CN101906281B - High-temperature resistant structural adhesive and preparation method thereof - Google Patents
High-temperature resistant structural adhesive and preparation method thereof Download PDFInfo
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- CN101906281B CN101906281B CN 201010241413 CN201010241413A CN101906281B CN 101906281 B CN101906281 B CN 101906281B CN 201010241413 CN201010241413 CN 201010241413 CN 201010241413 A CN201010241413 A CN 201010241413A CN 101906281 B CN101906281 B CN 101906281B
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Abstract
The invention discloses a high-temperature resistant structural adhesive and a preparation method thereof. The high-temperature structural adhesive is prepared by compounding aromatic series multi-element primary amine and poly-functional group epoxy resin, wherein the mass ratio of the aromatic series multi-element primary amine to the poly-functional group epoxy resin 30-90:10-30. A preparation process of the high-temperature resistant structural adhesive is simple, the usage temperature is high, and the maximum usage temperature can reach 400 DEG C; the high-temperature bonding strength is high, the room temperature bonding strength (butt-joint and pull-apart method) after high-temperature curing reaches 30 to 40 MPa, the bonding strength at 250 DEG C reaches 6 to 7 MPa, and the bonding agent at 350 DEG C reaches 3 to 4 MPa; and all used raw materials are commercial products which are cheap and easy to get.
Description
Technical field
The present invention relates to a kind of high-temperature resistant structural adhesive that is used for metal and metal or metal and resin bonding and preparation method thereof.
Background technology
Existing high-temperature resistance adhesive generally will add mineral filler; Though can reach resistant to elevated temperatures purpose of moment; But ubiquity tackiness agent toughness extreme difference; Enduring quality and unfailing performance are just lower like this, can only be used for non-sealing structure, can't satisfy performance requriements such as vibration resistance and antifatigue in standing storage or the short-term use.Disclose a kind of high-temperature resistance adhesive like CN 101486886A, it is made up of resin and mineral filler, adopts the organic silicon modified phenolic resin, adds zinc oxide then, and titanium oxide etc. are filled.In the high temperature use, tackiness agent not only can with mineral filler generation condensation, and resol can with inorganic materials generation chemical reactions such as zinc oxide, titanium oxide, form the carbonization metallic substance, reach resistant to elevated temperatures purpose.But the hole that forms after the carbonization makes that the mechanical property of tackiness agent is very poor, under less vibration, will lose efficacy.
Virtue heterocyclic polymer such as polyimide receive increasing concern as high-temperature resistance adhesive.Polyimide has good temperature resistance ability and good mechanics, dielectric and radiation resistance.It becomes field indispensable material such as space flight, aviation, machinery, chemical industry, microelectronics as structured material or as functional material, has broad application prospects, and use still receives great restriction but it is as tackiness agent." Chinese patent: 00120274.X " reported the polyimide that can be used for high-temperature adhesives; It adopts different diamines and dianhydride or its mixture staple as synthesis of polyimides presoma-polyamic acid; Through adding part tertiary amine or quaternary amine; Break chain-like structure, reduced the interchain tap density, increased the fusing suitability of polyimide.The insulation tape that makes with this polyamic acid or polyimide; Can carry out bondingly under 450 ℃ not being higher than, but, can introduce hole in the melting process because it is to carry out bondingly through fusing under the hot conditions; Must cause high temperature bonding intensity not high, and its use temperature is only about 300 ℃.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide a kind of and have excellent mechanical performances, resistance to elevated temperatures is good and easy construction, do not influence the structure glue of primary structure outward appearance.
High-temperature resistant structural adhesive of the present invention is to be composited by polynary primary amine of aromatic series and polyfunctional epoxy resin, and the mass ratio of polynary primary amine of its aromatic series and polyfunctional epoxy resin is 30 ~ 90:10 ~ 30.
Said polyfunctional epoxy resin is four-functional group epoxy resin AG-80 or trifunctional epoxy resin AFG-90, and its structural formula is distinguished as follows:
The polynary primary amine of said aromatic series is 4,4 '-diaminodiphenylsulfone(DDS) (DDS) or 4,4 '-MDA (DDM).Its structural formula is distinguished as follows:
The preparation method of high-temperature resistant structural adhesive may further comprise the steps:
(1) 30～50 parts in acetone by weight ratio, 100～200 parts of amounts of getting of the polynary primary amine of aromatic series are mixed, and stir the polynary primary amine of aromatic series is dissolved fully, make the polynary primary amine liquid solution of aromatic series;
(2) polyfunctional epoxy resin is made into the acetone soln of 40～50% concentration;
(3) get 10～30 parts of the polynary primary amine solution of aromatic series by weight ratio, get polyfunctional epoxy resin solution and mix for 30～90 parts;
(4) will mix the back component and at room temperature place 7～10 days, or dry by the fire 3～5 hours down,, be finished product solvent evaporates at 80 ℃.
This invention has following tangible advantage: (1) preparation technology is simple, after only needing used epoxy resin and the polynary primary amine of aromatic series mixed, solvent is dried, and promptly obtains desired thermal structure glue; (2) use temperature is high, and maximum operation (service) temperature reaches 400 ℃; (3) high temperature bonding intensity is high, and behind hot setting, room temperature bonding strength (method is drawn back in butt joint) reaches 30～40MPa, and 250 ℃ of bonding strengths reach 6～7MPa, and 350 ℃ of bonding strengths reach 3～4MPa; (4) raw materials used all from commercially available article, cheap and easy to get.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1:
Acetone is 30 parts by weight ratio, and 4,100 parts of amounts of getting of 4 '-diaminodiphenylsulfone(DDS) (DDS) are mixed, and are stirred to dissolving fully, make 4,4 '-diaminodiphenylsulfone(DDS) liquid solution.Polyfunctional epoxy resin AG-80 is made into the acetone soln of 40% concentration.Get gained 4 by weight ratio, 10 parts of 4 '-diaminodiphenylsulfone(DDS) solution are got 30 parts of mixing of gained AG-80 solution, stir.To mix the back component and at room temperature place 7～10 days, or dry by the fire 3～5 hours down,, be finished product solvent evaporates at 80 ℃.
The high-temperature resistant structural adhesive of preparation as stated above evenly is coated on the aluminium post surface of Φ 20mm, docks with another same aluminium post then, this coating was respectively in the time of hot setting: 120 ℃ is 3 hours, and 150 ℃ is 1 hour, and 180 ℃ is 1 hour.Butt joint aluminium column compartment temperature bonding strength after the curing is 30MPa (method of pressing GB/T5210-1985 detects), is 8MPa 250 ℃ of bonding strengths, is 4MPa 350 ℃ of bonding strengths.
Embodiment 2:
Acetone is 40 parts by weight ratio, and 4,150 parts of amounts of getting of 4 '-diaminodiphenylsulfone(DDS) are mixed, and are stirred to dissolving fully, make 4,4 '-diaminodiphenylsulfone(DDS) liquid solution.Polyfunctional epoxy resin AFG-90 is made into the acetone soln of 40% concentration.Get gained 4 by weight ratio, 20 parts of 4 '-diaminodiphenylsulfone(DDS) solution are got 60 parts of mixing of gained AFG-90 solution, stir.To mix the back component and at room temperature place 7～10 days, or dry by the fire 3～5 hours down,, be finished product solvent evaporates at 80 ℃.
The high-temperature resistant structural adhesive of preparation as stated above evenly is coated on the aluminium post surface of ф 20mm, docks with another same aluminium post then, it is 3 hours that this coating is respectively 120 ℃ in the time of hot setting, and 150 ℃ is 1 hour, and 180 ℃ is 1 hour.Butt joint aluminium column compartment temperature bonding force after the curing is 29MPa (method of pressing GB/ T5210-1985 detects), is 7MPa 250 ℃ of high temperature bonding power, is 3MPa 300 ℃ of high temperature bonding power.
Embodiment 3:
Acetone is 30 parts by weight ratio, and 4,100 parts of amounts of getting of 4 '-MDA (DDM) are mixed, and stir and make 4,4 '-MDA liquid solution.Polyfunctional epoxy resin AG-80 is made into the acetone soln of 40% concentration.Get gained 4 by weight ratio, 10 parts of 4 '-MDA solution are got 40 parts of mixing of gained AG-80 solution, stir.To mix the back component and at room temperature place 7～10 days, or dry by the fire 3～5 hours down,, be finished product solvent evaporates at 80 ℃.
The high-temperature resistant structural adhesive of preparation as stated above evenly is coated on the aluminium post surface of Φ 20mm, docks with another same aluminium post then, it is 3 hours that this coating is respectively 120 ℃ in the time of hot setting, and 150 ℃ is 1 hour, and 180 ℃ is 1 hour.Butt joint aluminium column compartment temperature bonding strength after the curing is 30MPa (method of pressing GB/T5210-1985 detects), is 7MPa 250 ℃ of bonding strengths, is 4MPa 350 ℃ of bonding strengths.
Embodiment 4:
Acetone is 50 parts by weight ratio, and 4,200 parts of amounts of getting of 4 '-MDA (DDM) are mixed, and stir and make 4,4 '-MDA liquid solution.Polyfunctional epoxy resin AFG-90 is made into the acetone soln of 40% concentration.Get gained 4 by weight ratio, 30 parts of 4 '-MDA solution are got 90 parts of mixing of gained AFG-90 solution, stir.To mix the back component and at room temperature place 7～10 days, or dry by the fire 3～5 hours down,, be finished product solvent evaporates at 80 ℃.
The high-temperature resistant structural adhesive of preparation as stated above evenly is coated on the aluminium post surface of Φ 20mm, docks with another same aluminium post then, it is 3 hours that this coating is respectively 120 ℃ in the time of hot setting, and 150 ℃ is 1 hour, and 180 ℃ is 1 hour.Butt joint aluminium column compartment temperature bonding strength after the curing is 28MPa (method of pressing GB/ T5210-1985 detects), is 6MPa 250 ℃ of bonding strengths, is 3MPa 350 ℃ of bonding strengths.
Claims (1)
1. the preparation method of a high-temperature resistant structural adhesive is characterized in that, may further comprise the steps:
(1) 30～50 parts in acetone by weight ratio, 100～200 parts of amounts of getting of the polynary primary amine of aromatic series are mixed, and stir, and the polynary primary amine of aromatic series is dissolved fully, make the polynary primary amine liquid solution of aromatic series;
(2) polyfunctional epoxy resin is made into the acetone soln of 40～50% concentration;
(3) get 10～30 parts of the polynary primary amine solution of aromatic series by weight ratio, get polyfunctional epoxy resin solution and mix for 30～90 parts;
(4) will mix the back component and at room temperature place 7～10 days, or dry by the fire 3～5 hours down,, be finished product solvent evaporates at 80 ℃;
The polynary primary amine of said aromatic series is 4,4 '-diaminodiphenylsulfone(DDS) or 4,4 '-MDA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201010241413 CN101906281B (en) | 2010-08-02 | 2010-08-02 | High-temperature resistant structural adhesive and preparation method thereof |
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| CN 201010241413 CN101906281B (en) | 2010-08-02 | 2010-08-02 | High-temperature resistant structural adhesive and preparation method thereof |
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| CN101906281A CN101906281A (en) | 2010-12-08 |
| CN101906281B true CN101906281B (en) | 2012-12-12 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB201119287D0 (en) * | 2011-11-08 | 2011-12-21 | Zephyros Inc | Improvements in or relating to structrual adhesives |
| CN116162225B (en) * | 2023-01-09 | 2024-04-02 | 华东理工大学 | Epoxy resin material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88101121A (en) * | 1988-03-01 | 1988-11-30 | 西北工业大学 | The sqtructural adhesive and the compound method thereof of high temperature resistant, buck |
| CN1995255A (en) * | 2006-12-20 | 2007-07-11 | 哈尔滨工程大学 | Thermostable epoxy resin adhesive and its preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4911981B2 (en) * | 2006-02-03 | 2012-04-04 | 旭化成イーマテリアルズ株式会社 | Curing agent for highly water-containing solvent-containing epoxy resin and epoxy resin composition |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88101121A (en) * | 1988-03-01 | 1988-11-30 | 西北工业大学 | The sqtructural adhesive and the compound method thereof of high temperature resistant, buck |
| CN1995255A (en) * | 2006-12-20 | 2007-07-11 | 哈尔滨工程大学 | Thermostable epoxy resin adhesive and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2007-204670A 2007.08.16 |
| 张绪刚等.室温固化高剥离耐热环氧树脂胶粘剂.《中国胶粘剂》.2006,第15卷(第1期), * |
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