CN105801859A - Method for preparing functional polymer micro-porous membrane with reaction-solution phase inversion control method - Google Patents
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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- C08G75/23—Polyethersulfones
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
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Abstract
The invention belongs to the technical field of functional polymer membrane separation, and relates to a method for preparing a crown-ether graft polymer micro-porous membrane with a reaction-solution phase inversion control method. The method includes the steps that a chloromethyl-containing polymer such as polysulfone or polyether sulfone or polyether ether ketone is dissolved into a reaction solvent, an active-amido containing crown ether compound such as 4-aminobenzene-15-crown-5 is added, and a crown ether graft polymer is prepared through a nucleophilic substitution reaction between chloromethyl and amino; the grafting ratio of the reaction is controlled; in other words, when a reaction system is in certain viscosity, the reaction is terminated to prevent gelatinizing, the reaction system at the moment serves as a membrane casting solution, and the crown-ether graft polymer micro-porous membrane is prepared with the solution phase inversion method. As a cross bond exists in the polymer system, it can be achieved that the polymer micro-porous membrane which is high in porosity ratio and breaking strength is prepared under the low solid content of the polyether, and the separation step and the purification step of the grafted polymer are omitted; as a crown ether group exists, the polymer membrane has excellent lithium isotope separation performance.
Description
Technical field
The invention belongs to functional polymer technical field of membrane separation, the method preparing crown ether graft polymers microporous membrane particularly to a kind of reaction-control immersion precipitation phase inversion process.
Background technology
Membrane separation technique is the new and high technology grown up mid-term 1960's, it is filter medium that utilization has separation selectivity chemosmotic separation film, by principles such as the sieving actoion of fenestra, charge effect and dissolving diffusions, the solute in mixture and solvent are separated, classification, the method extracting and be enriched with.Compared with common filter medium, separate film and there is controlled aperture and narrower pore-size distribution, higher separation accuracy.Phase inversion is to prepare porous membranes or composite membrane basement membrane most common method.It is polymer and additive to be dissolved in solvent, forms homogeneous phase transparent solution, then by making polymer solution be changed into thermodynamic instability state someway, makes polymer solution gradually solidify, ultimately form the process of the polymer microporous film with specific modality.According to different solution thermodynamics state induction reasons of changes, inversion of phases film-forming method includes: solvent evaporation phase inversion, thermal induction phase inversion, gaseous phase deposition phase inversion and solution phase inversion.The most widely used is solution phase inversion, its process is: first the casting solution that polymer and solvent form is coated in gripper shoe (such as glass plate), immerse after spreading to thin film in coagulating bath, solvent and non-solvent generation double diffusion in coagulating bath in casting solution immediately, solvent diffuse enters coagulating bath, rather than solvent diffuse is in the thin film spread to.Exchange between solvent and non-solvent reaches to a certain degree, and now solution becomes thermodynamic instability state, thus split-phase occurs, and polymer solidify to form microporous membrane.In solution inversion of phases film-forming process, casting solution thermodynamics and solvent-nonsolvent double diffusion kinetics are the keys of solution phase inversion masking.
And for functionalized polymer microporous membrane, its preparation process has two kinds of methods.Film matrix, for first to prepare polymer microporous film matrix, is then modified or the grafting of function thing by first method.Chinese patent CN104289119A reports a kind of method that ultraviolet light irradiation polysulphones hyperfiltration membrane is modified, it is specially polysulfones to clean through methanol, be dried, then it is soaked in photosensitizer benzophenone/acetone soln, the dried polysulfone membrane processed being put into seals preservation in the ethanol water containing polymerization inhibitor, and it is passed through nitrogen to remove oxygen, finally by the irradiation under the 1000W uviol lamp of 253.7nm of polysulfone membrane in ethanol solution, i.e. complete polysulfone membrane modified.Chinese patent CN1468278A discloses a kind of polyether sulfone and the method for polysulfones ultraviolet auxiliary graft modification.Polyarylsufone film is immersed in the monomer solution containing chain-transferring agent by this patent, polymeric film is carried out ultraviolet light irradiation to complete the modification of polymeric film from monomer solution after being taken out by polymeric film in the presence of light filter.United States Patent (USP) US5462867 reports a kind of method that polysulfone membrane surface carries out hydroxylating modification, method particularly includes: first molded polysulfone membrane is dipped in hot sodium hydrate aqueous solution, then film is placed in the sodium hydroxide solution containing 10wt% Ethylene glycol diglycidyl ether 4 hours, after washing, film be impregnated in again in the sodium hydrate aqueous solution containing 2wt% hydroxyethyl cellulose 16 hours and complete modification.Periodical " macromolecule journal " the 7th phase 924-931 page in 2010 reports a kind of ion exchange polysulfone membrane preparation method.It is specially and first prepares chloromethyl polysulphone film, treat film molding and make film have charged and ion-exchange performance with the cross-linking agent process containing amino after drying.After film forming, basement membrane modification is had the disadvantage that and not enough: modified homogeneity is poor, can only be modified film surfaces externally and internally；And owing to membrane surface is dense, chemical modification resistance is relatively big, poor to film inter-modification effect；Film forming post-modification also can make established membrane structure change further, and the controllability of membrane structure is deteriorated.
Second method is the polymer first prepared and have specific function, then uses certain method to prepare functional copolymer membrane.United States Patent (USP) US5376689 reports the preparation method of a kind of aminated polysulfone film, concrete grammar is polysulfones and aminated polysulfone to be dissolved in the N-Methyl pyrrolidone (NMP) containing Ketohexamethylene, filter and after deaeration, polymer solution scratched on non-weaving cloth, after evaporating 10～15 seconds in atmosphere, non-weaving cloth being impregnated in and solidification bath water completes inversion of phases formation amination polysulfone membrane.Chinese patent CN103495353A discloses the preparation method of a kind of Quaterisation chitosan modified polysulphone super-filter membrane, polysulfones and Quaterisation chitosan are dissolved in NMP and dimethyl sulfoxide respectively, by solution deaeration and be coated in polyester non-woven fabric after mixing, non-weaving cloth is submerged in water generation phase conversion reaction and prepares modified polysulfone film.
Additionally, Chinese patent CN1038299A reports a kind of functionalized polymer membrane chromatography lithium isotope isolation technics.The amino benzo-crown ether with Isotope seperation is grafted on chloromethyl polysulphone and cause phase inversion by non-solvent and prepare crown ether grafting polysulfones microporous membrane, and microporous membrane is tailored preparation membrane chromatography post film in certain specification chromatography column, utilize crown ether to be grafted the abundant microcellular structure of polysulfones microporous membrane and high-specific surface area, achieve process for lithium isotope separation serialization and high efficiency by drip washing membrane chromatography separate mode.But, in polymer microporous film preparation process, for obtaining the crown ether grafting polysulfone polymer microporous membrane of bigger supported quantity, gelatin phenomenon is there will be owing to the extent of reaction is excessive in amino crown ether with chloromethyl polysulfones process of grafting, make to generate that polymer is insoluble does not melts, it is impossible to by conventional non-solvent induction phase conversion method film forming.About-problem, Chinese patent CN1038299A is not described.
Summary of the invention
Not enough for prior art, the technical problem that the present invention intends to solve is to provide a kind of graft polymers microporous membrane preparation method with lithium isotope separation function.It is characterized in that: chloromethylated polymer is dissolved in organic solvent configuration finite concentration polymer solution, it is added thereto to the crown compound containing active amino again, by nucleophilic substitution between amino and chloromethyl, crown compound is grafted on polymer molecule side chain prepare crown ether graft polymers；Meanwhile, the percent grafting controlling reaction i.e. terminates when reaction system reaches certain viscosity reacting to prevent gelation, and directly using reaction system this moment as casting solution, uses immersion precipitation phase inversion process to prepare crown ether graft polymers microporous membrane.
Described polymer microporous film main chain is containing chloro-methyl group polymer, predominantly polysulfones, polyether sulfone or polyether-ether-ketone, and the described crown compound containing active amino is that amino replaces benzo-crown ether or Azacrown ether containing, and its general structure is as follows:
Wherein n is 1,2,3 or 4.
It is described that to have polyether compound supported quantity in lithium isotope separating property polymer microporous film be 0.1mmol/g～1.0mmol/g.
This crown ether graft polymers microporous membrane preparation method is as follows: first chloromethylated polymer is dissolved in organic solvent configuration finite concentration polymer solution, it is added thereto to the crown compound containing active amino again, react certain time at desired temperatures, directly using reaction system this moment as casting solution, immersion precipitation phase inversion process is used to prepare crown ether graft polymers microporous membrane.
Solvent can be selected for DMF, DMAc, NMP, one or both in Isosorbide-5-Nitrae-dioxane, or DMSO.
In reaction system, being 10%-100% containing chloromethyl substitution value in chloromethyl polymer, be 3%-25% (w/w) containing chloromethyl polymer solution concentration, crown compound is 0.5: 1～5: 1 with chloromethyl mol ratio in polymer.Being 40 DEG C～80 DEG C in reaction temperature, the response time is to make crown compound graft on main polymer chain by nucleophilic substitution under 2h～24h, graft polymers XPS spectrum figure result as in figure 2 it is shown, infared spectrum as shown in Figure 3.Owing in crown ether, amino is 2 degree of functionality reactants, it can crosslink reaction with chloromethyl polysulphone substep, and cross-linking reaction process is shown in Fig. 4.
Reaction terminate after using reaction solution as casting solution, 20 DEG C of vacuum defoamation 1h, be coated on glass pane surface, and glass plate be placed in coagulating bath together with casting solution, inversion of phases film forming.
Described coagulating bath is water, one or more mixed liquors in ethanol, methanol, DMF and DMAc, and coagulation bath temperature is 10 DEG C～80 DEG C of arbitrary temperature.
Compared with prior art, the reaction of the present invention-control inversion of phases film-forming method can prepare polymer microporous film under low-solid content (3%～25%), and can prepare, with extent of reaction difference, the film that micro structure is different.Different structure polymer section structure is prepared as shown in Figure 5 especially by the regulation and control extent of reaction.
Owing to casting solution solid content is relatively low, prepared polymer microporous film has higher porosity (50%～80%), compared with pure polysulfone membrane, owing to molecule interchain crosslinked action crown ether grafting polysulfone polymer microporous membrane fracture strength improves 10%～23%.
The invention have the advantages that: the crown ether grafting polysulfone polymer microporous membrane structure that (1) uses the method to prepare is easily controllable, and porosity is high, crown ether supported quantity is high, shows excellent lithium isotope separating property.(2) this preparation method operating condition gentleness, environmental protection.With polymer reaction system as casting solution, eliminate the isolated and purified process of graft polymers, solve cross linked polymer insoluble molten cannot the difficult problem of film forming, provide new thinking for cross linked polymer for preparing polyalcohol stephanoporate functional membrane.(3) owing in film forming procedure, polymer solids level is low and there is cross-bond effect, prepared polymeric film porosity is high, and mechanical property is preferable.
Accompanying drawing explanation
Fig. 1 prepares crown ether grafting polysulfone polymer microporous membrane schematic flow sheet for reaction-control phase inversion.
Fig. 2 is chloromethyl polysulphone and 4-amino benzo-15-crown-5 grafting polysulfone polymer microporous membrane XPS spectrum figure, and wherein CMPSF-g-AB15C5 prepares under being low reaction degree gelation reaction polymer does not occurs.
Fig. 3 is polysulfones, chloromethyl polysulphone and 4-amino benzo-15-crown-5 grafting polysulfone polymer microporous membrane infrared spectrum.
Fig. 4 is that 4-amino benzo-15-crown-5 reacts preparation grafting polysulfone polymer chemical reaction process with chloromethyl polysulphone.
Fig. 5 is the 4-amino benzo-15-crown-5 grafting polysulfone polymer microporous membrane profile scanning Electronic Speculum figure controlling preparation under differential responses degree.
Detailed description of the invention
The following examples can make those skilled in the art be more completely understood by the present invention, but limits the present invention never in any form.
Embodiment 1
Reaction-control phase inversion prepares 4-amino benzo-15-hat 5 grafting polysulfones microporous membranes, specific as follows: to weigh 3g chloromethyl polysulphone (chloromethyl substitution value is 20%) and be dissolved in 57ml DMF, 4-amino benzo-15-crown-5 1.9g it is added thereto to after being completely dissolved, 20 DEG C of vacuum defoamations after 45 DEG C of reaction 22h, then casting solution is coated on glass plate, glass plate is placed in solidification bath water (20 DEG C), take out after coagulation forming 30min and be dried, prepare 4-amino benzo-15-hat 5 grafting polysulfone polymer microporous membrane.The polymer microporous film above-mentioned condition prepared circulation absorption 100mL 0.5mol/L lithium iodide solution 30 minutes under 0.05MPa pressure when 20 DEG C, obtaining 4-amino benzo-15-hat 5 grafting polysulfone polymer microporous membrane separation factors is 1.035.
Embodiment 2
Reaction-control phase inversion is prepared 4-amino benzo-15-and is preced with 5 graft polyether sulfone microporous membranes, specific as follows: to weigh 3g chloromethylation polyether sulfone (chloromethyl substitution value is 50%) and be dissolved in 57ml DMF, 4-amino benzo-15-crown-5 1.9g it is added thereto to after being completely dissolved, 20 DEG C of vacuum defoamations after 45 DEG C of reaction 15h, then casting solution is coated on glass plate, glass plate is placed in solidification bath water (20 DEG C), take out after coagulation forming 30min and be dried, prepare 4-amino benzo-15-and be preced with 5 graft polyether sulfone polymer microporous membranes.The polymer microporous film above-mentioned condition prepared circulation absorption 100mL 0.5mol/L lithium iodide solution 30 minutes under 0.05MPa pressure when 20 DEG C, obtain 4-amino benzo-15-being preced with 5 graft polyether sulfone polymer microporous membrane separation factors is 1.040.
Embodiment 3
Reaction-control phase inversion prepares 4-amino benzo-12-hat 4 grafting polysulfones microporous membranes, specific as follows: to weigh 3g chloromethyl polysulphone (chloromethyl substitution value is 20%) and be dissolved in 57ml DMF, 4-amino benzo-15-crown-5 1.7g it is added thereto to after being completely dissolved, 20 DEG C of vacuum defoamations after 45 DEG C of reaction 22h, then casting solution is coated on glass plate, glass plate is placed in solidification bath water (20 DEG C), take out after coagulation forming 30min and be dried, prepare 4-amino benzo-15-hat 5 grafting polysulfone polymer microporous membrane.The polymer microporous film above-mentioned condition prepared circulation absorption 100mL 0.5mol/L lithium iodide solution 30 minutes under 0.05MPa pressure when 20 DEG C, obtaining 4-amino benzo-12-hat 4 grafting polysulfone polymer microporous membrane separation factors is 1.035.
Embodiment 4
Reaction-control phase inversion preparation single azabenzo15crown5 grafting polysulfones microporous membrane, specific as follows: to weigh 3g chloromethyl polysulphone (chloromethyl substitution value is 20%) and be dissolved in 57ml DMF, single azabenzo15crown5 ether 1.7g it is added thereto to after being completely dissolved, 20 DEG C of vacuum defoamations after 65 DEG C of reaction 22h, then casting solution is coated on glass plate, glass plate is placed in solidification bath water (20 DEG C), take out after coagulation forming 30min and be dried, prepare single azabenzo15crown5 grafting polysulfone polymer microporous membrane.The polymer microporous film above-mentioned condition prepared circulation absorption 100mL 0.5mol/L lithium iodide solution 30 minutes under 0.05MPa pressure when 20 DEG C, obtaining single azabenzo15crown5 grafting polysulfone polymer microporous membrane separation factor is 1.035.
Embodiment 5
Reaction-single azepine benzo 18-crown-6 of control phase inversion preparation is grafted polysulfones microporous membrane, specific as follows: to weigh 3g chloromethyl polysulphone (chloromethyl substitution value is 20%) and be dissolved in 57ml DMF, single azepine benzo 18-crown-6 ether 1.7g it is added thereto to after being completely dissolved, 20 DEG C of vacuum defoamations after 65 DEG C of reaction 22h, then casting solution is coated on glass plate, glass plate is placed in solidification bath water (20 DEG C), take out after coagulation forming 30min and be dried, prepare single azepine benzo 18-crown-6 and be grafted polysulfone polymer microporous membrane.The polymer microporous film above-mentioned condition prepared circulation absorption 100mL 0.5mol/L lithium iodide solution 30 minutes under 0.05MPa pressure when 20 DEG C, obtain single azepine benzo 18-crown-6 being grafted polysulfone polymer microporous membrane separation factor is 1.035.
Embodiment 6
Reaction-control phase inversion prepares 4-amino benzo-15-hat 5 grafting polysulfones microporous membranes, specific as follows: to weigh 3g chloromethyl polysulphone (chloromethyl substitution value is 20%) and be dissolved in 57ml DMF, 4-amino benzo-15-crown-5 0.8g it is added thereto to after being completely dissolved, 20 DEG C of vacuum defoamations after 45 DEG C of reaction 22h, then casting solution is coated on glass plate, glass plate is placed in solidification bath water (20 DEG C), take out after coagulation forming 30min and be dried, prepare 4-amino benzo-15-hat 5 grafting polysulfone polymer microporous membrane.The polymer microporous film above-mentioned condition prepared circulation absorption 100mL 0.5mol/L lithium iodide solution 30 minutes under 0.05MPa pressure when 20 DEG C, obtaining 4-amino benzo-15-hat 5 grafting polysulfone polymer microporous membrane separation factors is 1.008.
Embodiment 7
Reaction-control phase inversion prepares 4-amino benzo-15-hat 5 grafting polysulfones microporous membranes, specific as follows: to weigh 3g chloromethyl polysulphone (chloromethyl substitution value is 20%) and be dissolved in 57ml DMF, 4-amino benzo-15-crown-5 1.9g it is added thereto to after being completely dissolved, 20 DEG C of vacuum defoamations after 45 DEG C of reaction 22h, then casting solution is coated on glass plate, glass plate is placed in coagulating bath 50% ethanol water (40 DEG C) solution, take out after coagulation forming 30min and be dried, prepare 4-amino benzo-15-hat 5 grafting polysulfone polymer microporous membrane.The polymer microporous film above-mentioned condition prepared circulation absorption 100mL0.5mol/L lithium iodide solution 30 minutes under 0.05MPa pressure when 20 DEG C, obtaining 4-amino benzo-15-hat 5 grafting polysulfone polymer microporous membrane separation factors is 1.045.
Claims (10)
1. the method that reaction-control solution phase inversion prepares functional polymer microporous membrane, it is characterised in that:
Chloromethylated polymer is dissolved in organic solvent configuration finite concentration polymer solution, then is added thereto to
Containing the crown compound of active amino, by nucleophilic substitution between amino and chloromethyl by crown compound
It is grafted on polymer molecule side chain prepare crown ether graft polymers；Meanwhile, control reaction percent grafting i.e. when
Reaction is terminated to prevent gelation and direct with the work of reaction system this moment when reaction system reaches certain viscosity
For casting solution, immersion precipitation phase inversion process is used to prepare crown ether graft polymers microporous membrane.
2. prepare functional polymer microporous membrane according to the reaction-control solution phase inversion described in claim 1
Method, it is characterised in that: two reactant degrees of functionality be all higher than or equal to 2 with ensure reaction system controlled
Crosslinking reaction, the most each reactant all can react with two or more other active groups.
3. prepare functional polymer microporous membrane according to the reaction-control solution phase inversion described in claim 1
Method, it is characterised in that: described polymer can be chloromethyl polysulphone, chloromethylation polyether sulfone, chlorine
Methylate in polyether-ether-ketone one or both；Crown compound containing amino can be amino benzo-crown ether,
One or both in Azacrown ether containing or double benzo amino crown ether, its general structure is as follows:
Wherein n is 1,2,3 or 4.
4. prepare functional polymer microporous membrane according to the reaction-control solution phase inversion described in claim 1
Method, it is characterised in that graft reaction and control condition be:
(1) chloromethylated polymer chloromethyl substitution value is 10%-100%, chloromethyl polymer residual
Being 3%～25%, amino is 0.5: 1～5: 1 with the mol ratio of chloromethyl consumption；
(2) organic solvent is DMF (DMF), N,N-dimethylacetamide (DMAc),
N-Methyl pyrrolidone (NMP), the one in Isosorbide-5-Nitrae-dioxane, or dimethyl sulfoxide (DMSO)
Or two kinds；
(3) reaction temperature is 40～80 DEG C, and the response time is 2～24h；
(4) reaction system viscosity span of control 200-2500mPa s.
5. prepare functional polymer microporous membrane according to the reaction-control solution phase inversion described in claim 1
Method, it is characterised in that: described functional graft Polymeric Crown Ethers supported quantity is
0.1mmol/g～1.0mmol/g.
6. prepare functional polymer microporous membrane according to the reaction-control solution phase inversion described in claim 1
Method, it is characterised in that: by controlling reactive grafting rate or system viscosity, directly using reaction system as
Casting solution masking, can avoid gelation, solves an insoluble insoluble difficult problem after graft polymers crosslinking, also saves
Go the isolated and purified of graft polymers.
7. prepare functional polymer microporous membrane according to the reaction-control solution phase inversion described in claim 1
Method, it is characterised in that: immersion precipitation or solution inversion of phases membrance casting condition be:
(1) casting solution is described graft reaction system, and its viscosity span of control is 200mPa s
～2500mPa s；
(2) one or more during coagulating bath is water, ethanol, methanol, DMF and DMAc, NMP are mixed
Close liquid；
(3) coagulation bath temperature is 10 DEG C～80 DEG C of arbitrary temperature.
8. prepare functional polymer microporous membrane according to the reaction-control solution phase inversion described in claim 1
Method, it is characterised in that: masking polymer concentration is 3%～25%.
9. prepare functional polymer microporous membrane according to the reaction-control solution phase inversion described in claim 1
Method, it is characterised in that: polymer microporous film section presents obvious synusia (blade) shape structure, and layer
Chip architecture is distributed along film macroscopic view horizontal direction, without obvious dense layer surface, finger-like pore or big cavity structure；Surface
Average pore size is 20nm～200nm, and porosity is 50%～90%, pure water flux 500L/m2·h
～3500L/m2·h。
10. according to described in claim 1 that reaction-control solution phase inversion prepares functional polymer is micro-
The method of pore membrane, it is characterised in that: prepared polymer microporous film carries out dynamic lithium isotope adsorption experiment,
Adsorbent solution is 0.5mol/L lithium iodide (100mL), temperature 20 DEG C, 30 minutes time, polymer micro
The membrance separation factor is 1.008～1.045.
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Cited By (5)
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| CN106943901A (en) * | 2017-05-12 | 2017-07-14 | 中南大学 | Biocompatibility PS membrane that sulfonation hydroxypropyl chitosan is modified and preparation method thereof |
| CN108619909A (en) * | 2018-02-05 | 2018-10-09 | 天津工业大学 | A kind of method of Multistage Membranes chromatography concatenation technology separation lithium isotope |
| CN113274895A (en) * | 2021-06-23 | 2021-08-20 | 天津工业大学 | Preparation method of polyether functionalized polymer membrane for oil extraction sewage treatment |
| CN115814602A (en) * | 2022-09-30 | 2023-03-21 | 中国科学技术大学 | Self-microporous polymer membrane for lithium isotope separation, preparation method thereof and electrodialysis separation application |
| CN115814602B (en) * | 2022-09-30 | 2024-05-24 | 中国科学技术大学 | Self-contained microporous polymer membrane for lithium isotope separation, preparation method thereof and electrodialysis separation application |
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| CN102911372A (en) * | 2012-08-03 | 2013-02-06 | 天津工业大学 | Benzo crown ether graft polymer material with lithium isotope separation effect and preparation method thereof |
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