CN106422818A - 自润湿多孔膜 - Google Patents
自润湿多孔膜 Download PDFInfo
- Publication number
- CN106422818A CN106422818A CN201610490969.0A CN201610490969A CN106422818A CN 106422818 A CN106422818 A CN 106422818A CN 201610490969 A CN201610490969 A CN 201610490969A CN 106422818 A CN106422818 A CN 106422818A
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- China
- Prior art keywords
- moistening
- perforated membrane
- hydrophobic polymer
- group
- monomer
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 44
- 238000009736 wetting Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 37
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 26
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 25
- 238000005266 casting Methods 0.000 claims abstract description 8
- 239000000080 wetting agent Substances 0.000 claims abstract description 7
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 N- methylimidazolyl Chemical group 0.000 claims description 56
- 229920000642 polymer Polymers 0.000 claims description 26
- 239000012530 fluid Substances 0.000 claims description 21
- 239000012634 fragment Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 13
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 10
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- 239000004696 Poly ether ether ketone Substances 0.000 claims description 9
- 239000004697 Polyetherimide Substances 0.000 claims description 9
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- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
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- 238000002360 preparation method Methods 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 241001044369 Amphion Species 0.000 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 4
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
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- 150000003839 salts Chemical class 0.000 claims description 4
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- WLWHLUQQCLCFNE-UHFFFAOYSA-N 1-ethenyl-3-methyl-2h-imidazole Chemical compound CN1CN(C=C)C=C1 WLWHLUQQCLCFNE-UHFFFAOYSA-N 0.000 claims 2
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- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 238000001471 micro-filtration Methods 0.000 abstract description 2
- 238000000108 ultra-filtration Methods 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract 3
- 238000001631 haemodialysis Methods 0.000 abstract 1
- 230000000322 hemodialysis Effects 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
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- 238000009434 installation Methods 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229960004592 isopropanol Drugs 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
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- 125000003277 amino group Chemical group 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 3
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- 125000003010 ionic group Chemical group 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明公开了自润湿多孔膜,其包含芳族疏水性聚合物如聚砜和润湿剂,所述润湿剂包含式A‑B或A‑B‑A的共聚物,其中A为包括式(I)CH2=C(R1)(R2)的聚合单体的亲水性片段,其中R1和R2是如本文所述,和B为芳族疏水聚合物片段,其中片段B和A通过酰氨基烷基硫基连接。本发明还公开了制备自润湿膜的方法,包括流延含有芳族疏水性聚合物和润湿剂的溶液,然后使流延溶液经受相转化。所述自润湿多孔膜用于血液透析、微滤和超滤。
Description
背景技术
芳族疏水性聚合物如聚砜和聚醚砜出于以下原因的一个或多个而作为成膜聚合物是有吸引力的:高玻璃化转变温度、无定形玻璃态、热和氧化稳定性、优异的强度和柔韧性、耐极端pH,和即使在升高的温度下的低蠕变性。然而,这些聚合物本身是疏水性的,并且因此由这些聚合物制得的多孔膜不被水润湿。
已尝试通过多种方法改进由这样的聚合物制得的多孔膜的表面润湿性,所述方法包括涂覆和交联亲水性聚合物,通过电子束、γ辐射或紫外线或其它辐射接枝亲水性单体,表面氧化,表面引发自由基接枝,与亲水性添加剂,如聚乙烯吡咯烷酮(PVP)、PVP的共聚物、聚乙烯醇(PVA)、PVA的共聚物、聚氧化乙烯(PEO)、PEO与聚氧化丙烯的共聚物共混,和亲水单体的原位聚合。
上述所尝试的方法的一种或多种伴随有缺陷。例如,采用涉及共混亲水性添加剂的方法中,添加剂在水性环境中长时间使用时倾向于浸出多孔膜。涉及涂覆和交联亲水性聚合物的方法倾向于收缩或改变膜孔,从而限制了膜的有用性。
前述表明存在以下未满足的需求:由会产生水可润湿表面的芳族疏水性聚合物制备多孔膜和在延长的使用期中表面润湿性稳定。
发明简述
本发明提供了自润湿多孔膜,其包含芳族疏水性聚合物和润湿剂,所述润湿剂包含式A-B或A-B-A的共聚物,其中,A为包括聚合的单体或单体混合物的亲水性片段,其中所述单体具有式(I):
CH2=C(R1)(R2) (I),
其中,R1是氢或烷基,和R2选自经取代的或未取代的杂环基、经取代的或未取代的杂芳基、甲酰基氨基、甲酰基氨基烷基、氨基羰基、烷基羰氧基、和氨基羰基烷基,其被两性离子基团取代,和B为芳族疏水性聚合物片段,其中,片段B和A通过酰氨基烷基硫基连接。本发明还提供了制备这样的自润湿多孔膜的方法。
本发明的自润湿多孔膜具有通过约83达因/cm2至约87达因/cm2的高临界润湿表面张力(CWST)证实的高的水可润湿性。润湿添加剂具有与芳族疏水性聚合物的高度相容性,因此不会浸出或仅以最低限度浸出。润湿添加剂本身也均匀地分布在所述多孔膜中。
附图说明
图1展示了根据在实施例10中阐释的本发明的实施方案的自润湿多孔膜的SEM显微照片。
发明详述
在一个实施方案中,本发明提供了自润湿多孔膜,其包含芳族疏水性聚合物和润湿剂,所述润湿剂包含式A-B或A-B-A的共聚物,其中,A为包括聚合的单体或单体混合物的亲水性片段,其中,所述单体具有式(I):
CH2=C(R1)(R2) (I),
其中,R1是氢或烷基,和R2选自经取代的或未取代的杂环基、经取代的或未取代的杂芳基、甲酰基氨基、甲酰基氨基烷基、氨基羰基、烷基羰氧基、和氨基羰基烷基,其被两性离子基团取代,和B是芳族疏水性聚合物片段,其中,片段B和A通过酰氨基烷基硫基连接。“A”还包括端基。
本文中所使用的术语“杂环基,,是指单环杂环基团或双环杂环基团。所述单环杂环是三元、四元、五元、六元或七元环,其含有至少一个独立地选自O、N、N(H)和S的杂原子。所述三元或四元环包含零个或一个双键和杂原子选自O、N、N(H)及S。所述五元环包含零个或一个双键,和一个、二个或三个选自O、N、N(H)及S的杂原子。所述六元环包含零个、一个或两个双键和一个、二个或三个选自O、N、N(H)及S的杂原子。所述七元环包含零个、一个、二个或三个双键和一个、二个或三个选自O、N、N(H)及S的杂原子。所述单环杂环可以是未取代的或经取代的和通过任何可取代的碳原子或包含在所述单环杂环内的任何可取代的氮原子连接到母体分子部分。
杂环基的实例包括吡啶基、哌啶基、哌嗪基、吡嗪基、吡咯基、吡喃基、四氢吡喃基、四氢噻喃基、吡咯烷基、吡咯烷酮基、呋喃基、四氢呋喃基、噻吩基、四氢噻吩基、嘌呤基、嘧啶基、噻唑基、噻唑烷基、噻唑啉基、噁唑基、***基、四唑基、四嗪基、苯并噁唑基、吗啉基、硫代磷杂环戊烯基(thiophorpholinyl)、喹啉基和异喹啉基。
术语“杂芳基”是指具有五个至十个环原子的环状芳族基团,所述环原子的至少一个原子是O、S或N,且其余原子是碳。杂芳基的实例包括吡啶基、吡嗪基、嘧啶基、吡咯基、吡唑基、咪唑基、噻唑基、噁唑基、异噁唑基、噻二唑基、噁二唑基、噻吩基、呋喃基、喹啉基、和异喹啉基。
杂环基或杂芳基结构部分上的取代基可以是烷基、卤代、羟基、硝基、羧基、酮基、氧代、氨基、磺酸氧基、磺酰基、磺酰氧基、磷酰基(phospho)、膦酰基或它们的任意组合。例如,环CH2基团可以被C=O基团替代。取代可以是在碳原子上或在杂原子如环氮上,例如,在环氮上的烷基提供季铵基团。
根据一个实施方案中,所述烷基优选为C1-C6烷基。烷基的实例包括甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、正己基等。
两性离子基团包括带正电荷的基团和带负电荷的基团,其通过合适的间隔原子如碳、氧或硫,或结构部分如烷基结构部分分开。带正电荷的基团的实例包括铵基团和季铵基团。带负电荷的基团的实例包括羧酸根、磺酸根和膦酸根。
在一个实施方案中,R1是氢或甲基,和R2选自吡咯烷酮基、吡啶基、咪唑基、N-甲基咪唑基、甲酰基氨基、甲酰基氨基甲基、氨基羰基、甲基羰氧基、和氨基羰基丙基,其被两性离子基团取代。
在一个具体的实施方案中,A为包括聚合的单体或单体混合物的亲水性片段,所述单体或单体混合物选自1-乙烯基吡咯烷-2-酮、N-[3-(二甲氨基)丙基]甲基丙烯酰胺、乙酸乙烯酯、1-乙烯基咪唑、1-乙烯基-3-烷基咪唑鎓、1-乙烯基-2-吡啶、1-乙烯基-4-吡啶、丙烯酰胺、N-乙烯基甲酰胺和N-烯丙基甲酰胺,和3-(甲基丙烯酰氨基丙基)二甲基(3-磺基丙基)铵内盐。
芳族疏水性聚合物可以选自聚砜(PSU)、聚苯醚砜(PPES)、聚醚砜(PES)、聚碳酸酯(PC)、聚醚醚酮(PEEK)、二氮杂萘酮联苯聚芳醚砜酮(poly(phthalazinone ether sulfoneketone))(PPESK)、聚苯硫醚(PPS)、聚苯醚(PPE)、聚氧化亚苯基(PPO)和聚醚酰亚胺(PEI),其具有以下结构:
芳族疏水性聚合物可以具有任何合适的分子量,例如,约25kDa至约250kDa,优选约50kDa至约100kDa的数均分子量。芳族疏水性聚合物中的“n”的值可以为约30至约300,优选约50至约250。
芳族疏水性聚合物片段B可以选自聚砜(PSU)、聚苯醚砜(PPES)、聚醚砜(PES)、聚醚醚酮(PEEK)、聚苯硫醚(PPS)、聚苯醚(PPE)、聚氧化亚苯基(PPO)或聚醚酰亚胺(PEI),它们每一个被一个或优选两个氨基取代的结构部分封端。这样的氨基取代的基团是本领域技术人员已知的,可通过附加氨基取代的端基,例如4-氨基苯酚而终止缩聚来引入。
每个上述芳族疏水性片段B内的重复单元的数量n可以为约10至约250,优选约20至约200,并且更优选约30至约100。
嵌段共聚物的数均分子量为约5,000至约50,000克/摩尔,优选约10,000至约30,000克/摩尔的范围。
B与A之间的连接基团为酰氨基烷基硫基,如本文中在方括号内示出:-(B)-[NH-C(=O)-(CH2)a-S]-(A),其中,a为1-6,优选1-3,且更优选1。
根据一个实施方案,所述共聚物具有式(Ia)或(Ib):
其中,B如上文所定义,A’是亲水性单体的聚合物片段,X为-NHC(=O)(CH2)pS-,其中p为1-3,T为端基,和Y为不同于氨基的基团。例如,Y为烷基、烷氧基、氯或羟基。
根据本发明的一个实施方案,所述共聚物具有下式:
其中,m1或m2为约5至约50,且优选约10至约30,和n为约20至约200,且优选约30至约100。
共聚物可以通过在具有硫醇作为端基的预形成的聚合物片段B上与链转移结合的乙烯基单体的自由基聚合制备。可以通过巯基烷基羧酸与片段的氨基末端之间的酰胺形成而将这样的基团引入聚合物。如本领域技术人员已知那样,可以通过用氨基取代的端基,如4-氨基苯酚终止缩聚而引入这样的胺结构部分。A-B型二嵌段共聚物可以从具有一个末端基团的聚合物片段B制备,A-B-A型三嵌段共聚物可以从具有两个末端基团的聚合物片段B制备。
商购可得的聚合物片段B的起始原料的实例是Solvay的双遥爪聚砜VW-30500RP,其具有胺(苯胺)端基。胺端基在缩合试剂例如丙基膦酸酐,T3P的存在下与巯基乙酸钠反应。产生的具有硫醇端基的聚合物片段B用于锚定在自由基聚合过程中形成的聚乙烯吡咯烷酮,如下所示:
可以使用任何合适的自由基引发剂,例如偶氮异丁腈(AIBN)、过氧化苯甲酰、过氧化乙酰、过氧化月桂酰、叔丁基过氧化物、过氧化异丙苯、过乙酸叔丁酯和叔丁基氢过氧化物。因此,该共聚物的端基的性质可以根据所使用的引发剂而变化。本发明的实施方案的共聚物中存在的2-甲基丙腈端基源自与AIBN产生的自由基共聚的终止。其它端基的实例可以是苯甲酸酯、乙酸酯、月桂酸酯、叔丁氧基、异丙苯氧基等。
本发明还提供了制备自润湿多孔膜的方法,包括:(i)将溶液流延成期望形状,所述溶液包含溶剂、芳族疏水性聚合物和式A-B-A的共聚物,其中,A为包括聚合的单体或单体混合物的亲水性片段,其中所述单体具有式(I):
CH2=C(R1)(R2) (I),
R1是氢或烷基,和R2选自经取代的或未取代的杂环基,经取代的或未取代的杂芳基,甲酰基氨基,甲酰基氨基烷基,氨基羰基,烷基羰氧基、和氨基羰基烷基,其被两性离子基团取代,和B是芳族疏水性聚合物片段,其中,片段B和A通过酰氨基烷基硫基连接;(ii)使流延溶液经受相转化,以形成自润湿多孔膜;和(iii)任选地用水冲洗所述自润湿多孔膜。
本发明还提供了通过上述方法制备的自润湿多孔膜。
根据本发明的一个实施方案,所述自润湿多孔膜是以下多孔膜,例如纳米多孔膜,例如具有1nm和100nm之间的直径的孔的膜,或具有1μ和10μm之间的直径的孔的微孔膜。
形成膜的聚合物溶液通过将聚合物溶于溶剂或溶剂混合物中制备。许多聚合物适合用作本发明中的形成膜的聚合物,并且是本领域已知的。合适的聚合物可以包括聚合物,例如,聚砜(PSU)、聚醚砜(PES)、聚苯醚(PPE)、聚苯醚砜(PPES)、聚氧化亚苯基(PPO)、聚碳酸酯(PC)、二氮杂萘酮联苯聚芳醚砜酮(PPESK)、聚醚醚酮(PEEK)、聚醚酮酮(PEKK)、聚醚酰亚胺(PEI)和它们的共混物。
除了一种或多种聚合物,典型的聚合物溶液包含至少一种溶剂,并且可以进一步包含至少一种非溶剂。合适的溶剂包括例如,N,N-二甲基甲酰胺(DMF);N,N-二甲基乙酰胺(DMAC);N-甲基吡咯烷酮(NMP);二甲基亚砜(DMSO),甲基亚砜,以及它们的混合物。合适的非溶剂包括例如,水;各种聚乙二醇(PEG;例如PEG-200、PEG-300、PEG-400、PEG-1000);各种聚丙二醇;各种醇,例如甲醇、乙醇、异丙醇(IPA)、戊醇、己醇、庚醇和辛醇。
典型地,本发明的共聚物A-B-A以从约3至约20重量%的范围,优选在约4至约15重量%的范围的量包括在膜流延溶液中。
除共聚物以外,膜流延溶液典型地包括约10至约30重量%的芳族疏水性聚合物,约0至约10重量%的添加剂如PEG,最多至约90重量%的量的极性溶剂或溶剂混合物如NMP、DMF和/或DMAc。也可包括非溶剂如水和/或醇。
在自润湿膜的形成中可以使用的典型骤冷浴包括但不限于,含有非溶剂如水、醇等,无论是其本身,还是与一种或多种极性溶剂组合的浴。
溶液的合适组分是本领域已知的。包括聚合物和示例性溶剂和非溶剂的示例性溶液包括公开于例如美国专利4,340,579;4,629,563;4,900,449;4,964,990,5,444,097;5,846,422;5,906,742;5,928,774;6,045,899;6,146,747和7,208,200中的那些。
将所述芳族疏水性聚合物,所述共聚物和所述溶剂和其它添加剂首先混合在一起,然后在约35至约75℃,优选约40至约50℃的温度加热,直至形成均匀的溶液。
可以在合适的基材如玻璃上通过使用刮刀流延具有合适厚度例如约0.005至约0.006英寸的厚度的膜而制备平片膜。将流延膜在骤冷浴中凝固,并在水中洗涤一段时间,所述时间足以浸出不直接结合到疏水基聚合物的任何材料。通过本领域技术人员已知的方法干燥所述膜。
除了制备平片膜,可以使用本领域中公知的方法将本发明的自润湿膜成型为褶皱膜、中空纤维膜、管状膜等。
本发明还提供了过滤流体的方法,所述方法包括使所述流体通过所述自润湿多孔膜。
根据本发明的实施方案的自润湿多孔膜可以用于多种应用中,包括例如,血液透析、微滤和超滤应用。此外,还发现它们可以用于诊断应用(包括例如,样品制备和/或诊断侧向流动装置),喷墨应用,平版印刷,例如,作为HD/UHMW PE基介质的替代,过滤制药工业的流体,金属去除,生产超纯水,工业和地表水的处理,过滤用于医学应用的流体(包括家用的和/或患者使用的,例如静脉内应用,还包括例如过滤生物流体如血液(例如,病毒清除)),过滤电子工业的流体,过滤食品和饮料工业的流体,啤酒过滤,澄清,过滤含抗体和/或含蛋白的流体,过滤含核酸的流体,细胞检测(包括原位),细胞收获,和/或过滤细胞培养液。可选地或额外地,根据本发明的实施方案的多孔膜可以用于过滤空气和/或气体和/或可以用于通气应用(例如,允许空气和/或气体从中通过,但不允许液体从中通过)。根据本发明的实施方案的多孔膜可以用于多种装置,包括外科装置和产品,例如,眼科手术产品。
根据本发明的实施方案,自润湿多孔膜可以具有多种构造,包括平面、平片、褶皱、管状、螺旋形和中空纤维。
根据本发明的实施方案的自润湿多孔膜典型地布置在包括至少一个入口和至少一个出口的壳体中,并且所述壳体在所述入口和所述出口之间限定至少一个流体流动路径,其中至少一个本发明的膜或包括至少一个本发明的膜的过滤器横跨所述流体流动路径,以提供过滤器装置或过滤器模块。在一个实施方案中,提供了一种过滤器装置,其包括含有入口和第一出口的壳体,并在所述入口和所述第一出口之间限定第一流体流动路径,以及至少一个本发明的膜或包括至少一个本发明的膜的过滤器,所述本发明的膜或包括至少一个本发明的膜的过滤器布置在壳体中横跨第一流体流动路径。
优选地,对于横向流应用,将至少一个本发明的多孔膜或包括至少一个本发明的膜的过滤器布置在包括至少一个入口和至少两个出口的壳体中,所述壳体在所述入口和所述第一出口之间至少限定第一流体流动路径,并在所述入口和所述第二出口之间限定第二流体流动路径,其中本发明的膜或包括至少一个本发明的膜的过滤器横跨所述第一流体流动路径,以提供过滤器装置或过滤器模块。在一个示例性实施方案中,所述过滤器装置包括横向流过滤器模块,包括入口、包括浓缩物出口的第一出口和包括渗透物出口的第二出口的壳体,并且所述壳体在所述入口和所述第一出口之间限定第一流体流动路径,并在所述入口和所述第二出口之间限定第二流体流动路径,其中横跨所述第一流体流动路径布置至少一个本发明的膜或包括至少一个本发明的膜的过滤器。
所述过滤器装置或模块可以是可消毒的。可以使用合适形状的任意壳体,并提供入口和一个或多个出口。
可以由任意合适的刚性不可渗透性材料,包括与被处理的流体相容的任意不可渗透性热塑性材料生产所述壳体。例如,可以由金属如不锈钢,或由聚合物,例如透明或半透明聚合物如丙烯酸系、聚丙烯、聚苯乙烯或聚碳酸酯树脂生产所述壳体。
以下实施例进一步阐释了本发明,但是当然不应该被认为是以任意方式限制本发明的范围。
原料和方法:起始原料是Solvay的双遥爪聚砜VW-30500RP(也称为PXM-10147),据描述,通过滴定测定,其具有密度为0.33毫当量的NH2/每克树脂的末端苯胺结构部分。通过在DMAc中的GPC分析测定,平均分子量为14kDa。所有引用数据已由制造商提供。
在具有0.05N LiBr的DMF中并以PMMA为标准进行内部(In-house)分析得到Mw值=17500,多分散性指数(PDI)为1.49。
1H NMR分析证实苯胺端基的存在,正如在5.10-5.15ppm之间(在DMSO-d6中)的宽峰所证明。将乙烯基单体进行真空蒸馏或通过包含抑制剂去除剂的柱。
实施例1
本实施例阐释根据本发明实施方案制备大分子-CTA(链转移剂)的方法。
起始二氨基大分子单体(24.0g;8mmol NH2)和巯基乙酸钠(2.74g;24mmol)溶于无水DMF(160mL)中,随后滴加T3P的50%的DMF溶液(15.3g;24mmol),并在环境温度剧烈搅拌。在24h后,将反应混合物通过倒入1.4L剧烈搅拌的水中猝灭。将形成的沉淀物滤出,用水(2次500mL),丙酮(500mL),和***(200mL)洗涤。将获得的固体通过溶于氯仿(300mL)并滴加到搅拌的甲醇(1.5L)中而再沉淀来进一步纯化。沉淀物通过过滤收集,用大量甲醇洗涤并在真空烘箱中于60℃干燥过夜,生成22.3g产物。
1H NMR分析(在DMSO-d6中)表明在5.10-5.15ppm处苯胺端基完全消失。GPC:Mw20119;PDI=1.59。
实施例2
本实施例阐释根据本发明实施方案制备共聚物A-B-A的通用规程。
将大分子-CTA溶于无水NMP,然后添加乙烯基单体和作为自由基引发剂的AIBN。将产生的混合物用氩气在环境温度吹扫至少2-5min,然后在80℃加热16-24小时。在该时间之后,将反应混合物对空气开放,并添加至过量剧烈搅拌的非溶剂,通常为至少10体积的2-丙醇中。将产生的沉淀物滤出(或在某些情况下离心),用2-丙醇充分冲洗,并在真空烘箱中于70℃干燥过夜。将获得的原料通过GPC(具有0.05N LiBr的DMF,并用PMMA的分子量标准校准)分析,并通过1H-NMR分析和元素分析测定组成。
实施例3
本实施例阐释根据本发明的技术方案制备PVP-b-PSU-b-PVP的方法,其中(m1+m2)/n=0.20。
将大分子-CTA(0.5g;0.165mmol的SH),1-乙烯基吡咯烷-2-酮(1.1mL;9.9mmol)和AIBN(3mg;0.018mmol)溶于无水NMP(2mL),并根据上述规程共聚,生成0.49g期望的产物。
通过比较在7.75-8.00ppm(PSU单元,4H)和3.00-4.00ppm(VP单元,3H)之间的信号的积分测定,1H NMR分析(在CDCl3中)表明20摩尔%的VP单元。元素分析(%N=0.80;%S=7.12)表明21摩尔%的VP。GPC:Mw=19833;PDI=1.85。
实施例4
本实施例阐释根据本发明的实施方案制备PVP-b-PSU-b-PVP的方法,其中(m1+m2)/n=0.47。
将大分子-CTA(0.5g;0.165mmol的SH),1-乙烯基吡咯烷-2-酮(0.71mL;6.6mmol)和AIBN(14mg;0.085mmol)溶于无水NMP(2mL),并根据所述通用规程共聚,生成0.44g产物。
通过比较在7.75-8.00ppm(PSU单元,4H)和3.00-4.00ppm(VP单元,3H)之间的信号的积分测定,1H NMR分析(在CDCl3中)表明47摩尔%的VP单元。元素分析表明46摩尔%的VP单元。GPC:Mw=23260;PDI=1.62。
实施例5
本实施例阐释根据本发明的实施方案制备PVP-b-PSU-b-PVP的方法,其中(m1+m2)/n=0.67。
将大分子-CTA(10.0g;3.33mmol的SH),1-乙烯基吡咯烷-2-酮(21.2mL;198mmol)和AIBN(0.56g;3.4mmol)溶于无水NMP(40mL),并根据所述通用规程共聚,生成12.25g产物。
通过比较在7.75-8.00ppm(PSU单元,4H)和3.00-4.00ppm(VP单元,3H)之间的信号的积分测定,1H NMR分析(在CDCl3中)表明67摩尔%的VP单元。元素分析(%N=3.78;%S=5.28)表明62摩尔%的VP单元。GPC:Mw=29122;PDI=1.73。
实施例6
本实施例阐释根据本发明的实施方案制备PDMAPMA-b-PSU-b-PDMAPMA的方法,其中(m1+m2)/n=0.34。
将大分子-CTA(3.0g;1mmol的SH),N-[3-(二甲基氨基)丙基]甲基丙烯酰胺(11.0mL;60mmol)和AIBN(0.164g;1mmol)溶于无水NMP(10mL),并根据所述通用规程共聚,生成3.05g产物。所得产物通过溶于氯仿并添加至10体积***中而再沉淀来纯化。最终产量为2.68g。
通过比较在7.75-8.00ppm(PSU单元,4H)和2.80-3.10ppm(DMAPMA单元,2H)之间的信号的积分测定,1H NMR分析(在DMSO-d6中)表明34摩尔%的DMAPMA单元。元素分析(%N=2.76;%S=6.18) 表明33摩尔%的DMAPMA。GPC:Mw=23024;PDI=1.64。
实施例7
本实施例阐释根据本发明的实施方案制备PVAc-b-PSU-b-PVAc的方法,其中(m1+m2)/n=0.34。
将大分子-CTA(0.50g;0.165mmol的SH),乙酸乙烯酯(0.92mL;9.9mmol)和AIBN(14mg;0.0825mmol)溶于无水NMP(2mL),并根据所述通用规程共聚,不同之处在于将甲醇用作非溶剂用于沉淀和洗涤产物。共聚物的产量为0.45g。
通过比较在7.75-8.00ppm(PSU单元,4H)和1.85-2.05ppm(VAc单元,3H)之间的信号的积分测定,1H NMR分析(在DMSO-d6中)表明41摩尔%的VAc单元。GPC:Mw=23042;PDI=1.76。
实施例8
本实施例阐释根据本发明的实施方案制备PVIm-b-PSU-b-PVIm的方法,其中(m1+m2)/n=0.57。
将大分子-CTA(0.50g;0.165mmol的SH),1-乙烯基咪唑(0.90mL;9.8mmol)和AIBN(14mg;0.0825mmol)溶于无水NMP(2mL)中,并根据所述通用规程共聚,不同之处在于将甲醇用作非溶剂用于沉淀和洗涤产物。共聚物的产量为0.35g。
通过比较在6.60-8.00ppm(PSU单元,16H和Vim单元,H)和1.50-1.70ppm(PSU单元,6H)之间的信号的积分测定,1H NMR分析(在DMSO-d6中)表明57摩尔%的VIm单元。元素分析(%N=7.03;%S=6.31)表明56摩尔%的VIm。GPC:Mw=25851;PDI=1.70。
实施例9
本实施例阐释根据本发明的实施方案制备PSZM-b-PSU-b-PSZM(聚磺基甜菜碱-两性离子-甲基丙烯酰胺共聚物)的方法,其中(m1+m2)/n=0.27。
将大分子-CTA(0.50g;0.165mmol的SH),3-(甲基丙烯酰氨基丙基)二甲基(3-磺基丙基)铵内盐(3.0g;9.9mmol)和AIBN(28mg;0.165mmol)悬浮于无水NMP(5mL)中,并根据所述通用规程共聚。用25mL的DMAc在环境温度萃取来自2-丙醇(2.1g)的粗制干燥沉淀物1h。将滗出的萃取物添加至10体积的2-丙醇中,然后添加至8体积的己烷。将产生的沉淀物收集,干燥,得到0.34g产物。
通过比较在7.75-8.00ppm之间(PSU单元,4H)和1.10-1.35ppm(SZM单元,3H)之间的信号的积分测定,1H NMR分析(在DMSO-d6中)表明27摩尔%的SZM单元。元素分析(%N=2.05;%S=7.70)表明30摩尔%的SZM单元。GPC:Mw=20419;PDI=1.81。
实施例10
本实施例阐释根据本发明技术方案制备自润湿膜的方法。
通过在46℃过夜搅拌各组分,并将其在室温存储24h制备包含聚醚砜(13重量%)、实施例5的共聚物PVP-b-PSU-b-PVP(0.9重量%),甘油(1重量%)、水(3重量%)、N-甲基吡咯烷酮(7.6重量%)、N,N-二甲基甲酰胺(10重量%)和聚乙二醇400(64.5重量%)的膜流延溶液。
将膜流延溶液流延在保持在29℃的玻璃板上,并在28℃/70%RH的气候室中放置10分钟,然后在水中浸没直至发生完全固化。该膜称为VIPS。
如下流延另一个膜。将流延溶液流延在29℃的玻璃板上,并立即浸没在80℃的水中,所产生的膜称为HTQ。
该膜在64%的SDA中浸出60分钟,然后在80℃的水中浸出60分钟,并在65℃下干燥40分钟。
所述VIPS膜的CWST为83达因/cm2(即时)和87达因/cm2(5秒)。所述HTQ膜的CWST为83达因/cm2(5秒)。非特异性蛋白(BSA)结合在23-27μg/cm2的范围内。
图1描述了VIPS膜的SEM显微照片。该膜具有高度开放的多孔结构。结节状形态也是明显的。
本文引用的所有参考文献,包括出版物、专利申请和专利,在此通过参考以如下相同的程度并入本文中:如同各参考文献单独且明确地表明通过参考且以其整体并入本文中或以其整体列举。
在描述本发明的上下文中(特别是在随后权利要求书的上下文中)的术语“一”和“一个”和“所述(该)”和“至少一个”和相似的术语的使用,除非本文另有说明或通过上下文明显矛盾,将被解释为涵盖单数和复数。跟随一系列一个或多个项目(例如,“A和B中的至少一个”)的术语“至少一个”的使用,除非本文另有说明或通过上下文明显矛盾,将被解释为本意是选自所列出的项目中的一项(A或B)或两个或更多个所列出的项目的任意组合(A和B)。除非另有说明,术语“包含”、“具有”、“包括”和“含有”将被解释为开放式术语(即,意为“包括,但不限于”)。除非本文另有说明,本文数值范围的记载仅意为简记法,其独立地涉及落在该范围内的每个单独的值,且将每个单独的值如同其独立地被记载在本文而并入说明书中。除非本文另有说明或通过上下文明显矛盾,本文描述的所有方法可以以任何合适的顺序实施。除非另有要求,任何和所有实例的使用或本文提供的示例性语言(例如,“例如(如)”)仅旨在更好地说明本发明而不对本发明的范围施加限制。在说明书中没有语言应该被解释为指示任何未要求保护的要素对本发明的实施是必要的。
在本文中描述了本发明优选的实施方案,包括本发明人已知的用于实施本发明的最佳模式。通过阅读上面的描述,这些优选的实施方案的变体对于本领域的普通技术人员可变得显而易见。本发明人预期本领域技术人员视情况而定会使用这些变体,且本发明人意在除了按照本文的具体描述不同地实践本发明。因此,本发明包括所附的权利要求中记载的主题的所有被适用的法律允许的变型和等价物。此外,除非本文另有说明或通过上下文明显矛盾,本发明涵盖了以其所有可能的变体形式的上述要素的任意组合。
Claims (20)
1.自润湿多孔膜,其包含芳族疏水性聚合物和润湿剂,所述润湿剂包含式A-B或A-B-A的共聚物,
其中A为包括聚合的单体或单体混合物的亲水性片段,其中所述单体具有式(I):
CH2=C(R1)(R2) (I),
其中R1为氢或烷基,和R2选自经取代的或未取代的杂环基、经取代的或未取代的杂芳基、甲酰基氨基、甲酰基氨基烷基、氨基羰基、烷基羰氧基、和氨基羰基烷基,其被两性离子基团取代,
和B为芳族疏水性聚合物片段,其中片段B和A通过酰氨基烷基硫基连接。
2.根据权利要求1所述的自润湿多孔膜,其中R1为氢或甲基,和R2选自吡咯烷酮基、吡啶基、咪唑基、N-甲基咪唑基、甲酰基氨基、甲酰基氨基甲基、氨基羰基、甲基羰氧基、和氨基羰基丙基,其被两性离子基团取代。
3.根据权利要求1或2所述的自润湿多孔膜,其中A的单体选自1-乙烯基吡咯烷-2-酮、N-[3-(二甲氨基)丙基]甲基丙烯酰胺、乙酸乙烯酯、1-乙烯基咪唑、1-乙烯基-3-甲基咪唑、1-乙烯基-2-吡啶、1-乙烯基-4-吡啶、丙烯酰胺、N-乙烯基甲酰胺和N-烯丙基甲酰胺和3-(甲基丙烯酰氨基丙基)二甲基(3-磺基丙基)铵内盐。
4.根据权利要求1-3中任一项所述的自润湿多孔膜,其中所述芳族疏水性聚合物片段B选自聚砜、聚醚砜、聚苯醚、聚苯醚砜、聚氧化亚苯基、聚醚醚酮、聚醚酮酮和聚醚酰亚胺。
5.根据权利要求1-4中任一项所述的自润湿多孔膜,其中所述芳族疏水性聚合物片段B为聚砜。
6.根据权利要求1-5中任一项所述的自润湿多孔膜,其中所述芳族疏水性聚合物选自聚砜、聚醚砜、聚苯醚、聚苯醚砜、聚氧化亚苯基、聚碳酸酯、二氮杂萘酮联苯聚芳醚砜酮、聚醚酮、聚醚醚酮、聚醚酮酮、聚酰亚胺、聚醚酰亚胺和聚酰胺酰亚胺。
7.根据权利要求1-6中任一项所述的自润湿多孔膜,其中所述芳族疏水性聚合物为聚砜或聚醚砜。
8.根据权利要求1-7任一项所述的自润湿多孔膜,所述共聚物具有式(Ia)或(Ib):
其中B为芳族疏水性聚合物片段,A,为亲水性单体的聚合物片段,X为-NHC(=O)(CH2)pS-,其中p为1-3,T为端基和Y为不同于氨基的基团。
9.根据权利要求1-8中任一项所述的自润湿多孔膜,其中所述共聚物具有下式:
其中m1或m2为约5至约50,n为约20至约200。
10.制备自润湿多孔膜的方法,包括:
(i)将溶液流延成期望的形状,所述溶液包含溶剂、芳族疏水性聚合物和式A-B或A-B-A的共聚物,其中A为包括聚合的单体或单体混合物的亲水性片段,其中所述单体具有式(I):
CH2=C(R1)(R2) (I),
R1为氢或烷基,和R2选自经取代的或未取代的杂环基、经取代的或未取代的杂芳基、甲酰基氨基、甲酰基氨基烷基、氨基羰基、烷基羰氧基、和氨基羰基烷基,其被两性离子基团取代,
和B为芳族疏水性聚合物片段,其中片段B和A通过酰氨基烷基硫基连接;
(ii)使流延溶液经受相转化,以形成自润湿多孔膜;和
(iii)任选地用水冲洗所述自润湿多孔膜。
11.根据权利要求10所述的方法,其中R1为氢或甲基,和R2选自吡咯烷酮基、吡啶基、咪唑基、N-甲基咪唑基、甲酰基氨基、甲酰基氨基甲基、氨基羰基、甲基羰氧基、和氨基羰基丙基,其被两性离子基团取代。
12.根据权利要求10或11所述的方法,其中A的单体选自1-乙烯基吡咯烷-2-酮、N-[3-(二甲氨基)丙基]甲基丙烯酰胺、乙酸乙烯酯、1-乙烯基咪唑、1-乙烯基-3-甲基咪唑、1-乙烯基-2-吡啶、1-乙烯基-4-吡啶、丙烯酰胺、N-乙烯基甲酰胺和N-烯丙基甲酰胺和3-(甲基丙烯酰氨基丙基)二甲基(3-磺基丙基)铵内盐。
13.根据权利要求10-12中任一项所述的方法,其中所述共聚物的芳族疏水性聚合物片段B选自聚砜、聚醚砜、聚苯醚、聚苯醚砜、聚氧化亚苯基、聚醚醚酮、聚苯硫醚和聚醚酰亚胺。
14.根据权利要求10-12中任一项所述的方法,其中所述共聚物的芳族疏水性聚合物片段B为聚砜。
15.根据权利要求10-14中任一项所述的方法,其中所述芳族疏水性聚合物选自聚砜、聚醚砜、聚苯醚、聚苯醚砜、聚氧化亚苯基、聚碳酸酯、二氮杂萘酮联苯聚芳醚砜酮、聚醚酮、聚醚醚酮、聚醚酮酮、聚酰亚胺、聚醚酰亚胺和聚酰胺-酰亚胺。
16.根据权利要求10-15中任一项所述的方法,其中所述芳族疏水性聚合物为聚砜或聚醚砜。
17.根据权利要求10-16中任一项所述的方法,其中所述共聚物具有式(Ia)或(Ib):
其中B为芳族疏水性聚合物片段,A’为亲水性单体的聚合物片段,X为-NHC(=O)(CH2)pS-,其中p为1-3,T为端基和Y为不同于氨基的基团。
18.根据权利要求10-17中任一项的方法,其中所述共聚物具有下式:
其中m1或m2为约5至约50,n为约20至约200。
19.通过根据权利要求10-18中任一项所述的方法制备的自润湿多孔膜。
20.过滤流体的方法,所述方法包括使所述流体通过根据权利要求1-9或权利要求19中的任一项所述的自润湿多孔膜。
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US9724649B2 (en) | 2017-08-08 |
TWI638682B (zh) | 2018-10-21 |
EP3108955B1 (en) | 2017-12-06 |
AU2016202721B2 (en) | 2020-02-27 |
KR20170001565A (ko) | 2017-01-04 |
JP6217995B2 (ja) | 2017-10-25 |
CN106422818B (zh) | 2019-09-10 |
US20160375409A1 (en) | 2016-12-29 |
EP3108955A1 (en) | 2016-12-28 |
SG10201603247RA (en) | 2017-01-27 |
TW201709971A (zh) | 2017-03-16 |
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KR101811820B1 (ko) | 2017-12-22 |
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