CN101698137B - Method for preparing polyelectrolyte complex/bentonite hybrid pervaporation membrane - Google Patents
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Abstract
The invention provides a method for preparing a polyelectrolyte complex/bentonite intercalation hybrid pervaporation membrane, which comprises the following steps: 1) preparing cationic polyelectrolyte into acidic aqueous solution; 2) preparing aqueous dispersing solution of bentonite hybrid anionic polyelectrolyte; 3) dripping the prepared cationic polyelectrolyte solution into the aqueous dispersing solution of bentonite hybrid anionic polyelectrolyte to obtain different types of nano hybrid precipitates; and 4) respectively dissolving the different types of nano hybrid precipitates into alkaline aqueous solution to prepare casting solution at certain concentration, filtering, standing, defoaming, and coating on a polysulphone base membrane to prepare the polyelectrolyte complex/bentonite intercalation hybrid pervaporation membrane. The layered inorganic/organic hybrid membrane prepared by the method has low cost, strong mechanical property, and high pervaporation separation of the polyelectrolyte complex membrane.
Description
Technical field
The present invention relates to a kind of preparation method of polyelectrolyte complex compound/bentonite hybrid pervaporation membrane, thereby improve the separation property of film and the mechanical property of reinforcing material.
Background technology
The infiltration evaporation technology is a kind of novel liquid mixture isolation technics, with its separative efficiency height, and the low focus of having paid close attention to and having studied for people of energy resource consumption.It is mainly used in organics dehydration, removes micro-content organism and organic mixture in the water and separates three big fields.Wherein organics dehydration is studied more extensively in academic and industrial quarters, the emphasis of research mainly concentrates on the new membrane material of exploitation, existing membrane material is carried out modification etc., hope can obtain the infiltrating and vaporizing membrane of big flux under the condition that guarantees certain separation factor.
Polyelectrolyte is a class hydrophilic macromolecule, and it is fine to be used for infiltration evaporation organics dehydration separating property by the formed polyelectrolyte complex compound film of opposite charges polyelectrolyte.It is crosslinked that polyelectrolyte complex compound has produced certain physical by big molecular anion and the effect of cation Coulomb force, be difficult for little molecule counter ion leakage takes place, so separating property is stable.Yet this class membrane material is that single ion complexation forms, and mechanical property is not high.Therefore, strengthening the mechanical property of membrane material and its permeation flux and the reduction membrane material cost of raising film is the research direction of this area.
Existing bibliographical information shows, inorganic material and polyalcohol intercalation can increase substantially the mechanical property of polymer.Bentonite is common inorganic material, and its reserves are abundant, cheap.Tool unique advantage on synthetic intercalation material.Bentonite has very strong hygroscopicity again, can adsorb be equivalent to own vol 8-20 doubly water and be expanded to 30 times.Therefore, if with the polyelectrolyte complex compound intercalation in bentonite, can keep on the one hand high score from performance with increase permeation flux, will improve the mechanical mechanics property of complex compound on the other hand greatly.Character characteristics insoluble and that do not melt can not be carried out conventional blend with bentonite based on polyelectrolyte complex compound, thereby obtain polyelectrolyte complex compound/bentonite organic.This patent proposes the new method that positive and negative polyelectrolyte carries out complexing-intercalation, has made polyelectrolyte complex compound/bentonite new material and corresponding infiltrating and vaporizing membrane thereof.
The infiltration evaporation of evaluated for film parameter separatory is permeation flux J (g/m
2H) and separation factor alpha
W/oIt is defined as follows:
See through liquid weight in the formula and obtain c ' by weighing
w, c '
oFor seeing through the liquid mass percent concentration; c
w, c
oBe feeding liquid mass percentage concentration water and organic mass percentage concentration, it is worth usually by gas Chromatographic Determination.
The mechanical mechanics property of polyelectrolyte complex compound/bentonite nano hybridized film material is weighed with hot strength, elongation at break usually.Use parameter σ respectively
tRepresent with ε.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of polyelectrolyte complex compound/bentonite hybrid pervaporation membrane is provided.
The preparation method of polyelectrolyte complex compound/bentonite intercalation hybrid pervaporation membrane comprises the steps:
1) in 20000～40000 mass parts water, adds 8～50 mass parts acid, be mixed with acid solution;
Then 20～60 mass parts poly dimethyl allyl ammoniums are dissolved in the above-mentioned acid solution of 20000～40000 mass parts and are made into the poly dimethyl allyl ammonium salt solution, 50～200 mass parts polymethyl acyl-oxygen ethyl-trimethyl salmiacs are dissolved in are made into polymethyl acyl-oxygen ethyl-trimethyl salmiac solution in the above-mentioned acid solution of 20000～40000 mass parts, 20～60 mass parts shitosans are dissolved in the above-mentioned acid solution of 20000～40000 mass parts are made into chitosan solution, 5～15 mass parts polymines are dissolved in the above-mentioned acid solution of 20000～40000 mass parts are made into the polyethyleneimine: amine aqueous solution, 50～100 mass parts sodium carboxymethylcelluloses are dissolved in the above-mentioned acid solution of 20000～40000 mass parts are made into carboxymethylcellulose sodium solution, 20～50 mass parts Sodium Polyacrylates are dissolved in the above-mentioned acid solution of 20000～40000 mass parts are made into sodium polyacrylate solution, 20～60 mass parts sodium alginates are dissolved in the above-mentioned acid solution of 20000～40000 mass parts are made into sodium alginate soln;
2) 1～20 mass parts bentonite is joined in 5000～10000 mass parts water soak 24～36h, stir 0.5～2h again and obtain the bentonite aqueous dispersions, then at 60～100 ℃, under 50～200W ultrasonic power and the 800～1000rpm stir speed (S.S.), with carboxymethylcellulose sodium solution, sodium polyacrylate solution or sodium alginate soln add in the bentonite aqueous dispersions, ultrasonic agitation 0.5～3h carries out intercalation, obtains the aqueous dispersions of sodium carboxymethylcellulose/bentonite hybrid thing, the aqueous dispersions of the aqueous dispersions of Sodium Polyacrylate/bentonite hybrid thing or sodium alginate/bentonite hybrid thing;
3) at 40～60 ℃, at ultrasonic power is under 50～200W and 800～1000rpm speed stir, with the poly dimethyl allyl ammonium salt solution, the poly dimethyl allyl ammonium salt solution, polymethyl acyl-oxygen ethyl-trimethyl salmiac solution, shitosan liquid or polymine solution splash into the aqueous dispersions of sodium carboxymethylcellulose/bentonite hybrid thing, in the aqueous dispersions of the aqueous dispersions of Sodium Polyacrylate/bentonite hybrid thing or sodium alginate/bentonite hybrid thing, obtain poly dimethyl allyl ammonium/sodium carboxymethylcellulose/bentonite hybrid thing, poly dimethyl allyl ammonium/Sodium Polyacrylate/bentonite hybrid thing, poly dimethyl allyl ammonium/sodium alginate/bentonite hybrid thing, polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium carboxymethylcellulose/bentonite hybrid thing, polymethyl acyl-oxygen ethyl-trimethyl salmiac/Sodium Polyacrylate/bentonite hybrid thing, polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium alginate/bentonite hybrid thing, shitosan/sodium carboxymethylcellulose/bentonite hybrid thing, shitosan/Sodium Polyacrylate/bentonite hybrid thing, shitosan/sodium alginate/bentonite hybrid thing, polymine/sodium carboxymethylcellulose/bentonite hybrid thing, polymine/Sodium Polyacrylate/bentonite hybrid thing, polymine/sodium alginate/bentonite hybrid thing;
4) above-mentioned hybrid is dissolved in respectively in the diluted alkaline aqueous solvent, is made into mass percent concentration and is 1～5% casting solution, the pH value is 7～8, after filtration, after the standing and defoaming, is coated with and scrapes on the polysulfones counterdie.
Described step 2) the bentonite mass parts in is preferably 1～15 part.Described step 2) the intercalation temperature described in is preferably 70～90 ℃.Described step 2) the ultrasonic agitation time is preferably 0.5～2h in.Ultrasonic power is preferably 50～100W.The mass percent concentration of hybrid in casting solution is preferably 2～4% in the described step 4).
The present invention prepares high score from the bentonitic nano hybridization infiltrating and vaporizing membrane of the homogeneous polyelectrolyte complex compound of performance and high strength solution processable with low-cost bentonite and polyelectrolyte complex compound hydridization.This inorganic organic nano hybrid pervaporation membrane has high flux aspect organics dehydration, the advantage of high selectivity and high mechanicalness mechanical property.Seven kinds of conventional polyelectrolyte that the present invention adopts are easy to get, low price or synthetic simple and convenient; The bentonite reserves are abundant, and are cheap.Technology of the present invention is controlled, favorable repeatability; The composition of preparation film is controlled, and the membrane structure homogeneous is keeping the higher optionally while, and flux is more than pure complex compound film height, and 70 ℃ of following flux can be greater than 4kg/m
2H.The hybrid material mechanical mechanics property is good, and hot strength is not less than 20MPa, and elongation at break also can arrive twenties percent.
The specific embodiment:
Embodiment 1
Get 1 mass parts bentonite and add in the 10000 mass parts water, soak 24h and stir 0.5h again; In 40000 mass parts water, add 30 mass parts hydrochloric acid then, be mixed with the acid water solvent, 100 mass parts sodium carboxymethylcelluloses are dissolved in the above-mentioned acid water solvent of 40000 mass parts are made into carboxymethylcellulose sodium solution, then at 80 ℃, under 80W ultrasonic power and the 800rpm stir speed (S.S.) carboxymethylcellulose sodium solution is splashed in the bentonite aqueous dispersions, ultrasonic agitation 1h carries out intercalation, obtain sodium carboxymethylcellulose/bentonite hybrid thing aqueous dispersions, in 50000 mass parts water, add 30 mass parts hydrochloric acid, be mixed with the acid water solvent; Then 40 mass parts poly dimethyl allyl ammoniums are dissolved in the above-mentioned acid water solvent of 50000 mass parts and are made into the poly dimethyl allyl ammonium salt solution, under 40 ℃, at ultrasonic power is under 80W and the 800rpm stir speed (S.S.) poly dimethyl allyl ammonium salt solution to be splashed in the aqueous dispersions of bentonite/sodium carboxymethylcellulose hybrid to obtain poly dimethyl allyl ammonium/sodium carboxymethylcellulose/bentonite hybrid thing, through repeatedly washing and drying.Poly dimethyl allyl ammonium/sodium carboxymethylcellulose/bentonite hybrid thing is dissolved in the diluted alkaline aqueous solvent, and being made into mass percent concentration is 2%, the casting solution of pH=7.Casting solution is coated with to scrape on the polysulfones counterdie, obtains poly dimethyl allyl ammonium/sodium carboxymethylcellulose/bentonite hybrid film.This film infiltration evaporation performance is: to feeding liquid is the isopropanol system of 90wt%, under 70 ℃: J=4500g/m
2H, α
W/o=440.The hybrid material mechanical mechanics property is: σ
t=38.16MPa, ε=25.32%.
Embodiment 2
Get 3 mass parts bentonites and add in the 5000 mass parts water, soak 30h and stir 0.5h again; In 20000 mass parts water, add 8 mass parts hydrochloric acid then, be mixed with the acid water solvent, 50 mass parts sodium carboxymethylcelluloses are dissolved in the above-mentioned acid water solvent of 20000 mass parts are made into carboxymethylcellulose sodium solution, then at 90 ℃, under 100W ultrasonic power and the 1000rpm stir speed (S.S.) carboxymethylcellulose sodium solution is splashed in the bentonite aqueous dispersions, ultrasonic agitation 0.5h carries out intercalation, obtain sodium carboxymethylcellulose/bentonite hybrid thing aqueous dispersions, in 50000 mass parts water, add 8 mass parts hydrochloric acid, be mixed with the acid water solvent; Then 20 mass parts poly dimethyl allyl ammoniums are dissolved in the above-mentioned acid water solvent of 50000 mass parts and are made into the poly dimethyl allyl ammonium salt solution, under 50 ℃, at ultrasonic power is under 100W and the 1000rpm stir speed (S.S.) poly dimethyl allyl ammonium salt solution to be splashed in the aqueous dispersions of sodium carboxymethylcellulose/bentonite hybrid thing to obtain poly dimethyl allyl ammonium/sodium carboxymethylcellulose/bentonite hybrid thing, through repeatedly washing and drying.Poly dimethyl allyl ammonium/sodium carboxymethylcellulose/bentonite hybrid thing is dissolved in the diluted alkaline aqueous solvent, being made into mass percent concentration is 2.5%, the casting solution of pH=7 is coated with casting solution to scrape obtains poly dimethyl allyl ammonium/sodium carboxymethylcellulose/bentonite hybrid film on the polysulfones counterdie.This film infiltration evaporation performance is: to feeding liquid is the isopropanol system of 90wt%, under 70 ℃: J=4380g/m
2H, α
W/o=920.The hybrid material mechanical mechanics property is: σ
t=36.79MPa, ε=24.21%.
Embodiment 3
Get 5 mass parts bentonites and add in the 10000 mass parts water, soak 36h and stir 0.5h again; In 30000 mass parts water, add 12 mass parts hydrochloric acid then, be mixed with the acid water solvent, 80 mass parts sodium carboxymethylcelluloses are dissolved in the above-mentioned acid water solvent of 30000 mass parts are made into carboxymethylcellulose sodium solution, then at 70 ℃, under 50W ultrasonic power and the 900rpm stir speed (S.S.) carboxymethylcellulose sodium solution is splashed in the bentonite aqueous dispersions, ultrasonic agitation 1h carries out intercalation, obtain sodium carboxymethylcellulose/bentonite hybrid thing aqueous dispersions, in 40000 mass parts water, add 12 mass parts hydrochloric acid, be mixed with the acid water solvent; Then 5 mass parts polymines are dissolved in the above-mentioned acid water solvent of 40000 mass parts and are made into the polyethyleneimine: amine aqueous solution, under 40 ℃, at ultrasonic power is under 50W and the 900rpm stir speed (S.S.) polymine solution to be splashed in sodium carboxymethylcellulose/bentonite hybrid thing aqueous dispersions to obtain polymine/sodium carboxymethylcellulose/bentonite hybrid thing, through repeatedly washing and drying.Polymine/sodium carboxymethylcellulose/bentonite hybrid thing is dissolved in the diluted alkaline aqueous solvent, being made into mass percent concentration is 3%, the casting solution of pH=8 is coated with casting solution to scrape obtains polymine/sodium carboxymethylcellulose/bentonite hybrid film on the polysulfones counterdie.This film infiltration evaporation performance is: to feeding liquid is the isopropanol system of 90wt%, under 70 ℃: J=2017g/m
2H, α
W/o=1160.
Embodiment 4
Get 7 mass parts bentonites and add in the 800 mass parts water, soak 32h and stir 0.5h again; In 40000 mass parts water, add 40 mass parts hydrochloric acid then, be mixed with the acid water solvent, 20 parts of Sodium Polyacrylates are dissolved in the above-mentioned acid water solvent of 40000 mass parts are made into sodium polyacrylate solution, then at 100 ℃, under 200W ultrasonic power and the 900rpm stir speed (S.S.) sodium polyacrylate solution is splashed in the bentonite aqueous dispersions, ultrasonic agitation 1h carries out intercalation, obtain bentonite/Sodium Polyacrylate hybrid aqueous dispersions, in 50000 mass parts water, add 40 mass parts hydrochloric acid, be mixed with the acid water solvent; Then 60 mass parts shitosans are dissolved in the above-mentioned acid water solvent of 50000 mass parts and are made into chitosan solution, under 40 ℃, at ultrasonic power is under 100W and the 900rpm stir speed (S.S.) chitosan solution to be splashed in Sodium Polyacrylate/bentonite hybrid thing aqueous dispersions to obtain shitosan/Sodium Polyacrylate/bentonite hybrid thing, through repeatedly washing and drying.With the dissolving of diluted alkaline aqueous solvent, being made into mass percent concentration is 1% with shitosan/Sodium Polyacrylate/bentonite hybrid thing, and the casting solution of pH=7 is coated with casting solution to scrape obtains shitosan/Sodium Polyacrylate bentonite hybrid film on the polysulfones counterdie.This film infiltration evaporation performance is: to feeding liquid is the isopropanol system of 90wt%, under 70 ℃: J=1826g/m
2H, α
W/o=1187.
Embodiment 5
Get 10 mass parts bentonites and add in the 10000 mass parts water, soak 36h and stir 1h again; In 30000 mass parts water, add 35 mass parts hydrochloric acid then, be mixed with the acid water solvent, 100 mass parts sodium carboxymethylcelluloses are dissolved in the above-mentioned acid water solvent of 30000 mass parts are made into carboxymethylcellulose sodium solution, then at 80 ℃, under 90W ultrasonic power and the 1000rpm stir speed (S.S.) carboxymethylcellulose sodium solution is splashed in the bentonite aqueous dispersions, ultrasonic agitation 2h carries out intercalation, obtain sodium carboxymethylcellulose/bentonite hybrid thing aqueous dispersions, in 40000 mass parts water, add 35 mass parts hydrochloric acid, be mixed with the acid water solvent; Then 60 mass parts poly dimethyl allyl ammoniums are dissolved in the above-mentioned acid water solvent of 50000 mass parts and are made into the poly dimethyl allyl ammonium salt solution, under 60 ℃, at ultrasonic power is under 100W and the 1000rpm stir speed (S.S.) poly dimethyl allyl ammonium salt solution to be splashed in sodium carboxymethylcellulose/bentonite hybrid thing aqueous dispersions to obtain poly dimethyl allyl ammonium/sodium carboxymethylcellulose/bentonite hybrid thing, through repeatedly washing and drying.Poly dimethyl allyl ammonium/sodium carboxymethylcellulose/bentonite hybrid thing is dissolved with the diluted alkaline aqueous solvent, being made into mass percent concentration is 3%, the casting solution of pH=8 is coated with casting solution to scrape obtains poly dimethyl allyl ammonium/sodium carboxymethylcellulose/bentonite hybrid film on the polysulfones counterdie.This film infiltration evaporation performance is: to feeding liquid is the isopropanol system of 90wt%, under 70 ℃: J=3138g/m
2H, α
W/o=1426.The hybrid material mechanical mechanics property is: σ
t=31.56MPa, ε=10.77%.
Embodiment 6
Get 2 parts of bentonites and add in 5000 parts of water, soak 24h and stir 2h again; In 30000 parts of water, add 10 parts of hydrochloric acid then, be mixed with the acid water solvent, 50 parts of sodium carboxymethylcelluloses are dissolved in 30000 parts of above-mentioned acid water solvents are made into carboxymethylcellulose sodium solution, then at 90 ℃, under 50W ultrasonic power and the 1000rpm stir speed (S.S.) carboxymethylcellulose sodium solution is splashed in the bentonite aqueous dispersions, ultrasonic agitation 0.5h carries out intercalation, obtain sodium carboxymethylcellulose/bentonite hybrid thing aqueous dispersions, in 40000 mass parts water, add 10 mass parts hydrochloric acid, be mixed with the acid water solvent; Then 50 mass parts polymethyl acyl-oxygen ethyl-trimethyl salmiacs are dissolved in and are made into polymethyl acyl-oxygen ethyl-trimethyl salmiac solution in the above-mentioned acid water solvent of 40000 mass parts, under 50 ℃, at ultrasonic power is under 100W and the 1000rpm stir speed (S.S.) polymethyl acyl-oxygen ethyl-trimethyl salmiac solution to be splashed in sodium carboxymethylcellulose/bentonite hybrid thing aqueous dispersions to obtain polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium carboxymethylcellulose/bentonite hybrid thing, through repeatedly washing and drying.Polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium carboxymethylcellulose/bentonite hybrid thing is dissolved with the diluted alkaline aqueous solvent, being made into mass percent concentration is 3%, the casting solution of pH=7 is coated with casting solution to scrape obtains polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium carboxymethylcellulose/bentonite hybrid film on the polysulfones counterdie.This film infiltration evaporation performance is: to feeding liquid is the isopropanol system of 90wt%, under 70 ℃: J=2414g/m
2H, α
W/o=982.The hybrid material mechanical mechanics property is: σ
t=26.8MPa, ε=13.71%.
Embodiment 7
Get 4 parts of bentonites and add in 10000 parts of water, soak 28h and stir 1h again; In 40000 parts of water, add 30 parts of hydrochloric acid then, be mixed with the acid water solvent, 60 parts of sodium alginates are dissolved in 40000 parts of above-mentioned acid water solvents are made into sodium alginate soln, then at 80 ℃, under 100W ultrasonic power and the 800rpm stir speed (S.S.) sodium alginate soln is splashed in the bentonite aqueous dispersions, ultrasonic agitation 1h carries out intercalation, obtains sodium alginate/bentonite hybrid thing aqueous dispersions, in 50000 parts of water, add 30 parts of hydrochloric acid, be mixed with the acid water solvent; Then 100 parts of polymethyl acyl-oxygen ethyl-trimethyl salmiacs are dissolved in and are made into polymethyl acyl-oxygen ethyl-trimethyl salmiac solution in 50000 parts of above-mentioned acid water solvents, under 40 ℃, at ultrasonic power is under 100W and the 800rpm stir speed (S.S.) polymethyl acyl-oxygen ethyl-trimethyl salmiac solution to be splashed in sodium carboxymethylcellulose/bentonite hybrid thing aqueous dispersions to obtain polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium carboxymethylcellulose/bentonite hybrid thing, through repeatedly washing and drying.Polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium carboxymethylcellulose/bentonite hybrid thing is dissolved with sig water, being made into mass percent concentration is 2%, the casting solution of pH=7 is coated with casting solution to scrape obtains polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium carboxymethylcellulose/bentonite hybrid film on the polysulfones counterdie.This film infiltration evaporation performance is: to feeding liquid is the isopropanol system of 90wt%, under 70 ℃: J=2579g/m
2H, α
W/o=955.The hybrid material mechanical mechanics property is: σ
t=24.70MPa, ε=11.35%.
Embodiment 8
Get 7 parts of bentonites and add in 900 parts of water, soak 24h and stir 2h again; In 30000 parts of water, add 25 parts of hydrochloric acid then, be mixed with the acid water solvent, 50 parts of Sodium Polyacrylates are dissolved in 40000 parts of above-mentioned acid water solvents are made into sodium polyacrylate solution, then at 60 ℃, under 200W ultrasonic power and the 1000rpm stir speed (S.S.) sodium polyacrylate solution is splashed in the bentonite aqueous dispersions, ultrasonic agitation 2h carries out intercalation, obtains Sodium Polyacrylate/bentonite hybrid thing aqueous dispersions, in 40000 parts of water, add 25 parts of hydrochloric acid, be mixed with the acid water solvent; Then 200 parts of polymethyl acyl-oxygen ethyl-trimethyl salmiacs are dissolved in and are made into polymethyl acyl-oxygen ethyl-trimethyl salmiac solution in 40000 parts of above-mentioned acid water solvents, under 50 ℃, at ultrasonic power is under 100W and the 1000rpm stir speed (S.S.) polymethyl acyl-oxygen ethyl-trimethyl salmiac solution to be splashed in Sodium Polyacrylate/bentonite hybrid thing aqueous dispersions to obtain polymethyl acyl-oxygen ethyl-trimethyl salmiac/Sodium Polyacrylate/bentonite hybrid thing, through repeatedly washing and drying.Polymethyl acyl-oxygen ethyl-trimethyl salmiac/Sodium Polyacrylate/bentonite hybrid thing is dissolved with the diluted alkaline aqueous solvent, being made into mass percent concentration is 4%, the casting solution of pH=7 is coated with casting solution to scrape obtains polymethyl acyl-oxygen ethyl-trimethyl salmiac/Sodium Polyacrylate/bentonite hybrid film on the polysulfones counterdie.This film infiltration evaporation performance is: to feeding liquid is the isopropanol system of 90wt%, under 70 ℃: J=2175g/m
2H, α
W/o=1027.
Embodiment 9
Get 15 parts of bentonites and add in 10000 parts of water, soak 30h and stir 0.5h again; In 30000 parts of water, add 35 parts of hydrochloric acid then, be mixed with the acid water solvent, 20 parts of sodium alginates are dissolved in 40000 parts of above-mentioned acid water solvents are made into sodium alginate soln, then at 70 ℃, 50W ultrasonic power and stir speed (S.S.) are under the 900rpm sodium alginate soln to be splashed in the bentonite aqueous dispersions, and ultrasonic agitation 3h carries out intercalation, obtain sodium alginate/bentonite hybrid thing aqueous dispersions, in 40000 parts of water, add 35 parts of hydrochloric acid, be mixed with the acid water solvent; Then 20 parts of shitosans are dissolved in 40000 parts of above-mentioned acid water solvents and are made into chitosan solution, under 40 ℃, at ultrasonic power is under 100W and the 900rpm stir speed (S.S.) chitosan solution to be splashed in sodium alginate/bentonite hybrid thing aqueous dispersions to obtain shitosan/sodium alginate/bentonite hybrid thing, through repeatedly washing and drying.With the dissolving of diluted alkaline aqueous solvent, being made into mass percent is 5% with shitosan/sodium carboxymethylcellulose/bentonite hybrid thing, and the casting solution of pH=8 is coated with casting solution to scrape obtains shitosan/sodium alginate/bentonite hybrid film on the polysulfones counterdie.This film infiltration evaporation performance is: to feeding liquid is the isopropanol system of 90wt%, under 70 ℃: J=1866g/m
2H, α
W/o=1089.
Embodiment 10
Get 20 parts of bentonites and add in 10000 parts of water, soak 24h and stir 2h again; In 40000 parts of water, add 30 parts of hydrochloric acid then, be mixed with the acid water solvent, 100 parts of sodium carboxymethylcelluloses are dissolved in 50000 parts of above-mentioned acid water solvents are made into carboxymethylcellulose sodium solution, then at 100 ℃, under 100W ultrasonic power and the 1000rpm stir speed (S.S.) carboxymethylcellulose sodium solution is splashed in the bentonite aqueous dispersions, ultrasonic agitation 3h carries out intercalation, obtain sodium carboxymethylcellulose/bentonite hybrid thing aqueous dispersions, in 50000 parts of water, add 30 parts of hydrochloric acid, be mixed with the acid water solvent; Then 15 parts of polymines are dissolved in 5000 parts of above-mentioned acid water solvents and are made into the polyethyleneimine: amine aqueous solution, under 60 ℃, at ultrasonic power is under 100W and the 1000rpm stir speed (S.S.) polymine solution to be splashed in sodium carboxymethylcellulose/bentonite hybrid thing aqueous dispersions to obtain polymine/sodium carboxymethylcellulose/bentonite hybrid thing, through repeatedly washing and drying.Polymine/sodium carboxymethylcellulose/bentonite hybrid thing is dissolved with the diluted alkaline aqueous solvent, being made into mass percent concentration is 4%, the casting solution of pH=7 is coated with casting solution to scrape obtains polymine/sodium carboxymethylcellulose/bentonite hybrid film on the polysulfones counterdie.This film infiltration evaporation performance is: to feeding liquid is the isopropanol system of 90wt%, under 70 ℃: J=1763g/m
2H, α
W/o=1103.
Claims (5)
1. the preparation method of a polyelectrolyte complex compound/bentonite hybrid pervaporation membrane is characterized in that comprising the steps:
1) in 20000～40000 mass parts water, adds 8～50 mass parts acid, be mixed with acid solution; Then 20～60 mass parts poly dimethyl allyl ammoniums are dissolved in the above-mentioned acid solution of 20000～40000 mass parts and are made into the poly dimethyl allyl ammonium salt solution, 50～200 mass parts polymethyl acyl-oxygen ethyl-trimethyl salmiacs are dissolved in are made into polymethyl acyl-oxygen ethyl-trimethyl salmiac solution in the above-mentioned acid solution of 20000～40000 mass parts, 20～60 mass parts shitosans are dissolved in the above-mentioned acid solution of 20000～40000 mass parts are made into chitosan solution, 5～15 mass parts polymines are dissolved in the above-mentioned acid solution of 20000～40000 mass parts are made into the polyethyleneimine: amine aqueous solution, 50～100 mass parts sodium carboxymethylcelluloses are dissolved in the above-mentioned acid solution of 20000～40000 mass parts are made into carboxymethylcellulose sodium solution, 20～50 mass parts Sodium Polyacrylates are dissolved in the above-mentioned acid solution of 20000～40000 mass parts are made into sodium polyacrylate solution, 20～60 mass parts sodium alginates are dissolved in the above-mentioned acid solution of 20000～40000 mass parts are made into sodium alginate soln;
2) 1～20 mass parts bentonite is joined in 5000～10000 mass parts water soak 24～36h, stir 0.5～2h again and obtain the bentonite aqueous dispersions, then at 60～100 ℃, under 50～200W ultrasonic power and the 800～1000rpm stir speed (S.S.), with carboxymethylcellulose sodium solution, sodium polyacrylate solution or sodium alginate soln add in the bentonite aqueous dispersions, ultrasonic agitation 0.5～3h carries out intercalation, obtains the aqueous dispersions of sodium carboxymethylcellulose/bentonite hybrid thing, the aqueous dispersions of the aqueous dispersions of Sodium Polyacrylate/bentonite hybrid thing or sodium alginate/bentonite hybrid thing;
3) at 40～60 ℃, at ultrasonic power is under 50～200W and 800～1000rpm speed stir, with the poly dimethyl allyl ammonium salt solution, polymethyl acyl-oxygen ethyl-trimethyl salmiac solution, shitosan liquid or polymine solution splash into the aqueous dispersions of sodium carboxymethylcellulose/bentonite hybrid thing, in the aqueous dispersions of the aqueous dispersions of Sodium Polyacrylate/bentonite hybrid thing or sodium alginate/bentonite hybrid thing, obtain poly dimethyl allyl ammonium/sodium carboxymethylcellulose/bentonite hybrid thing, poly dimethyl allyl ammonium/Sodium Polyacrylate/bentonite hybrid thing, poly dimethyl allyl ammonium/sodium alginate/bentonite hybrid thing, polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium carboxymethylcellulose/bentonite hybrid thing, polymethyl acyl-oxygen ethyl-trimethyl salmiac/Sodium Polyacrylate/bentonite hybrid thing, polymethyl acyl-oxygen ethyl-trimethyl salmiac/sodium alginate/bentonite hybrid thing, shitosan/sodium carboxymethylcellulose/bentonite hybrid thing, shitosan/Sodium Polyacrylate/bentonite hybrid thing, shitosan/sodium alginate/bentonite hybrid thing, polymine/sodium carboxymethylcellulose/bentonite hybrid thing, polymine/Sodium Polyacrylate/bentonite hybrid thing, polymine/sodium alginate/bentonite hybrid thing;
4) above-mentioned hybrid is dissolved in respectively in the diluted alkaline aqueous solution, is made into the casting solution that mass percent concentration is 1～5 %, the pH value is 7～8, after filtration, after the standing and defoaming, is coated with and scrapes on the polysulfones counterdie.
2. the preparation method of a kind of polyelectrolyte complex compound/bentonite hybrid pervaporation membrane according to claim 1 is characterized in that described step 2) in the bentonite mass parts be 1～15 part.
3. the preparation method of a kind of polyelectrolyte complex compound/bentonite hybrid pervaporation membrane according to claim 1 is characterized in that described step 2) described in the intercalation temperature be 70～90 ℃.
4. the preparation method of a kind of polyelectrolyte complex compound/bentonite hybrid pervaporation membrane according to claim 1 is characterized in that described step 2) in the ultrasonic agitation time be 0.5～2h, ultrasonic power is preferably 50～100W.
5. the preparation method of a kind of polyelectrolyte complex compound/bentonite hybrid pervaporation membrane according to claim 1 is characterized in that the mass percent concentration of hybrid in casting solution is 2～4% in the described step 4).
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|---|---|---|---|---|
| CN1358212A (en) * | 1999-04-30 | 2002-07-10 | 托马斯·翰翎 | Composites and composite membranes |
| US20070265174A1 (en) * | 2004-03-26 | 2007-11-15 | Florida State University Research Foundation, Inc. | Hydrophobic Fluorinated Polyelectrolyte Complex Films And Associated Methods |
| CN101219343A (en) * | 2007-09-26 | 2008-07-16 | 浙江大学 | Process for producing high throughout pervaporation membrane for sodium alginate and dimethyl-allyl-ammonium complex compound |
| CN101219342A (en) * | 2007-09-26 | 2008-07-16 | 浙江大学 | Process for producing weak-weak polyelectrolyte complex compound homogeneity permeation vaporisation film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358212A (en) * | 1999-04-30 | 2002-07-10 | 托马斯·翰翎 | Composites and composite membranes |
| US20070265174A1 (en) * | 2004-03-26 | 2007-11-15 | Florida State University Research Foundation, Inc. | Hydrophobic Fluorinated Polyelectrolyte Complex Films And Associated Methods |
| CN101219343A (en) * | 2007-09-26 | 2008-07-16 | 浙江大学 | Process for producing high throughout pervaporation membrane for sodium alginate and dimethyl-allyl-ammonium complex compound |
| CN101219342A (en) * | 2007-09-26 | 2008-07-16 | 浙江大学 | Process for producing weak-weak polyelectrolyte complex compound homogeneity permeation vaporisation film |
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| 邹健等.聚电解质渗透汽化膜.《高分子通报》.2001,(第5期),44-52. * |
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