CN113024790A - Intrinsic flame-retardant acrylate oligomer and acrylate structural adhesive - Google Patents
Intrinsic flame-retardant acrylate oligomer and acrylate structural adhesive Download PDFInfo
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
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- 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
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- 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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
- C09J167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
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Abstract
The intrinsic flame-retardant acrylate oligomer is prepared by the reaction between acrylic acid and phosphine pentachloride, then the intrinsic flame-retardant acrylate oligomer is prepared by the polycondensation reaction between unsaturated phosphonate, epoxy acrylic acid and long-chain dibasic acid, and the intrinsic flame-retardant acrylate oligomer is applied to the acrylate structural adhesive to prepare the intrinsic flame-retardant acrylate structural adhesive. The invention unexpectedly discovers that the addition of the unsaturated silane monomer improves the humidity-heat-aging resistance of the acrylate structural adhesive, and simultaneously, the unsaturated silane monomer can be cooperated with the intrinsic flame-retardant acrylate oligomer to further improve the flame retardant property of the acrylate structural adhesive. The structural adhesive prepared by the invention has good heat-conducting property, is convenient for heat release, and is suitable for the field of electric appliances with heat dissipation problems.
Description
Technical Field
The invention belongs to the technical field of acrylate structural adhesives, and particularly relates to an intrinsic flame-retardant acrylate oligomer and an acrylate structural adhesive.
Background
The acrylate structural adhesive is prepared by a free radical copolymerization method, can be rapidly cured at room temperature, and has the characteristics of high strength, oil surface adhesion, strong adaptability, convenient use and the like. The two-component acrylate structural adhesive consists of two liquids (liquid A and liquid B), and when the two-component acrylate structural adhesive is used, the two liquids are coated on two bonded surfaces respectively, so that effective bonding can be generated within dozens of seconds to dozens of minutes. The solution A generally comprises acrylate monomers, polymer elastomers, stabilizers and initiators; the solution B usually comprises an accelerator, an auxiliary accelerator, a solvent and the like. Compared with other double-component structural adhesives, the double-component acrylate structural adhesive has high curing speed; the two components do not need to be strictly metered, and the dual-component injection is convenient to use (can be used after being mixed) and is convenient for automatic operation; the bondable material is wide; the bonding strength is high; the two-component acrylate structural adhesive has high impact strength, good high and low temperature resistance and good boiling resistance, and is widely applied to the hot door fields of aerospace, automobiles, electronic appliances and the like due to the excellent properties.
Patent CN201911065629.3 discloses the development of a flame-retardant bi-component structure bonding acrylate adhesive, which comprises the following components by weight: (1) the main agent comprises the following components: 30-60 parts of at least 1 vinyl acrylic monomer, 15-35 parts of elastomer, 5-20 parts of flame-retardant monomer, 0.1-5 parts of stabilizer and 1-8 parts of peroxide initiator; (2) curing agent component: 25-50 parts of at least 1 vinyl acrylic monomer, 5-30 parts of elastomer, 5-20 parts of flame-retardant monomer, 0.01-0.5 part of stabilizer, 1-10 parts of accelerator, 0-25 parts of methacrylic acid and 1-5 parts of auxiliary accelerator, wherein the flame-retardant monomer is TCEP, TXP, CDP, TCPP or a mixture thereof. Patent CN201711341293.X discloses an acrylate structural adhesive bonded with an aluminum shell of a flame-retardant power battery and a preparation method thereof, wherein the structural adhesive comprises 10-30 parts of flame retardant, the flame retardant is at least two of ammonium polyphosphate, melamine cyanurate, tris (2-chloroethyl) phosphate, triaryl phosphate and tris (2-chloropropyl) phosphate, and the structural adhesive has a flame-retardant effect and can effectively improve the safety and reliability of the battery. The structural adhesive disclosed in the above patent has both good mechanical properties and excellent flame retardant properties, but since the flame retardant is an additive flame retardant, the flame retardant is easily precipitated after a certain period of time or at a high temperature, resulting in a decrease or loss of the flame retardant effect.
Therefore, in order to solve the migration and precipitation phenomena of the additive flame retardant in the acrylate adhesive, it is very necessary to develop an intrinsic flame retardant structural adhesive to promote the application of the structural adhesive in the field of structural adhesives.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an intrinsic flame-retardant acrylate oligomer and an acrylate structural adhesive. Wherein, in the preparation process of the acrylate oligomer: firstly, unsaturated phosphonate is prepared through the reaction between acrylic acid and phosphorus pentachloride, then the intrinsic flame-retardant acrylate oligomer is prepared through the polycondensation reaction among the unsaturated phosphonate, epoxy acrylic acid and long-chain dibasic acid, the main chain segment of the oligomer contains unsaturated double bonds and flame-retardant functional groups, namely phosphonate groups, and the intrinsic flame-retardant acrylate structural adhesive can be prepared by applying the oligomer to the acrylate structural adhesive, and has excellent flame-retardant performance. In addition, unexpected discovery is also found that the addition of a part of unsaturated silane monomers in the acrylate structural adhesive can improve the humidity and heat aging resistance of the acrylate structural adhesive, and meanwhile, the unsaturated silane monomers can cooperate with the intrinsic flame-retardant acrylate oligomer to further improve the flame retardant property of the acrylate structural adhesive.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
an inherently flame retardant acrylate oligomer, having the structure:
R2is C9-C16 straight chain alkylene;
m is an integer of 10 to 20.
The weight average molecular weight of the oligomer was 5000-10000 g/mol.
A preparation method of an intrinsic flame-retardant acrylate oligomer comprises the following steps:
s1, preparing unsaturated phosphonate: adding phosphorus pentachloride into an acrylic acid solution, controlling the temperature, reacting at constant temperature, filtering unreacted phosphorus pentachloride, adding water into the filtrate, heating, hydrolyzing at constant temperature under stirring, and distilling under reduced pressure to obtain viscous unsaturated phosphonate;
s2, synthesizing an oligomer: adding epoxy resin and an organic solvent into a reaction kettle in an inert atmosphere, heating for the first time, dropwise adding a mixture of long-chain dibasic acid, a polymerization inhibitor and a catalyst into the reaction kettle, reacting at constant temperature for the first time, cooling when the acid value is less than 10mg/KOH/g, dropwise adding the unsaturated phosphonate obtained in the step S1, continuing reacting at constant temperature, stopping the reaction when the acid value is less than 5mg/KOH/g, and distilling under reduced pressure to obtain the intrinsic flame-retardant acrylate oligomer.
The preparation method of the unsaturated phosphonate in the step S1 is one of the common synthetic methods in the field of preparing phosphonate flame retardants: the unsaturated hydrocarbon is reacted with phosphine pentachloride and then hydrolyzed.
The molar ratio of the acrylic acid to the phosphorus pentachloride in the step S1 is 1: 1.05-1.2; the solvent of the acrylic acid solution is not particularly limited, and is commonly used in the art, including but not limited to diethyl ether; the temperature-controlled constant-temperature reaction temperature is 10-20 ℃, the reaction time is 1-3h, the temperature is raised to 60-100 ℃, and the hydrolysis reaction time is 1-3 h;
in the step S2, the epoxy resin is bisphenol A type epoxy resin, and the epoxy value is 0.44-0.51; the molar ratio of the epoxy resin to the long-chain dibasic acid to the unsaturated phosphonate ester is 1-1.2:1: 0.05-0.15; the organic solvent is not particularly limited and is commonly used in the artIncluding but not limited to toluene; the temperature is raised to 90-120 ℃ for the first time; the long-chain dibasic acid has a general formula of HOOC-R2-COOH, wherein R2Is a straight chain alkylene with 9-16 carbon atoms, namely the long-chain dibasic acid is selected from at least one of undecanedioic acid to octadecanedioic acid; the polymerization inhibitor is not particularly limited, and is commonly used in the art, and includes but is not limited to at least one of hydroquinone and p-hydroxyanisole; the catalyst is not particularly limited and is commonly used in the art and includes, but is not limited to, tetrabutylammonium bromide; the dropping time of the mixture of the long-chain dicarboxylic acid, the polymerization inhibitor and the catalyst is 0.5-1 h; the first constant-temperature reaction time is 1-5 h; the temperature is reduced to 70-850 ℃; the dropping time of the unsaturated phosphonate is 0.5-1 h; the continuous constant-temperature reaction time is 3-10 h.
Preferably, the molar ratio of the epoxy resin, the long-chain dibasic acid and the unsaturated phosphonate ester is 1.05-1.2:1: 0.05-0.15. The epoxy resin is slightly excessive, the polycondensate terminated by the epoxy group is obtained, and then the reaction is continued with the unsaturated phosphate to obtain the oligomer with the end group of the unsaturated phosphate, namely the intrinsic flame-retardant acrylate oligomer.
The invention also provides an acrylate structural adhesive, which comprises A, B components, wherein the A, B components respectively comprise the following raw materials:
the component A comprises: acrylate monomer, the intrinsic flame-retardant acrylate oligomer, polymer elastomer, reducing agent, stabilizer and heat-conducting filler;
the component B comprises: peroxide and toughening agent.
Further, the A, B components respectively comprise the following raw materials in parts by weight:
the component A comprises: 30-60 parts of acrylate monomers, 20-30 parts of intrinsic flame-retardant acrylate oligomers, 1-10 parts of polymer elastomers, 0.1-1 part of reducing agents, 0.1-1 part of stabilizing agents and 10-30 parts of heat-conducting fillers;
the component B comprises: 20-50 parts of peroxide and 10-20 parts of toughening agent.
The acrylic ester monomer in the component A comprises at least one of acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, tetrahydrofuran methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, 2-phenoxyethyl methacrylate and tetraethylene glycol dimethacrylate;
the polymer elastomer in the a component is not particularly limited, and may be one commonly used in the art, and includes at least one of neoprene, nitrile rubber, SBS, urethane rubber, and acrylate rubber.
The stabilizer in the component A comprises at least one of hydroquinone, methyl hydroquinone, 1, 4-naphthoquinone and p-hydroxyanisole.
The reducing agent in the component A comprises at least one of N, N-dimethyl-p-toluidine, N-dihydroxyethyl-p-toluidine, tetramethyl thiourea and 3, 5-diethyl-1, 2-dihydro-1-phenyl-2-propyl pyridine.
The heat-conducting filler in the component A comprises at least one of aluminum oxide, magnesium oxide, zinc oxide, boron nitride and aluminum nitride.
The peroxide in the component B comprises at least one of oxidizing agents such as benzoyl peroxide, cumene hydroperoxide, lauroyl peroxide, methyl ethyl ketone peroxide and the like.
The toughening agent in the component B is epoxy resin, and the epoxy value of the epoxy resin is 0.41-0.54.
Preferably, the component A can also comprise 3-5 parts of unsaturated silane monomers.
More preferably, the unsaturated silane monomer is at least one selected from the group consisting of allyl tert-butyldimethylsilane, 2-allyltrimethylsilane, and dimethylallylenesilane.
The preparation method of the acrylate structural adhesive comprises the following steps:
and (T1) preparing a component A: adding an acrylate monomer, a stabilizer and an intrinsic flame-retardant acrylate oligomer into a container, stirring for 1-3h at 50-80 ℃, uniformly mixing, cooling to 15-35 ℃, adding a polymer elastomer, a reducing agent and a heat-conducting filler, and finally defoaming in vacuum to obtain the A adhesive.
And (T2) preparing a component B: adding peroxide and a toughening agent into a container, uniformly mixing, and performing vacuum defoaming to obtain a B glue;
when in use, the component A and the component B are uniformly mixed according to the volume ratio of 8-15: 1.
The unsaturated silane monomer is added after the temperature of step T1 is reduced.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, unsaturated phosphonate is prepared through the reaction between acrylic acid and phosphorus pentachloride, and then the intrinsic flame-retardant acrylate oligomer is prepared through the polycondensation reaction between the unsaturated phosphonate, epoxy resin and long-chain dibasic acid, wherein the main chain segment of the oligomer contains unsaturated double bonds and a flame-retardant functional group, namely phosphonate group, and the intrinsic flame-retardant acrylate structural adhesive can be prepared by applying the oligomer to the acrylate structural adhesive, and has excellent flame-retardant property.
The invention unexpectedly discovers that the moisture-heat-aging resistance of the acrylate structural adhesive can be improved by adding a certain amount of unsaturated silane monomer into the component A, and meanwhile, the unsaturated silane monomer can be cooperated with the intrinsic flame-retardant acrylate oligomer to further improve the flame retardant property of the acrylate structural adhesive.
The structural adhesive prepared by the invention has good heat-conducting property, is convenient for heat release, and is suitable for the field of electric appliances with heat dissipation problems.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the descriptions in the following. Unless otherwise specified, "parts" in the examples of the present invention are parts by weight. All reagents used are commercially available in the art.
Preparation of intrinsic flame-retardant acrylate oligomer
Preparation example 1
S1, preparing unsaturated phosphonate: adding 1.2mol of phosphorus pentachloride into an ether solution dissolved with 1mol of acrylic acid, controlling the temperature to be 15 ℃, reacting for 3 hours at constant temperature, filtering out unreacted phosphorus pentachloride, adding water into filtrate, heating to 90 ℃, hydrolyzing at constant temperature under the stirring condition of the rotating speed of 100r/min, distilling under reduced pressure, and removing water and ether to obtain viscous unsaturated phosphonate;
s2, synthesizing an oligomer: under the atmosphere of nitrogen, 22mol of epoxy resin E-51 and 120mol of toluene are added into a reaction kettle, the temperature is raised to 100 ℃ for the first time, a mixture of 20mol of octadecanedioic acid, 0.001mol of hydroquinone and 0.5mol of tetrabutylammonium bromide is dripped into the reaction kettle, after dripping is finished within 0.5h, the isothermal reaction is carried out for 3h, when the acid value is measured to be less than 10mg/KOH/g, the temperature is lowered to 80 ℃, 1.6mol of the unsaturated phosphonate obtained in the step S1 is dripped, after dripping is finished within 0.5h, the isothermal reaction is continued for 5h, when the acid value is reduced to be less than 5mg/KOH/g, the reaction is stopped, and reduced pressure distillation is carried out, thus obtaining the intrinsic acrylic ester oligomer.
Preparation example 2
The same as in production example 1 except that the unsaturated phosphonic acid ester obtained in step S1 in step S2 was used in an amount of 3 mol.
Preparation example 3
The same as preparation example 1 except that the unsaturated phosphonate prepared in step S1 was used in an amount of 3.6mol in step S2.
Preparation example 4
The same as preparation example 1 except that the unsaturated phosphonate prepared in step S1 was used in an amount of 1.3mol in step S2.
Application example 1
And (T1) preparing a component A: adding 30 parts of methyl methacrylate, 0.5 part of p-hydroxyanisole and 20 parts of the intrinsic flame retardant acrylate oligomer prepared in preparation example 1 into a container, stirring for 1h at 60 ℃, uniformly mixing, cooling to 25 ℃, adding 8 parts of SBS, 0.5 part of N, N-dimethyl-p-toluidine and 20 parts of aluminum nitride, and finally vacuumizing and defoaming to obtain the adhesive A.
And (T2) preparing a component B: adding 50 parts of benzoyl peroxide and 10 parts of epoxy resin E-44 into a container, uniformly mixing, and then vacuumizing and defoaming to obtain B glue;
when in use, the component A and the component B are uniformly mixed according to the volume ratio of 10: 1.
Application example 2
The rest is the same as in application example 1 except that 30 parts of the inherently flame retardant acrylate oligomer prepared in preparation example 1 was used in step T1.
Application example 3
The same as in application example 1 except that methyl methacrylate was used in an amount of 60 parts in step T1.
Application example 4
The rest is the same as application example 1, except that the raw material added after the temperature of step T1 is reduced further comprises 3 parts of allyl tert-butyl dimethyl silicon.
Application example 5
The rest is the same as application example 1, except that the raw material added after the temperature of step T1 is reduced further comprises 5 parts of allyl tert-butyl dimethyl silicon.
Application example 6
The rest was the same as in application example 1, except that the intrinsic flame retardant acrylate oligomer of step T1 was prepared for preparation example 2.
Application example 7
The rest was the same as in application example 1, except that the inherently flame retardant acrylate oligomer of step T1 was prepared for preparation example 3.
Application example 8
The rest was the same as in application example 1, except that the inherently flame retardant acrylate oligomer of step T1 was prepared for preparation example 4.
The following performance tests were performed on the intrinsic flame retardant acrylate oligomer prepared in the preparation example and the structural adhesive prepared in the application example, and the test results are shown in the table:
oligomer weight average molecular weight determination: the test was carried out using a gel chromatography system (samples were dissolved in tetrahydrofuran at a concentration of 5-10 mg/ml).
Flame retardant property: the test was carried out with reference to the standard GB/T5455-1997.
V-0: after two 10 second burn tests on the samples, the flame was extinguished within 30s and no combustibles could fall.
V-1: after two 10 second burn tests on the samples, the flame was extinguished within 60s and no combustibles could fall.
V-2: after two 10 second burn tests on the samples, the flame extinguished within 60s and any combustibles could fall.
And (3) continuous combustion: the samples were continuously burned with flame after removal of the flame source under defined laboratory conditions.
The time of continuous combustion: the duration of combustion, the time of flaming combustion, of the sample after removal of the flame source under defined laboratory conditions.
Coefficient of thermal conductivity: the test was performed with reference to ISO 8302.
Shear strength: the test was performed with reference to the standard GB/T7124-.
Resistance to wet heat aging: and (3) putting the cured shear test piece into a damp-heat aging box (50 +/-2 ℃) to carry out an aging test in an environment with the humidity of 95%, and carrying out a shear strength retention rate test according to the standard GB/T7124-2008.
TABLE 1
TABLE 2
As can be seen from Table 2, the acrylate structural adhesive prepared by the invention has excellent comprehensive performance, particularly, the flame retardant grade of the structural adhesive after being cured in application example 1 is V-0 grade, the after-burning time is shorter by 4.1s, and the shear strength retention rate is as high as 70.1%.
In addition, the addition of the unsaturated silane monomer can improve the humidity and heat aging resistance of the acrylate structural adhesive, and meanwhile, the unsaturated silane monomer can be cooperated with the intrinsic flame-retardant acrylate oligomer to further improve the flame retardant property of the acrylate structural adhesive.
The structural adhesive prepared by the invention has good heat-conducting property, is convenient for heat release, and is suitable for the field of electric appliances with heat dissipation problems.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (10)
2. The acrylate oligomer of claim 1 wherein the weight average molecular weight of the oligomer is 5000-10000 g/mol.
3. A process for preparing the acrylate oligomer of claim 1 or 2, comprising the steps of:
s1, preparing unsaturated phosphonate: adding phosphorus pentachloride into an acrylic acid solution, controlling the temperature, reacting at constant temperature, filtering unreacted phosphorus pentachloride, adding water into the filtrate, heating, hydrolyzing at constant temperature under stirring, and distilling under reduced pressure to obtain viscous unsaturated phosphonate;
s2, synthesizing an oligomer: adding epoxy resin and an organic solvent into a reaction kettle in an inert atmosphere, heating for the first time, dropwise adding a mixture of long-chain dibasic acid, a polymerization inhibitor and a catalyst into the reaction kettle, reacting at constant temperature for the first time, cooling when the acid value is less than 10mg/KOH/g, dropwise adding the unsaturated phosphonate obtained in the step S1, continuing reacting at constant temperature, stopping the reaction when the acid value is less than 5mg/KOH/g, and distilling under reduced pressure to obtain the intrinsic flame-retardant acrylate oligomer.
4. The method according to claim 3, wherein the epoxy resin in step S2 is a bisphenol A type epoxy resin having an epoxy value of 0.44 to 0.51; and/or the molar ratio of the epoxy resin, the long-chain dibasic acid and the unsaturated phosphonate ester is 1-1.2:1: 0.08-0.15; and/or the long chain dibasic acid comprises at least one of undecanedioic acid to octadecanedioic acid;
preferably, the molar ratio of the epoxy resin, the long-chain dibasic acid and the unsaturated phosphonate ester is 1.05-1.2:1: 0.05-0.15.
5. The method of claim 3, wherein the first temperature is raised to 90-120 ℃; the dropping time of the mixture of the long-chain dicarboxylic acid, the polymerization inhibitor and the catalyst is 0.5-1 h; the first constant-temperature reaction time is 1-5 h; the temperature is reduced to 70-85 ℃; the dropping time of the unsaturated phosphonate is 0.5-1 h; the continuous constant-temperature reaction time is 3-10 h.
6. An acrylate structural adhesive comprising A, B components:
the component A comprises the following raw materials: an acrylate monomer, the intrinsic flame retardant acrylate oligomer of claim 1 or 2, a polymer elastomer, a reducing agent, a stabilizer, a thermally conductive filler;
the component B comprises the following raw materials: peroxide and toughening agent.
7. The acrylate structural adhesive according to claim 6, wherein the A, B components respectively comprise the following raw materials in parts by weight:
the component A comprises: 30-60 parts of acrylate monomer, 20-30 parts of intrinsic flame retardant acrylate oligomer according to claim 1 or 2, 1-10 parts of polymer elastomer, 0.1-1 part of reducing agent, 0.1-1 part of stabilizer and 10-30 parts of heat conducting filler;
and B component: 20-50 parts of peroxide and 10-20 parts of toughening agent.
8. The acrylate structural adhesive of claim 6, wherein said component a further comprises 3-5 parts of an unsaturated silane monomer;
preferably, the unsaturated silane monomer is selected from at least one of allyl tertiary butyl dimethyl silane, 2-allyl trimethyl silane and dimethyl allyl silane.
9. The method for preparing the acrylate structural adhesive of any one of claims 6-8, comprising the following steps:
and (T1) preparing a component A: adding an acrylate monomer, a stabilizer and an intrinsic flame-retardant acrylate oligomer into a container, heating and stirring at constant temperature, uniformly mixing, cooling, adding a polymer elastomer, a reducing agent and a heat-conducting filler, and finally defoaming in vacuum to obtain the A glue;
and (T2) preparing a component B: adding peroxide and a toughening agent into a container, uniformly mixing, and performing vacuum defoaming to obtain a B glue;
when in use, the component A and the component B are uniformly mixed according to the volume ratio of 8-15: 1.
10. The method according to claim 9, wherein the temperature in step T1 is raised to 50-80 ℃, the stirring time is 1-3h, and the temperature is lowered to 15-35 ℃.
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