CN105694756A - High-temperature-resisting structural adhesive film capable of being stored for long time at room temperature and preparation method thereof - Google Patents
High-temperature-resisting structural adhesive film capable of being stored for long time at room temperature and preparation method thereof Download PDFInfo
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- CN105694756A CN105694756A CN201610150513.XA CN201610150513A CN105694756A CN 105694756 A CN105694756 A CN 105694756A CN 201610150513 A CN201610150513 A CN 201610150513A CN 105694756 A CN105694756 A CN 105694756A
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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
- 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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- 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
- 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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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention provides a high-temperature-resisting structural adhesive film capable of being stored for a long time at the room temperature and a preparation method thereof and relates to a structural adhesive film and a method for preparing the adhesive film. The structural adhesive film and the method for preparing the adhesive film aim to solve the problems that an existing structural adhesive film is short in room temperature storage life, and combusted smoke is high in toxin. The adhesive film is composed of polybenzoxazine resin, a toughening agent, modifier, a heat conduction material, a coupling agent, inorganic filler and a carrier. The preparation method includes the steps that firstly, process modifier and toughening modifier are subjected to prepolymerization in a reaction kettle, then the polybenzoxazine resin is added and stirred to be uniform, and modified polybenzoxazine resin is obtained; then, the modified polybenzoxazine resin is subjected to vacuum kneading with the silane coupling agent, the heat conduction material and the inorganic filler through a kneading machine, and an adhesive material is obtained; finally, the adhesive material is subjected to hot pressing with the carrier on an adhesive film calender to be made into the film, and the high-temperature-resisting structural adhesive film can be obtained. The high-temperature-resisting structural adhesive film has the advantages of being flame retardant, low in smoke, low in toxin, capable of achieving complete curing at the temperature of 185 DEG C, high in adhesion strength and good in high temperature resistance; the adhesive film is stored for 180 days at the room temperature, and process performance and adhesion performance maintain unchanged.
Description
Technical field
The present invention relates to a kind of structural film adhesive and the method preparing this glued membrane。
Background technology
The high-temperature-resistant structure adhesive of aerospace field mainly has epoxy resin type, bismaleimide resin type and cyanate ester resin type。These adhesive generally need low tempertaure storage, and general storage about 20 days under room temperature, additionally these adhesive are as, when without fire retardant, the smoke toxicity that great majority discharge after combustion is big。Cigarette fire-retardant, low and hypotoxicity requirement can not be met。
Therefore, it is long to develop a kind of room temperature storage phase, cigarette fire-retardant, low and hypotoxicity glued membrane, has great importance meeting the aerospace field requirement to high-temperature Resistance Adhesives, it is contemplated that be applied on Aero-Space Multiple Type。
Summary of the invention
The present invention is short in order to solve existing structure glued membrane pot life at room temperature, the problem of the burning big grade of smoke toxicity。Thering is provided under a kind of room temperature can the high-temperature-resistant structure glued membrane and preparation method thereof of long-term storage。The method completes under condition of no solvent, pollution-free, and technique is simple。
Under a kind of room temperature of the present invention can the high-temperature-resistant structure glued membrane of long-term storage, be made up of the benzoxazine resins of 75～100 parts, 10～20 parts of process modification agent, the plasticized modifier of 10～20 parts, 1～2 part of coupling agent, 1～3 part of Heat Conduction Material, the inorganic filler of 1～3 part and carrier according to mass fraction。
Can the preparation method of high-temperature-resistant structure glued membrane of long-term storage be carry out according to following steps under a kind of room temperature of the present invention:
One, the inorganic filler of the benzoxazine resins of 75～100 parts, the process modification agent of 10～20 parts, 10～20 parts of plasticized modifiers, 1～2 part of coupling agent, 1～3 part of Heat Conduction Material and 1～3 part is weighed by mass parts；
Two, the process modification agent weighed in step one is heated in the reactor with agitating device, stirred, when heating is to 175 DEG C～200 DEG C, the plasticized modifier weighed in step one is added reactor, 10min～15min is kept at 175 DEG C～200 DEG C temperature, after toughener all dissolves, temperature of reaction kettle is reduced to 130 DEG C～140 DEG C, then the benzoxazine resins weighed in step one addition is stirred, obtain thick resin, it is modified benzoxazine resins, pours out standby；
Three, kneader is adopted to mix homogeneously at 75 DEG C-80 DEG C the modified benzoxazine resins prepared in the step 2 coupling agent with step one and Heat Conduction Material and inorganic filler, then evacuation 15～20min, namely obtain sizing material；
Four, the sizing material in step 3 preheating 20min～40min in the baking oven of 60 DEG C～80 DEG C, then by carrier hot calender film forming on the glued membrane calender that roller temperature is 60 DEG C～80 DEG C, namely obtaining under room temperature can the high-temperature-resistant structure glued membrane of long-term storage。
The benzoxazine resins of the present invention is by bisphenol A-type benzimidazole dihydrochloridePhenolphthalein type benzimidazole dihydrochlorideBisphenol-f type benzimidazole dihydrochloride4,4-MDA type benzimidazole dihydrochlorideDicyclopentadiene type benzimidazole dihydrochlorideThiobis phenolic benzimidazole dihydrochlorideIn one or more by arbitrarily than forming。
Plasticized modifier, by the polyether-ketone with terminal hydroxy group, has the Polyetherimide of terminal hydroxy group, amine end groups or acid anhydride end group, has the polyphenylene oxide of terminal hydroxy group, has one or more in the PAEK of terminal hydroxy group by arbitrarily than composition。
When there is no chemical compatibility; engineering plastics and matrix resin often observe stripping and granule layering; the shortage compatibility frequently can lead to the interface between granule and substrate and caused too early micro-crack, and after phase reversal, thermostability and solvent resistance are affected。The present invention adopts response type high performance engineering plastics to carry out toughness reinforcing to adhesive, increases its interface cohesion with interlaminar resin and adhesion strength, it is achieved the chemical bonding of particle and matrix resin, it is possible to effectively play resin toughening and opposing micro-crack extension ability。
Process modification agent is by N, N, N, N-four glycidyl group-4,4 '-MDAAnd N, N, O-triglycidyl group para-aminophenolIn one or both by arbitrarily than forming。
Process modification agent is possible not only to improve benzoxazine resins film property, in the curing process can also and benzoxazine resins between there is polyreaction, can increase resin crosslink density, improve glue-joint strength。
Coupling agent is made up of by arbitrarily ratio one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane, methyl tri-tert peroxy-silane。
Heat Conduction Material is made up of by arbitrarily ratio one or more in aluminium nitride, boron nitride, thermal conductivity graphene, superconduction carbon fiber。
The adding purpose of Heat Conduction Material is to be passed by the heat gathered in glued membrane solidification process, it is prevented that the generation of the phenomenon such as hot-spot or implode, causes bonding defect。
By in aerosil, Rutile type titanium dioxide, one or both form by arbitrarily ratio in inorganic filler。
Carrier is made up of by arbitrarily ratio the one in glass fiber woven cloth, glass fibre non-woven or polyester non-woven fabric。
Under a kind of room temperature of the present invention can high-temperature-resistant structure glued membrane and preparation method thereof the advantage of long-term storage as follows:
1, the present invention is using the benzoxazine resins matrix resin as structural film adhesive, benzoxazine resins has fire-retardant compared with other thermosetting resins, low cigarette, low toxicity characteristic, additionally benzoxazine resins low cost of manufacture, structure is easy to get, building-up process can be passed through different structure and give benzoxazine resins different qualities, matrix resin of the present invention adopts bisphenol A-type benzimidazole dihydrochloride, phenolphthalein type benzimidazole dihydrochloride, bisphenol-f type benzimidazole dihydrochloride, 4, 4-MDA type benzimidazole dihydrochloride, dicyclopentadiene type benzimidazole dihydrochloride, one or more in thiobis phenolic benzimidazole dihydrochloride press any combination。
2, the high-temperature-resistant structure glued membrane of long-term storage can realizing being fully cured (see Fig. 1) at 185 DEG C under the room temperature of the present invention, have high temperature resistant feature simultaneously, glass transition temperature reaches 224 DEG C (see Fig. 2)；In air, the thermal weight loss rate of 5% has reached 400 DEG C (see Fig. 3)；Good ablation resistance, high fixing carbon is one of mark of Flame Retardancy, and in this glued membrane nitrogen, carbon yield 48% (see Fig. 3) when 800 DEG C, is 5-8 times of epoxy jelly membrane；This glued membrane bonding reliability is high, room temperature shear strength can reach more than 25.0MPa, 140 DEG C of shear strengths can reach more than 28.0MPa, 200 DEG C of shear strengths can reach more than 15.0MPa, 90 ° of plates of room temperature/plate peel strength can reach more than 20.0N/cm, and 140 DEG C of planar stretch intensity can reach more than 6.0MPa。
3, under the room temperature of the present invention can maximum being also advantageous in that of the high-temperature-resistant structure glued membrane of long-term storage this glued membrane stores and with the obvious advantage in transportation, it is not necessary to cold preservation, room temperature storage 180 days, processing performance and adhesive property remain unchanged。
The high-temperature-resistant structure glued membrane of long-term storage " under a kind of room temperature can " of the present invention belongs to hot setting structural adhesive research field, is mainly used in the splicing between aerospace field metal and composite。The present invention adopts benzoxazine resins to be matrix resin, response type high performance engineering plastics is toughening material, add process modification agent and other auxiliary agent be prepared under a kind of room temperature can the high-temperature-resistant structure glued membrane of long-term storage, this glued membrane have room temperature storage phase length, cigarette fire-retardant, low and hypotoxicity, high temperature resistant, glued joint that reliability is high, the feature such as processing performance is good。Compared with epoxy resin glued membrane, under room temperature, the high-temperature-resistant structure glued membrane of long-term storage can show outstanding thermostability, cigarette fire-retardant, resistance to and gas defence performance。With tego film the difference is that, the high-temperature-resistant structure glued membrane of long-term storage can release without little molecule in the curing process under room temperature, micro-flaw or bubble will not be produced, durability is better。Although span glued membrane is than benzoxazine glued membrane slightly advantage in operating temperature, but the high-temperature-resistant structure glued membrane of long-term storage can there is significant advantage in cost and solidification temperature under room temperature, it is only necessary to 185 DEG C, 3h can complete to solidify。
Accompanying drawing illustrates:
Fig. 1 be test 1 room temperature under can the DSC curve figure of high-temperature-resistant structure glued membrane of long-term storage；
Fig. 2 be test 1 room temperature under can the DMA curve chart of high-temperature-resistant structure glued membrane of long-term storage；Wherein, A is storage modulus E,；B is mechanical loss Tan δ；
Fig. 3 be test 1 room temperature under can the TG curve chart of high-temperature-resistant structure glued membrane of long-term storage；Wherein, A is TG curve in air；B is TG curve in nitrogen。
Detailed description of the invention
Technical solution of the present invention is not limited to act detailed description of the invention set forth below, also includes the combination in any between each detailed description of the invention。
Detailed description of the invention one: under a kind of room temperature of present embodiment can the high-temperature-resistant structure glued membrane of long-term storage, according to mass fraction by the benzoxazine resins of 75～100 parts, the process modification agent of 10～20 parts, 10～20 parts of plasticized modifiers, 1～2 part of coupling agent, 1～3 part of Heat Conduction Material and 1～3 part inorganic filler and carrier make。
Detailed description of the invention two: present embodiment and detailed description of the invention one the difference is that: benzoxazine resins is made up of by arbitrarily ratio one or more in bisphenol A-type benzimidazole dihydrochloride, phenolphthalein type benzimidazole dihydrochloride, bisphenol-f type benzimidazole dihydrochloride, 4,4-MDA type benzimidazole dihydrochloride, dicyclopentadiene type benzimidazole dihydrochloride, thiobis phenolic benzimidazole dihydrochloride。Other is identical with detailed description of the invention one。
Detailed description of the invention three: present embodiment and detailed description of the invention one or two the difference is that: plasticized modifier is by the polyether-ketone with terminal hydroxy group, there is the Polyetherimide of terminal hydroxy group, amine end groups or acid anhydride end group, there is the polyphenylene oxide of terminal hydroxy group, there are one or more in the PAEK of terminal hydroxy group by arbitrarily than composition。Other is identical with detailed description of the invention one or two。
Detailed description of the invention four: present embodiment and detailed description of the invention one to three the difference is that: process modification agent is by N, N, N, N-four glycidyl group-4, one or both in 4 '-MDA and N, N, O-triglycidyl group para-aminophenol are by arbitrarily than composition；Other is identical with detailed description of the invention one to three。
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four the difference is that: coupling agent is made up of by arbitrarily ratio one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane, methyl tri-tert peroxy-silane；Other is identical with one of detailed description of the invention one to four。
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five the difference is that: Heat Conduction Material is made up of by arbitrarily ratio one or more in aluminium nitride, boron nitride, thermal conductivity graphene, superconduction carbon fiber；Other is identical with one of detailed description of the invention one to five。
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six the difference is that: by aerosil and Rutile type titanium dioxide, one or both form by arbitrarily ratio in inorganic filler；Other is identical with one of detailed description of the invention one to six。
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven the difference is that: carrier is made up of the one in glass fiber woven cloth, glass fibre non-woven or polyester non-woven fabric。Other is identical with one of detailed description of the invention one to seven。
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight the difference is that: can the high-temperature-resistant structure glued membrane of long-term storage be made up of the benzoxazine resins of 80～90 parts, 10～20 parts of process modification agent, the plasticized modifier of 10～20 parts, 1～2 part of coupling agent, 1～3 part of Heat Conduction Material, the inorganic filler of 1～3 part and carrier according to mass fraction under room temperature。Other is identical with one of detailed description of the invention one to eight。
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine the difference is that: can be made up of the benzoxazine resins of 90～100 parts, 10～20 parts of process modification agent, the plasticized modifier of 10～20 parts, 1～2 part of coupling agent, 1～3 part of Heat Conduction Material, the inorganic filler of 1～3 part and carrier according to mass fraction the high-temperature-resistant structure glued membrane of long-term storage under room temperature。Other is identical with one of detailed description of the invention one to nine。
Detailed description of the invention 11: one of present embodiment and detailed description of the invention one to ten the difference is that: can be made up of the benzoxazine resins of 75～85 parts, 10～20 parts of process modification agent, the plasticized modifier of 10～20 parts, 1～2 part of coupling agent, 1～3 part of Heat Conduction Material, the inorganic filler of 1～3 part and carrier according to mass fraction the high-temperature-resistant structure glued membrane of long-term storage under room temperature。Other is identical with one of detailed description of the invention one to ten。
Detailed description of the invention 12: can the preparation method of high-temperature-resistant structure glued membrane of long-term storage carry out according to following steps under a kind of room temperature of the present embodiment present invention:
One, the inorganic filler of the benzoxazine resins of 75～100 parts, the process modification agent of 10～20 parts, 10～20 parts of plasticized modifiers, 1～2 part of coupling agent, 1～3 part of Heat Conduction Material and 1～3 part is weighed by mass parts；
Two, the process modification agent weighed in step one is heated in the reactor with agitating device, stirred, when heating is to 175 DEG C～200 DEG C, the plasticized modifier weighed in step one is added reactor, 10min～15min is kept at 175 DEG C～200 DEG C temperature, after toughener all dissolves, temperature of reaction kettle is reduced to 130 DEG C～140 DEG C, then the benzoxazine resins weighed in step one addition is stirred, obtain thick resin, it is modified benzoxazine resins, pours out standby；
Three, kneader is adopted to mix homogeneously at 75 DEG C-80 DEG C the modified benzoxazine resins prepared in the step 2 coupling agent with step one and Heat Conduction Material and inorganic filler, then evacuation 15～20min, both obtained sizing material；
Four, the sizing material in step 3 preheating 20min～40min in the baking oven of 60 DEG C～80 DEG C, then by carrier hot calender film forming on the glued membrane calender that roller temperature is 60 DEG C～80 DEG C, namely obtaining under room temperature can the high-temperature-resistant structure glued membrane of long-term storage。
Detailed description of the invention 13: present embodiment and detailed description of the invention 12 the difference is that: step 3 kneader vacuum is not less than-0.092MPa。Other is identical with detailed description of the invention 12。
Detailed description of the invention 14: present embodiment and detailed description of the invention 12 or 13 the difference is that: in step 4, sizing material preheat 30min in the baking oven of 65 DEG C～70 DEG C, adopts three rollers to turn and is coated with film forming on film-making machine, and film-forming temperature is 70～75 DEG C。Other is identical with detailed description of the invention 12 or 13。
Detailed description of the invention 15: one of present embodiment and detailed description of the invention ten two to ten four the difference is that: step one weighs the inorganic filler of the benzoxazine resins of 80～90 parts, 10～20 parts of process modification agent, the plasticized modifier of 10～20 parts, 1～2 part of coupling agent, 1～3 part of Heat Conduction Material and 1～3 part。Other is identical with one of detailed description of the invention ten two to ten four。
Beneficial effects of the present invention is verified by tests below:
Test 1, can the preparation method of high-temperature-resistant structure glued membrane of long-term storage sequentially include the following steps: under a kind of room temperature of this test
One, the inorganic filler of the benzoxazine resins of 80 parts, the process modification agent of 10 parts, 10 parts of plasticized modifiers, 1 part of coupling agent, 2 parts of Heat Conduction Materials and 2 parts is weighed by mass parts；
Two, the process modification agent weighed in step one is heated in the reactor with agitating device, stirred, when heating is to 175 DEG C～200 DEG C, the plasticized modifier weighed in step one is added reactor, keep 175 DEG C～200 DEG C, 10min～15min, after toughener all dissolves, temperature of reaction kettle is reduced between 130 DEG C～140 DEG C rapidly, then the benzoxazine resins weighed in step one addition is stirred, obtain thick resin, pour out standby；
Three, kneader is adopted to mix homogeneously at 75 DEG C～80 DEG C the modified benzoxazine resins prepared in step 2 and silane coupler and Heat Conduction Material and other inorganic fillers, then evacuation 15～20min, both obtained sizing material；
Four, the sizing material in step 3 preheating 20min～40min in the baking oven of 60 DEG C～80 DEG C, then by carrier hot calender film forming on the glued membrane calender that roller temperature is 60 DEG C～80 DEG C, namely obtaining under room temperature can the high temperature resistant benzoxazine resins structural film adhesive of long-term storage。
The benzoxazine resins of this test is made up of phenolphthalein type benzimidazole dihydrochloride and 4,4-MDA type benzoxazine resins, and the consumption of the two is the ratio composition of 5:3 in mass ratio；
Process modification agent is N, N, O-triglycidyl group para-aminophenol；
Plasticized modifier is made up of for 2:1 ratio with the polyphenylene oxide with terminal hydroxy group in mass ratio the polyether-ketone with terminal hydroxy group；
Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Heat Conduction Material is made up of the ratio that boron nitride and thermal conductivity graphene are 10:1 in mass ratio；
Inorganic filler is made up of the ratio that Rutile type titanium dioxide and fumed silica are 10:1 in mass ratio；
Vacuum kneader vacuum is not less than-0.092MPa；
Carrier is glass fibre non-woven。
Test 2, can the preparation method of high-temperature-resistant structure glued membrane of long-term storage sequentially include the following steps: under a kind of room temperature of this test
One, the inorganic filler of the benzoxazine resins of 80 parts, the process modification agent of 12 parts, 12 parts of plasticized modifiers, 1 part of coupling agent, 2 parts of Heat Conduction Materials and 2 parts is weighed by mass parts；
Two, the process modification agent weighed in step one is heated in the reactor with agitating device, stirred, when heating is to 175 DEG C～200 DEG C, the plasticized modifier weighed in step one is added reactor, keep 175 DEG C～200 DEG C, 10min～15min, after toughener all dissolves, temperature of reaction kettle is reduced between 130 DEG C～140 DEG C rapidly, then the benzoxazine resins weighed in step one addition is stirred, obtain thick resin, pour out standby；
Three, kneader is adopted to mix homogeneously at 75 DEG C～80 DEG C the modified benzoxazine resins prepared in step 2 and silane coupler and Heat Conduction Material and other inorganic fillers, then evacuation 15～20min, both obtained sizing material；
Four, the sizing material in step 3 preheating 20min～40min in the baking oven of 60 DEG C～80 DEG C, then by carrier hot calender film forming on the glued membrane calender that roller temperature is 60 DEG C～80 DEG C, namely obtaining under room temperature can the high temperature resistant benzoxazine resins structural film adhesive of long-term storage。
The benzoxazine resins of this test is made up of bisphenol-f type benzimidazole dihydrochloride and 4,4-MDA type benzoxazine resins, and the consumption of the two is the ratio composition of 5:3 in mass ratio；
Process modification agent is N, N, N, N-four glycidyl group-4,4 '-MDA；
Plasticized modifier is the polyether-ketone with terminal hydroxy group；
Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Heat Conduction Material is made up of the ratio that boron nitride and superconduction carbon fiber are 10:1 in mass ratio；
Inorganic filler is made up of the ratio that Rutile type titanium dioxide and fumed silica are 10:1 in mass ratio；
Vacuum kneader vacuum is not less than-0.092MPa；
Carrier is glass fibre non-woven。
Test 3, can the preparation method of high-temperature-resistant structure glued membrane of long-term storage sequentially include the following steps: under a kind of room temperature of this test
One, the inorganic filler of the benzoxazine resins of 90 parts, the process modification agent of 15 parts, 15 parts of plasticized modifiers, 1 part of coupling agent, 2 parts of Heat Conduction Materials and 2 parts is weighed by mass parts；
Two, the process modification agent weighed in step one is heated in the reactor with agitating device, stirred, when heating is to 175 DEG C～200 DEG C, the plasticized modifier weighed in step one is added reactor, keep 175 DEG C～200 DEG C, 10min～15min, after toughener all dissolves, temperature of reaction kettle is reduced between 130 DEG C～140 DEG C rapidly, then the benzoxazine resins weighed in step one addition is stirred, obtain thick resin, pour out standby；
Three, kneader is adopted to mix homogeneously at 75 DEG C～80 DEG C the modified benzoxazine resins prepared in step 2 and silane coupler and Heat Conduction Material and other inorganic fillers, then evacuation 15～20min, both obtained sizing material；
Four, the sizing material in step 3 preheating 20min～40min in the baking oven of 60 DEG C～80 DEG C, then by carrier hot calender film forming on the glued membrane calender that roller temperature is 60 DEG C～80 DEG C, namely obtaining under room temperature can the high temperature resistant benzoxazine resins structural film adhesive of long-term storage。
The benzoxazine resins of this test is made up of bisphenol-f type benzimidazole dihydrochloride and phenolphthalein type benzoxazine resins, and the consumption of the two is the ratio composition of 5:3 in mass ratio；
Process modification agent is N, N, N, N-four glycidyl group-4,4 '-MDA；
Plasticized modifier is made up of for 2:1 ratio with the polyphenylene oxide with terminal hydroxy group in mass ratio the polyether-ketone with terminal hydroxy group；
Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Heat Conduction Material is made up of the ratio that boron nitride and superconduction carbon fiber are 10:1 in mass ratio；
Inorganic filler is made up of the ratio that Rutile type titanium dioxide and fumed silica are 10:1 in mass ratio；
Vacuum kneader vacuum is not less than-0.092MPa；
Carrier is glass fibre non-woven。
Test 4, can the preparation method of high-temperature-resistant structure glued membrane of long-term storage sequentially include the following steps: under a kind of room temperature of this test
One, the inorganic filler of the benzoxazine resins of 90 parts, the process modification agent of 15 parts, 10 parts of plasticized modifiers, 1 part of coupling agent, 2 parts of Heat Conduction Materials and 2 parts is weighed by mass parts；
Two, the process modification agent weighed in step one is heated in the reactor with agitating device, stirred, when heating is to 175 DEG C～200 DEG C, the plasticized modifier weighed in step one is added reactor, keep 175 DEG C～200 DEG C, 10min～15min, after toughener all dissolves, temperature of reaction kettle is reduced between 130 DEG C～140 DEG C rapidly, then the benzoxazine resins weighed in step one addition is stirred, obtain thick resin, pour out standby；
Three, kneader is adopted to mix homogeneously at 75 DEG C～80 DEG C the modified benzoxazine resins prepared in step 2 and silane coupler and Heat Conduction Material and other inorganic fillers, then evacuation 15～20min, both obtained sizing material；
Four, the sizing material in step 3 preheating 20min～40min in the baking oven of 60 DEG C～80 DEG C, then by carrier hot calender film forming on the glued membrane calender that roller temperature is 60 DEG C～80 DEG C, namely obtaining under room temperature can the high temperature resistant benzoxazine resins structural film adhesive of long-term storage。
The benzoxazine resins of this test is made up of phenolphthalein type benzimidazole dihydrochloride and bisphenol-f type benzoxazine resins, and the consumption of the two is the ratio composition of 5:3 in mass ratio；
Process modification agent is N, N, O-triglycidyl group para-aminophenol；
Plasticized modifier is the polyether-ketone with terminal hydroxy group；
Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Heat Conduction Material is made up of the ratio that boron nitride and thermal conductivity graphene are 10:1 in mass ratio；
Inorganic filler is made up of the ratio that Rutile type titanium dioxide and fumed silica are 10:1 in mass ratio；
Vacuum kneader vacuum is not less than-0.092MPa；
Carrier is glass fibre non-woven。
Test 1～test 4 prepares under room temperature can the high temperature resistant benzoxazine resins structural film adhesive key property such as table 1 below of long-term storage:
Can the high temperature resistant benzoxazine resins structural film adhesive performance of long-term storage under table 1 room temperature
From table 1 it will be seen that under room temperature can the high-temperature resistant structural adhesive membrane process performance of long-term storage good, softness is prone to paving。This glued membrane adhesive strength is high, meets structural design requirement of strength。Room temperature shear strength can reach more than 25.0MPa, the shear strength of 140 DEG C can reach more than 28.0MPa, 200 DEG C of shear strengths can reach more than 15.0MPa, and 90 ° of plates of room temperature/plate peel strength can reach more than 20.0N/cm, and 140 DEG C of planar stretch intensity can reach more than 6.0MPa。
Test 1 prepares under room temperature and can the high temperature resistant benzoxazine resins structural film adhesive of long-term storage store under room temperature (20 DEG C-25 DEG C), lucifuge, dry environment, performance such as table 2 below in the storage phase:
Table 2 stores performance test in the phase
From table 2 it will be seen that under room temperature of the present invention can the high temperature resistant benzoxazine resins structural film adhesive of long-term storage in 180 days glued membrane flexibility do not change, still there is good paving processing performance。In storage period, the adhesive strength of glued membrane is held essentially constant。
Claims (10)
1. can the high-temperature-resistant structure glued membrane of long-term storage under a room temperature, it is characterised in that it is made up of the benzoxazine resins of 75～100 parts, 10～20 parts of process modification agent, the plasticized modifier of 10～20 parts, 1～2 part of coupling agent, 1～3 part of Heat Conduction Material, the inorganic filler of 1～3 part and carrier according to mass fraction。
2. can the high-temperature-resistant structure glued membrane of long-term storage under a kind of room temperature according to claim 1, it is characterised in that it is made up of the benzoxazine resins of 80～90 parts, 10～20 parts of process modification agent, the plasticized modifier of 10～20 parts, 1～2 part of coupling agent, 1～3 part of Heat Conduction Material, the inorganic filler of 1～3 part and carrier according to mass fraction。
3. can the high-temperature-resistant structure glued membrane of long-term storage under a kind of room temperature according to claim 1 and 2, it is characterized in that benzoxazine resins is made up of by arbitrarily ratio one or more in bisphenol A-type benzimidazole dihydrochloride, phenolphthalein type benzimidazole dihydrochloride, bisphenol-f type benzimidazole dihydrochloride, 4,4-MDA type benzimidazole dihydrochlorides, dicyclopentadiene type benzimidazole dihydrochloride, thiobis phenolic benzimidazole dihydrochloride。
4. can the high-temperature-resistant structure glued membrane of long-term storage under a kind of room temperature according to claim 1 and 2, it is characterized in that plasticized modifier is by the polyether-ketone with terminal hydroxy group, there is the Polyetherimide of terminal hydroxy group, amine end groups or acid anhydride end group, there is the polyphenylene oxide of terminal hydroxy group, there are one or more in the PAEK of terminal hydroxy group by arbitrarily than composition。
5. can the high-temperature-resistant structure glued membrane of long-term storage under a kind of room temperature according to claim 1, it is characterised in that process modification agent is by N, N, N, N-four glycidyl group-4,4 '-MDA and N, one or both in N, O-triglycidyl group para-aminophenol are by arbitrarily than composition。
6. can the high-temperature-resistant structure glued membrane of long-term storage under a kind of room temperature according to claim 1 and 2, it is characterised in that silane coupler is made up of by arbitrarily ratio one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane, methyl tri-tert peroxy-silane。
7. can the high-temperature-resistant structure glued membrane of long-term storage under a kind of room temperature according to claim 1 and 2, it is characterised in that Heat Conduction Material is made up of by arbitrarily ratio one or more in aluminium nitride, boron nitride, thermal conductivity graphene, superconduction carbon fiber。
8. can the high-temperature-resistant structure glued membrane of long-term storage under a kind of room temperature according to claim 1 and 2, it is characterised in that by aerosil and Rutile type titanium dioxide, one or both form by arbitrarily ratio in inorganic filler。
9. can the high-temperature-resistant structure glued membrane of long-term storage under a kind of room temperature according to claim 1 and 2, it is characterised in that carrier is made up of the one in glass fiber woven cloth, glass fibre non-woven or polyester non-woven fabric。
10. can the preparation method of high-temperature-resistant structure glued membrane of long-term storage under a kind of room temperature as claimed in claim 1, it is characterised in that it is to carry out according to following steps:
One, the inorganic filler of the benzoxazine resins of 75～100 parts, the process modification agent of 10～20 parts, 10～20 parts of plasticized modifiers, 1～2 part of coupling agent, 1～3 part of Heat Conduction Material and 1～3 part is weighed by mass parts；
Two, the process modification agent weighed in step one is heated in the reactor with agitating device, stirred, when heating is to 175 DEG C～200 DEG C, the plasticized modifier weighed in step one is added reactor, 10min～15min is kept at 175 DEG C～200 DEG C temperature, after toughener all dissolves, temperature of reaction kettle is reduced to 130 DEG C～140 DEG C, then the benzoxazine resins weighed in step one addition is stirred, obtain thick resin, it is modified benzoxazine resins, pours out standby；
Three, the coupling agent of the modified benzoxazine resins and the step one that prepare in rapid two and Heat Conduction Material and inorganic filler employing kneader are mixed homogeneously at 75 DEG C～80 DEG C, then evacuation 15～20min, both obtained sizing material；
Four, the sizing material in step 3 preheating 20min～40min in the baking oven of 60 DEG C～80 DEG C, then by carrier hot calender film forming on the glued membrane calender that roller temperature is 60 DEG C～80 DEG C, namely obtaining under room temperature can the high-temperature-resistant structure glued membrane of long-term storage。
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| CN112140252A (en) * | 2020-09-21 | 2020-12-29 | 千年舟新材科技集团有限公司 | Ecological plate and one-step composite forming process thereof |
| CN113174650A (en) * | 2021-06-10 | 2021-07-27 | 杭州红港化纤有限公司 | Wear-resistant DTY and production process thereof |
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| CN102732029A (en) * | 2012-06-21 | 2012-10-17 | 广东生益科技股份有限公司 | Halogen-free resin composition, bonding sheet and copper-clad laminate |
| CN103131346A (en) * | 2013-03-25 | 2013-06-05 | 黑龙江省科学院石油化学研究院 | High temperature-resistant carrier adhesive film and preparation method thereof |
| WO2015179618A1 (en) * | 2014-05-22 | 2015-11-26 | Cytec Industries Inc. | Functionalized polymer particles for use as toughening agent |
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| CN102732029A (en) * | 2012-06-21 | 2012-10-17 | 广东生益科技股份有限公司 | Halogen-free resin composition, bonding sheet and copper-clad laminate |
| CN103131346A (en) * | 2013-03-25 | 2013-06-05 | 黑龙江省科学院石油化学研究院 | High temperature-resistant carrier adhesive film and preparation method thereof |
| WO2015179618A1 (en) * | 2014-05-22 | 2015-11-26 | Cytec Industries Inc. | Functionalized polymer particles for use as toughening agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112140252A (en) * | 2020-09-21 | 2020-12-29 | 千年舟新材科技集团有限公司 | Ecological plate and one-step composite forming process thereof |
| CN113174650A (en) * | 2021-06-10 | 2021-07-27 | 杭州红港化纤有限公司 | Wear-resistant DTY and production process thereof |
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