种薄膜复合膜,具有至少一个层厚度在10至500nm范围内的分离层,所述分离层由聚酰胺,聚氨酯,聚脲或其共混物,或混合物制成,至少一个另外的聚合物层以及聚合物载体结构。所述分离层因此具有如上所述的防污涂层。优选地,分离层由芳族聚酰胺组成。
薄膜复合膜具有优选具有在50至300nm范围内厚度的分离层和具有在30至100μm范围内厚度的至少一个另外的聚合物层和具有50至100μm范围厚度的聚合物载体结构。
所述至少一个分离层优选用通过受控生长聚合制备的聚乙烯类,聚丙烯酸酯和/或聚甲基丙烯酸酯的末端聚合物链密度为0.01至2的聚合物链,特别优选0.05至1的聚合物链改性,而不使薄膜复合膜的分离性质和渗透性被削弱超过20%。
所述至少一个另外的聚合物层包括或基本由优选选自下组的材料组成:聚砜,聚醚砜,聚丙烯腈,醋酸纤维素,聚酰亚胺,聚醚酰亚胺或这些聚合物的组合作为混合物或共聚物。通常,也可以使用其它不对称的成膜聚合物。优选地,所述至少一个另外的聚合物层由聚砜或聚醚砜组成。
优选地,所述至少一个载体结构由筛网,机织织物,多孔层或其组合组成。这些可以由聚酯,聚酰胺,聚烯烃或另一种聚合物线材料形成。优选地,聚合物线材料由聚酯组成。优选地,载体结构是筛网。
根据本发明所述的膜用于水处理,特别是用于饮用水生产,工业用水供应和废水净化或用于食品和生物技术中。
如本发明所述方法制备的膜的优点在于良好防污性能,和高分离性能和渗透性。因此,通过如本发明所述的方法提供特别耐用和选择性的膜,使膜不再需要如此频繁地更换,因此降低了成本。
参考后续实施例更详细地解释本发明的主题,所述主题不限于本文所示的具体实施方案。
实施例1
通过在气相中引入含溴分子基团的官能化
对于在低压等离子体中反渗透膜的溴官能化,使用烯丙基溴,溴仿和1-溴丙烷。反渗透膜(用于微咸水,高排斥)由IAB离子交换器(Ionenaustauscher)股份有限公司(GmbH),朗盛(LANXESS)AG提供。对于膜表面的温和的溴官能化,溴化烃的沉积或改性是从低压等离子体实现的。为此目的,将膜样品固定在两个板电极(直径:150mm,间距:100mm)的下部,并将反应室密封。在设定0.1Pa的负压之后,通过针阀引入烯丙基溴,溴仿或溴丙烷,直到达到所需的处理压力2至4Pa。单体气体的点燃通过在50Hz下向两个电极板施加900-1100V范围内的限定电压来进行。指示的处理时间对应于施加电压的持续时间。在1100伏的电压和4Pa的处理压力下,用烯丙基溴,溴仿或溴丙烷分别改性一个薄膜复合膜的3个膜样品。烯丙基溴(99%,AB)从阿法埃莎(Alfa Aesar)获得,并使用。处理持续时间为5秒。可以通过X射线光子光谱(XPS)在这样的涂覆或处理的膜上检测溴。
表1示出了靠近表面的元素组成。数据以原子百分比[at%]示出。偏差是3个平行样品上9个测量位置的标准偏差。
表1:
样品 | Br[at%] | C[at%] | N[at%] | O[at%] |
未处理 | - | 72.1±0.41 | 10.4±0.64 | 14.3±0.65 |
烯丙基溴 | 3.4±1.18 | 73.0±0.79 | 9.0±0.88 | 11.4±0.75 |
溴仿 | 1.6±0.28 | 66.1±0.75 | 11.3±0.60 | 17.9±0.51 |
溴丙烷 | 4.2±0.62 | 71.6±0.58 | 8.6±0.78 | 12.3±0.91 |
对于100个原子,存在1至5个溴原子。
实施例2
在膜表面的分子官能化之后的原子转移的自由基接枝聚合
低聚物或聚合物在膜表面上的生长在排除氧气的情况下通过原子转移(原子转移自由基聚合,ATRP)的自由基聚合进行。这里提到的实施例的方法的基本过程随后描述。将溴化铜(I)(CuBr,纯度>99.99%)和配体2,2’-联吡啶(bpy,纯度99%,西格玛奥德里奇(Sigma Aldrich))转移到舒伦克(Schlenk)瓶中以所需量混合,并通过用氮气重复换气脱气。类似地,分别使用单体2-甲基丙烯酸羟乙酯(99+%,HEMA),2-甲基丙烯酰氧基乙基磷酰胆碱(97%,MPC)或[2-(甲基丙烯酰氧基)乙基]二甲基-(3-磺丙基)氢氧化铵转移到另一舒伦克瓶中并脱气。将甲醇(99.9%p.a.)和两次蒸馏水分别装入另一个容器中并同样脱气。随后,使用的所有容器通过锁转移到具有氩气气氛(>99%)的通风橱中。作为下一步,反应溶液1的制备通过将CuBr和bpy溶解在甲醇中来进行。通过搅拌完全溶解后,得到深红色反应溶液。反应溶液2通过将单体溶解在水中制备。将反应溶液1加入反应溶液2中,并充分搅拌约30秒。随后,加入游离的和溶解的引发剂β-溴异丁酸乙酯(98%,EBIB),将所得溶液搅拌约30秒。将溶液置于特别用于膜修饰的反应容器中。然后将膜样品松散地储存或在不同设计的反应池中拉伸,这使得仅在被切出的圆形(直径约75mm)的膜样品的一侧与反应溶液接触。通过将反应容器转移到位于通风橱内部的空气恒温器中进行反应的温度控制,其温度调节在10和60℃之间。在反应时间结束后,根据用于反应的比例首先在甲醇-水混合物中小心地清洗膜样品,然后在纯水中清洗,随后将样品干燥。
实施例2.1
将聚2-羟乙基甲基丙烯酸酯(聚HEMA)和聚[2-(甲基丙烯酰氧基)乙基]二甲基-(3-磺基丙烷)(聚SBMA)在用烯丙基溴官能化的膜上聚合。试剂的浓度为50mmol/l HEMA或SBMA,1mmol/l EBIB,1mmol/l CuBr和2mmol/l bpy。使用水与甲醇的9:1混合物作为溶剂。反应持续时间为在20℃下1.5小时,3小时和20小时。通过XPS,能够测量反应时间与膜表面的氧含量(HEMA)或硫含量(SBMA)的增加的关系。
表2显示根据实施例2.1的ATRP改性的膜样品的表面组成。数据以原子百分比[at%]表示。偏差是在4个测量位置处执行分析的标准偏差。
表2
样品 | Br[at%] | C[at%] | N[at%] | O[at%] | S[at%] |
PHEMA 1.5h | 0.2±0.12 | 73.8±0.35 | 8.9±0.19 | 15.2±0.19 | - |
PHEMA 3h | 0.1±0.02 | 72.8±0.26 | 7.3±0.21 | 18.5±0.37 | - |
PHEMA 24h | 0.2±0.06 | 72.8±0.12 | 6.6±0.19 | 19.1±0.17 | - |
PSBMA 1.5h | 0.6±0.05 | 71.7±0.76 | 8.8±0.39 | 15.5±0.54 | 2.2±0.13 |
PSBMA 3h | 0.5±0.04 | 70.2±0.34 | 7.8±0.50 | 17.6±0.77 | 2.9±0.34 |
PSBMA 24h | 0.5±0.06 | 67.8±0.39 | 4.6±0.21 | 22.1±0.30 | 22.1±0.30 |
实施例2.2
将聚-2-甲基丙烯酰氧基乙基磷酰胆碱(聚-MPC)在用溴仿(BF)或溴丙烷(BP)官能化的膜上聚合。加入50mmol/l MPC,1mmol/l EBIB,1mmol/l CuBr和2mmol/l bpy。使用水和甲醇的1:1混合物作为溶剂。在20℃下反应持续时间为2小时。
通过XPS,可以检测膜表面的磷含量的增加,其与聚合的单体的量相关。由于可用的初始化基团的表面浓度几乎保持恒定,因此也可以从结合的磷的量推断出平均聚合度。
表3显示根据实施例2.2的ATRP改性的膜样品的表面组成。数据以原子百分比[at%]表示。偏差是在3个测量位置进行分析的标准偏差。
表3
样品 | Br[at%] | C[at%] | N[at%] | O[at%] | S[at%]10 |
PMPC(BF) | 1.1±0.09 | 66.3±0.94 | 7.9±0.66 | 21.3±0.04 | 2.5±0.07 |
PMPC(BP) | 1.6±0.19 | 68.9±0.48 | 7.0±0.52 | 19.2±1.01 | 2.2±0.11 |
实施例2.3
聚-BSMA在用烯丙基溴官能化的膜上聚合。使用50mmol/l SBMA,1mmol/l EBIB,1mmol/l CuBr和2mmol/l bpy。此外,向反应溶液中加入20mmol/l葡萄糖作为还原剂。使用水和甲醇的1:1混合物作为溶剂。反应持续时间为20小时。反应温度为20℃,35℃或50℃。通过XPS,可以检测反应温度与膜表面的硫含量的增加的关系,并提供接枝的聚合物链的实现的分子量的测量。
表4显示了根据实施例2.3的ATRP改性的膜样品的表面组成。数据以原子百分比[at%]表示。所示的标准偏差由在膜表面上3个位置测量的值产生。
表4
样品 | Br[at%] | C[at%] | N[at%] | O[at%] | S[at%] |
PSBMA(20℃) | 1.2±0.02 | 68.2±0.23 | 5.4±0.11 | 21.3±0.19 | 3.9±0.05 |
PSBMA(35℃) | 1.1±0.06 | 66.6±0.23 | 4.7±0.07 | 23.8±0.18 | 4.5±0.12 |
PSBMA(50℃) | 0.4±0.32 | 67.0±1.10 | 4.9±0.14 | 22.S±0.81 | 5.2±0.60 |
Claims (15)
1.一种生产用于反渗透,纳滤和超滤的薄膜复合膜的防污涂层的方法,其特征在于,
·在第一步中,通过等离子体化学和/或光化学活化至少一种卤素-有机化合物来实施气相中的膜的初级分子官能化,所述卤素-有机化合物转化成气相并共价结合到膜表面;和
·在第二步中,通过自由基接枝聚合实施官能化膜的湿化学改性。
2.如权利要求1所述的方法,其特征在于,所述至少一种卤素-有机化合物选自下组:烯丙基卤化物,C1-C8亚烷基卤化物,优选C1-C4亚烷基卤化物,特别是亚甲基卤化物,C1-C8烷基卤化物,优选C1至C4烷基卤化物,特别是卤代甲烷及其混合物,优选丙基溴,乙基溴,烯丙基溴,烯丙基氯,二溴甲烷,二氯甲烷,甲基溴,甲基氯,及其混合物。
3.如前述权利要求之一所述的方法,其特征在于,所述共价结合通过亚烷基桥及其衍生物进行。
4.如前述权利要求之一所述的方法,其特征在于,所述初级分子官能化在气相中在大气压下进行,特别是在100至1000毫巴的压力范围内或在0.01至100毫巴的压力范围内的真空中,和温度在20至150℃的范围内,但最多至聚合物膜层的分解温度,特别是在20至40℃的范围内。
5.如前述权利要求之一所述的方法,其特征在于,所述等离子体化学处理是用直流电压,交流电压,高频或微波放电或电子回旋共振等离子体(ECR)进行的。
6.如前述权利要求之一所述的方法,其特征在于,所述卤素-有机化合物的卤素原子被光化学或通过催化效应分裂,优选Cu(I)-和Cu(II)络合物以及Ru(III)络合物与选定的配体,优选多齿配体,优选固定化自由基形成下的多齿胺和吡啶配体。
7.如上述权利要求所述的方法,其特征在于,所述固定化自由基从所述共价键合的卤素原子开始产生,基于其自由基接枝聚合,特别是活性的,受控原子转移聚合采用烯烃开始,操作优选在水-醇溶液中,于10至80℃,优选20至50℃的温度下,在常压下及在铜(I)络合物的存在下进行。
8.如上述权利要求所述的方法,其特征在于,通过自由基接枝聚合,形成阻碍或防止生物聚合物,优选蛋白质、腐殖酸和微生物结合的层的低聚或聚合物质,优选聚丙烯酸酯、聚甲基丙烯酸酯和其他聚乙烯类从结合在膜表面上的官能团开始生长,优选卤素原子并远离膜表面定向。
9.如前述权利要求之一所述的方法,其特征在于,所述膜具有待改性的膜表面,并且至少所述待改性的膜表面分别由优选具有芳族结构的聚酰胺、聚氨酯或聚脲及其复合材料组成。
10.一种薄膜复合膜,其特征在于,所述薄膜复合膜具有:
·至少一个分离层,由聚酰胺、聚氨酯或聚脲制成,层厚度在10至500nm范围内;
·至少一个另外的聚合物层,以及
·聚合物载体结构,
所述分离层具有根据前述权利要求之一生产的防污涂层。
11.如权利要求10所述的薄膜复合膜,其特征在于,所述分离层具有50至300nm范围内的厚度和/或所述至少一个另外的聚合物层具有在30至100μm范围内的厚度和/或所述聚合物载体结构具有在50至100μm范围内的厚度。
12.如权利要求10或11所述的薄膜复合膜,其特征在于,所述至少一个分离层用通过受控生长聚合制备的聚乙烯,聚丙烯酸酯和/或聚甲基丙烯酸酯的末端聚合物链密度为0.01至2的聚合物链,优选0.05至1的聚合物链改性,而不使薄膜复合膜的分离性质和渗透性被削弱超过20%。
13.如权利要求10至12之一所述的薄膜复合膜,其特征在于,所述至少一个另外的聚合物层包括或基本由聚砜、聚醚砜、聚丙烯腈、乙酸纤维素、聚酰亚胺、聚醚酰亚胺或作为混合物或共聚物的这些聚合物的组合构成。
14.如权利要求10至13之一所述的薄膜复合膜,其特征在于,所述至少一个载体结构由筛网,机织织物,多孔层或其组合组成。
15.一种如权利要求10至14之一所述的薄膜复合膜的用途,其特征在于,通过反渗透和纳滤用于水处理,特别是用于饮用水生产、生活用水供应和废水净化,或用于食品和生物技术中。
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CN113509840A (zh) * | 2020-04-09 | 2021-10-19 | 中国石油化工股份有限公司 | 一种复合纳滤膜及其制备方法与应用 |
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