CN108084896B - A kind of acrylic structural adhesive bonded to aluminum casing of flame-retardant power battery and preparation method thereof - Google Patents

Abstract

The invention discloses an acrylate structural adhesive bonded to an aluminum casing of a flame-retardant power battery, which comprises an oxidizing agent component and a reducing agent component, and the volume ratio of the oxidizing agent component and the reducing agent component is 1:1; Including isobornyl methacrylate, 2-phenoxyethyl acrylate, 3,3,5-trimethylcycloethane methacrylate, nitrile rubber, methyl methacrylate-butyl acrylate dimethacrylate Block copolymers, flame retardants, peroxides and stabilizers; reducing agent components include tetrahydrofurfuryl methacrylate, isooctyl methacrylate, 2-hydroxyethyl methacrylate phosphate, end- Carboxyl-modified neoprene, methyl methacrylate-butyl acrylate diblock copolymer, flame retardants, substituted thioureas, cobalt naphthenates, additives and stabilizers. The invention also discloses a preparation method. The invention has low heat release during use, no pores and lines appear on the surface of the adhesive layer, and can also play a flame retardant role, thereby effectively improving the safety and reliability of the battery.

Description

A kind of acrylic structural adhesive bonded to aluminum casing of flame-retardant power battery and its preparation method

technical field

The invention relates to the technical field of acrylate structural adhesives, in particular to an acrylate structural adhesive bonded to an aluminum casing of a flame-retardant power battery and a preparation method thereof.

Background technique

As a power source that provides power sources for electric vehicles, electric trains, etc., power batteries not only require high energy and power, but also require high energy density and safety and reliability.

At present, the aluminum casing of the square power battery and the structural bonding between the aluminum casing and the battery pack are usually realized by the second-generation acrylate structural adhesive. The main reason is that the second-generation acrylate structural adhesive is a fully reacted two-component acrylate structural adhesive, which has many advantages, such as fast curing at room temperature and adjustable curing speed, oil surface bonding, and does not require strict Wide range of surface treatments and bonding materials.

However, when the existing acrylate structural adhesive is used, the heat generation cannot be controlled, and a large amount of mixing (above 10g) will cause a violent exothermic reaction, resulting in a large number of pores and lines on the surface of the adhesive layer; the power battery after bonding is used. During the process, if the vehicle vibrates or the ambient temperature changes, the internal structure of the battery will change, the safety performance of the battery will be reduced, it is more dangerous, and even combustion may occur, causing car crashes and fatal accidents.

SUMMARY OF THE INVENTION

In view of the defects in the prior art, the purpose of the present invention is to provide an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery, which has low heat release during use, no pores and lines on the surface of the adhesive layer, and can also It plays a flame retardant role and effectively improves the safety and reliability of the battery.

In order to achieve the above purpose, the technical solution adopted in the present invention is: an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery, which includes an oxidizing agent component and a reducing agent component;

The volume ratio of the oxidizing agent component and the reducing agent component is 1:1;

In parts by mass, every 100 parts of the oxidizing agent component includes 10-40 parts of isobornyl methacrylate, 1-20 parts of 2-phenoxyethyl acrylate, 5-15 parts of 3,3,5 -Trimethylcyclohexane methacrylate, 1-15 parts nitrile rubber, 1-10 parts methyl methacrylate-butyl acrylate diblock copolymer, 10-30 parts flame retardant, 1-6 parts parts peroxide and 1 to 4 parts stabilizer;

In terms of parts by mass, every 100 parts of the reducing agent component includes 10-40 parts of tetrahydrofurfuryl methacrylate, 1-10 parts of isooctyl methacrylate, 1-10 parts of 2-hydroxyethyl methyl methacrylate 1-15 parts of carboxyl-terminated chloroprene rubber, 1-10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 10-30 parts of flame retardant, 0.5-2 parts of substitution Thiourea, 1-4 parts of cobalt naphthenate, 0.5-5 parts of auxiliary agent and 1-4 parts of stabilizer.

Further, the volume ratio of the oxidant component and the reducing agent component is 1:1;

In parts by mass, every 100 parts of the oxidant component includes 25-35 parts of isobornyl methacrylate, 5-15 parts of 2-phenoxyethyl acrylate, 8-12 parts of 3,3,5 - Trimethylcyclohexane methacrylate, 5-12 parts of nitrile rubber, 3-8 parts of methyl methacrylate-butyl acrylate diblock copolymer, 15-25 parts of flame retardant, 2-5 parts parts peroxide and 2 to 3 parts stabilizer;

In terms of parts by mass, every 100 parts of the reducing agent component includes 28-35 parts of tetrahydrofurfuryl methacrylate, 5-8 parts of isooctyl methacrylate, 3-8 parts of 2-hydroxyethyl methyl methacrylate Acrylate Phosphate, 5-10 Parts of Carboxyl-Terminated Neoprene Rubber, 3-9 Parts of Methyl Methacrylate-Butyl Acrylate Diblock Copolymer, 25-30 Parts of Flame Retardant, 1-1.5 Parts of Substitution Thiourea, 1.5-3 parts of cobalt naphthenate, 1-3 parts of auxiliary agent and 1.5-2 parts of stabilizer.

Further, the volume ratio of the oxidant component and the reducing agent component is 1:1;

In parts by mass, every 100 parts of the oxidant component includes 30 parts of isobornyl methacrylate, 12 parts of 2-phenoxyethyl acrylate, 8 parts of 3,3,5-trimethylcyclohexane Alkyl methacrylate, 10 parts of nitrile rubber, 8 parts of methyl methacrylate-butyl acrylate diblock copolymer, 25 parts of flame retardant, 5 parts of peroxide and 2 parts of stabilizer;

In parts by mass, every 100 parts of the reducing agent component includes 35 parts of tetrahydrofurfuryl methacrylate, 8 parts of isooctyl methacrylate, 6 parts of 2-hydroxyethyl methacrylate phosphate, 8 parts of carboxyl-terminated chloroprene rubber, 8 parts of methyl methacrylate-butyl acrylate diblock copolymer, 28 parts of flame retardant, 1.5 parts of substituted thiourea, 2 parts of cobalt naphthenate, 2 parts of auxiliary and 1.5 parts stabilizer.

Further, the stabilizer is at least two of hydroquinone, naphthoquinone, 2,6-di-tert-butyl-p-(dimethylaminomethyl)phenol, disodium EDTA and p-methoxyphenol.

Further, the peroxide is one or both of cumene hydrogen peroxide, benzoyl peroxide, methyl ethyl ketone peroxide and cyclohexanone peroxide.

Further, the flame retardant is ammonium polyphosphate, melamine polyphosphate, melamine urethane, tris(2-chloroethyl) phosphate, triaryl phosphate and tris(2-chloropropyl phosphate) ) at least two of the esters.

Further, the auxiliary agent is at least one of paraffin, methacrylic acid, maleic acid and maleic acid.

The present invention also provides a preparation method of the acrylate structural adhesive bonded to the aluminum casing of the flame-retardant power battery as described above, which comprises the following steps:

The oxidant component and the reductant component are prepared, and the order of preparing the oxidant component and the reductant component is not limited;

The preparation method of the oxidizing agent component is as follows: adding isobornyl methacrylate, 2-phenoxyethyl acrylate, 3,3,5-trimethylcyclohexane methacrylate and nitrile rubber into dynamic In the mixer, stir at high speed until the nitrile rubber is completely dissolved, add methyl methacrylate-butyl acrylate diblock copolymer, flame retardant and stabilizer, stir at high speed for 0.5 to 1 hour, then add peroxide, low speed Stirring for 0.5 to 1 hour to obtain the oxidant component;

The preparation method of the reducing agent component is as follows: adding tetrahydrofurfuryl methacrylate, isooctyl methacrylate, 2-hydroxyethyl methacrylate phosphate and carboxyl-terminated chloroprene rubber into a dynamic mixer Inside, stir at high speed until the carboxyl-terminated chloroprene rubber is completely dissolved, add methyl methacrylate-butyl acrylate diblock copolymer, flame retardant, auxiliary and stabilizer, stir at high speed for 0.5 to 1 hour, add the replacement Thiourea and cobalt naphthenate are stirred at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidant component and the reductant component are packaged separately, and the oxidant component and the reductant component are mixed in a volume ratio of 1:1 to obtain a flame-retardant power battery aluminum casing bonded. Acrylic structural adhesive.

Compared with the prior art, the advantages of the present invention are:

(1) After the oxidizing agent component and the reducing agent component in the present invention are mixed, while ensuring sufficient reaction speed, the heat of reaction is greatly reduced, the excessively fast reaction can be avoided to cause a large amount of concentrated exothermic heat, and the exothermic heat of the product can be reduced. The peak value is controlled below 80°C to avoid danger caused by heat accumulation, and it can also prevent the acrylate structural adhesive from overflowing due to thermal expansion due to excessive temperature during use, and prevent the acrylic structural adhesive layer from generating bubbles and lines and volume changes after cooling. Large, in this example, the volume shrinkage of the cured product is less than 1%.

(2) In the present invention, using isobornyl methacrylate, tetrahydrofurfuryl methacrylate and isooctyl methacrylate to replace methyl methacrylate, the temperature of the product can be effectively reduced, and the strength of the product after cooling can be ensured simultaneously .

(3) In the present invention, the use of mixed organophosphorus nitrogen flame retardants can achieve V1 level flame retardant on the premise that the amount of flame retardants used does not exceed 30%, and at the same time, the product has a strong adhesion to aluminum after curing. above 16MPa.

Detailed ways

The present invention will be described in further detail below in conjunction with the embodiments.

The embodiment of the invention provides an acrylate structural adhesive bonded to an aluminum casing of a flame-retardant power battery, which includes an oxidizing agent component and a reducing agent component, wherein:

The volume ratio of the oxidizing agent component and the reducing agent component is 1:1;

In parts by mass, every 100 parts of the oxidizing agent component includes 10-40 parts of isobornyl methacrylate, 1-20 parts of 2-phenoxyethyl acrylate, 5-15 parts of 3,3,5-trimethylacrylate Methylcyclohexane methacrylate, 1-15 parts nitrile rubber, 1-10 parts methyl methacrylate-butyl acrylate diblock copolymer, 10-30 parts flame retardant, 1-6 parts oxide and 1 to 4 parts of stabilizer;

In parts by mass, each 100 parts of the reducing agent component includes 10-40 parts of tetrahydrofurfuryl methacrylate, 1-10 parts of isooctyl methacrylate, 1-10 parts of 2-hydroxyethyl methacrylate Ester phosphate, 1-15 parts of carboxyl-terminated neoprene, 1-10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 10-30 parts of flame retardant, 0.5-2 parts of substituted thiourea , 1-4 parts of cobalt naphthenate, 0.5-5 parts of auxiliary agent and 1-4 parts of stabilizer.

After the oxidant component and the reductant component in the present invention are mixed, the heat of the reaction is greatly reduced while the sufficient reaction speed is ensured, a large amount of concentrated exothermic heat caused by the reaction is avoided, and the exothermic peak value of the product can be controlled at Below 80°C, it can avoid the danger caused by heat accumulation, and can also prevent the acrylate structural adhesive from overflowing due to thermal expansion when the temperature is too high. In this example, the volume shrinkage of the cured product is less than 1%.

In the present invention, using isobornyl methacrylate, tetrahydrofurfuryl methacrylate and isooctyl methacrylate instead of methyl methacrylate can effectively reduce the temperature of the product and at the same time ensure the strength of the product after cooling.

In the present invention, the use of mixed organophosphorus nitrogen flame retardant can achieve V1 level flame retardant on the premise that the amount of the flame retardant does not exceed 30%, and the bonding strength of the product to aluminum after curing can reach more than 16MPa .

The proportion of the acrylate structural adhesive in the present invention can be selected within the above range according to actual needs. In this embodiment, the proportion can also be:

The volume ratio of the oxidizing agent component and the reducing agent component is 1:1;

In parts by mass, every 100 parts of the oxidizing agent component includes 25-35 parts of isobornyl methacrylate, 5-15 parts of 2-phenoxyethyl acrylate, 8-12 parts of 3,3,5-trimethylacrylate Methylcyclohexane methacrylate, 5-12 parts nitrile rubber, 3-8 parts methyl methacrylate-butyl acrylate diblock copolymer, 15-25 parts flame retardant, 2-5 parts oxide and 2 to 3 parts of stabilizer;

In parts by mass, every 100 parts of the reducing agent component includes 28-35 parts of tetrahydrofurfuryl methacrylate, 5-8 parts of isooctyl methacrylate, 3-8 parts of 2-hydroxyethyl methacrylate Ester Phosphate, 5-10 Parts of Carboxy-Terminated Neoprene Rubber, 3-9 Parts of Methyl Methacrylate-Butyl Acrylate Diblock Copolymer, 25-30 Parts of Flame Retardant, 1-1.5 Parts of Substituted Thiourea , 1.5-3 parts of cobalt naphthenate, 1-3 parts of auxiliary agent and 1.5-2 parts of stabilizer.

The optimum proportioning of the present invention is:

The volume ratio of the oxidizing agent component and the reducing agent component is 1:1;

In parts by mass, every 100 parts of the oxidant component includes 30 parts of isobornyl methacrylate, 12 parts of 2-phenoxyethyl acrylate, 8 parts of 3,3,5-trimethylcyclohexanemethane base acrylate, 10 parts of nitrile rubber, 8 parts of methyl methacrylate-butyl acrylate diblock copolymer, 25 parts of flame retardant, 5 parts of peroxide and 2 parts of stabilizer;

In parts by mass, every 100 parts of the reducing agent component includes 35 parts of tetrahydrofurfuryl methacrylate, 8 parts of isooctyl methacrylate, 6 parts of 2-hydroxyethyl methacrylate phosphate, 8 parts of Carboxyl-terminated neoprene, 8 parts methyl methacrylate-butyl acrylate diblock copolymer, 28 parts flame retardant, 1.5 parts substituted thiourea, 2 parts cobalt naphthenate, 2 parts auxiliary and 1.5 parts parts of stabilizer.

The stabilizer is at least two of hydroquinone, naphthoquinone, 2,6-di-tert-butyl-p-(dimethylaminomethyl)phenol, disodium EDTA and p-methoxyphenol.

The peroxide is one or both of cumene hydroperoxide, benzoyl peroxide, methyl ethyl ketone peroxide and cyclohexanone peroxide.

The flame retardant is at least one of ammonium polyphosphate, melamine polyphosphate, melamine urethane, tris(2-chloroethyl) phosphate, triaryl phosphate and tris(2-chloropropyl) phosphate two kinds. The use of mixed organophosphorus nitrogen flame retardant can achieve V1 level flame retardant under the premise that the amount of flame retardant does not exceed 30%, and the bonding strength of the product to aluminum after curing can reach more than 16MPa.

The auxiliary agent is at least one of paraffin, methacrylic acid, maleic acid and maleic acid.

The present invention also provides a preparation method of the acrylate structural adhesive bonded to the aluminum casing of the flame-retardant power battery as described above, which comprises the following steps:

The oxidant component and the reductant component are prepared, and the order of preparing the oxidant component and the reductant component is not limited;

The preparation method of the oxidant component is as follows: adding isobornyl methacrylate, 2-phenoxyethyl acrylate, 3,3,5-trimethylcyclohexane methacrylate and nitrile rubber into a dynamic mixer Inside, stir at high speed until the nitrile rubber is completely dissolved, add methyl methacrylate-butyl acrylate diblock copolymer, flame retardant and stabilizer, stir at high speed for 0.5 to 1 hour, then add peroxide, stir at low speed for 0.5 ~1 hour to obtain the oxidant component;

The preparation method of the reducing agent component is as follows: adding tetrahydrofurfuryl methacrylate, isooctyl methacrylate, 2-hydroxyethyl methacrylate phosphate and carboxyl-terminated chloroprene rubber into a dynamic mixer, Stir at high speed until the carboxyl-terminated chloroprene rubber is completely dissolved, add methyl methacrylate-butyl acrylate diblock copolymer, flame retardant, auxiliary and stabilizer, stir at high speed for 0.5 to 1 hour, add substituted thiourea and cobalt naphthenate, stirring at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidant component and the reductant component are packaged separately, and the oxidant component and the reductant component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery.

Among them, the specific selection and proportioning of stabilizers, peroxides, flame retardants and auxiliary agents within the above ranges have no substantial impact on the final strength and flame retardant properties of the acrylate structural adhesive. than strictly limited.

The present invention will be described in detail below through 11 examples and 1 comparative example.

Example 1:

Add 30 parts of isobornyl methacrylate, 12 parts of 2-phenoxyethyl acrylate, 8 parts of 3,3,5-trimethylcyclohexane methacrylate and 10 parts of nitrile rubber to the kinematic mixer Inside, stir at high speed until the nitrile rubber is completely dissolved, add 8 parts of methyl methacrylate-butyl acrylate diblock copolymer, 25 parts of flame retardant and 2 parts of stabilizer, stir at high speed for 0.5 to 1 hour, and then add 5 parts of Peroxide, stirring at low speed for 0.5 to 1 hour to obtain the oxidant component;

Add 35 parts of tetrahydrofurfuryl methacrylate, 8 parts of isooctyl methacrylate, 6 parts of 2-hydroxyethyl methacrylate phosphate and 8 parts of carboxyl-terminated neoprene rubber into the dynamic mixer, stir at high speed Until the carboxyl-terminated chloroprene rubber is completely dissolved, add 8 parts of methyl methacrylate-butyl acrylate diblock copolymer, 28 parts of flame retardant, 2 parts of auxiliary agent and 1.5 parts of stabilizer, and stir at high speed for 0.5-1 part hour, add 1.5 parts of substituted thiourea and 2 parts of cobalt naphthenate, and stir at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidizing agent component and the reducing agent component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery.

Example 2:

40 parts of isobornyl methacrylate, 15 parts of 2-phenoxyethyl acrylate, 5 parts of 3,3,5-trimethylcyclohexane methacrylate and 5 parts of nitrile rubber were added to the mixer Inside, stir at high speed until the nitrile rubber is completely dissolved, add 10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 15 parts of flame retardant and 4 parts of stabilizer, stir at high speed for 0.5 to 1 hour, and then add 6 parts of Peroxide, stirring at low speed for 0.5 to 1 hour to obtain the oxidant component;

Add 40 parts of tetrahydrofurfuryl methacrylate, 5 parts of isooctyl methacrylate, 8 parts of 2-hydroxyethyl methacrylate phosphate and 5 parts of carboxyl-terminated neoprene rubber into the dynamic mixer, high speed Stir until the carboxyl-terminated chloroprene rubber is completely dissolved, add 10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 20 parts of flame retardant, 5 parts of auxiliary agent and 2 parts of stabilizer, and stir at high speed for 0.5~ For 1 hour, add 2 parts of substituted thiourea and 3 parts of cobalt naphthenate, and stir at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidizing agent component and the reducing agent component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery.

Example 3:

Add 35 parts of isobornyl methacrylate, 20 parts of 2-phenoxyethyl acrylate, 15 parts of 3,3,5-trimethylcyclohexane methacrylate and 15 parts of nitrile rubber to the mixer Inside, stir at high speed until the nitrile rubber is completely dissolved, add 3 parts of methyl methacrylate-butyl acrylate diblock copolymer, 10 parts of flame retardant and 1 part of stabilizer, stir at high speed for 0.5 to 1 hour, and then add 1 Peroxide, stirring at low speed for 0.5 to 1 hour to obtain the oxidant component;

Add 28 parts of tetrahydrofurfuryl methacrylate, 9 parts of isooctyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate phosphate and 10 parts of carboxyl-terminated neoprene rubber into the dynamic mixer, high speed Stir until the carboxyl-terminated chloroprene rubber is completely dissolved, add 9 parts of methyl methacrylate-butyl acrylate diblock copolymer, 30 parts of flame retardant, 1 part of auxiliary agent and 3 parts of stabilizer, and stir at high speed for 0.5~ For 1 hour, add 1 part of substituted thiourea and 4 parts of cobalt naphthenate, and stir at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidizing agent component and the reducing agent component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery.

Example 4:

Add 25 parts of isobornyl methacrylate, 5 parts of 2-phenoxyethyl acrylate, 10 parts of 3,3,5-trimethylcyclohexane methacrylate and 12 parts of nitrile rubber to the mixer Inside, stir at high speed until the nitrile rubber is completely dissolved, add 9 parts of methyl methacrylate-butyl acrylate diblock copolymer, 30 parts of flame retardant and 4 parts of stabilizer, stir at high speed for 0.5 to 1 hour, and then add 5 parts of Peroxide, stirring at low speed for 0.5 to 1 hour to obtain the oxidant component;

Add 31 parts of tetrahydrofurfuryl methacrylate, 10 parts of isooctyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate phosphate and 15 parts of carboxyl-terminated neoprene rubber into the dynamic mixer, high speed Stir until the carboxyl-terminated chloroprene rubber is completely dissolved, add 3 parts of methyl methacrylate-butyl acrylate diblock copolymer, 25 parts of flame retardant, 3 parts of auxiliary agent and 1 part of stabilizer, stir at high speed for 0.5～ For 1 hour, add 0.5 parts of substituted thiourea and 1.5 parts of cobalt naphthenate, and stir at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidizing agent component and the reducing agent component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery.

Example 5:

Add 34 parts of isobornyl methacrylate, 18 parts of 2-phenoxyethyl acrylate, 13 parts of 3,3,5-trimethylcyclohexane methacrylate and 8 parts of nitrile rubber to the mixer Inside, stir at high speed until the nitrile rubber is completely dissolved, add 1 part of methyl methacrylate-butyl acrylate diblock copolymer, 21 parts of flame retardant and 3 parts of stabilizer, stir at high speed for 0.5 to 1 hour, and then add 2 Peroxide, stirring at low speed for 0.5 to 1 hour to obtain the oxidant component;

Add 28 parts of tetrahydrofurfuryl methacrylate, 10 parts of isooctyl methacrylate, 9 parts of 2-hydroxyethyl methacrylate phosphate and 14 parts of carboxyl-terminated neoprene rubber into the dynamic mixer, high speed Stir until the carboxyl-terminated chloroprene rubber is completely dissolved, add 1 part of methyl methacrylate-butyl acrylate diblock copolymer, 26 parts of flame retardant, 4 parts of auxiliary and 2.5 parts of stabilizer, and stir at high speed for 0.5~ For 1 hour, add 2 parts of substituted thiourea and 3.5 parts of cobalt naphthenate, and stir at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidizing agent component and the reducing agent component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery.

Example 6:

Add 10 parts of isobornyl methacrylate, 18 parts of 2-phenoxyethyl acrylate, 11 parts of 3,3,5-trimethylcyclohexane methacrylate and 14 parts of nitrile rubber to the mixer Inside, stir at high speed until the nitrile rubber is completely dissolved, add 10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 28 parts of flame retardant and 4 parts of stabilizer, stir at high speed for 0.5 to 1 hour, and then add 5 Peroxide, stirring at low speed for 0.5 to 1 hour to obtain the oxidant component;

Add 40 parts of tetrahydrofurfuryl alcohol methacrylate, 10 parts of isooctyl methacrylate, 3 parts of 2-hydroxyethyl methacrylate phosphate and 15 parts of carboxyl-terminated neoprene rubber into the dynamic mixer, high speed Stir until the carboxyl-terminated chloroprene rubber is completely dissolved, add 10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 13 parts of flame retardant, 3.5 parts of auxiliary agent and 2.5 parts of stabilizer, stir at high speed for 0.5-1 part hour, add 2 parts of substituted thiourea and 1 part of cobalt naphthenate, and stir at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidizing agent component and the reducing agent component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery.

Example 7:

38 parts of isobornyl methacrylate, 1 part of 2-phenoxyethyl acrylate, 10 parts of 3,3,5-trimethylcyclohexane methacrylate and 7 parts of nitrile rubber were added to the kinematic mixer Inside, stir at high speed until the nitrile rubber is completely dissolved, add 10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 26 parts of flame retardant and 3.5 parts of stabilizer, stir at high speed for 0.5 to 1 hour, and then add 4.5 parts of Peroxide, stirring at low speed for 0.5 to 1 hour to obtain the oxidant component;

Add 40 parts of tetrahydrofurfuryl methacrylate, 10 parts of isooctyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate phosphate and 10.5 parts of carboxyl-terminated neoprene rubber into the dynamic mixer, high speed Stir until the carboxyl-terminated chloroprene rubber is completely dissolved, add 10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 10 parts of flame retardant, 0.5 part of auxiliary agent and 3 parts of stabilizer, and stir at high speed for 0.5～ For 1 hour, add 2 parts of substituted thiourea and 4 parts of cobalt naphthenate, and stir at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidizing agent component and the reducing agent component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery.

Example 8:

Add 30 parts of isobornyl methacrylate, 4 parts of 2-phenoxyethyl acrylate, 12 parts of 3,3,5-trimethylcyclohexane methacrylate, and 9 parts of nitrile rubber to the mixer Inside, stir at high speed until the nitrile rubber is completely dissolved, add 9 parts of methyl methacrylate-butyl acrylate diblock copolymer, 28 parts of flame retardant and 4 parts of stabilizer, stir at high speed for 0.5 to 1 hour, and then add 4 parts of Peroxide, stirring at low speed for 0.5 to 1 hour to obtain the oxidant component;

Add 25 parts of tetrahydrofurfuryl alcohol methacrylate, 10 parts of isooctyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate phosphate, 1 part of carboxyl-terminated neoprene rubber into the dynamic mixer, high speed Stir until the carboxyl-terminated chloroprene rubber is completely dissolved, add 10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 30 parts of flame retardant, 5 parts of auxiliary agent and 3 parts of stabilizer, and stir at high speed for 0.5~ For 1 hour, add 2 parts of substituted thiourea and 4 parts of cobalt naphthenate, and stir at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidizing agent component and the reducing agent component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery.

Example 9:

Add 38 parts of isobornyl methacrylate, 9 parts of 2-phenoxyethyl acrylate, 10 parts of 3,3,5-trimethylcyclohexane methacrylate, and 10 parts of nitrile rubber to the dynamic mixer Inside, stir at high speed until the nitrile rubber is completely dissolved, add 7 parts of methyl methacrylate-butyl acrylate diblock copolymer, 20 parts of flame retardant and 2.5 parts of stabilizer, stir at high speed for 0.5 to 1 hour, and then add 3.5 parts of Peroxide, stirring at low speed for 0.5 to 1 hour to obtain the oxidant component;

Add 10 parts of tetrahydrofurfuryl methacrylate, 10 parts of isooctyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate phosphate, and 15 parts of carboxyl-terminated neoprene rubber into the dynamic mixer, high speed Stir until the carboxyl-terminated chloroprene rubber is completely dissolved, add 10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 30 parts of flame retardant, 5 parts of auxiliary agent and 4 parts of stabilizer, and stir at high speed for 0.5~ For 1 hour, add 2 parts of substituted thiourea and 4 parts of cobalt naphthenate, and stir at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidizing agent component and the reducing agent component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery.

Example 10:

Add 34 parts of isobornyl methacrylate, 10 parts of 2-phenoxyethyl acrylate, 13 parts of 3,3,5-trimethylcyclohexane methacrylate, and 7 parts of nitrile rubber to the mixer Inside, stir at high speed until the nitrile rubber is completely dissolved, add 10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 21 parts of flame retardant, 2 parts of stabilizer, stir at high speed for 0.5 to 1 hour, and then add 3 parts of peroxide, stirring at low speed for 0.5 to 1 hour to obtain the oxidant component;

Add 20 parts of tetrahydrofurfuryl methacrylate, 1 part of isooctyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate phosphate, and 15 parts of carboxyl-terminated neoprene rubber into the dynamic mixer, high speed Stir until the carboxyl-terminated chloroprene rubber is completely dissolved, add 10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 30 parts of flame retardant, 4.5 parts of auxiliary agent and 3.5 parts of stabilizer, and stir at high speed for 0.5~ For 1 hour, add 2 parts of substituted thiourea and 4 parts of cobalt naphthenate, and stir at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidizing agent component and the reducing agent component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery.

Example 11:

Add 36 parts of isobornyl methacrylate, 15 parts of 2-phenoxyethyl acrylate, 7 parts of 3,3,5-trimethylcyclohexane methacrylate, and 9 parts of nitrile rubber to the mixer Inside, stir at high speed until the nitrile rubber is completely dissolved, add 7 parts of methyl methacrylate-butyl acrylate diblock copolymer, 22 parts of flame retardant, 1.5 parts of stabilizer, stir at high speed for 0.5 to 1 hour, and then add 2.5 parts of Peroxide, stirring at low speed for 0.5 to 1 hour to obtain the oxidant component;

Add 30 parts of tetrahydrofurfuryl alcohol methacrylate, 7 parts of isooctyl methacrylate, 1 part of 2-hydroxyethyl methacrylate phosphate, and 9 parts of carboxyl-terminated neoprene rubber into the dynamic mixer, high speed Stir until the carboxyl-terminated chloroprene rubber is completely dissolved, add 10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 28 parts of flame retardant, 5 parts of auxiliary agents and 4 parts of stabilizer, and stir at high speed for 0.5~ For 1 hour, add 2 parts of substituted thiourea and 4 parts of cobalt naphthenate, and stir at low speed for 0.5 to 1 hour to obtain the reducing agent component;

The oxidizing agent component and the reducing agent component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery.

Comparative Example 1:

Add 40 parts of methyl methacrylate, 5 parts of methacrylic acid, and 9 parts of nitrile rubber into the mixer, stir at high speed until the nitrile rubber is completely dissolved, and add 7 parts of methyl methacrylate-butadiene-styrene Terpolymer, 34 parts of flame retardant and 2 parts of stabilizer, stir at high speed for 1 hour, then add 2 parts of peroxide, and stir at low speed for 1 hour to obtain the oxidant component;

Add 30 parts of methyl methacrylate, 9 parts of cyclohexyl methacrylate and 8 parts of carboxyl-terminated chloroprene rubber into the mixer, stir at high speed until the carboxyl-terminated chloroprene rubber is completely dissolved, add 10 parts of methyl methacrylate Methyl acrylate-butadiene-styrene terpolymer, 30 parts of flame retardant, 5 parts of auxiliary agent and 3 parts of stabilizer, stir at high speed for 1 hour, add 2 parts of N,N-dimethylaniline, 3 parts of Parts of N,N-dimethyl-p-toluidine were stirred at low speed for 1 hour to obtain a reducing agent component;

The oxidizing agent component and the reducing agent component are mixed in a volume ratio of 1:1 to obtain an acrylate structural adhesive.

The performance test of the acrylate structural adhesives prepared by the above 11 examples and 1 comparative example is carried out below.

Referring to Table 1, according to the GB/T2791-1995 adhesive T peel strength test method, using a flexible material to a flexible material, the T peel strength of the embodiment of the present invention can reach 6.4N/mm, and the failure form is cohesive failure, indicating that The present invention has good toughness.

According to GB/T7124-2008 Determination of Tensile Shear Strength of Adhesives, the bond strength to aluminum sheets at room temperature is tested, and the bond strength of the embodiment of the present invention can reach 16.8MPa.

The high and low temperature resistance is tested by the cold and heat cycle test. The cold and heat cycle test conditions are: 25℃ for 0.5h, 25℃～90℃ for 0.5h, 90℃ for 4h, 90℃～-40℃ for 1h, -40℃ for 4h, -40 ℃～25℃ for 0.5h, this cycle is 14 times, a total of 147h; the bonding strength of the present invention to aluminum is 17.2MPa, and the strength does not decay after thermal shock aging;

According to the UL94 standard test, the flame retardant performance of the embodiments of the present invention can reach V1 level.

Table 1. Performance test results of Examples 1 to 11 and Comparative Example 1

The present invention is not limited to the above-mentioned embodiments. For those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications are also regarded as the protection of the present invention. within the range. Contents not described in detail in this specification belong to the prior art known to those skilled in the art.

Claims (7)

1. an acrylate structural adhesive bonded by a flame-retardant power battery aluminum casing, comprising an oxidizing agent component and a reducing agent component, and is characterized in that: The volume ratio of the oxidizing agent component and the reducing agent component is 1:1; In parts by mass, every 100 parts of the oxidizing agent component includes 10-40 parts of isobornyl methacrylate, 1-20 parts of 2-phenoxyethyl acrylate, 5-15 parts of 3,3,5 -Trimethylcyclohexane methacrylate, 1-15 parts nitrile rubber, 1-10 parts methyl methacrylate-butyl acrylate diblock copolymer, 10-30 parts flame retardant, 1-6 parts parts peroxide and 1 to 4 parts stabilizer; In terms of parts by mass, every 100 parts of the reducing agent component includes 10-40 parts of tetrahydrofurfuryl methacrylate, 1-10 parts of isooctyl methacrylate, 1-10 parts of 2-hydroxyethyl methyl methacrylate 1-15 parts of carboxyl-terminated chloroprene rubber, 1-10 parts of methyl methacrylate-butyl acrylate diblock copolymer, 10-30 parts of flame retardant, 0.5-2 parts of substitution Thiourea, 1-4 parts of cobalt naphthenate, 0.5-5 parts of auxiliary agent and 1-4 parts of stabilizer, the auxiliary agent is at least one of paraffin, methacrylic acid and maleic acid. 2. The acrylate structural adhesive bonded to the flame-retardant power battery aluminum casing as claimed in claim 1, characterized in that: The volume ratio of the oxidizing agent component and the reducing agent component is 1:1; In parts by mass, every 100 parts of the oxidant component includes 25-35 parts of isobornyl methacrylate, 5-15 parts of 2-phenoxyethyl acrylate, 8-12 parts of 3,3,5 - Trimethylcyclohexane methacrylate, 5-12 parts of nitrile rubber, 3-8 parts of methyl methacrylate-butyl acrylate diblock copolymer, 15-25 parts of flame retardant, 2-5 parts parts peroxide and 2 to 3 parts stabilizer; In terms of parts by mass, every 100 parts of the reducing agent component includes 28-35 parts of tetrahydrofurfuryl methacrylate, 5-8 parts of isooctyl methacrylate, 3-8 parts of 2-hydroxyethyl methyl methacrylate Acrylate Phosphate, 5-10 Parts of Carboxyl-Terminated Neoprene Rubber, 3-9 Parts of Methyl Methacrylate-Butyl Acrylate Diblock Copolymer, 25-30 Parts of Flame Retardant, 1-1.5 Parts of Substitution Thiourea, 1.5-3 parts of cobalt naphthenate, 1-3 parts of auxiliary agent and 1.5-2 parts of stabilizer. 3. The acrylate structural adhesive bonded to the flame-retardant power battery aluminum casing as claimed in claim 1, characterized in that: The volume ratio of the oxidizing agent component and the reducing agent component is 1:1; In parts by mass, every 100 parts of the oxidant component includes 30 parts of isobornyl methacrylate, 12 parts of 2-phenoxyethyl acrylate, 8 parts of 3,3,5-trimethylcyclohexane Alkyl methacrylate, 10 parts of nitrile rubber, 8 parts of methyl methacrylate-butyl acrylate diblock copolymer, 25 parts of flame retardant, 5 parts of peroxide and 2 parts of stabilizer; In parts by mass, every 100 parts of the reducing agent component includes 35 parts of tetrahydrofurfuryl methacrylate, 8 parts of isooctyl methacrylate, 6 parts of 2-hydroxyethyl methacrylate phosphate, 8 parts of carboxyl-terminated chloroprene rubber, 8 parts of methyl methacrylate-butyl acrylate diblock copolymer, 28 parts of flame retardant, 1.5 parts of substituted thiourea, 2 parts of cobalt naphthenate, 2 parts of auxiliary and 1.5 parts stabilizer. 4. The acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery according to claim 1, wherein the stabilizer is hydroquinone, naphthoquinone, 2,6-di-tert-butylparaffin At least two of (dimethylaminomethyl)phenol, EDTA disodium salt, and p-methoxyphenol. 5. The acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery according to claim 1, wherein the peroxide is cumene hydrogen peroxide, benzoyl peroxide, methyl ethyl ketone peroxide one or both of cyclohexanone peroxide and cyclohexanone peroxide. 6 . The acrylate structural adhesive bonded to the aluminum casing of a flame-retardant power battery according to claim 1 , wherein the flame retardant is ammonium polyphosphate, melamine polyphosphate, and melamine urethane. 7 . , at least two of tris(2-chloroethyl) phosphate, triaryl phosphate and tris(2-chloropropyl) phosphate. 7. A preparation method of the acrylate structural adhesive bonded to the aluminum casing of a flame-retardant type power battery as described in any one of claims 1-6, characterized in that, it comprises the steps: The oxidant component and the reductant component are prepared, and the order of preparing the oxidant component and the reductant component is not limited; The preparation method of the oxidizing agent component is as follows: adding isobornyl methacrylate, 2-phenoxyethyl acrylate, 3,3,5-trimethylcyclohexane methacrylate and nitrile rubber into dynamic In the mixer, stir at high speed until the nitrile rubber is completely dissolved, add methyl methacrylate-butyl acrylate diblock copolymer, flame retardant and stabilizer, stir at high speed for 0.5 to 1 hour, then add peroxide, low speed Stirring for 0.5 to 1 hour to obtain the oxidant component; The preparation method of the reducing agent component is as follows: adding tetrahydrofurfuryl methacrylate, isooctyl methacrylate, 2-hydroxyethyl methacrylate phosphate and carboxyl-terminated chloroprene rubber into a dynamic mixer Inside, stir at high speed until the carboxyl-terminated chloroprene rubber is completely dissolved, add methyl methacrylate-butyl acrylate diblock copolymer, flame retardant, auxiliary and stabilizer, stir at high speed for 0.5 to 1 hour, add the replacement Thiourea and cobalt naphthenate are stirred at low speed for 0.5 to 1 hour to obtain the reducing agent component; The oxidant component and the reductant component are packaged separately, and the oxidant component and the reductant component are mixed in a volume ratio of 1:1 to obtain a flame-retardant power battery aluminum casing bonded. Acrylic structural adhesive.