Disclosure of Invention
Aiming at the problems, the invention provides an environment-friendly flame-retardant high-thermal-conductivity metal-based copper-clad plate which comprises a circuit layer, a thermal insulation layer and a metal base layer which are sequentially arranged from top to bottom, wherein the thermal insulation layer comprises the following components in parts by weight:
100 parts of epoxy resin, 12-48 parts of flame-retardant heat-conducting filler, 3-10 parts of curing accelerator and 30-50 parts of curing agent;
the flame-retardant heat-conducting filler is obtained by compounding nano tungsten ditelluride and a copper-chromium-based organic metal framework material.
Preferably, the epoxy resin is a mixture of bisphenol A epoxy resin, naphthalene ring epoxy resin and biphenyl epoxy resin, and the weight ratio of the bisphenol A epoxy resin to the naphthalene ring epoxy resin to the biphenyl epoxy resin is 20-40.
Preferably, the curing agent is at least one of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dimer acid-based polyamide, 4,4-diaminodiphenyl sulfone.
Preferably, the cure accelerator is 2,4,6-tris (dimethylaminomethyl) phenol and/or N, N-dimethylbenzylamine.
Preferably, the particle size of the nano tungsten ditelluride is 5-20 nm, and the particle size of the copper-chromium-based organic metal framework material is 300-800 nm.
Preferably, the preparation method of the copper-chromium-based organic metal framework material comprises the following steps:
s1, weighing copper sulfate, adding the copper sulfate into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a copper sulfate ethanol solution; weighing 2-pyridinecarboxamide and chromium picolinate, adding the weighed materials into absolute ethyl alcohol, and stirring the materials uniformly to obtain an organic-inorganic mixed solution;
wherein in the copper sulfate ethanol solution, the mass ratio of copper sulfate to absolute ethyl alcohol is 1; in the organic-inorganic mixed solution, the mass ratio of the 2-pyridine carboxamide to the chromium picolinate to the absolute ethyl alcohol is 1;
s2, slowly adding the organic-inorganic mixed solution into a copper sulfate ethanol solution which is continuously stirred at room temperature, stirring at the speed of 500-800 rpm for 8-12 h after the addition is finished, standing in a shade place for 12-15 h, filtering, washing the filter residue for 3-5 times by using ethanol, drying the washed filter residue at the temperature of 45-65 ℃ to constant weight, and crushing to obtain a copper-chromium-based organic metal framework material;
wherein the mass ratio of the organic-inorganic mixed solution to the copper sulfate ethanol solution is 1.12-1.24.
Preferably, the preparation method of the flame-retardant heat-conducting filler comprises the following steps:
(1) Weighing a copper-chromium-based organic metal framework material, adding the copper-chromium-based organic metal framework material into deionized water, and uniformly stirring and dispersing to obtain a copper-chromium-based organic metal framework material mixed solution; weighing nano tungsten ditelluride, adding the nano tungsten ditelluride into deionized water, adding gamma-aminopropyltriethoxysilane, and performing ultrasonic treatment for 0.5-1 h to obtain a nano tungsten ditelluride mixed solution;
wherein, in the mixed solution of the copper-chromium-based organic metal framework material, the mass ratio of the copper-chromium-based organic metal framework material to the deionized water is 1; in the mixed solution of the nano tungsten ditelluride, the mass ratio of the nano tungsten ditelluride, the gamma-aminopropyltriethoxysilane to the deionized water is 1;
(2) Adding MES buffer solution into the copper-chromium-based organic metal framework material mixed solution, adjusting the pH of the mixed solution to 5.0-5.5, then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, uniformly mixing, heating to 65-80 ℃, dropwise adding the nano tungsten ditelluride mixed solution while stirring, after completely dropwise adding, continuously stirring for 0.5-1 h, then pouring into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle at 150-180 ℃ for reaction treatment for 8-12 h, and after cooling to room temperature, obtaining reaction mixed solution;
wherein the mass ratio of the mixed solution of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the nano tungsten ditelluride to the mixed solution of the copper-chromium-based organic metal framework material is 0.01;
(3) And carrying out vacuum filtration on the reaction mixed liquid, collecting filter residues, washing the filter residues for 3-5 times by using ethanol, washing the filter residues into washing liquid by using distilled water, and then drying the filter residues under a vacuum condition to constant weight to obtain the flame-retardant heat-conducting filler.
Preferably, the curing temperature of the epoxy resin is 100-180 ℃, and the curing time is 1-3 h.
The beneficial effects of the invention are as follows:
1. the invention discloses an environment-friendly flame-retardant high-heat-conductivity metal-based copper-clad plate which comprises a circuit layer, a heat-conducting insulating layer and a metal base layer which are sequentially arranged from top to bottom, wherein the heat-conducting insulating layer takes epoxy resin as a matrix, flame-retardant heat-conducting filler is added and simultaneously taken as a heat-conducting agent and a flame retardant, and the flame-retardant heat-conducting filler is obtained by compounding nano tungsten ditelluride and a copper-chromium-based organic metal framework material. The heat-conducting insulating layer prepared by the invention is different from the traditional halogen flame retardant, is a halogen-free environment-friendly material, and not only has better flame retardance, but also has excellent heat-conducting property.
2. The flame-retardant heat-conducting filler prepared by the invention is obtained by loading nano tungsten ditelluride cross-linked on a copper-chromium-based organic metal framework material. Among them, tungsten ditelluride is a transition metal ditelluride, which is also a two-dimensional layered material, and has attracted much attention because of its excellent properties such as unique and remarkable electrical and optical properties. However, the use of such a material as a heat conductive material is rare in the prior art because it does not perform well as a heat conductive filler alone. The invention uses the copper-chromium-based organic metal framework material as a heat conducting framework, uses the nano tungsten ditelluride as a supporting body, and utilizes the properties of two-dimensional layered and topological insulators of the nano tungsten ditelluride to ensure that the copper-chromium-based organic metal framework material has larger specific surface area and stronger stability, and the heat dissipation performance of the copper-chromium-based organic metal framework material is improved.
The copper-chromium-based organic metal framework material is prepared by adopting 2-pyridine carboxamide as a ligand and metal ion copper and organic metal chromium-based as a central body which are connected with each other through self-assembly. The organic metal framework material prepared by the invention simultaneously contains metal copper and metal chromium, wherein copper is used as a main element and chromium is used as an auxiliary element, the surface of the prepared organic metal framework material contains abundant organic functional groups, metal ion copper in a central body has stronger heat conductivity, organic metal chromium-based chromium picolinate has stronger flame retardance and smoke suppression performance, and the heat conductivity is higher, so that the metal ion copper and the organic metal chromium-based material can be matched with each other to form a material with heat conductivity and flame retardance.
3. The prepared copper-chromium-based organic metal framework material has larger specific surface energy of metal ions and organic molecules, and the thermal stability cannot reach an ideal level, so that nano tungsten ditelluride is selected and packaged in the copper-chromium-based organic metal framework material, the nano tungsten ditelluride is modified by aminosilane firstly and then undergoes hydrothermal reaction with the copper-chromium-based organic metal framework material in the packaging process, and in the reaction process, the amino on the surface of the modified nano tungsten ditelluride can be combined with an active organic functional group in the copper-chromium-based organic metal framework material, so that the nano tungsten ditelluride is more stably packaged in the copper-chromium-based organic metal framework material. Therefore, the specific surface energy of the metal framework material is reduced, the thermal stability of the metal framework material is improved, more active sites are added, and the flame retardance and the flame retardant efficiency of the copper-chromium-based organic metal framework material are improved. In addition, the flame-retardant heat-conducting filler prepared by the invention additionally improves the toughness of the epoxy resin and improves the mechanical property of the epoxy resin.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.
Compared with a copper-chromium-based organic metal framework material, the pore volume, the pore diameter and the specific surface area of the flame-retardant heat-conducting filler prepared by the invention are reduced, so that the specific surface energy is reduced, and the thermal stability is improved. The flame-retardant mechanism of the flame-retardant heat-conducting filler is a double flame-retardant mechanism, namely in the combustion process, the copper-chromium-based organic metal framework material can absorb a large amount of heat, so that the framework structure is gradually decomposed along with the rise of temperature, and finally collapses, which is a first double flame-retardant mechanism, and then after the framework structure collapses, the nano tungsten ditelluride serving as the packaging material in the framework structure can be released, and the instantaneous flame-retardant behavior of gas phase and condensed phase is shown, which is a second double flame-retardant mechanism, and the double flame-retardant mechanism can better play a better flame-retardant effect on the original material.
The invention is further described below with reference to the following examples.
Example 1
The utility model provides a fire-retardant high heat conduction metal base copper-clad plate of environment-friendly, includes from last circuit layer, heat conduction insulation layer and the metal-based layer that sets gradually down, and heat conduction insulation layer calculates according to part by weight, includes following composition:
100 parts of epoxy resin, 30 parts of flame-retardant heat-conducting filler, 6 parts of curing accelerator and 40 parts of curing agent;
the flame-retardant heat-conducting filler is obtained by compounding nano tungsten ditelluride and a copper-chromium-based organic metal framework material.
The epoxy resin is a mixture of bisphenol A epoxy resin, naphthalene epoxy resin and biphenyl epoxy resin, and the weight ratio of the bisphenol A epoxy resin to the naphthalene epoxy resin to the biphenyl epoxy resin is 30.
The curing agent is methyl tetrahydrophthalic anhydride.
The curing accelerator is 2,4,6-tris (dimethylaminomethyl) phenol.
The grain size of the nano tungsten ditelluride is 5-20 nm, and the grain size of the copper-chromium-based organic metal framework material is 300-800 nm.
The preparation method of the copper-chromium-based organic metal framework material comprises the following steps:
s1, weighing copper sulfate, adding the copper sulfate into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a copper sulfate ethanol solution; weighing 2-pyridinecarboxamide and chromium picolinate, adding the weighed materials into absolute ethyl alcohol, and stirring the materials uniformly to obtain an organic-inorganic mixed solution;
wherein in the copper sulfate ethanol solution, the mass ratio of copper sulfate to absolute ethyl alcohol is 1; in the organic-inorganic mixed solution, the mass ratio of the 2-pyridinecarboxamide to the chromium picolinate to the absolute ethyl alcohol is 1;
s2, slowly adding the organic-inorganic mixed solution into a copper sulfate ethanol solution which is continuously stirred at room temperature, stirring at the speed of 500-800 rpm for 8-12 h after the addition is finished, standing in a shade place for 12-15 h, filtering, washing the filter residue for 3-5 times by using ethanol, drying the washed filter residue at the temperature of 45-65 ℃ to constant weight, and crushing to obtain a copper-chromium-based organic metal framework material;
wherein the mass ratio of the organic-inorganic mixed solution to the copper sulfate ethanol solution is 1.18.
The preparation method of the flame-retardant heat-conducting filler comprises the following steps:
(1) Weighing a copper-chromium-based organic metal framework material, adding the copper-chromium-based organic metal framework material into deionized water, and uniformly stirring and dispersing to obtain a copper-chromium-based organic metal framework material mixed solution; weighing nano tungsten ditelluride, adding the nano tungsten ditelluride into deionized water, adding gamma-aminopropyltriethoxysilane, and carrying out ultrasonic treatment for 0.5-1 h to obtain a nano tungsten ditelluride mixed solution;
wherein in the mixed solution of the copper-chromium-based organic metal framework material, the mass ratio of the copper-chromium-based organic metal framework material to the deionized water is 1; in the mixed solution of the nano tungsten ditelluride, the mass ratio of the nano tungsten ditelluride, the gamma-aminopropyltriethoxysilane to the deionized water is 1;
(2) Adding MES buffer solution into the copper-chromium-based organic metal framework material mixed solution, adjusting the pH of the mixed solution to 5.0-5.5, then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, uniformly mixing, heating to 65-80 ℃, dropwise adding the nano tungsten ditelluride mixed solution while stirring, after completely dropwise adding, continuously stirring for 0.5-1 h, then pouring into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle at 150-180 ℃ for reaction treatment for 8-12 h, and after cooling to room temperature, obtaining reaction mixed solution;
wherein the mass ratio of the mixed liquid of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the nano tungsten ditelluride to the mixed liquid of the copper-chromium-based organic metal framework material is 0.01;
(3) And carrying out vacuum filtration on the reaction mixed liquid, collecting filter residues, washing the filter residues for 3-5 times by using ethanol, washing the filter residues into washing liquid by using distilled water, and then drying the filter residues under a vacuum condition to constant weight to obtain the flame-retardant heat-conducting filler.
The curing temperature of the epoxy resin is 100-180 ℃, and the curing time is 1-3 h.
Example 2
The utility model provides a fire-retardant high heat conduction metal base copper-clad plate of environment-friendly, includes from last circuit layer, heat conduction insulation layer and the metal-based layer that sets gradually down, and heat conduction insulation layer calculates according to part by weight, includes following composition:
100 parts of epoxy resin, 12 parts of flame-retardant heat-conducting filler, 3 parts of curing accelerator and 30 parts of curing agent;
the flame-retardant heat-conducting filler is obtained by compounding nano tungsten ditelluride and a copper-chromium-based organic metal framework material.
The epoxy resin is a mixture of bisphenol A epoxy resin, naphthalene ring epoxy resin and biphenyl epoxy resin, and the weight ratio of the bisphenol A epoxy resin to the naphthalene ring epoxy resin to the biphenyl epoxy resin is 20.
The curing agent is 4,4-diaminodiphenyl sulfone.
The curing accelerator is N, N-dimethylbenzylamine.
The grain diameter of the nano tungsten ditelluride is 5-20 nm, and the grain diameter of the copper-chromium-based organic metal framework material is 300-800 nm.
The preparation method of the copper-chromium-based organic metal framework material comprises the following steps:
s1, weighing copper sulfate, adding the copper sulfate into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a copper sulfate ethanol solution; weighing 2-pyridinecarboxamide and chromium picolinate, adding the weighed materials into absolute ethyl alcohol, and stirring the materials uniformly to obtain an organic-inorganic mixed solution;
wherein in the copper sulfate ethanol solution, the mass ratio of copper sulfate to absolute ethyl alcohol is 1; in the organic-inorganic mixed solution, the mass ratio of the 2-pyridinecarboxamide to the chromium picolinate to the absolute ethyl alcohol is 1;
s2, slowly adding the organic-inorganic mixed solution into a copper sulfate ethanol solution which is continuously stirred at room temperature, stirring at the speed of 500-800 rpm for 8-12 hours after the addition is finished, standing in a shade place for 12-15 hours, filtering, washing the filter residue with ethanol for 3-5 times, drying the washed filter residue at the temperature of 45-65 ℃ to constant weight, and crushing to obtain the copper-chromium-based organic metal framework material;
wherein the mass ratio of the organic-inorganic mixed solution to the copper sulfate ethanol solution is 1.12.
The preparation method of the flame-retardant heat-conducting filler comprises the following steps:
(1) Weighing a copper-chromium-based organic metal framework material, adding the copper-chromium-based organic metal framework material into deionized water, and uniformly stirring and dispersing to obtain a copper-chromium-based organic metal framework material mixed solution; weighing nano tungsten ditelluride, adding the nano tungsten ditelluride into deionized water, adding gamma-aminopropyltriethoxysilane, and performing ultrasonic treatment for 0.5-1 h to obtain a nano tungsten ditelluride mixed solution;
wherein in the mixed solution of the copper-chromium-based organic metal framework material, the mass ratio of the copper-chromium-based organic metal framework material to the deionized water is 1; in the mixed solution of the nano tungsten ditelluride, the mass ratio of the nano tungsten ditelluride, the gamma-aminopropyltriethoxysilane to the deionized water is 1;
(2) Adding MES buffer solution into the copper-chromium-based organic metal framework material mixed solution, adjusting the pH of the mixed solution to 5.0-5.5, then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, uniformly mixing, heating to 65-80 ℃, dropwise adding the nano tungsten ditelluride mixed solution while stirring, after completely dropwise adding, continuously stirring for 0.5-1 h, then pouring into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle at 150-180 ℃ for reaction treatment for 8-12 h, and after cooling to room temperature, obtaining reaction mixed solution;
wherein the mass ratio of the mixed liquid of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the nano tungsten ditelluride to the mixed liquid of the copper-chromium-based organic metal framework material is 0.01;
(3) And carrying out vacuum filtration on the reaction mixed liquid, collecting filter residues, washing the filter residues for 3-5 times by using ethanol, washing the filter residues into washing liquid by using distilled water, and then drying the filter residues under a vacuum condition to constant weight to obtain the flame-retardant heat-conducting filler.
The curing temperature of the epoxy resin is 100-180 ℃, and the curing time is 1-3 h.
Example 3
The utility model provides a fire-retardant high heat conduction metal base copper-clad plate of environment-friendly, includes from last circuit layer, heat conduction insulation layer and the metal-based layer that sets gradually down, and heat conduction insulation layer calculates according to part by weight, includes following composition:
100 parts of epoxy resin, 48 parts of flame-retardant heat-conducting filler, 10 parts of curing accelerator and 50 parts of curing agent;
the flame-retardant heat-conducting filler is obtained by compounding nano tungsten ditelluride and a copper-chromium-based organic metal framework material.
The epoxy resin is a mixture of bisphenol A epoxy resin, naphthalene ring epoxy resin and biphenyl epoxy resin, and the weight ratio of the bisphenol A epoxy resin to the naphthalene ring epoxy resin to the biphenyl epoxy resin is 40.
The curing agent is methyl hexahydrophthalic anhydride.
The curing accelerator is 2,4,6-tris (dimethylaminomethyl) phenol.
The grain diameter of the nano tungsten ditelluride is 5-20 nm, and the grain diameter of the copper-chromium-based organic metal framework material is 300-800 nm.
The preparation method of the copper-chromium-based organic metal framework material comprises the following steps:
s1, weighing copper sulfate, adding the copper sulfate into absolute ethyl alcohol, and stirring the mixture uniformly to obtain a copper sulfate ethanol solution; weighing 2-pyridinecarboxamide and chromium picolinate, adding the weighed materials into absolute ethyl alcohol, and stirring the materials uniformly to obtain an organic-inorganic mixed solution;
wherein in the copper sulfate ethanol solution, the mass ratio of copper sulfate to absolute ethyl alcohol is 1; in the organic-inorganic mixed solution, the mass ratio of the 2-pyridinecarboxamide to the chromium picolinate to the absolute ethyl alcohol is 1;
s2, slowly adding the organic-inorganic mixed solution into a copper sulfate ethanol solution which is continuously stirred at room temperature, stirring at the speed of 500-800 rpm for 8-12 h after the addition is finished, standing in a shade place for 12-15 h, filtering, washing the filter residue for 3-5 times by using ethanol, drying the washed filter residue at the temperature of 45-65 ℃ to constant weight, and crushing to obtain a copper-chromium-based organic metal framework material;
wherein the mass ratio of the organic-inorganic mixed solution to the copper sulfate ethanol solution is 1.24.
The preparation method of the flame-retardant heat-conducting filler comprises the following steps:
(1) Weighing the copper-chromium-based organic metal framework material, adding the copper-chromium-based organic metal framework material into deionized water, and uniformly stirring and dispersing to obtain a copper-chromium-based organic metal framework material mixed solution; weighing nano tungsten ditelluride, adding the nano tungsten ditelluride into deionized water, adding gamma-aminopropyltriethoxysilane, and carrying out ultrasonic treatment for 0.5-1 h to obtain a nano tungsten ditelluride mixed solution;
wherein in the mixed solution of the copper-chromium-based organic metal framework material, the mass ratio of the copper-chromium-based organic metal framework material to the deionized water is 1; in the mixed solution of the nano tungsten ditelluride, the mass ratio of the nano tungsten ditelluride, the gamma-aminopropyltriethoxysilane to the deionized water is 1;
(2) Adding MES buffer solution into the copper-chromium-based organic metal framework material mixed solution, adjusting the pH of the mixed solution to 5.0-5.5, then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, uniformly mixing, heating to 65-80 ℃, dropwise adding the nano tungsten ditelluride mixed solution while stirring, after completely dropwise adding, continuously stirring for 0.5-1 h, then pouring into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle at 150-180 ℃ for reaction treatment for 8-12 h, and after cooling to room temperature, obtaining reaction mixed solution;
wherein the mass ratio of the mixed liquid of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the nano tungsten ditelluride to the mixed liquid of the copper-chromium-based organic metal framework material is 0.01;
(3) And carrying out vacuum filtration on the reaction mixed liquid, collecting filter residues, washing the filter residues for 3-5 times by using ethanol, washing the filter residues into washing liquid by using distilled water, and then drying the filter residues under a vacuum condition to constant weight to obtain the flame-retardant heat-conducting filler.
The curing temperature of the epoxy resin is 100-180 ℃, and the curing time is 1-3 h.
Comparative example
The utility model provides a fire-retardant high heat conduction metal base copper-clad plate of environment-friendly, includes from last circuit layer, heat conduction insulation layer and the metal-based layer that sets gradually down, and heat conduction insulation layer calculates according to part by weight, includes following composition:
100 parts of epoxy resin, 30 parts of flame-retardant heat-conducting filler, 6 parts of curing accelerator and 40 parts of curing agent;
wherein the flame-retardant heat-conducting filler is nano tungsten ditelluride.
The epoxy resin is a mixture of bisphenol A epoxy resin, naphthalene ring epoxy resin and biphenyl epoxy resin, and the weight ratio of the bisphenol A epoxy resin to the naphthalene ring epoxy resin to the biphenyl epoxy resin is 30.
The curing agent is methyl tetrahydrophthalic anhydride.
The curing accelerator is 2,4,6-tris (dimethylaminomethyl) phenol.
The grain diameter of the nano tungsten ditelluride is 5-20 nm.
The curing temperature of the epoxy resin is 100-180 ℃, and the curing time is 1-3 h.
For a more clear description of the present invention, the thermal insulation layers prepared in examples 1 to 3 of the present invention and comparative example were subjected to performance test and comparison, wherein the tensile strength was measured according to the standard GB1042-1979, and the thermal conductivity was measured using a DRH-300 thermal conductivity tester from Shanghai group research and instrumentation Co., ltd, and the results are shown in Table 1.
TABLE 1 comparison of the Properties of different thermally conductive and insulating layers
|
Example 1
|
Example 2
|
Example 3
|
Comparative example
|
Coefficient of thermal conductivity (W/m.K) -1 )
|
2.78
|
2.14
|
3.05
|
0.72
|
Tensile Strength (MPa)
|
103
|
98
|
107
|
82
|
Oxygen index OI (%)
|
32
|
30
|
33
|
28
|
High temperature resistance/DEG C
|
>250
|
>250
|
>250
|
<210 |
As can be seen from table 1, the heat conducting insulating layers prepared in embodiments 1 to 3 of the present invention have good thermal conductivity, mechanical properties, flame retardancy, and high temperature resistance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.