阅读说明：本技术 一种长操作时间双组份丙烯酸酯结构胶及其制备方法 (Long-operation-time two-component acrylate structural adhesive and preparation method thereof ) 是由 易晨凤 罗善国 于 2020-07-23 设计创作，主要内容包括：本发明公开了一种长操作时间双组份丙烯酸酯结构胶及其制备方法,该双组份丙烯酸酯结构胶由A组分和B组分组成,且A组分与B组分按照体积比1∶1配合使用；A组分包括以下重量份数的原料：(甲基)丙烯酸酯类单体35～65份、增韧剂8～25份、稳定剂0.1～2份、促进剂2～15份、氧化剂3～15分、聚氨酯丙烯酸酯齐聚物3～10份、助剂1～5份；B组分包括以下重量份数的原料：(甲基)丙烯酸类单体30～70份、增韧剂5～20份、稳定剂0.1～2份、促进剂1～10份、还原剂3～18份、聚氨酯丙烯酸酯齐聚物3～10份、助剂1～5份。本发明不仅具备较长的操作时间,而且对常见基材具备较理想的粘接能力,强度较高,适用于大面积粘接的工况。(The invention discloses a long-operation-time two-component acrylate structural adhesive and a preparation method thereof, wherein the two-component acrylate structural adhesive consists of a component A and a component B, and the component A and the component B are matched according to the volume ratio of 1: 1; the component A comprises the following raw materials in parts by weight: 35-65 parts of (methyl) acrylate monomer, 8-25 parts of toughening agent, 0.1-2 parts of stabilizer, 2-15 parts of accelerator, 3-15 parts of oxidant, 3-10 parts of polyurethane acrylate oligomer and 1-5 parts of auxiliary agent; the component B comprises the following raw materials in parts by weight: 30-70 parts of (methyl) acrylic monomer, 5-20 parts of toughening agent, 0.1-2 parts of stabilizer, 1-10 parts of accelerator, 3-18 parts of reducing agent, 3-10 parts of polyurethane acrylate oligomer and 1-5 parts of auxiliary agent. The invention has longer operation time, ideal bonding capability to common base materials and higher strength, and is suitable for large-area bonding working conditions.)

1. A long-operation-time two-component acrylate structural adhesive is characterized by consisting of a component A and a component B, wherein the component A and the component B are matched according to the volume ratio of 1: 1; wherein the content of the first and second substances,

the component A comprises the following raw materials in parts by weight: 35-65 parts of (methyl) acrylate monomer, 8-25 parts of toughening agent, 0.1-2 parts of stabilizer, 2-15 parts of accelerator, 3-15 parts of oxidant, 3-10 parts of polyurethane acrylate oligomer and 1-5 parts of auxiliary agent;

the component B comprises the following raw materials in parts by weight: 30-70 parts of (methyl) acrylic monomer, 5-20 parts of toughening agent, 0.1-2 parts of stabilizer, 1-10 parts of accelerator, 3-18 parts of reducing agent, 3-10 parts of polyurethane acrylate oligomer and 1-5 parts of auxiliary agent.

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

the component A comprises the following raw materials in parts by weight: 45-60 parts of (methyl) acrylate monomers, 10-15 parts of toughening agents, 0.2-0.8 part of stabilizing agents, 2-7 parts of accelerators, 5-10 parts of oxidants, 5-7 parts of polyurethane acrylate oligomers and 1-5 parts of auxiliaries;

the component B comprises the following raw materials in parts by weight: 30-50 parts of (methyl) acrylate monomer, 10-15 parts of toughening agent, 0.5-1 part of stabilizer, 5-8 parts of accelerator, 5-12 parts of reducing agent, 5-10 parts of polyurethane acrylate oligomer and 1-5 parts of auxiliary agent.

3. The long-working-time two-component acrylate structural adhesive according to claim 1 or 2, the (methyl) acrylate monomer comprises at least one of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, lauryl methacrylate, dodecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, methacrylic acid, methyl acrylate, benzyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, tetrahydrofuran methacrylate, ethoxytriethylene methacrylate, ethylene glycol dimethacrylate, glycidyl methacrylate, lauryl acrylate, tridecyl acrylate and hydroxypropyl acrylate.

4. The long-operating-time two-component acrylate structural adhesive according to claim 1 or 2, wherein the toughening agent comprises at least one of nitrile rubber, styrene-butadiene rubber, chloroprene rubber, acrylate rubber, methacrylic acid-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-based block copolymer, ethylene-butylene triblock copolymer, natural rubber, polysulfide rubber, chlorosulfonated polyethylene, butadiene rubber, isoprene rubber, ethylene-propylene rubber, polyvinyl acetate, unsaturated polyester.

5. The long-working-time two-component acrylate structural adhesive according to claim 1 or 2, wherein the stabilizer comprises at least one of hydroquinone, p-benzoquinone, 2, 6-di-tert-butyl-p-cresol, benzoquinone, 1, 4-naphthoquinone, EDTA-4Na salt, EDTA-2Na salt, 4-methoxyphenol, anthraquinone, stearic acid, p-hydroxyanisole, oxalic acid, 2,6, 6-tetramethylpiperidine oxide.

6. The long-working-time two-component acrylate structural adhesive according to claim 1 or 2, wherein the accelerator comprises at least one of gamma-aminopropyltriethoxysilane, Glymo A-187 coupling agent, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, zinc methacrylate, zinc dimethacrylate, phosphate accelerators, triphenylphosphine, iron naphthenate, copper isooctanoate, cobalt isooctanoate, methyl ethyl ketone ethoxylate, and zinc permanganate.

7. The long-working-time two-component acrylate structural adhesive according to claim 1 or 2, wherein the reducing agent comprises at least one of N, N-dimethyl-p-toluidine, N-diethyl-p-toluidine, N-dimethyl-o-toluidine, phthalimide, N-dimethylaniline, tetramethylthiourea, tributylamine, 2-thiolylbenzothiazole, N-butyraldehyde-aniline condensate, triethylenediamine, di-N-butylamine, N-dihydroxyethyl-p-toluidine, 2-methylimidazole, 1-vinyl-2-thiourea, and N-acrylylthiourea;

the oxidant comprises at least one of benzoyl peroxide, tert-butyl perbenzoate, azobisisobutyronitrile, tert-butyl hydroperoxide, cumene hydroperoxide and methyl ethyl ketone peroxide.

8. The long-working-time two-component acrylate structural adhesive according to claim 1 or 2, wherein the urethane acrylate oligomer comprises at least one of a polyester urethane acrylate oligomer or a polyether urethane acrylate oligomer.

9. The long-operation-time two-component acrylate structural adhesive according to claim 1 or 2, wherein the auxiliary agent comprises at least one of pigment, fumed silica and wax auxiliary agent.

10. A preparation method of a long-operation-time two-component acrylate structural adhesive is characterized by comprising the following steps:

weighing the raw materials of the component A and the raw materials of the component B according to the long-operation-time two-component acrylate structural adhesive of any one of the claims 1 to 9;

preparation of component A:

mixing a (methyl) acrylate monomer and a toughening agent, stirring and dispersing at a high speed until the toughening agent is completely dissolved, then adding a stabilizer, an accelerator, an oxidant, a polyurethane acrylate oligomer and an auxiliary agent, stirring for 6-8 hours under high-speed dispersion until all raw materials are dissolved into uniform and continuous glue solution, and defoaming in vacuum for 10-20 min to obtain a component A;

preparation of the component B:

mixing a (methyl) acrylate monomer and a toughening agent, stirring and dispersing at a high speed until the toughening agent is completely dissolved, then adding a stabilizer, an accelerator, a reducing agent, a polyurethane acrylate oligomer and an auxiliary agent, stirring for 6-8 hours under high-speed dispersion until all raw materials are dissolved into uniform and continuous glue solution, and defoaming in vacuum for 10-20 min to obtain a component B;

the A component and the B component are matched according to the volume ratio of 1: 1 to form the long-operation-time two-component acrylate structural adhesive according to any one of the claims 1 to 9.

Technical Field

The invention relates to the field of acrylate structural adhesives, in particular to a long-operation-time two-component acrylate structural adhesive and a preparation method thereof.

Background

The acrylate adhesive has a wide variety of types, has wide bonding capability on metal and nonmetal base materials, is quick to cure and complete in reaction, and has wide application in various fields. The acrylate adhesive takes acrylate as a matrix, and can quickly react under the action of various initiators, so that the acrylate adhesive can be quickly positioned within a few minutes, and can reach more than 70% of the final strength within half an hour, the pressing time is short, and the working cycle is fast. Although the acrylate adhesive is firm in bonding most of base materials and excellent in comprehensive performance, the acrylate monomer is high in activity, free radical reaction is adopted, and curing speed is high, so that under the working conditions of large-area bonding, a large amount of glue gel and even curing can be generated when the conventional acrylate product is used for gluing, and the glue gel and even curing are replaced by epoxy, polyurethane or silicon rubber and other adhesives, so that the strength and toughness cannot be considered, the curing speed is low, the complete curing can be realized within ten hours or even several days, the working progress of a client is delayed, and a certain potential risk can exist. Therefore, a two-component acrylate structural adhesive with long operation time is urgently needed to be developed to solve the contradiction.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides the long-operation-time two-component acrylate structural adhesive and the preparation method thereof, which not only have longer operation time, but also have ideal bonding capability on common base materials (for example, the common base materials can be various metals and engineering plastics), have higher strength and are suitable for the working condition of large-area bonding.

The purpose of the invention is realized by the following technical scheme:

a long-operation-time two-component acrylate structural adhesive is composed of a component A and a component B, wherein the component A and the component B are used in a matched mode according to the volume ratio of 1: 1; wherein the content of the first and second substances,

the component A comprises the following raw materials in parts by weight: 35-65 parts of (methyl) acrylate monomer, 8-25 parts of toughening agent, 0.1-2 parts of stabilizer, 2-15 parts of accelerator, 3-15 parts of oxidant, 3-10 parts of polyurethane acrylate oligomer and 1-5 parts of auxiliary agent;

the component B comprises the following raw materials in parts by weight: 30-70 parts of (methyl) acrylic monomer, 5-20 parts of toughening agent, 0.1-2 parts of stabilizer, 1-10 parts of accelerator, 3-18 parts of reducing agent, 3-10 parts of polyurethane acrylate oligomer and 1-5 parts of auxiliary agent.

Preferably, the component A comprises the following raw materials in parts by weight: 45-60 parts of (methyl) acrylate monomers, 10-15 parts of toughening agents, 0.2-0.8 part of stabilizing agents, 2-7 parts of accelerators, 5-10 parts of oxidants, 5-7 parts of polyurethane acrylate oligomers and 1-5 parts of auxiliaries.

Preferably, the component B comprises the following raw materials in parts by weight: 30-50 parts of (methyl) acrylate monomer, 10-15 parts of toughening agent, 0.5-1 part of stabilizer, 5-8 parts of accelerator, 5-12 parts of reducing agent, 5-10 parts of polyurethane acrylate oligomer and 1-5 parts of auxiliary agent.

Preferably, the (meth) acrylate monomer includes at least one of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, lauryl methacrylate, dodecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, methacrylic acid, methyl acrylate, benzyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, tetrahydrofuran methacrylate, ethoxytriethylene methacrylate, ethylene glycol dimethacrylate, glycidyl methacrylate, lauryl acrylate, tridecyl acrylate, hydroxypropyl acrylate.

Preferably, the toughening agent comprises at least one of nitrile rubber, styrene-butadiene rubber, chloroprene rubber, acrylate rubber, methacrylic acid-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene block copolymer, ethylene-butylene triblock copolymer, natural rubber, polysulfide rubber, chlorosulfonated polyethylene, butadiene rubber, isoprene rubber, ethylene propylene rubber, polyvinyl acetate and unsaturated polyester.

Preferably, the stabilizer comprises at least one of hydroquinone, p-benzoquinone, 2, 6-di-tert-butyl-p-cresol, benzoquinone, 1, 4-naphthoquinone, EDTA-4Na salt, EDTA-2Na salt, 4-methoxyphenol, anthraquinone, stearic acid, p-hydroxyanisole, oxalic acid and 2,2,6, 6-tetramethylpiperidine oxide.

Preferably, the accelerator comprises at least one of gamma-aminopropyltriethoxysilane, Glymo A-187 coupling agent, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, zinc methacrylate, zinc dimethacrylate, phosphate accelerators, triphenylphosphine, iron naphthenate, copper isooctanoate, cobalt isooctanoate, methyl ethyl ketone ethoxylate, and zinc permanganate.

Preferably, the reducing agent includes at least one of N, N-dimethyl-p-toluidine, N-diethyl-p-toluidine, N-dimethyl-o-toluidine, phthalimide, N-dimethylaniline, tetramethylthiourea, tributylamine, 2-mercaptobenzothiazole, a N-butyraldehyde-aniline condensate, triethylenediamine, di-N-butylamine, N-dihydroxyethyl-p-toluidine, 2-methylimidazole, 1-vinyl-2-thiourea, and N-acrylylthiourea.

Preferably, the oxidizing agent comprises at least one of benzoyl peroxide, tert-butyl perbenzoate, azobisisobutyronitrile, tert-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide.

Preferably, the urethane acrylate oligomer comprises at least one of a polyester urethane acrylate oligomer or a polyether urethane acrylate oligomer.

Preferably, the auxiliary agent comprises at least one of pigment, fumed silica and wax auxiliary agent.

A preparation method of a long-operation-time two-component acrylate structural adhesive comprises the following steps:

weighing the raw materials of the component A and the raw materials of the component B according to the long-operation-time double-component acrylate structural adhesive;

preparation of component A: mixing a (methyl) acrylate monomer and a toughening agent, stirring and dispersing at a high speed until the toughening agent is completely dissolved, then adding a stabilizer, an accelerator, an oxidant, a polyurethane acrylate oligomer and an auxiliary agent, stirring for 6-8 hours under high-speed dispersion until all raw materials are dissolved into uniform and continuous glue solution, and defoaming in vacuum for 10-20 min to obtain a component A;

preparation of the component B: mixing a (methyl) acrylate monomer and a toughening agent, stirring and dispersing at a high speed until the toughening agent is completely dissolved, then adding a stabilizer, an accelerator, a reducing agent, a polyurethane acrylate oligomer and an auxiliary agent, stirring for 6-8 hours under high-speed dispersion until all raw materials are dissolved into uniform and continuous glue solution, and defoaming in vacuum for 10-20 min to obtain a component B;

the component A and the component B are matched according to the volume ratio of 1: 1 to form the long-operation-time two-component acrylate structural adhesive.

According to the technical scheme provided by the invention, the composition formula and the preparation method are adjusted, so that the prepared double-component acrylate structural adhesive has longer operation time, ideal bonding capability to common base materials and higher strength, and is suitable for large-area bonding working conditions.

Detailed Description

The technical solutions in the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.

The long-operating-time two-component acrylate structural adhesive and the preparation method thereof provided by the invention are described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.

A long-operation-time two-component acrylate structural adhesive is composed of a component A and a component B, wherein the component A and the component B are used in a matched mode according to the volume ratio of 1: 1; wherein the content of the first and second substances,

the component A comprises the following raw materials in parts by weight: 35-65 parts of (methyl) acrylate monomer, 8-25 parts of toughening agent, 0.1-2 parts of stabilizer, 2-15 parts of accelerator, 3-15 parts of oxidant, 3-10 parts of polyurethane acrylate oligomer and 1-5 parts of auxiliary agent;

the component B comprises the following raw materials in parts by weight: 30-70 parts of (methyl) acrylic monomer, 5-20 parts of toughening agent, 0.1-2 parts of stabilizer, 1-10 parts of accelerator, 3-18 parts of reducing agent, 3-10 parts of polyurethane acrylate oligomer and 1-5 parts of auxiliary agent.

Specifically, the long-operation-time two-component acrylate structural adhesive can comprise the following embodiments:

(1) the component A preferably comprises the following raw materials in parts by weight: 45-60 parts of (methyl) acrylate monomers, 10-15 parts of toughening agents, 0.2-0.8 part of stabilizing agents, 2-7 parts of accelerators, 5-10 parts of oxidants, 5-7 parts of polyurethane acrylate oligomers and 1-5 parts of auxiliaries.

The component B preferably comprises the following raw materials in parts by weight: 30-50 parts of (methyl) acrylate monomer, 10-15 parts of toughening agent, 0.5-1 part of stabilizer, 5-8 parts of accelerator, 5-12 parts of reducing agent, 5-10 parts of polyurethane acrylate oligomer and 1-5 parts of auxiliary agent.

(2) The (methyl) acrylic ester monomer comprises lower ester of (methyl) acrylic acid or higher ester of (methyl) acrylic acid; preferably, the (meth) acrylate monomer preferably includes at least one of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, methacrylic acid, methyl acrylate, benzyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, tetrahydrofuryl methacrylate, ethoxytriethylene methacrylate, ethylene glycol dimethacrylate, glycidyl methacrylate, lauryl acrylate, tridecyl acrylate, hydroxypropyl acrylate.

(3) The toughening agent comprises a high-molecular elastomer, a prepolymer, an oligomer and a copolymer; preferably, the toughening agent preferably comprises at least one of nitrile rubber, styrene-butadiene rubber, chloroprene rubber, acrylate rubber, methacrylic acid-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-based block copolymer, ethylene-butylene triblock copolymer, natural rubber, polysulfide rubber, chlorosulfonated polyethylene, butadiene rubber, isoprene rubber, ethylene propylene rubber, polyvinyl acetate and unsaturated polyester.

(4) The stabilizer comprises at least one of hydroquinone, p-benzoquinone, 2, 6-di-tert-butyl-p-cresol, benzoquinone, 1, 4-naphthoquinone, EDTA-4Na salt, EDTA-2Na salt, 4-methoxyphenol, anthraquinone, stearic acid, p-hydroxyanisole, oxalic acid and 2,2,6, 6-tetramethylpiperidine oxide.

(5) The accelerator comprises an adhesion promoter, a curing speed accelerator, a coupling agent and the like; preferably, the accelerator preferably comprises at least one of gamma-aminopropyltriethoxysilane, Glymo A-187 coupling agent, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, zinc methacrylate, zinc dimethacrylate, phosphate accelerators, triphenylphosphine, iron naphthenate, copper isooctanoate, cobalt isooctanoate, methyl ethyl ketone ethoxylate, and zinc permanganate.

(6) The reducing agent comprises ammonia accelerator, imidazole accelerator, thiourea accelerator and the like; preferably, the reducing agent preferably includes at least one of N, N-dimethyl-p-toluidine, N-diethyl-p-toluidine, N-dimethyl-o-toluidine, phthalimide, N-dimethylaniline, tetramethylthiourea, tributylamine, 2-mercaptobenzothiazole, a N-butyraldehyde-aniline condensate, triethylenediamine, di-N-butylamine, N-dihydroxyethyl-p-toluidine, 2-methylimidazole, 1-vinyl-2-thiourea, and N-acrylylthiourea.

(7) The oxidant comprises an organic oxide or an inorganic oxide; preferably, the oxidizing agent preferably comprises at least one of benzoyl peroxide, tert-butyl perbenzoate, azobisisobutyronitrile, tert-butyl hydroperoxide, cumene hydroperoxide, and methyl ethyl ketone peroxide.

(8) The polyurethane acrylate oligomer comprises at least one of polyester polyurethane acrylate oligomer or polyether polyurethane acrylate oligomer.

(9) The auxiliary agent comprises at least one of pigment, fumed silica and wax auxiliary agent.

Further, the preparation method of the long-operation-time two-component acrylate structural adhesive can comprise the following steps:

(1) and weighing the raw materials of the component A and the component B according to the long-operation-time double-component acrylate structural adhesive.

(2) Preparation of component A: mixing a (methyl) acrylate monomer and a toughening agent, stirring and dispersing at a high speed until the toughening agent is completely dissolved, then adding a stabilizer, an accelerator, an oxidant, a polyurethane acrylate oligomer and an auxiliary agent, stirring for 6-8 hours under high-speed dispersion until the raw materials are dissolved into a uniform and continuous glue solution, and then defoaming in vacuum for 10-20 min to obtain the component A. In practical application, when the toughening agent in the component A is a rubber toughening agent, the toughening agent can be firstly thinned through by using a double-roller machine for 3-5 times and 6-8 times, then sliced, and then the (methyl) acrylate monomer and the toughening agent are mixed.

(3) Preparation of the component B: mixing a (methyl) acrylate monomer and a toughening agent, stirring and dispersing at a high speed until the toughening agent is completely dissolved, then adding a stabilizer, an accelerator, a reducing agent, a polyurethane acrylate oligomer and an auxiliary agent, stirring for 6-8 hours under high-speed dispersion until all raw materials are dissolved into a uniform and continuous glue solution, and then defoaming in vacuum for 10-20 min to obtain the component B. In practical application, when the toughening agent in the component B is a rubber toughening agent, the toughening agent can be firstly thinned through by using a double-roller machine for 3-5 times and 6-8 times, then sliced, and the (methyl) acrylate monomer and the toughening agent are mixed.

(4) The component A and the component B are matched according to the volume ratio of 1: 1 to form the long-operation-time two-component acrylate structural adhesive.

Compared with the prior art, the long-operation-time two-component acrylate structural adhesive disclosed by the invention at least has the following advantages:

(1) the long-operation-time two-component acrylate structural adhesive provided by the invention can be operated for more than 45min, and can meet the demand of gluing in a larger area.

(2) The long-operation-time two-component acrylate structural adhesive provided by the invention has excellent storage stability, and the storage time at normal temperature can reach more than 12 months.

(3) The long-operation-time two-component acrylate structural adhesive provided by the invention has good bonding property on various base materials and higher strength, and can meet the bonding requirements of different base materials.

(4) The long-operation-time two-component acrylate structural adhesive provided by the invention is convenient in operation process, has good thixotropy, and can be used for gluing inclined planes, vertical planes and top surfaces.

In conclusion, the embodiment of the invention has the advantages of longer operation time, ideal bonding capability to common base materials and higher strength, and is suitable for large-area bonding working conditions.

In order to more clearly show the technical scheme and the technical effects provided by the present invention, the long-operating-time two-component acrylate structural adhesive and the preparation method thereof are described in detail in the following embodiments.