CN104861847A - Organic and inorganic composite water-based coating material and preparation method thereof - Google Patents
Organic and inorganic composite water-based coating material and preparation method thereof Download PDFInfo
- Publication number
- CN104861847A CN104861847A CN201510260651.9A CN201510260651A CN104861847A CN 104861847 A CN104861847 A CN 104861847A CN 201510260651 A CN201510260651 A CN 201510260651A CN 104861847 A CN104861847 A CN 104861847A
- Authority
- CN
- China
- Prior art keywords
- coating material
- cellulose
- based coating
- water
- organo
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Abstract
The invention relates to an organic and inorganic composite water-based coating material and a preparation method thereof. The coating material comprises materials in percentage by mass as follows: 10%-60% of an inorganic nanoparticle water-based dispersion liquid, 2%-30% of a cellulose hydrogel dispersion liquid, 0.2%-4% of a surfactant and the balance of deionized water. The prepared cellulose hydrogel has good thermal stability and has a better adhesion effect at a low solid content state, and the viscosity can be up to 10 cp or higher when the solid content is lower than 10%; the water-based coating obtained through composition of cellulose base hydrogel and inorganic nanoparticles can be firmly adhered to a substrate, namely a polyolefin thin film, large-scale production of diaphragms is facilitated, and the thermal stability, the mechanical property, the wettability and other performance of the diaphragms are improved; the prepared cellulose hydrogel replaces a traditional organic solvent system and has the advantages of safety and environment protection. The organic and inorganic composite water-based coating material and the preparation method have great significance in improvement of the safety performance, the mechanical performance, the electrochemical performance and the like of lithium-ion battery diaphragms.
Description
Technical field
The present invention relates to a kind of organo-mineral complexing water-based coating material and preparation method thereof.
Background technology
Being widely used of microporous membrane, have can as lithium ion battery separator under the condition such as certain porosity, good mechanical properties.Barrier film is its important composition parts, the effect played isolation positive and negative electrode, allow lithium ion to pass through, most important to the security of lithium ion battery.
The diaphragm material major part of lithium ion battery has polyolefins now, and as polyethylene, polypropylene or both matrix materials etc., they have good void distribution, mechanical property, chemical resistance.But there is the shortcoming such as poor heat stability, electrolytic solution wettability difference in polyolefine material, in order to improve safety performance and the chemical property of lithium ion battery further, needs the thermostability of raising barrier film further, mechanical property and lyophily.
The present invention prepares a kind of novel cellulose based aquagel dispersion system, and this and inorganic nanoparticles compound are prepared a kind of water-based coating material of organo-mineral complexing, after the water-based coating material modified micropore film of this organo-mineral complexing, enhance thermal stability and the mechanical property of substrate microporous membrane, have significant raising to the security of lithium ion battery.
The present invention compared with prior art, has following outstanding substantive distinguishing features and marked improvement: first, cellulose base hydrogel prepared by the present invention has Heat stability is good, has good bond effect under low-solid content; Secondly, because cellulose base hydrogel has good water retention, this is conducive to improving barrier film to the maintenance effect of electrolytic solution; 3rd, increase substantially thermostability and the physical strength of substrate microporous membrane; 4th, bond firmly with the aqueous coating after this cellulose base hydrogel dispersion system and inorganic nanoparticles compound and substrate film, be conducive to barrier film large-scale production, and improve the thermostability of barrier film, mechanical property, wettability and ionic conductivity; Finally, the gel of preparation is aqueous phase system, instead of the organic solvent systems such as PVDF or PVDF-HFP of traditional modified diaphragm use, has the feature of safety, green, environmental protection.The present invention is significant to aspects such as raising lithium ion battery separator battery safety, chemical property and work-ing lifes.
Summary of the invention
One of the object of the invention is to provide a kind of organo-mineral complexing water-based coating material, this coating material uses a kind of hydrogel dispersion system of cellulose base, this gel dispersion system instead of traditional organic phase system, there is the feature of low-solid content height bond effect, make the production more environmental protection of battery.
Two of object of the present invention is the preparation method providing this coating material.
For achieving the above object, the present invention is synthetic cellulose based aquagel first, then by cellulose base hydrogel and inorganic nanoparticles compound, synthetic cellulose based aquagel, first first Mierocrystalline cellulose is dissolved in acetone, butanone, the one or more kinds of mixtures of 2-butanone, wherein cellulosic is Nitrocellulose, single cellulose acetate, one in Cellulose diacetate or cellulosetri-acetate, molecular weight cellulose is 5000-50000, in Mierocrystalline cellulose, hydroxyl accounts for mass percent is 3%-10%, ethanoyl mass percentage 75-82%, the mol ratio of Mierocrystalline cellulose and organic many isocyanide esters is 1-5, Mierocrystalline cellulose and prepolymer temperature of reaction are 65-85 DEG C, reaction times is 1-2.5 hour,
Above-mentioned Mierocrystalline cellulose organic solution and isocyanide ester functional prepolymer are carried out graft reaction, wherein the mol ratio of Mierocrystalline cellulose and organic many isocyanide esters is 1-5, temperature of reaction is 65-85 DEG C, reaction times is 1-2.5 hour, catalysts is dibutyltin dilaurate, the one in dibutyl tin dilaurate; Add triethylamine or quadrol neutralizes after reaction terminates, degree of neutralization is 0.8-1.0; Then add deionized water emulsification, underpressure distillation steams organic solvent and forms cellulose aqueous gel aqueous dispersion liquid.
One of the present invention is used for organo-mineral complexing water-based coating material, it is characterized in that the composition of this coating material and mass percentage are:
Inorganic nano-particle aqueous liquid dispersion 10 ~ 60%
Cellulose aquagel dispersion liquid 2 ~ 30%
Tensio-active agent 0.2 ~ 4%
Deionized water surplus;
Described cellulose aquagel dispersion liquid is the three-dimensional reticular fiber hydrogel dispersion system that Mierocrystalline cellulose organic solution and isocyanide ester functional prepolymer carry out graft polymerization reaction in aqueous and formed, the percentage of grafting of the polymkeric substance formed is 10 ~ 50%, and its solid content is: 2 ~ 10%; Described isocyanide ester functional prepolymer is the isocyanide ester functional prepolymer obtained through prepolymerization by hydrophilic chain extender and organic many isocyanide esters.
Above-mentioned cellulose aquagel average particle size particle size is at 50 ~ 800nm.
Above-mentioned Mierocrystalline cellulose is Nitrocellulose, single cellulose acetate, Cellulose diacetate or cellulosetri-acetate; Mierocrystalline cellulose weight average relative molecular weight is 5000 ~ 50000; in Mierocrystalline cellulose, hydroxyl accounts for mass percent is 3% ~ 10%, ethanoyl mass percentage 75 ~ 82%.
Above-mentioned organic many isocyanide esters are: the one in isophorone diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, diphenylmethanediisocyanate and hexamethylene diisocyanate.
The solid content of above-mentioned inorganic nano-particle aqueous liquid dispersion is 10 ~ 60%, inorganic nano-particle is wherein: at least one in silicon dioxide granule, aluminium sesquioxide particle, TiO 2 particles, zirconium dioxide particle, Ti-Si zeolite, Si-Al molecular sieve, and particle diameter is 50 ~ 100nm.
Above-mentioned tensio-active agent is at least one in polyvinylpyrrolidone PVP, polyoxyethylene glycol, polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer P123, polyethers F127, polysorbate, sodium laurylsulfate.
Above-mentioned hydrophilic chain extender is dimethylol propionic acid, diaminobenzoic acid, BDO-2-sodium sulfonate or polyoxyethylene glycol.
Prepare a method for above-mentioned organo-mineral complexing water-based coating material, it is characterized in that the concrete steps of the method are:
A. organic many isocyanide esters class and hydrophilic chain extender are pressed 1:(0.2 ~ 0.8) mixed in molar ratio after, at 45 ~ 65 DEG C of temperature, carry out prepolymerization, the pre-polymerization time is 0.5 ~ 1.5 hour, obtains isocyanide ester functional prepolymer;
B. cellulosic acetone or butanone solution and step a gained isocyanide ester functional prepolymer are carried out graft reaction, wherein the mol ratio of Mierocrystalline cellulose and isocyanide ester functional prepolymer is 1:(1 ~ 5), temperature of reaction is 65 ~ 85 DEG C, reaction times is 1 ~ 2.5 hour, and catalysts is dibutyltin dilaurate or dibutyl tin dilaurate; Triethylamine is added or quadrol neutralizes after reaction terminates, degree of neutralization (degree of neutralization refers to the degree that neutralization reaction is carried out. neutralization reaction is carboxyl and amino neutralization here, and degree of neutralization 0.8 refers to the carboxyl that amino reacts away 80% .) be 0.8-1.0; Then add deionized water emulsification, underpressure distillation steams organic solvent and forms cellulose aquagel dispersion liquid;
C. inorganic nano-particle dispersion is mixed with inorganic nano-particle aqueous liquid dispersion in deionized water;
D. step c gained inorganic nano-particle aqueous liquid dispersion, rapid b gained cellulose aquagel dispersion liquid, tensio-active agent, deionized water are mixed and form organo-mineral complexing water-based coating material.
Dip coating, rolling method, spraying method or casting method is adopted organo-mineral complexing water-based coating material of the present invention to be coated on the one or both sides of microporous membrane, then at 40-70 DEG C, dry 1-10min, obtain coating modified microporous membrane, its one-sided coatings thickness is 1-4 μm; Microporous membrane used is cellulosefilm, non-woven fabrics, polyethylene porous film, polypropylene porous membrane, polypropylene, polyethylene/polypropylene composite materials porous membrane.
The present invention compared with prior art, has following outstanding substantive distinguishing features and marked improvement:
1, the cellulose base hydrogel that prepared by the present invention has Heat stability is good, has better bond effect under low-solid content, and solid content can reach more than 10cp being less than 10% time its viscosity;
2, bond firmly with the aqueous coating after above-mentioned cellulose base hydrogel and inorganic nanoparticles compound and substrate polyolefin film, be conducive to barrier film large-scale production, and improve the performance such as thermostability, mechanical property, wettability of barrier film;
3, the cellulose base hydrogel of preparation is aqueous phase system, instead of traditional organic solvent system, has the feature of safety, green, environmental protection.The present invention is significant to aspects such as raising lithium ion battery separator battery safety, mechanical property and chemical properties.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
The medicine of cellulose base hydrogel dispersion system is prepared as organic many isocyanide esters, hydrophilic chain extender wherein, Nitrocellulose, single cellulose acetate, Cellulose diacetate or cellulosetri-acetate are adopted to such as Aladdin, Sigma, lark Wei Deng Reagent Company.
Wherein said tensio-active agent is polyvinylpyrrolidone PVP, at least one in polyoxyethylene glycol, polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer P123, polyethers F127, polysorbate, sodium laurylsulfate is adopted to such as Aladdin, Sigma, lark prestige etc. Reagent Company.
Wherein involved inorganic nanoparticles aqueous liquid dispersion such as titanium dioxide TiO2, silicon-dioxide SiO2, aluminium sesquioxide Al2O3, zirconium dioxide ZrO2 colloidal sol all adopt commercial prod.As the ZrO2 dispersion liquid of ashland Nyacol Nanotec Solution of the U.S., the SiO2 dispersion liquid of Shanghai Chemical Co., Ltd. of Hang Seng, the Al2O3 dispersion liquid of this promise New Chemical Material science and technology company limited of Dalian, the TiO of Wuhan Hong Xinkang Fine Chemical Co., Ltd
2dispersion liquid.
Wherein involved Ti-Si zeolite is according to document Preparation of Colloidal Suspensions of Discrete TS-1 Crystal. Chemistry of materials, and 1997,9 (1): 210-217. obtain.
Wherein involved Si-Al molecular sieve is according to document Comparing synthesis routes to nano-crystalline zeolite ZSM-5. Microporous and mesoporous materials, 2003,57 (1): 83-92. obtain.
Set forth with water-based organo-mineral complexing coating example 1-5 respectively by the preparation of cellulose base hydrogel dispersion system below:
Embodiment 1
The cellulose base hydrogel dispersion system of the modification lithium-ion battery barrier film of the present embodiment, comprise following raw material: isophorone diisocyanate 5g, dimethylol propionic acid 1.21g, Nitrocellulose 2g is dissolved in 65g acetone, dibutyl tin dilaurate catalyzer 0.02g, deionized water 60g, diethylamino 0.8g
The specific solution of the modification lithium-ion battery barrier film cellulose base hydrogel dispersion system of this example comprises following step:
1) getting 5g isophorone diisocyanate as having dissolved in the solution of 1.21g dimethylol propionic acid, being warmed up to 45 DEG C, being uniformly mixed, prepolymerization time is 30 minutes, and prepolymerization temperature is 45 DEG C,
2) then 2g Nitrocellulose is dissolved in the acetone soln of 65g, adds dibutyl tin dilaurate 0.02g and mix, then the mixing solutions of Mierocrystalline cellulose and catalyzer is added in prepolymer react 1.5 hours,
3) after question response completes, cool to room temperature, first adding diethylamino quality is that 0.8g fully mixes, then adds deionized water quality 60g and carry out emulsification, and underpressure distillation obtains hydrogel dispersion system C1,
The microporous membrane of modification in the present embodiment is prepared with following material:
The cellulose aquagel dispersion system C1 15% of above-mentioned preparation
Water-based silicon oxide dispersion liquid 50%
Tensio-active agent is PVP 0.2%
Deionized water 34.8%
Substrate film is polyethylene film,
Coating method is dip-coating method, preparation process is as follows: cellulose aquagel dispersion system C1 deionized water is diluted to solid content 3.75%, substrate film to be immersed in above four kinds of different aqueous gel dispersion liquids 2 minutes, to obtain laminated film, put into 70 DEG C of oven dryings 10 minutes.Record film longitudinal phase tensile strength 120.3MPa and add more than 14% than the 100MPa of original substrate PE film, be about 5% 150 DEG C of lower diaphragm plate shrinking percentages, and pure PE film is 94%.
Embodiment 2
The cellulose base hydrogel dispersion system of the present embodiment, comprises the raw material of following weight: tolylene diisocyanate 5g, diaminobenzoic acid 2.41g, single cellulose acetate 2g is dissolved in 70g acetone, dibutyl tin dilaurate catalyzer 0.02g, deionized water 60g, diethylamino 0.8g
The specific solution of the modification lithium-ion battery barrier film cellulose base hydrogel dispersion system of this example comprises following step:
1) getting 5g tolylene diisocyanate as having dissolved in the solution of 2.41g diaminobenzoic acid, being warmed up to 45 DEG C, being uniformly mixed, prepolymerization time is 30 minutes, and prepolymerization temperature is 45 DEG C,
2) the mono-cellulose acetate dissolves of 2g is in the acetone soln of 70g, adds dibutyl tin dilaurate 0.02g and mixes, then is added in prepolymer by the mixing solutions of Mierocrystalline cellulose and catalyzer and react 1.5 hours,
3) after question response completes, cool to room temperature, first add diethylamino 0.8g and fully mix, then add deionized water quality 60g and carry out emulsification, underpressure distillation obtains hydrogel dispersion system C2
The microporous membrane of this example modification is prepared with following material:
The cellulose aquagel dispersion system C2 10% of above-mentioned preparation
Aluminum oxide nanoparticles aqueous liquid dispersion 50%
Tensio-active agent is P123 0.5%
Deionized water 39.5%
Substrate film is PET film,
Coating method is dip-coating method, preparation process is as follows: first by cellulose aquagel dispersion system C2 and aluminum oxide nanoparticles aqueous liquid dispersion and deionized water mix and blend 1 hour, after being uniformly dispersed, substrate film to be immersed in coating fluid 2 minutes, then lift obtains laminated film, puts into 70 DEG C of oven dryings 10 minutes.Record film longitudinal phase tensile strength 210.3MPa, substantially do not shrink at 150 DEG C of lower diaphragm plates.
Embodiment 3
The cellulose base hydrogel dispersion system of the present embodiment, comprise the raw material of following weight: diphenylmethanediisocyanate 5g, 1,4-butyleneglycol-2-sodium sulfonate 1.53g, Cellulose diacetate 2g is dissolved in 70g butanone, dibutyl tin dilaurate catalyzer 0.02g, deionized water 60g, diethylamino 0.8g
The specific solution of the modification lithium-ion battery barrier film cellulose base hydrogel dispersion system of this example comprises following step:
1) getting 5g diphenylmethanediisocyanate as having dissolved in the solution of 1.53g1,4-butyleneglycol-2-sodium sulfonate, being warmed up to 45 DEG C, being uniformly mixed, after mixing, 45 DEG C of prepolymerizations 30 minutes,
2) 2g Cellulose diacetate is dissolved in the butanone solution of 70g, adds dibutyl tin dilaurate 0.02g and mixes, then is added in prepolymer by the mixing solutions of Mierocrystalline cellulose and catalyzer and react 1.5 hours
3) after question response completes, cool to room temperature, first adding diethylamino quality is that 0.8g fully mixes, then adds deionized water quality 60g and carry out emulsification, and underpressure distillation obtains hydrogel dispersion system C3
The microporous membrane of modification in the present embodiment is prepared with following material:
The cellulose aquagel dispersion system C3 10% of above-mentioned preparation
Titania nanoparticles aqueous liquid dispersion 50%
Tensio-active agent is polyoxyethylene glycol 4%
Deionized water 36%
Substrate film is non-woven fabrics,
Coating method is dip-coating method, preparation process is as follows: first by cellulose aquagel dispersion system C3 and titania nanoparticles aqueous liquid dispersion and deionized water mix and blend 1 hour, after being uniformly dispersed, substrate film to be immersed in coating fluid 2 minutes, then lift obtains laminated film, puts into 70 DEG C of oven dryings 5 minutes.Record film substantially not shrink at 150 DEG C of lower diaphragm plates.
Embodiment 4
The cellulose base hydrogel dispersion system of the present embodiment, comprises the raw material of following weight: cyclohexyl isocyanate 5g, polyoxyethylene glycol 1.21g, cellulosetri-acetate 2g is dissolved in 70g butanone, dibutyl tin cinnamic acid alkene catalyzer 0.02g, deionized water 50g, diethylamino 0.8g
The specific solution of the modification lithium-ion battery barrier film cellulose base hydrogel dispersion system of this example comprises following step:
1) getting 5g cyclohexyl isocyanate as having dissolved in the solution of 1.21g polyoxyethylene glycol, being warmed up to 55 DEG C, being uniformly mixed, prepolymerization 45 minutes under 55 DEG C of conditions,
2) 2g cellulosetri-acetate is dissolved in the butanone solution of 70g, adds dibutyl tin cinnamic acid 0.02g and mixes, then is added in prepolymer by the mixing solutions of Mierocrystalline cellulose and catalyzer and react 2 hours,
3) after question response completes, cool to room temperature, first adding diethylamino quality is that 0.8g fully mixes, then adds deionized water quality 50g and carry out emulsification, and underpressure distillation obtains dispersion system C4
The microporous membrane of modification in the present embodiment is prepared with following material:
The cellulose aquagel dispersion system C4 30% of above-mentioned preparation
Titania nanoparticles aqueous liquid dispersion 10%
Tensio-active agent is polyethers F127 5%
Deionized water 55%
Substrate film is polypropylene,
Coating method is dip-coating method, preparation process is as follows: first by cellulose aquagel dispersion system C4 with titania nanoparticles aqueous liquid dispersion and deionized water mix and blend 1 hour, adopt lift coating method to be coated on polypropylene diaphragm both sides after being uniformly dispersed, then put into 70 DEG C of oven dryings 5 minutes.Recording film longitudinal phase tensile strength 157.3MPa to increase obviously than original base polypropylene film, be 16.5%, and pure PP film is 85% 150 DEG C of lower diaphragm plate shrinking percentages.
Embodiment 5
The cellulose base hydrogel dispersion system of the present embodiment, comprises the raw material of following weight: hexamethylene diisocyanate 5g, dimethylol propionic acid 2.41g, Nitrocellulose 2g is dissolved in 70g acetone, dibutyl tin dilaurate catalyzer 0.02g, deionized water 60g, diethylamino 0.8g
The specific solution of the modification lithium-ion battery barrier film cellulose base hydrogel dispersion system of this example comprises following step:
1) getting 5g hexamethylene diisocyanate as having dissolved in the solution of 2.41g dimethylol propionic acid, being warmed up to 45 DEG C, being uniformly mixed, prepolymerization time is 30 minutes, and prepolymerization temperature is 45 DEG C,
2) 2g Nitrocellulose is dissolved in the acetone soln of 70g, adds dibutyl tin dilaurate 0.02g and mixes, then is added in prepolymer by the mixing solutions of Mierocrystalline cellulose and catalyzer and react 1.5 hours,
3) after question response completes, cool to room temperature, first add diethylamino 0.8g and fully mix, then add deionized water quality 60g and carry out emulsification, underpressure distillation obtains hydrogel dispersion system C5
The microporous membrane of modification in the present embodiment is prepared with following material:
The cellulose aquagel dispersion system C5 12.7% of above-mentioned preparation
Zirconium dioxide nanoparticles aqueous liquid dispersion 60%
Tensio-active agent is polysorbate 0.3%
Deionized water 17%
Substrate polyethylene polypropylene polyethylene multilayer film,
Coating method is dip-coating method, preparation process is as follows: first by cellulose aquagel dispersion system C1, C2, C3, one in C4 and zirconium dioxide nanoparticles aqueous liquid dispersion and deionized water mix and blend 1 hour, adopt the coating of lift coating method in barrier film both sides, then put into 70 DEG C of oven dryings 5 minutes.Record film substantially not shrink at 150 DEG C of lower diaphragm plates.
Claims (8)
1., for an organo-mineral complexing water-based coating material, it is characterized in that the composition of this coating material and mass percentage are:
Inorganic nano-particle aqueous liquid dispersion 10 ~ 60%
Cellulose aquagel dispersion liquid 2 ~ 30%
Tensio-active agent 0.2 ~ 4%
Deionized water surplus;
Described cellulose aquagel dispersion liquid is the three-dimensional reticular fiber hydrogel dispersion system that Mierocrystalline cellulose organic solution and isocyanide ester functional prepolymer carry out graft polymerization reaction in aqueous and formed, the percentage of grafting of the polymkeric substance formed is 10 ~ 50%, and its solid content is: 2 ~ 10%; Described isocyanide ester functional prepolymer is the isocyanide ester functional prepolymer obtained through prepolymerization by hydrophilic chain extender and organic many isocyanide esters.
2. organo-mineral complexing water-based coating material according to claim 1, is characterized in that cellulose aquagel average particle size particle size is at 50 ~ 800nm.
3. organo-mineral complexing water-based coating material according to claim 1; it is characterized in that described Mierocrystalline cellulose is Nitrocellulose, single cellulose acetate, Cellulose diacetate or cellulosetri-acetate; Mierocrystalline cellulose weight average relative molecular weight is 5000 ~ 50000; in Mierocrystalline cellulose, hydroxyl accounts for mass percent is 3% ~ 10%, ethanoyl mass percentage 75 ~ 82%.
4. organo-mineral complexing water-based coating material according to claim 1, is characterized in that described organic many isocyanide esters are: the one in isophorone diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, diphenylmethanediisocyanate and hexamethylene diisocyanate.
5. organo-mineral complexing water-based coating material according to claim 1, it is characterized in that the solid content of inorganic nano-particle aqueous liquid dispersion is 10 ~ 60%, inorganic nano-particle is wherein: at least one in silicon dioxide granule, aluminium sesquioxide particle, TiO 2 particles, zirconium dioxide particle, Ti-Si zeolite, Si-Al molecular sieve, and particle diameter is 50 ~ 100nm.
6. organo-mineral complexing water-based coating material according to claim 1, is characterized in that tensio-active agent is at least one in polyvinylpyrrolidone PVP, polyoxyethylene glycol, polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer P123, polyethers F127, polysorbate, sodium laurylsulfate.
7. organo-mineral complexing water-based coating material according to claim 1, is characterized in that hydrophilic chain extender is dimethylol propionic acid, diaminobenzoic acid, BDO-2-sodium sulfonate or polyoxyethylene glycol.
8. prepare a method for the organo-mineral complexing water-based coating material according to any one of claim 1 ~ 7, it is characterized in that the concrete steps of the method are:
A. organic many isocyanide esters class and hydrophilic chain extender are pressed 1:(0.2 ~ 0.8) mixed in molar ratio after, at 45 ~ 65 DEG C of temperature, carry out prepolymerization, the pre-polymerization time is 0.5 ~ 1.5 hour, obtains isocyanide ester functional prepolymer;
B. cellulosic acetone or butanone solution and step a gained isocyanide ester functional prepolymer are carried out graft reaction, wherein the mol ratio of Mierocrystalline cellulose and isocyanide ester functional prepolymer is 1:(1 ~ 5), temperature of reaction is 65 ~ 85 DEG C, reaction times is 1 ~ 2.5 hour, and catalysts is dibutyltin dilaurate or dibutyl tin dilaurate; Triethylamine is added or quadrol neutralizes after reaction terminates, degree of neutralization (degree of neutralization refers to the degree that neutralization reaction is carried out. neutralization reaction is carboxyl and amino neutralization here, and degree of neutralization 0.8 refers to the carboxyl that amino reacts away 80% .) be 0.8-1.0; Then add deionized water emulsification, underpressure distillation steams organic solvent and forms cellulose aquagel dispersion liquid;
C. inorganic nano-particle dispersion is mixed with inorganic nano-particle aqueous liquid dispersion in deionized water;
D. step c gained inorganic nano-particle aqueous liquid dispersion, rapid b gained cellulose aquagel dispersion liquid, tensio-active agent, deionized water are mixed and form organo-mineral complexing water-based coating material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510260651.9A CN104861847B (en) | 2015-05-21 | 2015-05-21 | Aqueous coating material of organo-mineral complexing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510260651.9A CN104861847B (en) | 2015-05-21 | 2015-05-21 | Aqueous coating material of organo-mineral complexing and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104861847A true CN104861847A (en) | 2015-08-26 |
| CN104861847B CN104861847B (en) | 2017-08-11 |
Family
ID=53908050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510260651.9A Active CN104861847B (en) | 2015-05-21 | 2015-05-21 | Aqueous coating material of organo-mineral complexing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104861847B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017113000A1 (en) * | 2015-12-29 | 2017-07-06 | Companhia Nitro Química Brasileira | Method for obtaining a colloidal dispersion, colloidal dispersion and use thereof |
| CN108630462A (en) * | 2018-05-22 | 2018-10-09 | 中南林业科技大学 | Nanofiber-based integrated film ultracapacitor of one kind and preparation method thereof |
| CN110423328A (en) * | 2019-08-16 | 2019-11-08 | 陕西科技大学 | A kind of carboxylic acid sulfonate type aqueous acetic acid fibre emulsion and preparation method thereof |
| CN110797494A (en) * | 2019-11-08 | 2020-02-14 | 华南理工大学 | Diaphragm functional coating material for lithium ion battery and preparation method thereof |
| CN115011053A (en) * | 2022-06-21 | 2022-09-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | High-reflection fractal structure hydrogel, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101405314A (en) * | 2006-03-17 | 2009-04-08 | 拜尔材料科学股份公司 | Aqueous dispersions based on nitrocellulose-polyurethane particles |
-
2015
- 2015-05-21 CN CN201510260651.9A patent/CN104861847B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101405314A (en) * | 2006-03-17 | 2009-04-08 | 拜尔材料科学股份公司 | Aqueous dispersions based on nitrocellulose-polyurethane particles |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017113000A1 (en) * | 2015-12-29 | 2017-07-06 | Companhia Nitro Química Brasileira | Method for obtaining a colloidal dispersion, colloidal dispersion and use thereof |
| US10934398B2 (en) | 2015-12-29 | 2021-03-02 | Companhia Nitro Quimica Brasileira | Method for obtaining a colloidal dispersion, colloidal dispersion and use thereof |
| CN108630462A (en) * | 2018-05-22 | 2018-10-09 | 中南林业科技大学 | Nanofiber-based integrated film ultracapacitor of one kind and preparation method thereof |
| CN108630462B (en) * | 2018-05-22 | 2020-05-22 | 中南林业科技大学 | Nanofiber-based integrated thin film supercapacitor and preparation method thereof |
| CN110423328A (en) * | 2019-08-16 | 2019-11-08 | 陕西科技大学 | A kind of carboxylic acid sulfonate type aqueous acetic acid fibre emulsion and preparation method thereof |
| CN110797494A (en) * | 2019-11-08 | 2020-02-14 | 华南理工大学 | Diaphragm functional coating material for lithium ion battery and preparation method thereof |
| WO2021089016A1 (en) * | 2019-11-08 | 2021-05-14 | 华南理工大学 | Functional coating material for lithium ion battery separator and preparation method therefor |
| CN115011053A (en) * | 2022-06-21 | 2022-09-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | High-reflection fractal structure hydrogel, and preparation method and application thereof |
| CN115011053B (en) * | 2022-06-21 | 2023-08-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | High-reflection fractal structure hydrogel, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104861847B (en) | 2017-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104861847A (en) | Organic and inorganic composite water-based coating material and preparation method thereof | |
| CN104521028B (en) | For the improved diaphragm and correlation technique of lithium ion battery | |
| CN104157818A (en) | Lithium battery diaphragm compounded from aqueous polymer and inorganic nanoparticles and preparation method thereof | |
| CN103078075B (en) | Composite film with high-temperature resistance layer, preparation method thereof and battery | |
| CN105206777B (en) | Lithium battery diaphragm of the porous inorganic oxide containing lithium ion conduction and preparation method thereof | |
| CN108034318A (en) | A kind of low moisture lithium ion battery separator | |
| TW201406452A (en) | Hybrid organic-inorganic nano-particles | |
| CN105552285B (en) | A kind of ceramic-coated separator and preparation method thereof and the application in lithium ion battery | |
| CN103545475B (en) | Barium sulfate diaphragm of lithium ion battery and preparation method thereof | |
| CN104993088A (en) | Non-woven type lithium battery diaphragm realizing hole closing at low temperature and being stable at high temperature and preparation method | |
| TW201351758A (en) | Isolation film of electrochemical device and manufacturing method thereof | |
| CN102569700A (en) | Ceramic coating membrane and preparation method thereof | |
| CN112142995A (en) | Organic-inorganic composite grape particle structure material, slurry, diaphragm and preparation method | |
| US20180277811A1 (en) | Separator of lithium ion battery and method for making the same | |
| CN111180641A (en) | Diaphragm with self-crosslinking function and preparation method thereof | |
| CN113594632A (en) | Low-moisture solvent type PVDF coating diaphragm | |
| CN106450115A (en) | Inorganic coated bacterial cellulose porous thin film and preparation method thereof | |
| CN111244368A (en) | Ceramic diaphragm with good bonding property, preparation method thereof and lithium ion battery comprising ceramic diaphragm | |
| CN108400272A (en) | A kind of lithium battery polypropylene diaphragm being compounded with kenyaite-aerosil | |
| CN104804569A (en) | Organic-inorganic hybrid coating material for polyolefin membrane of lithium ion battery | |
| CN108586757B (en) | Adhesive for battery diaphragm coating and preparation method thereof | |
| CN111063849A (en) | Dual-drive self-assembly-based lithium ion battery isolating membrane and preparation method thereof | |
| CN106366823A (en) | Composite energy-storage latex-modified polyurethane acrylate waterproof coating material and preparation method thereof | |
| CN110205018B (en) | Heat-resistant coating and preparation method thereof | |
| CN104466060A (en) | Method for preparing lithium battery composite diaphragm by multi-layer coextrusion coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |