CN116489838B

CN116489838B - Electrothermal wire with intelligent temperature control function and heating module assembly prepared by utilizing electrothermal wire

Info

Publication number: CN116489838B
Application number: CN202310465258.8A
Authority: CN
Inventors: 请求不公布姓名
Original assignee: Zhejiang Danting New Material Co ltd
Current assignee: Zhejiang Danting New Material Co ltd
Priority date: 2023-04-24
Filing date: 2023-04-24
Publication date: 2024-01-26
Anticipated expiration: 2043-04-24
Also published as: CN116489838A

Abstract

The application relates to the technical field of electric heating materials, in particular to an electric heating wire with an intelligent temperature control function and a heating module component prepared by using the same. An electric heating wire with an intelligent temperature control function comprises a core wire and an outer wire compounded on the outer wall of the core wire, wherein the core wire is a graphene wire; the external line is prepared from the following raw materials: conductive composition, reinforcing aid for silk thread, antioxidant composition, ultraviolet resistance aid, dispersant and matrix resin. Compared with the existing heat tracing band and PTC heating wire, the heating wire has relatively excellent mechanical strength, flexibility, electric conduction performance and weather resistance, and is wider in application field and better in market prospect. The heating module component in the application is wide in application, can replace the existing heat tracing belt and PTC heating wire products, is excellent in physical and chemical properties and weather resistance, can be applied to multiple fields, fully plays an intelligent temperature control function, and improves the competitiveness of the products.

Description

Electrothermal wire with intelligent temperature control function and heating module assembly prepared by utilizing electrothermal wire

Technical Field

The application relates to the technical field of electric heating materials, in particular to an electric heating wire with an intelligent temperature control function and a heating module component prepared by using the same.

Background

The heating wire is a heating wire capable of releasing heat when electrified, and is mostly applied to the field of heating and heat preservation. Currently, conventional electric heating wires mainly consist of conductive core wires and insulating sheaths. The conductive core wire is usually a metal wire, a graphene wire, a carbon fiber wire or the like, and has the main characteristic of good conductive performance. The heating power output by the material heating wire after being connected with the power supply is constant, and the power difference is +/-5%, namely the constant-power heating wire. At present, the price of the graphene wire produced by the carbon slurry process is 0.08-0.25 yuan/m, and the price of the carbon fiber wire is 1.0-1.5 yuan/m, so that the graphene wire produced by the carbon slurry process has a good development prospect as an electric heating wire. However, the graphene wires produced by the carbon slurry process have a fatal problem: conductive substances such as graphene and the like on the carbon paste composite are worn, so that the overall conductive performance of the wire is uneven, and if the conductive substances at the friction parts are easy to fall off, the resistance is large, the heating uniformity is poor, and the processability is poor, so that the conductive substances are adopted as the electric heating wire, have a small application range, and limit the development and application of the conductive substances. In addition, the graphene wire produced by the carbon slurry process needs to be externally connected with an electronic control module for temperature control in order to be considered safely, so that potential safety hazards caused by overhigh temperature are reduced, and the adaptability and safety of the device are ensured. Therefore, the application provides an electric heating wire with an intelligent temperature control function.

Disclosure of Invention

In order to solve the technical problem, the application provides an electric heating wire with an intelligent temperature control function and a heating module assembly prepared by using the electric heating wire.

In a first aspect, the application provides an electrothermal wire with intelligent temperature control function, which is realized through the following technical scheme:

an electric heating wire with an intelligent temperature control function comprises a core wire and an outer wire compounded on the outer wall of the core wire, wherein the core wire is a graphene wire with the dimension of 100-600D; the external line is prepared from the following raw materials in percentage by mass: 15.0-20.0% of conductive composition, 8.0-10.0% of reinforcing auxiliary agent for silk threads, 1.35-1.74% of antioxidant composition, 0.24-0.35% of uvioresistant auxiliary agent, 0.10-0.40% of dispersing agent and the balance of matrix resin; the matrix resin mainly comprises PP resin, HDPE resin and EVA resin; the mass ratio of the PP resin to the EVA resin to the HDPE resin is controlled to be (780-800): 180-200): 400-440; the conductive composition is at least one of nano titanium diboride, nano carbon black, nano tin oxide, nano nickel oxide, nano indium oxide, nano carbon fiber, nano graphite powder, graphene, carbon nano tube and titanium nitride whisker; the reinforcing auxiliary agent for the silk thread is at least one of nano zinc oxide matched with nano zirconium oxide, nano aluminum nitride, nano aluminum oxide, titanium tin carbide superfine micro powder, boron nitride nano tube and boron nitride whisker.

Compared with the existing heat tracing band and PTC heating wire, the heating wire has relatively excellent mechanical strength, flexibility, electric conduction performance and weather resistance, and is wider in application field and better in market prospect.

Preferably, the PP treeThe mass ratio of the fat to the EVA resin to the HDPE resin is controlled at 795:185:420; the electric heating wire with the intelligent temperature control function is placed at 10 ℃ to measure the wire resistance as A1, and the A1 is controlled at 1.0 x 10 ³ -5*10 ⁴ Ω×m; the electric heating wire with the intelligent temperature control function is placed at the temperature of minus 40 ℃ to measure the wire resistance as A2, and the A1 is 1.5-3.0 times of the A2; the electric heating wire with the intelligent temperature control function is placed at 60 ℃ to measure the wire resistance as A3, wherein A3 is 1.5-2.0 times of A1; the electric heating wire with the intelligent temperature control function is placed at 80 ℃ to measure the wire resistance to be A4, and the A4 is 2.5-10 times of the A1.

By adopting the technical scheme, the prepared electric heating wire has a better intelligent temperature control function. Specifically, the prepared heating wire has relatively high power at low temperature, can perform thermal compensation more quickly, and accelerates the temperature rise; when the prepared electric heating wire is at 60-110 ℃, the heating power is attenuated by more than 30%, the thermal compensation rate is reduced, namely the heating speed is slowed down, a relatively constant temperature value is maintained, and the intelligent temperature control function is safe.

Preferably, the conductive composition mainly comprises nano titanium diboride, nano carbon black, nano carbon fiber, nano graphite powder and titanium nitride whisker; the average grain diameter of the nano titanium diboride is 0.05-3 microns, and the nano titanium diboride is hexagonal; the nano graphite powder is flake graphite powder, and the average particle size is 0.2-1.0 microns; the mass ratio of the nano titanium diboride to the nano carbon black to the nano carbon fiber to the nano graphite powder to the titanium nitride whisker is controlled to be (5-10), 60-80, 5-20, 10-40 and 0.5-5.

By adopting the technical scheme, the prepared electric heating wire resistor can be adjusted, is applicable to voltages with different voltages, and can realize personalized design to meet the demands of different consumers. In addition, the conductive composition prepared by mixing the nano titanium diboride, the nano carbon black, the nano carbon fiber, the nano graphite powder and the titanium nitride whisker according to a specific proportion can also play a role in improving the mechanical strength, the weather resistance and the wear resistance of the electric heating wire.

Preferably, the reinforcing auxiliary agent for the silk thread mainly comprises nano zinc oxide, nano zirconium oxide, titanium tin carbide superfine micropowder and boron nitride nanosheets; the mass ratio of the nanometer zinc oxide to the nanometer zirconium oxide to the superfine titanium tin carbide micro powder to the boron nitride nano sheet is controlled to be (55-90)/(5-20)/(0.5-5); the dispersing agent is at least one of stearate and a coupling agent.

By adopting the technical scheme, the prepared electric heating wire is endowed with the functions of shielding infrared rays and ultraviolet rays, sterilizing, protecting health and keeping warm, and simultaneously is endowed with relatively excellent mechanical strength, flexibility, conductivity, weather resistance and wear resistance, and has relatively durable service life.

Preferably, the antioxidant composition mainly comprises at least one of nano zirconium carbide, nano zirconium silicide and nano titanium carbide matched with an organic antioxidant; the organic antioxidant is at least one of antioxidant 1024, antioxidant 697 and antioxidant BHT, and is matched with antioxidant DSTP and/or antioxidant DBHQ.

By adopting the technical scheme, the integral heating performance, ageing resistance, mechanical strength and flexibility of the electric heating wire can be improved, and the specifications of the obtained electric heating wire can be adjusted and can be individually processed into the heating module component.

Preferably, the antioxidant composition mainly comprises nano zirconium carbide, nano titanium carbide, an antioxidant 1024, an antioxidant 697 and an antioxidant DBHQ; the mass ratio of the nanometer zirconium carbide to the nanometer titanium carbide to the antioxidant 1024 to the antioxidant 697 to the antioxidant DBHQ is 10: (5-20): 100: (20-80): (5-40).

The variety and proportion of the antioxidant auxiliary agent are optimized and selected through experiments, so that the overall ageing performance and ultraviolet ageing resistance of the electric heating wire can be improved, and the electric heating wire is ensured to have relatively excellent mechanical strength, flexibility, electric conductivity and weather resistance.

Preferably, the ultraviolet resistance auxiliary agent mainly comprises at least one of nano titanium dioxide, nano titanium nitride and nano silicon nitride matched with an organic ultraviolet resistance reagent; the organic anti-ultraviolet agent is mainly prepared from at least one of UV-531 and UV-234 and at least one of UV622, UV-770, UV-944 and UV-783.

By adopting the technical scheme, the infrared and ultraviolet aging resistance of the whole electric heating wire can be improved.

Preferably, the ultraviolet resistance auxiliary agent mainly comprises nano silicon nitride, nano titanium nitride, UV-234, UV622 and UV-944; the mass ratio of the nano silicon nitride to the nano titanium nitride to the UV-234 to the UV622 to the UV-944 is 10: (5-20): 100: (5-40): (5-40).

The variety and the proportion of the ultraviolet-resistant auxiliary agent are optimized and selected through experiments, so that the aging performance and the ultraviolet-resistant aging performance of the whole electric heating wire can be improved by the synergistic antioxidant composition, and the electric heating wire is ensured to have relatively excellent mechanical strength, flexibility, electric conductivity and weather resistance.

Preferably, the preparation method of the electric heating wire with the intelligent temperature control function comprises the following steps: s1, placing the dried matrix resin, the conductive composition with accurate measurement, the reinforcing auxiliary agent for silk threads, the antioxidant composition, the ultraviolet resistance auxiliary agent and the dispersing agent into an internal mixer, and carrying out internal mixing after uniformly mixing at 160-168 ℃ for 280-350S; s2, placing the banburying material obtained in the S1 into a double-screw extruder for melt extrusion, wiredrawing, cooling and granulating to obtain 1.0-2.0mm spinning master batch, and drying until the moisture is lower than 0.1%; and S3, taking the graphene wire as a core wire, putting the spinning master batch into a double-screw extruder, extruding at 175-200 ℃, adhering the obtained extruded molten material to the outer surface of the core wire, and performing water cooling, heat treatment and drying to obtain a finished product of the heating wire.

The preparation method of the electric heating wire with the intelligent temperature control function is relatively simple, low in operation difficulty, convenient to realize industrial production and manufacture, and convenient to popularize in the market at a lower price.

In a second aspect, the application provides a heating module prepared by using an electrothermal wire with an intelligent temperature control function, which is realized by the following technical scheme:

the heating module component prepared by utilizing the electric heating wire with the intelligent temperature control function comprises heating cloth, connecting wires and a power connector, wherein the connecting wires are communicated with the heating cloth; the heating cloth, the connecting wires, the power connector and the power supply form a current loop, and the heating cloth is electrified to generate heat to play a heating role; the heating cloth comprises an insulating heat-conducting film and a heating net positioned in the insulating heat-conducting film, the heating net is of a plain weave structure, warp threads in the heating net comprise weaving yarns A and a plurality of metal conductive wires, the metal conductive wires are parallel to the weaving yarns A, and the metal conductive wires are positioned at two ends of the warp threads of the heating net in the warp direction; the weft in the heating net comprises a knitting yarn B and a plurality of electric heating wires with intelligent temperature control function as claimed in any one of claims 1 to 9, wherein the electric heating wires are parallel to the knitting yarn B, and two ends of the electric heating wires are connected with adjacent metal conductive wires; one end of the metal conductive wire is connected with the connecting wire.

Or a heating module component prepared by an electric heating wire with an intelligent temperature control function comprises heating cloth, a connecting wire and a power connector, wherein the connecting wire is communicated with the heating cloth; the heating cloth, the connecting wires, the power connector and the power supply form a current loop, and the heating cloth is electrified to generate heat to play a heating role; the heating cloth is prepared by adopting a spray melting process or a spunbonding process; the heating cloth comprises heating wires with the diameter of 0.1-1.0mm, wherein the heating wires comprise an electric heating wire with an intelligent temperature control function and an insulating heat-conducting TPU protective outer film layer as a core layer in any one of claims 1-9; the electric heating wire in the heating wire is communicated with a power supply through the connecting wire and the power connector to form current reflux, so that the effect of electrifying and heating is achieved; the heat conductivity coefficient of the insulating heat conducting TPU protective outer film layer is 1.0-3.5W/M.

The utility model provides a can be applied to fields such as carpet, ground mat, mattress, yoga mat, physiotherapy mat, cushion, dress filler, waistband, muffler, binder, sofa, flower art, crops are planted, poultry, heating meal package, waistcoat dorsad, silica gel heating plate, heating water pipe, new energy automobile battery keep warm, petroleum transportation pipeline, wind power host computer heating, the cushion includes aircraft cushion, train cushion, high-speed railway cushion, car cushion, bus cushion, realizes safe intelligent temperature control function purpose.

Preferably, the thickness ratio of the electric heating wire to the insulating heat-conducting TPU protective outer film layer is controlled to be (6-8) (1-4); the insulation heat conduction TPU protective outer film layer is mainly prepared from the following raw materials in parts by weight: 100 parts of TPU resin granules with the Shore hardness of 30-90A, 15-25 parts of insulating heat conducting filler, 1-3 parts of coupling agent, 0.5-2 parts of dispersing agent, 0.5-2 parts of antioxidant and 0.3-0.8 part of antioxidant auxiliary agent; the insulating heat-conducting filler is at least one of nano aluminum nitride, nano boron nitride, heat-conducting spherical aluminum oxide, nano magnesium silicon nitride, nano silicon carbide and carbon nano tube grafted boron nitride heat-conducting filler.

The insulating heat conduction TPU protection adventitia in this application not only can play better protection electrothermal wire's effect, and can be convenient for electrothermal wire heat derive the heat dissipation, promotes holistic safety in utilization. In the test process, the heat conduction performance of the protective outer film layer is poor, so that the heat release of the electric heating wire is slow, the problem of burning through the protective outer film occurs after the local heat accumulation, and the problem of potential safety hazard easily occurs.

In summary, the present application has the following advantages:

1. compared with the existing heat tracing band and PTC heating wire, the heating wire has relatively excellent mechanical strength, flexibility, electric conduction performance and weather resistance, and is wider in application field and better in market prospect.

2. The heating module component in the application is wide in application, can replace the existing heat tracing belt and PTC heating wire products to be used, and can be applied to multiple fields due to excellent physical and chemical properties, so that the intelligent temperature control function is fully exerted, and the product competitiveness is improved.

3. The preparation method is relatively simple, low in operation difficulty and convenient to realize industrial production and manufacture.

Drawings

FIG. 1 is a schematic diagram showing the resistance versus temperature change of the heating wires in examples 5, 8, 31 and comparative examples 15 to 16 in the present application.

FIG. 2 is a graph showing the resistance versus temperature change of the heating wires in examples 24, 28-31 and comparative example 17 in the present application.

Fig. 3 is a graph showing the change of the resistance of the heating wire with respect to the temperature in comparative example 18 in the present application.

Detailed Description

The present application is described in further detail below in conjunction with comparative examples and examples.

Examples

The application discloses an electrothermal wire with intelligent temperature control function, including heart yearn and compound in the outside line of heart yearn outer wall, wherein the heart yearn is 100-600D's graphite alkene line (the new material of alkene wang). The external line is prepared from the following raw materials in percentage by mass: 15.0-20.0% of conductive composition, 8.0-10.0% of reinforcing auxiliary agent for silk threads, 1.35-1.74% of antioxidant composition, 0.24-0.35% of ultraviolet resistance auxiliary agent, 0.10-0.40% of dispersing agent and the balance of matrix resin.

The matrix resin mainly comprises PP resin, EVA resin and HDPE resin, and the mass ratio of the PP resin to the EVA resin to the HDPE resin is controlled to be 780-800:180-200:400-440. The conductive composition is at least one of nano titanium diboride, nano carbon black, nano tin oxide, nano nickel oxide, nano indium oxide, nano carbon fiber, nano graphite powder, graphene, carbon nano tube and titanium nitride whisker. The reinforcing auxiliary agent for the silk thread is at least one of nano zinc oxide matched with nano zirconium oxide, nano aluminum nitride, nano aluminum oxide, titanium tin carbide superfine micropowder, boron nitride nanotube and boron nitride whisker.

The preparation method of the heating wire with the intelligent temperature control function comprises the following steps of:

s1, placing the dried matrix resin, the conductive composition with accurate measurement, the reinforcing auxiliary agent for silk threads, the antioxidant composition, the ultraviolet resistance auxiliary agent and the dispersing agent into an internal mixer, and carrying out internal mixing after uniformly mixing at 160-163 ℃ for 280-350S;

s2, placing the banburying material obtained in the S1 into a double-screw extruder for melt extrusion, wiredrawing, cooling and granulating to obtain 1-2mm spinning master batch, and drying until the moisture is lower than 0.1%;

and S3, taking the graphene wire as a core wire, putting the spinning master batch into a double-screw extruder, extruding at 160-185 ℃, adhering the obtained extruded molten material to the outer surface of the core wire, and performing water cooling, heat treatment and drying to obtain the finished product of the heating wire.

Preferably, the mass ratio of the PP resin, the HDPE resin and the EVA resin is controlled to be 795:185:420. The prepared electrothermal wire with intelligent temperature control function is placed at 10 ℃ to measure the wire resistance as A1, and the A1 is controlled at 1.0 x 10 ³ -5*10 ⁴ Ω×m. The electric heating wire with the intelligent temperature control function is placed at the temperature of minus 40 ℃ to measure the wire resistance to be A2, and A1 is 1.5-3.0 times of A2. The electric heating wire with the intelligent temperature control function is placed at 60 ℃ to measure the wire resistance to be A3, and A3 is 1.5-2 times of A1. The electric heating wire with the intelligent temperature control function is placed at 80 ℃ to measure the wire resistance to be A4, and A4 is 2.5-10 times of A1.

A heating module assembly prepared by an electric heating wire with an intelligent temperature control function comprises heating cloth, connecting wires and a power connector, wherein the connecting wires are communicated with the heating cloth. The connecting wire is fixedly connected with the power connector, the heating cloth, the connecting wire, the power connector and the power supply form a current loop, and the heating cloth is electrified to generate heat to play a heating role. The heating cloth comprises an insulating heat conducting film and a heating net positioned in the insulating heat conducting film, and the heating net is a plain weave structure. The warp threads in the heating net comprise weaving yarns A and two groups of metal conductive wires, wherein the metal conductive wires are parallel to the weaving yarns A, and the metal conductive wires are positioned at two ends of the heating net in the warp direction. The weft in the heating net comprises a knitting yarn B and a plurality of electric heating wires with intelligent temperature control function, wherein the electric heating wires are parallel to the knitting yarn B and are connected with the metal conductive wires. One end of the metal conductive wire is connected with the connecting wire.

The insulating heat conducting film is a silicon rubber film filled and modified by adopting insulating heat conducting filler, and the insulating heat conducting filler can be selected from nano aluminum nitride, nano boron nitride, heat conducting spherical aluminum oxide, nano silicon carbide, carbon nanotube grafted boron nitride heat conducting filler and the like. The heat conductivity coefficient of the insulating heat conducting film is 1.0-3.0W/M.

The formula of the insulating heat conducting film is as follows: 40-70 parts of methyl vinyl crude rubber, 10-15 parts of gas-phase carbon black, 15-20 parts of insulating heat-conducting filler, 1-5 parts of hydroxyl silicone oil, 0.1-0.5 part of zinc stearate, 0.2-2 parts of silane coupling agent, 2-6 parts of hydrogen-containing silicone oil, 4-8 parts of vinyl silicone oil, 0.3-1 part of bis (2, 4-dichloro benzoyl peroxide) and 0.1-0.3 part of 3-methyl-1-butyn-3-ol.

The specific formula of the insulation heat conduction TPU protective outer film is as follows: 54.6 parts of methyl vinyl crude rubber, 10 parts of gas-phase carbon black, 20 parts of insulating heat-conducting filler, 4 parts of hydroxyl silicone oil, 0.4 part of zinc stearate, 0.8 part of silane coupling agent KH570, 5 parts of hydrogen-containing silicone oil, 4.6 parts of vinyl silicone oil, 0.4 part of bis (2, 4-dichloro benzoyl peroxide) and 0.2 part of 3-methyl-1-butyn-3-ol.

The preparation of the insulating heat conducting TPU protective outer film is as follows: putting methyl vinyl crude rubber, hydroxyl silicone oil, KH570 coupling agent and zinc stearate with accurate measurement into a vacuum kneader, and kneading for 10min to obtain a mixture; then adding the fumed silica and the insulating heat-conducting filler into a high-speed stirring kettle, dripping KH550 surface treatment agent at the speed of 1 drop/2 s to obtain a finished product filler, uniformly dividing the obtained finished product filler into 5 parts, adding the finished product filler into the high-speed stirring kettle for 5 times for kneading, wherein the single addition interval is 80s, kneading for 100s after the addition, heating the inside of the kneader to 160 ℃ and vacuumizing to-0.02 MPa, preserving heat and maintaining the pressure for 2.0h to obtain a silica gel group, naturally cooling the obtained silica gel group to 80 ℃ at room temperature, controlling the temperature to be 78-80 ℃, adding hydrogen-containing silicone oil with the hydrogen content of 0.5%, vinyl silicone oil with the vinyl content of 5% and bis (2, 4-dichlorobenzoyl peroxide) in 5 batches at the temperature of 78-80 ℃, kneading for 30min after the single addition interval is finished, rolling and rolling to form a film, naturally cooling and rolling to obtain the finished product insulating heat-conducting protective outer film, and hot-pressing the insulating heat-conducting protective TPU on the lower surface of a heating network to obtain the heating TPU component with the intelligent heat-controlling function of an outer film.

The prepared insulating heat-conducting film has the advantages of good insulating safety performance of 10.8kv/mm, tensile strength of 16.5MPa, tensile fracture rate of 280.6 percent, light transmittance of 78.4 percent, and good mechanical strength and flexibility.

Or, the heating module component prepared by the electric heating wire with the intelligent temperature control function comprises heating cloth, a connecting wire and a power connector, wherein the connecting wire is communicated with the heating cloth. The connecting wire is fixedly connected with the power connector, the heating cloth, the connecting wire, the power connector and the power supply form a current loop, and the heating cloth is electrified to generate heat to play a heating role. The heating cloth is prepared by adopting a spray melting process or a spunbonding process. The heating cloth contains heating wires with the diameter of 0.1-1.0mm, and the heating wires comprise the heating wires with the intelligent temperature control function and the insulating heat conduction TPU protective outer film layer which are used as core layers. The electric heating wire in the heating wire is communicated with a power supply through the connecting wire and the power connector to form current reflux, so that the effect of electrifying and heating is achieved. The heat conductivity coefficient of the insulating heat conducting TPU protective outer film layer is 1.0-3.5W/M. The thickness ratio of the electric heating wire to the insulating heat conducting TPU protective outer film layer is controlled to be (6-8) (1-4).

The formula of the insulating heat-conducting TPU protective outer film layer is as follows: 100 parts of TPU resin granules with the Shore hardness of 30-90A, 15-25 parts of insulating heat conducting filler, 1-3 parts of coupling agent, 0.5-2 parts of dispersing agent, 0.5-2 parts of antioxidant and 0.3-0.8 part of anti-aging auxiliary agent. The insulating heat-conducting filler is at least one of nano aluminum nitride, nano boron nitride, heat-conducting spherical aluminum oxide, nano magnesium silicon nitride, nano silicon carbide and carbon nano tube grafted boron nitride heat-conducting filler.

The specific formula of the insulation heat conduction TPU protective outer film is as follows: 100 parts of TPU resin granules with the Shore hardness of 80A (Basf 1180A10 TPU resin), 20 parts of insulating heat conducting filler, 2.4 parts of coupling agent KH570, 1.2 parts of dispersing agent-zinc stearate, 0.8 part of antioxidant 1024, 0.2 part of antioxidant 300, 0.3 part of antioxidant 168 and 0.5 part of anti-ultraviolet auxiliary agent UV-531. The insulating heat-conducting filler can be commercially available nano aluminum nitride or carbon nano tube connected with boron nitride heat-conducting filler.

Example 1

The external line is prepared from the following raw materials in percentage by mass: 795g PP resin (Yangzi petrochemical K8003), 420g HDPE resin (bench plastic HDPE 8001), 185g EVA resin (bench plastic EVA 7340M, VA content: 28 wt%), 292g carbon black (Bote conductive carbon black VVC 72), 8g titanium diboride (planetary ball milled to an average particle size of 0.5-1 micron, hexagonal crystal), 160g nano zinc oxide (average particle size 500nm, spherical crystal), 18g antioxidant 1024, 10.8g antioxidant 697, 3.6g antioxidant DBHQ, 1.8g nano zirconium carbide (average particle size 200nm, cubic crystal), 1.8g nano titanium carbide (average particle size 200nm, cubic crystal), 0.29g nano titanium nitride (average particle size 700nm, cubic crystal, SW-TiN-003), 0.58g nano silicon nitride (average particle size 800nm, face centered cubic crystal), 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.

s1, drying PP resin, HDPE resin and EVA resin until the moisture is lower than 0.1% for later use;

mixing 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 18g of antioxidant 1024, 10.8g of antioxidant 697, 3.6g of antioxidant DBHQ, 1.8g of nano zirconium carbide, 1.8g of nano titanium carbide, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate in an internal mixer uniformly, and carrying out internal mixing at 165 ℃ for 300s;

s2, placing the banburying material obtained in the S1 into a double-screw extruder for melt extrusion, wherein the extrusion temperature is 175-195 ℃, and specifically, the banburying material is divided into five heating temperature areas, wherein the first temperature area is 170 ℃ +/-0.5 ℃, the second temperature area is 180 ℃ +/-0.5 ℃, the third temperature area is 190 ℃ +/-0.5 ℃, the fourth temperature area is 195 ℃ +/-0.5 ℃, the fifth temperature area is 195 ℃ +/-0.5 ℃, the screw speed is 38r/min, the die head temperature is 193.6 ℃, and the spinning masterbatch with the thickness of 1.0-1.2mm is obtained through wire drawing, water cooling and granulating, and drying until the moisture is lower than 0.1% for standby;

s3, taking 300D graphene wires (novel materials with a wire resistance of 1025.6 omega m) as core wires, placing spinning master batches in a double-screw extruder, wherein the extrusion temperature is 175-195 ℃, and specifically five heating temperature zones are formed, the first temperature zone is 170 ℃ +/-0.5 ℃, the second temperature zone is 180 ℃ +/-0.5 ℃, the third temperature zone is 190 ℃ +/-0.5 ℃, the fourth temperature zone is 195 ℃ +/-0.5 ℃, the fifth temperature zone is 195 ℃ +/-0.5 ℃, the screw rotating speed is 38r/min, the die head temperature is 192.8 ℃, the obtained extruded molten materials are adhered to the outer surface of the 300D graphene wires, the traction speed is 10.0cm/S, and the water cooling and heat treatment are carried out: the semi-finished yarn after water cooling is placed in a 60 ℃ oven for 3.6m of travel, enters a 80 ℃ oven for 5.4m of travel, enters a 60 ℃ oven for 3.6m of travel, and is subjected to air cooling at room temperature for 5.4m to obtain a 800D finished product heating wire. When the finished heating wire is used as the heating wire, the metal wire is connected with the outer layer of the finished heating wire instead of the core wire.

Control group 1: the difference from example 1 is that the extrusion temperature in S2 is 160-180℃and is specifically divided into five heating temperature zones, the first 150.+ -. 0.5 ℃, the second 165.+ -. 0.5 ℃, the third 170.+ -. 0.5 ℃, the fourth 180.+ -. 0.5 ℃, the fifth 180.+ -. 0.5 ℃, the screw speed is 35r/min, the die temperature is 179.3 ℃, drawing, water cooling and pelleting, and the 1.0-1.2mm spinning master batch is obtained. The tensile force of the finished product heating wire prepared by the obtained master batch is 150-200N (can be broken by manpower), the mechanical property is poor, particles can be seen outside the finished product heating wire, and the smoothness is relatively poor.

Control group 2: the difference from example 1 is that the extrusion temperature in S2 is 180-205 ℃, specifically five heating temperature zones are divided, the first temperature zone is 180 ℃ +/-0.5 ℃, the second temperature zone is 195 ℃ +/-0.5 ℃, the third temperature zone is 200 ℃ +/-0.5 ℃, the fourth temperature zone is 205 ℃ +/-0.5 ℃, the fifth temperature zone is 205 ℃ +/-0.5 ℃, the screw speed is 38r/min, the die head temperature is 203.8 ℃, and the spinning master batch of 1.0-1.2mm is obtained through drawing, water cooling and granulation. The tensile force of the finished product heating wire prepared by the obtained master batch is between 250 and 400N, which is greatly different from the mechanical property of the finished product heating wire in the embodiment 1. Although the finish on the outside of the finished heater wire was better in control 2 than control 1, filler particles were also observed locally.

In summary, the extrusion process parameters of the finished product heater wire in the present application are controlled as follows: the extrusion temperature is 175-195 ℃, and is specifically divided into five heating temperature areas, wherein the first temperature area is 170 ℃ +/-0.5 ℃, the second temperature area is 180 ℃ +/-0.5 ℃, the third temperature area is 190 ℃ +/-0.5 ℃, the fourth temperature area is 195 ℃ +/-0.5 ℃, the fifth temperature area is 195 ℃ +/-0.5 ℃, the screw speed is 38r/min, the die head temperature is 193.6 ℃, and the integral quality and the quality stability of the finished product heating wire can be ensured. And the subsequent research and development are carried out according to the extrusion process parameters.

Example 2

Example 2 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 20g of antioxidant 1024, 13g of antioxidant 697, 3g of nano zirconium carbide, 0.87g of nano silicon nitride, 2.9g of UV-531, 2.03g of UV-622 and 4g of zinc stearate.

Example 3

Example 3 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 20g of antioxidant 1024, 13g of antioxidant 697, 3g of nano zirconium carbide, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770, 4g of zinc stearate.

Example 4

Example 4 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 18g of antioxidant 1024, 9g of antioxidant 697, 3.6g of antioxidant DBHQ, 1.8g of nano zirconium carbide, 3.6g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate.

Example 5

Example 5 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate.

Example 6

Example 6 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 18g of antioxidant 1024, 8g of antioxidant 697, 4g of antioxidant DBHQ, 3g of nano zirconium carbide, 3g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770, 4g of zinc stearate.

Example 7

Example 7 differs from example 1 in that: and (3) controlling the banburying temperature in the step S1 at 160 ℃ for 350S.

Example 8

Example 8 differs from example 1 in that: and (3) controlling the banburying temperature in the step S1 at 165 ℃ for 320S.

Example 9

Example 9 differs from example 1 in that: and (3) controlling the banburying temperature in the step S1 at 168 ℃ for 280S.

Example 10

Example 10 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate. And the banburying temperature in the step S1 is controlled to be 165 ℃ for 300S.

Example 11

Example 11 differs from example 5 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 145g of nano zinc oxide, 15g of nano zirconium oxide (CAS No. 1314-23-4, hua Xiangke. Mu.), 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9gUV-234, 1.16g of UV-622, 0.87g of UV-770, 4g of zinc stearate.

Example 12

Example 12 differs from example 11 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 145g of nano zinc oxide, 15g of titanium tin carbide ultrafine powder (sub-Mei nanometer, average particle size 500 nm), 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770, 4g of zinc stearate.

Example 13

Example 13 differs from example 11 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 145g of nano zinc oxide, 10g of nano zirconium oxide, 5g of titanium tin carbide superfine powder, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate.

Example 14 differs from example 11 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 143g of nano zinc oxide, 10g of nano zirconium oxide, 5g of titanium tin carbide superfine powder, 2g of boron nitride nano tube (specification 1-3 microns, model AM-HBN-W-2), 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770, 4g of zinc stearate.

Example 15

Example 15 differs from example 11 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 143g of nano zinc oxide, 10g of nano zirconium oxide, 5g of titanium tin carbide superfine powder, 2g of boron nitride whisker (length of 10-20um 99.9%, average diameter: 1um, granularity: 10-20um, fibrous, andi number 0128), 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770, 4g of zinc stearate.

Example 16

Example 16 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 105.6g of nano zinc oxide, 16g of nano zirconium oxide, 32g of titanium tin carbide superfine powder, 6.4g of boron nitride nano-sheet (200 nm hexagonal boron nitride nano-sheet, rayleigh customization), 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770, 4g of zinc stearate.

Example 17

Example 17 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 140.8g of nano zinc oxide, 8g of nano zirconium oxide, 8g of titanium tin carbide superfine powder, 3.2g of boron nitride nano sheet, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate.

Example 18

Example 18 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine powder, 3.2g of boron nitride nano-sheet, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770, 4g of zinc stearate.

Example 19

Example 19 differs from example 18 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 270g of carbon black, 8g of titanium diboride, 22g of nano carbon fiber (heat-conducting and electric-conducting carbon fiber VGCF), 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine micropowder, 3.2g of boron nitride nanosheets, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770, and 4g of zinc stearate.

Example 20

Example 20 differs from example 18 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 270g of carbon black, 8g of titanium diboride, 22g of nano graphite powder (AM-C2-063-1 amorphous with average particle size of 100 nm), 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine micropowder, 3.2g of boron nitride nano sheet, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9gUV-234, 1.16g of UV-622, 0.87g of UV-770, 4g of zinc stearate.

Example 21

Example 21 differs from example 18 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 270g of carbon black, 8g of titanium diboride, 20g of nano graphite powder, 2g of titanium nitride whisker (length 10-20um 99.9%, average diameter: 1um, granularity: 10-20um, fiber form, andi No. 0128), 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine micropowder, 3.2g of boron nitride nanosheets, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770, 4g of zinc stearate.

Example 22

Example 22 differs from example 18 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 270g of carbon black, 8g of titanium diboride, 17g of graphene (heat conduction coefficient: 5300W/mK, brand-grade Zhaozhao), 5g of carbon nano tube (CAS: 308068-56-6), 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine micropowder, 3.2g of boron nitride nano sheet, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770, and 4g of zinc stearate.

Example 23

Example 23 differs from example 18 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 270g of carbon black, 8g of titanium diboride, 2g of titanium nitride whisker, 15g of graphene, 5g of carbon nano tube, 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine micropowder, 3.2g of boron nitride nano sheet, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate.

Example 24

Example 24 differs from example 18 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 270g of carbon black, 8g of titanium diboride, 2g of titanium nitride whisker, 12g of carbon nanofiber, 10g of nano graphite powder, 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine powder, 3.2g of boron nitride nano sheet, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9gUV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate.

Example 25

Example 25 differs from example 18 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 180g of carbon black, 15g of titanium diboride, 45g of nano carbon fiber, 54g of nano graphite powder, 6g of titanium nitride whisker, 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine micropowder, 3.2g of boron nitride nanosheet, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9gUV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate.

Example 26

Example 26 differs from example 18 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 234g of carbon black, 15g of titanium diboride, 15g of nano carbon fiber, 30g of nano graphite powder, 6g of titanium nitride whisker, 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine micropowder, 3.2g of boron nitride nanosheet, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9gUV-234, 1.16g of UV-622, 0.87g of UV-770, 4g of zinc stearate.

Example 27

Example 27 differs from example 18 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 210g of carbon black, 18g of titanium diboride, 36g of nano carbon fiber, 30g of nano graphite powder, 6g of titanium nitride whisker, 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine micropowder, 3.2g of boron nitride nanosheet, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9gUV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate.

Example 28

Example 28 differs from example 18 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 186g of carbon black, 20g of titanium diboride, 45g of nano carbon fiber, 30g of nano graphite powder, 4g of titanium nitride whisker, 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine micropowder, 3.2g of boron nitride nanosheet, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9gUV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate.

Example 29

Example 29 differs from example 18 in that: the carbon black was selected from Japanese, ECP 600JD.

Example 30

Example 30 differs from example 18 in that: the carbon black was selected as Czech AC-80 (type B).

Example 31

Example 31 differs from example 18 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine powder, 3.2g of boron nitride nano-sheet, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770, 2.5g of zinc stearate and 5g of KH570.

292g of carbon black, 8g of titanium diboride, 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine powder, 3.2g of boron nitride nano sheet, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride and 0.58g of nano silicon nitride are uniformly mixed to obtain a mixture A, and the mixture A is subjected to dry blending with 5g of KH570 coupling agent, and stirred at 300rpm for 30min to obtain a mixture B;

mixing 795g of PP resin, 420g of HDPE resin and 185g of EVA resin which are dried with the mixture B, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770 and 2.5g of zinc stearate in an internal mixer uniformly, and banburying at 165 ℃ for 300s;

S3, taking 300D graphene wires (novel materials with a wire resistance of 1025.6 omega m) as core wires, placing spinning master batches in a double-screw extruder, wherein the extrusion temperature is 175-195 ℃, and specifically five heating temperature zones are formed, the first temperature zone is 170 ℃ +/-0.5 ℃, the second temperature zone is 180 ℃ +/-0.5 ℃, the third temperature zone is 190 ℃ +/-0.5 ℃, the fourth temperature zone is 195 ℃ +/-0.5 ℃, the fifth temperature zone is 195 ℃ +/-0.5 ℃, the screw rotating speed is 38r/min, the die head temperature is 192.8 ℃, the obtained extruded molten materials are adhered to the outer surface of the 300D graphene wires, the traction speed is 10.0cm/S, and the water cooling and heat treatment are carried out: the semi-finished yarn after water cooling is placed in a 60 ℃ oven for 3.6m of travel, enters a 80 ℃ oven for 5.4m of travel, enters a 60 ℃ oven for 3.6m of travel, and is subjected to air cooling at room temperature for 5.4m to obtain a 800D finished product heating wire.

Comparative example

Comparative example 1 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 28.8g of antioxidant 1010, 3.6g of antioxidant 168, 3.6g of antioxidant DLTP, 0.87g of nano silicon nitride, 2.9g of UV-531, 2.03g of UV-622 and 4g of zinc stearate.

Comparative example 2 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 28.8g of antioxidant 1010, 3.6g of antioxidant 168, 3.6g of antioxidant 300, 0.87g of nano silicon nitride, 2.9g of UV-531, 2.03g of UV-622 and 4g of zinc stearate.

Comparative example 3 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 28.8g of antioxidant 1076, 3.6g of antioxidant 168, 3.6g of antioxidant DLTP, 0.87g of nano silicon nitride, 2.9g of UV-531, 2.03g of UV-622 and 4g of zinc stearate.

Comparative example 4 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 9g of antioxidant 1010, 9g of antioxidant 1024, 9g of antioxidant 626, 9g of antioxidant 2246A, 0.87g of nano silicon nitride, 2.9g of UV-531, 2.03g of UV-622, 4g of zinc stearate.

Comparative example 5 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 19.8g of antioxidant 1024, 10.8g of antioxidant 697, 5.4g of antioxidant DBHQ, 0.87g of nano silicon nitride, 2.9g of UV-531, 2.03g of UV-622 and 4g of zinc stearate.

Comparative example 6 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 20g of antioxidant 1024, 13g of antioxidant 697, 3g of nano zirconium carbide, 3.2g of UV-531, 2.6g of UV-234 and 4g of zinc stearate.

Comparative example 7 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 20g of antioxidant 1024, 13g of antioxidant 697, 3g of nano zirconium carbide, 2.9g of UV-326, 2.9g of UV-327 and 4g of zinc stearate.

Comparative example 8 differs from example 2 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of nano zinc oxide, 20g of antioxidant 1024, 13g of antioxidant 697, 3g of nano zirconium carbide, 4.5g of UV-531, 1.3g of UV-622 and 4g of zinc stearate.

Comparative example 9 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g PP resin, 420g HDPE resin, 185g EVA resin, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 20g antioxidant 1024, 13g antioxidant 697, 3g nano zirconium carbide, 2.9g UV-234, 1.74g UV-622, 1.16g UV-770, 4g zinc stearate.

Comparative example 10 differs from example 1 in that: the external line is prepared from the following raw materials in percentage by mass: 795g PP resin, 420g HDPE resin, 185g EVA resin, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 20g antioxidant 1024, 13g antioxidant 697, 3g nano zirconium carbide, 1.2g UV-326, 0.5g UV-327, 0.3g nano titanium dioxide, 3.2g UV-531, 0.6g UV-622, 4g zinc stearate.

Comparative example 11 differs from example 1 in that: and (3) controlling the banburying temperature in the step S1 at 160 ℃ for 400S.

Comparative example 12 differs from example 1 in that: and (3) controlling the banburying temperature in the step S1 at 168 ℃ for 250S.

Comparative example 13 differs from example 1 in that: and (3) controlling the banburying temperature in the step S1 to 158 ℃, and banburying for 420S.

Comparative example 14 differs from example 1 in that: s3, taking the graphene wire as a core wire, placing the spinning master batch in a double-screw extruder, wherein the extrusion temperature is 175-195 ℃, and specifically, the spinning master batch is divided into five heating temperature areas, wherein the first temperature area is 170 ℃ +/-0.5 ℃, the second temperature area is 180 ℃ +/-0.5 ℃, the third temperature area is 190 ℃ +/-0.5 ℃, the fourth temperature area is 195 ℃ +/-0.5 ℃, the fifth temperature area is 195 ℃ +/-0.5 ℃, the screw speed is 38r/min, the die head temperature is 193.3 ℃, the obtained extrusion molten material is attached to the outer surface of the graphene wire, the traction speed is 10cm/S, and the semi-finished yarn after water cooling and water cooling is placed in a room temperature air duct for 5.4m of air cooling travel, so as to obtain the finished product heating wire.

Comparative example 15 differs from example 5 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 145g of nano zinc oxide (average particle size 20nm, spherical crystal form), 15g of nano zirconium oxide, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770, 4g of zinc stearate.

Comparative example 16 differs from example 5 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 292g of carbon black, 8g of titanium diboride, 160g of ultrafine zinc oxide (average particle size of 1-3 microns), 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate.

Comparative example 17 differs from example 18 in that: the external line is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of EVA resin, 300g of carbon black, 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine powder, 3.2g of boron nitride nano-sheet, 18g of antioxidant 1024, 10g of antioxidant 697, 3.0g of antioxidant DBHQ, 2.2g of nano zirconium carbide, 2.9g of nano titanium carbide, 0.29g of nano titanium nitride, 0.58g of nano silicon nitride, 2.9g of UV-234, 1.16g of UV-622, 0.87g of UV-770 and 4g of zinc stearate.

Comparative example 18

The heating wire is prepared from the following raw materials in parts by mass: 1200g of HDPE resin, 450g of EVA resin, 480g of PP resin, 540g of conductive carbon black, 15g of nickel powder, 120g of nano zinc oxide, 2.4g of PE wax, 3g of zinc stearate, 60g of antioxidant 1010, 45g of antioxidant 1024, 36.6g of antioxidant 626 and 48g of antioxidant 2246A.

The preparation method comprises the following steps:

firstly, weighing HDPE resin, EVA resin and PP resin for drying treatment, and weighing 1200g of dried HDPE resin, 450g of EVA resin and 480g of PP resin for standby;

step two, weighing 540g of conductive carbon black, 15g of nickel powder, 120g of nano zinc oxide, 2.4g of PE wax, 3g of zinc stearate, 60g of antioxidant 1010, 45g of antioxidant 1024, 36.6g of antioxidant 626 and 48g of antioxidant 2246A, and adding the mixture into a high-speed dispersion kettle together with 1200g of HDPE resin, 450g of EVA resin and 480g of PP resin which are dried, and uniformly mixing to obtain a mixture;

placing the obtained mixture into an internal mixer for banburying at 160 ℃ for 300 seconds, enabling the material to be in a flowing state, placing the obtained flowing state material into an extruder for melt extrusion, drawing, cooling and solidifying the extruded material, sending the solidified strip material into a granulator for granulation, obtaining spinning master batches with the particle size of 1.0-1.2mm, drying the obtained spinning master batches, and then preserving the dried spinning master batches in vacuum for later use;

and step four, adopting 300D cotton thread as a connection yarn, extruding spinning master batch at 160-170 ℃, adhering extruded molten materials to the outer surface of the polyester yarn, water-cooling, and drying to obtain a finished product of electric heating wire.

Performance test

Detection method/test method

1. A 12.0cm electrothermal wire is selected as a test object, and the resistance is the test condition: -40 ℃ to 85 ℃,65% rh; the power supply voltage is 36V or 220V; the test length was 12.0cm, and the copper wire was used to connect the two ends of the heating wire, and the resistance of the connection copper wire was 0.1. OMEGA. And (3) power test: the test was performed using a multichannel power analyzer 8962A1 of a green intelligent instrument. Resistance test: the test was performed using an XR-1A fiber specific resistance tester from Shanghai New fiber instruments. The electric heating wire is subjected to continuous electrifying test, and the change condition of the resistance of the electric heating wire at different temperatures is recorded.

2. Mechanical strength test: tensile force test according to the test method for measuring the tensile property of GBT 1040.2-2006 plastic, the external fracture of the outer layer of the electric heating wire is used as a tensile force measurement test standard. Elongation at break test method according to the determination of tensile properties of GBT 1040.2-2006 plastics.

3. Flexibility test: bending at room temperature 90 ° and repeating bending 10 ⁴ Next, it was observed whether or not cracks appear on the wire surface. Bending at-40 ℃ for 90 degrees and repeating bending for 100 times, and visually observing whether cracks appear on the surface of the wire rod.

4. The ageing resistance is kept at 85 ℃/80% humidity, and oxygen is continuously blown; and (3) placing the sample in a model YSGJS high-low temperature damp-heat aging box for aging for 1000 hours, and testing the tensile force, elongation at break and power change.

5. Ultraviolet resistance test: the model SHA-PV ultraviolet ageing oven is set, wherein the air conditioner operates for half an hour before the test, and whether the instrument parts are normal or not is checked; the total irradiation amount was set to about 22.5kwh/m ² The temperature of the blackboard is 60 ℃ and the condensing temperature is 40 ℃; placing the test pieces into an ultraviolet aging oven (each block for ensuring sufficient radiation of the test piecesAt most two samples are placed on the sample plate), ultraviolet light irradiation and condensation are alternately performed every 4 hours, the total irradiation time is 1000 hours, and the tensile force, the elongation at break and the power change are tested.

Data analysis

Table 1 shows the mechanical and weather-resistant test parameters of the electric wires in examples 1 to 10 and comparative examples 1 to 14

Table 2 is a table of bending test parameters of the electric wires in examples 1 to 10 and comparative examples 1 to 14

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As can be seen in combination with examples 1-10 and comparative examples 1-14 and in combination with tables 1-2, example 2 compares with comparative examples 1-5 to see: the mechanical property, bending resistance and weather resistance of the electric heating wire in the embodiment 2 are superior to those of the comparative examples 1-5, namely the mechanical property of the electric heating wire prepared by compounding the antioxidant composition and the ultraviolet resistance auxiliary agent provided by the application is obviously improved, the thermal oxygen degradation in the processing process is effectively slowed down under the synergistic effect of the two auxiliary agents, the integral mechanical property can be improved, the integral processing technology can be optimized, the banburying temperature can reach 162-168 ℃, the banburying tolerance time is improved, the flowability of the material is better, the material is more convenient to fully and uniformly mix with the filler, the internal defects of the electric heating wire of the product are reduced, and the mechanical property and flexibility of the finished product electric heating wire are obviously optimized and improved. Therefore, the antioxidant composition is composed of at least one of nano zirconium carbide, nano zirconium silicide and nano titanium carbide matched with at least one of antioxidant 1024, antioxidant 697 and antioxidant BHT matched with antioxidant DSTP and/or antioxidant DBHQ, and the combined ultraviolet resistance auxiliary agent is composed of at least one of nano titanium dioxide, nano titanium nitride and nano silicon nitride matched with at least one of UV-531 and UV-234 matched with at least one of UV622, UV-770, UV-944 and UV-783, and the prepared electric heating wire has good mechanical strength, bending resistance and flexibility.

As can be seen in combination with examples 1-10 and comparative examples 1-14 and in combination with tables 1-2, example 2 compares with comparative examples 6-10: the mechanical properties, bending resistance and weather resistance of the electric heating wire in example 2 are better than those of comparative examples 6-10, namely the mechanical properties of the electric heating wire prepared by the antioxidant composition and the ultraviolet resistance auxiliary agent provided by the application are obviously improved, and the selection of the ultraviolet resistance auxiliary agent and the specific antioxidant composition have positive effects on improving the overall processing performance and mechanical strength. Therefore, the antioxidant composition is composed of at least one of nano zirconium carbide, nano zirconium silicide and nano titanium carbide matched with at least one of antioxidant 1024, antioxidant 697 and antioxidant BHT matched with antioxidant DSTP and/or antioxidant DBHQ, and the combined ultraviolet resistance auxiliary agent is composed of at least one of nano titanium dioxide, nano titanium nitride and nano silicon nitride matched with at least one of UV-531 and UV-234 matched with at least one of UV622, UV-770, UV-944 and UV-783, and the prepared electric heating wire has good mechanical strength, bending resistance and flexibility.

As can be seen from the combination of examples 1 to 10 and comparative examples 1 to 14 and the combination of tables 1 to 2, when example 1 is compared with examples 2 to 6, the UV-resistant auxiliary agent is composed of nano silicon nitride, nano titanium nitride, UV-234, UV622, UV-944 and the mass ratio of nano silicon nitride, nano titanium nitride, UV-234, UV622, UV-944 is 10: (5-20): 100: (5-40): (5-40); the antioxidant composition consists of nano zirconium carbide, nano titanium carbide, an antioxidant 1024, an antioxidant 697 and an antioxidant DBHQ, wherein the mass ratio of the nano zirconium carbide to the nano titanium carbide to the antioxidant 1024 to the antioxidant 697 to the antioxidant DBHQ is 10: (5-20): 100: (20-80): the electric heating wire prepared in the step (5-40) has good mechanical strength, bending resistance and flexibility. The resulting combination of the optimal antioxidant composition plus uv resistant aid is biased towards example 1 based on cost considerations and example 5 is selected based on performance advantages. The best protocol for the test was example 10 after optimizing the mixing temperature of the heating wire on the basis of example 5.

As can be seen from the combination of examples 1-10 and comparative examples 1-14 and the combination of tables 1-2, the internal mixing temperature and internal mixing time have a critical effect on the mechanical properties and flexibility of the heating wire, and the internal mixing temperature is 160-168 ℃ and the time is 280-350s, which are more suitable based on the formula of the application. Too high banburying temperature can lead to the reduction of the mechanical properties of the finished product electric heating wire, too low banburying temperature can lead to uneven mixing of the filler, and the reduction of the mechanical properties of the finished product electric heating wire is serious, shenzhen can not agglomerate, and the subsequent adding and extruding process is influenced. The control of the banburying time is not easy to be overlong, otherwise, the mechanical property of the finished product electric heating wire is reduced, the filler is unevenly mixed due to the fact that the control of the banburying time is too short, the mechanical property of the finished product electric heating wire is severely reduced, the forming of clusters is not realized, and the subsequent adding and extrusion process is influenced. In the test process, under the combination of the formula of the application, the mechanical property and the folding resistance of the electric wire prepared by banburying at 165 ℃ in S1 and banburying for 300S are relatively excellent, and the filler can be fully and uniformly mixed, so that the later extrusion processing is facilitated. The antioxidant composition and the ultraviolet-resistant auxiliary agent provided by the application can influence the processing technology of the electric heating wire, slow down the thermooxygen degradation in the processing process, expand the banburying temperature threshold value, ensure that the fluidity of materials is better, are convenient to be fully and uniformly mixed with filler, reduce the internal defects of the electric heating wire of the product, ensure that the mechanical property and the flexibility of the electric heating wire of the final finished product are relatively obviously optimized, and further optimize the formula of the electric heating wire based on the formula.

Table 3 shows the mechanical and weather-resistant test parameters of the heating wires in examples 5, 11 to 18 and comparative examples 15 to 16

Table 4 is a table of bending resistance test parameters of the heating wires in examples 5, 11 to 18 and comparative examples 15 to 16

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As can be seen in combination with examples 5, 11-18 and comparative examples 15-16 and in combination with tables 3-4, example 5 compares with comparative examples 15-16: the mechanical property and bending resistance of the prepared electric wire with the average particle diameter of the nano zinc oxide controlled between 20 and 500nm are relatively good.

As can be seen in combination with examples 5, 11-18 and comparative examples 15-16 and in combination with tables 3-4, a comparison between example 5 and examples 11-18 shows that: the reinforcing auxiliary agent for the silk thread mainly comprises nano zinc oxide, nano zirconium oxide, titanium tin carbide superfine micropowder and boron nitride nanotube, wherein the mass ratio of the nano zinc oxide, the nano zirconium oxide, the titanium tin carbide superfine micropowder and the boron nitride nanotube is controlled to be (55-90): 5-20): 0.5-5, and the prepared electric heating wire has better mechanical strength and weather resistance, and the mass ratio of the nano zinc oxide, the nano zirconium oxide, the titanium tin carbide superfine micropowder and the boron nitride nanotube is preferably controlled to be (78-88): 5-8): 5-12): 2.

Table 5 is an intelligent control performance test table of the heating wires in example 5 and comparative examples 15 to 16

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As can be seen in combination with example 5, example 18 and comparative examples 15-16 and in combination with tables 3-5, example 5 compares with comparative examples 15-16: the electric heating wire prepared by controlling the average grain diameter of the adopted nano zinc oxide at 500nm has relatively good mechanical property and bending resistance and has good intelligent temperature control effect.

As can be seen in combination with example 5, example 18 and comparative examples 15-16 and in combination with tables 3-5, a comparison of example 18 with example 5 shows that: the reinforcing auxiliary agent for the silk thread is composed of nano zinc oxide, nano zirconium oxide, titanium tin carbide superfine micropowder and boron nitride nano tube, the mass ratio of the nano zinc oxide, the nano zirconium oxide, the titanium tin carbide superfine micropowder and the boron nitride nano tube is controlled at 78:8:12:2, the intelligent temperature control effect of the prepared electric heating wire is similar to that of the embodiment 5, but the mechanical property and bending resistance of the electric heating wire in the embodiment 18 are obviously improved, and the application range of the electric heating wire provided in the scheme of the embodiment 18 is widened.

Table 6 shows the mechanical and weather resistance test parameters of examples 18 to 31 and comparative examples 17 to 18

Table 7 shows the bending resistance test parameters of the heating wires of examples 18 to 31 and comparative examples 17 to 18

Table 8 shows intelligent control performance test tables of heating wires in examples 24, 28 to 31 and comparative examples 17 to 18

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It can be seen from the combination of examples 18 to 31 and comparative examples 17 to 18 and the combination of tables 6 to 8 and tables 1 to 3 that the addition of nano titanium diboride improves the electrical conductivity and also improves the mechanical strength, flexibility and weather resistance of the heating wire as compared with comparative example 17 in example 18.

As can be seen from the combination of examples 18 to 31 and comparative examples 17 to 18 and tables 6 to 8 and tables 1 to 3, the mechanical strength of the heating wire is significantly improved by adding the coupling agent in example 18 as compared with example 31, but the intelligent temperature control performance of the heating wire is reduced with the addition of the coupling agent. The electrothermal wire product is suitable for being applied to scenes with high requirements on mechanical properties of wires and intelligent temperature control performance, such as novel covering materials in a seventh subclass of 'novel textile materials' in a third subclass of the national torch plan priority development field.

As can be seen from the combination of examples 18-31 and comparative examples 17-18 and the combination of tables 6-8 and tables 1-3, the electric heating wires prepared in the present application are superior to the electric heating wires of the prior art in terms of conductivity, mechanical strength, flexibility, weather resistance, and broaden the application fields, as compared with comparative example 18. And the intelligent temperature control performance of the heating wire in the application is more excellent, the heating wire can be suitable for 36V power supply heating, the use safety performance is relatively better, and the application field is wider. In the design process of the heating module, the length (interval) of the heating wire with the intelligent temperature control function in the heating cloth can be designed longer, so that the whole production cost is low, the heating uniformity performance is improved, and the application field is wider, such as the application in the fields of sleeping bags, yoga mats, physiotherapy mats and the like.

As can be seen from the combination of examples 18 to 31 and comparative examples 17 to 18 and the combination of tables 6 to 8 and tables 1 to 3, the comparison between examples 18 to 31 shows that the electric heating wire prepared from the conductive composition consisting of nano titanium diboride, nano carbon black, nano carbon fiber, nano graphite powder and titanium nitride whisker is easier to form a conductive network, improves the conductive performance of the finished product electric heating wire, and widens the application field. In addition, the prepared electric heating wire has relatively better mechanical property, flexibility, weather resistance and wear resistance, and can further widen the application field.

As can be seen in combination with examples 18-31 and comparative examples 17-18 and in combination with tables 6-8 and tables 1-3, example 18 was found during the actual test as compared with examples 29-30: the different sources of carbon black have a significant effect on the overall conductivity, i.e., have a greater effect on the quality of the finished heating wire, and in this application, the bot conductive carbon black VXC72 is preferred. In addition, the conductive composition in the application is at least one of nano titanium diboride, nano carbon black, nano tin oxide, nano nickel oxide, nano indium oxide, nano carbon fiber, nano graphite powder, graphene, carbon nano tube and titanium nitride whisker, and the wire resistance of the finished product heating wire is regulated by adopting at least one material of the nano titanium diboride, the nano tin oxide, the nano nickel oxide, the nano indium oxide, the nano carbon fiber, the nano graphite powder, the graphene, the carbon nano tube and the titanium nitride whisker, which are matched with the carbon black, so that the conductive performance, the mechanical strength, the flexibility and the weather resistance can be well improved, and the stability of the quality stability of the finished product is better regulated.

In conclusion, compared with the existing heat tracing band and PTC heating wire, the heating wire has relatively good mechanical strength, flexibility, electric conduction performance and weather resistance, and is wider in application field and better in market prospect. The heating module component in the application is wide in application, can replace the existing heat tracing belt and PTC heating wire products to be used, and can be applied to multiple fields due to excellent physical and chemical properties, so that the intelligent temperature control function is fully exerted, and the product competitiveness is improved.

The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims

1. An electric heating wire with intelligent temperature control function, which is characterized in that: the graphene composite wire comprises a core wire and an outer wire compounded on the outer wall of the core wire, wherein the core wire is a graphene wire with the dimension of 100-600D; the external line is prepared from the following raw materials in percentage by mass: 15.0-20.0% of conductive composition, 8.0-10.0% of reinforcing auxiliary agent for silk threads, 1.35-1.74% of antioxidant composition, 0.24-0.35% of uvioresistant auxiliary agent, 0.10-0.40% of dispersing agent and the balance of matrix resin;

The matrix resin mainly comprises PP resin, HDPE resin and EVA resin; the mass ratio of the PP resin to the EVA resin to the HDPE resin is controlled to be 795:185:420;

the electric heating wire with the intelligent temperature control function is placed at 10 ℃ to measure the wire resistance as A1, and the A1 is controlled at 1.0 x 10 ³ -5*10 ⁴ Ω×m; the electric heating wire with the intelligent temperature control function is placed at the temperature of minus 40 ℃ to measure the wire resistance as A2, and the A1 is 1.5-3.0 times of the A2; the electric heating wire with the intelligent temperature control function is placed at 60 ℃ to measure the wire resistance as A3, wherein A3 is 1.5-2.0 times of A1; the electric heating wire with the intelligent temperature control function is placed at 80 ℃ to measure the wire resistance as A4, wherein A4 is 2.5-10 times of A1;

the conductive composition mainly comprises nano titanium diboride, nano carbon black, nano carbon fiber, nano graphite powder and titanium nitride whisker; the average grain diameter of the nano titanium diboride is 0.05-3 microns, and the nano titanium diboride is hexagonal; the nano graphite powder is flake graphite powder, and the average particle size is 0.2-1.0 microns;

the mass ratio of the nano titanium diboride to the nano carbon black to the nano carbon fiber to the nano graphite powder to the titanium nitride whisker is controlled to be (5-10), 60-80, 5-20, 10-40 and 0.5-5;

the reinforcing auxiliary agent for the silk thread mainly comprises nano zinc oxide, nano zirconium oxide, titanium tin carbide superfine micropowder and boron nitride nanosheets; the mass ratio of the nanometer zinc oxide to the nanometer zirconium oxide to the superfine titanium tin carbide micro powder to the boron nitride nano sheet is controlled to be (55-90)/(5-20)/(0.5-5);

The dispersing agent is at least one of stearate and a coupling agent;

the antioxidant composition mainly comprises nano zirconium carbide, nano titanium carbide, an antioxidant 1024, an antioxidant 697 and an antioxidant DBHQ; the mass ratio of the nanometer zirconium carbide to the nanometer titanium carbide to the antioxidant 1024 to the antioxidant 697 to the antioxidant DBHQ is 10: (5-20): 100: (20-80): (5-40);

the ultraviolet resistance auxiliary agent mainly comprises nano silicon nitride, nano titanium nitride, UV-234, UV622 and UV-944; the mass ratio of the nano silicon nitride to the nano titanium nitride to the UV-234 to the UV622 to the UV-944 is 10: (5-20): 100: (5-40): (5-40);

the preparation method of the electric heating wire with the intelligent temperature control function comprises the following steps of: s1, placing the dried matrix resin, the conductive composition with accurate measurement, the reinforcing auxiliary agent for silk threads, the antioxidant composition, the ultraviolet resistance auxiliary agent and the dispersing agent into an internal mixer, and carrying out internal mixing after uniformly mixing at 160-168 ℃ for 280-350S; s2, placing the banburying material obtained in the S1 into a double-screw extruder for melt extrusion, wiredrawing, cooling and granulating to obtain 1.0-2.0mm spinning master batch, and drying until the moisture is lower than 0.1%; and S3, taking the graphene wire as a core wire, putting the spinning master batch into a double-screw extruder, extruding at 175-200 ℃, adhering the obtained extruded molten material to the outer surface of the core wire, and performing water cooling, heat treatment and drying to obtain a finished product of the heating wire.

2. A heating module assembly, characterized in that: the electric heating device comprises heating cloth, a connecting wire and a power connector, wherein the connecting wire is communicated with the heating cloth; the heating cloth, the connecting wires, the power connector and the power supply form a current loop, and the heating cloth is electrified to generate heat to play a heating role; the heating cloth comprises an insulating heat-conducting film and a heating net positioned in the insulating heat-conducting film, the heating net is of a plain weave structure, warp threads in the heating net comprise weaving yarns A and a plurality of metal conductive wires, the metal conductive wires are parallel to the weaving yarns A, and the metal conductive wires are positioned at two ends of the warp threads of the heating net in the warp direction; the wefts in the heating net comprise knitting yarns B and a plurality of electric heating wires with intelligent temperature control functions in claim 1, the electric heating wires are parallel to the knitting yarns B, and two ends of the electric heating wires are connected with adjacent metal conductive wires; one end of the metal conductive wire is connected with the connecting wire.

3. A heating module assembly as set forth in claim 2 wherein: be applied to carpet, ground mat, mattress, yoga mat, physiotherapy pad, cushion, dress filler, waistband, muffler, binder, sofa, flower art, crops are planted, the poultry field, the cushion includes aircraft cushion, train cushion, high-speed railway cushion, car cushion, bus cushion, realizes safe intelligent control by temperature change function purpose.

4. A heating module assembly, characterized in that: the electric heating device comprises heating cloth, a connecting wire and a power connector, wherein the connecting wire is communicated with the heating cloth; the heating cloth, the connecting wires, the power connector and the power supply form a current loop, and the heating cloth is electrified to generate heat to play a heating role; the heating cloth is prepared by adopting a spray melting process or a spunbonding process; the heating cloth comprises heating wires with the diameter of 0.1-1.0mm, wherein the heating wires comprise an electric heating wire with an intelligent temperature control function and an insulating heat conduction TPU protective outer film layer which are used as a core layer in the claim 1; the electric heating wire in the heating wire is communicated with a power supply through the connecting wire and the power connector to form current reflux, so that the effect of electrifying and heating is achieved; the heat conductivity coefficient of the insulating heat conducting TPU protective outer film layer is 1.0-3.5W/M x K; the thickness ratio of the electric heating wire to the insulating heat conducting TPU protective outer film layer is controlled to be (6-8) (1-4); the insulation heat conduction TPU protective outer film layer is mainly prepared from the following raw materials in parts by weight: 100 parts of TPU resin granules with the Shore hardness of 30-90A, 15-25 parts of insulating heat conducting filler, 1-3 parts of coupling agent, 0.5-2 parts of dispersing agent, 0.5-2 parts of antioxidant and 0.3-0.8 part of antioxidant auxiliary agent; the insulating heat-conducting filler is at least one of nano aluminum nitride, nano boron nitride, heat-conducting spherical aluminum oxide, nano magnesium silicon nitride, nano silicon carbide and carbon nano tube grafted boron nitride heat-conducting filler.