CN104906969A - Crosslinked-type polyelectrolyte-surfactant composition preparation method and application - Google Patents
Crosslinked-type polyelectrolyte-surfactant composition preparation method and application Download PDFInfo
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- CN104906969A CN104906969A CN201510261718.0A CN201510261718A CN104906969A CN 104906969 A CN104906969 A CN 104906969A CN 201510261718 A CN201510261718 A CN 201510261718A CN 104906969 A CN104906969 A CN 104906969A
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- ammonium chloride
- trimethyl ammonium
- methacryloyloxyethyltrimethyl trimethyl
- hydroxyalkyl acrylate
- sulfonic acid
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Abstract
The invention discloses a preparation method and an application of a crosslinked-type polyelectrolyte-surfactant composition. According to the invention, a poly(methylacryloyloxyethyl ammonium chloride-hydroxyalkyl acrylate) copolymer is prepared with a free radical polymerization manner. The polyelectrolyte-surfactant composition is prepared with a solution titration complexation manner. The polyelectrolyte-surfactant composition and a crosslinking agent are dissolved in an organic solvent together; and the crosslinked-type polyelectrolyte-surfactant composition membrane is prepared with an in-situ crosslinking manner. With an ionic crosslinking structure inside the molecules of the crosslinked-type polyelectrolyte-surfactant composition, the stability of the composition structure can be effectively maintained. With the crosslinking effect of the crosslinking agent between molecular chains, excessive swelling of the composition membrane in an alcohol/water feed solution can be effectively inhibited. Through regulating the copolymerization ratio of the copolymer and the type of the crosslinking agent, a membrane structure can be effectively regulated. The preparation method of the alcohol-penetration-priority membrane is simple and feasible, and has low cost and a good industrial application prospect.
Description
Technical field
The invention belongs to Polymer materialspreparation and UF membrane field, particularly relate to a kind of Preparation method and use of cross-linking type polyelectrolyte surfactant complexes.
Background technology
Infiltration evaporation (Pervaporation, PV) is a kind of energy-conservation, efficient membrane separation technique, organics dehydration, underwater micro-organic matter reclaim to be separated with organic mixture system etc. in there is obvious advantage.PV isolation technics is used for biofermentation prepare alcohols bio-fuel can significantly improve efficiency, reduce energy consumption and reduce pollute.Membrane material is the core of membrane separation technique research, and the ethanol-permselective membrane material of research separating property excellence is most important for the development promoting embrane method bio-fuel.At present, ethanol-permselective membrane material mainly silicon-containing polymer, especially rubbery state dimethyl silicone polymer (PDMS).PDMS, due to the submissive state of height of molecule and hydrophobic meth side chain, makes the diffusion of its applicable organic molecule.But uncrosslinked PDMS film is very easily swelling, and film forming, mechanical performance and separating property poor (Chem. Technol. Biotechnol., 2005,80:603-629).Therefore researcher's many employings PDMS material self-crosslinking or there is the polymer graft of good filming, block copolymerization, blended or form interpenetrating networks, to improve its stability and permselective property with other in bibliographical information.Researcher has prepared the separation (J. Appl. Polym. Sci., 2014,6:1 ~ 9) of in-situ cross-linked PDMS-BPPO tubular ceramic film for alcohol/aqueous systems, and the film after crosslinked has in high separation selectivity and During prolonged operation and has good stability.But mostly existing macromolecule alcohol permselective membrane is modification based on siliceous class material and hydridization.Along with the expansion day by day in application of membrane separation technology field, market penetration vaporization organic matter also gets more and more through the demand of film, and existing membrane material kind is single, significantly limit the industrial applications of infiltration evaporation alcohol permselective membrane.Therefore, from infiltration evaporation dissolving-diffusion mass transfer model, according to Preferential adsorption and the principle through alcohol molecule, the hydrophobic type high free volume membrane material designing other nonrubber classes is very necessary.
Polyelectrolyte surfactant complexes (Polyelectrolyte ~ surfactant complex, PESC) is formed the macromolecular complex with rock-steady structure by electrostatic interaction by polyelectrolyte and oppositely charged surfactant.Bibliographical information is deposited on (J. Appl. Polym. Sci. on poly-(acrylic acid-b-acrylonitrile) counterdie by cation quaternary ammonium salt and polyacrylic acid being adopted the mode of LBL, 2008,110:3234 – 3241), and use it for Ultra filtration membrane technology, experiment finds the increase along with the deposition number of plies, and water permeability reduces.Sodium carboxymethylcellulose is used for dewatering from the quaternized poly 4 vinyl pyridine compound of different alkyl chain length by bibliographical information, experiment finds the increase with alkyl chain length in quaternized poly 4 vinyl pyridine, complexes membrane has and is hydrophilicly converted into hydrophobic (J. Membr. Sci., 2013,429:181-189).Therefore by the compound of polyelectrolyte and cousin's activating agent, effectively can improve the hydrophilic and hydrophobic of surfactant, and the hydrophobic long-chain of surfactant in PESC film and the hydrophobic main chain of polyelectrolyte, can effectively provide film to the preferentially selective sorption of alcohol and through.Crosslinked is on the active position of polymer molecule, two large intermolecular generation chemical bonds, makes linear macromolecule or has the large molecule of slight cladodification to form three-dimensional net structure.Functional group is introduced in polyelectrolyte, adopt in-situ cross-linked mode to be cross-linked, not only can stablize the hydrophobic microcell in PESC, also give the stability of PESC film simultaneously.Therefore, by selecting and synthesizing polyelectrolyte and surfactant, control compound condition, adopt crosslinked method, improve hydrophobicity and the stability of film, prepare the infiltrating and vaporizing membrane of preferential alcohol thoroughly in a class water, will open up in a class new type water and remove organic matter membrane material.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of Preparation method and use of cross-linking type polyelectrolyte surfactant complexes is provided.
The preparation method of cross-linking type polyelectrolyte surfactant complexes comprises the following steps:
1) MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and hydroxyalkyl acrylate monomer being made into mass percent concentration is 10 ~ 30 wt% aqueous solution, pass into nitrogen, add water soluble oxidized-reduction initator that mass percent concentration is 1 ~ 3 wt%, adopt solution polymerization process, be polymerized 5 ~ 24 h at 30 ~ 50 DEG C after, with acetone precipitation, repeatedly after washing, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) copolymer, for subsequent use after vacuum drying;
2) will gather (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) copolymer joins in deionized water, 3 ~ 12 h are stirred at 20 ~ 60 DEG C, treat to dissolve completely, regulate pH value of solution, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) aqueous copolymers solution; Sulfonic acid type surfactant is joined in deionized water in proportion, at 20 ~ 60 DEG C, stirs 3 ~ 12 h, treat to dissolve completely, regulate pH value of solution, obtain the sulfonic acid type surfactant aqueous solution; The sulfonic acid type surfactant aqueous solution is dropwise joined in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) aqueous copolymers solution with the speed of 10 mL/min, and adopt light transmittance experimental monitoring titration process, treat that light transmission rate arrives minimum of a value, reach titration complexing terminal, repeatedly filter, washing, obtains solid-state poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound;
3) will gather that (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound joins in organic solvent, stirred at ambient temperature 5 ~ 24 h, until completely dissolved, add crosslinking agent, after stirring 1 ~ 5 h, regulate pH, leave standstill 0.5 ~ 2 h, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound dispersion liquid; Adopt the scraper that 400 μm thick, to gather the painting of (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound homogeneous dispersion ground scrapes on the supporting layer of drying, at 20 ~ 60 DEG C after dry 2 ~ 5 h, crosslinking curing, obtains poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-the hydroxyalkyl acrylate)-sulfonic acid type anion surfactant complexes membrane of cross-linking type.
The monomer of hydroxyalkyl acrylate described in step 1) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate, step 2) described in sulfonic acid type surfactant be dodecyl sodium sulfate, neopelex or perfluoro butyl sulfonic acid, crosslinking agent described in step 3) is MTES, tetramethoxy-silicane, tetraethyl orthosilicate, VTES, tetrapropoxysilane, ethyl triethoxysilane, (3-mercaptopropyi) trimethoxy silane, MTMS, methacryloxypropyl three (trimethylsiloxane group) silane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, trimethyoxysilane, n-octytriethoxysilane, phenyl triethoxysilane, triethoxysilane, diethylenetriamine base propyl trimethoxy silicane, triethoxy (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-ten trifluoro octyl group) silane, 3-chloropropyl triethoxysilane, N-propyl-triethoxysilicane or N-aminoethyl-γ-aminopropyltrimethoxysilane.
The copolymerization mass ratio of the monomer of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride described in step 1) and hydroxyalkyl acrylate monomer is 14:1 ~ 1:1.
Oxidant in oxidation-reduction initiator described in step 1) is ammonium persulfate or potassium peroxydisulfate, and the reducing agent in described oxidation-reduction initiator is sodium hydrogensulfite, and the mass ratio of Oxidizing and Reducing Agents is 1:1.
Step 2) described in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) aqueous copolymers solution or the molar concentration of the sulfonic acid type surfactant aqueous solution be 0.001 ~ 1 mol/L; Step 2) described in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) aqueous copolymers solution and the pH value range of the sulfonic acid type surfactant aqueous solution be 4 ~ 9.
Organic solvent described in step 3) is methyl alcohol, ethanol, isopropyl alcohol or n-butanol; Described in step 3), the mass percent concentration of poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound dispersion liquid is 0.01 ~ 20 wt%.
In step 3), the mass percentage concentration of crosslinking agent is 0.5 ~ 20 wt%.
Supporting layer described in step 3) is polysulphone flat ultrafiltration membrane or polyacrylonitrile flat milipore filter.
Crosslinking curing temperature described in step 3) is 50 ~ 120 DEG C, and crosslinking time is 2 ~ 10 h.
Cross-linking type cross-linking type polyelectrolyte surfactant complexes is for the preparation of evaporation alcohol permselective membrane.
Polyelectrolyte surfactants compound has structure-controllable and special nano particle structure and good hydrophobic property, intramolecular ionomer structure effectively can keep the stability of composite structure, simultaneously effectively can suppress excessively swelling in alcohol/water feed liquid of this complexes membrane by the crosslinked action of crosslinking agent between strand.Be applied to infiltration evaporation alcohol-water separation, the excessive swelling action of ethanol molecule to film can be significantly improved, effectively can improve the stability of film.The present invention, by adopting silane coupler and the hydroxyl reaction in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound, introduces the stability that hydrophobic group effectively can improve film while crosslinked.When being separated the ethanol/water mixed liquor of 5 wt% at 30 DEG C, permeate concentration brings up to 15wt%, and when long-play, shows good stability.In addition, the material surface active agent structures that the present invention is used for preparing poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-the hydroxyalkyl acrylate)-sulfonic acid type anion surfactant composite pervaporation ethanol-permselective membrane of cross-linking type is various, can be effective to membrane structure.Therefore, raw materials of the present invention is conveniently easy to get, and the preparation technology of film is easy, production cost is low, and film properties is excellent, has good industrial applicibility.
Detailed description of the invention
The preparation method of poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-the hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound of cross-linking type comprises the following steps:
1) MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and hydroxyalkyl acrylate monomer being made into mass percent concentration is 10 ~ 30 wt% aqueous solution, pass into nitrogen, add water soluble oxidized-reduction initator that mass percent concentration is 1 ~ 3 wt%, adopt solution polymerization process, be polymerized 5 ~ 24 h at 30 ~ 50 DEG C after, with acetone precipitation, repeatedly after washing, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) copolymer, for subsequent use after vacuum drying;
2) will gather (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) copolymer joins in deionized water, 3 ~ 12 h are stirred at 20 ~ 60 DEG C, treat to dissolve completely, regulate pH value of solution, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) aqueous copolymers solution; Sulfonic acid type surfactant is joined in deionized water in proportion, at 20 ~ 60 DEG C, stirs 3 ~ 12 h, treat to dissolve completely, regulate pH value of solution, obtain the sulfonic acid type surfactant aqueous solution; The sulfonic acid type surfactant aqueous solution is dropwise joined in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) aqueous copolymers solution with the speed of 10 mL/min, and adopt light transmittance experimental monitoring titration process, treat that light transmission rate arrives minimum of a value, reach titration complexing terminal, repeatedly filter, washing, obtains solid-state poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound;
3) will gather that (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound joins in organic solvent, stirred at ambient temperature 5 ~ 24 h, until completely dissolved, add crosslinking agent, after stirring 1 ~ 5 h, regulate pH, leave standstill 0.5 ~ 2 h, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound dispersion liquid; Adopt the scraper that 400 μm thick, to gather the painting of (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound homogeneous dispersion ground scrapes on the supporting layer of drying, at 20 ~ 60 DEG C after dry 2 ~ 5 h, crosslinking curing, obtains poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-the hydroxyalkyl acrylate)-sulfonic acid type anion surfactant complexes membrane of cross-linking type.
The monomer of hydroxyalkyl acrylate described in step 1) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate, step 2) described in sulfonic acid type surfactant be dodecyl sodium sulfate, neopelex or perfluoro butyl sulfonic acid, crosslinking agent described in step 3) is MTES, tetramethoxy-silicane, tetraethyl orthosilicate, VTES, tetrapropoxysilane, ethyl triethoxysilane, (3-mercaptopropyi) trimethoxy silane, MTMS, methacryloxypropyl three (trimethylsiloxane group) silane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, trimethyoxysilane, n-octytriethoxysilane, phenyl triethoxysilane, triethoxysilane, diethylenetriamine base propyl trimethoxy silicane, triethoxy (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-ten trifluoro octyl group) silane, 3-chloropropyl triethoxysilane, N-propyl-triethoxysilicane or N-aminoethyl-γ-aminopropyltrimethoxysilane.
The copolymerization mass ratio of the monomer of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride described in step 1) and hydroxyalkyl acrylate monomer is 14:1 ~ 1:1.
Oxidant in oxidation-reduction initiator described in step 1) is ammonium persulfate or potassium peroxydisulfate, and the reducing agent in described oxidation-reduction initiator is sodium hydrogensulfite, and the mass ratio of Oxidizing and Reducing Agents is 1:1.
Step 2) described in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) aqueous copolymers solution or the molar concentration of the sulfonic acid type surfactant aqueous solution be 0.001 ~ 1 mol/L; Step 2) described in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) aqueous copolymers solution and the pH value range of the sulfonic acid type surfactant aqueous solution be 4 ~ 9.
Organic solvent described in step 3) is methyl alcohol, ethanol, isopropyl alcohol or n-butanol; Described in step 3), the mass percent concentration of poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound dispersion liquid is 0.01 ~ 20 wt%.
In step 3), the mass percentage concentration of crosslinking agent is 0.5 ~ 20 wt%.
Supporting layer described in step 3) is polysulphone flat ultrafiltration membrane or polyacrylonitrile flat milipore filter.
Crosslinking curing temperature described in step 3) is 50 ~ 120 DEG C, and crosslinking time is 2 ~ 10 h.
Poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-the hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound of cross-linking type is applied to and prepares evaporation alcohol permselective membrane.
The separating property method of testing of cross-linking type cross-linking type polyelectrolyte surfactant complexes evaporation alcohol permselective membrane is as follows: alcohol permselective membrane is placed in stainless steel membrane cisterna, and effective area is 18.09cm
2, under film, lateral pressure keeps 300Pa, opens vavuum pump, adopt liquid nitrogen condensation collect in certain hour through thing, the composition through thing adopts gas-chromatography to analyze.Measure the permeation flux (J) of film and separation factor (α), its computing formula is: J=m/(A. Δ t); α=(y
i/ y
j)/(x
i/ x
j); Wherein A is membrane area, and Δ t is the operating time, and m is the permeate quality of the PV film being A by area in the Δ t time, and x, y represent feed liquid and penetrating fluid composition respectively, and subscript i, j represent component i and j respectively.
Provide embodiments of the invention below, but the present invention is not by the restriction of embodiment:
embodiment 1:
By MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and acrylic acid-2-hydroxyl acetate monomer with quality proportioning for 14:1, being made into mass percent concentration is the 30 wt% aqueous solution, pass into nitrogen, add water soluble oxidized-reduction initator that mass percent concentration is 1 wt%, adopt solution polymerization process, at 40 DEG C, be polymerized 8 h, with acetone precipitation, repeatedly after washing, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) copolymer, for subsequent use after vacuum drying.Getting 0.99 g copolymer quality joins in 500 g deionized waters than poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) copolymer for 14:1, stir 4h at 30 DEG C to dissolve completely, regulate pH value of solution=4, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution; Get 1.44 g dodecyl sodium sulfates to join in 500 g deionized waters, stir 4 h at 30 DEG C and dissolve completely, regulate pH value of solution=4, obtain sodium dodecyl sulfate aqueous solution; Sodium dodecyl sulfate aqueous solution is dropwise joined in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution with the speed of 10 mL/min, and adopt light transmittance experimental monitoring titration process, treat that light transmission rate arrives minimum of a value, reach titration complexing terminal.Repeatedly filter, washing, dry, obtain solid-state poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate compound.By the polymethyl acyloxyethyl ammonium chloride monomer of 0.8g-acrylic acid-2-hydroxyl ethyl ester/dodecyl sodium sulfate compound joins in the ethanol of 20g, 12 h are stirred at 25 DEG C, after dissolving completely, after leaving standstill 1 h, adopt the scraper that 400 μm thick, just above-mentioned dissolution homogeneity ground is coated with to be scraped on the polyacrylonitrile ultrafiltration counterdie of drying, at 40 DEG C after dry 2 h, is gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate complexes membrane.Measure film to the separating resulting of 5.0 wt% ethanol/water solution is under 30 DEG C of conditions: permeation flux is 4.68 kgm
-2h
-1, permeate concentration of alcohol is 12.74 wt%, and separation factor is 2.77.
embodiment 2:
By MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and acrylic acid-2-hydroxyl acetate monomer with quality proportioning for 1:1, being made into mass percent concentration is the 10 wt% aqueous solution, pass into nitrogen, add water soluble oxidized-reduction initator that mass percent concentration is 1 wt%, adopt solution polymerization process, at 40 DEG C, be polymerized 5 h, with acetone precipitation, repeatedly after washing, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) copolymer, for subsequent use after vacuum drying.Getting 0.75 g copolymer quality joins in 500 g deionized waters than poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) copolymer for 1:1, stir 4 h at 30 DEG C to dissolve completely, regulate pH value of solution=9, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution; Getting 2.07 g dodecyl sodium sulfates joins in 500g deionized water, stirs 4h and dissolve completely at 50 DEG C, regulates pH value of solution=9, obtains sodium dodecyl sulfate aqueous solution; Sodium dodecyl sulfate aqueous solution is dropwise joined in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution with the speed of 10 mL/min, and adopt light transmittance experimental monitoring titration process, treat that light transmission rate arrives minimum of a value, reach titration complexing terminal.Repeatedly filter, washing, dry, obtain solid-state poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) copolymer-dodecyl sodium sulfate compound.Poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) copolymer-dodecyl sodium sulfate compound of 0.8 g is joined in the ethanol of 20 g, 12 h are stirred at 25 DEG C, after dissolving completely, after leaving standstill 1 h, adopt the scraper that 400 μm thick, just above-mentioned dissolution homogeneity ground is coated with to be scraped on the polyacrylonitrile ultrafiltration counterdie of drying, at 40 DEG C after dry 2 h, obtain polymethyl acyloxyethyl ammonium chloride-acrylic acid-2-hydroxyl methacrylate copolymers/dodecyl sodium sulfate complexes membrane.Measure film to the separating resulting of 5.0 wt% ethanol/water solution is under 40 DEG C of conditions: permeation flux is 10.54 kgm
-2h
-1, permeate concentration of alcohol is 8.85 wt%, and separation factor is 1.84.
embodiment 3:
By MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and acrylic acid-2-hydroxyl acetate monomer with quality proportioning for 9:1, being made into mass percent concentration is the 30 wt% aqueous solution, pass into nitrogen, add water soluble oxidized-reduction initator that mass percent concentration is 1 wt%, adopt solution polymerization process, at 40 DEG C, be polymerized 5 h, with acetone precipitation, repeatedly after washing, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) copolymer, for subsequent use after vacuum drying.Getting 0.96 g copolymer quality joins in 500 g deionized waters than poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) copolymer for 9:1, stir 4 h at 30 DEG C to dissolve completely, regulate pH value of solution=9, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution; Get 2.07 g dodecyl sodium sulfates to join in 500 g deionized waters, stir 4 h at 50 DEG C and dissolve completely, regulate pH value of solution=9, obtain sodium dodecyl sulfate aqueous solution; Sodium dodecyl sulfate aqueous solution is dropwise joined in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution with the speed of 10 mL/min, and adopt light transmittance experimental monitoring titration process, treat that light transmission rate arrives minimum of a value, reach titration complexing terminal.Repeatedly filter, washing, dry, obtain solid-state poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate compound.Poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate compound of 0.8 g is joined in the ethanol of 20 g, 12 h are stirred at 25 DEG C, after dissolving completely, after leaving standstill 1 h, adopt the scraper that 400 μm thick, just above-mentioned dissolution homogeneity ground is coated with to be scraped on the polyacrylonitrile ultrafiltration counterdie of drying, at 40 DEG C after dry 2h, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate complexes membrane.Measure film to the separating resulting of 5.0 wt% ethanol/water solution is under 40 DEG C of conditions: permeation flux is 6.24 kgm
-2h
-1, permeate concentration of alcohol is 10.13 wt%, and separation factor is 2.14.
embodiment 4:
By MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and acrylic acid-2-hydroxyl acetate monomer with quality proportioning for 9:1, being made into mass percent concentration is the 30 wt% aqueous solution, pass into nitrogen, add water soluble oxidized-reduction initator that mass percent concentration is 1 wt%, adopt solution polymerization process, at 40 DEG C, be polymerized 5 h, with acetone precipitation, repeatedly after washing, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) copolymer, for subsequent use after vacuum drying.Getting 0.96 g copolymer quality joins in 500 g deionized waters than poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) copolymer for 9:1, stir 4 h at 30 DEG C to dissolve completely, regulate pH value of solution=9, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution; Get 2.61 g neopelexes to join in 500 g deionized waters, stir 4 h at 50 DEG C and dissolve completely, regulate pH value of solution=9, obtain sodium dodecyl benzene sulfonate aqueous solution; Sodium dodecyl benzene sulfonate aqueous solution is dropwise joined in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution with the speed of 10 mL/min, and adopt light transmittance experimental monitoring titration process, treat that light transmission rate arrives minimum of a value, reach titration complexing terminal.Repeatedly filter, washing, dry, obtain solid-state poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-neopelex compound.Poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-neopelex compound of 0.8 g is joined in the ethanol of 20 g, 12 h are stirred at 25 DEG C, after dissolving completely, after leaving standstill 1 h, adopt the scraper that 400 μm thick, just above-mentioned dissolution homogeneity ground is coated with to be scraped on the polyacrylonitrile ultrafiltration counterdie of drying, at 40 DEG C after dry 2h, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-neopelex complexes membrane.Measure film to the separating resulting of 5.0 wt% ethanol/water solution is under 40 DEG C of conditions: permeation flux is 5.38 kgm
-2h
-1, permeate concentration of alcohol is 13.27 wt%, and separation factor is 2.91.
embodiment 5:
By MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and acrylic acid-2-hydroxyl acetate monomer with quality proportioning for 9:1, being made into mass percent concentration is the 30 wt% aqueous solution, pass into nitrogen, add water soluble oxidized-reduction initator that mass percent concentration is 1 wt%, adopt solution polymerization process, at 40 DEG C, be polymerized 5 h, with acetone precipitation, repeatedly after washing, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) copolymer, for subsequent use after vacuum drying.Getting 0.96 g copolymer quality joins in 500 g deionized waters than poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) copolymer for 9:1, stir 4 h at 30 DEG C to dissolve completely, regulate pH value of solution=9, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution; Get 4.22 g perfluoro butyl sulfonic acid to join in 500 g deionized waters, stir 4 h at 50 DEG C and dissolve completely, regulate pH value of solution=9, obtain the perfluoro butyl sulfonic acid aqueous solution; Sodium dodecyl benzene sulfonate aqueous solution is dropwise joined in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution with the speed of 10 mL/min, and adopt light transmittance experimental monitoring titration process, treat that light transmission rate arrives minimum of a value, reach titration complexing terminal.Repeatedly filter, washing, dry, obtain solid-state poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-perfluoro butyl sulfonic acid compound.Poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-perfluoro butyl sulfonic acid compound of 0.8 g is joined in the ethanol of 20 g, 12 h are stirred at 25 DEG C, after dissolving completely, after leaving standstill 1 h, adopt the scraper that 400 μm thick, just above-mentioned dissolution homogeneity ground is coated with to be scraped on the polyacrylonitrile ultrafiltration counterdie of drying, at 40 DEG C after dry 2h, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-perfluoro butyl sulfonic acid complexes membrane.Measure film to the separating resulting of 5.0 wt% ethanol/water solution is under 40 DEG C of conditions: permeation flux is 6.47 kgm
-2h
-1, permeate concentration of alcohol is 9.38 wt%, and separation factor is 1.97.
embodiment 6:
By MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and acrylic acid-2-hydroxyl acetate monomer with quality proportioning for 9:1, being made into mass percent concentration is the 30 wt% aqueous solution, pass into nitrogen, add water soluble oxidized-reduction initator that mass percent concentration is 1 wt%, adopt solution polymerization process, at 40 DEG C, be polymerized 5 h, with acetone precipitation, repeatedly after washing, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) copolymer, for subsequent use after vacuum drying.Getting 0.96 g copolymer quality joins in 500 g deionized waters than poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) copolymer for 9:1, stir 4 h at 30 DEG C to dissolve completely, regulate pH value of solution=9, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution; Get 14.4 g dodecyl sodium sulfates to join in 500 g deionized waters, stir 4 h at 50 DEG C and dissolve completely; Surfactant solution is dropwise joined in copolymer solution with the speed of 10 mL/min, and adopts light transmittance experimental monitoring titration process, treat that light transmission rate arrives minimum of a value, reach titration complexing terminal.Repeatedly filter, washing, obtain solid-state poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate compound.Poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate compound of 0.8 g is joined in the ethanol of 20g, 12h is stirred at 25 DEG C, after dissolving completely, add 0.1 g VTES, after stirring 2 h, regulate pH=4.0, the scraper that rear employing 400 μm is thick, just above-mentioned dissolution homogeneity ground is coated with to be scraped on the polyacrylonitrile ultrafiltration counterdie of drying, at 40 DEG C after dry 2 h, and crosslinked 3 h at 50 DEG C.Obtain crosslinked poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate complexes membrane.Measure film to the separating resulting of 5.0 wt% ethanol/water solution is under 30 DEG C of conditions: permeation flux is 5.38 kgm
-2h
-1, permeate concentration of alcohol is 14.78 wt%, and separation factor is 3.30.
embodiment 7:
By MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and acrylic acid-2-hydroxyl acetate monomer with quality proportioning for 9:1, being made into mass percent concentration is the 30 wt% aqueous solution, pass into nitrogen, add water soluble oxidized-reduction initator that mass percent concentration is 1 wt%, adopt solution polymerization process, at 40 DEG C, be polymerized 5 h, with acetone precipitation, repeatedly after washing, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) copolymer, for subsequent use after vacuum drying.Getting 48 g copolymer qualities joins in 500 g deionized waters than poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) copolymer for 9:1, stir 4 h at 30 DEG C to dissolve completely, regulate pH value of solution=9, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution; Get 72 g dodecyl sodium sulfates to join in 500 g deionized waters, stir 4 h at 50 DEG C and dissolve completely, regulate pH value of solution=9, obtain sodium dodecyl sulfate aqueous solution; Sodium dodecyl sulfate aqueous solution is dropwise joined in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution with the speed of 10 mL/min, and adopt light transmittance experimental monitoring titration process, treat that light transmission rate arrives minimum of a value, reach titration complexing terminal.Repeatedly filter, washing, obtain solid-state poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate compound.Poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate compound of 0.8 g is joined in the ethanol of 20g, 12h is stirred at 25 DEG C, after dissolving completely, add 4 g VTESs, after stirring 2 h, regulate pH=4.0, the scraper that rear employing 400 μm is thick, just above-mentioned dissolution homogeneity ground is coated with to be scraped on the polyacrylonitrile ultrafiltration counterdie of drying, at 40 DEG C after dry 2 h, and crosslinked 3 h at 50 DEG C.Obtain crosslinked poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate complexes membrane.Measure film to the separating resulting of 5.0 wt% ethanol/water solution is under 30 DEG C of conditions: permeation flux is 4.25 kgm
-2h
-1, permeate concentration of alcohol is 15.54 wt%, and separation factor is 3.50.
embodiment 8:
By MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and acrylic acid-2-hydroxyl acetate monomer with quality proportioning for 9:1, being made into mass percent concentration is the 30 wt% aqueous solution, pass into nitrogen, add water soluble oxidized-reduction initator that mass percent concentration is 1 wt%, adopt solution polymerization process, at 40 DEG C, be polymerized 5 h, with acetone precipitation, repeatedly after washing, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) copolymer, for subsequent use after vacuum drying.Getting 0.96 g copolymer quality joins in 500 g deionized waters than poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) copolymer for 9:1, stir 4 h at 30 DEG C to dissolve completely, regulate pH value of solution=9, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution; Get 2.07 g dodecyl sodium sulfates to join in 500 g deionized waters, stir 4 h at 50 DEG C and dissolve completely, regulate pH value of solution=9, obtain sodium dodecyl sulfate aqueous solution; Sodium dodecyl sulfate aqueous solution is dropwise joined in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester) aqueous copolymers solution with the speed of 10 mL/min, and adopt light transmittance experimental monitoring titration process, treat that light transmission rate arrives minimum of a value, reach titration complexing terminal.Repeatedly filter, washing, obtain solid-state poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate compound.Poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer-acrylic acid-2-hydroxyl ethyl ester)-dodecyl sodium sulfate compound of 0.4 g is joined in the ethanol of 20 g, 12 h are stirred at 25 DEG C, after dissolving completely, add 0.2 g 17 fluorine decyl triethoxysilane, after stirring 2 h, regulate pH=9.0, the scraper that rear employing 400 μm is thick, just above-mentioned dissolution homogeneity ground is coated with to be scraped on the polyacrylonitrile ultrafiltration counterdie of drying, at 40 DEG C after dry 2 h, and crosslinked 3 h at 60 DEG C.Obtain cross-linked poly methyl acrylyl oxy-ethyl ammonium chloride-acrylic acid-2-hydroxyl methacrylate copolymers/surfactant complex film.Measure film to the separating resulting of 5.0 wt% ethanol/water solution is under 40 DEG C of conditions: permeation flux is 4.43 kgm
-2h
-1, permeate concentration of alcohol is 16.84 wt%, and separation factor is 3.84.
Claims (10)
1. a preparation method for cross-linking type cross-linking type polyelectrolyte surfactant complexes, is characterized in that comprising the following steps:
1) MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride monomer and hydroxyalkyl acrylate monomer being made into mass percent concentration is 10 ~ 30 wt% aqueous solution, pass into nitrogen, add water soluble oxidized-reduction initator that mass percent concentration is 1 ~ 3 wt%, adopt solution polymerization process, be polymerized 5 ~ 24 h at 30 ~ 50 DEG C after, with acetone precipitation, repeatedly after washing, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) copolymer, for subsequent use after vacuum drying;
2) will gather (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) copolymer joins in deionized water, 3 ~ 12 h are stirred at 20 ~ 60 DEG C, treat to dissolve completely, regulate pH value of solution, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) aqueous copolymers solution; Sulfonic acid type surfactant is joined in deionized water in proportion, at 20 ~ 60 DEG C, stirs 3 ~ 12 h, treat to dissolve completely, regulate pH value of solution, obtain the sulfonic acid type surfactant aqueous solution; The sulfonic acid type surfactant aqueous solution is dropwise joined in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) aqueous copolymers solution with the speed of 10 mL/min, and adopt light transmittance experimental monitoring titration process, treat that light transmission rate arrives minimum of a value, reach titration complexing terminal, repeatedly filter, washing, obtains solid-state poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound;
3) will gather that (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound joins in organic solvent, stirred at ambient temperature 5 ~ 24 h, until completely dissolved, add crosslinking agent, after stirring 1 ~ 5 h, regulate pH, leave standstill 0.5 ~ 2 h, gathered (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound dispersion liquid; Adopt the scraper that 400 μm thick, to gather the painting of (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound homogeneous dispersion ground scrapes on the supporting layer of drying, at 20 ~ 60 DEG C after dry 2 ~ 5 h, crosslinking curing, obtains poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-the hydroxyalkyl acrylate)-sulfonic acid type anion surfactant complexes membrane of cross-linking type.
2. the method for claim 1, is characterized in that the monomer of hydroxyalkyl acrylate described in step 1) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate, step 2) described in sulfonic acid type surfactant be dodecyl sodium sulfate, neopelex or perfluoro butyl sulfonic acid, crosslinking agent described in step 3) is MTES, tetramethoxy-silicane, tetraethyl orthosilicate, VTES, tetrapropoxysilane, ethyl triethoxysilane, (3-mercaptopropyi) trimethoxy silane, MTMS, methacryloxypropyl three (trimethylsiloxane group) silane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, trimethyoxysilane, n-octytriethoxysilane, phenyl triethoxysilane, triethoxysilane, diethylenetriamine base propyl trimethoxy silicane, triethoxy (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-ten trifluoro octyl group) silane, 3-chloropropyl triethoxysilane, N-propyl-triethoxysilicane or N-aminoethyl-γ-aminopropyltrimethoxysilane.
3. preparation method as claimed in claim 1, is characterized in that the copolymerization mass ratio of the monomer of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride described in step 1) and hydroxyalkyl acrylate monomer is 14:1 ~ 1:1.
4. preparation method as claimed in claim 1, it is characterized in that the oxidant in the oxidation-reduction initiator described in step 1) is ammonium persulfate or potassium peroxydisulfate, reducing agent in described oxidation-reduction initiator is sodium hydrogensulfite, and the mass ratio of Oxidizing and Reducing Agents is 1:1.
5. preparation method as claimed in claim 1, is characterized in that step 2) described in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) aqueous copolymers solution or the molar concentration of the sulfonic acid type surfactant aqueous solution be 0.001 ~ 1 mol/L; Step 2) described in poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate) aqueous copolymers solution and the pH value range of the sulfonic acid type surfactant aqueous solution be 4 ~ 9.
6. preparation method as claimed in claim 1, is characterized in that the organic solvent described in step 3) is methyl alcohol, ethanol, isopropyl alcohol or n-butanol; Described in step 3), the mass percent concentration of poly-(MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-co-hydroxyalkyl acrylate)-sulfonic acid type anion surfactant compound dispersion liquid is 0.01 ~ 20 wt%.
7. preparation method as claimed in claim 1, is characterized in that the mass percentage concentration of crosslinking agent in step 3) is 0.5 ~ 20 wt%.
8. preparation method as claimed in claim 1, is characterized in that the supporting layer described in step 3) is polysulphone flat ultrafiltration membrane or polyacrylonitrile flat milipore filter.
9. preparation method as claimed in claim 1, it is characterized in that the crosslinking curing temperature described in step 3) is 50 ~ 120 DEG C, crosslinking time is 2 ~ 10 h.
10. the purposes of cross-linking type cross-linking type polyelectrolyte surfactant complexes prepared of method as claimed in claim 1, is characterized in that cross-linking type cross-linking type polyelectrolyte surfactant complexes is for the preparation of evaporation alcohol permselective membrane.
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