CN113845775A - Preparation method of hyperbranched polymer modified boron nitride heat-conducting and insulating composite material - Google Patents
Preparation method of hyperbranched polymer modified boron nitride heat-conducting and insulating composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a hyperbranched polymer modified boron nitride heat-conducting and insulating composite material, which comprises the following steps: (1) adding a hyperbranched polymer, a boron nitride filler and an organic solvent into a container, performing ultrasonic treatment, centrifuging and drying to obtain hyperbranched polymer modified boron nitride; (2) and (2) mixing the hyperbranched polymer modified boron nitride prepared in the step (1) with matrix resin, a curing agent and a curing agent accelerator, and curing to prepare the heat-conducting and insulating composite material. The invention reduces the processing viscosity of the composite material, improves the processing performance of the composite material, improves the dispersibility of boron nitride and the interface compatibility of the boron nitride and a resin matrix, and prepares the composite material with high heat conductivity coefficient and excellent mechanical property.
Description
Technical Field
The invention relates to the technical field of insulating composite materials, in particular to a preparation method of a hyperbranched polymer modified boron nitride heat-conducting insulating composite material.
Background
With the development of electronic components toward integration and miniaturization, the internal heating power thereof is rapidly increased, and the working efficiency and the service life of the electronic devices and the electronic equipment are seriously influenced. According to the statistics of the air force avionics in the united states, about 55% of the electronic components are destroyed by the temperature rise. Therefore, effective heat dissipation of electronic devices is a problem to be solved, and the development of high thermal conductivity electronic packaging materials is a key to solve the problem.
The polymer has the advantages of low cost, light weight, excellent processing performance and the like, and is widely applied to the field of electronic packaging. However, most polymers have no free electrons, the heat conduction is mainly carried out by phonons serving as heat conduction carriers, the heat transfer mechanism is only based on lattice vibration or phonon transfer, the heat conductivity of the polymers is poor, and the heat conductivity coefficient is only 0.1-0.5W/(m.K), so that the preparation of high-heat-conductivity polymer materials becomes a research hotspot for meeting the requirements of scientific and social development. The intrinsic heat-conducting polymer material has high requirements on equipment and process conditions, and industrial production is difficult to realize, and the filling type heat-conducting composite material prepared by adding the filler with high heat conductivity coefficient into the polymer matrix can be industrially produced due to simple process, convenient operation and low processing cost, so that the filling type heat-conducting composite material becomes the mainstream in the field of heat-conducting materials.
Boron Nitride (BN) is a crystal composed of nitrogen atoms and boron atoms, and has several different variants, hexagonal BN (h-BN), rhombohedral BN (r-BN), cubic BN (c-BN), and hexagonal close-packed BN (w-BN). Sp in hexagonal boron nitride2The hybridized layered structure is similar to graphite and is also called as 'white graphene', the heat conductivity coefficient is high, the insulativity is good, and the nano sheets and the nano tubes are considered as ideal fillers for preparing heat-conducting insulating electronic packaging materials. However, boron nitride is not uniformly dispersed in the polymer matrix and tends to agglomerate. In addition, phonon scattering at the interface of the filler and the matrix can be realizedThe resulting high interface thermal resistance limits the great improvement of the thermal conductivity of the composite material. Therefore, how to carry out surface treatment on the h-BN, the problem of agglomeration of the h-BN in a matrix is solved, and the problem of improving the interface compatibility of the filler and the resin matrix is the first difficult problem of preparing the heat-conducting insulating composite material.
The surface modification of BN fillers, which can solve the above problems, is generally performed by covalent or non-covalent modification. Patent publication No. CN109280332A discloses a method for preparing an epoxy resin composite material by covalently modifying boron nitride with a silane coupling agent. However, chemical bonding at the surface of the filler destroys the original structure of the filler, thereby lowering the inherent thermal conductivity of the BN filler, resulting in a limited thermal conductivity enhancement of the composite. The surface functionalization can be realized by means of the non-covalent interaction between various functional surfactants (polythiophene, polyvinylpyrrolidone and the like) and the BN surface, however, the related synthesis process routes of the functional small molecular compounds or linear polymers are often relatively complex, the volume is small, and the effect of improving the dispersibility is limited. The patent with application number 202110725733.1 discloses a method for modifying boron nitride nanotubes by hyperbranched polymer HB (A-M) through hydrogen bond interaction, but the interaction between the modified BN and a matrix is weak, and the mechanical property of the composite material is greatly deteriorated when the modified BN is added in a high amount.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a hyperbranched polymer modified boron nitride heat-conducting and insulating composite material. The invention reduces the processing viscosity of the composite material, improves the processing performance of the composite material, improves the dispersibility of boron nitride and the interface compatibility of the boron nitride and a resin matrix, and prepares the composite material with high heat conductivity coefficient and excellent mechanical property.
The technical scheme of the invention is as follows:
a preparation method of a hyperbranched polymer modified boron nitride heat conduction and insulation composite material comprises the following steps:
(1) adding a hyperbranched polymer, a boron nitride filler and an organic solvent into a container, performing ultrasonic treatment, centrifuging and drying to obtain hyperbranched polymer modified boron nitride;
(2) and (2) mixing the hyperbranched polymer modified boron nitride prepared in the step (1) with matrix resin, a curing agent and a curing agent accelerator, and curing to prepare the heat-conducting and insulating composite material.
In the preferred scheme, in the step (1), the end of the hyperbranched polymer contains both epoxy group and polycyclic aromatic group, and the preparation method comprises the following steps:
firstly, taking a tri-functionality epoxy monomer and a bisphenol monomer as raw materials, and reacting for 4-24 hours at the temperature of 80-120 ℃ under the action of a catalyst tetrabutylammonium bromide;
secondly, adding a terminating agent, and reacting at the temperature of 80-120 ℃ for 4-12 h for modification to obtain the hyperbranched polymer;
the trifunctional epoxy monomer is one or more of trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, glycerol triglycidyl ether, triglycidyl p-aminophenol, triglycidyl amino-m-cresol, triglycidyl m-aminophenol, tris (4-hydroxyphenyl) methane triglycidyl ether and trimethylolpropane triglycidyl ether;
the bisphenol monomer is one or more of 4,4' -biphenol, bisphenol fluorene, bisphenol A, bisphenol F, bisphenol AF, bisphenol S, butanediol, 1, 3-cyclohexanediol, ethylene glycol, propylene glycol, resorcinol, hydroquinone, catechol, 1, 3-naphthalenediol, 1, 8-naphthalenediol, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 2, 3-naphthalenediol, 2, 6-naphthalenediol and 2, 7-naphthalenediol;
the structure of the end-capping reagent is COOH-R, wherein R is pyrene, fluorene, acenaphthene, phenanthrene, anthracene or perylene.
More preferably, the molar ratio of the trifunctional epoxy monomer to the bisphenol monomer is 1.2: 1-4: 1; the dosage of the catalyst tetrabutylammonium bromide is 1-5 wt% of the trifunctional epoxy monomer; the amount of the end capping agent is 5 to 60 percent of the molar weight of epoxy in the reaction product in the step (1);
the end-capping reagent is one or more of 1-pyrenebutanoic acid, 1-pyrene formic acid, 9-fluorene acetic acid, fluorene-4-carboxylic acid, 5-acenaphthenecarboxylic acid, 2-phenanthrenecarboxylic acid, 3-phenanthrenecarboxylic acid, phenanthrene-9-formic acid, 9-anthracenecarboxylic acid, 1-anthracenecarboxylic acid, 2-anthracenecarboxylic acid and 3-perylene carboxylic acid.
Preferably, in the step (1), the boron nitride filler is one or more of flaky hexagonal boron nitride, tubular hexagonal boron nitride, rhombic boron nitride and cubic boron nitride; the organic solvent is one or more of isopropanol, tetrahydrofuran, ethanol, N-dimethylformamide and acetone;
the mass ratio of the hyperbranched polymer to the boron nitride filler is 0.01: 1-10: 1; the concentration of boron nitride in the reaction system is 1-100 g/L.
In the step (1), the ultrasonic power is 100-1000W, the ultrasonic time is 2-24 h, and the centrifugal rotating speed is 3000-10000 rpm.
Preferably, in the step (2), the curing agent is an acid anhydride, a polyamine or a polyphenol; the acid anhydride is one or more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, methylcyclohexane tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, trimellitic anhydride and polyazelaic anhydride; the polyamine is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, divinyl propylamine, polyamide, menthane diamine, isophorone diamine, N-aminoethyl piperazine, bis (4-amino-3-methyl cyclohexyl) methane, bis (4-amino cyclohexyl) methane, m-xylylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, m-phenylenediamine, dicyandiamide and adipic dihydrazide; the polyhydric phenol is one or more of allyl bisphenol A, phenol type linear phenolic resin, cresol type linear phenolic resin, phenolic resin modified by dicyclopentadiene, biphenyl type aralkyl phenolic resin, p-xylene type aralkyl phenolic resin and triphenol methane type linear phenolic resin; the curing accelerator is 2,4, 6-tri (dimethylaminomethyl) phenol, benzyldimethylamine, acetylacetone metal salt, triphenylphosphine and the triphenylphosphine
One or more of salts, substituted ureas, addition products of aryl isocyanate and imidazole compounds, active chromium tris (2-ethylhexanoate), organic acid salt-amine complexes, 1, 8-diaza-bicyclo (5,4,0) -7-undecene, 2-mercaptobenzothiazole, peroxides, thiourea and derivatives thereof, cycloalkyl imidazolines, 2-phenylimidazolines, epoxy-containing tertiary aromatic amines, titanate accelerators, ferrocenyl accelerators, chromium halide-anhydride complexes.
Preferably, in the step (2), the matrix resin is bismaleimide resin or epoxy resin; the bismaleimide resin is N, N '-4,4' -diphenylmethane bismaleimide, oligomer of phenylmethaneimide, N '-m-phenylenedimaleimide, N' -m-xylene bismaleimide, N '-p-xylylenebismaleimide, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane, bis (3-ethyl-5-methyl-4-maleimidobenzene) methane, N- (4-methyl-1, 3-phenylene) bismaleimide, 4 '-diphenylether bismaleimide, 4' -diphenylsulfone bismaleimide, 1, 3-bis (3-maleimidophenoxy) benzene, N '-m-xylylenebismaleimide, N' -p-xylylenebismaleimide, N '-bis (4-maleimidophenoxy) benzene, N' -N-p-phenylene-diphenylether bismaleimide, 4-diphenylether bismaleimide, 4-bis (4-phenylene) bismaleimide, N-p-phenylene) bismaleimide, N-phenylene, N-p-phenylene, N-diphenylether bismaleimide, N-maleimide and N-bismaleimide, N-maleimide or N-bismaleimide, N-bismaleimide resin or N-imide resin or N, N-p-imide resin or N-bismaleimide resin or a mixture of, 1, 3-bis (4-maleimidophenoxy) benzene, N ' -p-benzophenone maleimide, N ' - (methylene-bistetrahydrophenyl) bismaleimide, N ' - (3,3' -dichloro) -4,4' -diphenylmethane bismaleimide, N ' -tolidine bismaleimide, N ' -isophorone bismaleimide, N ' -p, p ' -diphenyldimethylsilyl bismaleimide, N ' -naphthalene bismaleimide, N ' -4,4' - (1,1' -diphenyl-cyclohexane) bismaleimide, N ' -3,5- (1,2, 4-triazole) bismaleimide, N ' -bis (4-methyl) maleimide), N ' -bis (2, 4-triazole) bismaleimide, N ' -bis (4-methyl-bis (p-methyl) maleimide), N ' -bis (3, N ' -bis (4-methyl-phenyl) bismaleimide), N ' -bis (4-bis (1,2, 4-triazole) bismaleimide, N ' -bis (4-bis) maleimide), N ' -isophorone bismaleimide, N ' -bis (2-bis (4-bis (maleimide), N-bis (2-bis) bismaleimide), N-bis (1, N-bis (2-bis (1-bis) maleimide), N-bis (1, 4-bis (2-bis) maleimide), N-bis (2-bis (1, 4-bis) maleimide), bis (1, 4-bis (2-bis) maleimide), bis (1-bis (2-bis) bismaleimide), or (1-bis (2-bis) bismaleimide), bis (2-bis (2) maleimide), bis (2) bismaleimide), or (2) bismaleimide), bis (2) bismaleimide), or (2-bis (2) imide), or (2) bis (2) imide) bis (2) imide) bis (2-bis (2) imide) bis (2, 4) bis (2-bis (2) imide) bis (2) imide, 4) bis (2) imide) bis (2, 4) or (2) bis (2) or (2) bis (2) or (2) bis (2) or (2) bis (2) or (2), One or more of N, N ' -pyridine-2, 6-diylbismaleimide, N ' -maleimide of 4,4' -diamino-triphenyl phosphate, 2-bis [ 3-chloro-4-maleimidophenoxy ] phenyl ] propane, 2-bis [ 3-methoxy-4- (4-maleimidophenoxy) phenyl ] propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane;
the epoxy resin is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin and alicyclic epoxy resin.
In the step (2), the mass ratio of the hyperbranched polymer modified boron nitride to the matrix resin is 0.05: 1-4: 1, the dosage of the curing agent is 10-85 wt% of the matrix resin, and the dosage of the curing accelerator is 0.5-10 wt% of the matrix resin.
Preferably, the curing mode is staged heating curing or twin-screw extrusion curing;
the conditions of stage temperature rise and solidification are as follows: 1h at 80 ℃, 1h at 100 ℃, 1h at 120 ℃, 1h at 140 ℃, 2h at 160 ℃ and 3 h;
the conditions of twin-screw extrusion curing are as follows: and (3) melting and kneading the mixture by a twin-screw kneader at the temperature of 70-110 ℃, cooling, crushing, and heating and molding under the pressure of 4MPa and at the temperature of 175 ℃.
The application of the heat-conducting and insulating composite material prepared by the preparation method is applied to the fields of aerospace, composite materials, heat-conducting adhesives, copper-clad plates or electronic packaging materials.
The beneficial technical effects of the invention are as follows:
the hyperbranched polymer containing the epoxy group and the polycyclic aromatic group at the tail end is prepared by a simple method, and the conjugated structure of the polycyclic aromatic group is favorable for phonon transmission and heat conductivity improvement; the polyaromatic groups are adsorbed to the surface of the boron nitride through pi-pi interaction to carry out non-covalent modification, so that the processing viscosity of the composite material is reduced, and the processing performance of the composite material is improved; the hyperbranched polymer adsorbed on the surface of the boron nitride improves the dispersibility of the boron nitride in resin, and the epoxy group at the tail end can participate in the crosslinking and curing of the resin, so that the interface compatibility of the filler and a matrix is improved, and the interface thermal resistance is reduced; in the heating and curing process, reaction induced phase separation occurs, and the boron nitride filler forms a phase by itself, which is beneficial to the construction of a heat conduction path. The hyperbranched polymer is used for modifying the surface of the boron nitride, and the composite material with good processing performance, high heat conductivity coefficient and excellent mechanical property is finally prepared.
Drawings
FIG. 1 is a nuclear magnetic spectrum of the hyperbranched polymer having both epoxy groups and polycyclic aromatic groups at the terminal prepared in examples 1 to 4.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Examples 1 to 9 are methods of non-covalent modification of BN with hyperbranched polymers having both epoxy groups and polycyclic aromatic groups at the ends to produce hyperbranched polymer-modified boron nitride; examples 10 to 24 are methods of preparing a heat conductive and insulating composite material using the hyperbranched polymer modified boron nitride in example 1; comparative examples 1 to 4 are methods of preparing a heat conductive and insulating composite material using unmodified boron nitride and commercial silica as heat conductive fillers.
Example 1:
a preparation method of hyperbranched polymer modified boron nitride comprises the following steps:
(1) 4,4' -biphenol (3.73g,20mmol), trimethylolpropane triglycidyl ether (18.14g,60mmol) and tetrabutylammonium bromide (1.93g,6mmol) were added in this order to a single-neck flask, and after reaction at 100 ℃ for 6 hours, 1-pyrenebutanoic acid (1.23g,4.3mmol) was added to the reaction mixture by titration of the epoxy value to 0.38 by the acetone hydrochloride method, and the system was allowed to continue to react at 100 ℃ for 4 hours. After the reaction was complete, it was precipitated in excess hot water to give a viscous yellow solid which was then redissolved with THF. Repeating the dissolving-precipitating for 3 times, finally cleaning the obtained precipitate by using a large amount of deionized water, and then performing vacuum drying for 12 hours at 50 ℃ to obtain hyperbranched polyether of which the tail end simultaneously contains an epoxy group and a polycyclic aromatic group;
(2) 24g h-BN is weighed and dispersed in 1000mL of isopropanol, hyperbranched polyether (6g) dissolved in 100mL of DMF is added under the condition of stirring, and the mixture is stirred and ultrasonically treated for 2h at room temperature under the condition of 400W of power, so that the h-BN is subjected to non-covalent modification. And after the ultrasonic treatment is finished, centrifuging for 15min at 5000rpm to remove the hyperbranched polyether which is not adsorbed to the h-BN surface, cleaning for 5 times by using acetone, and drying for 6h at 60 ℃ in a vacuum oven to obtain the hyperbranched polymer modified boron nitride.
Example 2:
a preparation method of hyperbranched polymer modified boron nitride comprises the following steps:
(1) 4,4' -biphenol (3.73g,20mmol), trimethylolpropane triglycidyl ether (18.14g,60mmol) and tetrabutylammonium bromide (1.93g,6mmol) were added in this order to a single-neck flask, and after reaction at 100 ℃ for 6 hours, 1-pyrenebutanoic acid (4.46g,8.5mmol) was added to the reaction mixture by titration of the epoxy value to 0.38 by the acetone hydrochloride method, and the system was allowed to continue to react at 100 ℃ for 4 hours.
After the reaction was complete, it was precipitated in excess hot water to give a viscous yellow solid which was then redissolved with THF. And repeating the dissolving-precipitating for 3 times, finally cleaning the obtained precipitate by using a large amount of deionized water, and then drying in vacuum at 50 ℃ for 12 hours to obtain the hyperbranched polyether of which the tail end simultaneously contains the epoxy group and the polycyclic aromatic group.
(2) 24g h-BN is weighed and dispersed in 2000mL of isopropanol, hyperbranched polyether (6g) dissolved in 100mL of DMF is added under the condition of stirring, and the mixture is stirred and ultrasonically treated for 2h at room temperature under the condition of 200W of power, so that the h-BN is subjected to non-covalent modification. And after the ultrasonic treatment is finished, centrifuging at 7000rpm for 15min to remove the hyperbranched polyether which is not adsorbed to the h-BN surface, cleaning for 5 times by using acetone, and drying in a vacuum oven at 60 ℃ for 6h to obtain the hyperbranched polymer modified boron nitride.
Example 3:
a preparation method of hyperbranched polymer modified boron nitride comprises the following steps:
(1) 4,4' -biphenol (3.73g,20mmol), trimethylolpropane triglycidyl ether (18.14g,60mmol) and tetrabutylammonium bromide (1.93g,6mmol) were added in this order to a single-neck flask, and after reaction at 100 ℃ for 6 hours, 1-pyrenebutanoic acid (7.35g,25.5mmol) was added to the reaction mixture by titration of the epoxy value to 0.38 by the acetone hydrochloride method, and the system was allowed to continue to react at 100 ℃ for 4 hours. After the reaction was complete, it was precipitated in excess hot water to give a viscous yellow solid which was then redissolved with THF. And repeating the dissolving-precipitating for 3 times, finally cleaning the obtained precipitate by using a large amount of deionized water, and then drying in vacuum at 50 ℃ for 12 hours to obtain the hyperbranched polyether of which the tail end simultaneously contains the epoxy group and the polycyclic aromatic group.
(2) 24g h-BN is weighed and dispersed in 4000mL of isopropanol, hyperbranched polyether (24g) dissolved in 400mL of DMF is added under the stirring condition, and the mixture is stirred and ultrasonically treated for 6h at room temperature under the condition of 600W power, so that the h-BN is subjected to non-covalent modification. And after the ultrasonic treatment is finished, centrifuging for 15min at 5000rpm to remove the hyperbranched polyether which is not adsorbed to the h-BN surface, cleaning for 5 times by using acetone, and drying for 6h at 60 ℃ in a vacuum oven to obtain the hyperbranched polymer modified boron nitride.
Example 4:
a preparation method of hyperbranched polymer modified boron nitride comprises the following steps:
(1) 4,4' -biphenol (3.73g,20mmol), trimethylolpropane triglycidyl ether (18.14g,60mmol) and tetrabutylammonium bromide (1.93g,6mmol) were added in this order to a single-neck flask, and after reaction at 100 ℃ for 6 hours, 1-pyrenebutanoic acid (14.7g,51mmol) was added to the reaction mixture by titration of the epoxy value to 0.38 by the acetone hydrochloride method, and the system was allowed to continue to react at 100 ℃ for 4 hours. After the reaction was complete, it was precipitated in excess hot water to give a viscous yellow solid which was then redissolved with THF. And repeating the dissolving-precipitating for 3 times, finally cleaning the obtained precipitate by using a large amount of deionized water, and then drying in vacuum at 50 ℃ for 12 hours to obtain the hyperbranched polyether of which the tail end simultaneously contains the epoxy group and the polycyclic aromatic group.
(2) 24g h-BN is weighed and dispersed in 4000mL of isopropanol, hyperbranched polyether (120g) dissolved in 400mL of DMF is added under the stirring condition, and the mixture is stirred and ultrasonically treated for 12h at room temperature under the condition of 400W power, so that the h-BN is subjected to non-covalent modification. And after the ultrasonic treatment is finished, centrifuging for 15min at 5000rpm to remove the hyperbranched polyether which is not adsorbed to the h-BN surface, cleaning for 5 times by using acetone, and drying for 6h at 60 ℃ in a vacuum oven to obtain the hyperbranched polymer modified boron nitride.
Example 5:
a preparation method of hyperbranched polymer modified boron nitride comprises the following steps:
(1) bisphenol fluorene (7.01g,20mmol), trimethylolpropane triglycidyl ether (12.6g,50mmol) and tetrabutylammonium bromide (0.49g,3mmol) were added to a single-neck flask in this order, reacted at 100 ℃ for 8 hours, then the epoxy value was titrated to 0.42 by the acetone hydrochloride method, 1-pyrenebutanoic acid (1.03g,8.4mmol) was added to the reaction mixture, and the system was allowed to react at 100 ℃ for 4 hours. After the reaction was complete, it was precipitated in excess hot water to give a viscous yellow solid which was then redissolved with THF. Repeating the dissolving-precipitating for 3 times, finally cleaning the obtained precipitate by using a large amount of deionized water, and then performing vacuum drying for 12 hours at 50 ℃ to obtain hyperbranched polyether of which the tail end simultaneously contains an epoxy group and a polycyclic aromatic group;
(2) 24g h-BN is weighed and dispersed in 1000mL of isopropanol, hyperbranched polyether (6g) dissolved in 100mL of DMF is added under the condition of stirring, and the mixture is stirred and ultrasonically treated for 2h at room temperature under the condition of 400W of power, so that the h-BN is subjected to non-covalent modification. And after the ultrasonic treatment is finished, centrifuging for 15min at 5000rpm to remove the hyperbranched polyether which is not adsorbed to the h-BN surface, cleaning for 5 times by using acetone, and drying for 6h at 60 ℃ in a vacuum oven to obtain the hyperbranched polymer modified boron nitride.
Example 6:
a preparation method of hyperbranched polymer modified boron nitride comprises the following steps:
(1) bisphenol A (9.13g,40mmol), triglycidyl isocyanurate (35.67g,120mmol) and tetrabutylammonium bromide (1.93g,6mmol) are added into a single-neck flask in sequence, after 8 hours of reaction, the epoxy value is titrated to 0.43 by an acetone hydrochloride method, 1-pyrenebutyric acid (2.91g,10.1mmol) is added into the reaction mixture after 6 hours of reaction at 100 ℃, and the system is continuously reacted for 4 hours at 100 ℃. After the reaction was complete, it was precipitated in excess hot water to give a viscous yellow solid which was then redissolved with THF. And repeating the dissolving-precipitating for 3 times, finally cleaning the obtained precipitate by using a large amount of deionized water, and then drying in vacuum at 50 ℃ for 12 hours to obtain the hyperbranched polyether of which the tail end simultaneously contains the epoxy group and the polycyclic aromatic group.
(2) 24g h-BN is weighed and dispersed in 1000mL of isopropanol, hyperbranched polyether (24g) dissolved in 100mL of DMF is added under the condition of stirring, and the mixture is stirred and ultrasonically treated for 2h at room temperature under the condition of 400W of power, so that the h-BN is subjected to non-covalent modification. And after the ultrasonic treatment is finished, centrifuging for 15min at 5000rpm to remove the hyperbranched polyether which is not adsorbed to the h-BN surface, cleaning for 5 times by using acetone, and drying for 6h at 60 ℃ in a vacuum oven to obtain the hyperbranched polymer modified boron nitride.
Example 7:
a preparation method of hyperbranched polymer modified boron nitride comprises the following steps:
(1) butanediol (3.60g,40mmol), triglycidyl isocyanurate (35.67g,120mmol) and tetrabutylammonium bromide (1.93g,6mmol) are added into a single-neck flask in sequence, after reaction for 8 hours at 100 ℃, the epoxy value is titrated to 0.45 by an acetone hydrochloride method, 1-pyrenebutyric acid (1.04g,3.6mmol) is added into the reaction mixture, and the system is continuously reacted for 4 hours at 100 ℃. After the reaction was complete, it was precipitated in excess hot water to give a viscous yellow solid which was then redissolved with THF. Repeating the dissolving-precipitating for 3 times, finally cleaning the obtained precipitate by using a large amount of deionized water, and then performing vacuum drying for 12 hours at 50 ℃ to obtain hyperbranched polyether of which the tail end simultaneously contains an epoxy group and a polycyclic aromatic group;
(2) 24g h-BN is weighed and dispersed in 1000mL of isopropanol, hyperbranched polyether (24g) dissolved in 100mL of DMF is added under the condition of stirring, and the mixture is stirred and ultrasonically treated for 2h at room temperature under the condition of 400W of power, so that the h-BN is subjected to non-covalent modification. And after the ultrasonic treatment is finished, centrifuging for 15min at 5000rpm to remove the hyperbranched polyether which is not adsorbed to the h-BN surface, cleaning for 5 times by using acetone, and drying for 6h at 60 ℃ in a vacuum oven to obtain the hyperbranched polymer modified boron nitride.
Example 8:
a preparation method of hyperbranched polymer modified boron nitride comprises the following steps:
(1) 4,4' -biphenol (3.73g,20mmol), trimethylolpropane triglycidyl ether (18.14g,60mmol) and tetrabutylammonium bromide (1.93g,6mmol) were added in this order to a single-neck flask, and after reaction at 100 ℃ for 6 hours, 3-perylene carboxylic acid (1.34g,4.5mmol) was added to the reaction mixture by titration of the epoxy value to 0.38 by the acetone hydrochloride method, and the system was allowed to continue to react at 100 ℃ for 4 hours. After the reaction was complete, it was precipitated in excess hot water to give a viscous yellow solid which was then redissolved with THF. Repeating the dissolving-precipitating for 3 times, finally cleaning the obtained precipitate by using a large amount of deionized water, and then performing vacuum drying for 12 hours at 50 ℃ to obtain hyperbranched polyether of which the tail end simultaneously contains an epoxy group and a polycyclic aromatic group;
(2) 24g h-BN is weighed and dispersed in 1000mL of isopropanol, hyperbranched polyether (16g) dissolved in 100mL of DMF is added under the condition of stirring, and the mixture is stirred and ultrasonically treated for 2h at room temperature under the condition of 400W of power, so that the h-BN is subjected to non-covalent modification. And after the ultrasonic treatment is finished, centrifuging for 15min at 5000rpm to remove the hyperbranched polyether which is not adsorbed on the h-BN surface, cleaning for 5 times by using acetone, and drying for 6h at 60 ℃ in a vacuum oven to obtain the modified boron nitride.
Example 9:
a preparation method of hyperbranched polymer modified boron nitride comprises the following steps:
(1) 4,4' -biphenol (7.46g,40mmol), trimethylolpropane triglycidyl ether (36.28g,120mmol) and tetrabutylammonium bromide (1.93g,6mmol) were added in this order to a single-neck flask, and after reaction at 100 ℃ for 6 hours, the epoxy value was titrated to 0.38 by the acetone hydrochloride method, 9-fluorenylacetic acid (2.02g,9mmol) was added to the reaction mixture, and the system was allowed to react at 100 ℃ for 4 hours. After the reaction was complete, it was precipitated in excess hot water to give a viscous yellow solid which was then redissolved with THF. And repeating the dissolving-precipitating for 3 times, finally cleaning the obtained precipitate by using a large amount of deionized water, and then drying in vacuum at 50 ℃ for 12 hours to obtain the hyperbranched polyether of which the tail end simultaneously contains the epoxy group and the polycyclic aromatic group.
(2) 24g h-BN is weighed and dispersed in 1000mL of isopropanol, hyperbranched polyether (36g) dissolved in 100mL of DMF is added under the condition of stirring, and the mixture is stirred and ultrasonically treated for 2h at room temperature under the condition of 400W of power, so that the h-BN is subjected to non-covalent modification. And after the ultrasonic treatment is finished, centrifuging for 15min at 5000rpm to remove the hyperbranched polyether which is not adsorbed to the h-BN surface, cleaning for 5 times by using acetone, and drying for 6h at 60 ℃ in a vacuum oven to obtain the hyperbranched polymer modified boron nitride.
Example 10:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
4.3g of the hyperbranched polymer-modified boron nitride prepared in example 1 was added to 20g of bisphenol A epoxy resin E51, 17g of methylhexahydrophthalic anhydride and 2g of the curing accelerator 2,4, 6-tris (dimethylaminomethyl) phenol were added dropwise and mixed in a container, and the mixture was tested by a rotational rheometer for viscosity 4.8 pas at 25 ℃ with a shear rate of 10/s. Pouring the mixture into a stainless steel mold, defoaming for about 2 hours in a vacuum oven at 60 ℃, finally putting the mold into the oven to be cured for 1 hour at 80 ℃, heating to 100 ℃ to be cured for 1 hour, heating to 120 ℃ to be cured for 1 hour, heating to 140 ℃ to be cured for 2 hours, and finally heating to 160 ℃ to be cured for 3 hours to obtain the heat-conducting insulating composite material prepared by adding 10 wt% of hyperbranched polymer modified boron nitride.
Example 11:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
9.8g of the hyperbranched polymer-modified boron nitride prepared in example 1 was added to 20g of bisphenol A epoxy resin E51, 17g of methylhexahydrophthalic anhydride and 2g of the curing accelerator 2,4, 6-tris (dimethylaminomethyl) phenol were added dropwise in a vessel, and the mixture was tested by a rotational rheometer for viscosity of 12.8 pas at 25 ℃ with a shear rate of 10/s. Pouring the mixture into a stainless steel mold, defoaming for about 2 hours in a vacuum oven at 60 ℃, finally putting the mold into the oven to be cured for 1 hour at 80 ℃, heating to 100 ℃ to be cured for 1 hour, heating to 120 ℃ to be cured for 1 hour, heating to 140 ℃ to be cured for 2 hours, and finally heating to 160 ℃ to be cured for 3 hours to obtain the heat-conducting insulating composite material prepared by adding 20 wt% of hyperbranched polymer modified boron nitride.
Example 12:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
adding 16.7g of hyperbranched polymer modified boron nitride prepared in example 1 into 20g of bisphenol A epoxy resin E51, dropwise adding 17g of methylhexahydrophthalic anhydride and 2g of curing accelerator 2,4, 6-tris (dimethylaminomethyl) phenol into a container, pouring the mixture into a stainless steel mold, defoaming for about 2h at 60 ℃ in a vacuum oven, finally placing the mold into an oven to cure for 1h at 80 ℃, heating to 100 ℃ to cure for 1h, heating to 120 ℃ to cure for 1h, heating to 140 ℃ to cure for 2h, and heating to 160 ℃ to cure for 3h to obtain the heat-conducting insulating composite material prepared by adding 30 wt% of hyperbranched polymer modified boron nitride.
Example 13:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
adding 26g of hyperbranched polymer modified boron nitride prepared in example 1 into 20g of bisphenol A epoxy resin E51, dropwise adding 17g of methylhexahydrophthalic anhydride and 2g of curing accelerator 2,4, 6-tris (dimethylaminomethyl) phenol into a container, pouring the mixture into a stainless steel mold, defoaming for about 2h at 60 ℃ in a vacuum oven, finally placing the mold into an oven for curing for 1h at 80 ℃, heating to 100 ℃ for curing for 1h, heating to 120 ℃ for curing for 1h, heating to 140 ℃ for curing for 2h, and heating to 160 ℃ for curing for 3h to obtain the heat-conducting insulating composite material prepared by adding 40 wt% of hyperbranched polymer modified boron nitride.
Example 14:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
adding 39g of hyperbranched polymer modified boron nitride prepared in example 1 into 20g of bisphenol A epoxy resin E51, dropwise adding 17g of methylhexahydrophthalic anhydride and 2g of curing accelerator 2,4, 6-tris (dimethylaminomethyl) phenol into a container, mixing, pouring into a stainless steel mold, defoaming for about 2h at 60 ℃ in a vacuum oven, finally placing the mold into the oven to cure for 1h at 80 ℃, heating to 100 ℃ to cure for 1h, heating to 120 ℃ to cure for 1h, heating to 140 ℃ to cure for 2h, and heating to 160 ℃ to cure for 3h to obtain the heat-conducting insulating composite material prepared by adding 50 wt% of hyperbranched polymer modified boron nitride.
Example 15:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
adding 58.5g of hyperbranched polymer modified boron nitride prepared in example 1 into 20g of bisphenol A epoxy resin E51, dropwise adding 17g of methylhexahydrophthalic anhydride and 2g of curing accelerator 2,4, 6-tris (dimethylaminomethyl) phenol into a container, mixing, pouring into a stainless steel mold, defoaming for about 2h at 60 ℃ in a vacuum oven, finally placing the mold into the oven to cure for 1h at 80 ℃, heating to 100 ℃ to cure for 1h, heating to 120 ℃ to cure for 1h, heating to 140 ℃ to cure for 2h, and heating to 160 ℃ to cure for 3h to obtain the heat-conducting insulating composite material prepared by adding 60 wt% of hyperbranched polymer modified boron nitride.
Example 16:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
2.2g of hyperbranched polymer modified boron nitride prepared in example 1 was added, mixed uniformly with 15g of bis (3-ethyl-5-methyl-4-maleimidobenzene) methane (BMI-70), 5g of phenol type novolac resin (PF-8011), 0.4g of polyfunctional epoxy resin (EPPN-501H) and 0.6g of 2-ethyl-4-methylimidazole (2-Et-4-MZ), and then the mixture was thoroughly mixed at room temperature at 800rpm by a high speed mixer, and melt-kneaded at 90 ℃ by a twin screw kneader, and then the kneaded mass was cooled and pulverized, and molded at 4MPa pressure and 175 ℃ to obtain a heat conductive and insulating composite prepared by adding 10 wt% of hyperbranched polymer modified boron nitride.
Example 17:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
5.0g of hyperbranched polymer modified boron nitride prepared in example 1 was added, mixed uniformly with 15g of bis (3-ethyl-5-methyl-4-maleimidobenzene) methane (BMI-70), 5g of phenol type novolac resin (PF-8011), 0.4g of polyfunctional epoxy resin (EPPN-501H) and 0.6g of 2-ethyl-4-methylimidazole (2-Et-4-MZ), and then the mixture was thoroughly mixed at room temperature at 800rpm by a high speed mixer, and melt-kneaded at 90 ℃ by a twin screw kneader, and then the kneaded mass was cooled and pulverized, and molded at 4MPa pressure and 175 ℃ to obtain a heat conductive and insulating composite prepared by adding 20 wt% of hyperbranched polymer modified boron nitride.
Example 18:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
10.7g of hyperbranched polymer modified boron nitride prepared in example 1 was added, mixed uniformly with 20g of bis (3-ethyl-5-methyl-4-maleimidobenzene) methane (BMI-70), 5g of phenol type novolac resin (PF-8011), 0.7g of polyfunctional epoxy resin (EPPN-501H) and 0.6g of 2-ethyl-4-methylimidazole (2-Et-4-MZ), and then the mixture was thoroughly mixed at room temperature at 800rpm by a high speed mixer, and melt-kneaded at 90 ℃ by a twin screw kneader, and then the kneaded mass was cooled and pulverized, and molded at 4MPa pressure and 175 ℃ to obtain a heat conductive and insulating composite prepared by adding 30 wt% of hyperbranched polymer modified boron nitride.
Example 19:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
16.7g of hyperbranched polymer modified boron nitride prepared in example 1 was added, mixed uniformly with 25g of bis (3-ethyl-5-methyl-4-maleimidobenzene) methane (BMI-70), 5g of phenol type novolac resin (PF-8011), 2.7g of polyfunctional epoxy resin (EPPN-501H) and 0.6g of 2-ethyl-4-methylimidazole (2-Et-4-MZ), and then the mixture was thoroughly mixed at room temperature at 800rpm by a high speed mixer, and melt-kneaded at 90 ℃ by a twin screw kneader, and then the kneaded mass was cooled and pulverized, and molded at 4MPa pressure and 175 ℃ to obtain a heat conductive and insulating composite prepared by adding 40 wt% of hyperbranched polymer modified boron nitride.
Example 20:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
20g of hyperbranched polymer modified boron nitride prepared in example 1, 15g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70), 5g of phenol type novolac resin (PF-8011), 0.4g of polyfunctional epoxy resin (EPPN-501H) and 0.6g of 2-ethyl-4-methylimidazole (2-Et-4-MZ) were added, mixed uniformly, mixed thoroughly at room temperature at 800rpm by a high speed mixer, melt-kneaded by a twin screw kneader at 90 ℃ and then cooled and pulverized, and molded at 175 ℃ under 4MPa pressure to obtain a thermally conductive and insulating composite material prepared by adding 50 wt% of hyperbranched polymer modified boron nitride.
Example 21:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
30g of hyperbranched polymer modified boron nitride prepared in example 1, 15g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70), 5g of phenol type phenolic resin (PF-8011), 2.7g of polyfunctional epoxy resin (EPPN-501H) and 0.4g of 2-ethyl-4-methylimidazole (2-Et-4-MZ) were added, mixed uniformly, mixed thoroughly at room temperature at 800rpm by a high-speed mixer, melt-kneaded by a twin-screw kneader at 90 ℃ and then cooled and pulverized, and molded at 175 ℃ under 4MPa to obtain a thermally conductive and insulating composite material prepared by adding 60 wt% of hyperbranched polymer modified boron nitride.
Example 22:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
46.7g of hyperbranched polymer modified boron nitride prepared in example 1 was added, mixed uniformly with 15g of bis (3-ethyl-5-methyl-4-maleimidobenzene) methane (BMI-70), 5g of phenol type novolac resin (PF-8011), 2.7g of polyfunctional epoxy resin (EPPN-501H) and 0.4g of 2-ethyl-4-methylimidazole (2-Et-4-MZ), and then the mixture was thoroughly mixed at room temperature at 800rpm by a high speed mixer, and melt-kneaded at 90 ℃ by a twin screw kneader, and then the kneaded mass was cooled and pulverized, and molded at 4MPa pressure and 175 ℃ to obtain a heat conductive and insulating composite prepared by adding 70 wt% of hyperbranched polymer modified boron nitride.
Example 23:
a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is prepared by the following steps:
80g of hyperbranched polymer modified boron nitride prepared in example 1, 15g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70), 5g of phenol type phenolic resin (PF-8011), 2.7g of polyfunctional epoxy resin (EPPN-501H) and 0.4g of 2-ethyl-4-methylimidazole (2-Et-4-MZ) were added, mixed uniformly, mixed thoroughly at room temperature at 800rpm by a high-speed mixer, melt-kneaded by a twin-screw kneader at 90 ℃ and then cooled and pulverized, and molded at 175 ℃ under 4MPa to obtain a heat-conductive and insulating composite material prepared by adding 80 wt% of hyperbranched polymer modified boron nitride.
Comparative example 1:
a boron nitride heat conduction and insulation composite material is prepared by the following steps:
9.8g of original hexagonal boron nitride is added into 20g of bisphenol A type epoxy resin E51, 17g of methyl hexahydrophthalic anhydride curing agent and 2g of curing accelerator 2,4, 6-tri (dimethylaminomethyl) phenol are dropwise added into a container, and the viscosity of the mixture is 25.3 pas under the conditions of 25 ℃ and 10/s of shear rate by a rotational rheometer. Pouring the mixture into a stainless steel mold, defoaming for about 2 hours in a vacuum oven at 60 ℃, finally putting the mold into the oven to be cured for 1 hour at 80 ℃, heating to 100 ℃ to be cured for 1 hour, heating to 120 ℃ to be cured for 1 hour, heating to 140 ℃ to be cured for 2 hours, and finally heating to 160 ℃ to be cured for 3 hours to obtain the heat-conducting insulating composite material prepared by adding 20 wt% of original boron nitride.
Comparative example 2:
a heat-conducting and insulating composite material is prepared by the following steps:
adding 9.8g of spherical fused silica into 20g of bisphenol A type epoxy resin E51, dropwise adding 17g of methyl hexahydrophthalic anhydride curing agent and 2g of curing accelerator 2,4, 6-tri (dimethylaminomethyl) phenol into a container, and testing the viscosity of the mixture at 25 ℃ and under the condition of a shear rate of 10/s by using a rotational rheometer to be 13.6 pas. Pouring the mixture into a stainless steel mold, defoaming for about 2 hours in a vacuum oven at 60 ℃, finally putting the mold into the oven to be cured for 1 hour at 80 ℃, heating to 100 ℃ to be cured for 1 hour, heating to 120 ℃ to be cured for 1 hour, heating to 140 ℃ to be cured for 2 hours, and finally heating to 160 ℃ to be cured for 3 hours to obtain the heat-conducting insulating composite material prepared by adding 20 wt% of silicon dioxide. (spherical fused silica, available from Admatechs corporation of Japan with an average particle size of 1 μm, model number SC2500, 10%; and available from Electrical chemical Co., Ltd of Japan with average particle sizes of 15 μm and 24 μm, model numbers FB-15D and FB-20D, respectively, at 37% and 53%)
Comparative example 3:
a heat-conducting and insulating composite material is prepared by the following steps:
20g of original hexagonal boron nitride, 15g of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70), 5g of phenol type novolac resin (PF-8011), 0.4g of multifunctional epoxy resin (EPPN-501H) and 0.6g of 2-ethyl-4-methylimidazole (2-Et-4-MZ) are added, mixed uniformly at room temperature at a rotation speed of 800rpm by a high-speed mixer, and then melt-kneaded by a twin-screw kneader at 90 ℃, the kneaded material is cooled and crushed, and molded at a pressure of 4MPa and a temperature of 175 ℃ to obtain the heat-conducting and insulating composite material added with 50 wt% of original boron nitride.
Comparative example 4:
a heat-conducting and insulating composite material is prepared by the following steps:
adding 20g of spherical fused silica, 15g of bis (3-ethyl-5-methyl-4-maleimidobenzene) methane (BMI-70), 5g of phenol type novolac resin (PF-8011), 0.4g of multifunctional epoxy resin (EPPN-501H) and 0.6g of 2-ethyl-4-methylimidazole (2-Et-4-MZ), uniformly mixing at room temperature and 800rpm by using a high-speed mixer, carrying out melt kneading by using a double-screw kneader at 90 ℃, cooling and crushing the kneaded material, and forming at 175 ℃ under the pressure of 4MPa to obtain the heat-conducting insulating composite material prepared by adding 50 wt% of silica.
Test example:
(1) the nuclear magnetic spectrum of the hyperbranched polymer with the terminal containing both epoxy group and polycyclic aromatic group prepared in examples 1-4 is shown in FIG. 1.
As can be seen from FIG. 1, the chemical shifts of 2.1, 2.5 and 3.5 are proton peaks of alkyl chain in pyrenebutyric acid; the proton peak of a conjugated benzene ring in pyrenebutyric acid is at a chemical shift of 7.9-8.5, which proves that pyrenebutyric acid is used as a blocking agent to successfully modify hyperbranched polyether, and the peak area is increased along with the increase of the content of the blocking agent in examples 1,2, 3 and 4. In addition, a signal at a chemical shift of 0.8-4.2 is a proton peak in trimethylolpropane triglycidyl ether; and a signal at a chemical shift of 7-7.5 is a proton peak on a 4,4' -biphenol benzene ring.
(2) The performance tests of the composite materials obtained in examples 11 to 13 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1
The thermal conductivity (λ) of the composite material is according to the formula λ ═ α × CpWhere the thermal diffusivity (alpha) is calculated by grinding the prepared epoxy resin-based composite material to a size of 10mm x 10mm and a thickness of 2mm, as measured by LFA 467 Nanoflash, and the specific heat capacity C of the materialpIs obtained from DSC and the density ρ is measured by the drainage method.
Flexural strength test (mechanical property test): the cured articles were tested for flexural strength using a 5967X dual column bench test system and tested using ASTM D790& ISO 178 standards. The sample strip is tested by a three-point bending method, the size of the sample strip is 80 +/-2 mm multiplied by 10 +/-0.2 mm multiplied by 4 +/-0.2 mm, and the span is 64 mm.
Example 11, comparative example 1 and comparative example 2 in Table 1 are respectively viscosity, thermal conductivity, bending strength and temperature T corresponding to 5% thermal decomposition of epoxy resin composite prepared by adding 20 wt% of filler5％. In example 11, hexagonal boron nitride modified by hyperbranched polymer is added, in comparative example 1, unmodified hexagonal boron nitride is added, and in comparative example 2, silica micropowder with commercial particle size is added. Example 12 is a composite material prepared by adding 30 wt% of hexagonal boron nitride modified by a hyperbranched polymer, and example 13 is a composite material prepared by adding 40 wt% of hexagonal boron nitride modified by a hyperbranched polymer. From the viscosity test before curing, it can be seen that the one prepared in example 11The viscosity of the epoxy resin composite material is far lower than that of the composite material prepared by using the original boron nitride in a comparative example 1, the viscosity of the epoxy resin composite material is equivalent to that of the composite material prepared by using the silicon dioxide micropowder in a comparative example 2, and the epoxy resin composite material has better processability; as can be seen from table 1, the thermal conductivity of the composite material prepared in example 11 using hyperbranched polymer-modified boron nitride is much higher than the comparative example using the same filler addition amount, and the thermal conductivity of the composite material increases significantly with the increase in the addition amount of hyperbranched polymer-modified boron nitride; example 11 the bending strength of the composite material prepared using hyperbranched polymer modified boron nitride is significantly better than that of the comparative example, improving the mechanical properties of the material. In addition, the thermal stability of the composite material is improved to some extent, and the beneficial effects are caused by the modification of the filler by the hyperbranched polymer.
(3) The performance tests of the composites obtained in example 20 and comparative examples 3-4 are shown in Table 2.
TABLE 2
Table 2 shows the viscosity, thermal conductivity, flexural strength and temperature T corresponding to 5% thermal decomposition of an epoxy resin composite material prepared by adding 50% of a filler5％The filler added in example 20 is hexagonal boron nitride modified by hyperbranched polymer, the filler added in comparative example 3 is unmodified hexagonal boron nitride, and the filler added in comparative example 4 is silica micropowder with commercial particle size compounding. It can be seen from the table that the thermal conductivity of the composite prepared in example 20 is much higher than that of the composite prepared using pristine boron nitride and commercial compounded silica; the bending strength of the composite material prepared in example 20 is obviously better than that of the comparative example, and the mechanical properties of the material are improved. In addition, the thermal stability of the composite material is improved to some extent, and the beneficial effects are caused by the modification of the filler by the hyperbranched polymer.
Claims (10)
1. A preparation method of a hyperbranched polymer modified boron nitride heat conduction and insulation composite material is characterized by comprising the following steps:
(1) adding a hyperbranched polymer, a boron nitride filler and an organic solvent into a container, performing ultrasonic treatment, centrifuging and drying to obtain hyperbranched polymer modified boron nitride;
(2) and (2) mixing the hyperbranched polymer modified boron nitride prepared in the step (1) with matrix resin, a curing agent and a curing agent accelerator, and curing to prepare the heat-conducting and insulating composite material.
2. The preparation method according to claim 1, wherein in step (1), the hyperbranched polymer contains both epoxy groups and polycyclic aromatic groups at the terminal, and the preparation method comprises:
firstly, taking a tri-functionality epoxy monomer and a bisphenol monomer as raw materials, and reacting for 4-24 hours at the temperature of 80-120 ℃ under the action of a catalyst tetrabutylammonium bromide;
secondly, adding a terminating agent, and reacting at the temperature of 80-120 ℃ for 4-12 h for modification to obtain the hyperbranched polymer;
the trifunctional epoxy monomer is one or more of trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, glycerol triglycidyl ether, triglycidyl p-aminophenol, triglycidyl amino-m-cresol, triglycidyl m-aminophenol, tris (4-hydroxyphenyl) methane triglycidyl ether and trimethylolpropane triglycidyl ether;
the bisphenol monomer is one or more of 4,4' -biphenol, bisphenol fluorene, bisphenol A, bisphenol F, bisphenol AF, bisphenol S, butanediol, 1, 3-cyclohexanediol, ethylene glycol, propylene glycol, resorcinol, hydroquinone, catechol, 1, 3-naphthalenediol, 1, 8-naphthalenediol, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 2, 3-naphthalenediol, 2, 6-naphthalenediol and 2, 7-naphthalenediol;
the structure of the end-capping reagent is COOH-R, wherein R is pyrene, fluorene, acenaphthene, phenanthrene, anthracene or perylene.
3. The method of claim 2, wherein the molar ratio of the trifunctional epoxy monomer to the bisphenol monomer is 1.2:1 to 4: 1; the dosage of the catalyst tetrabutylammonium bromide is 1-5 wt% of the trifunctional epoxy monomer; the amount of the end capping agent is 5 to 60 percent of the molar weight of epoxy in the reaction product in the step (1);
the end-capping reagent is one or more of 1-pyrenebutanoic acid, 1-pyrene formic acid, 9-fluorene acetic acid, fluorene-4-carboxylic acid, 5-acenaphthenecarboxylic acid, 2-phenanthrenecarboxylic acid, 3-phenanthrenecarboxylic acid, phenanthrene-9-formic acid, 9-anthracenecarboxylic acid, 1-anthracenecarboxylic acid, 2-anthracenecarboxylic acid and 3-perylene carboxylic acid.
4. The preparation method according to claim 1, wherein in the step (1), the boron nitride filler is one or more of platelet hexagonal boron nitride, tubular hexagonal boron nitride, rhombohedral boron nitride and cubic boron nitride; the organic solvent is one or more of isopropanol, tetrahydrofuran, ethanol, N-dimethylformamide and acetone;
the mass ratio of the hyperbranched polymer to the boron nitride filler is 0.01: 1-10: 1; the concentration of boron nitride in the reaction system is 1-100 g/L.
5. The preparation method according to claim 1, wherein in the step (1), the power of the ultrasonic wave is 100-1000W, the ultrasonic time is 2-24 h, and the rotation speed of the centrifugal is 3000-10000 rpm.
6. The production method according to claim 1, wherein in the step (2), the curing agent is an acid anhydride, a polyamine or a polyphenol; the acid anhydride is one or more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, methylcyclohexane tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, trimellitic anhydride and polyazelaic anhydride; the polyamine is diethylenetriamine, triethylene tetramine, tetraethylene pentamine, divinyl propylamine, polyamide, menthane diamine, isophorone diamine, and N-ammoniaOne or more of ethyl piperazine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, dicyandiamide, adipic acid dihydrazide; the polyhydric phenol is one or more of allyl bisphenol A, phenol type linear phenolic resin, cresol type linear phenolic resin, phenolic resin modified by dicyclopentadiene, biphenyl type aralkyl phenolic resin, p-xylene type aralkyl phenolic resin and triphenol methane type linear phenolic resin; the curing accelerator is 2,4, 6-tri (dimethylaminomethyl) phenol, benzyldimethylamine, acetylacetone metal salt, triphenylphosphine and the triphenylphosphine
One or more of salts, substituted ureas, addition products of aryl isocyanate and imidazole compounds, active chromium tris (2-ethylhexanoate), organic acid salt-amine complexes, 1, 8-diaza-bicyclo (5,4,0) -7-undecene, 2-mercaptobenzothiazole, peroxides, thiourea and derivatives thereof, cycloalkyl imidazolines, 2-phenylimidazolines, epoxy-containing tertiary aromatic amines, titanate accelerators, ferrocenyl accelerators, chromium halide-anhydride complexes.
7. The production method according to claim 1, wherein in the step (2), the matrix resin is a bismaleimide resin or an epoxy resin; the bismaleimide resin is N, N '-4,4' -diphenylmethane bismaleimide, oligomer of phenylmethaneimide, N '-m-phenylenedimaleimide, N' -m-xylene bismaleimide, N '-p-xylylenebismaleimide, 2' -bis [4- (4-maleimidophenoxy) phenyl ] propane, bis (3-ethyl-5-methyl-4-maleimidobenzene) methane, N- (4-methyl-1, 3-phenylene) bismaleimide, 4 '-diphenylether bismaleimide, 4' -diphenylsulfone bismaleimide, 1, 3-bis (3-maleimidophenoxy) benzene, N '-m-xylylenebismaleimide, N' -p-xylylenebismaleimide, N '-bis (4-maleimidophenoxy) benzene, N' -N-p-phenylene-diphenylether bismaleimide, 4-diphenylether bismaleimide, 4-bis (4-phenylene) bismaleimide, N-p-phenylene) bismaleimide, N-phenylene, N-p-phenylene, N-diphenylether bismaleimide, N-maleimide and N-bismaleimide, N-maleimide or N-bismaleimide, N-bismaleimide resin or N-imide resin or N, N-p-imide resin or N-bismaleimide resin or a mixture of, 1, 3-bis (4-maleimidophenoxy) benzene, N ' -p-benzophenone maleimide, N ' - (methylene-bistetrahydrophenyl) bismaleimide, N ' - (3,3' -dichloro) -4,4' -diphenylmethane bismaleimide, N ' -tolidine bismaleimide, N ' -isophorone bismaleimide, N ' -p, p ' -diphenyldimethylsilyl bismaleimide, N ' -naphthalene bismaleimide, N ' -4,4' - (1,1' -diphenyl-cyclohexane) bismaleimide, N ' -3,5- (1,2, 4-triazole) bismaleimide, N ' -bis (4-methyl) maleimide), N ' -bis (2, 4-triazole) bismaleimide, N ' -bis (4-methyl-bis (p-methyl) maleimide), N ' -bis (3, N ' -bis (4-methyl-phenyl) bismaleimide), N ' -bis (4-bis (1,2, 4-triazole) bismaleimide, N ' -bis (4-bis) maleimide), N ' -isophorone bismaleimide, N ' -bis (2-bis (4-bis (maleimide), N-bis (2-bis) bismaleimide), N-bis (1, N-bis (2-bis (1-bis) maleimide), N-bis (1, 4-bis (2-bis) maleimide), N-bis (2-bis (1, 4-bis) maleimide), bis (1, 4-bis (2-bis) maleimide), bis (1-bis (2-bis) bismaleimide), or (1-bis (2-bis) bismaleimide), bis (2-bis (2) maleimide), bis (2) bismaleimide), or (2) bismaleimide), bis (2) bismaleimide), or (2-bis (2) imide), or (2) bis (2) imide) bis (2) imide) bis (2-bis (2) imide) bis (2, 4) bis (2-bis (2) imide) bis (2) imide, 4) bis (2) imide) bis (2, 4) or (2) bis (2) or (2) bis (2) or (2) bis (2) or (2) bis (2) or (2), One or more of N, N ' -pyridine-2, 6-diylbismaleimide, N ' -maleimide of 4,4' -diamino-triphenyl phosphate, 2-bis [ 3-chloro-4-maleimidophenoxy ] phenyl ] propane, 2-bis [ 3-methoxy-4- (4-maleimidophenoxy) phenyl ] propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane;
the epoxy resin is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin and alicyclic epoxy resin.
8. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the hyperbranched polymer modified boron nitride to the matrix resin is 0.05: 1-4: 1, the amount of the curing agent is 10-85 wt% of the matrix resin, and the amount of the curing accelerator is 0.5-10 wt% of the matrix resin.
9. The preparation method according to claim 1, wherein the curing manner is a stepwise temperature rise curing or a twin-screw extrusion curing;
the conditions of stage temperature rise and solidification are as follows: 1h at 80 ℃, 1h at 100 ℃, 1h at 120 ℃, 1h at 140 ℃, 2h at 160 ℃ and 3 h;
the conditions of twin-screw extrusion curing are as follows: and (3) melting and kneading the mixture by a twin-screw kneader at the temperature of 70-110 ℃, cooling, crushing, and heating and molding under the pressure of 4MPa and at the temperature of 175 ℃.
10. The application of the heat-conducting and insulating composite material prepared by the preparation method of claim 1 is characterized by being applied to the fields of aerospace, composite materials, heat-conducting adhesives, copper-clad plates or electronic packaging materials.
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