Source: https://patents.google.com/patent/CN103657429B/en
Timestamp: 2020-02-17 09:05:50
Document Index: 273725587

Matched Legal Cases: ['art～5', 'art～50', 'art～60', 'art～5', 'art～50', 'art～60']

CN103657429B - A kind of method without the cationic finishing of supporter porous polymeric membrane for separation of heat cure - Google Patents
A kind of method without the cationic finishing of supporter porous polymeric membrane for separation of heat cure Download PDF
CN103657429B
CN103657429B CN201310556653.3A CN201310556653A CN103657429B CN 103657429 B CN103657429 B CN 103657429B CN 201310556653 A CN201310556653 A CN 201310556653A CN 103657429 B CN103657429 B CN 103657429B
CN201310556653.3A
CN103657429A (en
2013-11-08 Application filed by 江南大学 filed Critical 江南大学
2013-11-08 Priority to CN201310556653.3A priority Critical patent/CN103657429B/en
2014-03-26 Publication of CN103657429A publication Critical patent/CN103657429A/en
2016-05-04 Publication of CN103657429B publication Critical patent/CN103657429B/en
The present invention relates to a kind of method with heat cure, to carrying out finishing without supporter porous polymeric membrane for separation, give film surface with cationic polymer layer, improve the permeation flux of film and process and contain the aqueous solution such as particulate and micelle or the suspension cation group to repulsive interaction. Its feature comprises the following steps: by the casting solution configuring knifing on carrying basement membrane, through coagulating bath film forming, wash, peel off, form without supporter porous polymeric membrane for separation; Film is immersed after the cationic finishing solution by thermal initiator, thermosetting cationic components, auxiliary agent and solvent composition, through being heating and curing, form cationic finishing type without supporter porous polymeric membrane for separation. The permanent crosslinked decorative layer the present invention relates to can in use not ooze out, and pollutes processed product, can not cause damage to the strand of polymeric membrane, keeps the original performance of membrane material.
A kind of method without the cationic finishing of supporter porous polymeric membrane for separation of heat cure
The method without the cationic finishing of supporter porous polymeric membrane for separation of heat cure, belongs to macromolecular materialTechnical field.
High molecular polymer porous membrane belongs to hydrophobic material mostly, generally need modify its surface, improvement membrane materialSurface characteristic, the requirement separating to adapt to different material.
Conventionally adopt Physical and two kinds of method of modifying of chemical method, Physical is in the time of masking, to sneak into hydrophilic material, as poly-second twoAlcohol (PEG), N, N-dimethyl pyrrolidone (PVP) etc. Prepared film is owing to being physical blend, in useHydrophilic material can constantly ooze out, and causes the liquid that sees through that film separates to produce the fingers such as total carbon (TOC) and content of organics (COD)Mark defectively, cause sanitation performance not up to standard. While, the aperture of film can change along with hydrophilic material constantly oozes out,Hydrophilicity can reduce. Chemical method refers to macromolecule polymer material by the method for chemical reaction, at high molecular polymer chainUpper grafting hydrophilic radical, the hydrophily of giving film, as sulfonation method, plasma method and irradiation method etc. The shortcoming of these methods existsIn the time that macromolecular chain is carried out to grafting, also can cause damage to strand, affect its performance, and these methods are to graftingThe kind limitation of functional group is stronger.
The present invention is based on porous membrane and modify with the film surface that separated liquid electrically mates, give respectively film permanent hydrophilicPerformance, surperficial cationic characteristic, can improve permeability of the membrane can and the resistance tocrocking of film to the different charge characteristic aqueous solution and butThe performances such as bacterium property.
The object of the invention is to research and develop a kind of method of heat cure, repair carrying out surface without supporter porous polymeric membrane for separationDecorations, give film surface with cationic polymer layer, improve the permeation flux of film and processing and contain cation group is had to repulsionThe aqueous solution such as particulate and micelle or the suspension of effect.
According to technical scheme provided by the invention, its component is mark meter by weight, and the casting solution configuring is scraped on carrying basement membraneFilm, through coagulating bath film forming and washing step, peels off porous polymer membrane and carrying basement membrane, forms high without supporter porousMolecular separation membrane; Remove after contained solvent, non-solvent and additive through washing, immerse by thermal initiator, thermosetting cation groupPoint, the cationic finishing solution of auxiliary agent and solvent composition; To soak through cationic finishing solution without supportBody porous polymeric membrane for separation is heating and curing, and makes thermosetting cationic components solidify to form the cationic finishing coat of bridging property,Clean through water, wash away residual organic matter; Through heated-air drying, obtain having cationic finishing coat without supporter porousPolymeric membrane for separation.
Described without supporter porous polymeric membrane for separation be porous polyether sulfone, polysulfones, poly-Kynoar, polyvinyl chloride,Polyacrylonitrile and chliorinated polyvinyl chloride.
Described carrying basement membrane is polyethylene, polypropylene, polyester film, and film thickness is 0.1mm～2mm.
Described cationic finishing solution composition is to count by weight: thermal initiator is 0.2 part～5 parts, thermosetting sunIon component is 0.5 part～50 parts, and auxiliary agent is 1 part～60 parts, and solvent is 2 parts～98 parts.
Described thermal initiator is that dibenzoyl peroxide, isopropyl benzene hydroperoxide, azo diisobutyl amidine hydrochloride, azo two are differentButamisole quinoline hydrochloride, azo dicyano valeric acid, azo diisopropyl imidazoline, azodiisobutyronitrile, ABVN,One or more in azo-bis-iso-dimethyl, hydrogen peroxide, ammonium persulfate and potassium peroxydisulfate.
Described thermosetting cationic components is N, N-methylene diacrylamine, N hydroxymethyl acrylamide, DAAM,One or more in dimethylaminoethyl methacrylate, acrylic acid dimethylamino ethyl ester, diethylaminoethyl methacrylate.
Described auxiliary agent is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, glycol dimethyl ether, ethylene glycol monobutyl ether, second twoAlcohol list ether, the tertiary butyl ether of ethylene glycol list, glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycolEther; Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, diethylene glycol diethyl ether, triethylene glycol diformazanOne or more in ether, Triethylene glycol ethyl ether, acetone.
Described solvent is one or more in water, methyl alcohol, ethanol, propyl alcohol and isopropyl alcohol
Described heat curing temperature is 30～140 DEG C, and thermal curing time is 0.3～48 hour.
It is one or more in clear water or deionized water that described water cleans.
Described heated-air drying is: 30～140 DEG C of hot blast temperatures, hot-blast pressure-0.098MPa～0.5MPa (gauge pressure), drying time2 seconds～5 hours.
The present invention is different from existing film Physical and chemic modified method, can in use not ooze out through permanent crosslinked decorative layer,Pollute processed product, can not cause damage to the strand of polymeric membrane, keep the original performance of membrane material.
Describe below in conjunction with detailed description of the invention, but described embodiment is not construed as limiting the invention.
The method without the cationic finishing of supporter porous polymeric membrane for separation of heat cure, its component parts by weightsNumber meter, comprises following processing step:
The polyethylene carrying of thickness as 0.25mm will be coated taking Kynoar (PVDF) polymer as the casting solution of membrane materialOn base film, after clear water coagulating bath film forming, washing, pvdf membrane and polyethylene carrying basement membrane is peeled off, formation porous withoutSupporter pvdf membrane; Enter deionized water washing trough washing, the porous after washing immerses and consists of without supporter pvdf membrane0.8 part of azo diisobutyl amidine hydrochloride, 1.5 parts of N hydroxymethyl acrylamides, 4 parts of DAAMs, 3 parts of methyl-propOlefin(e) acid dimethylamine ethyl ester, 1 part of N, N-methylene diacrylamine, 12 parts of glycol monoethyl ethers, 50 parts of ethanol and 32 parts go fromThe cationic finishing solution that sub-water forms soaked after 10 minutes, entered heating cabinet, and heating-up temperature is 60 DEG C, while solidifyingBetween 4. Film through heat cure enters deionized water washing trough again, and 25 DEG C of washing temperature, enter hot air drier, hot blast after washing90 DEG C of temperature, hot-blast pressure 0.002MPa (gauge pressure), 1 hour drying time, the dry product that obtains. Gained without supporterThe water content of PVDF perforated membrane is 0.1%, membrane aperture 0.5 μ m, film pure water flux 10.5m3/(m2.h.0.1MPa), water contact angleMeasurement result is: it is that time of 10 ° is 19 seconds that contact angle drops to by 75 °; Within 25 DEG C, 24 hours, soak test oxygen demand is (with OMeter) recruitment 0.10mg/L.
The polyester carrying base of film thickness as 0.3mm will be coated taking polyvinyl chloride (PVC) polymer as the casting solution of membrane materialOn film, after clear water coagulating bath film forming, washing, PVC film and polyester carrying basement membrane are peeled off, formed porous without supporterPVC diffusion barrier; Enter deionized water washing trough washing, the porous after washing immerses and consists of 0.9 part without supporter PVC filmAzodiisobutyronitrile, 3 parts of N hydroxymethyl acrylamides, 8 parts of DAAMs, 1 part of N, N-methylene diacrylamine,The cationic finishing solution of 12 parts of glycol monoethyl ethers, 40 parts of ethanol and 42 parts of deionized water formation soaked after 8 minutes,Enter heating cabinet, heating-up temperature is 45 DEG C, 6 hours hardening times. Film through heat cure enters deionized water washing trough, water againWash away except after residual organic matter and enter hot blast vacuum desiccator, 45 DEG C of hot blast temperatures, hot blast vacuum desiccator vacuum0.07MPa, 2 hours drying times, the dry product that obtains. The water content without supporter PVC perforated membrane of gained is 0.15%,Membrane aperture 0.1 μ m, film pure water flux 1.5m3/(m2.h.0.1MPa), water contact angle measurement result is: contact angle by 75 ° drop to intoThe time of 10 ° is 20 seconds; 25 DEG C, 24 hours soak test oxygen demand (in O) recruitment 0.16mg/L.
To coat thickness taking polyether sulfone (PES) polymer as the casting solution of membrane material on the polyester carrying base film of 0.25mm,After clear water coagulating bath film forming, washing, PES film and polyester carrying basement membrane are peeled off, form porous without supporter PES film;Enter deionized water washing trough washing, the porous after washing immerses and consists of 0.8 part of azo diisobutyl without supporter PES filmAmidine hydrochloride, 1.5 parts of N hydroxymethyl acrylamides, 4 parts of DAAMs, 3 parts of dimethylaminoethyl methacrylates, 1Part N, it is cationic that N-methylene diacrylamine, 12 parts of glycol monoethyl ethers, 50 parts of ethanol and 32 parts of deionized waters formFinishing solution soaked after 10 minutes, entered heating cabinet, and heating-up temperature is 80 DEG C, hardening time 3. Through the film of heat cure againInferiorly enter deionized water washing trough, 25 DEG C of washing temperature, enter hot air drier after washing, 110 DEG C of hot blast temperatures, hot-blast pressure0.002MPa, 0.5 hour drying time, the dry product that obtains. The water content without supporter PES perforated membrane of gained is 0.1%,Membrane aperture 0.2 μ m, film pure water flux 9.5m3/(m2.h.0.1MPa), water contact angle measurement result is: contact angle by 75 ° drop to intoThe time of 10 ° is 8 seconds; 25 DEG C, 24 hours soak test oxygen demand (in O) recruitment 0.13mg/L.
1. the method without the cationic finishing of supporter porous polymeric membrane for separation of a heat cure, it is characterized in that, comprise following processing step: (1) is by the high molecular polymer casting solution configuring knifing on carrying basement membrane, through coagulating bath film forming and washing step, porous polymer membrane and carrying basement membrane are peeled off, formed without supporter porous polymeric membrane for separation; (2) remove after contained solvent, non-solvent and additive through washing, immerse the cationic finishing solution by thermal initiator, thermosetting cationic components, auxiliary agent and solvent composition; By heating without supporter porous polymeric membrane for separation of soaking through cationic finishing solution, make cationic components solidify to form the cationic finishing coat of bridging property; (3) heat cure forms cleaning through water without supporter porous polymeric membrane for separation of the cationic finishing coat of bridging property, washes away residual organic matter; Through heated-air drying, obtain cationic finishing type without the high-molecular porous property of supporter diffusion barrier;
Described cationic finishing solution composition is that its component is mark meter by weight: thermal initiator is 0.2 part～5 parts, and thermosetting cationic components is 0.5 part～50 parts, and auxiliary agent is 1 part～60 parts, and solvent is 2 parts～98 parts;
Described thermal initiator is one or more in dibenzoyl peroxide, isopropyl benzene hydroperoxide, azo diisobutyl amidine hydrochloride, azo two isobutyl imidazoline salt hydrochlorates, azo dicyano valeric acid, azo diisopropyl imidazoline, azodiisobutyronitrile, ABVN, azo-bis-iso-dimethyl, hydrogen peroxide, ammonium persulfate and potassium peroxydisulfate;
Described thermosetting cationic components is N, one or more in N-methylene diacrylamine, N hydroxymethyl acrylamide, DAAM, dimethylaminoethyl methacrylate, acrylic acid dimethylamino ethyl ester, diethylaminoethyl methacrylate;
Described auxiliary agent is one or more in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, glycol dimethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, the tertiary butyl ether of ethylene glycol list, glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, diethylene glycol diethyl ether, TRIGLYME, Triethylene glycol ethyl ether, acetone;
Described solvent is one or more in water, methyl alcohol, ethanol, propyl alcohol and isopropyl alcohol;
Described heat curing temperature is 30～140 DEG C, and thermal curing time is 0.3～48 hour; It is one or more in clear water or deionized water that described water cleans; Described heated-air drying is: 30～140 DEG C of hot blast temperatures, hot-blast pressure is gauge pressure-0.098～0.5MPa, 2 seconds～5 hours drying time.
2. the method without the cationic finishing of supporter porous polymeric membrane for separation of heat cure according to claim 1, it is characterized in that, described is polyether sulfone, Kynoar, polyvinyl chloride, polyacrylonitrile and chliorinated polyvinyl chloride without its high molecular polymer of supporter porous polymeric membrane for separation; Described carrying basement membrane is that polyethylene, polypropylene, film thickness are 0.1mm～2mm.
CN201310556653.3A 2013-11-08 2013-11-08 A kind of method without the cationic finishing of supporter porous polymeric membrane for separation of heat cure CN103657429B (en)
CN201310556653.3A CN103657429B (en) 2013-11-08 2013-11-08 A kind of method without the cationic finishing of supporter porous polymeric membrane for separation of heat cure
CN103657429A CN103657429A (en) 2014-03-26
CN103657429B true CN103657429B (en) 2016-05-04
ID=50296923
CN (1) CN103657429B (en)
CN105080362A (en) * 2015-08-07 2015-11-25 无锡桥阳机械制造有限公司 Preparation method for hydrophilic polyvinyl chloride hollow fiber membrane
CN1623639A (en) * 2004-09-24 2005-06-08 浙江大学 Process for modifying reaction at surface of separating film of polymer
CN101537316A (en) * 2009-03-20 2009-09-23 淮阴师范学院 Preparation method for temperature sensitive response type intelligent ceramic composite membrane and product
CN101612527A (en) * 2009-07-21 2009-12-30 清华大学 Method for modifying surfaces of polymer porous membranes and membrane pores
CN101711952A (en) * 2009-12-22 2010-05-26 济南大学 Polyvinylidene fluoride hollow fiber ultrafiltration membrane with permanent hydrophilcity and preparation method thereof
CN102029117A (en) * 2009-09-29 2011-04-27 中国科学院大连化学物理研究所 Method for modifying surface of ultrafiltration membrane
CN103272493A (en) * 2013-04-27 2013-09-04 新疆大学 Method for hydrophilic modification of polyvinylidene fluoride membrane
CN1077804C (en) * 1994-07-28 2002-01-16 米利波尔公司 Porous composite membrane and its making process
2013-11-08 CN CN201310556653.3A patent/CN103657429B/en active IP Right Grant
高分子多孔膜的表面改性与抗污染研究;袁晓燕等;《化学工业与工程》;20030430;第20卷(第2期);第96页第1.2节 *
CN103657429A (en) 2014-03-26
CN105289316B (en) 2017-08-04 A kind of preparation method of interpenetration network hydrogel filled composite seperation film
Liang et al. 2012 A novel ZnO nanoparticle blended polyvinylidene fluoride membrane for anti-irreversible fouling
Li et al. 2013 Deformation and reinforcement of thin-film composite (TFC) polyamide-imide (PAI) membranes for osmotic power generation
RU2011115842A (en) 2012-10-27 Method for attaching components with power supply in ophthalmic lens
EP1827664B1 (en) 2011-06-08 Membrane post treatment
Peng et al. 2011 Protein fouling resistant membrane prepared by amphiphilic pegylated polyethersulfone
Lebrun et al. 2002 Elaboration of ion‐exchange membranes with semi‐interpenetrating polymer networks containing poly (vinyl alcohol) as polymer matrix
NZ563980A (en) 2011-07-29 Cross linking treatment of polymer membranes
CN1895760A (en) 2007-01-17 Composite membrane
JP2015516891A5 (en) 2016-03-31
JP5378235B2 (en) 2013-12-25 Caustic resistant film
Kim et al. 2004 Long-term stability of plasma oxidized PDMS surfaces
Su et al. 2004 Preparation and characterization of quaternized poly (phthalazinone ether sulfone ketone) NF membranes
CN103492054B (en) 2015-06-03 Method for cleaning membrane module
WO2010098867A8 (en) 2011-04-28 Membrane with sulfonic groups for removing protein aggregates