CN108611001A - A kind of high-temperature resistant carrier glued membrane and preparation method thereof - Google Patents
A kind of high-temperature resistant carrier glued membrane and preparation method thereof Download PDFInfo
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- CN108611001A CN108611001A CN201611105292.0A CN201611105292A CN108611001A CN 108611001 A CN108611001 A CN 108611001A CN 201611105292 A CN201611105292 A CN 201611105292A CN 108611001 A CN108611001 A CN 108611001A
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- Prior art keywords
- temperature resistant
- temperature
- glued membrane
- thermosetting resin
- thermally labile
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- 239000012528 membrane Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 52
- 238000009835 boiling Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 36
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 35
- 239000003292 glue Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 239000000835 fiber Substances 0.000 claims abstract description 24
- 238000007711 solidification Methods 0.000 claims abstract description 16
- 230000008023 solidification Effects 0.000 claims abstract description 16
- 239000012745 toughening agent Substances 0.000 claims abstract description 14
- 238000000354 decomposition reaction Methods 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 17
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 28
- 229910052751 metal Inorganic materials 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract description 21
- 239000006260 foam Substances 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 4
- 230000008646 thermal stress Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 229920000049 Carbon (fiber) Polymers 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 238000010008 shearing Methods 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- -1 phenolic aldehyde Chemical class 0.000 description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 230000016507 interphase Effects 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000007719 peel strength test Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 230000009970 fire resistant effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920006259 thermoplastic polyimide Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 241001274660 Modulus Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000003473 lipid group Chemical group 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C09J179/085—Unsaturated polyimide precursors
-
- 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
- C09J2461/00—Presence of condensation polymers of aldehydes or ketones
-
- 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
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
-
- 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
- C09J2481/00—Presence of sulfur containing polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A kind of high-temperature resistant carrier glued membrane of present invention proposition and preparation method thereof, is prepared using solwution method on fiber carrier by mixed glue solution, it is characterised in that：The mixed glue solution includes high temperature resistant thermosetting resin, toughener, thermally labile oligomer and high boiling solvent, and the fiber carrier is chopped mat.The present invention is based on bondings and thermal stress to buffer difunctional design, on the one hand glued membrane is enable to realize foam in place at a temperature of high solidification, another aspect glued membrane high tenacity can realize the bonds well of composite material and metal structure, improve peel strength, while can avoid potential corrosion.
Description
Technical field
The present invention relates to a kind of high-temperature resistant carrier glued membranes and preparation method thereof, belong to technical field of composite materials.
Background technology
With the rapid development of aeronautical and space technology, the flying speed of guided missile and aircraft is getting faster, structural bearing material
It is also higher and higher to expect that weight and temperature resistant grade require.Polymer matrix composites have high ratio modulus, high specific strength, can design at present
Property strong, anti-fatigue performance and the features such as corrosion resistance and good be widely used to the components such as primary load bearing, secondary load.Due to flying at present
The Service Environment temperature of row device structure is higher and higher, fire resistant resin based composites be widely used in aircraft missile wing, rudder face,
In the structures such as structure bay section, antenna house.
Current most of connection structures require to mostly use metal structure for reliability and being dismounted for multiple times, i.e., use at present
Structure is mainly metal structure+composite material skin structure.Since metal structure and composite structure coefficient of thermal expansion differ
It causes and there are the reasons such as certain potential corrosion, the at present main processing of carbon-fibre reinforced epoxy resin intermediate temperature setting structural adhesive bonding
Mode is then asphalt mixtures modified by epoxy resin to be coated between metal structure and composite structure after metal structure carries out anodization blasting treatment
Lipid structures adhesive film realizes that co-curing is glued, and intermediate temperature setting epoxy resin is since solidification temperature is relatively low, metal and composite material
The displacement that expands with heat and contract with cold it is smaller, can effectively realize interfacial adhesion.High temperature resistant composite is since solidification temperature is higher, solid
Change and cooling procedure in cause metal structure and composite structure coefficient of thermal expansion inconsistent, and make it in cooling procedure very
It is easy to happen unsticking, while high temperature resistant composite solidification and temperature in use are higher, temperature is higher, the difference of two kinds of material heat expansions
It is different bigger.Traditional epoxies glued membrane is since temperature resistant grade is inadequate, and when high temperature resistant composite cures, glued membrane has carbonized point
It solves or performance is caused drastically to decline, while effective interphase match and good splicing cannot be formed in curing cooling procedure.
Therefore, there is an urgent need for a kind of carrier adhesives can be suitably used for composite material and metal structure, to solve hot setting resin
Based composites and the interphase match of metal structure, bonding are coated with craftsmanship problem.
Invention content
It is an object of the invention to overcome the shortage of prior art, one kind is provided and can effectively improve under high temperature (200 DEG C or more)
Composite material and metal structure interphase match and the high-temperature resistant carrier glued membrane and preparation method thereof of adhesive property.
Technical solution of the invention：A kind of high-temperature resistant carrier glued membrane is carried using solwution method in fiber by mixed glue solution
It is prepared on body, the mixed glue solution includes high temperature resistant thermosetting resin, toughener, thermally labile oligomer and higher boiling
Solvent, fiber carrier are chopped mat；
The thermally labile oligomer is the polymerization that gas or small molecule can be decomposed to give off when reaching heat decomposition temperature
Body, heat decomposition temperature are higher than the boiling point of high boiling solvent, and less than the solidification temperature of high temperature resistant thermosetting resin, additive amount is
The 0.5%~5% of high temperature resistant thermosetting resin quality；
The high boiling solvent is the organic solvent that boiling point is not less than 100 DEG C；The toughener additive amount is resistance to height
Warm the 5%~20% of thermosetting resin quality.
The high temperature resistant thermosetting resin of the present invention is the basic components of glued membrane, and preferred consolidation temperature is at least neater than thermally labile
High 30 DEG C of polymers heat decomposition temperature or more.The present invention is not particularly limited the type of high temperature resistant thermosetting resin, as long as heat-resisting
Property meet and use, solidification temperature meets above-mentioned requirements, such as using bismaleimide (BMI), cyanate (CE), phenolic aldehyde
One in resin, organic siliconresin, polyphenyl Bing oxazines resin, polyimides (PI) resin and polybenzimidazoles (PBI) resin etc.
Kind is several.Those skilled in the art select the high temperature resistant thermosetting tree of suitable temperature resistant grade according to glued membrane use temperature range
Fat.
Toughener main function is the toughness for increasing glued membrane, improves the modulus of shearing of glued membrane, additive amount is very little, and glued membrane is tough
Property it is low, caking property and form-dependent character are influenced after glued membrane foaming, since toughener glass transition temperature is relatively low, if its additive amount is too
It is more, it is easy charing at high temperature, influences bonding and shear strength.It is preferred that additive amount is the 5%~20% of thermosetting property quality, it is identical
Under the conditions of, the toughness of additive amount increase glued membrane is higher within this range, modulus of shearing is higher.The present invention is to toughener resin types
It is not particularly limited, as long as can function as described above, generally uses thermoplastic resin matrix, thermotropic liquid crystal poly- in engineering
Object or liquid rubber etc. are closed, thermoplastic resin matrix generally uses polyether-ether-ketone, polyether sulfone, polyetherimide, thermoplasticity polyamides
The one or more of imines etc..
The thermally labile oligomer of the present invention can decompose to give off gas or small molecule under heat 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 glued membrane 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 heat decomposition temperature point
Liberate out gas or small molecule, and heat decomposition temperature is higher than high boiling solvent boiling point, less than the solidification temperature of thermosetting resin
Can, polyethylene, polyvinyl chloride, polyvinyl alcohol, polypropylene oxide, polymethyl methacrylate, polystyrene, poly- first such as can be used
The condensates such as base styrene, poly- valerolactone and polycaprolactone.Its additive amount is preferably the 0.5% of high temperature resistant thermosetting resin quality
~5%, more preferably 0.5%~3%；If thermally labile oligomer content is too low, swell increment is small at high temperature, cannot form original
Position foaming can not generate displacement progress " occupy-place ", if content is too high to expanding with heat and contract with cold, it is not easy to disperse, be easy to reunite, influence to glue
Knotting strength.Optimum addition is the 0.9%~1.1% of thermosetting resin quality, and in the case that other conditions are constant, glued membrane glues
To meet normal distribution between knot performance and the additive amount of thermally labile oligomer, the bonding of its glued membrane at 0.9%~1.1%
Performance is best.
Further, the solubility parameters of thermally labile oligomer to be differed with the solubility parameters of high temperature resistant thermosetting resin compared with
Greatly, to ensure to form microphase-separated；Thermally labile oligomer and high temperature resistant thermosetting resin form microphase-separated under stiring, heat
Unstable oligomer dispersion is more uniform, and Dispersed Phase Size is smaller, and the abscess to foam is more uniform, and glued membrane interfacial contact area is got over
Greatly, 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, energy when blending
It dissolves each other, separation phase cannot be formed, solubility parameters difference is too big, is easy to reunite, it is not easy to detach, 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 follow-up glued membrane adhesive property,
It can be neglected in engineering.
Further, the heat decomposition temperature of thermally labile oligomer wants moderate, the too low volatilization that cannot be guaranteed solvent, thermal decomposition
Temperature is preferably more than 40 DEG C of high boiling solvent boiling point or more, 30 DEG C of the solidification temperature or more less than thermosetting resin, thermal decomposition
It can quantify and control, and small molecule can be resolved into, be easy to escape from thermosetting resin matrix.
The fiber carrier that the present invention uses is chopped mat, and the chopped strand on surface is in glued membrane expansion process, with gold
Belong to structure and composite structure forms micromechanics connection, carries out " Z " to reinforcing, increase adhesion strength, while the fibre that is chopped is made
Carrier adhesive is tieed up, glued membrane is enhanced and is coated with craftsmanship.The ratio of fiber carrier and mixed glue solution is the known of carrier adhesive preparation
The gel content of technology, general carrier adhesive is 40~60%.
The fiber carrier is chopped mat, and surface density is 20~80g/m2, fiber carrier surface density is too low, glued membrane
The resin layer generated in foaming process in situ is connect with composite material or metal, and brittleness is larger, and toughness is insufficient, in cooling meat
It is easily peeled off in the process, fiber carrier surface density is too high, and thickness is caused to increase, and influences film-forming process and resin to chopped strand
Wellability.Fiber carrier surface density most preferably 30~50g/m2, in the case that other conditions are constant, the adhesive property of glued membrane with
To meet normal distribution between fiber carrier surface density, in 30~50g/m2Most preferably.Kinds of fibers of the present invention does not limit, as long as
The requirement of glued membrane temperature in use can be met, can be the one or more of carbon fiber, glass fibre, aramid fiber or quartz fibre etc.
Mixing, is selected as needed.
The high boiling solvent of the present invention is used for dissolving resin, and participates in solwution method and prepare glued membrane, 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, can 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.Height boiling
The additive amount of point solvent prepares glued membrane technique to select according to the viscosity of dissolubility, mixed solution to resin and solwution method, is
Techniques well known, its additive amount is generally the 150%~400% of thermosetting resin quality in engineering.The present invention is to its kind
Class is also not particularly limited, as long as meeting the requirement of boiling point, n,N-dimethylacetamide (DMAC), diformazan such as may be used
The organic solvents such as base formamide (DMF), N-Methyl pyrrolidone (NMP), N,N-dimethylformamide, dioxane.
Principle analysis：
Boundary layer of the present invention as metal structure and fiber reinforced high-temperature-resistant composite material, due to metal material with it is compound
Material heat expansion performance difference is larger, when metal material cures together in a mold with composite material, becomes in compression and temperature
When change, it may occur that deformation it is inconsistent, the present invention in the curing process, since thermally labile oligomer is dispersed in matrix resin
In, solvent is removed under less than thermally labile oligomer decomposition temperature, when reaching outer layer of composite material solidification temperature, reaches heat
The decomposition temperature of unstable oligomer, since the decomposition of thermally labile segment is foamed, in the curing process, metal with it is compound
Buffer layer is formed between material, is carried out " occupy-place ", and as temperature reduces, metal structure and composite structure are shunk, and work as generation
When relative displacement trend, the present invention can alleviate the relative motion between two media, play bonding and protective effect.Chopped strand carries
Body layer forms micromechanics in boundary layer expansion process, with metal structure and composite structure and connect, progress " Z " to reinforcing,
Increase adhesion strength.
A kind of high-temperature resistant carrier glue film manufacturing process, is realized by following steps：
The first step prepares mixed glue solution,
A1.1, thermosetting resin and toughener resin be added in high boiling solvent in proportion, molten less than higher boiling
It is fully dissolved at a temperature of agent boiling point, obtains mixed glue solution A；
The toughener resin quality is the 5%~20% of thermosetting resin quality, and when dissolving is stirred, and temperature is excellent
40 DEG C~80 DEG C less than high boiling solvent boiling point are selected as, if temperature is too low when dissolving can influence solution rate and resin dissolving
Rate, temperature is too close apart from boiling point, solvent can be caused to volatilize, same to influence resin dissolution rate.
A1.2, thermally labile oligomer is added in the mixed glue solution A that step A1.1 is obtained, is uniformly mixed, is mixed
Glue liquid B；
The thermally labile oligomer additive amount is the 0.5%~5% of thermosetting resin quality, the thermally labile
30 DEG C of solidification temperature of the heat decomposition temperature of oligomer higher than 40 DEG C of high boiling solvent boiling point or more, less than thermosetting resin with
On.Mixing, which can be used, to be stirred or the uniform equal usual manners of ultrasonic disperse.
Second step, solwution method prepare carrier adhesive,
Fiber carrier is got out, the first step is obtained mixed glue solution obtains carrier glue using solwution method dipping fiber carrier
Film dries at 40~80 DEG C according to control thickness is required, obtains the glued membrane of microphase-separated.This step is known in the art skill
Art, those skilled in the art carry out the settings such as specific process parameter according to actual production.
The high-temperature resistant carrier glued membrane that the present invention is prepared is in use, glued membrane is attached on metalwork, on glued membrane
It is coated with high temperature resistant prepreg, is cured according to fire resistant resin curing process, is decomposed when temperature reaches thermally labile oligomer
When temperature, the thermally labile oligomer of microphase-separated starts to foam, filling thermal dilation difference generate displacement, improve caking property and
Metalwork and composite material matching.
The advantageous effect of the present invention compared with prior art：
(1) the present invention is based on bondings and thermal stress to buffer difunctional design, on the one hand enables glued membrane in high solidification temperature
Lower realization foam in place, another aspect glued membrane high tenacity can realize the bonds well of composite material and metal structure, improve stripping
From intensity, while potential corrosion can be avoided；
(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 fiber carrier layer chopped strand realizes foam in place, foam in place layer and chopped mat surface fiber energy in the curing process
It enough realizes the micro-force sensing between composite material and metal structure, realizes micromechanics " anchor ", promote adhesion strength；
(3) present invention prepares carrier adhesive by toughening agent modified thermosetting resin using solwution method, improves glue first
The toughness and shear strength of film promote the shear strain of glue-line, increase the peel strength of metal structure and composite structure；
(4) present invention by thermally labile oligomer in thermosetting resin solution microphase-separated, in the curing process, by
It is dispersed in matrix resin in thermally labile oligomer, solvent is removed under less 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 thermally labile segment
Decomposition is foamed, and in the curing process, is formed buffer layer between metal and composite material, is carried out " occupy-place ", as temperature drops
Low, metal structure and composite structure are shunk, and when relative displacement trend occurs, which can alleviate between two media
Bonding and protective effect are played in relative motion.
Specific implementation mode
With reference to specific example, the present invention is described in detail.
Embodiment 1
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) (166 DEG C of boiling point), at 115 DEG C stir 3h, it is to be mixed uniformly be completely dissolved after, then be added 1 part of polyphenyl second
Alkene oligomer (325 DEG C of heat decomposition temperature) ultrasonic mixing is uniform, and preparation surface density is 30g/m2Chopped carbon fiber felt, utilizes solution
The glue prepared is enclosed isolation film by method in chopped carbon fiber felt by predetermined thickness dual coating in 60 DEG C of h heat baking 0.5h,
The glued membrane that thickness is 0.1mm is made.45# steel discs are bonded using the glued membrane, by 240 DEG C/2h+370 DEG C/3h, 3MPa pressure conditions
Lower hot-press solidifying, by GB/T 7122-1996 peel strength tests methods and GB/T 7124-1986 method for testing shear strength,
Room temperature and 400 DEG C of peel strengths and shear strength are tested respectively, and shear strength is 13.78MPa, peel strength at room temperature
2.15KN/m, 400 DEG C of shear strengths of high temperature are 6.34MPa, peel strength 0.93KN/m.
Embodiment 2
100 part of 5428 bismaleimide (BMI), 20 parts of thermoplastic poly ether sulfones are added to 250 parts of dioxane (boiling points
101.5 DEG C) in, stir 3h at 55 DEG C, it is to be mixed be uniformly completely dissolved after, 5 parts of polyethylene oligomers (thermal decomposition temperature is then added
142 DEG C of degree) ultrasonic mixing is uniform, and preparations surface density is 30g/m2Chopped carbon fiber felt, using solwution method the glue prepared
It is coated on fiber carrier by predetermined thickness, dries 0.5h in 60 DEG C of h heat, enclose isolation film, the interface that thickness is 0.1mm is made
Layer.45# steel discs are bonded using the glued membrane, by 180 DEG C/2h+200 DEG C/3h, hot-press solidifying under 3MPa pressure conditions, by GB/T
7122-1996 peel strength tests method and GB/T 7124-1986 method for testing shear strength test room temperature and 250 DEG C respectively
Peel strength and shear strength, shear strength is 10.94MPa at room temperature, and peel strength 1.42KN/m, 250 DEG C of shearings of high temperature are by force
Degree is 4.94MPa, peel strength 0.84KN/m.
Embodiment 3
100 parts of Novolac types cyanates, 20 parts of thermoplastic poly ether ether ketones are added to 250 parts of dimethylformamides (DMF)
In (152 DEG C of boiling point), at 110 DEG C stir 3h, it is to be mixed uniformly be completely dissolved after, then be added 1 part of polypropylene oxide oligomer
(200 DEG C of heat decomposition temperature) ultrasonic mixing is uniform, and preparation surface density is 30g/m2Chopped carbon fiber felt, using solwution method preparation
Good glue is coated in by predetermined thickness on fiber carrier, is dried 0.5h in 60 DEG C of h heat, is enclosed isolation film, it is 0.1mm that thickness, which is made,
Glued membrane.45# steel discs are bonded using the glued membrane, by 240 DEG C/2h+300 DEG C/3h, hot-press solidifying under 3MPa pressure conditions, by GB/
T 7122-1996 peel strength tests methods and GB/T 7124-1986 method for testing shear strength test room temperature and 300 respectively
DEG C peel strength and shear strength, shear strength is 14.68MPa, peel strength 1.89KN/m, 300 DEG C of shearings of high temperature at room temperature
Intensity is 7.94MPa, peel strength 0.99KN/m.
Embodiment 4
Except Vespel thermoplastic polyimide is 10 especially, remaining obtains glued membrane with embodiment 1, test respectively room temperature and
400 DEG C of peel strengths and shear strength, shear strength is 11.83MPa, peel strength 1.62KN/m at room temperature, and 400 DEG C of high temperature cuts
Shearing stress is 5.91MPa, peel strength 0.72KN/m.
Embodiment 5
Except polystyrene oligomer is 3 especially, remaining obtains glued membrane with embodiment 1, tests room temperature and 400 DEG C of strippings respectively
From intensity and shear strength, shear strength is 10.71MPa, peel strength 1.33KN/m, 400 DEG C of shear strengths of high temperature at room temperature
For 4.63MPa, peel strength 0.54KN/m.
Embodiment 6
Except polystyrene oligomer is that 0.5 especially, remaining is consistent with embodiment 1, obtains glued membrane, test respectively room temperature and
400 DEG C of peel strengths and shear strength, shear strength is 11.56MPa, peel strength 1.69KN/m at room temperature, and 400 DEG C of high temperature cuts
Shearing stress is 5.27MPa, peel strength 0.79KN/m.
Embodiment 7
Except chopped carbon fiber surface density is 20g/m2Outside, remaining is consistent with embodiment 1, obtains glued membrane, tests room temperature respectively
And 400 DEG C of peel strengths and shear strength, shear strength is 11.84MPa, peel strength 1.78KN/m, 400 DEG C of high temperature at room temperature
Shear strength is 5.64MPa, peel strength 0.79KN/m.
Embodiment 8
Except chopped carbon fiber surface density is 80g/m2Outside, remaining is consistent with embodiment 1, obtains glued membrane, cuts at room temperature respectively
Shearing stress is 10.65MPa, and peel strength 1.15KN/m, 400 DEG C of shear strengths of high temperature are 4.35MPa, peel strength 0.55KN/
m。
From implementing 1,4 as can be seen that under the same terms, increase the additive amount of toughener, the toughness of carrier adhesive is higher, cuts
Shear modulu is higher；It can be seen that under the same terms from embodiment 1,5,6, it is high with the variation of thermally labile oligomer additive amount
The adhesive property of the lower glued membrane of temperature is in normal distribution, reaches peak value when additive amount is 1% or so；It can be with from embodiment 1,7,8
To find out, under the same terms, with the variation of chopped strand carrier surface density, the adhesive property of glued membrane is in normal distribution under high temperature,
Surface density is 30~50g/m2Reach peak value when left and right.
Unspecified part of the present invention is known to the skilled person technology.
Claims (10)
1. a kind of high-temperature resistant carrier glued membrane is prepared using solwution method on fiber carrier by mixed glue solution, it is characterised in that：
The mixed glue solution includes high temperature resistant thermosetting resin, toughener, thermally labile oligomer and high boiling solvent, the fibre
Dimension carrier is chopped mat；
The thermally labile oligomer heat decomposition temperature is higher than the boiling point of high boiling solvent, and is less than high temperature resistant thermosetting resin
Solidification temperature, additive amount be high temperature resistant thermosetting resin quality 0.5%~5%；
The high boiling solvent is the organic solvent that boiling point is not less than 100 DEG C；The toughener additive amount is high temperature heat-resistant
The 5%~20% of thermosetting resin quality.
2. a kind of high-temperature resistant carrier glued membrane according to claim 1, it is characterised in that：The thermally labile oligomer adds
Dosage is the 0.5%~3% of high temperature resistant thermosetting resin quality.
3. a kind of high-temperature resistant carrier glued membrane according to claim 1, it is characterised in that：The thermally labile oligomer adds
Dosage is the 0.9%~1.1% of high temperature resistant thermosetting resin quality.
4. a kind of high-temperature resistant carrier glued membrane according to claim 1, it is characterised in that：The thermally labile oligomer
Solubility parameters will differ 0.8~3.7 with the solubility parameters of high temperature resistant thermosetting resin.
5. a kind of high-temperature resistant carrier glued membrane according to claim 1, it is characterised in that：The thermally labile oligomer
Heat decomposition temperature is higher than 40 DEG C of high boiling solvent boiling point or more, less than 30 DEG C of the solidification temperature or more of thermosetting resin.
6. a kind of high-temperature resistant carrier glued membrane according to claim 1, it is characterised in that：The face of the chopped mat is close
Degree is 20~80g/m2。
7. a kind of high-temperature resistant carrier glued membrane according to claim 1, it is characterised in that：The face of the chopped mat is close
Degree is 30~50g/m2。
8. a kind of high-temperature resistant carrier glue film manufacturing process, which is characterized in that realized by following steps：
The first step prepares mixed glue solution,
A1.1, thermosetting resin and toughener resin be added in high boiling solvent in proportion, boiled less than high boiling solvent
It is fully dissolved at a temperature of point, obtains mixed glue solution A；
A1.2, thermally labile oligomer is added in the mixed glue solution A that step A1.1 is obtained, is uniformly mixed, obtains mixed glue solution
B；
Second step, solwution method prepare carrier adhesive.
9. a kind of high-temperature resistant carrier glue film manufacturing process according to claim 8, it is characterised in that：In the step A1.1
Toughener resin quality be the 5%~20% of thermosetting resin quality, when dissolving, is stirred, and temperature is preferably less than height boiling
40 DEG C~80 DEG C of point solvent boiling point.
10. a kind of high-temperature resistant carrier glue film manufacturing process according to claim 8, it is characterised in that：The step A1.2
Middle thermally labile oligomer additive amount is the 0.5%~5% of thermosetting resin quality, the heat point of the thermally labile oligomer
It solves temperature and is higher than 40 DEG C of high boiling solvent boiling point or more, less than 30 DEG C of the solidification temperature or more of thermosetting resin.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110861382A (en) * | 2019-10-18 | 2020-03-06 | 成都鲁晨新材料科技有限公司 | Solvent-free aramid bulletproof prepreg and composite material thereof |
| CN112874078A (en) * | 2019-11-29 | 2021-06-01 | 航天特种材料及工艺技术研究所 | Electromagnetic insulation support and preparation method thereof |
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| JP2010132891A (en) * | 2008-10-31 | 2010-06-17 | Nippon Synthetic Chem Ind Co Ltd:The | Adhesive for optical member, optical member having adhesive layer attached thereto and obtained by using the same, and adhesive composition for active energy beam-setting and/or thermosetting optical member |
| CN204196371U (en) * | 2014-09-30 | 2015-03-11 | 张家港长泰汽车饰件材料有限公司 | The numb fine composite plate of a kind of automotive trim |
| CN105058669A (en) * | 2015-07-27 | 2015-11-18 | 无锡吉兴汽车声学部件科技有限公司 | Manufacturing process for automobile acoustic component sound insulating pad |
| CN205467724U (en) * | 2016-01-19 | 2016-08-17 | 广州金发碳纤维新材料发展有限公司 | Composite plate |
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| JP2010132891A (en) * | 2008-10-31 | 2010-06-17 | Nippon Synthetic Chem Ind Co Ltd:The | Adhesive for optical member, optical member having adhesive layer attached thereto and obtained by using the same, and adhesive composition for active energy beam-setting and/or thermosetting optical member |
| CN204196371U (en) * | 2014-09-30 | 2015-03-11 | 张家港长泰汽车饰件材料有限公司 | The numb fine composite plate of a kind of automotive trim |
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| CN110861382A (en) * | 2019-10-18 | 2020-03-06 | 成都鲁晨新材料科技有限公司 | Solvent-free aramid bulletproof prepreg and composite material thereof |
| CN112874078A (en) * | 2019-11-29 | 2021-06-01 | 航天特种材料及工艺技术研究所 | Electromagnetic insulation support and preparation method thereof |
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