CN111607058B - High-thermal-conductivity thermoplastic imidized polyurethane material and preparation method thereof - Google Patents
High-thermal-conductivity thermoplastic imidized polyurethane material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polyurethane materials, and discloses a high-thermal-conductivity thermoplastic imidized polyurethane material which comprises the following formula raw materials and components: the modified boron nitride supported carbon nanotube comprises a modified boron nitride supported carbon nanotube, polytetrahydrofuran ether glycol, 1, 5-diisocyanato naphthalene, a chain extender, 1, 4-butanediol and a catalyst. The thermoplastic imidization polyurethane material with high heat conductivity takes 1, 5-diisocyanato naphthalene containing naphthyl groups as a monomer and perylene tetracarboxylic dianhydride containing naphthyl groups as a chain extender to react with isocyanate groups of polyurethane, chemically stable imide groups and naphthyl groups are introduced into a polyurethane molecular chain, the initial decomposition temperature of the polyurethane is improved, the thermal stability of the polyurethane material is enhanced, nano boron nitride is deposited on the surface of an L-tryptophan graft modified carbon nano tube, and the L-tryptophan improves the dispersibility and compatibility of the carbon nano tube and boron nitride in the polyurethane and enhances the heat conductivity of the polyurethane material.
Description
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a high-heat-conductivity thermoplastic imidized polyurethane material and a preparation method thereof.
Background
Polyurethane is a high molecular material, mainly formed by polymerization of diisocyanate and polyol, and is divided into polyester polyurethane and polyether polyurethane, wherein soft polyurethane has a thermoplastic linear structure, has strong chemical resistance, good rebound resilience and excellent mechanical properties, can be used as a packaging material, a sound insulation material, a filtering material and the like, hard polyurethane is light in weight, good in heat insulation performance, excellent in electrical property and easy to process, is mainly applied to the fields of building materials, automobile machinery, aviation industry and the like, polyurethane products mainly comprise polyurethane plastics, polyurethane films, polyurethane fibers, polyurethane elastomers and the like, and has wide application in the fields of household appliances, buildings, transportation and the like.
However, the existing polyurethane material has poor heat conductivity and is not high-temperature resistant, the polyurethane material is easy to deform at high temperature, the mechanical property is greatly reduced, the polyimide containing imide groups has high thermal stability and stable mechanical property, the imide groups can be introduced into a polyurethane molecular chain, and the heat resistance and the thermal stability of the polyurethane are improved.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a high-heat-conductivity thermoplastic imidized polyurethane material and a preparation method thereof, and solves the problem that the polyurethane material has poor heat conductivity and heat resistance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a high-thermal-conductivity thermoplastic imidized polyurethane material comprises the following formula raw materials in parts by weight and components, and is characterized in that: 5-24 parts of modified boron nitride loaded carbon nano tube, 36-42 parts of polytetrahydrofuran ether glycol, 30-34 parts of 1, 5-diisocyanatonaphthalene, 5-10 parts of chain extender, 5-8 parts of 1, 4-butanediol and 0.2-1 part of catalyst.
Preferably, the chain extender is perylene tetracarboxylic dianhydride.
Preferably, the catalyst is dibutyltin dilaurate.
Preferably, the preparation method of the boron nitride modified carbon nanotube comprises the following steps:
(1) adding distilled water and aminated carbon nano tubes into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment for 30-60min, adding distilled water, L-tryptophan and sodium hydroxide into a beaker, carrying out ultrasonic dispersion treatment for 30-60min on the solution, pouring the solution in the beaker into the reaction bottle, carrying out ultrasonic dispersion treatment for 20-40min, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60-80 ℃, stirring at a constant speed for activation for 2-4h, transferring the solution into an automatic hydrothermal reaction kettle, heating to 120-.
(2) Adding the modified carbon nano tube and the nano boron nitride into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment for 1-2h at the temperature of 40-80 ℃, wherein the ultrasonic frequency is 25-35KHz, carrying out vacuum drying on the solution to remove the solvent, and fully drying to prepare the boron nitride modified carbon nano tube.
Preferably, the mass ratio of the carbon nano tube to the L-tryptophan to the sodium hydroxide is 1:1.2-1.8: 1.5-2.
Preferably, the mass ratio of the modified carbon nanotube to the nano boron nitride is 1: 2.5-4.
Preferably, automatic hydrothermal reaction kettle include the reation kettle lid swing joint have the piston and fixture block swing joint piston fixedly connected with spring leaf and reation kettle body fixed connection, the external fixedly connected with heat preservation of reation kettle body the left side below of reation kettle body is provided with the reation kettle filter membrane, reation kettle body right side below be provided with the reation kettle baffle reation kettle body below and filtrating kettle body swing joint, filtrating kettle body upper left side is provided with filtrating kettle baffle, filtrating kettle body upper right side is provided with filtrating kettle body filter membrane.
Preferably, the preparation method of the high thermal conductive thermoplastic imidized polyurethane material comprises the following steps:
(1) introducing nitrogen into a reaction bottle to discharge air, adding N-methyl pyrrolidone solvent, 5-24 parts of modified boron nitride loaded carbon nano tube, 36-42 parts of polytetrahydrofuran ether glycol and 30-34 parts of 1, 5-diisocyanatonaphthalene, stirring and dissolving, adding 0.2-1 part of catalyst dibutyltin dilaurate, placing the reaction bottle in an oil bath pot, heating to 35-55 ℃, stirring at a constant speed for reaction for 1-3h, adding 5-10 parts of chain extender perylenetetracarboxylic dianhydride, heating to 80-90 ℃, stirring at a constant speed for reaction for 2-3h, heating to 130-140 ℃, stirring at a constant speed for reaction for 2-4h, cooling to 35-50 ℃, adding 5-8 parts of 1, 4-butanediol, stirring at a constant speed for reaction for 1-2h, pouring the solution into a film forming mold, and (3) placing the mixture in an oven, heating the mixture to 80-100 ℃, and drying the solvent to solidify and form a film to prepare the high-thermal-conductivity thermoplastic imidized polyurethane material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the thermoplastic imidization polyurethane material with high thermal conductivity takes 1, 5-diisocyanato naphthalene containing naphthyl groups as a monomer and perylene tetracarboxylic dianhydride containing naphthyl groups as a chain extender to react with isocyanate groups of polyurethane, so that imide groups and naphthyl groups with stable chemical properties are successfully introduced into a polyurethane molecular chain, the initial decomposition temperature of the polyurethane is greatly improved, the thermal stability of the polyurethane material is enhanced, and the polyurethane material can still maintain good mechanical properties such as toughness and strength at high temperature.
According to the high-thermal-conductivity thermoplastic imidization polyurethane material, the carbon nano tube and boron nitride have excellent thermal conductivity, active carboxyl of L-tryptophan and amino in the aminated carbon nano tube are subjected to amidation reaction, the L-tryptophan is grafted and modified with the carbon nano tube, the modified carbon nano tube is used as a matrix, nano boron nitride is deposited on the surface of the carbon nano tube, polyurethane is generated outside the carbon nano tube modified by the boron nitride through an in-situ polymerization method, an amino group in the L-tryptophan and an imino group and an amido group in the polyurethane form a hydrogen bond, and a benzene ring structure of the L-tryptophan has similar compatibility with a naphthyl group, so that the dispersibility and compatibility of the carbon nano tube and the boron nitride in the polyurethane are greatly improved, and the thermal conductivity of the polyurethane material is enhanced.
Drawings
FIG. 1 is a schematic front view of a heat-insulating structure of an ultrasonic processor;
fig. 2 is a schematic diagram of a top cover adjusting ring structure.
1. A reaction kettle cover; 2. a piston; 3. a clamping block; 4. a spring plate; 5. a reaction kettle body; 6. a heat-insulating layer; 7. a baffle plate of the reaction kettle; 8. filtering the membrane in the reaction kettle; 9. a filtrate kettle body; 10. a filtrate kettle baffle; 11. and (5) filtering the filtrate by a filter membrane.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a high-thermal-conductivity thermoplastic imidized polyurethane material comprises the following formula raw materials in parts by weight and components, and is characterized in that: 5-24 parts of modified boron nitride loaded carbon nano tube, 36-42 parts of polytetrahydrofuran ether glycol, 30-34 parts of 1, 5-naphthalene diisocyanate, 5-10 parts of chain extender, 5-8 parts of 1, 4-butanediol and 0.2-1 part of catalyst, wherein the chain extender is perylene tetracarboxylic dianhydride, and the catalyst is dibutyltin dilaurate.
The preparation method of the boron nitride modified carbon nanotube comprises the following steps:
(1) adding distilled water and aminated carbon nanotubes into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 30-60min, adding distilled water, L-tryptophan and sodium hydroxide into a beaker, wherein the mass ratio of the carbon nanotubes to the L-tryptophan to the sodium hydroxide is 1:1.2-1.8:1.5-2, performing ultrasonic dispersion treatment for 30-60min, pouring the solution in the beaker into the reaction bottle, performing ultrasonic dispersion treatment for 20-40min, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60-80 ℃, uniformly stirring and activating for 2-4h, transferring the solution into an automatic hydrothermal reaction kettle, wherein the automatic hydrothermal reaction kettle comprises a reaction kettle cover, a piston is movably connected with the reaction kettle cover, the piston is movably connected with a clamping block, the piston is fixedly connected with a spring piece, and the spring piece is fixedly connected with the reaction kettle body, the outer layer of the reaction kettle body is fixedly connected with a heat preservation layer, a reaction kettle filter membrane is arranged on the left lower side of the reaction kettle body, a reaction kettle baffle is arranged on the right lower side of the reaction kettle body, the lower side of the reaction kettle body is movably connected with the filtrate kettle body, a filtrate kettle baffle is arranged on the left upper side of the filtrate kettle body, a filtrate kettle filter membrane is arranged on the right upper side of the filtrate kettle body, the reaction kettle is heated to 120 ℃ plus 140 ℃, the reaction is carried out for 15-25h, the solution is cooled to the room temperature, the solvent is removed by filtration, the solid product is washed by distilled water and fully dried, and the L-tryptophan esterified modified carbon nanotube is prepared.
(2) Adding the modified carbon nano tube and the nano boron nitride into a reaction bottle in a mass ratio of 1:2.5-4, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1-2h at 40-80 ℃, wherein the ultrasonic frequency is 25-35KHz, performing vacuum drying on the solution to remove the solvent, and fully drying to prepare the boron nitride modified carbon nano tube.
The preparation method of the thermoplastic imidized polyurethane material with high thermal conductivity comprises the following steps:
(1) introducing nitrogen into a reaction bottle to discharge air, adding N-methyl pyrrolidone solvent, 5-24 parts of modified boron nitride loaded carbon nano tube, 36-42 parts of polytetrahydrofuran ether glycol and 30-34 parts of 1, 5-diisocyanatonaphthalene, stirring and dissolving, adding 0.2-1 part of catalyst dibutyltin dilaurate, placing the reaction bottle in an oil bath pot, heating to 35-55 ℃, stirring at a constant speed for reaction for 1-3h, adding 5-10 parts of chain extender perylenetetracarboxylic dianhydride, heating to 80-90 ℃, stirring at a constant speed for reaction for 2-3h, heating to 130-140 ℃, stirring at a constant speed for reaction for 2-4h, cooling to 35-50 ℃, adding 5-8 parts of 1, 4-butanediol, stirring at a constant speed for reaction for 1-2h, pouring the solution into a film forming mold, and (3) placing the mixture in an oven, heating the mixture to 80-100 ℃, and drying the solvent to solidify and form a film to prepare the high-thermal-conductivity thermoplastic imidized polyurethane material.
Example 1
(1) Preparing a modified carbon nanotube component 1: adding distilled water and aminated carbon nanotubes into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 30min, adding distilled water, L-tryptophan and sodium hydroxide into a beaker, wherein the mass ratio of the carbon nanotubes to the L-tryptophan to the sodium hydroxide is 1:1.2:1.5, performing ultrasonic dispersion treatment for 30min, pouring the solution in the beaker into the reaction bottle, performing ultrasonic dispersion treatment for 20min, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60 ℃, stirring at a constant speed for activation for 2h, transferring the solution into an automatic hydrothermal reaction kettle, wherein the automatic hydrothermal reaction kettle comprises a reaction kettle cover, the reaction kettle cover is movably connected with a piston, the piston is movably connected with a clamping block, the piston is fixedly connected with a spring leaf, the spring leaf is fixedly connected with a reaction kettle body, the outer layer of the reaction kettle body is fixedly connected with a heat insulation layer, and a reaction kettle filter membrane is arranged below the reaction kettle body, a reaction kettle baffle is arranged at the right lower part of the reaction kettle body, the lower part of the reaction kettle body is movably connected with the filtrate kettle body, a filtrate kettle baffle is arranged at the left upper part of the filtrate kettle body, a filtrate kettle filter membrane is arranged at the right upper part of the filtrate kettle body, the reaction is carried out for 15 hours after the reaction is carried out when the temperature is increased to 120 ℃, the solution is cooled to the room temperature, the solvent is removed by filtration, the solid product is washed by distilled water and fully dried, and the L-tryptophan esterified modified carbon nano tube component 1 is prepared.
(2) Preparing a boron nitride modified carbon nanotube component 1: adding the modified carbon nanotube component 1 and the nano boron nitride into a reaction bottle in a mass ratio of 1:2.5, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1h at 40 ℃, wherein the ultrasonic frequency is 25KHz, performing vacuum drying on the solution to remove the solvent, and fully drying to prepare the boron nitride modified carbon nanotube component 1.
(3) Preparation of a highly thermally conductive thermoplastic imidized polyurethane material 1: introducing nitrogen into a reaction bottle to discharge air, adding N-methyl pyrrolidone solvent, 24 parts of modified boron nitride loaded carbon nanotube component 1, 36 parts of polytetrahydrofuran ether glycol and 30 parts of 1, 5-naphthalene diisocyanate, stirring and dissolving, adding 0.2 part of catalyst dibutyltin dilaurate, placing the reaction bottle in an oil bath pot, heating to 35 ℃, stirring at a constant speed for reaction for 1 hour, adding 5 parts of chain extender perylenetetracarboxylic dianhydride, heating to 80 ℃, stirring at a constant speed for reaction for 2 hours, heating to 130 ℃, stirring at a constant speed for reaction for 2 hours, cooling to 35 ℃, adding 5 parts of 1, 4-butanediol, stirring at a constant speed for reaction for 1 hour, pouring the solution into a film forming mold, placing in a drying oven, heating to 80 ℃, drying the solvent to solidify into a film, and preparing the high-thermal-conductivity thermoplastic imidized polyurethane material 1.
Example 2
(1) Preparing a modified carbon nanotube component 2: adding distilled water and aminated carbon nanotubes into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 60min, adding distilled water, L-tryptophan and sodium hydroxide into a beaker, wherein the mass ratio of the carbon nanotubes to the L-tryptophan to the sodium hydroxide is 1:1.8:1.5, performing ultrasonic dispersion treatment for 30min, pouring the solution in the beaker into the reaction bottle, performing ultrasonic dispersion treatment for 40min, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60 ℃, stirring at a constant speed for activation for 4h, transferring the solution into an automatic hydrothermal reaction kettle, wherein the automatic hydrothermal reaction kettle comprises a reaction kettle cover, the reaction kettle cover is movably connected with a piston, the piston is movably connected with a clamping block, the piston is fixedly connected with a spring leaf, the spring leaf is fixedly connected with a reaction kettle body, the outer layer of the reaction kettle body is fixedly connected with a heat insulation layer, and a reaction kettle filter membrane is arranged below the reaction kettle body, a reaction kettle baffle is arranged at the right lower part of the reaction kettle body, the lower part of the reaction kettle body is movably connected with the filtrate kettle body, a filtrate kettle baffle is arranged at the left upper part of the filtrate kettle body, a filtrate kettle filter membrane is arranged at the right upper part of the filtrate kettle body, the reaction is carried out for 15 hours after the reaction is carried out for heating to 140 ℃, the solution is cooled to the room temperature, the solvent is removed by filtration, the solid product is washed by distilled water and fully dried, and the L-tryptophan esterified modified carbon nano tube component 2 is prepared.
(2) Preparing a boron nitride modified carbon nanotube component 2: adding the modified carbon nanotube component 2 and the nano boron nitride into a reaction bottle in a mass ratio of 1:2.5, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2 hours at 40 ℃, wherein the ultrasonic frequency is 35KHz, performing vacuum drying on the solution to remove the solvent, and fully drying to prepare the boron nitride modified carbon nanotube component 2.
(3) Preparation of a highly thermally conductive thermoplastic imidized polyurethane material 2: introducing nitrogen into a reaction bottle to discharge air, adding N-methyl pyrrolidone solvent, 19 parts of modified boron nitride loaded carbon nanotube component 2, 37.5 parts of polytetrahydrofuran ether glycol and 31 parts of 1, 5-diisocyanatonaphthalene, stirring and dissolving, adding 0.4 part of catalyst dibutyltin dilaurate, placing the reaction bottle in an oil bath pot, heating to 55 ℃, stirring at a constant speed for reaction for 3 hours, adding 6.5 chain extender perylenetetracarboxylic dianhydride, heating to 80 ℃, stirring at a constant speed for reaction for 2 hours, heating to 140 ℃, stirring at a constant speed for reaction for 2 hours, cooling to 50 ℃, adding 6 parts of 1, 4-butanediol, stirring at a constant speed for reaction for 1 hour, pouring the solution into a film forming mold, placing in an oven, heating to 80 ℃, drying the solvent and curing to form a film to prepare the high-thermal-conductivity thermoplastic imidized polyurethane material 2.
Example 3
(1) Preparing a modified carbon nanotube component 3: adding distilled water and aminated carbon nanotubes into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument for ultrasonic dispersion treatment for 40min, adding distilled water, L-tryptophan and sodium hydroxide into a beaker, wherein the mass ratio of the carbon nanotubes to the L-tryptophan to the sodium hydroxide is 1:1.5:1.8, performing ultrasonic dispersion treatment for 50min, pouring the solution in the beaker into the reaction bottle for ultrasonic dispersion treatment for 30min, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, stirring at a constant speed for activation for 3h, transferring the solution into an automatic hydrothermal reaction kettle, wherein the automatic hydrothermal reaction kettle comprises a reaction kettle cover, a piston is movably connected with the reaction kettle cover, the piston is movably connected with a clamping block, a spring leaf is fixedly connected with the piston, the spring leaf is fixedly connected with the reaction kettle body, a heat insulation layer is fixedly connected with the outer layer of the reaction kettle body, A reaction kettle filter membrane is arranged on the left lower side of the reaction kettle body, a reaction kettle baffle is arranged on the right lower side of the reaction kettle body, the lower side of the reaction kettle body is movably connected with the filtrate kettle body, a filtrate kettle baffle is arranged on the left upper side of the filtrate kettle body, a filtrate kettle filter membrane is arranged on the right upper side of the filtrate kettle body, the reaction kettle body is heated to 130 ℃, the reaction is carried out for 20 hours, the solution is cooled to room temperature, the solvent is removed by filtration, the solid product is washed by distilled water and fully dried, and the L-tryptophan esterified modified carbon nanotube component 3 is prepared.
(2) Preparing a boron nitride modified carbon nanotube component 3: adding the modified carbon nanotube component 3 and the nano boron nitride into a reaction bottle in a mass ratio of 1:3, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1.5h at 60 ℃, wherein the ultrasonic frequency is 30KHz, performing vacuum drying on the solution to remove the solvent, and fully drying to prepare the boron nitride modified carbon nanotube component 3.
(3) Preparation of a highly thermally conductive thermoplastic imidized polyurethane material 3: introducing nitrogen into a reaction bottle to discharge air, adding N-methyl pyrrolidone solvent, 15 parts of modified boron nitride loaded carbon nanotube component 3, 39 parts of polytetrahydrofuran ether glycol and 32 parts of 1, 5-diisocyanatonaphthalene, stirring and dissolving, adding 0.6 part of catalyst dibutyltin dilaurate, placing the reaction bottle in an oil bath pot, heating to 45 ℃, uniformly stirring and reacting for 2h, adding 7.5 chain extender perylenetetracarboxylic dianhydride, heating to 85 ℃, uniformly stirring and reacting for 2.5h, heating to 135 ℃, uniformly stirring and reacting for 3h, cooling to 40 ℃, adding 6.5 parts of 1, 4-butanediol, uniformly stirring and reacting for 1.5h, pouring the solution into a film forming mold, placing in an oven, heating to 90 ℃, drying the solvent and curing to form a film, thus preparing the high-thermal-conductivity thermoplastic imidized polyurethane material 3.
Example 4
(1) Preparing a modified carbon nanotube component 4: adding distilled water and aminated carbon nanotubes into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 45min, adding distilled water, L-tryptophan and sodium hydroxide into a beaker, wherein the mass ratio of the carbon nanotubes to the L-tryptophan to the sodium hydroxide is 1:1.8:1.5, performing ultrasonic dispersion treatment for 60min, pouring the solution in the beaker into the reaction bottle, performing ultrasonic dispersion treatment for 20min, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, stirring at a constant speed for activation for 2h, transferring the solution into an automatic hydrothermal reaction kettle, wherein the automatic hydrothermal reaction kettle comprises a reaction kettle cover, the reaction kettle cover is movably connected with a piston, the piston is movably connected with a clamping block, the piston is fixedly connected with a spring leaf, the spring leaf is fixedly connected with a reaction kettle body, the outer layer of the reaction kettle body is fixedly connected with a heat insulation layer, and a reaction kettle filter membrane is arranged below the reaction kettle body, a reaction kettle baffle is arranged at the right lower part of the reaction kettle body, the lower part of the reaction kettle body is movably connected with the filtrate kettle body, a filtrate kettle baffle is arranged at the left upper part of the filtrate kettle body, a filtrate kettle filter membrane is arranged at the right upper part of the filtrate kettle body, the reaction is carried out for 25 hours after the reaction is carried out when the temperature is 140 ℃, the solution is cooled to the room temperature, the solvent is removed by filtration, the solid product is washed by distilled water and fully dried, and the L-tryptophan esterified modified carbon nano tube component 4 is prepared.
(2) Preparing a boron nitride modified carbon nanotube component 4: adding the modified carbon nanotube component 4 and the nano boron nitride into a reaction bottle in a mass ratio of 1:2.5, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2 hours at 40 ℃, wherein the ultrasonic frequency is 35KHz, performing vacuum drying on the solution to remove the solvent, and fully drying to prepare the boron nitride modified carbon nanotube component 4.
(3) Preparation of a highly thermally conductive thermoplastic imidized polyurethane material 4: introducing nitrogen into a reaction bottle to discharge air, adding N-methyl pyrrolidone solvent, 9 parts of modified boron nitride loaded carbon nanotube component 4, 41 parts of polytetrahydrofuran ether glycol and 33 parts of 1, 5-diisocyanatonaphthalene, stirring and dissolving, adding 0.8 part of catalyst dibutyltin dilaurate, placing the reaction bottle in an oil bath pot, heating to 55 ℃, stirring at a constant speed for reaction for 3 hours, adding 9 chain extender perylenetetracarboxylic dianhydride, heating to 80 ℃, stirring at a constant speed for reaction for 2 hours, heating to 140 ℃, stirring at a constant speed for reaction for 2 hours, cooling to 50 ℃, adding 7 parts of 1, 4-butanediol, stirring at a constant speed for reaction for 2 hours, pouring the solution into a film forming mold, placing in a drying oven, heating to 100 ℃, drying the solvent to solidify into a film, and preparing the high-thermal-conductivity thermoplastic imidized polyurethane material 4.
Example 5
(1) Preparing a modified carbon nanotube component 5: adding distilled water and aminated carbon nanotubes into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 60min, adding distilled water, L-tryptophan and sodium hydroxide into a beaker, wherein the mass ratio of the carbon nanotubes to the L-tryptophan to the sodium hydroxide is 1:1.8:2, performing ultrasonic dispersion treatment for 60min, pouring the solution in the beaker into the reaction bottle, performing ultrasonic dispersion treatment for 40min, placing the reaction bottle into a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed for activation for 4h, transferring the solution into an automatic hydrothermal reaction kettle, wherein the automatic hydrothermal reaction kettle comprises a reaction kettle cover, a piston is movably connected with the reaction kettle cover, the piston is movably connected with a fixture block, the piston is fixedly connected with a spring leaf, the spring leaf is fixedly connected with the reaction kettle body, an insulating layer is fixedly connected to the outer layer of the reaction kettle, and a reaction kettle filter membrane is arranged below the left of the reaction kettle body, a reaction kettle baffle is arranged at the right lower part of the reaction kettle body, the lower part of the reaction kettle body is movably connected with the filtrate kettle body, a filtrate kettle baffle is arranged at the left upper part of the filtrate kettle body, a filtrate kettle filter membrane is arranged at the right upper part of the filtrate kettle body, the reaction is carried out for 25 hours after the reaction is carried out when the temperature is 140 ℃, the solution is cooled to the room temperature, the solvent is removed by filtration, the solid product is washed by distilled water and fully dried, and the L-tryptophan esterified modified carbon nano tube component 5 is prepared.
(2) Preparing a boron nitride modified carbon nanotube component 5: adding the modified carbon nanotube component 5 and the nano boron nitride into a reaction bottle in a mass ratio of 1:4, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2 hours at 80 ℃, wherein the ultrasonic frequency is 35KHz, performing vacuum drying on the solution to remove the solvent, and fully drying to prepare the boron nitride modified carbon nanotube component 5.
(3) Preparation of a highly thermally conductive thermoplastic imidized polyurethane material 5: introducing nitrogen into a reaction bottle to discharge air, adding N-methyl pyrrolidone solvent, 5 parts of modified boron nitride loaded carbon nanotube component 5, 42 parts of polytetrahydrofuran ether glycol and 34 parts of 1, 5-naphthalene diisocyanate, stirring and dissolving, adding 1 part of catalyst dibutyltin dilaurate, placing the reaction bottle in an oil bath pot, heating to 55 ℃, uniformly stirring and reacting for 3 hours, adding 10 chain extender perylene tetracarboxylic dianhydride, heating to 90 ℃, uniformly stirring and reacting for 3 hours, heating to 140 ℃, uniformly stirring and reacting for 4 hours, cooling to 50 ℃, adding 8 parts of 1, 4-butanediol, uniformly stirring and reacting for 2 hours, pouring the solution into a film forming mold, placing in a drying oven, heating to 80 ℃, drying the solvent to solidify into a film, and preparing the high-thermal-conductivity thermoplastic imidized polyurethane material 5.
The thermal conductivity of the highly thermally conductive thermoplastic imidized polyurethane materials of examples 1-5 were tested using a BDR-003A material thermal conductivity coefficient tester, with the test standard GBT 29288-2012.
In summary, the thermoplastic imidization polyurethane material with high thermal conductivity takes 1, 5-diisocyanato naphthalene containing naphthyl group as a monomer, perylene tetracarboxylic dianhydride containing naphthyl group as a chain extender, and reacts with isocyanic acid group of polyurethane, so that imide group and naphthyl group with stable chemical property are successfully introduced into polyurethane molecular chain, the initial decomposition temperature of polyurethane is greatly improved, the thermal stability of polyurethane material is enhanced, and the polyurethane material can still keep good mechanical properties such as toughness and strength at high temperature.
The carbon nano tube and the boron nitride have excellent heat-conducting property, active carboxyl of L-tryptophan and amino in the aminated carbon nano tube are subjected to amidation reaction to graft and modify the L-tryptophan, the modified carbon nano tube is used as a matrix, the nano boron nitride is deposited on the surface of the carbon nano tube, polyurethane is generated outside the boron nitride modified carbon nano tube through an in-situ polymerization method, an amino group in the L-tryptophan and an imino group and an amido group in the polyurethane form a hydrogen bond, and a benzene ring structure of the L-tryptophan has similar compatibility with a naphthyl group, so that the dispersibility and compatibility of the carbon nano tube and the boron nitride in the polyurethane are greatly improved, and the heat-conducting property of the polyurethane material is enhanced.
Claims (4)
1. A high-thermal-conductivity thermoplastic imidized polyurethane material comprises the following formula raw materials in parts by weight and components, and is characterized in that: 5-24 parts of modified boron nitride loaded carbon nano tube, 36-42 parts of polytetrahydrofuran ether glycol, 30-34 parts of 1, 5-diisocyanatonaphthalene, 5-10 parts of chain extender, 5-8 parts of 1, 4-butanediol and 0.2-1 part of catalyst; the chain extender is perylene tetracarboxylic dianhydride; the catalyst is dibutyltin dilaurate; the preparation method of the modified boron nitride loaded carbon nanotube comprises the following steps:
(1) adding distilled water and aminated carbon nano tubes into a reaction bottle, carrying out ultrasonic dispersion treatment on the solution for 30-60min, adding distilled water, L-tryptophan and sodium hydroxide into a beaker, carrying out ultrasonic dispersion treatment on the solution for 30-60min, pouring the solution in the beaker into the reaction bottle, carrying out ultrasonic dispersion treatment for 20-40min, heating the solution to 60-80 ℃, stirring and activating at a constant speed for 2-4h, transferring the solution into an automatic hydrothermal reaction kettle, heating to 140 ℃ for 120 plus materials, reacting for 15-25h, removing the solvent from the solution, washing a solid product and drying to prepare the L-tryptophan esterified modified carbon nano tubes;
(2) adding the modified carbon nano tube and the nano boron nitride into a reaction bottle, performing ultrasonic dispersion treatment on the solution at 40-80 ℃ for 1-2h, wherein the ultrasonic frequency is 25-35KHz, removing the solvent from the solution, and drying to prepare the modified boron nitride loaded carbon nano tube; automatic hydrothermal reaction kettle includes the reation kettle lid swing joint have the piston with fixture block swing joint piston fixedly connected with spring leaf spring and reation kettle body fixed connection, the external fixedly connected with heat preservation of reation kettle body the left side below of reation kettle body is provided with the reation kettle filter membrane, reation kettle body right side below is provided with the reation kettle baffle reation kettle body below and filtrating kettle body swing joint, filtrating kettle body upper left side is provided with filtrating kettle baffle, filtrating kettle body upper right side is provided with filtrating kettle filter membrane.
2. The highly thermally conductive thermoplastic imidized polyurethane material according to claim 1, wherein: the mass ratio of the carbon nano tube to the L-tryptophan to the sodium hydroxide is 1:1.2-1.8: 1.5-2.
3. The highly thermally conductive thermoplastic imidized polyurethane material according to claim 1, wherein: the mass ratio of the modified carbon nano tube to the nano boron nitride is 1: 2.5-4.
4. The highly thermally conductive thermoplastic imidized polyurethane material according to claim 1, wherein: the preparation method of the high-thermal-conductivity thermoplastic imidized polyurethane material comprises the following steps:
introducing nitrogen into a reaction bottle to discharge air, adding an N-methyl pyrrolidone solvent, 5-24 parts of modified boron nitride loaded carbon nano tube, 36-42 parts of polytetrahydrofuran ether glycol and 30-34 parts of 1, 5-diisocyanatonaphthalene, stirring and dissolving, adding 0.2-1 part of catalyst dibutyltin dilaurate, heating the solution to 35-55 ℃, reacting for 1-3h, adding 5-10 parts of chain extender perylenetetracarboxylic dianhydride, raising the temperature to 80-90 ℃, reacting for 2-3h, raising the temperature to 130-, the thermoplastic imidized polyurethane material with high thermal conductivity is prepared.
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