CN113980241B - Purifying method and application of macromolecular surface modifier - Google Patents
Purifying method and application of macromolecular surface modifier Download PDFInfo
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- CN113980241B CN113980241B CN202111189176.2A CN202111189176A CN113980241B CN 113980241 B CN113980241 B CN 113980241B CN 202111189176 A CN202111189176 A CN 202111189176A CN 113980241 B CN113980241 B CN 113980241B
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- surface modifier
- macromolecular surface
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- membrane
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- 239000003607 modifier Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000004090 dissolution Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005191 phase separation Methods 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 238000009295 crossflow filtration Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 17
- 238000000746 purification Methods 0.000 abstract description 8
- 239000012982 microporous membrane Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- -1 acrylic ester Chemical class 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- IRTFYNWQADJCSC-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,5-undecafluoropentan-1-ol Chemical compound OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F IRTFYNWQADJCSC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- ANLVEXKNRYNLDH-UHFFFAOYSA-N 1,3-dioxonan-2-one Chemical compound O=C1OCCCCCCO1 ANLVEXKNRYNLDH-UHFFFAOYSA-N 0.000 description 1
- PBKFPDHTSQEJEJ-UHFFFAOYSA-N 2-benzofuran-1,3-dione;hexane-1,6-diol Chemical compound OCCCCCCO.C1=CC=C2C(=O)OC(=O)C2=C1 PBKFPDHTSQEJEJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920009405 Polyvinylidenefluoride (PVDF) Film Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/82—Post-polymerisation treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- 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
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a purification method and application of a macromolecular surface modifier. Purification and application include: (1) dissolution of macromolecular surface modifier; (2) purification of macromolecular surface modifier; (3) blending the macromolecular surface modifier with a matrix material; (4) preparation of modified materials. The purified macromolecular surface modifier and the matrix material have better solubility and transparency, and the material added with the macromolecular surface modifier can obtain corresponding surface energy change and has better stability and reusability.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a purification method and application of a macromolecular surface modifier.
Background
The macromolecular surface modifier is a polymer with molecular weight more than 1000, and has the advantages of multiple structure, controllable molecular weight, various functional groups, functional diversity and the like compared with the micromolecular modifier. In recent years, as macromolecular surface modifiers have potential use value in industry and commerce, as an industrially important raw material, they are increasingly favored by researchers and are being studied extensively, so that macromolecular modifiers of different types and structures are developed. The macromolecular surface modifier is applied to matrix materials which do not have specific surface hydrophobicity, oleophobicity, hydrophilicity and oleophilicity, and the surface of the matrix materials is modified to obtain corresponding modified materials.
In the prior art, common polymerization modes include ring-opening polymerization, group Transfer Polymerization (GTP), atom Transfer Radical Polymerization (ATRP) and reversible addition fragmentation chain transfer polymerization (RAFT). Invention CN103131079B discloses a microporous membrane and a battery separator containing the microporous membrane. The microporous membrane takes polyolefin as a main raw material, and macromolecular surface modifier is dispersed in the microporous membrane; one end of the macromolecular surface modifier is provided with a polyolefin chain segment with a parent matrix, and the other end is provided with a block or a graft chain segment of polyester or polyether with an electrolyte. The invention CN1970649B discloses a macromolecular surface modifier for ceramic nano surface modification, which is an oligomer with a molecular weight of 3000-9000, and is prepared by free radical initiated copolymerization of (methyl) acrylic ester, vinyl siloxane and (methyl) acrylic acid, maleic anhydride, styrene, vinyl acetate, acrylonitrile and other monomers in an organic solvent. The invention CN101508754B discloses surface modified sericite, which is sericite powder obtained by coating and modifying sericite by a liquid phase method through a terpolymer, and the application of the surface modified sericite powder is the application of the surface modified sericite powder serving as a modifier in the preparation of rubber/sericite composite materials. The macromolecular surface modifier related to the three inventions is applied to the respective fields, and the purification and the use of the macromolecular surface modifier in the field of separation membranes are not related.
Because the macromolecular surface modifier prepared by different methods all involve the problem of subsequent purification, including cutting of different molecular weights, removal of insoluble components (including raw materials, polymers, byproducts and the like), and the product performance in the subsequent use process can be ensured only by purifying the macromolecular surface modifier through a proper post-treatment process. Therefore, aiming at the common problems in the technical fields of macromolecular surface modifier purification and post-treatment, a high-efficiency and simple process technology is needed to solve.
Disclosure of Invention
In view of the foregoing, it is desirable to provide a method for purifying macromolecular surface modifiers and applications thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for purifying a macromolecular surface modifier, comprising the steps of:
s1: dissolving a macromolecular surface modifier in a solvent;
s2: filtering the dissolved macromolecular surface modifier by a membrane to remove insoluble impurities, thereby obtaining a purified macromolecular surface modifier solution;
the adding ratio of the macromolecular surface modifier to the solvent is 1:3 to 13.
Further, the temperature of the dissolution operation in S1 is 25-80 ℃.
Preferably, the temperature of the dissolution operation of S1 is 40-60 ℃.
Further, the solvent of S1 includes at least one of dimethylformamide, dimethylacetamide, diethyl ether, dioxane, tetrahydrofuran, acetone, dichloromethane, dimethyl sulfoxide, methanol, ethanol, and water.
Further, the membrane filtration mode described in S2 includes dead-end filtration and cross-flow filtration.
Further, the pore diameter of the filtering membrane of the S2 is 0.1-1 μm.
The purified macromolecular surface modifier is applied to preparing modified materials such as medical care materials, medical instruments, membrane materials and the like.
The method for preparing the modified material by adopting the purified macromolecular surface modifier comprises the following steps:
s11: mixing the purified macromolecular surface modifier solution with a matrix material;
s21: preparing the mixed solution of the S11 to obtain a modified material;
the mass percentage of the mixture of the macromolecular surface modifier solution and the matrix material is 0.1-50%.
Preferably, the mass percentage of the macromolecular surface modifier mixed with the matrix material is 5% -15%.
Further, the matrix material of S11 includes at least one of polysulfones, polyamides, polyolefins, polyhaloolefins, polycarbonates, polyacrylonitriles, cellulose acetate, and polyethersulfones.
Further, the method for preparing the modified material by the mixed solution in S21 comprises a thermally induced phase method, a non-solvent induced phase separation method, an evaporation induced phase separation method and an injection extrusion method.
As some of these embodiments, the macromolecular surface modifier comprises the following structure (1): g- [ B-A ]] n -B-G(1)
Wherein:
a is a hydroxyl-containing matrix segment;
b is a segment containing isocyanate groups;
g is a surface active group;
n is an integer of 1 to 10.
Further, the hydroxyl-containing matrix segment comprises poly (ethylene hydroxy-terminated adipate); diallyl phthalate; hydroxyl-terminated polybutadiene; poly (diethylene glycol) adipic acid; poly (hexamethylene carbonate) diol; poly (ethylene-co-1, 2-butene) diol; hydroxyl-terminated polytetramethylene ether; hydroxyl-terminated hydrogenated polybutadiene; 1, 6-hexanediol phthalic anhydride polyester polyol; one or more of poly (2, 2-dimethyl-1, 3-propyl carbonate).
Further, the isocyanate group-containing segment includes isophorone diisocyanate; tetramethyl xylylene diisocyanate; dicyclohexylmethane diisocyanate; hexamethylene diisocyanate; one or more of the isophorone diisocyanate.
Further, the surface active groups include C1-C15 alkyl monools; a C1-C15 fluorinated alkyl monoalcohol; a C1-C15 alkyl polyol; a C1-C15 fluorinated alkyl polyol; C1-C15 alkylamines; one or more of C1-C15 fluorinated alkylamines.
Preferably, in the macromolecular surface modifier, n is 1 or 2.
Further, the macromolecular surface modifier has a molecular weight of 1000-10000.
Further, the molecular weight of the hydroxyl group-containing matrix segment A is between 1000 and 3500 daltons.
Further, the molecular weight of the surface active group G is in the range of 100-1500 daltons.
As some examples thereof, the macromolecular surface modifier may be synthesized by the following method:
s01, respectively dissolving a hydroxyl-containing basal body chain segment A, an isocyanate-containing chain segment B and a catalyst in a solvent;
s02, mixing and reacting a solution of a hydroxyl-containing matrix segment A, an isocyanate-containing segment B and a catalyst in a nitrogen atmosphere under anhydrous conditions at a certain temperature;
s03, adding a surface active group G into the mixed material in the S02 under the nitrogen atmosphere, mixing and reacting.
Further, the catalyst in S01 is an organometallic catalyst.
Preferably, the metal catalyst comprises one of an organotin catalyst, an organobismuth catalyst and an organozinc catalyst.
Further, the solvent described in S01 is an organic high boiling point solvent.
Preferably, the organic high boiling point solvent comprises one of dimethylacetamide, dimethylsulfoxide, toluene, dimethylformamide and chlorobenzene.
Further, the temperature of S02 is 50-80 ℃. When the temperature is too low, the reaction is incomplete, and when the temperature is too high, the reaction byproducts are increased, and the polymers are increased.
Further, the mixing time of A, B and the catalyst described in S02 is 0.1 to 1 hour.
Further, the reaction time of S02 is 5-15 hours.
Further preferably, the time of the reaction of S02 is 5 to 8 hours. When the temperature is too low, the reaction is incomplete, and when the temperature is too high, the byproducts are increased and the polymers are increased.
Further, the mixing time of the mixture of S03 and G is 0.1-1 hour.
Further, the temperature at which S03 is added to the surface active group G is 30 to 60 ℃.
Further, the mixing reaction time of S03 is 12-20 hours.
Further, the molar (mass) ratio of the hydroxyl group-containing base segment A, the isocyanate group-containing segment B, and the surface active group G was 1: 1-3:1-6.
The content of the catalyst is 1-10wt% of the hydroxyl base chain segment A.
Further, the method also comprises the steps of adding a poor solvent into the materials after the S03 reaction to precipitate a product, filtering, cleaning and drying to obtain the product.
Further, the poor solvent comprises one or more of water, methanol, ethanol and acetonitrile.
Further, the cleaning agent comprises one or more of tetrahydrofuran, methanol, water, ethanol, ethylenediamine tetraacetic acid sodium salt, acetonitrile and acetone.
The beneficial effects of the invention are as follows:
(1) The purification method of the macromolecular surface modifier provided by the invention can effectively and selectively remove the polymer, the high polymer and insoluble components in the crude product, and retain the main components of the oligomeric macromolecular surface modifier;
(2) The purified macromolecular surface modifier provided by the invention ensures that the obtained modified material has better solubility and transparency and better stability and reusability when being correspondingly modified.
Drawings
FIG. 1 is a graph of a modified Polyethersulfone (PES) film contact angle test;
FIG. 2 is a graph of a polyethersulfone film contact angle test;
FIG. 3 is a graph showing a contact angle test of a modified polyvinylidene fluoride (PVDF) film;
fig. 4 is a graph showing a contact angle test of polyvinylidene fluoride film.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be further clearly and completely described in the following in conjunction with the embodiments of the present invention. It should be noted that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Macromolecular surface modifier:
(1) Synthesizing a macromolecular surface modifier A:
all containers for synthesizing macromolecular surface modifiers were thoroughly dried at 110 ℃. 72mmol of hydroxyl-terminated poly (2, 2-dimethyl-1, 3-propyl carbonate) was added to a 1000ml glass dry three-neck flask, and the raw materials in the vessel were thoroughly introduced with ultra-pure nitrogen gas to dry and remove water overnight. 525ml of dimethylacetamide are measured with a 1000ml measuring cylinder, sealed with a rubber stopper and the solvent is pushed in with ultra-pure nitrogen. Dimethylacetamide was pushed into a three-necked flask with a double-ended needle and was miscible with hydroxy-terminated poly (2, 2-dimethyl-1, 3-propyl carbonate) and stirred well. The temperature is kept between 65 and 70 ℃ during stirring. To a 250ml glass-dry three-necked flask was added 151mmol of isophorone diisocyanate. 150ml of dimethylacetamide was measured with a 250ml measuring cylinder, sealed with a rubber stopper and the solvent was pushed with ultra pure nitrogen. Dimethylacetamide was pushed into a three-necked flask with a double-ended needle and was miscible with isophorone diisocyanate and stirred uniformly. To a 50ml glass dry round bottom flask was added 8g (10% w/w hydroxyl terminated starting weight) organotin reagent, 26ml dimethylacetamide was measured with a 50ml measuring cylinder, sealed with a rubber stopper and the solvent was purged with ultra pure nitrogen. Dimethylacetamide was pushed into a round bottom flask with a double-ended needle and was miscible with the organotin reagent and stirred well. The solution in which isophorone diisocyanate was dissolved was pushed through a double-ended needle with nitrogen into the solution in which hydroxyl-terminated poly (2, 2-dimethyl-1, 3-propyl carbonate) was dissolved, followed immediately by the addition of the solution in which organotin reagent was dissolved. The mixture was stirred uniformly and maintained at 70℃for 5 hours.
180mmol of perfluoro pentanol was added to another 50ml dry round bottom flask, sealed with a rubber stopper and the reagent pushed with ultra pure nitrogen. To the above mixture system was added perfluoro pentanol by double-ended needle, and the mixture system was kept uniformly stirred for 18 hours at 45 ℃. Finally synthesizing the macromolecular surface modifier A. The system was cooled to room temperature and was a milky white turbid liquid. Distilled water was added to the turbid liquid to produce a precipitate, and the precipitate was washed with an isopropanol/ethylenediamine tetraacetic acid solution to remove unreacted raw materials, catalyst and solvent. And gradually heating up and vacuum drying in an oven at 40-120 ℃. The final product is obtained.
The macromolecular surface modifier A has the structural formula:
(2) Macromolecular surface modifier B: the macromolecular surface modifier was obtained according to the example radical initiated polymerization process preparation method in invention CN 1970649B.
Example 1
And (3) placing the raw material of the macromolecular surface modifier A into an oven at 40-120 ℃ to gradually heat and dry in vacuum for 12 hours. Weighing 100g of dried macromolecular surface modifier according to the weight ratio of 1 (macromolecular surface modifier): 10 (dioxane): 1 (dimethylformamide) and the three components are fully stirred and mixed at 60 ℃ to be uniformly dissolved, and the mixture is kept for 12 hours.
The homogeneous solution was passed through a 0.22 μm organic microporous filter membrane by dead-end filtration. And collecting filtrate, namely the purified macromolecular surface modifier solution.
Example 2
And (3) placing the raw material of the macromolecular surface modifier A into an oven at 40-120 ℃ to gradually heat and dry in vacuum for 6 hours. Weighing 100g of dried macromolecular surface modifier according to the weight ratio of 1 (macromolecular surface modifier) to 5 (acetone): 1 (dichloromethane) and the three components are fully stirred and mixed at 40 ℃ to be uniformly dissolved, and the mixture is kept for 6 hours.
The homogeneous solution was passed through a 0.45 μm organic microporous filter by dead-end filtration. And collecting filtrate, namely the purified macromolecular surface modifier solution.
Example 3
And (3) placing the raw material of the macromolecular surface modifier B into an oven at 40-120 ℃ to gradually heat up and dry in vacuum for 10 hours. Weighing 100g of dried macromolecular surface modifier according to the weight ratio of 1 (macromolecular surface modifier): 4 (dimethylacetamide): 1 (methanol) and mixing the three components, fully stirring and mixing at 60 ℃ to dissolve uniformly, and keeping for 12 hours.
The homogeneous solution was filtered through a 200nm ceramic membrane by cross-flow filtration. And collecting filtrate, namely the purified macromolecular surface modifier solution.
Example 4
And (3) placing the raw material of the macromolecular surface modifier B into an oven at 40-120 ℃ to gradually heat and dry in vacuum for 4 hours. 100g of dried macromolecular surface modifier is weighed according to the weight ratio of 1 (macromolecular surface modifier) to 2.5 (diethyl ether): 0.5 (tetrahydrofuran) and the three components are mixed, fully stirred and uniformly dissolved at 30 ℃ and kept for 10 hours.
The homogeneous solution was filtered through a 500nm ceramic membrane by cross-flow filtration. And collecting filtrate, namely the purified macromolecular surface modifier solution.
Example 5
And (3) placing the raw material of the macromolecular surface modifier B into an oven at 40-120 ℃ to gradually heat up and dry in vacuum for 3 hours. Weighing 100g of dried macromolecular surface modifier according to the weight ratio of 1 (macromolecular surface modifier) to 3 (ethanol): 3 (water) mixing the three components, fully stirring and mixing at 50 ℃ to dissolve uniformly, and keeping for 12 hours.
The homogeneous solution was filtered through a 200nm ceramic membrane by cross-flow filtration. And collecting filtrate, namely the purified macromolecular surface modifier solution.
Example 6
The macromolecular surface modifier solution purified in example 1 was mixed with other matrix materials according to 1 (polyethersulfone): 1 (PVP): 1 (macromolecular surface modifier solution): 6 (dimethylacetamide): 1 (acetone) and is fully stirred and mixed at 45 ℃ to be dissolved uniformly, and the mixture is kept for 12 hours.
After stirring and dissolving uniformly, stopping stirring and standing for 6 hours. The organic microporous membrane is prepared by adopting a non-solvent induced phase separation method and is marked as microporous membrane A1.
Example 7
The macromolecular surface modifier solution purified in example 2 was mixed with other matrix materials according to 1 (polyethersulfone): 1 (PVP): 1 (macromolecular surface modifier solution): 6 (dimethylacetamide): 1 (acetone) and is fully stirred and mixed at 45 ℃ to be dissolved uniformly, and the mixture is kept for 12 hours.
After stirring and dissolving uniformly, stopping stirring and standing for 6 hours. The non-solvent induced phase separation method is adopted to prepare the organic microporous membrane, and the microporous membrane is marked as microporous membrane A2.
Example 8
The macromolecular surface modifier solution purified in example 3 was mixed with other matrix materials according to 1 (polyvinylidene fluoride): 1.5 (PVP): 0.5 (macromolecular surface modifier solution): 6.5 (dimethylacetamide): 0.5 (dioxane) and fully stirring at 60 ℃ to uniformly dissolve, and keeping for 12 hours.
After stirring and dissolving uniformly, stopping stirring and standing for 6 hours. The organic microporous membrane is prepared by adopting a non-solvent induced phase separation method and is marked as microporous membrane B1.
Example 9
The macromolecular surface modifier solution purified in example 4 was mixed with other matrix materials according to 1 (polyvinylidene fluoride): 1 (PVP): 1 (macromolecular surface modifier solution): 6 (dimethylacetamide): 1 (dioxane), and fully stirring and uniformly dissolving at 60 ℃ and keeping for 12 hours.
After stirring and dissolving uniformly, stopping stirring and standing for 6 hours. The organic microporous membrane is prepared by adopting a non-solvent induced phase separation method and is marked as microporous membrane B2.
Example 10
The non-purified macromolecular surfactant is selected, and the modified materials prepared according to the preparation of the examples 6 and 8 are respectively marked as A0B 0 in sequence under other conditions; meanwhile, PES film and PVDF film without macromolecular surface modifier are prepared, modified materials prepared according to the other conditions of examples 7 and 9 are marked as A3 and B3 respectively, and contact angle tests are carried out, and the results are as follows:
table 1 experimental group
| Numbering device | A1 | A2 | B1 | B2 |
| Angle/° | 99.1 | 90.6 | 73.5 | 74.1 |
Table 2 control group
| Numbering device | A0 | A3 | B0 | B3 |
| Angle/° | 94.1 | 66.6 | 72.2 | 71.8 |
Example 11
The separation membrane A1 modified by the purified modifier, the separation membrane A0 modified by the unpurified modifier and the separation membrane A3 not modified are respectively selected for carrying out A1 g/L BSA solution membrane flux test (1 Bar), and then are soaked and washed for 3 hours by 0.3mol/L sodium hydroxide, so that the flux recovery condition is tested. The results are shown in the following table:
table 3 membrane flux test data
The small knot: after the purified macromolecular surface modifier is added into the membrane material, the membrane material has better anti-pollution capability and cleaning regeneration capability compared with the membrane material which is not modified to obtain the corresponding hydrophobic (or hydrophilic) performance; although the unpurified macromolecular modifier may achieve a similar effect, the presence of impurities may result in a lower porosity and lower flux of the membrane material.
Claims (5)
1. The preparation method of the modified material is characterized by comprising the following steps:
a method for purifying a macromolecular surface modifier, wherein the macromolecular surface modifier has the structural formula:
；
the method comprises the following steps:
s1: dissolving a macromolecular surface modifier in a solvent;
s2: filtering the dissolved macromolecular surface modifier by a membrane to remove insoluble impurities, thereby obtaining a purified macromolecular surface modifier solution;
the solvent in S1 is a mixture of dioxane and dimethylformamide; the weight ratio of the macromolecular surface modifier is that dioxane: dimethylformamide=1: 10:1,
mixing the purified macromolecular surface modifier solution with polyethersulfone, PVP, dimethylacetamide and acetone according to the following ratio of 1:1:1:6:1, fully stirring and uniformly dissolving at 45 ℃ for 12 hours, stopping stirring after uniformly stirring and dissolving, and standing for 6 hours, thus obtaining the modified material.
2. The method for producing a modified material according to claim 1, wherein the temperature of the dissolution operation of S1 is 25 to 80 ℃.
3. The method for preparing a modified material according to claim 1, wherein the membrane filtration mode of S2 comprises dead-end filtration and cross-flow filtration.
4. The method for producing a modified material according to claim 1, wherein the pore size of the filtration membrane in S2 is 0.1 to 1. Mu.m.
5. The method for preparing a modified material according to claim 1, wherein the method for preparing the modified material from the mixed solution comprises a thermally induced phase method, a non-solvent induced phase separation method, an evaporation induced phase separation method, and an injection extrusion method.
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