CN102627927A - Medium temperature curing high temperature resistant phenolic adhesive - Google Patents
Medium temperature curing high temperature resistant phenolic adhesive Download PDFInfo
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- CN102627927A CN102627927A CN2012100821019A CN201210082101A CN102627927A CN 102627927 A CN102627927 A CN 102627927A CN 2012100821019 A CN2012100821019 A CN 2012100821019A CN 201210082101 A CN201210082101 A CN 201210082101A CN 102627927 A CN102627927 A CN 102627927A
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Abstract
A medium temperature curing high temperature resistant phenolic adhesive relates to an adhesive. The invention solves technical problems of phenolic high curing temperature and weak temperature tolerance of adhesive. The adhesive of the present invention consists of modified phenolic resin solution, toughening agent, curing agent, heat-resistant reinforced resin and filler. The adhesive of the invention has a low curing temperature, can be cured at 100 DEG C and obtain good adhesive strength. Curing at 100 DEG C for 6 hours, the adhesive can reach shear strength of 13.5MP and still have shear strength of 2.3MPa at 1000 DEG C. The adhesive further conducts complex reaction in high temperature usage environment and generates product with better heat resistance, thereby realizing the echelon curing and echelon temperature resistance, which are difficult for other type of high temperature resistant glue to achieve.
Description
Technical field
The present invention relates to a kind of tackiness agent.
Background technology
In recent years, along with progress of science and technology, the performance of high-temperature resistance adhesive improves constantly, and has been widely used in various high-tech sectors at present, and particularly in fields such as Aeronautics and Astronautics and electronics, high-temperature resistance adhesive is being brought into play irreplaceable effect; Simultaneously, these fields are also more and more high to the requirement of the high thermal resistance of tackiness agent.For example, temperature was up to 260～270 ℃ when ultra sonic aloft flew, and some structure position of these aircrafts need adopt high strength titanium alloy to replace duraluminum, correspondingly just needed to use the bonding titanium alloy of high-temperature resistance adhesive in large area; On guided missile, require high-temperature resistance adhesive in 540 ℃ high temperature, to keep 1s; In microelectronics, the envrionment temperature of bonding base material in processing link is up to 400 ℃.Therefore, tackiness agent will have enough heat resistances, to guarantee at high temperature to keep good adhesiveproperties; On the other hand, require to improve the use characteristics of tackiness agent, make it and to solidify at a lower temperature, satisfy by the needs in the sticking material processing in some occasions.
Resol has excellent mechanical intensity and resistance toheat, especially has outstanding instantaneous high temperature resistant ablation property, be widely used in above field, but existing modified phenolic adhesive solidification value is high, temperature tolerance is poor.
Summary of the invention
The invention solves the technical problem of existing modified phenolic adhesive solidification value height, temperature tolerance difference, a kind of intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is provided.
Intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is processed by 100 parts modified phenolic resin lipoprotein solution, 5～40 parts toughner, 10～55 parts solidifying agent, 20～100 parts heat-resistant reinforced resin and 50～400 parts filler by ratio of quality and the number of copies.
Described toughner is paracril, Z 150PH, Z 150PH furfural, polyvinyl butyral acetal and Z 150PH contract a kind of in the chaff butyraldehyde or several kinds mixture wherein.Described solidifying agent is vulkacit H or Paraformaldehyde 96.Described heat-resistant reinforced resin is a thermoset polyimide resin.Described filler is a copper powder; Bronze; Silver powder; Zinc oxide; Red stone; Iron powder; Mica powder; Talcum powder; Lime carbonate; Glass putty; Natural manganese dioxide; Zinc powder; Quicklime; Aluminium powder; Zirconium white; Fossil meal; Aluminum oxide; Kaolin; Chromic oxide; Cupric oxide; Titanium oxide; Weisspiessglanz; Silicon-dioxide; Wollastonite; Graphite; Silica sand; Calcite; Manganese oxide; Carbon black; Spun glass; Glass microsphere; Ceramics powder; SP 1; A kind of in asbestos and the norbide or several kinds mixture wherein.
The preparation method of described modified phenolic resin lipoprotein solution is following:
One, phenolic cpd, 20～150g aldehyde compound and the catalyzer with 20～130g reacted 1～6 hour down at 50～100 ℃, and dehydration promptly gets the phenolic aldehyde prepolymer to 1～20,000 centipoise;
Two, 70～200g mixing an organosilane monomer, 6～24g boron compound and 30～60g water are mixed; React 5～10h down at 60～120 ℃ then, underpressure distillation, and under 110～140 ℃, keep 3～6h; Add solvent then, be mixed with mass concentration and be 50% organic silicon-boron resin solution;
Three, the organic silicon-boron resin solution with 100 parts of phenolic aldehyde prepolymers and 20～60 parts mixes, and at 60～120 ℃ of reaction 3～5h down, the water that is generated in the reaction process is told by water trap, and reaction promptly gets the modified phenolic resin lipoprotein solution after finishing.
Phenolic cpd described in the step 1 is phenol, methylphenol, a kind of in amino-phenol, pyrocatechol, Resorcinol, alkyl resorcinol, Phloroglucinol, Resorcinol, bisphenol-A, bisphenol-f and the xenol or several kinds mixture wherein partially; Aldehyde compound described in the step 1 is a kind of in formaldehyde, Paraformaldehyde 96, furfural, salicylic aldehyde and the acetaldehyde or several kinds mixture wherein.Catalyzer described in the step 1 is a kind of in hydrochloric acid, oxalic acid, acetic acid, tosic acid, benzene sulfonyl chloride, Tosyl chloride, p-chlorobenzenesulfonic acid, zinc acetate, zinc oxide, chromium acetate, manganese acetate and the neutralized verdigris or several kinds mixture wherein.Mixing an organosilane monomer described in the step 2 is several kinds a mixture in SWS-F 221, hexamethyldisilazane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, Union carbide A-162,3,5-dimethylphenyl Ethoxysilane, methyltrimethoxy silane, methyl ethylene diethoxy silane, methyl ethylene dimethoxy silane, tetramethyl divinyl silane, vinyltriethoxysilane, vinyltrimethoxy silane, phenylbenzene diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, γ-An Bingjisanyiyangjiguiwan, β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, tetraethoxysilane and the dodecyl triethoxyl silane.Boron compound described in the step 2 is boric acid, phenyl-boron dihydroxide, 3-anisole ylboronic acid and to a kind of in the bromo phenyl-boron dihydroxide or several kinds mixture wherein; Solvent described in the step 2 is a kind of in ETHYLE ACETATE, acetone, toluene, ethanol, THF, YLENE and the DMAC N,N or several kinds mixture wherein.
Adhesive solidification temperature of the present invention is lower, can solidify down at 100 ℃, can obtain good bonding strength; Can reach 13.5MPa 100 ℃ of room temperature shearing resistances after solidifying 6 hours, still have the shearing resistance of 2.3MPa under 1000 ℃, under the high temperature environment for use; Complicated reaction further taking place, cause thaumatropy, generates the higher product of temperature tolerance; Thereby realize that echelon is solidified, the echelon heatproof, this is that the high-temperature plastic of other type is difficult to realize.
Description of drawings
Fig. 1 is the thermogravimetric comparison diagram of modified phenolic resins and unmodified resol under the embodiment ten air atmosphere, among the figure---the thermogravimetric curve of expression modified phenolic resins,----represented the thermogravimetric curve of unmodified resol; Fig. 2 is experiment one gained intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent thermogravimetric curve under different atmosphere in the embodiment ten, among the figure---and be illustrated in airborne thermogravimetric curve,----is illustrated in the thermogravimetric curve in the nitrogen.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: this embodiment intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is processed by 100 parts modified phenolic resin lipoprotein solution, 5～40 parts toughner, 10～55 parts solidifying agent, 20～100 parts heat-resistant reinforced resin and 50～400 parts filler by ratio of quality and the number of copies.
Embodiment two: this embodiment and embodiment one are different is that described toughner is paracril, Z 150PH, Z 150PH furfural, polyvinyl butyral acetal and Z 150PH contract a kind of in the chaff butyraldehyde or several kinds mixture wherein.Other is identical with embodiment one.
When the toughner described in this embodiment is mixture between each composition for arbitrarily than.
Embodiment three: what this embodiment was different with embodiment one or two is that described solidifying agent is vulkacit H or Paraformaldehyde 96.Other is identical with embodiment one or two.
Embodiment four: what this embodiment was different with one of embodiment one to three is that described heat-resistant reinforced resin is a thermoset polyimide resin.Other is identical with one of embodiment one to three.
Embodiment five: what this embodiment was different with one of embodiment one to four is that described filler is a copper powder; Bronze; Silver powder; Zinc oxide; Red stone; Iron powder; Mica powder; Talcum powder; Lime carbonate; Glass putty; Natural manganese dioxide; Zinc powder; Quicklime; Aluminium powder; Zirconium white; Fossil meal; Aluminum oxide; Kaolin; Chromic oxide; Cupric oxide; Titanium oxide; Weisspiessglanz; Silicon-dioxide; Wollastonite; Graphite; Silica sand; Calcite; Manganese oxide; Carbon black; Spun glass; Glass microsphere; Ceramics powder; SP 1; A kind of in asbestos and the norbide or several kinds mixture wherein.Other is identical with one of embodiment one to four.
When the filler described in this embodiment is mixture between each composition for arbitrarily than.
Embodiment six: the preparation method of this embodiment modified phenolic resin lipoprotein solution is following:
One, phenolic cpd, 20～150g aldehyde compound and the catalyzer with 20～130g reacted 1～6 hour down at 50～100 ℃, and dehydration promptly gets the phenolic aldehyde prepolymer to 1～20,000 centipoise;
Two, 70～200g mixing an organosilane monomer, 6～24g boron compound and 30～60g water are mixed; React 5～10h down at 60～120 ℃ then, underpressure distillation, and under 110～140 ℃, keep 3～6h; Add solvent then, be mixed with mass concentration and be 50% organic silicon-boron resin solution;
Three, the organic silicon-boron resin solution with 100 parts of phenolic aldehyde prepolymers and 20～60 parts mixes, and at 60～120 ℃ of reaction 3～5h down, the water that is generated in the reaction process is told by water trap, and reaction promptly gets the modified phenolic resin lipoprotein solution after finishing.
Embodiment seven: this embodiment and embodiment six are different is that the phenolic cpd described in the step 1 is phenol, methylphenol, a kind of in amino-phenol, pyrocatechol, Resorcinol, alkyl resorcinol, Phloroglucinol, Resorcinol, bisphenol-A, bisphenol-f and the xenol or several kinds mixture wherein partially; Aldehyde compound described in the step 1 is a kind of in formaldehyde, Paraformaldehyde 96, furfural, salicylic aldehyde and the acetaldehyde or several kinds mixture wherein.Other and embodiment six phase are together.
When the phenolic cpd described in this embodiment is mixture between each composition for arbitrarily than.When the aldehyde compound described in this embodiment is mixture between each composition for arbitrarily than.
Embodiment eight: this embodiment is different with embodiment six or seven is that the catalyzer described in the step 1 is a kind of in hydrochloric acid, oxalic acid, acetic acid, tosic acid, benzene sulfonyl chloride, Tosyl chloride, p-chlorobenzenesulfonic acid, zinc acetate, zinc oxide, chromium acetate, manganese acetate and the neutralized verdigris or several kinds mixture wherein.Other is identical with embodiment six or seven.
When the catalyzer described in this embodiment is mixture between each composition for arbitrarily than.
Embodiment nine: this embodiment is different with one of embodiment six to eight is that the mixing an organosilane monomer described in the step 2 is several kinds a mixture in SWS-F 221, hexamethyldisilazane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, Union carbide A-162,3,5-dimethylphenyl Ethoxysilane, methyltrimethoxy silane, methyl ethylene diethoxy silane, methyl ethylene dimethoxy silane, tetramethyl divinyl silane, vinyltriethoxysilane, vinyltrimethoxy silane, phenylbenzene diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, γ-An Bingjisanyiyangjiguiwan, β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, tetraethoxysilane and the dodecyl triethoxyl silane.Other is identical with one of embodiment six to eight.
When the mixing an organosilane monomer described in this embodiment is mixture between each composition for arbitrarily than.
Embodiment ten: this embodiment is different with one of embodiment six to nine is that boron compound described in the step 2 is boric acid, phenyl-boron dihydroxide, 3-anisole ylboronic acid and to a kind of in the bromo phenyl-boron dihydroxide or several kinds mixture wherein; Solvent described in the step 2 is a kind of in ETHYLE ACETATE, acetone, toluene, ethanol, THF, YLENE and the DMAC N,N or several kinds mixture wherein.Other is identical with one of embodiment six to nine.
When the boron compound described in this embodiment is mixture between each composition for arbitrarily than.
This embodiment adopts following experimental verification effect of the present invention:
Experiment one: intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is processed by 100 parts modified phenolic resin lipoprotein solution, 5 parts paracril, 10 parts vulkacit H, 20 parts thermoset polyimide resin and 50 parts copper powder by ratio of quality and the number of copies.
Experiment two: intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is processed by 100 parts modified phenolic resin lipoprotein solution, 5 parts Z 150PH, 10 parts vulkacit H, 20 parts thermoset polyimide resin and 50 parts zinc oxide by ratio of quality and the number of copies.
Experiment three: intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is processed by 100 parts modified phenolic resin lipoprotein solution, 5 parts Z 150PH furfural, 10 parts vulkacit H, 20 parts thermoset polyimide resin and 50 parts fossil meal by ratio of quality and the number of copies.
Experiment four: intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is processed by 100 parts modified phenolic resin lipoprotein solution, 5 parts polyvinyl butyral acetal, 10 parts Paraformaldehyde 96,20 parts thermoset polyimide resin and 50 parts wollastonite by ratio of quality and the number of copies.
Experiment five: intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is processed by contract chaff butyraldehyde, 10 parts Paraformaldehyde 96,20 parts thermoset polyimide resin and 50 parts mica powder of 100 parts modified phenolic resin lipoprotein solution, 5 parts Z 150PH by ratio of quality and the number of copies.
Modified phenolic resins solution manufacturing method in experiment one to the experiment five is following:
One, phenol, 50g formaldehyde and the zinc oxide with 30g reacted 2 hours down at 80 ℃, and dehydration promptly gets the phenolic aldehyde prepolymer to 10,000 centipoises;
Two, 100g SWS-F 221,20g phenyl-boron dihydroxide and 40g water are mixed, then at 100 ℃ of reaction 8h down, underpressure distillation, and keep 4h down at 120 ℃ adds ETHYLE ACETATE then, is mixed with mass concentration and is 50% organic silicon-boron resin solution;
Three, the organic silicon-boron resin solution with 100 parts of phenolic aldehyde prepolymers and 50 parts mixes, and at 80 ℃ of reaction 3～5h down, the water that is generated in the reaction process is told by water trap, and reaction promptly gets the modified phenolic resin lipoprotein solution after finishing.
The initial decomposition temperature of being found out modified phenolic resins by Fig. 1 is corresponding to 457 ℃.450 ℃ to 750 ℃ is the main section of tackiness agent thermal weight loss, and along with temperature raises, curve tends towards stability, and modified phenolic resins residual heavy rate in the time of 1000 ℃ is 6.5%.The modified phenolic resins resistance toheat is superior to unmodified resol, and this is because have boron oxygen key, siliconoxygen bond in the resin structure, has improved the thermotolerance of resol.
Find out that by Fig. 2 intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent about 200 ℃ after fixing to a certain degree can take place, the process that has free phenol, formaldehyde, water etc. to discharge causes tackiness agent that small size weightlessness is arranged.Temperature continue to raise, reach the initial decomposition temperature of modified phenolic resins after tackiness agent tangible weightlessness is arranged, the initial decomposition temperature under the nitrogen atmosphere is 544 ℃, exceeds 69 ℃ than the initial decomposition temperature under the air atmosphere.Tackiness agent reaches maximum weightless, residual heavy by 89.0% under the nitrogen atmosphere in about 658 ℃, and tackiness agent reaches maximum weightless, residual heavy by 85.5% under the air atmosphere in about 571 ℃.With tackiness agent under two kinds of atmosphere of temperature rising the process that increases weight is rapidly arranged all afterwards.Residually under 1000 ℃ of nitrogen and the air atmosphere heavyly be respectively 98.0% and 100.1%.
Experiment one to shearing resistance such as the following table of intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent under differing temps of experiment five preparations:
Table 1
Claims (10)
1. intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is characterized in that intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent processed by 100 parts modified phenolic resin lipoprotein solution, 5～40 parts toughner, 10～55 parts solidifying agent, 20～100 parts heat-resistant reinforced resin and 50～400 parts filler by ratio of quality and the number of copies.
2. according to the said intermediate temperature setting type of claim 1 high temperature resistance phenolic aldehyde tackiness agent, it is characterized in that described toughner is paracril, Z 150PH, Z 150PH furfural, polyvinyl butyral acetal and Z 150PH contract a kind of in the chaff butyraldehyde or several kinds mixture wherein.
3. according to claim 1 or 2 said intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent, it is characterized in that described solidifying agent is vulkacit H or Paraformaldehyde 96.
4. according to claim 1 or 2 said intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent, it is characterized in that described heat-resistant reinforced resin is a thermoset polyimide resin.
5. according to claim 1 or 2 said intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent, it is characterized in that described filler is a kind of in copper powder, bronze, silver powder, zinc oxide, red stone, iron powder, mica powder, talcum powder, lime carbonate, glass putty, Natural manganese dioxide, zinc powder, quicklime, aluminium powder, zirconium white, fossil meal, aluminum oxide, kaolin, chromic oxide, cupric oxide, titanium oxide, weisspiessglanz, silicon-dioxide, wollastonite, graphite, silica sand, calcite, manganese oxide, carbon black, spun glass, glass microsphere, ceramics powder, SP 1, asbestos and the norbide or several kinds mixture wherein.
6. according to the said intermediate temperature setting type of claim 1 high temperature resistance phenolic aldehyde tackiness agent, it is characterized in that the preparation method of described modified phenolic resin lipoprotein solution is following:
One, phenolic cpd, 20～150g aldehyde compound and the catalyzer with 20～130g reacted 1～6 hour down at 50～100 ℃, and dehydration promptly gets the phenolic aldehyde prepolymer to 1～20,000 centipoise;
Two, 70～200g mixing an organosilane monomer, 6～24g boron compound and 30～60g water are mixed; React 5～10h down at 60～120 ℃ then, underpressure distillation, and under 110～140 ℃, keep 3～6h; Add solvent then, be mixed with mass concentration and be 50% organic silicon-boron resin solution;
Three, the organic silicon-boron resin solution with 100 parts of phenolic aldehyde prepolymers and 20～60 parts mixes, and at 60～120 ℃ of reaction 3～5h down, the water that is generated in the reaction process is told by water trap, and reaction promptly gets the modified phenolic resin lipoprotein solution after finishing.
7. the preparation method of modified phenolic resin lipoprotein solution according to claim 6 is characterized in that the phenolic cpd described in the step 1 is phenol, methylphenol, a kind of in amino-phenol, pyrocatechol, Resorcinol, alkyl resorcinol, Phloroglucinol, Resorcinol, bisphenol-A, bisphenol-f and the xenol or several kinds mixture wherein partially; Aldehyde compound described in the step 1 is a kind of in formaldehyde, Paraformaldehyde 96, furfural, salicylic aldehyde and the acetaldehyde or several kinds mixture wherein.
8. according to the preparation method of claim 6 or 7 described modified phenolic resin lipoprotein solutions, it is characterized in that the catalyzer described in the step 1 is a kind of in hydrochloric acid, oxalic acid, acetic acid, tosic acid, benzene sulfonyl chloride, Tosyl chloride, p-chlorobenzenesulfonic acid, zinc acetate, zinc oxide, chromium acetate, manganese acetate and the neutralized verdigris or several kinds mixture wherein.
9. according to the preparation method of claim 6 or 7 described modified phenolic resin lipoprotein solutions; It is characterized in that the mixing an organosilane monomer described in the step 2 is several kinds a mixture in SWS-F 221, hexamethyldisilazane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, Union carbide A-162,3,5-dimethylphenyl Ethoxysilane, methyltrimethoxy silane, methyl ethylene diethoxy silane, methyl ethylene dimethoxy silane, tetramethyl divinyl silane, vinyltriethoxysilane, vinyltrimethoxy silane, phenylbenzene diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, γ-An Bingjisanyiyangjiguiwan, β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, tetraethoxysilane and the dodecyl triethoxyl silane.
10. according to the preparation method of claim 6 or 7 described modified phenolic resin lipoprotein solutions, it is characterized in that boron compound described in the step 2 is boric acid, phenyl-boron dihydroxide, 3-anisole ylboronic acid and to a kind of in the bromo phenyl-boron dihydroxide or several kinds mixture wherein; Solvent described in the step 2 is a kind of in ETHYLE ACETATE, acetone, toluene, ethanol, THF, YLENE and the DMAC N,N or several kinds mixture wherein.
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