CN103923280A - Preparation method of segmented copolymer mesoporous membrane containing cyclodextrin chain units and having pH responsiveness - Google Patents
Preparation method of segmented copolymer mesoporous membrane containing cyclodextrin chain units and having pH responsiveness Download PDFInfo
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Abstract
The invention relates to a preparation method of a segmented copolymer mesoporous membrane containing cyclodextrin chain units and having pH responsiveness. The preparation method comprises the step: firstly, preparing polystyrene-b-poly(methacrylic acid-N,N-diethylaminoethyl-co-monovinyl-hexamethylenediamine beta-cyclodextrin) with narrower molecular weight distribution and controllable molecular weight by using a reversible addition-fragmentation chain transfer (RAFT) polymerization method, which provides an effective premise to a subsequent membrane preparation; in addition, the mesoporous membrane has a pH sensitivity due to containing of a poly(methacrylic acid-N,N-diethylaminoethyl) chain segment, the structure of the intelligent separation membrane can be reversibly changed with the change of outside stimulation, which causes that the membrane performances such as pore size and hydrophily and hydrophobicity change, and thus the flux of the membrane is controlled, and the selectivity of the membrane is improved; meanwhile a beta-CD chain segment provides space and molecular recognition of a second coated medicine except for micro-nano pores for a mesoporous membrane material, and a lyophobic cavity provides a space of the second coated medicine except for micro-nano pores for the membrane material.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of preparation method who contains cyclodextrin chain link and there is the segmented copolymer mesoporous film of pH responsiveness.
Background technology
Segmented copolymer mesoporous film is a kind of Microphase Structure material of high-sequential, such film contains a large amount of pores arrays, purifies and there is important application potential in the field such as selective separation at preparation, the water of growth, metal or the orderly template of semi-conductor of one-dimensional micro-nanometer structure.The segmented copolymer mesoporous film with stimulating responsive is one more special in such film, its feature is that the hole of film can reversibly change the variation of surrounding environment, cause film properties as the change of pore size, hydrophilic and hydrophobic etc., thus the flux of controlling diaphragm, the selectivity of raising film.
Document 1 " Roshan B Vasani; Steven J P McInnes; Martin A Cole et al.Stimulus-Responsiv-eness and Drug Release from Porous Silicon Films ATRP-Grafted with Poly (N-isopropylacrylamide) .Langmuir; 2011; 27:7843 – 7853 " discloses a kind of preparation method of porous silicon film, and has studied its application in medicine controlled releasing field.But because its work program is comparatively complicated and need multistep operation, and silicon fiml poor mechanical property, the easy shortcoming such as broken, therefore limit its range of application.
Document 2 " Chun-Xia Liu; Wan-Zhong Lang; Bin-Bin Shi et al.Fabrication of ordered honeycomb porous polyvinyl chloride (PVC) films by breath figures method.Materials Letters; 2013; 107:53-55 " discloses the preparation method of a kind of polyvinyl chloride (PVC) microporous membrane, they are taking tetrahydrofuran (THF) (THF) as solvent, by breathe pattern legal system standby PVC porous-film, studied the polymerization degree and the impact of atmospheric moisture on film pattern of polymer concentration, PVC.PVC has good chemical stability, but it does not have environment-responsive, can not be applied to intelligent separatory membrane field.
Document 3 " Tao Cai; Min Li; Koon-Gee Neoh et al.Surface-functionalizable membranes of polycaprolactone-click-hyperbranched polyglycerol copolymers from combined atom transfer radical polymerization; ring-opening polymerization and click chemistry.J.Mater.Chem.B; 2013,1:1304 – 1315 " discloses a kind of preparation method of the micron pore membrane based on hyperbranched polymer.The method that they utilize atom transfer radical polymerization (ATRP), ring-opening polymerization and click chemistry to combine synthesizes hyperbranched polymer PCL-click-HPG, then utilize the method for phase reversion to prepare and there is surface-active microporous membrane, finally further prepare PCL-click-HPG-b-PMPC film on its surface by ATRP method.Although film prepared by this method has excellent antifouling and anti-microbial property, preparation process is loaded down with trivial details consuming time, and aperture is difficult to control.
Summary of the invention
The technical problem solving
For fear of the deficiencies in the prior art part, the present invention proposes a kind of preparation method who contains cyclodextrin chain link and have the segmented copolymer mesoporous film of pH responsiveness, overcomes the deficiency of the aspects such as the functionalization degree Modulatory character low and molecular structure of work program complexity that existing micro-nano hole membrane preparation technology exists, film is poor.
Technical scheme
Contain cyclodextrin chain link and there is the preparation method of the segmented copolymer mesoporous film of pH responsiveness, it is characterized in that step is as follows:
Step 1: the acetone that is 20:1 by volume ratio and potassiumphosphate mix, magnetic agitation 8h～12h; Then dropping and the thiohydracrylic acid that potassiumphosphate mol ratio is 1:1, continue magnetic agitation 2h～3h; Dropping and the dithiocarbonic anhydride that potassiumphosphate mol ratio is 1:3, continue magnetic agitation 2h～3h again; The bromotoluene that to add with potassiumphosphate mol ratio be 1:1 again, continues stirring reaction 2h～3h and obtains reaction product;
Add successively after completion of the reaction with the saturated aqueous common salt of reaction product volume equivalent and ether and extract and wash, collect ether layer, after underpressure distillation yellow liquid; Wash to adding in yellow liquid saturated aqueous common salt and ether to carry out secondary extraction again, collect final organic layer;
Add again the anhydrous sodium sulphate with 2 times of volumes of final organic layer, after magnetic agitation 2h～3h, remove by filter anhydrous sodium sulphate with G4 sand core funnel, after collecting filtrate and carrying out underpressure distillation, obtain yellow liquid, add again with the isopyknic acetone of yellow liquid after by cold normal hexane repeated precipitation 3 times, gained solid product is in 25 DEG C～30 DEG C vacuum-dryings 3 days～obtain for the 5 days trithio benzyl propionate of faint yellow crystalline solid;
Step 2: add successively vinylbenzene, trithio benzyl propionate and Diisopropyl azodicarboxylate for 6070:10:1 in molar ratio in dry Schlenk pipe, with 1,4-dioxane is solvent, after dissolving completely, utilize Schlenk technology to remove the dissolved oxygen in reaction flask, under air-proof condition, react to liquid and become sticky in 100 DEG C～120 DEG C subsequently;
After reaction finishes, system is exposed in air and is cooled to room temperature, then, by product repeated precipitation filtering 2 times in cold methanol, at 30 DEG C, vacuum-drying, to constant weight, obtains the macromole evocating agent polystyrene of faint yellow solid subsequently;
Step 3: make beta-cyclodextrin, quadrol and the solvent DMF of sulfonylation mix dissolving completely under magnetic agitation condition, react 4～5h in 75 DEG C subsequently under air-proof condition; After reaction finishes, system is exposed in air and is cooled to room temperature, then, by product repeated precipitation filter 23 in cold acetone, vacuum-drying subsequently, to constant weight, obtains the quadrol beta-cyclodextrin of faint yellow solid; The beta-cyclodextrin of described sulfonylation and the ratio 1:22 of quadrol;
Step 4: with N, dinethylformamide is as solvent, add quadrol beta-cyclodextrin, under magnetic agitation condition, it is dissolved completely, then add Resorcinol, under 60 DEG C, magnetic agitation condition, add glycidyl methacrylate, after dissolving completely, under air-proof condition, in 60 DEG C of oil baths, react 6h;
Reaction is cooled to room temperature after finishing, and then, by product repetitive scrubbing 3 times in cold acetone, under room temperature, vacuum-drying, to constant weight, obtains mono-vinyl-quadrol beta-cyclodextrin of faint yellow solid subsequently; The mol ratio of described Resorcinol and quadrol beta-cyclodextrin is 160:1; The mol ratio of described glycidyl methacrylate and quadrol beta-cyclodextrin is 1:5.6;
Step 5: in dry Schlenk pipe in molar ratio for 10:330:80:1 adds mono-vinyl-quadrol beta-cyclodextrin and the Diisopropyl azodicarboxylate in polystyrene in step 2, NIPA, step 4 successively, with N, dinethylformamide is solvent, after dissolving completely, utilize Schlenk technology to remove the dissolved oxygen in reaction flask, under air-proof condition, react 48h in 90 DEG C subsequently; After reaction finishes, with dialysis tubing at N, in dinethylformamide, dialyse 7～8 days, liquid in dialysis tubing is revolved to steaming to be precipitated with distilled water when remaining 1～2mL, be dried to constant weight with G4 sand core funnel filtration product final vacuum, obtain poly-(NIPA-co-mono-vinyl-quadrol beta-cyclodextrin) segmented copolymer of polystyrene-b-of faint yellow solid;
Step 6: gather (NIPA-co-mono-vinyl-quadrol beta-cyclodextrin) segmented copolymer as solute taking the polystyrene-b-of gained in step 5, with
n-Methyl pyrrolidonefor solvent, be mixed with the solution containing solute;
Slide glass is placed in spin coater cavity, spin coater drips solution on slide glass, the nano-pore membrane based on poly-(NIPA-co-mono-vinyl-quadrol beta-cyclodextrin) Self-Assembling of Block Copolymer of polystyrene-b-of the white tympan obtaining on slide glass after solvent evaporates, is called the segmented copolymer mesoporous film that contains cyclodextrin chain link and have pH responsiveness.
Beneficial effect
A kind of preparation method who contains cyclodextrin chain link and there is the segmented copolymer mesoporous film of pH responsiveness that the present invention proposes, the method that adopts phase inversion to combine with spin-coating method is prepared the mesoporous film based on poly-(methacrylic acid-N, the N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) segmented copolymer of polystyrene-b-.First, the method of utilizing reversible addition-fracture chain to shift (RAFT) polymerization has been prepared the poly-(methacrylic acid-N of polystyrene-b-that molecular weight distribution is narrower, molecular size range is controlled, N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin), for follow-up masking provides effective prerequisite; In addition, this mesoporous film is because containing polymethyl acrylic acid-N, N-lignocaine ethyl ester segment and there is pH sensitivity characteristic, the structure of this intelligent separatory membrane can reversibly change with the variation of external stimulus, cause film properties as the change of pore size, hydrophilic and hydrophobic etc., thereby the flux of controlling diaphragm, the selectivity of raising film; Meanwhile, β-CD chain link exist for porous film material and provide space and the molecular recognition of the second bag medicine carrying thing except micro-nano hole, its hydrophobic cavity provides the space of the second bag medicine carrying thing except micro-nano hole for mould material.
Brief description of the drawings
Fig. 1 is the schematic arrangement of the prepared polystyrene-b-of the inventive method embodiment 1 poly-(methacrylic acid-N, N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin)
Fig. 2 is the scanning electron microscope diagram of the prepared mesoporous film based on poly-(methacrylic acid-N, the N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) self-assembly of polystyrene-b-of the inventive method embodiment 1
Embodiment
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
The embodiment of the present invention solves the technical scheme that its technical problem adopts and comprises the following steps:
Step a: in dry single port flask by volume for 20:1 adds acetone and potassiumphosphate, magnetic agitation 8h～12h.To the thiohydracrylic acid that to drip with potassiumphosphate mol ratio in above-mentioned flask be 1:1, continue after magnetic agitation 2h～3h, again to dithiocarbonic anhydride that to drip with potassiumphosphate mol ratio in above-mentioned flask be 1:3, continue magnetic agitation 2h～3h, the bromotoluene that then to add with potassiumphosphate mol ratio be 1:1 and continue stirring reaction 2h～3h.Extract and wash to adding successively in single port flask with the saturated aqueous common salt of reaction product volume equivalent and ether after completion of the reaction, collect ether layer, after underpressure distillation yellow liquid.Wash to adding in yellow liquid saturated aqueous common salt and ether to carry out secondary extraction again, collect final organic layer, toward wherein adding and the anhydrous sodium sulphate of 2 times of products therefrom volumes, after magnetic agitation 2h～3h, remove by filter anhydrous sodium sulphate with G4 sand core funnel, underpressure distillation obtains yellow liquid, to adding in yellow liquid after the acetone of equal volume by cold normal hexane repeated precipitation 3 times (each normal hexane used is 300mL～500mL), gained solid product obtains faint yellow crystalline solid in 3 days～5 days in 25 DEG C～30 DEG C vacuum-dryings, is trithio benzyl propionate.
Step b: add successively vinylbenzene, trithio benzyl propionate and Diisopropyl azodicarboxylate for 6070:10:1 in molar ratio in dry Schlenk pipe, with 1,4-dioxane is solvent, after dissolving completely, utilize Schlenk technology to remove the dissolved oxygen in reaction flask, under air-proof condition, react to liquid and become sticky in 100 DEG C～120 DEG C subsequently.After reaction finishes, system is exposed in air and is cooled to room temperature, then, by product repeated precipitation filtering 2 times in cold methanol, at 30 DEG C, vacuum-drying, to constant weight, obtains faint yellow solid and is macromole evocating agent polystyrene subsequently.
Step c: be the beta-cyclodextrin that 22:1 adds hexanediamine and sulfonylation successively in molar ratio in dry single port flask; and add 20～30mL N; dinethylformamide, as solvent, dissolves it completely under magnetic agitation condition, reacts 6h subsequently under air-proof condition in 75 DEG C.After reaction finishes, system is exposed in air and is cooled to room temperature, then, by product repeated precipitation filter 23 in cold acetone, vacuum-drying subsequently, to constant weight, obtains faint yellow solid and is hexanediamine beta-cyclodextrin.
Steps d: add above-mentioned hexanediamine beta-cyclodextrin in dry single port flask, and add N, dinethylformamide, as solvent, dissolves it completely under magnetic agitation condition, and pressing subsequently with quadrol beta-cyclodextrin mol ratio is that 1:147 adds Resorcinol to avoid two keys to react.Under 60 DEG C, magnetic agitation condition, by being 6:1 with hexanediamine beta-cyclodextrin mol ratio, amount adds glycidyl methacrylate, after dissolving completely, under air-proof condition, in 60 DEG C of oil baths, reacts 6h.Reaction is cooled to room temperature after finishing, and then, by product repetitive scrubbing 3 times in cold acetone, under room temperature, vacuum-drying, to constant weight, obtains faint yellow solid and is mono-vinyl-hexanediamine beta-cyclodextrin subsequently.
Step e: add successively polystyrene, the methacrylic acid-N in step b for 10:360:180:1 in molar ratio in dry Schlenk pipe, mono-vinyl-hexanediamine beta-cyclodextrin and Diisopropyl azodicarboxylate in N-lignocaine ethyl ester, steps d, with N, dinethylformamide is solvent, after dissolving completely, utilize Schlenk technology to remove the dissolved oxygen in reaction flask, under air-proof condition, react 48h in 90 DEG C subsequently.After reaction finishes, the dialysis tubing that is 3500D with molecular weight cut-off is at N, in dinethylformamide, dialyse 7～8 days, liquid in dialysis tubing is revolved to steaming to be precipitated with distilled water when remaining 1～2mL, be dried to constant weight with G4 sand core funnel filtration product final vacuum, obtain faint yellow solid and be poly-(methacrylic acid-N, the N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) segmented copolymer of polystyrene-b-.
Step f: the N-Methyl pyrrolidone solution that configures 23wt% in dry bottle, clean slide glass is placed in spin coater cavity, be 50% in atmospheric moisture, air velocity is 1.5L/min, spin coater rotating speed is under 2000rpm condition, the solution preparing is dripped on slide glass, after solvent evaporates 20s, slide glass is dipped in ultrapure water, after coming off completely slide glass, take out slide glass until film, the white tympan obtaining is poly-(methacrylic acid-N based on polystyrene-b-, N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) mesoporous film of Self-Assembling of Block Copolymer.
In step a, described cold normal hexane, refers to: normal hexane is inserted to 2 DEG C～6 DEG C cold compartment of refrigerator and place gained after 30min.
In step a, described in normal hexane repeated precipitation 3 times, refer to: precipitate the crystalline solid powder obtaining with normal hexane, then use minimum acetone solution, and then with normal hexane precipitation, so repeatedly dissolution precipitation operation 3 times.
In step b, e, described Schlenk technology, refers to: reactant, first with after liquid nitrogen freezing, under argon gas atmosphere, is vacuumized, then pass into argon gas, and then liquid nitrogen freezing, so repeatedly freeze-thaw-refrigeration operation 3 times.
In step b, described cold methanol, refers to: methyl alcohol is inserted to 2 DEG C～6 DEG C cold compartment of refrigerator and place gained after 30min.
In step b, described by product repeated precipitation filter 2 times and refer in cold methanol: after reacting products therefrom cold methanol precipitation, to filter with G4 sand core funnel again, gained faint yellow solid powder is dissolved with a small amount of tetrahydrofuran (THF), and then with filtering with sand core funnel after cold methanol precipitation, twice of repeatable operation like this.
In step c, d, described cold acetone, refers to: acetone is inserted to 2 DEG C～6 DEG C cold compartment of refrigerator and place gained after 30min.
In step c, described product repeated precipitation filter 23 time in cold acetone are referred to: will react after products therefrom cold acetone precipitation again with the filtration of G4 sand core funnel, gained faint yellow solid powder is dissolved with the mixing solutions of a small amount of methyl alcohol and water, and then with filtering with sand core funnel after cold acetone precipitation, repeatable operation 3 times like this.
Specific embodiment is as follows:
Embodiment mono-:
In dry single port flask, add potassiumphosphate (2g, 9.43mmol) and 16mL acetone, magnetic agitation 8h fully dissolves it.By thiohydracrylic acid (1g, 9.43mmol) be added drop-wise in above-mentioned flask, continue magnetic agitation 2h, in above-mentioned flask, drip dithiocarbonic anhydride (2.15g, 28.3mmol), continue bromotoluene (1.61g, 9.43mmol) to be added after magnetic agitation 2h and continue stirring reaction 2h.Extract and wash to adding successively in single port flask with the saturated aqueous common salt of reaction product volume equivalent and ether after completion of the reaction, collect the ether layer of gained, underpressure distillation obtains yellow liquid.Wash to adding in yellow liquid the saturated aqueous common salt of equivalent and ether to carry out secondary extraction, collect final organic layer, add wherein the anhydrous sodium sulphate with 2 times of products therefrom volumes, after magnetic agitation 2h, remove by filter anhydrous sodium sulphate with G4 sand core funnel, underpressure distillation is removed ether and is obtained yellow liquid, to adding in yellow liquid after isopyknic acetone by cold normal hexane repeated precipitation 3 times (each normal hexane used is 300mL～500mL), gained solid product obtains the faint yellow crystalline solid of 2.2g for 3 days in 25 DEG C～30 DEG C vacuum-dryings, is trithio benzyl propionate.
In dry Schlenk pipe, add successively vinylbenzene (3.156g, 30.35mmol), trithio benzyl propionate (13.6mg, 0.05mmol) and Diisopropyl azodicarboxylate (0.82mg, 0.005mmol), and add 1,4-dioxane (5mL) is as solvent, after dissolving completely, utilizes Schlenk technology to remove the dissolved oxygen in reaction flask, reacts to liquid and becomes sticky subsequently under air-proof condition in 110 DEG C.After reaction finishes, system is exposed in air and is cooled to room temperature, then, by product repeated precipitation filtering 2 times in cold methanol, at 30 DEG C, vacuum-drying, to constant weight, obtains faint yellow solid and is macromole evocating agent polystyrene subsequently.
In dry single port flask, add successively hexanediamine (10g; 0.086mol) and the beta-cyclodextrin (5g of sulfonylation; 0.0039mol); and add 20mL N; dinethylformamide is as solvent; under magnetic agitation condition, it is dissolved completely, under air-proof condition, react 6h in 75 DEG C subsequently.After reaction finishes, system is exposed in air and is cooled to room temperature, then by product repeated precipitation filter 23 time in cold acetone, vacuum-drying is subsequently to constant weight, obtains faint yellow solid and be the beta-cyclodextrin of hexanediamine.
In dry single port flask, add above-mentioned hexanediamine beta-cyclodextrin (5g, 0.004mol), and add 30mL N, dinethylformamide is as solvent, under magnetic agitation condition, it is dissolved completely, and add Resorcinol (2.99mg, 0.0272mmol) to avoid two key reactions.Under 60 DEG C, magnetic agitation condition, add glycidyl methacrylate (3.4116g, 0.024mol), after dissolving completely, under air-proof condition, in 60 DEG C of oil baths, react 6h.Reaction is cooled to room temperature after finishing, and then, by product repetitive scrubbing 3 times in cold acetone, under room temperature, vacuum-drying, to constant weight, obtains faint yellow solid and is mono-vinyl-hexanediamine beta-cyclodextrin subsequently.
In dry Schlenk pipe, add successively the polystyrene (537.36mg in step b, 0.015mmol), methacrylic acid-N, N-lignocaine ethyl ester (100.44mg, 0.54mmol), the mono-vinyl-hexanediamine beta-cyclodextrin (370.98mg in steps d, 0.27mmol) and Diisopropyl azodicarboxylate (0.246mg, 0.0015mmol), and add 5mLN, dinethylformamide is as solvent, after dissolving completely, utilize Schlenk technology to remove the dissolved oxygen in reaction flask, under air-proof condition, react 48h in 90 DEG C subsequently.After reaction finishes, the dialysis tubing that is 3500D with molecular weight cut-off is at N, in dinethylformamide, dialyse 7～8 days, liquid in dialysis tubing is revolved to steaming to be precipitated with distilled water when remaining 1～2mL, be dried to constant weight with G4 sand core funnel filtration product final vacuum, obtain faint yellow solid and be poly-(methacrylic acid-N, the N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) segmented copolymer of polystyrene-b-.
In dry bottle, add successively 11.5mg polystyrene-b-to gather (methacrylic acid-N, N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) and 38.5mg N-Methyl pyrrolidone it is dissolved completely, clean slide glass is placed in spin coater cavity, be 50% in atmospheric moisture, air velocity is 1.5L/min, spin coater rotating speed is under 2000rpm condition, the solution preparing is dripped on slide glass, after solvent evaporates 20s, slide glass is dipped in ultrapure water, after coming off completely slide glass, take out slide glass until film, the white tympan obtaining is poly-(methacrylic acid-N based on polystyrene-b-, N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) mesoporous film of Self-Assembling of Block Copolymer.
Can find out from the SEM figure of Fig. 2, the structure of the prepared mesoporous film based on poly-(methacrylic acid-N, the N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) Self-Assembling of Block Copolymer of polystyrene-b-of the present embodiment is with designed consistent.
Embodiment bis-:
In dry single port flask, add potassiumphosphate (4g, 18.86mmol) and 30mL acetone, magnetic agitation 10h.Thiohydracrylic acid (2g, 18.86mmol) is added drop-wise in above-mentioned flask, continues magnetic agitation 2h, by dithiocarbonic anhydride (4.3g, 56.6mmol) be added drop-wise in above-mentioned flask and continue to stir 2h, again bromotoluene (3.22g, 18.86mmol) added afterwards and continue stirring 2h.Extract and wash to adding successively in single port flask with the saturated aqueous common salt of reaction product volume equivalent and ether after completion of the reaction, collect the ether layer of gained, underpressure distillation obtains yellow liquid.Extract again and wash one time with saturated aqueous common salt and ether, collect final organic layer, add wherein the anhydrous sodium sulphate of 2 times of products therefrom volumes, after magnetic agitation 2h, remove by filter anhydrous sodium sulphate with G4 sand core funnel, underpressure distillation obtains yellow liquid, to adding in yellow liquid after isopyknic acetone by cold normal hexane repeated precipitation 3 times (each normal hexane used is 300mL～500mL), gained solid product obtains the faint yellow crystalline solid of 4.1g for 3 days in 30 DEG C of vacuum-dryings, is trithio benzyl propionate.
In dry Schlenk pipe, add successively vinylbenzene (6.312g, 60.7mmol), trithio benzyl propionate (27.2mg, 0.10mmol) and Diisopropyl azodicarboxylate (1.64mg, 0.01mmol), and add 1,4-dioxane (8mL) is as solvent, after dissolving completely, utilizes Schlenk technology to remove the dissolved oxygen in reaction flask, reacts to liquid and becomes sticky subsequently under air-proof condition in 110 DEG C.After reaction finishes, system is exposed in air and is cooled to room temperature, then, by product repeated precipitation filtering 2 times in cold methanol, at 30 DEG C, vacuum-drying, to constant weight, obtains faint yellow solid and is macromole evocating agent polystyrene subsequently.
In dry single port flask, add successively hexanediamine (15g; 0.129mol) and the beta-cyclodextrin (7.5g of sulfonylation; 0.0059mol); and add 20mLN; dinethylformamide is as solvent; under magnetic agitation condition, it is dissolved completely, under air-proof condition, react 6h in 75 DEG C subsequently.After reaction finishes, system is exposed in air and is cooled to room temperature, then by product repeated precipitation filter 23 time in cold acetone, vacuum-drying is subsequently to constant weight, obtains faint yellow solid and be the beta-cyclodextrin of hexanediamine.
In dry single port flask, add above-mentioned hexanediamine beta-cyclodextrin (7.5g, 0.006mol), and add 30mLN, dinethylformamide is as solvent, under magnetic agitation condition, it is dissolved completely, and add Resorcinol (4.4mg, 0.0408mmol) to avoid two key reactions.Under 60 DEG C, magnetic agitation condition, add glycidyl methacrylate (5.1174g, 0.036mol), after dissolving completely, under air-proof condition, in 60 DEG C of oil baths, react 6h.Reaction is cooled to room temperature after finishing, and then, by product repetitive scrubbing 3 times in cold acetone, under room temperature, vacuum-drying, to constant weight, obtains faint yellow solid and is mono-vinyl-hexanediamine beta-cyclodextrin subsequently.
In dry Schlenk pipe, add successively the polystyrene (806.04mg in step b, 0.0225mmol), methacrylic acid-N, N-lignocaine ethyl ester (150.66mg, 0.81mmol), the mono-vinyl-hexanediamine beta-cyclodextrin (556.47mg in steps d, 0.405mmol) and Diisopropyl azodicarboxylate (0.369mg, 0.00225mmol), and add 6mL N, dinethylformamide is as solvent, after dissolving completely, utilize Schlenk technology to remove the dissolved oxygen in reaction flask, under air-proof condition, react 48h in 90 DEG C subsequently.After reaction finishes, the dialysis tubing that is 3500D with molecular weight cut-off is at N, in dinethylformamide, dialyse 7～8 days, liquid in dialysis tubing is revolved to steaming to be precipitated with distilled water when remaining 1～2mL, be dried to constant weight with G4 sand core funnel filtration product final vacuum, obtain faint yellow solid and be poly-(methacrylic acid-N, the N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) segmented copolymer of polystyrene-b-.
In dry bottle, add successively 17.25mg polystyrene-b-to gather (methacrylic acid-N, N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) and 57.75mg N-Methyl pyrrolidone it is dissolved completely, clean slide glass is placed in spin coater cavity, be 50% in atmospheric moisture, air velocity is 1.5L/min, rotating speed is under 2000rpm condition, the solution preparing is dripped on slide glass, after solvent evaporates 20s, slide glass is dipped in ultrapure water, after coming off completely slide glass, take out slide glass until film, the white tympan obtaining is poly-(methacrylic acid-N based on polystyrene-b-, N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) mesoporous film of Self-Assembling of Block Copolymer.
Embodiment tri-:
In dry single port flask, add magnetic agitation 12h in the acetone of potassiumphosphate (6g, 28.29mmol) and 46mL.By thiohydracrylic acid (3g, 28.29mmol) be added drop-wise in above-mentioned flask, continue to stir after 2h dithiocarbonic anhydride (6.45g, 84.9mmol) be added drop-wise to and in above-mentioned flask, continue magnetic agitation 2h, again bromotoluene (4.83g, 28.29mmol) added afterwards and continue stirring reaction 2h.Extract and wash to adding successively in single port flask with the saturated aqueous common salt of reaction product volume equivalent and ether after completion of the reaction, collect the ether layer of gained, underpressure distillation obtains yellow liquid.Extract again and wash one time with saturated aqueous common salt and ether, collect final organic layer, add wherein the anhydrous sodium sulphate of 2 times of products therefrom volumes, after magnetic agitation 2h, remove by filter anhydrous sodium sulphate with G4 sand core funnel, underpressure distillation obtains yellow liquid, to adding in yellow liquid after isopyknic acetone by cold normal hexane repeated precipitation 3 times (each normal hexane used is 300mL～500mL), gained solid product obtains the faint yellow crystalline solid of 5.8g in 3 days in 30 DEG C of vacuum-dryings, is trithio benzyl propionate.
In dry Schlenk pipe, add successively vinylbenzene (9.468g, 91.05mmol), trithio benzyl propionate (40.8mg, 0.15mmol) and Diisopropyl azodicarboxylate (2.46mg, 0.015mmol), and add 1,4-dioxane (10mL) is as solvent, after dissolving completely, utilizes Schlenk technology to remove the dissolved oxygen in reaction flask, reacts to liquid and becomes sticky subsequently under air-proof condition in 110 DEG C.After reaction finishes, system is exposed in air and is cooled to room temperature, then, by product repeated precipitation filtering 2 times in cold methanol, at 30 DEG C, vacuum-drying, to constant weight, obtains faint yellow solid and is macromole evocating agent polystyrene subsequently.
In dry single port flask, add successively hexanediamine (20g; 0.172mol) and the beta-cyclodextrin (10g of sulfonylation; 0.0078mol); and add 25mLN; dinethylformamide is as solvent; under magnetic agitation condition, it is dissolved completely, under air-proof condition, react 6h in 75 DEG C subsequently.After reaction finishes, system is exposed in air and is cooled to room temperature, then by product repeated precipitation filter 23 time in cold acetone, vacuum-drying is subsequently to constant weight, obtains faint yellow solid and be the beta-cyclodextrin of hexanediamine.
In dry single port flask, add above-mentioned hexanediamine beta-cyclodextrin (10g, 0.008mol), and add 30mL N, dinethylformamide is as solvent, under magnetic agitation condition, it is dissolved completely, and add Resorcinol (5.5mg, 0.05mmol) to avoid two key reactions.Under 60 DEG C, magnetic agitation condition, add glycidyl methacrylate (6.8232g, 0.048mol), after dissolving completely, under air-proof condition, in 60 DEG C of oil baths, react 6h.Reaction is cooled to room temperature after finishing, and then, by product repetitive scrubbing 3 times in cold acetone, under room temperature, vacuum-drying, to constant weight, obtains faint yellow solid and is mono-vinyl-hexanediamine beta-cyclodextrin subsequently.
In dry Schlenk pipe, add successively the polystyrene (1074.72mg in step b, 0.03mmol), methacrylic acid-N, N-lignocaine ethyl ester (200.88mg, 1.08mmol), the mono-vinyl-hexanediamine beta-cyclodextrin (741.96mg in steps d, 0.54mmol) and Diisopropyl azodicarboxylate (0.492mg, 0.003mmol), and add 7mL N, dinethylformamide is as solvent, after dissolving completely, utilize Schlenk technology to remove the dissolved oxygen in reaction flask, under air-proof condition, react 48h in 90 DEG C subsequently.After reaction finishes, the dialysis tubing that is 3500D with molecular weight cut-off is at N, in dinethylformamide, dialyse 7～8 days, liquid in dialysis tubing is revolved to steaming to be precipitated with distilled water when remaining 1～2mL, be dried to constant weight with G4 sand core funnel filtration product final vacuum, obtain faint yellow solid and be poly-(methacrylic acid-N, the N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) segmented copolymer of polystyrene-b-.
In dry bottle, add successively 23mg polystyrene-b-to gather (methacrylic acid-N, N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) and 77mg N-Methyl pyrrolidone it is dissolved completely, clean slide glass is placed in spin coater cavity, be 50% in atmospheric moisture, air velocity is 1.5L/min, spin coater rotating speed is under 2000rpm condition, the solution preparing is dripped on slide glass, after solvent evaporates 20s, slide glass is dipped in ultrapure water, after coming off completely slide glass, take out slide glass until film, the white tympan obtaining is poly-(methacrylic acid-N based on polystyrene-b-, N-lignocaine ethyl ester-co-mono-vinyl-hexanediamine beta-cyclodextrin) mesoporous film of Self-Assembling of Block Copolymer.
Claims (7)
1. contain cyclodextrin chain link and there is the preparation method of the segmented copolymer mesoporous film of pH responsiveness, it is characterized in that step is as follows:
Step 1: the acetone that is 20:1 by volume ratio and potassiumphosphate mix, magnetic agitation 8h～12h; Then dropping and the thiohydracrylic acid that potassiumphosphate mol ratio is 1:1, continue magnetic agitation 2h～3h; Dropping and the dithiocarbonic anhydride that potassiumphosphate mol ratio is 1:3, continue magnetic agitation 2h～3h again; The bromotoluene that to add with potassiumphosphate mol ratio be 1:1 again, continues stirring reaction 2h～3h and obtains reaction product;
Add successively after completion of the reaction with the saturated aqueous common salt of reaction product volume equivalent and ether and extract and wash, collect ether layer, after underpressure distillation yellow liquid; Wash to adding in yellow liquid saturated aqueous common salt and ether to carry out secondary extraction again, collect final organic layer;
Add again the anhydrous sodium sulphate with 2 times of volumes of final organic layer, after magnetic agitation 2h～3h, remove by filter anhydrous sodium sulphate with G4 sand core funnel, after collecting filtrate and carrying out underpressure distillation, obtain yellow liquid, add again with the isopyknic acetone of yellow liquid after by cold normal hexane repeated precipitation 3 times, gained solid product is in 25 DEG C～30 DEG C vacuum-dryings 3 days～obtain for the 5 days trithio benzyl propionate of faint yellow crystalline solid;
Step 2: add successively vinylbenzene, trithio benzyl propionate and Diisopropyl azodicarboxylate for 6070:10:1 in molar ratio in dry Schlenk pipe, with 1,4-dioxane is solvent, after dissolving completely, utilize Schlenk technology to remove the dissolved oxygen in reaction flask, under air-proof condition, react to liquid and become sticky in 100 DEG C～120 DEG C subsequently;
After reaction finishes, system is exposed in air and is cooled to room temperature, then, by product repeated precipitation filtering 2 times in cold methanol, at 30 DEG C, vacuum-drying, to constant weight, obtains the macromole evocating agent polystyrene of faint yellow solid subsequently;
Step 3: make beta-cyclodextrin, quadrol and the solvent DMF of sulfonylation mix dissolving completely under magnetic agitation condition, react 4～5h in 75 DEG C subsequently under air-proof condition; After reaction finishes, system is exposed in air and is cooled to room temperature, then, by product repeated precipitation filter 23 in cold acetone, vacuum-drying subsequently, to constant weight, obtains the quadrol beta-cyclodextrin of faint yellow solid; The beta-cyclodextrin of described sulfonylation and the ratio 1:22 of quadrol;
Step 4: with N, dinethylformamide is as solvent, add quadrol beta-cyclodextrin, under magnetic agitation condition, it is dissolved completely, then add Resorcinol, under 60 DEG C, magnetic agitation condition, add glycidyl methacrylate, after dissolving completely, under air-proof condition, in 60 DEG C of oil baths, react 6h;
Reaction is cooled to room temperature after finishing, and then, by product repetitive scrubbing 3 times in cold acetone, under room temperature, vacuum-drying, to constant weight, obtains mono-vinyl-quadrol beta-cyclodextrin of faint yellow solid subsequently; The mol ratio of described Resorcinol and quadrol beta-cyclodextrin is 160:1; The mol ratio of described glycidyl methacrylate and quadrol beta-cyclodextrin is 1:5.6;
Step 5: in dry Schlenk pipe in molar ratio for 10:330:80:1 adds mono-vinyl-quadrol beta-cyclodextrin and the Diisopropyl azodicarboxylate in polystyrene in step 2, NIPA, step 4 successively, with N, dinethylformamide is solvent, after dissolving completely, utilize Schlenk technology to remove the dissolved oxygen in reaction flask, under air-proof condition, react 48h in 90 DEG C subsequently; After reaction finishes, with dialysis tubing at N, in dinethylformamide, dialyse 7～8 days, liquid in dialysis tubing is revolved to steaming to be precipitated with distilled water when remaining 1～2mL, be dried to constant weight with G4 sand core funnel filtration product final vacuum, obtain poly-(NIPA-co-mono-vinyl-quadrol beta-cyclodextrin) segmented copolymer of polystyrene-b-of faint yellow solid;
Step 6: poly-(NIPA-co-mono-vinyl-quadrol beta-cyclodextrin) segmented copolymer of polystyrene-b-taking gained in step 5, as solute, taking N-Methyl pyrrolidone as solvent, is mixed with the solution containing solute;
Slide glass is placed in spin coater cavity, spin coater drips solution on slide glass, the nano-pore membrane based on poly-(NIPA-co-mono-vinyl-quadrol beta-cyclodextrin) Self-Assembling of Block Copolymer of polystyrene-b-of the white tympan obtaining on slide glass after solvent evaporates, is called the segmented copolymer mesoporous film that contains cyclodextrin chain link and have pH responsiveness.
2. contain according to claim 1 cyclodextrin chain link and there is the preparation method of the segmented copolymer mesoporous film of pH responsiveness, it is characterized in that: will in step 6, form the slide glass of white tympan, immerse in ultrapure water, the tympan of white comes off from slide glass, obtains film.
3. contain according to claim 1 cyclodextrin chain link and there is the preparation method of the segmented copolymer mesoporous film of pH responsiveness, it is characterized in that: described Schlenk technology is: by reactant first with after liquid nitrogen freezing, under argon gas atmosphere, vacuumize, pass into again argon gas, and then liquid nitrogen freezing, freeze-thaw-refrigeration operation is repeatedly repeatedly.
4. contain according to claim 1 cyclodextrin chain link and there is the preparation method of the segmented copolymer mesoporous film of pH responsiveness, it is characterized in that: poly-(NIPA-co-mono-vinyl-quadrol beta-cyclodextrin) segmented copolymer of described polystyrene-b-taking gained in step 5 is solute, taking N-Methyl pyrrolidone as solvent, when obtain solution, the content of solute is 23wt%.
5. contain according to claim 1 cyclodextrin chain link and there is the preparation method of the segmented copolymer mesoporous film of pH responsiveness, it is characterized in that: the condition that described spin coater drips solution on slide glass is: atmospheric moisture is 50%, air velocity is 1.5L/min, and spin coater rotating speed is under 2000rpm condition.
6. contain according to claim 1 cyclodextrin chain link and there is the preparation method of the segmented copolymer mesoporous film of pH responsiveness, it is characterized in that: the molecular weight cut-off of described dialysis tubing is 3500D.
7. according to containing cyclodextrin chain link described in step 1 in claim 1 and thering is the preparation method of the segmented copolymer mesoporous film of pH responsiveness, it is characterized in that: cold normal hexane refers to that normal hexane is inserted to 2 DEG C～6 DEG C cold compartment of refrigerator places gained after 30min.
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