CN114752308A

CN114752308A - Bi-component acrylate structural adhesive

Info

Publication number: CN114752308A
Application number: CN202210240958.2A
Authority: CN
Inventors: 曹芳维; 李建华; 高瀚文
Original assignee: Fule Suzhou New Material Co ltd; Beijing Tianshan New Material Technology Co ltd
Current assignee: Fule Suzhou New Material Co ltd; Beijing Tianshan New Material Technology Co ltd
Priority date: 2022-03-10
Filing date: 2022-03-10
Publication date: 2022-07-15
Anticipated expiration: 2042-03-10
Also published as: CN114752308B

Abstract

The invention provides a bi-component acrylate structural adhesive. The structural adhesive comprises a component A and a component B, wherein the volume ratio of the component A to the component B is (0.8-1.2): 1; the component A comprises a first acrylate monomer, a first toughening agent, a first anti-shrinking agent, a first accelerating agent and an initiating agent; the component B comprises a second acrylate monomer, a second toughening agent, a second anti-shrinking agent and a second accelerator. According to the invention, through compounding of the toughening agent and the anti-shrinkage agent, the shrinkage stress in the curing process is reduced, and when a large-gap structural member is bonded, the bi-component acrylate structural adhesive has high bonding strength and good failure form, and can realize cohesive failure. The bi-component acrylate structural adhesive also has excellent wet and heat aging performance and high strength retention rate in a high-temperature and high-humidity environment, and is suitable for long-term use in bonding of large-gap structural members.

Description

Bi-component acrylate structural adhesive

Technical Field

The invention relates to the field of engineering adhesives, and particularly relates to a bi-component acrylate structural adhesive.

Background

The acrylate adhesive has the advantages of rapid curing at room temperature, high bonding strength, wide bonding materials and the like, is an important classification of engineering adhesives, and is widely applied to the fields of industry, rail transit, automobiles and the like. For structural bonding, it is important that the bonding ability is durable, that the bonding gap is large, and that high temperature and high humidity aging is a main cause of bonding failure. When the bonding interface is affected by the permeation of water vapor, the bonding force can be rapidly attenuated, and particularly when the bonding gap is large, the shrinkage stress generated by the curing of the colloid is larger, so that the permeation speed of the water vapor of the interface is accelerated, the reduction of the humidity and heat aging resistance is more obvious, and a series of safety problems such as low retention rate of high-temperature high-humidity aging strength, easy cracking after aging and the like are reflected.

The double bond functional group density of the acrylate structural adhesive is high, so that the curing shrinkage rate of the acrylate structural adhesive is large, and the volume shrinkage rate is about 10% on average. When the bonding gap is large, the acrylate structural adhesive is easy to cause the problems of tensile deformation of the base material or bonding cracking. The larger the gap is, the larger the curing shrinkage volume of the acrylate structural adhesive is, so that the bonding stress on the bonding interface of the base material is larger, and the bonding failure is more easily caused. At present, various commercially available acrylate structural adhesives are not suitable for large-gap bonding or have poor high-temperature high-humidity aging performance, and the application range of the acrylate structural adhesives is seriously influenced.

Therefore, there is a need for a new acrylate structural adhesive which is suitable for large gap bonding and has more excellent high temperature, high humidity and aging properties.

Disclosure of Invention

The invention mainly aims to provide a bi-component acrylic ester structural adhesive to solve the problem that the acrylic ester structural adhesive in the prior art has poor humidity and heat resistance and aging resistance under the condition of large-gap bonding.

In order to achieve the purpose, according to one aspect of the invention, the two-component acrylate structural adhesive comprises a component A and a component B, wherein the volume ratio of the component A to the component B is (0.8-1.2): 1; the component A comprises a first acrylate monomer, a first toughening agent, a first anti-shrinking agent, a first accelerating agent and an initiating agent; the component B comprises a second acrylate monomer, a second toughening agent, a second anti-shrinking agent and a second accelerator.

Further, the component A comprises, by weight, 30-70 parts of a first acrylate monomer, 10-45 parts of a first toughening agent, 5-15 parts of a first anti-shrinking agent, 0.5-15 parts of a first accelerating agent and 0.5-10 parts of an initiating agent; preferably, the component A comprises 40-60 parts of a first acrylate monomer, 20-40 parts of a first toughening agent, 5-10 parts of a first anti-shrinking agent, 0.5-11 parts of a first accelerating agent and 0.5-5 parts of an initiating agent; the component B comprises 30-70 parts by weight of a second acrylate monomer, 10-30 parts by weight of a second toughening agent, 5-15 parts by weight of a second anti-shrinking agent and 0.1-5 parts by weight of a second accelerating agent; preferably, the component B comprises 40-60 parts of a second acrylate monomer, 20-40 parts of a second toughening agent, 5-10 parts of a second anti-shrinking agent and 1-3 parts of a second accelerating agent.

Further, the first anti-shrinking agent and the second anti-shrinking agent are respectively and independently selected from one or more of polyvinyl acetate, polyvinyl butyral, polyvinyl pyrrolidone and polyvinyl alcohol; preferably, the first and second anti-shrinking agents are each independently selected from polyvinyl acetate and/or polyvinyl butyral; more preferably, the first and second anti-shrinking agents are the same; the first toughening agent and the second toughening agent are respectively and independently selected from one or more of neoprene, MBS resin, ABS resin, SBS resin, nitrile rubber and chlorosulfonated polyethylene; preferably, the first toughening agent and the second toughening agent both comprise an MBS resin.

Further, the first acrylate monomer and the second acrylate monomer are each independently selected from one or more of methyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethoxylated bisphenol a dimethacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, (propoxy) tripropylene alcohol triacrylate; preferably, the first acrylate monomer and the second acrylate monomer are each independently selected from one or more of methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, lauryl methacrylate and ethoxylated bisphenol a dimethacrylate.

Further, the first accelerator is one or more of acrylic acid, methacrylic acid, hydroxyethyl methacrylate phosphate, di (methacryloyloxyethyl) hydrogen phosphate, ethylene glycol methacrylate phosphate, alkyl acrylate phosphate, acid anhydride and o-sulfonylbenzene imide; the acid anhydride is one or more of maleic anhydride, methacrylic anhydride and pyromellitic dianhydride; preferably, the first accelerator is one or more of methacrylic acid, phosphoric acid hydroxyethyl methacrylate, maleic anhydride; the second accelerator is one or more of nitrogen-containing organic compounds, sulfur-containing organic compounds and transition metal compounds; preferably, the nitrogen-containing organic compound is one or more of ethylenediamine, dimethyl-p-toluidine, N-diethyl-p-toluidine and aldehyde-amine condensate, and the aldehyde-amine condensate is one or more of butyraldehyde aniline condensate, hexamethylenetetramine and 3, 5-diethyl-1, 2-dihydro-1-phenyl-2-propylpyridine (PDHP); the sulfur-containing organic compound is one or more of tetramethyl thiourea, 1-vinyl-2-thiourea and N-acryloyl thiourea; the transition metal compound is one or more of ferrocene, copper salt of acetylacetone, iron salt of acetylacetone, manganese salt of acetylacetone, copper salt of ethyl acetoacetate, iron salt of ethyl acetoacetate, manganese salt of ethyl acetoacetate, copper salt of methacrylic acid, iron salt of methacrylic acid, manganese salt of methacrylic acid, copper salt of hexanoic acid, iron salt of hexanoic acid and manganese salt of hexanoic acid; more preferably, the second accelerator is one or more of N, N-diethyl-p-toluidine, an aldehyde amine condensate, N-acrylylthiourea.

Further, the initiator is one or more of hydroperoxide, ester peroxide or acyl peroxide; preferably, the hydroperoxide is cumene hydroperoxide and/or tert-butyl hydroperoxide; the ester peroxide is peroxybenzoate and/or tert-butyl peroxybenzoate; the acyl peroxide is benzoyl peroxide and/or lauroyl peroxide; more preferably, the initiator is cumene hydroperoxide and/or tert-butyl hydroperoxide.

Further, the component A also comprises 0.1-2 parts by weight of a first stabilizer; the component B also comprises 0.1-2 parts by weight of a second stabilizer; preferably, the first stabilizer and the second stabilizer are respectively and independently selected from one or more of 2, 6-di-tert-butyl-4-methylphenol, hydroquinone, p-benzoquinone, EDTA-4Na salt and methoxyphenol; more preferably, the first stabilizer and the second stabilizer are each independently selected from one or more of 2, 6-di-tert-butyl-4-methylphenol, p-benzoquinone, EDTA-4Na salt.

Further, the component A also comprises 0.1-5 parts by weight of a first surface drying auxiliary agent; the component B also comprises 0.1-5 parts by weight of a second surface drying auxiliary agent; preferably, the first and second drying aids are each independently selected from paraffin and/or paraffin oil.

Further, the component B also comprises 7-20 parts by weight of a plasticizer; preferably, the plasticizer is one or more of diisodecyl adipate, PEG 2000-benzoate and phthalate; more preferably, the plasticizer is PEG 2000-benzoate.

Further, the component A comprises 40-50 parts by weight of methyl methacrylate, 5-10 parts by weight of hydroxyethyl methacrylate, 15-25 parts by weight of chlorosulfonated polyethylene, 5-15 parts by weight of MBS resin, 5-10 parts by weight of polyvinyl acetate, 0.3-0.6 part by weight of EDTA-4Na salt, 0.1-0.2 part by weight of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part by weight of p-benzoquinone, 5-10 parts by weight of methacrylic acid, 0.5-1 part by weight of hydroxyethyl methacrylate phosphate, 0.5-5 parts by weight of cumene hydroperoxide and 1-2 parts by weight of paraffin; the component B comprises, by weight, 40-50 parts of methyl methacrylate, 5-10 parts of lauryl methacrylate, 5-15 parts of MBS resin, 15-25 parts of SBS resin, 5-10 parts of polyvinyl acetate, 0.3-0.6 part of EDTA-4Na salt, 0.1-0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part of p-benzoquinone, 7-10 parts of PEG 2000-benzoate, 1-3 parts of butyraldehyde aniline condensation product and 1-2 parts of paraffin; or,

The component A comprises, by weight, 40-50 parts of methyl methacrylate, 5-10 parts of hydroxypropyl methacrylate, 10-20 parts of chlorosulfonated polyethylene, 5-15 parts of MBS resin, 5-10 parts of SBS resin, 5-8 parts of polyvinyl acetate, 0.1-0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part of p-benzoquinone, 5-8 parts of methacrylic acid, 0.5-1 part of hydroxyethyl methacrylate phosphate, 0.5-2 parts of cumene hydroperoxide and 1-2 parts of paraffin; the component B comprises, by weight, 45-50 parts of methyl methacrylate, 5-10 parts of lauryl methacrylate, 5-10 parts of MBS resin, 5-10 parts of SBS resin, 5-10 parts of ABS resin, 5-8 parts of polyvinyl acetate, 0.1-0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part of p-benzoquinone, 8-10 parts of PEG 2000-benzoate, 0.1-1 part of butyraldehyde aniline condensation compound, 0.5-2 parts of tetramethyl thiourea and 1-2 parts of paraffin; or,

the component A comprises, by weight, 40-50 parts of methyl methacrylate, 5-10 parts of hydroxyethyl methacrylate, 8-12 parts of chloroprene rubber, 8-12 parts of chlorosulfonated polyethylene, 8-12 parts of MBS resin, 5-8 parts of polyvinyl acetate butyral, 0.3-0.6 part of EDTA-4Na salt, 0.1-0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part of p-benzoquinone, 0.5-1 part of maleic anhydride, 1-2 parts of tert-butyl hydroperoxide and 1-2 parts of paraffin; the component B comprises, by weight, 45-50 parts of methyl methacrylate, 5-10 parts of ethoxylated bisphenol A dimethacrylate, 15-25 parts of chloroprene rubber, 5-10 parts of MBS resin, 5-8 parts of polyvinyl acetate butyral, 0.3-0.6 part of EDTA-4Na salt, 0.1-0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part of p-benzoquinone, 8-10 parts of PEG 2000-benzoate, 0.1-0.5 part of butyraldehyde aniline condensate, 0.5-1 part of N, N-diethyl-p-toluidine and 1-2 parts of paraffin.

By applying the technical scheme of the invention, the shrinkage stress in the curing process of the bi-component acrylic ester structural adhesive is reduced by compounding the toughening agent and the anti-shrinking agent. When a large-gap structural member is bonded, the bi-component acrylate structural adhesive has high bonding strength, good failure form, excellent damp-heat aging performance and high strength retention rate in a high-temperature and high-humidity environment. In addition, the initial fixing time can be adjusted within 3-40 minutes by adjusting the redox system, so that the requirements of different process beats are met, and the application range is wider. In short, the invention not only can realize stable bonding to the large-gap structural member, but also has excellent humidity and heat aging resistance, and is suitable for long-term use of bonding of the large-gap structural member.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

As described in the background of the invention, the prior art has the problem of poor wet heat aging resistance of the acrylic structural adhesive under the condition of large-gap bonding. In order to solve the problems, in an exemplary embodiment of the invention, a two-component acrylate structural adhesive is provided, which comprises an A component and a B component, wherein the volume ratio of the A component to the B component is (0.8-1.2): 1; the component A comprises a first acrylate monomer, a first toughening agent, a first anti-shrinking agent, a first accelerating agent and an initiating agent; the component B comprises a second acrylate monomer, a second toughening agent, a second anti-shrinking agent and a second accelerator.

The acrylic structural adhesive disclosed by the invention reduces the shrinkage stress in the curing process by compounding the toughening agent and the anti-shrinkage agent, and simultaneously sets the redox system to carry out gradient initiation polymerization, so that the curing stress is further reduced. In addition, through the adjustment of a redox system, the initial setting time can be adjusted within 3-40 minutes, so that the requirements of different process beats are met, the application range is wider, the strength is high when large-gap bonding is carried out, cohesive failure of colloid can be realized, and meanwhile, the adhesive can still have high strength retention rate after long-term high-temperature high-humidity aging, and is suitable for long-term use of large-gap structural member bonding.

Specifically, in a preferred embodiment, the component A comprises 30-70 parts by weight of a first acrylate monomer, 10-45 parts by weight of a first toughening agent, 5-15 parts by weight of a first anti-shrinking agent, 0.5-15 parts by weight of a first accelerator and 0.5-10 parts by weight of an initiator; preferably, the component A comprises 40-60 parts of a first acrylate monomer, 20-40 parts of a first toughening agent, 5-10 parts of a first anti-shrinking agent, 0.5-11 parts of a first accelerating agent and 0.5-5 parts of an initiating agent; the component B comprises 30-70 parts by weight of a second acrylate monomer, 10-30 parts by weight of a second toughening agent, 5-15 parts by weight of a second anti-shrinking agent and 0.1-5 parts by weight of a second accelerating agent; preferably, the component B comprises 40-60 parts of a second acrylate monomer, 20-40 parts of a second toughening agent, 5-10 parts of a second anti-shrinking agent and 1-3 parts of a second accelerating agent.

When the acrylate monomer is polymerized, the monomer molecules generate polymerization reaction to form a network macromolecule connected by covalent bonds, the intermolecular distance is reduced to cause volume shrinkage, the binder is broken when the shrinkage stress is overlarge, the surface quality of a product is also reduced, and particularly, deformation and warpage are easy to generate when a large-gap structural member is bonded. The dosage relation of the raw materials is controlled within the range, so that the action degree between the main agent and each functional auxiliary agent in the component A and the component B can be further controlled, the action effect can be optimized, the synergistic action of the toughening agent and the anti-shrinking agent can be further exerted, the shrinkage stress in the curing process can be better reduced, the bonding strength of the bonding agent can be increased, and the structural adhesive has better humidity and heat resistance and aging resistance when a large-gap structural member is bonded.

It should be noted that when the component a and the component B are mixed according to the respective parts by weight, the dimensions of the two components are not related, and in the actual preparation process, the component a and the component B are mixed according to the volume ratio (0.8-1.2): 1 after the component a and the component B are respectively prepared according to the respective dimensions in parts by weight.

To further reduce shrinkage stress during curing, in a preferred embodiment, the first and second shrink resistant agents are each independently selected from one or more of polyvinyl acetate, polyvinyl butyral, polyvinyl pyrrolidone, and polyvinyl alcohol; the anti-shrinkage agent is flexible and moisture-proof, can further reduce shrinkage stress in the curing process, and also has excellent substrate adhesion capacity, particularly, polyvinyl butyral molecules contain longer branched chains, so that the anti-shrinkage agent has good flexibility, high tensile strength and impact strength, and high adhesion with various substrates. More importantly, the anti-shrinkage agent is used, so that better fusion can be formed between the anti-shrinkage agent and other components in a bi-component acrylate structural adhesive system, and the overall performance of the structural adhesive is better improved. Preferably, the first and second anti-shrink agents are each independently selected from polyvinyl acetate and/or polyvinyl butyral; more preferably, the first and second anti-shrink agents are the same.

The purpose of adding the toughening agent is to reduce the shrinkage stress of the two-component acrylate structural adhesive in cooperation with the anti-shrinking agent, and in order to better exert the effect, in a preferred embodiment, the first toughening agent and the second toughening agent are respectively and independently selected from one or more of neoprene, MBS resin, ABS resin, SBS resin, nitrile rubber and chlorosulfonated polyethylene; preferably, the first toughening agent and the second toughening agent both comprise an MBS resin. The resin and rubber toughening agents have better elasticity after being heated, have more excellent instant bonding capability and lower toxicity. Meanwhile, the toughening agent has better compatibility with other components, the structural adhesive has better and uniform performance, and the comprehensive performance in the use process is also better.

More importantly, the anti-shrinking agent and the toughening agent both have long-chain molecular structures with certain polymerization degrees, when the anti-shrinking agent and the toughening agent are used in a matching way, the free volumes of molecules before and after polymerization are not changed greatly, and meanwhile, the anti-shrinking agent and the toughening agent can play a role of a skeleton structure in a polymer, occupy certain space between molecular chains, destroy the close packing mode of the molecular chains, increase the spacing between the molecular chains, and play a good role of reducing the volume shrinkage rate, so that the structural adhesive can be applied to the adhesion of large-gap structural members, has high adhesion strength, and simultaneously has excellent humidity-heat-aging resistance.

As a major source of structural gel strength, in a preferred embodiment, the first acrylate monomer and the second acrylate monomer are each independently selected from one or more of methyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethoxylated bisphenol a dimethacrylate, isobornyl methacrylate, tetrahydrofuryl methacrylate, trimethylolpropane trimethacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, (propoxy) tripropylene alcohol triacrylate. The structural adhesive provided by the invention provides flexibility and resilience through the cross combination of a plurality of acrylate polymers, so that the initial adhesion and the buffer performance of the structural adhesive are more excellent, and the weather resistance and the aging resistance of the product are also improved.

Preferably, the first acrylate monomer and the second acrylate monomer are each independently selected from one or more of methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, lauryl methacrylate and ethoxylated bisphenol a dimethacrylate. The methyl methacrylate and the analogue thereof have excellent bonding effect no matter the methyl methacrylate and the analogue thereof permeate or infiltrate the surface of the bonding material by depending on the characteristics of self low molecular structure, thereby playing unique advantages.

For the purpose of further improving (increasing the curing speed of the structural adhesive) the full degree of curing reaction to reduce internal stress and further improving the adhesion of the curing reaction on the surface of a substrate, the invention arranges that different first accelerators react with different second accelerators to form salts with different stability, thereby further reducing the curing stress. In a preferred embodiment, the first accelerator is one or more of acrylic acid, methacrylic acid, hydroxyethyl methacrylate phosphate, di (methacryloyloxyethyl) hydrogen phosphate, ethylene glycol methacrylate phosphate, alkyl acrylate phosphate, acid anhydride, o-sulfonylbenzimide; the acid anhydride is one or more of maleic anhydride, methacrylic anhydride and pyromellitic dianhydride; preferably, the first accelerator is one or more of methacrylic acid, phosphoric acid hydroxyethyl methacrylate, maleic anhydride; the second accelerator is one or more of nitrogen-containing organic compounds, sulfur-containing organic compounds and transition metal compounds; preferably, the nitrogen-containing organic compound is one or more of ethylenediamine, dimethyl-p-toluidine, N-diethyl-p-toluidine and aldehyde-amine condensate, and the aldehyde-amine condensate is one or more of butyraldehyde aniline condensate, hexamethylenetetramine and 3, 5-diethyl-1, 2-dihydro-1-phenyl-2-propylpyridine (PDHP); the sulfur-containing organic compound is one or more of tetramethyl thiourea, 1-vinyl-2-thiourea and N-acryloyl thiourea; the transition metal compound is one or more of ferrocene, copper salt of acetylacetone, iron salt of acetylacetone, manganese salt of acetylacetone, copper salt of ethyl acetoacetate, iron salt of ethyl acetoacetate, manganese salt of ethyl acetoacetate, copper salt of methacrylic acid, iron salt of methacrylic acid, manganese salt of methacrylic acid, copper salt of hexanoic acid, iron salt of hexanoic acid and manganese salt of hexanoic acid; more preferably, the second accelerator is one or more of N, N-diethyl-p-toluidine, an aldehyde amine condensate, N-acrylylthiourea.

The first accelerator particularly selected by the invention contains more acidic groups, when the component A and the component B are mixed to prepare the structural adhesive, the acidic groups react with a nitrogen-containing organic compound, a sulfur-containing organic compound or a transition metal compound in the second accelerator to generate a product, and then the product reacts with an initiator to generate free radicals to jointly initiate the polymerization of acrylic ester, and the free radicals can be generated in different stages of the reaction by adjusting the types of the first accelerator and the second accelerator, so that the gradient polymerization can be controlled as required, the reaction completeness is promoted, excellent adhesion is provided, firm and impact-resistant adhesion is realized, and durability is realized.

In a preferred embodiment, the initiator is one or more of a hydroperoxide, an ester peroxide, or an acyl peroxide; preferably, the hydroperoxide is cumene hydroperoxide and/or tert-butyl hydroperoxide; the ester peroxide is peroxybenzoate and/or tert-butyl peroxybenzoate; the acyl peroxide is benzoyl peroxide and/or lauroyl peroxide; the initiator can generate covalent bond homolytic fracture to generate free radicals to initiate the monomer to carry out polymerization reaction, thereby ensuring the smooth proceeding of the polymerization reaction process and improving the polymerization reaction rate. More preferably, the initiator is cumene hydroperoxide and/or tert-butyl hydroperoxide. The monomers have wide sources, the initiation speed is higher, and the polymerization reaction rate can be further improved.

In a preferred embodiment, the component A further comprises 0.1-2 parts by weight of a first stabilizer; the component B also comprises 0.1-2 parts by weight of a second stabilizer; preferably, the first stabilizer and the second stabilizer are respectively and independently selected from one or more of 2, 6-di-tert-butyl-4-methylphenol, hydroquinone, p-benzoquinone, EDTA-4Na salt and methoxyphenol; more preferably, the first stabilizer and the second stabilizer are each independently selected from one or more of 2, 6-di-tert-butyl-4-methylphenol, p-benzoquinone, EDTA-4Na salt. These stabilizers, either reducing, retard or inhibit the progress of the polymer oxidation process, thereby preventing polymer aging and extending its useful life; or can be used as a good metal ion chelating agent to remove impurity metal ions in the components of the structural adhesive, reduce the influence of the impurity metal ions on the decomposition of the polymer, further improve the storage stability of the structural adhesive and enhance the ageing resistance of the structural adhesive.

In a preferred embodiment, the component A further comprises 0.1-5 parts by weight of a first surface dry auxiliary agent; the component B also comprises 0.1-5 parts by weight of a second surface drying auxiliary agent; preferably, the first and second drying aids are each independently selected from paraffin and/or paraffin oil. The surface drying auxiliary agent is added, so that the surface drying time can be shortened, the bonded object can be quickly positioned, the curing is accelerated, the operation time is shortened, and the working efficiency is improved.

In order to further improve the flexibility of the structural adhesive, in a preferred embodiment, the component B further comprises 7-20 parts by weight of a plasticizer; preferably, the plasticizer is one or more of diisodecyl adipate, PEG 2000-benzoate and phthalate; more preferably, the plasticizer is PEG 2000-benzoate for environmental reasons.

In order to enable the structural adhesive to have better strength retention rate after long-term high-temperature high-humidity aging and be more suitable for long-term use of bonding of large-gap structural members, in a preferred embodiment, the component A comprises 40-50 parts by weight of methyl methacrylate, 5-10 parts by weight of hydroxyethyl methacrylate, 15-25 parts by weight of chlorosulfonated polyethylene, 5-15 parts by weight of MBS resin, 5-10 parts by weight of polyvinyl acetate, 0.3-0.6 part by weight of EDTA-4Na salt, 0.1-0.2 part by weight of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part by weight of p-benzoquinone, 5-10 parts by weight of methacrylic acid, 0.5-1 part by weight of hydroxyethyl methacrylate phosphate, 0.5-5 parts by weight of cumene hydroperoxide and 1-2 parts by weight of paraffin; the component B comprises, by weight, 40-50 parts of methyl methacrylate, 5-10 parts of lauryl methacrylate, 5-15 parts of MBS resin, 15-25 parts of SBS resin, 5-10 parts of polyvinyl acetate, 0.3-0.6 part of EDTA-4Na salt, 0.1-0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part of p-benzoquinone, 7-10 parts of PEG 2000-benzoate, 1-3 parts of butyraldehyde aniline condensation compound and 1-2 parts of paraffin;

Or the component A comprises 40-50 parts by weight of methyl methacrylate, 5-10 parts by weight of hydroxypropyl methacrylate, 10-20 parts by weight of chlorosulfonated polyethylene, 5-15 parts by weight of MBS resin, 5-10 parts by weight of SBS resin, 5-8 parts by weight of polyvinyl acetate, 0.1-0.2 part by weight of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part by weight of p-benzoquinone, 5-8 parts by weight of methacrylic acid, 0.5-1 part by weight of hydroxyethyl methacrylate phosphate, 0.5-2 parts by weight of cumene hydroperoxide and 1-2 parts by weight of paraffin; the component B comprises, by weight, 45-50 parts of methyl methacrylate, 5-10 parts of lauryl methacrylate, 5-10 parts of MBS resin, 5-10 parts of SBS resin, 5-10 parts of ABS resin, 5-8 parts of polyvinyl acetate, 0.1-0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part of p-benzoquinone, 8-10 parts of PEG 2000-benzoate, 0.1-1 part of butyraldehyde aniline condensation compound, 0.5-2 parts of tetramethyl thiourea and 1-2 parts of paraffin;

or the component A comprises 40-50 parts by weight of methyl methacrylate, 5-10 parts by weight of hydroxyethyl methacrylate, 8-12 parts by weight of chloroprene rubber, 8-12 parts by weight of chlorosulfonated polyethylene, 8-12 parts by weight of MBS resin, 5-8 parts by weight of polyvinyl acetate butyral, 0.3-0.6 part by weight of EDTA-4Na salt, 0.1-0.2 part by weight of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part by weight of p-benzoquinone, 0.5-1 part by weight of maleic anhydride, 1-2 parts by weight of tert-butyl hydroperoxide and 1-2 parts by weight of paraffin; the component B comprises, by weight, 45-50 parts of methyl methacrylate, 5-10 parts of ethoxylated bisphenol A dimethacrylate, 15-25 parts of chloroprene rubber, 5-10 parts of MBS resin, 5-8 parts of polyvinyl acetate butyral, 0.3-0.6 part of EDTA-4Na salt, 0.1-0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part of p-benzoquinone, 8-10 parts of PEG 2000-benzoate, 0.1-0.5 part of butyraldehyde aniline condensate, 0.5-1 part of N, N-diethyl-p-toluidine and 1-2 parts of paraffin.

On the basis of providing the bi-component acrylic ester structural adhesive, the invention also provides a preparation method of the bi-component acrylic ester structural adhesive, which comprises the following steps: preparation of the component A: mixing a first methacrylate monomer and a first toughening agent, stirring at a high speed for dispersing until the first toughening agent is completely dissolved, then adding a first stabilizing agent, a first accelerating agent, an initiating agent, a first anti-shrinking agent and a first auxiliary agent, stirring for 2-6 h under high-speed dispersion, and then defoaming in vacuum for 10-20 min to obtain a component A; preparation of the component B: mixing a second methacrylate monomer and a second toughening agent, stirring at a high speed for dispersing until the second toughening agent is completely dissolved, adding a second stabilizing agent, a second accelerating agent, a second anti-shrinkage agent, a plasticizer and a second surface drying auxiliary agent, mixing, dispersing at a high speed for 2-6 hours, and defoaming in vacuum for 20-30 min to obtain a component B; the component A and the component B are used in a matching way according to the volume ratio (0.8-1.2) to 1, and then the bi-component acrylate structural adhesive is formed. The method is simple and convenient to prepare, and the product has excellent adhesive property and damp-heat aging resistance.

The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the present application as claimed.

And (4) performance testing:

1. initial fixation time: mixing 10g of the double-component acrylate structural adhesive, timing from the uniform mixing, and calculating the time when the temperature of the double-component acrylate structural adhesive reaches 50 ℃ as initial setting time.

2. Shear strength: cutting the base material into standard cutting sheets with the size of 25mm multiplied by 100mm, then coating the mixed double-component acrylate structural adhesive on the standard cutting sheets, controlling the thickness by using glass sheets, and bonding according to the bonding area specified in GB/T7124. The plates were allowed to stand at room temperature (25 ℃) for 24 hours and tested for the strength required to pull the two cut plates apart in parallel.

3. Resistance to wet heat aging: and (3) preparing a sample according to a tensile shear strength testing method, standing for 24h, placing the bonded test piece into an aging test box with the temperature of 85 ℃/humidity of 85%, standing for 1000 h, cooling to room temperature, and testing the strength according to the tensile shear strength testing method.

4. Aging and cracking time of large-gap bonding: aluminum plates of 100X 25X 3mm size were bonded using a hard material of 30mm thickness, such as a carbon steel block, with a controlled amount of gap, with a controlled bonding area of 40X 25mm, left to stand at room temperature (25 ℃) for 24 hours for complete curing, and then placed in an aging test chamber at 85 ℃/85% humidity, and the time to complete cracking was examined.

Comparative example 1

Preparation of the component A: adding 44.7 parts of methyl methacrylate, 10 parts of methacrylic acid, 11 parts of hydroxyethyl methacrylate and 20 parts of nitrile rubber into a reaction kettle, stirring at a high speed for dispersing for 5 hours until the nitrile rubber is completely dissolved, then sequentially adding 0.5 part of EDTA-4Na salt, 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, 0.2 part of p-benzoquinone, 0.5 part of hydroxyethyl methacrylate phosphate, 1 part of cumene hydroperoxide, 2 parts of paraffin and 10 parts of MBS resin, stirring for 3 hours under high-speed dispersion, and then carrying out vacuum defoamation for 15 minutes to obtain the component A.

Preparation of the component B: adding 47 parts of methyl methacrylate, 8 parts of PEG 2000-benzoate, 5 parts of methacrylic laurate and 20 parts of nitrile rubber into a reaction kettle, stirring at a high speed for dispersing for 5 hours until the nitrile rubber is completely dissolved, then sequentially adding 0.5 part of EDTA-4Na salt, 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, 0.2 part of p-benzoquinone, 1.2 parts of N, N-diethyl-p-toluidine, 2 parts of wax assistant and 10 parts of MBS resin, stirring for 4 hours under the high speed dispersion, and defoaming for 15 minutes in vacuum to obtain the component B.

The component A and the component B are matched according to the volume ratio of 1: 1 to form the double-component acrylate structural adhesive, and the performance test results are shown in table 1.

Example 1

Preparation of the component A: adding 44.7 parts of methyl methacrylate, 5 parts of hydroxyethyl methacrylate and 20 parts of chlorosulfonated polyethylene into a reaction kettle, stirring and dispersing at a high speed for 5 hours until the chlorosulfonated polyethylene is completely dissolved, then sequentially adding 0.5 part of EDTA-4Na salt, 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, 0.2 part of p-benzoquinone, 10 parts of methacrylic acid, 0.5 part of hydroxyethyl methacrylate phosphate, 10 parts of polyvinyl acetate, 1 part of cumene hydroperoxide, 2 parts of paraffin and 10 parts of MBS resin, stirring for 3 hours under high-speed dispersion, and then carrying out vacuum deaeration for 15 minutes to obtain the component A.

Preparation of the component B: adding 47 parts of methyl methacrylate, 8 parts of PEG 2000-benzoate, 5 parts of methacrylic laurate and 20 parts of SBS resin into a reaction kettle, stirring at a high speed for dispersing for 5 hours until the SBS resin is completely dissolved, then sequentially adding 0.5 part of EDTA-4Na salt, 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, 0.2 part of p-benzoquinone, 1.2 parts of butyraldehyde aniline condensate, 10 parts of polyvinyl acetate, 2 parts of paraffin and 10 parts of MBS resin, stirring for 4 hours under the high speed dispersion, and then defoaming for 15 minutes in vacuum, thereby obtaining the component B.

Example 2

Preparation of the component A: adding 44.7 parts of methyl methacrylate, 5 parts of hydroxypropyl methacrylate, 15 parts of chlorosulfonated polyethylene and 5 parts of SBS into a reaction kettle, stirring at a high speed for 5 hours until the chlorosulfonated polyethylene and the SBS resin are completely dissolved, then sequentially adding 0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.3 part of p-benzoquinone, 5 parts of methacrylic acid, 0.5 part of hydroxyethyl methacrylate phosphate, 8 parts of polyvinyl acetate, 0.7 part of cumene hydroperoxide, 2 parts of paraffin and 10 parts of MBS resin, stirring at a high speed for 3 hours, and then carrying out vacuum defoamation for 15 minutes to obtain the component A.

Preparation of the component B: adding 47 parts of methyl methacrylate, 8 parts of PEG 2000-benzoate, 10 parts of methacrylic laurate, 10 parts of SBS resin and 10 parts of ABS resin into a reaction kettle, stirring and dispersing at a high speed for 5 hours until the SBS resin and the ABS resin are completely dissolved, then sequentially adding 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, 0.2 part of p-benzoquinone, 0.5 part of butyraldehyde aniline condensate, 0.8 part of tetramethyl thiourea, 8 parts of polyvinyl acetate, 2 parts of paraffin and 10 parts of MBS resin, stirring at a high speed for 4 hours, and then defoaming in vacuum for 15 minutes to obtain the component B.

Example 3

Preparation of the component A: adding 44.7 parts of methyl methacrylate, 5 parts of hydroxyethyl methacrylate, 10 parts of chloroprene rubber and 10 parts of chlorosulfonated polyethylene into a reaction kettle, stirring and dispersing for 5 hours at a high speed until the chloroprene rubber and the chlorosulfonated polyethylene are completely dissolved, then sequentially adding 0.5 part of EDTA-4Na salt, 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, 0.2 part of p-benzoquinone, 0.5 part of maleic anhydride, 6 parts of polyvinyl acetate butyral, 1 part of tert-butyl hydroperoxide and 2 parts of paraffin, 10 parts of MBS resin, stirring for 3 hours under high-speed dispersion, and then carrying out vacuum deaeration for 15 minutes to obtain the component A.

Preparation of the component B: adding 47 parts of methyl methacrylate, 8 parts of PEG 2000-benzoate, 5 parts of ethoxylated bisphenol A dimethacrylate and 20 parts of chloroprene rubber into a reaction kettle, stirring and dispersing at a high speed for 5 hours until the chloroprene rubber is completely dissolved, then sequentially adding 0.5 part of EDTA-4Na salt, 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, 0.2 part of p-benzoquinone, 0.3 part of butyraldehyde aniline condensate, 0.9 part of N, N-diethyl-p-toluidine, 6 parts of polyvinyl acetate butyral, 2 parts of paraffin and 10 parts of MBS resin, stirring for 4 hours under high-speed dispersion, and then defoaming in vacuum for 15 minutes to obtain the component B.

TABLE 1

As can be seen from table 1: the two-component acrylate structural adhesive prepared by the embodiment of the invention has higher shear strength and excellent failure form for the bonding of large-gap structural members, and the initial setting time can be adjusted in a wider range, so that various large-gap bonding requirements are met. In addition, the embodiment of the invention can realize excellent moisture and heat resistance strength retention rate, has long aging cracking time of large-gap bonding and can be used for a long time.

Examples 4 to 6

Examples 4 to 6 differ from example 3 only in the volume ratio of the a component to the B component in the structural adhesive, and the results of the performance tests are shown in table 2.

TABLE 2

As can be seen from Table 2, when the volume ratio of the component A to the component B is (0.8-1.2): 1, the shear strength and the strength retention rate of the acrylate structural adhesive are both high, but the performance of the structural adhesive is reduced on the contrary when the dosage of the component A is continuously increased; in summary, the volume ratio of the component A to the component B is (0.8-1.2): 1.

Example 7

Example 7 is different from example 3 only in that the first acrylate-based monomer includes 35 parts by weight of methyl methacrylate and 5 parts by weight of hydroxypropyl methacrylate, the second acrylate-based monomer includes 40 parts by weight of methyl methacrylate and 5 parts by weight of hydroxypropyl methacrylate, and the results of the performance test are shown in table 3.

Example 8

Example 8 differs from example 3 only in that the first acrylate-based monomer comprises, by weight, 45 parts methyl methacrylate and 5 parts lauryl methacrylate, and the second acrylate-based monomer comprises 45 parts methyl methacrylate and 5 parts lauryl methacrylate, and the performance test results are shown in table 3.

Example 9

Example 9 differs from example 3 only in that the first acrylate monomer comprises 65 parts by weight of hydroxyethyl methacrylate and 5 parts by weight of tetrahydrofuran methacrylate, the second acrylate monomer comprises 65 parts by weight of methyl methacrylate and 5 parts by weight of isobornyl methacrylate, and the performance test results are shown in table 3.

TABLE 3

As can be seen from Table 3, when the preferred types and weight parts of the first acrylate monomer and the second acrylate monomer are selected, the shear strength and strength retention rate of the acrylate structural adhesive are high.

Example 10

Example 10 differs from example 3 only in that the first toughener comprises 8 parts by weight of neoprene, 8 parts by weight of chlorosulfonated polyethylene, 8 parts by weight of MBS resin, the second toughener comprises 15 parts by weight of neoprene, and 5 parts by weight of MBS resin, and the performance test results are shown in table 4.

Example 11

Example 11 example 3 differs only in that the first toughener comprises 12 parts neoprene, 12 parts chlorosulfonated polyethylene, 12 parts MBS resin, the second toughener comprises 25 parts neoprene, 10 parts MBS resin, by weight, and the performance test results are shown in table 4.

Example 12

Example 12 differs from example 3 only in that the first toughener comprises 10 parts by weight of neoprene and 25 parts by weight of ABS resin, 10 parts by weight of MBS resin, the second toughener comprises 20 parts by weight of chlorosulfonated polyethylene, 10 parts by weight of ABS resin, and the performance test results are shown in table 4.

TABLE 4

As can be seen from table 4, when the preferred types and parts by weight of the first toughening agent and the second toughening agent are selected, the shear strength and the strength retention rate of the acrylate structural adhesive are high.

Example 13

Example 13 differs from example 3 only in that the first anti-shrinkage agent is 5 parts by weight of polyvinyl butyral and the second anti-shrinkage agent is 5 parts by weight of polyvinyl butyral and the results of the performance tests are given in table 5.

Example 14

Example 14 differs from example 3 only in that the first anti-shrinkage agent is 10 parts by weight polyvinyl butyral and the second anti-shrinkage agent is 10 parts by weight polyvinyl acetate and the results of the performance tests are shown in table 5.

Example 15

Example 15 differs from example 3 only in that the first anti-shrinkage agent is 15 parts by weight polyvinyl butyral and the second anti-shrinkage agent is 15 parts by weight polyvinyl pyrrolidone, and the results of the performance tests are shown in table 5.

Example 16

Example 16 differs from example 3 only in that the first anti-shrinkage agent is 20 parts by weight polyvinyl butyral and the second anti-shrinkage agent is 20 parts by weight polyvinyl alcohol and the results of the performance tests are shown in table 5.

TABLE 5

As can be seen from Table 5, when the preferred types and weight parts of the first anti-shrinking agent and the second anti-shrinking agent are selected, the shear strength, the strength retention rate and the aging cracking time performance of the large-gap adhesive are all better.

Example 17

Example 17 differs from example 3 only in that the first acrylate monomer is 50 parts hydroxypropyl methacrylate, the second acrylate monomer is 50 parts isobornyl methacrylate, the first anti-shrinkage agent is 15 parts of polyvinylpyrrolidone, the second anti-shrinkage agent is 10 parts of polyvinyl alcohol, the first toughening agent is 20 parts of nitrile rubber, the second toughening agent is 30 parts of ABS resin, the first accelerant is 5 parts of methacrylic acid, the second accelerant is 1 part of N, N-diethyl-p-toluidine, the initiator is 0.5 part of benzoperoxide, the first stabilizer is 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, the second stabilizer is 2 parts of EDTA-4Na salt, the first surface drying auxiliary agent is 0.1 part of paraffin, the second surface drying auxiliary agent is 5 parts of paraffin oil, and the toughening agent is 7 parts of diisodecyl adipate. The results of the performance tests are shown in Table 6.

Example 18

Example 18 differs from example 3 only in that, by weight, the first acrylate monomer is 40 parts hydroxypropyl methacrylate, the second acrylate monomer is 40 parts isobornyl methacrylate, the first anti-shrinking agent is 10 parts polyvinylpyrrolidone, the second anti-shrinking agent is 20 parts polyvinyl alcohol, the first toughening agent is 30 parts nitrile rubber, the second toughening agent is 30 parts ABS resin, the first accelerator is 11 parts hydroxyethyl methacrylate phosphate, the second accelerator is 3 parts butyraldehyde aniline condensate, the initiator is 5 parts benzoyl peroxide, the first stabilizer is 1 part p-benzoquinone, the second stabilizer is 1 part EDTA-4Na salt, the first dry-form additive is 1 part paraffin, the second dry-form additive is 2 parts paraffin oil, and the toughening agent is 20 parts phthalate. The results of the performance tests are shown in Table 6.

Example 19

Example 19 differs from example 3 only in that the a component does not contain the first stabilizer and the first dry aid, the B component does not contain the second stabilizer, the second dry aid and the plasticizer, and the results of the performance tests are shown in table 6.

TABLE 6

As can be seen from Table 6, compared with the comparative example, the two-component acrylate structural adhesive prepared by adopting the components and the proportion of the invention has the advantages that the comprehensive performances such as the shear strength, the strength retention rate, the aging and cracking time of large-gap bonding and the like are obviously improved, and the two-component acrylate structural adhesive is suitable for long-term use of large-gap structural member bonding.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The bi-component acrylate structural adhesive is characterized by comprising a component A and a component B, wherein the volume ratio of the component A to the component B is (0.8-1.2): 1; wherein,

the component A comprises a first acrylate monomer, a first toughening agent, a first anti-shrinking agent, a first accelerating agent and an initiating agent;

the component B comprises a second acrylate monomer, a second toughening agent, a second anti-shrinking agent and a second accelerator.

2. The two-component acrylate structural adhesive of claim 1,

the component A comprises 30-70 parts by weight of the first acrylate monomer, 10-45 parts by weight of the first toughening agent, 5-15 parts by weight of the first anti-shrinkage agent, 0.5-15 parts by weight of the first accelerating agent and 0.5-10 parts by weight of the initiator; preferably, the component A comprises 40-60 parts of a first acrylate monomer, 20-40 parts of the first toughening agent, 5-10 parts of the first anti-shrinkage agent, 0.5-11 parts of the first accelerating agent and 0.5-5 parts of the initiator;

The component B comprises 30-70 parts by weight of the second acrylate monomer, 10-30 parts by weight of the second toughening agent, 5-15 parts by weight of the second anti-shrinkage agent and 0.1-5 parts by weight of the second accelerator; preferably, the component B comprises 40-60 parts of the second acrylate monomer, 20-40 parts of the second toughening agent, 5-10 parts of the second anti-shrinkage agent and 1-3 parts of the second accelerator.

3. The two-component acrylate structural adhesive of claim 1 or 2,

the first and second anti-shrinkage agents are each independently selected from one or more of polyvinyl acetate, polyvinyl butyral, polyvinyl pyrrolidone, and polyvinyl alcohol; preferably, the first and second anti-shrink agents are each independently selected from polyvinyl acetate and/or polyvinyl butyral; more preferably, the first and second anti-shrink agents are the same;

the first toughening agent and the second toughening agent are respectively and independently selected from one or more of chloroprene rubber, MBS resin, ABS resin, SBS resin, nitrile rubber and chlorosulfonated polyethylene; preferably, the first toughening agent and the second toughening agent both comprise an MBS resin.

4. The two-component acrylate structural adhesive of claim 1 or 2,

the first acrylate monomer and the second acrylate monomer are each independently selected from one or more of methyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethoxylated bisphenol a dimethacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, (propoxy) tripropylene alcohol triacrylate; preferably, the first acrylate monomer and the second acrylate monomer are each independently selected from one or more of methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, lauryl methacrylate and ethoxylated bisphenol a dimethacrylate.

5. The two-component acrylate structural adhesive of claim 1 or 2,

the first accelerator is one or more of acrylic acid, methacrylic acid, phosphoric acid hydroxyethyl methacrylate, hydrogen phosphate di (methacryloyloxyethyl) ester, glycol methacrylate phosphate, alkyl acrylate phosphate, anhydride and o-sulfonyl phthalimide; preferably, the acid anhydride is one or more of maleic anhydride, methacrylic anhydride and pyromellitic dianhydride; preferably, the first accelerator is one or more of methacrylic acid, phosphoric acid hydroxyethyl methacrylate and maleic anhydride;

The second accelerator is one or more of a nitrogen-containing organic compound, a sulfur-containing organic compound and a transition metal compound; preferably, the nitrogen-containing organic compound is one or more of ethylenediamine, dimethyl-p-toluidine, N-diethyl-p-toluidine and aldehyde-amine condensate, and the aldehyde-amine condensate is one or more of butyraldehyde aniline condensate, hexamethylenetetramine and 3, 5-diethyl-1, 2-dihydro-1-phenyl-2-propyl pyridine; the sulfur-containing organic compound is one or more of tetramethyl thiourea, 1-vinyl-2-thiourea and N-acryloyl thiourea; the transition metal compound is one or more of ferrocene, copper salt of acetylacetone, iron salt of acetylacetone, manganese salt of acetylacetone, copper salt of ethyl acetoacetate, iron salt of ethyl acetoacetate, manganese salt of ethyl acetoacetate, copper salt of methacrylic acid, iron salt of methacrylic acid, manganese salt of methacrylic acid, copper salt of hexanoic acid, iron salt of hexanoic acid and manganese salt of hexanoic acid; more preferably, the second accelerator is one or more of N, N-diethyl-p-toluidine, an aldehyde amine condensate, and N-acrylylthiourea.

6. The two-component acrylate structural adhesive of claim 1 or 2, wherein the initiator is one or more of a hydroperoxide, an ester peroxide, or an acyl peroxide; preferably, the hydroperoxide is cumene hydroperoxide and/or tert-butyl hydroperoxide; the ester peroxide is peroxybenzoate and/or tert-butyl peroxybenzoate; the acyl peroxide is benzoyl peroxide and/or lauroyl peroxide; more preferably, the initiator is cumene hydroperoxide and/or tert-butyl hydroperoxide.

7. The two-component acrylate structural adhesive according to any one of claims 1 to 6, wherein the A component further comprises 0.1 to 2 parts by weight of a first stabilizer; the component B also comprises 0.1-2 parts by weight of a second stabilizer; preferably, the first stabilizer and the second stabilizer are respectively and independently selected from one or more of 2, 6-di-tert-butyl-4-methylphenol, hydroquinone, p-benzoquinone, EDTA-4Na salt and methoxyphenol; more preferably, the first stabilizer and the second stabilizer are respectively and independently selected from one or more of 2, 6-di-tert-butyl-4-methylphenol, p-benzoquinone and EDTA-4Na salt.

8. The two-component acrylate structural adhesive of claim 7, wherein the component A further comprises 0.1-5 parts by weight of a first surface drying auxiliary agent; the component B also comprises 0.1-5 parts by weight of a second surface dry auxiliary agent; preferably, the first and second drying aids are each independently selected from paraffin and/or paraffin oil.

9. The two-component acrylate structural adhesive according to claim 8, wherein the component B further comprises 7 to 20 parts by weight of a plasticizer; preferably, the plasticizer is one or more of diisodecyl adipate, PEG 2000-benzoate and phthalate; more preferably, the plasticizer is PEG 2000-benzoate.

10. The two-component acrylate structural adhesive of claim 9,

the component A comprises 40-50 parts by weight of methyl methacrylate, 5-10 parts by weight of hydroxyethyl methacrylate, 15-25 parts by weight of chlorosulfonated polyethylene, 5-15 parts by weight of MBS resin, 5-10 parts by weight of polyvinyl acetate, 0.3-0.6 part by weight of EDTA-4Na salt, 0.1-0.2 part by weight of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part by weight of p-benzoquinone, 5-10 parts by weight of methacrylic acid, 0.5-1 part by weight of hydroxyethyl methacrylate phosphate, 0.5-5 parts by weight of cumene hydroperoxide and 1-2 parts by weight of paraffin; the component B comprises, by weight, 40-50 parts of methyl methacrylate, 5-10 parts of lauryl methacrylate, 5-15 parts of MBS resin, 15-25 parts of SBS resin, 5-10 parts of polyvinyl acetate, 0.3-0.6 part of EDTA-4Na salt, 0.1-0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part of p-benzoquinone, 7-10 parts of PEG 2000-benzoate, 1-3 parts of butyraldehyde aniline condensation product and 1-2 parts of paraffin; or,

the component A comprises 40-50 parts by weight of methyl methacrylate, 5-10 parts by weight of hydroxypropyl methacrylate, 10-20 parts by weight of chlorosulfonated polyethylene, 5-15 parts by weight of MBS resin, 5-10 parts by weight of SBS resin, 5-8 parts by weight of polyvinyl acetate, 0.1-0.2 part by weight of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part by weight of p-benzoquinone, 5-8 parts by weight of methacrylic acid, 0.5-1 part by weight of hydroxyethyl methacrylate phosphate, 0.5-2 parts by weight of cumene hydroperoxide and 1-2 parts by weight of paraffin; the component B comprises, by weight, 45-50 parts of methyl methacrylate, 5-10 parts of lauryl methacrylate, 5-10 parts of MBS resin, 5-10 parts of SBS resin, 5-10 parts of ABS resin, 5-8 parts of polyvinyl acetate, 0.1-0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part of p-benzoquinone, 8-10 parts of PEG 2000-benzoate, 0.1-1 part of butyraldehyde aniline condensation product, 0.5-2 parts of tetramethyl thiourea and 1-2 parts of paraffin; or,

The component A comprises, by weight, 40-50 parts of methyl methacrylate, 5-10 parts of hydroxyethyl methacrylate, 8-12 parts of chloroprene rubber, 8-12 parts of chlorosulfonated polyethylene, 8-12 parts of MBS resin, 5-8 parts of polyvinyl acetate butyral, 0.3-0.6 part of EDTA-4Na salt, 0.1-0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part of p-benzoquinone, 0.5-1 part of maleic anhydride, 1-2 parts of tert-butyl hydroperoxide and 1-2 parts of paraffin; the component B comprises, by weight, 45-50 parts of methyl methacrylate, 5-10 parts of ethoxylated bisphenol A dimethacrylate, 15-25 parts of chloroprene rubber, 5-10 parts of MBS resin, 5-8 parts of polyvinyl acetate butyral, 0.3-0.6 part of EDTA-4Na salt, 0.1-0.2 part of 2, 6-di-tert-butyl-4-methylphenol, 0.1-0.3 part of p-benzoquinone, 8-10 parts of PEG 2000-benzoate, 0.1-0.5 part of butyraldehyde aniline condensation product, 0.5-1 part of N, N-diethyl-p-toluidine and 1-2 parts of paraffin.