CN1793267A - Epoxy resin type high strength structure adhesive - Google Patents
Epoxy resin type high strength structure adhesive Download PDFInfo
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- CN1793267A CN1793267A CN 200510120503 CN200510120503A CN1793267A CN 1793267 A CN1793267 A CN 1793267A CN 200510120503 CN200510120503 CN 200510120503 CN 200510120503 A CN200510120503 A CN 200510120503A CN 1793267 A CN1793267 A CN 1793267A
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Abstract
The invention relates to new type epoxy resin high strength structural adhesive. It is formed by two components. The first component is made up of epithio-epoxy reactive diluent, epoxy resin and/or epithio-epoxy composite resin. The second component is made up of curing agent or the mixture of curing agent and curing accelerating agent. Compared with the corresponding epoxy resin structural adhesive, the high strength structural adhesive has higher shear strength, peeling strength, and faster curing speed.
Description
Technical field
The invention belongs to chemical field and cakingagent field, relate to a kind of novel epoxide resin type high strength structural adhesion.
Technical background
Characteristics such as Resins, epoxy is a kind of structure glue of excellent performance, and it has, and adhesiveproperties is good, shrinking percentage is low, stability (thermotolerance, water tolerance and chemical proofing) is good, electrical insulating property is good, physical strength is high, the processibility operability is good.Therefore it is widely used in the every field of national economy.
Resins, epoxy and solidifying agent are materials the most basic in the epoxy resin component, but they are difficult to satisfy all construction and application requiring before non-modified.For example when Resins, epoxy is applied in application, dipping, the casting, can different requirements be proposed to the viscosity of epoxy resin component on the technology.Usually can adopt thinner to dissolve, disperse and the dilution epoxy resin component, thereby reach the viscosity that reduces epoxy resin component (glue), improve the coating and the mobile effect of glue, play the effect that increases the service life in addition.
According to reactive behavior, thinner can be divided into two kinds of non-activated thinner and reactive thinners.Non-activated thinner can not react with Resins, epoxy and solidifying agent, and it only plays the solvency action of physical property in epoxy resin component.Non-activated thinner mostly is high boiling liquid, when Resins, epoxy uses non-activated thinner, the chemical reagent resistance of material is had disadvantageous effect; When consumption was big, condensate performance degenerated.Simultaneously because the volatilization of thinner in solidification process can cause that also the shrinking percentage of cured product increases.Reactive thinner generally is meant the low molecular compound that has 1 or 1 above epoxy group(ing) in molecular structure, they can participate in the curing reaction of Resins, epoxy directly, become the part of epoxy resin cured product cross-linked network structure, performance to cured product does not almost have influence, can also increase the toughness of curing system sometimes.
The compound that has the epoxy group(ing) more than two or two in the molecular structure is called many epoxy group(ing) reactive thinner.When in composition epoxy resin, adding this thinner,, just can not reduce the cross-linking density of system as long as consumption and curing are suitable, therefore with the Resins, epoxy of routine relatively, the physical strength of its cured product and chemical-resistant change little.
Summary of the invention
Physical strength and the chemical-resistant of purpose of the present invention in order not influence the epoxy resin cure product can improve its shearing resistance, stripping strength and curing speed faster again, and a kind of novel epoxide resin type high strength structural adhesion is provided.
A kind of novel epoxide resin type high strength structural adhesion, form by two kinds of components, wherein the first component is made up of epithio-epoxy active diluent and Resins, epoxy and/or epithio-composite epoxy resin, component B is the mixture of solidifying agent or solidifying agent and curing catalyst, can not add to solidify promotor when using the amino-type solidifying agent.
Epithio-epoxy active diluent used in the present invention is the one group of compound that contains epoxide group and epithio group in molecular structure.Because the electronegativity of S atomic ratio O atom is little and atomic radius is big, than the epoxy group(ing) of triatomic ring bigger ring strain is arranged as the epithio base of triatomic ring, the epithio base is than the easier open loop of epoxy group(ing) under the same conditions, and the curing system that therefore has epithio-epoxy compounds has curing speed, lower solidification value, shorter set time, lower reaction heat, lower cure shrinkage, high glass transition (T faster than common epoxy curing systems
g) and high shearing resistance; In addition because sulfydryl (SH) can form sulphur-metallic bond with many kinds of metals, epithio group is easier to react with copper, iron, aluminium and alloy surface thereof thereby make, form the structure of stable surface chemistry key, so can reach the adhesiveproperties that improves composition epoxy resin, improve the purpose of bonding strength.Because less sulphur (S) atom of polarity has replaced bigger oxygen (O) atom of segment polarity, reduce hydroxyl and the contour polar group of ehter bond in the system, thereby reduced the water-intake rate of system simultaneously, improved the water resistance of resin.
Studies show that: when the epoxide group in the epoxide diluent was replaced by epithio group fully, formed compound was a kind of crystalline compounds, so can't play the effect of epoxy resin diluent.But the epithio-epoxy cpd that forms after part epoxy group(ing) in this compounds is replaced by the epithio base is still a kind of unbodied product, this series products not only can keep its dissolving to Resins, epoxy, dilution function, and the composition that can also give this novel thinner and Resins, epoxy is to the better bond performance of metal, nonmetal and macromolecular material.
Employed in the present invention epithio-epoxy active diluent by corresponding epoxy active diluent by the epithio prepared in reaction, wherein the epithio rate is controlled at 20%～80%, and the epithio rate is defined as the molar fraction that epoxy group(ing) in the raw material epoxide diluent is converted into the epithio base.Be the epithio-epoxy active diluent of feedstock production with the ethylene glycol diglycidylether for example, according to the difference of epithio rate, the structure of epithio-epoxy active diluent can be thought by following three kinds of mixtures that compound is formed:
The preparation method of epithio-composite epoxy resin or epoxy active diluent is: in the reactor that agitator, reflux exchanger and thermometer are housed, add raw material epoxy resin or epoxy active diluent, catalyzer and solvent, unlatching is stirred, heating up dissolves Resins, epoxy fully.Under constant temp, drip the organic solution of ring vulcanizing agent.Dropwising the back continues to react 1-10h under this temperature.After reaction finishes, decompression and solvent recovery.Add the organic extractant dissolving again, filter.Filtrate changes in another reactor, adds distilled water wash, standing demix, remove drying behind the water layer, activated carbon decolorizing after decompression steam solvent, obtain colourless to light yellow transparent viscous liquid.This liquid is epithio-composite epoxy resin or epoxy active diluent.
The raw material that is used to prepare epithio-epoxy active diluent proposed by the invention has following glycidyl ether type compound, and the structure of its compound is as shown in table 1:
The title of table 1 epoxide diluent used in the present invention and structure
The same with the ethylene glycol diglycidylether epoxy active diluent, according to the epithio rate of raw material, be a kind of mixture by the formed epithio-epoxy active diluent of this class epoxy compounds, its structure can be described with table 2.
The structure of table 2 institute of the present invention synthetic epithio-epoxy active diluent
The first component of structure glue proposed by the invention is made up of epithio-epoxy active diluent and Resins, epoxy and/or epithio-composite epoxy resin, and its mass ratio is: epithio-epoxy active diluent: Resins, epoxy and/or epithio-composite epoxy resin=10～150: 100; Wherein employed Resins, epoxy has bisphenol A type epoxy resin, bisphenol f type epoxy resin to obtain corresponding epithio-composite epoxy resin with phenolic resin type Resins, epoxy and this resinoid through after the epithioization.
Component B used herein is the general solidifying agent of Resins, epoxy, and anhydride type curing agent such as Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, MALEIC ANHYDRIDE, tung oil acid anhydride, tetrahydrochysene phthalate anhydride, hexahydrophthalic acid anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydrophthalic anhydride are arranged; Aliphatic polyamine type solidifying agent is as quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren; Aromatic series aliphatic amide type solidifying agent is as the modifier of m-xylene diamine, m-xylene diamine; Aromatic amine type solidifying agent is as mphenylenediamine, diaminodiphenyl-methane, diaminodiphenylsulfone(DDS); Polyamide-based solidifying agent; Other class solidifying agent is as imidazoles, methylimidazole, Dyhard RU 100,2-ethyl-4-methyl, 2-ethyl-4-methylimidazole, piperidines.
Described component B curing catalyst has: 2,4, and 6-three (dimethylaminomethyl) phenol, benzyldimethylamine, 2-benzothiazolyl mercaptan, thiocarbamide, cycloalkyl tetrahydroglyoxaline, 2-benzylimidazoline; Or, salt compounds: 2,4, three of 6-three (dimethylaminomethyl) phenol-(2-ethyl acetic acid) salt, acetyl acetone salt, triphenylphosphine and phosphonium salt thereof; The consumption of curing catalyst is 0～20% of a first component total amount.
The consumption of first, component B should carry out stoichiometry by the mode of amounts such as functional group according to the total value of the oxirane value of first component and epithio value and decide the quality of component B: first component quality=1～100: 100.
Structure glue of the present invention is at physical strength that does not influence the epoxy resin cure product and chemical-resistant, can improve its shearing resistance, stripping strength and curing speed faster again.
Embodiment
Embodiment 1:
The first component: it is in 50% butanediol diglycidyl ether type epithio-epoxy active diluent that 75 gram E44 bisphenol A epoxide resins are dissolved in 25 gram epithio rates; Component B: 0.1 gram benzyldimethylamine is dissolved in the solution of being formed in the 40 gram methyl tetrahydro phthalic anhydrides, first, component B is mixed just obtain the Resins, epoxy high strength structural adhesion.
Embodiment 2:
The first component: it is in 53% ethylene glycol diglycidylether type epithio-epoxy active diluent that 75 gram E44 type bisphenol A epoxide resins are dissolved in 25 gram epithio rates; Component B: 0.1 gram benzyldimethylamine is dissolved in the solution of being formed in the 40 gram methyl hexahydrophthalic anhydrides, first, component B is mixed just obtain the Resins, epoxy high strength structural adhesion.
Embodiment 3:
The first component: it is in 50% neopentylglycol diglycidyl ether type epithio-epoxy active diluent that 80 gram E44 type bisphenol A epoxide resins are dissolved in 20 gram epithio rates; Component B: 10 restrain diethylenetriamine, first, component B is mixed just obtain the Resins, epoxy high strength structural adhesion.
Embodiment 4:
The first component: with 73 gram epithio-oxirane values be 0.44, the epithio rate is that to be dissolved in 25 gram epithio rates be in 30% butanediol diglycidyl ether type epithio-epoxy active diluent for Bisphenol F type epithio-Resins, epoxy of 30%; Component B: 0.1 gram benzyldimethylamine is dissolved in the solution of being formed in the 40 gram methyl tetrahydro phthalic anhydrides, first, component B is mixed just obtain the Resins, epoxy high strength structural adhesion.
Embodiment 5:
The first component: it is in 50% diglycidyl ether-type epithio-epoxy active diluent that 70 gram F44 novolac epoxys are dissolved in 25 gram epithio rates; Component B: 0.1 gram benzyldimethylamine is dissolved in the solution of being formed in the 40 gram methyl tetrahydro phthalic anhydrides, first, component B is mixed just obtain the Resins, epoxy high strength structural adhesion.
Wherein, the bond performance of embodiment 1,2,3,4,5 structure glue is as shown in table 3:
The performance of three kinds of bicomponent structural adhesives of table 3
Annotate:
(1) it is condition of cure that condition of cure: embodiment 1,2,4,5 adopts 60 ℃ 2h+100 ℃ 2h+150 ℃ of 1h; Embodiment 3 is self-vulcanizing 3 days.
(2) shearing resistance: adopt the 45# steel disc, oven dry after sand papering, chromic acid lotion are handled, washed is coated with adhesive curing.Press GB/T7124-1986 tackiness agent tensile shear strength experimental technique, on WDW-20 type microcomputer control electronics universal testing machine, test.Rate of extension is 10mmmin
-1
(3) stripping strength (the T type is peeled off): widely be coated with adhesive curing for the 150mm nylon canvas for (25 ± 0.1) mm, length with two.By GB 8808-88 " soft composite plastics material is peeled off experimental technique ", on WDW-20 type microcomputer control electronics universal testing machine, test.Rate of extension is 50mmmin
-1
(4) the first component is the corresponding reactive thinner and corresponding ratio Resins, epoxy compound system that does not pass through the epithio processing among each embodiment in the blank; Corresponding component B and consumption are all constant.
Claims (5)
1, a kind of novel epoxide resin type high strength structural adhesion, form by two kinds of components, wherein the first component is made up of epithio-epoxy active diluent and Resins, epoxy and/or epithio-composite epoxy resin, and component B is the mixture of solidifying agent or solidifying agent and curing catalyst.
2, structure glue according to claim 1, it is characterized in that: described epithio-epoxy active diluent is through the formed mixture that contains one or more epithio bases in molecular structure of epithio reaction by corresponding epoxy active diluent, wherein the epithio rate is controlled at 20%～80%, the epithio rate is defined as the molar fraction that epoxy group(ing) in the raw material epoxide diluent is converted into the epithio base, just with following epoxy active diluent: ethylene glycol diglycidylether, the glycol ether diglycidylether, the glycerine epoxy is the glycerol triglycidyl ether just, neopentylglycol diglycidyl ether, 1, the 4-butanediol diglycidyl ether, 1, the 3-butanediol diglycidyl ether, the TriMethylolPropane(TMP) glycidyl ether, diglycidylether generates corresponding through the epithio reaction: ethylene glycol diglycidylether type epithio-epoxy active diluent, glycol ether diglycidyl ether-type epithio-epoxy active diluent, glycerine epoxy type epithio-epoxy active diluent, neopentylglycol diglycidyl ether type epithio-epoxy active diluent, butanediol diglycidyl ether type epithio-epoxy active diluent, 1,3 butylene glycol diglycidyl ether-type epithio-epoxy active diluent, trihydroxymethylpropanyltri diglycidyl ether type epithio-epoxy active diluent and diglycidyl ether-type epithio-epoxy active diluent.
3, structure glue according to claim 1, it is characterized in that: described Resins, epoxy is: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic resin type Resins, epoxy, corresponding epithio-composite epoxy resin that described epithio-composite epoxy resin is formed through the epithio reaction by bisphenol A type epoxy resin, bisphenol f type epoxy resin or phenolic resin type Resins, epoxy.
4, structure glue according to claim 1 is characterized in that: the mass ratio of described epithio-epoxy active diluent and Resins, epoxy and/or epithio-composite epoxy resin=10～150: 100.
5, structure glue according to claim 1, it is characterized in that: the consumption of described first, component B should carry out stoichiometry by the mode of the amount of functional group according to the total value of the oxirane value of first component and epithio value and decide the quality of component B: first component quality=1～100: 100.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101205033A CN100396748C (en) | 2005-12-22 | 2005-12-22 | Epoxy resin type high strength structure adhesive |
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| CNB2005101205033A CN100396748C (en) | 2005-12-22 | 2005-12-22 | Epoxy resin type high strength structure adhesive |
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| CN1793267A true CN1793267A (en) | 2006-06-28 |
| CN100396748C CN100396748C (en) | 2008-06-25 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010097051A1 (en) | 2009-02-27 | 2010-09-02 | 汉高（中国）投资有限公司 | Room-temperature curable epoxy structural adhesive composition and preparation method thereof |
| CN102516912A (en) * | 2011-11-30 | 2012-06-27 | 安徽中铁工程材料科技有限公司 | Method for preparing composite curing agent modified bisphenol F thermosetting adhesive repairing agent special for ballastless track gap and crack damage |
| CN102604088A (en) * | 2012-03-14 | 2012-07-25 | 北京化工大学 | Macromolecule mercaptan and synthetic method thereof |
| CN102634314A (en) * | 2012-04-25 | 2012-08-15 | 嘉兴荣泰高分子新材料研究所 | Heat-conducting epoxy dipped adhesive and preparation method |
| CN102643621A (en) * | 2012-04-20 | 2012-08-22 | 浙江荣泰科技企业有限公司 | Epoxy resin adhesive for impregnation with high heat resistance and preparation method thereof |
| CN101851387B (en) * | 2009-03-31 | 2013-03-27 | 太阳控股株式会社 | Thermosetting resin composition and cured product thereof |
| CN109824500A (en) * | 2018-08-09 | 2019-05-31 | 阜阳市诗雅涤新材料科技有限公司 | A kind of preparation method and application of 2- benzylimidazoline and Pyromellitic Acid anhydride adduct |
| CN110785282A (en) * | 2017-07-10 | 2020-02-11 | Dic株式会社 | Laminate, printed wiring board using same, flexible printed wiring board, and molded article |
| CN113480829A (en) * | 2021-06-04 | 2021-10-08 | 牧世复合材料科技(苏州)有限公司 | Low-viscosity epoxy/episulfide resin composition and epoxy/episulfide matrix resin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3253919B2 (en) * | 1997-05-19 | 2002-02-04 | 横浜ゴム株式会社 | Adhesive composition |
| CN1583875A (en) * | 2004-06-01 | 2005-02-23 | 武汉化工学院 | Epithio-epoxy composite resin and preparing process thereof |
-
2005
- 2005-12-22 CN CNB2005101205033A patent/CN100396748C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010097051A1 (en) | 2009-02-27 | 2010-09-02 | 汉高（中国）投资有限公司 | Room-temperature curable epoxy structural adhesive composition and preparation method thereof |
| CN101851387B (en) * | 2009-03-31 | 2013-03-27 | 太阳控股株式会社 | Thermosetting resin composition and cured product thereof |
| CN102516912B (en) * | 2011-11-30 | 2013-09-04 | 安徽中铁工程材料科技有限公司 | Method for preparing composite curing agent modified bisphenol F thermosetting adhesive repairing agent special for ballastless track gap and crack damage |
| CN102516912A (en) * | 2011-11-30 | 2012-06-27 | 安徽中铁工程材料科技有限公司 | Method for preparing composite curing agent modified bisphenol F thermosetting adhesive repairing agent special for ballastless track gap and crack damage |
| CN102604088A (en) * | 2012-03-14 | 2012-07-25 | 北京化工大学 | Macromolecule mercaptan and synthetic method thereof |
| CN102604088B (en) * | 2012-03-14 | 2013-11-13 | 北京化工大学 | Macromolecule mercaptan and synthetic method thereof |
| CN102643621A (en) * | 2012-04-20 | 2012-08-22 | 浙江荣泰科技企业有限公司 | Epoxy resin adhesive for impregnation with high heat resistance and preparation method thereof |
| CN102634314B (en) * | 2012-04-25 | 2013-06-19 | 嘉兴荣泰高分子新材料研究所 | Heat-conducting epoxy dipped adhesive and preparation method |
| CN102634314A (en) * | 2012-04-25 | 2012-08-15 | 嘉兴荣泰高分子新材料研究所 | Heat-conducting epoxy dipped adhesive and preparation method |
| CN110785282A (en) * | 2017-07-10 | 2020-02-11 | Dic株式会社 | Laminate, printed wiring board using same, flexible printed wiring board, and molded article |
| CN110785282B (en) * | 2017-07-10 | 2022-06-24 | Dic株式会社 | Laminate, printed wiring board using same, flexible printed wiring board, and molded article |
| CN109824500A (en) * | 2018-08-09 | 2019-05-31 | 阜阳市诗雅涤新材料科技有限公司 | A kind of preparation method and application of 2- benzylimidazoline and Pyromellitic Acid anhydride adduct |
| CN113480829A (en) * | 2021-06-04 | 2021-10-08 | 牧世复合材料科技(苏州)有限公司 | Low-viscosity epoxy/episulfide resin composition and epoxy/episulfide matrix resin |
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| Publication number | Publication date |
|---|---|
| CN100396748C (en) | 2008-06-25 |
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