CN102627927B - Medium temperature curing high temperature resistant phenolic adhesive - Google Patents
Medium temperature curing high temperature resistant phenolic adhesive Download PDFInfo
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- CN102627927B CN102627927B CN2012100821019A CN201210082101A CN102627927B CN 102627927 B CN102627927 B CN 102627927B CN 2012100821019 A CN2012100821019 A CN 2012100821019A CN 201210082101 A CN201210082101 A CN 201210082101A CN 102627927 B CN102627927 B CN 102627927B
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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 scientific and technical progress, the performance of high-temperature resistance adhesive improves constantly, and has been widely used at present various high-tech sectors, 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, when supersonic plane aloft flies, temperature is up to 260～270 ℃, and some structure position of these aircrafts need adopt high strength titanium alloy to replace aluminium alloy, correspondingly just needs to use high-temperature resistance adhesive bonding titanium alloy in large area; On guided missile, require high-temperature resistance adhesive to maintain 1s in the high temperature of 540 ℃; 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 processing performance of tackiness agent in some occasion, make it to solidify at a lower temperature, meet by the needs in sticky material processing.
Resol has good physical strength and resistance toheat, especially has outstanding instantaneous high temperature resistant ablation property, in above field, be widely used, but existing modified phenolic adhesive solidification value is high, temperature tolerance is poor.
Summary of the invention
The invention solves the existing technical problem that the modified phenolic adhesive solidification value is high, temperature tolerance is poor, 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 made by the modified phenolic resin lipoprotein solution of 100 parts, the toughner of 5～40 parts, the solidifying agent of 10～55 parts, the heat-resistant reinforced resin of 20～100 parts and the filler of 50～400 parts by ratio of quality and the number of copies.
Described toughner is a kind of in paracril, polyvinyl alcohol, polyvinyl alcohol furfural, polyvinyl butyral acetal and polyvinyl alcohol contracting chaff butyraldehyde or several mixture wherein.Described solidifying agent is vulkacit H or paraformaldehyde.Described heat-resistant reinforced resin is thermoset polyimide resin.Described filler is copper powder, bronze, silver powder, zinc oxide, ferric oxide, iron powder, mica powder, talcum powder, calcium carbonate, glass putty, magnesium oxide, zinc powder, calcium oxide, aluminium powder, zirconium white, fossil meal, aluminum oxide, kaolin, chromic oxide, cupric oxide, titanium oxide, weisspiessglanz, silicon-dioxide, wollastonite, graphite, quartz sand, calcite, manganese oxide, carbon black, glass fibre, glass microsphere, ceramics powder, boron nitride, a kind of in asbestos and norbide or several mixture wherein.
The preparation method of described modified phenolic resin lipoprotein solution is as follows:
One, the phenolic compound of 20～130g, 20～150g aldehyde compound and catalyzer are reacted 1～6 hour under 50～100 ℃, dehydration, to 1～20,000 centipoise, obtains the phenolic aldehyde prepolymer;
Two, 70～200g mixing organosilane monomer, 6～24g boron compound and 30～60g water are mixed, then react 5～10h under 60～120 ℃, underpressure distillation, and keep 3～6h under 110～140 ℃, then add solvent, the organic silicon-boron resin solution that to be mixed with mass concentration be 50%;
Three, the organic silicon-boron resin solution of 100 parts of phenolic aldehyde prepolymers and 20～60 parts is mixed, under 60～120 ℃, react 3～5h, the water generated in reaction process is separated by water trap, and reaction obtains the modified phenolic resin lipoprotein solution after finishing.
Phenolic compound described in step 1 is phenol, methylphenol, a kind of in amino-phenol, pyrocatechol, Resorcinol, alkyl resorcinol, Phloroglucinol, Resorcinol, bisphenol-A, bisphenol-f and xenol or several mixture wherein partially; Aldehyde compound described in step 1 is a kind of in formaldehyde, paraformaldehyde, furfural, salicylic aldehyde and acetaldehyde or several mixture wherein.Catalyzer described in 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 neutralized verdigris or several mixture wherein.Mixing organosilane monomer described in step 2 is hexamethyldisiloxane, hexamethyldisilazane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, Union carbide A-162, the 3,5-dimethylphenyl Ethoxysilane, methyltrimethoxy silane, the methyl ethylene diethoxy silane, methyl ethylene dimethoxy silane, tetramethyl divinyl silane, vinyltriethoxysilane, vinyltrimethoxy silane, the phenylbenzene diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, γ-aminopropyl triethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, several mixture in tetraethoxysilane and dodecyl triethoxyl silane.Boron compound described in 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 mixture wherein; Solvent described in step 2 is a kind of in ethyl acetate, acetone, toluene, ethanol, tetrahydrofuran (THF), dimethylbenzene and N,N-dimethylacetamide or several mixture wherein.
Adhesive solidification temperature of the present invention is lower, can under 100 ℃, solidify, can obtain good bonding strength, the room temperature shearing resistance at 100 ℃ after solidifying 6 hours can reach 13.5MPa, still has the shearing resistance of 2.3MPa under 1000 ℃, under the applied at elevated temperature environment, complicated reaction further occurring, 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 realization.
The accompanying drawing explanation
Fig. 1 is the thermogravimetric comparison diagram of modified phenolic resins and unmodified resol under embodiment ten Air atmosphere, in figure---and mean the thermogravimetric curve of modified phenolic resins,----mean 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 embodiment ten, in figure---and be illustrated in airborne thermogravimetric curve,----be illustrated in the thermogravimetric curve in nitrogen.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is made by the modified phenolic resin lipoprotein solution of 100 parts, the toughner of 5～40 parts, the solidifying agent of 10～55 parts, the heat-resistant reinforced resin of 20～100 parts and the filler of 50～400 parts by ratio of quality and the number of copies.
Embodiment two: present embodiment is different from embodiment one is that described toughner is a kind of in paracril, polyvinyl alcohol, polyvinyl alcohol furfural, polyvinyl butyral acetal and polyvinyl alcohol contracting chaff butyraldehyde or several mixture wherein.Other is identical with embodiment one.
When the toughner described in present embodiment is mixture between each composition for arbitrarily than.
Embodiment three: what present embodiment was different from embodiment one or two is that described solidifying agent is vulkacit H or paraformaldehyde.Other is identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is that described heat-resistant reinforced resin is thermoset polyimide resin.Other is identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is that described filler is copper powder, bronze, silver powder, zinc oxide, ferric oxide, iron powder, mica powder, talcum powder, calcium carbonate, glass putty, magnesium oxide, zinc powder, calcium oxide, aluminium powder, zirconium white, fossil meal, aluminum oxide, kaolin, chromic oxide, cupric oxide, titanium oxide, weisspiessglanz, silicon-dioxide, wollastonite, graphite, quartz sand, calcite, manganese oxide, carbon black, glass fibre, glass microsphere, ceramics powder, boron nitride, a kind of in asbestos and norbide or several mixture wherein.Other is identical with one of embodiment one to four.
When the filler described in present embodiment is mixture between each composition for arbitrarily than.
Embodiment six: the preparation method of present embodiment modified phenolic resin lipoprotein solution is as follows:
One, the phenolic compound of 20～130g, 20～150g aldehyde compound and catalyzer are reacted 1～6 hour under 50～100 ℃, dehydration, to 1～20,000 centipoise, obtains the phenolic aldehyde prepolymer;
Two, 70～200g mixing organosilane monomer, 6～24g boron compound and 30～60g water are mixed, then react 5～10h under 60～120 ℃, underpressure distillation, and keep 3～6h under 110～140 ℃, then add solvent, the organic silicon-boron resin solution that to be mixed with mass concentration be 50%;
Three, the organic silicon-boron resin solution of 100 parts of phenolic aldehyde prepolymers and 20～60 parts is mixed, under 60～120 ℃, react 3～5h, the water generated in reaction process is separated by water trap, and reaction obtains the modified phenolic resin lipoprotein solution after finishing.
Embodiment seven: present embodiment is different from embodiment six is that the phenolic compound described in step 1 is phenol, methylphenol, a kind of in amino-phenol, pyrocatechol, Resorcinol, alkyl resorcinol, Phloroglucinol, Resorcinol, bisphenol-A, bisphenol-f and xenol or several mixture wherein partially; Aldehyde compound described in step 1 is a kind of in formaldehyde, paraformaldehyde, furfural, salicylic aldehyde and acetaldehyde or several mixture wherein.Other is identical with embodiment six.
When the phenolic compound described in present embodiment is mixture between each composition for arbitrarily than.When the aldehyde compound described in present embodiment is mixture between each composition for arbitrarily than.
Embodiment eight: present embodiment is different from embodiment six or seven is that the catalyzer described in 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 neutralized verdigris or several mixture wherein.Other is identical with embodiment six or seven.
When the catalyzer described in present embodiment is mixture between each composition for arbitrarily than.
Embodiment nine: what present embodiment was different from one of embodiment six to eight is that the mixing organosilane monomer described in step 2 is hexamethyldisiloxane, hexamethyldisilazane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, Union carbide A-162, the 3,5-dimethylphenyl Ethoxysilane, methyltrimethoxy silane, the methyl ethylene diethoxy silane, methyl ethylene dimethoxy silane, tetramethyl divinyl silane, vinyltriethoxysilane, vinyltrimethoxy silane, the phenylbenzene diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, γ-aminopropyl triethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, several mixture in tetraethoxysilane and dodecyl triethoxyl silane.Other is identical with one of embodiment six to eight.
When the mixing organosilane monomer described in present embodiment is mixture between each composition for arbitrarily than.
Embodiment ten: present embodiment is different from one of embodiment six to nine is that boron compound described in 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 mixture wherein; Solvent described in step 2 is a kind of in ethyl acetate, acetone, toluene, ethanol, tetrahydrofuran (THF), dimethylbenzene and N,N-dimethylacetamide or several mixture wherein.Other is identical with one of embodiment six to nine.
When the boron compound described in present embodiment is mixture between each composition for arbitrarily than.
Present embodiment adopts following experimental verification effect of the present invention:
Experiment one: intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is made by the modified phenolic resin lipoprotein solution of 100 parts, the paracril of 5 parts, the vulkacit H of 10 parts, the thermoset polyimide resin of 20 parts and the copper powder of 50 parts by ratio of quality and the number of copies.
Experiment two: intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is made by the modified phenolic resin lipoprotein solution of 100 parts, the polyvinyl alcohol of 5 parts, the vulkacit H of 10 parts, the thermoset polyimide resin of 20 parts and the zinc oxide of 50 parts by ratio of quality and the number of copies.
Experiment three: intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is made by the modified phenolic resin lipoprotein solution of 100 parts, the polyvinyl alcohol furfural of 5 parts, the vulkacit H of 10 parts, the thermoset polyimide resin of 20 parts and the fossil meal of 50 parts by ratio of quality and the number of copies.
Experiment four: intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is made by the modified phenolic resin lipoprotein solution of 100 parts, the polyvinyl butyral acetal of 5 parts, the paraformaldehyde of 10 parts, the thermoset polyimide resin of 20 parts and the wollastonite of 50 parts by ratio of quality and the number of copies.
Experiment five: intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent is made by the modified phenolic resin lipoprotein solution of 100 parts, the polyvinyl alcohol contracting chaff butyraldehyde of 5 parts, the paraformaldehyde of 10 parts, the thermoset polyimide resin of 20 parts and the mica powder of 50 parts by ratio of quality and the number of copies.
Experiment one is as follows to the modified phenolic resins solution manufacturing method in experiment five:
One, the phenol of 30g, 50g formaldehyde and zinc oxide are reacted 2 hours under 80 ℃, dehydration, to 10,000 centipoises, obtains the phenolic aldehyde prepolymer;
Two, 100g hexamethyldisiloxane, 20g phenyl-boron dihydroxide and 40g water are mixed, then under 100 ℃, react 8h, underpressure distillation, and keep 4h under 120 ℃, then add ethyl acetate, the organic silicon-boron resin solution that to be mixed with mass concentration be 50%;
Three, the organic silicon-boron resin solution of 100 parts of phenolic aldehyde prepolymers and 50 parts is mixed, under 80 ℃, react 3～5h, the water generated in reaction process is separated by water trap, and reaction obtains the modified phenolic resin lipoprotein solution after finishing.
Found out that by Fig. 1 the initial decomposition temperature of modified phenolic resins 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 better than unmodified resol, and this is because have boron oxygen key, siloxane bond in 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, at about 200 ℃, after fixing to a certain degree can occur, the process that has free phenol, formaldehyde, water etc. to discharge, cause tackiness agent that small size weightlessness is arranged.Temperature continue to raise, reach the initial decomposition temperature of modified phenolic resins after tackiness agent obvious weightlessness is arranged, the initial decomposition temperature under nitrogen atmosphere is 544 ℃, than the initial decomposition temperature under air atmosphere, exceeds 69 ℃.Under nitrogen atmosphere, tackiness agent reaches maximum weightless, residual heavy by 89.0% in 658 ℃ of left and right, and under air atmosphere, tackiness agent reaches maximum weightless, residual heavy by 85.5% in 571 ℃ of left and right.With tackiness agent under two kinds of atmosphere of temperature rising, the process that increases weight is rapidly all arranged afterwards.Residually under 1000 ℃ of nitrogen and air atmosphere heavyly be respectively 98.0% and 100.1%.
Experiment one to the shearing resistances of intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent under differing temps of experiment five preparations as following table:
Table 1
Claims (8)
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 made by the modified phenolic resin lipoprotein solution of 100 parts, the toughner of 5～40 parts, the solidifying agent of 10～55 parts, the heat-resistant reinforced resin of 20～100 parts and the filler of 50～400 parts by ratio of quality and the number of copies;
The preparation method of described modified phenolic resin lipoprotein solution is as follows:
One, the phenolic compound of 20～130g, 20～150g aldehyde compound and catalyzer are reacted 1～6 hour under 50～100 ℃, dehydration, to 1～20,000 centipoise, obtains the phenolic aldehyde prepolymer;
Two, 70～200g mixing organosilane monomer, 6～24g boron compound and 30～60g water are mixed, then react 5～10h under 60～120 ℃, underpressure distillation, and keep 3～6h under 110～140 ℃, then add solvent, the organic silicon-boron resin solution that to be mixed with mass concentration be 50%;
Three, the organic silicon-boron resin solution of 100 parts of phenolic aldehyde prepolymers and 20～60 parts is mixed, under 60～120 ℃, react 3～5h, the water generated in reaction process is separated by water trap, and reaction obtains the modified phenolic resin lipoprotein solution after finishing; Boron compound described in 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 mixture wherein; Solvent described in step 2 is a kind of in ethyl acetate, acetone, toluene, ethanol, tetrahydrofuran (THF), dimethylbenzene and N,N-dimethylacetamide or several mixture wherein.
2. intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent according to claim 1, is characterized in that described toughner is a kind of in paracril, polyvinyl alcohol, polyvinyl alcohol furfural and polyvinyl butyral acetal or several mixture wherein.
3. according to the described intermediate temperature setting type of claim 1 or 2 high temperature resistance phenolic aldehyde tackiness agent, it is characterized in that described solidifying agent is vulkacit H or paraformaldehyde.
4. according to the described intermediate temperature setting type of claim 1 or 2 high temperature resistance phenolic aldehyde tackiness agent, it is characterized in that described heat-resistant reinforced resin is thermoset polyimide resin.
5. according to the described intermediate temperature setting type of claim 1 or 2 high temperature resistance phenolic aldehyde tackiness agent, it is characterized in that described filler is copper powder, bronze, silver powder, zinc oxide, ferric oxide, iron powder, mica powder, talcum powder, calcium carbonate, glass putty, magnesium oxide, zinc powder, calcium oxide, aluminium powder, zirconium white, fossil meal, aluminum oxide, kaolin, chromic oxide, cupric oxide, titanium oxide, weisspiessglanz, silicon-dioxide, wollastonite, graphite, quartz sand, calcite, manganese oxide, carbon black, glass fibre, glass microsphere, ceramics powder, boron nitride, a kind of in asbestos and norbide or several mixture wherein.
6. intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent according to claim 1, is characterized in that the phenolic compound described in step 1 is a kind of in phenol, methylphenol, pyrocatechol, Resorcinol, alkyl resorcinol, Phloroglucinol, Resorcinol, bisphenol-A, bisphenol-f and xenol or several mixture wherein; Aldehyde compound described in step 1 is a kind of in formaldehyde, paraformaldehyde, furfural, salicylic aldehyde and acetaldehyde or several mixture wherein.
7. intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent according to claim 1, is characterized in that the catalyzer described in 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 neutralized verdigris or several mixture wherein.
8. intermediate temperature setting type high temperature resistance phenolic aldehyde tackiness agent according to claim 1, it is characterized in that the mixing organosilane monomer described in step 2 is hexamethyldisiloxane, hexamethyldisilazane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, Union carbide A-162, the 3,5-dimethylphenyl Ethoxysilane, methyltrimethoxy silane, the methyl ethylene diethoxy silane, methyl ethylene dimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, the phenylbenzene diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, γ-aminopropyl triethoxysilane, β-(3, 4-epoxy cyclohexyl) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, several mixture in tetraethoxysilane and dodecyl triethoxyl silane.
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2012
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