CN112126377A - Preparation method of low-odor high-temperature-resistant acrylate structural adhesive - Google Patents
Preparation method of low-odor high-temperature-resistant acrylate structural adhesive Download PDFInfo
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- CN112126377A CN112126377A CN202011024804.7A CN202011024804A CN112126377A CN 112126377 A CN112126377 A CN 112126377A CN 202011024804 A CN202011024804 A CN 202011024804A CN 112126377 A CN112126377 A CN 112126377A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09J109/02—Copolymers with acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of low-odor high-temperature-resistant acrylate structural adhesive, wherein before the structural adhesive is compounded and used, a modified epoxy acrylic prepolymer independently exists from a component A and a component B, and when the structural adhesive is used, acrylate monomers of the component A and the component B are fully crosslinked and then are blended with the modified epoxy acrylic prepolymer, so that an interpenetrating network structure is formed with a bisphenol A structure in the modified epoxy acrylic prepolymer, and the high-temperature resistance of the structural adhesive is improved.
Description
Technical Field
The invention relates to the technical field of adhesive preparation, in particular to a preparation method of low-odor high-temperature-resistant acrylate structural adhesive.
Background
The second-generation acrylate structural adhesive SGA is a fully-reacted two-component adhesive and has many advantages, and the adhesive has strong smell and volatility, so that the adhesive is subjected to certain resistance in bonding application. The low-odor high-temperature-resistant SGA has the advantages that the characteristics of low odor ensure the field air quality of the glue operation environment and improve the working environment of operators.
Since the acrylic acid adhesive enterprises at abroad have mature products, the research and development and preparation of low-odor high-temperature-resistant environment-friendly acrylic acid ester structural adhesive at home are still in the germinating stage, and the research on the process and long-term temperature-resistant phase structure of low-odor high-temperature-resistant acrylic acid ester structural adhesive is less.
Disclosure of Invention
The invention aims to provide a preparation method of a low-odor high-temperature-resistant acrylate structural adhesive, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of low-odor high-temperature-resistant acrylate structural adhesive comprises the following steps,
s1) preparation of component a: plasticating and thinly passing nitrile rubber, then taking out sheets, putting an acrylate monomer, a toughening agent, a polymerization inhibitor and the nitrile rubber into a reaction kettle, introducing cooling water, stirring until the nitrile rubber is completely dissolved, putting filler, stirring for 3-4h to uniformly disperse the filler, then adding methacrylic acid and a first initiator, stirring uniformly, and discharging for later use;
s2) preparing a component B: putting an acrylate monomer, a toughening agent and an accelerant into a reaction kettle in proportion, uniformly stirring, and discharging for later use;
s3) preparing a modified epoxy acrylic prepolymer: putting epoxy resin, methacrylic acid, a polymerization inhibitor and a second initiator into a three-neck flask, heating to 105-140 ℃, reacting for 8-12h, cooling to 55-60 ℃, and discharging for later use;
s4) preparing a structural adhesive: and uniformly mixing the component A, the component B and the modified epoxy acrylic prepolymer when in use to obtain the low-temperature high-temperature-resistant acrylate structural adhesive.
For further optimization, the component A comprises 3-20 parts of nitrile rubber, 30-50 parts of acrylate monomer, 10-30 parts of toughening agent, 1-10 parts of polymerization inhibitor, 1-15 parts of filler, 5-20 parts of methacrylic acid and 1-5 parts of first initiator in parts by weight; the component B comprises 30-50 parts of acrylate monomer, 10-30 parts of toughening agent and 1-5 parts of accelerator according to parts by weight; the modified epoxy acrylic prepolymer comprises, by weight, 15-35 parts of epoxy resin, 1-5 parts of methacrylic acid, 1-10 parts of a polymerization inhibitor and 1-5 parts of a second initiator.
As a further optimization, the acrylate monomer is one or more of methyl methacrylate, hydroxyethyl methacrylate and isobornyl methacrylate.
As a further optimization, the epoxy resin is one or more of E51, E44, E42 and E39D.
As a further optimization, the toughening agent is an MBS toughening agent.
As a further optimization, the polymerization inhibitor is one or more of hydroquinone, 1, 4-naphthoquinone, p-hydroxy methyl ether, copper N, N-di-N-butyl dithiocarbamate and phenothiazine.
As a further optimization, the filler is one or more of asbestos powder, silicic acid powder, porcelain powder, titanium dioxide powder and graphite powder.
As a further optimization, the first initiator is one or more of cumene hydroperoxide, benzoyl peroxide, cyclohexanone peroxide and azobisisobutyronitrile; the second initiator is one or more of azobisisoheptonitrile, tert-butyl hydroperoxide and cumene hydroperoxide.
As a further optimization, the accelerator is one or more of ethylene thiourea, tetramethylthiuram disulfide and tetramethylthiourea.
Compared with the prior art, the invention has the beneficial effects that:
1. the molecular chain of the modified epoxy acrylic prepolymer contains a bisphenol A structure, so that the modified epoxy acrylic prepolymer has the advantages and disadvantages of epoxy resin, before the structural adhesive is compounded and used, the modified epoxy acrylic prepolymer independently exists from the component A and the component B, and after acrylic ester monomers of the component A and the component B are fully crosslinked during use, the structural adhesive is blended with the modified epoxy acrylic prepolymer, so that an interpenetrating network structure is formed with the bisphenol A structure in the modified epoxy acrylic prepolymer, the high temperature resistance of the adhesive is better improved, and meanwhile, the high temperature strength of the adhesive is obviously increased along with the synergistic effect of the filler;
2. the raw materials used in the invention have better environmental protection property and lower volatility, and meet the requirement of low odor.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1
A low-odor high-temperature-resistant acrylate structural adhesive comprises a component A, a component B and a modified epoxy acrylic prepolymer, wherein the component A comprises 10 parts by weight of nitrile rubber, 15 parts by weight of methyl methacrylate, 10 parts by weight of hydroxyethyl methacrylate, 20 parts by weight of isobornyl methacrylate, 10 parts by weight of MBS toughening agent, 2 parts by weight of hydroquinone, 5 parts by weight of silicic acid powder, 10 parts by weight of methacrylic acid and 2 parts by weight of cumene hydroperoxide; the component B comprises 10 parts by weight of methyl methacrylate, 20 parts by weight of hydroxyethyl methacrylate, 12 parts by weight of isobornyl methacrylate, 15 parts by weight of MBS toughening agent and 2 parts by weight of ethylene thiourea; the modified epoxy acrylic prepolymer comprises, by weight, epoxy resin E5120 parts, methacrylic acid 2 parts, hydroquinone 2 parts and cumene hydroperoxide 1 part.
The preparation method comprises the following steps: s1) preparation of component a: plasticating and thinly passing nitrile rubber, then taking out sheets, putting methyl methacrylate, hydroxyethyl methacrylate, isobornyl methacrylate, MBS toughening agent, hydroquinone and nitrile rubber into a reaction kettle, stirring by introducing cooling water until the nitrile rubber is completely dissolved, putting silicic acid powder, stirring for 3-4h to uniformly disperse the nitrile rubber, then adding methacrylic acid and cumene hydroperoxide, stirring uniformly, and discharging for later use; s2) preparing a component B: putting methyl methacrylate, hydroxyethyl methacrylate, isobornyl methacrylate, MBS toughening agent and ethylene thiourea into a reaction kettle in proportion, uniformly stirring, and discharging for later use; s3) preparing a modified epoxy acrylic prepolymer: putting epoxy resin E51, methacrylic acid, hydroquinone and cumene hydroperoxide into a three-neck flask, heating to 110 ℃, reacting for 8 hours, cooling to 55-60 ℃, and discharging for later use.
Example 2
A low-odor high-temperature-resistant acrylate structural adhesive comprises a component A, a component B and a modified epoxy acrylic prepolymer, wherein the component A comprises 20 parts by weight of nitrile rubber, 18 parts by weight of methyl methacrylate, 10 parts by weight of hydroxyethyl methacrylate, 15 parts by weight of isobornyl methacrylate, 15 parts by weight of MBS toughening agent, 1 part by weight of 1, 4-naphthoquinone, 15 parts by weight of porcelain powder, 15 parts by weight of methacrylic acid and 3 parts by weight of benzoyl peroxide; the component B comprises 15 parts by weight of methyl methacrylate, 10 parts by weight of hydroxyethyl methacrylate, 16 parts by weight of isobornyl methacrylate, 10 parts by weight of MBS toughening agent and 2 parts by weight of tetramethyl thiourea; the modified epoxy acrylic prepolymer comprises, by weight, epoxy resin E5115 parts, methacrylic acid 5 parts, 1, 4-naphthoquinone 2 parts and tert-butyl hydroperoxide 1 part.
The preparation method comprises the following steps: s1) preparation of component a: plasticating and thinly passing nitrile rubber, then taking out sheets, putting methyl methacrylate, hydroxyethyl methacrylate, isobornyl methacrylate, MBS flexibilizer, 1, 4-naphthoquinone and nitrile rubber into a reaction kettle, stirring with cooling water until the nitrile rubber is completely dissolved, putting porcelain powder, stirring for 3-4h to uniformly disperse the porcelain powder, then adding methacrylic acid and benzoyl peroxide, stirring uniformly, and discharging for later use; s2) preparing a component B: putting methyl methacrylate, hydroxyethyl methacrylate, isobornyl methacrylate, MBS toughening agent and tetramethyl thiourea into a reaction kettle in proportion, uniformly stirring, and discharging for later use; s3) preparing a modified epoxy acrylic prepolymer: putting epoxy resin E51, methacrylic acid, 1, 4-naphthoquinone and tert-butyl hydroperoxide into a three-neck flask, heating to 110 ℃, reacting for 8 hours, cooling to 55-60 ℃, and discharging for later use.
Example 3
A low-odor high-temperature-resistant acrylate structural adhesive comprises a component A, a component B and a modified epoxy acrylic prepolymer, wherein the component A comprises 15 parts by weight of nitrile rubber, 20 parts by weight of methyl methacrylate, 12 parts by weight of hydroxyethyl methacrylate, 16 parts by weight of isobornyl methacrylate, 15 parts by weight of MBS toughening agent, 2 parts by weight of hydroquinone, 8 parts by weight of titanium dioxide powder, 5 parts by weight of methacrylic acid and 2 parts by weight of cumene hydroperoxide; the component B comprises 13 parts by weight of methyl methacrylate, 18 parts by weight of hydroxyethyl methacrylate, 15 parts by weight of isobornyl methacrylate, 20 parts by weight of MBS toughening agent and 3 parts by weight of tetramethyl thiourea; the modified epoxy acrylic prepolymer comprises, by weight, epoxy resin E4425 parts, methacrylic acid 5 parts, p-hydroxy methyl ether 2 parts and cumene hydroperoxide 1 part.
The preparation method comprises the following steps: s1) preparation of component a: plasticating and thinly passing nitrile rubber, then taking out sheets, putting methyl methacrylate, hydroxyethyl methacrylate, isobornyl methacrylate, MBS toughening agent, hydroquinone and nitrile rubber into a reaction kettle, introducing cooling water, stirring until the nitrile rubber is completely dissolved, putting titanium dioxide powder, stirring for 3-4h to uniformly disperse the titanium dioxide powder, then adding methacrylic acid and cumene hydroperoxide, stirring uniformly, and discharging for later use; s2) preparing a component B: putting methyl methacrylate, hydroxyethyl methacrylate, isobornyl methacrylate, MBS toughening agent and tetramethyl thiourea into a reaction kettle in proportion, uniformly stirring, and discharging for later use; s3) preparing a modified epoxy acrylic prepolymer: putting epoxy resin E44, methacrylic acid, p-hydroxy methyl ether and cumene hydroperoxide into a three-neck flask, heating to 105 ℃, reacting for 10 hours, cooling to 55-60 ℃, and discharging for later use.
Application examples
The end of the test piece is polished by sand paper, the surface of the test piece is flat and bright and has no concave-convex surface, the surface of the test piece is cleaned by an organic solvent before use, and the test piece is dried by an oven at 60 ℃. The component A, the component B and the modified epoxy acrylic prepolymer (1:1:1) are uniformly mixed and stirred, blade-coated on the bonded end face of the test piece, and cured for 24 hours at room temperature. The tensile shear strength and the strength retention rate (percentage value of high-temperature strength to normal-temperature strength) are tested at room temperature and 120 ℃, the test is carried out on a universal electronic tensile machine by referring to GB/T7124-1986 standard, wherein the comparative example is the conventional acrylate structural adhesive.
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Shear strength at room temperature/MPa | 22.4 | 24.3 | 25.04 | 20.4 |
| 120 ℃ shear strength/MPa | 14.6 | 16.2 | 17.21 | 8.0 |
| Strength retention ratio/%) | 65.2 | 65.5 | 66.10 | 39.2 |
According to experimental data, the structural adhesive has good normal-temperature shear strength, good high-temperature shear strength and good strength retention rate.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (9)
1. A preparation method of low-odor high-temperature-resistant acrylate structural adhesive is characterized by comprising the following steps of,
s1) preparation of component a: plasticating and thinly passing nitrile rubber, then taking out sheets, putting an acrylate monomer, a toughening agent, a polymerization inhibitor and the nitrile rubber into a reaction kettle, introducing cooling water, stirring until the nitrile rubber is completely dissolved, putting filler, stirring for 3-4h to uniformly disperse the filler, then adding methacrylic acid and a first initiator, stirring uniformly, and discharging for later use;
s2) preparing a component B: putting an acrylate monomer, a toughening agent and an accelerant into a reaction kettle in proportion, uniformly stirring, and discharging for later use;
s3) preparing a modified epoxy acrylic prepolymer: putting epoxy resin, methacrylic acid, a polymerization inhibitor and a second initiator into a three-neck flask, heating to 105-140 ℃, reacting for 8-12h, cooling to 55-60 ℃, and discharging for later use;
s4) preparing a structural adhesive: and uniformly mixing the component A, the component B and the modified epoxy acrylic prepolymer when in use to obtain the low-temperature high-temperature-resistant acrylate structural adhesive.
2. The preparation method of the low-odor high-temperature-resistant acrylate structural adhesive according to claim 1, wherein the component A comprises 3-20 parts by weight of nitrile rubber, 30-50 parts by weight of acrylate monomer, 10-30 parts by weight of toughening agent, 1-10 parts by weight of polymerization inhibitor, 1-15 parts by weight of filler, 5-20 parts by weight of methacrylic acid and 1-5 parts by weight of first initiator; the component B comprises 30-50 parts of acrylate monomer, 10-30 parts of toughening agent and 1-5 parts of accelerator according to parts by weight; the modified epoxy acrylic prepolymer comprises, by weight, 15-35 parts of epoxy resin, 1-5 parts of methacrylic acid, 1-10 parts of a polymerization inhibitor and 1-5 parts of a second initiator.
3. The preparation method of the low-odor high-temperature-resistant acrylate structural adhesive according to claim 1 or 2, wherein the acrylate monomer is one or more of methyl methacrylate, hydroxyethyl methacrylate and isobornyl methacrylate.
4. The method for preparing the low-odor high-temperature-resistant acrylate structural adhesive according to claim 1 or 2, wherein the epoxy resin is one or more of E51, E44, E42 and E39D.
5. The preparation method of the low-odor high-temperature-resistant acrylate structural adhesive according to claim 1 or 2, wherein the toughening agent is an MBS toughening agent.
6. The preparation method of the low-odor high-temperature-resistant acrylate structural adhesive as claimed in claim 1 or 2, wherein the polymerization inhibitor is one or more of hydroquinone, 1, 4-naphthoquinone, p-hydroxy methyl ether, copper N, N-di-N-butyl dithiocarbamate and phenothiazine.
7. The preparation method of the low-odor high-temperature-resistant acrylate structural adhesive as claimed in claim 1 or 2, wherein the filler is one or more of asbestos powder, silicic acid powder, porcelain powder, titanium dioxide powder and graphite powder.
8. The method for preparing the low-odor high-temperature-resistant acrylate structural adhesive according to claim 1 or 2, wherein the first initiator is one or more of cumene hydroperoxide, benzoyl peroxide, cyclohexanone peroxide and azobisisobutyronitrile; the second initiator is one or more of azobisisoheptonitrile, tert-butyl hydroperoxide and cumene hydroperoxide.
9. The method for preparing the low-odor high-temperature-resistant acrylate structural adhesive according to claim 1 or 2, wherein the accelerator is one or more of ethylene thiourea, tetramethylthiuram disulfide and tetramethylthiourea.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011024804.7A CN112126377A (en) | 2020-09-25 | 2020-09-25 | Preparation method of low-odor high-temperature-resistant acrylate structural adhesive |
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| CN202011024804.7A CN112126377A (en) | 2020-09-25 | 2020-09-25 | Preparation method of low-odor high-temperature-resistant acrylate structural adhesive |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59221372A (en) * | 1983-05-31 | 1984-12-12 | Yokohama Rubber Co Ltd:The | Structural adhesive |
| CN101402830A (en) * | 2008-10-10 | 2009-04-08 | 淮安市恒星电子有限公司 | Stable epoxy acrylic acid structure glue and production method thereof |
| CN111019569A (en) * | 2019-12-02 | 2020-04-17 | 上海康达化工新材料集团股份有限公司 | High-toughness acrylate structural adhesive and preparation method thereof |
-
2020
- 2020-09-25 CN CN202011024804.7A patent/CN112126377A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59221372A (en) * | 1983-05-31 | 1984-12-12 | Yokohama Rubber Co Ltd:The | Structural adhesive |
| CN101402830A (en) * | 2008-10-10 | 2009-04-08 | 淮安市恒星电子有限公司 | Stable epoxy acrylic acid structure glue and production method thereof |
| CN111019569A (en) * | 2019-12-02 | 2020-04-17 | 上海康达化工新材料集团股份有限公司 | High-toughness acrylate structural adhesive and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| 张鹏等: "《丙烯酸树脂防腐蚀涂料及应用》", 30 September 2003, 化学工业出版社 * |
| 李国莱等: "《合成树脂及玻璃钢》", 31 January 1989, 化学工业出版社 * |
| 桂武标等: "高性能丙烯酸酯结构胶的研制", 《粘接》 * |
| 王国全: "《聚合物改性（第三版）》", 31 May 2016, 中国轻工业出版社 * |
| 王禹阶: "《有机·无机玻璃钢技术问答》", 31 March 2001, 化学工业出版社 * |
| 程曾越: "《通用树脂使用技术手册》", 30 November 1999, 中国石化出版社 * |
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Application publication date: 20201225 |