CN101440268A - Low temperature curing high temperature resistant inorganic / organic hybridization epoxy adhesive and preparation thereof - Google Patents
Low temperature curing high temperature resistant inorganic / organic hybridization epoxy adhesive and preparation thereof Download PDFInfo
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- CN101440268A CN101440268A CNA2008102098475A CN200810209847A CN101440268A CN 101440268 A CN101440268 A CN 101440268A CN A2008102098475 A CNA2008102098475 A CN A2008102098475A CN 200810209847 A CN200810209847 A CN 200810209847A CN 101440268 A CN101440268 A CN 101440268A
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Abstract
The invention discloses a low-temperature curing high temperature-resistant inorganic/organic hybrid epoxy adhesive and a preparation method thereof, which relate to an inorganic/organic hybrid epoxy adhesive and a preparation method thereof. The invention solves the problems that inorganic/organic hybrid epoxy adhesive prepared by the prior art has poor high-temperature thermal aging resistance and needs high curing temperature. The low-temperature curing high temperature-resistant inorganic/organic hybrid epoxy adhesive is prepared by an epoxy resin, an epoxy resin low-temperature curing agent, a coupling agent, an inorganic active hybrid material and a dispersant. The preparation method comprises the following steps: the epoxy resin, the epoxy resin low-temperature curing agent and the coupling agent are mixed and stirred evenly, and then the inorganic active hybrid material and the dispersant are added into the mixture to be stirred evenly to obtain the low-temperature curing high temperature-resistant inorganic/organic hybrid epoxy adhesive. The low-temperature curing high temperature-resistant inorganic/organic hybrid epoxy adhesive has high high-temperature bonding strength, good high-temperature thermal aging performance and low curing temperature. The low-temperature curing high temperature-resistant inorganic/organic hybrid epoxy adhesive has the advantages of simple production technology, convenient operation and broad application.
Description
Technical field
The present invention relates to a kind of inorganic/organic hybrid epoxy adhesive and preparation method thereof.
Background technology
In recent years, along with developing rapidly of high-tech industries such as aerospace, aircraft manufacturing, precise electronic and mechanical workout, high strength and thermotolerance to tackiness agent are had higher requirement, and the locking of screw element such as for example bonding at the transmitter of oil engine, rocket engine, nuclear reactor, flange and gas thread has all proposed demand to the high-strength high temperature-resistant tackiness agent.
Characteristics such as epoxy adhesive has that bonding strength height, volumetric shrinkage are little, low-temperature curable and suitability are extensive are so obtained using widely in each field.But because the epoxy glue thermotolerance is relatively poor relatively, so on using, be subjected to bigger restriction.The inorganic adhesive good heat resistance, use temperature can reach more than 500 ℃, but its fragility is big, the tensile shear bonding strength is low, not impact resisting vibrating, and cured article vesicular structure stopping property is not so good as organic gel.
Inorganic/organic hybrid epoxy adhesive is epoxy adhesive and inorganic adhesive advantage separately comprehensively, as thermostability, rigidity and the dimensional stability of inorganic adhesive, and the toughness of epoxy adhesive and processibility, thereby demonstrate great application prospect.Present inorganic/organic hybrid adhesive system mainly by organic resin (as organosilicon (boron) resin, resol, Resins, epoxy) and asbestos, inorganic materials such as aluminium powder are formed, as external product HT-424, BK-18 and domestic J-09, KH-505 etc. all belong to this type of glue kind, its hydridization is reflected under the hot conditions and takes place, form a kind of inorganic hybrid cross-linked structure, can improve the high-temperature behavior of epoxy adhesive greatly, this type of hybrid material instantaneous at high temperature is bigger, but after elevated temperature heat is aging, the strength degradation rate is bigger, and needs about 200 ℃ hot setting.
Summary of the invention
The objective of the invention is for solved prior art for preparing inorganic/organic hybrid epoxy adhesive high temperature heat-resistant aging resistance difference and the high problem of solidification value, and provide a kind of low temperature curing high temperature resistant inorganic/organic hybrid epoxy adhesive and preparation method thereof.
Low temperature curing high temperature resistant is inorganic/and the organic hybrid epoxy adhesive made by 100 parts of Resins, epoxy, 20～100 parts of low Temperature Curing Agent for Epoxy Resin, 1～20 part of coupling agent, 20～500 parts of inorganic active hybrid materials and 0.5～10 part of dispersion agent by ratio of weight and the number of copies.
Low temperature curing high temperature resistant is inorganic/and the preparation method of organic hybrid epoxy adhesive realizes according to the following steps: one, by ratio of weight and the number of copies 100 parts of Resins, epoxy, 20～100 parts of low Temperature Curing Agent for Epoxy Resin and 1～20 part of coupling agent mixed, is stirred to evenly; Two, add 20～500 parts of inorganic active hybrid materials and 0.5～10 part of dispersion agent again, stir, promptly get low temperature curing high temperature resistant inorganic/the organic hybrid epoxy adhesive.
Low temperature curing high temperature resistant of the present invention is inorganic/and the organic hybrid epoxy adhesive is complementary by Resins, epoxy and inorganic materials, inorganic cementitious system and epoxy resin glue junctor are tied up to interpenetrate in the gelation process and direct hydridization takes place, hydridization is reflected at below 100 ℃ and can finishes under the low-temperature heat condition of cure, the synchronous cross-linking and curing reaction of organic and inorganic takes place, formed the crosslinking structure that inorganic network and organic network intert mutually, this structure has been improved the fragility of inorganic materials at normal temperatures, improves its bonding strength; Under the high temperature ageing condition, the skeleton of inorganic network still exists, and therefore can improve the high temperature heat-resistant aging resistance of epoxy adhesive greatly, and after low-temperature heat was solidified, the heat-proof aging temperature can reach more than 500 ℃, and has good adhesiveproperties and toughness; The coupling agent that adds in the inventive method has inorganic materials and the chemical each other effect that is connected of organic materials in the inorganic/organic hybrid epoxy adhesive of raising; The dispersion agent that adds in the inventive method has the effect that improves inorganic materials and the mutual consistency of organic materials in the tackiness agent.Production technique of the present invention is simple, and is easy to operate, is widely used.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the present embodiment low temperature curing high temperature resistant is inorganic/and the organic hybrid epoxy adhesive made by 100 parts of Resins, epoxy, 20～100 parts of low Temperature Curing Agent for Epoxy Resin, 1～20 part of coupling agent, 20～500 parts of inorganic active hybrid materials and 0.5～10 part of dispersion agent by ratio of weight and the number of copies.
Embodiment two: the present embodiment low temperature curing high temperature resistant is inorganic/and the organic hybrid epoxy adhesive made by 100 parts of Resins, epoxy, 20～100 parts of low Temperature Curing Agent for Epoxy Resin, 0.001～50 part of toughner, 1～20 part of coupling agent, 20～500 parts of inorganic active hybrid materials and 0.5～10 part of dispersion agent by ratio of weight and the number of copies; Wherein toughner is active end group liquid acrylonitrile butadiene rubber or active end group organopolysiloxane; Wherein the active end group liquid acrylonitrile butadiene rubber is selected liquid acrylonitrile butadiene rubber X820, liquid acrylonitrile butadiene rubber X840, liquid acrylonitrile butadiene rubber X350 for use; The active end group organopolysiloxane selects for use 107 terminal hydroxy group organopolysiloxane or 108 to contain the phenyl organopolysiloxane.
Toughner can reduce the fragility after the curing and improve its shock strength and unit elongation.
Embodiment three: what present embodiment was different with embodiment one or two is that Resins, epoxy is bisphenol A type epoxy resin E-54, bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-44, bisphenol A type epoxy resin E-42, bisphenol A type epoxy resin E-35, bisphenol A type epoxy resin E-31, bisphenol A type epoxy resin E-20, bisphenol A type epoxy resin E-14, bisphenol A type epoxy resin E-12, bisphenol A type epoxy resin E-06, bisphenol A type epoxy resin E-04, bisphenol A type epoxy resin E-03, novolac epoxy resin F-51, novolac epoxy resin F-44, novolac epoxy resin F-46, bisphenol-s epoxy resin 185S, bisphenol-s epoxy resin 300SS, tetrabromo-bisphenol type Resins, epoxy EX-28, tetrabromo-bisphenol type Resins, epoxy EX-25, tetrabromo-bisphenol type Resins, epoxy EX-21, tetrabromo-bisphenol type Resins, epoxy EX-14, resorcinol diglycidyl ether Resins, epoxy 680#, diglycidyl ether of ethylene glycol Resins, epoxy, the glycol ether tetraglycidel ether epoxy resin, Polyethylene Glycol Bisglycidyl Ether Resins, epoxy 600E, polypropylene glycol tetraglycidel ether epoxy resin 663, the tetrahydrophthalic acid 2-glycidyl ester epoxy resin, o-phthalic acid diglycidyl ester Resins, epoxy, the m-phthalic acid 2-glycidyl ester epoxy resin, interior methyne tetrahydrophthalic acid ethylene oxidic ester epoxy resin, tricyanic acid three-glycidyl amine Resins, epoxy, organosilicon epoxy resin 665, cycloaliphatic epoxy resin CER-107, organotitanium epoxy resin 670, in the organic silicon-boron modified epoxy one or more.Other is identical with embodiment one or two.
When Resins, epoxy was two or more in the present embodiment, each component was pressed arbitrary proportion and is mixed.
Embodiment four: what present embodiment and embodiment three were different is that low Temperature Curing Agent for Epoxy Resin is aromatic amine, cycloaliphatic amines, aliphatics amine, organic acid anhydride, trolamine, imidazoles, glyoxal ethyline, Dyhard RU 100, polymeric amide 200
#, kymene 00
#In one or more; Wherein aromatic amine is selected mphenylenediamine, diaminodiphenyl-methane or diaminodiphenylsulfone(DDS) for use; Cycloaliphatic amines is selected N-aminoethyl piperazine, isophorone diamine, 1 for use, two (aminomethyl) hexanaphthenes or 4 of 3-, 4 '-diamino-dicyclohexyl methane; The aliphatics amine is selected diethylenetriamine, Triethylenetetramine (TETA), quadrol, hexanediamine, diethyl amino propylamine or m-xylene diamine for use; Organic acid anhydride is selected Tetra hydro Phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, MALEIC ANHYDRIDE, tung oil acid anhydride, tetrahydrochysene phthalate anhydride, hexahydrophthalic acid anhydride or Pyroglutaric acid for use.Other is identical with embodiment three.
When low Temperature Curing Agent for Epoxy Resin was two or more in the present embodiment, each component was pressed arbitrary proportion and is mixed.
Embodiment five: what present embodiment and embodiment one, two or four were different is that the inorganic active hybrid material is the silicate inorganic cementitious system; The silicate inorganic cementitious system is made up of host, solidifying agent, whisker and metal-powder, wherein host is one or more in water glass, potassium silicate, lithium silicate, the pure aluminium silicate, solidifying agent is one or more in magnesium oxide, zinc oxide, ferric oxide, aluminum oxide, calcium oxide, zinc hydroxide, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, the silicon-dioxide, whisker is selected silicon carbide or potassium titanate for use, and metal-powder is selected aluminium powder, iron powder or copper powder for use.Other is identical with embodiment one, two or four.
When host was two or more in the present embodiment, each component was pressed arbitrary proportion and is mixed.
When solidifying agent was two or more in the present embodiment, each component was pressed arbitrary proportion and is mixed.
Embodiment six: what present embodiment and embodiment five were different is that coupling agent is silane coupling agent or titanate coupling agent; Wherein silane coupling agent is a γ-An Bingjisanyiyangjiguiwan, γ-glycidyl ethers propyl trimethoxy silicane, γ-(methacrylate based) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, vinyl silane tri-butyl peroxide, γ-vinyltriethoxysilane, phenylamino Union carbide A-162 or γ-aminoethyl-β-aminopropyl trimethoxysilane, titanate coupling agent are sec.-propyl three oleic acid acyloxy titanic acid ester, the compound of three hard ester acid isopropyl titanates, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, Di(dioctylpyrophosphato) ethylene titanate, Di(dioctylpyrophosphato) ethylene titanate, the inner complex of trolamine or tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanic acid ester.Other is identical with embodiment five.
Embodiment seven: present embodiment and embodiment one, two, four or six different be that dispersion agent is OP-10, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyether silicone oil BD-3032, polyether silicone oil BD-3033, polyether silicone oil BD-3034, polyether silicone oil BD-3055, polyether silicone oil BD-3056, polyether silicone oil BD-3071, polyether silicone oil BD-3078, polyether silicone oil BD-3091, polyether silicone oil BD-3231, polyether silicone oil BD-3307, polyether silicone oil BD-3141, silicone oil of carboxyl, in the nonyl phenol one or more.Other is identical with embodiment one, two, four or six.
When dispersion agent was two or more in the present embodiment, each component was pressed arbitrary proportion and is mixed.
Embodiment eight: the present embodiment low temperature curing high temperature resistant is inorganic/and the preparation method of organic hybrid epoxy adhesive realizes according to the following steps: one, by ratio of weight and the number of copies 100 parts of Resins, epoxy, 20～100 parts of low Temperature Curing Agent for Epoxy Resin and 1～20 part of coupling agent mixed, is stirred to evenly; Two, add 20～500 parts of inorganic active hybrid materials and 0.5～10 part of dispersion agent again, stir, promptly get low temperature curing high temperature resistant inorganic/the organic hybrid epoxy adhesive.
Embodiment nine: the present embodiment low temperature curing high temperature resistant is inorganic/and the preparation method of organic hybrid epoxy adhesive realizes according to the following steps: one, by ratio of weight and the number of copies 100 parts of Resins, epoxy, 20～100 parts of low Temperature Curing Agent for Epoxy Resin, 0.001～50 part of toughner and 1～20 part of coupling agent mixed, is stirred to evenly; Two, add 20～500 parts of inorganic active hybrid materials and 0.5～10 part of dispersion agent again, stir, promptly get low temperature curing high temperature resistant inorganic/the organic hybrid epoxy adhesive; Wherein toughner is active end group liquid acrylonitrile butadiene rubber or active end group organopolysiloxane; Wherein the active end group liquid acrylonitrile butadiene rubber is selected liquid acrylonitrile butadiene rubber X820, liquid acrylonitrile butadiene rubber X840, liquid acrylonitrile butadiene rubber X350 for use; The active end group organopolysiloxane selects for use 107 terminal hydroxy group organopolysiloxane or 108 to contain the phenyl organopolysiloxane.
Embodiment ten: what present embodiment was different with embodiment eight or nine is that Resins, epoxy is bisphenol A type epoxy resin E-54 in the step 1, bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-44, bisphenol A type epoxy resin E-42, bisphenol A type epoxy resin E-35, bisphenol A type epoxy resin E-31, bisphenol A type epoxy resin E-20, bisphenol A type epoxy resin E-14, bisphenol A type epoxy resin E-12, bisphenol A type epoxy resin E-06, bisphenol A type epoxy resin E-04, bisphenol A type epoxy resin E-03, novolac epoxy resin F-51, novolac epoxy resin F-44, novolac epoxy resin F-46, bisphenol-s epoxy resin 185S, bisphenol-s epoxy resin 300SS, tetrabromo-bisphenol type Resins, epoxy EX-28, tetrabromo-bisphenol type Resins, epoxy EX-25, tetrabromo-bisphenol type Resins, epoxy EX-21, tetrabromo-bisphenol type Resins, epoxy EX-14, resorcinol diglycidyl ether Resins, epoxy 680#, diglycidyl ether of ethylene glycol Resins, epoxy, the glycol ether tetraglycidel ether epoxy resin, Polyethylene Glycol Bisglycidyl Ether Resins, epoxy 600E, polypropylene glycol tetraglycidel ether epoxy resin 663, the tetrahydrophthalic acid 2-glycidyl ester epoxy resin, o-phthalic acid diglycidyl ester Resins, epoxy, the m-phthalic acid 2-glycidyl ester epoxy resin, interior methyne tetrahydrophthalic acid ethylene oxidic ester epoxy resin, tricyanic acid three-glycidyl amine Resins, epoxy, organosilicon epoxy resin 665, cycloaliphatic epoxy resin CER-107, organotitanium epoxy resin 670, in the organic silicon-boron modified epoxy one or more.Other is identical with embodiment eight or nine.
When Resins, epoxy was two or more in the present embodiment, each component was pressed arbitrary proportion and is mixed.
Embodiment 11: what present embodiment was different with embodiment eight or nine is that low Temperature Curing Agent for Epoxy Resin is aromatic amine, cycloaliphatic amines, aliphatics amine, organic acid anhydride, trolamine, imidazoles, glyoxal ethyline, Dyhard RU 100, polymeric amide 200 in the step 1
#, kymene 00
#In one or more; Wherein aromatic amine is selected mphenylenediamine, diaminodiphenyl-methane or diaminodiphenylsulfone(DDS) for use; Cycloaliphatic amines is selected N-aminoethyl piperazine, isophorone diamine, 1 for use, two (aminomethyl) hexanaphthenes or 4 of 3-, 4 '-diamino-dicyclohexyl methane; The aliphatics amine is selected diethylenetriamine, Triethylenetetramine (TETA), quadrol, hexanediamine, diethyl amino propylamine or m-xylene diamine for use; Organic acid anhydride is selected Tetra hydro Phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, MALEIC ANHYDRIDE, tung oil acid anhydride, tetrahydrochysene phthalate anhydride, hexahydrophthalic acid anhydride or Pyroglutaric acid for use.Other is identical with embodiment eight or nine.
When low Temperature Curing Agent for Epoxy Resin was two or more in the present embodiment, each component was pressed arbitrary proportion and is mixed.
Embodiment 13: what present embodiment was different with embodiment eight or nine is that the inorganic active hybrid material is the silicate inorganic cementitious system in the step 2; The silicate inorganic cementitious system is made up of host, solidifying agent, whisker and metal-powder, wherein host is one or more in water glass, potassium silicate, lithium silicate, the pure aluminium silicate, solidifying agent is one or more in magnesium oxide, zinc oxide, ferric oxide, aluminum oxide, calcium oxide, zinc hydroxide, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, the silicon-dioxide, whisker is selected silicon carbide or potassium titanate for use, and metal-powder is selected aluminium powder, iron powder or copper powder for use.Other is identical with embodiment eight or nine.
When host was two or more in the present embodiment, each component was pressed arbitrary proportion and is mixed.
When solidifying agent was two or more in the present embodiment, each component was pressed arbitrary proportion and is mixed.
Embodiment 15: what present embodiment was different with embodiment eight or nine is that coupling agent is silane coupling agent or titanate coupling agent in the step 1; Wherein silane coupling agent is a γ-An Bingjisanyiyangjiguiwan, γ-glycidyl ethers propyl trimethoxy silicane, γ-(methacrylate based) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, vinyl silane tri-butyl peroxide, γ-vinyltriethoxysilane, phenylamino Union carbide A-162 or γ-aminoethyl-β-aminopropyl trimethoxysilane, titanate coupling agent are sec.-propyl three oleic acid acyloxy titanic acid ester, the compound of three hard ester acid isopropyl titanates, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, Di(dioctylpyrophosphato) ethylene titanate, Di(dioctylpyrophosphato) ethylene titanate, the inner complex of trolamine or tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanic acid ester.Other is identical with embodiment eight or nine.
Embodiment 16: what present embodiment was different with embodiment eight or nine is that dispersion agent is OP-10 in the step 2, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyether silicone oil BD-3032, polyether silicone oil BD-3033, polyether silicone oil BD-3034, polyether silicone oil BD-3055, polyether silicone oil BD-3056, polyether silicone oil BD-3071, polyether silicone oil BD-3078, polyether silicone oil BD-3091, polyether silicone oil BD-3231, polyether silicone oil BD-3307, polyether silicone oil BD-3141, silicone oil of carboxyl, in the nonyl phenol one or more.Other is identical with embodiment eight or nine.
When dispersion agent was two or more in the present embodiment, each component was pressed arbitrary proportion and is mixed.
Embodiment 17: the present embodiment low temperature curing high temperature resistant is inorganic/and the preparation method of organic hybrid epoxy adhesive realizes according to the following steps: one,, stirs by ratio of weight and the number of copies with 100 parts of bisphenol A type epoxy resin E-51,25 parts of trolamine solidifying agent, 1 part of KH-550; Two, add 100 parts of water glass, 60 parts of silicon-dioxide, 40 parts of magnesium oxide, 40 parts of aluminum oxide and 50 parts of aluminium powders, 50 parts of silicon carbide whiskers, 2 parts of silicone oil again, stir, promptly get low temperature curing high temperature resistant inorganic/the organic hybrid epoxy adhesive.
The low temperature curing high temperature resistant that present embodiment makes is inorganic/and the organic hybrid epoxy adhesive solidifies 4h at 80 ℃, and its bonding test piece is the stainless steel test piece, and the normal temperature tensile shear strength is tested by GB/T 7124-1986, and test result is 14.7MPa; The drawing by high temperature shearing resistance is tested by GJB 444-1988, and the test result under 300 ℃ of conditions is 7.31MPa; Heat ageing test is the stainless steel test piece after solidifying to be put into the baking oven of assigned temperature, reach corresponding digestion time after, take out, be cooled to room temperature, then according to GB/T
7124-1986 tests tensile shear strength, and 400 ℃ aging down after 30min minute, and test result is 6.15
MPa, 500 ℃ are aging down after 30min minute, and test result is 6.78MPa.
Embodiment 18: the present embodiment low temperature curing high temperature resistant is inorganic/preparation method of organic hybrid epoxy adhesive realizes according to the following steps: one, by ratio of weight and the number of copies with 50 parts of bisphenol A type epoxy resin E-51,50 parts of phenolic aldehyde epoxies, 5 part 2,4-imidazoles, 10 parts of polymeric amide, 15 parts of liquid carboxy nitrile rubbers, 1 part of KH-550 stir; Two, add 140 parts of potassium silicates, 80 parts of silicon-dioxide, 60 parts of magnesium oxide, 60 parts of aluminum oxide and 80 parts of aluminium powders, 50 parts of silicon carbide whiskers, 2 parts of OP-10 again, stir, promptly get low temperature curing high temperature resistant inorganic/the organic hybrid epoxy adhesive.
The low temperature curing high temperature resistant that present embodiment makes is inorganic/and the organic hybrid epoxy adhesive solidifies 6h at 80 ℃, and its bonding test piece is the stainless steel test piece, and the normal temperature tensile shear strength is tested by GB/T 7124-1986, and test result is 11.01MPa; The drawing by high temperature shearing resistance is tested by GJB 444-1988, and the test result under 300 ℃ of conditions is 5.3MPa; Heat ageing test is the stainless steel test piece after solidifying to be put into the baking oven of assigned temperature, after reaching corresponding digestion time, take out, be cooled to room temperature, then according to GB/T7124-1986 test tensile shear strength, 400 ℃ aging down after 30min minute, test result is 5.7MPa, and 400 ℃ aging down after 60min minute, and test result is 4.31MPa, 400 ℃ aging down after 180min minute, test result is 5.12MPa, and 400 ℃ aging down after 300min minute, and test result is 4.61MPa, 400 ℃ aging down after 360min minute, test result is 7.21MPa, and 400 ℃ aging down after 540min minute, and test result is 6.87MPa, 500 ℃ aging down after 30min minute, and test result is 5.02MPa.
Embodiment 19: the present embodiment low temperature curing high temperature resistant is inorganic/and the preparation method of organic hybrid epoxy adhesive realizes according to the following steps: one,, stirs by ratio of weight and the number of copies with 80 parts of bisphenol A type epoxy resin E-51,20 parts of resorcinol diglycidyl ether Resins, epoxy, 8 parts of Dyhard RU 100s, 12 parts of polymeric amide, 4 parts of polyethylene polyamines, 1 part of KH-550; Two, add 140 parts of potassium silicates, 80 parts of silicon-dioxide, 60 parts of magnesium oxide, 60 parts of aluminum oxide and 80 parts of aluminium powders, 50 parts of silicon carbide whiskers, 2 parts of silicone oil again, promptly get low temperature curing high temperature resistant inorganic/the organic hybrid epoxy adhesive.
The low temperature curing high temperature resistant that present embodiment makes is inorganic/and the organic hybrid epoxy adhesive solidifies 2h at 90 ℃, and its bonding test piece is the stainless steel test piece, and the normal temperature tensile shear strength is tested by GB/T 7124-1986, and test result is 10.63MPa; The drawing by high temperature shearing resistance is tested by GJB 444-1988, and the test result under 300 ℃ of conditions is 5.10MPa; Heat ageing test is the stainless steel test piece after solidifying to be put into the baking oven of assigned temperature, after reaching corresponding digestion time, take out, be cooled to room temperature, according to GB/T7124-1986 test tensile shear strength, 400 ℃ aging after 30min minute down then, and test result is 6.60MPa, 500 ℃ aging down after 30min minute, and test result is 3.81MPa.
Claims (9)
1, low temperature curing high temperature resistant inorganic/the organic hybrid epoxy adhesive, it is characterized in that low temperature curing high temperature resistant inorganic/the organic hybrid epoxy adhesive made by 100 parts of Resins, epoxy, 20～100 parts of low Temperature Curing Agent for Epoxy Resin, 1～20 part of coupling agent, 20～500 parts of inorganic active hybrid materials and 0.5～10 part of dispersion agent by ratio of weight and the number of copies.
2, low temperature curing high temperature resistant according to claim 1 inorganic/the organic hybrid epoxy adhesive, it is characterized in that low temperature curing high temperature resistant inorganic/component of organic hybrid epoxy adhesive also comprises 0.001～50 part of toughner; Wherein toughner is active end group liquid acrylonitrile butadiene rubber or active end group organopolysiloxane; Wherein the active end group liquid acrylonitrile butadiene rubber is selected liquid acrylonitrile butadiene rubber X820, liquid acrylonitrile butadiene rubber X840, liquid acrylonitrile butadiene rubber X350 for use; The active end group organopolysiloxane selects for use 107 terminal hydroxy group organopolysiloxane or 108 to contain the phenyl organopolysiloxane.
3, low temperature curing high temperature resistant according to claim 1 and 2 is inorganic/the organic hybrid epoxy adhesive, it is characterized in that Resins, epoxy is bisphenol A type epoxy resin E-54, bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-44, bisphenol A type epoxy resin E-42, bisphenol A type epoxy resin E-35, bisphenol A type epoxy resin E-31, bisphenol A type epoxy resin E-20, bisphenol A type epoxy resin E-14, bisphenol A type epoxy resin E-12, bisphenol A type epoxy resin E-06, bisphenol A type epoxy resin E-04, bisphenol A type epoxy resin E-03, novolac epoxy resin F-51, novolac epoxy resin F-44, novolac epoxy resin F-46, bisphenol-s epoxy resin 185S, bisphenol-s epoxy resin 300SS, tetrabromo-bisphenol type Resins, epoxy EX-28, tetrabromo-bisphenol type Resins, epoxy EX-25, tetrabromo-bisphenol type Resins, epoxy EX-21, tetrabromo-bisphenol type Resins, epoxy EX-14, resorcinol diglycidyl ether Resins, epoxy 680#, diglycidyl ether of ethylene glycol Resins, epoxy, the glycol ether tetraglycidel ether epoxy resin, Polyethylene Glycol Bisglycidyl Ether Resins, epoxy 600E, polypropylene glycol tetraglycidel ether epoxy resin 663, the tetrahydrophthalic acid 2-glycidyl ester epoxy resin, o-phthalic acid diglycidyl ester Resins, epoxy, the m-phthalic acid 2-glycidyl ester epoxy resin, interior methyne tetrahydrophthalic acid ethylene oxidic ester epoxy resin, tricyanic acid three-glycidyl amine Resins, epoxy, organosilicon epoxy resin 665, cycloaliphatic epoxy resin CER-107, organotitanium epoxy resin 670, in the organic silicon-boron modified epoxy one or more.
4, low temperature curing high temperature resistant according to claim 3 inorganic/the organic hybrid epoxy adhesive, it is characterized in that low Temperature Curing Agent for Epoxy Resin is aromatic amine, cycloaliphatic amines, aliphatics amine, organic acid anhydride, trolamine, imidazoles, glyoxal ethyline, Dyhard RU 100, polymeric amide 200
#, kymene 00
#In one or more; Wherein aromatic amine is selected mphenylenediamine, diaminodiphenyl-methane or diaminodiphenylsulfone(DDS) for use; Cycloaliphatic amines is selected N-aminoethyl piperazine, isophorone diamine, 1 for use, two (aminomethyl) hexanaphthenes or 4 of 3-, 4 '-diamino-dicyclohexyl methane; The aliphatics amine is selected diethylenetriamine, Triethylenetetramine (TETA), quadrol, hexanediamine, diethyl amino propylamine or m-xylene diamine for use; Organic acid anhydride is selected Tetra hydro Phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, MALEIC ANHYDRIDE, tung oil acid anhydride, tetrahydrochysene phthalate anhydride, hexahydrophthalic acid anhydride or Pyroglutaric acid for use.
5, according to claim 1,2 or 4 described low temperature curing high temperature resistants inorganic/the organic hybrid epoxy adhesive, it is characterized in that the inorganic active hybrid material is the silicate inorganic cementitious system; The silicate inorganic cementitious system is made up of host, solidifying agent, whisker and metal-powder, wherein host is one or more in water glass, potassium silicate, lithium silicate, the pure aluminium silicate, solidifying agent is one or more in magnesium oxide, zinc oxide, ferric oxide, aluminum oxide, calcium oxide, zinc hydroxide, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, the silicon-dioxide, whisker is selected silicon carbide or potassium titanate for use, and metal-powder is selected aluminium powder, iron powder or copper powder for use.
6, low temperature curing high temperature resistant according to claim 5 inorganic/the organic hybrid epoxy adhesive, it is characterized in that coupling agent is silane coupling agent or titanate coupling agent; Wherein silane coupling agent is a γ-An Bingjisanyiyangjiguiwan, γ-glycidyl ethers propyl trimethoxy silicane, γ-(methacrylate based) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, vinyl silane tri-butyl peroxide, γ-vinyltriethoxysilane, phenylamino Union carbide A-162 or γ-aminoethyl-β-aminopropyl trimethoxysilane, titanate coupling agent are sec.-propyl three oleic acid acyloxy titanic acid ester, the compound of three hard ester acid isopropyl titanates, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, Di(dioctylpyrophosphato) ethylene titanate, Di(dioctylpyrophosphato) ethylene titanate, the inner complex of trolamine or tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanic acid ester.
7, according to claim 1,2,4 or 6 described low temperature curing high temperature resistants inorganic/the organic hybrid epoxy adhesive, it is characterized in that dispersion agent is one or more in OP-10, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyether silicone oil BD-3032, polyether silicone oil BD-3033, polyether silicone oil BD-3034, polyether silicone oil BD-3055, polyether silicone oil BD-3056, polyether silicone oil BD-3071, polyether silicone oil BD-3078, polyether silicone oil BD-3091, polyether silicone oil BD-3231, polyether silicone oil BD-3307, polyether silicone oil BD-3141, silicone oil of carboxyl, the nonyl phenol.
8, according to claim 1 low temperature curing high temperature resistant inorganic/preparation method of organic hybrid epoxy adhesive, it is characterized in that low temperature curing high temperature resistant inorganic/preparation method of organic hybrid epoxy adhesive realizes according to the following steps: one, by ratio of weight and the number of copies 100 parts of Resins, epoxy, 20～100 parts of low Temperature Curing Agent for Epoxy Resin and 1～20 part of coupling agent are mixed, are stirred to evenly; Two, add 20～500 parts of inorganic active hybrid materials and 0.5～10 part of dispersion agent again, stir, promptly get low temperature curing high temperature resistant inorganic/the organic hybrid epoxy adhesive.
9, low temperature curing high temperature resistant according to claim 8 inorganic/preparation method of organic hybrid epoxy adhesive, it is characterized in that also having added in the step 1 0.001～50 part of toughner; Wherein toughner is active end group liquid acrylonitrile butadiene rubber or active end group organopolysiloxane; Wherein the active end group liquid acrylonitrile butadiene rubber is selected liquid acrylonitrile butadiene rubber X820, liquid acrylonitrile butadiene rubber X840, liquid acrylonitrile butadiene rubber X350 for use; The active end group organopolysiloxane selects for use 107 terminal hydroxy group organopolysiloxane or 108 to contain the phenyl organopolysiloxane.
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