CN114634779A - Hybrid acrylate AB adhesive and preparation method thereof - Google Patents
Hybrid acrylate AB adhesive and preparation method thereof Download PDFInfo
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- CN114634779A CN114634779A CN202210197254.1A CN202210197254A CN114634779A CN 114634779 A CN114634779 A CN 114634779A CN 202210197254 A CN202210197254 A CN 202210197254A CN 114634779 A CN114634779 A CN 114634779A
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J155/00—Adhesives based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09J123/00 - C09J153/00
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Abstract
The invention discloses a hybrid acrylate AB adhesive which comprises a component A in percentage by mass: 50.0-65.0 percent of polymerized monomer, 5.0-10.0 percent of functional monomer, 5.0-10.0 percent of modified tackifying alkyd resin, 10.0-25.0 percent of reinforced resin, 10.0-20.0 percent of toughened rubber, 2.0-6.0 percent of reducing agent and 0.1-2.0 percent of stabilizing agent; and B component: 55.0 to 65.0 percent of polymerized monomer, 2.0 to 8.0 percent of functional monomer, 1.0 to 5.0 percent of methylacrylic acid wax, 20.0 to 35.0 percent of reinforced resin, 5.0 to 15.0 percent of toughened rubber, 1.0 to 6.0 percent of oxidant and 0.5 to 5.0 percent of stabilizer. The invention also discloses a preparation method of the hybrid acrylate AB adhesive. According to the invention, through compounding of the raw materials, the prepared hybrid acrylate AB adhesive has excellent adhesive force to engineering plastics such as ABS, ASA and the like, and has the characteristics of low odor, good curing and tack-removing property, strong adhesive force, high toughness, fatigue resistance, creep resistance, good heat resistance, good weather resistance and wide range of bonding materials, and can meet the bonding requirements of new energy automobile body materials.
Description
Technical Field
The invention relates to the technical field of adhesives, and particularly relates to a hybrid acrylate AB adhesive and a preparation method thereof.
Background
In recent years, the energy problem and the environmental pollution problem become more serious, and the development of new energy automobiles is an important strategy for meeting the national requirements of energy conservation, emission reduction and low-carbon economy. Different from the traditional automobiles, the new energy automobile body materials are more prone to lightweight materials, such as high-strength steel, aluminum alloy, magnesium alloy, carbon fiber, various engineering plastics and the like. The traditional acrylate AB adhesive in the market at present has the characteristics of simple and convenient operation, quick curing at normal temperature and high bonding strength, but also has the defects of poor toughness, fatigue resistance and creep resistance, poor adhesion to engineering plastics for new energy automobiles such as ABS, ASA and the like, and can not meet the use requirements. Therefore, the development of the hybrid acrylic ester AB adhesive which has low odor, good curing tack-free property, strong adhesive force, high toughness, fatigue resistance, creep resistance, good heat resistance, good weather resistance and wide range of bonding materials is very necessary.
Disclosure of Invention
The invention aims to provide an acrylate AB adhesive which has low odor, good curing tack-free property, strong adhesive force, high toughness, fatigue resistance, creep resistance, good heat resistance, good weather resistance, wide range of bonding materials and convenient use, and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme: the hybrid acrylate AB adhesive comprises the following components in percentage by mass:
the component A comprises:
and B component:
further, the polymerization monomer is one or a mixture of more than two monomers of 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, polyethylene glycol dimethacrylate, methacrylic acid, acrylic acid, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, allyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and bisphenol A polyoxyethylene ether dimethacrylate.
Further, the functional monomer is one or a mixture of two monomers of pentaerythritol triacrylate and trimethylolpropane trimethacrylate.
Further, the modified tackifying alkyd resin is prepared by performing alcoholysis on almond oil and then performing alkyd polycondensation on the almond oil, maleic anhydride and nadic anhydride to obtain the almond oil alkyd tackifying resin, wherein the mass ratio of the almond oil, the glycerin, the maleic anhydride and the nadic anhydride is 70:25:25: 21.
Further, the reinforced resin is one or a mixture of two or more of modified hydroxyl acrylic resin, MBS resin, ABS resin, polymethyl methacrylate and styrene-butadiene transparent impact-resistant resin; the toughened rubber is one or a mixture of two of chlorosulfonated polyethylene, chloroprene rubber and nitrile rubber.
Further, the reducing agent is one or a mixture of more than two of N, N-dimethylbenzylamine, N-dimethylaniline, ethylenediamine, triethylamine, triethanolamine, vinylthiourea, diphenylthiourea and tetramethylthiourea.
Further, the stabilizer is one or a mixture of more than two of hydroquinone, 2, 6-di-tert-butyl-4-methylphenol, p-methoxyphenol and p-benzoquinone.
Further, the methacrylated wax is obtained by carrying out a grafting reaction on liquid paraffin and methacrylic acid under the initiation of benzoyl peroxide, wherein the weight ratio of the liquid paraffin to the methacrylic acid to the benzoyl peroxide is 100:30: 2.
Further, the oxidant is one or a mixture of more than two of cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, tert-amyl hydroperoxide and tert-butyl hydroperoxide.
The invention also provides a preparation method of the hybrid acrylate AB adhesive, which comprises the following specific steps:
preparation of component A:
a. preparing modified tackifying alkyd resin: weighing the raw materials according to the mass percentage, adding glycerol into the almond oil, stirring and heating to 220 ℃, carrying out alcoholysis reaction for 1-2 hours, then cooling to 160 ℃, adding maleic anhydride and nadic anhydride, stirring and heating to 190 ℃, carrying out alkyd polycondensation reaction for 5-6 hours, and cooling to obtain almond oil alkyd tackifying resin;
b. weighing the raw materials according to the mass percentage, putting a polymerization monomer, a functional monomer and a stabilizer into a reaction kettle, adding a reducing agent, modified tackifying alkyd resin, toughening rubber and reinforcing resin in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and defoaming in vacuum to obtain a component A;
preparation of the component B:
a. preparation of methacrylated wax: weighing the raw materials according to the mass percentage, adding methacrylic acid into liquid paraffin, stirring and heating to 60-80 ℃, adding benzoyl peroxide, carrying out grafting reaction for 3-4 hours, and cooling to obtain the methacrylated wax;
b. weighing the raw materials according to the mass percentage, putting the polymerization monomer, the functional monomer and the stabilizer into a reaction kettle, adding the oxidant, the methacrylated wax, the toughened rubber and the reinforced resin in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and carrying out vacuum defoamation to obtain the component B.
Compared with the prior art, the invention has the following beneficial effects:
1. in the invention, a functional monomer (one or a mixture of two monomers of pentaerythritol triacrylate (PETA) and trimethylolpropane trimethacrylate) is added into a reaction system, the substance has the characteristic of typical acrylate, a side chain hydroxyl group is also arranged in a molecule, on one hand, the polarity of the molecule is enhanced by the existence of the hydroxyl group, the volatility is reduced, and the prepared glue solution has low smell; on the other hand, the polymer can be used as a reaction site to carry out grafting reaction with a polymerization monomer, and the product has high glass transition temperature and high temperature resistance.
2. The modified tackifying alkyd resin in the component A adopts almond oil alkyd tackifying resin, the almond oil is newly developed renewable vegetable oil, and the alkyd resin prepared by the modified tackifying alkyd resin has high molecular weight, high hydroxyl content and excellent flexibility and adhesive force. In the curing process, unsaturated double bonds contained in the almond oil alkyd tackifying resin can be copolymerized with acrylate monomers to form a hybrid polymer, so that the adhesive force of the adhesive solution to engineering plastics such as ABS, ASA and the like can be increased, and the fatigue resistance and creep resistance of the adhesive solution can be improved.
3. The component B of the invention adopts methacrylic acid wax, paraffin is a hydrocarbon mixture, after methacrylic acid grafting, the molecular chain is introduced with acrylate-philic groups, the compatibility with the glue solution is greatly improved, and the acrylic acid ester-philic groups can be directionally arranged on the surface of the glue solution to form a compact monomolecular adsorption layer, thereby effectively blocking oxygen in air, improving the surface dryness of the glue solution after curing and leading the adhesive to achieve the effect of quick debonding.
4. According to the invention, through compounding of the raw materials, the prepared hybrid acrylate AB adhesive has excellent adhesive force to engineering plastics such as ABS, ASA and the like, and has the characteristics of low odor, good curing and tack-removing property, strong adhesive force, high toughness, fatigue resistance, creep resistance, good heat resistance, good weather resistance and wide range of bonding materials, and can meet the bonding requirements of new energy automobile body materials.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The hybrid acrylate AB adhesive comprises the following components in percentage by mass:
the component A comprises:
and B component:
example 2
A hybrid acrylate AB glue comprises the following components in percentage by mass:
the component A comprises:
and the component B comprises:
the preparation method of the hybrid acrylate AB glue of the embodiment 1 and the embodiment 2 comprises the following steps:
preparing a component A:
a. preparation of modified tackifying alkyd resin (almond oil alkyd tackifying resin): weighing the raw materials according to the mass percentage, adding glycerol into almond oil, stirring and heating to 220 ℃, carrying out alcoholysis reaction for 1-2 hours, then cooling to 160 ℃, adding maleic anhydride and nadic anhydride, stirring and heating to 190 ℃, carrying out alkyd polycondensation reaction for 5-6 hours, and cooling to obtain the almond oil modified tackifying resin;
b. weighing the raw materials according to the mass percentage, putting pentaerythritol triacrylate, 2-phenoxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid and hydroquinone into a reaction kettle, adding tetramethyl thiourea, triethanolamine, almond oil alkyd tackifying resin, nitrile rubber and ABS resin in sequence while stirring, heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and defoaming in vacuum to obtain the component A.
B, preparation of a component:
a. preparation of methacrylated wax: weighing the raw materials according to the mass percentage, adding methacrylic acid into liquid paraffin, stirring and heating to 60-80 ℃, adding a benzoyl peroxide initiator, carrying out grafting reaction for 3-4 hours, and cooling to obtain the methacrylated wax;
b. weighing the raw materials according to the mass percentage, putting pentaerythritol triacrylate, 2-phenoxyethyl methacrylate, hydroxypropyl methacrylate and hydroquinone into a reaction kettle, adding cumene hydroperoxide, methacrylic acid wax, nitrile rubber and ABS resin in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and defoaming in vacuum to obtain the component B.
The use of glue solution: the prepared component A and the prepared component B are uniformly mixed according to the volume ratio of 1:1, and then bonding can be carried out.
Example 3
The hybrid acrylate AB adhesive comprises the following components in percentage by mass:
the component A comprises:
and B component:
the preparation method of the hybrid acrylate AB glue of the embodiment 3 comprises the following specific steps:
preparation of component A:
a. preparation of modified tackifying alkyd resin (almond oil alkyd tackifying resin): weighing the raw materials according to the mass percentage, adding glycerol into the almond oil, stirring and heating to 220 ℃, carrying out alcoholysis reaction for 1-2 hours, then cooling to 160 ℃, adding maleic anhydride and nadic anhydride, stirring and heating to 190 ℃, carrying out alkyd polycondensation reaction for 5-6 hours, and cooling to obtain almond oil alkyd tackifying resin;
b. weighing the raw materials according to the mass percentage, putting polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, bisphenol A polyoxyethylene ether dimethacrylate, acrylic acid and 2, 6-di-tert-butyl-4-methylphenol into a reaction kettle, adding N, N-dimethylaniline, vinyl thiourea, almond oil alkyd tackifying resin, nitrile rubber, ABS resin and butylbenzene transparent impact-resistant resin in sequence while stirring, stirring and heating to 45 ℃, continuously stirring for 3 hours, cooling to below 30 ℃, and carrying out vacuum defoamation to obtain a component A;
preparation of the component B:
a. preparation of methacrylated wax: weighing the raw materials according to the mass percentage, adding methacrylic acid into liquid paraffin, stirring and heating to 60-80 ℃, adding a benzoyl peroxide initiator, carrying out grafting reaction for 3-4 hours, and cooling to obtain the methacrylated wax;
b. weighing the raw materials according to the mass percentage, putting diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, butanediol dimethacrylate, tetrahydrofurfuryl methacrylate and p-benzoquinone into a reaction kettle, sequentially adding dicumyl peroxide, methacrylated wax, MBS resin and chloroprene rubber under stirring, heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and defoaming in vacuum to obtain the component B.
The use of glue solution: the prepared component A and the prepared component B are uniformly mixed according to the volume ratio of 1:1, and then bonding can be carried out.
Example 4
A hybrid acrylate AB glue comprises the following components in percentage by mass:
the component A comprises:
and B component:
the preparation method of the hybrid acrylate AB glue of the embodiment 4 comprises the following specific steps:
preparation of component A:
a. preparation of almond oil alkyd tackifying resin: weighing the raw materials according to the mass percentage, adding glycerol into the almond oil, stirring and heating to 220 ℃, carrying out alcoholysis reaction for 1-2 hours, then cooling to 160 ℃, adding maleic anhydride and nadic anhydride, stirring and heating to 190 ℃, carrying out alkyd polycondensation reaction for 5-6 hours, and cooling to obtain almond oil alkyd tackifying resin;
b. weighing the raw materials according to the mass percentage, putting 2-phenoxyethyl acrylate, pentaerythritol triacrylate, butylene glycol dimethacrylate, methacrylic acid and p-methoxyphenol into a reaction kettle, sequentially adding ethylenediamine, tetramethylthiourea, almond oil alkyd tackifying resin, modified hydroxyacrylic acid resin, polymethyl methacrylate and chlorosulfonated polyethylene under stirring, stirring and heating to 45 ℃, continuously stirring for 3 hours, cooling to below 30 ℃, and carrying out vacuum deaeration to obtain a component A;
preparation of the component B:
a. preparation of methacrylated wax: weighing the raw materials according to the mass percentage, adding methacrylic acid into liquid paraffin, stirring and heating to 60-80 ℃, adding a benzoyl peroxide initiator, carrying out grafting reaction for 3-4 hours, and cooling to obtain the methacrylated wax;
b. weighing the raw materials according to the mass percentage, putting hydroxypropyl methacrylate, triethylene glycol dimethacrylate, pentaerythritol triacrylate and p-methoxyphenol into a reaction kettle, adding tert-amyl hydroperoxide, methacrylic wax, polymethyl methacrylate and chlorosulfonated polyethylene in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and carrying out vacuum defoamation to obtain the component B. The use of glue solution: the prepared component A and the prepared component B are uniformly mixed according to the volume ratio of 1:1, and then bonding can be carried out.
Comparative example 1
The acrylate AB adhesive comprises a component A and a component B, and comprises the following raw materials in percentage by mass as shown in Table 1:
table 1 comparative example 1 acrylic ester AB collagen material ratio
| Name of raw materials | Component A (%) | B component (%) |
| 2-Phenoxyethyl methacrylate | 33.0 | 45.0 |
| Hydroxypropyl methacrylate | 12.5 | 16.0 |
| Methacrylic acid | 15.0 | — |
| ABS resin | 18.0 | 27.0 |
| Nitrile rubber | 18.0 | 8 |
| Cumene hydroperoxide | — | 3.0 |
| Tetramethyl thiourea | 2.0 | — |
| Triethanolamine | 1.0 | — |
| Hydroquinone | 0.5 | 1.0 |
The preparation method of the acrylate AB glue of comparative example 1 is as follows:
preparation of a component A:
weighing the raw materials according to the mass percentage, putting 2-phenoxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid and hydroquinone into a reaction kettle, adding tetramethyl thiourea, triethanolamine, nitrile rubber and ABS resin in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and defoaming in vacuum to obtain a component A;
b, preparation of a component:
weighing the raw materials according to the mass percentage, putting 2-phenoxyethyl methacrylate, hydroxypropyl methacrylate and hydroquinone into a reaction kettle, adding cumene hydroperoxide, toughened rubber and ABS resin in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and defoaming in vacuum to obtain the component B. The prepared component A and the component B are uniformly mixed according to the volume ratio of 1:1, and then bonding can be carried out.
Comparative example 2
The acrylate AB glue comprises a component A and a component B, and comprises the following raw materials in percentage by mass as shown in Table 2:
table 2 comparative example 2 acrylic ester AB collagen material ratio
| Name of raw materials | Component A (%) | B component (%) |
| 2-Phenoxyethyl methacrylate | 32.5 | 45.0 |
| Methacrylic acidHydroxy propyl ester acid | 10.0 | 15.0 |
| Methacrylic acid | 15.0 | — |
| ABS resin | 16.0 | 25.5 |
| Nitrile rubber | 15.0 | 8.0 |
| Almond oil alkyd tackifying resin | 8.0 | — |
| Methacrylated wax | — | 2.5 |
| Cumene hydroperoxide | — | 3.0 |
| Tetramethyl thiourea | 2.0 | — |
| Triethanolamine | 1.0 | — |
| Hydroquinone | 0.5 | 1.0 |
The preparation method of the acrylate AB glue of comparative example 2 is as follows:
preparing a component A:
a. preparation of almond oil alkyd tackifying resin: weighing the raw materials according to the mass percentage, adding glycerol into the almond oil, stirring and heating to 220 ℃, carrying out alcoholysis reaction for 1-2 hours, then cooling to 160 ℃, adding maleic anhydride and nadic anhydride, stirring and heating to 190 ℃, carrying out alkyd polycondensation reaction for 5-6 hours, and cooling to obtain almond oil alkyd tackifying resin;
b. weighing the raw materials according to the mass percentage, putting 2-phenoxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid and hydroquinone into a reaction kettle, adding tetramethyl thiourea, triethanolamine, almond oil alkyd tackifying resin, nitrile rubber and ABS resin in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and carrying out vacuum defoamation to obtain the component A.
B, preparation of a component:
a. preparation of methacrylated wax: weighing the raw materials according to the mass percentage, adding methacrylic acid into liquid paraffin, stirring and heating to 60-80 ℃, adding a benzoyl peroxide initiator, carrying out grafting reaction for 3-4 hours, and cooling to obtain the methacrylated wax;
b. weighing the raw materials according to the mass percentage, putting the 2-phenoxyethyl methacrylate, the hydroxypropyl methacrylate and the hydroquinone into a reaction kettle, adding the cumene hydroperoxide, the methacrylated wax, the toughened rubber and the ABS resin in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and defoaming in vacuum to obtain the component B.
The use of glue solution: the prepared component A and the component B are uniformly mixed according to the volume ratio of 1:1, and then bonding can be carried out.
Comparative example 3
The acrylate AB adhesive comprises a component A and a component B, and comprises the following raw materials in percentage by mass as shown in Table 3:
table 3 comparative example 3 acrylic ester AB collagen material ratio
| Name of raw materials | Component A (%) | B component (%) |
| Pentaerythritol triacrylate | 7.0 | 5.0 |
| 2-Phenoxyethyl methacrylate | 33.0 | 40.0 |
| Hydroxypropyl methacrylate | 9.5 | 14.0 |
| Methacrylic acid | 15.0 | — |
| ABS resin | 11.0 | 28.0 |
| Nitrile rubber | 13.0 | 10.0 |
| Almond oil alkyd tackifying resin | 8.0 | — |
| Cumene hydroperoxide | — | 2.0 |
| Tetramethyl thiourea | 2.0 | — |
| Triethanolamine | 1.0 | — |
| Hydroquinone | 0.5 | 1.0 |
The preparation method of the acrylate AB glue of comparative example 3 is as follows:
preparation of a component A:
a. preparation of almond oil alkyd tackifying resin: weighing the raw materials according to the mass percentage, adding glycerol into the almond oil, stirring and heating to 220 ℃, carrying out alcoholysis reaction for 1-2 hours, then cooling to 160 ℃, adding maleic anhydride and nadic anhydride, stirring and heating to 190 ℃, carrying out alkyd polycondensation reaction for 5-6 hours, and cooling to obtain the almond oil modified tackifying resin;
b. weighing the raw materials according to the mass percentage, putting pentaerythritol triacrylate, 2-phenoxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid and hydroquinone into a reaction kettle, adding tetramethyl thiourea, triethanolamine, almond oil alkyd tackifying resin, nitrile rubber and ABS resin in sequence while stirring, heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and defoaming in vacuum to obtain the component A.
B, preparation of a component:
weighing the raw materials according to the mass percentage, putting pentaerythritol triacrylate, 2-phenoxyethyl methacrylate, hydroxypropyl methacrylate and hydroquinone into a reaction kettle, adding cumene hydroperoxide, toughened rubber and ABS resin in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and defoaming in vacuum to obtain the component B.
The use of glue solution: the prepared component A and the component B are uniformly mixed according to the volume ratio of 1:1, and then bonding can be carried out.
Comparative example 4
The acrylate AB adhesive comprises a component A and a component B, and comprises the following raw materials in percentage by mass as shown in Table 4:
table 4 comparative example 4 acrylic ester AB collagen formulation
| Name of raw materials | Component A (%) | B component (%) |
| Pentaerythritol triacrylate | 7.0 | 5.0 |
| 2-Phenoxyethyl methacrylate | 35.0 | 42.0 |
| Hydroxypropyl methacrylate | 10.0 | 12.5 |
| Methacrylic acid | 15.0 | — |
| ABS resin | 15.5 | 25.0 |
| Nitrile rubber | 14.0 | 10.0 |
| Methacrylated wax | — | 2.5 |
| Cumene hydroperoxide | — | 2.0 |
| Tetramethyl thiourea | 2.0 | — |
| Triethanolamine | 1.0 | — |
| Hydroquinone | 0.5 | 1.0 |
The preparation of the acrylate AB glue of comparative example 4 was as follows:
preparing a component A:
weighing the raw materials according to the mass percentage, putting pentaerythritol triacrylate, 2-phenoxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid and hydroquinone into a reaction kettle, adding tetramethyl thiourea, triethanolamine, nitrile rubber and ABS resin in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and carrying out vacuum defoamation to obtain the component A.
B, preparation of a component:
a. preparation of methacrylated wax: weighing the raw materials according to the mass percentage, adding methacrylic acid into liquid paraffin, stirring and heating to 60-80 ℃, adding a benzoyl peroxide initiator, carrying out grafting reaction for 3-4 hours, and cooling to obtain the methacrylated wax;
b. weighing the raw materials according to the mass percentage, putting pentaerythritol triacrylate, 2-phenoxyethyl methacrylate, hydroxypropyl methacrylate and hydroquinone into a reaction kettle, adding cumene hydroperoxide, methacrylated wax, toughened rubber and ABS resin in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and carrying out vacuum defoamation to obtain the component B.
The use of glue solution: the prepared component A and the component B are uniformly mixed according to the volume ratio of 1:1, and then bonding can be carried out.
The performance tests of the hybrid acrylate AB glue prepared in the examples 1-4 and the acrylate AB glue prepared in the comparative examples 1-4 are specifically shown in Table 5:
TABLE 5 comparison table of performance test
Continuation table
As can be seen from Table 5, the hybrid acrylate AB glue prepared in the embodiments 1 to 4 of the invention has the characteristics of good curing tack-free property, low odor, strong adhesion, high toughness, fatigue resistance, creep resistance, good heat resistance, good weather resistance and the like.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The hybrid acrylate AB adhesive is characterized by comprising the following components in percentage by mass:
and (2) component A:
and the component B comprises:
2. the hybrid acrylate AB glue of claim 1, wherein the polymeric monomer is one or a mixture of two or more monomers selected from the group consisting of 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, polyethylene glycol dimethacrylate, methacrylic acid, acrylic acid, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, allyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, bisphenol A polyoxyethylene ether dimethacrylate.
3. A hybrid acrylate AB glue according to claim 1, wherein the functional monomer is one or a mixture of pentaerythritol triacrylate and trimethylolpropane trimethacrylate.
4. The hybrid acrylate AB glue of claim 1, wherein the modified tackifying alkyd resin is an almond oil alkyd tackifying resin prepared by carrying out alkyd polycondensation reaction on almond oil after glycerolysis and maleic anhydride and nadic anhydride, wherein the mass ratio of the almond oil to the glycerol to the maleic anhydride to the nadic anhydride is 70:25:25: 21.
5. The hybrid acrylate AB glue of claim 1, wherein the reinforcing resin is one or a mixture of two or more of modified hydroxyacrylic acid resin, MBS resin, ABS resin, polymethyl methacrylate and styrene-butadiene transparent impact-resistant resin; the toughening rubber is one or a mixture of two of chlorosulfonated polyethylene, chloroprene rubber and nitrile rubber.
6. The hybrid acrylate AB glue of claim 1, wherein the reducing agent is one or a mixture of two or more of N, N-dimethylbenzylamine, N-dimethylaniline, ethylenediamine, triethylamine, triethanolamine, vinylthiourea, diphenylthiourea and tetramethylthiourea.
7. The hybrid acrylate AB glue of claim 1, wherein the stabilizer is one or a mixture of more than two of hydroquinone, 2, 6-di-tert-butyl-4-methylphenol, p-methoxyphenol and p-benzoquinone.
8. The hybrid acrylate AB glue of claim 1, wherein the methacrylated wax is obtained by the graft reaction of liquid paraffin and methacrylic acid under the initiation of benzoyl peroxide, and the weight ratio of the liquid paraffin, the methacrylic acid and the benzoyl peroxide is 100:30: 2.
9. A hybrid acrylate AB glue according to claim 1 wherein the oxidant is one or a mixture of two or more of cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, t-amyl hydroperoxide, t-butyl hydroperoxide.
10. The preparation method of the hybrid acrylate AB glue according to any one of claims 1 to 9, characterized in that the method comprises the following specific steps:
preparation of component A:
a. preparing modified tackifying alkyd resin: weighing the raw materials according to the mass percentage, adding glycerol into the almond oil, stirring and heating to 220 ℃, carrying out alcoholysis reaction for 1-2 hours, then cooling to 160 ℃, adding maleic anhydride and nadic anhydride, stirring and heating to 190 ℃, carrying out alkyd polycondensation reaction for 5-6 hours, and cooling to obtain almond oil alkyd tackifying resin;
b. weighing the raw materials according to the mass percentage, putting a polymerization monomer, a functional monomer and a stabilizer into a reaction kettle, adding a reducing agent, modified tackifying alkyd resin, toughening rubber and reinforcing resin in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and defoaming in vacuum to obtain a component A;
preparation of the component B:
a. preparation of methacrylated wax: weighing the raw materials according to the mass percentage, adding methacrylic acid into liquid paraffin, stirring and heating to 60-80 ℃, adding benzoyl peroxide, carrying out grafting reaction for 3-4 hours, and cooling to obtain the methacrylated wax;
b. weighing the raw materials according to the mass percentage, putting the polymerization monomer, the functional monomer and the stabilizer into a reaction kettle, adding the oxidant, the methacrylated wax, the toughened rubber and the reinforced resin in sequence while stirring, stirring and heating to 45 ℃, continuing stirring for 3 hours, cooling to below 30 ℃, and carrying out vacuum defoamation to obtain the component B.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074000A (en) * | 2013-01-06 | 2013-05-01 | 北京海斯迪克新材料有限公司 | Novel environmental-friendly double-component acrylate adhesive and preparation method thereof |
| CN106189886A (en) * | 2016-08-12 | 2016-12-07 | 哥俩好（辽宁）新材料有限公司 | A kind of high tenacity transparent two-component acrylicester adhesive and preparation method thereof |
| CN110734718A (en) * | 2019-10-25 | 2020-01-31 | 重庆德天新材料科技股份有限公司 | high-strength low-odor double-component acrylate structural adhesive and preparation method thereof |
| WO2021138433A1 (en) * | 2020-01-02 | 2021-07-08 | Avery Dennison Corporation | Hybrid alkyd-acrylic based pressure sensitive adhesives and methods of making and using thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074000A (en) * | 2013-01-06 | 2013-05-01 | 北京海斯迪克新材料有限公司 | Novel environmental-friendly double-component acrylate adhesive and preparation method thereof |
| CN106189886A (en) * | 2016-08-12 | 2016-12-07 | 哥俩好（辽宁）新材料有限公司 | A kind of high tenacity transparent two-component acrylicester adhesive and preparation method thereof |
| CN110734718A (en) * | 2019-10-25 | 2020-01-31 | 重庆德天新材料科技股份有限公司 | high-strength low-odor double-component acrylate structural adhesive and preparation method thereof |
| WO2021138433A1 (en) * | 2020-01-02 | 2021-07-08 | Avery Dennison Corporation | Hybrid alkyd-acrylic based pressure sensitive adhesives and methods of making and using thereof |
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