CN104877583A - High-temperature-resistant phenolic unsupported structural adhesive film and preparation method thereof - Google Patents
High-temperature-resistant phenolic unsupported structural adhesive film and preparation method thereof Download PDFInfo
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- CN104877583A CN104877583A CN201510333468.7A CN201510333468A CN104877583A CN 104877583 A CN104877583 A CN 104877583A CN 201510333468 A CN201510333468 A CN 201510333468A CN 104877583 A CN104877583 A CN 104877583A
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Abstract
The invention discloses a high-temperature-resistant phenolic unsupported structural adhesive film and a preparation method thereof, relates to a phenolic adhesive film and a preparation method thereof, and aims to solve the problems that the existing phenolic structural adhesive film is complex in preparation process, weak in high temperature resistance and poor in toughness. The high-temperature-resistant phenolic unsupported structural adhesive film is prepared from the following raw materials in part by weight: 70-100 parts of toughened silicone phenolic resin, 10-25 parts of fiber reinforcement material, 5-35 parts of film-forming agent, 30-70 parts of heat-resistant filler and 1-3 parts of compatibilizer. The preparation method comprises the following steps: firstly, the raw materials are weighed; secondly, the toughened silicone phenolic resin, a film former and the heat-resistant filler are mixed in an open mill to obtain a mixture, and then the fiber reinforcement material and the compatibilizer are added into the mixture and are mixed in the open mill to obtain a mixed material; the mixed material is calendered by using a two-roll calender to obtain the high-temperature-resistant phenolic unsupported structural adhesive film. According to the invention, the high-temperature-resistant phenolic unsupported structural adhesive film can be obtained.
Description
Technical field
The present invention relates to a kind of phenolic aldehyde glued membrane and preparation method thereof.
Background technology
Sqtructural adhesive is the tackiness agent that a class is applied on stressed member, has higher intensity, its adhesively bonded joint can bear with by the suitable load of the sticky strength of materials.Require that tackiness agent itself has the performances such as excellent thermotolerance, media-resistant, resistance to atmospheric aging simultaneously.
A kind of form very important in heat-resistant structural adhesive is glued membrane.In existing high temperature resistant glued membrane, most widely used is modified epoxy glued membrane, but the thermostability of this kind of glued membrane is poor, and upper limit use temperature can only reach 200 DEG C ~ 250 DEG C, is difficult to meet service requirements under the high temperature conditions.Modified phenolic resin adhesive has excellent heat resistance, but little with the report of glued membrane form application.Patent CN201410772580.6 discloses a kind of preparation method of high temperature resistant glued membrane, but glued membrane adopts solution coating process to make, complex process, contaminate environment, and heatproof is at about 400 DEG C, is difficult to meet higher heatproof requirement.
Summary of the invention
The present invention will solve existing phenolic structure glued membrane complicated process of preparation, resistance to elevated temperatures is not enough and the problem of poor toughness, provides a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive and preparation method thereof.
A kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive is prepared from by 70 parts ~ 100 parts toughness silicon resol, 10 parts ~ 25 parts fiber reinforcements, 5 parts ~ 35 parts membrane-forming agents, 30 parts ~ 70 parts heat-resistant fillers and 1 part ~ 3 parts expanding materials by weight.
A preparation method for high temperature resistance phenolic aldehyde carrier free structural film adhesive, completes according to the following steps:
One, weighing: take 70 parts ~ 100 parts toughness silicon resol, 10 parts ~ 25 parts fiber reinforcements, 5 parts ~ 35 parts membrane-forming agents, 30 parts ~ 70 parts heat-resistant fillers and 1 part ~ 3 parts expanding materials by weight;
Toughness silicon resol described in step one is prepared by the following method:
1. 70 parts ~ 130 parts phenolic compounds, 70 parts ~ 150 parts aldehyde compounds, 0.5 part ~ 5 parts catalyzer, 50 parts ~ 100 parts organosilicons, 30 parts ~ 50 parts solvents and 10 parts ~ 25 parts paracrils, are taken by weight;
Step 1. described in phenolic compound be a kind of or wherein several mixture in phenol, methylphenol, partially amino-phenol, pyrocatechol, Resorcinol, alkyl resorcinol, Phloroglucinol, Resorcinol, bisphenol-A, bisphenol-f and xenol;
Step 1. described in aldehyde compound be a kind of or wherein several mixture in formaldehyde, paraformaldehyde, furfural, salicylic aldehyde, acetaldehyde;
Step 1. described in catalyzer be a kind of or wherein several mixture in hydrochloric acid, oxalic acid, acetic acid, tosic acid, benzene sulfonyl chloride, Tosyl chloride, p-chlorobenzenesulfonic acid, zinc acetate, zinc oxide, sodium hydroxide and potassium hydroxide;
Step 1. described in organosilicon be hexamethyldisiloxane, hexamethyldisilazane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, Union carbide A-162, 3,5-dimethylphenyl Ethoxysilane, methyltrimethoxy silane, methyl vinyl diethoxysilane, methylvinyldimethoxysilane, tetramethyl divinyl silane, vinyltriethoxysilane, vinyltrimethoxy silane, diphenyl diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, γ-aminopropyl triethoxysilane, β-(3, 4-epoxy cyclohexyl) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, a kind of or wherein several mixture in tetraethoxysilane and dodecyl triethoxysilane,
Step 1. described in solvent be the mixture of one or more in ethyl acetate, acetone, butanone, methylethylketone, dimethylbenzene, toluene, methylene dichloride, mibk and butylacetate;
Step 1. described in paracril in acrylonitrile content be 24% ~ 42%, the mooney viscosity of paracril is 50M ~ 77M;
2., by step 1. in 70 parts ~ 130 parts phenolic compounds, 70 parts ~ 150 parts aldehyde compounds and 0.5 part ~ 5 parts catalyzer that take join in container, 3h ~ 6h is reacted again at temperature is 60 DEG C ~ 100 DEG C, dewater again, obtain the reactant A that viscosity is 0.5 ten thousand centipoises ~ 10,000 centipoises;
3., by step 1. in 50 parts ~ 100 parts organosilicons taking join step 2. in the viscosity that obtains be in the reactant A of 0.5 ten thousand centipoises ~ 10,000 centipoises, then react 2h ~ 5h at temperature is 60 DEG C ~ 80 DEG C, obtain reactant B;
4., by step 1. in 10 parts ~ 25 parts paracrils taking be dissolved in 30 parts ~ 50 parts solvents, obtain nitrile rubber solution, again nitrile rubber solution is joined in reactant B, 1h ~ 3h is reacted again at temperature is 80 DEG C ~ 100 DEG C, at temperature is 100 DEG C ~ 120 DEG C, carry out underpressure distillation 30min ~ 60min again, obtain toughness silicon resol;
Step 4. described in the viscosity of toughness silicon resol be 30,000 centipoises ~ 100,000 centipoises;
Heat-resistant filler described in step one is the mixture of one or more in mica powder, antimonous oxide, talcum powder, aluminum oxide, silicon-dioxide, wollastonite, norbide, boron nitride, kaolin;
Expanding material described in step one is one or more mixtures formed in any proportion in γ-aminopropyl triethoxysilane, vinyltriethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, monoalkoxy unsaturated fatty acids titanic acid ester, Di(dioctylpyrophosphato) ethylene titanate;
Two, be 25 DEG C ~ 50 DEG C by 70 parts that take in step one ~ 100 parts toughness silicon resol, 5 parts ~ 35 parts membrane-forming agents and 30 parts ~ 70 parts heat-resistant fillers in temperature, rotating speed be 50r/min ~ 180r/min mill on mixing 10min ~ 40min, add 10 parts ~ 25 parts fiber reinforcements and 1 part ~ 3 parts expanding materials that take in step one again, it is 35 DEG C ~ 50 DEG C in temperature again, rotating speed be 50r/min ~ 180r/min mill on mixing 15min ~ 30min, obtain mixing after material; Use two roll calender to be rolled at temperature is 30 DEG C ~ 70 DEG C by the material after mixing, obtain high temperature resistance phenolic aldehyde carrier free structural film adhesive;
Principle of the present invention:
The present invention, by Effect of Organosilicon-modified Phenol-formaldehyde Resin, improves toughness and the resistance to elevated temperatures of high temperature resistance phenolic aldehyde carrier free structural film adhesive; In building-up process, introduce Macromolecule acrylonitrile rubber simultaneously participate in reaction, Effect of Organosilicon-modified Phenol-formaldehyde Resin is carried out further toughness reinforcing; With obtained toughness silicon resol for matrix, being skeleton with fiber reinforcement, is that membrane-forming agent is aided with heat-resistant filler and expanding material simultaneously with high performance engineering resins, and the mode of prolonging by opening the blended and two roll-in of refining has finally prepared high temperature phenolic aldehyde carrier free structural film adhesive.
Advantage of the present invention:
One, the present invention introduces and has flexibility and the silicone segments of heat resistance excellence in the structure of resol, improves toughness and the temperature tolerance of resol simultaneously, obtains the Effect of Organosilicon-modified Phenol-formaldehyde Resin of excellent performance;
Two, in Effect of Organosilicon-modified Phenol-formaldehyde Resin, add Macromolecule acrylonitrile rubber participate in reaction, do further raising from the toughness of molecule rank to Effect of Organosilicon-modified Phenol-formaldehyde Resin; Because the consumption of paracril is little, very little on the heat resistance impact of Effect of Organosilicon-modified Phenol-formaldehyde Resin while toughness reinforcing; The present invention prepares the matrix resin that high temperature phenolic aldehyde carrier free structural film adhesive uses and has good toughness and temperature tolerance;
Three, the present invention is on the basis of obtained toughness silicon resol, the blended fiber reinforcement of heat-resisting long and short fiber is utilized to provide forming skeleton for toughness silicon resol, be simultaneously membrane-forming agent with high performance engineering resins, heat-resistant filler is additive, silane compound and titanate compound are expanding material, adopt and simply open the mode that the blended and two roll-in of refining prolongs and prepare toughness better, and there is the high temperature phenolic aldehyde carrier free structural film adhesive of excellent high temperature resistance performance; High temperature phenolic aldehyde carrier free structural film adhesive prepared by the present invention has excellent resistance toheat and bonding strength, is expected to obtain application in the manufacture of aerospace field refractory metal or matrix material;
Four, the initial decomposition temperature of high temperature resistance phenolic aldehyde carrier free structural film adhesive that prepared by the present invention corresponds to 485 DEG C ~ 490 DEG C, and 485 DEG C ~ 780 DEG C is the main section of thermal weight loss; Temperature reaches maximum weightlessness when rising to 764 DEG C ~ 780 DEG C, residual heavy be 59.4% ~ 62%; Temperature continues to raise, and high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by the present invention is residual heavyly no longer to be reduced, and has lasting increase on the contrary, when temperature is 1000 DEG C residual heavy be 62.2% ~ 64%;
Five, the present invention is residual heavy by 90% ~ 91% during ablation 10h under 450 DEG C of high temperature, and the ablation time tends towards stability more than weight-loss curve after 14h; Experience 20h ablation after, high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by the present invention still can keep 80% ~ 81% residual heavy;
Six, bonding No. 45 steel discs of high temperature resistance phenolic aldehyde carrier free structural film adhesive using the present invention to prepare, when 25 DEG C, shearing resistance is 12.9MPa ~ 14MPa, and shearing resistance when 450 DEG C is 4.3MPa ~ 5MPa, and shearing resistance when 600 DEG C is 2.1MPa ~ 2.6MPa.
The present invention can obtain a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive.
Accompanying drawing explanation
Fig. 1 is the thermogravimetric curve figure of high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by embodiment one;
Fig. 2 is constant temperature weight-loss curve at the high temperature resistance phenolic aldehyde carrier free structural film adhesive 450 DEG C of embodiment one preparation.
Embodiment
Embodiment one: present embodiment is that a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive is prepared from by 70 parts ~ 100 parts toughness silicon resol, 10 parts ~ 25 parts fiber reinforcements, 5 parts ~ 35 parts membrane-forming agents, 30 parts ~ 70 parts heat-resistant fillers and 1 part ~ 3 parts expanding materials by weight.
The principle of present embodiment:
Present embodiment, by Effect of Organosilicon-modified Phenol-formaldehyde Resin, improves toughness and the resistance to elevated temperatures of high temperature resistance phenolic aldehyde carrier free structural film adhesive; In building-up process, introduce Macromolecule acrylonitrile rubber simultaneously participate in reaction, Effect of Organosilicon-modified Phenol-formaldehyde Resin is carried out further toughness reinforcing; With obtained toughness silicon resol for matrix, being skeleton with fiber reinforcement, is that membrane-forming agent is aided with heat-resistant filler and expanding material simultaneously with high performance engineering resins, and the mode of prolonging by opening the blended and two roll-in of refining has finally prepared high temperature phenolic aldehyde carrier free structural film adhesive.
The advantage of present embodiment:
One, present embodiment is introduced and is had flexibility and the silicone segments of heat resistance excellence in the structure of resol, improves toughness and the temperature tolerance of resol simultaneously, obtains the Effect of Organosilicon-modified Phenol-formaldehyde Resin of excellent performance;
Two, in Effect of Organosilicon-modified Phenol-formaldehyde Resin, add Macromolecule acrylonitrile rubber participate in reaction, do further raising from the toughness of molecule rank to Effect of Organosilicon-modified Phenol-formaldehyde Resin; Because the consumption of paracril is little, very little on the heat resistance impact of Effect of Organosilicon-modified Phenol-formaldehyde Resin while toughness reinforcing; Present embodiment is prepared the matrix resin that high temperature phenolic aldehyde carrier free structural film adhesive uses and is had good toughness and temperature tolerance;
Three, present embodiment is on the basis of obtained toughness silicon resol, the blended fiber reinforcement of heat-resisting long and short fiber is utilized to provide forming skeleton for toughness silicon resol, be simultaneously membrane-forming agent with high performance engineering resins, heat-resistant filler is additive, silane compound and titanate compound are expanding material, adopt and simply open the mode that the blended and two roll-in of refining prolongs and prepare toughness better, and there is the high temperature phenolic aldehyde carrier free structural film adhesive of excellent high temperature resistance performance; High temperature phenolic aldehyde carrier free structural film adhesive prepared by present embodiment has excellent resistance toheat and bonding strength, is expected to obtain application in the manufacture of aerospace field refractory metal or matrix material;
Four, the initial decomposition temperature of high temperature resistance phenolic aldehyde carrier free structural film adhesive that prepared by present embodiment corresponds to 485 DEG C ~ 490 DEG C, and 485 DEG C ~ 780 DEG C is the main section of thermal weight loss; Temperature reaches maximum weightlessness when rising to 764 DEG C ~ 780 DEG C, residual heavy be 59.4% ~ 62%; Temperature continues to raise, and the high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared of present embodiment is residual heavyly no longer to be reduced, and has lasting increase on the contrary, when temperature is 1000 DEG C residual heavy be 62.2% ~ 64%;
Five, present embodiment is residual heavy by 90% ~ 91% during ablation 10h under 450 DEG C of high temperature, and the ablation time tends towards stability more than weight-loss curve after 14h; Experience 20h ablation after, high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by present embodiment still can keep 80% ~ 81% residual heavy;
Six, bonding No. 45 steel discs of high temperature resistance phenolic aldehyde carrier free structural film adhesive using present embodiment to prepare, when 25 DEG C, shearing resistance is 12.9MPa ~ 14MPa, and shearing resistance when 450 DEG C is 4.3MPa ~ 5MPa, and shearing resistance when 600 DEG C is 2.1MPa ~ 2.6MPa.
Present embodiment can obtain a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive.
Embodiment two: present embodiment and embodiment one difference are: described toughness silicon resol is prepared by the following method:
1. 70 parts ~ 130 parts phenolic compounds, 70 parts ~ 150 parts aldehyde compounds, 0.5 part ~ 5 parts catalyzer, 50 parts ~ 100 parts organosilicons, 30 parts ~ 50 parts solvents and 10 parts ~ 25 parts paracrils, are taken by weight;
Step 1. described in phenolic compound be a kind of or wherein several mixture in phenol, methylphenol, partially amino-phenol, pyrocatechol, Resorcinol, alkyl resorcinol, Phloroglucinol, Resorcinol, bisphenol-A, bisphenol-f and xenol;
Step 1. described in aldehyde compound be a kind of or wherein several mixture in formaldehyde, paraformaldehyde, furfural, salicylic aldehyde, acetaldehyde;
Step 1. described in catalyzer be a kind of or wherein several mixture in hydrochloric acid, oxalic acid, acetic acid, tosic acid, benzene sulfonyl chloride, Tosyl chloride, p-chlorobenzenesulfonic acid, zinc acetate, zinc oxide, sodium hydroxide and potassium hydroxide;
Step 1. described in organosilicon be hexamethyldisiloxane, hexamethyldisilazane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, Union carbide A-162, 3,5-dimethylphenyl Ethoxysilane, methyltrimethoxy silane, methyl vinyl diethoxysilane, methylvinyldimethoxysilane, tetramethyl divinyl silane, vinyltriethoxysilane, vinyltrimethoxy silane, diphenyl diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, γ-aminopropyl triethoxysilane, β-(3, 4-epoxy cyclohexyl) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, a kind of or wherein several mixture in tetraethoxysilane and dodecyl triethoxysilane,
Step 1. described in solvent be the mixture of one or more in ethyl acetate, acetone, butanone, methylethylketone, dimethylbenzene, toluene, methylene dichloride, mibk and butylacetate;
Step 1. described in paracril in acrylonitrile content be 24% ~ 42%, the mooney viscosity of paracril is 50M ~ 77M;
2., by step 1. in 70 parts ~ 130 parts phenolic compounds, 70 parts ~ 150 parts aldehyde compounds and 0.5 part ~ 5 parts catalyzer that take join in container, 3h ~ 6h is reacted again at temperature is 60 DEG C ~ 100 DEG C, dewater again, obtain the reactant A that viscosity is 0.5 ten thousand centipoises ~ 10,000 centipoises;
3., by step 1. in 50 parts ~ 100 parts organosilicons taking join step 2. in the viscosity that obtains be in the reactant A of 0.5 ten thousand centipoises ~ 10,000 centipoises, then react 2h ~ 5h at temperature is 60 DEG C ~ 80 DEG C, obtain reactant B;
4., by step 1. in 10 parts ~ 25 parts paracrils taking be dissolved in 30 parts ~ 50 parts solvents, obtain nitrile rubber solution, again nitrile rubber solution is joined in reactant B, 1h ~ 3h is reacted again at temperature is 80 DEG C ~ 100 DEG C, at temperature is 100 DEG C ~ 120 DEG C, carry out underpressure distillation 30min ~ 60min again, obtain toughness silicon resol;
Step 4. described in the viscosity of toughness silicon resol be 30,000 centipoises ~ 100,000 centipoises.Other steps are identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two difference is: described fiber reinforcement by length be the fiber of 0.1mm ~ 1.0mm, length be the fiber of 1.0mm ~ 5mm and length is the fibrous of 5mm ~ 20mm; In described fiber reinforcement, length is the massfraction of the fiber of 0.1mm ~ 1.0mm is 20% ~ 40%, and length is the massfraction of the fiber of 1.0mm ~ 5mm is 30% ~ 60%, and length is the massfraction of the fiber of 5mm ~ 20mm is 10% ~ 35%; Described fiber reinforcement is mineral fibre, glass fibre or ceramic fiber; Wherein, described mineral fibre is asbestos, and described glass fibre is alkali free glass fibre, and described ceramic fiber is alumina-silicate ceramic fibre.Other steps are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: described membrane-forming agent is the mixture of one or more in polyarylsulphone, polyethersulfone, poly (arylene ether nitrile), polybenzimidazole, polyetherimide, thermoplastic polyimide, polyetherketone and polyether-ether-ketone.Other steps are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: described heat-resistant filler is the mixture of one or more in mica powder, antimonous oxide, talcum powder, aluminum oxide, silicon-dioxide, wollastonite, norbide, boron nitride, kaolin.Other steps are identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five difference is: described expanding material is one or more mixtures formed in any proportion in γ-aminopropyl triethoxysilane, vinyltriethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, monoalkoxy unsaturated fatty acids titanic acid ester, Di(dioctylpyrophosphato) ethylene titanate.Other steps are identical with embodiment one to five.
Embodiment seven: present embodiment is that a kind of preparation method of high temperature resistance phenolic aldehyde carrier free structural film adhesive completes according to the following steps:
One, weighing: take 70 parts ~ 100 parts toughness silicon resol, 10 parts ~ 25 parts fiber reinforcements, 5 parts ~ 35 parts membrane-forming agents, 30 parts ~ 70 parts heat-resistant fillers and 1 part ~ 3 parts expanding materials by weight;
Toughness silicon resol described in step one is prepared by the following method:
1. 70 parts ~ 130 parts phenolic compounds, 70 parts ~ 150 parts aldehyde compounds, 0.5 part ~ 5 parts catalyzer, 50 parts ~ 100 parts organosilicons, 30 parts ~ 50 parts solvents and 10 parts ~ 25 parts paracrils, are taken by weight;
Step 1. described in phenolic compound be a kind of or wherein several mixture in phenol, methylphenol, partially amino-phenol, pyrocatechol, Resorcinol, alkyl resorcinol, Phloroglucinol, Resorcinol, bisphenol-A, bisphenol-f and xenol;
Step 1. described in aldehyde compound be a kind of or wherein several mixture in formaldehyde, paraformaldehyde, furfural, salicylic aldehyde, acetaldehyde;
Step 1. described in catalyzer be a kind of or wherein several mixture in hydrochloric acid, oxalic acid, acetic acid, tosic acid, benzene sulfonyl chloride, Tosyl chloride, p-chlorobenzenesulfonic acid, zinc acetate, zinc oxide, sodium hydroxide and potassium hydroxide;
Step 1. described in organosilicon be hexamethyldisiloxane, hexamethyldisilazane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, Union carbide A-162, 3,5-dimethylphenyl Ethoxysilane, methyltrimethoxy silane, methyl vinyl diethoxysilane, methylvinyldimethoxysilane, tetramethyl divinyl silane, vinyltriethoxysilane, vinyltrimethoxy silane, diphenyl diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, γ-aminopropyl triethoxysilane, β-(3, 4-epoxy cyclohexyl) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, a kind of or wherein several mixture in tetraethoxysilane and dodecyl triethoxysilane,
Step 1. described in solvent be the mixture of one or more in ethyl acetate, acetone, butanone, methylethylketone, dimethylbenzene, toluene, methylene dichloride, mibk and butylacetate;
Step 1. described in paracril in acrylonitrile content be 24% ~ 42%, the mooney viscosity of paracril is 50M ~ 77M;
2., by step 1. in 70 parts ~ 130 parts phenolic compounds, 70 parts ~ 150 parts aldehyde compounds and 0.5 part ~ 5 parts catalyzer that take join in container, 3h ~ 6h is reacted again at temperature is 60 DEG C ~ 100 DEG C, dewater again, obtain the reactant A that viscosity is 0.5 ten thousand centipoises ~ 10,000 centipoises;
3., by step 1. in 50 parts ~ 100 parts organosilicons taking join step 2. in the viscosity that obtains be in the reactant A of 0.5 ten thousand centipoises ~ 10,000 centipoises, then react 2h ~ 5h at temperature is 60 DEG C ~ 80 DEG C, obtain reactant B;
4., by step 1. in 10 parts ~ 25 parts paracrils taking be dissolved in 30 parts ~ 50 parts solvents, obtain nitrile rubber solution, again nitrile rubber solution is joined in reactant B, 1h ~ 3h is reacted again at temperature is 80 DEG C ~ 100 DEG C, at temperature is 100 DEG C ~ 120 DEG C, carry out underpressure distillation 30min ~ 60min again, obtain toughness silicon resol;
Step 4. described in the viscosity of toughness silicon resol be 30,000 centipoises ~ 100,000 centipoises;
Heat-resistant filler described in step one is the mixture of one or more in mica powder, antimonous oxide, talcum powder, aluminum oxide, silicon-dioxide, wollastonite, norbide, boron nitride, kaolin;
Expanding material described in step one is one or more mixtures formed in any proportion in γ-aminopropyl triethoxysilane, vinyltriethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, monoalkoxy unsaturated fatty acids titanic acid ester, Di(dioctylpyrophosphato) ethylene titanate;
Two, be 25 DEG C ~ 50 DEG C by 70 parts that take in step one ~ 100 parts toughness silicon resol, 5 parts ~ 35 parts membrane-forming agents and 30 parts ~ 70 parts heat-resistant fillers in temperature, rotating speed be 50r/min ~ 180r/min mill on mixing 10min ~ 40min, add 10 parts ~ 25 parts fiber reinforcements and 1 part ~ 3 parts expanding materials that take in step one again, it is 35 DEG C ~ 50 DEG C in temperature again, rotating speed be 50r/min ~ 180r/min mill on mixing 15min ~ 30min, obtain mixing after material; Use two roll calender to be rolled at temperature is 30 DEG C ~ 70 DEG C by the material after mixing, obtain high temperature resistance phenolic aldehyde carrier free structural film adhesive.
The principle of present embodiment:
Present embodiment, by Effect of Organosilicon-modified Phenol-formaldehyde Resin, improves toughness and the resistance to elevated temperatures of high temperature resistance phenolic aldehyde carrier free structural film adhesive; In building-up process, introduce Macromolecule acrylonitrile rubber simultaneously participate in reaction, Effect of Organosilicon-modified Phenol-formaldehyde Resin is carried out further toughness reinforcing; With obtained toughness silicon resol for matrix, being skeleton with fiber reinforcement, is that membrane-forming agent is aided with heat-resistant filler and expanding material simultaneously with high performance engineering resins, and the mode of prolonging by opening the blended and two roll-in of refining has finally prepared high temperature phenolic aldehyde carrier free structural film adhesive.
The advantage of present embodiment:
One, present embodiment is introduced and is had flexibility and the silicone segments of heat resistance excellence in the structure of resol, improves toughness and the temperature tolerance of resol simultaneously, obtains the Effect of Organosilicon-modified Phenol-formaldehyde Resin of excellent performance;
Two, in Effect of Organosilicon-modified Phenol-formaldehyde Resin, add Macromolecule acrylonitrile rubber participate in reaction, do further raising from the toughness of molecule rank to Effect of Organosilicon-modified Phenol-formaldehyde Resin; Because the consumption of paracril is little, very little on the heat resistance impact of Effect of Organosilicon-modified Phenol-formaldehyde Resin while toughness reinforcing; Present embodiment is prepared the matrix resin that high temperature phenolic aldehyde carrier free structural film adhesive uses and is had good toughness and temperature tolerance;
Three, present embodiment is on the basis of obtained toughness silicon resol, the blended fiber reinforcement of heat-resisting long and short fiber is utilized to provide forming skeleton for toughness silicon resol, be simultaneously membrane-forming agent with high performance engineering resins, heat-resistant filler is additive, silane compound and titanate compound are expanding material, adopt and simply open the mode that the blended and two roll-in of refining prolongs and prepare toughness better, and there is the high temperature phenolic aldehyde carrier free structural film adhesive of excellent high temperature resistance performance; High temperature phenolic aldehyde carrier free structural film adhesive prepared by present embodiment has excellent resistance toheat and bonding strength, is expected to obtain application in the manufacture of aerospace field refractory metal or matrix material;
Four, the initial decomposition temperature of high temperature resistance phenolic aldehyde carrier free structural film adhesive that prepared by present embodiment corresponds to 485 DEG C ~ 490 DEG C, and 485 DEG C ~ 780 DEG C is the main section of thermal weight loss; Temperature reaches maximum weightlessness when rising to 764 DEG C ~ 780 DEG C, residual heavy be 59.4% ~ 62%; Temperature continues to raise, and the high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared of present embodiment is residual heavyly no longer to be reduced, and has lasting increase on the contrary, when temperature is 1000 DEG C residual heavy be 62.2% ~ 64%;
Five, present embodiment is residual heavy by 90% ~ 91% during ablation 10h under 450 DEG C of high temperature, and the ablation time tends towards stability more than weight-loss curve after 14h; Experience 20h ablation after, high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by present embodiment still can keep 80% ~ 81% residual heavy;
Six, bonding No. 45 steel discs of high temperature resistance phenolic aldehyde carrier free structural film adhesive using present embodiment to prepare, when 25 DEG C, shearing resistance is 12.9MPa ~ 14MPa, and shearing resistance when 450 DEG C is 4.3MPa ~ 5MPa, and shearing resistance when 600 DEG C is 2.1MPa ~ 2.6MPa.
Present embodiment can obtain a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive.
Embodiment eight: the difference of present embodiment and embodiment seven is: the membrane-forming agent described in step one is the mixture of one or more in polyarylsulphone, polyethersulfone, poly (arylene ether nitrile), polybenzimidazole, polyetherimide, thermoplastic polyimide, polyetherketone and polyether-ether-ketone.Other steps are identical with embodiment seven.
Embodiment nine: one of present embodiment and embodiment seven to eight difference is: the fiber reinforcement described in step one by length be the fiber of 0.1mm ~ 1.0mm, length be the fiber of 1.0mm ~ 5mm and length is the fibrous of 5mm ~ 20mm; In described fiber reinforcement, length is the massfraction of the fiber of 0.1mm ~ 1.0mm is 20% ~ 40%, and length is the massfraction of the fiber of 1.0mm ~ 5mm is 30% ~ 60%, and length is the massfraction of the fiber of 5mm ~ 20mm is 10% ~ 35%; Described fiber reinforcement is mineral fibre, glass fibre or ceramic fiber; Wherein, described mineral fibre is asbestos, and described glass fibre is alkali free glass fibre, and described ceramic fiber is alumina-silicate ceramic fibre.Other steps are identical with embodiment seven to eight.
Embodiment ten: one of present embodiment and embodiment seven to nine difference is: the thickness of the high temperature resistance phenolic aldehyde carrier free structural film adhesive described in step 2 is 0.3mm ~ 0.5mm.Other steps are identical with embodiment seven to nine.
Embodiment 11: one of present embodiment and embodiment seven to ten difference is: take 100 parts of toughness silicon resol, 15 parts of fiber reinforcements, 25 parts of membrane-forming agents, 30 parts of heat-resistant fillers and 2 parts of expanding materials in step one by weight.Other steps are identical with embodiment seven to ten.
Embodiment 12: one of present embodiment and embodiment seven to ten one difference is: take 100 parts of toughness silicon resol, 20 parts of fiber reinforcements, 15 parts of membrane-forming agents, 40 parts of heat-resistant fillers and 2 parts of expanding materials in step one by weight.Other steps are identical with embodiment seven to ten one.
Embodiment 13: one of present embodiment and embodiment seven to ten two difference is: be 40 DEG C by the 100 parts of toughness silicon resol taken in step one, 25 parts of membrane-forming agents and 30 parts of heat-resistant fillers in temperature in step 2, rotating speed be 60r/min mill on mixing 30min, add the 15 parts of fiber reinforcements and 2 parts of expanding materials that take in step one again, it is 40 DEG C in temperature again, rotating speed be 120r/min mill on mixing 20min, obtain mixing after material; Use two roll calender to be roll at the temperature of 70 DEG C in temperature by the material after mixing, obtain high temperature resistance phenolic aldehyde carrier free structural film adhesive.Other steps are identical with embodiment seven to ten two.
Embodiment 14: one of present embodiment and embodiment seven to ten three difference is: be 40 DEG C by the 100 parts of toughness silicon resol taken in step one, 15 parts of membrane-forming agents and 40 parts of heat-resistant fillers in temperature in step 2, rotating speed be 60r/min mill on mixing 30min, add the 20 parts of fiber reinforcements and 2 parts of expanding materials that take in step one again, it is 40 DEG C in temperature again, rotating speed be 120r/min mill on mixing 20min, obtain mixing after material; Use two roll calender to be roll at the temperature of 70 DEG C in temperature by the material after mixing, obtain high temperature resistance phenolic aldehyde carrier free structural film adhesive.Other steps are identical with embodiment seven to ten three.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one: a kind of preparation method of high temperature resistance phenolic aldehyde carrier free structural film adhesive, completes according to the following steps:
One, weighing: take 100 parts of toughness silicon resol, 15 parts of fiber reinforcements, 25 parts of membrane-forming agents, 30 parts of heat-resistant fillers and 2 parts of expanding materials by weight;
Toughness silicon resol described in step one is prepared by the following method:
1. 100 parts of phenolic compounds, 130 parts of aldehyde compounds, 2 parts of catalyzer, 50 parts of organosilicons, 50 parts of solvents and 10 parts of paracrils, are taken by weight;
Step 1. described in phenolic compound be the mixture of phenol and Resorcinol; Described phenol and the mass ratio of Resorcinol are 10:1;
Step 1. described in aldehyde compound be formaldehyde;
Step 1. described in catalyzer be zinc oxide;
Step 1. described in organosilicon be the mixture of Union carbide A-162,3,5-dimethylphenyl Ethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, tetraethoxysilane and dodecyl triethoxysilane; The ratio of described Union carbide A-162,3,5-dimethylphenyl Ethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, tetraethoxysilane and dodecyl triethoxysilane is 10:5:5:3:2:5;
Step 1. described in solvent be the mixture of ethyl acetate, acetone and butanone; The ratio of described ethyl acetate, acetone and butanone is 8:2:3;
Step 1. described in paracril in acrylonitrile content be 42%, the mooney viscosity of paracril is 70M;
2., by step 1. in the 100 parts of phenolic compounds, 130 parts of aldehyde compounds and the 2 parts of catalyzer that take join in container, then react 3h at temperature is 70 DEG C, then dewater, obtain the reactant A that viscosity is 10,000 centipoises;
3., by step 1. in 50 parts of organosilicons taking join step 2. in the viscosity that obtains be in the reactant A of 10,000 centipoises, then react 3h at temperature is 70 DEG C, obtain reactant B;
4., by step 1. in 10 parts of paracrils taking be dissolved in 50 parts of solvents, obtain nitrile rubber solution, then nitrile rubber solution is joined in reactant B, then react 3h at temperature is 90 DEG C, at temperature is 120 DEG C, carry out underpressure distillation 30min again, obtain toughness silicon resol;
Step 4. described in the viscosity of toughness silicon resol be 4.8 ten thousand centipoises;
Heat-resistant filler described in step one is mica powder, antimonous oxide and kaolinic mixture; Described mica powder, antimonous oxide and kaolinic ratio are 4:3:3;
Expanding material described in step one is the mixture of vinyltriethoxysilane, monoalkoxy unsaturated fatty acids titanic acid ester and Di(dioctylpyrophosphato) ethylene titanate; The mass ratio of described vinyltriethoxysilane, monoalkoxy unsaturated fatty acids titanic acid ester and Di(dioctylpyrophosphato) ethylene titanate is 3:1:1;
Membrane-forming agent described in step one is the mixture of polyarylsulphone and polyethersulfone; Described polyarylsulphone and the mass ratio of polyethersulfone are 7:3;
Fiber reinforcement described in step one by length be the fiber of 0.1mm ~ 1.0mm, length be the fiber of 1.0mm ~ 5mm and length is the fibrous of 5mm ~ 20mm; In described fiber reinforcement, length is the massfraction of the fiber of 0.1mm ~ 1.0mm is 25%, and length is the massfraction of the fiber of 1.0mm ~ 5mm is 50%, and length is the massfraction of the fiber of 5mm ~ 20mm is 25%; Described fiber reinforcement is mineral fibre; Wherein, described mineral fibre is asbestos;
Two, be 40 DEG C by the 100 parts of toughness silicon resol taken in step one, 25 parts of membrane-forming agents and 30 parts of heat-resistant fillers in temperature, rotating speed be 60r/min mill on mixing 30min, add the 15 parts of fiber reinforcements and 2 parts of expanding materials that take in step one again, it is 40 DEG C in temperature again, rotating speed be 120r/min mill on mixing 20min, obtain mixing after material; Use two roll calender to be rolled at temperature is 70 DEG C by the material after mixing, obtain high temperature resistance phenolic aldehyde carrier free structural film adhesive;
The thickness of the high temperature resistance phenolic aldehyde carrier free structural film adhesive described in step 2 is 0.3mm.
Test high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by embodiment one in air atmosphere, heat-up rate is 10 DEG C/min; As shown in Figure 1;
Fig. 1 is the thermogravimetric curve figure of high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by embodiment one; As can be seen from Figure 1, the initial decomposition temperature of high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by embodiment one corresponds to 485 DEG C, and 485 DEG C ~ 774 DEG C is the main section of thermal weight loss; Temperature reaches maximum weightlessness when rising to 774 DEG C, residual heavy be 59.4%; Temperature continues to raise, and the high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared of embodiment one is residual heavyly no longer to be reduced, and has lasting increase on the contrary, when temperature is 1000 DEG C residual heavy be 62.2%.
Fig. 2 is the weight-loss curve of high temperature resistance phenolic aldehyde carrier free structural film adhesive at constant temperature 450 DEG C prepared by embodiment one; As can be seen from Figure 2, high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by embodiment one is residual heavy by 91% during ablation 10h under 450 DEG C of high temperature, and the ablation time tends towards stability more than weight-loss curve after 14h.Experience 20h ablation after, embodiment one prepare high temperature resistance phenolic aldehyde carrier free structural film adhesive still can keep 81% residual heavy.
Use bonding No. 45 steel discs of high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by embodiment one, when 25 DEG C, shearing resistance is 12.9MPa, and shearing resistance when 450 DEG C is 4.7MPa, and shearing resistance when 600 DEG C is 2.5MPa.
Embodiment two: a kind of preparation method of high temperature resistance phenolic aldehyde carrier free structural film adhesive completes according to the following steps:
One, weighing: take 100 parts of toughness silicon resol, 20 parts of fiber reinforcements, 15 parts of membrane-forming agents, 40 parts of heat-resistant fillers and 2 parts of expanding materials by weight;
Toughness silicon resol described in step one is prepared by the following method:
1. 80 parts of phenolic compounds, 100 parts of aldehyde compounds, 4 parts of catalyzer, 60 parts of organosilicons, 40 parts of solvents and 15 parts of paracrils, are taken by weight;
Step 1. described in phenolic compound be the mixture of phenol and Resorcinol; Described phenol and the mass ratio of pyrocatechol are 5:1;
Step 1. described in aldehyde compound be formaldehyde;
Step 1. described in catalyzer be sodium hydroxide;
Step 1. described in organosilicon be the mixture of 3,5-dimethylphenyl Ethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane and dodecyl triethoxysilane; Described 3,5-dimethylphenyl Ethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane and dodecyl triethoxysilane ratio are 5:5:3:2;
Step 1. described in solvent be the mixture of ethyl acetate, acetone and butanone; The ratio of described ethyl acetate, acetone and butanone is 8:3:2;
Step 1. described in paracril in acrylonitrile content be 28%, the mooney viscosity of paracril is 60M;
2., by step 1. in the 80 parts of phenolic compounds, 100 parts of aldehyde compounds and the 4 parts of catalyzer that take join in container, then react 3h at temperature is 70 DEG C, then dewater, obtain the reactant A that viscosity is 0.85 ten thousand centipoise;
3., by step 1. in 60 parts of organosilicons taking join step 2. in the viscosity that obtains be in the reactant A of 10,000 centipoises, then react 2h at temperature is 70 DEG C, obtain reactant B;
4., by step 1. in 15 parts of paracrils taking be dissolved in 40 parts of solvents, obtain nitrile rubber solution, then nitrile rubber solution is joined in reactant B, then react 2h at temperature is 90 DEG C, at temperature is 120 DEG C, carry out underpressure distillation 30min again, obtain toughness silicon resol;
Step 4. described in the viscosity of toughness silicon resol be 4.2 ten thousand centipoises;
Heat-resistant filler described in step one is the mixture of mica powder, talcum powder and boron nitride; The ratio of described mica powder, talcum powder and boron nitride is 5:3:2;
Expanding material described in step one is the mixture of sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester and Di(dioctylpyrophosphato) ethylene titanate; Described sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester and the mass ratio of Di(dioctylpyrophosphato) ethylene titanate are 3:1;
Membrane-forming agent described in step one is the mixture of poly (arylene ether nitrile) and polyethersulfone; Described poly (arylene ether nitrile) and the mass ratio of polyethersulfone are 1:1;
Fiber reinforcement described in step one by length be the fiber of 0.1mm ~ 1.0mm, length be the fiber of 1.0mm ~ 5mm and length is the fibrous of 5mm ~ 20mm; In described fiber reinforcement, length is the massfraction of the fiber of 0.1mm ~ 1.0mm is 20%, and length is the massfraction of the fiber of 1.0mm ~ 5mm is 50%, and length is the massfraction of the fiber of 5mm ~ 20mm is 30%; Described fiber reinforcement is glass fibre; Wherein, described described glass fibre is alkali free glass fibre;
Two, be 40 DEG C by the 100 parts of toughness silicon resol taken in step one, 15 parts of membrane-forming agents and 40 parts of heat-resistant fillers in temperature, rotating speed be 60r/min mill on mixing 30min, add the 20 parts of fiber reinforcements and 2 parts of expanding materials that take in step one again, it is 40 DEG C in temperature again, rotating speed be 120r/min mill on mixing 20min, obtain mixing after material; Use two roll calender to be rolled at temperature is 70 DEG C by the material after mixing, obtain high temperature resistance phenolic aldehyde carrier free structural film adhesive;
The thickness of the high temperature resistance phenolic aldehyde carrier free structural film adhesive described in step 2 is 0.33mm.
Test high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by embodiment two in air atmosphere, heat-up rate is 10 DEG C/min; The initial decomposition temperature of high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by embodiment two corresponds to 488 DEG C, and 488 DEG C ~ 764 DEG C is the main section of thermal weight loss; Temperature reaches maximum weightlessness when rising to 764 DEG C, residual heavy be 61.4%; Temperature continues to raise, and the high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared of embodiment two is residual heavyly no longer to be reduced, and has lasting increase on the contrary, when temperature is 1000 DEG C residual heavy be 63.2%;
High temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by embodiment two is residual heavy by 90% during ablation 10h under 450 DEG C of high temperature, and the ablation time tends towards stability more than weight-loss curve after 14h.Experience 20h ablation after, embodiment two prepare high temperature resistance phenolic aldehyde carrier free structural film adhesive still can keep 80% residual heavy.
Use bonding No. 45 steel discs of high temperature resistance phenolic aldehyde carrier free structural film adhesive prepared by embodiment two, when 25 DEG C, shearing resistance is 13.5MPa, and shearing resistance when 450 DEG C is 4.3MPa, and shearing resistance when 600 DEG C is 2.1MPa.
Claims (10)
1. a high temperature resistance phenolic aldehyde carrier free structural film adhesive, is characterized in that a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive is prepared from by 70 parts ~ 100 parts toughness silicon resol, 10 parts ~ 25 parts fiber reinforcements, 5 parts ~ 35 parts membrane-forming agents, 30 parts ~ 70 parts heat-resistant fillers and 1 part ~ 3 parts expanding materials by weight.
2. a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive according to claim 1, is characterized in that described toughness silicon resol is prepared by the following method:
1. 70 parts ~ 130 parts phenolic compounds, 70 parts ~ 150 parts aldehyde compounds, 0.5 part ~ 5 parts catalyzer, 50 parts ~ 100 parts organosilicons, 30 parts ~ 50 parts solvents and 10 parts ~ 25 parts paracrils, are taken by weight;
Step 1. described in phenolic compound be a kind of or wherein several mixture in phenol, methylphenol, partially amino-phenol, pyrocatechol, Resorcinol, alkyl resorcinol, Phloroglucinol, Resorcinol, bisphenol-A, bisphenol-f and xenol;
Step 1. described in aldehyde compound be a kind of or wherein several mixture in formaldehyde, paraformaldehyde, furfural, salicylic aldehyde, acetaldehyde;
Step 1. described in catalyzer be a kind of or wherein several mixture in hydrochloric acid, oxalic acid, acetic acid, tosic acid, benzene sulfonyl chloride, Tosyl chloride, p-chlorobenzenesulfonic acid, zinc acetate, zinc oxide, sodium hydroxide and potassium hydroxide;
Step 1. described in organosilicon be hexamethyldisiloxane, hexamethyldisilazane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, Union carbide A-162, 3,5-dimethylphenyl Ethoxysilane, methyltrimethoxy silane, methyl vinyl diethoxysilane, methylvinyldimethoxysilane, tetramethyl divinyl silane, vinyltriethoxysilane, vinyltrimethoxy silane, diphenyl diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, γ-aminopropyl triethoxysilane, β-(3, 4-epoxy cyclohexyl) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, a kind of or wherein several mixture in tetraethoxysilane and dodecyl triethoxysilane,
Step 1. described in solvent be the mixture of one or more in ethyl acetate, acetone, butanone, methylethylketone, dimethylbenzene, toluene, methylene dichloride, mibk and butylacetate;
Step 1. described in paracril in acrylonitrile content be 24% ~ 42%, the mooney viscosity of paracril is 50M ~ 77M;
2., by step 1. in 70 parts ~ 130 parts phenolic compounds, 70 parts ~ 150 parts aldehyde compounds and 0.5 part ~ 5 parts catalyzer that take join in container, 3h ~ 6h is reacted again at temperature is 60 DEG C ~ 100 DEG C, dewater again, obtain the reactant A that viscosity is 0.5 ten thousand centipoises ~ 10,000 centipoises;
3., by step 1. in 50 parts ~ 100 parts organosilicons taking join step 2. in the viscosity that obtains be in the reactant A of 0.5 ten thousand centipoises ~ 10,000 centipoises, then react 2h ~ 5h at temperature is 60 DEG C ~ 80 DEG C, obtain reactant B;
4., by step 1. in 10 parts ~ 25 parts paracrils taking be dissolved in 30 parts ~ 50 parts solvents, obtain nitrile rubber solution, again nitrile rubber solution is joined in reactant B, 1h ~ 3h is reacted again at temperature is 80 DEG C ~ 100 DEG C, at temperature is 100 DEG C ~ 120 DEG C, carry out underpressure distillation 30min ~ 60min again, obtain toughness silicon resol;
Step 4. described in the viscosity of toughness silicon resol be 30,000 centipoises ~ 100,000 centipoises.
3. a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive according to claim 1, it is characterized in that described fiber reinforcement by length be the fiber of 0.1mm ~ 1.0mm, length be the fiber of 1.0mm ~ 5mm and length is the fibrous of 5mm ~ 20mm; In described fiber reinforcement, length is the massfraction of the fiber of 0.1mm ~ 1.0mm is 20% ~ 40%, and length is the massfraction of the fiber of 1.0mm ~ 5mm is 30% ~ 60%, and length is the massfraction of the fiber of 5mm ~ 20mm is 10% ~ 35%; Described fiber reinforcement is mineral fibre, glass fibre or ceramic fiber; Wherein, described mineral fibre is asbestos, and described glass fibre is alkali free glass fibre, and described ceramic fiber is alumina-silicate ceramic fibre.
4. a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive according to claim 1, is characterized in that described membrane-forming agent is the mixture of one or more in polyarylsulphone, polyethersulfone, poly (arylene ether nitrile), polybenzimidazole, polyetherimide, thermoplastic polyimide, polyetherketone and polyether-ether-ketone.
5. a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive according to claim 1, is characterized in that described heat-resistant filler is the mixture of one or more in mica powder, antimonous oxide, talcum powder, aluminum oxide, silicon-dioxide, wollastonite, norbide, boron nitride, kaolin.
6. a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive according to claim 1, is characterized in that described expanding material is one or more mixtures formed in any proportion in γ-aminopropyl triethoxysilane, vinyltriethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, monoalkoxy unsaturated fatty acids titanic acid ester, Di(dioctylpyrophosphato) ethylene titanate.
7. a preparation method for high temperature resistance phenolic aldehyde carrier free structural film adhesive, is characterized in that a kind of preparation method of high temperature resistance phenolic aldehyde carrier free structural film adhesive completes according to the following steps:
One, weighing: take 70 parts ~ 100 parts toughness silicon resol, 10 parts ~ 25 parts fiber reinforcements, 5 parts ~ 35 parts membrane-forming agents, 30 parts ~ 70 parts heat-resistant fillers and 1 part ~ 3 parts expanding materials by weight;
Toughness silicon resol described in step one is prepared by the following method:
1. 70 parts ~ 130 parts phenolic compounds, 70 parts ~ 150 parts aldehyde compounds, 0.5 part ~ 5 parts catalyzer, 50 parts ~ 100 parts organosilicons, 30 parts ~ 50 parts solvents and 10 parts ~ 25 parts paracrils, are taken by weight;
Step 1. described in phenolic compound be a kind of or wherein several mixture in phenol, methylphenol, partially amino-phenol, pyrocatechol, Resorcinol, alkyl resorcinol, Phloroglucinol, Resorcinol, bisphenol-A, bisphenol-f and xenol;
Step 1. described in aldehyde compound be a kind of or wherein several mixture in formaldehyde, paraformaldehyde, furfural, salicylic aldehyde, acetaldehyde;
Step 1. described in catalyzer be a kind of or wherein several mixture in hydrochloric acid, oxalic acid, acetic acid, tosic acid, benzene sulfonyl chloride, Tosyl chloride, p-chlorobenzenesulfonic acid, zinc acetate, zinc oxide, sodium hydroxide and potassium hydroxide;
Step 1. described in organosilicon be hexamethyldisiloxane, hexamethyldisilazane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, Union carbide A-162, 3,5-dimethylphenyl Ethoxysilane, methyltrimethoxy silane, methyl vinyl diethoxysilane, methylvinyldimethoxysilane, tetramethyl divinyl silane, vinyltriethoxysilane, vinyltrimethoxy silane, diphenyl diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, γ-aminopropyl triethoxysilane, β-(3, 4-epoxy cyclohexyl) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, a kind of or wherein several mixture in tetraethoxysilane and dodecyl triethoxysilane,
Step 1. described in solvent be the mixture of one or more in ethyl acetate, acetone, butanone, methylethylketone, dimethylbenzene, toluene, methylene dichloride, mibk and butylacetate;
Step 1. described in paracril in acrylonitrile content be 24% ~ 42%, the mooney viscosity of paracril is 50M ~ 77M;
2., by step 1. in 70 parts ~ 130 parts phenolic compounds, 70 parts ~ 150 parts aldehyde compounds and 0.5 part ~ 5 parts catalyzer that take join in container, 3h ~ 6h is reacted again at temperature is 60 DEG C ~ 100 DEG C, dewater again, obtain the reactant A that viscosity is 0.5 ten thousand centipoises ~ 10,000 centipoises;
3., by step 1. in 50 parts ~ 100 parts organosilicons taking join step 2. in the viscosity that obtains be in the reactant A of 0.5 ten thousand centipoises ~ 10,000 centipoises, then react 2h ~ 5h at temperature is 60 DEG C ~ 80 DEG C, obtain reactant B;
4., by step 1. in 10 parts ~ 25 parts paracrils taking be dissolved in 30 parts ~ 50 parts solvents, obtain nitrile rubber solution, again nitrile rubber solution is joined in reactant B, 1h ~ 3h is reacted again at temperature is 80 DEG C ~ 100 DEG C, at temperature is 100 DEG C ~ 120 DEG C, carry out underpressure distillation 30min ~ 60min again, obtain toughness silicon resol;
Step 4. described in the viscosity of toughness silicon resol be 30,000 centipoises ~ 100,000 centipoises;
Heat-resistant filler described in step one is the mixture of one or more in mica powder, antimonous oxide, talcum powder, aluminum oxide, silicon-dioxide, wollastonite, norbide, boron nitride, kaolin;
Expanding material described in step one is one or more mixtures formed in any proportion in γ-aminopropyl triethoxysilane, vinyltriethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, monoalkoxy unsaturated fatty acids titanic acid ester, Di(dioctylpyrophosphato) ethylene titanate;
Two, be 25 DEG C ~ 50 DEG C by 70 parts that take in step one ~ 100 parts toughness silicon resol, 5 parts ~ 35 parts membrane-forming agents and 30 parts ~ 70 parts heat-resistant fillers in temperature, rotating speed be 50r/min ~ 180r/min mill on mixing 10min ~ 40min, add 10 parts ~ 25 parts fiber reinforcements and 1 part ~ 3 parts expanding materials that take in step one again, it is 35 DEG C ~ 50 DEG C in temperature again, rotating speed be 50r/min ~ 180r/min mill on mixing 15min ~ 30min, obtain mixing after material; Use two roll calender to be rolled at temperature is 30 DEG C ~ 70 DEG C by the material after mixing, obtain high temperature resistance phenolic aldehyde carrier free structural film adhesive.
8. the preparation method of a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive according to claim 7, is characterized in that the membrane-forming agent described in step one is the mixture of one or more in polyarylsulphone, polyethersulfone, poly (arylene ether nitrile), polybenzimidazole, polyetherimide, thermoplastic polyimide, polyetherketone and polyether-ether-ketone.
9. the preparation method of a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive according to claim 7, it is characterized in that the fiber reinforcement described in step one by length be the fiber of 0.1mm ~ 1.0mm, length be the fiber of 1.0mm ~ 5mm and length is the fibrous of 5mm ~ 20mm; In described fiber reinforcement, length is the massfraction of the fiber of 0.1mm ~ 1.0mm is 20% ~ 40%, and length is the massfraction of the fiber of 1.0mm ~ 5mm is 30% ~ 60%, and length is the massfraction of the fiber of 5mm ~ 20mm is 10% ~ 35%; Described fiber reinforcement is mineral fibre, glass fibre or ceramic fiber; Wherein, described mineral fibre is asbestos, and described glass fibre is alkali free glass fibre, and described ceramic fiber is alumina-silicate ceramic fibre.
10. the preparation method of a kind of high temperature resistance phenolic aldehyde carrier free structural film adhesive according to claim 7, is characterized in that the thickness of the high temperature resistance phenolic aldehyde carrier free structural film adhesive described in step 2 is 0.3mm ~ 0.5mm.
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