CN108034402B - A kind of polyimides glue film and preparation method thereof - Google Patents
A kind of polyimides glue film and preparation method thereof Download PDFInfo
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- CN108034402B CN108034402B CN201610955698.1A CN201610955698A CN108034402B CN 108034402 B CN108034402 B CN 108034402B CN 201610955698 A CN201610955698 A CN 201610955698A CN 108034402 B CN108034402 B CN 108034402B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C09J7/00—Adhesives in the form of films or foils
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The present invention proposes a kind of polyimides glue film and preparation method thereof, the thermoplastic polyimide of Thermocurable polyimide and excellent tenacity resistant to high temperature mixes, it adds micro-nano chopped strand and thermally labile oligomer is uniformly mixed in a solvent, certain thickness glue film is then made using solwution method.The present invention is based on bondings and thermal stress to buffer difunctional design, on the one hand glue film is enable to realize foam in place at a temperature of high solidification, another aspect glue film high tenacity can be realized the bonds well of composite material and metal structure, improve peel strength, while can be avoided potential corrosion.
Description
Technical field
The present invention relates to a kind of polyimides glue films and preparation method thereof, belong to technical field of composite materials.
Background technique
With the rapid development of aeronautical and space technology, guided missile and aircraft are just towards high speed, long-range and structure function one
The direction of change is developed, and guided missile and vehicle flight speeds are up to Ma3~4, and part even breaches Ma6, and remote high-speed causes
Serious Aerodynamic Heating problem, so that body structure is faced with increasingly harsher working environment, hot environment is also limited very
The utilization of the more common body structure material of subsonic speed such as aluminium alloys, epoxies composite material, further to adapt to the big load of aircraft
Bullet amount and the long range multiple demand of guided missile, body structure need further loss of weight.Polyimides is that comprehensive performance is optimal
One of high-molecular organic material, heat resisting temperature reach as high as 600 DEG C or more, long-term use temperature range at 200~500 DEG C,
Composite polyimide material is the material of main part of high temperature resistant general in the world, high-mechanic structure at present.
Carbon fiber reinforcement polyimide composite material is widely used in aircraft missile wing, rudder face, structure bay section, antenna house etc.
In structure, molding mode is predominantly pressed and molded, is Wrapping formed, high temperature RTM is formed etc., advanced High Temperature Resistant Polyimide Composites are made
Based on bearing structure be typically necessary and be mechanically connected with other components, current most of connection structures are for reliability
And being dismounted for multiple times requires to mostly use metal structure, i.e., currently used structure is mainly metal structure+composite material skin structure.
Since metal structure and composite structure thermal expansion coefficient are inconsistent and there are due to certain potential corrosion etc., conventional carbon fiber
The processing method for tieing up reinforced epoxy structure is then the metal structure and compound after metal structure carries out anodization blasting treatment
Epoxy resin structure glue film layer is coated between material structure, come prevent potential corrosion and formed buffer layer prevent metal structure with
Composite material unsticking.Carbon fiber reinforcement polyimide composite material is since solidification temperature is higher, about 400 DEG C, solidification and
Cause in cooling procedure metal structure and composite structure thermal expansion coefficient it is inconsistent be easy to occur in cooling procedure it is de-
It is viscous, while composite polyimide material solidifies and uses temperature higher, temperature is higher, and the difference of two kinds of material heat expansions is bigger,
Traditional epoxy and bismaleimide resin glue film is no longer applicable in high temperature system, and in polyimide curing temperature, glue film has been carbonized point
Solution, so being badly in need of the boundary layer that exploitation is suitable for carbon fiber reinforcement polyimide composite material and metal structure, to solve high temperature
The interphase match and bonding problem of solidified resin based composites and metal structure.
Summary of the invention
It is an object of the invention to overcome the shortage of prior art, providing one kind can effectively improve under high temperature (200 DEG C or more)
Polyimide-based composite material and metal structure interphase match and the polyimides glue film of adhesive property and preparation method thereof.
Technical solution of the invention: a kind of polyimides glue film is prepared by mixed raw material using solwution method, institute
The mixed raw material stated includes thermoset polyimide resin, thermoplastic polyimide resin, thermally labile oligomer, micro-nano short
Cut fiber and high boiling solvent；
The thermally labile oligomer is the polymerization that gas or small molecule can be decomposed to give off when reaching thermal decomposition temperature
Body, thermal decomposition temperature is higher than the boiling point of high boiling solvent, and is lower than the solidification temperature of thermoset polyimide resin, additive amount
It is the 0.5%~3% of thermoset polyimide resin quality；
The high boiling solvent is the organic solvent that boiling point is not less than 100 DEG C；The thermoplastic polyimide resin
Additive amount is the 5%~20% of thermoset polyimide resin quality, and the micro-nano chopped strand additive amount is thermosetting property
The 0.05%~2% of polyimide resin quality.
Thermoset polyimide resin of the invention is the basic components of glue film, and preferred consolidation temperature at least compares thermally labile
High 40 DEG C of oligomer thermal decomposition temperature or more.The present invention is not particularly limited the type of thermoset polyimide resin, as long as
Heat resistance, which meets, to be used, and solidification temperature meets above-mentioned requirements, such as using acetylene sealing end, allyl norbornene sealing end or
One or more of Phenylethynyl terminated imides resin etc..
Thermoplastic polyimide resin main function is the toughness for increasing glue film, improves the modulus of shearing of glue film, is added
Amount is very little, and glue film toughness is low, caking property and form-dependent character is influenced after glue film foaming, due to thermoplastic polyimide resin vitrifying
Transition temperature is lower, if its additive amount is too many, is easy charing at high temperature, influences bonding and shear strength.It is preferred that additive amount is
The 5%~20% of thermoset polyimide resin quality, under the same terms, the toughness that additive amount increases glue film within this range is got over
Height, modulus of shearing are higher.The present invention is not particularly limited thermoplastic polyimide resin type, as long as can function as described above
, condensation polymer type polyimides is generally used in engineering, as Vespel polyimides, Ul tem and Extem polyetherimide,
The one or more of Torlon polyamidoimide, UPIMOL polyimides and Aurum polyimides etc..
Thermally labile oligomer of the invention can decompose to give off gas or small molecule under thermal decomposition temperature, reach hot unstable
When determining the decomposition temperature of oligomer, since the decomposition of thermally labile segment carries out foam in place, in glue film solidification process, in metal
Buffer layer is formed between composite material, is carried out " occupy-place ", as temperature reduces, metal structure and composite structure are shunk,
When relative displacement trend occurs for the two, buffer layer can alleviate the relative motion between two media, play bonding and protective effect.
The present invention is not particularly limited thermally labile oligomerisation species, as long as can meet above-mentioned under thermal decomposition temperature point
Gas or small molecule are liberated out, and thermal decomposition temperature meets higher than high boiling solvent boiling point, is lower than thermoset polyimide resin
Solidification temperature, polypropylene oxide, polymethyl methacrylate, polystyrene, polymethylstyrene, poly- penta such as can be used
The condensates such as lactone and polycaprolactone.Its additive amount is preferably the 0.5%~3% of thermoset polyimide resin quality, if hot
Unstable oligomer content is too low, and swell increment is small at high temperature, cannot form foam in place, can not generate displacement to expanding with heat and contract with cold
It carries out " occupy-place ", if content is too high, it is not easy to disperse, be easy to reunite, influence adhesion strength.Optimum addition is thermosetting property polyamides
The 0.9~1.1 of imide resin quality, in the case that other conditions are constant, adhesive property and the thermally labile oligomer of glue film
To meet normal distribution between additive amount, at 0.9~1.1%, the adhesive property of its glue film is best.
Further, the solubility parameters of thermally labile oligomer to be differed with the solubility parameters of thermoset polyimide resin compared with
Greatly, to guarantee to form microphase-separated；Thermally labile oligomer and thermoset polyimide resin form microphase-separated under stiring,
The dispersion of thermally labile oligomer is more uniform, and Dispersed Phase Size is smaller, and the abscess to foam is more uniform, glue film interfacial contact area
Bigger, adhesion strength is better.The preferred scope of the solubility parameters difference of the two is 0.8~3.7, and solubility parameters is close, when blending
It can dissolve each other, separation phase cannot be formed, solubility parameters difference is too big, is easy to reunite, it is not easy to separate, the foam structure size of formation
Greatly, caking property is influenced.The solubility parameters difference of the two changes within the scope of above-mentioned requirements influences less subsequent glue film adhesive property,
It can be neglected in engineering.
Further, the thermal decomposition temperature of thermally labile oligomer wants moderate, too low it cannot be guaranteed that the volatilization of solvent and acyl are sub-
The completion of amination, the thermal decomposition temperature of thermally labile oligomer are preferably higher than 40 DEG C of high boiling solvent boiling point or more, lower than thermosetting
Property 40 DEG C of solidification temperature or more of polyimide resin, thermal decomposition can be controlled quantitatively, and can resolve into small molecule, be easy from polyamides
It is escaped in imine matrix.
The micro nanometer fiber that the present invention uses is micron or the fiber of nanoscale, and micro nanometer fiber is in glue film expansion process
In, micromechanics is formed with metal structure and composite structure and is connect, " Z " Xiang Qianghua is carried out, and increases adhesion strength.Its additive amount
Preferably the 0.05%~2% of thermoset polyimide resin quality, micro nanometer fiber additive amount is very little, and glue film foams in situ
The resin layer generated in the process is connect with composite material or metal, and brittleness is larger, and toughness is insufficient, is easy during cooling meat
Removing, micro nanometer fiber content is too many, increases gelatin viscosity, influences film-forming process.The optimum addition of micro nanometer fiber
It is the 0.08~0.12% of thermoset polyimide resin quality；In the case that other conditions are constant, the adhesive property of glue film with
To meet normal distribution between the additive amount of micro nanometer fiber, at 0.08~0.12%, the adhesive property of its glue film is best.This
Invention is not particularly limited the type of fiber, can be carbon fiber, glass fibers as long as being able to satisfy glue film using temperature requirement
One or more of combinations of dimension, aramid fiber, basalt fibre etc..
High boiling solvent of the invention is used to dissolving resin, and participates in solwution method and prepare glue film, if boiling point is too low, in room temperature
Lower solvent is easy to volatilize, and the resin for causing to dissolve in a solvent is precipitated, and picking state occurs, if boiling point is too high, will increase heat
Unstable oligomer selects difficulty (to play thermally labile oligomer foam in place, to realize occupy-place, the heat of thermally labile oligomer
Decomposition temperature is higher than the boiling point of high boiling solvent), preferred boiling point is preferably to be not higher than 250 DEG C not less than 100 DEG C.It is high boiling
The additive amount of point solvent prepares glue film technique according to the viscosity of dissolubility, mixed solution to resin and solwution method to select, and is
Techniques well known, its additive amount is generally the 150%~400% of thermoset polyimide resin quality in engineering.This hair
It is bright that its type is also not particularly limited, as long as meeting the requirement of boiling point, it can such as use n,N-dimethylacetamide
(DMAC), the organic solvents such as dimethylformamide (DMF), dioxane.
Principle analysis:
Boundary layer of the present invention as metal structure and fiber reinforced high-temperature-resistant composite polyimide material, due to metal material
Material differs larger with Composite Thermal Expansion performance, when metal material solidifies together in a mold with composite material, is being pressurized
And when temperature change, it may occur that deformation is inconsistent, the present invention in the curing process, due to thermally labile oligomer and micro-nano short
It cuts fiber to be dispersed in matrix resin, lower than solvent is removed under thermally labile oligomer decomposition temperature, is reaching outer layer
When composite material solidification temperature, first reach the decomposition temperature of thermally labile oligomer, since the decomposition of thermally labile segment carries out
Foaming forms buffer layer in the curing process between metal and composite material, carry out " occupy-place ", as temperature reduces, metal knot
Structure and composite structure are shunk, and when relative displacement trend occurs, the present invention can alleviate the relative motion between two media, are risen
To bonding and protective effect.Micro nanometer fiber is formed micro- in boundary layer expansion process with metal structure and composite structure
Mechanical connection carries out " Z " Xiang Qianghua, increases adhesion strength.
A kind of polyimides glue film manufacturing process, is realized by following steps:
The first step prepares mixed glue solution,
A1.1, thermoset polyimide resin and thermoplastic polyimide resin be added to high boiling solvent in proportion
In, lower than high boiling solvent boiling point at a temperature of sufficiently dissolve, obtain mixed glue solution A；
The thermoplastic polyimide resin quality is the 5%~20% of thermoset polyimide resin quality, dissolution
When be stirred, temperature is preferably less than 50 DEG C~70 DEG C of high boiling solvent boiling point, if dissolution when temperature too it is low will affect it is molten
Speed and resin dissolution rate are solved, temperature is too close apart from boiling point, will cause solvent volatilization, same to influence resin dissolution rate.
A1.2, thermally labile oligomer and micro nanometer fiber are added in the mixed glue solution A that step A1.1 is obtained, mixing is equal
It is even, obtain mixed glue solution B；
The thermally labile oligomer additive amount is the 0.5%~3% of thermoset polyimide resin quality, described
Micro nanometer fiber additive amount is the 0.05%~2% of thermoset polyimide resin quality.Mixing, which can be used, to be stirred or surpasses
Sound, which is uniformly dispersed, waits usual manners.The thermal decomposition temperature of the thermally labile oligomer be higher than 40 DEG C of high boiling solvent boiling point with
Above, lower than 40 DEG C of solidification temperature or more of thermoset polyimide resin.
Second step, solwution method prepare glue film,
The first step is obtained into mixed glue solution and carries out film using solwution method glue film equipment, according to control thickness is required, 40
It is dried at~80 DEG C, obtains the glue film of microphase-separated.This step is techniques well known, and those skilled in the art are according to reality
Production carries out the setting such as specific process parameter.
Polyimides glue film that the present invention is prepared is spread on glue film in use, glue film is attached on metalwork
Polyimides prepreg is covered, is solidified according to polyimide curing technique, decomposes temperature when temperature reaches thermally labile oligomer
When spending, the thermally labile oligomer of microphase-separated starts to foam, and the displacement that filling thermal dilation difference generates improves caking property and gold
Belong to part and composite material matching.
The present invention compared with prior art the utility model has the advantages that
(1) the present invention is based on bondings and thermal stress to buffer difunctional design, on the one hand enables glue film in high solidification temperature
Lower realization foam in place, another aspect glue film high tenacity can be realized the bonds well of composite material and metal structure, improve stripping
From intensity, while it can be avoided potential corrosion；
(2) the present invention is based on bondings and thermal stress to buffer difunctional design, passes through the thermally labile oligomer of microphase-separated
And micro nanometer fiber realizes foam in place in the curing process, foam in place layer and micro nanometer fiber can be realized composite material with
Micro-force sensing between metal structure is realized micromechanics " anchor ", and adhesion strength is promoted；
(3) present invention prepares glue film using solwution method by thermoplastic polyimide modified Thermocurable polyimide, first
The toughness and shear strength for improving glue film promote the shear strain of glue-line, increase the stripping of metal structure and composite structure
From intensity；
(4) present invention is by thermally labile oligomer microphase-separated in polyimide solution, in the curing process, due to
Thermally labile oligomer is dispersed in matrix resin, removes solvent in the case where being lower than thermally labile oligomer decomposition temperature,
When reaching outer layer of composite material solidification temperature, reach the decomposition temperature of thermally labile oligomer, due to point of thermally labile segment
Solution foams, and in the curing process, forms buffer layer between metal and composite material, carries out " occupy-place ", as temperature reduces,
Metal structure and composite structure are shunk, and when relative displacement trend occurs, which can alleviate the phase between two media
To movement, bonding and protective effect are played.
Specific embodiment
Below with reference to specific example, the present invention is described in detail.
Embodiment 1
100 parts of YH-550 polyimides, 10 parts of Vespel thermoplastic polyimide are added to 250 parts of N, N- dimethyl second
In amide (DMAC) (166 DEG C of boiling point), in 115 DEG C of stirring 3h, it is to be mixed be uniformly completely dissolved after, 1 part of polyphenyl second is then added
The chopped carbon fiber ultrasonic mixing that alkene oligomer (325 DEG C of thermal decomposition temperature) and 0.1 part of length are 50 microns is uniform, utilizes solution
Method is coated in the glue prepared on isolation paper by predetermined thickness, dries 0.5h in 60 DEG C of h heat, encloses isolation film, thickness is made
For the glue film of 0.1mm.45# steel disc is bonded using the glue film, by 240 DEG C/2h+370 DEG C/3h, hot pressing is solid under 3MPa pressure condition
Change, by GB/T7122-1996 peel strength test method and GB/T 7124-1986 method for testing shear strength, difference test cabinet
Temperature and 400 DEG C of peel strengths and shear strength, shear strength is 11.95MPa, peel strength 1.65KN/m, high temperature 400 at room temperature
DEG C shear strength is 5.95MPa, peel strength 0.75KN/m.
Embodiment 2
100 parts of YH-550 polyimides, 20 parts of Vespel thermoplastic polyimide are added to 250 parts of N, N- dimethyl second
In amide (DMAC), in 115 DEG C of stirring 3h, it is to be mixed be uniformly completely dissolved after, be then added 1 part of polystyrene oligomer and
The chopped carbon fiber ultrasonic mixing that 0.1 part of length is 50 microns is uniform, using solwution method the glue prepared by predetermined thickness
Coated on isolation paper, 0.5h is dried in 60 DEG C of h heat, isolation film is enclosed, the glue film with a thickness of 0.1mm is made.It is viscous using the glue film
45# steel disc is tied, by 240 DEG C/2h+370 DEG C/3h, hot-press solidifying under 3MPa pressure condition, by GB/T 7122-1996 peel strength
Test method and GB/T7124-1986 method for testing shear strength, test room temperature and 400 DEG C of peel strengths respectively and shearing is strong
Degree, shear strength is 12.46MPa at room temperature, and peel strength 1.95KN/m, 400 DEG C of shear strengths of high temperature are 6.15MPa, removing
Intensity 0.89KN/m.
Embodiment 3
Except polystyrene oligomer is that 3 especially, remaining is consistent with embodiment 2, glue film is obtained, tests room temperature and 400 respectively
DEG C peel strength and shear strength, shear strength is 10.75MPa, peel strength 1.35KN/m, 400 DEG C of high temperature shearings at room temperature
Intensity is 4.65MPa, peel strength 0.55KN/m.
Embodiment 4
Except chopped carbon fiber is that 2 especially, remaining is consistent with embodiment 2, glue film is obtained, tests room temperature and 400 DEG C of strippings respectively
From intensity and shear strength, shear strength is 12.75MPa, peel strength 1.25KN/m, 400 DEG C of shear strengths of high temperature at room temperature
For 4.65MPa, peel strength 0.65KN/m.
Embodiment 5
Except polystyrene oligomer is that 0.5 especially, remaining is consistent with embodiment 2, obtain glue film, test respectively room temperature and
400 DEG C of peel strengths and shear strength, shear strength is 11.58MPa, peel strength 1.68KN/m at room temperature, and 400 DEG C of high temperature are cut
Shearing stress is 5.24MPa, peel strength 0.71KN/m.
Embodiment 6
Except chopped carbon fiber is that 0.05 especially, remaining is consistent with embodiment 2, glue film is obtained, tests room temperature and 400 DEG C respectively
Peel strength and shear strength, shear strength is 11.76MPa, peel strength 1.71KN/m at room temperature, and 400 DEG C of high temperature shearings are strong
Degree is 5.65MPa, peel strength 0.73KN/m.
Embodiment 7
100 parts of KH-420 polyimides, 20 parts of Extem polyetherimide are added to 250 parts of dimethylformamides (DMF)
In (152.8 DEG C of boiling point), in 115 DEG C of stirring 3h, it is to be mixed be uniformly completely dissolved after, 1 part of polymethylstyrene (heat is then added
290 DEG C of decomposition temperature) and 0.1 part of length be 50 microns chopped carbon fiber ultrasonic mixing it is uniform, using solwution method preparing
Glue be coated on isolation paper by predetermined thickness, dry 0.5h in 60 DEG C of h heat, enclose isolation film, the glue with a thickness of 0.1mm is made
Film.45# steel disc is bonded using the glue film, by 240 DEG C/2h+350 DEG C/3h, hot-press solidifying under 3MPa pressure condition, by GB/T
7122-1996 peel strength test method and GB/T 7124-1986 method for testing shear strength test room temperature and 400 DEG C respectively
Peel strength and shear strength, shear strength is 12.56MPa, peel strength 1.98KN/m at room temperature, and 400 DEG C of high temperature shearings are strong
Degree is 5.35MPa, peel strength 0.59KN/m.
From implementing 1,2 as can be seen that increase the additive amount of thermoplastic polyimide resin under the same terms, glue film it is tough
Property is higher, modulus of shearing is higher；It can be seen that under the same terms from embodiment 2,3,5, with thermally labile oligomer additive amount
Variation, the adhesive property of glue film is in normal distribution under high temperature, reaches peak value when additive amount is 1% or so；From embodiment 2,
4, in 6 as can be seen that under the same terms, with the variation of chopped strand additive amount, the adhesive property of glue film is in normal state point under high temperature
Cloth reaches peak value when additive amount is 0.1% or so；It can be seen that from embodiment 2,7 under the same conditions, due to glue film base
The high-temperature behavior difference of body causes the high-temperature behavior of glue film different.
Unspecified part of the present invention is known to the skilled person technology.
Claims (10)
1. a kind of polyimides glue film, it is characterised in that: be prepared by mixed raw material using solwution method, the mixed raw material
Including thermoset polyimide resin, thermoplastic polyimide resin, thermally labile oligomer, micro-nano chopped strand and high boiling
Point solvent；
The thermal decomposition temperature of the thermally labile oligomer is higher than the boiling point of high boiling solvent, and is lower than Thermocurable polyimide
The solidification temperature of resin, additive amount be thermoset polyimide resin quality 0.5%~3%, thermally labile oligomer with
The solubility parameters difference 0.8~3.7 of thermoset polyimide resin；
The high boiling solvent is the organic solvent that boiling point is not less than 100 DEG C, the thermoplastic polyimide resin addition
Amount is the 5%~20% of thermoset polyimide resin quality, and the micro-nano chopped strand additive amount is thermosetting property polyamides
The 0.05%~2% of imide resin quality.
2. a kind of polyimides glue film according to claim 1, it is characterised in that: the thermally labile oligomer adds
Dosage is the 0.9~1.1% of thermoset polyimide resin quality.
3. a kind of polyimides glue film according to claim 1, it is characterised in that: the micro-nano chopped strand adds
Dosage is the 0.08~0.12% of thermoset polyimide resin quality.
4. a kind of polyimides glue film according to claim 1, it is characterised in that: the thermoset polyimide resin
For one or more of acetylene sealing end, allyl norbornene sealing end or Phenylethynyl terminated imides resin；The heat
Plastic polyimide resin is condensation polymer type polyimides；The thermally labile oligomer is polypropylene oxide, polymethyl
Sour methyl esters, polystyrene, polymethylstyrene, poly- valerolactone or polycaprolactone.
5. a kind of polyimides glue film according to claim 1 or 4, it is characterised in that: the thermally labile oligomer
Thermal decomposition temperature be higher than 40 DEG C of boiling point or more of high boiling solvent, and be lower than the solidification temperature 40 of thermoset polyimide resin
DEG C or more.
6. a kind of polyimides glue film according to claim 1, it is characterised in that: the boiling point of the high boiling solvent is
Not higher than 250 DEG C, additive amount is the 150%~400% of thermoset polyimide resin quality.
7. a kind of preparation method of polyimides glue film described in claim 1, which is characterized in that realized by following steps:
The first step prepares mixed glue solution,
A1.1, thermoset polyimide resin and thermoplastic polyimide resin be added in high boiling solvent in proportion,
Lower than sufficiently dissolving at a temperature of high boiling solvent boiling point, mixed glue solution A is obtained；
A1.2, thermally labile oligomer and micro nanometer fiber are added in the mixed glue solution A that step A1.1 is obtained, are uniformly mixed,
Obtain mixed glue solution B；
Second step, solwution method prepare glue film.
8. a kind of polyimides glue film manufacturing process according to claim 7, it is characterised in that: hot in the step A1.1
Plastic polyimide resin quality is the 5%~20% of thermoset polyimide resin quality, and solution temperature is lower than higher boiling
50 DEG C of solvent boiling point~70 DEG C.
9. a kind of polyimides glue film manufacturing process according to claim 7, it is characterised in that: hot in the step A1.2
Unstable oligomer additive amount is the 0.5%~3% of thermoset polyimide resin quality, the micro nanometer fiber additive amount
It is the 0.05%~2% of thermoset polyimide resin quality；The thermal decomposition temperature of the thermally labile oligomer is higher than height
40 DEG C of boiling point solvent boiling point or more, lower than 40 DEG C of solidification temperature or more of thermoset polyimide resin.
10. a kind of polyimides glue film manufacturing process according to claim 7 or 9, it is characterised in that: the step A1.2
Middle thermally labile oligomer additive amount is the 0.9~1.1% of thermoset polyimide resin quality, and the micro nanometer fiber adds
Dosage is the 0.08~0.12% of thermoset polyimide resin quality.
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| CN111574953B (en) * | 2020-04-30 | 2022-04-22 | 航天材料及工艺研究所 | High-temperature-resistant honeycomb core strip glue, and preparation method and application thereof |
| CN112029473A (en) * | 2020-07-23 | 2020-12-04 | 航天材料及工艺研究所 | High-temperature-resistant thin-wall glass cloth honeycomb core strip glue and preparation method and application thereof |
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| JP5824237B2 (en) * | 2011-04-28 | 2015-11-25 | 三井化学株式会社 | Method for producing polyimide film |
| JP5915090B2 (en) * | 2011-11-01 | 2016-05-11 | 宇部興産株式会社 | Method for producing polyimide laminate, method for producing polyimide film, and polyimide precursor solution composition |
| CN104726045B (en) * | 2013-12-24 | 2017-08-11 | 上海海鹰粘接科技有限公司 | A kind of heat-resistant fireproof epoxy glue and preparation method thereof |
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