CN1353626A - 具有聚环氧烷改善聚酰胺表面的复合膜 - Google Patents
具有聚环氧烷改善聚酰胺表面的复合膜 Download PDFInfo
- Publication number
- CN1353626A CN1353626A CN00808461A CN00808461A CN1353626A CN 1353626 A CN1353626 A CN 1353626A CN 00808461 A CN00808461 A CN 00808461A CN 00808461 A CN00808461 A CN 00808461A CN 1353626 A CN1353626 A CN 1353626A
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- Prior art keywords
- described method
- polyalkylene oxide
- oxide groups
- different
- amine
- Prior art date
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- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 51
- 229920000233 poly(alkylene oxides) Polymers 0.000 title claims abstract description 38
- 239000004952 Polyamide Substances 0.000 title claims abstract description 27
- 229920002647 polyamide Polymers 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000000126 substance Substances 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- -1 succinimido ester Chemical class 0.000 claims description 21
- 230000004069 differentiation Effects 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 150000002924 oxiranes Chemical class 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 150000003457 sulfones Chemical class 0.000 claims description 7
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- WROAZRATAZZDRS-UHFFFAOYSA-N (2,3,4-trichlorophenyl) hydrogen carbonate Chemical compound OC(=O)OC1=CC=C(Cl)C(Cl)=C1Cl WROAZRATAZZDRS-UHFFFAOYSA-N 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 150000001263 acyl chlorides Chemical class 0.000 claims 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 150000003839 salts Chemical class 0.000 abstract description 10
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- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 4
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- 239000012966 redox initiator Substances 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000001263 FEMA 3042 Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 2
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 2
- 229940033123 tannic acid Drugs 0.000 description 2
- 235000015523 tannic acid Nutrition 0.000 description 2
- 229920002258 tannic acid Polymers 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101000598921 Homo sapiens Orexin Proteins 0.000 description 1
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
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- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
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- ILCGOAVZOBXTIE-UHFFFAOYSA-L potassium sodium sulfonatooxy sulfate Chemical compound S(=O)(=O)([O-])OOS(=O)(=O)[O-].[K+].[Na+] ILCGOAVZOBXTIE-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
-
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- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/31725—Of polyamide
- Y10T428/31728—Next to second layer of polyamide
- Y10T428/31732—At least one layer is nylon type
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31739—Nylon type
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/31725—Of polyamide
- Y10T428/31739—Nylon type
- Y10T428/31743—Next to addition polymer from unsaturated monomer[s]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
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Abstract
一种复合膜及其制备方法,包括多孔载体和具有聚环氧烷基团接枝于其上的交联聚酰胺表面。本发明的膜在提供良好的流量和盐通过性能的同时,具有改善的防积垢性能。本发明的方法可容易地适用于工业规模,而且不需要使用化学引发剂。
Description
反渗透或纳米过滤膜是用来从溶剂或分散介质如水中分离出溶解或分散的物质即溶质。这是可以实现的,因为膜对被分离混合物中的某些组分是选择性渗透的。通常,水是能够渗透过这类膜的组分。分离方法通常包括使含水进料溶液在压力作用下与膜的一个表面接触,这样,在阻止溶解或分散物质透过膜的同时,使含水相渗透流过膜。
反渗透和纳米过滤膜通常都具有一个固定在多孔载体上的区分层(discriminating layer),称之为复合膜。超过滤和微量过滤膜也可以具有复合结构。载体提供了机械强度,但由于其孔隙度的缘故也为流率带来了阻力。另一方面,区分层是少孔的,并排斥溶解或分散的物质。因此,一般来说,区分层决定了排斥率(即被排斥的特定溶解物质的百分比),和流量(即溶液流过膜的流率)。
反渗透膜和纳米过滤膜对于不同离子和有机化合物的不渗透性程度彼此是不同的。反渗透膜对几乎所有离子包括氯化钠,相对地是不可渗透的。由于反渗透膜的NaCl排斥率通常为95-100%,因此反渗透膜被广泛地用于含盐水或海水的脱盐,为工业、商业或家庭使用提供相对的无盐水。
另一方面,纳米过滤膜对于离子的排斥通常是更为特定的。一般来说,纳米过滤膜可排斥二价离子包括镭、镁、钙、硫酸根和硝酸根。而且,纳米过滤膜一般不渗透分子量超过200的有机化合物。此外,纳米过滤膜一般较反渗透膜具有更高的流量。这些性能使纳米过滤膜可用于如“软化”水和除去水中农药之类不同的应用中。举例来说,纳米过滤膜一般具有的NaCl排斥率为0-95%,但它对如硫酸镁之类的盐和某些情况下的有机化合物如莠去津(atrazine),却具有较高的排斥率。
其区分层为聚酰胺的那些膜是用于反渗透和纳米过滤应用的特别有用的膜之一。用于反渗透膜的聚酰胺区分层常常是通过多官能团的芳族胺与多官能团的酰基卤之间的界面缩聚反应而得到的,举例来说,如US4277344中所述。与反渗透膜相反,用于纳米过滤膜的聚酰胺区分层通常是由哌嗪或胺取代的哌啶或环己烷与多官能团的酰基卤之间的界面聚合反应而得到的,如US4769148和US4859384中所述。另一种获得适合用于纳米过滤的聚酰胺区分层的方法是采用如US4765897、US4812270和US4824574中所述的方法。这些专利描述了将反渗透膜,如US4277344中的渗透膜改变为纳米过滤膜的方法。
膜积垢是许多膜应用中关心的问题。“积垢”表明碎片和有机物质聚集在膜表面上,它可导致降低的流量。这种物质通常包括单宁酸和腐殖酸、蛋白质、碳水化合物、细菌和其它水源中经常能发现的有机物。表面活性剂也可能是膜积垢的重要来源。这些物质与膜表面结合并降低膜的可溶性,从而导致降低的流量。
S.Belfer等人在Journal of Membrane Science,volume 139,no.2,page 175-181(1998)中,描述了一种防止膜积垢的方法,该方法是通过直接在商用RO复合膜(例如,“FT-30 BWTM”,可由FilmTecCorporation购得)的聚酰胺表面上完全接枝甲基丙烯酸或聚甲基丙烯酸乙二醇酯而实现的。这种方法需要使用氧化还原引发剂(过硫酸钾-偏亚硫酸氢钠),形成游离基物种,它们随后可与膜表面进行反应,并在该处形成接技。遗憾的是,游离基一旦形成,它是非常活泼的,必须在形成后的刹那间就与膜表面进行接触;否则,游离基就将与存在的其它物质反应而不与膜表面反应。其结果是,这种方法难以适用于工业规模,并需要对化学引发剂进行附加的控制。
因此,人们在寻求改进复合膜表面以降低积垢的方法。而且,人们在寻求可适用于工业规模的膜生产方法,优选不使用化学引发剂。此外,希望这类膜有降低积垢,而不损害流量和溶质通过(盐通过)的膜性能。
本发明提供了降低积垢的复合膜及其制备方法。除了降低积垢外,本发明的优选实施方案还提高了溶质通过性能。尽管本发明对反渗透膜和纳米膜可能具有最大的效用,但本发明也可适用于其它过滤膜,包括,但不局限于超滤膜和微量过滤膜。
本发明可适用于工业规模的膜生产,并且优选不包括使用化学引发剂。更具体地说,本发明的方法包括通过化学接枝聚环氧烷基团到区分层表面,改进包含多孔载体和交联聚酰胺区分层的复合膜表面;其中,聚环氧烷基团可以相同或不同,它们可由下式表示:
RO-(OCxHx+2)y-L-E其中,x相同或不同,其值为2或3;y相同或不同,其值为2-1000;R相同或不同,选自:氢、E和具有1-4个碳原子的烷基或链烯基;L相同或不同,选自:连接键或连接基,当聚环氧烷基团通过化学方法接枝到区分层时,它基本上是非活性的;和E相同或不同,选自可与存在于区分层表面上的官能团反应,以在该处形成共价化学键的非丙烯酸酯亲电基。
本发明提供了一种表面防积垢的复合膜及其制备方法。更具体地说,本发明包括一种复合膜,该复合膜包含一种多孔(也称作“微孔”)载体和一种较薄的交联聚酰胺区分层。根据本发明,聚环氧烷基团被接枝到交联的聚酰胺区分层表面。这种接枝可以作为对预形成膜(例如,一种复合聚酰胺反渗透膜,“FT-30TM”,可由FilmTecCorporation购得)的后处理而实现。此外,本发明的接枝还可以在膜的生产过程中实现,例如,在聚胺和多官能团酰基卤的界面聚合反应刚起动之后进行。这些聚环氧烷基团的存在,可为膜提供一种不易积垢的表面。
在工业规模生产中,复合膜通常是通过用多官能的胺单体即“聚胺”的水溶液涂敷多微孔载体作为连续操作的一部分而制成的。如前所述,聚胺可以具有伯氨基或仲氨基,并可以为芳族或脂族。优选聚胺物质的实例包括具有2个或3个氨基的芳族伯胺,尤其是间苯二胺,和具有2个氨基的脂族仲胺,尤其是哌嗪。聚胺通常是以水溶液形式涂敷到多微孔载体上。水溶液含有0.1-20重量%,优选为0.5-6重量%的聚胺。当涂敷到多微孔载体上之后,非必须地,可以除去过量含水聚胺溶液。
然后,使涂敷的多微孔载体与一种单体多官能团酰基卤接触,优选是在非极性有机溶剂中进行,尽管多官能团酰基卤可由蒸气相中释放出来(对于具有足够蒸气压的聚酰基卤化物)。实质上多官能团酰基卤优选为芳族,而且每个分子中含有至少两个优选三个酰基卤。相对于溴化物或碘化物来说,氯化物通常是优选的,这是由于它们的低成本和较大的可获得性。一种优选的多官能团酰基卤为苯三酸酰氯(trimesoyl chloride)。多官能团酰基卤通常是以0.01-10.0wt%(更优选地为0.05-3wt%)范围溶解在一种非极性有机溶剂中,并释放出来,作为连续涂敷操作的一部分。合适的非极性有机溶剂是那些可溶解多官能团酰基卤而不与水混融的有机溶剂。优选的溶剂包括那些不会对臭氧层形成威胁的物质,并且不必采用额外的预防措施,就其闪点和易燃性来说可足够安全地进行常规加工处理。高沸点的烃,即那些沸点大于约90℃如C8-C14烃其及混合物,它们较其C5-C7对应物具有更良好的闪点,但是它们具有较低的挥发性。
一旦与涂敷在多微孔载体上的含水聚胺溶液接触,多官能团酰基卤就会在表面界面与聚酰胺反应,形成交联聚酰胺区分层。反应时间通常小于1秒,但接触时间经常是在1-60秒之间,之后,非必须地除去过量的液体,例如,采用气刀、水浴和/或干燥器。过量水和/或有机溶剂的除去,最为便利地是通过在较高温度下如40-120℃干燥而实现的,当然也可采用在室温下的空气干燥。
本发明的聚环氧烷接枝表面处理,可由多种能够容易地适用于前述商用膜生产工艺的方法来完成。本发明的一个实例包括对预形成复合膜的后处理,如FilmTec Corporation的FT-30TM。后处理包括在适合接枝进行的条件下使预形成的复合膜与本发明聚环氧烷基团接触。根据聚环氧烷的端基反应活性,可能需要使用加热或其它条件。在下面给出的实例中,将预形成的膜浸没在加热的含有聚双环氧乙烷(polyethylene diepoxide)的水溶液中。环氧化物官能性需要加热的溶液以优化接枝。
此外,本发明的接枝还可以作为膜生产工艺的一部分而进行。在一个优选实施方案中,在与水浴或干燥步骤的任何接触之前,使聚环氧烷物质与刚刚形成的聚酰胺区分层(即,在加入多官能团酰基卤之后)进行接触。这可采用与使用含水聚胺溶液涂敷多微孔载体相似方法,通过涂敷聚酰胺层而完成。在这类实施方式中,聚环氧烷物种可包括高度活性的端基如异氰酸酯、胺、和硫醇,它们对于能与存在于聚酰胺区分层上的异氰酸酯反应的酰基氯或胺是非常活泼的,但是其它方面是稳定的。
在另一种实施方案中,使聚环氧烷物质在膜刚要流过干燥器之前与聚酰胺表面进行接触。在工业生产中,干燥器通常是用来从水浴中除去残留的有机溶剂或溶液;但是,干燥器的热量可用来引发聚环氧烷接枝到聚酰胺表面上。具有环氧端基的聚环氧烷特别适合于这种方法。这些环氧化物端基通常与膜表面上的游离胺和羧酸部分反应,特别是在干燥器温度高于约30℃时。
本方法优于通过氧化还原引发剂实现接枝的现有技术方法,由于本方法可以更加容易地整合到传统的复合膜生产中。更具体地说,现有技术方法所需要的氧化还原引发剂会形成趋于不稳定的高度活性的物种。因而,反应物不可能容易地在贮存中保持以为连续操作;而且,它们必须要补充并快速地使用。
用来处理聚酰胺区分层的聚环氧烷基团,可以采用溶液、纯净的、或甚至气相的形式,只要它能与聚酰胺进行接触即可。
溶剂可为任何聚环氧烷基团能溶于其中的溶剂,只要膜的流量增加和性能不会由于与溶剂接触受影响即可。常用溶剂可包括水和有机化合物,如醇类和烃类,条件是载体不会被溶剂所溶解。
接枝步骤优选是在不采用化学引发剂如上述的氧化还原引发剂体系条件下完成的。用于本方法中的聚环氧烷基团,可由下述通式表示:
RO-(OCxHx+2)y-L-E其中,每个单独符号定义如下:x相同或不同,其值为2或3;y相同或不同,其值为2-1000,优选为4-10。R相同或不同,选自:氢、E和具有1-4个碳原子的烷基或链烯基,它们可以是分支的或不分支的。R优选为氢,特别是希望提高聚环氧烷物质的可溶性时。L相同或不同,选自:连接键或连接基团。L的选用不作特别要求,只要当聚环氧烷基团化学接枝到区分层上时,连接键或基团本质上是非活性的即可。适合基团的具体实例包括:化学健、烷基、苯基、酯、醚、氧、硫化物、尿烷、酰胺、胺、金属、磷酸酯和砜。L优选为具有1-12个碳原子的醚基和烷基。E相同或不同,选自非丙烯酸酯亲电基团,该非丙烯酸酯亲电基团可与存在于区分层表面上的官能团反应,在该处形成共价化学键,优选地不使用化学引发剂。具体实例包括以下基团:琥珀酰亚胺基酯、琥珀酰亚胺基酰胺、琥珀酰亚胺基亚胺、氧碳酰咪唑(oxycarbonyldimidazoles)、氮化物、环氧化物、醛、tresylates、异氰酸酯、砜类(例如,乙烯基砜)、碳酸硝基苯基酯、碳酸三氯苯基酯、碳酸苯并三唑、缩水甘油醚、硅烷、酸酐、胺类(包括脂族、杂环族、芳族)、羟基和硫醇。E优选为胺或环氧化物(例如,缩水甘油醚)。胺基与酰氯基团反应,并与酰氯基团形成化学接枝;而环氧化物基团与表面上的游离胺、羟基和羧酸基团反应。
术语“相同或不同”是用来表示接枝到膜表面上的单个聚亚烷基聚合物彼此是不同的,例如,聚环氧乙烷和聚环氧丙烷都可以采用,或者,环氧乙烷和环氧丙烷的共聚物可存在于一个给定的聚合物中。而且,单个聚合物可具有不同的“L”、“E”和“R”基团。
适合用于本发明的商业可得聚环氧烷物质的实例,是从Shearwater Polymers,Inc.,2305 Spring Branch Road,HuntsvilleAlabama 35801商购的。
本发明对于复合膜多孔载体的构造材料不作严格要求。任何能够为区分层提供机械强度的多孔载体都可采用,只要其有足够大的孔尺寸,以允许渗透无阻碍地通过,但又不会大到会干扰最终区分层的桥连。典型的孔尺寸范围是在10-1000纳米之间。本领域公知的常用载体材料包括纤维素酯、聚砜、聚醚、砜、聚氯乙烯、氯化聚氯乙烯、聚偏氟乙烯、聚苯乙烯、聚碳酸酯、聚酰亚胺、聚丙烯腈和聚酯。特别优选的一类载体材料为聚砜。这类载体的制备公开在US3926798、US4039440和US4277344中。多微孔载体的厚度通常为25-125微米,优选为40-75微米。
可商购到不同形状的膜,并将其可用于本发明。这些包括螺旋卷型、空心纤维、管形、或平板型膜。至于膜的组成,经常地,区分层除了聚酰胺外,还有吸湿聚合物涂敷在区分层表面上。这些聚合物为聚合物表面活性剂、聚乙烯醇和聚丙烯酸。这些聚合物的存在,通常不会影响本发明,只要该聚环氧烷物质和聚酰胺区分层能够接触即可。如果膜是在它呈最终膜形状后被接触的,那么,膜的形状和组成就应该能够使得聚酰胺区分层与上述聚环氧烷化合物接触。
用于本申请中的下述术语定义如下:“排斥率”为不与溶剂流过膜的特定溶解或分散物质(即溶质)的百分比。排斥率等于100减去流过膜的溶解或分散物质的百分比,即溶质通过量,如果溶解物质为一种盐,则为“盐通过量”。“流量”为溶剂通常为水流过膜时的流率。“反渗透膜”为这样一种膜,它对于NaCl具有95-100%的排斥率。“纳米过滤膜”为这样一种膜,它对于NaCl具有0-95%的排斥率,并且,对于至少一种二价离子或有机化合物具有20-100%的排斥率。“聚酰胺”为一种聚合物,其中的酰胺键合(-C(O)NH-)存在于分子链中。除非另有规定,“聚环氧烷基团”包括聚环氧烷聚合物如聚双环氧化乙烷,和曾经接枝到区分层表面上的聚环氧烷部分。
本发明的具体实施方案
下述实施例将对本发明作详细的说明,但不构成对所附权利要求范围的限定。
实施例1:
FT-30反渗透复合膜是从FilmTec Corporation of Edina,Minnesota获得的。通过将适量的水加热到60℃(除非另有规定),接着加入适量的聚(乙二醇)n缩水甘油醚(CAS#26403-72-5)(此后称为“PEG双环氧化物”,可由Polyscience Inc.of Warrington,Pennsylvania获得)制备含水处理溶液。上述膜浸没在PEG双环氧化物溶液中约10分钟。接着采用一种含有约2000ppmNaCl的含水测试溶液于225psi的横跨膜的压力下测试该膜。这种测试的结果列在表1-3中。采用PEG二环氧化物处理的膜表现出改善的防积垢性能。
表1
PEG双环氧化物浓度(%),mw=3400 | 盐通过百分比 | 流量(gfd) |
0.0(未加热) | 0.964 | 29.50 |
0.0 | 0.689 | 22.44 |
1.0 | 0.349 | 6.05 |
2.0 | 0.587 | 4.79 |
4.0 | 0.421 | 4.70 |
表2
PEG双环氧化物浓度(%),mw=200 | 盐通过百分比 | 流量(gfd) |
0.0(未加热) | 0.769 | 29.58 |
0.0 | 0.634 | 24.29 |
0.2 | 0.249 | 9.59 |
0.4 | 0.390 | 8.25 |
1.2 | 0.267 | 6.32 |
如表1和表2所示,具有较低浓度的PEG双环氧化物的处理溶液,比那些用较高浓度处理的情形,可提供改善的盐通过量和较高的流量。
表3
处理溶液的温度*(℃) | 盐通过百分比 | 流量(gfd) |
30 | 0.705 | 21.31 |
40 | 0.508 | 19.00 |
50 | 0.512 | 13.34 |
60 | 0.401 | 11.88 |
70 | 0.493 | 9.05 |
*0.037wt%聚(乙二醇)n缩水甘油醚,其中n=600
较高的温度处理倾向于降低流量,但会提高盐通过量。低于约60℃的处理温度是优选的,温度为40-50℃更为优选。
实施例2:
“LE 440TM”复合膜是从FilmTec Corporation of Edina,Minnesota获得的。将膜浸泡在50℃水中30分钟,接着按实施例1所述的处理预处理测试膜。处理溶液是由0.3%的PEG二环氧化物(分子量约为200)溶液组成的。接着用一种含有约1500ppm NaCl的水溶液的测试溶液于150psi的横跨膜的压力下测试上述膜。在这些条件下连续使用3小时后,测量其流量以确定基线流量。之后,用含有约1500ppmNaCl和100mM的十二烷基三甲基溴化铵的水溶液(在表4中称作“表面活性剂A”)代替测试溶液,将它应用3小时,在该时间之后,测量膜的流量,并以基线流量的百分比表示如下。接着采用净化的水在150psi下对膜漂洗2小时,接着,测量2000ppmNaCl溶液的流量。所测得的流量以基线流量的百分比表示。之后,用含有约1500ppm NaCl和100ppm的十二烷基硫酸钠(在表4中称作“表面活性剂B”)的水溶液代替测试溶液,将它应用3小时,在该时间之后,测量膜的流量,并以基线流量的百分比表示如下。接着采用测试溶液在150psi下对膜漂洗2小时,接着,测量其流量,以基线流量的百分比表示。
表4
样品 | 表面活性剂A的流量% | 2小时漂洗后的流量% | 表面活性剂B的流量% | 2小时漂洗后的流量% |
未处理 | 78 | 85 | 69 | 84 |
处理 | 89 | 94 | 80 | 100 |
由表4中的数据可以看出,按照本发明方法处理过的膜对于表面活性剂具有更好的防积垢性能,正如在长时间置于表面活性剂之后的较高的百分比流量所表明的。
如果在实施例2中采用单宁酸代替表面活性剂,进行类似的测试,可以获得类似的结果。
Claims (21)
1.一种改进复合膜表面的方法,该复合膜包含多孔载体和交联聚酰胺区分层,该方法是通过化学接枝聚环氧烷基团到所述区分层表面上而实现的;其中,所述聚环氧烷基团可以相同或不同,并由下式表示:
RO-(OCxHx+2)y-L-E其中,
x相同或不同,其值为2或3;
y相同或不同,其值为2-1000;
R相同或不同,它是选自:氢、E和具有1-4个碳原子的烷基或链烯基;
L相同或不同,选自一个连接键或一个连接基团,当所述聚环氧烷基团被化学接枝到所述区分层上时,该连接键或连接基团本质上是非活性的;
和E相同或不同,选自非丙烯酸酯亲电基团,其可与存在于所述区分层表面的官能团反应,在该处形成共价化学键。
2.权利要求1所述的方法,其中E选自包括下述的物质:琥珀酰亚胺基酯、琥珀酰亚胺基酰胺、琥珀酰亚胺基亚胺、氧碳酰咪唑、氮化物、环氧化物、醛、tresylates、异氰酸酯、砜类、碳酸硝基苯基酯、碳酸三氯苯基酯、碳酸苯并三唑、缩水甘油醚、硅烷、酸酐、胺类、羟基和硫醇。
3.权利要求2所述的方法,其中E是选自胺和环氧化物基团中的至少一种。
4.权利要求1所述的方法,其中E是与所述区分层表面上的至少一种下述官能团化学反应,形成化学接枝:羧酸、酰氯和胺。
5.权利要求1所述的方法,其中L选自:烷基、苯基、酯、醚、氧、硫化物、尿烷、酰胺、胺、金属、磷酸酯和砜。
6.权利要求5所述的方法,其中L选自具有1-12个碳原子的醚基和烷基中的至少一种。
7.权利要求1所述的方法,其中R为氢。
8.权利要求1所述的方法,其中y为4-10。
9.权利要求1所述的方法,其中,所述聚环氧烷基团是通过使所述区分层与含有所述聚环氧烷基团的溶液接触而被接枝到所述聚酰胺区分层表面上的。
10.权利要求9所述的方法,其中所述含有所述聚环氧烷基团溶液的温度为30℃-70℃。
11.权利要求10所述的方法,其中所述含有所述聚环氧烷基团溶液的温度低于约60℃。
12.权利要求9所述的方法,其中所述膜在与含有所述聚环氧烷基团的溶液接触之后被加热。
13.一种包含多孔载体和交联聚酰胺区分层的复合膜,其中,可由下述通式表示的聚环氧烷基团被化学接枝到区分层表面上:
RO-(OCxHx+2)y-L-E
其中:
x相同或不同,其值为2或3;
y相同或不同,其值为2-1000;
R相同或不同,它是选自:氢、E和具有1-4个碳原子的烷基或烯基;
L相同或不同,选自一个连接键或一个连接基,当所述聚环氧烷基团被化学接枝到所述区分层上时,该连接键或连接基团本质上是非活性的;和
E相同或不同,选自非丙烯酸酯亲电基团,其与存在于所述区分层表面上的官能团进行反应,在该处形成共价化学键,而不需要使用化学引发剂。
14.权利要求13所述的方法,其中E选自包括下述的物质:琥珀酰亚胺基酯、琥珀酰亚胺基酰胺、琥珀酰亚胺基亚胺、氧碳酰咪唑、氮化物、环氧化物、醛、tresylates、异氰酸酯、砜类、碳酸硝基苯基酯、碳酸三氯苯基酯、碳酸苯并三唑、缩水甘油醚、硅烷、酸酐、胺类、羟基和硫醇。
15.权利要求14所述的方法,其中E选自胺和环氧化物基团中的至少一种。
16.权利要求14所述的方法,其中E与所述区分层表面上的至少一种下述官能团反应:羧酸、酰氯和胺。
17.权利要求13所述的方法,其中L选自包括下述的物质:烷基、苯基、酯、醚、氧、硫化物、尿烷、酰胺、胺、金属、磷酸酯和砜。
18.权利要求17所述的方法,其中L选自具有1-12个碳原子的醚基和烷基的至少一种。
19.权利要求13所述的方法,其中R为氢。
20.权利要求13所述的方法,其中y为4-10。
21.权利要求13所述的方法,其中,所述化学接枝到所述区分层表面上的聚环氧烷基团,使得所述膜具有更高的排斥率。
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Also Published As
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JP2003501249A (ja) | 2003-01-14 |
CA2374817C (en) | 2008-02-19 |
AU774426B2 (en) | 2004-06-24 |
ES2312343T3 (es) | 2009-03-01 |
WO2000076641A1 (en) | 2000-12-21 |
EP1200178A1 (en) | 2002-05-02 |
KR100618454B1 (ko) | 2006-08-31 |
CA2374817A1 (en) | 2000-12-21 |
DE60040791D1 (de) | 2008-12-24 |
ATE413914T1 (de) | 2008-11-15 |
US6280853B1 (en) | 2001-08-28 |
TWI224980B (en) | 2004-12-11 |
CN1180876C (zh) | 2004-12-22 |
KR20020012262A (ko) | 2002-02-15 |
EP1200178B1 (en) | 2008-11-12 |
AU5041200A (en) | 2001-01-02 |
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