CN102898963B - Acrylate structure adhesive and preparation method thereof - Google Patents
Acrylate structure adhesive and preparation method thereof Download PDFInfo
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- CN102898963B CN102898963B CN201210398920.4A CN201210398920A CN102898963B CN 102898963 B CN102898963 B CN 102898963B CN 201210398920 A CN201210398920 A CN 201210398920A CN 102898963 B CN102898963 B CN 102898963B
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Abstract
The invention discloses a novel acrylate structure adhesive and a preparation method thereof. The two-component acrylate structure adhesive comprises components A and B, wherein the volume ratio of the component A to the component B is (10-2):1; the component A comprises 55 to 75 parts of acrylate monomer, 0 to 25 parts of toughening agent, 10 to 35 parts of oligomer, 0.1 to 5 parts of reducing agent, 0.1 to 2 parts of stabilizer, and 0.1 to 10 parts of aids; and the component B comprises 15 to 50 parts of oxidant, 15 to 25 parts of toughening agent, 15 to 50 parts of plasticizer, and 0.1 to 10 parts of aids. Compared with the conventional acrylate adhesive (SGA), the novel acrylate structure adhesive prepared by the method has the advantages that under the condition of guaranteeing the same tensile shear strength, the elongation at break is over 30%, which is much higher than the 5% of elongation at break of common acrylate adhesives available in the market.
Description
Technical field
The present invention relates to structural adhesive and preparation method thereof technical field, particularly a kind of Structural acrylate glue and preparation method thereof.
Background technology
S-generation acrylate structural adhesive (SGA) is the two component sizing agents of a kind of response type, have that bonding strength is high, room temperature fast-curing, can Sealant etc. advantage, over more than 30 year, in the industry fields such as machinery, electronic apparatus, railway, building, be widely used, development rapidly.
Commercially available s-generation acrylate structural adhesive mostly is 1:1 proportioning at present, and product bonding strength is high, but sizing agent body toughness is not high, and elongation at break is generally less than 5%; And sizing agent is proposed except having high bonding strength at some electronic apparatuss, machinery industry, also need to have the performance requriements of good long-term vibration resistance.
Summary of the invention
One of technical problem to be solved by this invention is to provide a kind of bonding strength high for the existing deficiency of acrylate structural adhesive, the Structural acrylate glue that elongation at break is greater than 30%.
Two of technical problem to be solved by this invention is to provide the preparation method of above-mentioned Structural acrylate glue.
As the acrylate structural adhesive of first aspect present invention, comprise host A component and solidifying agent B component, described A, the volume ratio of B two components is the situation that equal proportion can not appear while supplementing in 10～2:1();
Wherein A component is prepared from by the raw material of following weight part: 55～75 parts of acrylic ester monomers, 5～25 parts of toughner, 10～35 parts of oligopolymer, 0.1～5 part of reductive agent, 0.1～2 part of stablizer, 0.1～10 part of auxiliary agent.
Wherein B component is prepared from by the raw material of following weight part: 15～50 parts of oxygenants; 15～25 parts of toughner; 15～50 parts of softening agent; 0.1～10 part of auxiliary agent.
In a preferred embodiment of the invention, in described A component, mentioned acrylic ester monomer comprises two or more mixing in methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, hydroxyethyl methylacrylate, Rocryl 410, isobornyl methacrylate, cyclohexyl methacrylate, THFMA, methacrylic acid laurate, methacrylic acid, two-tube energy acrylate, trifunctional acrylate, vinylformic acid, methacrylic acid.
In a preferred embodiment of the invention, in described A component, mentioned toughner comprises one or more mixing of chloroprene rubber, ABS resin, paracril, SIS, SBS, chlorosulfonated polyethylene.
In a preferred embodiment of the invention, in described A component, mentioned oligopolymer is a kind of in epoxy modification acrylate, polyurethane-modified polyacrylate or both mixing.
In a preferred embodiment of the invention, in described A component, mentioned reductive agent is tertiary amine.
In a preferred embodiment of the invention, in described A component, mentioned reductive agent is aryl tertiary amine.
In a preferred embodiment of the invention, in described A component, mentioned reductive agent is N, accelerine, N, N-Diethyl Aniline, N, one or more mixing of N-dimethyl-p-toluidine, N-methyl-N-hydroxyethyl para-totuidine, N-methyl-N-hydroxyethyl para-totuidine.
In a preferred embodiment of the invention, in described A component, mentioned stablizer is one or more mixing of 2,6 di tert butyl 4 methyl phenol, Resorcinol, MEHQ, disodium edta.
In a preferred embodiment of the invention, in described B component, mentioned oxygenant is one or more mixing of methylethyl ketone peroxide, isopropyl benzene hydroperoxide, dicumyl peroxide, benzoyl peroxide.
In a preferred embodiment of the invention, one or more mixing in the novolac epoxy that in described B component, mentioned toughner is oxirane value is the bisphenol A type epoxy resin of 0.51mol/100g, bisphenol A type epoxy resin that oxirane value is 0.44mol/100g, oxirane value is 0.20mol/100g bisphenol A type epoxy resin, oxirane value is 0.51mol/100g, the novolac epoxy that oxirane value is 0.44mol/100g.
In a preferred embodiment of the invention, in described B component, mentioned softening agent is phthalic easter plastizer or aliphatic dibasic acid lipid softening agent.
In a preferred embodiment of the invention, in described A component and B component, mentioned auxiliary agent comprises one or more mixing of pigment, phosphoric acid ester, gas-phase silica, paraffin, Microcrystalline Wax.
In a preferred embodiment of the invention, described A, the volume ratio of B two components is 10:1, wherein said A component is prepared from by the raw material of following weight part:
35 parts of methyl methacrylates, 5 parts of Rocryl 410s, 10 parts of methacrylic acid laurates, 8 parts of polyurethane-modified polyacrylates, 5 parts of epoxy modification acrylates, methacrylic acid 10 minutes, 10 parts of chloroprene rubbers, 3 parts of N-methyl-N-hydroxyethyl para-totuidine, 2 parts of MEHQ, 2 parts of EDTA-Na, 5 parts of pigment, 5 parts of gas-phase silicas;
Described B component is prepared from by the raw material of following weight part: 40 parts of benzoyl peroxides, 25 parts of epoxy resin, 25 parts of dioctyl terephthalates, 5 parts of pigment, 5 parts of gas-phase silicas.
As the preparation method of the Structural acrylate glue of second aspect present invention, concrete steps are as follows:
1, A component preparation
By formula ratio, take acrylic ester monomer, after mixing with the stablizer of formula ratio, stir, after adding oligopolymer, toughner fully to dissolve to stir, add reductive agent and auxiliary agent to stir, deaeration under vacuum environment;
2, B component preparation
By the oxygenant of formula ratio, toughner, softening agent, auxiliary agent mixing and stirring, deaeration under vacuum environment;
During use, by A component and the 10～2:1 preparation by volume of B component.
Structural acrylate glue prepared by the present invention, compare with existing SGA acrylate adhesive, in the situation that tensile shear strength remains unchanged substantially, elongation at break reaches more than 30%, far above general in the market acrylate adhesive (elongation at break is less than 5%) product performance.The international esbablished corporation like product of Yu Mou is compared, and tensile shear strength improves more than 20%, and elongation at break improves 100%.
Embodiment
According to embodiment, the present invention is further illustrated below, but the present invention is not limited to this:
Embodiment 1:
The formula of A component is as follows:
The formula of B component is as follows:
Preparation method is as follows:
By methyl methacrylate, hydroxyethyl methylacrylate, trimethylolpropane trimethacrylate, methacrylic acid mix and blend, add Resorcinol, EDTA-Na to stir, then after adding polyurethane-modified polyacrylate, chloroprene rubber to be uniformly dissolved, add again the auxiliary agent vacuum defoamations such as tertiary amine, pigment, gas-phase silica, make A component.
The parameters C AB-O-of gas-phase silica
tS-720 specific surface area 100 ± 20m2/g, pigment is milori blue.
Benzoyl peroxide, epoxy resin, dioctyl terephthalate are mixed, then add pigment, the vacuum defoamation of gas-phase silica auxiliary agent, make B component.
In this formula, epoxy resin used is D.E.R.330 epoxy resin, the parameters C AB-O-of gas-phase silica
tS-720 specific surface area 100 ± 20m
2/ g, the GROMOPHTAL YELLOW 8GN that pigment is Ciba fine chemicals.
During use, by A component and the 10:1 preparation by volume of B component.
Embodiment 2:
The formula of A component is as follows:
The formula of B component is as follows:
By methyl methacrylate, Rocryl 410, methacrylic acid laurate, methacrylic acid mix and blend, add MEHQ, EDTA-Na to stir, then after adding polyurethane-modified polyacrylate, epoxy modification acrylate, paracril to be uniformly dissolved, add again the auxiliary agent vacuum defoamations such as N-methyl-N-hydroxyethyl para-totuidine, pigment, gas-phase silica, make A component.
The parameters C AB-O-of gas-phase silica
tS-720 specific surface area 100 ± 20m2/g, pigment is milori blue.
Benzoyl peroxide, epoxy resin, dioctyl terephthalate are mixed, then add pigment, the vacuum defoamation of gas-phase silica auxiliary agent, make B component.
In this formula, epoxy resin used is D.E.R.330 epoxy resin, the parameters C AB-O-of gas-phase silica
tS-720 specific surface area 100 ± 20m
2/ g, the GROMOPHTAL YELLOW 8GN that pigment is Ciba fine chemicals.
During use, by A component and the 10:1 preparation by volume of B component.
Pass through embodiment, mensuration according to the mensuration of GB/T 7124 tackiness agent tensile shear strengths and GB/T 528 tensile stress-strain performances is carried out Performance Detection to the tensile shear strength of material and elongation at break, and tensile shear strength used test sheet material is aluminium alloy.Compare with the international esbablished corporation acrylate structural adhesive of domestic general acrylate structural adhesive (volume ratio 1:1) Ji Mou (volume ratio 10:1), result is as shown in table 1 below simultaneously:
Table 1 embodiment of the present invention and currently available products performance comparison
From upper table, tensile shear strength rises, and elongation at break decline can only be sought an optimum balance in performance in this system formulation.
Claims (1)
1. acrylate structural adhesive, comprises host A component and solidifying agent B component, it is characterized in that,
The formula of A component is as follows:
By methyl methacrylate, Rocryl 410, methacrylic acid laurate, methacrylic acid mix and blend, add MEHQ, EDTA-Na to stir, then after adding polyurethane-modified polyacrylate, epoxy modification acrylate, paracril to be uniformly dissolved, add again N-methyl-N-hydroxyethyl para-totuidine, pigment, the vacuum defoamation of gas-phase silica auxiliary agent, make A component;
The parameters C AB-O-of the gas-phase silica in A component
tS-720 specific surface area 100 ± 20m2/g, pigment is milori blue;
Benzoyl peroxide, epoxy resin, dioctyl terephthalate are mixed, then add pigment, the vacuum defoamation of gas-phase silica auxiliary agent, make B component;
In B component, epoxy resin used is D.E.R.330 epoxy resin, the parameters C AB-O-of gas-phase silica
tS-720 specific surface area 100 ± 20m
2/ g, the GROMOPHTAL YELLOW8GN that pigment is Ciba fine chemicals;
During use, by A component and the 10:1 preparation by volume of B component.
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| CN201210398920.4A CN102898963B (en) | 2012-10-18 | 2012-10-18 | Acrylate structure adhesive and preparation method thereof |
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| CN201210398920.4A CN102898963B (en) | 2012-10-18 | 2012-10-18 | Acrylate structure adhesive and preparation method thereof |
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| CN102898963B true CN102898963B (en) | 2014-03-26 |
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| CN103694905A (en) * | 2013-12-10 | 2014-04-02 | 中国航空工业集团公司金城南京机电液压工程研究中心 | Fast curing dual-component adhesive |
| CN104804702A (en) * | 2014-01-28 | 2015-07-29 | 上海铂优新材料有限公司 | Silane modified two-component acrylate structure adhesive |
| CN105419658B (en) * | 2016-01-05 | 2018-09-28 | 北京天山新材料技术有限公司 | A kind of high elongation rate two-component acrylic adhesive and preparation method thereof |
| CN105694774B (en) * | 2016-04-28 | 2017-12-08 | 湖南把兄弟新材料股份有限公司 | A kind of low taste acrylate AB glue without strict measurement impregnation ratio |
| CN106634633B (en) * | 2016-12-14 | 2020-09-08 | 湖北回天新材料股份有限公司 | Acrylate adhesive for packaging power battery |
| CN107603497A (en) * | 2017-09-18 | 2018-01-19 | 烟台德邦科技有限公司 | The acrylic ester structural adhesive that a kind of solvent resistant is cleaned |
| CN108192508A (en) * | 2017-12-20 | 2018-06-22 | 上海康达化工新材料股份有限公司 | A kind of high temperature resistant bi-component acrylic sqtructural adhesive |
| CN108102556A (en) * | 2017-12-20 | 2018-06-01 | 上海康达新能源材料有限公司 | A kind of double cured adhesives of two-component |
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| CN108264876B (en) * | 2017-12-29 | 2020-09-08 | 天永诚高分子材料（常州）有限公司 | Double-component acrylate structural adhesive for adhering PET material with untreated surface and preparation method thereof |
| CN108314980A (en) * | 2018-02-05 | 2018-07-24 | 东莞市科惠工业材料有限公司 | A kind of adhesive and its application method |
| CN108395850B (en) * | 2018-03-27 | 2021-04-27 | 绍兴市林森五金化工有限公司 | Adhesive, two-component adhesive containing same, bonding method and combination |
| CN109705777A (en) * | 2018-12-26 | 2019-05-03 | 珠海市盛西源机电设备有限公司 | A kind of high intensity entity plane materiel adhesive and preparation method thereof |
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| FR3103487B1 (en) * | 2019-11-25 | 2022-03-04 | Bostik Sa | Composition based on (meth)acrylate monomers |
| CN111117497A (en) * | 2019-12-19 | 2020-05-08 | 北京高盟新材料股份有限公司 | Double-component acrylate structural adhesive and preparation method thereof |
| CN111087953A (en) * | 2019-12-19 | 2020-05-01 | 北京高盟新材料股份有限公司 | Acrylate adhesive for bonding resin-based composite material and preparation method thereof |
| CN112040387B (en) * | 2020-09-01 | 2022-12-06 | 昆山联滔电子有限公司 | Telephone receiver and preparation method thereof, and loudspeaker and preparation method thereof |
| CN115044342B (en) * | 2021-03-09 | 2024-03-26 | 3M创新有限公司 | Two-component adhesive composition |
| CN114231189B (en) * | 2022-01-13 | 2023-11-17 | 湖北回天新材料股份有限公司 | Bi-component acrylic ester structural adhesive and preparation method thereof |
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| IT1251642B (en) * | 1991-10-29 | 1995-05-17 | Mini Ricerca Scient Tecnolog | STRUCTURAL ACRYLIC BASED ADHESIVES |
| CN1124325C (en) * | 1999-11-08 | 2003-10-15 | 成都正光科技股份有限公司 | Structural acrylate glue |
| CN101792576B (en) * | 2010-03-18 | 2012-07-04 | 上海新天和树脂有限公司 | Epoxy acrylate prepolymer resin, preparation method thereof and application thereof in bicomponent structural adhesive |
| CN101805564B (en) * | 2010-03-22 | 2013-10-02 | 北京天山新材料技术股份有限公司 | Low-odor acrylate structural adhesive and preparation method thereof |
| CN102115641A (en) * | 2010-12-03 | 2011-07-06 | 烟台德邦科技有限公司 | High-toughness acrylate structural adhesive and preparation method thereof |
| CN102286253B (en) * | 2011-06-21 | 2014-03-19 | 北京天山新材料技术股份有限公司 | Novel two-component acrylate structural adhesive and preparation method thereof |
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Address after: 169 Leizhou Road, Fengxian District, Shanghai, 201419 Patentee after: Kangda new material (Group) Co.,Ltd. Address before: 169 Leizhou Road, Fengxian District, Shanghai, 201419 Patentee before: Shanghai Kangda Chemical New Material Group Co.,Ltd. |
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