CN116769097A - Amphiphilic terpolymer and preparation method and application thereof - Google Patents
Amphiphilic terpolymer and preparation method and application thereof Download PDFInfo
- Publication number
- CN116769097A CN116769097A CN202210220489.8A CN202210220489A CN116769097A CN 116769097 A CN116769097 A CN 116769097A CN 202210220489 A CN202210220489 A CN 202210220489A CN 116769097 A CN116769097 A CN 116769097A
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- China
- Prior art keywords
- formula
- terpolymer
- amphiphilic
- amphiphilic terpolymer
- ultrafiltration membrane
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001897 terpolymer Polymers 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims description 125
- 238000000108 ultra-filtration Methods 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000002033 PVDF binder Substances 0.000 claims description 27
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 21
- 238000005266 casting Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 7
- 229960003237 betaine Drugs 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 229920006027 ternary co-polymer Polymers 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 229920001600 hydrophobic polymer Polymers 0.000 abstract description 2
- 238000005191 phase separation Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 239000011259 mixed solution Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- 239000007788 liquid Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- 239000011521 glass Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 229910021642 ultra pure water Inorganic materials 0.000 description 17
- 239000012498 ultrapure water Substances 0.000 description 17
- 230000004907 flux Effects 0.000 description 13
- 108090000623 proteins and genes Proteins 0.000 description 11
- 102000004169 proteins and genes Human genes 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000007790 scraping Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 7
- 229940098773 bovine serum albumin Drugs 0.000 description 7
- 230000010874 maintenance of protein location Effects 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000005345 coagulation Methods 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- -1 for example Chemical compound 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000009285 membrane fouling Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002953 phosphate buffered saline Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D71/28—Polymers of vinyl aromatic compounds
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
- C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/14—Homopolymers or copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Abstract
The invention discloses an amphiphilic terpolymer and a preparation method and application thereof, wherein the amphiphilic terpolymer has a structure shown in the following formula I. The amphiphilic ternary copolymer prepared by the invention can realize good intersolubility with a hydrophobic polymer and good intersolubility with an organic solvent by adjusting the proportion of the hydrophilic and hydrophobic chain segments, avoid the difficult problem of phase separation and simultaneously show excellent hydrophilic antifouling efficacy.
Description
Technical Field
The invention belongs to the technical field of membrane separation and water treatment, and particularly relates to an amphiphilic terpolymer and a preparation method and application thereof.
Background
With the development of society, the problem of water resource pollution becomes a global common problem. The membrane separation technology can be used for deep purification of water treatment, and is a novel green and efficient separation technology. The membrane separation technology has the advantages of simple process, high separation efficiency, no environmental pollution and the like, is widely applied to the field of water treatment, and is an important technology for solving the problems of current energy, resources and environment. However, during actual operation, membrane fouling is a major bottleneck limiting the application of membrane separation technology to water treatment. Membrane fouling refers to the phenomenon of reduced membrane permeability during filtration due to the accumulation of impurities (physical, chemical and biological species) in solution on the surface of or within the membrane material. Protein macromolecules or microorganisms in the water body are adsorbed on the surface of the membrane in the use process, so that the water flux of the membrane is directly reduced, the energy consumption is increased, the service life of the membrane is shortened, and the method is one of main reasons for improving the application cost of the membrane. Therefore, the method for effectively providing the best prevention and control of the membrane pollution becomes the key point of the research and application of the ultrafiltration membrane by deeply analyzing the ultrafiltration membrane pollution mechanism.
At present, the commonly used separation membranes are mainly organic polymer membranes, such as polysulfones, polyacrylonitrile, polyvinylidene fluoride, polyether ketone, polyether ether ketone and the like. Among them, polyvinylidene fluoride (PVDF) is the most commonly used separation membrane material due to its good chemical stability, thermal stability and mechanical properties. The polyvinylidene fluoride (PVDF) ultrafiltration membrane is a membrane material with excellent performance, has the characteristics of high strength, high temperature resistance, chemical corrosion resistance and the like, is used for separating components smaller than the pore diameter in a solution, and has the characteristics of low operating pressure, high flux, low cost and the like. However, ultrafiltration membranes are prone to membrane contamination due to factors such as protein adsorption, deposition, denaturation, etc. at the membrane and solution interface. And the extremely strong hydrophobicity leads to low flux and easy pollution, and severely limits the application of the membrane method sewage treatment field.
At present, the treatment method for pollution of PVDF membrane is mainly hydrophilic modification, and mainly comprises surface grafting, surface coating, physical blending and the like. Surface coating (physical modification) and surface grafting (chemical modification) are two common modification methods, but hydrophilic polymers in the surface coating method are adsorbed on the surface of the polymers through physical action, so that the anti-fouling coating is easy to fall off. The surface grafting modification method has stable bonding of the functional layer, but has harsh operation conditions and higher technical process requirements, and is not suitable for industrialized production. Therefore, how to prepare an ultrafiltration membrane with high performance is a technical problem to be solved.
Disclosure of Invention
The invention aims to improve the hydrophilic performance of an ultrafiltration membrane, in particular to a PVDF ultrafiltration membrane, so as to improve the anti-fouling performance of the ultrafiltration membrane and realize high-flux and low-resistance filtration. Therefore, an amphiphilic terpolymer and a preparation method and application thereof are provided. The amphiphilic terpolymer is used for preparing the ultrafiltration membrane, so that the prepared amphiphilic terpolymer modified ultrafiltration membrane can obviously improve the surface hydrophilicity of the ultrafiltration membrane, reduce the adhesion and deposition of proteins, has obvious anti-pollution effect, and has important significance for industrialized production of the ultrafiltration membrane, in particular to PVDF (polyvinylidene fluoride) ultrafiltration membrane.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
an amphiphilic terpolymer having the structure shown in formula I:
wherein R is 1 ～R 9 Identical or different, independently of one another, from H, -C 1-12 An alkyl group;
R 10 、R 11 identical or different, independently of one another, from H, -C 1-12 alkylene-SO 3 H, or R 10 、R 11 Forms a structure with the N atom as shown in the following formula II:
R 12 selected from phenyl or-C (=O) O-C 1-12 An alkyl group;
R 13 selected from-OH or-N + (C 1-12 Alkyl group 2 -C 1-12 alkylene-COO - ；
m is an integer of 2 to 35, and n is an integer of 2 to 35; k is an integer of 2 to 35; p is an integer of 1 to 12.
According to an embodiment of the invention, R 1 ～R 9 Identical or different, independently of one another, from H, -C 1-6 An alkyl group;
R 10 、R 11 identical or different, independently of one another, from H, -C 1-6 alkylene-SO 3 H, or R 10 、R 11 Form a structure shown in a formula II together with an N atom;
R 12 selected from phenyl or-C (=O) O-C 1-6 An alkyl group;
R 13 selected from-OH or-N + (C 1-6 Alkyl group 2 -C 1-6 alkylene-COO - ；
p is an integer of 1 to 6.
According to an embodiment of the invention, R 1 ～R 9 Are all H, or R 1 ～R 8 Are all H, R 9 Is methyl;
R 10 、R 11 identical or different, independently of one another, from H, -C 4 alkylene-SO 3 H, or R 10 、R 11 Form a structure shown in a formula II together with an N atom;
R 12 selected from phenyl or-C (=O) O-CH 3 ；
R 13 Selected from-OH or-N + (CH 3 ) 2 -C 2 H 4 -COO - The method comprises the steps of carrying out a first treatment on the surface of the p is 2.
Illustratively, the amphiphilic terpolymer has a structure as shown in formula III or formula IV below;
wherein in the formula III, m is an integer of 2-35, and n is an integer of 2-35; k is an integer of 2 to 35;
in the formula IV, m is an integer of 3-25, and n is an integer of 3-25; k is an integer of 3 to 25.
The invention also provides a preparation method of the amphiphilic terpolymer, which comprises the following steps:
under the protection of inert gas, sequentially adding an initiator, a compound shown in a formula A, a compound shown in a formula B and a compound shown in a formula C into an organic solvent for reaction to prepare an amphiphilic terpolymer shown in a formula I;
wherein R is 1 ～R 13 Having the meaning as above.
According to an embodiment of the present invention, the initiator may be Azobisisobutyronitrile (AIBN).
According to an embodiment of the present invention, the organic solvent is selected from at least one of tetrahydrofuran, methanol, ethanol. Preferably a mixture of tetrahydrofuran and methanol, for example tetrahydrofuran, methanol in a volume ratio of 10:1; also preferred is a mixture of tetrahydrofuran and ethanol, for example, tetrahydrofuran, ethanol in a volume ratio of 10:1.
According to the embodiment of the invention, the mass volume ratio of the compound shown in the formula A, the compound shown in the formula B, the compound shown in the formula C, the initiator and the organic solvent is (1-30) g (6-60) g (5-50) g (1 g) (200-1500) mL, preferably (4-20) g (10-40) g (6-30) g (1 g) (300-1200) mL.
According to an embodiment of the present invention, the compound represented by formula a may be Acryloylmorpholine (ACMO) or 2-acrylamido-2-methylpropanesulfonic Acid (AMPS).
According to an embodiment of the present invention, the compound represented by formula B may be styrene, or methyl methacrylate.
According to an embodiment of the present invention, the compound represented by formula C may be a carboxylic acid betaine methacrylate (CBMA), or 2-hydroxyethyl acrylate (HEA);
wherein the carboxylic acid betaine methacrylate has the following structural formula:
according to an embodiment of the present invention, the temperature of the reaction is 140 to 350 ℃, and is exemplified by 140 ℃, 150 ℃, 160 ℃, 180 ℃, 200 ℃, 210 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃, 350 ℃; the reaction time is 16-48 h.
According to an embodiment of the invention, the method further comprises a post-treatment step: and washing the product after the reaction is finished, taking the precipitate, and drying to prepare the purified amphiphilic terpolymer.
Illustratively, deionized water is used for washing.
Illustratively, vacuum drying is employed at a temperature of 200-350 ℃ for a time of 24-60 hours.
According to an embodiment of the invention, the inert gas is, for example, nitrogen or argon.
As an exemplary embodiment of the present invention, when the amphiphilic terpolymer has a structure represented by formula III above, the preparation method of the amphiphilic terpolymer includes the steps of:
step 1, sequentially adding Azobisisobutyronitrile (AIBN), acryloylmorpholine (ACMO), styrene and methacrylic acid carboxylic acid betaine ester (CBMA) into a tetrahydrofuran and methanol mixed solution under the protection of inert gas, and stirring and reacting for 18-48 hours to obtain a mixed system;
step 2, pouring the mixed system into deionized water to separate out a precipitate;
and step 3, vacuum drying the precipitate at 200-300 ℃ for 24-48 h to obtain the amphiphilic terpolymer.
As an exemplary embodiment of the present invention, when the amphiphilic terpolymer has a structure represented by formula IV above, the preparation method of the amphiphilic terpolymer includes the steps of:
step A, sequentially adding Azodiisobutyronitrile (AIBN), 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), methyl methacrylate and 2-hydroxyethyl acrylate (HEA) into a tetrahydrofuran and ethanol mixed solution under the protection of inert gas, and stirring and reacting for 16-46h to obtain a mixed system;
step B, pouring the mixed system into deionized water, and standing to separate out a precipitate;
and C, vacuum drying the precipitate at 250-350 ℃ for 24-60h to obtain the amphiphilic terpolymer.
As an exemplary embodiment of the present invention, the reaction process of the amphiphilic terpolymer having the structure shown in formula III above is as follows:
as an exemplary embodiment of the present invention, the reaction process of the amphiphilic terpolymer having the structure shown in formula IV above is as follows:
the invention also provides an amphiphilic terpolymer modified ultrafiltration membrane, which comprises the amphiphilic terpolymer. Preferably, the ultrafiltration membrane is a polyvinylidene fluoride ultrafiltration membrane.
The invention also provides a preparation method of the amphiphilic terpolymer modified ultrafiltration membrane, which comprises the following steps:
s1: mixing the amphiphilic ternary copolymer and polyvinylidene fluoride in a solvent to prepare a casting solution;
s2: and (3) solidifying the membrane casting solution in the step (S1) to form a membrane, and preparing the amphiphilic terpolymer modified ultrafiltration membrane.
According to an embodiment of the present invention, in step S1, the mass ratio of the amphiphilic terpolymer, polyvinylidene fluoride and solvent is 0.02-2:1:3-50, preferably 0.04-1:1:4-30.
According to an embodiment of the present invention, in step S1, the solvent may be N, N-dimethylacetamide (DMAc).
According to an embodiment of the present invention, in step S1, the temperature of mixing is 30 to 120 ℃ and the time of mixing is 10 to 50 hours.
According to an embodiment of the present invention, in step S1, after the completion of the mixing, the mixture may be further subjected to a defoaming treatment, for example, the defoaming temperature is 30 to 120 ℃ and the defoaming time is 12 to 48 hours.
Illustratively, in step S2, the manner of curing the film may be: coating the casting solution on a substrate (such as a glass plate), scraping the film, standing the film in air for 10-90 s, solidifying the film in ultrapure water at 15-25 ℃ for 10-72h, and removing the solvent to obtain the amphiphilic terpolymer modified ultrafiltration membrane.
As an exemplary embodiment of the present invention, the preparation method of the amphiphilic terpolymer modified ultrafiltration membrane comprises the following steps:
step 1-1, blending the amphiphilic terpolymer and DMAc to obtain a mixed solution B, carrying out ultrasonic treatment until the amphiphilic terpolymer and DMAc are completely dissolved, adding polyvinylidene fluoride into the mixed solution B, and stirring for 12-48h at 30-100 ℃; then standing and defoaming for 12-48 hours at the constant temperature of 30-100 ℃ to obtain casting film liquid;
step 2-1, pouring the casting solution in the step 1-1 on a clean glass plate, and scraping the film; the scraped liquid film is stagnated in the air for 10 to 80 seconds and is put into ultra-pure water coagulating bath at 25 ℃ to be solidified into a film; finally, the ultrafiltration membrane which is fallen off from the glass plate is placed in ultrapure water to be soaked for 12 to 72 hours to eliminate residual DMAc solvent in the membrane, and the amphiphilic terpolymer modified ultrafiltration membrane is prepared.
As an exemplary embodiment of the present invention, the preparation method of the amphiphilic terpolymer modified ultrafiltration membrane comprises the following steps:
step 1-2, blending the amphiphilic terpolymer and DMAc to obtain a mixed solution B, carrying out ultrasound until the amphiphilic terpolymer is completely dissolved, adding polyvinylidene fluoride into the mixed solution B, and stirring for 10-50h at 45-120 ℃; then, standing and defoaming for 12-48 hours at the constant temperature of 45-120 ℃ to obtain casting film liquid;
step 2-2, pouring the casting solution in the step 1-2 on a clean glass plate, and scraping the film; the scraped liquid film is stagnated in the air for 15-90s and is put into an ultra-pure water coagulating bath with the temperature of 15-25 ℃ to be solidified into a film; finally, the ultrafiltration membrane which is fallen off from the glass plate is placed in ultrapure water to be soaked for 10-72 hours to eliminate residual DMAc solvent in the membrane, and the amphiphilic terpolymer modified ultrafiltration membrane is prepared.
The invention also provides application of the amphiphilic terpolymer or the amphiphilic terpolymer modified ultrafiltration membrane in the field of water treatment.
The invention has the beneficial effects that:
(1) The amphiphilic ternary copolymer prepared by the invention can realize good intersolubility with a hydrophobic polymer and good intersolubility with an organic solvent by adjusting the proportion of the hydrophilic and hydrophobic chain segments, avoid the difficult problem of phase separation and simultaneously show excellent hydrophilic antifouling efficacy.
(2) The invention adopts a blending method to modify the membrane, so that the polymer can be uniformly distributed in the membrane, and the polymer can not run off in the filtration process, so that the performance of the membrane is more durable and stable.
(3) The amphiphilic terpolymer provided by the invention not only has a hydrophilic modification effect, but also has Kong Gongxiao, and has higher protein retention rate and anti-pollution capability while ensuring high water flux.
(4) The preparation method disclosed by the invention is simple to operate and high in practicability, and the amphiphilic terpolymer is used for preparing the amphiphilic terpolymer modified ultrafiltration membrane, so that the amphiphilic terpolymer modified ultrafiltration membrane has excellent mechanical strength, thermal stability, antifouling effect and permeability, and has a wide application prospect in the field of water treatment.
Interpretation of the terms
The term "C 1-12 Alkyl "is understood to mean straight-chain and branched alkyl radicals having 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms," C 1-6 Alkyl "means straight and branched alkyl groups having 1,2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl, or 1, 2-dimethylbutyl, or the like, or an isomer thereof.
The term "C 1-12 Alkylene "is understood to mean C as described above 1-12 The alkyl radical losing oneH, and a group formed after H.
Drawings
FIG. 1 is a schematic diagram of the synthesis of an amphiphilic terpolymer of examples 1-2;
FIG. 2 is a graph showing the variation of contact angle of the amphiphilic terpolymer modified ultrafiltration membrane prepared in example 1 and comparative example 1 according to the concentration of the amphiphilic terpolymer, wherein the concentration of the terpolymer is 0.0wt% corresponding to comparative example 1, the concentration of the terpolymer is 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt% corresponding to example 1, and the monomer ratio m: n: k=1:3:1 in the amphiphilic terpolymer;
FIG. 3 is a graph showing the water flux of the amphiphilic terpolymer modified ultrafiltration membranes prepared in example 1 and comparative example 1 according to the present invention, wherein the concentration of the terpolymer is 0.0wt% corresponding to comparative example 1, and the concentration of the terpolymer is 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt% corresponding to example 1, wherein the monomer ratio m: n: k=1:3:1 in the amphiphilic terpolymer;
FIG. 4 is a graph showing the change of the protein retention rate of the amphiphilic terpolymer-modified ultrafiltration membrane prepared in example 1 and comparative example 1 according to the concentration of the amphiphilic terpolymer, wherein the concentration of the terpolymer is 0.0wt% corresponding to comparative example 1, and the concentration of the terpolymer is 0.5wt%, 1.0wt%, 1.5wt%, and 2.0wt% corresponding to example 1, wherein the monomer ratio m: n: k=1:3:1 in the amphiphilic terpolymer;
fig. 5 is a cross-sectional morphology diagram (left) and a surface morphology diagram (right) of an amphiphilic terpolymer modified ultrafiltration membrane prepared in example 1 of the invention after a protein entrapment experiment, wherein the concentration of the amphiphilic terpolymer is 1.5%, and the monomer ratio m: n: k=1:3:1
FIG. 6 is a schematic representation of the preparation of amphiphilic terpolymers of examples 3-4;
FIG. 7 is a graph showing the variation of contact angle of the amphiphilic terpolymer modified ultrafiltration membrane prepared in example 4 and comparative example 2 according to the concentration of the amphiphilic terpolymer, wherein the concentration of the terpolymer is 0.0wt% corresponding to comparative example 2, the concentration of the terpolymer is 0.75wt%, 1.0wt%, 1.25wt%, 1.5wt%, 1.75wt% corresponding to example 4, and the monomer ratio m: n: k=3:2:1 in the amphiphilic terpolymer;
FIG. 8 is a graph showing the water flux of the amphiphilic terpolymer modified ultrafiltration membranes prepared in example 4 and comparative example 2 according to the concentration of the amphiphilic terpolymer, wherein the concentration of the terpolymer is 0.0wt% corresponding to comparative example 2, the concentration of the terpolymer is 0.75wt%, 1.0wt%, 1.25wt%, 1.5wt%, 1.75wt% corresponding to example 4, and the monomer ratio m: n: k=3:2:1 in the amphiphilic terpolymer;
FIG. 9 is a graph showing the change of protein retention rate of the amphiphilic terpolymer-modified ultrafiltration membrane prepared in example 4 and comparative example 2 according to the concentration of the amphiphilic terpolymer, wherein the concentration of the terpolymer is 0.0wt% corresponding to comparative example 2, and the concentration of the terpolymer is 0.75wt%, 1.0wt%, 1.25wt%, 1.5wt%, 1.75wt% corresponding to example 4, and wherein the monomer ratio m: n: k=3: 2:1, a step of;
fig. 10 is a scanning electron microscope image of an amphiphilic terpolymer modified ultrafiltration membrane prepared in example 4 of the present invention, wherein the concentration of the amphiphilic terpolymer is 1.75%, and the monomer ratio m is n: 2:1.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Comparative example 1
Preparing a polyvinylidene fluoride film;
1.5g of polyvinylidene fluoride powder was added to 8.5g of DMAc and stirred at 80℃for 24 hours; then, the mixture is kept stand still for deaeration for 24 hours at the constant temperature of 80 ℃ to obtain the casting solution. Pouring the prepared casting film liquid on a clean glass plate, and scraping the film; stopping the scraped liquid film in air for 45s, and putting the liquid film into an ultra-pure water coagulation bath at 22 ℃ to be solidified into a film; finally, the ultrafiltration membrane which is detached from the glass plate is soaked in ultrapure water for 24 hours to eliminate residual DMAc solvent in the membrane, so as to obtain the polyvinylidene fluoride membrane (the concentration of the amphiphilic terpolymer is 0).
Example 1
Preparation of amphiphilic terpolymer and preparation of amphiphilic terpolymer modified ultrafiltration membrane:
preparation of amphiphilic terpolymer: as shown in the synthetic schematic diagram of the amphiphilic terpolymer shown in FIG. 1, firstly, 0.25g of AIBN is dissolved in 100ml of mixed solution A of tetrahydrofuran and methanol with the volume ratio of 10:1 under the protection of nitrogen, a mixed system is obtained after stirring and reacting for 6 hours, 1.25g of Acryloylmorpholine (ACMO) is added into the mixed system, stirring is carried out for 12 hours at 180 ℃ under the protection of nitrogen, then 3.4g of styrene is added into the solution, stirring is carried out for 10 hours at 200 ℃ under the protection of nitrogen, finally, 2.0g of betaine methacrylate (CBMA) is added into the mixed solution A, stirring is carried out for 16 hours at 240 ℃ under the protection of nitrogen, and the mixed system is poured into deionized water to precipitate; finally, vacuum drying the precipitate for 24 hours at 220 ℃ to obtain an amphiphilic terpolymer, wherein m is 10, n is 30, and k is 10;
preparing an amphiphilic terpolymer modified ultrafiltration membrane: blending 0.2g of amphiphilic terpolymer with 16.8g of DMAc to obtain a mixed solution B, wherein the concentration of the amphiphilic terpolymer is 1.0wt% (in addition, adjusting the content of the amphiphilic terpolymer, respectively preparing an amphiphilic terpolymer modified ultrafiltration membrane when the concentration of the amphiphilic terpolymer is 0.5wt%, 1.5wt% and 2 wt%), carrying out ultrasonic treatment until the amphiphilic terpolymer is completely dissolved, adding 3g of polyvinylidene fluoride into the mixed solution B, and stirring for 24 hours at 80 ℃; then, the mixture is kept stand still for deaeration for 24 hours at the constant temperature of 80 ℃ to obtain the casting solution. Pouring the prepared casting film liquid on a clean glass plate, and scraping the film; stopping the scraped liquid film in air for 45s, and putting the liquid film into an ultra-pure water coagulation bath at 22 ℃ to be solidified into a film; finally, the ultrafiltration membrane which is fallen off from the glass plate is placed in ultrapure water to be soaked for 48 hours to eliminate residual DMAc solvent in the membrane, and the amphiphilic terpolymer modified ultrafiltration membrane is obtained.
Example 2
Preparation of amphiphilic terpolymer and preparation of amphiphilic terpolymer modified ultrafiltration membrane:
preparation of amphiphilic terpolymer: as shown in the synthetic schematic diagram of the amphiphilic terpolymer shown in FIG. 1, firstly, 0.35g of AIBN is dissolved in 115ml of mixed solution A of tetrahydrofuran and methanol with the volume ratio of 10:1 under the protection of nitrogen, a mixed system is obtained after stirring and reacting for 8 hours, 1.55g of Acryloylmorpholine (ACMO) is added into the mixed system, stirring is carried out for 14 hours at 200 ℃ under the protection of nitrogen, then 3.9g of styrene is added into the solution, stirring is carried out for 12 hours at 210 ℃ under the protection of nitrogen, finally, 4.2g of betaine methacrylate (CBMA) is added into the mixed solution A, stirring is carried out for 18 hours at 260 ℃ under the protection of nitrogen, and the mixed system is poured into deionized water to precipitate; finally, vacuum drying the precipitate for 48 hours at 240 ℃ to obtain an amphiphilic terpolymer, wherein m is 10, n is 25, and k is 20;
preparing an amphiphilic terpolymer modified ultrafiltration membrane: blending 0.3g of amphiphilic terpolymer with 16.7g of DMAc to obtain a mixed solution B, wherein the concentration of the amphiphilic terpolymer is 1.5wt%, and adding 3g of polyvinylidene fluoride into the mixed solution B after ultrasonic treatment until the amphiphilic terpolymer is completely dissolved, and stirring for 28 hours at 90 ℃; then, the mixture is kept stand still and defoamed for 30 hours at the constant temperature of 90 ℃ to obtain the casting solution. Pouring the prepared casting film liquid on a clean glass plate, and scraping the film; stopping the scraped liquid film in air for 60s, and putting the liquid film into an ultra-pure water coagulation bath at 25 ℃ to be solidified into a film; finally, the ultrafiltration membrane which is fallen off from the glass plate is placed in ultrapure water to be soaked for 72 hours to eliminate residual DMAc solvent in the membrane, and the amphiphilic terpolymer modified ultrafiltration membrane is obtained.
Comparative example 2
Preparing a polyvinylidene fluoride film;
1.5g of polyvinylidene fluoride was added to.5 g of DMAc and stirred at 80℃for 24h; then, the mixture is kept stand still for deaeration for 24 hours at the constant temperature of 80 ℃ to obtain the casting solution. Pouring the prepared casting film liquid on a clean glass plate, and scraping the film; stopping the scraped liquid film in air for 60s, and putting the liquid film into an ultra-pure water coagulation bath at 25 ℃ to be solidified into a film; finally, the ultrafiltration membrane which is detached from the glass plate is soaked in ultrapure water for 24 hours to eliminate residual DMAc solvent in the membrane, so as to obtain the polyvinylidene fluoride membrane (the concentration of the amphiphilic terpolymer is 0).
Example 3
Preparation of amphiphilic terpolymer and preparation of amphiphilic terpolymer modified ultrafiltration membrane:
preparation of amphiphilic terpolymer: as shown in the synthetic schematic diagram of the amphiphilic terpolymer shown in FIG. 6, firstly, 0.16g of AIBN is dissolved in 120ml of mixed solution A of tetrahydrofuran and ethanol with the volume ratio of 10:1 under the protection of nitrogen, a mixed system is obtained after stirring reaction for 5 hours, 1.05g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) is added into the mixed solution A, stirring is carried out for 16 hours under the protection of nitrogen at 200 ℃, then 2.8g of Methyl Methacrylate (MMA) is added into the mixed solution A, stirring is carried out for 12 hours under the protection of nitrogen at 240 ℃, finally 1.8g of 2-hydroxyethyl acrylate is added into the mixed solution A, stirring is carried out for 13 hours under the protection of nitrogen at 260 ℃, and the mixed system is poured into deionized water to precipitate; finally, vacuum drying the precipitate for 24 hours at 280 ℃ to obtain an amphiphilic terpolymer, wherein m is 5, n is 3 and k is 15;
preparing an amphiphilic terpolymer modified ultrafiltration membrane: blending 0.25g of amphiphilic terpolymer with 17.25g of DMAc to obtain a mixed solution B, wherein the concentration of the amphiphilic terpolymer is 1.25wt% (in addition, adjusting the content of the amphiphilic terpolymer, respectively preparing an amphiphilic terpolymer modified ultrafiltration membrane when the concentration of the amphiphilic terpolymer is 0.75wt%, 1wt%, 1.5wt% and 1.75 wt%), carrying out ultrasonic treatment until the amphiphilic terpolymer is completely dissolved, adding 2.5g of polyvinylidene fluoride into the mixed solution B, and stirring for 30h at 100 ℃; then, the mixture is kept stand still and defoamed for 30 hours at the constant temperature of 100 ℃ to obtain the casting solution. Pouring the prepared casting film liquid on a clean glass plate, and scraping the film; stopping the scraped liquid film in air for 60s, and putting the liquid film into an ultra-pure water coagulation bath at 25 ℃ to be solidified into a film; finally, the ultrafiltration membrane which is fallen off from the glass plate is placed in ultrapure water to be soaked for 72 hours to eliminate residual DMAc solvent in the membrane, and the amphiphilic terpolymer modified ultrafiltration membrane is obtained.
Example 4
Preparation of amphiphilic terpolymer and preparation of amphiphilic terpolymer modified ultrafiltration membrane:
preparation of amphiphilic terpolymer: as shown in the synthetic schematic diagram of the amphiphilic terpolymer shown in FIG. 6, firstly, 0.12g of AIBN is dissolved in 110ml of mixed solution A of tetrahydrofuran and ethanol with the volume ratio of 10:1 under the protection of nitrogen, a mixed system is obtained after stirring reaction for 4 hours, 1.45g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) is added into the mixed solution A, stirring is carried out for 15 hours under the protection of nitrogen at 210 ℃, then 3.5g of Methyl Methacrylate (MMA) is added into the solution A, stirring is carried out for 13 hours under the protection of nitrogen at 250 ℃, finally 2.4g of 2-hydroxyethyl acrylate (HEM) is added into the mixed solution A, stirring is carried out for 15 hours under the protection of nitrogen at 280 ℃, and the mixed system is poured into deionized water to precipitate; finally, vacuum drying the precipitate for 24 hours at 300 ℃ to obtain an amphiphilic terpolymer, wherein m is 6, n is 4, and k is 2;
preparing an amphiphilic terpolymer modified ultrafiltration membrane: blending 0.35g of amphiphilic terpolymer with 16.85g of DMAc to obtain a mixed solution B, wherein the concentration of the amphiphilic terpolymer is 1.75wt% (in addition, adjusting the content of the amphiphilic terpolymer, respectively preparing an amphiphilic terpolymer modified ultrafiltration membrane when the concentration of the amphiphilic terpolymer is 0.75wt%, 1wt%, 1.5wt% and 1.75 wt%), carrying out ultrasonic treatment until the amphiphilic terpolymer is completely dissolved, adding 2.8g of polyvinylidene fluoride PVDF into the mixed solution B, and stirring for 28h at 90 ℃; then, standing and defoaming for 28 hours at the constant temperature of 90 ℃ to obtain the casting solution. Pouring the prepared casting film liquid on a clean glass plate, and scraping the film; stopping the scraped liquid film in the air for 50s, and putting the liquid film into an ultra-pure water coagulation bath at 20 ℃ to be solidified into a film; finally, the ultrafiltration membrane which is fallen off from the glass plate is placed in ultrapure water to be soaked for 60 hours to eliminate residual DMAc solvent in the membrane, and the amphiphilic terpolymer modified ultrafiltration membrane is obtained.
Test case
The morphology of the terpolymer modified ultrafiltration membrane was observed using a scanning electron microscope.
The contact angle test process is as follows: the water static contact angle of the film surface was measured by an antenna tester at room temperature. Ensuring the surface of the film to be dry before testing; the water droplet size for each test was 2 μl; five points were tested for each specimen and averaged.
The protein retention rate test process comprises the following steps: the membrane was tested for protein rejection by replacing deionized water in the ultrafilter cup with a Bovine Serum Albumin (BSA) solution. BSA was dissolved in phosphate buffered saline (PBS, ph=7.4) at a concentration of 1.0g/L, the pressure was set at 0.2MPa, the temperature was 25 ℃, and the test time was 1h. The calculation formula is shown in formula (2-4).
Wherein R is the protein retention (%);
C 0 -concentration of BSA in the original solution (mg/mL);
C 1 concentration of BSA in the filtrate (mg/mL).
The specific concentration of BSA is obtained by testing the absorbance at 280nm of an ultraviolet spectrophotometer, and substituting the absorbance into a formula (2-5) of the relation between the calibrated BSA concentration (C) and absorbance (A).
A＝0.51871C+0.00356(R 2 ＝0.9991) (2-5)
Wherein A is absorbance;
C-BSA concentration.
The water flux test process is as follows:
putting the sheared membrane into a self-made ultra-filtration cup, injecting deionized water, and filtering at 25deg.C with an effective area of 12.56cm 2 . Firstly, prepressing the membrane for more than 30 minutes under the pressure of 0.2MPa until the pore diameter of the membrane becomes solid, and stabilizing the flow passing through the membrane; the volume of water passing through the membrane at a pressure of 0.2MPa in 10 minutes was then tested. Flux of water (J) w ) The calculation formula is shown in formula (2-3).
In J w -water flux (L/(m) 2 h))；
V-the volume of pure water (L) permeated;
a-effective Membrane area during filtration (m 2 )；
Δt filtration time (h)
FIG. 2 is a plot of contact angle of the amphiphilic terpolymer ultrafiltration membranes prepared in example 1 and comparative example 1 as a function of additive terpolymer concentration (terpolymer concentration 0, 0.5wt%, 1wt%, 1.5wt%, 2 wt%) respectively, where m: n: k=1:3:1; as can be seen from fig. 2, the water contact angle decreases with increasing copolymer concentration, and the copolymer modified ultrafiltration membrane has better hydrophilicity. In FIG. 2, the terpolymer concentration of 0 is comparative example 1.
Fig. 3 is a graph showing the change of water flux of the amphiphilic terpolymer modified ultrafiltration membrane prepared in example 1 and comparative example 1 along with the concentration of the amphiphilic terpolymer (the concentration of the amphiphilic terpolymer is 0, 0.5wt%, 1wt%, 1.5wt%, and 2 wt%) respectively, wherein m: n: k=1:3:1 in the amphiphilic terpolymer, and as the concentration of the amphiphilic terpolymer increases, the water flux gradually increases, which indicates that the amphiphilic terpolymer has a pore-forming effect and can improve the porosity.
FIG. 4 is a graph showing the change of the protein retention rate of the amphiphilic terpolymer-modified ultrafiltration membrane prepared in example 1 and comparative example 1 according to the concentration of the amphiphilic terpolymer (the concentration of the amphiphilic terpolymer is 0, 0.5wt%, 1wt%, 1.5wt%, 2wt%, respectively), wherein m: n: k=1:3:1; as can be seen from fig. 4, as the ternary polymerization system increases, the protein rejection rate increases, which illustrates that the copolymer has the function of preparing nano-pore channels, can reject protein impurities, and the modified membrane can be applied to water treatment.
Fig. 5 is a morphology diagram of the amphiphilic terpolymer modified ultrafiltration membrane prepared in example 1, wherein the concentration of the amphiphilic terpolymer is 1.5%, and m: n: k=1:3:1, wherein the left graph in fig. 5 is a surface morphology diagram of a section view of the ultrafiltration membrane. As can be seen from fig. 5, the nano-pore structure produced by the terpolymer ensures the high flux during the application of the ultrafiltration membrane. From the right graph of fig. 5, it can be seen that the appearance of the ultrafiltration membrane surface is smooth after the protein interception experiment, and the ultrafiltration membrane surface does not adsorb any protein impurities, thus proving that the ultrafiltration membrane modification effect is successful.
FIG. 7 is a graph showing the variation of contact angle of the amphiphilic terpolymer modified ultrafiltration membrane prepared in example 4 and comparative example 2 with the concentration of amphiphilic terpolymer (concentration of amphiphilic terpolymer is 0, 0.75wt%, 1wt%, 1.25wt%, 1.5wt%, 1.75wt%, respectively), wherein m: n: k=3:2:1; as can be seen from fig. 7, the water contact angle decreases with increasing copolymer concentration, and the copolymer modified ultrafiltration membrane has better hydrophilicity. In FIG. 7, the terpolymer concentration of 0 is comparative example 2.
FIG. 8 is a graph showing the water flux of the amphiphilic terpolymer modified ultrafiltration membranes prepared in example 4 and comparative example 2 as a function of the concentration of the amphiphilic terpolymer (the concentration of the amphiphilic terpolymer is 0, 0.75wt%, 1wt%, 1.25wt%, 1.5wt%, 1.75wt%, respectively), wherein m: n: k=3:2:1; from fig. 8, it can be seen that the amphiphilic terpolymer has a pore-forming effect, and can improve the porosity.
FIG. 9 is a graph showing the protein retention rate of the amphiphilic terpolymer modified ultrafiltration membranes prepared in example 4 and comparative example 2 as a function of additive amphiphilic terpolymer concentration (amphiphilic terpolymer concentration 0, 0.75wt%, 1wt%, 1.25wt%, 1.5wt%, 1.75wt%, respectively), wherein m: n: k=3:2:1; as can be seen from fig. 9, as the ternary polymerization system increases, the protein rejection rate increases, which illustrates that the copolymer has the function of preparing nano-pore channels, can reject protein impurities, and the modified membrane can be applied to water treatment.
Fig. 10 is a scanning electron microscope image of the surface of the amphiphilic terpolymer modified ultrafiltration membrane prepared in example 4, wherein the amphiphilic terpolymer concentration is 1.75%, m: n: k=3:2:1. From fig. 10, the nanopore structure can be seen, demonstrating that the terpolymer has a nanopore effect.
The embodiments of the present invention have been described above by way of example. However, the scope of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art, which fall within the spirit and principles of the present invention, are intended to be included within the scope of the present invention.
Claims (10)
1. An amphiphilic terpolymer characterized by having the structure of formula I:
wherein R is 1 ～R 9 Identical or different, independently of one another, from H, -C 1-12 An alkyl group;
R 10 、R 11 identical or different, independently of one another, from H, -C 1-12 alkylene-SO 3 H, or R 10 、R 11 Forms a structure with the N atom as shown in the following formula II:
R 12 selected from phenyl or-C (=O) O-C 1-12 An alkyl group;
R 13 selected from-OH or-N + (C 1-12 Alkyl group 2 -C 1-12 alkylene-COO - ；
m is an integer of 2 to 35, and n is an integer of 2 to 35; k is an integer of 2 to 35; p is an integer of 1 to 12.
2. The amphiphilic terpolymer according to claim 1, wherein R 1 ～R 9 Identical or different, independently of one another, from H, -C 1-6 An alkyl group;
R 10 、R 11 identical or different, independently of one another, from H, -C 1-6 alkylene-SO 3 H, or R 10 、R 11 Form a structure shown in a formula II together with an N atom;
R 12 selected from phenyl or-C (=O) O-C 1-6 An alkyl group;
R 13 selected from-OH or-N + (C 1-6 Alkyl group 2 -C 1-6 alkylene-COO - ；
p is an integer of 1 to 6.
3. The amphiphilic terpolymer according to claim 1 or 2, wherein R 1 ～R 9 Are all H, or R 1 ～R 8 Are all H, R 9 Is methyl;
R 10 、R 11 identical or different, independently of one another, from H, -C 4 alkylene-SO 3 H, or R 10 、R 11 Form a structure shown in a formula II together with an N atom;
R 12 selected from phenyl or-C (=O) O-CH 3 ；
R 13 Selected from-OH or-N + (CH 3 ) 2 -C 2 H 4 -COO - The method comprises the steps of carrying out a first treatment on the surface of the p is 2.
Preferably, the amphiphilic terpolymer has a structure as shown in formula III or formula IV below;
wherein in the formula III, m is an integer of 2-35, and n is an integer of 2-35; k is an integer of 2 to 35;
in the formula IV, m is an integer of 3-25, and n is an integer of 3-25; k is an integer of 3 to 25.
4. A method for preparing an amphiphilic terpolymer according to any one of claims 1 to 3, comprising the steps of:
under the protection of inert gas, sequentially adding an initiator, a compound shown in a formula A, a compound shown in a formula B and a compound shown in a formula C into an organic solvent for reaction to prepare an amphiphilic terpolymer shown in a formula I;
wherein R is 1 ～R 13 Having the meaning as above.
5. The method of claim 4, wherein the initiator is azobisisobutyronitrile;
the organic solvent is selected from at least one of tetrahydrofuran, methanol and ethanol.
6. The method according to claim 4 or 5, wherein the mass-to-volume ratio of the compound represented by formula A, the compound represented by formula B, the compound represented by formula C, the initiator and the organic solvent is (1-30) g, (6-60) g, (5-50) g:1g, (200-1500) mL, preferably (4-20) g, (10-40) g, (6-30) g:1g (300-1200) mL.
7. The method according to any one of claims 4 to 6, wherein the compound of formula a is Acryloylmorpholine (ACMO) or 2-acrylamido-2-methylpropanesulfonic Acid (AMPS).
Preferably, the compound of formula B is styrene or methyl methacrylate.
Preferably, the compound of formula C is a carboxylic acid betaine methacrylate (CBMA) or 2-hydroxyethyl acrylate (HEA);
wherein the carboxylic acid betaine methacrylate has the following structural formula:
preferably, the temperature of the reaction is 140 to 350 ℃.
8. An amphiphilic terpolymer modified ultrafiltration membrane, characterized in that the ultrafiltration membrane comprises the amphiphilic terpolymer of any one of claims 1-3.
Preferably, the ultrafiltration membrane is a polyvinylidene fluoride ultrafiltration membrane.
9. The method for preparing the amphiphilic terpolymer modified ultrafiltration membrane according to claim 8, wherein the method comprises the following steps:
s1: mixing an amphiphilic terpolymer and polyvinylidene fluoride in a solvent to prepare a casting solution;
s2: and (3) solidifying the membrane casting solution in the step (S1) to form a membrane, and preparing the amphiphilic terpolymer modified ultrafiltration membrane.
Preferably, in step S1, the mass ratio of the amphiphilic terpolymer, polyvinylidene fluoride and solvent is 0.02-2:1:3-50, preferably 0.04-1:1:4-30.
Preferably, in step S1, the solvent is N, N-dimethylacetamide (DMAc).
Preferably, in step S1, the temperature of mixing is 30-120℃and the time of mixing is 10-50 hours.
10. Use of the amphiphilic terpolymer of any one of claims 1-3 or the amphiphilic terpolymer modified ultrafiltration membrane of claim 8 in the field of water treatment.
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