CN114933876A - High-low temperature resistant auxiliary agent added with aviation acrylic glue and preparation method thereof - Google Patents
High-low temperature resistant auxiliary agent added with aviation acrylic glue and preparation method thereof Download PDFInfo
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- CN114933876A CN114933876A CN202210714298.7A CN202210714298A CN114933876A CN 114933876 A CN114933876 A CN 114933876A CN 202210714298 A CN202210714298 A CN 202210714298A CN 114933876 A CN114933876 A CN 114933876A
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- 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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- Organic Chemistry (AREA)
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Abstract
The invention relates to the technical field of aviation materials, and particularly discloses a mould-resistant auxiliary agent added with an aviation acrylic adhesive, which comprises the following raw materials in parts by weight: 10-15 parts of hydroxyl acrylic resin, 1-3 parts of coupling agent, 1-2 parts of lubricating agent, 0.5-0.8 part of crosslinking auxiliary agent, 0.1-0.3 part of low-temperature auxiliary agent, 0.05-0.1 part of stabilizing agent, 0.3-0.8 part of film-forming auxiliary agent and 0.1-0.3 part of reinforcing agent, wherein the part of deionized water is 5-10 parts, and the hydroxyl acrylic resin serving as a main component can form a uniform and continuous protective film on the surface of an auxiliary agent molecule under the combined action of the film-forming auxiliary agent and the lubricating agent, so that the plasticity of the hydroxyl acrylic resin is improved; the crosslinking auxiliary agent used in the invention is convenient for the bridging connection with other auxiliary agents; the low-temperature assistant adopted by the invention can improve the low-temperature resistance of the assistant, and the stabilizer can provide the high-temperature resistance of the assistant; the reinforcing agent high-density polyethylene or polyimide modified graft is used in the acrylic adhesive, and can improve the high-temperature and low-temperature resistance of the adhesive.
Description
Technical Field
The invention relates to the technical field of aviation material processing, in particular to a high and low temperature resistant auxiliary agent added with an aviation acrylic adhesive and a preparation method thereof.
Background
The aviation material is a material guarantee for developing and producing aviation products, and is a technical basis for enabling the aviation products to achieve performance, service life and reliability expected by people. Due to the basic position of the aviation material and the continuous improvement of the contribution rate of the aviation material to aviation products, the aviation material, an aircraft engine and an information technology become one of three parallel aviation key technologies and are also one of six technologies which have important influence on the development of the aviation products.
The aviation material has extremely high requirements on the adhesive used by the aviation material, the acrylate adhesive is one of the adhesives used by the aviation material, the acrylate adhesive is prepared by taking acrylate monomers containing hydrogen ester groups (such as ethyl methacrylate, butyl acrylate and 2-ethylhexyl acrylate) as main materials, copolymerizing the acrylate monomers with unsaturated olefin monomers (such as styrene, acrylonitrile or vinyl acetate) and adding a proper amount of auxiliary agents, however, the existing auxiliary agents are insufficient in temperature resistance, part of the auxiliary agents can resist high temperature but cannot resist low temperature, and part of the auxiliary agents can resist low temperature but cannot resist high temperature.
Disclosure of Invention
The invention aims to provide a high and low temperature resistant auxiliary agent added with an aerospace acrylic adhesive and a preparation method thereof, which are used for solving the technical problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: the mold-resistant additive added with the aviation acrylic glue comprises the following raw materials in parts by weight:
10-15 parts of hydroxyl acrylic resin
1-3 parts of coupling agent
1-2 parts of lubricant
0.5 to 0.8 portion of crosslinking assistant
0.1 to 0.3 portion of low-temperature auxiliary agent
0.05 to 0.1 portion of stabilizer
0.3-0.8 part of film-forming assistant
0.1 to 0.3 portion of reinforcing agent
Wherein the weight of the deionized water is 5-10 parts.
In a further improvement, the coupling agent is one of a propyloxysilane or an epoxysilane.
In a further improvement, the lubricant is at least one of pentaerythritol stearate or ethylene bis stearamide or polyethylene wax.
The further improvement is that the cross-linking agent is a mixture of dicumyl peroxide and triphenyl phosphite, and the mass ratio of the dicumyl peroxide to the triphenyl phosphite is (2-2.4): 1.
the further improvement is that the low-temperature auxiliary agent is at least one of a nylon toughening agent or maleic anhydride and acrylate bifunctional grafted ethylene elastomer.
In a further improvement, the stabilizer is one of glass fiber or sorbitan fatty acid.
The further improvement is that the film forming assistant is at least one of ethylene glycol monobutyl ether or propylene glycol butyl ether or propylene glycol methyl ether acetate or propylene glycol phenyl ether.
The further improvement is that the reinforcing agent is one of high-density polyethylene or polyimide modified graft, wherein the polyimide modified graft has high and low temperature resistance after polymerization.
The invention also provides a preparation method of the high and low temperature resistant auxiliary agent added with the aviation acrylic glue, which comprises the following steps:
(1) weighing 10-15 parts of hydroxyl acrylic resin, 1-3 parts of coupling agent, 1-2 parts of lubricant, 0.5-0.8 part of crosslinking assistant, 0.1-0.3 part of low-temperature assistant, 0.05-0.1 part of stabilizer, 0.3-0.8 part of film-forming assistant, 0.1-0.3 part of reinforcing agent and 5-10 parts of deionized water for later use;
(2) sequentially adding 10-15 parts of hydroxyl acrylic resin, 1-3 parts of coupling agent, 0.5-0.8 part of crosslinking aid, 0.1-0.3 part of low-temperature aid, 0.3-0.8 part of film-forming aid, 1-3 parts of deionized water and 0.5-1 part of lubricant into a stirring cylinder A, stirring for 30-40min, and stirring uniformly;
(3) sequentially adding 0.05-0.1 part of stabilizer, the rest of lubricant and deionized water into the stirring cylinder B, stirring uniformly, continuously adding 0.1-0.3 part of reinforcing agent, and continuously stirring uniformly;
(4) and pouring the mixture in the stirring cylinder B into the stirring cylinder A, stirring while pouring, stirring uniformly, and standing to obtain the high and low temperature resistant auxiliary agent added with the aviation acrylic glue.
Compared with the prior art, the invention has the beneficial effects that:
the main material adopted by the invention is the hydroxy acrylic resin, and the corresponding frame joint part has the best durability, crack resistance and high and low temperature impact resistance;
the main component of the hydroxyl acrylic resin adopted by the invention can form a uniform and continuous protective film on the surface of an auxiliary molecule under the combined action of a film-forming auxiliary agent and a lubricant, so that the plasticity (frame joint performance) of the protective film is improved;
the crosslinking auxiliary agent used in the invention adopts a mixture of dicumyl peroxide and triphenyl phosphite, wherein the triphenyl phosphite plays a role in inhibiting side reaction, and the addition of the dicumyl peroxide enables the molecular chains of the hydroxy acrylic resin to form a bridge bond, thereby facilitating the bridging connection with other auxiliary agents;
the low-temperature auxiliary agent adopted by the invention is a nylon toughening agent or a maleic anhydride and acrylate bifunctional grafted ethylene elastomer, so that the low-temperature resistance of the auxiliary agent can be improved, and the stabilizing agent is glass fiber or fatty acid sorbitan, so that the high-temperature resistance of the auxiliary agent can be provided;
the reinforcing agent high-density polyethylene or polyimide modified graft is used in the acrylic adhesive, and can improve the high-temperature and low-temperature resistance of the adhesive.
Detailed Description
The technical solution of the present invention will be further described with reference to the following specific examples, but the present invention is not limited to these examples.
Example 1
The embodiment provides a preparation method of a high and low temperature resistant auxiliary agent added with an aerospace acrylic adhesive, which comprises the following steps:
(1) weighing 10 parts of hydroxy acrylic resin, 1 part of propyl oxysilane, 1 part of pentaerythritol stearate, 0.5 part of crosslinking assistant, 0.1 part of nylon toughening agent, 0.05 part of glass fiber, 0.3 part of ethylene glycol monobutyl ether, 0.1 part of high-density polyethylene and 5 parts of deionized water for later use, wherein the crosslinking agent is a mixture of dicumyl peroxide and triphenyl phosphite, and the mass ratio of the dicumyl peroxide to the triphenyl phosphite is 2: 1;
(2) sequentially adding 10 parts of hydroxyl acrylic resin, 1 part of propyl oxysilane, 0.5 part of crosslinking assistant, 0.1 part of nylon toughening agent, 0.3 part of butyl cellosolve, 1 part of deionized water and 0.5 part of pentaerythritol stearate into a stirring cylinder A, stirring for 30min, and stirring uniformly;
(3) sequentially adding 0.05 part of glass fiber, the rest of pentaerythritol stearate and deionized water into the stirring cylinder B, stirring uniformly, continuously adding 0.1 part of high-density polyethylene, and continuously stirring uniformly;
(4) the mixture in the stirring tank B was poured into the stirring tank a, stirred while being poured, stirred until uniform, and left to stand to obtain example 1.
Example 2
(1) Weighing 15 parts of hydroxy acrylic resin, 3 parts of epoxy silane, 2 parts of ethylene bis-stearic acid amide, 0.8 part of crosslinking assistant, 0.3 part of maleic anhydride, acrylate bifunctional grafted ethylene elastomer, 0.1 part of fatty acid sorbitan, 0.8 part of propylene glycol monobutyl ether, 0.3 part of polyimide modified graft and 10 parts of deionized water for later use, wherein the crosslinking agent is a mixture of dicumyl peroxide and triphenyl phosphite, and the mass ratio of the dicumyl peroxide to the triphenyl phosphite is 2.4: 1;
(2) adding 15 parts of hydroxy acrylic resin, 3 parts of epoxy silane, 0.8 part of crosslinking assistant, 0.3 part of maleic anhydride, acrylate bifunctional grafted ethylene elastomer, 0.8 part of propylene glycol butyl ether, 3 parts of deionized water and 1 part of ethylene bis stearamide into a stirring cylinder A in sequence, stirring for 40min, and stirring uniformly;
(3) sequentially adding 0.1 part of sorbitan fatty acid, the rest of ethylene bis stearamide and deionized water into a stirring cylinder B, stirring uniformly, then continuously adding 0.3 part of polyimide for modification grafting, and stirring uniformly;
(4) the mixture in the stirring tank B was poured into the stirring tank a, stirred while being poured, stirred until uniform, and left to stand to obtain example 2.
Example 3
(1) Weighing 12 parts of hydroxy acrylic resin, 2 parts of propyl oxysilane, 1.5 parts of polyethylene wax, 0.6 part of crosslinking auxiliary agent, 0.2 part of nylon toughening agent, 0.07 part of glass fiber, 0.6 part of propylene glycol phenyl ether, 0.2 part of polyimide modified graft and 7 parts of deionized water for later use, wherein the crosslinking agent is a mixture of dicumyl peroxide and triphenyl phosphite, and the mass ratio of the dicumyl peroxide to the triphenyl phosphite is 2.1: 1;
(2) sequentially adding 12 parts of hydroxy acrylic resin, 2 parts of propyl oxysilane, 0.6 part of crosslinking assistant, 0.2 part of nylon toughening agent, 0.6 part of propylene glycol phenyl ether, 2 parts of deionized water and 0.7 part of polyethylene wax into a stirring cylinder A, stirring for 35min, and stirring uniformly;
(3) sequentially adding 0.07 part of glass fiber, the rest of polyethylene wax and deionized water into the stirring cylinder B, stirring uniformly, then continuously adding 0.2 part of polyimide for modification grafting, and stirring uniformly;
(4) the mixture in the stirring tank B was poured into the stirring tank a, stirred while being poured, stirred until uniform, and left to stand to obtain example 3.
Example 4
(1) Weighing 12 parts of hydroxy acrylic resin, 2 parts of epoxy silane, 2 parts of pentaerythritol stearate, 0.8 part of crosslinking assistant, 0.2 part of maleic anhydride, acrylate bifunctional grafted ethylene elastomer, 0.07 part of glass fiber, 0.6 part of ethylene glycol monobutyl ether, 0.2 part of polyimide modified graft and 8 parts of deionized water for later use, wherein the crosslinking agent is a mixture of dicumyl peroxide and triphenyl phosphite, and the mass ratio of the dicumyl peroxide to the triphenyl phosphite is 2.3: 1;
(2) adding 12 parts of hydroxyl acrylic resin, 2 parts of epoxy silane, 0.8 part of crosslinking assistant, 0.2 part of maleic anhydride, acrylate bifunctional grafted ethylene elastomer, 0.6 part of ethylene glycol monobutyl ether, 1 part of deionized water and 0.5 part of pentaerythritol stearate into a stirring cylinder A in sequence, stirring for 30min, and stirring uniformly;
(3) sequentially adding 0.07 part of glass fiber, the rest of pentaerythritol stearate and deionized water into a stirring cylinder B, stirring uniformly, continuously adding 0.2 part of polyimide for modified grafting, and stirring uniformly;
(4) the mixture in the stirring cylinder B was poured into the stirring cylinder A, stirred while being poured, stirred until uniform, and allowed to stand to obtain example 4.
Comparative example 1: comparative example 1 differs from example 3 in that: comparative example 1 is distinguished by the absence of 1.5 parts of polyethylene wax.
Comparative example 2: comparative example 2 differs from example 3 in that: comparative example 2 differs by the absence of 0.6 parts of crosslinking coagent.
Comparative example 3: comparative example 3 differs from example 3 in that: comparative example 3 is distinguished by the absence of 0.2 parts of nylon toughening agent.
Comparative example 4: comparative example 4 differs from example 3 in that: comparative example 4 differs by the absence of 0.07 parts of glass fiber.
Comparative example 5: comparative example 5 differs from example 3 in that: comparative example 5 differs by the absence of 0.6 parts of propylene glycol phenyl ether.
Comparative example 6: comparative example 6 differs from example 3 in that: comparative example 5 differs by the absence of 0.2 parts of polyimide modified graft.
Performance testing
The concrete performance of the acrylic adhesive is tested by preparing the acrylic adhesive from the examples 1 to 4 and the comparative examples 1 to 6 according to the above concrete embodiment and preparing the acrylic adhesive from the examples 1 to 4 and the comparative examples 1 to 6 under the same conditions of other auxiliary materials and processes.
1. The shear strength test method comprises the following steps: cutting various base materials into standard sheets with the size of 25mm multiplied by 100mm, then uniformly coating the uniformly mixed structural adhesive on a cutting sheet, and overlapping a bonding area with the size of 12.5mm multiplied by 25 mm. Applying a 100N external force, curing for 24 hours at 23 ℃, after the curing is finished, clamping the non-lap-jointed area of the sample by using a tensile testing machine, and testing the tensile shear strength of the sample at the speed of 5 mm/min;
2. the cold and hot shear strength test method comprises the following steps: the sample preparation method is the same as the shear strength test method, the clamp and the sample are heated or cooled to a set temperature by using an oven or a refrigerating box carried by a tensile testing machine during testing, then the sample is clamped on the clamp, the oven is closed, the sample is heated or cooled to a set temperature, then the shear strength test is carried out, and the test results are as follows:
as can be seen from the above table, the adhesive abilities of examples 1-4 and comparative examples 1-6 are similar at normal temperature, but the adhesive abilities of examples 1-4 are still good at high temperature of 150 ℃ and low temperature of-30 ℃, while the adhesive abilities of comparative examples 1-6 are weakened.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (9)
1. The mold-resistant additive added with the aviation acrylic glue is characterized by comprising the following raw materials in parts by weight:
10-15 parts of hydroxyl acrylic resin
1-3 parts of coupling agent
1-2 parts of lubricant
0.5 to 0.8 portion of crosslinking assistant
0.1 to 0.3 portion of low-temperature auxiliary agent
0.05 to 0.1 portion of stabilizer
0.3-0.8 part of film-forming assistant
0.1 to 0.3 portion of reinforcing agent
Wherein the weight of the deionized water is 5-10 parts.
2. The high and low temperature resistant additive added with the aerospace acrylic adhesive as claimed in claim 1, wherein the coupling agent is one of propyl oxysilane or epoxy silane.
3. The high and low temperature resistant auxiliary agent added with the aircraft acrylic glue as claimed in claim 1, wherein the lubricant is at least one of pentaerythritol stearate or ethylene bis stearamide or polyethylene wax.
4. The high and low temperature resistant auxiliary agent added with the aviation acrylic adhesive is characterized in that the crosslinking agent is a mixture of dicumyl peroxide and triphenyl phosphite, and the mass ratio of the dicumyl peroxide to the triphenyl phosphite is (2-2.4): 1.
5. the high and low temperature resistant auxiliary agent added with the aerospace acrylic adhesive as claimed in claim 1, wherein the low temperature resistant auxiliary agent is at least one of a nylon toughening agent or a maleic anhydride and acrylate bifunctional grafted ethylene elastomer.
6. The high and low temperature resistant auxiliary agent added with the aerospace acrylic adhesive as claimed in claim 1, wherein the stabilizer is one of glass fiber or sorbitan fatty acid.
7. The high and low temperature resistant auxiliary added with the aviation acrylic glue as claimed in claim 1, wherein the film forming aid is at least one of ethylene glycol monobutyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate or propylene glycol phenyl ether.
8. The high and low temperature resistant additive added with the aerospace acrylic adhesive as claimed in claim 1, wherein the reinforcing agent is one of high density polyethylene or polyimide modified graft.
9. The preparation method of the high and low temperature resistant auxiliary agent added with the aviation acrylic glue according to any one of claims 1 to 8, characterized by comprising the following steps:
(1) weighing 10-15 parts of hydroxyl acrylic resin, 1-3 parts of coupling agent, 1-2 parts of lubricant, 0.5-0.8 part of crosslinking assistant, 0.1-0.3 part of low-temperature assistant, 0.05-0.1 part of stabilizer, 0.3-0.8 part of film-forming assistant, 0.1-0.3 part of reinforcing agent and 5-10 parts of deionized water for later use;
(2) sequentially adding 10-15 parts of hydroxyl acrylic resin, 1-3 parts of coupling agent, 0.5-0.8 part of crosslinking assistant, 0.1-0.3 part of low-temperature assistant, 0.3-0.8 part of film-forming assistant, 1-3 parts of deionized water and 0.5-1 part of lubricant into a stirring cylinder A, stirring for 30-40min, and stirring uniformly;
(3) sequentially adding 0.05-0.1 part of stabilizer, the rest of lubricant and deionized water into the stirring cylinder B, stirring uniformly, continuously adding 0.1-0.3 part of reinforcing agent, and continuously stirring uniformly;
(4) and pouring the mixture in the stirring cylinder B into the stirring cylinder A, stirring while pouring, stirring uniformly, and standing to obtain the high and low temperature resistant auxiliary agent added with the aviation acrylic glue.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210714298.7A CN114933876A (en) | 2022-06-23 | 2022-06-23 | High-low temperature resistant auxiliary agent added with aviation acrylic glue and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210714298.7A CN114933876A (en) | 2022-06-23 | 2022-06-23 | High-low temperature resistant auxiliary agent added with aviation acrylic glue and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101796439A (en) * | 2007-09-03 | 2010-08-04 | 住友化学株式会社 | Optical film with adhesive and optical laminate |
| CN104356978A (en) * | 2014-12-03 | 2015-02-18 | 张亦彬 | Preparation method of adhesive |
| CN107699166A (en) * | 2017-10-25 | 2018-02-16 | 浙江星丰科技有限公司 | A kind of high temperature resistant adhesive and preparation method thereof |
| CN107974083A (en) * | 2017-12-14 | 2018-05-01 | 广东思汗新材料有限公司 | Nylon cable tie composite material and preparation method thereof |
| CN109810220A (en) * | 2017-11-21 | 2019-05-28 | 万华化学（北京）有限公司 | A kind of preparation method of Hydroxylated acrylic resin |
-
2022
- 2022-06-23 CN CN202210714298.7A patent/CN114933876A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101796439A (en) * | 2007-09-03 | 2010-08-04 | 住友化学株式会社 | Optical film with adhesive and optical laminate |
| CN104356978A (en) * | 2014-12-03 | 2015-02-18 | 张亦彬 | Preparation method of adhesive |
| CN107699166A (en) * | 2017-10-25 | 2018-02-16 | 浙江星丰科技有限公司 | A kind of high temperature resistant adhesive and preparation method thereof |
| CN109810220A (en) * | 2017-11-21 | 2019-05-28 | 万华化学（北京）有限公司 | A kind of preparation method of Hydroxylated acrylic resin |
| CN107974083A (en) * | 2017-12-14 | 2018-05-01 | 广东思汗新材料有限公司 | Nylon cable tie composite material and preparation method thereof |
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