CN113801597B - PI adhesive tape based on lithium battery welding spot protection and preparation method thereof - Google Patents
PI adhesive tape based on lithium battery welding spot protection and preparation method thereof Download PDFInfo
- Publication number
- CN113801597B CN113801597B CN202111215934.3A CN202111215934A CN113801597B CN 113801597 B CN113801597 B CN 113801597B CN 202111215934 A CN202111215934 A CN 202111215934A CN 113801597 B CN113801597 B CN 113801597B
- Authority
- CN
- China
- Prior art keywords
- stirring
- reaction
- solution
- condition
- temperature
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a PI adhesive tape based on lithium battery welding spot protection and a preparation method thereof, and relates to the technical field of welding spot protection.
Description
Technical Field
The invention relates to the technical field of welding spot protection, in particular to a PI adhesive tape based on lithium battery welding spot protection and a preparation method thereof.
Background
In the assembly production process of lithium ion batteries, special adhesive tapes are generally used for fixing, insulating and protecting lug parts of the lithium ion batteries. The special adhesive tape for the lithium battery generally adopts a polymer PI film as a base material, and is coated with special glue with the thickness of 20-100mm. The special adhesive tape for the lithium battery generally has the advantages of good adhesiveness, no residual adhesive left after the adhesive tape is uncovered, high temperature resistance, electrolyte resistance, high electrical insulation and the like.
The acrylate adhesive has the characteristics of simple operation, rapid curing at room temperature, adjustable curing rate, oil surface adhesion, no need of strict metering of the bi-component proportion, strong adhesion, wide applicability and the like; therefore, the acrylate adhesive is widely applied to structural bonding in the industries of rail transit, electronics, electric appliances, automobiles, aviation, ships and the like in recent years.
However, the existing acrylic ester adhesive has poor high temperature resistance, and under the condition that a non-sticking knife cannot be realized, the stripping force is improved to be more than 3N/mm, and the bonding spot part is stuck, and the bonding is realized without glue opening after baking for 24H at 85 ℃.
Therefore, there is a need for a PI tape based on lithium battery solder joint protection and a method for preparing the same to solve the above problems.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a PI adhesive tape based on lithium battery welding spot protection and a preparation method thereof: the PI adhesive tape based on lithium battery welding spot protection is obtained by taking methyl methacrylate, butyl acrylate, hydroxypropyl methacrylate and acrylic acid as polymerization monomers, realizing polymerization through carbon-carbon double bonds under the action of an initiator to form polyacrylic acid glue, then adding modified phenolic resin and a modified curing agent into the polyacrylic acid glue to prepare high-temperature-resistant glue, and coating the high-temperature-resistant glue on a PI film to prepare the adhesive tape, so that the problem that the adhesive tape is not adhesive after bonding and opening is realized after the bonding of a welding spot part is baked for 24 hours at 85 ℃ under the conditions that the high-temperature resistance of the existing acrylic acid ester adhesive is poor and a non-adhesive knife cannot be realized is solved.
The aim of the invention can be achieved by the following technical scheme:
a PI adhesive tape based on lithium battery welding spot protection comprises the following components in parts by weight:
100-150 parts of polyacrylic acid glue, 4-6 parts of modified phenolic resin and 2.5-4.5 parts of modified curing agent;
the modified phenolic resin is prepared by the following steps:
step one: adding phenol, formaldehyde solution and sodium hydroxide solution into a three-neck flask provided with a stirrer, an air duct, a thermometer and a reflux condenser, introducing nitrogen for protection, heating to 70-75 ℃ at constant temperature under the condition of stirring speed of 200-300r/min, controlling heating speed to 1-3 ℃/min, continuing to stir at constant temperature for 1-2h to obtain an intermediate 1, rotationally evaporating the intermediate 1 to remove water, adding molybdic acid, continuing to stir for reaction for 50-90min under the condition of stirring speed of 300-500r/min at 85-95 ℃, and cooling a reaction product to room temperature after the reaction is finished to obtain an intermediate 2;
the reaction principle is as follows:
step two: adding phosphorus oxychloride and anhydrous aluminum trichloride into a three-neck flask provided with a thermometer, a stirrer and a constant-pressure dropping funnel, heating to 60-65 ℃ at constant temperature under the condition of stirring speed of 200-300r/min, controlling heating speed to 1-3 ℃/min, then adding phenol and dichloroethane into the constant-pressure dropping funnel after uniformly mixing, dropwise adding mixed solution of phenol and dichloroethane, controlling dripping speed to 1 drop/s, continuing constant-temperature stirring reaction for 10-20h after dripping, adding distilled water into a reaction product after the reaction is finished, continuing stirring for 10-20min, filtering, distilling filtrate at normal pressure to remove low-boiling-point material dichloroethane, and then performing reduced pressure distillation, and collecting fractions at 140-160 ℃ under the condition of pressure of 0.399KPa to obtain an intermediate 2;
the reaction principle is as follows:
step three: adding the intermediate 2, chlorobenzene and potassium hydroxide into a three-neck flask provided with a thermometer, a stirrer and an air duct, introducing nitrogen for protection, stirring for 10-20min under the conditions of the temperature of-5-0 ℃ and the stirring speed of 800-1200r/min, adding the intermediate 3, continuing stirring for reaction for 10-30min, after the reaction is finished, removing the chlorobenzene by rotary evaporation of a reaction product under the conditions of the temperature of 80-90 ℃, adding the evaporation product into chloroform for dissolution, washing for 2-3 times by using hydrochloric acid solution and distilled water in sequence, standing for layering, and removing the chloroform by rotary evaporation of an organic layer to obtain the modified phenolic resin.
The reaction principle is as follows:
as a further scheme of the invention: the formaldehyde solution in the first step is a solution with the mass fraction of 35-40% formed by dissolving formaldehyde in deionized water, the sodium hydroxide solution is a solution with the mass fraction of 30-40% formed by dissolving sodium hydroxide in deionized water, and the mole ratio of phenol, formaldehyde, sodium hydroxide and molybdic acid is 1.0:1.2-1.4:0.01-0.03:0.04-0.08.
As a further scheme of the invention: the dosage ratio of phosphorus oxychloride, anhydrous aluminum trichloride, phenol, dichloroethane and distilled water in the second step is 30-35g:1.5-2.0g:35-40g:20mL:10-20mL.
As a further scheme of the invention: the dosage ratio of the intermediate 2 to the chlorobenzene to the potassium hydroxide to the intermediate 3 in the third step is 10g:30mL:3.5g:5-10g, wherein the mass fraction of the hydrochloric acid solution is 10-15%.
As a further scheme of the invention: the modified curing agent is prepared by the following steps:
adding thiourea and diethylenetriamine into a four-neck flask provided with a thermometer, a stirrer and a reflux condenser, heating to 130-135 ℃ at constant temperature under the condition of stirring rate of 100-300r/min, controlling heating rate to 1-5 ℃/min, stirring at constant temperature under the condition of stirring rate of 300-500r/min, reacting for 2-3h, and cooling the reaction product to room temperature after the reaction is finished to obtain the modified curing agent.
The reaction principle is as follows:
as a further scheme of the invention: the molar ratio of thiourea to diethylenetriamine is 0.5-0.75:1.
a preparation method of a PI adhesive tape based on lithium battery welding spot protection comprises the following steps:
s1: adding methyl methacrylate, butyl acrylate, hydroxypropyl methacrylate and acrylic acid into a three-neck flask provided with a stirrer and a constant-pressure dropping funnel, dropwise adding an azodiisobutyronitrile solution as an initiator while stirring at the temperature of 100-105 ℃ and the stirring rate of 500-700r/min, controlling the dropping rate to be 1 drop/s, heating to 110-115 ℃ after the dropping, continuously stirring and reacting for 2.5h, and rotationally evaporating a reaction product after the reaction is finished to obtain a viscous fluid with the solid content of 50-80%, thereby obtaining polyacrylic glue;
s2: adding modified phenolic resin and modified curing agent into polyacrylic glue, dispersing for 3-8 hours under the condition of stirring speed of 2000-3000r/min to obtain high-temperature-resistant glue, and coating the high-temperature-resistant glue on a PI film to prepare a tape, so as to obtain the PI tape based on lithium battery welding spot protection.
As a further scheme of the invention: the mass ratio of the methyl methacrylate, butyl acrylate, hydroxypropyl methacrylate, acrylic acid and azodiisobutyronitrile solution in the step S1 is 20-45g:15-25g:5-25g:30-50g:75-150mL of azobisisobutyronitrile solution is azobisisobutyronitrile according to 0.5-1.5g:100mL of the solution was dissolved in methyl isobutyl ketone.
The invention has the beneficial effects that:
according to the PI adhesive tape based on lithium battery welding spot protection and the preparation method thereof, methyl methacrylate, butyl acrylate, hydroxypropyl methacrylate and acrylic acid are used as polymerization monomers, polymerization is achieved through carbon-carbon double bonds under the action of an initiator to form polyacrylic acid glue, then modified phenolic resin and a modified curing agent are added into the polyacrylic acid glue to prepare high-temperature-resistant glue, the high-temperature-resistant glue is coated on a PI film to prepare the adhesive tape based on lithium battery welding spot protection, the high-temperature-resistant glue takes the polyacrylic acid glue as a main body, the modified curing agent is used for increasing cohesive force of the adhesive, so that non-sticking of a cutter is achieved, mainly, the crosslinking density is increased, solvent residues are reduced, the temperature stability of the adhesive layer is greatly improved while the adhesive property of the adhesive layer is improved, and the fact that the welding spot is not opened due to heat emitted by a lithium ion battery during operation is ensured.
In the process of preparing the PI adhesive tape based on lithium battery welding spot protection, a modified phenolic resin is also prepared, intermediate 1 is generated through the reaction of phenol and formaldehyde, then intermediate 1 is polymerized to form a polymer after the reaction of the intermediate 1 and molybdic acid, so that molybdenum element is introduced into a molecular chain of the polymer to obtain intermediate 2, intermediate 3 is generated through the catalysis of phenol and phosphorus oxychloride under the catalysis of anhydrous aluminum trichloride, intermediate 3 is introduced into intermediate 2 through the reaction of intermediate 2 and intermediate 3, namely benzene ring and phosphorus element are introduced into the molecular chain of the polymer, so that the phenolic resin containing phosphorus element, molybdenum element and multiple benzene rings is formed, the phenolic resin contains a large amount of benzene rings, so that the phenolic resin has excellent flame-retardant heat resistance, the phenolic resin contains a large amount of phenolic hydroxyl groups, oxidation reaction and water absorption reaction are easy to occur, the introduced benzene ring and phosphorus element are removed through the reaction of intermediate 2, and the introduced benzene ring has high stability, and the introduced molybdenum element and phosphorus element can form a bond with high chemical bond, so that the heat resistance of the phenolic resin is improved, and the PI adhesive tape based on lithium battery can be effectively protected by adding the modified phenolic resin.
In the process of preparing the PI adhesive tape based on lithium battery welding spot protection, a modified curing agent is also prepared, sulfur is introduced through the reaction polymerization of thiourea and diethylenetriamine, so that an amine curing agent containing sulfur is generated, the molecular weight of an amine curing agent product modified through thiourea is increased, the reactivity is enhanced, meanwhile, the thermal deformation temperature of the curing product is improved to a greater extent, and the high temperature resistance of the PI adhesive tape based on lithium battery welding spot protection is further improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the embodiment is a preparation method of modified phenolic resin, comprising the following steps:
step one: adding 0.1mol of phenol, 0.12mol of formaldehyde into a formaldehyde solution with the mass fraction of 35% formed by dissolving 0.001mol of formaldehyde into deionized water and a sodium hydroxide solution with the mass fraction of 30% formed by dissolving 0.001mol of sodium hydroxide into a three-neck flask provided with a stirrer, an air duct, a thermometer and a reflux condenser, introducing nitrogen for protection, heating to 70 ℃ at constant temperature under the condition of stirring rate of 200r/min, controlling the heating rate to be 1 ℃/min, continuing to stir at constant temperature for 1h to obtain an intermediate 1, rotationally evaporating the intermediate 1 to remove water, adding 0.004mol of molybdic acid, continuing to stir for 50min under the condition of stirring rate of 300r/min at 85 ℃, and cooling a reaction product to room temperature to obtain the intermediate 2 after the reaction is finished;
step two: adding 30g of phosphorus oxychloride and 1.5g of anhydrous aluminum trichloride into a three-neck flask provided with a thermometer, a stirrer and a constant-pressure dropping funnel, heating to 60 ℃ at constant temperature under the condition of stirring rate of 200r/min, controlling heating rate to be 1 ℃/min, then uniformly mixing 35g of phenol and 20mL of dichloroethane, adding into the constant-pressure dropping funnel, dropwise adding mixed solution of phenol and dichloroethane, controlling dripping rate to be 1 drop/s, continuing constant-temperature stirring for reaction for 10h after dripping, adding 10mL of distilled water into a reaction product after the reaction is finished, continuing stirring for 10min, filtering, distilling filtrate at normal pressure to remove low-boiling-point material dichloroethane, then performing reduced pressure distillation, and collecting a fraction at 140 ℃ under the condition of pressure of 0.399KPa to obtain an intermediate 2;
step three: 10g of intermediate 2, 30mL of chlorobenzene and 3.5g of potassium hydroxide are added into a three-neck flask provided with a thermometer, a stirrer and an air duct, nitrogen is introduced for protection, stirring is carried out for 10min under the condition that the temperature is-5 ℃ and the stirring rate is 800r/min, then 5g of intermediate 3 is added for continuous stirring reaction for 10min, the reaction product is subjected to rotary evaporation at the temperature of 80 ℃ after the reaction is finished to remove the chlorobenzene, then the evaporation product is added into chloroform to be dissolved, then hydrochloric acid solution with the mass fraction of 10% and distilled water are sequentially used for washing for 2 times, standing and layering are carried out, and the chloroform is removed by rotary evaporation of an organic layer to obtain the modified phenolic resin.
Example 2:
the embodiment is a preparation method of modified phenolic resin, comprising the following steps:
step one: adding a 40% formaldehyde solution formed by dissolving 0.1mol of phenol and 0.14mol of formaldehyde in deionized water and a 40% sodium hydroxide solution formed by dissolving 0.003mol of sodium hydroxide in deionized water into a three-neck flask provided with a stirrer, an air duct, a thermometer and a reflux condenser, introducing nitrogen for protection, heating to 75 ℃ at constant temperature under the condition of stirring rate of 300r/min, controlling the heating rate to 3 ℃/min, continuing to stir at constant temperature for 2h to obtain an intermediate 1, rotationally evaporating the intermediate 1 to remove water, adding 0.008mol of molybdic acid, continuing to stir for 90min under the condition of stirring rate of 500r/min at 95 ℃, and cooling a reaction product to room temperature to obtain the intermediate 2 after the reaction is finished;
step two: adding 35g of phosphorus oxychloride and 2.0g of anhydrous aluminum trichloride into a three-neck flask provided with a thermometer, a stirrer and a constant-pressure dropping funnel, heating to 65 ℃ at constant temperature under the condition of stirring rate of 300r/min, controlling heating rate to 3 ℃/min, then uniformly mixing 40g of phenol and 20mL of dichloroethane, adding into the constant-pressure dropping funnel, dropwise adding mixed solution of phenol and dichloroethane, controlling dripping rate to 1 drop/s, continuing constant-temperature stirring reaction for 20h after dripping, adding 20mL of distilled water into a reaction product after the reaction is finished, continuing stirring for 20min, filtering, distilling filtrate at normal pressure to remove low-boiling-point material dichloroethane, and then distilling under reduced pressure, collecting 160 ℃ fraction under the condition of pressure of 0.399KPa to obtain an intermediate 2;
step three: 10g of intermediate 2, 30mL of chlorobenzene and 3.5g of potassium hydroxide are added into a three-neck flask provided with a thermometer, a stirrer and an air duct, nitrogen is introduced for protection, stirring is carried out for 20min under the condition that the temperature is 0 ℃ and the stirring rate is 1200r/min, then 10g of intermediate 3 is added for continuous stirring reaction for 30min, the reaction product is subjected to rotary evaporation at the temperature of 90 ℃ after the reaction is finished to remove the chlorobenzene, then the evaporation product is added into chloroform to be dissolved, then hydrochloric acid solution with the mass fraction of 15% and distilled water are sequentially used for washing for 3 times, standing and layering are carried out, and the chloroform is removed by rotary evaporation of an organic layer to obtain the modified phenolic resin.
Example 3:
the embodiment is a preparation method of a modified curing agent, comprising the following steps:
adding 0.5mol of thiourea, 1mol of diethylenetriamine, thiourea and diethylenetriamine into a four-neck flask provided with a thermometer, a stirrer and a reflux condenser, heating to 130 ℃ at constant temperature under the condition of stirring rate of 100r/min, controlling the heating rate to be 1 ℃/min, stirring at constant temperature under the condition of stirring rate of 300r/min, reacting for 2h, and cooling the reaction product to room temperature after the reaction is finished to obtain the modified curing agent.
Example 4:
the embodiment is a preparation method of a modified curing agent, comprising the following steps:
adding 0.75mol of thiourea, 1mol of diethylenetriamine, thiourea and diethylenetriamine into a four-neck flask provided with a thermometer, a stirrer and a reflux condenser, heating to 135 ℃ at constant temperature under the condition of stirring rate of 300r/min, controlling the heating rate to 5 ℃/min, stirring at constant temperature under the condition of stirring rate of 500r/min, reacting for 3h, and cooling the reaction product to room temperature after the reaction is finished to obtain the modified curing agent.
Example 5:
the embodiment relates to a preparation method of a PI adhesive tape based on lithium battery welding spot protection, which comprises the following steps:
s1:20g of methyl methacrylate, 15g of butyl acrylate, 5g of hydroxypropyl methacrylate and 30g of acrylic acid were charged into a three-necked flask equipped with a stirrer and a constant-pressure dropping funnel, and 75mL of azobisisobutyronitrile was added dropwise while stirring at a temperature of 100℃and a stirring rate of 500r/min in accordance with 0.5g:100mL of azobisisobutyronitrile solution formed by dissolving methyl isobutyl ketone is controlled to have a dropping rate of 1 drop/s, the temperature is raised to 110 ℃ after the dropping is finished, stirring is continued for 2.5 hours, and the reaction product is rotationally evaporated after the reaction is finished to obtain viscous fluid with a solid content of 50%, so as to obtain polyacrylic glue;
s2: adding 4g of modified phenolic resin from example 1 and 2.5g of modified curing agent from example 3 into 100g of polyacrylic glue, dispersing for 3 hours under the condition of stirring rate of 2000r/min to obtain high-temperature-resistant glue, and coating the high-temperature-resistant glue on a PI film to prepare a tape, so as to obtain the PI tape based on lithium battery welding spot protection.
Example 6:
the embodiment relates to a preparation method of a PI adhesive tape based on lithium battery welding spot protection, which comprises the following steps:
s1:45g of methyl methacrylate, 25g of butyl acrylate, 25g of hydroxypropyl methacrylate and 50g of acrylic acid were charged into a three-necked flask equipped with a stirrer and a constant-pressure dropping funnel, and 150mL of azobisisobutyronitrile was added dropwise with stirring at a temperature of 105℃and a stirring rate of 700r/min in accordance with 1.5g:100mL of azobisisobutyronitrile solution formed by dissolving methyl isobutyl ketone is controlled to have a dropping rate of 1 drop/s, the temperature is raised to 115 ℃ after the dropping is finished, stirring is continued for 2.5 hours, and the reaction product is rotationally evaporated after the reaction is finished to obtain viscous fluid with a solid content of 80%, so as to obtain polyacrylic glue;
s2: 6g of modified phenolic resin from example 2 and 4.5g of modified curing agent from example 4 are added into 150g of polyacrylic glue, dispersed for 8 hours under the condition of stirring speed of 3000r/min, high-temperature resistant glue is obtained, and the high-temperature resistant glue is coated on a PI film to prepare a tape, so that the PI tape based on lithium battery welding spot protection is obtained.
Comparative example 1:
comparative example 1 differs from example 6 in that no modified phenolic resin was added.
Comparative example 2:
comparative example 2 differs from example 6 in that no modified curing agent was added.
Comparative example 3;
comparative example 3 differs from example 6 in that no modified phenolic resin or modified curing agent was added.
The performance of the PI tapes based on lithium battery solder joint protection of examples 5-6 and comparative examples 1-3 were tested and the test results are shown in the following table:
referring to the data in the table, according to the comparison between the examples and the comparative example 3, it can be known that the high temperature resistance obtained by using only a single polyacrylic acid glue is poor, the high temperature resistance is obviously improved by adding the modified phenolic resin and the modified curing agent, and the main effect of improving the high temperature resistance by adding the modified phenolic resin can be known by comparing the examples with the comparative examples 1-2.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (1)
1. PI adhesive tape based on lithium battery welding spot protection is characterized by comprising the following components in parts by weight: 100-150 parts of polyacrylic acid glue, 4-6 parts of modified phenolic resin and 2.5-4.5 parts of modified curing agent;
the modified phenolic resin is prepared by the following steps:
step one: adding phenol, formaldehyde solution and sodium hydroxide solution into a three-neck flask, introducing nitrogen for protection, heating to 70-75 ℃ at constant temperature under the condition of stirring speed of 200-300r/min, continuing to stir and react for 1-2h at constant temperature to obtain an intermediate 1, rotationally evaporating the intermediate 1, adding molybdic acid, continuing to stir and react for 50-90min under the condition of stirring speed of 300-500r/min at 85-95 ℃, cooling a reaction product to room temperature after the reaction is finished, and obtaining an intermediate 2, wherein the reaction principle is as follows:
step two: adding phosphorus oxychloride and anhydrous aluminum trichloride into a three-neck flask, heating to 60-65 ℃ at constant temperature under the condition of stirring speed of 200-300r/min, then adding phenol and dichloroethane into a constant pressure dropping funnel after uniformly mixing, dropwise adding mixed solution of phenol and dichloroethane, continuing constant temperature stirring reaction for 10-20h after the dropwise adding, adding distilled water into a reaction product after the reaction is finished, continuing stirring for 10-20min, filtering, and collecting fractions at 140-160 ℃ from filtrate under the condition of pressure of 0.399KPa to obtain an intermediate 3, wherein the reaction principle is as follows:
step three: adding an intermediate 2, chlorobenzene and potassium hydroxide into a three-neck flask, introducing nitrogen for protection, stirring for 10-20min under the conditions of the temperature of-5-0 ℃ and the stirring rate of 800-1200r/min, adding an intermediate 3, continuing stirring for reacting for 10-30min, performing rotary evaporation on a reaction product after the reaction is finished, adding the reaction product into chloroform for dissolving, washing with hydrochloric acid solution and distilled water for 2-3 times in sequence, standing for layering, performing rotary evaporation on an organic layer to remove chloroform, and obtaining the modified phenolic resin, wherein the reaction principle is as follows:
the mass fraction of the formaldehyde solution in the first step is 35-40%, the mass fraction of the sodium hydroxide solution is 30-40%, and the mole ratio of the phenol, formaldehyde, sodium hydroxide and molybdic acid is 1.0:1.2-1.4:0.01-0.03:0.04-0.08;
the dosage ratio of phosphorus oxychloride, anhydrous aluminum trichloride, phenol, dichloroethane and distilled water in the second step is 30-35g:1.5-2.0g:35-40g:20mL:10-20mL;
the dosage ratio of the intermediate 2 to the chlorobenzene to the potassium hydroxide to the intermediate 3 in the third step is 10g:30mL:3.5g:5-10g of hydrochloric acid solution, wherein the mass fraction of the hydrochloric acid solution is 10-15%;
the modified curing agent is prepared by the following steps:
adding thiourea and diethylenetriamine into a four-neck flask, heating to 130-135 ℃ at constant temperature under the condition of stirring speed of 100-300r/min, stirring at constant temperature under the condition of stirring speed of 300-500r/min, reacting for 2-3h, and cooling the reaction product to room temperature after the reaction is finished to obtain a modified curing agent;
the molar ratio of thiourea to diethylenetriamine is 0.5-0.75:1, a step of;
the preparation method of the PI adhesive tape based on lithium battery welding spot protection comprises the following steps:
s1: adding methyl methacrylate, butyl acrylate, hydroxypropyl methacrylate and acrylic acid into a three-neck flask, dropwise adding an azodiisobutyronitrile solution while stirring at the temperature of 100-105 ℃ and the stirring rate of 500-700r/min, heating to 110-115 ℃ after the dropwise adding, continuing stirring and reacting for 2.5h, and rotationally evaporating a reaction product after the reaction is finished to obtain a viscous fluid with the solid content of 50-80%, thereby obtaining polyacrylic glue;
s2: adding modified phenolic resin and modified curing agent into polyacrylic glue, dispersing for 3-8 hours under the condition of stirring speed of 2000-3000r/min to obtain high-temperature-resistant glue, and coating the high-temperature-resistant glue on a PI film to prepare a tape, so as to obtain the PI tape based on lithium battery welding spot protection;
the mass ratio of the methyl methacrylate, butyl acrylate, hydroxypropyl methacrylate, acrylic acid and azodiisobutyronitrile solution in the step S1 is 20-45g:15-25g:5-25g:30-50g:75-150mL of azobisisobutyronitrile solution is azobisisobutyronitrile according to 0.5-1.5g:100mL of the solution was dissolved in methyl isobutyl ketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111215934.3A CN113801597B (en) | 2021-10-19 | 2021-10-19 | PI adhesive tape based on lithium battery welding spot protection and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111215934.3A CN113801597B (en) | 2021-10-19 | 2021-10-19 | PI adhesive tape based on lithium battery welding spot protection and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113801597A CN113801597A (en) | 2021-12-17 |
| CN113801597B true CN113801597B (en) | 2023-06-06 |
Family
ID=78897994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111215934.3A Active CN113801597B (en) | 2021-10-19 | 2021-10-19 | PI adhesive tape based on lithium battery welding spot protection and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113801597B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114644742A (en) * | 2022-04-22 | 2022-06-21 | 彤程电子材料(镇江)有限公司 | Preparation process of high-uniformity phenolic resin |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105576284A (en) * | 2016-02-18 | 2016-05-11 | 福建蓝海黑石科技有限公司 | Anode aqueous binder of lithium ion battery and preparation method thereof |
| CN105838024A (en) * | 2016-05-16 | 2016-08-10 | 安徽德全新型建材科技有限公司 | Building external wall panel |
| CN109355025A (en) * | 2018-10-14 | 2019-02-19 | 佛山市顺德区永创翔亿电子材料有限公司 | Tab electrolyte resistance pressure-sensitive adhesive agent and preparation method and electrolyte resistance polar ear adhesive belt |
| CN109868078A (en) * | 2019-01-16 | 2019-06-11 | 东莞市澳中电子材料有限公司 | A kind of manufacturing method of lithium battery double-sided adhesive |
| CN109868089A (en) * | 2019-01-28 | 2019-06-11 | 东莞市澳中电子材料有限公司 | A kind of PI film non-flammable adhesive tape |
| CN112126385B (en) * | 2020-09-30 | 2023-01-31 | 东莞市骏青电子科技有限公司 | Acrylate pressure-sensitive adhesive and adhesive tape for protecting lithium battery electrode material in processing process and preparation method thereof |
| CN112920727A (en) * | 2021-02-05 | 2021-06-08 | 深圳鑫富艺科技股份有限公司 | High-temperature-resistant acrylic protective film with excellent air release property and preparation method thereof |
-
2021
- 2021-10-19 CN CN202111215934.3A patent/CN113801597B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113801597A (en) | 2021-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113801597B (en) | PI adhesive tape based on lithium battery welding spot protection and preparation method thereof | |
| JP6977839B2 (en) | Adhesive composition | |
| CN102533189B (en) | Wet-heat resisting automobile folding adhesive and preparation method thereof | |
| CN1289621C (en) | Cationic polymerizable adhesive composition and anisotropically electroconductive adhesive composition | |
| CN113278391A (en) | Ultrahigh-temperature-resistant acrylate pressure-sensitive adhesive | |
| CN1646657A (en) | Cationic polymerizable adhesive composition and anisotropically electroconductive adhesive composition | |
| JP2011026383A (en) | Heat curing type thermally conductive adhesive composition | |
| CN109385235B (en) | Electrolyte-resistant adhesive for lithium battery, preparation method of electrolyte-resistant adhesive and adhesive tape for lithium battery | |
| CN113930174B (en) | High-flame-retardant heat-insulation functional adhesive tape and preparation process thereof | |
| JP2012167051A (en) | Sulfonium benzene sulfonate complex and resin composition | |
| CN115322721A (en) | Room-temperature-cured epoxy heat-conducting adhesive for lithium battery, heat-conducting shell and preparation method of heat-conducting shell | |
| CN114437489A (en) | Prepreg prepared from boron nitride modified by continuous method and high-thermal-conductivity thermosetting high-frequency copper-clad plate | |
| CN114059354A (en) | Process for preparing Teflon high-temperature cloth based on impregnation method | |
| CN111826104A (en) | Flame-retardant adhesive for termination adhesive tape, flame-retardant termination adhesive tape and preparation method thereof | |
| WO2020157616A1 (en) | Photocurable adhesive composition and photocurable adhesive tape | |
| CN117050668B (en) | Protective film applied to new energy battery shell and preparation method thereof | |
| EP4286488A1 (en) | Snap-cure flexible electrically conductive one-component (1k) epoxy adhesive composition | |
| CN114656888A (en) | High-temperature-resistant corrosion-resistant polyimide label material and preparation method thereof | |
| JP2006107832A (en) | Separator for battery and manufacturing method for battery using it | |
| JPS6363770A (en) | Adhesive for copper-clad laminate | |
| CN111116781B (en) | Acrylic thermoplastic resin for halogen-free flame-retardant glass fiber reinforced composite material and preparation method thereof | |
| CN113861855A (en) | PI adhesive tape for protecting lithium battery tab | |
| CN115197667A (en) | Special adhesive for connecting fluoroplastic lining layers and preparation method thereof | |
| JP3205915B2 (en) | Metal-containing epoxy resin composition and method for producing the same | |
| CN116496737A (en) | Conductive adhesive sealant with high adhesive strength, low permanent compression deformation rate and low air permeability and preparation method thereof |
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 |