CN110698989A - Development of flame-retardant acrylate adhesive with bi-component structure - Google Patents
Development of flame-retardant acrylate adhesive with bi-component structure Download PDFInfo
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- CN110698989A CN110698989A CN201911065629.3A CN201911065629A CN110698989A CN 110698989 A CN110698989 A CN 110698989A CN 201911065629 A CN201911065629 A CN 201911065629A CN 110698989 A CN110698989 A CN 110698989A
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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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
- C09J11/06—Non-macromolecular additives organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Development of a flame-retardant acrylate adhesive with a bi-component structure. The flame-retardant bi-component structural bonding acrylate adhesive comprises the following components in parts by weight: (1) the main agent comprises the following components: 30-60 parts of at least 1 vinyl acrylic monomer, 15-35 parts of elastomer, 5-20 parts of flame-retardant monomer, 0.1-5 parts of stabilizer and 1-8 parts of peroxide initiator; (2) curing agent component: 25-50 parts of at least 1 vinyl acrylic monomer, 5-30 parts of elastomer, 5-20 parts of flame retardant monomer, 0.01-0.5 part of stabilizer, 1-10 parts of accelerator, 0-25 parts of methacrylic acid and 1-5 parts of auxiliary accelerator. The invention has good flame retardant property and good mechanical property, and is mainly used for bonding acrylate adhesive with a flame retardant structure.
Description
Technical Field
The invention belongs to the technical field of bi-component acrylate adhesives, and particularly relates to a flame-retardant bi-component structural adhesive acrylate adhesive.
Technical Field
The acrylate structural adhesive is widely used for structural bonding in industries such as automobiles, machinery, electronic and electric appliances, furniture, toys, railway vehicles, artware and the like due to the characteristics of rapid curing at room temperature, high strength, good toughness, simple and convenient operation and the like.
With the development of the automobile industry technology and the further requirements on automobile products, fuel automobiles are gradually replaced by new energy automobiles. The power battery used by the new energy automobile has high requirement on flame retardant performance, and the common acrylate structural adhesive cannot meet the flame retardant requirement. Therefore, the development of a flame-retardant two-component adhesive acrylate adhesive has become one of the important issues in the research field.
Disclosure of Invention
The invention aims to provide a flame-retardant acrylate adhesive with a bi-component structure, which has good mechanical property and excellent flame retardance.
The technical solution adopted by the invention to solve the technical problems is as follows: a double-component acrylate adhesive is a double-component adhesive, comprises a curing agent and a main agent, and is characterized in that:
(1) the main agent comprises the following components: 30-60 parts of at least 1 vinyl acrylic monomer, 15-35 parts of elastomer, 5-20 parts of flame-retardant monomer, 0.1-5 parts of stabilizer and 1-8 parts of peroxide initiator;
(2) curing agent component: 25-50 parts of at least 1 vinyl acrylic monomer, 5-30 parts of elastomer, 5-20 parts of flame retardant monomer, 0.01-0.5 part of stabilizer, 1-10 parts of accelerator, 0-25 parts of methacrylic acid and 1-5 parts of auxiliary accelerator.
In the present invention, the at least one vinyl acrylate monomer may be methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-phenoxyethyl methacrylate, tetrahydrofuryl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or a mixture thereof;
in the invention, the rubber elastomer containing at least one elastomer of nitrile rubber, chloroprene rubber, chlorosulfonated polyethylene, flame-retardant ABS, MBS and the like or a mixture thereof;
in the present invention, the stabilizer is a phenolic compound, a quinone compound, oxalic acid, a sodium salt, phenothiazine or a mixture thereof;
in the present invention, the peroxide initiator is a mixture of hydrogen peroxide;
in the invention, the stabilizer is a phenolic compound, a quinone compound or a mixture thereof;
in the invention, the accelerant is amines, thiourea, aldehyde-amine condensate or a mixture thereof;
in the present invention, the flame retardant monomer is TCEP, TXP, CDP, TCPP or mixtures thereof;
in the invention, the auxiliary accelerator is phosphate ester monomer.
Detailed Description
For better illustration of the invention and for easy understanding of the technical solution of the invention, exemplary but non-limiting examples of the invention are as follows:
example 1:
the main agent comprises the following components:
methyl methacrylate 38.00% Wt
Methacrylic acid 2-phenoxyethyl ester 10.00% Wt
Flame retardant grade ABS 29.75% Wt
MBS 2.00%Wt
BHT 0.20%Wt
TXP 15.00%Wt
0.05% wt. of hydroquinone
Cumene hydroperoxide 5.00% Wt
Curing agent component:
methyl methacrylate 27.30% Wt
Methacrylic acid 23.50% Wt
Methacrylic acid 2-phenoxyethyl ester 10.00% Wt
Flame retardant grade ABS 8.50% Wt
MBS 2.00%Wt
Nitrile rubber 14.50% Wt
BHT 0.20%Wt
2.00% Wt of Tetramethylthiourea
P-2M 2.00%Wt
CDP 10.00%Wt
The preparation method comprises the following steps:
(1) the main agent comprises the following components: putting a methacrylate monomer into a reaction kettle, heating to 60 ℃, adding an elastomer, stirring until the elastomer is completely dissolved, adding a stabilizer, stirring uniformly, cooling to below 40 ℃, adding a flame-retardant monomer and cumene hydroperoxide, and stirring uniformly.
(2) Curing agent component: putting methacrylate monomer into a reaction kettle, heating to 60 ℃, adding elastomer, stirring until the elastomer is completely dissolved, adding stabilizer, stirring uniformly, cooling to below 40 ℃, adding accelerator, flame-retardant monomer and auxiliary accelerator, and stirring uniformly.
Example 2:
the main agent comprises the following components:
methyl methacrylate 38.00% Wt
Methacrylic acid 2-phenoxyethyl ester 10.00% Wt
Flame retardant grade ABS 29.75% Wt
MBS 2.00%Wt
BHT 0.20%Wt
TCEP 15.00%Wt
0.05% wt. of hydroquinone
Cumene hydroperoxide 5.00% Wt
Curing agent component:
methyl methacrylate 27.30% Wt
Methacrylic acid 23.50% Wt
Methacrylic acid 2-phenoxyethyl ester 10.00% Wt
Flame retardant grade ABS 8.50% Wt
MBS 2.00%Wt
Chloronitriles rubber 14.50% Wt
BHT 0.20%Wt
Ethylene Thiourea 2.00% Wt
P-2M 2.00%Wt
TXP 10.00%Wt
The preparation method is the same as example 1.
Example 3:
the main agent comprises the following components:
methyl methacrylate 38.00% Wt
Tetrahydrofuran methacrylate 10.00% Wt
Flame retardant grade ABS 29.75% Wt
MBS 2.00%Wt
BHT 0.20%Wt
TCEP 15.00%Wt
0.05% wt. of hydroquinone
Cumene hydroperoxide 5.00% Wt
Curing agent component:
methyl methacrylate 27.30% Wt
Methacrylic acid 23.50% Wt
Tetrahydrofuran methacrylate 10.00% Wt
Flame retardant grade ABS 8.50% Wt
MBS 2.00%Wt
Nitrile rubber 14.50% Wt
0.20% Wt of p-benzoquinone
2.00% Wt of Tetramethylthiourea
P-2M 2.00%Wt
TCEP 10.00%Wt
The preparation method is the same as example 1.
The performance tests are as follows:
| test items | Example 1 | Example 2 | Example 3 |
| Reaction time (min) | 5 | 4.5 | 5.5 |
| Tensile shear Strength (MPa) | 20 | 19 | 21 |
| Flame retardant rating | V0 | V0 | V0 |
| Stability (80 ℃ C. 6 h) | Non-gelling | Non-gelling | Non-gelling |
Claims (2)
1. The flame-retardant bi-component structural adhesive acrylate adhesive is characterized by comprising the following components:
(1) the main agent comprises the following components:
(A) 30-60 Wt% of the total weight of the composition contains at least 1 vinyl acrylate monomer;
(B) 15-35 Wt% of at least one elastomer;
(C) 0.1 to 5 weight percent of stabilizer;
(D) 1-8 Wt% of peroxide initiator;
(E) 5-20 Wt% of flame-retardant monomer;
(2) curing agent component:
(A) 25-50 Wt% of the total weight of the composition contains at least 1 vinyl acrylate monomer;
(B) 5-35 Wt% of at least one elastomer;
(C) 0.01 to 5 weight percent of stabilizer;
(D) 1-10 Wt% of accelerator;
(E) 1-5 Wt% of auxiliary accelerator;
(F) 0-25 Wt% of methacrylic acid;
(G) 5 to 20 weight percent of flame-retardant monomer.
2. The flame retardant bi-component structural adhesive acrylic according to claim 1, wherein:
(A) the monomer containing at least one vinyl acrylate can be methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-phenoxyethyl methacrylate, tetrahydrofuran methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or a mixture thereof;
(B) the rubber elastomer comprises at least one elastomer of nitrile rubber, chloroprene rubber, chlorosulfonated polyethylene, flame-retardant ABS, MBS and the like or a mixture thereof;
(C) the stabilizer is phenolic compound, quinone compound, oxalic acid, sodium salt, phenothiazine or their mixture;
(D) the peroxide initiator is a hydrogen peroxide mixture;
(E) the stabilizer is a phenolic compound, a quinone compound or a mixture thereof;
(F) the accelerant is amines, thiourea, aldehyde-amine condensate or a mixture thereof;
(G) the flame-retardant monomer is TCEP, TXP, CDP, TCPP or a mixture thereof;
(H) the auxiliary accelerator is phosphate ester monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911065629.3A CN110698989A (en) | 2019-11-04 | 2019-11-04 | Development of flame-retardant acrylate adhesive with bi-component structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911065629.3A CN110698989A (en) | 2019-11-04 | 2019-11-04 | Development of flame-retardant acrylate adhesive with bi-component structure |
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| Publication Number | Publication Date |
|---|---|
| CN110698989A true CN110698989A (en) | 2020-01-17 |
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| CN201911065629.3A Pending CN110698989A (en) | 2019-11-04 | 2019-11-04 | Development of flame-retardant acrylate adhesive with bi-component structure |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001262107A (en) * | 2000-03-23 | 2001-09-26 | Denki Kagaku Kogyo Kk | Flame-retardant resin composition, flame-retardant adhesive composition and metal-joined article |
| CN102533131A (en) * | 2010-12-16 | 2012-07-04 | 湖北回天胶业股份有限公司 | Acrylate adhesive for spot welding process |
| CN103834330A (en) * | 2012-11-23 | 2014-06-04 | 湖北回天胶业股份有限公司 | Flame retardant acrylate adhesive |
| CN109735236A (en) * | 2019-01-17 | 2019-05-10 | 福建省昌德胶业科技有限公司 | A kind of development of low smell bicomponent structure bonding acrylic adhesive |
| EP2958968B1 (en) * | 2013-02-20 | 2020-07-15 | Illinois Tool Works Inc. | Galvanized metal bonding adhesive formulation and process for the use thereof |
-
2019
- 2019-11-04 CN CN201911065629.3A patent/CN110698989A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001262107A (en) * | 2000-03-23 | 2001-09-26 | Denki Kagaku Kogyo Kk | Flame-retardant resin composition, flame-retardant adhesive composition and metal-joined article |
| CN102533131A (en) * | 2010-12-16 | 2012-07-04 | 湖北回天胶业股份有限公司 | Acrylate adhesive for spot welding process |
| CN103834330A (en) * | 2012-11-23 | 2014-06-04 | 湖北回天胶业股份有限公司 | Flame retardant acrylate adhesive |
| EP2958968B1 (en) * | 2013-02-20 | 2020-07-15 | Illinois Tool Works Inc. | Galvanized metal bonding adhesive formulation and process for the use thereof |
| CN109735236A (en) * | 2019-01-17 | 2019-05-10 | 福建省昌德胶业科技有限公司 | A kind of development of low smell bicomponent structure bonding acrylic adhesive |
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Application publication date: 20200117 |