CN110684232A - TPU (thermoplastic polyurethane) foamed bead with conductive surface coating and preparation method and application thereof - Google Patents

TPU (thermoplastic polyurethane) foamed bead with conductive surface coating and preparation method and application thereof Download PDF

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CN110684232A
CN110684232A CN201910959389.5A CN201910959389A CN110684232A CN 110684232 A CN110684232 A CN 110684232A CN 201910959389 A CN201910959389 A CN 201910959389A CN 110684232 A CN110684232 A CN 110684232A
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tpu
beads
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expanded beads
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CN110684232B (en
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戴成章
戴尧
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Shanghai Yucheng Polymer Material Co Ltd
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Shanghai Yucheng Polymer Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/12—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic in rotating drums
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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  • Health & Medical Sciences (AREA)
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Abstract

The invention discloses a TPU foaming bead with a conductive surface coating, which comprises the following components: (1) TPU expanded beads; and (2) spraying and coating the aqueous polyurethane solution containing the carbon nano tube and the graphene on the surface of the TPU foamed bead to form an aqueous polyurethane conductive coating with the thickness of 10-200 mu m; the TPU foamed beads are prepared by adopting a kettle internal gas impregnation method, and the surfaces of the TPU foamed beads are subjected to ultrasonic wave surface cleaning and degreasing and low-temperature plasma activation treatment; the aqueous polyurethane solution comprises: the carbon nanotube-based composite material comprises waterborne polyurethane, carbon nanotube waterborne slurry, graphene waterborne slurry, a waterborne antioxidant, a cross-linking agent and deionized water. The TPU foamed bead with the conductive surface coating has uniform conductivity and antistatic property, stable static dissipative property and green and environment-friendly preparation process.

Description

TPU (thermoplastic polyurethane) foamed bead with conductive surface coating and preparation method and application thereof
Technical Field
The invention relates to the field of high polymer materials, and particularly relates to TPU (thermoplastic polyurethane) foamed beads with a conductive surface coating, and a preparation method and application thereof.
Background
The thermoplastic polyurethane TPU elastomer has the advantages of good rebound resilience, wear resistance, low compression set, low temperature resistance, good mechanical property and the like, is mainly applied to the shoe material industry, and also applied to a plurality of fields such as runways, helmets, logistics packaging materials, new home materials, educational equipment, sporting goods, automotive interiors and the like, and has great development potential.
However, thermoplastic polyurethane TPU materials are easily triboelectrically charged due to their high electrical insulation properties, but in some locations in the modern electronics high-end manufacturing industry, it is required to impart excellent static dissipative properties to the materials.
At present, adding a conductive agent into a polymer matrix is one of the main methods for preparing a high-molecular conductive composite material. In order to make a polymer material have excellent static electricity dissipation and certain conductivity, a good conductive network needs to be formed in the polymer material, and the addition amount of a general conductive agent is large, so that the physical properties of a polymer matrix are greatly changed, and therefore, the reduction of the addition amount of the conductive agent is a main direction for developing a polymer antistatic and conductive composite material. The carbon nano tube and the graphene are novel carbon conductive fillers which are rapidly developed in recent years, have the advantages of small addition amount, small influence on the physical properties and the foaming performance of matrix resin and the like, but have high price, and if the carbon nano tube and the graphene are added into the matrix resin foamed by the TPU, the cost is high, and the carbon nano tube and the graphene are not easy to disperse uniformly.
Disclosure of Invention
The invention aims to solve the problems and provides TPU foamed beads with conductive surface coatings, a preparation method and application thereof, wherein the TPU foamed beads are uniform in conductivity and antistatic property, stable in static dissipative property and green and environment-friendly in preparation process.
The purpose of the invention is realized as follows:
the invention relates to a surface coating conductive TPU foamed bead, which comprises the following components:
(1) TPU expanded beads; and
(2) spraying an aqueous polyurethane solution containing carbon nanotubes and graphene on the surface of the TPU foamed beads to form an aqueous polyurethane conductive coating with the thickness of 10-200 mu m;
the TPU foamed beads are prepared by adopting a kettle internal gas impregnation method, and the surfaces of the TPU foamed beads are subjected to ultrasonic wave surface cleaning and degreasing and low-temperature plasma activation treatment;
the aqueous polyurethane solution comprises: the carbon nanotube-based composite material comprises waterborne polyurethane, carbon nanotube waterborne slurry, graphene waterborne slurry, a waterborne antioxidant, a cross-linking agent and deionized water.
The waterborne polyurethane in the TPU foamed beads with the conductive surface coatings is carboxyl type thermoplastic waterborne polyurethane emulsion.
The addition amount of the carbon nano tubes and the graphene in the TPU foamed beads with the conductive surface coating is 3.0-7.0 wt% of the total amount of the conductive coating of the TPU foamed beads, and the addition amount ratio of the carbon nano tubes to the graphene is 4: 1.
the aqueous antioxidant in the surface coating conductive TPU foamed bead is a dispersion containing hindered phenol antioxidant.
The aqueous antioxidant in the surface coating conductive TPU foaming bead is aqueous antioxidant dispersion liquid containing triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, wherein the amount of the aqueous antioxidant is 0.5-5% of the solid amount of the aqueous polyurethane.
The cross-linking agent in the conductive TPU foamed bead of the surface coating adopts an aziridine type cross-linking agent, the cross-linking agent is used for improving the water resistance of the aqueous polyurethane coating, but the cross-linking degree needs to be controlled, so that the aqueous polyurethane coating coated on the surface of the TPU foamed bead after drying does not lose the thermal bonding capability, and the addition amount of the cross-linking agent is 0.05-2% of the mass percent of the aqueous polyurethane emulsion.
The solid content of the aqueous polyurethane solution containing the carbon nano tube and the graphene in the TPU foamed bead with the conductive surface coating is 1-20%.
In the TPU foamed beads with the conductive surface coating, the specific gravity of the TPU foamed bead surface coating before spraying the waterborne polyurethane conductive coating is 0.1-0.8 g/cm3The average particle size is 2 to 4 mm.
The invention also provides a preparation method of the TPU expanded bead with the conductive surface coating, which adopts a spray coating drying device and at least comprises the following steps:
a drum-shaped rotating drum with an open upper end;
a hot air pipe with an outlet communicated with the interior of the rotary drum and connected with a hot air blowing device outside the rotary drum;
a stirrer installed in the drum for assisting in dispersing the TPU expanded beads; and
the spray gun is used for atomization, and an outlet of the spray gun is positioned in the rotary drum and is connected with a liquid tank outside the rotary drum through a pipeline;
the preparation method of the TPU expanded beads with the conductive surface coating comprises the following steps:
1) cleaning the surface of the TPU foamed beads by adopting an ultrasonic cleaning process, and drying at 50-100 ℃ after cleaning;
2) processing the surface of the cleaned TPU foamed beads by adopting a low-temperature plasma processing process;
3) uniformly stirring waterborne polyurethane, carbon nanotube waterborne slurry, graphene waterborne slurry, a waterborne antioxidant, a cross-linking agent and deionized water, and preparing a waterborne polyurethane spray solution containing carbon nanotubes and graphene for later use by matching ultrasonic dispersion;
4) adding the TPU foamed beads into a rotary drum of a spray drying device, starting the rotary drum to rotate and heat, introducing hot air to dry materials, after the TPU foamed beads are preheated to a set drying temperature of 80-105 ℃, starting a stirrer to assist in dispersing the TPU foamed beads, spraying the aqueous polyurethane spray solution containing the carbon nano tubes and the graphene prepared in the step 3) on the surfaces of the TPU foamed beads by using a spray gun, continuously heating and drying the surfaces of the TPU foamed beads while intermittently spraying the aqueous polyurethane spray solution containing the carbon nano tubes and the graphene for multiple times in the process of uniformly rolling and dispersing the TPU foamed beads in the rotary drum until the aqueous polyurethane spray solution is completely consumed, stopping spraying, finally forming uniform coatings on the surfaces of the TPU foamed beads, and continuously drying until the surface coatings of the TPU foamed beads are dried.
In the preparation method of the surface coating conductive TPU foamed bead, the ultrasonic cleaning process in the step 1) adopts at least one anionic surfactant or non-anionic surfactant with the concentration of 1-20%Water-based cleaning agents with ionic surfactants, ultrasonic frequency>20KHz, power density>0.3W/cm2。
In the preparation method of the TPU foamed beads with the conductive surface coating, the working gas adopted in the low-temperature plasma treatment process in the step 2) is one or a mixture of several gases of argon, nitrogen, oxygen, ammonia and carbon dioxide, the gas flow is 30-900 sccm, the working pressure is 10-300 Pa, the treatment time is 20 s-10 min, the temperature is 20-130 ℃, and the treatment power is 1500W-12000W.
In the preparation method of the TPU foamed beads with the conductive surface coating, the rotary drum is arranged on a base, and the installation inclination angle is 30-45 degrees; the outer wall of the drying box is provided with an auxiliary electric heating dryer.
A molded body of TPU foamed beads with conductive surface coating is prepared by the following steps:
adding the TPU foamed beads with the conductive surface coatings into a mold of a foamed bead forming machine, heating by adopting steam, cooling and demolding to obtain the TPU foamed beads;
the surface resistivity of the TPU foamed bead forming body with the conductive surface coating is 104～105Ω。
The TPU foamed bead with the conductive surface coating, the preparation method and the application thereof have the advantages of uniform conductivity and antistatic property, stable static dissipative property and green and environment-friendly preparation process.
Drawings
Fig. 1 is a schematic configuration diagram of a spray coating drying apparatus of the present invention.
Detailed Description
The surface-coated electrically conductive TPU expanded beads of the present invention comprise:
(1) TPU expanded beads; and
(2) spraying an aqueous polyurethane solution containing carbon nanotubes and graphene on the surface of the TPU foamed beads to form an aqueous polyurethane conductive coating with the thickness of 10-200 mu m;
the TPU foamed beads are prepared by adopting a kettle internal gas impregnation method, and the surfaces of the TPU foamed beads are subjected to ultrasonic wave surface cleaning and degreasing and low-temperature plasma activation treatment;
the aqueous polyurethane solution comprises: the carbon nanotube-based composite material comprises waterborne polyurethane, carbon nanotube waterborne slurry, graphene waterborne slurry, a waterborne antioxidant, a cross-linking agent and deionized water.
Wherein the waterborne polyurethane is carboxyl type thermoplastic waterborne polyurethane emulsion;
the adding amount of the carbon nano tube and the graphene is 3.0 wt% -7.0 wt% of the total amount of the TPU foamed bead conductive coating, preferably, the adding amount of the carbon nano tube and the graphene is 4: 1;
the water-based antioxidant is a dispersion liquid containing hindered phenol antioxidants; preferably aqueous antioxidant dispersion containing triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (CAS NO:36443-68-2), wherein the antioxidant amount is 0.5-5% of the solid amount of the aqueous polyurethane;
the cross-linking agent is an aziridine type cross-linking agent, the cross-linking agent is used for improving the water resistance of the aqueous polyurethane coating, but the cross-linking degree needs to be controlled, so that the aqueous polyurethane coating coated on the surface of the TPU foamed beads after drying does not lose the thermal bonding capability, and the addition amount of the cross-linking agent is 0.05-2% of the mass percent of the aqueous polyurethane emulsion;
the solid content of the aqueous polyurethane emulsion containing the carbon nano tube and the graphene is 1-20 percent;
the proportion of the TPU foamed bead surface coating before spraying of the waterborne polyurethane conductive coating is 0.1-0.8 g/cm3；
The preparation method of the TPU foamed beads with the conductive surface coating comprises the following steps:
1) cleaning the surface of the TPU foamed beads by adopting an ultrasonic cleaning process, and drying at 50-100 ℃ after cleaning;
2) processing the surface of the cleaned TPU foamed beads by adopting a low-temperature plasma processing process;
3) uniformly stirring waterborne polyurethane, carbon nanotube waterborne slurry, graphene waterborne slurry, a waterborne antioxidant, a cross-linking agent and deionized water, and preparing a waterborne polyurethane spray solution containing carbon nanotubes and graphene for later use by matching ultrasonic dispersion;
4) placing a stirrer 3 in a rotary drum 1 of a spray coating drying device to assist in dispersing TPU (thermoplastic polyurethane) foaming beads, introducing hot air into the rotary drum 1 to dry materials in the rotary drum 1, additionally installing an auxiliary electric heating dryer outside the rotary drum 1, adding the TPU foaming beads needing surface coating conduction into the rotary drum 1, starting the rotary drum 1 to rotate and heat, starting the stirrer 3 after the TPU foaming beads are preheated to a set drying temperature (namely 80-105 ℃), spraying the aqueous polyurethane spraying solution containing the carbon nano tubes and the graphene prepared in the step 3) on the surfaces of the TPU foaming beads in the rotary drum 1 by using a spray gun 4 with an atomization effect, so that the surfaces of the TPU foaming beads are continuously heated and dried while being sprayed with the aqueous polyurethane spraying solution containing the carbon nano tubes and the graphene for a plurality of times in the process of uniformly rolling and dispersing in the rotary drum 1 until the aqueous polyurethane solution is completely consumed, and stopping the spray gun 4, finally forming a uniform coating on the surface of the TPU beads, and continuously drying until the surface coating of the TPU foamed beads is dried.
Preferably, the ultrasonic cleaning process in the step 1) adopts a water-based cleaning agent containing at least one anionic surfactant or nonionic surfactant with the concentration of 1-20%, and the ultrasonic frequency is>20KHz, power density>0.3W/cm2。
Preferably, the working gas adopted by the low-temperature plasma treatment process in the step 2) is one or a mixture of several of argon, nitrogen, oxygen, ammonia and carbon dioxide, the gas flow is 30-900 sccm, the working pressure is 10-300 Pa, the treatment time is 20 s-10 min, the temperature is 20-130 ℃, and the treatment power is 1500-12000W.
Preferably, as shown in fig. 1, the spray coating drying device in step 4) includes:
a rotating drum 1 with an opening at the upper end, wherein the rotating drum 1 is arranged on a base 11;
a hot air pipe 2 with an outlet communicated with the interior of the rotary drum 1 and connected with a hot air blowing device 21 outside the rotary drum 1;
an agitator 3 installed in the drum 1 for assisting in dispersing the TPU expanded beads; and
a spray gun 4 for atomization, the outlet of which is located in the rotating drum 1 and is connected with a liquid tank outside the rotating drum 1 through a pipeline.
Preferably, the installation inclination angle of the rotary drum 1 is 30-45 degrees;
preferably, the drum type stainless steel drum of drum 1;
preferably, an auxiliary electric heating dryer is installed on the outer wall of the rotary drum 1;
the invention also provides a molded body of the TPU foamed bead with the conductive surface coating, and the preparation method comprises the following steps:
and adding the TPU foamed beads with the conductive surface coatings into a mold of a foamed bead forming machine, heating by adopting steam, cooling, and demolding to obtain the TPU foamed bead forming body with the conductive surface coatings. Softening the surface of the white TPU foamed beads and the aqueous polyurethane coating outside the white TPU foamed beads in a steam heating mode, enabling molecular chains of interfaces between the white TPU foamed beads and the aqueous polyurethane coating and between the aqueous polyurethane coatings to be mutually diffused to form firmer adhesion, enabling the carbon nanotubes and the graphene in the coating to be wrapped by the molecular chains to be stably distributed on each interface layer, extruding and fixing the conductive material wrapped on the surface of the TPU foamed beads on the surface and inside the forming body, enabling the forming body to have uniform and stable electrostatic dissipation performance and certain conductivity, and enabling the surface resistivity of the forming body to be 104～105Ω。
The present invention will be further described with reference to examples 1 to 2.
Example 1
The specific gravity of the product prepared by the in-kettle gas immersion method is 0.11g/cm3The average particle diameter of the white TPU expanded beads of (1) is 3.5 mm.
1) Firstly, grease and dirt on the surface of white TPU foamed beads are removed, rinsed and dried at 50-100 ℃ by utilizing an ultrasonic cleaning process, wherein the cleaning liquid is a water-based cleaning liquid containing 10% of a surfactant 6501, the ultrasonic frequency is 25KHz, and the power density is 0.35W/cm2；
2) Then carrying out low-temperature plasma treatment on the surface of the treated white TPU foamed beads, wherein the working gas is nitrogen, the working gas pressure is 100Pa, and the temperature is 80 ℃;
3) preparing carboxyl type aqueous polyurethane spraying solution containing carbon nano tubes and graphene with solid content of 10%, which comprises the following steps:
a. the total adding amount of the carbon nano tubes and the graphene is 3.5 wt% of the total solid amount of the aqueous polyurethane spray liquid, and the adding amount ratio of the carbon nano tubes to the graphene is 4: 1;
b. selecting an aqueous antioxidant dispersion liquid containing triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (CAS NO:36443-68-2), wherein the antioxidant amount is 2% of the solid amount of the aqueous polyurethane;
c. the cross-linking agent adopts aziridine cross-linking agent SAC-100, and the addition amount of the aziridine cross-linking agent is 0.2 percent of the mass percentage of the aqueous polyurethane emulsion;
4) adding the white TPU expanded beads treated in the step 2) into a spray coating drying device (shown in the attached figure 1), setting the hot air temperature to be 100 ℃, setting the solid content of the aqueous polyurethane spray solution containing the carbon nano tubes and the graphene prepared in the step 3) to be 28 percent of the amount of the white TPU expanded beads, and obtaining the TPU composite expanded beads with the conductive surface coating, wherein the specific gravity of the prepared TPU composite expanded beads is about 0.14g/cm3；
5) And putting the prepared TPU composite foamed beads with the conductive surface coating into a mold, heating by adopting steam, cooling, and demolding to obtain the TPU composite foamed bead forming body with the conductive surface coating.
Tests prove that the surface coating of the black TPU composite foaming bead forming body is uniform in electric conduction and 1.3 x 10 in surface resistivity5Omega; the color of the paint is not faded by external force wiping after passing a water resistance test of 60 ℃, 95 percent of relative humidity and seven days.
Example 2
The specific gravity of the product prepared by the in-kettle gas immersion method is 0.16g/cm3The average particle diameter of the white TPU expanded beads of (1) is 3.5 mm.
1) Firstly, grease and dirt on the surface of white TPU foamed beads are removed, rinsed and dried at 50-100 ℃ by utilizing an ultrasonic cleaning process, wherein the cleaning liquid is a water-based cleaning liquid containing 10% of a surfactant 6501, the ultrasonic frequency is 25KHz, and the power density is 0.35W/cm2；
2) Then carrying out low-temperature plasma treatment on the surface of the treated white TPU foamed beads, wherein the working gas is nitrogen, the working gas pressure is 100Pa, and the temperature is 80 ℃;
3) preparing carboxyl type aqueous polyurethane spraying solution containing carbon nano tubes and graphene with solid content of 10%, which comprises the following steps:
a. the total adding amount of the carbon nano tubes and the graphene is 6.5 wt% of the total solid amount of the aqueous polyurethane spray liquid, and the adding amount ratio of the carbon nano tubes to the graphene is 4: 1;
b. selecting an aqueous antioxidant dispersion liquid containing triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (CAS NO:36443-68-2), wherein the antioxidant amount is 2% of the solid amount of the aqueous polyurethane;
c. the cross-linking agent adopts aziridine cross-linking agent SAC-100, and the addition amount of the aziridine cross-linking agent is 0.2 percent of the mass percentage of the aqueous polyurethane emulsion;
4) adding the white TPU expanded beads treated in the step 2) into a spray coating drying device (shown in the attached figure 1), setting the hot air temperature to be 100 ℃, setting the solid content of the aqueous polyurethane spray solution containing the carbon nano tubes and the graphene prepared in the step 3) to be 36 percent of the amount of the white TPU expanded beads, and obtaining the TPU composite expanded beads with the conductive surface coating, wherein the specific gravity of the prepared TPU composite expanded beads is about 0.16g/cm3；
5) And putting the prepared TPU composite foamed beads with the conductive surface coating into a mold, heating by adopting steam, cooling, and demolding to obtain the TPU composite foamed bead forming body with the conductive surface coating.
Tests prove that the surface coating of the black TPU composite foaming bead forming body is uniform in electric conduction and 2.8 x 10 in surface resistivity4Omega, passing a water resistance test at 60 ℃, relative humidity 95%, seven days, no discoloration upon external wiping.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.

Claims (10)

1. A surface-coated electrically conductive TPU expanded bead, comprising:
(1) TPU expanded beads; and
(2) spraying an aqueous polyurethane solution containing carbon nanotubes and graphene on the surface of the TPU foamed beads to form an aqueous polyurethane conductive coating with the thickness of 10-200 mu m;
the TPU foamed beads are prepared by adopting a kettle internal gas impregnation method, and the surfaces of the TPU foamed beads are subjected to ultrasonic wave surface cleaning and degreasing and low-temperature plasma activation treatment;
the aqueous polyurethane solution comprises: the carbon nanotube-based composite material comprises waterborne polyurethane, carbon nanotube waterborne slurry, graphene waterborne slurry, a waterborne antioxidant, a cross-linking agent and deionized water.
2. The topcoat conductive TPU expanded beads of claim 1, wherein the aqueous polyurethane is a carboxyl-type thermoplastic aqueous polyurethane emulsion;
the water-based antioxidant is a dispersion liquid containing hindered phenol antioxidants;
the cross-linking agent adopts aziridine cross-linking agent.
3. The surface-coated conductive TPU expanded beads of claim 1 or 2, wherein the addition amount of the carbon nanotubes and the graphene is 3.0 wt% to 7.0 wt% of the total amount of the conductive coating of the TPU expanded beads, and the ratio of the addition amount of the carbon nanotubes to the graphene is 4: 1;
the amount of the water-based antioxidant is 0.5 to 5 percent of the solid amount of the water-based polyurethane;
the addition amount of the cross-linking agent is 0.05-2% of the mass of the aqueous polyurethane emulsion;
the solid content of the aqueous polyurethane solution containing the carbon nano tube and the graphene is 1-20 percent;
the proportion of the TPU foamed bead surface coating before spraying of the waterborne polyurethane conductive coating is 0.1-0.8 g/cm3The average particle size is 2 to 4 mm.
4. The topcoat conductive TPU expanded beads of claim 2 wherein the aqueous antioxidant is an aqueous antioxidant dispersion comprising triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate.
5. The method of claim 1, wherein the spray coating and drying apparatus is used to prepare the surface-coated conductive TPU expanded beads, and the method comprises at least:
a drum-shaped rotating drum with an open upper end;
a hot air pipe with an outlet communicated with the interior of the rotary drum and connected with a hot air blowing device outside the rotary drum;
a stirrer installed in the drum for assisting in dispersing the TPU expanded beads; and
the spray gun is used for atomization, and an outlet of the spray gun is positioned in the rotary drum and is connected with a liquid tank outside the rotary drum through a pipeline;
the preparation method of the surface coating conductive TPU foamed bead comprises the following steps:
1) cleaning the surface of the TPU foamed beads by adopting an ultrasonic cleaning process, and drying at 50-100 ℃ after cleaning;
2) processing the surface of the cleaned TPU foamed beads by adopting a low-temperature plasma processing process;
3) uniformly stirring waterborne polyurethane, carbon nanotube waterborne slurry, graphene waterborne slurry, a waterborne antioxidant, a cross-linking agent and deionized water, and preparing a waterborne polyurethane spray solution containing carbon nanotubes and graphene for later use by matching ultrasonic dispersion;
4) adding the TPU expanded beads into a rotary drum of the spray drying device, starting the rotary drum to rotate and heat, introducing hot air to dry materials, after the TPU expanded beads are preheated to a set drying temperature of 80-105 ℃, starting a stirrer to assist in dispersing the TPU expanded beads, spraying the aqueous polyurethane spray solution containing the carbon nano tubes and the graphene prepared in the step 3) on the surfaces of the TPU expanded beads by using a spray gun, wherein in the process that the TPU expanded beads are uniformly rolled and dispersed in the rotary drum, the surfaces of the TPU expanded beads are continuously heated and dried while being sprayed with the aqueous polyurethane spray solution containing the carbon nano tubes and the graphene for multiple times and discontinuously until the aqueous polyurethane solution is completely consumed, stopping spraying, finally forming a uniform coating on the surfaces of the TPU expanded beads, and continuously drying until the surface coating of the TPU expanded beads is dried by moisture, and (4) finishing.
6. The method for preparing the surface-coated conductive TPU expanded beads of claim 5, wherein the ultrasonic cleaning process in step 1) is carried out by using a water-based cleaning agent containing at least one anionic surfactant or nonionic surfactant at a concentration of 1-20%, and the ultrasonic frequency is controlled>20KHz, power density>0.3W/cm2。
7. The method for preparing the TPU expanded beads with the conductive surface coating according to claim 5, wherein the working gas adopted in the low-temperature plasma treatment process in the step 2) is one or a mixture of several of argon, nitrogen, oxygen, ammonia and carbon dioxide, the gas flow is 30-900 sccm, the working pressure is 10-300 Pa, the treatment time is 20 s-10 min, the temperature is 20-130 ℃, and the treatment power is 1500W-12000W.
8. The method for preparing the surface-coated electrically conductive TPU expanded beads of claim 5, wherein the drum is mounted on a base at an inclination angle of 30 to 45 °; the outer wall of the drying box is provided with an auxiliary electric heating dryer.
9. A molded body of the TPU expanded beads with conductive surface coating according to any of claims 1 to 8; characterized in that the surface resistivity of the TPU foamed bead forming body with the conductive surface coating is 104～105Ω。
10. A method for producing a molded article of the surface-coated electrically conductive TPU expanded beads of claim 9, comprising the steps of:
and adding the TPU foamed beads with the conductive surface coatings into a mold of a foamed bead forming machine, heating by adopting steam, cooling and demolding to obtain the TPU foamed beads.
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