CN104877583B - 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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- CN104877583B CN104877583B CN201510333468.7A CN201510333468A CN104877583B CN 104877583 B CN104877583 B CN 104877583B CN 201510333468 A CN201510333468 A CN 201510333468A CN 104877583 B CN104877583 B CN 104877583B
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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 adhesive that a class is applied on stressed member, has higher intensity, its gluded joint energy
Bear with by the suitable load of the viscous strength of materials.Require adhesive to have excellent thermostability, media-resistant, resistance to air in itself old simultaneously
The performances such as change.
In heat-resistant structural adhesive, a kind of critically important form is glued membrane.In existing high temperature resistant glued membrane, most widely used
General is modified epoxy glued membrane, but the heat stability of this kind of glued membrane is poor, and the upper limit can only achieve 200 DEG C～250 using temperature
DEG C it is difficult to meet use requirement under the high temperature conditions.Modified phenolic resin adhesive has excellent heat resistance, but with
The report of glued membrane form application is little.Patent cn201410772580.6 discloses a kind of preparation method of high temperature resistant glued membrane, but
Glued membrane is made using solution coating process, complex process, pollution environment, and heatproof at 400 DEG C about it is difficult to meet higher resistance to
Temperature requires.
Content of the invention
The invention solves the problems that existing phenolic structure glued membrane complicated process of preparation, resistance to elevated temperatures be not enough and the asking of poor toughness
A kind of topic, there is provided high temperature resistance phenolic aldehyde carrier-free structure glued membrane and preparation method thereof.
A kind of high temperature resistance phenolic aldehyde carrier-free structure glued membrane by weight by 70 parts～100 parts toughness silicon phenolic resin, 10
Part～25 parts of fiber reinforcements, 5 parts～35 parts film former, 30 parts～70 parts heat-resistant fillers and 1 part～3 parts bulking agents are prepared from.
A kind of preparation method of high temperature resistance phenolic aldehyde carrier-free structure glued membrane, completes according to the following steps:
First, weighing: weigh by weight 70 parts～100 parts toughness silicon phenolic resin, 10 parts～25 parts fiber reinforcements, 5
Part～35 parts of film former, 30 parts～70 parts heat-resistant fillers and 1 part～3 parts bulking agents；
Toughness silicon phenolic resin described in step one is prepared as follows:
1., weigh by weight 70 parts～130 parts phenolic compounds, 70 parts～150 parts aldehyde compounds, 0.5 part～5
Part catalyst, 50 parts～100 parts organosilicons, 30 parts～50 parts solvents and 10 parts～25 parts nitrile rubbers；
Step 1. described in phenolic compound be phenol, methylphenol, inclined amino-phenol, catechol, resorcinol,
One of alkyl-resorcin, phloroglucinol, hydroquinone, bis-phenol-a, bis-phenol-f and xenol or wherein several mixing
Thing；
Step 1. described in aldehyde compound be one of formaldehyde, paraformaldehyde, furfural, salicylide, acetaldehyde or its
In several mixture；
Step 1. described in catalyst be hydrochloric acid, oxalic acid, acetic acid, p-methyl benzenesulfonic acid, benzene sulfonyl chloride, tolysulfonyl
One of chlorine, p-chlorobenzenesulfonic acid, zinc acetate, zinc oxide, sodium hydroxide and potassium hydroxide or wherein several mixture；
Step 1. described in organosilicon be hexamethyl disiloxane, hexamethyldisiloxane, dimethyl diethoxy silicon
Alkane, dimethyldimethoxysil,ne, MTES, 3,5-dimethylphenyl Ethoxysilane, MTMS,
Methyl vinyl diethoxysilane, methylvinyldimethoxysilane, tetramethyl divinyl silane, vinyl three ethoxy
Base silane, vinyltrimethoxy silane, diphenyl diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxy
Silane, phenyltrimethoxysila,e, methyl triacetoxysilane, gamma-aminopropyl-triethoxy-silane, β-(3,4- epoxide ring
Base) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, tetraethoxysilane and
One of dodecyl triethoxysilane or wherein several mixture；
Step 1. described in solvent be ethyl acetate, acetone, butanone, butanone, dimethylbenzene, toluene, dichloromethane, first
The mixture of one or more of base isobutyl ketone and butyl acetate；
Step 1. described in nitrile rubber in acrylonitrile content be 24%～42%, the Mooney viscosity of nitrile rubber is
50m～77m；
2., by step 1. in weigh 70 parts～130 parts phenolic compounds, 70 parts～150 parts aldehyde compounds and 0.5 part
～5 parts of catalyst are added in container, then react 3h～6h at temperature is 60 DEG C～100 DEG C, then are dehydrated, and obtain viscosity
Reactant a for 0.5 ten thousand centipoises～10,000 centipoises；
3., by step 1. in 50 parts～100 parts organosilicons weighing be added to step 2. in the viscosity that obtains be 0.5 ten thousand lis
In the reactant a of pool～1 ten thousand centipoise, 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 nitrile rubbers weighing be dissolved in 30 parts～50 parts solvents, obtain butyronitrile
Rubber solutions, then nitrile rubber solution is added in reactant b, then react 1h～3h at temperature is 80 DEG C～100 DEG C, then
Carry out vacuum distillation 30min～60min at temperature is 100 DEG C～120 DEG C, obtain toughness silicon phenolic resin；
Step 4. described in toughness silicon phenolic resin viscosity be 30,000 centipoises～100,000 centipoises；
Heat-resistant filler described in step one is mica powder, antimony oxide, Pulvis Talci, aluminium oxide, silicon dioxide, silicon ash
The mixture of one or more of stone, boron carbide, boron nitride, Kaolin；
Bulking agent described in step one is gamma-aminopropyl-triethoxy-silane, VTES, γ-contracting
Water glycerol ether oxygen propyl trimethoxy silicane, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, monoalkoxy are unsaturated
It is mixed that one or more of fatty acid titanate esters, Di(dioctylpyrophosphato) ethylene titanate form in any proportion
Compound；
2nd, by weigh in step one 70 parts～100 parts toughness silicon phenolic resin, 5 parts～35 parts film former and 30 parts～
70 parts of heat-resistant fillers are 25 DEG C～50 DEG C in temperature, rotating speed be mixing 10min in the mill of 50r/min～180r/min～
40min, adds 10 parts～25 parts fiber reinforcements weighing in step one and 1 part～3 parts bulking agents, then temperature be 35 DEG C～
50 DEG C, rotating speed is to knead 15min～30min, the material after being kneaded in the mill of 50r/min～180r/min；Use
Material after kneading is rolled at temperature is 30 DEG C～70 DEG C by two roll calender, obtains high temperature resistance phenolic aldehyde carrier-free structure
Glued membrane；
The principle of the present invention:
The present invention passes through Effect of Organosilicon-modified Phenol-formaldehyde Resin, improves the toughness of high temperature resistance phenolic aldehyde carrier-free structure glued membrane and resistance to
High-temperature behavior；Introduce Macromolecule acrylonitrile rubber simultaneously and participate in reaction in building-up process, Effect of Organosilicon-modified Phenol-formaldehyde Resin is carried out
Further toughness reinforcing；With prepared toughness silicon phenolic resin as matrix, with fiber reinforcement as skeleton, with high performance engineering resins
It is aided with heat-resistant filler and bulking agent for film former simultaneously, by way of mill blending and double roller calendering, finally prepared high temperature
Phenolic aldehyde carrier-free structure glued membrane.
Advantages of the present invention:
First, the present invention introduces in the structure of phenolic resin and has flexibility and the excellent silicone segments of heat resistance,
Improve toughness and the temperature tolerance of phenolic resin simultaneously, obtain the Effect of Organosilicon-modified Phenol-formaldehyde Resin of excellent performance；
2nd, Macromolecule acrylonitrile rubber is added to participate in reaction, from molecule rank to organic in Effect of Organosilicon-modified Phenol-formaldehyde Resin
The toughness of Si modification phenolic resin has done further raising；Because the consumption of nitrile rubber is little, to organosilicon while toughness reinforcing
The heat resistance impact very little of phenol-formaldehyde resin modified；The present invention prepares the matrix tree that high temperature phenolic aldehyde carrier-free structure glued membrane is used
Fat has good toughness and temperature tolerance；
3rd, the present invention is on the basis of prepared toughness silicon phenolic resin, using the fiber bone of heat-resisting long and short fiber blending
Frame provides forming skeleton for toughness silicon phenolic resin, and simultaneously with high performance engineering resins as film former, heat-resistant filler is additive,
Silane compound and titanate compound are bulking agent, prepare toughness by the way of the blending of simple mill and double roller calendering
Preferably, and there is the high temperature phenolic aldehyde carrier-free structure glued membrane of excellent high temperature resistance performance；High temperature phenolic aldehyde no-load prepared by the present invention
Body structural film adhesive has excellent heat resistance and adhesive strength, is expected in aerospace field refractory metal or composite
Manufacture in obtain application；
4th, the initial decomposition temperature of the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of present invention preparation corresponds to 485 DEG C～490
DEG C, 485 DEG C～780 DEG C be thermal weight loss main section；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 structure glued membrane of present invention preparation is residual heavy no longer to be reduced, instead
And have lasting increase, when temperature be 1000 DEG C when residual heavy be 62.2%～64%；
5th, the present invention is residual heavy by 90%～91% during ablation 10h under 450 DEG C of high temperature, and the ablation time is weightless bent more than after 14h
Line tends towards stability；After the ablation of experience 20h, the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of present invention preparation remains to keep 80%～
81% residual heavy；
6th, use high temperature resistance phenolic aldehyde No. 45 steel discs of carrier-free structure glued membrane bonding of present invention preparation, shear strong when 25 DEG C
Spend for 12.9mpa～14mpa, shear strength when 450 DEG C is 4.3mpa～5mpa, shear strength when 600 DEG C is 2.1mpa
～2.6mpa.
The present invention can obtain a kind of high temperature resistance phenolic aldehyde carrier-free structure glued membrane.
Brief description
Fig. 1 is the thermogravimetric curve figure of the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of embodiment one preparation；
Fig. 2 is constant temperature weight-loss curve at 450 DEG C of high temperature resistance phenolic aldehyde carrier-free structure glued membrane prepared by embodiment one.
Specific embodiment
Specific embodiment one: present embodiment is a kind of high temperature resistance phenolic aldehyde carrier-free structure glued membrane by weight by 70
Part～100 parts of toughness silicon phenolic resin, 10 parts～25 parts fiber reinforcements, 5 parts～35 parts film former, 30 parts～70 parts heat-resistant fillers
It is prepared from 1 part～3 parts bulking agents.
The principle of present embodiment:
Present embodiment passes through Effect of Organosilicon-modified Phenol-formaldehyde Resin, improves the toughness of high temperature resistance phenolic aldehyde carrier-free structure glued membrane
And resistance to elevated temperatures；Introduce Macromolecule acrylonitrile rubber simultaneously and participate in reaction, to Effect of Organosilicon-modified Phenol-formaldehyde Resin in building-up process
Carry out further toughness reinforcing；With prepared toughness silicon phenolic resin as matrix, with fiber reinforcement as skeleton, with high-performance engineering
Resin is aided with heat-resistant filler and bulking agent for film former simultaneously, is finally prepared by way of mill blending and double roller calendering
High temperature phenolic aldehyde carrier-free structure glued membrane.
The advantage of present embodiment:
First, present embodiment introduces in the structure of phenolic resin and has flexibility and the excellent organosilicon chain of heat resistance
Section, improves toughness and the temperature tolerance of phenolic resin simultaneously, obtains the Effect of Organosilicon-modified Phenol-formaldehyde Resin of excellent performance；
2nd, Macromolecule acrylonitrile rubber is added to participate in reaction, from molecule rank to organic in Effect of Organosilicon-modified Phenol-formaldehyde Resin
The toughness of Si modification phenolic resin has done further raising；Because the consumption of nitrile rubber is little, to organosilicon while toughness reinforcing
The heat resistance impact very little of phenol-formaldehyde resin modified；Present embodiment prepares the base that high temperature phenolic aldehyde carrier-free structure glued membrane is used
Body resin has good toughness and temperature tolerance；
3rd, present embodiment is on the basis of prepared toughness silicon phenolic resin, using the fibre of heat-resisting long and short fiber blending
Dimension skeleton provides forming skeleton for toughness silicon phenolic resin, and simultaneously with high performance engineering resins as film former, heat-resistant filler is to add
Plus agent, silane compound and titanate compound are bulking agent, prepare by the way of the blending of simple mill and double roller are rolled
Go out toughness preferably, and there is the high temperature phenolic aldehyde carrier-free structure glued membrane of excellent high temperature resistance performance；Height prepared by present embodiment
Warm phenolic aldehyde carrier-free structure glued membrane has excellent heat resistance and adhesive strength, is expected in aerospace field refractory metal
Or in the manufacture of composite, obtain application；
4th, the initial decomposition temperature of the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of present embodiment preparation corresponds to 485 DEG C
～490 DEG C, 485 DEG C～780 DEG C be thermal weight loss main section；Temperature reaches maximum weightlessness when rising to 764 DEG C～780 DEG C, residual
It is 59.4%～62% again；Temperature continue raise, present embodiment preparation high temperature resistance phenolic aldehyde carrier-free structure glued membrane residual heavy not
Reduce again, have lasting increase on the contrary, when temperature be 1000 DEG C when residual heavy be 62.2%～64%；
5th, present embodiment is residual heavy by 90%～91% during ablation 10h under 450 DEG C of high temperature, and the ablation time loses more than after 14h
Weight curve tends towards stability；After the ablation of experience 20h, the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of present embodiment preparation remains to protect
Hold 80%～81% residual heavy；
6th, use high temperature resistance phenolic aldehyde No. 45 steel discs of carrier-free structure glued membrane bonding of present embodiment preparation, cut when 25 DEG C
Shearing stress is 12.9mpa～14mpa, and shear strength when 450 DEG C is 4.3mpa～5mpa, and shear strength when 600 DEG C is
2.1mpa～2.6mpa.
Present embodiment can obtain a kind of high temperature resistance phenolic aldehyde carrier-free structure glued membrane.
Specific embodiment two: present embodiment with specific embodiment one difference is: described toughness silicon phenolic aldehyde tree
Fat is prepared as follows:
1., weigh by weight 70 parts～130 parts phenolic compounds, 70 parts～150 parts aldehyde compounds, 0.5 part～5
Part catalyst, 50 parts～100 parts organosilicons, 30 parts～50 parts solvents and 10 parts～25 parts nitrile rubbers；
Step 1. described in phenolic compound be phenol, methylphenol, inclined amino-phenol, catechol, resorcinol,
One of alkyl-resorcin, phloroglucinol, hydroquinone, bis-phenol-a, bis-phenol-f and xenol or wherein several mixing
Thing；
Step 1. described in aldehyde compound be one of formaldehyde, paraformaldehyde, furfural, salicylide, acetaldehyde or its
In several mixture；
Step 1. described in catalyst be hydrochloric acid, oxalic acid, acetic acid, p-methyl benzenesulfonic acid, benzene sulfonyl chloride, tolysulfonyl
One of chlorine, p-chlorobenzenesulfonic acid, zinc acetate, zinc oxide, sodium hydroxide and potassium hydroxide or wherein several mixture；
Step 1. described in organosilicon be hexamethyl disiloxane, hexamethyldisiloxane, dimethyl diethoxy silicon
Alkane, dimethyldimethoxysil,ne, MTES, 3,5-dimethylphenyl Ethoxysilane, MTMS,
Methyl vinyl diethoxysilane, methylvinyldimethoxysilane, tetramethyl divinyl silane, vinyl three ethoxy
Base silane, vinyltrimethoxy silane, diphenyl diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxy
Silane, phenyltrimethoxysila,e, methyl triacetoxysilane, gamma-aminopropyl-triethoxy-silane, β-(3,4- epoxide ring
Base) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, tetraethoxysilane and
One of dodecyl triethoxysilane or wherein several mixture；
Step 1. described in solvent be ethyl acetate, acetone, butanone, butanone, dimethylbenzene, toluene, dichloromethane, first
The mixture of one or more of base isobutyl ketone and butyl acetate；
Step 1. described in nitrile rubber in acrylonitrile content be 24%～42%, the Mooney viscosity of nitrile rubber is
50m～77m；
2., by step 1. in weigh 70 parts～130 parts phenolic compounds, 70 parts～150 parts aldehyde compounds and 0.5 part
～5 parts of catalyst are added in container, then react 3h～6h at temperature is 60 DEG C～100 DEG C, then are dehydrated, and obtain viscosity
Reactant a for 0.5 ten thousand centipoises～10,000 centipoises；
3., by step 1. in 50 parts～100 parts organosilicons weighing be added to step 2. in the viscosity that obtains be 0.5 ten thousand lis
In the reactant a of pool～1 ten thousand centipoise, 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 nitrile rubbers weighing be dissolved in 30 parts～50 parts solvents, obtain butyronitrile
Rubber solutions, then nitrile rubber solution is added in reactant b, then react 1h～3h at temperature is 80 DEG C～100 DEG C, then
Carry out vacuum distillation 30min～60min at temperature is 100 DEG C～120 DEG C, obtain toughness silicon phenolic resin；
Step 4. described in toughness silicon phenolic resin viscosity be 30,000 centipoises～100,000 centipoises.Other steps with concrete
Embodiment one is identical.
Specific embodiment three: present embodiment with one of specific embodiment one or two difference is: described fiber
The fiber that skeleton is 1.0mm～5mm by the fiber for 0.1mm～1.0mm for the length, length and length are the fiber of 5mm～20mm
Composition；In described fiber reinforcement, the mass fraction of the fiber for 0.1mm～1.0mm for the length is 20%～40%, and length is
The mass fraction of the fiber of 1.0mm～5mm is 30%～60%, and length is the mass fraction of the fiber of 5mm～20mm is 10%
～35%；Described fiber reinforcement is mineral fibres, glass fibre or ceramic fibre；Wherein, described mineral fibres is asbestos,
Described glass fibre is alkali-free glass fibre, and described ceramic fibre is alumina-silicate ceramic fibre.Other steps and specifically reality
Apply mode one or two identical.
Specific embodiment four: present embodiment with one of specific embodiment one to three difference is: described film forming
Agent is polyarylsulfone (PAS), polyether sulfone, poly (arylene ether nitrile), polybenzimidazoles, Polyetherimide, TPI, polyether-ketone and polyethers
The mixture of one or more of ether ketone.Other steps are identical with specific embodiment one to three.
Specific embodiment five: present embodiment with one of specific embodiment one to four difference is: described is heat-resisting
Filler is mica powder, antimony oxide, Pulvis Talci, aluminium oxide, silicon dioxide, wollastonite, boron carbide, boron nitride, in Kaolin
The mixture of one or more.Other steps are identical with specific embodiment one to four.
Specific embodiment six: present embodiment with one of specific embodiment one to five difference is: described increase-volume
Agent be gamma-aminopropyl-triethoxy-silane, VTES, γ-glycidyl ether oxygen propyl trimethoxy silicane,
Isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acid titanate esters, double (two octyloxy Jiao's phosphorus
Perester radical) mixture that forms in any proportion of one or more of ethylene titanate esters.Other steps and specific embodiment
One to five is identical.
Specific embodiment seven: present embodiment be a kind of preparation method of high temperature resistance phenolic aldehyde carrier-free structure glued membrane be by
Following steps complete:
First, weighing: weigh by weight 70 parts～100 parts toughness silicon phenolic resin, 10 parts～25 parts fiber reinforcements, 5
Part～35 parts of film former, 30 parts～70 parts heat-resistant fillers and 1 part～3 parts bulking agents；
Toughness silicon phenolic resin described in step one is prepared as follows:
1., weigh by weight 70 parts～130 parts phenolic compounds, 70 parts～150 parts aldehyde compounds, 0.5 part～5
Part catalyst, 50 parts～100 parts organosilicons, 30 parts～50 parts solvents and 10 parts～25 parts nitrile rubbers；
Step 1. described in phenolic compound be phenol, methylphenol, inclined amino-phenol, catechol, resorcinol,
One of alkyl-resorcin, phloroglucinol, hydroquinone, bis-phenol-a, bis-phenol-f and xenol or wherein several mixing
Thing；
Step 1. described in aldehyde compound be one of formaldehyde, paraformaldehyde, furfural, salicylide, acetaldehyde or its
In several mixture；
Step 1. described in catalyst be hydrochloric acid, oxalic acid, acetic acid, p-methyl benzenesulfonic acid, benzene sulfonyl chloride, tolysulfonyl
One of chlorine, p-chlorobenzenesulfonic acid, zinc acetate, zinc oxide, sodium hydroxide and potassium hydroxide or wherein several mixture；
Step 1. described in organosilicon be hexamethyl disiloxane, hexamethyldisiloxane, dimethyl diethoxy silicon
Alkane, dimethyldimethoxysil,ne, MTES, 3,5-dimethylphenyl Ethoxysilane, MTMS,
Methyl vinyl diethoxysilane, methylvinyldimethoxysilane, tetramethyl divinyl silane, vinyl three ethoxy
Base silane, vinyltrimethoxy silane, diphenyl diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxy
Silane, phenyltrimethoxysila,e, methyl triacetoxysilane, gamma-aminopropyl-triethoxy-silane, β-(3,4- epoxide ring
Base) ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, tetraethoxysilane and
One of dodecyl triethoxysilane or wherein several mixture；
Step 1. described in solvent be ethyl acetate, acetone, butanone, butanone, dimethylbenzene, toluene, dichloromethane, first
The mixture of one or more of base isobutyl ketone and butyl acetate；
Step 1. described in nitrile rubber in acrylonitrile content be 24%～42%, the Mooney viscosity of nitrile rubber is
50m～77m；
2., by step 1. in weigh 70 parts～130 parts phenolic compounds, 70 parts～150 parts aldehyde compounds and 0.5 part
～5 parts of catalyst are added in container, then react 3h～6h at temperature is 60 DEG C～100 DEG C, then are dehydrated, and obtain viscosity
Reactant a for 0.5 ten thousand centipoises～10,000 centipoises；
3., by step 1. in 50 parts～100 parts organosilicons weighing be added to step 2. in the viscosity that obtains be 0.5 ten thousand lis
In the reactant a of pool～1 ten thousand centipoise, 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 nitrile rubbers weighing be dissolved in 30 parts～50 parts solvents, obtain butyronitrile
Rubber solutions, then nitrile rubber solution is added in reactant b, then react 1h～3h at temperature is 80 DEG C～100 DEG C, then
Carry out vacuum distillation 30min～60min at temperature is 100 DEG C～120 DEG C, obtain toughness silicon phenolic resin；
Step 4. described in toughness silicon phenolic resin viscosity be 30,000 centipoises～100,000 centipoises；
Heat-resistant filler described in step one is mica powder, antimony oxide, Pulvis Talci, aluminium oxide, silicon dioxide, silicon ash
The mixture of one or more of stone, boron carbide, boron nitride, Kaolin；
Bulking agent described in step one is gamma-aminopropyl-triethoxy-silane, VTES, γ-contracting
Water glycerol ether oxygen propyl trimethoxy silicane, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, monoalkoxy are unsaturated
It is mixed that one or more of fatty acid titanate esters, Di(dioctylpyrophosphato) ethylene titanate form in any proportion
Compound；
2nd, by weigh in step one 70 parts～100 parts toughness silicon phenolic resin, 5 parts～35 parts film former and 30 parts～
70 parts of heat-resistant fillers are 25 DEG C～50 DEG C in temperature, rotating speed be mixing 10min in the mill of 50r/min～180r/min～
40min, adds 10 parts～25 parts fiber reinforcements weighing in step one and 1 part～3 parts bulking agents, then temperature be 35 DEG C～
50 DEG C, rotating speed is to knead 15min～30min, the material after being kneaded in the mill of 50r/min～180r/min；Use
Material after kneading is rolled at temperature is 30 DEG C～70 DEG C by two roll calender, obtains high temperature resistance phenolic aldehyde carrier-free structure
Glued membrane.
The principle of present embodiment:
Present embodiment passes through Effect of Organosilicon-modified Phenol-formaldehyde Resin, improves the toughness of high temperature resistance phenolic aldehyde carrier-free structure glued membrane
And resistance to elevated temperatures；Introduce Macromolecule acrylonitrile rubber simultaneously and participate in reaction, to Effect of Organosilicon-modified Phenol-formaldehyde Resin in building-up process
Carry out further toughness reinforcing；With prepared toughness silicon phenolic resin as matrix, with fiber reinforcement as skeleton, with high-performance engineering
Resin is aided with heat-resistant filler and bulking agent for film former simultaneously, is finally prepared by way of mill blending and double roller calendering
High temperature phenolic aldehyde carrier-free structure glued membrane.
The advantage of present embodiment:
First, present embodiment introduces in the structure of phenolic resin and has flexibility and the excellent organosilicon chain of heat resistance
Section, improves toughness and the temperature tolerance of phenolic resin simultaneously, obtains the Effect of Organosilicon-modified Phenol-formaldehyde Resin of excellent performance；
2nd, Macromolecule acrylonitrile rubber is added to participate in reaction, from molecule rank to organic in Effect of Organosilicon-modified Phenol-formaldehyde Resin
The toughness of Si modification phenolic resin has done further raising；Because the consumption of nitrile rubber is little, to organosilicon while toughness reinforcing
The heat resistance impact very little of phenol-formaldehyde resin modified；Present embodiment prepares the base that high temperature phenolic aldehyde carrier-free structure glued membrane is used
Body resin has good toughness and temperature tolerance；
3rd, present embodiment is on the basis of prepared toughness silicon phenolic resin, using the fibre of heat-resisting long and short fiber blending
Dimension skeleton provides forming skeleton for toughness silicon phenolic resin, and simultaneously with high performance engineering resins as film former, heat-resistant filler is to add
Plus agent, silane compound and titanate compound are bulking agent, prepare by the way of the blending of simple mill and double roller are rolled
Go out toughness preferably, and there is the high temperature phenolic aldehyde carrier-free structure glued membrane of excellent high temperature resistance performance；Height prepared by present embodiment
Warm phenolic aldehyde carrier-free structure glued membrane has excellent heat resistance and adhesive strength, is expected in aerospace field refractory metal
Or in the manufacture of composite, obtain application；
4th, the initial decomposition temperature of the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of present embodiment preparation corresponds to 485 DEG C
～490 DEG C, 485 DEG C～780 DEG C be thermal weight loss main section；Temperature reaches maximum weightlessness when rising to 764 DEG C～780 DEG C, residual
It is 59.4%～62% again；Temperature continue raise, present embodiment preparation high temperature resistance phenolic aldehyde carrier-free structure glued membrane residual heavy not
Reduce again, have lasting increase on the contrary, when temperature be 1000 DEG C when residual heavy be 62.2%～64%；
5th, present embodiment is residual heavy by 90%～91% during ablation 10h under 450 DEG C of high temperature, and the ablation time loses more than after 14h
Weight curve tends towards stability；After the ablation of experience 20h, the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of present embodiment preparation remains to protect
Hold 80%～81% residual heavy；
6th, use high temperature resistance phenolic aldehyde No. 45 steel discs of carrier-free structure glued membrane bonding of present embodiment preparation, cut when 25 DEG C
Shearing stress is 12.9mpa～14mpa, and shear strength when 450 DEG C is 4.3mpa～5mpa, and shear strength when 600 DEG C is
2.1mpa～2.6mpa.
Present embodiment can obtain a kind of high temperature resistance phenolic aldehyde carrier-free structure glued membrane.
Specific embodiment eight: the difference from specific embodiment seven for the present embodiment is: becoming described in step one
Membrane is polyarylsulfone (PAS), polyether sulfone, poly (arylene ether nitrile), polybenzimidazoles, Polyetherimide, TPI, polyether-ketone and poly-
The mixture of one or more of ether ether ketone.Other steps are identical with specific embodiment seven.
Specific embodiment nine: present embodiment with one of specific embodiment seven to eight difference is: institute in step one
Fiber that the fiber reinforcement stated is 1.0mm～5mm by the fiber for 0.1mm～1.0mm for the length, length and length be 5mm～
The fiber composition of 20mm；In described fiber reinforcement length be 0.1mm～1.0mm fiber mass fraction be 20%～
40%, length is the mass fraction of the fiber of 1.0mm～5mm is 30%～60%, and length is the quality of the fiber of 5mm～20mm
Fraction is 10%～35%；Described fiber reinforcement is mineral fibres, glass fibre or ceramic fibre；Wherein, described mineral
Fiber is asbestos, and described glass fibre is alkali-free glass fibre, and described ceramic fibre is alumina-silicate ceramic fibre.Other steps
Rapid identical with specific embodiment seven to eight.
Specific embodiment ten: present embodiment with one of specific embodiment seven to nine difference is: institute in step 2
The thickness of the high temperature resistance phenolic aldehyde carrier-free structure glued membrane stated is 0.3mm～0.5mm.Other steps and specific embodiment seven to nine
Identical.
Specific embodiment 11: present embodiment with one of specific embodiment seven to ten difference is: in step one
Weigh 100 parts of toughness silicon phenolic resin, 15 parts of fiber reinforcements, 25 parts of film former, 30 parts of heat-resistant fillers and 2 parts of increasings by weight
Hold agent.Other steps are identical with specific embodiment seven to ten.
Specific embodiment 12: present embodiment with one of specific embodiment seven to ten one difference is: step one
In weigh 100 parts of toughness silicon phenolic resin, 20 parts of fiber reinforcements, 15 parts of film former, 40 parts of heat-resistant fillers and 2 parts by weight
Bulking agent.Other steps are identical with specific embodiment seven to ten one.
Specific embodiment 13: present embodiment with one of specific embodiment seven to ten two difference is: step 2
Middle weigh in step one 100 parts of toughness silicon phenolic resin, 25 parts of film former and 30 parts of heat-resistant fillers are 40 DEG C in temperature, turn
Speed kneads 30min in the mill for 60r/min, adds the 15 parts of fiber reinforcements weighing in step one and 2 parts of bulking agents, then
It is 40 DEG C in temperature, rotating speed is to knead 20min, the material after being kneaded in the mill of 120r/min；Rolled using double roller
Material after kneading is rolled at a temperature of temperature is 70 DEG C by machine, obtains high temperature resistance phenolic aldehyde carrier-free structure glued membrane.Its
His step is identical with specific embodiment seven to ten two.
Specific embodiment 14: present embodiment with one of specific embodiment seven to ten three difference is: step 2
Middle weigh in step one 100 parts of toughness silicon phenolic resin, 15 parts of film former and 40 parts of heat-resistant fillers are 40 DEG C in temperature, turn
Speed kneads 30min in the mill for 60r/min, adds the 20 parts of fiber reinforcements weighing in step one and 2 parts of bulking agents, then
It is 40 DEG C in temperature, rotating speed is to knead 20min, the material after being kneaded in the mill of 120r/min；Rolled using double roller
Material after kneading is rolled at a temperature of temperature is 70 DEG C by machine, obtains high temperature resistance phenolic aldehyde carrier-free structure glued membrane.Its
His step is identical with specific embodiment seven to ten three.
Using following examples checking beneficial effects of the present invention:
Embodiment one: a kind of preparation method of high temperature resistance phenolic aldehyde carrier-free structure glued membrane, complete according to the following steps:
First, weighing: weigh by weight 100 parts of toughness silicon phenolic resin, 15 parts of fiber reinforcements, 25 parts of film former, 30
Part heat-resistant filler and 2 parts of bulking agents；
Toughness silicon phenolic resin described in step one is prepared as follows:
1., weigh by weight 100 parts of phenolic compounds, 130 parts of aldehyde compounds, 2 parts of catalyst, 50 parts organic
Silicon, 50 parts of solvents and 10 parts of nitrile rubbers；
Step 1. described in phenolic compound be phenol and resorcinol mixture；Described phenol and resorcinol
Mass ratio be 10:1；
Step 1. described in aldehyde compound be formaldehyde；
Step 1. described in catalyst be zinc oxide；
Step 1. described in organosilicon be MTES, 3,5-dimethylphenyl Ethoxysilane, phenyl front three
The mixture of TMOS, methyl triacetoxysilane, tetraethoxysilane and dodecyl triethoxysilane；Described
MTES, 3,5-dimethylphenyl Ethoxysilane, phenyltrimethoxysila,e, methyl triacetoxysilane, four
The ratio of Ethoxysilane and dodecyl triethoxysilane is 10:5:5:3:2:5；
Step 1. described in solvent be ethyl acetate, acetone and butanone mixture；Described ethyl acetate, acetone and
The ratio of butanone is 8:2:3；
Step 1. described in nitrile rubber in acrylonitrile content be 42%, the Mooney viscosity of nitrile rubber is 70m；
2., by step 1. in the 100 parts of phenolic compounds, 130 parts of aldehyde compounds and the 2 parts of catalyst that weigh be added to appearance
In device, then react 3h at temperature is 70 DEG C, then be dehydrated, obtain the reactant a that viscosity is 10,000 centipoises；
3., by step 1. in 50 parts of organosilicons weighing be added to step 2. in the viscosity that obtains be 10,000 centipoises reaction
In thing a, then react 3h at temperature is 70 DEG C, obtain reactant b；
4., by step 1. in 10 parts of nitrile rubbers weighing be dissolved in 50 parts of solvents, obtain nitrile rubber solution, then will
Nitrile rubber solution is added in reactant b, then reacts 3h at temperature is 90 DEG C, then is reduced pressure at temperature is 120 DEG C
Distillation 30min, obtains toughness silicon phenolic resin；
Step 4. described in toughness silicon phenolic resin viscosity be 4.8 ten thousand centipoises；
Heat-resistant filler described in step one is mica powder, antimony oxide and kaolinic mixture；Described Muscovitum
Powder, antimony oxide and kaolinic ratio are 4:3:3；
Bulking agent described in step one be VTES, monoalkoxy unsaturated fatty acid titanate esters and
The mixture of Di(dioctylpyrophosphato) ethylene titanate；Described VTES, monoalkoxy are not
The mass ratio of satisfied fatty acid titanate esters and Di(dioctylpyrophosphato) ethylene titanate is 3:1:1；
Film former described in step one is the mixture of polyarylsulfone (PAS) and polyether sulfone；Described polyarylsulfone (PAS) and the matter of polyether sulfone
Amount ratio is 7:3；
Fiber reinforcement described in step one is the fibre of 1.0mm～5mm by the fiber for 0.1mm～1.0mm for the length, length
Peacekeeping length is the fiber composition of 5mm～20mm；In described fiber reinforcement, length is the quality of the fiber of 0.1mm～1.0mm
Fraction is 25%, and length is the mass fraction of the fiber of 1.0mm～5mm is 50%, and length is the quality of the fiber of 5mm～20mm
Fraction is 25%；Described fiber reinforcement is mineral fibres；Wherein, described mineral fibres is asbestos；
2nd, by weigh in step one 100 parts of toughness silicon phenolic resin, 25 parts of film former and 30 parts of heat-resistant fillers in temperature
For 40 DEG C, rotating speed is to knead 30min in the mill of 60r/min, adds the 15 parts of fiber reinforcements weighing in step one and 2 parts
Bulking agent, then it is 40 DEG C in temperature, rotating speed is to knead 20min, the material after being kneaded in the mill of 120r/min；Use
Material after kneading is rolled at temperature is 70 DEG C by two roll calender, obtains high temperature resistance phenolic aldehyde carrier-free structure glued membrane；
The thickness of the high temperature resistance phenolic aldehyde carrier-free structure glued membrane described in step 2 is 0.3mm.
In air atmosphere the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of embodiment one preparation is tested, programming rate
For 10 DEG C/min；As shown in Figure 1；
Fig. 1 is the thermogravimetric curve figure of the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of embodiment one preparation；From fig. 1, it can be seen that it is real
The initial decomposition temperature applying the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of example one preparation corresponds to 485 DEG C, and 485 DEG C～774 DEG C are
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, embodiment
One preparation high temperature resistance phenolic aldehyde carrier-free structure glued membrane residual heavy no longer reduce, have lasting increase on the contrary, when temperature be 1000 DEG C
When residual heavy be 62.2%.
Fig. 2 is the weight-loss curve at 450 DEG C of constant temperature for the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of embodiment one preparation；From
Fig. 2 understands, the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of embodiment one preparation is residual heavy by 91% during ablation 10h under 450 DEG C of high temperature,
The ablation time tends towards stability more than weight-loss curve after 14h.After the ablation of experience 20h, the high temperature resistance phenolic aldehyde of embodiment one preparation is no
Carrier structure glued membrane remain to keep 81% residual heavy.
Using high temperature resistance phenolic aldehyde No. 45 steel discs of carrier-free structure glued membrane bonding of embodiment one preparation, shear strength when 25 DEG C
For 12.9mpa, shear strength when 450 DEG C is 4.7mpa, and shear strength when 600 DEG C is 2.5mpa.
Embodiment two: a kind of preparation method of high temperature resistance phenolic aldehyde carrier-free structure glued membrane completes according to the following steps:
First, weighing: weigh by weight 100 parts of toughness silicon phenolic resin, 20 parts of fiber reinforcements, 15 parts of film former, 40
Part heat-resistant filler and 2 parts of bulking agents；
Toughness silicon phenolic resin described in step one is prepared as follows:
1., weigh by weight 80 parts of phenolic compounds, 100 parts of aldehyde compounds, 4 parts of catalyst, 60 parts of organosilicons,
40 parts of solvents and 15 parts of nitrile rubbers；
Step 1. described in phenolic compound be phenol and resorcinol mixture；Described phenol and catechol
Mass ratio be 5:1；
Step 1. described in aldehyde compound be formaldehyde；
Step 1. described in catalyst be sodium hydroxide；
Step 1. described in organosilicon be 3,5-dimethylphenyl Ethoxysilane, phenyltrimethoxysila,e, methyl three second
Acyloxy silane and the mixture of dodecyl triethoxysilane；Described 3,5-dimethylphenyl Ethoxysilane, phenyl front three
TMOS, methyl triacetoxysilane and dodecyl triethoxysilane ratio are 5:5:3:2；
Step 1. described in solvent be ethyl acetate, acetone and butanone mixture；Described ethyl acetate, acetone and
The ratio of butanone is 8:3:2；
Step 1. described in nitrile rubber in acrylonitrile content be 28%, the Mooney viscosity of nitrile rubber is 60m；
2., by step 1. in the 80 parts of phenolic compounds, 100 parts of aldehyde compounds and the 4 parts of catalyst that weigh be added to appearance
In device, then react 3h at temperature is 70 DEG C, then be dehydrated, obtain the reactant a that viscosity is 0.85 ten thousand centipoises；
3., by step 1. in 60 parts of organosilicons weighing be added to step 2. in the viscosity that obtains be 10,000 centipoises reaction
In thing a, then react 2h at temperature is 70 DEG C, obtain reactant b；
4., by step 1. in 15 parts of nitrile rubbers weighing be dissolved in 40 parts of solvents, obtain nitrile rubber solution, then will
Nitrile rubber solution is added in reactant b, then reacts 2h at temperature is 90 DEG C, then is reduced pressure at temperature is 120 DEG C
Distillation 30min, obtains toughness silicon phenolic resin；
Step 4. described in toughness silicon phenolic resin viscosity be 4.2 ten thousand centipoises；
Heat-resistant filler described in step one is the mixture of mica powder, Pulvis Talci and boron nitride；Described mica powder, cunning
The ratio of stone powder and boron nitride is 5:3:2；
Bulking agent described in step one is isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters and double (two octyloxies
Pyrophosphoric acid ester group) ethylene titanate esters mixture；Described isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters and double (two
Octyloxy pyrophosphoric acid ester group) ethylene titanate esters mass ratio be 3:1；
Film former described in step one is the mixture of poly (arylene ether nitrile) and polyether sulfone；Described poly (arylene ether nitrile) and polyether sulfone
Mass ratio be 1:1；
Fiber reinforcement described in step one is the fibre of 1.0mm～5mm by the fiber for 0.1mm～1.0mm for the length, length
Peacekeeping length is the fiber composition of 5mm～20mm；In described fiber reinforcement, length is the quality of the fiber of 0.1mm～1.0mm
Fraction is 20%, and length is the mass fraction of the fiber of 1.0mm～5mm is 50%, and length is the quality of the fiber of 5mm～20mm
Fraction is 30%；Described fiber reinforcement is glass fibre；Wherein, described described glass fibre is alkali-free glass fibre；
2nd, by weigh in step one 100 parts of toughness silicon phenolic resin, 15 parts of film former and 40 parts of heat-resistant fillers in temperature
For 40 DEG C, rotating speed is to knead 30min in the mill of 60r/min, adds the 20 parts of fiber reinforcements weighing in step one and 2 parts
Bulking agent, then it is 40 DEG C in temperature, rotating speed is to knead 20min, the material after being kneaded in the mill of 120r/min；Use
Material after kneading is rolled at temperature is 70 DEG C by two roll calender, obtains high temperature resistance phenolic aldehyde carrier-free structure glued membrane；
The thickness of the high temperature resistance phenolic aldehyde carrier-free structure glued membrane described in step 2 is 0.33mm.
In air atmosphere the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of embodiment two preparation is tested, programming rate
For 10 DEG C/min；The initial decomposition temperature of the high temperature resistance phenolic aldehyde carrier-free structure glued membrane of embodiment two preparation corresponds to 488 DEG C,
488 DEG C～764 DEG C be thermal weight loss main section；Temperature reaches maximum weightlessness when rising to 764 DEG C, residual heavy be 61.4%；Temperature
Continue raise, embodiment two preparation high temperature resistance phenolic aldehyde carrier-free structure glued membrane residual heavy no longer reduce, have lasting increase on the contrary,
When temperature be 1000 DEG C when residual heavy be 63.2%；
The high temperature resistance phenolic aldehyde carrier-free structure glued membrane of embodiment two preparation is residual heavy by 90% during ablation 10h under 450 DEG C of high temperature,
The ablation time tends towards stability more than weight-loss curve after 14h.After the ablation of experience 20h, the high temperature resistance phenolic aldehyde of embodiment two preparation is no
Carrier structure glued membrane remain to keep 80% residual heavy.
Using high temperature resistance phenolic aldehyde No. 45 steel discs of carrier-free structure glued membrane bonding of embodiment two preparation, shear strength when 25 DEG C
For 13.5mpa, shear strength when 450 DEG C is 4.3mpa, and shear strength when 600 DEG C is 2.1mpa.
Claims (5)
1. a kind of high temperature resistance phenolic aldehyde carrier-free structure glued membrane is it is characterised in that a kind of high temperature resistance phenolic aldehyde carrier-free structure glued membrane presses weight
Amount number by 70 parts～100 parts toughness silicon phenolic resin, 10 parts～25 parts fiber reinforcements, 5 parts～35 parts film former, 30 parts～70
Part heat-resistant filler and 1 part～3 parts bulking agents are prepared from；
Described toughness silicon phenolic resin is prepared as follows:
1., weigh by weight 70 parts～130 parts phenolic compounds, 70 parts～150 parts aldehyde compounds, 0.5 part～5 parts urge
Agent, 50 parts～100 parts organosilicons, 30 parts～50 parts solvents and 10 parts～25 parts nitrile rubbers；
Step 1. described in phenolic compound be phenol, methylphenol, inclined amino-phenol, catechol, resorcinol, alkyl
One of resorcinol, phloroglucinol, hydroquinone, bis-phenol-a, bis-phenol-f and xenol or wherein several mixture；
Step 1. described in aldehyde compound be one of formaldehyde, paraformaldehyde, furfural, salicylide, acetaldehyde or wherein several
The mixture planted；
Step 1. described in catalyst be hydrochloric acid, oxalic acid, acetic acid, p-methyl benzenesulfonic acid, benzene sulfonyl chloride, paratoluensulfonyl chloride, right
One of chlorobenzenesulfonic acid, zinc acetate, zinc oxide, sodium hydroxide and potassium hydroxide or wherein several mixture；
Step 1. described in organosilicon be hexamethyl disiloxane, hexamethyldisiloxane, dimethyldiethoxysilane, two
Methyl dimethoxysilane, MTES, 3,5-dimethylphenyl Ethoxysilane, MTMS, methyl
Methylvinyldiethoxysilane, methylvinyldimethoxysilane, tetramethyl divinyl silane, vinyl triethoxyl silicon
Alkane, vinyltrimethoxy silane, diphenyl diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane,
Phenyltrimethoxysila,e, methyl triacetoxysilane, gamma-aminopropyl-triethoxy-silane, β-(3,4- epoxy cyclohexyl)
Ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, tetraethoxysilane and 12
One of alkyl triethoxysilane or wherein several mixture；
Step 1. described in solvent be ethyl acetate, acetone, butanone, dimethylbenzene, toluene, dichloromethane, methylisobutylketone and
The mixture of one or more of butyl acetate；
Step 1. described in nitrile rubber in acrylonitrile content be 24%～42%, the Mooney viscosity ml (1+4) of nitrile rubber
100 DEG C is 50～77；
2., by step 1. in weigh 70 parts～130 parts phenolic compounds, 70 parts～150 parts aldehyde compounds and 0.5 part～5
Part catalyst is added in container, then reacts 3h～6h at temperature is 60 DEG C～100 DEG C, then is dehydrated, and obtaining viscosity is
The reactant a of 0.5 ten thousand centipoises～10,000 centipoises；
3., by step 1. in 50 parts～100 parts organosilicons weighing be added to step 2. in the viscosity that obtains be 0.5 ten thousand centipoises～
In the reactant a of 10000 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 nitrile rubbers weighing be dissolved in 30 parts～50 parts solvents, obtain nitrile rubber
Solution, then nitrile rubber solution is added in reactant b, then react 1h～3h at temperature is 80 DEG C～100 DEG C, then in temperature
Spend and carry out vacuum distillation 30min～60min at 100 DEG C～120 DEG C, obtain toughness silicon phenolic resin；
Step 4. described in toughness silicon phenolic resin viscosity be 30,000 centipoises～100,000 centipoises；
By the fiber for 0.1mm～1.0mm for the length, length, the fiber being 1.0mm～5mm and length are described fiber reinforcement
The fiber composition of 5mm～20mm；In described fiber reinforcement, the mass fraction of the fiber for 0.1mm～1.0mm for the length is 20%
～40%, length is the mass fraction of the fiber of 1.0mm～5mm is 30%～60%, and length is the matter of the fiber of 5mm～20mm
Amount fraction is 10%～35%；Described fiber reinforcement is mineral fibres, glass fibre or ceramic fibre；Wherein, described ore deposit
Fibres are asbestos, and described glass fibre is alkali-free glass fibre, and described ceramic fibre is alumina-silicate ceramic fibre；
Described film former is polyarylsulfone (PAS), polyether sulfone, poly (arylene ether nitrile), polybenzimidazoles, Polyetherimide, thermoplasticity polyamides are sub-
The mixture of one or more of amine, polyether-ketone and polyether-ether-ketone；
Described heat-resistant filler is mica powder, antimony oxide, Pulvis Talci, aluminium oxide, silicon dioxide, wollastonite, boron carbide, nitrogen
Change the mixture of one or more of boron, Kaolin；
Described bulking agent is gamma-aminopropyl-triethoxy-silane, VTES, γ-glycidyl ether oxygen third
Base trimethoxy silane, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acid titanate esters,
The mixture that one or more of Di(dioctylpyrophosphato) ethylene titanate forms in any proportion.
2. a kind of preparation method of high temperature resistance phenolic aldehyde carrier-free structure glued membrane is it is characterised in that a kind of high temperature resistance phenolic aldehyde carrier-free is tied
The preparation method of structure glued membrane completes according to the following steps:
First, weighing: weigh by weight 70 parts～100 parts toughness silicon phenolic resin, 10 parts～25 parts fiber reinforcements, 5 parts～
35 parts of film former, 30 parts～70 parts heat-resistant fillers and 1 part～3 parts bulking agents；
Toughness silicon phenolic resin described in step one is prepared as follows:
1., weigh by weight 70 parts～130 parts phenolic compounds, 70 parts～150 parts aldehyde compounds, 0.5 part～5 parts urge
Agent, 50 parts～100 parts organosilicons, 30 parts～50 parts solvents and 10 parts～25 parts nitrile rubbers；
Step 1. described in phenolic compound be phenol, methylphenol, inclined amino-phenol, catechol, resorcinol, alkyl
One of resorcinol, phloroglucinol, hydroquinone, bis-phenol-a, bis-phenol-f and xenol or wherein several mixture；
Step 1. described in aldehyde compound be one of formaldehyde, paraformaldehyde, furfural, salicylide, acetaldehyde or wherein several
The mixture planted；
Step 1. described in catalyst be hydrochloric acid, oxalic acid, acetic acid, p-methyl benzenesulfonic acid, benzene sulfonyl chloride, paratoluensulfonyl chloride, right
One of chlorobenzenesulfonic acid, zinc acetate, zinc oxide, sodium hydroxide and potassium hydroxide or wherein several mixture；
Step 1. described in organosilicon be hexamethyl disiloxane, hexamethyldisiloxane, dimethyldiethoxysilane, two
Methyl dimethoxysilane, MTES, 3,5-dimethylphenyl Ethoxysilane, MTMS, methyl
Methylvinyldiethoxysilane, methylvinyldimethoxysilane, tetramethyl divinyl silane, vinyl triethoxyl silicon
Alkane, vinyltrimethoxy silane, diphenyl diethoxy silane, dimethoxydiphenylsilane, phenyl triethoxysilane,
Phenyltrimethoxysila,e, methyl triacetoxysilane, gamma-aminopropyl-triethoxy-silane, β-(3,4- epoxy cyclohexyl)
Ethyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, tetraethoxysilane and 12
One of alkyl triethoxysilane or wherein several mixture；
Step 1. described in solvent be ethyl acetate, acetone, butanone, dimethylbenzene, toluene, dichloromethane, methylisobutylketone and
The mixture of one or more of butyl acetate；
Step 1. described in nitrile rubber in acrylonitrile content be 24%～42%, the Mooney viscosity ml (1+4) of nitrile rubber
100 DEG C is 50～77；
2., by step 1. in weigh 70 parts～130 parts phenolic compounds, 70 parts～150 parts aldehyde compounds and 0.5 part～5
Part catalyst is added in container, then reacts 3h～6h at temperature is 60 DEG C～100 DEG C, then is dehydrated, and obtaining viscosity is
The reactant a of 0.5 ten thousand centipoises～10,000 centipoises；
3., by step 1. in 50 parts～100 parts organosilicons weighing be added to step 2. in the viscosity that obtains be 0.5 ten thousand centipoises～
In the reactant a of 10000 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 nitrile rubbers weighing be dissolved in 30 parts～50 parts solvents, obtain nitrile rubber
Solution, then nitrile rubber solution is added in reactant b, then react 1h～3h at temperature is 80 DEG C～100 DEG C, then in temperature
Spend and carry out vacuum distillation 30min～60min at 100 DEG C～120 DEG C, obtain toughness silicon phenolic resin；
Step 4. described in toughness silicon phenolic resin viscosity be 30,000 centipoises～100,000 centipoises；
Heat-resistant filler described in step one be mica powder, antimony oxide, Pulvis Talci, aluminium oxide, silicon dioxide, wollastonite,
The mixture of one or more of boron carbide, boron nitride, Kaolin；
Bulking agent described in step one is gamma-aminopropyl-triethoxy-silane, VTES, γ-shrink are sweet
Oily ether oxygen propyl trimethoxy silicane, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated fatty acidss
The mixing that one or more of sour titanate esters, Di(dioctylpyrophosphato) ethylene titanate form in any proportion
Thing；
2nd, by weigh in step one 70 parts～100 parts toughness silicon phenolic resin, 5 parts～35 parts film former and 30 parts～70 parts
Heat-resistant filler is 25 DEG C～50 DEG C in temperature, and rotating speed is to knead 10min～40min in the mill of 50r/min～180r/min,
Add 10 parts～25 parts fiber reinforcements weighing in step one and 1 part～3 parts bulking agents, then be 35 DEG C～50 DEG C in temperature,
Rotating speed is to knead 15min～30min, the material after being kneaded in the mill of 50r/min～180r/min；Using double roller pressure
Prolong machine to be rolled the material after kneading at temperature is 30 DEG C～70 DEG C, obtain high temperature resistance phenolic aldehyde carrier-free structure glued membrane.
3. a kind of preparation method of high temperature resistance phenolic aldehyde carrier-free structure glued membrane according to claim 2 is it is characterised in that walk
Film former described in rapid one is polyarylsulfone (PAS), polyether sulfone, poly (arylene ether nitrile), polybenzimidazoles, Polyetherimide, thermoplasticity polyamides are sub-
The mixture of one or more of amine, polyether-ketone and polyether-ether-ketone.
4. a kind of preparation method of high temperature resistance phenolic aldehyde carrier-free structure glued membrane according to claim 2 is it is characterised in that walk
By the fiber for 0.1mm～1.0mm for the length, length, the fiber being 1.0mm～5mm and length are fiber reinforcement described in rapid one
The fiber composition of 5mm～20mm；In described fiber reinforcement, the mass fraction of the fiber for 0.1mm～1.0mm for the length is 20%
～40%, length is the mass fraction of the fiber of 1.0mm～5mm is 30%～60%, and length is the matter of the fiber of 5mm～20mm
Amount fraction is 10%～35%；Described fiber reinforcement is mineral fibres, glass fibre or ceramic fibre；Wherein, described ore deposit
Fibres are asbestos, and described glass fibre is alkali-free glass fibre, and described ceramic fibre is alumina-silicate ceramic fibre.
5. a kind of preparation method of high temperature resistance phenolic aldehyde carrier-free structure glued membrane according to claim 2 is it is characterised in that walk
The thickness of the high temperature resistance phenolic aldehyde carrier-free structure glued membrane described in rapid two is 0.3mm～0.5mm.
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| CN105111980B (en) * | 2015-08-19 | 2018-06-12 | 苏州金枪新材料股份有限公司 | Special modified phenolic aldehyde high-temperature Resistance Adhesives |
| CN105440569A (en) * | 2015-12-23 | 2016-03-30 | 佛山早稻田科技服务有限公司 | Insulating material with high temperature resistance |
| CN106750702A (en) * | 2016-12-01 | 2017-05-31 | 陕西日日新生物科技有限公司 | A kind of preparation method of flame retardant plastics film |
| CN108611002B (en) * | 2016-12-05 | 2019-09-13 | 航天特种材料及工艺技术研究所 | A kind of polyimide support glue film and preparation method thereof |
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| CN107603539A (en) * | 2017-08-23 | 2018-01-19 | 无锡海特新材料研究院有限公司 | A kind of thermostable phenolic resin adhesive and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486886A (en) * | 2009-02-26 | 2009-07-22 | 费金华 | High temperature resistant adhesive |
| CN101875830A (en) * | 2009-11-23 | 2010-11-03 | 黑龙江省科学院石油化学研究院 | Phenolic resin/phosphate hybrid adhesive and preparation method thereof |
| CN101921565A (en) * | 2010-08-31 | 2010-12-22 | 黑龙江省科学院石油化学研究院 | Preparation method of solvent-free and high temperature-resistant adhesive |
| CN103242767A (en) * | 2013-05-20 | 2013-08-14 | 黑龙江省科学院石油化学研究院 | High-temperature-resistant bismaleimide resin carrier structure adhesive film and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2974104B1 (en) * | 2011-04-15 | 2014-08-15 | Saint Gobain Isover | SIZING COMPOSITION FOR FIRE RESISTANT MINERAL WOOL AND ISOLATING PRODUCT OBTAINED |
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- 2015-06-16 CN CN201510333468.7A patent/CN104877583B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486886A (en) * | 2009-02-26 | 2009-07-22 | 费金华 | High temperature resistant adhesive |
| CN101875830A (en) * | 2009-11-23 | 2010-11-03 | 黑龙江省科学院石油化学研究院 | Phenolic resin/phosphate hybrid adhesive and preparation method thereof |
| CN101921565A (en) * | 2010-08-31 | 2010-12-22 | 黑龙江省科学院石油化学研究院 | Preparation method of solvent-free and high temperature-resistant adhesive |
| CN103242767A (en) * | 2013-05-20 | 2013-08-14 | 黑龙江省科学院石油化学研究院 | High-temperature-resistant bismaleimide resin carrier structure adhesive film and preparation method thereof |
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