Acrylate structural adhesive with excellent flame-retardant hydraulic oil resistance

Abstract

The invention discloses an acrylate structural adhesive with excellent flame-retardant hydraulic oil resistance. The problem that an existing acrylate structural adhesive is poor in flame-retardant hydraulic oil resistance is mainly solved. The volume ratio of the reducing agent to the oxidizing agent is 10: 1. The reducing agent is prepared from the following components in percentage by weight: 40 to 70 percent of (methyl) acrylate monomer, 5 to 15 percent of hydrogenated butadiene-acrylonitrile rubber, 5 to 40 percent of flexibilizer, 3 to 10 percent of unsaturated acid monomer, 1 to 10 percent of accelerant, 0.1 to 0.5 percent of stabilizer and 1 to 5 percent of additive; the oxidizing agent is prepared from the following components in percentage by weight: 30 to 50 percent of dibutyl phthalate, 10 to 30 percent of alicyclic epoxy resin, 5 to 30 percent of high rubber powder, 10 to 20 percent of benzoyl peroxide and 1 to 5 percent of additive. The flame-retardant hydraulic oil resistance of the acrylate adhesive is remarkably improved under the preferable proportion, and the crosslinking density and the swelling resistance of the product are improved due to the addition of the high-oil-resistance rubber.

Description

Technical Field

[0001] The invention belongs to the technical field of acrylic structural adhesives, and specifically relates to an acrylic structural adhesive with excellent flame retardant hydraulic oil resistance, which can be widely used in oil surface bonding. The adhesive has excellent flame retardant hydraulic oil resistance after curing. Background Art

[0002] Since two-component acrylic adhesives are widely used in different parts of construction machinery and need to withstand a variety of environments, they need to be able to withstand strong shear forces after being immersed in different fluids to ensure continuous and reliable bonding.

[0003] Two-component acrylic adhesives have attracted the attention of the industry due to their advantages such as fast curing speed, high strength, no need for strict control of the ratio, and oil-based bonding. Their products are constantly being innovated and their application areas are constantly expanding. However, in actual application scenarios where two-component acrylic adhesives are exposed to different media (oils and solvents), their mechanical properties will be significantly attenuated. Summary of the invention

[0004] The purpose of the present invention is to overcome the deficiencies in the above technical background and provide an acrylic structural adhesive with excellent flame retardant hydraulic oil resistance for practical application scenarios exposed in different media (oils and solvents).

[0005] The technical solution of the present invention to solve the above technical problems is as follows: An acrylate structural adhesive with excellent flame retardant hydraulic oil resistance, comprising a reducing agent and an oxidizing agent in a volume ratio of 10:1; Calculated by weight percentage, the reducing agent includes: 40-70% of (meth) acrylate monomer, 5-15% of hydrogenated nitrile rubber, 5-40% of toughening agent, 3-10% of unsaturated acid monomer, 1-10% of accelerator, 0.1-0.5% of stabilizer and 1-5% of auxiliary agent; Calculated by weight percentage, the oxidant includes: 30-50% of dibutyl phthalate, 10-30% of alicyclic epoxy resin, 5-30% of high-glue powder, 10-20% of benzoyl peroxide and 1-5% of auxiliary agent.

[0006] Based on the above technical solution, the present invention can also be improved as follows.

[0007] Furthermore, in the above-mentioned acrylic structural adhesive with excellent flame-retardant hydraulic oil resistance, the (meth) acrylic ester monomer includes at least one of tetrahydrofuran methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, trimethylolpropane trimethacrylate, lauryl methacrylate, dodecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, ethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate phosphate, lauryl acrylate, and hydroxypropyl acrylate.

[0008] Furthermore, in the above-mentioned acrylic structural adhesive with excellent flame-retardant hydraulic oil resistance, the toughening agent includes at least one of liquid nitrile rubber, methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-based block copolymer, styrene dimethyl methacrylate copolymer, polyvinyl acetate, and unsaturated polyester.

[0009] Furthermore, in the above-mentioned acrylic structural adhesive with excellent flame-retardant hydraulic oil resistance, the unsaturated acid monomer includes at least one of maleic acid, itaconic acid, acrylic acid, methacrylic acid, and oxalic acid.

[0010] Furthermore, in the above-mentioned acrylic structural adhesive with excellent flame-retardant hydraulic oil resistance, the accelerator includes at least one of N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-o-toluidine, o-benzenesulfonimide, N,N-dimethylaniline, tetramethylthiourea, triethylenediamine, di-n-butylamine, N,N-dihydroxyethyl-p-toluidine, 2-methylimidazole, and 1-vinyl-2-thiourea.

[0011] Furthermore, in the above-mentioned acrylic structural adhesive with excellent flame-retardant hydraulic oil resistance, the stabilizer includes at least one of hydroquinone, p-benzoquinone, 2,6-di-tert-butyl-p-cresol, benzoquinone, 1,4-naphthoquinone, EDTA-4Na salt, EDTA-2Na salt, hydroquinone, and anthraquinone.

[0012] Furthermore, in the above-mentioned acrylic structural adhesive with excellent flame-retardant hydraulic oil resistance, the auxiliary agent includes at least one of pigment, fumed silica, paraffin, and glass microbeads.

[0013] Furthermore, in the above-mentioned acrylic structural adhesive with excellent flame-retardant hydraulic oil resistance, the high-glue powder is at least one of ABS high-glue powder and MBS high-glue powder.

[0014] Furthermore, in the above-mentioned acrylic structural adhesive with excellent flame-retardant hydraulic oil resistance, the alicyclic epoxy resin is at least one of Syna Epoxy S-100A and Syna Epoxy S-06E.

[0015] Compared with the prior art, the technical solution of the present invention has the following beneficial technical effects: In view of the shortcomings of the prior art, the present invention introduces (meth) acrylate monomers into the formula to form an effective covalent connection between the product and the bonding surface, and has excellent rigid structural bonding performance for composite materials and lightweight alloys, and effectively improves the tensile shear strength of the product; introduces high oil-resistant rubber, namely hydrogenated nitrile rubber, into the formula to improve the crosslinking density and anti-swelling performance of the product, so that the product has excellent oil resistance and chemical medium resistance, and significantly improves the flame retardant hydraulic oil resistance of the acrylic adhesive. The performance does not show obvious attenuation after being exposed to different media (oil and solvent) for 14 days, and meets the tensile shear requirements. The present invention also studies the effect of the amount of hydrogenated nitrile rubber on the strength change of the two-component acrylic adhesive. After adding hydrogenated nitrile rubber foam oil, the tensile shear attenuation amplitude is within 11%, and as the amount of hydrogenated nitrile rubber increases (from 5% to 15%), the attenuation amplitude gradually decreases, but as the amount increases, the overall viscosity of the system increases, which will lead to poor operating performance, while the attenuation amplitude of the system without adding hydrogenated nitrile is more than 20%. DETAILED DESCRIPTION

[0016] In order to facilitate understanding of the present application, the present application will be described more comprehensively below. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0018] The present invention is further described in detail below with reference to specific embodiments.

[0019] In the examples of the present invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art; in the examples of the present invention, unless otherwise specified, the technical means used are conventional means well known to those skilled in the art. The following products are the products used in the experimental process of the present invention. As long as the ingredients are the same, other commercially available products can also achieve the corresponding effects.

[0020] Tetrahydrofuran methacrylate: manufacturer is Sartomer Guangzhou (Chemical) Co., Ltd., model SR203; Methyl methacrylate: The manufacturer is Mitsubishi Chemical Chemical Materials (Shanghai) Co., Ltd.; 2-Hydroxyethyl methacrylate phosphate: manufacturer is Allnex Resins (China) Co., Ltd., model EBECRYL™ 168; Hydrogenated nitrile rubber: manufacturer is Japan Zeon, model is ZETPOL 1020; Acrylonitrile-butadiene-styrene copolymer: the manufacturer is Jilin Petrochemical Company, model number is 0215A; Methacrylic acid: The manufacturer is Taiwan Plastics Industry Co., Ltd.; N, N-dimethyl-p-toluidine: the manufacturer is Binhai Henglian Chemical Co., Ltd.; p-Benzoquinone: The manufacturer is Hubei Kaiyuan Chemical Technology Co., Ltd.; Dibutyl phthalate: The manufacturer is Shanghai Kunrui Chemical Co., Ltd.; Syna Epoxy S-100A: The manufacturer is Nantong Synasia New Materials Co., Ltd., and the model is Syna Epoxy S-100A; Syna Epoxy S-06E: The manufacturer is Nantong Synasia New Materials Co., Ltd., and the model is Syna Epoxy S-06E; ABS: The manufacturer is Ningbo LG Yongxing Chemical Co., Ltd., model is HI-121H; MBS: The manufacturer is Japan Kaneka Chemical, model is KANE ACE MZ-200; Benzoyl peroxide: manufacturer is Nouryon Chemicals (Ningbo) Co., Ltd., model number is BTW-50; Fumed silica: The manufacturer is Evonik of Germany, and the model is AEROSIL 200.

[0021] Calculated by weight percentage, the reducing agent includes: 40-70% of (meth) acrylate monomer, 5-15% of hydrogenated nitrile rubber, 5-40% of toughening agent, 3-10% of unsaturated acid monomer, 1-10% of accelerator, 0.1-0.5% of stabilizer and 1-5% of auxiliary agent; Calculated by weight percentage, the oxidant includes: 30-50% of dibutyl phthalate, 10-30% of alicyclic epoxy resin, 5-30% of high-glue powder, 10-20% of benzoyl peroxide and 1-5% of auxiliary agent.

[0022] The following tensile shear strength test method is: GB / T7124-2008 adhesive tensile shear strength.

[0023] The embodiment of the present invention provides an acrylic structural adhesive with excellent flame retardant hydraulic oil resistance.

[0024] Embodiment 1: This embodiment provides an acrylate structural adhesive with excellent flame retardant hydraulic oil resistance, and its components and the mass percentage of each component are shown in the following table: Table 1 Components and mass percentage of each component in this example

[0025] Embodiment 2: This embodiment provides an acrylate structural adhesive with excellent flame retardant hydraulic oil resistance, and its components and the mass percentage of each component are shown in the following table: Table 2 Components and mass percentage of each component in this example

[0026] Embodiment 3: This embodiment provides an acrylate structural adhesive with excellent flame retardant hydraulic oil resistance, and its components and the mass percentage of each component are shown in the following table: Table 3 Components and mass percentage of each component in this example

[0027] Embodiment 4: This embodiment provides an acrylate structural adhesive with excellent flame retardant hydraulic oil resistance, and its components and the mass percentage of each component are shown in the following table: Table 4 Components and mass percentage of each component in this example

[0028] Embodiment 5: This embodiment provides an acrylate structural adhesive with excellent flame retardant hydraulic oil resistance, and its components and the mass percentage of each component are shown in the following table: Table 5 Components and mass percentage of each component in this example

[0029] Embodiment 6: This embodiment provides an acrylate structural adhesive with excellent flame retardant hydraulic oil resistance, and its components and the mass percentage of each component are shown in the following table: Table 6 Components and mass percentage of each component in this example

[0030] Comparative Example 1: This comparative example provides a structural adhesive, which is basically the same as Example 1, except that acrylonitrile-butadiene-styrene copolymer is used instead of hydrogenated nitrile rubber, that is, no hydrogenated nitrile rubber is contained, and the content of acrylonitrile-butadiene-styrene copolymer is adjusted from 15% to 30%. In detail, its components and the mass percentage of each component are shown in the following table: Table 7 Components of this comparative example and the mass percentage of each component

[0031] Comparative Example 2: This comparative example provides a structural adhesive, which is basically the same as Example 1, except that chloroprene rubber is used instead of hydrogenated nitrile rubber. In detail, its components and the mass percentage of each component are shown in the following table: Table 8 Components of this comparative example and the mass percentage of each component

[0032] Comparative Example 3: This comparative example provides a structural adhesive, which is basically the same as Example 1, except that nitrile rubber is used instead of hydrogenated nitrile rubber. In detail, its components and the mass percentage of each component are shown in the following table: Table 9 Components of this comparative example and the mass percentage of each component

[0033] Performance Test: The reducing agent and the oxidizing agent in the embodiment and the comparative example were mixed at a volume ratio of 10:1 to obtain an adhesive, and the adhesive was tested for tensile shear strength (MPa) according to the method of tensile shear strength of adhesives in GB / T7124-2008. The test results are shown in Table 10 below:

[0034] From the comparison of the test results of the above embodiments and the comparative examples, it can be seen that the addition of hydrogenated nitrile rubber can effectively reduce the attenuation of the shear strength performance of the glue after being immersed in flame-retardant hydraulic oil. The tensile shear attenuation amplitude after adding hydrogenated nitrile rubber soaking oil is within 11%, and as the amount of hydrogenated nitrile rubber increases (from 5% to 15%), the attenuation amplitude gradually decreases, but as the amount increases, the overall viscosity of the system increases, which will lead to poor operating performance, while the attenuation amplitude of the system without adding hydrogenated nitrile is more than 20%.

[0035] The invention relates to an acrylic structural adhesive with excellent flame-retardant hydraulic oil resistance. Compared with traditional two-component acrylic adhesive, the adhesive has the following advantages: by adding hydrogenated nitrile, the product has excellent oil resistance and chemical medium resistance, and the performance does not show obvious attenuation after being exposed to flame-retardant hydraulic oil for 14 days. The product can be widely used in oil surface bonding, thereby expanding the application scenarios of acrylic adhesive.

[0036] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An acrylic structural adhesive having excellent flame retardant hydraulic oil resistance, characterized in that: It includes a reducing agent and an oxidizing agent in a volume ratio of 10:1; Calculated by weight percentage, the reducing agent includes: 40-70% of (meth) acrylate monomer, 5-15% of hydrogenated nitrile rubber, 5-40% of toughening agent, 3-10% of unsaturated acid monomer, 1-10% of accelerator, 0.1-0.5% of stabilizer and 1-5% of auxiliary agent; Calculated by weight percentage, the oxidant includes: 30-50% of dibutyl phthalate, 10-30% of alicyclic epoxy resin, 5-30% of high-glue powder, 10-20% of benzoyl peroxide and 1-5% of auxiliary agent.

2. The acrylic structural adhesive having excellent flame retardant hydraulic oil resistance according to claim 1, characterized in that: The (meth)acrylate monomer includes at least one of tetrahydrofuran methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, trimethylolpropane trimethacrylate, lauryl methacrylate, dodecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, ethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate phosphate, lauryl acrylate, and hydroxypropyl acrylate.

3. The acrylic structural adhesive having excellent flame retardant hydraulic oil resistance according to claim 1, characterized in that: The toughening agent includes at least one of liquid nitrile rubber, methacrylic acid-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene block copolymer, styrene dimethyl methacrylate copolymer, polyvinyl acetate, and unsaturated polyester.

4. The acrylic structural adhesive having excellent flame retardant hydraulic oil resistance according to claim 1, characterized in that: The unsaturated acid monomer includes at least one of maleic acid, itaconic acid, acrylic acid, methacrylic acid and oxalic acid.

5. The acrylic structural adhesive having excellent flame retardant hydraulic oil resistance according to claim 1, characterized in that: The accelerator includes at least one of N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-o-toluidine, o-benzenesulfonimide, N,N-dimethylaniline, tetramethylthiourea, triethylenediamine, di-n-butylamine, N,N-dihydroxyethyl-p-toluidine, 2-methylimidazole, and 1-vinyl-2-thiourea.

6. The acrylic structural adhesive having excellent flame retardant hydraulic oil resistance according to claim 1, characterized in that: The stabilizer includes at least one of hydroquinone, p-benzoquinone, 2,6-di-tert-butyl-p-cresol, benzoquinone, 1,4-naphthoquinone, EDTA-4Na salt, EDTA-2Na salt, hydroquinone and anthraquinone.

7. The acrylic structural adhesive having excellent flame retardant hydraulic oil resistance according to claim 1, characterized in that: The auxiliary agent includes at least one of pigment, fumed silica, paraffin wax and glass microbeads.

8. The acrylic structural adhesive having excellent flame retardant hydraulic oil resistance according to claim 1, characterized in that: The high-glue powder is at least one of ABS high-glue powder and MBS high-glue powder.

9. The acrylic structural adhesive having excellent flame retardant hydraulic oil resistance according to claim 1, characterized in that: The alicyclic epoxy resin is at least one of Syna Epoxy S-100A and Syna Epoxy S-06E.

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