CN111378232A - UV (ultraviolet) curing solvent-free sealing material for lithium battery and preparation method thereof - Google Patents
UV (ultraviolet) curing solvent-free sealing material for lithium battery and preparation method thereof Download PDFInfo
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- CN111378232A CN111378232A CN202010197822.9A CN202010197822A CN111378232A CN 111378232 A CN111378232 A CN 111378232A CN 202010197822 A CN202010197822 A CN 202010197822A CN 111378232 A CN111378232 A CN 111378232A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
-
- 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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
- C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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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
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/183—Sealing members
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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 sealing material for sealing protection of a cylindrical battery and a preparation method thereof, wherein a photoinitiator is added into a mixed material of reactive PIB (polyisobutylene), low molecular weight polyisoprene, terpene resin, long alkyl carbene, cis-poly 1, 2-butadiene, a flame retardant IPPP50, a polymerization inhibitor, an antioxidant 1010 and the like to perform copolymerization under the irradiation of UV light to generate a compact flexible flame-retardant protective layer, so that the barrier property of a sealing ring to water vapor and air and the performances of high and low temperature resistance, impact resistance, acid and alkali corrosion resistance and the like are effectively improved. The UV curing system mixed material does not contain volatile solvent, can be rapidly cured to form a film, has simple and convenient operation process, and the product meets the requirements of environmental protection and flame retardance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a UV-cured solvent-free sealing material for sealing a cylindrical battery and a preparation method thereof.
Background
The battery is widely applied, and in order to ensure the stability of the internal material of the battery under the conditions of alternating temperature, thermal expansion and cold contraction and prevent the leakage and pollution of electrolyte, a layer of high polymer material is coated on the upper edge of a battery sealing ring and a rolling groove on the inner wall of a cylindrical battery shell and at related positions for further protection. At present, most of high molecular protective materials are solvent-based systems, and film forming substances adopt thermoplastic polyolefin elastomers and butyl rubber mixed petroleum tackifying resins; the solvent is made of materials such as toluene, xylene, butanone and butyl acetate, and the solvent is difficult to recover in the process, thereby causing irreparable damage to the environment and the human body of an operator. Therefore, the technical problem to be solved by the invention is to research and develop a high polymer protective sealing material which has simple operation process, no VOC emission, excellent flame retardance and excellent barrier property.
Disclosure of Invention
The invention aims to provide a protective flame-retardant sealing material for a lithium ion battery plastic gasket, which has flame retardance, high and low temperature resistance, alkali resistance and electrolyte resistance, and a preparation method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
a UV-cured solvent-free sealing material for a lithium battery comprises the following components in percentage by mass:
the sum of the mass percentages of the components is 100 percent.
The components of the invention comprise reactive polyisobutylene, low molecular weight polyisoprene, long alkyl carbene and cis-poly 1, 2-butadiene, and because double bonds exist in the molecular structures, the double bonds in the block copolymer can be opened by ultraviolet irradiation, thereby carrying out chemical crosslinking and improving the cohesive strength of the sealing material; in addition, low molecular weight polyisoprene, long alkyl carbene and low molecular weight olefin are adopted, so that the viscosity of the system can be reduced, and the machine gluing is facilitated; and secondly, the flexibility of the cured adhesive layer is improved, so that the sealing property of the sealing material is improved. The terpene resin mainly plays a role in tackifying and improves the adhesive force of the adhesive layer to the base material.
Preferably, the molecular weight Mn of the reactive polyisobutylene is 600-; in the invention, the molecular weight of the reactive polyisobutene is controlled to mainly play a role in controlling the viscosity of a system and facilitating the gluing of a machine; the reaction activity of the system is improved, and the energy required by the curing of the system is reduced.
Preferably, the terpene resin is the product of T-80, T-90, T-110 and T-120.
Preferably, the molecular weight Mn of the low molecular weight polyisoprene is 10000-; the molecular weight Mn of the cis-poly-1, 2-butadiene is 1000-; in the invention, low molecular weight polyisoprene is selected to mainly reduce the viscosity of the system and facilitate the gluing of a machine; the flexibility of the cured glue layer is improved, so that the sealing property of the sealing material is improved.
Preferably, the long alkyl carbene is one or a mixture of two or more of undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene and heptadecene.
Preferably, the photoinitiator consists of the following raw materials in percentage by mass: 2-hydroxy-2-methyl-1-phenyl-1-propanone: methyl benzoylformate: 4-dimethylamino-benzoic acid ethyl ester 5:2: 1.
Preferably, the flame retardant is isopropylated triphenyl phosphate.
Preferably, the polymerization inhibitor is imidazoquinone.
Preferably, the antioxidant is antioxidant 1010.
The invention also discloses a method for preparing the UV-cured solvent-free sealing material for the lithium battery, which comprises the following steps:
a. mixing reactive polyisobutylene, low molecular weight polyisoprene, long alkyl carbene, cis-poly 1, 2-butadiene, a flame retardant, a polymerization inhibitor and an antioxidant, adding into a heating kettle, and uniformly stirring at 70 +/-2 ℃;
b. adding terpene resin into the mixed solution a, keeping the temperature at 70 +/-2 ℃, continuing stirring for 30-60 min, and cooling to room temperature after the solid resin is completely dissolved;
c. and (4) adding a photoinitiator into the cooling liquid b, stirring for 10-15 min until the mixture is uniform, and discharging to obtain the product.
In summary, the technical scheme of the invention has the following beneficial effects: the sealing material disclosed by the invention is copolymerized under the irradiation of UV light to generate a compact flexible flame-retardant protective layer, so that the barrier property of the sealing ring on water vapor and air and the performances of high and low temperature resistance, impact resistance, acid and alkali corrosion resistance and the like are effectively improved. The invention adopts the phosphorus flame retardant, achieves the effect of automatically extinguishing flame, has good plasticizing effect, and can improve the high and low temperature resistance, impact resistance, acid and alkali resistance and other protective properties of the material. The UV curing system mixed material does not contain volatile solvent, can be rapidly cured to form a film, is simple and convenient in operation process, and the product meets the requirements of environmental protection and flame retardance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following embodiments of the present invention, but the technical solutions do not limit the scope of the present invention.
Example 1
a. Mixing 50g of reaction type PIB (molecular weight Mn is 800), 8g of polyisoprene (molecular weight Mn is 13000), 12g of tridecene, 33g of cis-poly 1, 2-butadiene (molecular weight Mn is 2600), 10g of flame retardant IPPP50, 0.03g of polymerization inhibitor and 0.3g of antioxidant 1010, adding the mixture into a heating kettle, and uniformly stirring at 70 +/-2 ℃;
b. adding 12g of terpene resin (T100) into the mixed solution a, keeping the temperature at 70 +/-2 ℃, continuing stirring for 30-60 min, and cooling to room temperature after the solid resin is completely dissolved;
c. and (b) adding 1.9g of photoinitiator into the cooling liquid b, stirring for 10-15 min until the mixture is uniform, and discharging.
Example 1, the test results are shown in the following table:
example 2
a. Mixing 55g of reactive PIB (molecular weight Mn is 1000), 10g of polyisoprene (molecular weight Mn is 15000), 10g of undecene, 37g of cis-poly 1, 2-butadiene (molecular weight Mn is 1000), 11g of flame retardant IPPP50, 0.04g of polymerization inhibitor and 0.4g of antioxidant 1010, adding the mixture into a heating kettle, and uniformly stirring at 70 +/-2 ℃;
b. adding 5g of terpene resin (T100) into the mixed solution a, keeping the temperature at 70 +/-2 ℃, continuing stirring for 30-60 min, and cooling to room temperature after the solid resin is completely dissolved;
c. and (b) adding 1.9g of photoinitiator into the cooling liquid b, stirring for 10-15 min until the mixture is uniform, and discharging.
Example 2, the test results are shown in the following table:
example 3
a. Mixing 52g of reaction type PIB (molecular weight Mn is 2400), 13g of polyisoprene (molecular weight Mn is 11000), 10g of hexadecene, 30g of cis-poly 1, 2-butadiene (molecular weight Mn is 1300), 12g of flame retardant IPPP50, 0.05g of polymerization inhibitor and 0.45g of antioxidant 1010 and the like, adding into a heating kettle, and uniformly stirring at 70 +/-2 ℃;
b. adding 6g of terpene resin (T110) into the mixed solution a, keeping the temperature at 70 +/-2 ℃, continuing stirring for 30-60 min, and cooling to room temperature after the solid resin is completely dissolved;
c. and (b) adding 2.2g of photoinitiator into the cooling liquid b, stirring for 10-15 min until the mixture is uniform, and discharging.
Example 3, the test results are shown in the following table:
example 4
a. Mixing 58g of reactive PIB (molecular weight Mn is 3000), 10g of polyisoprene (molecular weight Mn is 12000), 12g of dodecene, 35g of cis-poly 1, 2-butadiene (molecular weight Mn is 1100), 13g of flame retardant IPPP50, 0.45g of polymerization inhibitor and 0.5g of antioxidant 1010, adding into a heating kettle, and uniformly stirring at 70 +/-2 ℃;
b. adding 6.5g of terpene resin (T90) into the mixed solution a, keeping the temperature at 70 +/-2 ℃, continuing stirring for 30-60 min, and cooling to room temperature after the solid resin is completely dissolved;
c. and (b) adding 2.6g of photoinitiator into the cooling liquid b, stirring for 10-15 min until the mixture is uniform, and discharging. Example 4, the test results are shown in the following table:
while the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. The UV-cured solvent-free sealing material for the lithium battery is characterized by comprising the following components in percentage by mass:
the sum of the mass percentages of the components is 100 percent.
2. The UV-curable solvent-free sealing material for a lithium battery as claimed in claim 1, wherein:
the molecular weight Mn of the reactive polyisobutylene is 600-5000, and the molecular chain terminal methylvinylidene is blocked, so that the reactive polyisobutylene has further reaction activity.
3. The UV-curable solvent-free sealing material for a lithium battery as claimed in claim 1, wherein:
the terpene resin is the product brands of T-80, T-90, T-110 and T-120.
4. The UV-curable solvent-free sealing material for a lithium battery as claimed in claim 1, wherein: the molecular weight Mn of the low molecular weight polyisoprene is 10000-; the molecular weight Mn of the cis-poly-1, 2-butadiene is 1000-.
5. The UV-curable solvent-free sealing material for a lithium battery as claimed in claim 1, wherein: the long alkyl carbene is one or a mixture of more than two of undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene and heptadecene.
6. The UV-curable solvent-free sealing material for a lithium battery as claimed in claim 1, wherein: the photoinitiator consists of the following raw materials in percentage by mass: 2-hydroxy-2-methyl-1-phenyl-1-propanone: methyl benzoylformate: 4-dimethylamino-benzoic acid ethyl ester 5:2: 1.
7. The UV-curable solvent-free sealing material for a lithium battery as claimed in claim 1, wherein: the flame retardant is isopropylated triphenyl phosphate.
8. The UV-curable solvent-free sealing material for a lithium battery as claimed in claim 1, wherein: the polymerization inhibitor is imidacloprid.
9. The UV-curable solvent-free sealing material for a lithium battery as claimed in claim 1, wherein: the antioxidant is antioxidant 1010.
10. A method for preparing the UV-curable solvent-free sealing material for a lithium battery as claimed in any one of claims 1 to 6, comprising the steps of:
a. mixing reactive polyisobutylene, low molecular weight polyisoprene, long alkyl carbene, cis-poly 1, 2-butadiene, a flame retardant, a polymerization inhibitor and an antioxidant, adding into a heating kettle, and uniformly stirring at 70 +/-2 ℃;
b. adding terpene resin into the mixed solution a, keeping the temperature at 70 +/-2 ℃, continuing stirring for 30-60 min, and cooling to room temperature after the solid resin is completely dissolved;
c. and (4) adding a photoinitiator into the cooling liquid b, stirring for 10-15 min until the mixture is uniform, and discharging to obtain the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010197822.9A CN111378232A (en) | 2020-03-19 | 2020-03-19 | UV (ultraviolet) curing solvent-free sealing material for lithium battery and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010197822.9A CN111378232A (en) | 2020-03-19 | 2020-03-19 | UV (ultraviolet) curing solvent-free sealing material for lithium battery and preparation method thereof |
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| CN111378232A true CN111378232A (en) | 2020-07-07 |
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| CN202010197822.9A Pending CN111378232A (en) | 2020-03-19 | 2020-03-19 | UV (ultraviolet) curing solvent-free sealing material for lithium battery and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316809A (en) * | 2022-01-10 | 2022-04-12 | 南亚新材料科技股份有限公司 | Sealant for lithium battery and preparation method thereof |
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| US20050165164A1 (en) * | 2002-07-27 | 2005-07-28 | Thomas Moeller | Fusible adhesives crosslinkable by radiation |
| JP2012057065A (en) * | 2010-09-09 | 2012-03-22 | Lintec Corp | Adhesive sheet for sealing, electronic device and organic device |
| WO2013031656A1 (en) * | 2011-08-26 | 2013-03-07 | 三菱化学株式会社 | Adhesive sealing film, method for manufacturing adhesive sealing film, and coating liquid for adhesive sealing film |
| US20150056757A1 (en) * | 2012-05-02 | 2015-02-26 | Henkel US IP LLC | Curable encapsulants and use thereof |
| CN104497935A (en) * | 2014-12-18 | 2015-04-08 | 唐山德生防水股份有限公司 | Reactive-type plasticizer-free SIS hot-melt pressure-sensitive adhesive |
| WO2017018546A1 (en) * | 2015-07-30 | 2017-02-02 | 株式会社スリーボンド | Photocurable resin composition, fuel cell, and sealing method |
-
2020
- 2020-03-19 CN CN202010197822.9A patent/CN111378232A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050165164A1 (en) * | 2002-07-27 | 2005-07-28 | Thomas Moeller | Fusible adhesives crosslinkable by radiation |
| JP2012057065A (en) * | 2010-09-09 | 2012-03-22 | Lintec Corp | Adhesive sheet for sealing, electronic device and organic device |
| WO2013031656A1 (en) * | 2011-08-26 | 2013-03-07 | 三菱化学株式会社 | Adhesive sealing film, method for manufacturing adhesive sealing film, and coating liquid for adhesive sealing film |
| US20150056757A1 (en) * | 2012-05-02 | 2015-02-26 | Henkel US IP LLC | Curable encapsulants and use thereof |
| CN104497935A (en) * | 2014-12-18 | 2015-04-08 | 唐山德生防水股份有限公司 | Reactive-type plasticizer-free SIS hot-melt pressure-sensitive adhesive |
| WO2017018546A1 (en) * | 2015-07-30 | 2017-02-02 | 株式会社スリーボンド | Photocurable resin composition, fuel cell, and sealing method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316809A (en) * | 2022-01-10 | 2022-04-12 | 南亚新材料科技股份有限公司 | Sealant for lithium battery and preparation method thereof |
| CN114316809B (en) * | 2022-01-10 | 2023-10-20 | 南亚新材料科技股份有限公司 | Sealant for lithium battery and preparation method thereof |
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Application publication date: 20200707 |