CN110066415B - Preparation method of porous membrane with functionalized surface - Google Patents
Preparation method of porous membrane with functionalized surface Download PDFInfo
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- CN110066415B CN110066415B CN201910326736.0A CN201910326736A CN110066415B CN 110066415 B CN110066415 B CN 110066415B CN 201910326736 A CN201910326736 A CN 201910326736A CN 110066415 B CN110066415 B CN 110066415B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J7/12—Chemical modification
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
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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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
Abstract
The invention relates to a method for preparing a porous membrane with a functionalized surface, which adopts the structural characteristic of molecular chain links
The vinylidene fluoride-chlorotrifluoroethylene copolymer with the m: n of 95: 5-80: 20 is used as a basement membrane, and chlorine groups in the molecular structure of the copolymer are utilized to react with amine compounds to prepare the vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane with positively charged surface. Then, the amino is used for reacting with molecules with epoxy groups, carboxyl groups, hydroxyl groups and other groups, and the required functional groups are grafted on the molecular chain of the vinylidene fluoride-chlorotrifluoroethylene copolymer for improving the pollution resistance, oil resistance, selective adsorption and the like of the vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane.
Description
Technical Field
The invention belongs to the field of membrane separation, relates to a modification technology of a porous membrane, and particularly relates to a preparation method of an organic porous membrane.
Background
The membrane separation process is usually carried out at normal temperature, does not produce secondary pollution, is an efficient and energy-saving separation and purification technology, and is widely applied to a plurality of industrial fields such as water purification and sewage resource treatment, material separation and purification of chemical engineering and medicines and the like and civil fields such as water purification, air purification and the like. As a new chemical fluid separation unit operation technology, a membrane separation technology represented by an organic separation membrane has been remarkably developed for thirty years, and plays an important role as a basic common technology in aspects such as environmental protection, technical promotion of a traditional industrial production process and the like, and a membrane material is the core of the membrane separation technology.
The porous membrane is a membrane separation material having through holes of several tens nanometers to several hundreds nanometers in the membrane wall, and is used not only for water-permeable and air-impermeable separation processes such as ultrafiltration, microfiltration, and dialysis, but also for water-permeable and air-impermeable separation processes such as membrane absorption, membrane distillation, membrane aeration, membrane degassing, and membrane crystallization, and is also a base membrane of a composite membrane such as reverse osmosis, forward osmosis, nanofiltration, pervaporation, and gas separation.
Currently, commonly used organic porous membrane materials include: polyvinylidene fluoride, polyvinyl chloride, polysulfone, polyethersulfone, cellulose acetate, nylon, polytetrafluoroethylene, polyethylene, polypropylene and the like, wherein the polyvinylidene fluoride material has excellent performance and is most widely applied. But the polyvinylidene fluoride membrane material still has the defects of poor alkali resistance, difficult chemical grafting modification on the surface and the like.
The prior report is that the amination hydrophilization modification is carried out on the polyvinylidene fluoride material, fluorine atoms in a polyvinylidene fluoride molecular chain are utilized to react with amine compounds, on one hand, the amine groups are not easy to be introduced into the molecular chain of the polymer, and simultaneously, the mechanical property of the polyvinylidene fluoride material is greatly influenced.
Disclosure of Invention
Aiming at the defects of poor alkali resistance, difficult surface chemical grafting modification and the like of a polyvinylidene fluoride membrane material, the invention provides a base membrane prepared from vinylidene fluoride-chlorotrifluoroethylene copolymer resin, utilizes a chlorine group in a molecular structure of the base membrane to react with a diamine compound to prepare a positively charged porous membrane, then reacts with carboxyl, epoxy and the like to form various functional groups, and prepares a negatively charged and electrically neutral porous membrane and a porous membrane with an adsorption function and response functions of pH, temperature and the like. The membrane separation pore size is 0.01-1.0 micron.
Under the condition of not obviously losing the strength of the membrane, required functional groups are introduced to the surface of the membrane, and functionalized surface porous membranes such as a vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane with positive charge, an anti-pollution porous membrane with negative charge, a polyvinyl alcohol or polyethylene glycol electric neutral anti-pollution porous membrane, an oil pollution resistant porous membrane, an intelligent response membrane, a porous membrane with a selective adsorption function and the like can be correspondingly prepared.
The molecular chain link structure of the vinylidene fluoride-chlorotrifluoroethylene copolymer is characterized as follows:
the prior vinylidene fluoride-chlorotrifluoroethylene copolymer mainly comprises two types: one is material mainly comprising molecular chain segment of trifluorochloroethylene, in the above molecular chain segment structural formula, m: n is 1:4, and m: n is 1: 9; the other is mainly vinylidene fluoride molecular chain segment, for example, m: n is 95: 5-80: 20.
Vinylidene fluoride-chlorotrifluoroethylene copolymer resin mainly comprising vinylidene fluoride molecular chain segments is currently used for cables, and is made use of the properties of high elasticity, high elongation and cold impact resistance. The invention adopts vinylidene fluoride-chlorotrifluoroethylene copolymer which takes vinylidene fluoride molecular chain segment as main component, and the vinylidene fluoride-chlorotrifluoroethylene copolymer is used for preparing the basement membrane of the porous membrane. Structural features of molecular chain links: vinylidene fluoride-chlorotrifluoroethylene copolymer with mn of 95:5, 90:10, 85:15, 80:20, wherein mn of 85:15 is preferred for porous membrane-based membrane production according to the present invention.
The polyvinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane base membrane used in the invention can adopt conventional thermal phase separation, melting stretching and other methods, can also adopt conventional non-solvent induced phase separation and low-temperature induced phase separation, and can also carry out subsequent stretching and shaping on the initially formed hollow or flat vinylidene fluoride-chlorotrifluoroethylene copolymer. Pore size range: 0.01-1.0 micron.
The structure form of the polyvinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane base membrane used in the invention can be various conventional porous membrane forms such as an internal pressure type hollow fiber membrane, an external pressure type hollow fiber membrane, a flat membrane, a roll-type membrane, a folding membrane, a tubular membrane and the like.
The invention directly carries out substitution reaction on diamine compounds and chlorine in a molecular chain segment of the vinylidene fluoride-chlorotrifluoroethylene copolymer, grafts an amino group which is easier to react on the molecular chain of the vinylidene fluoride-chlorotrifluoroethylene copolymer, then utilizes the amino group to react with molecules with epoxy group, carboxyl group, hydroxyl group and the like, and grafts the required functional group on the molecular chain of the vinylidene fluoride-chlorotrifluoroethylene copolymer, and is used for improving the pollution resistance, oil resistance, selective adsorption and the like of the vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane.
The preparation method of the vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane comprises the step of reacting the vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane base membrane with diamine aqueous solutions with the concentration of 0.1-3.0mol/L, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine, hexamethylenediamine and the like, at the temperature range of room temperature to 90 ℃, wherein the reaction time is 2-48 hours, and the positive charge vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane is prepared firstly. And then respectively reacting with a compound containing carboxyl or epoxy groups again to obtain the functional surface porous membranes such as the negative charge anti-pollution porous membrane, the polyvinyl alcohol or polyethylene glycol type neutral anti-pollution porous membrane, the oil pollution resistant porous membrane, the intelligent response membrane, the porous membrane with the selective adsorption function and the like. Preferably: diethylenetriamine and triethylene tetramine
The preparation method of the polyvinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane comprises the step of reacting the polyvinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane base membrane with 0.1-3.0mol/L aqueous solution of ethanolamine, diethanol amine and the like at the temperature ranging from room temperature to 90 ℃, wherein the reaction time is 2-48 hours, and the porous membrane with hydrophilic surface is directly obtained.
The aminated positive charge vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane can react with compounds containing carboxyl groups, such as oxalic acid, malic acid, citric acid, itaconic acid, maleic anhydride, fumaric acid, maleic anhydride and low molecular weight polyacrylic acid (the molecular weight is below 5000 daltons) to prepare functionalized surface porous membranes such as negative charge anti-pollution porous membranes and porous membranes with selective adsorption function. Then, the reaction with polyvinyl alcohol or polyethylene glycol can be continued to prepare the neutral anti-pollution porous membrane and the porous membrane with selective adsorption function.
The aminated positive charge vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane can react with hydroxypropionic acid and gluconic acid to prepare an electrically neutral membrane, and reactants have small molecular weight, can not block membrane pores and reduce membrane flux.
The surface hydrophilic porous membrane can be obtained by reacting the active polyamine group on the surface of the aminated positively charged vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane with a compound containing an epoxy group, such as liquid low molecular weight bisphenol A type resin, bisphenol F type resin, bisphenol S type resin, alicyclic diepoxide, glycidyl ester type epoxy resin, hydantoin epoxy resin, and the like. And then, the introduced epoxy group can be continuously utilized to continuously react with the amine compound to prepare the porous membrane with positive charge or selective adsorption function. And the introduced epoxy group can be continuously utilized to continuously react with the carboxyl compound to prepare the porous membrane with negative charge or selective adsorption function.
The invention has the advantages and positive effects that:
according to the method, chlorine atoms with higher reactivity than fluorine atoms in a vinylidene fluoride-chlorotrifluoroethylene copolymer molecular chain are directly subjected to substitution reaction with primary amines and secondary amines in a multi-amino compound, the amino groups with higher reactivity are grafted and introduced into the vinylidene fluoride-chlorotrifluoroethylene copolymer molecular chain, and the negative effect of elimination reaction of hydrogen fluoride in the polymer molecular chain on the mechanical property of a membrane material is reduced. Under the condition of not obviously losing the strength of the membrane, required functional groups are introduced on the surface of the membrane, and functionalized surface porous membranes such as a vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane with positive charge, an anti-pollution porous membrane with negative charge, a polyvinyl alcohol or polyvinyl glycol electrically neutral anti-pollution porous membrane, an oil pollution resistant porous membrane, an intelligent response membrane, a porous membrane with a selective adsorption function and the like can be correspondingly prepared.
Drawings
FIG. 1 is a graph showing the color change of PVDF and PVDF-CTFE after amination treatment;
FIG. 2 is a graph showing the change in strength of PVDF and PVDF-CTFE after 1.5mol/L amination treatment.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are illustrative only and not limiting, and the scope of the present invention is not limited thereby.
Example 1
PVDF-CTFE copolymer film is taken and immersed into a diethylenetriamine aqueous solution of 0, 0.30, 1.0 and 1.5mol/L at the temperature of 80 ℃ respectively for reaction for 6 hours. After the reaction, the mixture is fully flushed by 50 percent (v/v) ethanol water solutionWashing, soaking in pure water, and drying. The modified membrane sheets were named CF2-CTFE raw membrane, CF2-CTFE-0.3, CF2-CTFE-1.0 and CF2-CTFE-1.5, respectively. Preparation of CF2-CTFE copolymer positively charged membranes.
Comparative example 1
The PVDF homopolymer membrane is taken and respectively immersed into 0, 0.30, 1.0 and 1.5mol/L diethylenetriamine aqueous solution at the temperature of 80 ℃ for reaction for 6 hours. After the reaction, the mixture was thoroughly washed with 50% (v/v) ethanol aqueous solution, rinsed with pure water, and dried. The modified membrane sheets are named as original CF2 membrane, CF2-0.3 membrane, CF2-1.0 membrane and CF2-1.5 membrane respectively.
As can be seen from FIG. 1, the PVDF-CTFE copolymer is significantly lighter than PVDF after the same concentration of aqueous solution of diethylenetriamine.
As shown in FIG. 2, after 1.5mol/L amination treatment, the rupture strength of the PVDF membrane is reduced from 1.432MPa to 0.39MPa, and the rupture strength of the PVDF-CTFE membrane is conversely increased from 0.964MPa before treatment to 1.172 MPa.
TABLE 1 chemical composition of membrane surface after alkaline treatment of CF2-CTFE and PVDF
As can be seen from Table 1, the presence of C-Cl bonds in the copolymer increases the extent of amination, especially at low concentrations of reaction conditions, at CF2The nitrogen element content of the surface of the CTFE membrane is obviously increased.
Example 2
The PVDF-CTFE copolymer hollow fiber membrane is taken and immersed into 1.0mol/L triethylene tetramine aqueous solution at the temperature of 60 ℃ for reaction for 4 hours. After the reaction, the mixture was rinsed with pure water and dried. Preparation of CF2-CTFE copolymer positively charged membranes.
Example 3
The modified film CF obtained in example 12-CTFE-1.0 was immersed in a toluene solution containing 10g/100ml of maleic anhydride and reacted at 30 ℃ for 6 hours. After the reaction is finished, the membrane is fully washed by absolute ethyl alcohol to remove the residual solvent toluene, then the membrane is completely washed by pure water and is placed into a constant-temperature drying oven for dryingAnd (4) completing. The grafting rate of the maleic anhydride was measured by weighing to be 0.532. mu. mol/cm2. Preparation of CF2-a CTFE copolymer negatively charged membrane.
Example 4
The modified film CF obtained in example 12-CTFE-1.0 was immersed in an aqueous solution containing 10g/100ml of itaconic acid and reacted at 80 ℃ for 12 hours. And after the reaction is finished, fully washing the membrane by using pure water, and completely drying the membrane in a constant-temperature drying oven. The grafting ratio of itaconic acid was measured by the weighing method to be 0.45. mu. mol/cm2. Preparation of CF2-a CTFE copolymer negatively charged membrane.
Example 5
The modified film CF obtained in example 12-CTFE-1.0 was immersed in an aqueous solution of polyacrylic acid having an average molecular weight of 5000 daltons of 10g/100ml, and reacted at 80 ℃ for 12 hours. And after the reaction is finished, fully washing the membrane by using absolute ethyl alcohol to remove residual unreacted substances, then completely washing by using pure water, and completely drying in a constant-temperature drying oven. The grafting rate of the polyacrylic acid is 1.35 mu mol/cm by weighing method2. Preparation of CF2-a CTFE copolymer negatively charged membrane.
Example 6
And (3) soaking a PVDF-CTFE copolymer membrane into 1.0mol/L triethylene tetramine aqueous solution at the temperature of 80 ℃ for reaction for 6 hours. After the reaction, the mixture was thoroughly washed with 50% (v/v) ethanol aqueous solution, rinsed with pure water, and dried. Preparation of CF2-a positively charged membrane of CTFE copolymer.
Example 7
The modified PVDF-CTFE copolymer film obtained in example 6 was immersed in an aqueous solution containing 10g/100ml of polyacrylic acid having an average molecular weight of 5000 daltons and reacted at 80 ℃ for 12 hours. And after the reaction is finished, fully washing the membrane with absolute ethyl alcohol to remove residual unreacted substances, then completely washing with pure water, and completely drying in a constant-temperature drying oven. The grafting rate of the polyacrylic acid is 1.35 mu mol/cm measured by a weighing method2. Preparation of CF2A CTFE copolymer negatively charged membrane, which has selective adsorption to heavy metal ions in water.
Example 8
The hollow fiber membrane of the modified PVDF-CTFE copolymer obtained in example 2 was immersed in hydantoin epoxy XB-0.54 and reacted at 80 ℃ for 2 hours. And after the reaction is finished, fully washing the reaction product by using absolute ethyl alcohol to remove residual unreacted substances, then completely washing the reaction product by using pure water, and completely drying the reaction product in a constant-temperature drying oven. The grafting rate of the hydantoin epoxy is 3.1 mu mol/cm measured by a weighing method2. Preparation of surface-neutral CF2-CTFE copolymer hollow fiber membranes.
Example 9
The hollow fiber membrane of modified PVDF-CTFE copolymer obtained in example 8 was immersed in a 1.0mol/L aqueous solution of triethylene tetramine at 80 ℃ and reacted for 6 hours. After the reaction, the mixture was thoroughly washed with 50% (v/v) ethanol aqueous solution, rinsed with pure water, and dried. Preparation of CF2-CTFE copolymer positively charged hollow fiber membranes.
Example 10
Immersing the modified PVDF-CTFE copolymer hollow fiber membrane obtained in the example 2 into a gluconic acid aqueous solution, and reacting for 2 hours at 80 ℃ to prepare CF with neutral surface charge2-CTFE copolymer hollow fiber membranes.
Example 11
Immersing the modified PVDF-CTFE copolymer hollow fiber membrane obtained in example 2 into a citric acid aqueous solution, and reacting at 80 ℃ for 2 hours to prepare CF with neutral surface charge2-CTFE copolymer hollow fiber membranes.
Example 12
And (2) contacting the vinylidene fluoride-chlorotrifluoroethylene copolymer hollow fiber porous membrane with ethanolamine liquid at the temperature range of room temperature to 90 ℃ for reaction for 8 hours to directly obtain the vinylidene fluoride-chlorotrifluoroethylene copolymer hollow fiber porous membrane with hydrophilic surface.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept, and these changes and modifications are all within the scope of the present invention.
Claims (7)
1. A method for preparing a porous membrane with a functionalized surface is characterized by comprising the following steps: adopts the molecular chain link structure as the Characteristic (CF)2—CH2）m（CF2—CClF）nThe vinylidene fluoride-chlorotrifluoroethylene copolymer is used as a base membrane, wherein m is 95: 5-80: 20, and a chlorine group in a copolymer molecular structure is utilized to react with an amine compound to prepare a vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane with a positively charged surface;
reacting the prepared vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane with positive charge on the surface with a compound containing a carboxyl group to prepare a negative charge anti-pollution porous membrane or a porous membrane with a selective adsorption function;
or reacting the prepared vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane with positive charge on the surface with hydroxypropionic acid or gluconic acid to prepare an electrically neutral porous membrane;
or the prepared vinylidene fluoride-chlorotrifluoroethylene copolymer porous membrane with positively charged surface and the compound containing epoxy group are continuously reacted to obtain the porous membrane with hydrophilized surface.
2. The porous film production method according to claim 1, characterized in that: the amine compound is one or a mixture of more than two of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine.
3. The porous film production method according to claim 2, characterized in that: the concentration of the amine compound is 0.1-3.0mol/L, and the amine compound reacts with the vinylidene fluoride-chlorotrifluoroethylene copolymer for 2-48 hours at the temperature of 20-90 ℃.
4. The porous film production method according to claim 1, characterized in that: the compound containing carboxyl groups is one or a mixture of more than two of oxalic acid, malic acid, citric acid, itaconic acid, maleic anhydride, fumaric acid, maleic anhydride, glue anhydride and polyacrylic acid with the molecular weight of below 5000 daltons.
5. The porous film production method according to claim 1, characterized in that: the compound containing the epoxy group is one or a mixture of more than two of bisphenol S type resin, alicyclic diepoxide, glycidyl ester type epoxy resin and hydantoin epoxy.
6. The porous film production method according to claim 1, characterized in that: and reacting the obtained porous membrane with the surface hydrophilization with an amine compound to prepare the porous membrane with positive charge or selective adsorption function, wherein the amine compound is one or a mixture of more than two of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
7. The porous film production method according to claim 1, characterized in that: and reacting the obtained surface-hydrophilized porous membrane with a carboxyl compound to prepare the porous membrane with negative charge or selective adsorption function, wherein the carboxyl compound is one or a mixture of more than two of oxalic acid, malic acid, citric acid, itaconic acid, maleic anhydride, fumaric acid, maleic anhydride, glue anhydride and polyacrylic acid with the molecular weight of below 5000 daltons.
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| CN111195485B (en) * | 2020-02-17 | 2022-09-02 | 天津工业大学 | Preparation method of polyvinyl chloride blood purification membrane |
| CN111659267A (en) * | 2020-07-23 | 2020-09-15 | 天津海龙津阳材料科技有限公司 | Pollution-resistant modified porous membrane and preparation method thereof |
| CN113083032B (en) * | 2021-04-26 | 2022-10-28 | 贵州省材料产业技术研究院 | Positively charged blended ultrafiltration membrane and preparation method thereof |
| CN116351384A (en) * | 2021-12-28 | 2023-06-30 | 比亚迪股份有限公司 | Lithium adsorbent and method for extracting lithium from salt lake |
| CN114534525B (en) * | 2021-12-31 | 2023-05-23 | 山东华夏神舟新材料有限公司 | Amination modified anti-pollution porous membrane and preparation method thereof |
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