CN104877165B - The preparation method of pH sensitiveness pellicles - Google Patents
The preparation method of pH sensitiveness pellicles Download PDFInfo
- Publication number
- CN104877165B CN104877165B CN201510314008.XA CN201510314008A CN104877165B CN 104877165 B CN104877165 B CN 104877165B CN 201510314008 A CN201510314008 A CN 201510314008A CN 104877165 B CN104877165 B CN 104877165B
- Authority
- CN
- China
- Prior art keywords
- sensitiveness
- pellicle
- solvent
- reactant
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
It the invention discloses a kind of preparation method of pH sensitiveness pellicle, can prepare that pH sensitiveness is good, changes water flux according to pH the simple pellicle of catastrophe point, technique occurs, can be applied to the sustained release of corrosion inhibiter in pipeline.PH responsive types pellicle prepared by the present invention is using miscible legal using ethylene vinyl acetate copolymer as base material film altogether, polystyrene maleic anhydride alternate copolymer is as functional material, formed by being mixed with solvent increase-volume, then pH sensitiveness pellicles are soaked in sodium hydroxide solution, neutralized again with HCl solution pickling, EVA/PSMA H carboxylic acid membranes are converted it into, anhydride group is converted into carboxyl, and water flux is maximum in an acidic solution for the film being modified.The present invention overcome existing grafting method and hole completion method film there are the defects of, technique is simple and time-consuming short, can control sensitivity size according to specific requirement, has the function that to improve efficiency, economizes on resources and reduce cost.
Description
Technical field
The present invention relates to a kind of polymer matrix preparation method, particularly a kind of pellicle with intelligent switch function
Preparation method, applied to sensitiveness functional material preparing technical field.
Background technology
PH sensitiveness pellicle can produce volume or morphologic change because of the change of pH value, and this change is to be based on molecular water
Flat and macromolecular level stimulating responsive, has reproducible characteristic, is a kind of and spreads disengaging simultaneously to certain molecule or ion
And selective film is passed through to different particles.In recent years, pH sensitive membranes are widely used in drug delivery and separated
Journey, including sea water desalination, water purifying, the separation of ethanol water etc..The pH sensitive membranes of polymer can be by mixing, connecing
It is prepared by branch and hole fill method etc..
With the continuous progressive of science and technology and constantly probing into pH sensitivity film properties, the performance and feature of pH sensitive membranes are found
The requirement of medicine controlled releasing can be reached, its Releasing Mechanism is mainly to contain ionic group in polymer, these ionic group phases
Active force between mutually can change as the pH value of external environment is different, medicine is obtained with the sub- association rate of internal water
To control, so that the medicine being embedded in pH sensitive membranes is released, achieve the purpose that slowly to discharge.Made using pH sensitive membranes
It for drug controlled release material, can not only solve the problems, such as that drug concentration is unstable, but also also reduce drug toxicity, improve
The effect of medicine.Compared with conventional medicament discharges, application of the intelligent pellicle in terms of drug controlled release have it is intelligent,
Can self-adjustable, the bioactivity of medicine hold time the remarkable advantage such as longer.
As the material for preparing pH sensitive membranes, generally use styrene-maleic anhydride copolymer (PSMA), on its strand
With ionogen maleic anhydride, there is pH sensitiveness, and also have very strong reactivity and derivative ability, but because of it
Poor mechanical property, copolymer p SMA cannot be used directly to prepare pH sensitive membranes.Up to the present, the semi-transparent of pH sensitiveness is still lacked
The simple effective preparation method of film.
The content of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The preparation method of pH sensitiveness pellicles, increases the functional groups of EVA film with styrene-maleic anhydride copolymer (PSMA)
Method, using miscible legal preparation pH responsive type pellicles altogether, it can change according to extraneous pH, and pore size changes, and draws
The change of permeability rate is played, corrosion inhibiter is reached the release action of one " on-off ", there is pH sensitiveness using prepared by the present invention
Hydrogel promote controlled drug delivery devices, can be directed to special pH under the conditions of water body environment carry out pH response medicament sustained release, acquisition
Preferable sensitiveness perceives and control effect.
Purpose is created to reach foregoing invention, the present invention uses following technical proposals：
A kind of preparation method of pH sensitiveness pellicle, includes the following steps：
1. at room temperature, choosing ethylene-vinyl acetate copolymer (EVA) is used as base material film raw material of substance, polyphenyl is chosen
Ethylene-maleic acid alternate copolymer (PSMA) is used as pH sensitiveness functional high molecule materials, according to ethylene-vinyl acetate
The mass ratio of copolymer and polystyrene-maleic anhydride alternate copolymer is 7:3~4:6 proportioning carries out reactant dispensing, adopts
By the use of the mixture of one or both of dichloromethane and chloroform as solvent, and according to solvent and reactant gross mass ratio
For 70:1~60:1 ratio is mixed reactant and solvent, reactant is dissolved in solvent；It is preferred that according to ethene-vinegar
The mass ratio of vinyl acetate copolymer and polystyrene-maleic anhydride alternate copolymer is 6:4 proportioning carries out reactant dispensing,
And preferably it is 70 according to solvent and reactant gross mass ratio:1 ratio is mixed reactant and solvent, dissolves reactant
Miscible synthesizing chemical-reacting altogether is carried out in solvent；It is preferred that it is 1 according to the mass ratio of dichloromethane and chloroform:1, using dichloro
The mixture of methane and chloroform is as solvent；
2. by the step 1. in solute reactant connect condensation reflux unit with solvent mixture, in ultrasound condition
Under, make altogether molten reaction product mixture dissolve 3 ~ 3.5h and carry out miscible synthesizing chemical-reacting altogether, obtain the pH sensitiveness pellicles of liquid
Material；It is preferred that ultrasonic dissolution reaction is carried out at 55 DEG C；
3. taking clean, dry flat glass plate, glass plate is kept horizontality, will by the step 2. after make
The pH sensitiveness semipermeable membrane material of standby liquid is directly poured rapidly in spreading out, the pH sensitiveness semipermeable membrane material of liquid on glass plate
It is thin, when natural drying 2 is small, the pH sensitiveness semipermeable membrane material of liquid is adhered to film-forming on a glass；
4. compound concentration is the lye of 0.005 ~ 0.01mol/L, at room temperature by the attachment of the step 3. middle preparation
The glass plate of dry pH sensitiveness pellicles is immersed in 0.5 ~ 1h in lye, makes pH sensitiveness pellicles automatic in lye
Come off floating with glass plate, pH sensitiveness pellicles are taken out from lye；The lye preferably uses NaOH solution；
5. HCl solution of the concentration for 0.005 ~ 0.01mol/L is used, it is quick to the pH that is taken out from the step 4. lye
Perceptual pellicle carries out pickling, and the lye of pH sensitiveness pellicle attachment is neutralized, and then makes pH sensitiveness pellicle certainly
It is so dry, you can to obtain pH sensitivity pellicles.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
The present invention is prepared for EVA/ PSMA pH sensitive membranes by molten mixed method altogether.Again through peracid after alkali process
Wash, anhydride group is changed into carboxyl, obtain the pH sensitive membranes of the carboxylic acid of EVA/ PSMA-H, otherwise carboxyl is combined with sodium ion,
Aperture reduces, and membrane flux reduces.Due to the presence of carboxyl, the film of the carboxylic acid shows preferable pH sensitiveness.Bar in pH=5
Under part, pH sensitivity pellicles permeability rate is maximum.EVA pellicles modified PSMA of the present invention are not reducing the mechanical property feelings of film
Its pH sensitiveness is greatly improved under condition.PSMA/EVA pellicles prepared by the present invention are a kind of loose structures, this structure
Impart the excellent water permeability of pellicle.PH sensitivities pellicle of the present invention can be used for medicament slow release, under the conditions of specific pH,
Molecule transmitance is different, passes through small molecule, retains macromolecular, obtains the film before and after pickling through basic hydrolysis after tested
Aperture respectively may be about 2 ~ 4 μm and 0.5 ~ 2 μm.Reaction time is short, and preparation process is simple, industrial production can be largely carried out, to human body
Have no toxic side effect.
Brief description of the drawings
Fig. 1 is the process flow diagram of the preparation method of one pH sensitiveness pellicles of the embodiment of the present invention.
Fig. 2 is to prepare pH sensitiveness pellicle using the embodiment of the present invention one to promote controlled drug delivery devices to show for hydrogel
It is intended to.
Fig. 3 is that the embodiment of the present invention one prepares pH sensitivity pellicles and is placed in the medicament slow release that delayed release device is tested
Curve.
Fig. 4 is the water flux curve under different pH of pH sensitivities pellicle made from the embodiment of the present invention one.
Embodiment
Details are as follows for the preferred embodiment of the present invention：
Embodiment one：
In the present embodiment, referring to Fig. 1 and Fig. 2, a kind of preparation method of pH sensitiveness pellicle, includes the following steps：
1. at room temperature, choosing ethylene-vinyl acetate copolymer (EVA) is used as base material film raw material of substance, polyphenyl is chosen
Ethylene-maleic acid alternate copolymer (PSMA) is used as pH sensitiveness functional high molecule materials, according to ethylene-vinyl acetate
The mass ratio of copolymer and polystyrene-maleic anhydride alternate copolymer is 6:4 proportioning carries out reactant dispensing and is placed in three necks
Using dichloromethane as solvent, and it is 70 according to dichloromethane and reactant gross mass ratio in flask:1 ratio is by solute
Reactant and solvent are mixed, and are poured into three-neck flask rapidly, reactant is dissolved in dichloromethane；
2. by equipped with mixture three-neck flask connect reflux condensing tube, connect condensed water, to the step 1. in
Solute reactant with connect condensed water in solvent mixture, under ultrasound condition, and at 55 DEG C, make molten reaction product mixture altogether
Dissolving 3.5h carries out miscible synthesizing chemical-reacting altogether, obtains the pH sensitiveness semipermeable membrane materials of liquid；
3. taking clean, dry flat glass plate, glass plate is placed on desktop, and glass plate appearance is adjusted with level meter
State, makes glass plate keep horizontality, by by the step 2. after liquid in the three-neck flask for preparing pH sensitiveness half
Antireflective film material is directly poured rapidly on glass plate, making the pH sensitiveness semipermeable membrane materials of liquid make thinner, and when natural drying 2 is small, is made
The pH sensitiveness semipermeable membrane material of liquid adheres to film-forming on a glass；
4. compound concentration be 0.01mol/L NaOH solution, at room temperature by the step 3. middle preparation attachment
The glass plate of dry pH sensitiveness pellicles is immersed in 1h in NaOH solution, make pH sensitiveness pellicles in NaOH solution from
Dynamic floating, then the taking-up pH sensitiveness pellicles from NaOH solution of coming off with glass plate；
5. HCl solution of the concentration for 0.01mol/L is used, to the pH sensitivities taken out from the step 4. NaOH solution
Property pellicle carry out pickling, to pH sensitiveness pellicle attachment NaOH solution neutralize, then make pH sensitiveness pellicles
Spontaneously dry, you can obtain pH sensitivity pellicles.
In the present embodiment, referring to Fig. 1 and Fig. 2, the pH sensitivities applied to corrosion inhibiter controlled release durg delivery system in pipeline are semi-transparent
Film and preparation method thereof, it can change according to extraneous pH, and pore size changes, and causes the change of permeability rate, makes corrosion inhibiter
Reach the release action of one " on-off ", belong to new pellicle.Pellicle manufactured in the present embodiment is applied to medicament slow release mould
Intend in device experiment, obtain preferable sensitivity effect.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, a kind of preparation method of pH sensitiveness pellicle, includes the following steps：
1. at room temperature, choosing ethylene-vinyl acetate copolymer (EVA) is used as base material film raw material of substance, polyphenyl is chosen
Ethylene-maleic acid alternate copolymer (PSMA) is used as pH sensitiveness functional high molecule materials, according to ethylene-vinyl acetate
The mass ratio of copolymer and polystyrene-maleic anhydride alternate copolymer is 7:3 proportioning carries out reactant dispensing and is placed in three necks
Using dichloromethane as solvent, and it is 70 according to dichloromethane and reactant gross mass ratio in flask:1 ratio is by solute
Reactant and solvent are mixed, and are poured into three-neck flask rapidly, reactant is dissolved in dichloromethane；
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 is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of preparation method of pH sensitiveness pellicle, includes the following steps：
1. at room temperature, choosing ethylene-vinyl acetate copolymer (EVA) is used as base material film raw material of substance, polyphenyl is chosen
Ethylene-maleic acid alternate copolymer (PSMA) is used as pH sensitiveness functional high molecule materials, according to ethylene-vinyl acetate
The mass ratio of copolymer and polystyrene-maleic anhydride alternate copolymer is 1:1 proportioning carries out reactant dispensing and is placed in three necks
Using dichloromethane as solvent, and it is 70 according to dichloromethane and reactant gross mass ratio in flask:1 ratio is by solute
Reactant and solvent are mixed, and are poured into three-neck flask rapidly, reactant is dissolved in dichloromethane；
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.
Example IV：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of preparation method of pH sensitiveness pellicle, includes the following steps：
1. at room temperature, choosing ethylene-vinyl acetate copolymer (EVA) is used as base material film raw material of substance, polyphenyl is chosen
Ethylene-maleic acid alternate copolymer (PSMA) is used as pH sensitiveness functional high molecule materials, according to ethylene-vinyl acetate
The mass ratio of copolymer and polystyrene-maleic anhydride alternate copolymer is 4:6 proportioning carries out reactant dispensing and is placed in three necks
Using dichloromethane as solvent, and it is 70 according to dichloromethane and reactant gross mass ratio in flask:1 ratio is by solute
Reactant and solvent are mixed, and are poured into three-neck flask rapidly, reactant is dissolved in dichloromethane；
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 is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of preparation method of pH sensitiveness pellicle, includes the following steps：
1. at room temperature, choosing ethylene-vinyl acetate copolymer (EVA) is used as base material film raw material of substance, polyphenyl is chosen
Ethylene-maleic acid alternate copolymer (PSMA) is used as pH sensitiveness functional high molecule materials, according to ethylene-vinyl acetate
The mass ratio of copolymer and polystyrene-maleic anhydride alternate copolymer is 6:4 proportioning carries out reactant dispensing and is placed in three necks
Using dichloromethane as solvent, and it is 60 according to dichloromethane and reactant gross mass ratio in flask:1 ratio is by solute
Reactant and solvent are mixed, and are poured into three-neck flask rapidly, reactant is dissolved in dichloromethane；
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 is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of preparation method of pH sensitiveness pellicle, includes the following steps：
1. at room temperature, choosing ethylene-vinyl acetate copolymer (EVA) is used as base material film raw material of substance, polyphenyl is chosen
Ethylene-maleic acid alternate copolymer (PSMA) is used as pH sensitiveness functional high molecule materials, according to ethylene-vinyl acetate
The mass ratio of copolymer and polystyrene-maleic anhydride alternate copolymer is 6:4 proportioning carries out reactant dispensing and is placed in three necks
It is 1 according to the mass ratio of dichloromethane and chloroform in flask:1, using the mixture conduct of dichloromethane and chloroform
Solvent, and be 70 according to solvent and reactant gross mass ratio:1~60:1 ratio is mixed solute reactant and solvent,
Pour into three-neck flask rapidly, reactant is 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 is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of preparation method of pH sensitiveness pellicle, includes the following steps：
1. at room temperature, choosing ethylene-vinyl acetate copolymer (EVA) is used as base material film raw material of substance, polyphenyl is chosen
Ethylene-maleic acid alternate copolymer (PSMA) is used as pH sensitiveness functional high molecule materials, according to ethylene-vinyl acetate
Copolymer (EVA), the mass ratio according to ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternate copolymer are
6:4 proportioning carries out reactant dispensing and is placed in three-neck flask, using chloroform as solvent, and according to chloroform and instead
It is 70 to answer thing total mass ratio:1 ratio is mixed solute reactant and solvent, is poured into three-neck flask rapidly, makes reaction
Thing is dissolved in chloroform；
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 is essentially identical with the various embodiments described above, is particular in that：
In this comparative example, a kind of preparation method of pH sensitiveness pellicle, includes the following steps：
1. styrene-maleic anhydride copolymer (PSMA) 1g at room temperature, is weighed as pH sensitiveness functional polymer materials
Material, is placed in three-neck flask, and weighs dichloromethane 70g and poured into as solvent in three-neck flask rapidly, makes styrene-maleic acid
Anhydride copolymer is dissolved in dichloromethane；
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, ionogen horse is carried on the strand of styrene-maleic anhydride copolymer (PSMA)
Carry out acid anhydrides, there is pH sensitiveness, and also have very strong reactivity and derivative ability, but because of its poor mechanical property, copolymer
PSMA cannot be used directly to prepare pH sensitive membranes.In this comparative example and above-described embodiment, ethylene-vinyl acetate copolymer
(EVA) there is good impact flexibility and environmental stress resistance as common plastics, pH sensitive half can be prepared as polymeric matrix
Permeable membrane.In the above-described embodiments, molten mixed method altogether will be used, i.e., adding dichloromethane at the same time dissolves PSMA and EVA, afterwards
Re-coating film forming is so as to prepare the pellicle with excellent pH sensitiveness.The PSMA-EVA pH prepared in above-described embodiment are quick
The control release action of medicine can be reached by the change of pH value to control permeability rate by feeling pellicle.Work as pH<When 7, pellicle
Aperture becomes larger, and permeability rate increase, equivalent to "ON", hydrogel water-swellable, promotes corrosion inhibiter to be released from release aperture, make
Corrosive pipeline speed significantly reduces or even complete inhibition corrosion；Work as pH>When 7, the hole of film can not be passed through equivalent to "Off", hydrone
Film, hydrogel are controlled with water molecules speed, and corrosion inhibiter does not work.Prepared by above-described embodiment has pH sensitiveness
Hydrogel promote controlled drug delivery devices can be directed to special pH under the conditions of water body environment carry out pH response medicament sustained release, above-mentioned reality
The PSMA-EVA pH sensitivities pellicle for applying example preparation can be as a kind of outstanding intelligent control function film.
Experimental analysis is tested：
Sustained release experiment：The pH sensitiveness pellicles prepared using embodiment one do sustained release experiment, referring to Fig. 2, pH is sensitive
Pellicle is placed in aids drug delayed release device, and the device is sensitive by needle tubing 1, syringe needle 2, elastic diaphragm 3, hydrogel 5 and pH
Pellicle 4 forms, and medicine 6 and hydrogel 5 are separated by elastic diaphragm 3 and be fitted into together in needle tubing 1, as shown in Fig. 2, hydrogel
During 5 propulsion medicine controlled releasing, using a kind of medication constant release device of water-driven, hydrogel 5 is using water as decentralized medium
Gel and certain form can be kept, from pH sensitivities pellicle 4 pass through water combined with hydrogel 4, expand, volume increasing
It is big to carry out SR test so as to promote medicine 5-sulphosalicylic acid to be released to from the release aperture of syringe needle 2 in extraneous aqueous solution.
Fig. 3 is that embodiment one reacts obtained pH sensitivity pellicles and is placed in the medicine tested in delayed release device and delays
Release curve, in rising trend, this shows that medicine slowly discharges, and it can be seen from Fig. 3 that release aperture aperture for 0.41mm,
Under the conditions of sustained release of the hydrogel quality for 2g, pH different aqueous solutions, PSMA/EVA pellicles burst size is different.Embodiment one is made
Standby pellicle is hydrolyzed without alkaline solution, i.e., acid anhydrides is not converted into carboxyl, its permeability rate is less than the pellicle containing carboxyl.
Meanwhile pellicle prepared by embodiment one is maximum in the quality of the drug in solution sustained release of pH=4, i.e., the permeability rate of film at this time
Highest, so that the water that hydrogel combines is most, motive force is bigger.Delayed release device is placed in by implementing the pH sensitivity pellicles prepared
The middle results showed that pellicle that carries out has the effect of sensitiveness under condition of different pH, and to acid-sensitive.
In addition, the pH sensitivity pellicles obtained with embodiment one do water flux experiment, using HBL-302 types water circulating pump and
Cup type funnel is to 0.6gEVA+0.4PSMA+70gCH2Cl2The pellicle being prepared carries out suction filtration experiment, during measurement solution with
The pump of the inlet pressure of 0.1MPa and the outlet pressure of 0MPa enters cup type funnel filter.Measured by water flux, obtain pH
The graph of a relation of value and water flux is shown in Fig. 4.It can clearly be seen that there is a jumping point, work as pH value of solution>When 7, water flux drastically declines.
To in the experiment of water flux, when selection carries out Acid-Base processing, the pH value of feedstock solution changes to 12.0 from 2.0 in an orderly manner；Selection
When carrying out alkali-acid treatment, the pH value of feedstock solution changes to 2.0 from 12.0 in an orderly manner.PSMA-EVA pH prepared by embodiment one
Sensitive membrane measures the flux that pH changes by the weighing of the filtered soln in definite time interval.For each pH
Value, penetrating fluid is all collected and measures weight, until the weight of time per unit does not change.As can be seen from Figure 4, with the value of pH
Improve, water flux increases to 141.25 from 71.08 and is down to 11.50ml/ (m2.H), i.e. water flux first increases and then decreases, it is maximum
The pH value range of water flux is near pH=5.
The various embodiments described above and comparative example are contrasted, according to above-mentioned experimental analysis, prepared by the above embodiment of the present invention
A kind of pH sensitiveness is good, changes water flux according to pH there is the simple pellicle of catastrophe point, technique, and preparation method thereof, can
Sustained release applied to corrosion inhibiter in pipeline.Above-described embodiment prepare pH responsive types pellicle using altogether it is miscible it is legal by ethene-
Vinyl acetate co-polymer（EVA）As base material film, polystyrene-maleic anhydride alternate copolymer（PSMA）As feature material
Material, is formed by being mixed with solvent increase-volume.Then the EVA/PSMA films are soaked in 0.005 at room temperature ~
In 0.01mol/L sodium hydroxide solutions 0.5 ~ 1 it is small when, then with the pickling of 0.005 ~ 0.01mol/L HCl solutions neutralize, make its turn
EVA/PSMA-H carboxylic acid membranes are melted into, anhydride group is converted into carboxyl, and the film being modified water flux in the solution of pH=5 is maximum.
Above-described embodiment overcome existing grafting method and hole completion method film there are the defects of, technique simply and it is time-consuming short while,
Also sensitivity size can be controlled according to specific requirement, have the function that to improve efficiency, economize on resources and reduce cost.
The embodiment of the present invention is illustrated above in conjunction with attached drawing, but the invention is not restricted to above-described embodiment, can be with
The purpose of innovation and creation according to the present invention makes a variety of changes, under all Spirit Essence and principle according to technical solution of the present invention
Change, modification, replacement, combination, the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention, only
Otherwise technical principle and inventive concept away from the preparation method of pH sensitiveness pellicle of the present invention, belong to the protection of the present invention
Scope.
Claims (5)
1. a kind of preparation method of pH sensitiveness pellicle, it is characterised in that include the following steps：
1. at room temperature, choosing ethylene-vinyl acetate copolymer (EVA) be used as base material film raw material of substance, and selection polystyrene-
Maleic anhydride alternate copolymer (PSMA) is used as pH sensitiveness functional high molecule materials, according to ethylene-vinyl acetate copolymer
Mass ratio with polystyrene-maleic anhydride alternate copolymer is 7:3~4:6 proportioning carries out reactant dispensing, using dichloro
The mixture of one or both of methane and chloroform is 70 as solvent, and according to solvent and reactant gross mass ratio:1
~60:1 ratio is mixed reactant and solvent, reactant is dissolved in solvent；
2. by the step 1. in solute reactant connect condensation reflux unit with solvent mixture, under ultrasound condition, make
3~3.5h of reactant dissolving of miscible conjunction carries out miscible conjunction altogether altogether, obtains the pH sensitiveness semipermeable membrane materials of liquid；
3. taking clean, dry flat glass plate, glass plate is kept horizontality, by by the step 2. after the liquid for preparing
The pH sensitiveness semipermeable membrane material of body is directly poured rapidly on glass plate, making the pH sensitiveness semipermeable membrane materials of liquid make thinner, certainly
When so drying 2 is small, the pH sensitiveness semipermeable membrane material of liquid is set to adhere to film-forming on a glass；
4. compound concentration is the lye of 0.005~0.01mol/L, will be done at room temperature in the attachment of the step 3. middle preparation
The glass plate of dry pH sensitiveness pellicles is immersed in 0.5~1h in lye, make pH sensitiveness pellicles in lye automatically with
Glass plate comes off floating, and pH sensitiveness pellicles are taken out from lye；
5. HCl solution of the concentration for 0.005~0.01mol/L is used, to the pH sensitiveness taken out from the step 4. lye
Pellicle carries out pickling, and the lye of pH sensitiveness pellicle attachment is neutralized, and then makes pH sensitiveness pellicle naturally dry
It is dry, you can to obtain pH sensitivity pellicles.
2. the preparation method of pH sensitiveness pellicle according to claim 1, it is characterised in that：The step 4. in, institute
State lye and use NaOH solution.
3. the preparation method of pH sensitiveness pellicle according to claim 1 or claim 2, it is characterised in that：The step 1. in,
It is 6 according to the mass ratio of ethylene-vinyl acetate copolymer and polystyrene-maleic anhydride alternate copolymer:4 proportioning carries out
Reactant dispensing, and be 70 according to solvent and reactant gross mass ratio:1 ratio is mixed reactant and solvent, is made anti-
Answer thing to be dissolved in solvent and carry out miscible conjunction altogether.
4. the preparation method of pH sensitiveness pellicle according to claim 1 or claim 2, it is characterised in that：The step 1. in,
It is 1 according to the mass ratio of dichloromethane and chloroform:1, using the mixture of dichloromethane and chloroform as solvent.
5. the preparation method of pH sensitiveness pellicle according to claim 1 or claim 2, it is characterised in that：The step 2. in,
Ultrasonic dissolution is carried out at 55 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510314008.XA CN104877165B (en) | 2015-06-10 | 2015-06-10 | The preparation method of pH sensitiveness pellicles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510314008.XA CN104877165B (en) | 2015-06-10 | 2015-06-10 | The preparation method of pH sensitiveness pellicles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104877165A CN104877165A (en) | 2015-09-02 |
| CN104877165B true CN104877165B (en) | 2018-04-27 |
Family
ID=53944862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510314008.XA Expired - Fee Related CN104877165B (en) | 2015-06-10 | 2015-06-10 | The preparation method of pH sensitiveness pellicles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104877165B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108395607B (en) * | 2017-02-08 | 2021-03-19 | 中国石油化工股份有限公司 | Ultraviolet-to-blue light conversion resin and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1280262C (en) * | 1985-05-23 | 1991-02-19 | Richard A. Hann | Asymmetric semi-permeable membrane having high salt rejection |
| CN102198112A (en) * | 2010-03-26 | 2011-09-28 | 北京天衡药物研究院 | Osmotic pump type controlled release tablets and preparation method thereof |
| CN102489185A (en) * | 2011-12-12 | 2012-06-13 | 天津工业大学 | Polyvinylidene fluoride (PVDF)/alternating copolymer blended pH-sensitive membrane and preparation method thereof |
| CN103191680A (en) * | 2013-03-26 | 2013-07-10 | 厦门大学 | PH-sensitive composite hollow microsphere and preparation method thereof |
-
2015
- 2015-06-10 CN CN201510314008.XA patent/CN104877165B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1280262C (en) * | 1985-05-23 | 1991-02-19 | Richard A. Hann | Asymmetric semi-permeable membrane having high salt rejection |
| CN102198112A (en) * | 2010-03-26 | 2011-09-28 | 北京天衡药物研究院 | Osmotic pump type controlled release tablets and preparation method thereof |
| CN102489185A (en) * | 2011-12-12 | 2012-06-13 | 天津工业大学 | Polyvinylidene fluoride (PVDF)/alternating copolymer blended pH-sensitive membrane and preparation method thereof |
| CN103191680A (en) * | 2013-03-26 | 2013-07-10 | 厦门大学 | PH-sensitive composite hollow microsphere and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Development of chitosan/polyethylene vinyl acetate co-matrix: controlled release of aspirin-heparin for preventing cardiovascular thrombosis";Sindhu C. Vasudev, et al.;《Biomaterials》;19980315;第18卷;第375-381页 * |
| "Preparation and characterization of modified polyethersulfone hollow fiber membranes by blending poly (styrene-alt-maleic anhydride)";Tao Xiang et al.;《Desalination》;20120423;第295卷;第26-34页 * |
| "PVDF/SMA共混膜的制备与性能";魏志峰等;《高分子材料科学与工程》;20120831;第28卷(第8期);第152-155页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104877165A (en) | 2015-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109806918B (en) | Preparation method of gelatin methacrylamide core-shell microspheres based on microfluidic technology | |
| Masuelli et al. | SPC/PVDF membranes for emulsified oily wastewater treatment | |
| CN108201795B (en) | A kind of preparation method of Selective Separation Enoxacin molecularly imprinted composite membrane material | |
| CN103408691B (en) | A kind of Acrylate pressure-sensitive adhesive emulsion and preparation method thereof and application | |
| CN104437124B (en) | A kind of self-cleaning type polyvinylidene fluoride microporous film and preparation method thereof | |
| CN103403043A (en) | Cold water soluble polyvinyl alcohol/alkyl acrylate copolymers and films thereof | |
| CN103173933B (en) | A kind of preparation method of glucose vinyl acetate/N-isopropylacrylamide copolymer nano tunica fibrosa | |
| CN101193955A (en) | Vinyl alcohol copolymers for use in aqueous dispersions and melt extruded articles | |
| CN102225249A (en) | Preparation method of organic-inorganic hybrid monolithic capillary column | |
| CN102068921B (en) | PH sensitive polyvinylidene fluoride gel film and preparation method thereof | |
| CN110314561A (en) | A kind of polymeric film material and preparation method thereof | |
| CN108939951A (en) | A kind of self-assembled modified polyamide reverse osmosis composite film and its application | |
| CN108310984A (en) | A kind of anti-pollution hydrophilic PVDF Modified Membrane and preparation method thereof | |
| WO2009035414A1 (en) | Chitosan construct and method of preparing the same | |
| CN104877165B (en) | The preparation method of pH sensitiveness pellicles | |
| Fang et al. | Kinetics of in vitro drug release from chitosan/gelatin hybrid membranes | |
| CN101829507A (en) | Method for preparing polypropylene separation membrane with durable hydrophilic property | |
| CN101974154B (en) | Modified polyethyleneimine and preparation method thereof | |
| CN104936681A (en) | Fouling inhibitor, filtration membrane and method for producing same | |
| CN103173934A (en) | Preparation method of galactose vinyl ester/isopropyl acrylamide copolymer nanofiber membrane | |
| CN103265660B (en) | Method for preparing amino acid molecularly imprinted membrane through bicontinuous phase micro emulsion in situ polymerization | |
| CN103614860A (en) | Method for preparing glucose azelaic acid divinyl ester/N-isopropylacrylamide copolymer nanofiber membrane | |
| CN103211791A (en) | Venlafaxine hydrochloride film-controlled slow-release pellet capsule | |
| CN103884802B (en) | A kind of memory loss shellfish poison molecular engram integral column and application thereof | |
| CN105131216B (en) | A kind of application of cationic amphiphic copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180427 Termination date: 20210610 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |