CN105368046A - Composition of cyanate ester resin and thermal conducting filler, and prepreg and application thereof - Google Patents

Abstract

The invention relates to a cyanate ester resin/thermally conductive filler composition, a prepreg and applications thereof. The composition includes a thermally conductive filler and a cyanate resin, wherein the mass percent content of the thermally conductive filler is 0.5 to 10%, and the mass percentage of the cyanate resin is The percentage content is 90-99.5%. The thermally conductive filler is one or a combination of multi-walled carbon nanotubes treated with monofunctional isocyanate or graphene treated with monofunctional isocyanate. If the thermally conductive filler is treated with monofunctional isocyanate The combination of multi-walled carbon nanotubes and graphene treated with monofunctional isocyanate, the mass ratio of the two is 20-80:80-20, the composition can be mixed with continuous fibers or fabrics to prepare prepregs, the combination of the present invention It can be used as a matrix resin for high-performance composite materials, or as a high-performance adhesive and coating, and can be used in many industries such as electronics, aviation, aerospace, and national defense.

Description

Cyanate resin/thermally conductive filler composition, prepreg and application thereof

technical field

The invention relates to a cyanate ester resin/thermally conductive filler composition, a prepreg and applications thereof. The prepreg can be used to prepare high-performance composite materials, high-performance adhesives and coatings.

Background technique

Cyanate resin refers to phenol derivatives containing two or more -OCN functional groups, and is a new type of high-performance polymer material.

There are many ways to synthesize cyanate ester resin monomers, the most commonly used and industrialized method is to prepare cyanate ester monomers by reacting cyanogen halides with phenolic compounds in the presence of alkali. Under the action of heat or a catalyst, the cyanate resin undergoes a three-cyclization reaction to generate a macromolecule with a high cross-linking density network structure containing a triazine ring. The cyanate resin with this structure has the characteristics of low dielectric coefficient and extremely small dielectric loss tangent, high glass transition temperature, low moisture absorption rate, low shrinkage rate, excellent mechanical properties and bonding properties. Cyanate resin has similar processability to epoxy resin, can be cured at 177°C, and no volatile small molecules are produced during the curing process. Moreover, it has high temperature resistance equivalent to bismaleimide resin, has better dielectric properties than polyamideimide, and has equivalent combustion resistance to phenolic resin.

The background technology about cyanate and its main synthetic method can refer to Chen Xiangbao in "High Performance Resin Matrix" (Chemical Industry Press, 1999 edition), Yan Fusheng, etc. in "the synthesis of bisphenol A type cyanate resin" ([J ]. Engineering Plastics Application, 1999, 27 (8)), SNOWAW in "The synthesis manufacture and characterization of cyanate ester monomers" ([J]. SAMPEJ, 2000 (36)), Hamerton et al. in "Recent developments in the chemistry of cyanate ester" ([J]. )), ChaplinA et al. in "Development of novel functionalized arylcyanate ester oligomers 1. Synthesis and thermal characterization of the monomers" ([J]. Macromolecules, 1994, 27 (18)) and other works and research background mentioned in the article.

Although cyanate resin has excellent properties, the thermal conductivity of its cured product is still low, which limits its application in the field of thermal conductive materials. In order to improve the thermal conductivity of cured products of cyanate resin, some cyanate resin composite systems have been reported. For example, Mi Yanan, 2013-Soochow University, Research on High Thermal Conductivity Aluminum Nitride-Carbon Nanotubes/Polymer Matrix Composites [Dissertation], mainly discusses aluminum nitride-carbon nanotubes/cyanate resin composites, The content of aluminum nitride-carbon nanotubes is 40-47.5% and 1.5-2.5%, respectively, and its thermal conductivity can reach 2.28-5W·m ^-1 ·K ^-1 , but the content of thermally conductive filler is very high, which is not suitable for use For prepreg resin.

For example (1) Su Lei, 2012-Nanjing University of Science and Technology, Preparation and Research of Cyanate Resin-Based Thermal Conductive Insulation Composite Materials [Dissertation]; (2) Zhao Chunbao, Su Lei, etc., Cyanate Resin/ZnO Whisker Composite Preparation and Properties of Materials, New Chemical Materials, 2013, 41(11), 62-64; (3) Zhao Chunbao, Su Lei, etc., Preparation and Properties of Cyanate Resin/Graphite Oxide Sheet Composite Materials, Functional Materials, 2013, 44(16), 2301-2304. In the above reports, silane coupling agent (KH550) was mainly used for surface treatment of tetrapod zinc oxide whiskers (T-ZnOw) and hexagonal boron nitride (h-BN), Select dodecylamine (DDA) to modify the surface of graphite oxide (GO); and prepare a series of cyanate esters such as T-ZnOw/CE, BN/CE, BN-ZnOw/CE, GO-DDA/CE, etc. Resin-based thermally conductive and insulating composite material, when the ZnOw content is 12%, the thermal conductivity of the composite material reaches 0.79W·m ^-1 ·K ^-1 ; when the volume fraction of BN is 24%, the thermal conductivity of the composite material reaches 1.33W· m ^-1 ·K ^-1 ; after adding 20% volume fraction of mixed filler (BN-ZnOw), the thermal conductivity of the composite material reaches 1.19W·m ^-1 ·K ^-1 ; when the content of GO-DDA is 1%, The thermal conductivity reaches 0.43W·m ^-1 ·K ^-1 . The above work can prepare a variety of thermally conductive composite materials, but it is not suitable for the preparation of thermally conductive resins for prepregs. Specifically, the high density of the fillers mentioned above increases the weight of composite materials, and is not suitable for aerospace applications that have strict requirements on structural weight. The silane coupling agent is a low-molecular substance, which may be precipitated in the space environment, and cannot meet the requirements for condensable volatiles in the space environment of the composite material; in addition, the amount added above is more than 10%, and the viscosity of the obtained resin Too large and poor fluidity cannot prepare prepregs.

Contents of the invention

The purpose of the present invention is to overcome the above-mentioned deficiencies of the prior art, and provide cyanate ester resin/thermally conductive filler composition, and this composition is suitable as the prepreg resin of fiber composite material, and its cured product has higher thermal conductivity and Excellent performance.

Another object of the present invention is to provide a cyanate ester resin/thermally conductive filler composition prepreg and its application.

Above-mentioned purpose of the present invention is mainly achieved through the following technical solutions:

A cyanate ester resin/thermally conductive filler composition, including a thermally conductive filler and a cyanate resin, wherein the mass percentage content of the thermally conductive filler is 0.5-10%, and the mass percentage content of the cyanate resin is 90-99.5%, and the thermally conductive filler It is one or a combination of multi-walled carbon nanotubes treated with monofunctional isocyanate or graphene treated with monofunctional isocyanate, if the thermally conductive filler is multi-walled carbon nanotubes treated with monofunctional isocyanate and graphene treated with monofunctional isocyanate For the combination of graphene, the mass ratio of the two is 20-80:80-20.

In the above cyanate resin/thermally conductive filler composition, the monofunctional isocyanate is octadecyl isocyanate, hexadecyl isocyanate or dodecyl isocyanate.

In the above-mentioned cyanate resin/thermally conductive filler composition, the specific method for treating multi-walled carbon nanotubes or graphene with monofunctional isocyanate is as follows:

Using toluene as a solvent, add multi-walled carbon nanotubes or graphene, monofunctional isocyanate, and dibutyltin dilaurate, stir and heat to 65-75°C, and react at a constant temperature for 10-13 hours; after the reaction is completed, filter the product and remove the residue Acetone was added to the mixture, stirred and washed for more than 2 hours, repeated 3-4 times, then separated, and vacuum-dried for 22-25 hours, and the product obtained was isocyanate-modified multi-walled carbon nanotubes or isocyanate-modified graphene.

In the above cyanate resin/thermally conductive filler composition, the mass ratio of multi-walled carbon nanotubes or graphene, monofunctional isocyanate and dibutyltin dilaurate is 1:0.9-1.1:0.3-0.6.

In the above cyanate resin/thermally conductive filler composition, the general formula of the cyanate resin is as follows:

N≡C-O-R′-O-C≡N

Wherein: R' is an alkylene group, an arylene group, an unsaturated group or an alicyclic group.

In the above cyanate resin/thermally conductive filler composition, the cyanate resin includes any one or combination of the following:

(1) Bisphenol A cyanate monomer

(2) Bisphenol E cyanate monomer

(3) Bisphenol E type cyanate monomer,

(4) Tetramethyl bisphenol F type cyanate monomer

(5) Tetramethyl bisphenol F cyanate monomer

(6) Bisphenol M type cyanate monomer

(7) Multifunctional cyanate monomer

(8) Dicyclopentadiene bisphenol cyanate monomer

In the above cyanate resin/thermally conductive filler composition, the cyanate resin can be replaced by a mixture or prepolymer of cyanate resin and epoxy resin, and the epoxy resin is glycidyl ether epoxy resin, shrink Glyceride epoxy resins, glycidylamine epoxy resins, aliphatic epoxy compounds or heterocyclic and mixed epoxy compounds.

In the above cyanate ester resin/thermally conductive filler composition, the epoxy resin is bisphenol A type epoxy resin, epoxidized phenolic resin, TDE-80# epoxy resin, amino tetrafunctional epoxy resin AG-80# .

A cyanate resin/thermally conductive filler composition prepreg, comprising the cyanate resin/thermally conductive filler composition and pitch-based thermally conductive carbon fiber or its fabric according to claims 1 to 8, wherein the cyanate resin/thermally conductive filler composition The mass percentage content of the pitch-based heat-conducting carbon fiber or its fabric is 57%-63%.

The application of the above-mentioned cyanate ester resin/thermally conductive filler composition, the cyanate ester resin/thermally conductive filler composition is used as the matrix resin of the composite material, and is used to prepare the composite material; the described cyanate ester resin/thermally conductive filler composition is used as an adhesive The matrix resin is used to prepare the adhesive; the cyanate resin/thermal conductive filler composition is used as the matrix resin of the coating and is used to prepare the coating.

Compared with the prior art, the present invention has the following beneficial effects:

(1), the present invention adopts a kind of in multi-walled carbon nanotube (OM-MWCNT) or graphene (OM-G) and composition thereof through monofunctional isocyanate surface treatment and mixes with cyanate resin, thus obtains The cyanate ester resin/thermally conductive filler composition is suitable as a resin for prepreg of fiber composite materials, and its cured product has high thermal conductivity and excellent performance.

(2), the present invention preferably adopts the composition of the multi-walled carbon nanotube of modification and graphene to mix with cyanate resin, and graphene sheet and carbon nanotube have obvious synergistic effect in the thermal conduction process of resin, can be more Better improve the X, Y, Z direction thermal conductivity of the composite material;

(3), the present invention adopts the mixture of cyanate resin and epoxy resin or prepolymer and the multi-walled carbon nanotube or graphene of modification to mix, compares adopting cyanate resin alone, epoxy resin can accelerate cyanide The reaction of ester resin, synergistic effect with cyanate resin, reduces its curing temperature and prolongs the shelf life of the resin;

(4), in the present invention, the addition amount of heat-conducting filler is within 10%, even within 4%, just can reach higher thermal conductivity, has overcome the viscosity of resin that adds too many heat-conducting fillers in the prior art and causes too much, Poor fluidity cannot prepare prepreg defects.

(5), the cyanate ester resin/thermally conductive filler composition and its prepreg of the present invention, wherein the cyanate resin/thermally conductive filler composition can adopt thermosetting resins and composite materials familiar to those skilled in the art through various molding processes The thermal conductivity of the composite material made from the cyanate resin/thermally conductive filler composition and its prepreg is excellent; as a matrix resin for high-performance composite materials, or as a high-performance adhesive and coating Layer, can be used in many industries such as electronics industry, aviation, aerospace, national defense and military industry.

detailed description

The present invention is described in further detail below by specific embodiment:

The invention provides a cyanate resin/thermally conductive filler composition, wherein the mass percent contents of the thermally conductive filler and the cyanate resin composition are respectively 0.5-10%, and 90-99.5%; One or both combinations of isocyanate-surface-treated multi-walled carbon nanotubes (OM-MWCNT) or monofunctional isocyanate-surface-treated graphene (OM-G). It is also possible to select the mass percent contents of the thermally conductive filler and the cyanate resin composition to be 1.5-3.5% and 96.5-98.5% respectively.

If the thermally conductive filler is a composition of multi-walled carbon nanotubes treated with monofunctional isocyanate and graphene treated with monofunctional isocyanate, the mass ratio of the two is 20-80:80-20.

In the present invention, cyanate resin refers to compounds, polymers and mixtures thereof that contain at least two cyanate groups in the molecule, and the general formula is as follows,

N≡C-O-R′-O-C≡N

Wherein R' can be an alkylene group, an arylene group, an unsaturated group or an alicyclic group.

In particular, in a preferred embodiment of the cyanate resin/thermally conductive filler composition according to the present invention, the cyanate resin refers to a cyanate unit containing structural units selected from the following (1)-(8). bodies and their mixtures:

(1) Bisphenol A type cyanate monomer (HF-1) represented by the following formula

The bisphenol A cyanate monomer (HF-1) is the earliest commercialized cyanate monomer, which is cheap and suitable for industrial applications;

(2) Bisphenol E type cyanate monomer (HF-9) represented by the following formula

The bisphenol E type cyanate monomer (HF-9) exists in the form of a low-viscosity liquid at room temperature and is suitable for application;

(3) Bisphenol E type cyanate monomer (HF-9) represented by the following formula

(4) Tetramethylbisphenol F type cyanate monomer shown in the following formula

(5) Tetramethyl bisphenol F type cyanate monomer shown in the following formula

(6) Bisphenol M type cyanate monomer (HF-7) represented by the following formula

(7) Multifunctional cyanate monomer (HF-5) represented by the following formula

(8) Dicyclopentadiene bisphenol type cyanate monomer (HF-3) represented by the following formula

In addition, cyanate resin can also comprise other kinds of cyanate resin monomers, for example, I.Hamerton mentions other kinds of cyanate monomers in "ChemistryandTechnologyofCyanateEsterResins" (I.Hamerton, ChemistryandTechnologyofCyanateEsterResins, BlackieAcademic&ProfessionalGlasgow, London, 1994 .), or other different structural cyanate esters produced by companies such as Cida, Lonza, Dow and Shanghai Huifeng Technology and Trade.

Among the present invention, cyanate resin can also adopt the mixture or prepolymer of cyanate resin and epoxy resin to replace, and wherein epoxy resin can utilize existing epoxy resin, or utilize the epoxy resin synthesized by prior art, for example Wang Duoren in "Synthesis and Application of Epoxy Resin" ([J]. Thermosetting Resin, 2001, 16 (1)), Chen Ping in "Epoxy Resin and Its Application" ([M]. Chemical Industry Press ,2004), MING-KUNGLISIMON etc. in "Epoxyresinpreparation process" ([P], EP86200962A, 1986), Peng Bingren et al. Epoxy resins and their synthesis methods mentioned in books and articles.

Wherein, epoxy resin is to contain and be selected from the epoxy resin monomer described in following (1)-(4) and their mixture:

(1) Glycidyl ethers

Glycidyl ether epoxy resins mainly include bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, and epoxidized phenolic resin.

Bisphenol A type epoxy resin is made of bisphenol A and epichlorohydrin into etherification and ring-closing two-step reaction value, such as E-55, E-51, E-20; bisphenol S type epoxy resin is made of bisphenol S High temperature resistant epoxy resin obtained by polycondensation of phenol S and excess epichlorohydrin under alkaline conditions; bisphenol F epoxy resin is made of bisphenol F and excess epichlorohydrin (1:10), in tetramethyl Under the condition of ammonium chloride and NaOH, it is formed by polycondensation through etherification and ring closure reaction; epoxy phenolic resin is formed by condensation of low molecular weight phenolic resin and epichlorohydrin under acid catalyst;

(2) Glycidyl esters

Glycidyl ester epoxy resin is a compound with two or more glycidyl ester groups in its molecular structure. For example, 711# epoxy resin, TDE-80# epoxy resin, 731# epoxy resin, CY-183# epoxy resin;

(3) Glycidylamines

Glycidylamine epoxy resins are compounds containing two or more glycidylamine groups synthesized from primary or secondary amines and epichlorohydrin. For example, amino tetrafunctional epoxy resin (AG-80#), AFG-90# epoxy resin;

(4) Aliphatic epoxy compounds

Aliphatic epoxy compounds are prepared from cycloaliphatics containing unsaturated double bond structures through double bond oxidation or addition epoxidation with hypochlorous acid. For example W-95# epoxy resin, 6221# epoxy resin, 6206# epoxy resin.

In addition, there are heterocyclic and mixed epoxy compounds, such as hydantoin resin, cyanuric acid epoxy resin, flame retardant resin, etc.

The epoxy resin preferably includes bisphenol A type epoxy resin, epoxidized phenolic resin, TDE-80# epoxy resin, amino tetrafunctional epoxy resin (AG-80#).

In the present invention, the thermally conductive filler is treated with monofunctional isocyanate, wherein the monofunctional isocyanate includes octadecyl isocyanate, hexadecyl isocyanate, and dodecyl isocyanate.

In the present invention, the specific method for thermally conductive filler to be treated with monofunctional isocyanate is as follows:

In the three-neck flask, add toluene, add multi-walled carbon nanotubes (or graphene), add monofunctional isocyanate, add a few drops of dibutyltin dilaurate, stir and heat to 65-75°C, and react at constant temperature for 10-13 hours . After the reaction is completed, filter the product, add acetone to the filter residue, stir and wash for more than 2 hours, repeat 3 to 4 times, then separate, and vacuum dry for 22 to 25 hours, and the product obtained is isocyanate-modified multi-walled carbon nanotubes (or isocyanate-modified permanent graphene). The mass ratio of multi-walled carbon nanotubes or graphene, monofunctional isocyanate and dibutyltin dilaurate added is 1:0.9-1.1:0.3-0.6.

In the cyanate resin/thermally conductive filler composition of the present invention, a commonly used modifier may be added to the cyanate resin.

In the cyanate resin/thermally conductive filler composition of the present invention, the cyanate resin can also be a mixture of various cyanate resins.

The inventors have found through experiments and research that the addition of surface-treated carbon nanomaterials significantly improves the thermal conductivity of cured cyanate resin products, as shown in the following examples and comparative examples.

The cyanate ester resin/thermally conductive filler composition proposed by the present invention can be combined with various reinforcing materials familiar to those skilled in the art, such as inorganic reinforcing materials such as silicon dioxide, calcium carbonate, carbon nanotubes, carbon fibers, etc., organic reinforcing materials such as aromatic It can be formulated into various compositions to obtain thermosetting resins and their products for different purposes.

The preparation method of the cyanate resin/thermally conductive filler composition of the present invention comprises mixing the cyanate resin and thermally conductive filler to obtain the cyanate resin/thermally conductive filler composition.

As the mixing method, methods such as mechanical mixing, solution mixing, and melt mixing well-known to those skilled in the art can be used, and methods such as auxiliary ultrasonic dispersion and high-speed stirring can also be used.

The present invention provides a thermosetting resin composition, comprising the above-mentioned cyanate resin/thermally conductive filler composition and other thermosetting resins.

Other thermosetting resins can be other commonly used thermosetting resins familiar to those skilled in the art, such as benzoxazine resin, epoxy resin, bismaleimide resin, thermosetting polyimide and the like. By using different thermosetting resins, thermosetting resins and their products for different purposes can be obtained.

The invention also provides a prepreg prepared from the cyanate resin/thermally conductive filler composition and the pitch-based thermally conductive carbon fiber or its fabric. The mass percent content of the cyanate resin/thermal conductive filler composition is 37%-43%, and the mass percent content of the pitch-based thermal conductive carbon fiber or its fabric is 57%-63%.

The preparation method of the prepreg of the cyanate resin/thermally conductive filler composition of the present invention is prepared by impregnating the cyanate resin/thermally conductive filler composition with the pitch-based thermally conductive carbon fiber or its fabric through a dry method or a wet method. Among them, the wet method refers to the impregnation of the resin solution and the pitch-based heat-conducting carbon fiber or its fabric to prepare the prepreg; the dry method includes impregnation processes such as the powder method and the hot-melt resin method.

The cyanate ester resin/thermally conductive filler composition and its prepreg proposed by the present invention, wherein the cyanate resin/thermally conductive filler composition can be made by using thermosetting resins and composite materials familiar to those skilled in the art through various molding processes into various products. The cyanate ester resin/thermally conductive filler composition, prepreg and the composite material thereof have excellent thermal conductivity; as a matrix resin for high-performance composite materials, or as a high-performance adhesive and coating, it can be used in the electronics industry, Aviation, aerospace, national defense and many other industries.

Example

The present invention will be described in more detail below through specific examples.

Raw material used in the embodiment, instrument are as follows:

Bisphenol A cyanate monomer (HF-1): Shangyu Shengda Biochemical Co., Ltd.

Multi-walled carbon nanotubes: FloTube9000, Beijing Tiannai Technology Co., Ltd.;

Graphene: graphenenanoplatelets, StremChemicals.

Perkin-ElmerPyris1 type DSC tester: used to measure the specific heat capacity of cured products, test conditions: N ₂ environment, heating rate 10°C/min, Al ₂ O ₃ as reference, test temperature range: 0～50°C.

Thermal conductivity test: laser flash thermal conductivity measuring instrument, LFA447 (Netzsch, Germany), 25°C, GB/T22588-2008, ASTME1269-5.

True density meter, QuantachromeUltrapycnometer1000 (United States Quanta company).

Surface treatment of multi-walled carbon nanotubes and graphene:

In a 1000ml three-necked bottle (equipped with a Teflon stirrer), add 500ml of toluene, add 10 grams of multi-walled carbon nanotubes (or 10 grams of graphene), add 10 grams of octadecyl isocyanate, drop 1 to 3 Dibutyltin dilaurate was dropped, stirred and heated to 70°C for 12 hours at a constant temperature. After the reaction is complete, filter the product, put the filter residue in a 500ml beaker, add 150-200ml of acetone to it, wash with electromagnetic stirring for more than 2 hours, filter and separate, repeat three times, and finally obtain a black solid that is vacuum-dried for 24 hours to obtain the product that is isocyanate Modified multi-walled carbon nanotubes (or isocyanate-modified graphene).

Comparative example 1

Take 5-10 grams of bisphenol A type cyanate resin, place it in a mold, and cure it in a vacuum oven. The curing process is: 100°C to 1 hour, 120°C to 1 hour, 140°C to 2 hours, 160°C to 2 hours, 180°C to 2 hours, 200°C to 2 hours, 220°C to 2 hours, 240°C to 1 Hour. The thermal conductivity of the cured product is 0.148 W·m ^-1 ·K ^-1 as measured by a laser flash method thermal conductivity measuring instrument.

Example 1

Using the solution blending method, mix 0.5 g of octadecyl isocyanate-modified multi-walled carbon nanotubes with 99.5 g of cyanate, add 500 ml of acetone to dissolve, ultrasonically disperse for 6 hours, and stand for volatilization for 48 hours; then vacuum-dry at 50°C 48 hours; taking 5-10 grams of the mixture and placing it in a mold, and curing it in a vacuum oven. The curing process is: 100°C to 1 hour, 120°C to 1 hour, 140°C to 2 hours, 160°C to 2 hours, 180°C to 2 hours, 200°C to 2 hours, 220°C to 2 hours, 240°C to 1 Hour. The thermal conductivity of the cured product is 0.167 W·m ^-1 ·K ^-1 as measured by a laser flash method thermal conductivity measuring instrument.

Example 2

Using the solution blending method, mix 3 g of octadecyl isocyanate-modified multi-walled carbon nanotubes with 97 g of cyanate, add 500 ml of acetone to dissolve, ultrasonically disperse for 6 hours, and leave to evaporate for 48 h; then vacuum dry at 50 °C 48 hours; taking 5-10 grams of the mixture and placing it in a mold, and curing it in a vacuum oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.203 W·m ^-1 ·K ^-1 as measured by a laser flash method thermal conductivity measuring instrument.

Example 3

Using the solution blending method, mix 10 grams of octadecyl isocyanate-modified multi-walled carbon nanotubes with 90 grams of cyanate, add 500 ml of acetone to dissolve, ultrasonically disperse for 6 hours, and stand for 48 hours to evaporate; then vacuum dry at 50 ° C 48 hours; taking 5-10 grams of the mixture and placing it in a mold, and curing it in a vacuum oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.332 W·m ^-1 ·K ^-1 as measured by a laser flash thermal conductivity measuring instrument.

Example 4

Using the solution blending method, mix 0.5 g of octadecyl isocyanate modified graphene with 99.5 g of cyanate, add 500 ml of acetone to dissolve, ultrasonically disperse for 6 hours, and stand for volatilization for 48 h; then vacuum dry at 50 ° C for 48 h; take 5-10 grams of the mixture is placed in a mold and cured in a vacuum oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.158 W·m ^-1 ·K ^-1 as measured by a laser flash method thermal conductivity measuring instrument.

Example 5

Using the solution blending method, mix 3 grams of octadecyl isocyanate-modified graphene with 97 grams of cyanate, add 500 ml of acetone to dissolve, ultrasonically disperse for 6 hours, and let it stand for volatilization for 48 hours; then vacuum dry at 50 ° C for 48 hours; take 5-10 grams of the mixture is placed in a mold and cured in a vacuum oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.297 W·m ^-1 ·K ^-1 as measured by a laser flash thermal conductivity measuring instrument.

Example 6

Using the solution blending method, mix 8 grams of octadecyl isocyanate-modified graphene with 92 grams of cyanate, add 500ml of acetone to dissolve, ultrasonically disperse for 6 hours, and let it stand for volatilization for 48 hours; then vacuum dry at 50°C for 48 hours; take 5-10 grams of the mixture is placed in a mold and cured in a vacuum oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.737 W·m ^-1 ·K ^-1 as measured by a laser flash method thermal conductivity measuring instrument.

Example 7

Using the solution blending method, mix 10 grams of octadecyl isocyanate-modified graphene with 90 grams of cyanate, add 500 ml of acetone to dissolve, ultrasonically disperse for 6 hours, and let it stand for volatilization for 48 hours; then vacuum dry at 50 ° C for 48 hours; take 5-10 grams of the mixture is placed in a mold and cured in a vacuum oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.759 W·m ^-1 ·K ^-1 as measured by a laser flash method thermal conductivity measuring instrument.

Example 8

Using solution blending method, octadecyl isocyanate modified multi-wall carbon nanotube (OM-MWCNT), octadecyl isocyanate modified graphene (OM-G) add up to 10 grams, wherein OM-MWCNT/OM- G=4/1, mixed with 90 grams of cyanate, added 500ml of acetone to dissolve, ultrasonically dispersed for 6 hours, left to volatilize for 48 hours; then vacuum dried at 50°C for 48 hours; 5-10 grams of the mixture was placed in a mold and dried in a vacuum Curing in an oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.377 W·m ^-1 ·K ^-1 as measured by a laser flash method thermal conductivity measuring instrument.

Example 9

Using solution blending method, octadecyl isocyanate modified multi-wall carbon nanotube (OM-MWCNT), octadecyl isocyanate modified graphene (OM-G) add up to 10 grams, wherein OM-MWCNT/OM- G=3/1, mixed with 90 grams of cyanate, dissolved in 500ml of acetone, ultrasonically dispersed for 6 hours, left to volatilize for 48 hours; then vacuum dried at 50°C for 48 hours; 5-10 grams of the mixture was placed in a mold, Curing in an oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.319 W·m ^-1 ·K ^-1 as measured by a laser flash method thermal conductivity measuring instrument.

Example 10

Using solution blending method, octadecyl isocyanate modified multi-wall carbon nanotube (OM-MWCNT), octadecyl isocyanate modified graphene (OM-G) add up to 10 grams, wherein OM-MWCNT/OM- G=2/1, mixed with 90g of cyanate ester, dissolved in 500ml of acetone, ultrasonically dispersed for 6 hours, left to volatilize for 48h; then vacuum dried at 50°C for 48h; Curing in an oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.454W·m ^-1 ·K ^-1 as measured by a laser flash thermal conductivity measuring instrument.

Example 11

Using solution blending method, octadecyl isocyanate modified multi-wall carbon nanotube (OM-MWCNT), octadecyl isocyanate modified graphene (OM-G) add up to 10 grams, wherein OM-MWCNT/OM- G=1/1, mixed with 90g of cyanate ester, dissolved in 500ml of acetone, ultrasonically dispersed for 6 hours, left to volatilize for 48h; then vacuum-dried at 50°C for 48h; 5-10g of the mixture was placed in a mold, Curing in an oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.474W·m ^-1 ·K ^-1 as measured by a laser flash method thermal conductivity measuring instrument.

Example 12

Using solution blending method, octadecyl isocyanate modified multi-wall carbon nanotube (OM-MWCNT), octadecyl isocyanate modified graphene (OM-G) add up to 10 grams, wherein OM-MWCNT/OM- G=1/2, mixed with 90 grams of cyanate, dissolved in 500ml of acetone, ultrasonically dispersed for 6 hours, left to volatilize for 48 hours; then vacuum dried at 50°C for 48 hours; 5-10 grams of the mixture was placed in a mold, Curing in an oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.633 W·m ^-1 ·K ^-1 as measured by a laser flash method thermal conductivity measuring instrument.

Example 13

Using solution blending method, octadecyl isocyanate modified multi-wall carbon nanotube (OM-MWCNT), octadecyl isocyanate modified graphene (OM-G) add up to 10 grams, wherein OM-MWCNT/OM- G=1/3, mixed with 90 grams of cyanate ester, dissolved in 500ml of acetone, ultrasonically dispersed for 6 hours, left to volatilize for 48 hours; then vacuum dried at 50°C for 48 hours; 5-10 grams of the mixture was placed in a mold and placed in a vacuum Curing in an oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.673 W·m ^-1 ·K ^-1 as measured by a laser flash method thermal conductivity measuring instrument.

Example 14

Using solution blending method, octadecyl isocyanate modified multi-wall carbon nanotube (OM-MWCNT), octadecyl isocyanate modified graphene (OM-G) add up to 10 grams, wherein OM-MWCNT/OM- G=1/4, mixed with 90 grams of cyanate ester, dissolved in 500ml of acetone, ultrasonically dispersed for 6 hours, left to volatilize for 48 hours; then vacuum dried at 50°C for 48 hours; 5-10 grams of the mixture was placed in a mold and placed in a vacuum Curing in an oven. Its curing process is consistent with embodiment 1. The thermal conductivity of the cured product is 0.682 W·m ^-1 ·K ^-1 as measured by a laser flash method thermal conductivity measuring instrument.

From above-mentioned embodiment and comparative example result as can be known, for surface-treated multi-walled carbon nanotubes, surface-treated graphene, and the composition of surface-treated multi-walled carbon nanotubes and surface-treated graphene, these thermally conductive fillers can significantly Improve the thermal conductivity of the cured product of the cyanate resin, the higher the content of the thermally conductive filler, the higher the thermal conductivity of the cured product of the cyanate resin.

The above is only the best specific implementation mode of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art can easily conceive of changes or modifications within the technical scope disclosed in the present invention. Replacement should be covered within the protection scope of the present invention.

The content that is not described in detail in the specification of the present invention belongs to the well-known technology of those skilled in the art.

Claims (10)

1. Cyanate ester resin/thermally conductive filler composition, characterized in that: it includes thermally conductive filler and cyanate resin, wherein the mass percentage content of thermally conductive filler is 0.5-10%, and the mass percentage content of cyanate resin is 90-99.5% %, the thermally conductive filler is one or a combination of multi-walled carbon nanotubes treated with monofunctional isocyanate or graphene treated with monofunctional isocyanate, if the thermally conductive filler is multi-walled carbon nanotubes treated with monofunctional isocyanate and When the combination of graphene treated with monofunctional isocyanate is used, the mass ratio of the two is 20-80:80-20. 2. The cyanate resin/thermally conductive filler composition according to claim 1, characterized in that: the monofunctional isocyanate is octadecyl isocyanate, hexadecyl isocyanate or dodecyl isocyanate. 3. cyanate ester resin/thermally conductive filler composition according to claim 1 or 2, is characterized in that: adopt monofunctional isocyanate to process the concrete method of multi-walled carbon nanotube or graphene as follows: Using toluene as a solvent, add multi-walled carbon nanotubes or graphene, monofunctional isocyanate, and dibutyltin dilaurate, stir and heat to 65-75°C, and react at a constant temperature for 10-13 hours; after the reaction is completed, filter the product and remove the residue Acetone was added to the mixture, stirred and washed for more than 2 hours, repeated 3-4 times, then separated, and vacuum-dried for 22-25 hours, and the product obtained was isocyanate-modified multi-walled carbon nanotubes or isocyanate-modified graphene. 4. cyanate resin/thermally conductive filler composition according to claim 3, is characterized in that: the mass ratio of the multi-walled carbon nanotubes or graphene, monofunctional isocyanate, dibutyltin dilaurate added is 1 :0.9～1.1:0.3～0.6. 5. The cyanate resin/thermally conductive filler composition according to claim 1 or 2, characterized in that: the general formula of the cyanate resin is as follows: N≡C-O-R′-O-C≡N Wherein: R' is an alkylene group, an arylene group, an unsaturated group or an alicyclic group. 6. The cyanate resin/thermally conductive filler composition according to claim 5, characterized in that: the cyanate resin comprises any one or combination of the following: (1) Bisphenol A cyanate monomer (2) Bisphenol E cyanate monomer (3) Bisphenol E type cyanate monomer, (4) Tetramethyl bisphenol F cyanate monomer (5) Tetramethyl bisphenol F cyanate monomer (6) Bisphenol M type cyanate monomer (7) Multifunctional cyanate monomer (8) Dicyclopentadiene bisphenol cyanate monomer 7. The cyanate resin/thermally conductive filler composition according to claim 1 or 2, characterized in that: the cyanate resin can be replaced by a mixture or prepolymer of cyanate resin and epoxy resin, so The epoxy resins are glycidyl ether epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, aliphatic epoxy compounds or heterocyclic and mixed epoxy compounds. 8. The cyanate ester resin/thermally conductive filler composition according to claim 7, characterized in that: the epoxy resin is bisphenol A type epoxy resin, epoxidized phenolic resin, TDE-80# epoxy resin , Amino tetrafunctional epoxy resin AG-80#. 9. A cyanate resin/thermally conductive filler composition prepreg, characterized in that: it comprises the cyanate resin/thermally conductive filler composition and pitch-based thermally conductive carbon fiber or its fabric according to claims 1 to 8, wherein the cyanate ester The mass percentage content of the resin/thermally conductive filler composition is 37%-43%, and the mass percentage content of the pitch-based thermally conductive carbon fiber or its fabric is 57%-63%. 10. The application of the cyanate resin/thermally conductive filler composition according to claims 1 to 8, characterized in that: the cyanate resin/thermally conductive filler composition is used as the matrix resin of the composite material for the preparation of the composite material; The cyanate resin/thermally conductive filler composition is used as a base resin of the adhesive for preparing the adhesive; the cyanate resin/thermally conductive filler composition is used as the base resin of the coating for preparing the coating.