CN116731375A - Polymer surface modification method, obtained surface modified polymer and application thereof - Google Patents
Polymer surface modification method, obtained surface modified polymer and application thereof Download PDFInfo
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- CN116731375A CN116731375A CN202310732572.8A CN202310732572A CN116731375A CN 116731375 A CN116731375 A CN 116731375A CN 202310732572 A CN202310732572 A CN 202310732572A CN 116731375 A CN116731375 A CN 116731375A
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- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- RHVPCSSKNPYQDU-UHFFFAOYSA-H neodymium(3+);trisulfate;hydrate Chemical compound O.[Nd+3].[Nd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RHVPCSSKNPYQDU-UHFFFAOYSA-H 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000004184 polymer manufacturing process Methods 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- HWZAHTVZMSRSJE-UHFFFAOYSA-H praseodymium(iii) sulfate Chemical compound [Pr+3].[Pr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HWZAHTVZMSRSJE-UHFFFAOYSA-H 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 1
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- 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
- C08J2327/04—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 at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- 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
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Abstract
The invention provides a polymer surface modification method, an obtained surface modified polymer and application thereof, wherein the modification method comprises the following steps: mixing the photoinitiator and the solvent, coating the mixture on the surface of the polymer, drying, and irradiating the mixture with ultraviolet light to obtain a surface modified polymer; the photoinitiator is a photoinitiator containing a photoreactive group and a hydrophilic group. The polymer surface modification method can be completed only by ultraviolet irradiation for 1-600 s under normal temperature, has few required raw materials and equipment, simple preparation process and effective combination with the polymer preparation process, and can improve the hydrophilicity, the pollution resistance and the ion adsorption capacity of the polymer.
Description
Technical Field
The invention belongs to the technical field of surface treatment of materials, and particularly relates to a polymer surface modification method, an obtained surface modified polymer and application thereof.
Background
The polymer product has good mechanical property, chemical stability, mechanical property, optical property and the like, and has wide application prospect in the fields of chemical industry, electric industry, medicine, food, environmental protection and the like. However, the polymer has poor wettability, adhesiveness, dyeing property and stain resistance due to low surface energy and strong hydrophobicity.
The problems described above can be solved by hydrophilic modification of the polymer. The hydrophilic modification method of the polymer comprises chemical modification and physical modification, wherein the physical modification is realized through material blending modification, surface coating or surface adsorption, but the chemical property of the surface is not changed fundamentally, and only the chemical composition on the surface is changed, so that the durability is poor, and the long-term stability is poor in the application process. The chemical modification combines hydrophilic groups with the polymer through chemical bonds, so that the stability and the service life of the polymer can be greatly improved.
CN101817931a discloses a method for modifying the surface of a polymer with a phenol derivative, said method of preparation being directed to the surface of an article of an organic polymer containing C-H bonds, said method comprising the steps of: and (3) coating a phenol derivative and a Roche reaction II type photoinitiator solution on the surface of the polymer to be modified, and carrying out ultraviolet light irradiation on the surface of the polymer. In the technical scheme, an acetone solution of a phenol derivative is required to be placed between a film or a sheet to be modified and an ultraviolet light transmitting material in the implementation process to form a sandwich type reactor structure, and ultraviolet light irradiation is carried out on the surface of a polymer covered with the solution, so that the hydrophilic performance of the surface of the polymer is effectively improved, and compared with the traditional chemical modification method, the reaction time is greatly reduced, and the reaction steps are simplified.
CN104031282a discloses a surface light grafting modification method for polyvinylidene fluoride micro-filtration membrane, which comprises the following specific implementation steps: (1) A preimpregnation adsorption photoinitiation system, (3) grafting polymerization by ultraviolet irradiation after the preimpregnation membrane adsorbs hydrophilic monomer liquid, and (2) post-treatment of the photoirafted modified membrane. The modification method provided by the technical scheme has obvious effect and proper cost, and can realize the rapid light grafting of the PVDF micro-filtration membrane surface modification method under the aerobic condition.
CN104857572a discloses a method for preparing a hydrophilic lubricating coating on the surface of an inert polymer material, the preparation method comprises the following steps: immersing the inert high polymer material into a grafting photoinitiator solution for 1-10 minutes; immersing the inert polymer material dipped with the grafting photoinitiator into a grafting monomer solution for 5-20 minutes, and carrying out ultraviolet irradiation modification and grafting polymerization to form a grafting modification layer on the surface of the inert polymer material; cleaning the inert polymer material subjected to the butt joint polymerization; immersing the cleaned inert polymer material into the hydrophilic gel solution for 1-10 minutes; and carrying out ultraviolet polymerization curing on the hydrophilic gel solution attached to the surface of the inert high polymer material, and forming a hydrophilic gel layer on the surface of the grafting modification layer. The hydrophilic lubricating coating prepared by the method has higher hydrophilic lubricating property and adhesive force.
Although the hydrophilicity of the polymer surface is improved to a certain extent, the chemical modification process is complex, the reaction condition is severe, the reaction time is long, and the preparation cost is high, wherein the ultraviolet light grafting process in the chemical modification needs to polymerize or graft in a solution, most of the conventional preparation processes of hot pressing, casting, blow molding and the like of the film or sheet belong to the melt processing and forming process, the time interval between the extrusion molding of the material and the completion of the product manufacturing is short, and the produced product has wide range or large size and is difficult to react in the solution for a long time. In the prior art, the modification method of the polymer surface is not matched with the polymer manufacturing process, and continuous and large-area industrial production of polymer preparation and modification combination is difficult to realize.
Therefore, there is a need to develop a simple, efficient method of modifying the polymer surface that can be combined with the polymer preparation process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polymer surface modification method, an obtained surface modified polymer and application thereof. The modification method has simple steps and short time, and can be effectively combined with the preparation process of the polymer.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for modifying a polymer surface, the method comprising mixing a photoinitiator and a solvent, coating the surface of the polymer, drying, and irradiating with ultraviolet light to obtain a surface modified polymer.
The photoinitiator is a photoinitiator containing a photoreactive group and a hydrophilic group.
In the present invention, the mixing of the photoinitiator and the solvent includes any one of dissolving and dispersing the photoinitiator in the solvent, suspending and dispersing the photoinitiator in the solvent, or dispersing the photoinitiator in the solvent in emulsion.
Preferably, the photoreactive group includes any one or a combination of at least two of an acyl group, a diazo group, or an azide group.
Preferably, the acyl group comprises any one or a combination of at least two of a benzophenone group, a propiophenone group, a benzil group, an anthrone group or an anthraquinone group.
Preferably, the hydrophilic group includes any one or a combination of at least two of a carboxyl group, an amino group, a hydroxyl group, a phosphate group, or a sulfonate group.
In the invention, the photoreactive group generates free radical under ultraviolet irradiation to react with hydrocarbon single bond in the polymer film, thereby grafting the photoinitiator containing hydrophilic group to the surface of the polymer, so that the surface of the polymer has hydrophilicity, and the modification method can carry out ultraviolet grafting reaction in a state without solution.
Preferably, the photoinitiator comprises 4-carboxybenzophenone, 2-carboxybenzophenone, 4 '-dicarboxybenzophenone, 2,4, 5-tricarboxybenzophenone, 3',4 '-tetracarboxylbenzophenone, 2',4,4 '-tetrahydroxybenzophenone, 2,3, 4-trihydroxybenzophenone, 4' -dihydroxybenzophenone, 2, 4-dihydroxybenzophenone, 4-hydroxybenzophenone, 3, 4-diaminobenzophenone, 4 '-diaminobenzophenone, 3', any one or a combination of at least two of 4,4 '-tetraminobenzophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylbenzophenone, 4-diazastilbene-2, 2-disulfonate, 4-azidobenzoic acid, azidoacetic acid, 2' -azidodeoxycuride, 2- (3-benzoylphenyl) propionic acid, (4- (2-aminoethyl) phenyl) (phenyl) methanone, 2-aminobenzophenone, 2-hydroxybenzophenone, 3-aminobenzophenone or azido-diethylene glycol-acetic acid.
Preferably, the mixing further comprises mixing an emulsifier with the photoinitiator and the solvent.
Illustratively, the emulsifying agent comprises any one or a combination of at least two of AEO-7, AEO-9, OP-10, APG-0810, PPG-200, PEG-10, or SR-10.
Preferably, the emulsifier is 0 to 20% by mass, for example 0%, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18% or 20% etc., based on 100% by mass of the total of the emulsifier, photoinitiator and solvent.
Illustratively, the emulsifier is mixed with the photoinitiator and the solvent to obtain a solution A, the emulsifier is added into deionized water to obtain a solution B, and then the solution A is dropwise added into the solution B to prepare the emulsion.
Preferably, the mixing further comprises mixing the micro-nanoparticles with optionally an emulsifier, a photoinitiator, and a solvent.
Preferably, the micro-nano particles are made of any one or a combination of at least two of silicon dioxide, calcium carbonate, zinc oxide, titanium dioxide, rare earth oxide, rare earth salt, graphene, copper or silver.
The micro-nanoparticles illustratively include, but are not limited to: any one or a combination of at least two of nano silicon dioxide, nano calcium carbonate, nano zinc oxide, micro nano titanium dioxide, micro nano rare earth oxide, micro nano graphene, nano copper or nano silver.
The rare earth oxides illustratively include, but are not limited to: any one or a combination of at least two of lanthanum oxide, cerium oxide, praseodymium oxide, yttrium oxide and neodymium oxide.
In the present invention, the cerium oxide refers to an oxide of trivalent cerium and/or an oxide of tetravalent cerium, and the cerium oxide includes ceria and/or ceria; the praseodymium oxide refers to an oxide of trivalent praseodymium and/or an oxide of tetravalent praseodymium, and the praseodymium oxide includes hexapraseodymium undecanoxide.
The rare earth salts illustratively include, but are not limited to: any one or a combination of at least two of rare earth chloride salt, rare earth nitrate salt, or rare earth sulfate salt, for example, any one or a combination of at least two of lanthanum chloride, lanthanum sulfate, lanthanum nitrate, cerium chloride, cerium sulfate, cerium nitrate, praseodymium chloride, praseodymium sulfate, praseodymium nitrate, yttrium chloride, yttrium sulfate, yttrium nitrate, neodymium chloride, neodymium sulfate, or neodymium nitrate.
In the invention, the addition of the micro-nano particles helps to improve the hydrophilicity of the polymer surface, because: wetting is a thermodynamic process according to the relationship between roughness and wettability proposed by Wenzel (Wenzel), where there are two processes of wetting the surface of the droplet and increasing the free surface of the droplet, and the net energy reduction of both determines the wetting rate. The micro-nano particles can increase the roughness of the solid surface, and for the hydrophilic surface, more solid surfaces are wetted under the same increase of the free liquid level of the liquid drop, so that the reduction amount of net energy is increased, the wetting speed is increased, and the hydrophilicity is increased. In addition, according to the difference of adding micro-nano particles, different functionalities are added to the polymer, for example, nano silicon dioxide, nano calcium carbonate, nano zinc oxide, micro nano titanium dioxide, micro nano rare earth oxide or micro nano graphene are added to enhance the anti-fouling performance of the prepared polymer with the surface modification, and nano copper and/or nano silver are added to enable the prepared polymer with the surface modification to have antibacterial performance.
Preferably, the micro-nano particles have a particle size of 0.005 μm to 100 μm, for example, 0.005 μm, 0.01 μm, 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 50 μm, 80 μm, 90 μm, 100 μm, or the like.
Preferably, the micro-nanoparticles are 0 to 30% by mass (e.g., 0%, 0.02%, 0.05%, 0.1%, 0.2%, 0.6%, 5%, 8%, 10%, 12%, 15%, 20%, 25%, 28% or 30%, etc.), based on the total mass of the micro-nanoparticles, optionally the emulsifier, the photoinitiator, and the solvent being 100%.
In the invention, the mass percentage of the micro-nano particles is 0-30%, the mass percentage of the micro-nano particles is more than 30%, the agglomeration phenomenon can occur, and the hydrophilic effect can be deteriorated.
Preferably, the solvent comprises any one or a combination of at least two of water, methanol, ethanol, acetonitrile, acetone, dimethyl sulfoxide, N-dimethylformamide, acetic acid, ethyl acetate, tetrahydrofuran, N-hexane, trifluoroethanol, dichloromethane, chloroform or toluene.
Preferably, the photoinitiator is 0.01% to 80% (e.g., 0.01%, 0.05%, 0.1%, 0.4%, 0.5%, 1%, 3%, 5%, 10%, 20%, 30%, 50%, 70%, 80%, etc.) by mass and the solvent is 20% to 99.99% (e.g., 20%, 40%, 50%, 60%, 80%, 90%, 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, 99.9%, etc.) by mass based on 100% by mass of the total mass of the photoinitiator and the solvent.
Preferably, the polymer comprises any one or a combination of at least two of polyethylene, polystyrene, polypropylene (PP), polyvinyl chloride (PVC), ethylene-vinyl acetate copolymer (EVA), polyolefin elastomer, polyurethane, polyimide, polyvinylidene fluoride (PVDF), polysulfone, polyethersulfone, polyacrylonitrile, nylon, or polycarbonate.
Preferably, the shape of the polymer includes any one of a film, a filter membrane, a filter cloth, a block, a fiber, a hollow fiber membrane, or a microsphere.
Illustratively, the filter membrane comprises any one of a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, or a reverse osmosis membrane.
Preferably, the polymer further comprises a pretreatment prior to coating.
Preferably, the pretreatment comprises any one or a combination of at least two of etching, ozone treatment, ultraviolet irradiation, corona treatment, plasma treatment, glow discharge treatment or high energy particle irradiation.
Preferably, the coating comprises any one or a combination of at least two of spraying, dipping, knife coating or surface printing.
Illustratively, the drying includes any one or a combination of at least two of natural drying, blow-drying under nitrogen atmosphere, hot air drying, microwave drying, ultraviolet drying, or infrared drying.
Preferably, the light source for ultraviolet irradiation includes any one or a combination of at least two of ultraviolet lamp, high-pressure mercury lamp, UV plasma, UV light emitting diode, UV xenon lamp, metal halide lamp, ultraviolet curing device, ultraviolet curing agent or UV LED surface light source.
Preferably, the ultraviolet light is irradiated for a period of 1 to 600s, for example, 1s, 5s, 10s, 60s, 120s, 180s, 240s, 300s, 420s, 480s, 540s, 600s, or the like.
Preferably, the intensity of the ultraviolet light is 10-2000 mW/cm 2 For example 10mW/cm 2 、50mW/cm 2 、100mW/cm 2 、400mW/cm 2 、600mW/cm 2 、800mW/cm 2 、1000mW/cm 2 、1500mW/cm 2 Or 2000mW/cm 2 Etc.
Preferably, the ultraviolet irradiation is performed under room temperature conditions.
Preferably, the ultraviolet light irradiation further comprises immersing the coating in a solvent to remove ungrafted photoinitiator.
Preferably, the soaking time is 0.1 to 24 hours, for example 0.1 hours, 1 hour, 3 hours, 5 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, 24 hours, etc.
In a second aspect, the present invention provides a surface modified polymer produced by the polymer surface modification process of the first aspect.
In a third aspect, the present invention provides the use of a surface modified polymer as described in the second aspect in aquaculture materials, filtration materials, adsorption materials, microalgae harvesting materials, biosensor materials, marine antifouling materials or wastewater treatment materials.
Illustratively, the surface modified polymer may be used in the manufacture of aquaculture net cages; the surface modified polymer can be used for a photobioreactor material for microalgae culture, so that the anti-fouling performance of the photobioreactor is improved; the surface modified polymer can be used for a filter material for microalgae harvesting, and can improve the water flux of the filter material to reduce the energy consumption and the anti-fouling performance of the surface of the filter material; the surface modified polymer can be used for municipal sewage, industrial wastewater or sea water desalination treatment materials; the surface modified polymer is used as an adsorption material to recover metal resources from wastewater or other water environments.
Compared with the prior art, the invention has the following beneficial effects:
the invention mixes the photoinitiator and the solvent, firstly coats the surface of the polymer, dries to form a coating, and then irradiates with ultraviolet light to modify the surface of the polymer. The polymer surface modification method can be completed only by ultraviolet irradiation for 1-600 s under normal temperature, and has the advantages of less required raw materials and equipment, simple preparation process, capability of performing light grafting under the condition of no solution and effective combination with the polymer preparation process. The polymer surface modification method can improve the hydrophilicity and the dirt resistance and the ion adsorption capacity of the polymer. The contact angle of the polymer modified by the polymer surface modification method is 5.1-79.8 degrees, and the contact angle is 5.1-57.2 degrees in a preferred condition.
Drawings
FIG. 1 is a scanning electron microscope image of an unmodified PVDF microfiltration membrane;
FIG. 2 is a scanning electron microscope image of the surface modified PVDF micro-filtration membrane provided in example 1;
FIG. 3 is a graph showing the change in filtered algae flux over time of the surface modified PVDF microfiltration membrane and the unmodified PVDF microfiltration membrane provided in example 1;
FIG. 4 is a graph of the adsorption kinetics of the surface modified PVDF microfiltration membrane provided in example 4;
FIG. 5 is an adsorption isotherm plot of the surface modified PVDF microfiltration membrane provided in example 4;
fig. 6 is a graph of the cyclic regeneration capacity evaluation of the surface modified PVDF microfiltration membrane provided in example 4.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a polymer surface modification method, an obtained surface modified polymer and application thereof, wherein the modification method comprises the following steps:
5mg of 3,3', 4' -tetracarboxylic benzophenone was dissolved in 1000mg of ethanol to prepare a coating solution. Soaking PVDF micro-filtration membrane with aperture of 1.2 μm in ethanol, ultrasonic cleaning for 30min, corona treating for 30s, spraying the coating solution on the surface of PVDF micro-filtration membrane, naturally drying at room temperature, irradiating under ultraviolet lamp for 180s, and ultraviolet light with intensity of 2000mW/cm 2 And then soaking in ethanol solution for 1h to remove ungrafted 3,3', 4' -tetracarboxyl benzophenone, and drying to obtain the surface modified PVDF micro-filtration membrane.
The performance test and results of the surface modified PVDF microfiltration membrane provided in example 1 are as follows.
(1) Contact angle: the contact angle of the unmodified PVDF micro-filtration membrane is 93.7 DEG + -3.4 DEG, and the contact angle of the surface modified PVDF micro-filtration membrane can reach 22 DEG + -6.1 deg.
(2) Morphology testing: scanning electron microscopy of unmodified PVDF microfiltration membrane is shown in FIG. 1, and scanning electron microscopy of surface modified PVDF microfiltration membrane is shown in FIG. 2.
(3) The performance of the surface-modified PVDF microfiltration membrane provided in example 1 applied to microalgae harvesting was examined, and the flux change of the filtered microalgae before and after modification was measured. The unmodified PVDF micro-filtration membrane and the surface modified PVDF micro-filtration membrane are respectively placed in an MSC300 cup type ultrafiltration device after being pre-wetted by ethanol, and microalgae filtration experiments are carried out by using chlorella liquid with the concentration of 1g/L under the transmembrane pressure difference of 1 bar. The flux of algae liquid is recorded every minute, the surface of the membrane is cleaned every 20 minutes, and backwashing is carried out for 5 minutes by deionized water, and total backwashing is carried out for 4 times.
The initial algae flux of the unmodified PVDF micro-filtration membrane is 938 kg/(m) 2 H.atm), the initial algae flux of the surface modified PVDF microfiltration membrane is 1128 kg/(m) 2 H.atm), 20.27% improvement.
The flux of the filtered algae solution before and after modification of the PVDF microfiltration membrane is shown in FIG. 3.
Example 2
The embodiment provides a polymer surface modification method, an obtained surface modified polymer and application thereof, wherein the modification method comprises the following steps:
500mg of 3,3', 4' -tetracarboxylic benzophenone was dissolvedA coating solution was prepared in 1000mg of ethanol. Soaking EVA film in ethanol, ultrasonic cleaning for 30min, corona treating for 30s, spreading the coating solution on the surface of EVA film, blow drying under nitrogen atmosphere, and irradiating under ultraviolet lamp for 300s with ultraviolet light intensity of 500mW/cm 2 And then soaking in ethanol solution for 1h to remove ungrafted 3,3', 4' -tetracarboxyl benzophenone, and drying to obtain the surface modified EVA film.
The surface modified EVA film provided in example 2 was tested for performance and the results are as follows.
(1) Contact angle: the contact angle of the unmodified EVA film was 94.0 ° ± 2.5 °, and the contact angle of the surface modified EVA film was 52.7 ° ± 2.7 °.
(2) The surface-modified EVA film provided in example 2 was examined for its ability to be used in the preparation of a photobioreactor, and the EVA film before and after modification was tested for biofouling resistance. After 3cm×3cm unmodified EVA film and 3cm×3cm surface modified EVA film were immersed in the chlorella culture system for 14 days, the number of algae cells attached to the surface of EVA film was measured.
The number of algae cells attached to the surface of the unmodified EVA film is 15.47 multiplied by 10 6 cells/cm 2 The surface-modified EVA film has an algae cell number of 8.07×10 6 cells/cm 2 Compared with the unmodified EVA film, the film is reduced by 47.83 percent.
Example 3
The embodiment provides a polymer surface modification method, an obtained surface modified polymer and application thereof, wherein the modification method comprises the following steps:
650mg of 3,3', 4' -tetracarboxylic benzophenone was dissolved in 1000mg of tetrahydrofuran, and 0.5mg of micro-nano particles (lanthanum oxide, particle size 0.045 μm) were added for ultrasonic dispersion to prepare a coating solution. Spraying the coating solution on the surface of the polyethylene film, drying with hot air, and irradiating with ultraviolet light for 180s, wherein the intensity of the ultraviolet light is 900mW/cm 2 To obtain the surface modified polyethylene film.
The surface modified polyethylene film provided in example 3 was tested for performance and the results are as follows.
(1) Contact angle: the contact angle of the unmodified polyethylene film is 90.2 DEG + -1.8 DEG, and the contact angle of the surface modified polyethylene film can reach 13.8 DEG + -2.6 deg.
(2) The surface-modified polyethylene film provided in example 3 was examined for its ability to be used in the preparation of a photobioreactor, and the polyethylene film was tested for anti-biofouling properties before and after modification. Respectively soaking a 3cm multiplied by 3cm unmodified polyethylene film and a 3cm multiplied by 3cm surface modified polyethylene film in a chlorella culture system of a 1L glass column type photo-bioreactor, wherein the initial concentration of algae liquid is 0.06g/L, taking out the films after culturing for 14 days, and testing the quantity of algae cells attached to the surfaces of the films before and after modification.
The number of algae cells attached to the surface of the unmodified polyethylene film is 13.83×10 6 cells/cm 2 The surface-modified polyethylene film has a surface-attached algae cell number of 6.29×10 6 cells/cm 2 54.52% less compared to unmodified polyethylene film.
Example 4
The embodiment provides a polymer surface modification method, an obtained surface modified polymer and application thereof, wherein the modification method comprises the following steps:
150mg of 3,3', 4' -tetracarboxylic benzophenone was dissolved in 1000mg of ethanol to prepare a coating solution. Soaking PVDF micro-filtration membrane with aperture of 0.22 μm in ethanol, ultrasonic cleaning for 30min, corona treating for 30s, soaking PVDF micro-filtration membrane in coating solution for 30s, taking out, hot air drying, irradiating under ultraviolet lamp for 180s, and ultraviolet light with intensity of 800mW/cm 2 And then soaking in ethanol solution for 1h to remove ungrafted 3,3', 4' -tetracarboxyl benzophenone, and drying to obtain the surface modified PVDF micro-filtration membrane.
The performance test and results of the surface modified PVDF microfiltration membrane provided in example 4 are as follows.
(1) Contact angle: the contact angle of the unmodified PVDF micro-filtration membrane is 99.5 degrees+/-2.2 degrees, and the contact angle of the surface modified PVDF micro-filtration membrane can reach 54.3 degrees+/-2.9 degrees.
(2) The surface modified PVDF micro-filtration membrane provided in example 4 was examined for application to separation and enrichment of rare earth ions, and the rare earth ion adsorption capacity and the cyclic regeneration capacity of the surface modified PVDF micro-filtration membrane were tested.
Adsorption kinetics curve test: 20mg of the surface-modified PVDF microfiltration membrane was placed in 20mL, pH=6, pr 3+ 、Eu 3 + 、Dy 3+ The adsorption test was performed on solutions having a concentration of 20.0ppm each independently, and the adsorption test time was set to 5min, 10min, 20min, 40min, 60min and 80min.
Test results: FIG. 4 is a graph of adsorption kinetics for a surface modified PVDF microfiltration membrane. The adsorption equilibrium is reached at 80min.
Adsorption isothermal curve test: 20mg of the surface-modified PVDF microfiltration membrane was placed in 20mL, pH=6, pr 3+ The adsorption test was performed for 80min on solutions with initial concentrations of 5, 10, 30, 50, 80 or 120ppm, respectively.
20mg of the surface-modified PVDF microfiltration membrane was placed in 20mL, pH=6, eu 3+ The adsorption test was performed for 80min on solutions with initial concentrations of 5, 10, 30, 50, 80 or 120ppm, respectively.
20mg of the surface-modified PVDF microfiltration membrane was placed in 20mL, pH=6, dy 3+ The adsorption test was performed for 80min on solutions with initial concentrations of 5, 10, 30, 50, 80 or 120ppm, respectively.
Test results: FIG. 5 surface modified PVDF microfiltration membrane was used for Pr respectively 3+ 、Eu 3+ 、Dy 3+ Adsorption isotherms of (a). Surface modified PVDF micro-filtration membrane pair Pr 3+ 、Eu 3+ 、Dy 3+ The maximum adsorption amounts of (C) are 16.75mg/g, 14.98mg/g and 18.67mg/g, respectively.
Cyclic regeneration capability: 20mg of the surface-modified PVDF microfiltration membrane was placed in 20mL, pH=6, pr 3+ 、Eu 3+ 、Dy 3+ The solutions each independently at a concentration of 20.0ppm were adsorbed for 80min. Then, five-time cyclic adsorption/desorption experiments are carried out by taking 0.5mol/L HCl solution to wash and adsorb rare earth ions as a desorption means.
Test results: FIG. 6 is a graph of the evaluation of the cyclic regeneration capacity of a surface-modified PVDF microfiltration membrane, the adsorption capacity still reaching 80% or more of the initial adsorption capacity after 5 times of repeated use.
Example 5
The embodiment provides a polymer surface modification method, an obtained surface modified polymer and application thereof, wherein the modification method comprises the following steps:
10mg of sodium 4, 4-diazidostilbene-2, 2-disulfonate was dissolved in 1000mg of water to prepare a coating solution. Soaking polypropylene filter cloth with aperture of 0.45 μm in ethanol, ultrasonic cleaning for 30min, corona treating for 30s, printing coating solution on the surface of polypropylene filter cloth, oven drying with hot air, irradiating under ultraviolet lamp for 60s, and ultraviolet light with intensity of 1000mW/cm 2 After that, ungrafted sodium 4, 4-diphenylazide stilbene-2, 2-disulfonate was removed by soaking in water for 1 h.
The surface modified polypropylene filter cloth provided in example 5 was tested for performance and the results are as follows.
(1) Contact angle: the contact angle of the unmodified polypropylene filter cloth is 97.3 degrees plus or minus 3.5 degrees, and the contact angle of the surface modified polypropylene filter cloth can reach 43.3 degrees plus or minus 4.7 degrees.
(2) The surface modified polypropylene filter cloth provided in example 5 was examined for application to separation and enrichment of rare earth ions, and the adsorption of rare earth ions by the surface modified polypropylene filter cloth was tested.
20mg of the surface-modified polypropylene filter cloth was placed in 20mL of 80ppm Dy 3+ The solution was adsorbed for 2 hours at an adsorption rate of 10.2mg/g.
Example 6
The embodiment provides a polymer surface modification method, an obtained surface modified polymer and application thereof, wherein the modification method comprises the following steps:
20mg of 3, 4-diaminobenzophenone was dissolved in 1000mg of methanol to prepare a coating solution. Soaking PVC microfiltration membrane with aperture of 0.45 μm in ethanol, ultrasonic cleaning for 30min, corona treating for 30s, spraying coating material on the surface of PVC microfiltration membrane, oven drying with hot air, and irradiating under ultraviolet lamp for 300s with ultraviolet light intensity of 900mW/cm 2 And then soaking in water for 1h to remove ungrafted 3, 4-diaminobenzophenone and drying to obtain the surface modified PVC microfiltration membrane.
The surface modified PVC microfiltration membrane provided in example 6 was tested for performance and the results are as follows.
(1) Contact angle: the contact angle of the unmodified PVC microfiltration membrane is 98.5 degrees plus or minus 3.6 degrees, and the contact angle of the surface modified PVC microfiltration membrane can reach 52.1 degrees plus or minus 4.3 degrees.
(2) Investigation of application of the surface-modified PVC microfiltration membrane provided in example 6 to PO 4 3- And ion adsorptivity of the surface-modified PVC microfiltration membrane was tested.
20mg of the surface-modified PVC microfiltration membrane was placed in 20mL 80ppm PO 4 3- The solution was subjected to adsorption test for 3 hours, and the adsorption amount thereof was 14.3mg/g.
Example 7
The embodiment provides a polymer surface modification method, an obtained surface modified polymer and application thereof, wherein the modification method comprises the following steps:
400mg of 3,3', 4' -tetracarboxylic benzophenone was dissolved in 1000mg of tetrahydrofuran, and 6mg of micro-nano particles (lanthanum oxide, particle size 50 μm) were added for ultrasonic dispersion to prepare a coating solution. Soaking polyethylene film in ethanol, ultrasonic cleaning for 30min, ozone treating for 30s, spraying the coating solution on the surface of polyethylene film, hot air drying, and irradiating with ultraviolet light for 180s at an intensity of 900mW/cm 2 To obtain the surface modified polyethylene film.
The surface modified polyethylene film provided in example 7 was tested for performance and the results are as follows.
(1) Contact angle: the contact angle of the unmodified polyethylene film is 90.2 DEG + -1.8 DEG, and the contact angle of the surface modified polyethylene film can reach 15.7 DEG + -1.9 deg.
(2) The surface-modified polyethylene film provided in example 7 was examined for its ability to be used in the preparation of a photobioreactor, and the anti-biofouling properties of the polyethylene film before and after modification were examined. Respectively soaking a 3cm multiplied by 3cm unmodified polyethylene film and a 3cm multiplied by 3cm surface modified polyethylene film in a chlorella culture system of a 1L glass column type photo-bioreactor, wherein the initial concentration of algae liquid is 0.06g/L, taking out the films after culturing for 14 days, and testing the quantity of algae cells attached to the surfaces of the films before and after modification.
The number of algae cells attached to the surface of the unmodified polyethylene film is 13.83 multiplied by 10 6 cells/cm 2 Surface-modified polyethylene film surface adhesionThe number of algal cells was 5.71×10 6 cells/cm 2 58.71% less compared to unmodified polyethylene film.
Example 8
The embodiment provides a polymer surface modification method, an obtained surface modified polymer and application thereof, wherein the modification method comprises the following steps:
60mg of 3,3', 4' -tetracarboxylic benzophenone was dissolved in 1000mg of tetrahydrofuran, and 0.2mg of micro-nano particles (cerium chloride, particle size 20 μm) were added for ultrasonic dispersion to prepare a coating solution. Spraying the coating solution on the surface of the polyethylene film, drying with hot air, and irradiating with ultraviolet light for 180s, wherein the intensity of the ultraviolet light is 900mW/cm 2 To obtain the surface modified polyethylene film.
The surface modified polyethylene film provided in example 8 was tested for performance and the results are as follows.
(1) Contact angle: the contact angle of the unmodified polyethylene film is 90.2 DEG + -1.8 DEG, and the contact angle of the surface modified polyethylene film can reach 15.1 DEG + -4.0 deg.
(2) The surface-modified polyethylene film provided in example 8 was examined for its ability to be used in the preparation of a photobioreactor, and the polyethylene film was tested for anti-biofouling properties before and after modification. Respectively soaking a polyethylene film with the surface modification of 3cm multiplied by 3cm and a polyethylene film with the surface modification of 3cm multiplied by 3cm in a chlorella culture system of a 1L glass column type photo-bioreactor, wherein the initial concentration of algae liquid is 0.06g/L, taking out the polyethylene film after culturing for 14 days, and testing the quantity of algae cells attached to the surfaces of the polyethylene film before and after modification.
The number of algae cells attached to the surface of the unmodified polyethylene film is 13.83 multiplied by 10 6 cells/cm 2 The surface-modified polyethylene film has a surface-attached algae cell number of 7.95X10 6 cells/cm 2 42.52% less compared to unmodified polyethylene film.
Example 9
The embodiment provides a polymer surface modification method, an obtained surface modified polymer and application thereof, wherein the modification method comprises the following steps:
150mg of 3,3', 4' -tetracarboxylic acid diphenylThe ketone was dissolved in 1000mg of tetrahydrofuran, and 2mg of micro-nano particles (silica, particle size 0.1 μm) were added to the solution for ultrasonic dispersion to prepare a coating solution. Spraying the coating solution on the surface of the polyethylene film, drying with hot air, and irradiating with ultraviolet light for 180s, wherein the intensity of the ultraviolet light is 900mW/cm 2 To obtain the surface modified polyethylene film.
The surface modified polyethylene film provided in example 9 was tested for performance and the results are as follows.
(1) Contact angle: the contact angle of the unmodified polyethylene film is 90.2 DEG + -1.8 DEG, and the contact angle of the surface modified polyethylene film can reach 8.7 DEG + -3.6 deg.
(2) The surface-modified polyethylene film provided in example 9 was examined for its ability to be used in the preparation of a photobioreactor, and the anti-biofouling properties of the polyethylene film before and after modification were examined. Respectively soaking a 3cm multiplied by 3cm unmodified polyethylene film and a 3cm multiplied by 3cm surface modified polyethylene film in a chlorella culture system of a 1L glass column type photo-bioreactor, wherein the initial concentration of algae liquid is 0.06g/L, taking out the films after culturing for 14 days, and testing the quantity of algae cells attached to the surfaces of the films before and after modification.
The number of algae cells attached to the surface of the unmodified polyethylene film is 13.83 multiplied by 10 6 cells/cm 2 The surface-modified polyethylene film has a surface-attached algae cell number of 5.27×10 6 cells/cm 2 61.89% less compared to unmodified polyethylene film.
Example 10
The embodiment provides a polymer surface modification method, an obtained surface modified polymer and application thereof, wherein the modification method comprises the following steps:
100mg of 4-hydroxybenzophenone was dissolved in 1000mg of dimethyl sulfoxide, and added dropwise to a mixed solution of 10mg of emulsifier (OP-10) and 1000mg of deionized water, followed by stirring to prepare a coating emulsion. Soaking EVA film in ethanol, ultrasonic cleaning for 30min, corona treating for 30s, spreading the coating emulsion on the surface of EVA film, blow drying under nitrogen atmosphere, and irradiating under ultraviolet lamp for 180s with ultraviolet light intensity of 800mW/cm 2 Then soaking in ethanol solution for 1h to remove ungrafted 4-hydroxybenzophenoneAnd naturally drying to obtain the surface modified EVA film.
The surface modified EVA film provided in example 10 was tested for performance and the results are as follows.
(1) Contact angle: the contact angle of the unmodified EVA film was 94.0 ° ± 2.5 °, and the contact angle of the surface modified EVA film was 56.3 ° ± 4.8 °.
(2) The surface-modified EVA film provided in example 10 was examined for its ability to be used in the preparation of a photobioreactor, and the EVA film before and after modification was tested for biofouling resistance. After 3cm×3cm unmodified EVA film and 3cm×3cm surface modified EVA film were immersed in the chlorella culture system for 14 days, the number of algae cells attached to the surface of EVA film was measured.
The number of algae cells attached to the surface of the unmodified EVA film is 15.47 multiplied by 10 6 cells/cm 2 The number of algae cells attached to the surface of the surface-modified EVA film is 8.32X10 6 cells/cm 2 46.22% less than unmodified EVA film.
Example 11
This example provides a method for modifying the surface of a polymer, the resulting surface-modified polymer and its use, which differs from example 1 only in that the mass of 3,3', 4' -tetracarboxylic benzophenone is 0.05mg, and other raw materials, amounts and preparation methods are the same as in example 1.
The performance test and results of the surface modified PVDF microfiltration membrane provided in example 11 are as follows.
(1) Contact angle: the contact angle of the unmodified PVDF microfiltration membrane was 93.7 ° ± 3.4 °, and the contact angle of the surface modified EVA film was 75 ° ± 4.8 °.
(2) Investigation example 11 the surface modified PVDF microfiltration membrane was applied to microalgae harvesting and the change in the flux of the filtered microalgae before and after modification was measured. The unmodified PVDF micro-filtration membrane and the surface modified PVDF micro-filtration membrane are respectively placed in an MSC300 cup type ultrafiltration device after being pre-wetted by ethanol, and microalgae filtration experiments are carried out by using chlorella liquid with the concentration of 1g/L under the transmembrane pressure difference of 1 bar. The flux of algae liquid is recorded every minute, the surface of the membrane is cleaned every 20 minutes, and backwashing is carried out for 5 minutes by deionized water, and total backwashing is carried out for 4 times.
The initial algae flux of the unmodified PVDF micro-filtration membrane is 938 kg/(m) 2 H.atm), the initial algae flux of the surface modified PVDF microfiltration membrane is 985 kg/(m) 2 ·h·atm)。
Example 12
This example provides a method for modifying the surface of a polymer, the resulting surface-modified polymer and its use, which differs from example 1 only in that the mass of 3,3', 4' -tetracarboxylic benzophenone is 4000mg, and other raw materials, amounts and preparation methods are the same as in example 1.
The performance test and results of the surface modified PVDF microfiltration membrane provided in example 12 are as follows.
Contact angle: the contact angle of the unmodified PVDF microfiltration membrane was 93.7 ° ± 3.4 °, and the contact angle of the surface modified PVDF microfiltration membrane was 15.6 ° ± 4.8 °.
Example 13
This example provides a method for modifying the surface of a polymer, the resulting surface-modified polymer and its use, which differs from example 1 only in that the mass of 3,3', 4' -tetracarboxylic benzophenone is 4900mg, and other raw materials, amounts and preparation methods are the same as in example 1.
The performance test and results of the surface modified PVDF microfiltration membrane provided in example 13 are as follows.
Contact angle: the contact angle of the unmodified PVDF microfiltration membrane was 93.7 ° ± 3.4 °, and the contact angle of the surface modified PVDF microfiltration membrane was 15.6 ° ± 3.9 °.
Comparative example 1
This comparative example provides a method for modifying the surface of a polymer, the resulting surface-modified polymer and its use, differing from example 1 only in that the 3,3', 4' -tetracarboxylic benzophenone is replaced by a benzophenone of the same quality, and other materials, amounts and preparation methods are the same as in example 1.
The performance test and results of the surface modified PVDF microfiltration membrane provided in comparative example 1 are as follows.
(1) Contact angle: the contact angle of the unmodified PVDF micro-filtration membrane is 93.7 degrees+/-3.4 degrees, and the contact angle of the surface modified PVDF micro-filtration membrane can reach 95.4 degrees+/-4.8 degrees.
(2) The surface-modified PVDF microfiltration membrane provided in comparative example 1 was examined for application to microalgae harvesting, and the change in flux of the filtered microalgae before and after modification was measured. The unmodified PVDF micro-filtration membrane and the surface modified PVDF micro-filtration membrane are respectively placed in an MSC300 cup type ultrafiltration device after being pre-wetted by ethanol, and microalgae filtration experiments are carried out by using chlorella liquid with the concentration of 1g/L under the transmembrane pressure difference of 1 bar. The flux of algae liquid is recorded every minute, the surface of the membrane is cleaned every 20 minutes, and backwashing is carried out for 5 minutes by deionized water, and total backwashing is carried out for 4 times.
The initial algae flux of the unmodified PVDF micro-filtration membrane is 938 kg/(m) 2 H.atm), the initial algae flux of the surface modified PVDF microfiltration membrane was 567 kg/(m) 2 ·h·atm)。
Comparative example 2
This comparative example provides a method for modifying the surface of a polymer, the resulting surface-modified polymer and its use, differing from example 1 only in that the 3,3', 4' -tetracarboxylic benzophenone is replaced by a 4-methylbenzophenone of the same mass, and other raw materials, amounts and preparation methods are the same as in example 1.
The performance test and results of the surface modified PVDF microfiltration membrane provided in comparative example 2 are as follows.
(1) Contact angle: the contact angle of the unmodified PVDF micro-filtration membrane is 93.7 degrees+/-3.4 degrees, and the contact angle of the surface modified PVDF micro-filtration membrane can reach 96.0 degrees+/-1.7 degrees.
(2) Investigation the surface-modified PVDF microfiltration membrane provided in comparative example 2 was applied to microalgae harvesting, and the change in the flux of the filtered microalgae before and after modification was measured. The unmodified PVDF micro-filtration membrane and the surface modified PVDF micro-filtration membrane are respectively placed in an MSC300 cup type ultrafiltration device after being pre-wetted by ethanol, and microalgae filtration experiments are carried out by using chlorella liquid with the concentration of 1g/L under the transmembrane pressure difference of 1 bar. The flux of algae liquid is recorded every minute, the surface of the membrane is cleaned every 20 minutes, and backwashing is carried out for 5 minutes by deionized water, and total backwashing is carried out for 4 times.
The initial algae flux of the unmodified PVDF micro-filtration membrane is 938 kg/(m) 2 H.atm), the initial algae flux of the surface modified PVDF microfiltration membrane is 482 kg/(m) 2 ·h·atm)。
Comparative example 3
The present comparative example provides a method for modifying the surface of a polymer, the resulting surface modified polymer and its use, the modification method being as follows:
5mg of 1, 4-phthalic acid was dissolved in 1000mg of ethanol to prepare a coating solution. Soaking PVDF micro-filtration membrane with aperture of 1.2 μm in ethanol, ultrasonic cleaning for 30min, corona treating for 30s, spraying the coating solution on the surface of PVDF micro-filtration membrane, naturally drying at room temperature, irradiating under ultraviolet lamp for 180s, and ultraviolet light with intensity of 1000mW/cm 2 Then soaking in ethanol solution for 1h, soaking in deionized water for 48 h, and drying to obtain the surface modified PVDF micro-filtration membrane.
The performance test and results of the surface modified PVDF microfiltration membrane provided in comparative example 3 are as follows.
(1) Contact angle: the contact angle of the unmodified PVDF micro-filtration membrane is 93.7 degrees+/-3.4 degrees, and the contact angle of the surface modified PVDF micro-filtration membrane can reach 91.9 degrees+/-5.5 degrees.
(2) The surface-modified PVDF microfiltration membrane provided in comparative example 3 was examined for application to microalgae harvesting, and the change in flux of the filtered microalgae before and after modification was measured. The unmodified PVDF micro-filtration membrane and the surface modified PVDF micro-filtration membrane are respectively placed in an MSC300 cup type ultrafiltration device after being pre-wetted by ethanol, and microalgae filtration experiments are carried out by using chlorella liquid with the concentration of 1g/L under the transmembrane pressure difference of 1 bar. The flux of algae liquid is recorded every minute, the surface of the membrane is cleaned every 20 minutes, and backwashing is carried out for 5 minutes by deionized water, and total backwashing is carried out for 4 times.
The initial algae flux of the unmodified PVDF micro-filtration membrane is 938 kg/(m) 2 H.atm), the initial algae flux of the surface modified PVDF microfiltration membrane is 944 kg/(m) 2 ·h·atm)。
From the test results of examples 1 to 13 and comparative examples 1 to 3, examples 1 to 13 provided surface-modified polymers having contact angles of 5.1 ° to 79.8 °.
The modification method provided in example 1 improves the hydrophilicity and initial algae flux of the PVDF microfiltration membrane, and the SEM (scanning electron microscope) image shows that the polymer surface modification method provided in example 1 enables the surface to be provided withGrafted with hydrophilic groups and produces a more porous surface structure. The polymer surface modification method provided in example 2 improves the hydrophilicity and biofouling resistance of the EVA film; the polymer surface modification method provided in example 3 improves the hydrophilicity and the anti-algal cell adhesion property of the polyethylene film; the polymer surface modification method provided in the embodiment 4 improves the hydrophilicity of the PVDF micro-filtration membrane, and the surface modified PVDF micro-filtration membrane has better rare earth ion adsorption capacity and cyclic regeneration capacity; the polymer surface modification method provided in the embodiment 5 improves the hydrophilicity of the polypropylene filter cloth, and the surface modified polypropylene filter cloth has better rare earth ion adsorption capacity; the polymer surface modification method provided in example 6 improves the hydrophilicity of the PVC microfiltration membrane, and the surface modified PVC microfiltration membrane has better PO 4 3- Ion adsorption capacity; the polymer surface modification methods provided in examples 7-9 improved the hydrophilicity and biofouling resistance of the polyethylene film.
If the addition amount of 3,3', 4' -tetracarboxylic benzophenone is too low (example 10) as compared to example 1, both hydrophilicity and initial algal liquid flux are decreased; in comparison of example 11 and example 12, as the content of 3,3', 4' -tetracarboxylic benzophenone increases, the contact angle does not change much, and the addition amount of 3,3', 4' -tetracarboxylic benzophenone is too high, which causes the waste of photoinitiator, and proves that the effect of modifying the polymer surface by adopting the photoinitiator in a specific mass percentage range is better.
If 3,3', 4' -tetracarboxylic benzophenone is replaced with benzophenone of the same quality or 4-methylbenzophenone (comparative example 1 or comparative example 2) as compared with example 1, the contact angle is large, the hydrophilic effect is poor, and the initial algae flux is lowered.
Compared with example 1, if 3,3', 4' -tetracarboxylic benzophenone is replaced with 1, 4-phthalic acid of the same quality, (comparative example 3), 1, 4-phthalic acid on the surface of the polymer is almost completely dissolved in water after being immersed in deionized water for 48 hours, and the hydrophilicity of the surface and the flux of initial algae liquid are not significantly changed compared with those before modification.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method of modifying a polymer surface, the method comprising the steps of: mixing a photoinitiator and a solvent, coating the mixture on the surface of a polymer, drying, and irradiating with ultraviolet light to obtain a surface modified polymer;
the photoinitiator is a photoinitiator containing a photoreactive group and a hydrophilic group.
2. The method of modifying a polymer surface of claim 1, wherein the photoreactive group comprises any one or a combination of at least two of an acyl group, a diazo group, or an azide group;
preferably, the acyl group comprises any one or a combination of at least two of a benzophenone group, a propiophenone group, a benzil group, an anthrone group or an anthraquinone group;
Preferably, the hydrophilic group includes any one or a combination of at least two of a carboxyl group, an amino group, a hydroxyl group, a phosphate group, or a sulfonate group;
preferably, the photoinitiator comprises 4-carboxybenzophenone, 2-carboxybenzophenone, 4 '-dicarboxybenzophenone, 2,4, 5-tricarboxybenzophenone, 3',4 '-tetracarboxylbenzophenone, 2',4,4 '-tetrahydroxybenzophenone, 2,3, 4-trihydroxybenzophenone, 4' -dihydroxybenzophenone, 2, 4-dihydroxybenzophenone, 4-hydroxybenzophenone, 3, 4-diaminobenzophenone, 4 '-diaminobenzophenone, 3', any one or a combination of at least two of 4,4 '-tetraminobenzophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylbenzophenone, 4-diazastilbene-2, 2-disulfonate, 4-azidobenzoic acid, azidoacetic acid, 2' -azidodeoxycuride, 2- (3-benzoylphenyl) propionic acid, (4- (2-aminoethyl) phenyl) (phenyl) methanone, 2-aminobenzophenone, 2-hydroxybenzophenone, 3-aminobenzophenone or azido-diethylene glycol-acetic acid.
3. The method of modifying a polymer surface according to claim 1 or 2, wherein the mixing further comprises mixing an emulsifier with the photoinitiator and the solvent;
Preferably, the mass percentage of the emulsifier is 0-20% based on 100% of the total mass of the emulsifier, the photoinitiator and the solvent.
4. The method of modifying a polymer surface of any one of claims 1-3, wherein the mixing further comprises mixing the micro-nanoparticles with optionally an emulsifier, a photoinitiator, and a solvent;
preferably, the micro-nano particles are made of any one or a combination of at least two of silicon dioxide, calcium carbonate, zinc oxide, titanium dioxide, rare earth oxide, rare earth salt, graphene, copper or silver;
preferably, the particle size of the micro-nano particles is 0.005-100 μm;
preferably, the micro-nano particles are 0 to 30% by mass based on 100% by mass of the total of the micro-nano particles, optionally the emulsifier, the photoinitiator and the solvent.
5. The method of modifying a polymer surface according to any one of claims 1 to 4, wherein the solvent comprises any one or a combination of at least two of water, methanol, ethanol, acetonitrile, acetone, dimethyl sulfoxide, N-dimethylformamide, acetic acid, ethyl acetate, tetrahydrofuran, N-hexane, trifluoroethanol, dichloromethane, chloroform, and toluene;
Preferably, the mass percent of the photoinitiator is 0.01-80% and the mass percent of the solvent is 20-99.99% based on 100% of the total mass of the photoinitiator and the solvent.
6. The method of modifying a polymer surface of any one of claims 1-5, wherein the polymer comprises any one or a combination of at least two of polyethylene, polystyrene, polypropylene, polyvinyl chloride, ethylene-vinyl acetate copolymer, polyolefin elastomer, polyurethane, polyimide, polyvinylidene fluoride, polysulfone, polyethersulfone, polyacrylonitrile, nylon, or polycarbonate;
preferably, the shape of the polymer includes any one of a film, a filter membrane, a filter cloth, a block, a fiber, a hollow fiber membrane, or a microsphere.
7. The method of modifying a polymer surface of any one of claims 1-6, wherein the polymer further comprises a pretreatment prior to coating;
preferably, the pretreatment comprises any one or a combination of at least two of etching, ozone treatment, ultraviolet irradiation, corona treatment, plasma treatment, glow discharge treatment or high-energy particle irradiation;
preferably, the coating comprises any one or a combination of at least two of spraying, dipping, knife coating or surface printing.
8. The method of modifying a polymer surface according to any one of claims 1 to 7, wherein the light source for ultraviolet irradiation comprises any one or a combination of at least two of an ultraviolet lamp, a high-pressure mercury lamp, a UV plasma, a UV light emitting diode, a UV xenon lamp, a metal halide lamp, an ultraviolet curing device, an ultraviolet curing agent, and a UV LED surface light source;
preferably, the ultraviolet irradiation time is 1-600 s;
preferably, the intensity of the ultraviolet light is 10-2000 mW/cm 2 ；
Preferably, the ultraviolet irradiation is performed under room temperature conditions;
preferably, the ultraviolet light irradiation further comprises immersing the coating in a solvent to remove ungrafted photoinitiator;
preferably, the soaking time is 0.1-24 hours.
9. A surface modified polymer produced by the polymer surface modification process of any one of claims 1 to 8.
10. Use of the surface modified polymer according to claim 9 in aquaculture materials, microalgae harvesting materials, filtration materials, adsorption materials, microalgae harvesting materials, biosensor materials, marine antifouling materials or wastewater treatment materials.
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| CN202310732572.8A CN116731375A (en) | 2023-06-20 | 2023-06-20 | Polymer surface modification method, obtained surface modified polymer and application thereof |
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