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WO2019075786A1 - 一种耐高温聚酰亚胺胶膜及其制备方法 - Google Patents

一种耐高温聚酰亚胺胶膜及其制备方法 Download PDF

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Publication number
WO2019075786A1
WO2019075786A1 PCT/CN2017/109142 CN2017109142W WO2019075786A1 WO 2019075786 A1 WO2019075786 A1 WO 2019075786A1 CN 2017109142 W CN2017109142 W CN 2017109142W WO 2019075786 A1 WO2019075786 A1 WO 2019075786A1
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Prior art keywords
polyimide
parts
high temperature
temperature
polyimide solution
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English (en)
French (fr)
Inventor
刘长威
肖万宝
曲春艳
王德志
宿凯
王勃
李洪峰
冯浩
关悦瑜
杨海东
王海民
张杨
杜程
周东鹏
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Institute of Petrochemistry of Heilongjiang Academy of Sciences
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Institute of Petrochemistry of Heilongjiang Academy of Sciences
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Priority to US16/307,897 priority Critical patent/US11028226B2/en
Publication of WO2019075786A1 publication Critical patent/WO2019075786A1/zh
Anticipated expiration legal-status Critical
Priority to US17/246,248 priority patent/US11685811B2/en
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    • C—CHEMISTRY; METALLURGY
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
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    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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    • B29B13/10—Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D179/00—Coating compositions 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 C09D161/00 - C09D177/00
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Definitions

  • the invention relates to a polyimide film and a preparation method thereof.
  • honeycomb-wall (board-core) sandwich structure at 300 ° C and above, especially 400 ° C ⁇ 500 ° C Has good mechanical properties and thermal stability.
  • the use of aluminum honeycomb, Nomex paper honeycomb, Kevler paper honeycomb, etc. can no longer meet the requirements of 300 ° C above the use of honeycomb, using polyimide honeycomb (such as Hexcel HEXCEL HRH327), titanium alloy honeycomb can meet the temperature requirements of the honeycomb Among them, titanium alloy honeycomb weight loss effect is not as good as polyimide honeycomb, but polyimide honeycomb honeycomb requires less curing pressure when curing.
  • the adhesive can be classified into a solution, a paste, and a film.
  • the core film has the advantages of uniform thickness, accurate glue application, simple construction process, large-area bonding, etc. It is the first choice for bonding honeycomb sandwich structure, and is widely used in the existing high temperature resistant adhesive film. It is a modified epoxy film, a cyanate film and a double horse film, but its use temperature generally does not exceed 300 ° C. As the temperature of the structure is increased, higher requirements are placed on the heat resistance of the film. In order to achieve a higher temperature resistance grade, a polyimide core film having more excellent heat resistance and high temperature bonding properties has become an inevitable choice.
  • adhesives that meet the adhesion of lightweight, high-strength polyimide honeycomb and composite panels require additional compliance with the following requirements:
  • the polyimide film is required to have better melt fluidity at a high temperature and a lower melt viscosity
  • the adhesive needs to have a certain degree of climbing at the bottom end of the honeycomb to have a high core peel strength and meet the process requirements.
  • the above phenomenon can be achieved by capillary action, melt flowability and thixotropy, and the polyimide-cured polyimide adhesive needs to be able to realize the film-forming property of the core film and the formation of the rubber film to stabilize the core structure. Sex has a great contribution.
  • the core film needs to meet the temperature resistance requirements of honeycomb and composite materials, that is, it can meet the requirements of use above 300 ° C, especially 400 ° C ⁇ 500 ° C, that is, high shear strength at high temperature, flat pull Strength and peel strength requirements.
  • the existing polyimide adhesives are classified into two types: polycondensation type and addition type.
  • LARC-TPI developed by NASA's Langley Research Center in 1980 is a typical polycondensation polyimide film (Polym.Inter). , 1996; 41: 193-207).
  • Tg is about 260 ° C, no weight loss phenomenon after 400 ° C treatment in air, and has good heat oxidation stability.
  • the shear strength of the bonded titanium alloy at room temperature was 36.5 MPa, and remained at 13.2 MPa at 232 °C.
  • thermoplastic polyimide films with different structures (J.Ahes., 1988; 30:185-198.), including p-phenylenediamine and m-phenylene.
  • the chemical structure of the monomer such as amine and diphenyl ether diamine also achieves good bonding properties.
  • Progar J. Adhes. Adhes., 1984; 4: 79-86.
  • et al. synthesized a polyimide film PISO 2 containing a sulfone group structure using BTDA and 3,3-DDS.
  • the heat resistance of the sulfone thermoplastic and polyimide, Tg is 273 ° C, when the titanium alloy is bonded, the shear strength at room temperature and 232 ° C is 32.0 and 18.1 MPa, respectively, after heat aging at 204 ° C for 5000 h, at 204 The shear strength at °C is still as high as 20.5 MPa. Maudgal et al. (J. Adhes.
  • LaRC-CPI Alrum PIXA
  • Ce of Advanced Materials and Process Engineering Series, 1977, 22: 221 has more bonding strength at room temperature and high temperature due to the use of more ketone carbonyl and ether bond monomers. Well, they reached 49.1 MPa and 25.3 MPa (232 ° C) respectively.
  • the Tg value of the above film does not exceed 300 ° C, and the use temperature is also difficult to exceed 300 ° C.
  • thermosetting polyimides include: (1) NA anhydride (5-norbornene-2,3-dicarboxylic anhydride) capped PMR type polyimide; (2) alkynyl terminated polyimide .
  • the PMR type polyimide is blocked with norbornene, and the low viscosity of the polyamic acid is formed by using the tetracarboxylic acid diester to control the solid content to 50% or more.
  • Cytec's FM35 design has a molecular weight of 1500 g/mol, a cure temperature of 329 ° C, a cure pressure of 0.35 MPa, and post cure at 343 ° C.
  • the Ti/Ti bond strength was 17.2 MPa (25 ° C) and 13.8 MPa (288 ° C) (12th Nat. SAMPE Tech. Con. f, 1980: 746-758).
  • the bond strength is rapidly lowered. This is due to the poor long-term thermal oxidation stability of the aliphatic norbornene group, so it does not satisfy the long-term bonding requirement of more than 300 ° C (or even 400 ° C to 500 ° C).
  • the alkynyl-terminated polyimides are acetylenic polyimide (cured at 250 ° C) and phenylethynyl polyimide (cured at 370 ° C). It has better long-term thermal oxidation stability than NA anhydride-terminated polyimide.
  • Hughes Aircraft Company of the United States introduced HR-600 acetylene-terminated polyimide (Thermid 600), which produced a cured product with a Tg of up to 350 ° C and a thermal decomposition temperature of over 500 ° C.
  • the processing window is narrow due to its high melting point and the initiation of polymerization immediately after melting.
  • ThermidMC-600 has a gel time of only 3 min at 190 °C, so this series of resins as an adhesive does not form a good wetting effect on the surface to be bonded (4 th Nat. SAMPE Tech. Con. f. 1982: 236-242) .
  • phenylethynyl-terminated polyimide prepolymers were developed in the 1980s. Compared with ethynyl groups, phenylethynyl-terminated prepolymers have better chemical stability and thermal stability, and their imide prepolymers have better fluidity and a wider processing window. Since the melting time of the resin before the reaction is long, the wettability of the adherend is increased. PETI-5 (molecular weight: 5000 g/mol) has the best shear strength (52 MPa, 25 ° C; 34 MPa, 177 ° C) (Polym. Prep. 1994, 35: 553). However, the above polycondensation type and addition type polyimide adhesives have the following problems in the application of the core structure (composite-honeycomb sandwich structure):
  • the low pressure curing ( ⁇ 0.5 MPa) that needs to meet the honeycomb needs to be a structure that can be thermally melted. If it is a polycondensed polyimide, it is thermoformed below 400 ° C (Tm (melting point) or Tg (glass transition temperature). ) ⁇ 400 ° C), the use temperature does not exceed 400 ° C, as reported in the above literature, and the use temperature is not more than 400 ° C.
  • addition-molded polyimide can meet the low processing viscosity and bring about a small molecular weight, and the material is brittle after curing.
  • the structural member is subject to subsequent cutting and bending problems.
  • the existing addition-molded polyimide film has not been reported in the literature and data, and can satisfy the Tg value of more than 400 ° C, the use temperature exceeds 400 ° C, and can meet the bonding of the core sandwich structure.
  • the adhesive needs to have a certain degree of climbing at the bottom end of the honeycomb to have a high core peel strength and meet the process requirements.
  • the above phenomenon can be achieved by capillary action, melt flowability and thixotropy, and the polyimide-cured polyimide adhesive needs to be able to realize the film-forming property of the core film and the formation of the rubber film to stabilize the core structure. Sex has a great contribution.
  • the formation of a climbable rubber film requires an adhesive having a suitable viscosity and viscosity. Regarding the effect of the film applied to the core of the film to control the climb and the formation of the gel, good adhesion has not been reported.
  • the invention solves the problems that the existing core-polyimide film of the bonded honeycomb and the skin panel has insufficient heat resistance, and the core structure is bonded without climbing and colloid, and provides a resistance. High-temperature polyimide film and preparation method thereof.
  • the high temperature resistant polyimide film is made by 100 parts by weight of polyimide solution, 10 parts to 40 parts of inorganic filler modifier and 0.1 part to 5 parts of interface coupling agent;
  • the inorganic filler modifier consists of a silica-based substance and a substance that increases interfacial bonding, the second The mass ratio of the silicon oxide substance to the substance which increases the interface bonding is 1: (0.1 to 0.5);
  • the silica-based substance is hollow ceramic microspheres, fumed silica, fused silica or amorphous silica;
  • the substance for increasing interface bonding is one or a mixture of aluminum hydroxide, magnesium hydroxide, molybdenum oxide, aluminum nitride, aluminum oxide, boron nitride and silicon carbide;
  • the structural formula of the polyimide in the polyimide solution is:
  • n 1 to 19;
  • the Ar 2 is
  • the R 1 is O or NH.
  • a preparation method of a high temperature resistant polyimide film is carried out according to the following steps:
  • the polyimide solution was prepared by adding N,N-dimethylacetamide to a three-necked flask and adding aroma to N,N-dimethylacetamide under a nitrogen atmosphere. Diamine, stirring for 1h ⁇ 5h, then adding aromatic dianhydride to the three-necked flask, stirring for 1h ⁇ 5h, to obtain a mixed solution, adding 4-phenylethynyl phthalic anhydride to the mixed solution, stirring reaction for 1h ⁇ 5h Then, adding toluene, heating to a temperature of 120 ° C ⁇ 130 ° C, at a temperature of 120 ° C ⁇ 130 ° C strip Under the condition, reflux reaction for 5h ⁇ 20h, to obtain a polyimide solution;
  • the molar ratio of the aromatic dianhydride to the aromatic diamine is (0.50-0.95): 1; the mass ratio of the N,N-dimethylacetamide to toluene is 1: (0.2-0.5);
  • the molar ratio of the aromatic diamine to 4-phenylethynyl phthalic anhydride is 1: (0.01-1); and the anhydride functional group of the aromatic dianhydride and 4-phenylethynyl phthalic anhydride
  • the total mole of the anhydride functional group is equal to the molar ratio of the amino functional group of the aromatic diamine;
  • the total mass ratio of the N,N-dimethylacetamide and toluene to 4-phenylethynylphthalic anhydride, aromatic dianhydride and aromatic diamine is (2.5 to 4): 1;
  • the aromatic dianhydride is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl dianhydride
  • the aromatic diamine is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • the R 1 is O or NH
  • the adhesive is filtered and degassed, cast onto a stainless steel drum loaded with carrier cloth and release paper to obtain a self-supporting film, and then heated at a temperature of 60 ° C ⁇ 150 ° C for 1 min ⁇ 60min, heating at a temperature of 150 ° C ⁇ 300 ° C, heating for 1min ⁇ 60min, and finally at a temperature of 50 ° C ⁇ 140 ° C, annealing for 1min ⁇ 20min, to obtain a high temperature resistant polyimide film;
  • the high temperature resistant polyimide film has a thickness of 0.30 mm to 0.60 mm;
  • the inorganic filler modifier described in the first step is composed of a silica-based substance and a substance which increases the interfacial bonding, and the mass ratio of the silica-based substance to the substance which increases the interfacial bonding is 1: (0.1 0.5);
  • the silica-based substance is hollow ceramic microspheres, fumed silica, fused silica or amorphous silica;
  • the substance for increasing interface bonding is one or a mixture of aluminum hydroxide, magnesium hydroxide, molybdenum oxide, aluminum nitride, aluminum oxide, boron nitride and silicon carbide;
  • the structural formula of the polyimide in the polyimide solution described in the first step is:
  • n 1 to 19;
  • the Ar 2 is
  • the R 1 is O or NH.
  • the invention has the beneficial effects that the existing core (composite-composite) structure uses polyimide film temperature resistance grade Can not meet the requirements of 300 ° C or above, especially 400 ° C ⁇ 500 ° C. Unable to meet the interface bonding requirements of the new structure.
  • the existing polyimide film has few reports on the formation of the glue-up climb (gelatin) required for high toughness, the shear strength at high and low temperatures, the flat tensile strength and the peel strength.
  • the present invention employs an aromatic diamine containing a nitrogen heterocyclic structure and polymerizes with an aromatic dianhydride to form a polyimide having a higher material modulus and a diamine having an ordinary benzene ring structure as reported in the literature and the literature.
  • Rigid, and the introduction of a benzimidazole or benzoxazole structure forms another coplanar rod-like structure other than the benzimidazole ring, which increases the glass transition temperature and heat resistance, and unexpectedly, Above the Tg value, due to the maintenance of the rigid structure, it still has a very high modulus value, and the modulus drops by 0.5 orders of magnitude, so that it has a performance exceeding Tg, and can satisfy the use of 400 ° C to 500 ° C.
  • the introduction of a flexible group in the aromatic diamine avoids the use of a rigid linear structure from the imide ring to the benzimidazole to the imide ring in each repeating unit to form a rigid segment.
  • the high temperature strength performance of the overall structure is further improved.
  • the use of a symmetrical structure of the diamine can further enhance the structural order of the material and obtain better high temperature strength.
  • the invention also uses a rotatably angle or a steric hindrance.
  • a group of aromatic dianhydride a rigid coplanar structure including pyromellitic dianhydride is not used, on the one hand, the flexibility of the segment can be improved, and the molecular weight is controlled by adjusting the number of repeating units to have a certain melt processing property.
  • thermosetting resin thermosetting resin alone. It is proposed to use carrier cloth to achieve self-supporting film formation. In addition, the use of electrodeless filler can better achieve film forming toughness and high surface quality, reduce crack generation and improve product. The thickness uniformity, among which, it was found through experiments that a silica-based substance was used to obtain a good effect.
  • thermosetting polyimide resin a resin with a low melt viscosity, which has a good fluidity, does not climb at the low end of the honeycomb, and cannot be bonded; a high melt viscosity Resin, which has poor fluidity, cannot form a capillary phenomenon at the low end of the honeycomb and cannot be bonded.
  • the invention adopts a flow control agent to control the thixotropic and capillary climbing effects of the resin, thereby forming a desired rubber tumor and obtaining a good bonding effect.
  • a mixture of oxides, carbides, and nitrides which control thixotropic properties and a mixture of oxides, carbides, and nitrides capable of increasing interfacial bonding can improve the fluidity of the meltable resin while suppressing the climbing resistance.
  • the mass ratio of the addition quality of the inorganic filler modifier to the polyimide solution is (0.1-0.4): 1, and a good core-structure bonding effect is obtained, which is mainly reflected in controlling suitable climbing and gel formation.
  • a large amount of filler affects the melt flow of the resin while impeding the capillary climb at the lower end of the honeycomb; too little filler does not control thixotropy.
  • the formula of the invention is reasonable, and the prepared film has the heat resistance of 300 ° C or more, especially the heat resistance of 400 ° C to 500 ° C and the bonding property of the core structure, and an excellent interface bonding effect can be obtained. It can be used for the bonding of polyimide honeycomb, titanium alloy honeycomb and polyimide composite materials, titanium alloy and stainless steel structural parts with high thermal performance, thus broadening the application of high temperature resistant adhesives in aerospace and other fields.
  • the invention is applied to a high temperature resistant polyimide film and a preparation method thereof.
  • 1 is an infrared spectrum
  • 1 is an infrared curve after curing of the polyimide solution prepared in Synthesis Example 1
  • 2 is an infrared curve after curing of the polyimide solution prepared in Synthesis Example 3;
  • 2 is a rheological graph
  • 1 is a rheological curve of polyimide in the polyimide solution prepared in Synthesis Example 1
  • 2 is a polyimide in the polyimide solution prepared in Synthesis Example 6.
  • Rheological curve, 3 is a rheological curve of polyimide in the polyimide solution prepared in Synthesis Example 3;
  • 3 is a dynamic thermomechanical curve
  • 1 is a dynamic thermomechanical curve after curing of the polyimide solution prepared in Synthesis Example 1
  • 2 is a dynamic thermomechanical curve after curing of the polyimide solution prepared in Synthesis Example 3.
  • 3 is a dynamic thermomechanical curve after curing of the polyimide solution prepared in Synthesis Example 5
  • 4 is a dynamic thermomechanical curve after curing of the polyimide solution prepared in Synthesis Example 8.
  • a high temperature resistant polyimide film of the present embodiment comprises 100 parts by weight of a polyimide solution, 10 parts to 40 parts of an inorganic filler modifier, and 0.1 to 5 parts of a interface couple. Made of a joint agent;
  • the inorganic filler modifier consists of a silica-based substance and a substance which increases the interfacial bonding, and the mass ratio of the silica-based substance to the substance which increases the interfacial bonding is 1: (0.1 to 0.5);
  • the silica-based substance is hollow ceramic microspheres, fumed silica, fused silica or amorphous silica;
  • the substance for increasing interface bonding is one or a mixture of aluminum hydroxide, magnesium hydroxide, molybdenum oxide, aluminum nitride, aluminum oxide, boron nitride and silicon carbide;
  • the structural formula of the polyimide in the polyimide solution is:
  • n 1 to 19;
  • the Ar 2 is
  • the R 1 is O or NH.
  • the structural formula of the polyimide in the polyimide solution contains a nitrogen heterocyclic structure, preferably imparts a nitrogen heterocyclic structure in the diamine structure, and contains a reactive terminal group, and 4-phenylethynyl phthalic acid is used.
  • the anhydride is capped.
  • the silica-based materials are capable of controlling flow thixotropy.
  • the beneficial effect of the present embodiment is that the temperature resistance grade of the polyimide core film used in the conventional core (composite-composite material) structure can not meet the requirements of 300 ° C or higher, especially 400 ° C to 500 ° C. Unable to meet the interface bonding requirements of the new structure.
  • the existing polyimide film has few reports on the formation of the glue-up climb (gelatin) required for high toughness, the shear strength at high and low temperatures, the flat tensile strength and the peel strength.
  • an aromatic diamine containing a nitrogen heterocyclic structure is used, and an aromatic dianhydride is polymerized to form a polyimide, which has a higher material modulus than a diamine having an ordinary benzene ring structure as reported in the literature and the literature.
  • rigid and the introduction of benzimidazole or benzoxazole structure forms another coplanar rod-like structure other than the benzimid ring, which increases the glass transition temperature and heat resistance, unexpectedly Above the Tg value, due to the retention of the rigid structure, it still has a very high modulus value, and the modulus drops by 0.5 orders of magnitude, so that it has a performance exceeding Tg, so that it can be used at 400 ° C to 500 ° C.
  • the introduction of flexible groups in the aromatic diamine avoids From the imide ring to the benzimidazole to the imide ring in each repeating unit, a rigid linear structure is formed to form a rigid segment.
  • the high temperature strength performance of the overall structure is further improved.
  • the use of a symmetrical structure of the diamine can further enhance the structural order of the material and obtain better high temperature strength.
  • the present embodiment simultaneously selects a rotation angle or a steric resistance.
  • a rigid coplanar structure including pyromellitic dianhydride is not used, on the one hand, the flexibility of the segment can be improved, and the molecular weight is controlled by adjusting the number of repeating units to have a certain melt processing property.
  • thermosetting resin thermosetting resin alone. It is proposed to use carrier cloth to achieve self-supporting film formation. In addition, the use of electrodeless filler can better achieve film forming toughness and high surface quality, reduce crack generation and improve product. The thickness uniformity, among which, it was found through experiments that a silica-based substance was used to obtain a good effect.
  • thermosetting polyimide resin a resin with a low melt viscosity, which has a good fluidity, does not climb at the low end of the honeycomb, and cannot be bonded; a high melt viscosity Resin, which has poor fluidity, cannot form a capillary phenomenon at the low end of the honeycomb and cannot be bonded.
  • the flow control agent is used to control the thixotropy and capillary climbing effect of the resin, thereby forming a desired rubber tumor, and obtaining a good bonding effect.
  • a mixture of oxides, carbides, and nitrides which control thixotropic properties and a mixture of oxides, carbides, and nitrides capable of increasing interfacial bonding can improve the fluidity of the meltable resin while suppressing the climbing resistance.
  • the mass ratio of the addition quality of the inorganic filler modifier to the polyimide solution is (0.1-0.4): 1, and a good core-structure bonding effect is obtained, which is mainly reflected in controlling suitable climbing and gel formation.
  • a large amount of filler affects the melt flow of the resin while impeding the capillary climb at the lower end of the honeycomb; too little filler does not control thixotropy.
  • the prepared film has the heat resistance of 300 ° C or more, especially 400 ° C to 500 ° C.
  • the bonding property with the core structure and excellent interface bonding effect can be used for the bonding of polyimide honeycomb, titanium alloy honeycomb and polyimide composite materials, titanium alloy and stainless steel structural parts with high thermal performance, thus broadening the application of high temperature resistant adhesives in aerospace and other fields.
  • Embodiment 2 This embodiment differs from Embodiment 1 in that the polyimide solution is prepared by adding N,N-dimethylacetamide to a three-necked flask. Adding aromatic diamine to N,N-dimethylacetamide under nitrogen atmosphere, stirring for 1h ⁇ 5h, then adding aromatic dianhydride to the three-necked flask, stirring for 1h ⁇ 5h, to obtain a mixed solution, adding to the mixed solution 4-phenylethynyl phthalic anhydride, stirring reaction for 1h ⁇ 5h, then adding toluene, heating to a temperature of 120 ° C ⁇ 130 ° C, at a temperature of 120 ° C ⁇ 130 ° C, reflux reaction for 5h ⁇ 20h, Obtaining a polyimide solution;
  • the molar ratio of the aromatic dianhydride to the aromatic diamine is (0.50-0.95): 1; the mass ratio of the N,N-dimethylacetamide to toluene is 1: (0.2-0.5);
  • the molar ratio of the aromatic diamine to 4-phenylethynyl phthalic anhydride is 1: (0.01-1); and the anhydride functional group of the aromatic dianhydride and 4-phenylethynyl phthalic anhydride
  • the total mole of the anhydride functional group is equal to the molar ratio of the amino functional group of the aromatic diamine;
  • the total mass ratio of the N,N-dimethylacetamide and toluene to 4-phenylethynylphthalic anhydride, aromatic dianhydride and aromatic diamine is (2.5 to 4): 1;
  • the aromatic dianhydride is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl dianhydride
  • the aromatic diamine is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • the R 1 is O or NH. Others are the same as in the first embodiment.
  • This embodiment differs from one or two of the specific embodiments in that: the inorganic filler modifier has an average particle diameter of 0.1 ⁇ m to 10 ⁇ m; and the interface coupling agent contains an ammonia end group. A silane coupling agent. Others are the same as the specific embodiment one or two.
  • the average particle diameter of the inorganic filler modifier is required to satisfy the dispersion uniformity, and the average particle diameter is preferably 0.5 ⁇ m to 3 ⁇ m.
  • This embodiment differs from one of the specific embodiments 1 to 3 in that the silane coupling agent containing an amino terminal group is ⁇ -aminopropyltriethoxysilane or 3-aminopropyltrimethyl Oxysilane or 3-aminopropylmethyldiethoxysilane. Others are the same as the specific embodiments one to three.
  • the preparation method of a high temperature resistant polyimide film according to the present embodiment is carried out according to the following steps:
  • the polyimide solution was prepared by adding N,N-dimethylacetamide to a three-necked flask and adding aroma to N,N-dimethylacetamide under a nitrogen atmosphere. Diamine, stirring for 1h ⁇ 5h, then adding aromatic dianhydride to the three-necked flask, stirring for 1h ⁇ 5h, to obtain a mixed solution, adding 4-phenylethynyl phthalic anhydride to the mixed solution, stirring reaction for 1h ⁇ 5h Then, toluene is added, the temperature is raised to 120 ° C to 130 ° C, and the reaction is carried out at a temperature of 120 ° C to 130 ° C for 5 h to 20 h to obtain a polyimide solution;
  • the molar ratio of the aromatic dianhydride to the aromatic diamine is (0.50-0.95): 1; the mass ratio of the N,N-dimethylacetamide to toluene is 1: (0.2-0.5);
  • the molar ratio of the aromatic diamine to 4-phenylethynyl phthalic anhydride is 1: (0.01-1); and the anhydride functional group of the aromatic dianhydride and 4-phenylethynyl phthalic anhydride
  • the total mole of the anhydride functional group is equal to the molar ratio of the amino functional group of the aromatic diamine;
  • the total mass ratio of the N,N-dimethylacetamide and toluene to 4-phenylethynylphthalic anhydride, aromatic dianhydride and aromatic diamine is (2.5 to 4): 1;
  • the aromatic dianhydride is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl dianhydride
  • the aromatic diamine is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • the R 1 is O or NH
  • the adhesive is filtered and degassed, cast onto a stainless steel drum loaded with carrier cloth and release paper to obtain a self-supporting film, and then heated at a temperature of 60 ° C ⁇ 150 ° C for 1 min ⁇ 60min, heating at a temperature of 150 ° C ⁇ 300 ° C, heating for 1min ⁇ 60min, and finally at a temperature of 50 ° C ⁇ 140 ° C, annealing for 1min ⁇ 20min, to obtain a high temperature resistant polyimide film;
  • the high temperature resistant polyimide film has a thickness of 0.30 mm to 0.60 mm;
  • the inorganic filler modifier described in the first step is composed of a silica-based substance and a substance which increases the interfacial bonding, and the mass ratio of the silica-based substance to the substance which increases the interfacial bonding is 1: (0.1 0.5);
  • the silica-based substance is hollow ceramic microspheres, fumed silica, fused silica or amorphous silica;
  • the substance for increasing interface bonding is one or a mixture of aluminum hydroxide, magnesium hydroxide, molybdenum oxide, aluminum nitride, aluminum oxide, boron nitride and silicon carbide;
  • the structural formula of the polyimide in the polyimide solution described in the first step is:
  • n 1 to 19;
  • the Ar 2 is
  • the R 1 is O or NH.
  • Embodiment 6 This embodiment differs from Embodiment 5 in that the inorganic filler modifier described in the first step has an average particle diameter of 0.1 ⁇ m to 10 ⁇ m. Others are the same as the fifth embodiment.
  • This embodiment differs from one of the fifth or sixth embodiment in that the interface coupling agent described in the first step is a silane coupling agent containing an amino terminal group. Others are the same as the fifth or sixth embodiment.
  • BEST MODE 8 This embodiment differs from one of the fifth to seventh embodiments in that: the silane coupling agent containing an amino terminal group is ⁇ -aminopropyltriethoxysilane or 3-aminopropyl group. Trimethoxysilane or 3-aminopropylmethyl Diethoxysilane. Others are the same as the specific embodiments 5 to 7.
  • Embodiment 9 This embodiment differs from one of the fifth to eighth embodiments in that: the carrier cloth described in step 2 is E glass fiber cloth, D glass fiber cloth, S glass fiber cloth, NE glass fiber cloth, T glass fiber cloth or Q glass fiber cloth. Others are the same as the specific embodiments 5 to 8.
  • the carrier cloth is a glass cloth carrier.
  • Known materials for various printed circuit boards, composite materials can be used.
  • these substrates it is more preferable to use glass fibers such as E glass which have a coefficient of expansion in the planar direction and excellent balance in drilling workability.
  • This embodiment differs from one of the fifth to ninth embodiments in that the carrier has a surface density of from 100 g/cm 2 to 110 g/cm 2 . Others are the same as the specific embodiments 5 to 9.
  • the polyimide solution was prepared by adding 189 g of N,N-dimethylacetamide to a three-necked flask and adding 41.65 g to N,N-dimethylacetamide under a nitrogen atmosphere ( 0.1mol) aromatic diamine, stirred for 1h, then added 14.71g (0.05mol) 3,3',4,4'-biphenyltetracarboxylic dianhydride to the three-necked flask, stirred for 5h, to obtain a mixed solution, to the mixed solution 24.82g (0.1mol) of 4-phenylethynylphthalic anhydride was added, stirred for 3h, then added with 62g of toluene, heated to a temperature of 130 ° C, and refluxed for 10 hours at a temperature of 130 ° C.
  • Polyimide solution Polyimide solution;
  • the aromatic diamine is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • aromatic diamine CAS number 4402-17-9;
  • the structural formula of the polyimide in the polyimide solution is:
  • the Ar 2 is
  • the polyimide solution was prepared by adding 175 g of N,N-dimethylacetamide to a three-necked flask and adding 41.65 g to N,N-dimethylacetamide under a nitrogen atmosphere ( 0.1mol) aromatic diamine, stirred for 1h, then added 23.54g (0.08mol) 3,3',4,4'-biphenyltetracarboxylic dianhydride to the three-necked flask, stirred for 5h, to obtain a mixed solution, to the mixed solution 9.93 g (0.04 mol) of 4-phenylethynylphthalic anhydride was added thereto, and the reaction was stirred for 3 hours, then 58 g of toluene was added thereto, and the temperature was raised to 130 ° C, and the reaction was refluxed for 10 hours at a temperature of 130 ° C. Polyimide solution;
  • the aromatic diamine is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • aromatic diamine CAS number 4402-17-9;
  • the structural formula of the polyimide in the polyimide solution is:
  • the Ar 2 is
  • the polyimide solution was prepared by adding 190 g of N,N-dimethylacetamide to a three-necked flask and adding 41.65 g to N,N-dimethylacetamide under a nitrogen atmosphere ( 0.1mol) aromatic diamine, stirred for 1h, then added 16.11g (0.05mol) 3,3',4,4'-benzophenone tetracarboxylic dianhydride to the three-necked flask, stirred for 5h, to obtain a mixed solution, 24.82 g (0.1 mol) of 4-phenylethynylphthalic anhydride was added to the mixed solution, and the reaction was stirred for 3 hours, then 63 g of toluene was added, and the temperature was raised to 130 ° C, and the reaction was refluxed for 10 hours at a temperature of 130 ° C. , obtaining a polyimide solution;
  • the aromatic diamine is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • aromatic diamine CAS number 4402-17-9;
  • the structural formula of the polyimide in the polyimide solution is:
  • the Ar 2 is
  • the polyimide solution was prepared by adding 180 g of N,N-dimethylacetamide to a three-necked flask and adding 41.65 g to N,N-dimethylacetamide under a nitrogen atmosphere ( 0.1 mol) aromatic diamine, stirring for 1 h, then adding 25.78 g (0.08 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride to the three-necked flask, stirring for 5 h, to obtain a mixed solution, 9.93 g (0.04 mol) of 4-phenylethynylphthalic anhydride was added to the mixed solution, and the reaction was stirred for 3 hours, then 60 g of toluene was added thereto, and the temperature was raised to 130 ° C, and the reaction was refluxed for 10 hours at a temperature of 130 ° C. , obtaining a polyimide solution;
  • the aromatic diamine is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • aromatic diamine CAS number 4402-17-9;
  • the structural formula of the polyimide in the polyimide solution is:
  • the Ar 2 is
  • the polyimide solution was prepared by adding 180 g of N,N-dimethylacetamide to a three-necked flask and adding 41.65 g to N,N-dimethylacetamide under a nitrogen atmosphere ( 0.1 mol) of aromatic diamine, stirring for 1 h, then adding 29.00 g (0.09 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride to the three-necked flask, stirring for 5 h, to obtain a mixed solution, 4.96 g (0.02 mol) of 4-phenylethynylphthalic anhydride was added to the mixed solution, and the reaction was stirred for 3 hours, and then 60 g of a group was added. Benzene, the temperature was raised to 130 ° C, and the reaction was refluxed for 10 h at a temperature of 130 ° C to obtain a polyimide solution;
  • the aromatic diamine is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • aromatic diamine CAS number 4402-17-9;
  • the structural formula of the polyimide in the polyimide solution is:
  • the Ar 2 is
  • a polyimide film is made by weight of 100 parts of polyimide solution, 20 parts of inorganic filler modifier and 1 part of interface coupling agent;
  • the inorganic filler modifier consists of 17 parts by weight of fumed silica and 3 parts of boron nitride by weight; the interface coupling agent is ⁇ -aminopropyltriethoxysilane;
  • the imide solution is a polyimide solution prepared in Synthesis Example 1;
  • the preparation method of the above polyimide film is carried out according to the following steps:
  • the adhesive is filtered and degassed, cast onto a stainless steel drum loaded with a carrier cloth and a release paper to obtain a self-supporting film, which is then heated at a temperature of 60 ° C for 60 min and then at a temperature. Heating at 150 ° C for 5 min, and finally annealing at a temperature of 60 ° C for 5 min to obtain a polyimide film;
  • the polyimide film has a thickness of 0.40 mm; the carrier cloth is an E glass fiber cloth having an areal density of 110 g/cm 2 ; and the inorganic filler modifier has an average particle diameter of 5 ⁇ m.
  • Example 2 This example differs from Example 1 in that the polyimide solution was a polyimide solution prepared in Synthesis Example 2. Others are the same as in the first embodiment.
  • Example 3 This example differs from Example 1 in that the polyimide solution was a polyimide solution prepared in Synthesis Example 3. Others are the same as in the first embodiment.
  • Example 4 This example differs from Example 1 in that the polyimide solution was a polyimide solution prepared in Synthesis Example 4. Others are the same as in the first embodiment.
  • Example 5 This example differs from Example 1 in that the polyimide solution was a polyimide solution prepared in Synthesis Example 5. Others are the same as in the first embodiment.
  • a polyimide film is made by weight of 100 parts of polyimide solution, 3 parts of inorganic filler modifier and 1 part of interface coupling agent;
  • the inorganic filler modifier comprises 2 parts by weight of fumed silica and 1 part of boron nitride by weight;
  • the interface coupling agent is ⁇ -aminopropyltriethoxysilane
  • the polyimide solution is a polyimide solution prepared in Synthesis Example 1;
  • a method for preparing a polyimide film is as follows:
  • the adhesive is filtered and degassed, cast onto a stainless steel drum loaded with a carrier cloth and a release paper to obtain a self-supporting film, which is then heated at a temperature of 60 ° C for 60 min and then at a temperature. Heating at 150 ° C for 5 min, and finally annealing at a temperature of 60 ° C for 5 min to obtain a polyimide film;
  • the polyimide film has a thickness of 0.4 mm; the carrier cloth is an E glass fiber cloth having an areal density of 110 g/cm 2 ; and the inorganic filler modifier has an average particle diameter of 5 ⁇ m.
  • Example 7 This example differs from Example 6 in that a polyimide film is composed of 100 parts by weight of polyimide solution, 36 parts of inorganic filler modifier and 2 parts of interface coupling agent in parts by weight.
  • the inorganic filler modifier is composed of 30 parts by weight of fused silica and 6 parts of aluminum hydroxide by weight. Others are the same as in the sixth embodiment.
  • Example 8 This example differs from Example 6 in that a polyimide film is composed of 100 parts by weight.
  • the polyimide solution, 79 parts of the inorganic filler modifier and 3 parts of the interface coupling agent are prepared; the inorganic filler modifier is 70 parts by weight of fused silica, 3 parts of aluminum hydroxide, 5 parts by weight. It consists of aluminum nitride and 1 part boron nitride. Others are the same as in the sixth embodiment.
  • Example 9 This example differs from Example 6 in that a polyimide film is composed of 100 parts by weight of polyimide solution, 20 parts of inorganic filler modifier and 1 part of interface coupling agent in parts by weight.
  • the inorganic filler modifier is composed of 17 parts by weight of amorphous silica and 3 parts of alumina. Others are the same as in the sixth embodiment.
  • Example 10 This example differs from Example 9 in that the polyimide solution was a polyimide solution prepared in Synthesis Example 3. Others are the same as in the embodiment 9.
  • Example 11 This example differs from Example 9 in that the inorganic filler modifier consists of 17 parts by weight of fumed silica and 3 parts of boron nitride by weight; the polyimide solution The polyimide solution prepared in Synthesis Example 1 and 50 parts of the polyimide solution prepared in Synthesis Example 3 were composed by parts by weight. Others are the same as in the embodiment 9.
  • Example 12 This example differs from Example 9 in that the inorganic filler modifier consists of 17 parts by weight of fumed silica and 3 parts of boron nitride by weight; the polyimide solution It consisted of 50 parts by weight of the polyimide solution prepared in Synthesis Example 1 and 50 parts of the polyimide solution prepared in Synthesis Example 4. Others are the same as in the embodiment 9.
  • Example 13 This example differs from Example 9 in that the inorganic filler modifier consists of 17 parts by weight of fumed silica and 3 parts of boron nitride by weight; the polyimide solution The polyimide solution prepared in Synthesis Example 1 and 70 parts of the polyimide solution prepared in Synthesis Example 4 were composed by parts by weight. Others are the same as in the embodiment 9.
  • Example 14 This example differs from Example 9 in that the inorganic filler modifier consists of 17 parts by weight of fumed silica and 3 parts of boron nitride by weight; the polyimide solution The polyimide solution prepared in Synthesis Example 1 and 30 parts of the polyimide solution prepared in Synthesis Example 4 were composed by parts by weight. Others are the same as in the embodiment 9.
  • the polyimide solution prepared in Synthesis Example 1 was filtered and degassed, cast onto a stainless steel drum loaded with a carrier cloth and a release paper to obtain a self-supporting film, and then at a temperature of 60 ° C. Next, heating for 60 min, heating at a temperature of 150 ° C for 5 min, and finally annealing at a temperature of 60 ° C for 5 min to obtain a polyimide film;
  • the carrier cloth was an E glass fiber cloth having an areal density of 110 g/cm 2 .
  • Example 16 This example differs from Example 15 in that the polyimide solution prepared in Synthesis Example 2 was filtered and degassed. Others are the same as in the fifteenth embodiment.
  • Example 17 This example differs from Example 15 in that the polyimide solution prepared in Synthesis Example 3 was filtered and degassed. Others are the same as in the fifteenth embodiment.
  • Example 18 This example differs from Example 15 in that the polyimide solution prepared in Synthesis Example 4 was filtered and degassed. Others are the same as in the fifteenth embodiment.
  • Example 19 This example differs from Example 15 in that the polyimide solution prepared in Synthesis Example 5 was filtered and degassed. Others are the same as in the fifteenth embodiment.
  • the polyimide solution was prepared by adding 113 g of N,N-dimethylacetamide to a three-necked flask and adding 10.8 g to N,N-dimethylacetamide under a nitrogen atmosphere ( 0.1 mol) p-phenylenediamine, stirring for 1 h, then adding 14.71 g (0.05 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride to the three-necked flask, stirring for 5 h, to obtain a mixed solution, to the mixture 24.82 g (0.1 mol) of 4-phenylethynylphthalic anhydride was added to the solution, and the reaction was stirred for 3 hours, then 38 g of toluene was added, the temperature was raised to 130 ° C, and the reaction was refluxed for 10 hours at a temperature of 130 ° C. Obtaining a polyimide solution;
  • the structural formula of the polyimide in the polyimide solution is:
  • the Ar 2 is
  • the polyimide solution was prepared by adding 113 g of N,N-dimethylacetamide to a three-necked flask and adding 10.8 g to N,N-dimethylacetamide under a nitrogen atmosphere ( 0.1 mol) of m-phenylenediamine, stirred for 1 h, then 14.71 g (0.05 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride was added to the three-necked flask, and stirred for 5 hours to obtain a mixed solution, which was mixed.
  • the structural formula of the polyimide in the polyimide solution is:
  • the Ar 2 is
  • the polyimide solution was prepared by adding 123 g of N,N-dimethylacetamide to a three-necked flask and adding 20.02 g to N,N-dimethylacetamide under a nitrogen atmosphere ( 0.1 mol) 4,4'-diaminodiphenyl ether, stirred for 1 h, then added 25.78 g (0.08 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride to the three-necked flask, stirring 5h, a mixed solution was obtained, 9.93 g (0.04 mol) of 4-phenylethynylphthalic anhydride was added to the mixed solution, and the reaction was stirred for 3 hours, then 41 g of toluene was added, and the temperature was raised to 130 ° C at a temperature of 130 ° C. Under the conditions, reflux reaction for 10 h, to obtain a polyimide solution;
  • the structural formula of the polyimide in the polyimide solution is:
  • the Ar 2 is
  • the polyimide solution was prepared by adding 174 g of N,N-dimethylacetamide to a three-necked flask and adding 41.65 g to N,N-dimethylacetamide under a nitrogen atmosphere ( 0.1 mol) of aromatic diamine, stirring for 1 h, then adding 10.9 g (0.05 mol) of pyromellitic dianhydride to a three-necked flask, stirring for 5 h to obtain a mixed solution, and adding 24.82 g (0.1 mol) to the mixed solution 4- Phenyl ethynyl phthalic anhydride, stirring reaction for 3 h, then adding 58 g of toluene, heating to a temperature of 130 ° C, at a temperature of 130 ° C, reflux reaction for 10 h, to obtain a polyimide solution;
  • the aromatic diamine is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • aromatic diamine CAS number 4402-17-9;
  • the structural formula of the polyimide in the polyimide solution is:
  • the Ar 2 is
  • the inorganic filler modifier consists of 17 parts by weight of fumed silica and 3 parts of boron nitride by weight; the interface coupling agent is ⁇ -aminopropyltriethoxysilane;
  • the imide solution is a polyimide solution prepared in Synthesis Example 6;
  • the adhesive is filtered and degassed, cast onto a stainless steel drum loaded with a carrier cloth and a release paper to obtain a self-supporting film, which is then heated at a temperature of 60 ° C for 60 min and then at a temperature. Heating at 150 ° C for 5 min, and finally annealing at a temperature of 60 ° C for 5 min to obtain a polyimide film;
  • the carrier cloth is an E glass fiber cloth having an areal density of 110 g/cm 2 ; and the inorganic filler modifier has an average particle diameter of 5 ⁇ m.
  • Comparative Experiment 2 This comparative experiment differs from Comparative Experiment 1 in that the polyimide solution was the polyimide solution prepared in Synthesis Example 7. The other is the same as Comparative Experiment 1.
  • Comparative Experiment 3 This comparative experiment differs from Comparative Experiment 1 in that the polyimide solution was the polyimide solution prepared in Synthesis Example 8. The other is the same as Comparative Experiment 1.
  • Comparative Experiment 4 This comparative experiment differs from Comparative Experiment 1 in that the polyimide solution was the polyimide solution prepared in Synthesis Example 9. The other is the same as Comparative Experiment 1.
  • the polyimide solution was filtered and degassed, cast onto a stainless steel drum loaded with a carrier cloth and a release paper to obtain a self-supporting film, and then heated at a temperature of 60 ° C for 60 minutes. Heating at a temperature of 150 ° C for 5 min, and finally annealing at a temperature of 60 ° C for 5 min to obtain a polyimide film;
  • the polyimide solution was a polyimide solution prepared in Synthesis Example 6; the carrier cloth was an E glass fiber cloth having an areal density of 100 g/cm 2 .
  • the polyimide solutions prepared in Synthesis Examples 1 to 9 were tested for glass transition temperature, thermal stability, rheology and infrared, as shown in Table 1 and Figures 1 to 3.
  • the polyimide solution curing process is: first heating at a temperature of 180 ° C and a pressure of 0.2 MPa for 1 h, and then heating at a temperature of 350 ° C and a pressure of 0.2 MPa for 4 h.
  • Rheology test The polyimide solution was introduced into distilled water, and the precipitate was washed with water, dried, and subjected to a rheological test.
  • the test conditions for each performance refer to the following standards (methods):
  • the glass transition temperature is a dynamic thermomechanical instrument (DMA). Heating rate: 5 ° C / min; frequency: 1 Hz.
  • DMA dynamic thermomechanical instrument
  • Thermal stability The test uses a thermal weight loss analyzer (TGA). Heating rate: 10 ° C / min; test atmosphere: air.
  • the polyimide films prepared in Examples 1 to 19 and Comparative Experiments 1 to 5 were placed between two materials to be bonded, and the curing process was as follows: first at a temperature of 180 ° C and a pressure of 0.2 MPa. Heating for 1 h, then heating at a temperature of 350 ° C and a pressure of 0.2 MPa for 4 h, and then testing the bonded material for shear strength, peel strength and flat tensile strength, as shown in Table 2 and Table 3, The test conditions for each performance refer to the following standards (methods):
  • Shear strength GB/T7124-2008 Determination of tensile shear strength of adhesive; GJB444-1988 adhesive high Temperature tensile shear strength test method.
  • Material 304 stainless steel.
  • the bonding member titanium alloy honeycomb and titanium alloy plate bonding
  • 1 is an infrared spectrum
  • 1 is an infrared curve after curing of the polyimide solution prepared in Synthesis Example 1
  • 2 is an infrared curve after curing of the polyimide solution prepared in Synthesis Example 3
  • 2 is a rheological graph
  • 1 is a rheological curve of polyimide in the polyimide solution prepared in Synthesis Example 1
  • 2 is a polyimide in the polyimide solution prepared in Synthesis Example 6.
  • the rheological curve, 3 is a rheological curve of the polyimide in the polyimide solution prepared in Synthesis Example 3; as can be seen from the figure, the polyimide solutions prepared in Synthesis Examples 1 and 3 have a wide range.
  • the processing interval and low melt viscosity ensure high temperature meltability and melt climbability in the core structure.
  • the polyimide solution prepared in Synthesis Example 6 does not use a benzimidazole diamine containing a flexible carbonyl group, a structure having a relatively large rigidity, such as p-phenylenediamine, causes high temperature to have no melt fluidity, and cannot climb, and cannot Bonding the core structure.
  • the polyimide solutions synthesized in Synthesis Examples 1 to 5 all have melt fluidity, and the inorganic filler is used to improve thixotropy and gel formation, and a good bonding effect can be obtained.
  • 3 is a dynamic thermomechanical graph
  • 1 is a dynamic thermomechanical curve after curing of the polyimide solution prepared in Synthesis Example 1
  • 2 is a dynamic heat after curing of the polyimide solution prepared in Synthesis Example 3.
  • Mechanical curve, 3 is the dynamic thermomechanical curve after curing of the polyimide solution prepared in Synthesis Example 5
  • 4 is the dynamic thermomechanical curve after curing of the polyimide solution prepared in Synthesis Example 8;
  • Tables 1, 2 and 3 the synthesis examples 1 to 5 were combined with a benzimidazole ring and a benzimimine ring, resulting in a Tg at 390 ° C, and the storage modulus was over 0.5 g at 30 ° C. Downtrends below the order of magnitude.
  • the flexible structure diamine is used to bring about melt processability, and the Tg value after curing is lowered, and the storage modulus retention rate is lowered (>2 orders of magnitude), resulting in a comparative experiment 3 high temperature. No intensity.
  • Example 15 to 19 prepared by using Synthesis Examples 1 to 5, the inorganic filler modifier was not added, and Example 6 prepared in Synthesis Example 1 was used, and the inorganic filler modifier was added in a small amount, and both of the above cases would be
  • the melt flow of the resin is caused to climb, but no gelation is formed at a high temperature, resulting in a low tensile strength of the core structure and a low peel strength of the roller.
  • Example 8 of the synthesis example 1 excessive addition of the inorganic filler modifier resulted in the bonding of the core structure, the resin could not be melted and climbed, and no gelation was formed at a high temperature, and the planar stretching of the core structure was also reduced. Strength and roll peel strength.
  • Comparative Experiments 1 to 5 prepared by Synthesis Examples 6 to 9 Comparative Examples 1, 2, 4, and 5 have a low fluidity and peel strength of the core structure due to the lack of resin melt fluidity, and a comparative experiment with fluidity 3 The combination of the benzimidazole ring and the benzoimine ring is not used, resulting in low Tg and high temperature shear strength.

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Abstract

一种耐高温聚酰亚胺胶膜及其制备方法，解决现有的粘接蜂窝和蒙皮壁板的板芯胶-聚酰亚胺胶膜存在耐热性不足，板芯结构粘接无爬升和胶瘤的问题。由聚酰亚胺溶液、无机填料改性剂及界面偶联剂制成。制备方法：在一定温度及搅拌条件下，将无机填料改性剂及界面偶联剂加入到聚酰亚胺溶液中，搅拌，得到胶粘剂；将胶粘剂过滤并脱气，流延到负载有载体布和隔离纸的不锈钢制转鼓上，得到具有自支撑性的膜，然后加热并退火，得到耐高温聚酰亚胺胶膜。

Description

一种耐高温聚酰亚胺胶膜及其制备方法 技术领域
本发明涉及聚酰亚胺胶膜及其制备方法。
背景技术
随着航空航天等行业研究和应用技术的发展，高速飞行器马赫数逐年增加，要求轻质结构的蜂窝-壁板(板-芯)夹层结构在300℃及以上，尤其是在400℃～500℃具有较好的力学性能和热稳定性。采用铝蜂窝、Nomex纸蜂窝、Kevler纸蜂窝等已经无法满足耐300℃以上蜂窝使用要求，采用聚酰亚胺蜂窝(如赫氏HEXCEL公司的HRH327)、钛合金蜂窝能够满足对蜂窝的耐温要求，其中钛合金蜂窝减重效果不如聚酰亚胺蜂窝，但是聚酰亚胺蜂窝固化时需要较小的固化压力。该类材料在航天装备制造上需求迫切，在蜂窝夹层结构的制造过程中，面板的质量及其与蜂窝芯子的粘结强度是影响夹层结构性能的关键因素。因此,粘接用胶的选用至关重要。
一般来说，胶粘剂可以分为溶液状、膏糊状及胶膜状等。其中板芯胶膜具有厚度均匀、施胶量准确、施工工艺简便，可用于大面积粘接等优点，是粘接蜂窝夹层结构的首选，在现有的耐高温胶膜中，应用较为广泛的是改性环氧胶膜、氰酸酯胶膜及双马胶膜，然而其使用温度一般不超过300℃。随着结构使用温度的提升，对胶膜的耐热性能提出了更高的要求。为了达到更高的耐温等级，具有更优异的耐热性能和高温粘接性能的聚酰亚胺板芯胶膜成为必然的选择。但是满足与轻质高强的聚酰亚胺蜂窝和复合材料壁板粘接的胶粘剂，需要额外满足以下要求：
首先，需要满足蜂窝的低压力固化(≤0.5MPa)，从而避免大压力固化导致的蜂窝坍塌，从而影响结构质量。这样就需要聚酰亚胺胶膜具有高温下更好的熔融流动性和较低的熔体粘度；
其次，蜂窝-芯材结构固化后，胶粘剂需要在蜂窝底端具有一定程度的爬升，才能够具有较高的板芯剥离强度，满足工艺使用要求。利用毛细作用、熔体流动性和触变性可以实现以上现象，与蜂窝-蒙皮固化成型的聚酰亚胺胶粘剂需要能够实现板芯胶膜的成膜性、胶瘤的形成对板芯结构稳定性具有极大贡献。
第三，板芯胶膜需要满足与蜂窝和复合材料的耐温等级要求，即满足能够达到300℃以上使用，尤其是400℃～500℃使用要求，即高温下的高剪切强度、平拉强度和剥离强度要求。
现有的聚酰亚胺胶粘剂分为缩聚型和加成型两种，其中美国NASA的Langley研究中心于1980年发展的LARC-TPI是一种典型的缩聚型聚酰亚胺胶膜(Polym.Inter,1996；41: 193-207)。其Tg约为260℃，在空气中经300℃处理后400℃之前无失重现象，具有良好的耐热氧化稳定性。固化后，室温下胶接钛合金的剪切强度为36.5MPa，232℃下仍保持为13.1MPa。为了进一步降低原料成本，Langley研究中心发展了一系列具有不同结构的热塑性聚酰亚胺胶膜(J.Ahes.,1988；30:185-198.)，采用包括对苯二胺、间苯二胺及二苯醚二胺等单体化学结构，也达到良好的粘接性能。Progar(J.Adhes.Adhes.,1984；4:79-86.)等人用BTDA和3,3-DDS合成了一种含砜基结构的聚酰亚胺胶膜PISO2，它兼有聚砜的热塑性和聚酰亚胺的耐热性，Tg为273℃，胶接钛合金时，室温及232℃下的剪切强度分别为32.0和18.1MPa，经204℃热老化5000h后，在204℃下的剪切强度仍高达20.5MPa。Maudgal等人(J.Adhes.Adhes.,1984；4:87-90.)通过将含有硅氧烷的1,3-双(氨丙基)四甲基硅氧烷与3,3-二氨基二苯酮一起同3,3,4,4-二苯甲酮四羧酸二酐(BTDA)共聚，得到AxBy型含有硅氧烷结构的热塑性聚酰亚胺胶膜，将聚酰亚胺的高温强度和硅氧烷的低温性能有机地结合起来。近年来，LaRC-CPI(Aurum PIXA)(Scince of Advanced Materials and Process Engineering Series,1977,22:221)由于采用更多的酮羰基和醚键单体，粘接钛合金室温和高温粘接强度更好，分别达到了49.1MPa和25.3MPa(232℃)。但以上胶膜的Tg值没有超过300℃，使用温度也难以超过300℃。
加成型聚酰亚胺胶粘剂，通过投料摩尔比例和封端剂，使酰亚胺预聚体溶于DMAc、DMF等有机溶剂作为胶黏剂使用，经加热交联固化粘接，主要针对短时耐高温的胶接条件，并且由于固化中无挥发物放出，因此适于大面积粘接。加成型聚酰亚胺胶黏剂由于固化后形成高度交联的体型结构，耐热性能优异优势，但其固化物的韧性不佳，难以制备高韧性要求的胶膜。目前常见的热固性聚酰亚胺包括：(1)NA酸酐(5-降冰片烯-2,3-二羧酸酐)封端PMR型聚酰亚胺；(2)炔基封端聚酰亚胺。
PMR型聚酰亚胺采用降冰片烯封端，利用四甲酸二酯形成聚酰胺酸的低粘度从而控制固含量在50％以上。Cytec公司的FM35设计分子量为1500g/mol，其固化温度为329℃，固化压力为0.35MPa，并在343℃后固化。Ti/Ti粘接强度17.2MPa(25℃)、13.8MPa(288℃)(12thNat.SAMPE Tech.Con.f,1980:746-758)。但是PMR型的聚酰亚胺经过316℃热氧老化125h后，粘接强度会迅速下降。这是由于脂肪族的降冰片烯基的长期热氧化稳定性欠佳造成的，所以并不满足超过300℃(甚至400℃～500℃)长时间的粘接需求。
炔基封端聚酰亚胺有乙炔基聚酰亚胺(250℃固化)和苯乙炔基聚酰亚胺(370℃固化)固化两种。与NA酸酐封端的聚酰亚胺相比，它的长期热氧化稳定性更佳。1974年美国Hughes飞机公司推出了HR-600乙炔基封端的聚酰亚胺(Thermid 600)，反应制得固化物的Tg高达350℃，热分解温度超过500℃。然而由于其熔点较高，而且在熔融后立即开始聚合因而加工窗口窄。例如ThermidMC-600，190℃凝胶时间只有3min，因此该系 列树脂作为胶黏剂无法对被粘表面形成良好的润湿作用(4th Nat.SAMPE Tech.Con.f.1982:236-242)。
由于用乙炔基封端的聚酰亚胺普遍存在加工窗口窄的缺点，在20世纪80年代又发展了苯乙炔基封端的聚酰亚胺预聚物。与乙炔基相比，苯乙炔基封端的预聚物有更好的化学稳定性和热稳定性，其酰亚胺预聚物具有较好的流动性，并具有较宽的加工窗口。由于反应前树脂的熔融时间较长，增加了对被粘物的润湿性PETI-5(分子量5000g/mol)具有最佳的剪切强度(52MPa，25℃；34MPa，177℃)(Polym.Prep.1994,35:553)。但是以上缩聚型和加成型的聚酰亚胺胶粘剂，在应用于板芯结构(复合材料-蜂窝夹层结构)普遍存在以下问题：
首先，需要满足蜂窝的的低压力固化(≤0.5MPa)需要采用可以热熔融的结构，如果是缩聚型聚酰亚胺，在400℃以下热成型(Tm(熔点)或者Tg(玻璃化转变温度)＜400℃)，使用温度不会超过400℃，如上述文献中报道的，并没有使用温度超过400℃。
采用加成型聚酰亚胺，能满足低的加工粘度会带来分子量小，固化后材料脆性大，对于板芯结构来说，会导致结构件面临后续切割、弯曲等存在破坏问题。同时现有的加成型聚酰亚胺胶膜，并没有文献和资料报道，能够满足Tg值大于400℃，使用温度超过400℃，同时能够满足板芯夹层结构粘接使用。
其次，蜂窝-芯材结构固化后，胶粘剂需要在蜂窝底端具有一定程度的爬升，才能够具有较高的板芯剥离强度，满足工艺使用要求。利用毛细作用、熔体流动性和触变性可以实现以上现象，与蜂窝-蒙皮固化成型的聚酰亚胺胶粘剂需要能够实现板芯胶膜的成膜性、胶瘤的形成对板芯结构稳定性具有极大贡献。但是通常情况下，形成可爬升的胶瘤需要胶粘剂具有适宜的粘度和粘性，关于适用于板芯的胶膜控制爬升和胶瘤形成效果，获得良好粘接性尚未见研究报道。
现有的资料和文献报道，多集中在加成型和缩聚型聚酰亚胺的结构设计，对于作为结构胶粘剂的高温下的剪切强度、平拉强度和剥离强度报道较少，对于耐高温(400℃～500℃)的板-芯粘接的聚酰亚胺胶膜并没有报道。对于如何同时满足耐高温、高粘接韧性和界面粘接效果，也没有资料报道。
发明内容
本发明要解决现有的粘接蜂窝和蒙皮壁板的板芯胶-聚酰亚胺胶膜存在耐热性不足，板芯结构粘接无爬升和胶瘤的问题，而提供一种耐高温聚酰亚胺胶膜及其制备方法。
一种耐高温聚酰亚胺胶膜按重量份数由100份聚酰亚胺溶液、10份～40份无机填料改性剂及0.1份～5份界面偶联剂制成；
所述的无机填料改性剂由二氧化硅类物质和增加界面结合作用的物质组成，所述的二 氧化硅类物质与增加界面结合作用的物质的质量比为1:(0.1～0.5)；
所述的二氧化硅类物质为中空陶瓷微球、气相二氧化硅、熔融二氧化硅或无定形二氧化硅；
所述的增加界面结合作用的物质为氢氧化铝、氢氧化镁、氧化钼、氮化铝、氧化铝、氮化硼和碳化硅中的一种或其中几种的混合物；
所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000001
所述的n为1～19；
所述的Ar1为
Figure PCTCN2017109142-appb-000002
Figure PCTCN2017109142-appb-000003
所述的Ar2为
Figure PCTCN2017109142-appb-000004
；所述的R1为O或NH。
一种耐高温聚酰亚胺胶膜的制备方法是按以下步骤进行：
一、按重量份数称取100份聚酰亚胺溶液、10份～40份无机填料改性剂及0.1份～5份界面偶联剂，在温度为90℃～120℃及搅拌条件下，将10份～40份无机填料改性剂及0.1份～5份界面偶联剂加入到100份聚酰亚胺溶液中，搅拌10min～30min，得到胶粘剂；
所述的聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入芳香二胺，搅拌1h～5h，然后向三颈瓶中加入芳香二酐，搅拌1h～5h，得到混合溶液，向混合溶液中加4-苯基乙炔基邻苯二甲酸酐，搅拌反应1h～5h，然后加入甲苯，升温至温度为120℃～130℃，在温度为120℃～130℃的条 件下，回流反应5h～20h，得到聚酰亚胺溶液；
所述的芳香二酐与芳香二胺的摩尔比为(0.50～0.95):1；所述的N,N-二甲基乙酰胺与甲苯的质量比为1:(0.2～0.5)；所述的芳香二胺与4-苯基乙炔基邻苯二甲酸酐的摩尔比为1:(0.01～1)；且所述的芳香二酐的酸酐官能团和4-苯基乙炔基邻苯二甲酸酐的酸酐官能团的总摩尔与芳香二胺的氨基官能团的摩尔相等；
所述的N,N-二甲基乙酰胺和甲苯的总质量与4-苯基乙炔基邻苯二甲酸酐、芳香二酐和芳香二胺的总质量比为(2.5～4):1；
所述的芳香二酐为
Figure PCTCN2017109142-appb-000005
所述的芳香二胺为
Figure PCTCN2017109142-appb-000006
；所述的R1为O或NH；
二、将胶粘剂过滤并脱气，流延到负载有载体布和隔离纸的不锈钢制转鼓上，得到具有自支撑性的膜，然后在温度为60℃～150℃的条件下，加热1min～60min，再在温度为150℃～300℃的条件下，加热1min～60min，最后在温度为50℃～140℃的条件下，退火处理1min～20min，得到耐高温聚酰亚胺胶膜；
所述的耐高温聚酰亚胺胶膜的厚度为0.30mm～0.60mm；
步骤一中所述的无机填料改性剂由二氧化硅类物质和增加界面结合作用的物质组成，所述的二氧化硅类物质与增加界面结合作用的物质的质量比为1:(0.1～0.5)；
所述的二氧化硅类物质为中空陶瓷微球、气相二氧化硅、熔融二氧化硅或无定形二氧化硅；
所述的增加界面结合作用的物质为氢氧化铝、氢氧化镁、氧化钼、氮化铝、氧化铝、氮化硼和碳化硅中的一种或其中几种的混合物；
步骤一中所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000007
所述的n为1～19；
所述的Ar1为
Figure PCTCN2017109142-appb-000008
Figure PCTCN2017109142-appb-000009
所述的Ar2为
Figure PCTCN2017109142-appb-000010
；所述的R1为O或NH。
本发明的有益效果是：现有的板芯(蜂窝-复合材料)结构用聚酰亚胺胶膜耐温等级 满足不了300℃以上要求，尤其是400℃～500℃。无法满足新结构的界面粘接需求。同时现有聚酰亚胺胶膜在高韧性所需的胶接爬升(胶瘤)的形成方面、高低温下的剪切强度、平拉强度和剥离强度等方面，报道较少。
本发明采用含有氮杂环结构的芳香二胺，与芳香二酐聚合形成聚酰亚胺，相比于资料和文献中报道的采用普通苯环结构的二胺，具有更高的材料模量和刚性，并且苯并咪唑或苯并噁唑结构的引入，形成了除苯并酰亚胺环以外的另一个共平面棒状结构，提高了玻璃化转变温度和耐热性，出乎意料的是，在超过Tg值以上，由于刚性结构的保持，依然具有极高的模量值，模量下跌在0.5个数量级内，使其具有超过Tg以上的使用性能，从而能够满足400℃～500℃使用的要求。此外，芳香二胺中避免引入柔性基团，从而保证每个重复单元中从酰亚胺环到苯并咪唑再到酰亚胺环，均采用刚性直链结构，形成刚性的链段。进一步提升了整体结构的高温强度表现。此外，采用对称结构的二胺，能够进一步提升材料的结构有序性，获得更佳的高温强度。
其次，本发明同时选用含有可旋转角度或空间位阻的
Figure PCTCN2017109142-appb-000011
Figure PCTCN2017109142-appb-000012
Figure PCTCN2017109142-appb-000013
作为芳香二酐的基团，并没有采用包括均苯四甲酸二酐等刚性共平面结构，一方面能够提高链段的柔韧性，通过调节重复单元数控制分子量，使其具有一定的熔融加工性能；另一方面，通过引入具有能与异质材料表面基团，如羟基、羧基等形成化学键联的C＝O、S＝O、C-F等，增加界面粘接性能，提高粘接强度和韧性，尤其是在提高耐热性的同时，显著提升了剥离强度。
单纯采用热固性树脂很难获得良好的成膜性，拟采用载体布实现成膜自支撑性，此外，采用无极填料能更好地获得成膜韧性和高表面质量，减少裂纹的产生，提高产品的厚度均匀性，其中，通过实验发现，采用二氧化硅类物质获得了较好的效果。
单纯依靠热固性聚酰亚胺树脂的热熔融行为很难形成良好界面粘接的效果：低熔体粘度的树脂，流动性过好，在蜂窝低端无爬升，无法粘接；高熔体粘度的树脂，流动性差，无法在蜂窝低端形成毛细现象的爬升，无法粘接。
本发明采用流动控制剂控制树脂的触变性和毛细爬升效果，从而形成所需要的胶瘤，获得良好的粘接效果。并且出乎意料的发现，采用控制触变性的二氧化硅类和能增加界面结合作用的氧化物、碳化物、氮化物类的混合物，能够将可熔融树脂的流动性提高，同时抑制爬升阻力，获得固化后依然保持的胶瘤效果，同时兼具更佳的剥离韧性；所述的二氧化硅类物质与增加界面结合作用的物质的质量比为1:(0.1～0.5)时，具有最好的综合效果。且无机填料改性剂的添加质量与聚酰亚胺溶液的质量比为(0.1～0.4):1，取得良好的板芯结构粘接效果，主要体现在控制适宜的爬升和胶瘤形成，过多的填料会影响树脂熔融流动，同时阻碍在蜂窝低端的毛细爬升作用；过少的填料无法起到控制触变性作用。
本发明配方合理，所制备的胶膜具有耐300℃以上，尤指400℃～500℃耐热性能和板芯结构的粘接性能，并可获得优异的界面结合效果。可用于对热性能要求较高的聚酰亚胺蜂窝、钛合金蜂窝与聚酰亚胺复合材料、钛合金、不锈钢结构件的胶接，从而拓宽了耐高温胶粘剂在航空航天等领域的应用。
本发明用于一种耐高温聚酰亚胺胶膜及其制备方法。
附图说明
图1为红外图谱，1为合成实施例1制备的聚酰亚胺溶液固化后的红外曲线，2为合成实施例3制备的聚酰亚胺溶液固化后的红外曲线；
图2为流变曲线图，1为合成实施例1制备的聚酰亚胺溶液中聚酰亚胺的流变曲线，2为合成实施例6制备的聚酰亚胺溶液中聚酰亚胺的流变曲线，3为合成实施例3制备的聚酰亚胺溶液中聚酰亚胺的流变曲线；
图3为动态热机械曲线图，1为合成实施例1制备的聚酰亚胺溶液固化后的动态热机械曲线，2为合成实施例3制备的聚酰亚胺溶液固化后的动态热机械曲线，3为合成实施例5制备的聚酰亚胺溶液固化后的动态热机械曲线，4为合成实施例8制备的聚酰亚胺溶液固化后的动态热机械曲线。
具体实施方式
具体实施方式一：本实施方式的一种耐高温聚酰亚胺胶膜按重量份数由100份聚酰亚胺溶液、10份～40份无机填料改性剂及0.1份～5份界面偶联剂制成；
所述的无机填料改性剂由二氧化硅类物质和增加界面结合作用的物质组成，所述的二氧化硅类物质与增加界面结合作用的物质的质量比为1:(0.1～0.5)；
所述的二氧化硅类物质为中空陶瓷微球、气相二氧化硅、熔融二氧化硅或无定形二氧化硅；
所述的增加界面结合作用的物质为氢氧化铝、氢氧化镁、氧化钼、氮化铝、氧化铝、氮化硼和碳化硅中的一种或其中几种的混合物；
所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000014
所述的n为1～19；
所述的Ar1为
Figure PCTCN2017109142-appb-000015
Figure PCTCN2017109142-appb-000016
所述的Ar2为
Figure PCTCN2017109142-appb-000017
；所述的R1为O或NH。
所述的聚酰亚胺溶液中聚酰亚胺的结构式含有氮杂环结构，优选在二胺结构中赋予氮杂环结构，同时含有反应性端基，采用4-苯基乙炔基邻苯二甲酸酐封端。
所述的二氧化硅类物质能控制流动触变性。
本实施方式的有益效果是：现有的板芯(蜂窝-复合材料)结构用聚酰亚胺胶膜耐温等级满足不了300℃以上要求，尤其是400℃～500℃。无法满足新结构的界面粘接需求。同时现有聚酰亚胺胶膜在高韧性所需的胶接爬升(胶瘤)的形成方面、高低温下的剪切强度、平拉强度和剥离强度等方面，报道较少。
本实施方式采用含有氮杂环结构的芳香二胺，与芳香二酐聚合形成聚酰亚胺，相比于资料和文献中报道的采用普通苯环结构的二胺，具有更高的材料模量和刚性，并且苯并咪唑或苯并噁唑结构的引入，形成了除苯并酰亚胺环以外的另一个共平面棒状结构，提高了玻璃化转变温度和耐热性，出乎意料的是，在超过Tg值以上，由于刚性结构的保持，依然具有极高的模量值，模量下跌在0.5个数量级内，使其具有超过Tg以上的使用性能，从而能够满足400℃～500℃使用的要求。此外，芳香二胺中避免引入柔性基团，从而保证 每个重复单元中从酰亚胺环到苯并咪唑再到酰亚胺环，均采用刚性直链结构，形成刚性的链段。进一步提升了整体结构的高温强度表现。此外，采用对称结构的二胺，能够进一步提升材料的结构有序性，获得更佳的高温强度。
其次，本实施方式同时选用含有可旋转角度或空间位阻的
Figure PCTCN2017109142-appb-000018
Figure PCTCN2017109142-appb-000019
Figure PCTCN2017109142-appb-000020
作为芳香二酐的基团，并没有采用包括均苯四甲酸二酐等刚性共平面结构，一方面能够提高链段的柔韧性，通过调节重复单元数控制分子量，使其具有一定的熔融加工性能；另一方面，通过引入具有能与异质材料表面基团，如羟基、羧基等形成化学键联的C＝O、S＝O、C-F等，增加界面粘接性能，提高粘接强度和韧性，尤其是在提高耐热性的同时，显著提升了剥离强度。
单纯采用热固性树脂很难获得良好的成膜性，拟采用载体布实现成膜自支撑性，此外，采用无极填料能更好地获得成膜韧性和高表面质量，减少裂纹的产生，提高产品的厚度均匀性，其中，通过实验发现，采用二氧化硅类物质获得了较好的效果。
单纯依靠热固性聚酰亚胺树脂的热熔融行为很难形成良好界面粘接的效果：低熔体粘度的树脂，流动性过好，在蜂窝低端无爬升，无法粘接；高熔体粘度的树脂，流动性差，无法在蜂窝低端形成毛细现象的爬升，无法粘接。
本实施方式采用流动控制剂控制树脂的触变性和毛细爬升效果，从而形成所需要的胶瘤，获得良好的粘接效果。并且出乎意料的发现，采用控制触变性的二氧化硅类和能增加界面结合作用的氧化物、碳化物、氮化物类的混合物，能够将可熔融树脂的流动性提高，同时抑制爬升阻力，获得固化后依然保持的胶瘤效果，同时兼具更佳的剥离韧性；所述的二氧化硅类物质与增加界面结合作用的物质的质量比为1:(0.1～0.5)时，具有最好的综合效果。且无机填料改性剂的添加质量与聚酰亚胺溶液的质量比为(0.1～0.4):1，取得良好的板芯结构粘接效果，主要体现在控制适宜的爬升和胶瘤形成，过多的填料会影响树脂熔融流动，同时阻碍在蜂窝低端的毛细爬升作用；过少的填料无法起到控制触变性作用。
本实施方式配方合理，所制备的胶膜具有耐300℃以上，尤指400℃～500℃耐热性能 和板芯结构的粘接性能，并可获得优异的界面结合效果。可用于对热性能要求较高的聚酰亚胺蜂窝、钛合金蜂窝与聚酰亚胺复合材料、钛合金、不锈钢结构件的胶接，从而拓宽了耐高温胶粘剂在航空航天等领域的应用。
具体实施方式二：本实施方式与具体实施方式一不同的是：所述的聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入芳香二胺，搅拌1h～5h，然后向三颈瓶中加入芳香二酐，搅拌1h～5h，得到混合溶液，向混合溶液中加4-苯基乙炔基邻苯二甲酸酐，搅拌反应1h～5h，然后加入甲苯，升温至温度为120℃～130℃，在温度为120℃～130℃的条件下，回流反应5h～20h，得到聚酰亚胺溶液；
所述的芳香二酐与芳香二胺的摩尔比为(0.50～0.95):1；所述的N,N-二甲基乙酰胺与甲苯的质量比为1:(0.2～0.5)；所述的芳香二胺与4-苯基乙炔基邻苯二甲酸酐的摩尔比为1:(0.01～1)；且所述的芳香二酐的酸酐官能团和4-苯基乙炔基邻苯二甲酸酐的酸酐官能团的总摩尔与芳香二胺的氨基官能团的摩尔相等；
所述的N,N-二甲基乙酰胺和甲苯的总质量与4-苯基乙炔基邻苯二甲酸酐、芳香二酐和芳香二胺的总质量比为(2.5～4):1；
所述的芳香二酐为
Figure PCTCN2017109142-appb-000021
Figure PCTCN2017109142-appb-000022
所述的芳香二胺为
Figure PCTCN2017109142-appb-000023
；所述的R1为O或NH。其它与具体实施方式一相同。
具体实施方式三：本实施方式与具体实施方式一或二之一不同的是：所述的无机填料改性剂平均粒径为0.1μm～10μm；所述的界面偶联剂为含有氨端基的硅烷偶联剂。其它与具体实施方式一或二相同。
所述的的无机填料改性剂平均粒径需满足分散均匀性要求，平均粒径优选0.5μm～3μm。
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是：所述的含有氨端基的硅烷偶联剂为γ-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷或3-氨丙基甲基二乙氧基硅烷。其它与具体实施方式一至三相同。
具体实施方式五：本实施方式一种耐高温聚酰亚胺胶膜的制备方法是按以下步骤进行：
一、按重量份数称取100份聚酰亚胺溶液、10份～40份无机填料改性剂及0.1份～5份界面偶联剂，在温度为90℃～120℃及搅拌条件下，将10份～40份无机填料改性剂及0.1份～5份界面偶联剂加入到100份聚酰亚胺溶液中，搅拌10min～30min，得到胶粘剂；
所述的聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入芳香二胺，搅拌1h～5h，然后向三颈瓶中加入芳香二酐，搅拌1h～5h，得到混合溶液，向混合溶液中加4-苯基乙炔基邻苯二甲酸酐，搅拌反应1h～5h，然后加入甲苯，升温至温度为120℃～130℃，在温度为120℃～130℃的条件下，回流反应5h～20h，得到聚酰亚胺溶液；
所述的芳香二酐与芳香二胺的摩尔比为(0.50～0.95):1；所述的N,N-二甲基乙酰胺与甲苯的质量比为1:(0.2～0.5)；所述的芳香二胺与4-苯基乙炔基邻苯二甲酸酐的摩尔比为1:(0.01～1)；且所述的芳香二酐的酸酐官能团和4-苯基乙炔基邻苯二甲酸酐的酸酐官能团的总摩尔与芳香二胺的氨基官能团的摩尔相等；
所述的N,N-二甲基乙酰胺和甲苯的总质量与4-苯基乙炔基邻苯二甲酸酐、芳香二酐和芳香二胺的总质量比为(2.5～4):1；
所述的芳香二酐为
Figure PCTCN2017109142-appb-000024
所述的芳香二胺为
Figure PCTCN2017109142-appb-000025
；所述的R1为O或NH；
二、将胶粘剂过滤并脱气，流延到负载有载体布和隔离纸的不锈钢制转鼓上，得到具有自支撑性的膜，然后在温度为60℃～150℃的条件下，加热1min～60min，再在温度为150℃～300℃的条件下，加热1min～60min，最后在温度为50℃～140℃的条件下，退火处理1min～20min，得到耐高温聚酰亚胺胶膜；
所述的耐高温聚酰亚胺胶膜的厚度为0.30mm～0.60mm；
步骤一中所述的无机填料改性剂由二氧化硅类物质和增加界面结合作用的物质组成，所述的二氧化硅类物质与增加界面结合作用的物质的质量比为1:(0.1～0.5)；
所述的二氧化硅类物质为中空陶瓷微球、气相二氧化硅、熔融二氧化硅或无定形二氧化硅；
所述的增加界面结合作用的物质为氢氧化铝、氢氧化镁、氧化钼、氮化铝、氧化铝、氮化硼和碳化硅中的一种或其中几种的混合物；
步骤一中所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000026
所述的n为1～19；
所述的Ar1为
Figure PCTCN2017109142-appb-000027
Figure PCTCN2017109142-appb-000028
所述的Ar2为
Figure PCTCN2017109142-appb-000029
；所述的R1为O或NH。
具体实施方式六：本实施方式与具体实施方式五不同的是：步骤一中所述的无机填料改性剂平均粒径为0.1μm～10μm。其它与具体实施方式五相同。
具体实施方式七：本实施方式与具体实施方式五或六之一不同的是：步骤一中所述的界面偶联剂为含有氨端基的硅烷偶联剂。其它与具体实施方式五或六相同。
具体实施方式八：本实施方式与具体实施方式五至七之一不同的是：所述的含有氨端基的硅烷偶联剂为γ-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷或3-氨丙基甲基 二乙氧基硅烷。其它与具体实施方式五至七相同。
具体实施方式九：本实施方式与具体实施方式五至八之一不同的是：步骤二中所述的载体布为E玻璃纤维布、D玻璃纤维布、S玻璃纤维布、NE玻璃纤维布、T玻璃纤维布或Q玻璃纤维布。其它与具体实施方式五至八相同。
所述的载体布为玻璃布载体。可以使用用于各种印刷电路板、复合材料的公知材料。在这些基材当中，更优选使用平面方向的膨胀系数与钻孔加工性平衡优异的E玻璃这些玻璃纤维。
具体实施方式十：本实施方式与具体实施方式五至九之一不同的是：所述的载体布面密度为100g/cm2～110g/cm2。其它与具体实施方式五至九相同。
采用以下实施例验证本发明的有益效果：
合成实施例1：
聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入189g N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入41.65g(0.1mol)芳香二胺，搅拌1h，然后向三颈瓶中加入14.71g(0.05mol)3,3’,4,4’-联苯四甲酸二酐，搅拌5h，得到混合溶液，向混合溶液中加24.82g(0.1mol)4-苯基乙炔基邻苯二甲酸酐，搅拌反应3h，然后加入62g甲苯，升温至温度为130℃，在温度为130℃的条件下，回流反应10h，得到聚酰亚胺溶液；
所述的3,3’,4,4’-联苯四甲酸二酐的结构式为
Figure PCTCN2017109142-appb-000030
所述的芳香二胺为
Figure PCTCN2017109142-appb-000031
；所述的芳香二胺CAS号：4402-17-9；
所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000032
Figure PCTCN2017109142-appb-000033
所述的Ar2为
Figure PCTCN2017109142-appb-000034
合成实施例2：
聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入175g N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入41.65g(0.1mol)芳香二胺，搅拌1h，然后向三颈瓶中加入23.54g(0.08mol)3,3’,4,4’-联苯四甲酸二酐，搅拌5h，得到混合溶液，向混合溶液中加9.93g(0.04mol)4-苯基乙炔基邻苯二甲酸酐，搅拌反应3h，然后加入58g甲苯，升温至温度为130℃，在温度为130℃的条件下，回流反应10h，得到聚酰亚胺溶液；
所述的3,3’,4,4’-联苯四甲酸二酐的结构式为
Figure PCTCN2017109142-appb-000035
所述的芳香二胺为
Figure PCTCN2017109142-appb-000036
；所述的芳香二胺CAS号：4402-17-9；
所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000037
所述的Ar2为
Figure PCTCN2017109142-appb-000038
合成实施例3：
聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入190g N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入41.65g(0.1mol)芳香二胺，搅拌1h，然后向三颈瓶中加入16.11g(0.05mol)3,3’,4,4’-二苯甲酮四甲酸二酐，搅拌5h，得到混合溶液，向混合溶液中加24.82g(0.1mol)4-苯基乙炔基邻苯二甲酸酐，搅拌反应3h，然后加入63g甲苯，升温至温度为130℃，在温度为130℃的条件下，回流反应10h，得到聚酰亚胺溶液；
所述的3,3’,4,4’-二苯甲酮四甲酸二酐的结构式为
Figure PCTCN2017109142-appb-000039
所述的芳香二胺为
Figure PCTCN2017109142-appb-000040
；所述的芳香二胺CAS号：4402-17-9；
所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000041
所述的Ar2为
Figure PCTCN2017109142-appb-000042
合成实施例4：
聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入180g N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入41.65g(0.1mol)芳香二胺，搅拌1h，然后向三颈瓶中加入25.78g(0.08mol)3,3’,4,4’-二苯甲酮四甲酸二酐，搅拌5h，得到混合溶液，向混合溶液中加9.93g(0.04mol)4-苯基乙炔基邻苯二甲酸酐，搅拌反应3h，然后加入60g甲苯，升温至温度为130℃，在温度为130℃的条件下，回流反应10h，得到聚酰亚胺溶液；
所述的3,3’,4,4’-二苯甲酮四甲酸二酐的结构式为
Figure PCTCN2017109142-appb-000043
所述的芳香二胺为
Figure PCTCN2017109142-appb-000044
；所述的芳香二胺CAS号：4402-17-9；
所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000045
所述的Ar2为
Figure PCTCN2017109142-appb-000046
合成实施例5：
聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入180g N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入41.65g(0.1mol)芳香二胺，搅拌1h，然后向三颈瓶中加入29.00g(0.09mol)3,3’,4,4’-二苯甲酮四甲酸二酐，搅拌5h，得到混合溶液，向混合溶液中加4.96g(0.02mol)4-苯基乙炔基邻苯二甲酸酐，搅拌反应3h，然后加入60g甲 苯，升温至温度为130℃，在温度为130℃的条件下，回流反应10h，得到聚酰亚胺溶液；
所述的3,3’,4,4’-二苯甲酮四甲酸二酐的结构式为
Figure PCTCN2017109142-appb-000047
所述的芳香二胺为
Figure PCTCN2017109142-appb-000048
；所述的芳香二胺CAS号：4402-17-9；
所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000049
所述的Ar2为
Figure PCTCN2017109142-appb-000050
实施例1：
一种聚酰亚胺胶膜按重量份数由100份聚酰亚胺溶液、20份无机填料改性剂及1份界面偶联剂制成；
所述的无机填料改性剂按重量份数由17份气相二氧化硅和3份氮化硼组成；所述的界面偶联剂为γ-氨丙基三乙氧基硅烷；所述的聚酰亚胺溶液为合成实施例1制备的聚酰亚胺溶液；
上述一种聚酰亚胺胶膜的制备方法是按以下步骤进行：
一、按重量份数称取100份聚酰亚胺溶液、20份无机填料改性剂及1份界面偶联剂，在温度为90℃及搅拌条件下，将20份无机填料改性剂及1份界面偶联剂加入到100份聚酰亚胺溶液中，搅拌30min，得到胶粘剂；
二、将胶粘剂过滤并脱气，流延到负载有载体布和隔离纸的不锈钢制转鼓上，得到具有自支撑性的膜，然后在温度为60℃的条件下，加热60min，再在温度为150℃的条件下，加热5min，最后在温度为60℃的条件下，退火处理5min，得到聚酰亚胺胶膜；
所述的聚酰亚胺胶膜的厚度为0.40mm；所述的载体布为E玻璃纤维布，面密度为110g/cm2；所述的无机填料改性剂平均粒径为5μm。
实施例2：本实施例与实施例1不同的是：所述的聚酰亚胺溶液为合成实施例2制备的聚酰亚胺溶液。其它与实施例1相同。
实施例3：本实施例与实施例1不同的是：所述的聚酰亚胺溶液为合成实施例3制备的聚酰亚胺溶液。其它与实施例1相同。
实施例4：本实施例与实施例1不同的是：所述的聚酰亚胺溶液为合成实施例4制备的聚酰亚胺溶液。其它与实施例1相同。
实施例5：本实施例与实施例1不同的是：所述的聚酰亚胺溶液为合成实施例5制备的聚酰亚胺溶液。其它与实施例1相同。
实施例6：
一种聚酰亚胺胶膜按重量份数由100份聚酰亚胺溶液、3份无机填料改性剂及1份界面偶联剂制成；
所述的无机填料改性剂按重量份数由2份气相二氧化硅和1份氮化硼组成；
所述的界面偶联剂为γ-氨丙基三乙氧基硅烷；
所述的聚酰亚胺溶液为合成实施例1制备的聚酰亚胺溶液；
一种聚酰亚胺胶膜的制备方法是按以下步骤进行：
一、按重量份数称取100份聚酰亚胺溶液、3份无机填料改性剂及1份界面偶联剂，在温度为90℃及搅拌条件下，将3份无机填料改性剂及1份界面偶联剂加入到100份聚酰亚胺溶液中，搅拌30min，得到胶粘剂；
二、将胶粘剂过滤并脱气，流延到负载有载体布和隔离纸的不锈钢制转鼓上，得到具有自支撑性的膜，然后在温度为60℃的条件下，加热60min，再在温度为150℃的条件下，加热5min，最后在温度为60℃的条件下，退火处理5min，得到聚酰亚胺胶膜；
所述的聚酰亚胺胶膜的厚度为0.4mm；所述的载体布为E玻璃纤维布，面密度为110g/cm2；所述的无机填料改性剂平均粒径为5μm。
实施例7：本实施例与实施例6不同的是：一种聚酰亚胺胶膜按重量份数由100份聚酰亚胺溶液、36份无机填料改性剂及2份界面偶联剂制成；所述的无机填料改性剂按重量份数由30份熔融二氧化硅和6份氢氧化铝组成。其它与实施例6相同。
实施例8：本实施例与实施例6不同的是：一种聚酰亚胺胶膜按重量份数由100份 聚酰亚胺溶液、79份无机填料改性剂及3份界面偶联剂制成；所述的无机填料改性剂按重量份数由70份熔融二氧化硅、3份氢氧化铝、5份氮化铝和1份氮化硼组成。其它与实施例6相同。
实施例9：本实施例与实施例6不同的是：一种聚酰亚胺胶膜按重量份数由100份聚酰亚胺溶液、20份无机填料改性剂及1份界面偶联剂制成；所述的无机填料改性剂按重量份数由17份无定形二氧化硅和3份氧化铝组成。其它与实施例6相同。
实施例10：本实施例与实施例9不同的是：所述的聚酰亚胺溶液为合成实施例3制备的聚酰亚胺溶液。其它与实施例9相同。
实施例11：本实施例与实施例9不同的是：所述的无机填料改性剂按重量份数由17份气相二氧化硅和3份氮化硼组成；所述的聚酰亚胺溶液按重量份数由50份合成实施例1制备的聚酰亚胺溶液和50份合成实施例3制备的聚酰亚胺溶液组成。其它与实施例9相同。
实施例12：本实施例与实施例9不同的是：所述的无机填料改性剂按重量份数由17份气相二氧化硅和3份氮化硼组成；所述的聚酰亚胺溶液按重量份数由50份合成实施例1制备的聚酰亚胺溶液和50份合成实施例4制备的聚酰亚胺溶液组成。其它与实施例9相同。
实施例13：本实施例与实施例9不同的是：所述的无机填料改性剂按重量份数由17份气相二氧化硅和3份氮化硼组成；所述的聚酰亚胺溶液按重量份数由30份合成实施例1制备的聚酰亚胺溶液和70份合成实施例4制备的聚酰亚胺溶液组成。其它与实施例9相同。
实施例14：本实施例与实施例9不同的是：所述的无机填料改性剂按重量份数由17份气相二氧化硅和3份氮化硼组成；所述的聚酰亚胺溶液按重量份数由70份合成实施例1制备的聚酰亚胺溶液和30份合成实施例4制备的聚酰亚胺溶液组成。其它与实施例9相同。
实施例15：
将合成实施例1制备的聚酰亚胺溶液过滤并脱气，流延到负载有载体布和隔离纸的不锈钢制转鼓上，得到具有自支撑性的膜，然后在温度为60℃的条件下，加热60min，再在温度为150℃的条件下，加热5min，最后在温度为60℃的条件下，退火处理5min，得到聚酰亚胺胶膜；
所述的载体布为E玻璃纤维布，面密度为110g/cm2。
实施例16：本实施例与实施例15不同的是：将合成实施例2制备的聚酰亚胺溶液过滤并脱气。其它与实施例15相同。
实施例17：本实施例与实施例15不同的是：将合成实施例3制备的聚酰亚胺溶液过滤并脱气。其它与实施例15相同。
实施例18：本实施例与实施例15不同的是：将合成实施例4制备的聚酰亚胺溶液过滤并脱气。其它与实施例15相同。
实施例19：本实施例与实施例15不同的是：将合成实施例5制备的聚酰亚胺溶液过滤并脱气。其它与实施例15相同。
合成实施例6：
聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入113g N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入10.8g(0.1mol)对苯二胺，搅拌1h，然后向三颈瓶中加入14.71g(0.05mol)3,3’,4,4’-联苯四甲酸二酐，搅拌5h，得到混合溶液，向混合溶液中加24.82g(0.1mol)4-苯基乙炔基邻苯二甲酸酐，搅拌反应3h，然后加入38g甲苯，升温至温度为130℃，在温度为130℃的条件下，回流反应10h，得到聚酰亚胺溶液；
所述的3,3’,4,4’-联苯四甲酸二酐为
Figure PCTCN2017109142-appb-000051
所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000052
所述的Ar2为
Figure PCTCN2017109142-appb-000053
合成实施例7：
聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入113g N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入10.8g(0.1mol)间苯二胺，搅拌1h，然后向三颈瓶中加入14.71g(0.05mol)3,3’,4,4’-联苯四甲酸二酐，搅拌5h，得到混合溶液，向混合溶液中加24.82g(0.1mol)4-苯基乙炔基邻苯二甲酸酐，搅拌反应3h，然后加入37g甲苯，升温至温度为130℃，在温度为130℃的条件下，回流反应10h，得到聚酰亚胺溶液；
所述的3,3’,4,4’-联苯四甲酸二酐为
Figure PCTCN2017109142-appb-000054
所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000055
所述的Ar2为
Figure PCTCN2017109142-appb-000056
合成实施例8：
聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入123g N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入20.02g(0.1mol)4,4’-二氨基二苯醚，搅拌1h，然后向三颈瓶中加入25.78g(0.08mol)3,3’,4,4’-二苯甲酮四甲酸二酐，搅拌5h，得到混合溶液，向混合溶液中加9.93g(0.04mol)4-苯基乙炔基邻苯二甲酸酐，搅拌反应3h，然后加入41g甲苯，升温至温度为130℃，在温度为130℃的条件下，回流反应10h，得到聚酰亚胺溶液；
所述的3,3’,4,4’-二苯甲酮四甲酸二酐的结构式为
Figure PCTCN2017109142-appb-000057
所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000058
所述的Ar2为
Figure PCTCN2017109142-appb-000059
合成实施例9：
聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入174g N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入41.65g(0.1mol)芳香二胺，搅拌1h，然后向三颈瓶中加入10.9g(0.05mol)均苯四甲酸二酐，搅拌5h，得到混合溶液，向混合溶液中加24.82g(0.1mol)4-苯基乙炔基邻苯二甲酸酐，搅拌反应3h，然后加入58g甲苯，升温至温度为130℃，在温度为130℃的条件下，回流反应10h，得到聚酰亚胺溶液；
所述的芳香二胺为
Figure PCTCN2017109142-appb-000060
；所述的芳香二胺CAS号：4402-17-9；
所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
Figure PCTCN2017109142-appb-000061
所述的Ar2为
Figure PCTCN2017109142-appb-000062
对比实验1：
一、按重量份数称取100份聚酰亚胺溶液、20份无机填料改性剂及1份界面偶联剂，在温度为90℃及搅拌条件下，将20份无机填料改性剂及1份界面偶联剂加入到100份聚酰亚胺溶液中，搅拌30min，得到胶粘剂；
所述的无机填料改性剂按重量份数由17份气相二氧化硅和3份氮化硼组成；所述的界面偶联剂为γ-氨丙基三乙氧基硅烷；所述的聚酰亚胺溶液为合成实施例6制备的聚酰亚胺溶液；
二、将胶粘剂过滤并脱气，流延到负载有载体布和隔离纸的不锈钢制转鼓上，得到具有自支撑性的膜，然后在温度为60℃的条件下，加热60min，再在温度为150℃的条件下，加热5min，最后在温度为60℃的条件下，退火处理5min，得到聚酰亚胺胶膜；
所述的载体布为E玻璃纤维布，面密度为110g/cm2；所述的无机填料改性剂平均粒径为5μm。
对比实验2：本对比实验与对比实验1不同的是：所述的聚酰亚胺溶液为合成实施例7制备的聚酰亚胺溶液。其它与对比实验1相同。
对比实验3：本对比实验与对比实验1不同的是：所述的聚酰亚胺溶液为合成实施例8制备的聚酰亚胺溶液。其它与对比实验1相同。
对比实验4：本对比实验与对比实验1不同的是：所述的聚酰亚胺溶液为合成实施例9制备的聚酰亚胺溶液。其它与对比实验1相同。
对比实验5：
将聚酰亚胺溶液过滤并脱气，流延到负载有载体布和隔离纸的不锈钢制转鼓上，得到具有自支撑性的膜，然后在温度为60℃的条件下，加热60min，再在温度为150℃的条件下，加热5min，最后在温度为60℃的条件下，退火处理5min，得到聚酰亚胺胶膜；
所述的聚酰亚胺溶液为合成实施例6制备的聚酰亚胺溶液；所述的载体布为E玻璃纤维布，面密度为100g/cm2。
对合成实施例一至九制备的聚酰亚胺溶液进行了玻璃化转变温度、热稳定性、流变和红外的测试，如表1及图1～3所示。聚酰亚胺溶液固化工艺为：首先在温度为180℃及压力为0.2MPa的条件下加热1h，然后在温度为350℃及压力为0.2MPa的条件下加热4h。流变测试：将聚酰亚胺溶液导入蒸馏水中，析出物经过水洗涤，烘干后，进行流变测试。各项性能的测试条件参照以下标准(方法)：
1、玻璃化转变温度采用动态热机械仪(DMA)。升温速率：5℃/min；频率：1Hz。
2、热稳定性：测试采用热失重分析仪(TGA)。升温速率：10℃/min；测试气氛：空气。
3、流变：采用旋转流变仪，升温速率4℃/min，测试气氛：空气。频率：1Hz。
4、红外光谱采用傅里叶红外光谱仪，采用溴化钾为背底，扫描次数为128次。
实施例1～19及对比实验1～5制备的聚酰亚胺胶膜置于两个待粘材料之间进行粘接，固化工艺为：首先在温度为180℃及压力为0.2MPa的条件下加热1h，然后在温度为350℃及压力为0.2MPa的条件下加热4h，然后对粘接后的材料进行了剪切强度、剥离强度及平拉强度测试，如表2及表3所示，各项性能的测试条件参照以下标准(方法)：
1、剪切强度：GB/T7124-2008胶粘剂拉伸剪切强度的测定；GJB444-1988胶粘剂高 温拉伸剪切强度试验方法。材料：304不锈钢。
2、剥离强度及平拉强度测试：GJB130.7-1986胶接铝蜂窝夹层结构滚筒剥离试验方法；GJB130.4-1986胶接铝蜂窝夹层结构平面拉伸试验方法。蜂窝采用钛合金蜂窝，面板采用钛合金板代替铝合金。
且对于剥离强度及平拉强度测试采用的粘接件(钛合金蜂窝与钛合金板粘接)，固化过程中进行熔融爬升的观察，固化后进行胶瘤定型的观察。
图1为红外图谱，1为合成实施例1制备的聚酰亚胺溶液固化后的红外曲线，2为合成实施例3制备的聚酰亚胺溶液固化后的红外曲线；从图中可以看出，在1780cm-1和1720cm-1处，都存在亚胺的特征吸收峰，即羰基的不对称和对称伸缩振动峰，1380cm-1存在酰亚胺环和苯并咪唑环的C-N的伸缩振动峰，1660cm-1处存在C＝O的吸收峰，说明二苯甲酮结构二酐的存在，3000cm-1～3500cm-1出现了咪唑特有的N-H键，在2200cm-1处的C≡C特征峰在350℃固化后消失，证明交联完全。
图2为流变曲线图，1为合成实施例1制备的聚酰亚胺溶液中聚酰亚胺的流变曲线，2为合成实施例6制备的聚酰亚胺溶液中聚酰亚胺的流变曲线，3为合成实施例3制备的聚酰亚胺溶液中聚酰亚胺的流变曲线；从图中可知，合成实施例1及3制备的聚酰亚胺溶液均具有较宽的加工区间和低的熔体粘度，保证了高温熔融性和在板芯结构中的熔融爬升性。而合成实施例6制备的聚酰亚胺溶液由于没有采用含有柔性羰基的苯并咪唑二胺，采用刚性较大的结构，如对苯二胺，导致高温不具有熔融流动性，不能爬升，不能粘接板芯结构。
因此，合成实施例1～5所合成的聚酰亚胺溶液均具有熔融流动性，配合无机填料改善触变性和胶瘤形成，能获得较好的粘接效果。
图3为动态热机械曲线图，1为合成实施例1制备的聚酰亚胺溶液固化后的的动态热机械曲线，2为合成实施例3制备的聚酰亚胺溶液固化后的的动态热机械曲线，3为合成实施例5制备的聚酰亚胺溶液固化后的的动态热机械曲线，4为合成实施例8制备的聚酰亚胺溶液固化后的的动态热机械曲线；图3结合表1、2及3可知，合成实施例1～5由于采用苯并咪唑环和苯并亚胺环结合，导致Tg在390℃上，并且储能模量在超过Tg+30℃，依然保持0.5个数量级以下的下降趋势。从而为400℃～450℃耐高温使用提供了基础，如采用合成实施例1～5制备的实施例1～19，具有400℃以上较好的剪切强度和260℃～300℃老化后的强度。而合成实施例8采用柔型结构二胺，带来熔融加工性的同时，降低了固化后Tg值，并且带来储能模量保持率的下降(＞2个数量级)，导致对比实验3高温没有强度。
实施例15～19和对比实验5中，没有采用加入无机填料改性剂，导致胶膜表面质量 差，裂纹加深比例高。
采用合成实施例1～5制备的实施例15～19中，没有加入无机填料改性剂，采用合成实施例1制备的实施例6，无机填料改性剂加入量少，以上两种情况均会导致有树脂的熔融流动爬升，但是在高温下并没有形成胶瘤，导致板芯结构平面拉伸强度低和滚筒剥离强度低。采用合成实施例1制备实施例8中，过多的加入无机填料改性剂，导致板芯结构粘接，树脂不能熔融爬升，在高温下并没有形成胶瘤，同样降低板芯结构平面拉伸强度和滚筒剥离强度。采用合成实施例6～9制备的对比实验1～5中，对比例1、2、4和5由于没有树脂熔融流动性导致板芯结构平拉强度和剥离强度低，具有流动性的对比实验3，没有采用苯并咪唑环和苯并亚胺环结合，导致Tg和高温剪切强度低。
表1：合成实施例的性能对比表
Figure PCTCN2017109142-appb-000063
表2：实施例1至11的性能对比表
Figure PCTCN2017109142-appb-000064
Figure PCTCN2017109142-appb-000065
表3：实施例12至19及对比实验1至5的性能对比表
Figure PCTCN2017109142-appb-000066

Claims (10)

  1. 一种耐高温聚酰亚胺胶膜，其特征在于一种耐高温聚酰亚胺胶膜按重量份数由100份聚酰亚胺溶液、10份～40份无机填料改性剂及0.1份～5份界面偶联剂制成；
    所述的无机填料改性剂由二氧化硅类物质和增加界面结合作用的物质组成，所述的二氧化硅类物质与增加界面结合作用的物质的质量比为1:(0.1～0.5)；
    所述的二氧化硅类物质为中空陶瓷微球、气相二氧化硅、熔融二氧化硅或无定形二氧化硅；
    所述的增加界面结合作用的物质为氢氧化铝、氢氧化镁、氧化钼、氮化铝、氧化铝、氮化硼和碳化硅中的一种或其中几种的混合物；
    所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
    Figure PCTCN2017109142-appb-100001
    所述的n为1～19；
    所述的Ar1为
    Figure PCTCN2017109142-appb-100002
    ——O——、
    Figure PCTCN2017109142-appb-100003
    ——、
    Figure PCTCN2017109142-appb-100004
    所述的Ar2为
    Figure PCTCN2017109142-appb-100005
    ；所述的R1为O或NH。
  2. 根据权利要求1所述的一种耐高温聚酰亚胺胶膜，其特征在于所述的聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入芳香二胺，搅拌1h～5h，然后向三颈瓶中加入芳香二酐，搅拌1h～5h，得到 混合溶液，向混合溶液中加4-苯基乙炔基邻苯二甲酸酐，搅拌反应1h～5h，然后加入甲苯，升温至温度为120℃～130℃，在温度为120℃～130℃的条件下，回流反应5h～20h，得到聚酰亚胺溶液；
    所述的芳香二酐与芳香二胺的摩尔比为(0.50～0.95):1；所述的N,N-二甲基乙酰胺与甲苯的质量比为1:(0.2～0.5)；所述的芳香二胺与4-苯基乙炔基邻苯二甲酸酐的摩尔比为1:(0.01～1)；且所述的芳香二酐的酸酐官能团和4-苯基乙炔基邻苯二甲酸酐的酸酐官能团的总摩尔与芳香二胺的氨基官能团的摩尔相等；
    所述的N,N-二甲基乙酰胺和甲苯的总质量与4-苯基乙炔基邻苯二甲酸酐、芳香二酐和芳香二胺的总质量比为(2.5～4):1；
    所述的芳香二酐为
    Figure PCTCN2017109142-appb-100006
    所述的芳香二胺为
    Figure PCTCN2017109142-appb-100007
    ；所述的R1为O或NH。
  3. 根据权利要求1所述的一种耐高温聚酰亚胺胶膜，其特征在于所述的无机填料改性剂平均粒径为0.1μm～10μm；所述的界面偶联剂为含有氨端基的硅烷偶联剂。
  4. 根据权利要求3所述的一种耐高温聚酰亚胺胶膜，其特征在于所述的含有氨端基的硅烷偶联剂为γ-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷或3-氨丙基甲基二乙氧基硅烷。
  5. 如权利要求1所述的一种耐高温聚酰亚胺胶膜的制备方法，其特征在于一种耐高温聚酰亚胺胶膜的制备方法是按以下步骤进行：
    一、按重量份数称取100份聚酰亚胺溶液、10份～40份无机填料改性剂及0.1份～5份界面偶联剂，在温度为90℃～120℃及搅拌条件下，将10份～40份无机填料改性剂及0.1份～5份界面偶联剂加入到100份聚酰亚胺溶液中，搅拌10min～30min，得到胶粘剂；
    所述的聚酰亚胺溶液是按下述步骤制备的：向三颈瓶中加入N,N-二甲基乙酰胺，在氮气气氛下，向N,N-二甲基乙酰胺中加入芳香二胺，搅拌1h～5h，然后向三颈瓶中加入芳香二酐，搅拌1h～5h，得到混合溶液，向混合溶液中加4-苯基乙炔基邻苯二甲酸酐，搅拌反应1h～5h，然后加入甲苯，升温至温度为120℃～130℃，在温度为120℃～130℃的条件下，回流反应5h～20h，得到聚酰亚胺溶液；
    所述的芳香二酐与芳香二胺的摩尔比为(0.50～0.95):1；所述的N,N-二甲基乙酰胺与甲苯的质量比为1:(0.2～0.5)；所述的芳香二胺与4-苯基乙炔基邻苯二甲酸酐的摩尔比为1:(0.01～1)；且所述的芳香二酐的酸酐官能团和4-苯基乙炔基邻苯二甲酸酐的酸酐官能团的总摩尔与芳香二胺的氨基官能团的摩尔相等；
    所述的N,N-二甲基乙酰胺和甲苯的总质量与4-苯基乙炔基邻苯二甲酸酐、芳香二酐和芳香二胺的总质量比为(2.5～4):1；
    所述的芳香二酐为
    Figure PCTCN2017109142-appb-100008
    Figure PCTCN2017109142-appb-100009
    所述的芳香二胺为
    Figure PCTCN2017109142-appb-100010
    ；所述的R1为O或NH；
    二、将胶粘剂过滤并脱气，流延到负载有载体布和隔离纸的不锈钢制转鼓上，得到具有自支撑性的膜，然后在温度为60℃～150℃的条件下，加热1min～60min，再在温度为150℃～300℃的条件下，加热1min～60min，最后在温度为50℃～140℃的条件下，退火处理1min～20min，得到耐高温聚酰亚胺胶膜；
    所述的耐高温聚酰亚胺胶膜的厚度为0.30mm～0.60mm；
    步骤一中所述的无机填料改性剂由二氧化硅类物质和增加界面结合作用的物质组成，所述的二氧化硅类物质与增加界面结合作用的物质的质量比为1:(0.1～0.5)；
    所述的二氧化硅类物质为中空陶瓷微球、气相二氧化硅、熔融二氧化硅或无定形二氧化硅；
    所述的增加界面结合作用的物质为氢氧化铝、氢氧化镁、氧化钼、氮化铝、氧化铝、氮化硼和碳化硅中的一种或其中几种的混合物；
    步骤一中所述的聚酰亚胺溶液中聚酰亚胺的结构式为：
    Figure PCTCN2017109142-appb-100011
    所述的n为1～19；
    所述的Ar1为
    Figure PCTCN2017109142-appb-100012
    ——O——、
    Figure PCTCN2017109142-appb-100013
    ——、
    Figure PCTCN2017109142-appb-100014
    所述的Ar2为
    Figure PCTCN2017109142-appb-100015
    ；所述的R1为O或NH。
  6. 根据权利要求5所述的一种耐高温聚酰亚胺胶膜的制备方法，其特征在于步骤一中所述的无机填料改性剂平均粒径为0.1μm～10μm。
  7. 根据权利要求5所述的一种耐高温聚酰亚胺胶膜的制备方法，其特征在于步骤一中所述的界面偶联剂为含有氨端基的硅烷偶联剂。
  8. 根据权利要求7所述的一种耐高温聚酰亚胺胶膜的制备方法，其特征在于所述的含有氨端基的硅烷偶联剂为γ-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷或3-氨丙基甲基二乙氧基硅烷。
  9. 根据权利要求5所述的一种耐高温聚酰亚胺胶膜的制备方法，其特征在于步骤二中所述的载体布为E玻璃纤维布、D玻璃纤维布、S玻璃纤维布、NE玻璃纤维布、T玻璃纤维布或Q玻璃纤维布。
  10. 根据权利要求9所述的一种耐高温聚酰亚胺胶膜的制备方法，其特征在于所述的载体布面密度为100g/cm2～110g/cm2。
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