CN101254417A - Crosslinked hyperbranched polyalcohol composite nano filter membrance and method of preparing the same - Google Patents
Crosslinked hyperbranched polyalcohol composite nano filter membrance and method of preparing the same Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 150000005846 sugar alcohols Polymers 0.000 title claims description 22
- 238000000034 method Methods 0.000 title description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 35
- 229920000642 polymer Polymers 0.000 claims description 33
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- 229920002492 poly(sulfone) Polymers 0.000 claims description 18
- 229920000728 polyester Polymers 0.000 claims description 17
- 239000008346 aqueous phase Substances 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- 229920006254 polymer film Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 4
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 3
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- PHEDXBVPIONUQT-RGYGYFBISA-N phorbol 13-acetate 12-myristate Chemical compound C([C@]1(O)C(=O)C(C)=C[C@H]1[C@@]1(O)[C@H](C)[C@H]2OC(=O)CCCCCCCCCCCCC)C(CO)=C[C@H]1[C@H]1[C@]2(OC(C)=O)C1(C)C PHEDXBVPIONUQT-RGYGYFBISA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 2
- PHEDXBVPIONUQT-UHFFFAOYSA-N Cocarcinogen A1 Natural products CCCCCCCCCCCCCC(=O)OC1C(C)C2(O)C3C=C(C)C(=O)C3(O)CC(CO)=CC2C2C1(OC(C)=O)C2(C)C PHEDXBVPIONUQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 42
- 230000004907 flux Effects 0.000 abstract description 19
- 238000004132 cross linking Methods 0.000 abstract description 11
- 238000000108 ultra-filtration Methods 0.000 abstract description 11
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 7
- 229920000587 hyperbranched polymer Polymers 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 150000001263 acyl chlorides Chemical class 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 150000008064 anhydrides Chemical class 0.000 abstract description 3
- 239000012074 organic phase Substances 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract description 2
- 238000001728 nano-filtration Methods 0.000 abstract 6
- 150000001412 amines Chemical class 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000002778 food additive Substances 0.000 abstract 1
- 235000013373 food additive Nutrition 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 150000007519 polyprotic acids Polymers 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 26
- 238000012360 testing method Methods 0.000 description 16
- 238000001914 filtration Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 150000008065 acid anhydrides Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 241000555268 Dendroides Species 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- -1 amino, hydroxyl Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000000412 dendrimer Substances 0.000 description 2
- 229920000736 dendritic polymer Polymers 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 201000007336 Cryptococcosis Diseases 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 241001602688 Pama Species 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a crosslinking hyper branched polymer composite nanofiltration membrane as well as the preparation method thereof. The crosslinking hyper branched polymer composite nanofiltration membrane is prepared by taking an ultrafiltration membrane as a basement membrane and crosslinking hyper branched polymer as a selecting layer through hyper branched polymer and the interfacial polymerization of polybasic acid, polybasic acyl chloride, polybasic anhydride and polybasic amine; and the interfacial polymerization takes the mixed solution of water and ethanol as the water phase and n-hexane, n-heptane or n-octane as the organic phase. As the hyper branched polymer has the spheroidal structure, a plurality of nano-voids exist in the interior of the molecule, so as to enable the selecting layer of the crosslinking hyper branched polymer composite nanofiltration membrane to be looser, and leads the nanofiltration membrane to maintain high flux and retention rate under the lower operating pressure. The nanofiltration membrane can be used in the fields of medicament, foodstuff, environmental protection, etc. The composite nanofiltration membrane is applicable to the separation and the condensation of high valence ions, low valence ions, neutral particles, drugs, food additives, etc.
Description
Technical field
The present invention relates to a kind of NF membrane material and technology of preparing thereof, a kind of crosslinked hyperbranched polyalcohol composite nano filter membrance and preparation method thereof is provided particularly.
Background technology
NF membrane (NF) is the domestic and international novel diffusion barrier of exploitation competitively in recent years, and its stalling characteristic is used widely in field such as petrochemical industry, biochemistry, medicine, food, papermaking, weaving, printing and dyeing and water treatment procedure between counter-infiltration and ultrafiltration.State's adventitia and membrane module be in the commercialization eighties, and step into the industrial applications stage.China's NF membrane research starts from the beginning of the nineties, and units such as National Bureau of Oceanography's water treatment centers, Tsing-Hua University, Fudan University, Dalian University of Technology, Beijing University of Chemical Technology all carry out number of research projects, obtain better effects, but majority are in laboratory stage.
NF membrane is subjected to the influence of chemical potential and potential gradient to the separation of inorganic salts, the molecule sieve effect of holding back mainly by the nanometer micropore of film of the uncharged material of neutrality (as glucose, maltose etc.) is caused, but its definite mechanism of mass transfer does not still have final conclusion.
For obtaining high-throughout NF membrane, prepare composite membrane usually.Method has coating process, interfacial polymerization and in-situ polymerization method etc.There is the scholar to adopt polyelectrolyte self assembly layer by layer to prepare NF membrane recently.
Interfacial polymerization is the most effective in the world present method for preparing NF membrane, also is the method that industrialization NF film kind is maximum, output is maximum.Interfacial polymerization is to utilize two kinds of monomers that reactivity is very high, at two immiscible solvents polymerization reaction take place at the interface, thereby forms skim on porous supporting body.In order to obtain better film properties, generally also need last handling processes such as chargedization of hydrolysis, ionizing radiation or heat treatment.The advantage of interfacial polymerization is: reaction has from inhibition; By changing the monomer concentration of two kinds of solution, can regulate and control the performance of selectivity rete well.The key of this method is choosing of basement membrane and prepares, regulates and control distribution coefficient and the diffusion velocity of two class reactants in two-phase, and optimization interface condensation condition, the top layer porousness is rationalized and try one's best to approach.The top layer chemical constitution of composite nanometer filtering film and surface topography also have very big influence to the performance of film.
Usually use charged membrane to have higher removal efficiency, so NF membrane generally is a charged membrane to charged particle.Charged membrane can be whole electrically charged also can be that the top layer is charged.The former adopts the direct film forming of charged material, and the then first film forming of the latter is charged by chemical surface treatment or impregnation method then, and Pama Mukherjee etc. adopt ionic-implantation to improve the electric charge on NF membrane surface.
The material of commercialization NF membrane mainly is polyamide (PA), polyvinyl alcohol (PVA), SPSF (SPS) sulfonated polyether sulfone (SPES), cellulose acetate (CA) etc. at present, and majority has negative electrical charge.Operating pressure is in the majority with 0.6-1MPa, and the monovalent ion removal efficiency is greater than 60%, and the divalent ion removal efficiency is greater than 90%.In conjunction with the present situation of China's NF membrane, the current problem that needs to solve mainly contains 2 points: the one, further reduce operating pressure by the control of selecting layer structure; The 2nd, the film contamination phenomenon of minimizing NF membrane.This will set about from the preparation of NF membrane, rationally regulate the porousness on top layer, have nanoscale (10 in a large number to form
-9M) hole, top layer.
Branching molecule is a kind of new polymers with unique topological structure, be divided into Dendriemrs and dissaving polymer two big classes, wherein the former is a kind of desirable single big molecule of branching that disperses, and has the highly branched three-dimensional structure of rule and the spherical shapes of rule, and the degree of branching approximates 1; Latter's structure neither has the so regular structure of Dendrimers and does not also have the such chain entanglement of linear molecule between Dendrimers and linear polymer.Compare with linear polymer, branching molecule have structure height branching, surface functional group density height, chemical stability good, surface-functionalized simple, be easy to characteristics such as film forming.Therefore people have carried out number of research projects in fields such as medicament slow release, biomedicine, information material, high absorbency material, nonlinear optical material, nano material, paint, photosensitive material, conductive material, biomembranes, and some field is obtained than quantum jump.The applicant once with dendroid poly-(acid amides-amine) (PAMAM) embedding obtain particle diameter about 4nm and finely dispersed nanometer copper particle, and replace PAMAM molecule embedded nano copper particle with hyperbranched poly (amine-ester), can prepare particle diameter about 10nm and finely dispersed nanometer copper particle.The application of branching molecule in diffusion barrier at present is a new research direction, and utility trees such as Chung dendritic poly-(acid amides-amine) (PAMAM) are cooked supported liquid membrane and improve CO
2Gas separation coefficient; Kovvali etc. do the terminal acid anhydrides of the crosslinked linear polyimides of crosslinking agent to promote CO with PAMAM
2Infiltration etc.
Recently, the superfine people of the Li Lian of Tsing-Hua University (PAMAM) has prepared NF membrane with the interface polymerization reaction of pyromellitic trimethylsilyl chloride by dendroid poly-(acid amides-amine), and is respond well.Applicant place seminar had once prepared composite nanometer filtering film with the PAMAM in different generations by interfacial polymerization, handled the MgSO of 1g/l with this film
4The time salt rejection rate up to 94%, and water flux is higher.But PAMAM molecule synthesis complexity, the separation and purification difficulty is difficult to accomplish scale production.At present, domestic for the research of dissaving polymer functionalized application aspect is mainly concentrated on: aspects such as preparation catalyst, preparation nano metal particles, gas separation membrane, self-assembled film, do not find to prepare the report of Nano filtering composite membrane as yet with dissaving polymer.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method who contains the composite nanometer filtering film of crosslinked hyperbranched polyalcohol be provided:
Crosslinked hyperbranched polyalcohol composite nano filter membrance is that the polymer milipore filter with porous is basement membrane, serves as to select layer with the crosslinked hyperbranched polyalcohol.
Described polymer milipore filter is Kynoar, polyether sulfone, polysulfones, polyacrylonitrile, polyethersulfone ketone or polyvinyl chloride milipore filter.
Described dissaving polymer is: molecular weight 1000 to 100,000, terminal groups are hyperbranched poly (acid amides-amine), hyperbranched poly (amine-ester), hyperbranched poly (propylene-imines), hyper-branched polyester or the hyperbranched poly acrylic acid of hydroxyl, amino or carboxyl.
The preparation method of crosslinked hyperbranched polyalcohol composite nano filter membrance may further comprise the steps:
1) the polymer milipore filter is immersed in the mixed solution of ethanol and water, soak time is 10s～1h;
2) dissaving polymer is dissolved in the mixed solution of ethanol and water, is made into aqueous phase solution, the concentration of dissaving polymer is: 1 * 10
-3～4 * 10
-2Mol/l;
3) being that 10～40 ℃, relative humidity are in 40～90% the air ambient in temperature, the polymer milipore filter after soaking in the step 1) be dipped into step 2 again) in the aqueous phase solution that is made into, soak time is 10s～10h, takes out the polymer milipore filter, dries in the shade;
4) crosslinking agent is dissolved in the solvent, is made into concentration and is: 4 * 10
-3～8 * 10
-2Cross-linking agent solution, the polymer film that dries in the shade that step 3) is obtained immerses in the cross-linking agent solution, reaction 10s～10h;
5) polymer film is taken out from cross-linking agent solution, place baking oven 5min～1h of 20～120 ℃, obtain crosslinked hyperbranched polyalcohol composite nano filter membrance.
Described crosslinked crosslinking agent is: glutaraldehyde, terephthalaldehyde, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, succinic anhydride, pyromellitic dianhydride, succinic acid, adipic acid, PMA, terephthalic acid (TPA), 1,4-butanediamine, ethylenediamine, hexamethylene diamine, 1,4-butanediol, ethylene glycol, diethylene glycol ether, 1, ammediol, 1,6-hexylene glycol, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, benzyl dichloride or molecular weight are two hydroxyl end groups polyethylene glycol of 200～2000.The mixed solution of ethanol and water, wherein the water volume percentage composition is: 1%～80%.The polymer milipore filter is 20s～8h in the soak time of aqueous phase solution.The solvent of crosslinking agent is n-hexane, normal heptane or normal octane.
The beneficial effect that the present invention has:
1) dissaving polymer has torulose structure, and there are a lot of nano apertures in intramolecule, makes the selection layer of this crosslinked hyperbranched polyalcohol composite nano filter membrance more loose, thereby makes this NF membrane keep high flux and high rejection under lower operating pressure;
2) dissaving polymer has a large amount of end groups, by the kind that the end group modification can be regulated the dissaving polymer end group easily, prepares the NF membrane of different charges;
3) dissaving polymer has a large amount of end groups, can regulate the aqueous medium that NF membrane is suitable for easily by regulating the hydrophilic and hydrophobic that the degree of cross linking is regulated NF membrane;
4) milipore filter preliminary treatment in ethanol and water mixed solution makes that dissaving polymer is easier to be adsorbed on the milipore filter surface, selects the easier milipore filter surface that is compounded in of layer thereby make;
5) dissaving polymer industrialization production, material are simple and easy to, and make this crosslinked hyperbranched polyalcohol composite nano filter membrance be easier to realize industrialization.
The specific embodiment
The preparation method who contains crosslinked hyperbranched polyalcohol composite nano filter membrance described in the present invention, its preparation process have three core procedures, are followed successively by:
(1) preparation of aqueous phase solution: dissaving polymer is dissolved in the ethanol, stirs dissolving in 10min～2h hour down at 10～60 ℃; In this solution, slowly add entry then, under 20～60 ℃ of temperature, continue again to stir 10min～2h hour, form aqueous phase solution.
Super branched molecule is: molecular weight is 1000～100,000, terminal groups is hyperbranched poly (acid amides-amine), hyperbranched poly (amine-ester), hyperbranched poly (propylene-imines), hyper-branched polyester or the hyperbranched poly acrylic acid of hydroxyl, amino or carboxyl.
(2) preparation of organic phase solution: cross-linker molecules is dissolved in the organic solvent, stirs dissolving in 10min～2h hour down, form organic phase solution at 10～60 ℃.
Crosslinking agent is: can be with the hydroxyl, amino or the carboxyl end groups radical reaction that adopt dissaving polymer, make super branched molecule form crosslinked dialdehyde, acid anhydrides, polyacid, diamines or glycol; Wherein dialdehyde is: glutaraldehyde (GA) or terephthalaldehyde (DBA); Acid anhydrides is: 3,3 ', 4, and 4 '-benzophenone tetracarboxylic acid dianhydride (BTDA), succinic anhydride or pyromellitic dianhydride (PMDA); Polyacid is: succinic acid (BDAC), PMA (BTA) or terephthalic acid (TPA); Diamines is: 1, and 4-butanediamine (BDAA), ethylenediamine or hexamethylene diamine; Dihydroxylic alcohols is: 1, and 4-butanediol (BDAH), ethylene glycol, diethylene glycol ether, 1, ammediol, 1,6-hexylene glycol, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, benzyl dichloride or molecular weight are 200～2000 hydroxyl carbowax.
Organic solvent is: n-hexane, normal heptane or normal octane.
(3) post processing: polymer film is taken out from cross-linking agent solution, place 20～120 ℃ baking oven to keep 5min～1h, obtain hyperbranched polyalcohol composite nano filter membrance.
The synthetic method of described super branched molecule can be with progressively method is synthetic without limits, also can be that one-step method or accurate one-step method are synthetic.Because molecular weight is more than 1000 in this invention, super branched molecule also can be called hyperbranched polymer molecule or dissaving polymer.
In the cross-linking reaction of super branched molecule, the chemistry amount of crosslinking agent reactive group is equivalent to adopt end group group stoichiometric 5～50% in the super branched molecule.Usually, the kind of crosslinking agent depends on the chemical constitution and the required crosslinked chain link of super branched molecule end group, as: amino and polyacid, polynary acyl chlorides or anhydride reactant form the acid amides cross-bond, hydroxyl and polyacid, polynary acyl chlorides or anhydride reactant form the ester cross-bond, and hydroxyl and dialdehyde reaction form acetal, hemiacetal cross-bond; The consumption of crosslinking agent depends on the selection of the super branched molecule degree of cross linking, and the degree of cross linking of general macroporous membrane is less, dosage of crosslinking agent is few; The cross-linking reaction temperature and time depends on the type of cross-linking reaction, and wherein carboxyl needs with cross-linking reaction amino, hydroxyl that temperature is higher, the time is longer; Acid anhydrides is low slightly with reaction needed temperature amino, hydroxyl, the time is short slightly; The reaction needed temperature of carboxyl, hydroxyl or amino and acyl chlorides is low, the time short.
Elaborate the present invention with embodiment below, but described embodiment is not construed as limiting the invention.
Super branched molecule is synthetic for the inventor among the embodiment, and the kind of super branched molecule and building-up process are seen patent (ZL 200410067256.0).
Ultrafiltration basement membrane among the embodiment is the commercially produced product of purchase.
Embodiment 1:
The polysulfones ultrafiltration basement membrane of buying is immersed in ethanol and 3: 2 the mixed solution of water volume ratio keeps 20min; Then this polysulphone super-filter membrane is immersed and contain 4.6 * 10 of hyper-branched polyester
-3In the aqueous phase solution of mol/l, take out behind the 40min, dry in the shade naturally; Then this film is immersed in 5.8 * 10 of pyromellitic trimethylsilyl chloride
-3In the mol/l hexane solution, take out behind the 20min; Place 60 ℃ baking oven to keep 20min this film then, obtain the hyper-branched polyester composite nanometer filtering film.Under 0.3Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 79.1l/m
2H, Na
2SO
4Removal efficiency be 80.4%.Under 0.6Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 115.4l/m
2H, Na
2SO
4Removal efficiency be 85.6%.
Embodiment 2:
The polysulfones ultrafiltration basement membrane of buying is immersed in ethanol and 3: 2 the mixed solution of water volume ratio keeps 10min; Then this polysulphone super-filter membrane is immersed and contain 4.6 * 10 of hyper-branched polyester
-3In the aqueous phase solution of mol/l, take out behind the 50min, dry in the shade naturally; Then this film is immersed in 8.3 * 10 of pyromellitic trimethylsilyl chloride
-3In the mol/l hexane solution, take out behind the 10min; Place 90 ℃ baking oven to keep 10min this film then, obtain the hyper-branched polyester composite nanometer filtering film.Under 0.3Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 38.9l/m
2H, Na
2SO
4Removal efficiency be 86.4%.Under 0.6Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 56.1l/m
2H, Na
2SO
4Removal efficiency be 90.2%.
Embodiment 3:
The polysulfones ultrafiltration basement membrane of buying is immersed in ethanol and 3: 2 the mixed solution of water volume ratio keeps 50min; Then this polysulphone super-filter membrane is immersed and contain 4.6 * 10 of hyper-branched polyester
-3In the aqueous phase solution of mol/l, take out behind the 20min, dry in the shade naturally; Then this film is immersed in 6.7 * 10 of pyromellitic trimethylsilyl chloride
-3In the mol/l hexane solution, take out behind the 30s; Place 40 ℃ baking oven to keep 50min this film then, obtain the hyper-branched polyester composite nanometer filtering film.Under 0.3Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 57.5l/m
2H, Na
2SO
4Removal efficiency be 85.3%.Under 0.6Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 96.5l/m
2H, Na
2SO
4Removal efficiency be 89.8%.
Embodiment 4:
The polysulfones ultrafiltration basement membrane of buying is immersed in ethanol and 3: 2 the mixed solution of water volume ratio keeps 30s; Then this polysulphone super-filter membrane is immersed and contain 8.9 * 10 of hyper-branched polyester
-3In the aqueous phase solution of mol/l, take out behind the 30s, dry in the shade naturally; Then this film is immersed in 1.3 * 10 of pyromellitic trimethylsilyl chloride
-2In the mol/l hexane solution, take out behind the 20s; Place 100 ℃ baking oven to keep 5min this film then, obtain the hyper-branched polyester composite nanometer filtering film.Under 0.3Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 30.5l/m
2H, Na
2SO
4Removal efficiency be 89.7%.Under 0.6Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 41.3l/m
2H, Na
2SO
4Removal efficiency be 91.3%.
Embodiment 5:
The polysulfones ultrafiltration basement membrane of buying is immersed in ethanol and 3: 2 the mixed solution of water volume ratio keeps 20s; Then this polysulphone super-filter membrane is immersed and contain 8.9 * 10 of hyper-branched polyester
-3In the aqueous phase solution of mol/l, take out behind the 10s, dry in the shade naturally; Then this film is immersed in 2.4 * 10 of paraphthaloyl chloride
-2In the mol/l hexane solution, take out behind the 5min; Place 70 ℃ baking oven to keep 10min this film then, obtain the hyper-branched polyester composite nanometer filtering film.Under 0.3Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 8-20l/m
2H, Na
2SO
4Removal efficiency be 94.3%.Under 0.6Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 10.3-30l/m
2H, Na
2SO
4Removal efficiency be 96.8%.
Embodiment 6:
The polysulfones ultrafiltration basement membrane of buying is immersed in ethanol and 3: 2 the mixed solution of water volume ratio keeps 1h; Then this polysulphone super-filter membrane is immersed and contain 1.5 * 10 of hyper-branched polyester
-3In the aqueous phase solution of mol/l, take out behind the 1.5h, dry in the shade naturally; Then this film is immersed in 4.5 * 10 of pyromellitic dianhydride
-3In the mol/l hexane solution, take out behind the 2h; Place 120 ℃ baking oven to keep 5min this film then, obtain the hyper-branched polyester composite nanometer filtering film.Under 0.3Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 24l/m
2H, Na
2SO
4Removal efficiency be 80.4%.Under 0.6Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 45.4l/m
2H, Na
2SO
4Removal efficiency be 86.6%.
Embodiment 7:
The polysulfones ultrafiltration basement membrane of buying is immersed in ethanol and 3: 2 the mixed solution of water volume ratio keeps 20min; Then this polysulphone super-filter membrane is immersed and contain 4.6 * 10 of hyperbranched poly (amine-ester)
-3In the aqueous phase solution of mol/l, take out behind the 3h, dry in the shade naturally; Then this film is immersed in 4.6 * 10 of pyromellitic trimethylsilyl chloride
-3In the mol/l hexane solution, take out behind the 40min; Place 80 ℃ baking oven to keep 10min this film then, obtain the hyper-branched polyester composite nanometer filtering film.Under 0.3Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 69.41/m
2H, Na
2SO
4Removal efficiency be 81.4%.Under 0.6Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 75.4l/m
2H, Na
2SO
4Removal efficiency be 86.6%.
Embodiment 8:
The polysulfones ultrafiltration basement membrane of buying is immersed in ethanol and 3: 2 the mixed solution of water volume ratio keeps 20min; Then this polysulphone super-filter membrane is immersed and contain 4.6 * 10 of hyperbranched poly (third rare-imines)
-3In the aqueous phase solution of mol/l, take out behind the 40min, dry in the shade naturally; Then this film is immersed in 5.8 * 10 of succinic anhydride
-2In the mol/l hexane solution, take out behind the 15min; Place 30 ℃ baking oven to keep 1h this film then, obtain the hyper-branched polyester composite nanometer filtering film.Under 0.3Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 60l/m
2H, Na
2SO
4Removal efficiency be 70.4%.Under 0.6Mpa pressure, be the Na of 1g/l with concentration
2SO
4Test, the water flux of this film is 85.41/m
2H, Na
2SO
4Removal efficiency be 82.6%.
Claims (8)
1, a kind of crosslinked hyperbranched polyalcohol composite nano filter membrance is characterized in that it being that polymer milipore filter with porous is basement membrane, serves as to select layer with the crosslinked hyperbranched polyalcohol.
2. a kind of crosslinked hyperbranched polyalcohol composite nano filter membrance according to claim 1 is characterized in that described polymer milipore filter is Kynoar, polyether sulfone, polysulfones, polyacrylonitrile, polyethersulfone ketone or polyvinyl chloride milipore filter.
3. a kind of crosslinked hyperbranched polyalcohol composite nano filter membrance according to claim 1 is characterized in that described dissaving polymer is: molecular weight 1000 to 100,000, terminal groups are hyperbranched poly (acid amides-amine), hyperbranched poly (amine-ester), hyperbranched poly (propylene-imines), hyper-branched polyester or the hyperbranched poly acrylic acid of hydroxyl, amino or carboxyl.
4, a kind of preparation method of crosslinked hyperbranched polyalcohol composite nano filter membrance according to claim 1 is characterized in that may further comprise the steps:
1) the polymer milipore filter is immersed in the mixed solution of ethanol and water, soak time is 10s～1h;
2) dissaving polymer is dissolved in the mixed solution of ethanol and water, is made into aqueous phase solution, the concentration of dissaving polymer is: 1 * 10
-3～4 * 10
-2Mol/l;
3) being that 10～40 ℃, relative humidity are in 40～90% the air ambient in temperature, the polymer milipore filter after soaking in the step 1) be dipped into step 2 again) in the aqueous phase solution that is made into, soak time is 10s～10h, takes out the polymer milipore filter, dries in the shade;
4) crosslinking agent is dissolved in the solvent, is made into concentration and is: 4 * 10
-3～8 * 10
-2Cross-linking agent solution, the polymer film that dries in the shade that step 3) is obtained immerses in the cross-linking agent solution, reaction 10s～10h;
5) polymer film is taken out from cross-linking agent solution, place baking oven 5min～1h of 20～120 ℃, obtain crosslinked hyperbranched polyalcohol composite nano filter membrance.
5. a kind of crosslinked hyperbranched polyalcohol composite nano filter membrance according to claim 4, it is characterized in that described crosslinked crosslinking agent is: glutaraldehyde, terephthalaldehyde, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, succinic anhydride, pyromellitic dianhydride, succinic acid, adipic acid, PMA, terephthalic acid (TPA), 1, the 4-butanediamine, ethylenediamine, hexamethylene diamine, 1, the 4-butanediol, ethylene glycol, diethylene glycol ether, 1, ammediol, 1, the 6-hexylene glycol, pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, benzyl dichloride or molecular weight are two hydroxyl end groups polyethylene glycol of 200～2000.
6, according to the preparation method of the described crosslinked hyperbranched polyalcohol composite nano filter membrance of claim 4, it is characterized in that, the mixed solution of described ethanol and water, wherein the water volume percentage composition is: 1%～80%.
According to the preparation method of the described crosslinked hyperbranched polyalcohol composite nano filter membrance of claim 4, it is characterized in that 7, described polymer milipore filter is 20s～8h in the soak time of aqueous phase solution.
According to the preparation method of the described crosslinked hyperbranched polyalcohol composite nano filter membrance of claim 4, it is characterized in that 8, the solvent of described crosslinking agent is n-hexane, normal heptane or normal octane.
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