CN114230691A - Micro-precipitation polymerization preparation method and application of water-based resin - Google Patents
Micro-precipitation polymerization preparation method and application of water-based resin Download PDFInfo
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- CN114230691A CN114230691A CN202111673577.5A CN202111673577A CN114230691A CN 114230691 A CN114230691 A CN 114230691A CN 202111673577 A CN202111673577 A CN 202111673577A CN 114230691 A CN114230691 A CN 114230691A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a micro-precipitation polymerization preparation method of water-based resin and application thereof. The preparation method of the micro-precipitation polymerization comprises the following steps: all reaction raw materials are water-soluble; the solvent used for the polymerization reaction only comprises water; no emulsifier and/or dispersant is added; the product is continuously separated out in the form of water-insoluble micro-precipitates in the polymerization reaction process and is uniformly dispersed in water, and finally the finished product of the water-based resin is obtained. The finished product obtained by the invention has good stability, uniformity and dispersibility, and does not settle, delaminate and/or separate out when the standing time is not more than 3 years. The lithium battery ceramic diaphragm prepared by using the water-based resin provided by the invention has good high heat resistance and low water absorption, and specifically, the transverse and longitudinal heat shrinkage rates of the diaphragm are not more than 5% at 150-200 ℃; moisture residue in the separator was measured using the karl fischer method, and the result showed that the residual moisture content was not more than 1500 ppm.
Description
Technical Field
The invention relates to preparation of resin, in particular to a micro-precipitation polymerization preparation method of water-based resin and application thereof.
Background
Aqueous resins, such as acrylate emulsion, vinyl acetate emulsion, SBR emulsion, etc., have been used in the lithium battery field due to their diversified properties, particularly their strong hydrophobicity. However, such products also suffer from the following drawbacks:
(1) emulsion polymerization processes are relatively complex, such as pre-emulsification processes which typically require a long time before reaction, reaction processes which typically require the selection of semi-continuous processes resulting in relatively complex equipment, etc.;
(2) the emulsifiers in the reaction formulation often cause some residue that is detrimental to the resin itself and the performance of the lithium battery.
On the other hand, the polymerization process for aqueous solution-type resins is relatively simple and the product is generally free of undesirable residues. However, although the above defects can be overcome by the products, the products generally have strong water absorption, and the characteristics are also unfavorable for the performance of the lithium battery. Therefore, it is highly desirable to find a method for preparing aqueous resins that combines the advantages of both emulsions and solutions. Although extensive research has been carried out on polymerization methods, a series of novel polymerization methods have been developed in addition to the conventional four major polymerization methods (bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization), but it is still difficult to meet the requirements in the field of lithium batteries, and the main drawback is that these polymerization methods generally rely on a large amount of dispersing aids, which are generally detrimental to the performance of lithium batteries. For example, "water-in-water" emulsion polymerization is a fully aqueous polymerization method different from conventional emulsion polymerization such as oil-in-water, water-in-oil, etc., and has been used for a long time in the field of preparation of high molecular weight polyacrylamide, etc., but the method still needs various additives to ensure the dispersion uniformity of the product, and usually needs to add inorganic small molecular salts. For another example, dispersion polymerization is a special solution-precipitation polymerization method, which utilizes the property of "monomer is soluble in solvent but polymer is insoluble in solvent" to make polymer continuously separate out during polymerization, and under the action of protective gum and dispersion aid which are added into the reaction system in advance, a uniform micro-suspension is formed. The stability of the dispersion polymerization product is closely related to the protective glue and the dispersion auxiliary agent, and meanwhile, a composite solvent system is usually used for dispersion polymerization, and a water-alcohol system is the most common system, so that the true full-aqueous polymerization is difficult to realize. Therefore, the research difficulty in the field is to find a fully aqueous resin with excellent performance, and reduce or even eliminate the use of a dispersing aid to meet the requirements of lithium battery manufacturing.
Disclosure of Invention
In order to solve the technical problems, the invention provides a micro-precipitation polymerization preparation method of water-based resin and application thereof.
The invention provides a method for preparing aqueous resin by micro-precipitation polymerization, wherein the 'micro-precipitation polymerization preparation method' refers to a polymerization method comprising the following characteristics: all reaction raw materials are water-soluble; the solvent used for the polymerization reaction only comprises water; no emulsifier and/or dispersant is added; the product is continuously separated out in the form of water-insoluble micro-precipitates in the polymerization reaction process and is uniformly dispersed in water, and finally the finished product of the water-based resin is obtained.
The applicant finds that the method for preparing the water-based resin by using the water-soluble raw materials can be realized by reasonably matching the material proportion, the feeding time, the process parameters and the like. If a specific neutralization-modifier is added in a specific step, various properties of the product can be adjusted and improved. Observing the reaction process, the applicants have found that as the polymerization proceeds, the product is continually precipitated as insoluble micro-precipitates. Although the reaction system is not added with the auxiliary agents such as the emulsifying agent, the dispersing agent and the like, the micro precipitates can still be uniformly dispersed in the reaction system, and the reaction system is gradually changed into a white and semitransparent heterogeneous dispersion liquid from a clear and transparent aqueous solution. After the material is received, the finished product can still keep good stability, uniformity and dispersibility.
Further, the preparation method of the micro-precipitation polymerization comprises the following steps:
(1) dissolving one or more than two monomers A, one or more than two monomers B, one or more than two skeleton molecules and a water-soluble initiator in deionized water, and fully stirring to obtain a clear aqueous solution;
(2) keeping stirring, raising the reaction temperature to 45-100 ℃, reacting for 2-12 h, cooling and collecting materials to obtain the product.
Further, the monomer A is a general name of a water-soluble monomer, and the structural general formula of the monomer A is shown as the formula (I):
wherein R is1Comprises one or more than two of hydrogen, alkyl or alkylene with 1-3 carbon atoms, carbonyl, hydroxyl, amido and halogen atoms; r2Comprises one or more than two of hydrogen, alkyl or alkylene with 1-3 carbon atoms, carbonyl, hydroxyl, amido and halogen atoms; r3Comprises one or more than two of hydrogen, alkyl or alkylene with 1-3 carbon atoms, carbonyl, hydroxyl, amido and halogen atoms; the one or two or more monomers A are one or two or more of the substances represented by the general formula (I).
Further, when R is1、R2And R3When both are hydrogen, monomer A is acrylic acid; when R is1、R2Is hydrogen, R3When methyl, monomer a is crotonic acid (crotonic acid); when R is2、R3Is hydrogen, R1When composed of a methylene group (alkylene group having 1 carbon atom) and a carboxyl group, the monomer A is itaconic acid, and the like.
Further, the monomer B is a general name of a water-soluble monomer, and the structural general formula of the monomer B is shown as a formula (II):
wherein R is4One or more of hydrogen, alkyl or alkylene with 1-3 carbon atoms, alkoxy or alkyleneoxy, phenyl, carbonyl, hydroxyl, amino, halogen atoms and sulfonic acid (salt) group; r5Comprises one or more than two of hydrogen, alkyl or alkylene with 1-3 carbon atoms, alkoxy or alkyleneoxy, phenyl, carbonyl, hydroxyl, amido, halogen atoms, sulfonic group and sulfonate group; r6Comprises one or more than two of hydrogen, alkyl or alkylene with 1-3 carbon atoms, alkoxy or alkyleneoxy, phenyl, carbonyl, hydroxyl, amido, halogen atoms, sulfonate and sulfonate; r7Comprises one or more than two of hydrogen, alkyl or alkylene with 1-3 carbon atoms, alkoxy or alkyleneoxy, phenyl, carbonyl, hydroxyl, amido, halogen atoms, sulfonic group and sulfonate group; the one or two or more monomers B are one or two or more of the substances represented by the general formula (II).
Further, when R is4、R5And R6Are each hydrogen, R7In the case of amide groups (consisting of carbonyl and amine groups), monomer B is acrylamide; when R is4、R5And R6Are each hydrogen, R7When the monomer B is a sodium benzene sulfonate group (consisting of phenyl and a sodium sulfonate group), the monomer B is sodium p-styrene sulfonate; when R is4、R5And R6Are each hydrogen, R7From amide, isopropyl, methylene and sulfonic acid (salts)) When the monomer B is composed of the following monomers, the monomer B is 2-acrylamide-2-methylpropanesulfonic acid (AMPS for short); when R is4Is methyl, R5、R6Is hydrogen, R7When consisting of carbonyl, ethyleneoxy and hydroxyl groups, the monomer B is hydroxyethyl methacrylate, and the like.
Further, the skeleton molecule is a general name of a water-soluble polymer with the molecular weight of 1000-10000000. Such as polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), Polyethyleneimine (PEI), PEDOT: PSS, and the like. It should be noted that these backbone molecules have different functions compared to the "protective gum" commonly used in dispersion polymerization and emulsion polymerization, although they are similar in species. The protective glue only plays a role in promoting dispersion and avoiding mutual adhesion of particles, and does not participate in reaction in the polymerization process; the skeleton molecule participates in the polymerization reaction, the monomer A and the monomer B can form graft on the skeleton molecule, and finally, the product with a specific molecular chain configuration is obtained.
Further, in the step (1), the addition of a neutralization-modifying agent A and/or a neutralization-modifying agent B is also included; in step (2), the addition of a neutralization-modifier A and/or a neutralization-modifier B is also included.
Further, the neutralization-modifier A is an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.; the neutralization-modifier B is ammonia water and/or organic amine, and the organic amine can be ethylamine, diethylamine, ethanolamine, diethylenetriamine and the like.
The aqueous resin obtained by the preparation method can be applied to the preparation of the ceramic diaphragm of the lithium battery and/or the lithium battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) the raw materials are water-soluble, only water is used as a solvent in the reaction process, an emulsifier and a dispersant are not required to be added, and the steps of pre-emulsification and the like are not required, so that the polymerization process is simple, green and environment-friendly, the product is purer, and no undesirable residue exists or the content is very low;
(2) the lithium battery ceramic diaphragm prepared by using the water-based resin provided by the invention has good high heat resistance and low water absorption, and specifically, the transverse and longitudinal heat shrinkage rates of the diaphragm are not more than 5% at 150-200 ℃; moisture residue in the separator was measured using the karl fischer method, and the result showed that the residual moisture content was not more than 1500 ppm.
(3) The finished product obtained by the invention has good stability, uniformity and dispersibility, and does not settle, delaminate and/or separate out when the standing time is not more than 3 years.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the present application will be clearly and completely described below with reference to the embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
EXAMPLE 1 preparation of aqueous resin
23g of methacrylic acid, 7g of methacrylamide, 80g of PVA aqueous solution with the mass fraction of 10% and 0.1g of initiator ammonium persulfate are put into a reaction device and fully stirred until all the materials are completely dissolved. Then, ammonia water and pure water were added to adjust the pH of the reaction solution to 4.5. + -. 0.1 and the mass concentration to 20%. + -. 1%. In this case, the reaction solution was a colorless clear aqueous solution and no precipitate, precipitate or the like was formed.
The stirring speed is kept at 250-300 rpm, and the reaction apparatus is kept in a nitrogen atmosphere. The reaction temperature was raised to 60 ℃ and kept for 6 h. As the reaction proceeded, the reaction gradually changed from clear to translucent and blue light characteristic of the emulsion appeared. After the heat preservation is finished, cooling to room temperature, and then adding lithium hydroxide and pure water to ensure that the pH value of the product is 9.0 +/-0.1 and the solid content is 20% +/-1%. Collecting the material to obtain a milky semitransparent waterborne resin product.
EXAMPLE 2 preparation of aqueous resin
In comparison with example 1, 23g of methacrylic acid was replaced with 21g of maleic acid, 7g of methacrylamide was replaced with 9g of sodium p-styrenesulfonate, 80g of a 10% by weight aqueous solution of PVA was replaced with 80g of a 1% by weight aqueous solution of CMC, aqueous ammonia was replaced with ethanolamine, and lithium hydroxide was replaced with sodium hydroxide, and the rest of the procedure was as in example 1.
EXAMPLE 3 preparation of aqueous resin
Compared with example 1, 23g of methacrylic acid is replaced by 18g of acrylic acid and 4g of itaconic acid, 7g of methacrylamide is replaced by 6g of hydroxyethyl acrylate and 2g of 2-acrylamido-2-methylpropanesulfonic acid, 80g of a 10% by mass aqueous solution of PVA is replaced by 80g of a 10% by mass aqueous solution of PEG400, and ammonia water is replaced by diethylenetriamine. The rest is the same as example 1.
Comparative example 1
According to the conventional method in the field, acrylic acid, methyl methacrylate, styrene, butyl acrylate and isooctyl acrylate are used as raw materials to prepare the water-based acrylate emulsion.
Comparative example 2
An aqueous acrylic copolymer solution is prepared by conventional methods in the art using acrylic acid and acrylamide as starting materials.
Example 4 preparation of separator
According to the conventional method in the field, using the various products of examples 1-3 and comparative examples 1-2, preparing lithium battery ceramic diaphragm slurry with the solid content of 40% +/-1%, then blade-coating the slurry on a polyolefin wet-process base film with the thickness of 7 microns, and drying to obtain the lithium battery ceramic diaphragm with the coating thickness of 2 microns.
Performance testing
The ceramic separator for a lithium battery as described in example 4 was tested for coating peel strength, heat resistance, and moisture content, respectively.
The peel strength of the coating was tested according to the method described in GB/T2792-2014.
Heat resistance is characterized by heat shrinkage and is tested as follows: cutting one ceramic diaphragm with the transverse length and the longitudinal length of 10cm, clamping the ceramic diaphragm between two pieces of A4 printing paper, horizontally putting the ceramic diaphragm into an electrothermal blowing dry box at 180 ℃, taking out the ceramic diaphragm after 1 hour, measuring the transverse length and the longitudinal length of the diaphragm, and calculating the thermal shrinkage rate of the ceramic diaphragm.
The moisture content was measured using the karl fischer method at a temperature of 120 ℃.
The test results are shown in the following table.
From the test results, when the water-based resin prepared by the method is applied to the lithium battery ceramic diaphragm, compared with the two products in the comparative example, the water-based resin can have the advantages of emulsion type products and solution type products, and has better performances in the aspects of coating peeling strength, heat shrinkage rate, moisture content and the like.
Claims (10)
1. The preparation method of the aqueous resin by micro-precipitation polymerization is characterized by comprising the following steps: all reaction raw materials are water-soluble; the solvent used for the polymerization reaction only comprises water; no emulsifier and/or dispersant is added; the product is continuously separated out in the form of water-insoluble micro-precipitates in the polymerization reaction process and is uniformly dispersed in water, and finally the finished product of the water-based resin is obtained.
2. The method of claim 1, wherein the method comprises the steps of:
(1) dissolving one or more than two monomers A, one or more than two monomers B, one or more than two skeleton molecules and a water-soluble initiator in deionized water, and fully stirring to obtain a clear aqueous solution;
(2) keeping stirring, raising the reaction temperature to 45-100 ℃, reacting for 2-12 h, cooling and collecting materials to obtain the product.
3. The method of claim 2, wherein the monomer A is a generic name of a water-soluble monomer having a general structural formula of formula (I):
wherein R is1Comprises one or more than two of hydrogen, alkyl or alkylene with 1-3 carbon atoms, carbonyl, hydroxyl, amido and halogen atoms; r2Comprises one or more than two of hydrogen, alkyl or alkylene with 1-3 carbon atoms, carbonyl, hydroxyl, amido and halogen atoms; r3Comprises one or more than two of hydrogen, alkyl or alkylene with 1-3 carbon atoms, carbonyl, hydroxyl, amido and halogen atoms.
4. The method of claim 2, wherein the monomer B is a generic name of a water-soluble monomer having a general structural formula of formula (II):
wherein R is4Comprises one or more than two of hydrogen, alkyl or alkylene with 1-3 carbon atoms, alkoxy or alkyleneoxy, phenyl, carbonyl, hydroxyl, amido, halogen atoms, sulfonic group and sulfonate group; r5Comprises one or more than two of hydrogen, alkyl or alkylene with 1-3 carbon atoms, alkoxy or alkyleneoxy, phenyl, carbonyl, hydroxyl, amido, halogen atoms, sulfonic group and sulfonate group; r6Comprises one or more than two of hydrogen, alkyl or alkylene with 1-3 carbon atoms, alkoxy or alkyleneoxy, phenyl, carbonyl, hydroxyl, amido, halogen atoms, sulfonic group and sulfonate group; r7Includes one or more of hydrogen, alkyl or alkylene group having 1 to 3 carbon atoms, alkoxy or alkyleneoxy group, phenyl group, carbonyl group, hydroxyl group, amino group, halogen atom, sulfonic group, and sulfonate group.
5. The method of claim 2, wherein the backbone molecule is a generic term for a water-soluble polymer having a molecular weight of 1000 to 10000000.
6. The method for preparing a waterborne resin by microprecipitation polymerization according to claim 2, wherein the step (1) further comprises adding a neutralization-modifier A and/or a neutralization-modifier B; in step (2), the addition of a neutralization-modifier A and/or a neutralization-modifier B is also included.
7. The method of claim 6, wherein the neutralization-modifier A is an alkali metal hydroxide.
8. The method of claim 6, wherein the neutralization-modifier B is ammonia and/or an organic amine.
9. Use of the aqueous resin obtained by the preparation method according to any one of claims 1 to 8 in the preparation of a ceramic separator for a lithium battery.
10. A lithium battery comprising the aqueous resin obtained by the preparation method according to any one of claims 1 to 8 and/or comprising a ceramic separator for lithium batteries obtained by the use according to claim 9.
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| CN110190235A (en) * | 2019-06-14 | 2019-08-30 | 湖南高瑞电源材料有限公司 | A kind of aqueous solution type lithium battery ceramic diaphragm adhesive specially and its preparation method and application |
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| CN102464754A (en) * | 2010-11-03 | 2012-05-23 | 展华化学工业股份有限公司 | Emulsifier-free acrylic ester emulsion polymerization method |
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