CN103965824B - Acetenyl polyimide modified cyanate ester adhesive and preparation method thereof - Google Patents

Abstract

An ethynyl polyimide modified cyanate adhesive and a preparation method thereof, relating to a cyanate adhesive and a preparation method thereof. The present invention aims to solve the problems of poor thermal stability and insufficient toughness in existing cyanate adhesives. The adhesive comprises cyanate ester resin, acetylene polyimide resin and inorganic filler modifier. Method: 1. Heat the cyanate resin; 2. Add the acetylene polyimide resin to the polar solvent, heat up, and stir to dissolve the mixture, then keep the temperature and add the mixture to the cyanate resin, stir, Then, the solvent is distilled off under reduced pressure to obtain the copolymer; 3. Add the inorganic filler modifier to the copolymer in a state of stirring, and the adhesive is obtained after stirring. The adhesive of the invention has good thermal stability and toughness. Used in the field of adhesives.

Description

A kind of ethynyl polyimide modified cyanate adhesive and preparation method thereof

technical field

The invention relates to a cyanate adhesive and a preparation method thereof.

Background technique

Adhesives have been widely used in various industries, and bonding technology has become one of the three major connection technologies. With the development of research and application technology in aerospace and other industries, the Mach number of high-speed aircraft is increasing year by year, which puts forward new requirements for the temperature resistance level of polymer materials. At the same time, in order to improve the wave-transmitting performance of the airborne radome, higher requirements are put forward for the dielectric properties of polymer materials including adhesives, such as the requirement to display low dielectric constant and low dielectric loss tangent in the GHz band region. Dielectric characteristics.

Since the cyanate resin can generate a triazine ring structure under the action of heat or a catalyst, the cyanate of this structure not only has a low dielectric constant, a very small dielectric loss tangent, low moisture absorption and good processability, At the same time, no volatile low-molecular substances are produced during the curing process. Therefore, as the above-mentioned adhesive material, a cyanate-based adhesive having good processability and dielectric properties is widely used. However, due to the high cross-linking density of the cyanate resin after curing, the material is brittle, and the presence of carbon-hydrogen bonds and ether bonds in the cyanate structure adversely affects the heat resistance of the material, which greatly limits its use. Applications in aerospace and other fields.

The use of rubber elastomers (such as active end-group liquid rubber, macromolecule butyl rubber, etc.) or thermoplastic engineering plastics (such as polysulfone, polyethersulfone, polyetherimide, etc.) can improve the toughness of the adhesive material, but it also reduces use temperature. Therefore, in order to improve the overall toughness and thermal aging properties of cyanate esters, thermosetting resins are commonly used to modify them: epoxy resins are used to modify cyanate esters, although they have good mechanical properties and adhesive properties after curing, but Poor heat resistance; bismaleimide resin is used to modify cyanate ester, and after curing, triazine resin (bismaleimide triazine, referred to as BT resin) has low dielectric properties and water absorption, but the cured product is brittle and peels off The strength is low, and the thermal aging performance of bisma resin is not good; although aryl acetylene has the advantages of good ablation resistance and high glass transition temperature, the polyphenyl ring structure and high crosslinking density of aryl acetylene cause greater brittleness of the matrix , the adhesive performance is poor, and it is difficult to improve the toughness of cyanate ester materials.

Contents of the invention

The invention aims to solve the problems of poor thermal stability and insufficient toughness in existing cyanate adhesives, and provides an ethynyl polyimide modified cyanate adhesive and a preparation method thereof.

The ethynyl polyimide modified cyanate ester adhesive of the present invention comprises 100 parts of cyanate resin, 1 to 100 parts of ethynyl polyimide resin and 1 to 10 parts of inorganic filler modifier in parts by weight; The cyanate resin is one of bisphenol A cyanate, dicyclopentadiene bisphenol cyanate, bisphenol F cyanate, phenolic cyanate or a mixture of several of them in any ratio. ; The inorganic filler modifier is one of hollow ceramic microspheres, fumed silica, bentonite, and nano-silicon carbide, or a mixture of several of them in any ratio.

The structural formula of described ethynyl polyimide resin is:

, where the degree of polymerization n is 1 to 9, and Ar ₁ is Ar ₂ is

The ethynyl polyimide resin is prepared according to the following steps: add N,N-dimethylacetamide in a three-necked bottle, and add N,N-dimethylacetamide to N,N-dimethylacetamide under a nitrogen atmosphere Add aromatic dianhydride, add aromatic diamine after stirring for 1 hour, stir for 1 to 5 hours to obtain a mixed solution; add m-ethynyl aniline to the mixed solution, stir for 1 to 5 hours, wherein aromatic The molar ratio to m-ethynylaniline is 1:0.5~0.9:0.2~1; then add toluene, heat up to 120~130°C for reflux reaction for 1~4 hours; after the solution drops to room temperature, drop it into absolute ethanol, Settling for 1 hour and then filtering, the precipitate was washed 3 times with absolute ethanol at 80°C, and then dried at 130-140°C to obtain ethynyl polyimide resin; N,N-dimethylacetamide and toluene The mass ratio is 10:3, the ratio of the total mass of N,N-dimethylacetamide and toluene to the total mass of m-ethynylaniline, aromatic dianhydride and aromatic diamine is 4:1; aromatic dianhydride is 3 ,3,4',4'-Biphenyl tetracarboxylic dianhydride, 2,3,3',4'-Biphenyl tetracarboxylic dianhydride, 3,3,4',4'-Diphenyl ether tetracarboxylic Acid dianhydride or 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride; aromatic diamine is 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether or 2 -(4-Aminophenyl)-5-aminobenzoxazole.

The preparation method of above-mentioned ethynyl polyimide modified cyanate ester adhesive, carries out according to the following steps:

1. Heat 100 parts of cyanate resin to 115-120°C in parts by weight;

2. Add 1 to 100 parts of ethynyl polyimide resin to 50 to 200 parts of polar solvent, raise the temperature to 130 to 160 ° C, and stir and dissolve for 30 minutes to obtain a mixture, then keep the temperature and add the mixture to cyanate In the resin, stir at 120-140°C for 30 minutes, then distill under reduced pressure to remove the solvent to obtain a copolymer;

3. Add 1-5 parts of inorganic filler modifier to the copolymer under stirring at 90-120°C, and stir for 10-30 minutes to prepare the adhesive;

The cyanate ester resin described in step 1 is one or several of them in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, bisphenol F cyanate, novolak type cyanate the composition of the mixture;

The polar solvent described in step 2 is one of toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or several of them are composed in any ratio mixture;

The inorganic filler modifier in step three is one of hollow ceramic microspheres, fumed silica, bentonite, and nano-silicon carbide, or a mixture of several of them in any ratio.

The present invention comprises following beneficial effect:

In the prior art, epoxy resin, bismaleimide resin and allyl compounds are used to modify cyanate resin to reduce the heat resistance of the adhesive; at the same time, it has a catalytic effect on the curing of cyanate ester, which affects the processing window and storage period; in order to avoid the deficiencies of the prior art, compared with the previous modification technology, the present invention adopts the mixture of cyanate resin/ethynyl polyimide as the main resin, and uses the inorganic filler as the modifying agent to prepare a kind of ethynyl polyimide Polyimide modified cyanate ester adhesive.

The present invention does not adopt the resin (such as bismaleimide, allyl compound, epoxy resin etc.) that has catalytic crosslinking effect to cyanate resin, on the one hand, does not affect the curing process of cyanate resin, keeps Its wide processing window and suitable gel time. At the same time, because ethynyl polyimide and cyanate have similar curing temperature ranges, they can be cured simultaneously; The electrical performance is not affected much.

The present invention adopts the acetylene-based polyimide containing the flexible segment as the main resin of the adhesive, and the introduction of the acetylene end group on the one hand makes the polyimide have a higher cross-linking density after curing. The above has better modulus retention, which improves the heat resistance and bonding strength of the adhesive; on the other hand, acetylene-terminated polyimide and cyanate have a similar curing temperature range, and the two can be cured simultaneously and mutually There is no cross-linking point between them, and the formed completely interpenetrating network structure can not only maintain the good dielectric properties of cyanate ester, but also reflect the excellent thermal stability and material toughness of polyimide.

The present invention adopts the polyimide containing meta-position structure and ether ketone structure in the main chain structure, so that it has a lower softening point and good solubility in organic solvents, and at the same time gives the adhesive better bonding performance and mechanical properties. Performance: By controlling the diamine/dianhydride type and the feeding ratio of ethynyl polyimide, the molecular weight and main chain structure of the polymer are controlled, so as to achieve the purpose of toughening and modifying cyanate resin/ethynyl polyimide .

The ethynyl polyimide modified cyanate ester adhesive prepared by the present invention has the following advantages:

(1) High heat resistance, 5% thermal decomposition temperature ≥ 410°C;

(2) Low dielectric loss and dielectric constant: ε<3.3, tanδ<0.015;

(3) High bonding performance, high shear strength and high temperature retention rate, its shear strength at room temperature is ≥15MPa, and its shear strength at 350°C is ≥10MPa;

(4) The manufacturability is good, the gel time is long, and the viscosity of the adhesive is moderate.

The formula of the invention is reasonable, and the prepared adhesive has good heat resistance, mechanical properties, and bonding properties, and can be used for the bonding of metal or composite material structural parts that require high thermal properties and dielectric properties, thereby broadening the scope of application. Application of high temperature resistant adhesives in aerospace and other fields. The adhesive of the present invention improves the heat resistance, mechanical properties and thermal oxidation properties of the adhesive on the basis of maintaining the excellent dielectric properties and good process properties of the cyanate resin, so as to meet the requirements of a new generation of high-performance wave-transparent adhesives for aerospace .

Description of drawings

Fig. 1 is the thermal weight loss curve graph of the adhesive prepared in Example 1 and Comparative Example 1.

Detailed ways

The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

Specific Embodiment 1: The ethynyl polyimide modified cyanate adhesive in this embodiment includes 100 parts by weight of cyanate resin, 1-100 parts of ethynyl polyimide resin and 1-10 parts of inorganic filler Modifier; wherein the cyanate resin is one or several of bisphenol A cyanate, dicyclopentadiene bisphenol cyanate, bisphenol F cyanate, novolac cyanate A mixture composed in any ratio; the inorganic filler modifier is one of hollow ceramic microspheres, fumed silica, bentonite, and nano-silicon carbide, or a mixture of several of them composed in an arbitrary ratio.

Specific embodiment two: the difference between this embodiment and specific embodiment one is: the structural formula of the ethynyl polyimide resin is:

, where the degree of polymerization n is 1 to 9, and Ar ₁ is Ar ₂ is Others are the same as in the first embodiment.

Specific embodiment three: the difference between this embodiment and specific embodiment one or two is that: the ethynyl polyimide resin is prepared according to the following steps: add N,N-dimethyl Acetamide, under a nitrogen atmosphere, add aromatic dianhydride to N,N-dimethylacetamide, add aromatic diamine after stirring for 1 hour, and stir for 1 to 5 hours to obtain a mixed solution; add dimethicone to the mixed solution Ethynylaniline, stirred and reacted for 1-5 hours, wherein the molar ratio of aromatic dianhydride, aromatic diamine and m-ethynylaniline is 1:0.5-0.9:0.2-1; then add toluene, heat up to 120-130°C for reflux reaction 1 to 4 hours; after the solution has dropped to room temperature, add it dropwise into absolute ethanol, precipitate for 1 hour and then filter, wash the precipitate with 80°C absolute ethanol for 3 times, and dry at 130°C to 140°C to obtain ethynyl Polyimide resin; wherein the mass ratio of N,N-dimethylacetamide and toluene is 10:3, the total mass of N,N-dimethylacetamide and toluene is mixed with m-ethynylaniline, aromatic dianhydride and The ratio of the total mass of the three aromatic diamines is 4:1; the aromatic dianhydride is 3,3,4',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic Acid dianhydride, 3,3,4',4'-diphenyl ether tetracarboxylic dianhydride or 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride; aromatic diamine is 4,4' - diaminodiphenyl ether, 3,4'-diaminodiphenyl ether or 2-(4-aminophenyl)-5-aminobenzoxazole. Others are the same as in the first or second embodiment.

Specific embodiment four: the preparation method of the ethynyl polyimide modified cyanate ester adhesive described in specific embodiment one, carry out according to the following steps:

1. Heat 100 parts of cyanate resin to 115-120°C in parts by weight;

2. Add 1 to 100 parts of ethynyl polyimide resin to 50 to 200 parts of polar solvent, raise the temperature to 130 to 160 ° C, and stir and dissolve for 30 minutes to obtain a mixture, then keep the temperature and add the mixture to cyanate In the resin, stir at 120-140°C for 30 minutes, then distill under reduced pressure to remove the solvent to obtain a copolymer;

3. Add 1-5 parts of inorganic filler modifier to the copolymer under stirring at 90-120°C, and stir for 10-30 minutes to prepare the adhesive;

The cyanate ester resin described in step 1 is one or several of them in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, bisphenol F cyanate, novolak type cyanate the composition of the mixture;

The polar solvent described in step 2 is one of toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or several of them are composed in any ratio mixture;

The inorganic filler modifier described in step 3 is one of hollow ceramic microspheres, fumed silica, bentonite, and nano-silicon carbide, or a mixture of several of them in any ratio;

The ethynyl polyimide resin described in step 2 is prepared according to the following steps: add N,N-dimethylacetamide in a three-necked bottle, and add N,N-dimethylacetamide to N,N-dimethylacetamide under a nitrogen atmosphere Add aromatic dianhydride to the mixture, add aromatic diamine after stirring for 1 hour, and stir for 1 to 5 hours to obtain a mixed solution; add m-ethynyl aniline to the mixed solution, stir and react for 1 to 5 hours, wherein aromatic dianhydride, aromatic di The molar ratio of amine to m-ethynylaniline is 1:0.5~0.9:0.2~1; then add toluene, heat up to 120~130°C for reflux reaction for 1~4 hours; after the solution drops to room temperature, add it dropwise into absolute ethanol , precipitated for 1 hour and then filtered, the precipitate was washed 3 times with absolute ethanol at 80°C, and then dried at 130-140°C to obtain ethynyl polyimide resin; wherein N,N-dimethylacetamide and toluene The mass ratio of N,N-dimethylacetamide and toluene to the total mass of m-ethynylaniline, aromatic dianhydride and aromatic diamine is 4:1; aromatic dianhydride is 3,3,4',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3,4',4'-diphenyl ether tetra Carboxylic acid dianhydride or 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride; aromatic diamine is 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether or 2-(4-Aminophenyl)-5-aminobenzoxazole.

Embodiment 5: This embodiment is different from Embodiment 4 in that: in step 2, the temperature is raised to 140-150°C. Others are the same as in Embodiment 4.

Embodiment 6: The difference between this embodiment and Embodiment 4 or 5 is that the molar ratio of aromatic dianhydride, aromatic diamine and m-ethynyl aniline is 1:0.8:0.4. Others are the same as in Embodiment 4 or 5.

Embodiment 7: This embodiment differs from Embodiment 4 or Embodiment 5 in that the molar ratio of aromatic dianhydride, aromatic diamine and m-ethynyl aniline is 1:0.5:1. Others are the same as in Embodiment 4 or 5.

Example 1:

The preparation method of the ethynyl polyimide modified cyanate ester adhesive of this embodiment is carried out according to the following steps:

1. Heat 100 parts of phenolic cyanate resin to 120°C in parts by weight;

2. Add 50 parts of acetylene-based polyimide resin to 100 parts of polar solvent, raise the temperature to 160°C, and stir and dissolve for 30 minutes to obtain a mixture, then keep the temperature and add the mixture to the cyanate ester resin. Stir for 30min, then remove the solvent by distillation under reduced pressure to obtain a copolymer;

3. Add 4 parts of fumed silica to the copolymer under stirring at 100°C, and stir for 30 minutes to prepare the adhesive;

The polar solvent in step 2 consists of 50 parts of N,N-dimethylformamide and 50 parts of N,N-dimethylacetamide.

The ethynyl polyimide resin described in step 2 is prepared according to the following steps: add 160mLN,N-dimethylacetamide in a three-necked bottle, and add N,N-dimethylacetamide to N,N-dimethylacetamide under a nitrogen atmosphere Add 31.02g (0.1mol) of 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, and after stirring for 1 hour, add 16.02g (0.08mol) of 3,4'-diaminodiphenyl ether, Stir for 3 hours to obtain a mixed solution; add 4.68g (0.04mol) m-ethynylaniline to the mixed solution, and stir for 3 hours; then add 50mL of toluene, heat up to 125°C and reflux for 4 hours; after the solution drops to room temperature, drop Add it to absolute ethanol, settling for 1 hour and then filter, wash the precipitate three times with absolute ethanol at 80°C, and dry at 140°C to obtain acetylene polyimide resin.

The structural formula of the prepared acetylene polyimide resin is:

The ethynyl polyimide modified cyanate ester adhesive prepared in this example is cured, the curing process is: 130°C/1h+200°C/2h, post-treatment 260°C/2h.

Example 2:

The preparation method of the ethynyl polyimide modified cyanate ester adhesive of this embodiment is carried out according to the following steps:

1. Heat 100 parts of phenolic cyanate resin to 120°C in parts by weight;

2. Add 50 parts of acetylene-based polyimide resin to 100 parts of polar solvent, raise the temperature to 160°C, and stir and dissolve for 30 minutes to obtain a mixture, then keep the temperature and add the mixture to the cyanate ester resin. Stir for 30min, then remove the solvent by distillation under reduced pressure to obtain a copolymer;

3. Add 4 parts of fumed silica to the copolymer under stirring at 100°C, and stir for 30 minutes to prepare the adhesive;

The polar solvent in step 2 consists of 50 parts of N,N-dimethylformamide and 50 parts of N,N-dimethylacetamide.

The ethynyl polyimide resin described in step 2 is prepared according to the following steps: add 162mLN,N-dimethylacetamide in a three-necked bottle, and add N,N-dimethylacetamide to N,N-dimethylacetamide under a nitrogen atmosphere Add 31.02g (0.1mol) 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, and add 10.01g (0.05mol) 3,4'-diaminodiphenyl ether after stirring for 1 hour, Stir for 3 hours to obtain a mixed solution; add 11.71 g (0.1 mol) m-ethynyl aniline to the mixed solution, and stir for 3 hours; then add 50 mL of toluene, heat up to 125 ° C and reflux for 4 hours; after the solution drops to room temperature, drop Add it to absolute ethanol, settling for 1 hour and then filter, wash the precipitate three times with absolute ethanol at 80°C, and dry at 140°C to obtain acetylene polyimide resin.

The structural formula of the prepared acetylene polyimide resin is:

The ethynyl polyimide modified cyanate ester adhesive prepared in this example is cured, the curing process is: 130°C/1h+200°C/2h, post-treatment 260°C/2h.

Example 3:

The preparation method of the ethynyl polyimide modified cyanate ester adhesive of this embodiment is carried out according to the following steps:

1. Heat 100 parts of phenolic cyanate resin to 120°C in parts by weight;

2. Add 70 parts of ethynyl polyimide resin to 150 parts of polar solvent, raise the temperature to 160°C, and stir and dissolve for 30 minutes to obtain a mixture, then keep the temperature and add the mixture to the cyanate resin, Stir for 30min, then remove the solvent by distillation under reduced pressure to obtain a copolymer;

3. Add 4 parts of fumed silica to the copolymer under stirring at 100°C, and stir for 30 minutes to prepare the adhesive;

The polar solvent described in step 2 consists of 75 parts of N,N-dimethylformamide and 75 parts of N,N-dimethylacetamide.

The ethynyl polyimide resin described in step 2 is prepared according to the following steps: add 160mLN,N-dimethylacetamide in a three-necked bottle, and add N,N-dimethylacetamide to N,N-dimethylacetamide under a nitrogen atmosphere Add 29.42g (0.1mol) of 3,3,4',4'-biphenyltetracarboxylic dianhydride, and after stirring for 1 hour, add 16.02g (0.08mol) of 3,4'-diaminodiphenyl ether, stir After 3 hours, a mixed solution was obtained; 4.68g (0.04mol) m-ethynyl aniline was added to the mixed solution, and the reaction was stirred for 3 hours; then 50mL of toluene was added, and the temperature was raised to 125°C for reflux reaction for 4 hours; after the solution was cooled to room temperature, dropwise added into dehydrated ethanol, settling for 1 hour and then filtering, the precipitate was washed 3 times with dehydrated ethanol at 80°C, and then dried at 140°C to obtain acetylene polyimide resin.

The structural formula of the prepared acetylene polyimide resin is:

The ethynyl polyimide modified cyanate ester adhesive prepared in this example is cured, the curing process is: 130°C/1h+200°C/2h, post-treatment 260°C/2h.

Example 4:

The preparation method of the ethynyl polyimide modified cyanate ester adhesive of this embodiment is carried out according to the following steps:

1. Heat 100 parts of phenolic cyanate resin to 120°C in parts by weight;

2. Add 50 parts of ethynyl polyimide resin to 150 parts of polar solvent, raise the temperature to 160°C, and stir and dissolve for 30 minutes to obtain a mixture, then keep the temperature and add the mixture to the cyanate resin, at 120°C Stir for 30min, then remove the solvent by distillation under reduced pressure to obtain a copolymer;

3. Add 4 parts of fumed silica to the copolymer under stirring at 100°C, and stir for 30 minutes to prepare the adhesive;

The polar solvent described in step 2 consists of 75 parts of N,N-dimethylformamide and 75 parts of N,N-dimethylacetamide.

The ethynyl polyimide resin described in step 2 is prepared according to the following steps: add 160mLN,N-dimethylacetamide in a three-necked bottle, and add N,N-dimethylacetamide to N,N-dimethylacetamide under a nitrogen atmosphere Add 29.42g (0.1mol) of 2,3,3',4'-biphenyltetracarboxylic dianhydride, and after stirring for 1 hour, add 16.02g (0.08mol) of 3,4'-diaminodiphenyl ether, stir After 3 hours, a mixed solution was obtained; 4.68g (0.04mol) m-ethynyl aniline was added to the mixed solution, and stirred for 3 hours; then toluene was added, and the temperature was raised to 125° C. for reflux reaction for 4 hours; after the solution was cooled to room temperature, it was added dropwise to Settling in absolute ethanol for 1 hour and then filtering, washing the precipitate three times with absolute ethanol at 80°C, and drying at 140°C to obtain acetylene polyimide resin.

The structural formula of the prepared acetylene polyimide resin is:

The ethynyl polyimide modified cyanate ester adhesive prepared in this example is cured, the curing process is: 130°C/1h+200°C/2h, post-treatment 260°C/2h.

Comparative example 1:

The preparation method of the adhesive of this comparative example is carried out according to the following steps: by weight, slowly heat 100 parts of phenolic cyanate ester resin to 120 °C in a beaker, add 4 parts of gas phase dioxide under stirring at 100 °C Silicon, after stirring for 30 minutes, the adhesive is prepared. The curing process of the adhesive is the same as in Examples 1-4.

Carry out heat treatment to the adhesive after embodiment 1 and comparative example 1 curing, test its thermogravity performance in air, the result refers to Fig. 1, and Fig. 1 is the thermogravity curve figure of the adhesive prepared in embodiment 1 and comparative example 1, wherein curve a is the thermogravimetric curve of the ethynyl polyimide modified cyanate ester adhesive prepared in Example 1, and curve b is the thermogravimetric curve of the adhesive provided in Comparative Example 1.

The glass transition temperature, thermal stability, shear strength, peel strength and dielectric properties of the cured adhesives prepared in the above five examples were tested, as shown in Table 1. The test conditions of various properties refer to the following standards (method):

1. Thermal stability: The test uses a thermogravimetric analyzer (TGA). Heating rate: 10°C/min; Test atmosphere: air.

2. Shear strength: test according to GB/T7124-2008 adhesive tensile shear strength test method. Material: LY12CZ aluminum alloy.

3. Dielectric properties: The test is conducted under the condition of 9.8GHz using the waveguide short-circuit method.

Table 1: The performance comparison table of embodiment and comparative example

Compared with the comparative example, the embodiment has good heat resistance, especially the carbon residue rate at 600°C under air, and the embodiment is much higher than the comparative example; at the same time, the high-temperature bonding strength of the embodiment is higher than that of the comparative example, and for the The dielectric properties do not have a great impact, and it is suitable for applications in the field of high temperature resistant adhesives.

The descriptions of the above embodiments are only for helping to understand the method of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims (5)

1. the polyimide modified cyanate ester adhesive of ethynyl, is characterized in that this tackiness agent comprises 100 parts of cyanate ester resins, 1 ~ 100 part of ethynyl polyimide resin and 1 ~ 10 part of mineral filler properties-correcting agent by weight; Wherein said cyanate ester resin is a kind of in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, Bisphenol F cyanate, Novolac Cyanate Eater Resin or wherein several by arbitrarily than the mixture formed; Described mineral filler properties-correcting agent is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by arbitrarily than the mixture formed;

The structural formula of described ethynyl polyimide resin is:

wherein polymerization degree n is 1 ~ 9, Ar ₁for

Described ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add N,N-dimethylacetamide, in a nitrogen atmosphere, in N,N-dimethylacetamide, add aromatic dianhydride, after 1 hour to be mixed, add aromatic diamines, stir 1 ~ 5 hour, obtain mixing solutions; In mixing solutions, add an acetylenylaniline, stirring reaction 1 ~ 5 hour, wherein the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.5 ~ 0.9:0.2 ~ 1; Then add toluene, be warming up to 120 ~ 130 DEG C of back flow reaction 1 ~ 4 hour; After solution is down to room temperature, be added drop-wise in dehydrated alcohol, precipitating was filtered after 1 hour, precipitated after the absolute ethanol washing 3 times of 80 DEG C, 130 ~ 140 DEG C of oven dry, obtained ethynyl polyimide resin; Wherein the mass ratio of N,N-dimethylacetamide and toluene is 10:3, and the ratio of the total mass of N,N-dimethylacetamide and toluene and an acetylenylaniline, aromatic dianhydride and aromatic diamines three total mass is 4:1; Aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3,4 ', 4 '-phenyl ether tetracarboxylic dianhydride or 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride; Aromatic diamines is 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide or 2-(4-aminophenyl)-5-An base benzoxazole.

2. the preparation method of the polyimide modified cyanate ester adhesive of ethynyl as claimed in claim 1, is characterized in that the method is carried out according to the following steps:

One, by weight, 100 parts of cyanate ester resins are heated to 115 ~ 120 DEG C;

Two, 1 ~ 100 part of ethynyl polyimide resin is joined in the polar solvent of 50 ~ 200 parts, be warming up to 130 ~ 160 DEG C, and stirring and dissolving 30min, obtain mixture, then temperature is kept to add in cyanate ester resin by mixture, at 120 ~ 140 DEG C, stir 30min, then underpressure distillation is removed solvent and is obtained multipolymer;

Three, multipolymer is added 1 ~ 5 part of mineral filler properties-correcting agent under 90 ~ 120 DEG C of whipped states, after stirring 10 ~ 30min, namely obtain tackiness agent;

Cyanate ester resin described in step one is a kind of in bisphenol A cyanate, dicyclopentadiene bisphenol type cyanate, Bisphenol F cyanate, Novolac Cyanate Eater Resin or wherein several by arbitrarily than the mixture formed;

Polar solvent described in step 2 is a kind of in toluene, dimethylbenzene, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone or wherein several by arbitrarily than the mixture formed;

Mineral filler properties-correcting agent described in step 3 is a kind of in ceramic microspheres, aerosil, wilkinite, nanometer silicon carbide or wherein several by arbitrarily than the mixture formed;

Described in step 2, ethynyl polyimide resin is prepared in the steps below: in three-necked bottle, add N,N-dimethylacetamide, in a nitrogen atmosphere, in N,N-dimethylacetamide, add aromatic dianhydride, after 1 hour to be mixed, add aromatic diamines, stir 1 ~ 5 hour, obtain mixing solutions; In mixing solutions, add an acetylenylaniline, stirring reaction 1 ~ 5 hour, wherein the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.5 ~ 0.9:0.2 ~ 1; Then add toluene, be warming up to 120 ~ 130 DEG C of back flow reaction 1 ~ 4 hour; After solution is down to room temperature, be added drop-wise in dehydrated alcohol, precipitating was filtered after 1 hour, precipitated after the absolute ethanol washing 3 times of 80 DEG C, 130 ~ 140 DEG C of oven dry, obtained ethynyl polyimide resin; Wherein the mass ratio of N,N-dimethylacetamide and toluene is 10:3, and the ratio of the total mass of N,N-dimethylacetamide and toluene and an acetylenylaniline, aromatic dianhydride and aromatic diamines three total mass is 4:1; Aromatic dianhydride is 3,3,4 ', 4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3,4 ', 4 '-phenyl ether tetracarboxylic dianhydride or 2,3,3 ', 4 '-phenyl ether tetracarboxylic dianhydride; Aromatic diamines is 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide or 2-(4-aminophenyl)-5-An base benzoxazole.

3. the preparation method of the polyimide modified cyanate ester adhesive of ethynyl according to claim 2, is characterized in that being warming up to 140 ~ 150 DEG C in step 2.

4. the preparation method of the polyimide modified cyanate ester adhesive of the ethynyl according to Claims 2 or 3, is characterized in that the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.8:0.4.

5. the preparation method of the polyimide modified cyanate ester adhesive of the ethynyl according to Claims 2 or 3, is characterized in that the mol ratio of aromatic dianhydride, aromatic diamines and an acetylenylaniline is 1:0.5:1.