CN112827367A - Diatomite modified polyvinyl chloride composite separation membrane with high thermal stability and preparation method thereof - Google Patents
Diatomite modified polyvinyl chloride composite separation membrane with high thermal stability and preparation method thereof Download PDFInfo
- Publication number
- CN112827367A CN112827367A CN202110091294.3A CN202110091294A CN112827367A CN 112827367 A CN112827367 A CN 112827367A CN 202110091294 A CN202110091294 A CN 202110091294A CN 112827367 A CN112827367 A CN 112827367A
- Authority
- CN
- China
- Prior art keywords
- diatomite
- polyvinyl chloride
- separation membrane
- thermal stability
- high thermal
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention relates to the technical field of diatom ooze, and discloses a diatomite modified polyvinyl chloride composite separation membrane with high thermal stability, wherein acid-treated diatomite contains hydroxyl, the hydroxyl is reacted with toluene-2, 4-diisocyanate under the action of a catalyst, a product is reacted with 1, 3-propanedithiol to obtain sulfhydrylated diatomite, and Ce is used for preparing the sulfhydrylated diatomite4+The mercapto group is an oxidation-reduction system, carbon free radicals are formed on carbon at the ortho position of the mercapto group, the carbon free radicals are used as active initiation sites to initiate vinyl chloride polymerization, the interface compatibility of the diatomite and the polyvinyl chloride is improved through the connection of chemical bonds, when the diatomite is subjected to external force, the polyvinyl chloride can be subjected to yield deformation, the expansion of cracks is hindered, and the diatomite can be subjected to external forceThe cross-linking density of the polyvinyl chloride is improved, the number of covalent bonds is increased, more energy is needed for the decomposition of the separation membrane, and the diatomite has adsorbability and can resist Pb2+、Cu2+The heavy metal ions are adsorbed, so that the comprehensive performance of the separation membrane is improved.
Description
Technical Field
The invention relates to the technical field of diatom ooze, in particular to a diatomite modified polyvinyl chloride composite separation membrane with high thermal stability and a preparation method thereof.
Background
The diatom ooze is a novel natural environment-friendly coating, the main component of the diatom ooze is diatomite, the main component of the diatom ooze mainly comprises inorganic metal oxides such as silicon dioxide, calcium oxide, aluminum oxide, magnesium oxide and the like, and the diatom ooze has good heat resistance, chemical stability, adsorbability and larger specific surface area, so the diatom ooze is widely applied to various fields such as filter media, decorative coatings, catalyst carriers and the like, and just because of having excellent performances, the diatom ooze can be used as functional reinforcing filler, the diatom ooze is filled into organic polymer materials such as polystyrene, polyvinyl chloride and the like, the excellent performances of the diatom ooze are blended into organic polymer materials such as polystyrene, polyvinyl chloride and the like, the comprehensive performances such as the adsorption performance, the mechanical property, the thermodynamic property and the like of the organic polymer materials are improved, however, the interface compatibility of the traditional diatom ooze and, it is difficult to form stable dispersion in organic polymer materials, and therefore the purpose of modifying polymers cannot be achieved, so that the surface modification of diatomite is needed, and currently, the most practical and effective modification method is to introduce organic functional groups on the surface of diatomite and improve the interface compatibility of the diatomite and the organic polymer materials through the interaction between the organic functional groups and the organic polymer materials, so as to achieve the purpose of modifying the organic polymer materials.
Polyvinyl chloride is a commodity general thermoplastic resin, is one of the most main organic polymer materials in the world at present, has good processability, chemical resistance, insulativity and other excellent properties, is widely applied to various fields such as wire sheaths, optical fiber sheaths, building decoration, medicines and the like, has strong selective separation effect, and has certain application in the field of wastewater treatment, however, the traditional polyvinyl chloride is mainly prepared by free radical polymerization, can form a great number of molecular isomers and structural defects, so that the structure of the traditional polyvinyl chloride is very unstable, the mechanical properties such as impact resistance, stretchability and the like of the traditional polyvinyl chloride are poor, meanwhile, the structural defects can influence the thermal stability of the polyvinyl chloride to a certain extent, so that functional reinforcing fillers need to be added into the polyvinyl chloride, and diatomite is used as a natural inorganic material with excellent properties, the functional reinforcing filler can be filled in a polyvinyl chloride matrix as a functional reinforcing filler, and the comprehensive properties of the polyvinyl chloride such as adsorption, mechanical property, thermal stability and the like are improved by combining the excellent properties of the diatomite, so that the application range of the polyvinyl chloride is further improved.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a diatomite modified polyvinyl chloride composite separation membrane with high thermal stability and a preparation method thereof, which solve the problem of poor dispersibility of diatomite and solve the problems of poor adsorption property, mechanical property and thermal stability of polyvinyl chloride.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a diatomite-modified polyvinyl chloride composite separation membrane with high thermal stability comprises the following steps:
(1) adding an ethyl acetate solvent, acid-treated diatomite, toluene-2, 4-diisocyanate and dibutyltin dilaurate into a three-necked bottle, introducing nitrogen to remove oxygen, ultrasonically dispersing for 10-20min, transferring into an oil bath pot, refluxing for reaction, repeatedly washing a product by using anhydrous toluene and deionized water, centrifuging after washing, and drying in a vacuum drying oven to obtain isocyanated diatomite;
(2) adding a tetrahydrofuran solvent, isocyanated diatomite and 1, 3-propanedithiol into a three-necked bottle, placing the three-necked bottle in an oil bath pot after uniform ultrasonic dispersion, stirring the three-necked bottle for click reaction, washing a product with absolute ethyl alcohol, centrifuging the washed product after washing, and placing the washed product in a vacuum drying oven for drying to obtain sulfhydrylated diatomite;
(3) adding a deionized water solvent, lauryl sodium sulfate and cetyl alcohol into a three-neck flask, adding sulfhydrylation diatomite and cerium ammonium sulfate after uniform ultrasonic dispersion, transferring the mixture into a high-pressure reaction kettle, filling nitrogen to remove oxygen, pressing chloroethylene into the kettle, stirring for 20-40min at 15-30 ℃, carrying out polymerization reaction, and cooling a product to obtain the diatomite-grafted polyvinyl chloride composite emulsion;
(4) adding a dimethylacetamide solvent, a diatomite grafted polyvinyl chloride composite emulsion, a pore-forming agent polyethylene glycol and a defoaming agent into a three-necked bottle, mechanically stirring for 20-40h at 15-30 ℃, transferring into a mold, and curing to obtain the diatomite modified polyvinyl chloride composite separation membrane with high thermal stability.
Preferably, the mass ratio of the diatomite, the toluene-2, 4-diisocyanate and the dibutyltin dilaurate in the step (1) is 100: 460-.
Preferably, the reaction temperature in the step (1) is 15-35 ℃, and the reaction is carried out for 2-8h under reflux in a nitrogen atmosphere.
Preferably, the mass ratio of the isocyanated diatomite to the 1, 3-propanedithiol in the step (2) is 100: 340-400.
Preferably, the temperature of the click reaction in the step (2) is 80-100 ℃, and the click reaction is carried out for 1-3h under the stirring of nitrogen atmosphere.
Preferably, the mass ratio of the sodium dodecyl sulfate, the hexadecanol, the thiolated diatomite, the cerium ammonium sulfate and the chloroethylene in the step (3) is 120-180:140-200:0.5-4:0.1-0.6: 100.
Preferably, the temperature of the polymerization reaction in the step (3) is 40-60 ℃, and the polymerization reaction is carried out for 4-10h in a nitrogen atmosphere.
Preferably, the mass ratio of the diatomite-grafted polyvinyl chloride composite emulsion, the pore-foaming agent polyethylene glycol and the defoaming agent in the step (4) is 100:40-60: 5-10.
Preferably, the defoaming agent in the step (4) may be any one of polyoxyethylene octylphenol ether, polyether-modified polysiloxane, and polyoxypropylene ethylene oxide glyceryl ether.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the diatomite modified polyvinyl chloride composite separation membrane with high thermal stability, the surface of diatomite treated by acid contains a large number of hydroxyl groups, and can react with one isocyanate group in toluene-2, 4-diisocyanate under the catalytic action of a catalyst dibutyltin dilaurate to obtain isocyanated diatomite, the isocyanate group in the isocyanated diatomite can perform click reaction with a mercapto group in 1, 3-propanedithiol to obtain the sulfhydrylated diatomite, and the hydroxyl group, the isocyanate group and the mercapto group are introduced into the surface of the diatomite through a chemical bond connection mode, so that the purpose of functionally modifying the functional groups on the surface of the diatomite is achieved, the dispersibility of the diatomite is effectively improved, and the application range of the diatomite is further improved.
According to the diatomite modified polyvinyl chloride composite separation membrane with high thermal stability, sulfydryl of sulfhydrylated diatomite is used as a reducing agent, and Ce in ammonium ceric sulfate4+The diatomite surface oxidation reduction initiation polymerization mode enables the diatomite and the polyvinyl chloride to be firmly grafted through chemical bonds, greatly improves the interface compatibility of the diatomite and the polyvinyl chloride, improves the dispersion stability of the diatomite in a polyvinyl chloride matrix, and avoids the secondary agglomeration phenomenon of the diatomite.
This high thermal stability's compound release film of diatomaceous earth modification polyvinyl chloride, when compound release film received the exogenic action, diatomaceous earth can form stress concentration, and make its nearby polyvinyl chloride base body take place the yield deformation and form shear band and silver line, this kind of yield strain can absorb a large amount of energy, and simultaneously, diatomaceous earth can make the crack passivation, and hinder the expansion of crack, thereby the mechanical properties of compound release film has been improved, in addition, diatomaceous earth passes through the mode of surface initiation polymerization, can improve polyvinyl chloride's crosslink density effectively, and more covalent bond has been increased, be in high crosslinking density when compound release film, be in compound release filmUnder the warm condition, the higher crosslinking density and more covalent bonds enable more energy to be required by the decomposition of the composite separation membrane, so that the thermal stability of the composite separation membrane is improved, meanwhile, the stably dispersed diatomite has stronger adsorption performance, and the porous structure in the composite separation membrane is combined, so that the composite separation membrane can resist Pb2+、Cu2+The heavy metal ions are adsorbed and recovered, and the good mechanical property can improve the recycling property of the composite separation membrane, so that the purification efficiency of the industrial wastewater is improved.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a diatomite modified polyvinyl chloride composite separation membrane with high thermal stability is prepared by the following steps:
(1) adding an ethyl acetate solvent, acid-treated diatomite, toluene-2, 4-diisocyanate and dibutyltin dilaurate into a three-necked bottle, wherein the mass ratio of the diatomite, the toluene-2, 4-diisocyanate and the dibutyltin dilaurate is 100: 460-;
(2) adding a tetrahydrofuran solvent, isocyanated diatomite and 1, 3-propanedithiol into a three-necked bottle, wherein the mass ratio of the isocyanated diatomite to the 1, 3-propanedithiol is 100: 340-;
(3) adding a deionized water solvent, lauryl sodium sulfate and cetyl alcohol into a three-neck flask, adding sulfhydrylation diatomite and ammonium ceric sulfate after uniform ultrasonic dispersion, transferring the mixture into a high-pressure reaction kettle, filling nitrogen to remove oxygen, pressing chloroethylene into the kettle, wherein the mass ratio of the lauryl sodium sulfate to the cetyl alcohol to the sulfhydrylation diatomite to the ammonium ceric sulfate to the chloroethylene is 120-;
(4) adding a dimethylacetamide solvent, a diatomite grafted polyvinyl chloride composite emulsion, a pore-forming agent polyethylene glycol and a defoaming agent into a three-necked bottle, wherein the mass ratio of the diatomite grafted polyvinyl chloride composite emulsion to the pore-forming agent polyethylene glycol to the defoaming agent is 100:40-60:5-10, the defoaming agent can be any one of octylphenol polyoxyethylene ether, polyether modified polysiloxane and polyoxypropylene ethylene oxide glycerol ether, mechanically stirring for 20-40h at 15-30 ℃, transferring the mixture into a mold, and curing to obtain the diatomite modified polyvinyl chloride composite separation membrane with high thermal stability.
Example 1
(1) Adding an ethyl acetate solvent, acid-treated diatomite, toluene-2, 4-diisocyanate and dibutyltin dilaurate into a three-necked bottle, wherein the mass ratio of the diatomite to the toluene-2, 4-diisocyanate to the dibutyltin dilaurate is 100:460:100, introducing nitrogen to remove oxygen, ultrasonically dispersing for 10min, transferring into an oil bath pot, refluxing at 15 ℃ in a nitrogen atmosphere for 2h, repeatedly washing a product with anhydrous toluene and deionized water, centrifuging after washing, and drying in a vacuum drying oven to obtain isocyanated diatomite;
(2) adding a tetrahydrofuran solvent, isocyanated diatomite and 1, 3-propanedithiol into a three-necked bottle, wherein the mass ratio of the isocyanated diatomite to the 1, 3-propanedithiol is 100:340, placing the mixture into an oil bath pot after uniform ultrasonic dispersion, stirring the mixture in a nitrogen atmosphere at 80 ℃ for click reaction for 1h, washing a product with absolute ethyl alcohol, centrifuging the product after washing, and placing the product into a vacuum drying oven for drying to obtain sulfhydrylated diatomite;
(3) adding a deionized water solvent, lauryl sodium sulfate and cetyl alcohol into a three-neck flask, adding sulfhydrylated diatomite and ammonium ceric sulfate after uniform ultrasonic dispersion, transferring the mixture into a high-pressure reaction kettle, filling nitrogen to remove oxygen, pressing chloroethylene into the kettle, wherein the mass ratio of the lauryl sodium sulfate to the cetyl alcohol to the sulfhydrylated diatomite to the ammonium ceric sulfate to the chloroethylene is 120:140:0.5:0.1:100, stirring the mixture for 20min at 15 ℃, carrying out polymerization reaction for 4h at 40 ℃ in a nitrogen atmosphere, and cooling the product to obtain the diatomite-grafted polyvinyl chloride composite emulsion;
(4) adding a dimethylacetamide solvent, a diatomite-grafted polyvinyl chloride composite emulsion, a pore-forming agent polyethylene glycol and a defoaming agent into a three-necked bottle, wherein the mass ratio of the diatomite-grafted polyvinyl chloride composite emulsion to the pore-forming agent polyethylene glycol to the defoaming agent polyether modified polysiloxane is 100:40:5, mechanically stirring for 20 hours at 15 ℃, transferring the mixture into a mold, and curing to obtain the diatomite-modified polyvinyl chloride composite separation membrane with high thermal stability.
Example 2
(1) Adding an ethyl acetate solvent, acid-treated diatomite, toluene-2, 4-diisocyanate and dibutyltin dilaurate into a three-necked bottle, wherein the mass ratio of the diatomite to the toluene-2, 4-diisocyanate to the dibutyltin dilaurate is 100:540:115, introducing nitrogen to remove oxygen, ultrasonically dispersing for 12min, transferring into an oil bath pot, refluxing at 20 ℃ in a nitrogen atmosphere for reaction for 3h, repeatedly washing a product with anhydrous toluene and deionized water, centrifuging after washing, and drying in a vacuum drying oven to obtain isocyanated diatomite;
(2) adding a tetrahydrofuran solvent, isocyanated diatomite and 1, 3-propanedithiol into a three-necked bottle, wherein the mass ratio of the isocyanated diatomite to the 1, 3-propanedithiol is 100:360, placing the mixture into an oil bath pot after uniform ultrasonic dispersion, stirring the mixture in a nitrogen atmosphere at 85 ℃ for click reaction for 1.5 hours, washing a product with absolute ethyl alcohol, centrifuging the product after washing, and placing the product in a vacuum drying oven for drying to obtain sulfhydrylated diatomite;
(3) adding a deionized water solvent, lauryl sodium sulfate and cetyl alcohol into a three-neck flask, adding sulfhydrylated diatomite and ammonium ceric sulfate after uniform ultrasonic dispersion, transferring the mixture into a high-pressure reaction kettle, filling nitrogen to remove oxygen, pressing chloroethylene into the kettle, wherein the mass ratio of the lauryl sodium sulfate to the cetyl alcohol to the sulfhydrylated diatomite to the ammonium ceric sulfate to the chloroethylene is 140:160:1.7:0.25:100, stirring the mixture for 25min at 18 ℃, carrying out polymerization reaction for 5h at 45 ℃ in a nitrogen atmosphere, and cooling the product to obtain the diatomite-grafted polyvinyl chloride composite emulsion;
(4) adding a dimethylacetamide solvent, a diatomite-grafted polyvinyl chloride composite emulsion, a pore-forming agent polyethylene glycol and a defoaming agent into a three-necked bottle, wherein the mass ratio of the diatomite-grafted polyvinyl chloride composite emulsion to the pore-forming agent polyethylene glycol to the defoaming agent polyether modified polysiloxane is 100:47:6.5, mechanically stirring for 25h at 20 ℃, transferring the mixture into a mold, and curing to obtain the diatomite-modified polyvinyl chloride composite separation membrane with high thermal stability.
Example 3
(1) Adding an ethyl acetate solvent, acid-treated diatomite, toluene-2, 4-diisocyanate and dibutyltin dilaurate into a three-necked bottle, wherein the mass ratio of the diatomite to the toluene-2, 4-diisocyanate to the dibutyltin dilaurate is 100:580:130, introducing nitrogen to remove oxygen, ultrasonically dispersing for 15min, transferring into an oil bath pot, refluxing at 30 ℃ in a nitrogen atmosphere for 6h, repeatedly washing a product with anhydrous toluene and deionized water, centrifuging after washing, and drying in a vacuum drying oven to obtain isocyanated diatomite;
(2) adding a tetrahydrofuran solvent, isocyanated diatomite and 1, 3-propanedithiol into a three-necked bottle, wherein the mass ratio of the isocyanated diatomite to the 1, 3-propanedithiol is 100:380, placing the mixture into an oil bath pot after uniform ultrasonic dispersion, carrying out click reaction for 2 hours under the stirring of 90 ℃ in a nitrogen atmosphere, washing a product with absolute ethyl alcohol, centrifuging after washing, and placing the product into a vacuum drying oven for drying to obtain sulfhydrylated diatomite;
(3) adding a deionized water solvent, lauryl sodium sulfate and cetyl alcohol into a three-neck flask, adding sulfhydrylated diatomite and ammonium ceric sulfate after uniform ultrasonic dispersion, transferring the mixture into a high-pressure reaction kettle, filling nitrogen to remove oxygen, pressing chloroethylene into the kettle, wherein the mass ratio of the lauryl sodium sulfate to the cetyl alcohol to the sulfhydrylated diatomite to the ammonium ceric sulfate to the chloroethylene is 160:180:3:0.4:100, stirring the mixture for 35min at 25 ℃, carrying out polymerization reaction for 8h at 55 ℃ in a nitrogen atmosphere, and cooling the product to obtain the diatomite-grafted polyvinyl chloride composite emulsion;
(4) adding a dimethylacetamide solvent, a diatomite grafted polyvinyl chloride composite emulsion, a pore-forming agent polyethylene glycol and a defoaming agent into a three-necked bottle, wherein the mass ratio of the diatomite grafted polyvinyl chloride composite emulsion to the pore-forming agent polyethylene glycol to the defoaming agent polyoxypropylene ethylene oxide glycerol ether is 100:54:8, mechanically stirring for 35 hours at 25 ℃, transferring the mixture into a mold, and curing to obtain the diatomite modified polyvinyl chloride composite separation membrane with high thermal stability.
Example 4
(1) Adding an ethyl acetate solvent, acid-treated diatomite, toluene-2, 4-diisocyanate and dibutyltin dilaurate into a three-necked bottle, wherein the mass ratio of the diatomite to the toluene-2, 4-diisocyanate to the dibutyltin dilaurate is 100:700:150, introducing nitrogen to remove oxygen, ultrasonically dispersing for 20min, transferring into an oil bath pot, refluxing at 35 ℃ in a nitrogen atmosphere for 8h, repeatedly washing a product with anhydrous toluene and deionized water, centrifuging after washing, and drying in a vacuum drying oven to obtain isocyanated diatomite;
(2) adding a tetrahydrofuran solvent, isocyanated diatomite and 1, 3-propanedithiol into a three-necked bottle, wherein the mass ratio of the isocyanated diatomite to the 1, 3-propanedithiol is 100:400, placing the mixture into an oil bath pot after ultrasonic dispersion is uniform, stirring the mixture in a nitrogen atmosphere at 100 ℃ for click reaction for 3 hours, washing a product with absolute ethyl alcohol, centrifuging the product after washing, and placing the product into a vacuum drying oven for drying to obtain sulfhydrylated diatomite;
(3) adding a deionized water solvent, lauryl sodium sulfate and cetyl alcohol into a three-neck flask, adding sulfhydrylated diatomite and ammonium ceric sulfate after uniform ultrasonic dispersion, transferring the mixture into a high-pressure reaction kettle, filling nitrogen to remove oxygen, pressing chloroethylene into the kettle, wherein the mass ratio of the lauryl sodium sulfate to the cetyl alcohol to the sulfhydrylated diatomite to the ammonium ceric sulfate to the chloroethylene is 180:200:4:0.6:100, stirring the mixture for 20min at 30 ℃, carrying out polymerization reaction for 10h at 40 ℃ in a nitrogen atmosphere, and cooling the product to obtain the diatomite-grafted polyvinyl chloride composite emulsion;
(4) adding a dimethylacetamide solvent, a diatomite grafted polyvinyl chloride composite emulsion, a pore-forming agent polyethylene glycol and a defoaming agent into a three-necked bottle, wherein the mass ratio of the diatomite grafted polyvinyl chloride composite emulsion to the pore-forming agent polyethylene glycol to the defoaming agent polyoxypropylene ethylene oxide glycerol ether is 100:60:10, mechanically stirring for 40h at 30 ℃, transferring the mixture into a mold, and curing to obtain the diatomite modified polyvinyl chloride composite separation membrane with high thermal stability.
Comparative example 1
(1) Adding an ethyl acetate solvent, acid-treated diatomite, toluene-2, 4-diisocyanate and dibutyltin dilaurate into a three-necked bottle, wherein the mass ratio of the diatomite to the toluene-2, 4-diisocyanate to the dibutyltin dilaurate is 100:420:85, introducing nitrogen to remove oxygen, ultrasonically dispersing for 5min, transferring into an oil bath pot, refluxing at 15 ℃ in a nitrogen atmosphere for 1h, repeatedly washing a product with anhydrous toluene and deionized water, centrifuging after washing, and drying in a vacuum drying oven to obtain isocyanated diatomite;
(2) adding a tetrahydrofuran solvent, isocyanated diatomite and 1, 3-propanedithiol into a three-necked bottle, wherein the mass ratio of the isocyanated diatomite to the 1, 3-propanedithiol is 100:320, placing the mixture into an oil bath pot after uniform ultrasonic dispersion, stirring the mixture in a nitrogen atmosphere at 80 ℃ for click reaction for 0.5h, washing a product with absolute ethyl alcohol, centrifuging the product after washing, and placing the product in a vacuum drying oven for drying to obtain sulfhydrylated diatomite;
(3) adding a deionized water solvent, lauryl sodium sulfate and cetyl alcohol into a three-neck flask, adding sulfhydrylated diatomite and ammonium ceric sulfate after uniform ultrasonic dispersion, transferring the mixture into a high-pressure reaction kettle, filling nitrogen to remove oxygen, pressing chloroethylene into the kettle, wherein the mass ratio of the lauryl sodium sulfate to the cetyl alcohol to the sulfhydrylated diatomite to the ammonium ceric sulfate to the chloroethylene is 100:120:0.1:0.01:100, stirring the mixture for 10min at 15 ℃, carrying out polymerization reaction for 2h at 40 ℃ in a nitrogen atmosphere, and cooling the product to obtain the diatomite-grafted polyvinyl chloride composite emulsion;
(4) adding a dimethylacetamide solvent, a diatomite-grafted polyvinyl chloride composite emulsion, a pore-forming agent polyethylene glycol and a defoaming agent into a three-necked flask, wherein the mass ratio of the diatomite-grafted polyvinyl chloride composite emulsion to the pore-forming agent polyethylene glycol to the defoaming agent octylphenol polyoxyethylene ether is 100:33:3.5, mechanically stirring for 10 hours at 15 ℃, transferring the mixture into a mold, and curing to obtain the diatomite-modified polyvinyl chloride composite separation membrane with high thermal stability.
Comparative example 2
(1) Adding an ethyl acetate solvent, acid-treated diatomite, toluene-2, 4-diisocyanate and dibutyltin dilaurate into a three-necked bottle, wherein the mass ratio of the diatomite to the toluene-2, 4-diisocyanate to the dibutyltin dilaurate is 100:740:165, introducing nitrogen to remove oxygen, ultrasonically dispersing for 30min, transferring into an oil bath pot, refluxing at 35 ℃ in a nitrogen atmosphere for 10h, repeatedly washing a product with anhydrous toluene and deionized water, centrifuging after washing, and drying in a vacuum drying oven to obtain isocyanated diatomite;
(2) adding a tetrahydrofuran solvent, isocyanated diatomite and 1, 3-propanedithiol into a three-necked bottle, wherein the mass ratio of the isocyanated diatomite to the 1, 3-propanedithiol is 100:420, placing the mixture into an oil bath pot after uniform ultrasonic dispersion, stirring the mixture in a nitrogen atmosphere at 100 ℃ for click reaction for 5 hours, washing a product with absolute ethyl alcohol, centrifuging the product after washing, and placing the product into a vacuum drying oven for drying to obtain sulfhydrylated diatomite;
(3) adding a deionized water solvent, lauryl sodium sulfate and cetyl alcohol into a three-neck flask, adding sulfhydrylated diatomite and ammonium ceric sulfate after uniform ultrasonic dispersion, transferring the mixture into a high-pressure reaction kettle, filling nitrogen to remove oxygen, pressing chloroethylene into the kettle, wherein the mass ratio of the lauryl sodium sulfate to the cetyl alcohol to the sulfhydrylated diatomite to the ammonium ceric sulfate to the chloroethylene is 200:220:5.2:0.75:100, stirring the mixture for 60min at 30 ℃, carrying out polymerization reaction for 12h at 60 ℃ in a nitrogen atmosphere, and cooling the product to obtain the diatomite-grafted polyvinyl chloride composite emulsion;
(4) adding a dimethylacetamide solvent, a diatomite-grafted polyvinyl chloride composite emulsion, a pore-forming agent polyethylene glycol and a defoaming agent into a three-necked bottle, wherein the mass ratio of the diatomite-grafted polyvinyl chloride composite emulsion to the pore-forming agent polyethylene glycol to the defoaming agent polyether modified polysiloxane is 100:67:11.5, mechanically stirring for 50h at 30 ℃, transferring the mixture into a mold, and curing to obtain the diatomite-modified polyvinyl chloride composite separation membrane with high thermal stability.
The rupture strength and the elastic modulus of the diatomite-modified polyvinyl chloride composite separation membrane with high thermal stability are tested by using a KRT-W rupture strength tester.
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| Breaking Strength (MPa) | 44.5 | 58.7 | 52.1 | 40.8 | 31.6 | 28.5 |
| Modulus of elasticity (MPa) | 1457.6 | 1658.0 | 1521.4 | 1319.0 | 1239.2 | 1106.5 |
The initial decomposition temperature and the final decomposition temperature of the diatomite-modified polyvinyl chloride composite separation membrane with high thermal stability are tested by using a DTA-1150 differential scanning calorimeter.
Adding 60mg/L CuCl into diatomite modified polyvinyl chloride composite separation membrane with high thermal stability2Uniformly mixing the solution, adsorbing for 2h to reach adsorption balance, and testing Cu in the mixed solution by using a UV-7502PC ultraviolet-visible spectrophotometer2+And the adsorption rate was calculated.
Claims (9)
1. A diatomite modified polyvinyl chloride composite separation membrane with high thermal stability is characterized in that: the preparation method of the diatomite modified polyvinyl chloride composite separation membrane with high thermal stability comprises the following steps:
(1) adding acid-treated diatomite, toluene-2, 4-diisocyanate and dibutyltin dilaurate into an ethyl acetate solvent, introducing nitrogen to remove oxygen, ultrasonically dispersing for 10-20min, transferring into an oil bath pot, refluxing for reaction, repeatedly washing a product by using anhydrous toluene and deionized water, centrifuging after washing, and drying in a vacuum drying oven to obtain isocyanated diatomite;
(2) adding isocyanated diatomite and 1, 3-propanedithiol into a tetrahydrofuran solvent, placing the mixture into an oil bath kettle after uniform ultrasonic dispersion, stirring the mixture to carry out click reaction, washing a product with absolute ethyl alcohol, centrifuging the washed product after washing, and placing the washed product into a vacuum drying oven for drying to obtain sulfhydrylated diatomite;
(3) adding lauryl sodium sulfate and cetyl alcohol into a deionized water solvent, adding sulfhydrylation diatomite and ammonium ceric sulfate after uniform ultrasonic dispersion, transferring the mixture into a high-pressure reaction kettle, filling nitrogen to remove oxygen, pressing chloroethylene into the kettle, stirring the mixture for 20 to 40min at 15 to 30 ℃, carrying out polymerization reaction, and cooling the product to obtain the diatomite grafted polyvinyl chloride composite emulsion;
(4) adding the diatomite grafted polyvinyl chloride composite emulsion, the pore-forming agent polyethylene glycol and the defoaming agent into a dimethylacetamide solvent, mechanically stirring for 20-40h at 15-30 ℃, transferring into a mold, and curing to obtain the diatomite modified polyvinyl chloride composite separation membrane with high thermal stability.
2. The composite separation membrane of diatomite modified polyvinyl chloride with high thermal stability as claimed in claim 1, wherein: the mass ratio of the diatomite, the toluene-2, 4-diisocyanate and the dibutyltin dilaurate in the step (1) is 100:460-700: 100-150.
3. The composite separation membrane of diatomite modified polyvinyl chloride with high thermal stability as claimed in claim 1, wherein: the reaction temperature in the step (1) is 15-35 ℃, and the reaction is carried out for 2-8h under reflux in a nitrogen atmosphere.
4. The composite separation membrane of diatomite modified polyvinyl chloride with high thermal stability as claimed in claim 1, wherein: the mass ratio of the isocyanated diatomite to the 1, 3-propanedithiol in the step (2) is 100: 340-400.
5. The composite separation membrane of diatomite modified polyvinyl chloride with high thermal stability as claimed in claim 1, wherein: the temperature of the click reaction in the step (2) is 80-100 ℃, and the click reaction is carried out for 1-3h under the stirring of nitrogen atmosphere.
6. The composite separation membrane of diatomite modified polyvinyl chloride with high thermal stability as claimed in claim 1, wherein: in the step (3), the mass ratio of the sodium dodecyl sulfate, the hexadecanol, the sulfhydrylation diatomite, the cerium ammonium sulfate and the chloroethylene is 120-180:140-200:0.5-4:0.1-0.6: 100.
7. The composite separation membrane of diatomite modified polyvinyl chloride with high thermal stability as claimed in claim 1, wherein: the temperature of the polymerization reaction in the step (3) is 40-60 ℃, and the polymerization reaction is carried out for 4-10h in the nitrogen atmosphere.
8. The composite separation membrane of diatomite modified polyvinyl chloride with high thermal stability as claimed in claim 1, wherein: in the step (4), the mass ratio of the diatomite grafted polyvinyl chloride composite emulsion to the pore-foaming agent polyethylene glycol to the defoaming agent is 100:40-60: 5-10.
9. The composite separation membrane of diatomite modified polyvinyl chloride with high thermal stability as claimed in claim 1, wherein: the defoaming agent in the step (4) can be any one of octyl phenol polyoxyethylene ether, polyether modified polysiloxane and polyoxypropylene ethylene oxide glycerol ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110091294.3A CN112827367B (en) | 2021-01-22 | 2021-01-22 | Diatomite modified polyvinyl chloride composite separation membrane with high thermal stability and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110091294.3A CN112827367B (en) | 2021-01-22 | 2021-01-22 | Diatomite modified polyvinyl chloride composite separation membrane with high thermal stability and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112827367A true CN112827367A (en) | 2021-05-25 |
| CN112827367B CN112827367B (en) | 2023-06-23 |
Family
ID=75931150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110091294.3A Active CN112827367B (en) | 2021-01-22 | 2021-01-22 | Diatomite modified polyvinyl chloride composite separation membrane with high thermal stability and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112827367B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115651418A (en) * | 2022-11-09 | 2023-01-31 | 深圳新红进科技有限公司 | Road asphalt anti-aging agent and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102172480A (en) * | 2011-03-15 | 2011-09-07 | 东华大学 | Polyvinyl chloride/diatomite composite membrane and preparation method and application thereof |
| CN102443120A (en) * | 2011-08-15 | 2012-05-09 | 中北大学 | Method for realizing efficient graft polymerization of acrylonitrile on surface of silica gel microparticles by utilizing mercapto-Ce(IV) salt redox initiation system |
| CN103752184A (en) * | 2014-01-23 | 2014-04-30 | 成都新柯力化工科技有限公司 | Inorganic-organic composite ultrafiltration membrane and preparation method thereof |
| CN106310967A (en) * | 2016-08-23 | 2017-01-11 | 北京碧水源膜科技有限公司 | Method for preparing hydrophilic nanohybrid enhancement type hollow fiber membrane |
| CN108409899A (en) * | 2018-02-06 | 2018-08-17 | 常州大学 | A kind of cerium salt causes the preparation method of attapulgite/polyacrylic complex thickener |
| CN108409970A (en) * | 2017-02-10 | 2018-08-17 | 中国科学院大连化学物理研究所 | The method that one kettle way quickly prepares organic-inorganic hybrid integral material |
| CN111548476A (en) * | 2020-06-12 | 2020-08-18 | 广东裕泰实业有限公司 | Flame-retardant environment-friendly polyurethane material and preparation method thereof |
-
2021
- 2021-01-22 CN CN202110091294.3A patent/CN112827367B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102172480A (en) * | 2011-03-15 | 2011-09-07 | 东华大学 | Polyvinyl chloride/diatomite composite membrane and preparation method and application thereof |
| CN102443120A (en) * | 2011-08-15 | 2012-05-09 | 中北大学 | Method for realizing efficient graft polymerization of acrylonitrile on surface of silica gel microparticles by utilizing mercapto-Ce(IV) salt redox initiation system |
| CN103752184A (en) * | 2014-01-23 | 2014-04-30 | 成都新柯力化工科技有限公司 | Inorganic-organic composite ultrafiltration membrane and preparation method thereof |
| CN106310967A (en) * | 2016-08-23 | 2017-01-11 | 北京碧水源膜科技有限公司 | Method for preparing hydrophilic nanohybrid enhancement type hollow fiber membrane |
| CN108409970A (en) * | 2017-02-10 | 2018-08-17 | 中国科学院大连化学物理研究所 | The method that one kettle way quickly prepares organic-inorganic hybrid integral material |
| CN108409899A (en) * | 2018-02-06 | 2018-08-17 | 常州大学 | A kind of cerium salt causes the preparation method of attapulgite/polyacrylic complex thickener |
| CN111548476A (en) * | 2020-06-12 | 2020-08-18 | 广东裕泰实业有限公司 | Flame-retardant environment-friendly polyurethane material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115651418A (en) * | 2022-11-09 | 2023-01-31 | 深圳新红进科技有限公司 | Road asphalt anti-aging agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112827367B (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104389176B (en) | Emulsion type carbon fiber sizing agent containing graphene oxide and preparation method thereof | |
| WO2021043123A1 (en) | Microcapsule with multiple times of self-repairing at room temperature, preparation method, and application | |
| CN110885664A (en) | Light-moisture curing adhesive with high-efficiency water-vapor barrier property and ultralow water absorption rate | |
| CN112662203A (en) | Modified silicon dioxide filler, preparation method thereof and resin composition | |
| CN112827367A (en) | Diatomite modified polyvinyl chloride composite separation membrane with high thermal stability and preparation method thereof | |
| CN110527300A (en) | A kind of high-strength epoxy with inierpeneirating network structure-silicon rubber modified material | |
| CN111073429B (en) | Self-layering polymer cement photocatalytic coating and preparation method and application thereof | |
| CN113234187A (en) | Preparation method of nano-silica hybrid modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier material | |
| CN106496450B (en) | A kind of stress response type polymethyl methacrylate modified silicon boron polymer microgel and preparation method thereof | |
| CN111825860B (en) | Graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere and preparation method thereof | |
| CN114031767A (en) | Cyclic carbonate prepolymer, silane modified non-isocyanate polyurethane resin, and preparation methods and applications thereof | |
| CN113004779A (en) | Polyurea coating for seepage prevention of storage power station warehouse basin and preparation method thereof | |
| CN112375182A (en) | Hydroxyl-terminated polybutadiene type waterborne polyurethane/acrylate material and preparation method and application thereof | |
| CN111925759A (en) | Solvent-free adhesive and preparation method and application thereof | |
| CN109608889B (en) | POSS (polyhedral oligomeric silsesquioxane) modified high-toughness solid buoyancy material and preparation method thereof | |
| CN116855209A (en) | Flame-retardant UV-cured polymer adhesive | |
| CN113528080B (en) | High-displacement anti-pollution silicone sealant and preparation method thereof | |
| CN112745476B (en) | Graphene modified polyurethane resin material with high thermal stability and preparation method thereof | |
| CN114940875A (en) | Waterproof roll filled with modified vitrified micro bubbles | |
| CN104877340B (en) | A kind of modified heat convertible resin and preparation method thereof | |
| CN115353840B (en) | Water-based adhesive for cast-in-situ runway and preparation method thereof | |
| CN112844257A (en) | Preparation method and application of functionalized graphene oxide-cyclodextrin composite hydrogel | |
| CN115260962B (en) | Epoxy resin adhesive fast in room temperature curing and preparation method thereof | |
| CN1312302A (en) | Continuous prepn of polyether polyol | |
| CN110564098A (en) | nano lignocellulose/graphite-like phase carbon nitride composite material, woodware coating, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |