CN104877165A - Preparing method of pH sensitive semi-permeable membrane - Google Patents
Preparing method of pH sensitive semi-permeable membrane Download PDFInfo
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Abstract
The invention discloses a preparing method of a pH sensitive semi-permeable membrane. The method can be used for preparing the semi-permeable membrane with the advantages that the pH sensitivity is high, water flux mutational sites can occur according to the pH change, and the process is simple. The semi-permeable membrane can be applied to slow release of inhibitors in a pipeline. The pH sensitive semi-permeable membrane prepared by the preparing method provided by the invention is prepared by adopting a consolute mixing method and using ethylene-vinyl acetate copolymers as a substrate membrane and polystyrene-maleic anhydride alternating copolymers as functional materials through being mixed under the solvent capacity-increase effect; then, the pH sensitive semi-permeable membrane is soaked into a sodium hydroxide solution; next, an HCl solution is used for acid washing and neutralization; so that the pH sensitive semi-permeable membrane is converted into an EVA/PSMA-H carboxylic acid membrane; anhydride groups are converted into carboxyls; the water flux of the modified membrane is the greatest in acid solution. The preparing method has the advantages that the detects of the existing grafting method and a pore filling method can be overcome, the process is simple; the time consumption is short; the sensitive degree can be controlled according to the concrete requirements; the effects of improving the efficiency, saving resources and reducing the cost are achieved.
Description
Technical field
The present invention relates to a kind of polymer matrix preparation method, particularly a kind of semi-permeable membranes preparation method with intelligent switch function, is applied to susceptibility functional materials preparing technical field.
Background technology
PH susceptibility semi-permeable membranes can produce volume or morphologic change because of the change of pH value, this change is the stimulating responsive based on molecular level and macromolecular level, having can reproducing characteristic, be a kind of to certain molecule or ion diffuse turnover and to different particle by having optionally film.In recent years, pH sensitive membrane is widely used in drug conveying and sepn process, comprises the separation etc. of sea water desaltination, desalt, aqueous ethanolic solution.The pH sensitive membrane of polymkeric substance can be prepared by mixing, grafting and pore filling method etc.
Along with the continuous progress of science and technology and constantly probing into pH sensitive membrane performance, find that the property and characteristic of pH sensitive membrane can reach the requirement of medicine controlled releasing, its Releasing Mechanism mainly in polymkeric substance containing ionic group, these ionic groups reactive force each other can change along with the pH value difference of external environment, water molecules speed in medicine and body is controlled, thus the medicine be embedded in pH sensitive membrane is released, reach the object of slow releasing.Adopt pH sensitive membrane as drug controlled release material, not only can solve the problem of drug level instability, but also reduce drug toxicity, improve the curative effect of medicine.Compared with discharging with conventional medicament, the application of intelligent semi-permeable membranes in drug controlled release have intellectuality, can self-adjustable, medicine biological activity to hold time the remarkable advantage such as longer.
As the material of preparation pH sensitive membrane, usual employing styrene-maleic anhydride copolymer (PSMA), with ionogen maleic anhydride on its molecular chain, there is pH susceptibility, and also have very strong reactive behavior and derivative ability, but because of its poor mechanical property, copolymer p SMA can not directly be used for preparing pH sensitive membrane.Up to the present, the simple and easy effective preparation method of semi-permeable membranes of pH susceptibility is still lacked.
Summary of the invention
In order to solve prior art problem, the object of the invention is to the deficiency overcoming prior art existence, a kind of preparation method of pH susceptibility semi-permeable membranes is provided, the method of the functional groups of EVA film is increased with styrene-maleic anhydride copolymer (PSMA), utilize miscible legal preparation pH responsive type semi-permeable membranes altogether, it can change according to extraneous pH, pore size changes, cause the change of permeability rate, inhibiter is made to reach the release action of " on-off ", the hydrogel with pH susceptibility adopting the present invention to prepare advances controlled drug delivery devices, pH can be carried out for the water body environment under special pH condition and respond medicament slowly-releasing, obtain good susceptibility perception and control effects.
Create object for reaching foregoing invention, the present invention adopts following technical proposals:
A preparation method for pH susceptibility semi-permeable membranes, comprises the steps:
1. at room temperature, choose ethylene-vinyl acetate copolymer (EVA) as base material film raw material of substance, choose polystyrene-maleic anhydride alternating copolymer (PSMA) as pH susceptibility functional high molecule material, the proportioning being 7:3 ~ 4:6 according to the mass ratio of ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternating copolymer carries out reactant batching, adopt one or both mixture in methylene dichloride and trichloromethane as solvent, and according to the ratio that solvent and reactant total mass ratio are 70:1 ~ 60:1, reactant and solvent are mixed, make reactants dissolved in solvent, the proportioning being preferably 6:4 according to the mass ratio of ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternating copolymer carries out reactant batching, and reactant and solvent mix by the ratio being preferably 70:1 according to solvent and reactant total mass ratio, make reactants dissolved carry out common miscible synthesizing chemical-reacting in solvent, be preferably 1:1 according to the mass ratio of methylene dichloride and trichloromethane, adopt the mixture of methylene dichloride and trichloromethane as solvent,
2. by described step 1. in solute reactant and solvent mixture connect condensation reflux unit, under ultrasound condition, make molten reaction product mixture altogether dissolve 3 ~ 3.5h and carry out common miscible synthesizing chemical-reacting, obtain the pH susceptibility semipermeable membrane material of liquid; Preferably at 55 DEG C, carry out ultrasonic dissolution reaction;
3. cleaning, dry flat glass plate is got, sheet glass is made to keep horizontality, by through described step 2. after the pH susceptibility semipermeable membrane material of liquid prepared directly water on sheet glass rapidly, the pH susceptibility semipermeable membrane material of liquid is made thinner, seasoning 2 hours, makes the pH susceptibility semipermeable membrane material of liquid adhere to film-forming on a glass;
4. compound concentration is the alkali lye of 0.005 ~ 0.01mol/L, at room temperature by described step 3. in the sheet glass of the dry pH susceptibility semi-permeable membranes of the attachment of preparation be immersed in 0.5 ~ 1h in alkali lye, make pH susceptibility semi-permeable membranes in alkali lye automatically and sheet glass come off floating, from alkali lye, take out pH susceptibility semi-permeable membranes; Described alkali lye preferably adopts NaOH solution;
5. employing concentration is the HCl solution of 0.005 ~ 0.01mol/L, pickling is carried out to the pH susceptibility semi-permeable membranes taken out from described step 4. alkali lye, the alkali lye of pH susceptibility semi-permeable membranes attachment is neutralized, then makes the seasoning of pH susceptibility semi-permeable membranes, the responsive semi-permeable membranes of pH can be obtained.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
The present invention, by being total to molten blending means, has prepared EVA/ PSMA pH sensitive membrane.Again through overpickling after alkaline purification, make anhydride group change into carboxyl, obtain the pH sensitive membrane of the carboxylic acid of EVA/ PSMA-H, otherwise carboxyl is combined with sodium ion, aperture reduces, and membrane flux reduces.Due to the existence of carboxyl, the film of this carboxylic acid shows good pH susceptibility.Under the condition of pH=5, the responsive semi-permeable membranes permeability rate of pH is maximum.The modified EVA semi-permeable membranes of PSMA of the present invention has increased substantially its pH susceptibility in the mechanical property situation not reducing film.PSMA/EVA semi-permeable membranes prepared by the present invention is a kind of vesicular structure, and this structure imparts the excellent water permeability of semi-permeable membranes.The responsive semi-permeable membranes of pH of the present invention can be used for medicament slow release, and under specific pH condition, molecule transmitance is different, makes small molecules can be through, retains macromole, obtains after tested being about 2 ~ 4 μm and 0.5 ~ 2 μm respectively through the membrane pore size of basic hydrolysis before and after pickling.Reaction times is short, and preparation technology is simple, can carry out industrial production in a large number, to human non-toxic's side effect.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the preparation method of the embodiment of the present invention one pH susceptibility semi-permeable membranes.
Fig. 2 utilizes the embodiment of the present invention one to prepare pH susceptibility semi-permeable membranes to advance controlled drug delivery devices schematic diagram for hydrogel.
Fig. 3 is that the embodiment of the present invention one is prepared the responsive semi-permeable membranes of pH and is placed in delayed release device and carries out testing the medicament slow release curve obtained.
Fig. 4 is the responsive semi-permeable membranes of pH water flux curve under different pH that the embodiment of the present invention one obtains.
Embodiment
Details are as follows for the preferred embodiments of the present invention:
embodiment one:
In the present embodiment, see Fig. 1 and Fig. 2, a kind of preparation method of pH susceptibility semi-permeable membranes, comprises the steps:
1. at room temperature, choose ethylene-vinyl acetate copolymer (EVA) as base material film raw material of substance, choose polystyrene-maleic anhydride alternating copolymer (PSMA) as pH susceptibility functional high molecule material, the proportioning being 6:4 according to the mass ratio of ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternating copolymer is carried out reactant batching and is placed in three-necked flask, adopt methylene dichloride as solvent, and according to the ratio that methylene dichloride and reactant total mass ratio are 70:1, solute reactant and solvent are mixed, pour into rapidly in three-necked flask, make reactants dissolved in methylene dichloride,
2. the three-necked flask that mixture is housed is connected reflux condensing tube, connect water of condensation, to described step 1. in solute reactant and solvent mixture in connect water of condensation, under ultrasound condition, and at 55 DEG C, make molten reaction product mixture altogether dissolve 3.5h and carry out common miscible synthesizing chemical-reacting, obtain the pH susceptibility semipermeable membrane material of liquid;
3. cleaning, dry flat glass plate is got, sheet glass is placed on desktop, and adjust sheet glass attitude with water level gauge, sheet glass is made to keep horizontality, by through described step 2. after the pH susceptibility semipermeable membrane material of liquid in the three-necked flask prepared directly water on sheet glass rapidly, the pH susceptibility semipermeable membrane material of liquid is made thinner, seasoning 2 hours, make the pH susceptibility semipermeable membrane material of liquid adhere to film-forming on a glass;
4. compound concentration is the NaOH solution of 0.01mol/L, at room temperature by described step 3. in the sheet glass of the dry pH susceptibility semi-permeable membranes of the attachment of preparation be immersed in 1h in NaOH solution, make pH susceptibility semi-permeable membranes in NaOH solution automatically and sheet glass come off floating, then from NaOH solution, take out pH susceptibility semi-permeable membranes;
5. employing concentration is the HCl solution of 0.01mol/L, pickling is carried out to the pH susceptibility semi-permeable membranes taken out from described step 4. NaOH solution, the NaOH solution of pH susceptibility semi-permeable membranes attachment is neutralized, then makes the seasoning of pH susceptibility semi-permeable membranes, the responsive semi-permeable membranes of pH can be obtained.
In the present embodiment, see Fig. 1 and Fig. 2, responsive semi-permeable membranes of pH being applied to inhibiter controlled release durg delivery system in pipeline and preparation method thereof, it can change according to extraneous pH, pore size changes, cause the change of permeability rate, make inhibiter reach the release action of " on-off ", belong to novel semi-permeable membranes.Semi-permeable membranes prepared by the present embodiment is applied in the experiment of medicament slow release simulator, obtains good sensitivity effect.
embodiment two:
The present embodiment is substantially identical with embodiment one, and special feature is:
In the present embodiment, a kind of preparation method of pH susceptibility semi-permeable membranes, comprises the steps:
1. at room temperature, choose ethylene-vinyl acetate copolymer (EVA) as base material film raw material of substance, choose polystyrene-maleic anhydride alternating copolymer (PSMA) as pH susceptibility functional high molecule material, the proportioning being 7:3 according to the mass ratio of ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternating copolymer is carried out reactant batching and is placed in three-necked flask, adopt methylene dichloride as solvent, and according to the ratio that methylene dichloride and reactant total mass ratio are 70:1, solute reactant and solvent are mixed, pour into rapidly in three-necked flask, make reactants dissolved in methylene dichloride,
2. this step is identical with embodiment one;
3. this step is identical with embodiment one;
4. this step is identical with embodiment one;
5. this step is identical with embodiment one.
embodiment three:
The present embodiment and previous embodiment are substantially identical, and special feature is:
In the present embodiment, a kind of preparation method of pH susceptibility semi-permeable membranes, comprises the steps:
1. at room temperature, choose ethylene-vinyl acetate copolymer (EVA) as base material film raw material of substance, choose polystyrene-maleic anhydride alternating copolymer (PSMA) as pH susceptibility functional high molecule material, the proportioning being 1:1 according to the mass ratio of ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternating copolymer is carried out reactant batching and is placed in three-necked flask, adopt methylene dichloride as solvent, and according to the ratio that methylene dichloride and reactant total mass ratio are 70:1, solute reactant and solvent are mixed, pour into rapidly in three-necked flask, make reactants dissolved in methylene dichloride,
2. this step is identical with embodiment one;
3. this step is identical with embodiment one;
4. this step is identical with embodiment one;
5. this step is identical with embodiment one.
embodiment four:
The present embodiment and previous embodiment are substantially identical, and special feature is:
In the present embodiment, a kind of preparation method of pH susceptibility semi-permeable membranes, comprises the steps:
1. at room temperature, choose ethylene-vinyl acetate copolymer (EVA) as base material film raw material of substance, choose polystyrene-maleic anhydride alternating copolymer (PSMA) as pH susceptibility functional high molecule material, the proportioning being 4:6 according to the mass ratio of ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternating copolymer is carried out reactant batching and is placed in three-necked flask, adopt methylene dichloride as solvent, and according to the ratio that methylene dichloride and reactant total mass ratio are 70:1, solute reactant and solvent are mixed, pour into rapidly in three-necked flask, make reactants dissolved in methylene dichloride,
2. this step is identical with embodiment one;
3. this step is identical with embodiment one;
4. this step is identical with embodiment one;
5. this step is identical with embodiment one.
embodiment five:
The present embodiment and previous embodiment are substantially identical, and special feature is:
In the present embodiment, a kind of preparation method of pH susceptibility semi-permeable membranes, comprises the steps:
1. at room temperature, choose ethylene-vinyl acetate copolymer (EVA) as base material film raw material of substance, choose polystyrene-maleic anhydride alternating copolymer (PSMA) as pH susceptibility functional high molecule material, the proportioning being 6:4 according to the mass ratio of ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternating copolymer is carried out reactant batching and is placed in three-necked flask, adopt methylene dichloride as solvent, and according to the ratio that methylene dichloride and reactant total mass ratio are 60:1, solute reactant and solvent are mixed, pour into rapidly in three-necked flask, make reactants dissolved in methylene dichloride,
2. this step is identical with embodiment one;
3. this step is identical with embodiment one;
4. this step is identical with embodiment one;
5. this step is identical with embodiment one.
embodiment six:
The present embodiment and previous embodiment are substantially identical, and special feature is:
In the present embodiment, a kind of preparation method of pH susceptibility semi-permeable membranes, comprises the steps:
1. at room temperature, choose ethylene-vinyl acetate copolymer (EVA) as base material film raw material of substance, choose polystyrene-maleic anhydride alternating copolymer (PSMA) as pH susceptibility functional high molecule material, the proportioning being 6:4 according to the mass ratio of ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternating copolymer is carried out reactant batching and is placed in three-necked flask, be 1:1 according to the mass ratio of methylene dichloride and trichloromethane, adopt the mixture of methylene dichloride and trichloromethane as solvent, and according to the ratio that solvent and reactant total mass ratio are 70:1 ~ 60:1, solute reactant and solvent are mixed, pour into rapidly in three-necked flask, make reactants dissolved in solvent,
2. this step is identical with embodiment one;
3. this step is identical with embodiment one;
4. this step is identical with embodiment one;
5. this step is identical with embodiment one.
embodiment seven:
The present embodiment and previous embodiment are substantially identical, and special feature is:
In the present embodiment, a kind of preparation method of pH susceptibility semi-permeable membranes, comprises the steps:
1. at room temperature, choose ethylene-vinyl acetate copolymer (EVA) as base material film raw material of substance, choose polystyrene-maleic anhydride alternating copolymer (PSMA) as pH susceptibility functional high molecule material, according to ethylene-vinyl acetate copolymer (EVA), the proportioning being 6:4 according to the mass ratio of ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternating copolymer is carried out reactant batching and is placed in three-necked flask, adopt trichloromethane as solvent, and according to the ratio that trichloromethane and reactant total mass ratio are 70:1, solute reactant and solvent are mixed, pour into rapidly in three-necked flask, make reactants dissolved in trichloromethane,
2. this step is identical with embodiment one;
3. this step is identical with embodiment one;
4. this step is identical with embodiment one;
5. this step is identical with embodiment one.
comparative example:
This comparative example and the various embodiments described above are substantially identical, and special feature is:
In this comparative example, a kind of preparation method of pH susceptibility semi-permeable membranes, comprises the steps:
1. at room temperature, take styrene-maleic anhydride copolymer (PSMA) 1g as pH susceptibility functional high molecule material, be placed in three-necked flask, and take methylene dichloride 70g and pour into rapidly in three-necked flask as solvent, make styrene-maleic anhydride copolymer be dissolved in methylene dichloride;
2. this step is identical with embodiment one;
3. this step is identical with embodiment one;
4. this step is identical with embodiment one;
5. this step is identical with embodiment one.
In this comparative example, with ionogen maleic anhydride on the molecular chain of styrene-maleic anhydride copolymer (PSMA), there is pH susceptibility, and also have very strong reactive behavior and derivative ability, but because of its poor mechanical property, copolymer p SMA can not directly be used for preparing pH sensitive membrane.In this comparative example and above-described embodiment, ethylene-vinyl acetate copolymer (EVA) has good impelling strength and environmental stress resistance as common plastics, can be used as polymeric matrix to prepare the responsive semi-permeable membranes of pH.In the above-described embodiments, by employing molten blending means altogether, namely add methylene dichloride simultaneously and PSMA and EVA is dissolved, apply film forming more afterwards thus prepare the semi-permeable membranes with excellent pH susceptibility.The responsive semi-permeable membranes of the PSMA-EVA pH prepared in above-described embodiment, by the change of pH value, controls permeability rate to reach the Co ntrolled release effect of medicine.As pH<7, semi-permeable membranes aperture becomes large, and permeability rate increases, and is equivalent to "ON", hydrogel water-swellable, promotes inhibiter and is released from release aperture, corrosive pipeline speed is significantly reduced and suppresses corrosion even completely; As pH>7, the hole of film is equivalent to "Off", and water molecules cannot through film, and hydrogel and water molecules speed are controlled, and inhibiter is inoperative.The hydrogel of pH susceptibility that prepared by above-described embodiment have advances controlled drug delivery devices can carry out pH for the water body environment under special pH condition and responds medicament slowly-releasing, and the responsive semi-permeable membranes of PSMA-EVA pH prepared of above-described embodiment can as the outstanding intelligent control function film of a class.
experimental analysis is tested:
Slowly-releasing is tested: the pH susceptibility semi-permeable membranes adopting embodiment one to prepare does slowly-releasing experiment, see Fig. 2, responsive for pH semi-permeable membranes is placed in aids drug delayed release device, this device is by needle tubing 1, syringe needle 2, elastic diaphragm 3, hydrogel 5 and the responsive semi-permeable membranes 4 of pH form, medicine 6 and hydrogel 5 load in needle tubing 1 together with being separated also by elastic diaphragm 3, as shown in Figure 2, when hydrogel 5 advances medicine controlled releasing, what adopt is a kind of medication constant releasing device of water-driven, hydrogel 5 be with water be dispersion medium gel and can certain form be kept, from the responsive semi-permeable membranes 4 of pH through water be combined with hydrogel 4, expand, volume increases thus promotes medicine 5-sulphosalicylic acid and is released in the extraneous aqueous solution from the release aperture of syringe needle 2 and carries out SR test.
Fig. 3 is that the responsive semi-permeable membranes of the pH that is obtained by reacting of embodiment one is placed in delayed release device and carries out testing the medicament slow release curve obtained, in rising trend, this shows medicine just at slow releasing, and found out by Fig. 3, release aperture aperture be 0.41mm, hydrogel quality be the aqueous solution that 2g, pH are different slowly-releasing condition under, PSMA/EVA semi-permeable membranes burst size is different.Semi-permeable membranes prepared by embodiment one is hydrolyzed without basic solution, and namely acid anhydrides is unconverted is carboxyl, and its permeability rate is lower than the semi-permeable membranes containing carboxyl.Meanwhile, semi-permeable membranes prepared by embodiment one is maximum in the quality of the drug in solution slowly-releasing of pH=4, and namely the permeability rate of film is now the highest, thus the water that hydrogel combines is maximum, and impellent is larger.The responsive semi-permeable membranes of the pH prepared from enforcement one is placed in delayed release device and carries out test-results, and semi-permeable membranes has the effect of susceptibility under condition of different pH, and to acid-sensitive.
In addition, the responsive semi-permeable membranes of the pH obtained with embodiment one does water flux test, uses HBL-302 type water circulating pump and cup type funnel to 0.6gEVA+0.4PSMA+70gCH
2cl
2the semi-permeable membranes be prepared from carries out suction filtration experiment, and during measurement, solution enters cup type funnel filter with the pump of the top hole pressure of the intake pressure of 0.1MPa and 0MPa.Measured by water flux, the graph of a relation obtaining pH value and water flux is shown in Fig. 4.Obviously can see there is a hop point, as pH value of solution >7, water flux sharply declines.To in the experiment of water flux, when selecting to carry out acid-alkali process, the pH value of feedstock solution changes to 12.0 from 2.0 in an orderly manner; When alkali-acid treatment is carried out in selection, the pH value of feedstock solution changes to 2.0 from 12.0 in an orderly manner.PSMA-EVA pH sensitive membrane prepared by embodiment one is measured by the weighing of the filtered soln within the timed interval determined the flux that pH changes.For each pH value, penetrating fluid is all collected and gravimetry, until the weight of time per unit does not change.As can be seen from Figure 4, along with the value of pH improves, water flux is increased to 141.25 from 71.08 and is down to again 11.50ml/ (m
2.h), i.e. water flux first increases and then decreases, the pH value range of maximum water flux is near pH=5.
Contrast the various embodiments described above and comparative example, known in conjunction with above-mentioned experimental analysis, the above embodiment of the present invention prepared a kind of pH susceptibility good, according to pH change water flux there is the simple semi-permeable membranes of catastrophe point, technique, and preparation method thereof, can be applicable to the slowly-releasing of inhibiter in pipeline.The pH responsive type semi-permeable membranes prepared of above-described embodiment adopt miscible altogether legal using ethylene-vinyl acetate copolymer (EVA) as base material film, polystyrene-maleic anhydride alternating copolymer (PSMA), as functional material, forms by being mixed with under solvent increase-volume.Then at room temperature this EVA/PSMA film to be soaked in 0.005 ~ 0.01mol/L sodium hydroxide solution 0.5 ~ 1 hour, the pickling of 0.005 ~ 0.01mol/L HCl solution is used to neutralize again, it is made to change into EVA/PSMA-H carboxylic acid membrane, anhydride group is converted into carboxyl, and the film be modified water flux in the solution of pH=5 is maximum.Above-described embodiment overcomes the defect that existing grafting method and pore filling legal system film exist, technique simple and consuming time short while, also can control sensitivity size according to specific requirement, reach the effect raised the efficiency, economize on resources and reduce costs.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above; but the invention is not restricted to above-described embodiment; multiple change can also be made according to the object of innovation and creation of the present invention; change, the modification made under all spirit according to technical solution of the present invention and principle, substitute, combination, to simplify; all should be the substitute mode of equivalence; as long as goal of the invention according to the invention; only otherwise deviate from know-why and the inventive concept of the preparation method of pH susceptibility semi-permeable membranes of the present invention, all protection scope of the present invention is belonged to.
Claims (5)
1. a preparation method for pH susceptibility semi-permeable membranes, is characterized in that, comprises the steps:
1. at room temperature, choose ethylene-vinyl acetate copolymer (EVA) as base material film raw material of substance, choose polystyrene-maleic anhydride alternating copolymer (PSMA) as pH susceptibility functional high molecule material, the proportioning being 7:3 ~ 4:6 according to the mass ratio of ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternating copolymer carries out reactant batching, adopt one or both mixture in methylene dichloride and trichloromethane as solvent, and according to the ratio that solvent and reactant total mass ratio are 70:1 ~ 60:1, reactant and solvent are mixed, make reactants dissolved in solvent,
2. by described step 1. in solute reactant and solvent mixture connect condensation reflux unit, under ultrasound condition, make molten reaction product mixture altogether dissolve 3 ~ 3.5h and carry out common miscible synthesizing chemical-reacting, obtain the pH susceptibility semipermeable membrane material of liquid;
3. cleaning, dry flat glass plate is got, sheet glass is made to keep horizontality, by through described step 2. after the pH susceptibility semipermeable membrane material of liquid prepared directly water on sheet glass rapidly, the pH susceptibility semipermeable membrane material of liquid is made thinner, seasoning 2 hours, makes the pH susceptibility semipermeable membrane material of liquid adhere to film-forming on a glass;
4. compound concentration is the alkali lye of 0.005 ~ 0.01mol/L, at room temperature by described step 3. in the sheet glass of the dry pH susceptibility semi-permeable membranes of the attachment of preparation be immersed in 0.5 ~ 1h in alkali lye, make pH susceptibility semi-permeable membranes in alkali lye automatically and sheet glass come off floating, from alkali lye, take out pH susceptibility semi-permeable membranes;
5. employing concentration is the HCl solution of 0.005 ~ 0.01mol/L, pickling is carried out to the pH susceptibility semi-permeable membranes taken out from described step 4. alkali lye, the alkali lye of pH susceptibility semi-permeable membranes attachment is neutralized, then makes the seasoning of pH susceptibility semi-permeable membranes, the responsive semi-permeable membranes of pH can be obtained.
2. the preparation method of pH susceptibility semi-permeable membranes according to claim 1, is characterized in that: described step 4. in, described alkali lye adopts NaOH solution.
3. the preparation method of pH susceptibility semi-permeable membranes according to claim 1 or 2, it is characterized in that: described step 1. in, the proportioning being 6:4 according to the mass ratio of ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternating copolymer carries out reactant batching, and according to the ratio that solvent and reactant total mass ratio are 70:1, reactant and solvent are mixed, make reactants dissolved in solvent, carry out common miscible synthesizing chemical-reacting.
4. the preparation method of pH susceptibility semi-permeable membranes according to claim 1 or 2, is characterized in that: described step 1. in, be 1:1 according to the mass ratio of methylene dichloride and trichloromethane, adopt the mixture of methylene dichloride and trichloromethane as solvent.
5. the preparation method of pH susceptibility semi-permeable membranes according to claim 1 or 2, is characterized in that: described step 2. in, at 55 DEG C, carry out ultrasonic dissolution reaction.
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