CN109312151B - 聚砜在n-酰基吗啉中的溶液在制备uf膜中的用途 - Google Patents
聚砜在n-酰基吗啉中的溶液在制备uf膜中的用途 Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims description 64
- 229920002492 poly(sulfone) Polymers 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 73
- 150000003457 sulfones Chemical class 0.000 claims abstract description 45
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 32
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 19
- -1 aromatic sulfone Chemical class 0.000 claims description 10
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical group O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims description 10
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- 238000010612 desalination reaction Methods 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 239000010842 industrial wastewater Substances 0.000 claims description 2
- 239000010841 municipal wastewater Substances 0.000 claims description 2
- 239000013535 sea water Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 48
- 239000002904 solvent Substances 0.000 description 24
- 238000000108 ultra-filtration Methods 0.000 description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
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- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 229940113088 dimethylacetamide Drugs 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- KYWXRBNOYGGPIZ-UHFFFAOYSA-N 1-morpholin-4-ylethanone Chemical compound CC(=O)N1CCOCC1 KYWXRBNOYGGPIZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 229910005960 SO2 a Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
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- 239000007800 oxidant agent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
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- 239000012466 permeate Substances 0.000 description 2
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- 229920012287 polyphenylene sulfone Polymers 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
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- 125000004958 1,4-naphthylene group Chemical group 0.000 description 1
- FEWLNYSYJNLUOO-UHFFFAOYSA-N 1-Piperidinecarboxaldehyde Chemical compound O=CN1CCCCC1 FEWLNYSYJNLUOO-UHFFFAOYSA-N 0.000 description 1
- AGRIQBHIKABLPJ-UHFFFAOYSA-N 1-Pyrrolidinecarboxaldehyde Chemical compound O=CN1CCCC1 AGRIQBHIKABLPJ-UHFFFAOYSA-N 0.000 description 1
- LNWWQYYLZVZXKS-UHFFFAOYSA-N 1-pyrrolidin-1-ylethanone Chemical compound CC(=O)N1CCCC1 LNWWQYYLZVZXKS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001733 carboxylic acid esters Chemical group 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000003950 cyclic amides Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009292 forward osmosis Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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Abstract
本发明涉及包含砜聚合物、水溶性聚合物和式I的N‑酰基吗啉的溶液,其中R1是氢原子或C1‑C3烷基。
Description
描述
本发明涉及包含砜聚合物、水溶性聚合物和式I的N-酰基吗啉的溶液:
其中R1是氢原子或C1-C3烷基。此外,本发明涉及制备膜的方法,其中使用该溶液。
砜聚合物如聚砜、聚醚砜和聚亚苯基砜是高性能聚合物,其由于它们的机械性能和它们的化学和热稳定性而用于各种技术应用。然而,砜聚合物在许多常见溶剂中具有有限的溶解度。特别是砜聚合物的低分子量级分引起砜聚合物溶液的浑浊,如J.G Wijmans和C.A.Smolders,Eur.Polym.J.19,第12期,第1143-1146页(1983)。US 5885456公开了作为砜聚合物的合适溶剂的N-甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAC)、二甲基丙烯酰胺(DMAD)或二甲亚砜(DMSO)。
一种主要的技术应用是使用砜聚合物作为制备膜,特别是超滤膜(UF膜)的原料,如US 4207182和US 5885456中所述。超滤膜应具有许多孔。然而,孔的尺寸应小。孔隙率应允许通过膜的高水渗透率。另一方面,水应尽可能地提纯,并且UF膜应尽可能好地保留任何聚合物,甚至水中存在的低分子量聚合物。
制备砜聚合物的UF膜的方法包括将砜聚合物和水溶性聚合物溶于溶剂中,使砜聚合物由该溶剂凝固和其他后处理步骤。溶剂的选择对于该方法是必需的并且影响所得膜的性能,包括但不限于膜的机械稳定性、水渗透性和孔的尺寸。
在GB 2047162中,公开了N-甲酰基吗啉和N-乙酰基吗啉在制备聚砜膜中的用途。在GB 2047162的实施例中,仅使用甲酰基哌啶。GB 2047162中公开的膜不适合作为UF膜,因为没有使用对膜的孔隙率而言必需的水溶性聚合物。
在溶剂领域,持续需求可替代目前特定应用中所用溶剂的替换溶剂。在砜聚合物的情况下,替换溶剂应能够制备允许高含量砜聚合物而无浑浊的溶液。就由其制备的UF膜而言,重要的是实现良好标准的UF膜质量。特别地,该膜的水渗透性应尽可能高,并且孔尺寸应低,使得即使是低分子量聚合物也尽可能地保留。
本发明的一个目的是提供用于制备膜,特别是UF膜的替换溶剂。替换溶剂应满足上述要求。
因此,已经发现了如上所定义的溶液和由其制备膜的方法。
砜聚合物
该溶液包含砜聚合物。术语“砜聚合物”应包括不同砜聚合物的混合物。
砜聚合物在聚合物中,优选在聚合物的主链中包含-SO2-单元。
优选地,砜聚合物包含每100克(g)聚合物至少0.02mol-SO2-单元,特别是至少0.05mol-SO2-单元。更优选包含每100g聚合物至少0.1mol-SO2-单元的砜聚合物。最优选包含每100g聚合物至少0.15SO2单元,特别是至少0.2mol-SO2-单元的砜聚合物。
通常砜聚合物确实包含每100克(g)聚合物最多2mol-SO2-单元,特别是最多1.5mol-SO2-单元。更优选包含每100克聚合物最多1mol-SO2-单元的砜聚合物。最优选包含每100克聚合物最多0.5-SO2-单元的砜聚合物。
优选地,砜聚合物包含芳族基团,简称为芳族砜聚合物。
在一个优选实施方案中,砜聚合物是芳族砜聚合物,其包含至少20重量%,特别是至少30重量%的芳族碳原子。芳族碳原子是作为芳族环体系的一部分的碳原子。
更优选包含至少40重量%,特别是至少45重量%的芳族碳原子的芳族砜聚合物。
最优选包含至少50重量%,特别是至少55重量%的芳族碳原子的芳族砜聚合物。
优选地,砜聚合物可包含选自1,4-亚苯基、1,3-亚苯基、1,2-亚苯基、4,4'-亚联苯基、1,4-亚萘基或3-氯-1,4-亚苯基的芳族基团。
芳族基团可以通过例如选自-SO2-、-SO-、-S-、-O-、-CH2-、-C(CH3)2的单元连接。
在一个优选实施方案中,砜聚合物包含至少80重量%,更优选至少约90重量%,最优选至少95重量%,或者至少98重量%的选自上述芳族基团和链接基团的基团。
优选的砜聚合物的实例是:
式II的聚砜
式III的聚醚砜
式IV的聚亚苯基砜
最优选式II的聚砜。
水溶性聚合物
水溶性聚合物在水中的溶解度在21℃,1巴下在100g水中优选为至少10g聚合物,特别是至少20g聚合物。更优选在水中的溶解度在21℃,1巴下在100g水中为至少30g聚合物的水溶性聚合物。最优选在水中的溶解度在21℃,1巴下在100g水中为至少50g聚合物的水溶性聚合物。
该类水溶性聚合物的实例是具有选自如下的官能团的聚合物:酸基团特别是醚基团,羧酸基团,酰胺基团,包括作为内酯或酯基团的环状酰胺基团,特别是羧酸酯基团,或其混合物。
优选地,水溶性聚合物总共包含至少0.01mol,特别是0.05mol,更优选至少0.1mol,或者至少0.2mol的该类官能团。
水溶性聚合物例如为聚亚烷基醚,例如聚氧化乙烯、聚氧化丙烯或聚四氢呋喃,聚丙烯酸,聚甲基丙烯酸或者丙烯酸或甲基丙烯酸的共聚物。
优选地,水溶性聚合物是乙烯基吡咯烷酮聚合物,其包含至少50重量%,特别是至少80重量%,更优选至少90重量%的N-乙烯基吡咯烷酮作为聚合单元。
最优选聚乙烯吡咯烷酮(PVP)作为水溶性聚合物。
优选地,该溶液包含每100重量份砜聚合物1-100重量份的水溶性聚合物。
特别地,该溶液包含每100g砜聚合物至少5重量份,优选至少20重量份。
更优选包含每100g砜聚合物20-80重量份,特别是20-60重量份的水溶性聚合物的溶液。
最优选包含每100g砜聚合物25-50重量份,特别是25-40重量份的水溶性聚合物的溶液。
N-酰基吗啉
式I的N-酰基吗啉中的R1是氢原子或C1-C3烷基。
N-酰基吗啉优选为N-甲酰基吗啉(R1=H)或N-乙酰基吗啉(R1=甲基)。
在一个最优选的实施方案中,R1是N-甲酰基吗啉。
本文所用术语“N-酰基吗啉”还应包括N-酰基吗啉的混合物。
溶液
除了式I的N-酰基吗啉之外,该溶液可以包含其他溶剂,下文中称为共溶剂。
优选可以任何比例与N-酰基吗啉混溶的共溶剂。合适共溶剂是例如N-甲酰基吡咯烷、N-乙酰基吡咯烷、N-甲基吡咯烷酮(NMP)、N-乙基吡咯烷酮(NEP)、二甲基乙酰胺(DMAc)、二甲基甲酰胺(DMF)、二甲基丙烯酰胺(DMAD)、二甲亚砜(DMSO)或碳酸亚烷基酯(例如特别是碳酸亚丙酯)。
在一个优选实施方案中,溶液中所有溶剂总量的至少30重量%,特别是至少50重量%是N-酰基吗啉。
在一个更优选实施方案中,溶液中所有溶剂总量的至少70重量%,特别是至少90重量%是N-酰基吗啉。在一个最优选的实施方案中,溶液中所有溶剂总量的至少95重量%,特别是至少98重量%是N-酰基吗啉。
在最优选中,在溶液中不使用共溶剂,而式I的N-酰基吗啉是所用的唯一溶剂。
优选地,溶液包含总量为每100重量份所有溶剂的总量5-200重量份,特别是10-100重量份,更优选20-70份,或者25-50重量份的砜聚合物和水溶性聚合物。
在一个最优选的实施方案中,该溶液包含总量为每100重量份式I的N-酰基吗啉总量5-200重量份,特别是10-100重量份,更优选20-70重量份,或者25-50重量份的砜聚合物和水溶性聚合物。
可以通过将砜聚合物加入溶剂中并根据本领域已知的任何方法溶解聚砜来制备溶液。溶解过程可以通过提高溶液温度和/或通过机械操作如搅拌辅助。在一个替换实施方案中,砜聚合物可以在N-酰基吡咯烷或包含N-酰基吗啉的溶剂混合物中合成。
制备膜的方法
上述溶液和优选的溶液可用于制备膜。
在本专利申请的上下文中,膜应理解为能够分离两种流体或由液体分离分子和/或离子组分或颗粒的半渗透性结构。膜作为选择性屏障,允许一些颗粒、物质或化学物质通过,同时保留其他物质。膜可具有各种几何形状,例如平板状、螺旋缠绕状、枕头状、管状、单孔中空纤维或多孔中空纤维。
例如,膜可以是反渗透(RO)膜、正向渗透(FO)膜、纳滤(NF)膜、超滤(UF)膜或微滤(MF)膜。这些膜类型通常是本领域已知的并且在文献中有详细描述。良好的概述可见于早期的欧洲专利申请No.15185604.4(PF 78652)中,其在此通过参考并入本文。优选的膜是超滤(UF)膜。
优选地,膜可以根据包括以下步骤的方法制备:
a)提供包含砜聚合物、水溶性聚合物和式I的N-酰基吗啉的溶液,
b)使溶液与凝结剂接触,
c)任选地氧化和洗涤所得膜。
步骤a)中的溶液对应于上述溶液。水溶性聚合物有助于调节溶液的粘度。水溶液聚合物的主要目的是辅助孔的形成。在随后的凝固步骤b)中,水溶性聚合物变为分布在凝固的膜中,且因此成为孔的位置占有者。
在进行下一步骤之前,可任选地将溶液脱气。
在步骤b)中,使溶液与凝结剂接触。在该步骤中,发生砜聚合物的凝固并形成膜结构。
砜聚合物应在凝结剂中具有低溶解度。合适的凝结剂是例如液态水、水蒸气、醇或其混合物。
合适的醇是例如单-、二-或三烷醇,如异丙醇、乙二醇或丙二醇。优选的凝结剂是液态水。
工艺步骤a)和b)的其他细节取决于所需的膜的几何结构和生产规模,包括实验室规模或商业规模。
对于平板膜,详细的工艺步骤a)和b)可以如下:
a1)提供包含砜聚合物、水溶性聚合物和式I的N-酰基吗啉的溶液,
a2)加热溶液直至获得粘稠溶液;通常将溶液保持在5-250℃,优选25-150℃,更优选50-90℃的温度下,
a3)进一步搅拌溶液直至形成均匀的混合物;通常均化在1-15小时内完成,优选在0.5-3小时内完成,
b1)将a3)中获得的溶液浇铸在载体上,然后将浇铸的膜转移至凝固浴中,凝固浴优选为水。
对于单孔中空纤维或多孔中空纤维的制备,步骤b1)可以通过将a3)中获得的溶液挤出通过具有所需数的中空针的挤出喷嘴来进行。在挤出过程中,凝固液通过中空针注入挤出的聚合物中,从而在挤出的聚合物中形成沿挤出方向延伸的平行连续通道。
优选地,挤出膜的外表面上的孔尺寸通过使离开挤出喷嘴后的外表面与温和凝结剂接触来控制,使得在外表面上固定形状而无活性层且随后使膜与强凝结剂接触。
其他工艺步骤c)是任选的。在一个优选实施方案中,进行工艺步骤c)。进行氧化和洗涤以除去水溶性聚合物并形成孔。氧化之后可以进行洗涤,反之亦然。氧化和洗涤也可以在一个步骤中同时进行。
对于氧化,可以使用任何氧化剂。优选水溶性氧化剂,例如特别是次氯酸钠。
根据本发明,所得砜聚合物溶液显现出没有或至少很少浊度。该溶液适用于制备膜。所得膜具有高机械稳定性并具有优异的分离特性。特别地,膜具有非常好的截留分子量(MWCO)。在一个优选实施方案中,膜M具有如实验部分所述测定小于20kDa(20.000g/mol)的截留分子量。膜还具有非常好的水渗透率值。在一个优选实施方案中,膜具有如实验部分所述测定至少300kg/h m2巴的纯水渗透率(PWP)。
通过本发明方法获得的膜可用于任何分离目的,例如水处理应用、工业或市政废水的处理、海水或微咸水的脱盐、渗析、质壁分离、食品加工。
实施例
实施例中使用的缩写和化合物:
DMAc 二甲基乙酰胺
PWP 纯水渗透率
MWCO 截留分子量
NFM N-甲酰基吗啉
S 6010 聚砜,粘度值(ISO 307,1157,1628;0.01g/mol苯酚/1,2邻二氯苯1:1溶液)为81;玻璃化转变温度(DSC,10℃/min;根据ISO 11357-1/-2)为187℃;分子量Mw(GPC,在THF中,PS标准):60000g/mol,Mw/Mn=3.7
使用超纯水(无盐水,通过Millipore UF体系过滤)使用直径为60mm的压力室测试膜的纯水渗透率(PWP)。高PWP允许高流速并且是期望的。
在随后的试验中,使用具有增加的分子量的PEG-标样的溶液作为进料,在0.15巴的压力下滤过膜。通过GPC-测量进料和渗透物,测定所用每种PEG标样的渗透物的分子量。膜(MWCO)的截留重均分子量(MW)是第一PEG标样的分子量,其至少90%被膜保留。例如,MWCO为18400意指保留至少90%分子量为18400或更高的PEG。期望具有尽可能低的MWCO。
使用NFM作为聚合物溶剂制备膜一般程序
向装有磁力搅拌器的三颈烧瓶中加入75ml如表1中所给出的溶剂S1,作为第二涂漆聚合物(dope polymer)的量在表1中给出的Luvitec K30(“K30”)和19或25g聚砜(S 6010)。将混合物在60℃下在温和搅拌下加热,直至获得均匀的澄清粘稠溶液,通常称为涂漆溶液(dope solution)。将溶液在室温下脱气过夜。
在表1中列出了DMAc(对比例1)和含有水溶性聚合物的NFM(实施例1)和不含水溶性聚合物(对比例2)的结果。
表1:基于不同溶剂S1的涂漆聚合物溶液的性能。
K30 | S 6010 | 溶剂S1 | 涂漆溶液外观 | |
对比例1 | 6 | 19 | DMAc | 浑浊 |
对比例2 | 0 | 25 | NFM | 清澈且透明 |
实施例1 | 6 | 19 | NFM | 清澈且透明 |
此后,将膜溶液在60℃下再加热2小时,并使用以5mm/min的速度操作的Erichsen涂布机在60℃下用浇铸刀(300微米)浇铸于玻璃板上。使膜薄膜静置30秒,然后浸入25℃的水浴中10分钟。在膜与玻璃板分离后,将膜小心地转移至水浴中12小时。此后将膜转移至50℃的含有2500ppm NaOCl的浴中4.5小时。然后将膜用60℃的水洗涤,用0.5重量%的亚硫酸氢钠溶液洗涤一次以除去活性氯。在用水进行几次洗涤步骤后,将膜湿储存,直至开始表征纯水渗透率(PWP)和最小孔尺寸(MWCO)。
表2总结了膜的性能。
表2:组成和制备的膜的性能;MWCO([Da]),PWP[kg/hm2巴]。
K30 | S6010 | 溶剂S1 | PWP | MWCO | |
对比例1 | 6 | 19 | DMAc | 180 | 21500 |
对比例2 | 0 | 25 | NFM | 0 | --- |
实施例1 | 6 | 19 | NFM | 390 | 18100 |
用根据本发明的NFM制备的膜显示出相对于现有技术已知的膜改善的分离特性。与现有技术中已知的膜相比,用NFM制备的膜显示出改进的(更小的)MWCO以及更高的渗透率值的组合。不使用水溶性聚合物,则所得膜不具有水渗透性。
Claims (17)
2.根据权利要求1的溶液,其中砜聚合物包含每100g砜聚合物至少0.02mol-SO2-单元。
3.根据权利要求1或2的溶液,其中砜聚合物是芳族砜聚合物,其包含至少30重量%的芳族碳原子。
5.根据权利要求1-4中任一项的溶液,其中水溶性聚合物在水中的溶解度在21℃,1巴下在100g水中为至少30g聚合物。
6.根据权利要求1-5中任一项的溶液,其中水溶性聚合物是乙烯基吡咯烷酮聚合物,其包含至少50重量%N-乙烯基吡咯烷酮。
7.根据权利要求1-6中任一项的溶液,其中水溶性聚合物是聚乙烯基吡咯烷酮(PVP)。
8.根据权利要求1-7中任一项的溶液,其中所述溶液包含每100重量份砜聚合物1-100重量份的水溶性聚合物。
9.根据权利要求1-8中任一项的溶液,其中N-酰基吗啉是N-甲酰基吗啉。
10.根据权利要求1-9中任一项的溶液,其中溶液包含总量为每100重量份N-酰基吗啉5-200重量份的砜聚合物和水溶性聚合物。
11.一种制备膜的方法,其中使用根据权利要求1-10中任一项的溶液。
12.根据权利要求11的制备膜的方法,包括以下步骤:
a)提供根据权利要求1-10中任一项的溶液,
b)使所述溶液与凝结剂接触,
c)任选地氧化和洗涤所得膜。
13.根据权利要求12的方法,其中步骤b)中的凝结剂是水。
14.根据权利要求11-13中任一项的方法,其中所得膜的截留重均分子量最大为20000g/mol。
16.通过根据权利要求11-15中任一项的方法获得的膜。
17.根据权利要求16的膜在水处理应用、工业或市政废水的处理、海水或微咸水的脱盐、渗析、质壁分离、食品加工中的用途。
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US20190329183A1 (en) | 2019-10-31 |
CN109312151A (zh) | 2019-02-05 |
WO2017220386A1 (en) | 2017-12-28 |
EP3475364A1 (en) | 2019-05-01 |
HUE059758T2 (hu) | 2023-01-28 |
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