CN102532572A - Preparation method of quaternized chitosan anion hybrid membrane doped with positive polystyrene latex - Google Patents

Preparation method of quaternized chitosan anion hybrid membrane doped with positive polystyrene latex Download PDF

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CN102532572A
CN102532572A CN2011104490237A CN201110449023A CN102532572A CN 102532572 A CN102532572 A CN 102532572A CN 2011104490237 A CN2011104490237 A CN 2011104490237A CN 201110449023 A CN201110449023 A CN 201110449023A CN 102532572 A CN102532572 A CN 102532572A
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composite package
preparation
positively charged
film
trimethyl chitosan
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CN102532572B (en
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何荣桓
王吉林
车全通
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Northeastern University China
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Northeastern University China
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Abstract

The invention relates to the technical field of fuel cells, in particular to a preparation method of a quaternized chitosan anion hybrid membrane doped with positive polystyrene latex. The preparation method comprises the following steps of: (1) preparing the positive polystyrene latex; (2) preparing quaternized chitosan; (3) dissolving the quaternized chitosan powder into acetic acid solution with the concentration being 2wt%, then adding the prepared positive polystyrene latex, forming membrane casting liquid, stirring the membrane casting liquid for 4 hours under the room temperature, and carrying out ultrasonic treatment for 20-40 minutes; then adding glutaraldehyde at the speed of 0.5mLmin<-1> with the adding amount accounting for 0.1-0.3% of the total volume of the membrane casting liquid, stirring for 1 hour, then carrying out ultrasonic treatment for 30 minutes, finally pouring the solution subjected to ultrasonic treatment on a horizontal glass plate, and evaporating a solvent at the temperature of 40 DEG C to form the hybrid membrane; and (4) carrying out after treatment on the hybrid membrane. According to the preparation method, the ion exchange capacity and the electric conductivity of the hybrid membrane are high, and the methanol penetration rate is low.

Description

A kind of preparation method of n-trimethyl chitosan chloride negatively charged ion composite package of the positively charged polystyrene emulsion of mixing
Technical field
The present invention relates to the fuel cell technology field, be specifically related to a kind of preparation method of n-trimethyl chitosan chloride negatively charged ion composite package of the positively charged polystyrene emulsion of mixing.
Background technology
In fuel cell field, DMFC (DMFC) is because have transportation and convenient for storing, and the energy density advantages of higher more and more comes into one's own.The film ionogen that in DMFC, uses at present mainly is the Nafion with perfluorinated sulfonic acid structure by du pont company production Film.Nafion The proton conductivity of film is higher; Chemicalstability is good, but the methanol permeability of this film is also higher, when it uses as the film ionogen in DMFC; Can cause fuel methanol to pass the film ionogen and produce mixed potential, and then influence the efficient of battery at negative electrode.Therefore, it is low to develop a kind of methanol permeability, and the new film electrolyte that has higher specific conductivity and chemicalstability simultaneously again is significant to the development of DMFC.Research is illustrated in the inorganic substance that mix in the film ionogen, zirconium phosphate for example, and zeolite and polynite etc. can effectively suppress the rate of permeation of fuel methanol.This mainly is because being added in of inorganic substance generated hydrophobic region in the membrane structure, has suppressed the diffusion of methanol molecules in film, and then has reduced methanol permeability.Although the doping of inorganic substance can suppress the transmitance of methyl alcohol, the problem of itself and polymkeric substance poor compatibility causes the following degradation of homogeneity, electroconductibility and the mechanical property of film again.For example have been found that at Nafion Doping NaA zeolite can effectively suppress the methanol permeation rate in the film, but also finds on the interface of inorganic doping thing and polymeric matrix, to have occurred simultaneously the micropore of nano-scale, and the appearance of these micropores may cause the rising again of methanol permeability.In addition, the doping of inorganic substance also can cause the decline of the electrolytical specific conductivity of film, and this mainly is to cause because the specific conductivity of adulterated inorganic substance self is low usually.The organic microballoon that has report to point out doping surfaces modification in the film ionogen can solve the poor compatibility that the inorganic doping thing brought and the problem of specific conductivity decline preferably.The research of this respect at present is primarily aimed at PEM to be carried out, and the polystyrene microsphere that will have a positive charge is entrained in the anionic polymer the electrolytical method of preparation anion-exchange membrane and does not appear in the newspapers as yet.
Summary of the invention
The objective of the invention is the deficiency that exists to prior art, a kind of preparation method of n-trimethyl chitosan chloride negatively charged ion composite package of polystyrene emulsion of the positively charged that mixes is provided, prepared anionic membrane material has high OH -Conductivity and favorable mechanical performance can be used as the anion-exchange membrane of alkaline fuel cell.
The technical scheme of realization the object of the invention is undertaken by following process step:
(1) successively add in container according to the proportioning of volume ratio 1:5:10 vinylbenzene, absolute ethyl alcohol and deionized water; Form mixed solution; In mixed solution, add cetyl trimethylammonium bromide and Potassium Persulphate then, wherein the add-on of cetyl trimethylammonium bromide is 0.5～5 % of mixed solution quality, and the add-on of Potassium Persulphate is 0.1～0.25 % of reaction mixture quality; Under the condition of nitrogen protection, react 6 h in 80 ℃; Process the polystyrene emulsion of positively charged, treat that temperature is reduced to room temperature after, airtight preservation is for use;
(2) chitosan and Virahol are placed container by mass ratio 1:4, heating in water bath is warming up to 85 ℃ under stirring, and adding concentration is 2 of 50wt%; The aqueous solution of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium makes 2, and the mass ratio of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium and chitosan is 1:1; Constant temperature stirs 10 h down; After 70 ℃ of underpressure distillation 2h remove deionized water and Virahol, product is tiled to petridish then, baking is taken out behind 40 min and is shredded in 80 ℃ baking oven; Continuation is dried by the fire 5 h to constant weight in 80 ℃ of baking ovens, process n-trimethyl chitosan chloride and pulverize to be powder;
(3) be in the 2wt% acetum with the n-trimethyl chitosan chloride powder dissolution in concentration; The polystyrene emulsion that adds the positively charged of preparation then; Form film-casting liquid; Wherein the polystyrene emulsion add-on is 15%～35% of a film-casting liquid quality, at room temperature stir film-casting liquid 4h after, carry out ultrasonication 20～40min; Again with 0.5 mLmin 1Speed add LUTARALDEHYDE, add-on is respectively 0.1～0.3 % that accounts for the film-casting liquid TV, stirs ultrasonication 30min behind 1 h, at last the solution after the ultrasonication is poured on the horizontal glass plate, becomes composite package in 40 ℃ of evaporating solvents;
(4) composite package that makes is immersed in the 100 mL deionized waters; Whenever change primary water at a distance from 20 min, soak 3 h after, dry the deionized water on composite package surface; In room temperature held 48 h; Slowly moisture in the distilling composite membranes is fixed on composite package between two blocks of ZX 21 plates again, places 80 ℃ of drying in oven to film constant weights;
(5) composite package that will dry after handling immerses 1.0 mol L -124 h carry out IX in the KOH aqueous solution, composite package are fixed between two blocks of ZX 21 plates again, place in 80 ℃ of baking ovens and dry once more to the film constant weight;
Described stirring velocity is: 600 r/min;
The quaternized substitution value of described n-trimethyl chitosan chloride is 32.32～37.72% mol ratios;
Described n-trimethyl chitosan chloride powder size is 40～80 orders;
The power of described ultrasonication is 70W;
Describedly Potassium Persulphate is divided into four parts when in vinylbenzene, absolute ethyl alcohol and deionized water mixed solution, adding Potassium Persulphate, every add at a distance from 1.5h a;
The polystyrene emulsion positively charged of described step (1) preparation, concentration is 6.25 wt%;
The mass percent of PS is 13～23 % in the composite package of described step (3) preparation.
With use compared with techniques at present, characteristics of the present invention and beneficial effect thereof are:
1, the composite package of the present invention's preparation has stable structure, through 10 mol L -1Dry film behind KOH solution soaking 10 h, its tensile strength explains that greater than 12 MPa (see figure 4)s composite package has satisfactory stability property under alkaline condition under the room temperature.And the linking agent LUTARALDEHYDE can improve the compactness and the stability of polystyrene microsphere in membrane structure of structure of composite membrane, and then improves the mechanical property of composite package;
2, Fig. 2 is embodiment 2; The infared spectrum of embodiment 4 and n-trimethyl chitosan chloride (QCS); By finding out that the characteristic peak of quaternary ammonium group and PS occurs among the figure in the spectrogram of this composite package; Explain that quaternary ammonium group has been grafted on the skeleton of chitosan, also have cetyl trimethylammonium bromide molecule stable existence in composite package in the membrane structure simultaneously;
3, the n-trimethyl chitosan chloride negatively charged ion composite package of the positively charged polystyrene emulsion of doping of the present invention's preparation is compared with the composite package that existing fuel cell uses, and has the following advantages:
(1) polystyrene microsphere of introducing positively charged in composite package helps the OH in the adsorbent solution -, the ion exchange capacity and the specific conductivity of raising composite package;
(2) hydrophobic polystyrene microsphere has reduced the methanol permeability of composite package.
Description of drawings
Fig. 1 prepares the synoptic diagram of process for composite package of the present invention;
Fig. 2 is the infared spectrum figure of the embodiment 2 and the composite package of embodiment 4 preparations;
Fig. 3 is the thermal stability determination result of composite package in air atmosphere of embodiment 1 and embodiment 2 preparations;
Fig. 4 is embodiment 1, and embodiment 2, and embodiment 3, and the composite package of embodiment 4 and embodiment 5 preparations is at ambient temperature in 10 mol L -1Stretching strength determination result in the KOH solution behind the immersion different time;
Fig. 5 is embodiment 1, and embodiment 2, and embodiment 3, the conductance measurement result of composite package under differing temps of embodiment 4 and embodiment 5 preparations.
Embodiment
Below in conjunction with embodiment the present invention is elaborated, but protection scope of the present invention is not limited only to following embodiment:
Embodiment 1:
(1) styrene, absolute ethyl alcohol and the deionized water proportioning according to volume ratio 1:5:10 is added in the container successively, form mixed liquor, in mixed liquor, add softex kw and potassium peroxydisulfate then; Wherein the addition of softex kw is 0.5 % of mixed liquor quality; Be disposable adding, the addition of potassium peroxydisulfate is 0.1 % of mixed liquor quality, adds fashionable it to be divided into four parts; Whenever add a at a distance from 1.5h; After softex kw and potassium peroxydisulfate added reaction mixture fully, in 80 ℃ of reaction 6 h, making concentration was the positively charged polystyrene emulsion of 6.25 wt% under the condition of nitrogen protection; After treating that temperature is reduced to room temperature, airtight preservation is for use;
(2) chitosan and Virahol are placed round-bottomed flask by mass ratio 1:4, low whipping speed is that heating in water bath is warming up to 85 ℃ under the mechanical stirring of 600 r/min, and adding concentration is 2 of 50wt%; The aqueous solution of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium; Make 2, the mass ratio of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium and chitosan is 1:1, and low whipping speed is mechanical stirring 10 h of 600 r/min under the constant temperature; Then after 70 ℃ of underpressure distillation 2h remove deionized water and Virahol; Product is tiled to petridish, and baking is taken out behind 40 min and is shredded in 80 ℃ baking oven, continues in 80 ℃ of baking ovens, to dry by the fire 5 h to constant weight; Processing n-trimethyl chitosan chloride and pulverizing is that powder to granularity is 40～80 orders, and the quaternized substitution value of n-trimethyl chitosan chloride is 35% mol ratio;
(3) be that 40～80 purpose n-trimethyl chitosan chloride powder dissolutions are in the 2wt% acetum in concentration with granularity; The concentration that adds preparation then is the positively charged polystyrene emulsion of 6.25wt %; Form film-casting liquid, wherein positively charged polystyrene emulsion add-on is 15% of a film-casting liquid quality, after at room temperature low whipping speed is mechanical stirring film-casting liquid 4 h of 600 r/min; Carry out ultrasonication 30min, the power of ultrasonication is 70W; Again with 0.5 mL min 1Speed add LUTARALDEHYDE; Add-on is respectively 0.2 % that accounts for the film-casting liquid TV; Low whipping speed is ultrasonication 40min behind mechanical stirring 1 h of 600 r/min, and the power of ultrasonication is 70W, at last solution is poured on the horizontal glass plate; In 40 ℃ of evaporating solvent film forming, the mass percent that makes PS in the composite package that makes is 13 %;
(4) composite package that makes is immersed in the 100 mL deionized waters; Whenever change primary water at a distance from 20 min, soak 3 h after, dry the deionized water on composite package surface; In room temperature held 48 h; Slowly moisture in the distilling composite membranes is fixed on composite package between two blocks of ZX 21 plates again, places 80 ℃ of drying in oven to film constant weights;
(5) composite package is immersed 1.0 mol L -124 h carry out IX in the KOH aqueous solution, composite package are fixed between two blocks of ZX 21 plates again, place 80 ℃ of drying in oven to film constant weights.
Embodiment 2:
(1) styrene, absolute ethyl alcohol and the deionized water proportioning according to volume ratio 1:5:10 is added in the container successively, form mixed liquor, in mixed liquor, add softex kw and potassium peroxydisulfate then; Wherein the addition of softex kw is 5% of a mixed liquor quality; Be disposable adding, the addition of potassium peroxydisulfate is 0.25% of a mixed liquor quality, adds fashionable it to be divided into four parts; Whenever add a at a distance from 1.5h; After softex kw and potassium peroxydisulfate added reaction mixture fully, in 80 ℃ of reaction 6 h, making concentration was the positively charged polystyrene emulsion of 6.25 wt% under the condition of nitrogen protection; After treating that temperature is reduced to room temperature, airtight preservation is for use;
(2) chitosan and Virahol are placed round-bottomed flask by mass ratio 1:4, low whipping speed is that heating in water bath is warming up to 85 ℃ under the mechanical stirring of 600 r/min, and adding concentration is 2 of 50wt%; The aqueous solution of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium; Make 2, the mass ratio of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium and chitosan is 1:1, and low whipping speed is mechanical stirring 10 h of 600 r/min under the constant temperature; Then after 70 ℃ of underpressure distillation 2h remove deionized water and Virahol; Product is tiled to petridish, and baking is taken out behind 40 min and is shredded in 80 ℃ baking oven, continues in 80 ℃ of baking ovens, to dry by the fire 5 h to constant weight; Processing n-trimethyl chitosan chloride and pulverizing is that powder to granularity is 40～80 orders, and the quaternized substitution value of n-trimethyl chitosan chloride is 35% mol ratio;
(3) be that 40～80 purpose n-trimethyl chitosan chloride powder dissolutions are in the 2wt% acetum in concentration with granularity; The concentration that adds preparation then is the positively charged polystyrene emulsion of 6.25wt %; Form film-casting liquid, wherein positively charged polystyrene emulsion add-on is 25% of a film-casting liquid quality, after at room temperature low whipping speed is mechanical stirring film-casting liquid 4 h of 600 r/min; Carry out ultrasonication 30min, the power of ultrasonication is 70W; Again with 0.5 mL min 1Speed add LUTARALDEHYDE; Add-on is respectively and accounts for 0.2% of film-casting liquid TV; Low whipping speed is ultrasonication 20min behind the mechanical stirring 1h of 600 r/min, and the power of ultrasonication is 70W, at last solution is poured on the horizontal glass plate; In 40 ℃ of evaporating solvent film forming, the mass percent that makes PS in the composite package that makes is 18 %;
(4) composite package that makes is immersed in the 100 mL deionized waters; Whenever change primary water at a distance from 20 min, soak 3 h after, dry the deionized water on composite package surface; In room temperature held 48 h; Slowly moisture in the distilling composite membranes is fixed on composite package between two blocks of ZX 21 plates again, places 80 ℃ of drying in oven to film constant weights;
(5) composite package is immersed 1.0 mol L -124 h carry out IX in the KOH aqueous solution, composite package are fixed between two blocks of ZX 21 plates again, place 80 ℃ of drying in oven to film constant weights.
Embodiment 3:
(1) styrene, absolute ethyl alcohol and the deionized water proportioning according to volume ratio 1:5:10 is added in the container successively, form mixed liquor, in mixed liquor, add softex kw and potassium peroxydisulfate then; Wherein the addition of softex kw is 3% of a mixed liquor quality; Be disposable adding, the addition of potassium peroxydisulfate is 0.2% of a mixed liquor quality, adds fashionable it to be divided into four parts; Whenever add a at a distance from 1.5h; After softex kw and potassium peroxydisulfate added reaction mixture fully, in 80 ℃ of reaction 6 h, making concentration was the positively charged polystyrene emulsion of 6.25 wt% under the condition of nitrogen protection; After treating that temperature is reduced to room temperature, airtight preservation is for use;
(2) chitosan and Virahol are placed round-bottomed flask by mass ratio 1:4, low whipping speed is that heating in water bath is warming up to 85 ℃ under the mechanical stirring of 600 r/min, and adding concentration is 2 of 50wt%; The aqueous solution of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium; Make 2, the mass ratio of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium and chitosan is 1:1, and low whipping speed is mechanical stirring 10 h of 600 r/min under the constant temperature; Then after 70 ℃ of underpressure distillation 2h remove deionized water and Virahol; Product is tiled to petridish, and baking is taken out behind 40 min and is shredded in 80 ℃ baking oven, continues in 80 ℃ of baking ovens, to dry by the fire 5 h to constant weight; Processing n-trimethyl chitosan chloride and pulverizing is that powder to granularity is 40～80 orders, and the quaternized substitution value of n-trimethyl chitosan chloride is 35% mol ratio;
(3) be that 40～80 purpose n-trimethyl chitosan chloride powder dissolutions are in the 2wt% acetum in concentration with granularity; The concentration that adds preparation then is the positively charged polystyrene emulsion of 6.25wt %; Form film-casting liquid, wherein positively charged polystyrene emulsion add-on is 35% of a film-casting liquid quality, after at room temperature low whipping speed is mechanical stirring film-casting liquid 4 h of 600 r/min; Carry out ultrasonication 30min, the power of ultrasonication is 70W; Again with 0.5 mL min 1Speed add LUTARALDEHYDE; Add-on is respectively 0.2 % that accounts for the film-casting liquid TV; Low whipping speed is ultrasonication 25min behind the mechanical stirring 1h of 600 r/min, and the power of ultrasonication is 70W, at last solution is poured on the horizontal glass plate; In 40 ℃ of evaporating solvent film forming, the mass percent that makes PS in the composite package that makes is 23%;
(4) composite package that makes is immersed in the 100 mL deionized waters; Whenever change primary water at a distance from 20 min, soak 3 h after, dry the deionized water on composite package surface; In room temperature held 48 h; Slowly moisture in the distilling composite membranes is fixed on composite package between two blocks of ZX 21 plates again, places 80 ℃ of drying in oven to film constant weights;
(5) composite package is immersed 1.0 mol L -124 h carry out IX in the KOH aqueous solution, composite package are fixed between two blocks of ZX 21 plates again, place 80 ℃ of drying in oven to film constant weights.
Embodiment 4:
(1) styrene, absolute ethyl alcohol and the deionized water proportioning according to volume ratio 1:5:10 is added in the container successively, form mixed liquor, in mixed liquor, add softex kw and potassium peroxydisulfate then; Wherein the addition of softex kw is 5% of a mixed liquor quality; Be disposable adding, the addition of potassium peroxydisulfate is 0.25% of a mixed liquor quality, adds fashionable it to be divided into four parts; Whenever add a at a distance from 1.5h; After softex kw and potassium peroxydisulfate added reaction mixture fully, in 80 ℃ of reaction 6 h, making concentration was the positively charged polystyrene emulsion of 6.25 wt% under the condition of nitrogen protection; After treating that temperature is reduced to room temperature, airtight preservation is for use;
(2) chitosan and Virahol are placed round-bottomed flask by mass ratio 1:4, low whipping speed is that heating in water bath is warming up to 85 ℃ under the mechanical stirring of 600 r/min, and adding concentration is 2 of 50wt%; The aqueous solution of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium; Make 2, the mass ratio of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium and chitosan is 1:1, and low whipping speed is mechanical stirring 10 h of 600 r/min under the constant temperature; Then after 70 ℃ of underpressure distillation 2h remove deionized water and Virahol; Product is tiled to petridish, and baking is taken out behind 40 min and is shredded in 80 ℃ baking oven, continues in 80 ℃ of baking ovens, to dry by the fire 5 h to constant weight; Processing n-trimethyl chitosan chloride and pulverizing is that powder to granularity is 40～80 orders, and the quaternized substitution value of n-trimethyl chitosan chloride is 35% mol ratio;
(3) be that 40～80 purpose n-trimethyl chitosan chloride powder dissolutions are in the 2wt% acetum in concentration with granularity; The concentration that adds preparation then is the positively charged polystyrene emulsion of 6.25wt %; Form film-casting liquid, wherein positively charged polystyrene emulsion add-on is 25% of a film-casting liquid quality, after at room temperature low whipping speed is mechanical stirring film-casting liquid 4 h of 600 r/min; Carry out ultrasonication 20min, the power of ultrasonication is 70W; Again with 0.5 mL min 1Speed add LUTARALDEHYDE; Add-on is respectively and accounts for 0.1% of film-casting liquid TV; Low whipping speed is ultrasonication 30min behind the mechanical stirring 1h of 600 r/min, and the power of ultrasonication is 70W, at last solution is poured on the horizontal glass plate; In 40 ℃ of evaporating solvent film forming, the mass percent that makes PS in the composite package that makes is 18%;
(4) composite package that makes is immersed in the 100 mL deionized waters; Whenever change primary water at a distance from 20 min, soak 3 h after, dry the deionized water on composite package surface; In room temperature held 48 h; Slowly moisture in the distilling composite membranes is fixed on composite package between two blocks of ZX 21 plates again, places 80 ℃ of drying in oven to film constant weights;
(5) composite package is immersed 1.0 mol L -124 h carry out IX in the KOH aqueous solution, composite package are fixed between two blocks of ZX 21 plates again, place 80 ℃ of drying in oven to film constant weights.
Embodiment 5:
(1) styrene, absolute ethyl alcohol and the deionized water proportioning according to volume ratio 1:5:10 is added in the container successively, form mixed liquor, in mixed liquor, add softex kw and potassium peroxydisulfate then; Wherein the addition of softex kw is 3% of a mixed liquor quality; Be disposable adding, the addition of potassium peroxydisulfate is 0.2% of a mixed liquor quality, adds fashionable it to be divided into four parts; Whenever add a at a distance from 1.5h; After softex kw and potassium peroxydisulfate added reaction mixture fully, in 80 ℃ of reaction 6 h, making concentration was the positively charged polystyrene emulsion of 6.25 wt% under the condition of nitrogen protection; After treating that temperature is reduced to room temperature, airtight preservation is for use;
(2) chitosan and Virahol are placed round-bottomed flask by mass ratio 1:4, low whipping speed is that heating in water bath is warming up to 85 ℃ under the mechanical stirring of 600 r/min, and adding concentration is 2 of 50wt%; The aqueous solution of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium; Make 2, the mass ratio of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium and chitosan is 1:1, and low whipping speed is mechanical stirring 10 h of 600 r/min under the constant temperature; Then after 70 ℃ of underpressure distillation 2h remove deionized water and Virahol; Product is tiled to petridish, and baking is taken out behind 40 min and is shredded in 80 ℃ baking oven, continues in 80 ℃ of baking ovens, to dry by the fire 5 h to constant weight; Processing n-trimethyl chitosan chloride and pulverizing is that powder to granularity is 40～80 orders, and the quaternized substitution value of n-trimethyl chitosan chloride is 35% mol ratio;
(3) be that 40～80 purpose n-trimethyl chitosan chloride powder dissolutions are in the 2wt% acetum in concentration with granularity; The concentration that adds preparation then is the positively charged polystyrene emulsion of 6.25wt %; Form film-casting liquid, wherein positively charged polystyrene emulsion add-on is 25% of a film-casting liquid quality, after at room temperature low whipping speed is mechanical stirring film-casting liquid 4 h of 600 r/min; Carry out ultrasonication 40min, the power of ultrasonication is 70W; Again with 0.5 mL min 1Speed add LUTARALDEHYDE; Add-on is respectively 0.3 % that accounts for the film-casting liquid TV; Low whipping speed is ultrasonication 30 min behind the mechanical stirring 1h of 600 r/min, and the power of ultrasonication is 70W, at last solution is poured on the horizontal glass plate; In 40 ℃ of evaporating solvent film forming, the mass percent that makes PS in the composite package that makes is 18%;
(4) composite package that makes is immersed in the 100 mL deionized waters; Whenever change primary water at a distance from 20 min, soak 3 h after, dry the deionized water on composite package surface; In room temperature held 48 h; Slowly moisture in the distilling composite membranes is fixed on composite package between two blocks of ZX 21 plates again, places 80 ℃ of drying in oven to film constant weights;
(5) composite package is immersed 1.0 mol L -124 h carry out IX in the KOH aqueous solution, composite package are fixed between two blocks of ZX 21 plates again, place 80 ℃ of drying in oven to film constant weights.

Claims (8)

1. the preparation method of the n-trimethyl chitosan chloride negatively charged ion composite package of the polystyrene emulsion of the positively charged that mixes is characterized in that step is following:
(1) successively add in container according to the proportioning of volume ratio 1:5:10 vinylbenzene, absolute ethyl alcohol and deionized water; Form mixed solution; In mixed solution, add cetyl trimethylammonium bromide and Potassium Persulphate then, wherein the add-on of cetyl trimethylammonium bromide is 0.5～5 % of mixed solution quality, and the add-on of Potassium Persulphate is 0.1～0.25 % of mixed solution quality; Under the condition of nitrogen protection, react 6 h in 80 ℃; Process the PS microemulsion of positively charged, treat that temperature is reduced to room temperature after, airtight preservation is for use;
(2) chitosan and Virahol are placed container by mass ratio 1:4, heating in water bath is warming up to 85 ℃ under stirring, and adding concentration is 2 of 50wt%; The aqueous solution of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium makes 2, and the mass ratio of 3-epoxypropyl epoxypropyl trimethylammonium chloride ammonium and chitosan is 1:1; Constant temperature stirs 10 h down; After 70 ℃ of underpressure distillation 2h remove deionized water and Virahol, product is tiled to petridish then, baking is taken out behind 40 min and is shredded in 80 ℃ baking oven; Continuation is dried by the fire 5 h to constant weight in 80 ℃ of baking ovens, process n-trimethyl chitosan chloride and pulverize to be powder;
(3) be in the 2wt% acetum with the n-trimethyl chitosan chloride powder dissolution in concentration; The PS microemulsion that adds the positively charged of preparation then; Form film-casting liquid; Wherein the polystyrene emulsion add-on is 15%～35% of a film-casting liquid quality, at room temperature stir film-casting liquid 4h after, carry out ultrasonication 20～40min; Again with 0.5 mLmin 1Speed add LUTARALDEHYDE, add-on is respectively 0.1～0.3 % that accounts for the film-casting liquid TV, stirs ultrasonication 30min behind 1 h, at last the solution after the ultrasonication is poured on the horizontal glass plate, becomes composite package in 40 ℃ of evaporating solvents;
(4) composite package that makes is immersed in the 100 mL deionized waters; Whenever change primary water at a distance from 20 min, soak 3 h after, dry the deionized water on composite package surface; In room temperature held 48 h; Slowly moisture in the distilling composite membranes is fixed on composite package between two blocks of ZX 21 plates again, places 80 ℃ of drying in oven to film constant weights;
(5) composite package that will dry after handling immerses 1.0 mol L -124 h carry out IX in the KOH aqueous solution, composite package are fixed between two blocks of ZX 21 plates again, place in 80 ℃ of baking ovens and dry once more to the film constant weight.
2. the preparation method of the n-trimethyl chitosan chloride negatively charged ion composite package of the polystyrene emulsion of a kind of positively charged that mixes according to claim 1 is characterized in that described stirring velocity is: 600 r/min.
3. the preparation method of the n-trimethyl chitosan chloride negatively charged ion composite package of the polystyrene emulsion of a kind of positively charged that mixes according to claim 1 is characterized in that the quaternized substitution value of n-trimethyl chitosan chloride is 32.32～37.72% mol ratios.
4. the preparation method of the n-trimethyl chitosan chloride negatively charged ion composite package of the polystyrene emulsion of a kind of positively charged that mixes according to claim 1 is characterized in that described n-trimethyl chitosan chloride powder size is 40～80 orders.
5. the preparation method of the n-trimethyl chitosan chloride negatively charged ion composite package of the polystyrene emulsion of a kind of positively charged that mixes according to claim 1 is characterized in that the power of described ultrasonication is 70W.
6. the preparation method of the n-trimethyl chitosan chloride negatively charged ion composite package of the polystyrene emulsion of a kind of positively charged that mixes according to claim 1; It is characterized in that; Described when in vinylbenzene, absolute ethyl alcohol and deionized water mixed solution, adding Potassium Persulphate; Potassium Persulphate is divided into four parts, every a at a distance from the 1.5h adding.
7. the preparation method of the n-trimethyl chitosan chloride negatively charged ion composite package of the polystyrene emulsion of a kind of positively charged that mixes according to claim 1 is characterized in that, the polystyrene emulsion positively charged that described step (1) is processed, and concentration is 6.25 wt%.
8. the preparation method of the n-trimethyl chitosan chloride negatively charged ion composite package of the polystyrene emulsion of a kind of positively charged that mixes according to claim 1 is characterized in that, the mass percent of PS is 13～23 % in the composite package of described step (3) preparation.
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CN103007791A (en) * 2012-12-26 2013-04-03 郑州大学 Preparation method of positively charged composite nanofiltration membrane
CN103554526A (en) * 2013-10-18 2014-02-05 辽宁石油化工大学 Double-quaternary ammonium positive ion molecule introduced anion-exchange membrane and preparation method thereof
CN104031210A (en) * 2014-06-23 2014-09-10 中国科学院化学研究所 Method for preparing quaternary ammonium salt surface-modified monodisperse polystyrene microsphere emulsion
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN103007791B (en) * 2012-12-26 2015-08-26 郑州大学 A kind of preparation method of Positively charged composite nanofiltration membrane
CN103554526A (en) * 2013-10-18 2014-02-05 辽宁石油化工大学 Double-quaternary ammonium positive ion molecule introduced anion-exchange membrane and preparation method thereof
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