CN116496570A - Electrothermal material with intelligent temperature control function and preparation method thereof - Google Patents

Electrothermal material with intelligent temperature control function and preparation method thereof Download PDF

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CN116496570A
CN116496570A CN202310460090.1A CN202310460090A CN116496570A CN 116496570 A CN116496570 A CN 116496570A CN 202310460090 A CN202310460090 A CN 202310460090A CN 116496570 A CN116496570 A CN 116496570A
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nano
resin
antioxidant
electric heating
temperature control
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CN116496570B (en
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Zhejiang Danting New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/40—Heating elements having the shape of rods or tubes
    • H05B3/54—Heating elements having the shape of rods or tubes flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Resistance Heating (AREA)

Abstract

The application relates to the technical field of electric heating materials, in particular to an electric heating material with an intelligent temperature control function and a preparation method thereof. An electrothermal material with intelligent temperature control function is mainly prepared from the following raw materials: conductive composition, auxiliary co-agent, antioxidant composition, ultraviolet resistance additive, dispersant and matrix resin; the matrix resin mainly comprises PP resin, HDPE resin and a compatilizer; the compatilizer is at least one of EAA, EVA, TPU, PCTG resins. The electric heating material can be prepared into an electric heating film and an electric heating wire, and has relatively excellent mechanical strength, flexibility, electric conduction performance and weather resistance compared with the existing electric heating material, and has wider application field and better market prospect.

Description

Electrothermal material with intelligent temperature control function and preparation method thereof
Technical Field
The application relates to the technical field of electric heating materials, in particular to an electric heating material with an intelligent temperature control function and a preparation method thereof.
Background
The heating wire is a heating wire capable of being electrified to release heat, 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. For safety, an external electronic control module is needed for temperature control, potential safety hazards caused by overhigh temperature are reduced, and the adaptation safety of the device is ensured. Therefore, the application provides an electric heating wire with an intelligent temperature control function.
Disclosure of Invention
In order to solve the technical problems, the application provides an electrothermal material with an intelligent temperature control function and a preparation method thereof.
In a first aspect, the application provides an electric heating material with intelligent temperature control function, which is realized through the following technical scheme:
the electric heating material with the intelligent temperature control function is mainly prepared from the following raw materials in percentage by mass: 15.0-20.0% of conductive composition, 5.0-10.0% of auxiliary synergistic auxiliary agent, 1.2-1.8% of antioxidant composition, 0.2-0.4% of uvioresistant auxiliary agent, 0.10-0.50% of dispersing agent and the balance of matrix resin; the matrix resin mainly comprises PP resin, HDPE resin and a compatilizer; the mass ratio of the PP resin to the HDPE resin to the compatilizer is controlled to be (750-800): 380-440): 180-250; the compatilizer is at least one of EAA resin, EVA resin, TPU resin and PCTG resin; 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 auxiliary synergistic agent is at least one of nano zinc oxide, nano zirconium oxide, nano aluminum nitride, nano aluminum oxide, titanium tin carbide superfine micropowder, boron nitride nanosheet and boron nitride whisker; the electrothermal material with the intelligent temperature control function is used for preparing an electrothermal film material with the intelligent temperature control function through a tape casting or calendaring process; or the electric heating material master batch spinning process with the intelligent temperature control function prepares the electric heating wire rod with the intelligent temperature control function.
The electric heating material can be prepared into an electric heating film and an electric heating wire, intelligent temperature control can be realized without externally connecting an electric control module for temperature control, and compared with the existing electric heating material, the electric heating material has relatively excellent mechanical strength, flexibility, electric conductivity and weather resistance, and has wider application field and better market prospect.
Preferably, when the electric heating material masterbatch spinning process with the intelligent temperature control function is used for preparing the electric heating wire rod with the intelligent temperature control function, the mass ratio of the PP resin to the HDPE resin to the compatilizer is controlled to be (790-800): 420-430): 180-200; the compatilizer consists of (10-20): 55-80): 10-25 by mass ratio of EAA resin, TPU resin and PCTG resin; the shore hardness of TPU resin in the electric heating wire is controlled to be 65-95A; the dispersing agent is at least one of stearate and a coupling agent.
By adopting the technical scheme, the bonding stability of the whole electric heating wire rod can be improved, and the whole electric heating wire rod is guaranteed to have better physical and chemical properties and weather resistance, longer service life and better market competitive advantage.
Preferably, when the electrothermal material with the intelligent temperature control function is prepared into the electrothermal film material with the intelligent temperature control function through a tape casting or calendaring process, the mass ratio of the PP resin to the HDPE resin to the compatilizer is controlled to be (790-800): (400-420): (220-250); the compatilizer consists of EAA resin and TPU resin; the mass ratio of the EAA resin to the TPU resin is (15-30) to (70-85); the shore hardness of TPU resin in the electrothermal film material is controlled to be 30-70A.
By adopting the technical scheme, the integral casting processing performance, mechanical properties (particularly the tensile fracture rate is obviously improved) and flexibility of the electrothermal film material can be improved, the electrothermal film material is endowed with longer service life, and the electrothermal film material has better market competitive advantage.
Preferably, the TPU resin in the electric heating wire rod is mainly prepared from the following raw materials: isocyanate composition, chain extender, polyol, catalyst and auxiliary agent; the auxiliary agent comprises at least one of a leveling agent, an antioxidant, an ultraviolet absorber, a flame retardant, a lubricant and a mold release agent; the catalyst is organic bismuth or organic tin; the mass of the catalyst is 0.01% -0.1% of the total mass of the isocyanate composition, the chain extender and the polyol; the isocyanate composition is composed of HDI and MDI; the molar ratio of MDI to HDI is (0.2-0.35): (0.65-0.80); the chain extender is composed of at least two of 3 methyl-1, 5-pentanediol, 1,4 butanediol, 1,6 hexanediol, ethylenediamine, hydrazine hydrate, 1, 4-butanediamine and 1,6 hexamethylenediamine and at least one of 2, 6-toluenediamine and diethyltoluenediamine; the polyalcohol mainly comprises polycarbonate diol with molecular weight of 1000-4000, propylene glycol polyether with molecular weight of 1000-4000 and polytetrahydrofuran diol with molecular weight of 1000-4000; the total mole of the propylene glycol polyether with the molecular weight of 1000-4000 and the polytetrahydrofuran glycol with the molecular weight of 1000-4000 accounts for 60-80% of the total mole of the polyol; the molar ratio of the propylene glycol polyether with the molecular weight of 1000-4000 to the polytetrahydrofuran glycol with the molecular weight of 1000-4000 is 1 (0.5-2); the ratio of the sum of the molar amounts of hydroxyl groups in the polyol and chain extender to the molar amount of-NCO-in the isocyanate composition is 1 (0.985-0.998); the hard segment content in the TPU resin is controlled to be 45-52wt%.
By adopting the technical scheme, the overall bonding stability of the electric heating wire rod can be further improved, and further the overall physical and chemical properties and weather resistance are guaranteed, the service life is prolonged, and the electric heating wire rod has better market competitive advantage.
Preferably, the TPU resin in the electrothermal film material is mainly prepared from the following raw materials: isocyanate composition, chain extender, polyol, catalyst and auxiliary agent; the auxiliary agent comprises at least one of a leveling agent, an antioxidant, an ultraviolet absorber, a flame retardant, a lubricant and a mold release agent; the catalyst is organic bismuth or organic tin; the mass of the catalyst is 0.01% -0.1% of the total mass of the isocyanate composition, the chain extender and the polyol; the isocyanate composition is composed of HDI and MDI; the molar ratio of MDI to HDI is (0.01-0.1): (0.9-0.99); the chain extender is composed of at least one of 3 methyl-1, 5-pentanediol, 1,4 butanediol, 1,6 hexanediol, glycerol, ethylene glycol and 1,3 propanediol, and at least one of ethylenediamine, hydrazine hydrate, 1, 4-butanediamine, 1,6 hexamethylenediamine, 2, 6-toluenediamine and diethyltoluenediamine; the polyalcohol mainly comprises polycarbonate diol with molecular weight of 1000-4000, polytetrahydrofuran diol with molecular weight of 1000-4000 and double-end diamine type reactive silicone with molecular weight of 5000-10000; the double-end diamine reactive silicone with the molecular weight of 5000-10000 accounts for 5-10% of the total mole of the polyol; the ratio of the sum of the molar amounts of hydroxyl groups in the polyol and chain extender to the molar amount of-NCO-in the isocyanate composition is 1 (0.985-0.998); the hard segment content in the TPU resin is controlled to be 40-46wt%.
By adopting the technical scheme, the overall tape casting processability, mechanical properties (particularly the tensile fracture rate is obviously improved) and flexibility of the electrothermal film material can be further improved, the electrothermal film material is endowed with longer service life, and the electrothermal film material has better market competitive advantage.
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 resistance of the prepared electric heating material can be adjusted, the electric heating material is applicable to voltages with different voltages, and personalized design can be realized to meet the requirements 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 auxiliary synergistic auxiliary agent 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 powder to the boron nitride nanosheets is controlled to be (55-90)/(5-20)/(0.5-5).
By adopting the technical scheme, the prepared electrothermal material has the advantages of better infrared and ultraviolet shielding, sterilization, health care and thermal insulation functions, relatively excellent mechanical strength, flexibility, conductivity, weather resistance and wear resistance, and relatively long 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.
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 the proportion of the antioxidant auxiliary agent are optimized and selected through experiments, so that the overall ageing performance and the ultraviolet ageing resistance of the electric heating wire can be improved, and the electric heating wire is further 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.
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 ultraviolet-resistant auxiliary agent type and proportion are optimized and selected through experiments, the aging performance and ultraviolet-resistant aging performance of the whole electric heating wire can be improved by the synergistic antioxidant composition, and the electric heating wire is further ensured to have relatively excellent mechanical strength, flexibility, conductivity and weather resistance.
In a second aspect, the present application provides a method for preparing an electrothermal material with an intelligent temperature control function, which is implemented by the following technical scheme:
A preparation method of an electric heating material with an intelligent temperature control function comprises the following steps of:
s1, placing the dried matrix resin, the conductive composition, the auxiliary synergistic additive, the antioxidant composition, the ultraviolet resistance additive and the dispersing agent which are accurately measured into an internal mixer, and mixing uniformly, wherein the internal mixing temperature is 160-168 ℃ and the time is 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%;
s3, taking the graphene wire or the carbon fiber 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 carrying out water cooling, heat treatment and drying to obtain the finished product heating wire.
The preparation method is relatively simple, low in operation difficulty and convenient to realize industrial production and manufacture.
The preparation method of the electric heating material with the intelligent temperature control function comprises the following steps of:
S1, placing the dried matrix resin, the conductive composition, the auxiliary synergistic additive, the antioxidant composition, the ultraviolet resistance additive and the dispersing agent which are accurately measured into an internal mixer, and mixing uniformly, wherein the internal mixing temperature is 160-168 ℃ and the time is 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 film-making master batch with the thickness of 1.0-2.0mm, and drying until the moisture is lower than 0.1%;
s3, placing the film-making master batch in the S3 into a double-screw extruder, extruding in a 140-185 ℃ melting environment, and carrying out tape casting on a melting material flowing out of an extrusion die head to obtain a semi-finished film material, and carrying out heat treatment, cooling and winding to obtain the finished electrothermal film material.
The preparation method is relatively simple, low in operation difficulty and convenient to realize industrial production and manufacture.
Preferably, the S3 twin-screw extruder is provided with five temperature areas, wherein the first temperature area is 135+/-2 ℃, the second temperature area is 150+/-2 ℃, the third temperature area is 175+/-2 ℃, the fourth temperature area is 178-180 ℃, the fifth temperature area is 178-180 ℃, the screw rotating speed is 35-60r/min, and the die head temperature is 175-180 ℃.
By adopting the technical scheme, the quality of the prepared finished product electrothermal film material and the quality stability of the same batch of products can be ensured.
In summary, the present application has the following advantages:
1. the electric heating material can be prepared into an electric heating film and an electric heating wire, and has relatively excellent mechanical strength, flexibility, electric conduction performance and weather resistance compared with the existing electric heating material, and has wider application field and better market prospect.
2. The preparation method is relatively simple, low in operation difficulty and convenient to realize industrial production and manufacture.
3. The heating module component prepared by the electrothermal film and the heating wire in the application is wide in application, can replace the existing heat tracing belt and PTC heating wire products, can be applied to multiple fields due to excellent physical and chemical properties, fully plays an intelligent temperature control function, and improves the competitiveness of the products.
4. The electric heating material with the intelligent temperature control function can be applied to the fields of carpets, ground mats, mattresses, yoga mats, physiotherapy mats, cushions, clothes fillers, waistbands, scarf, bellyband, sofas, flower art, crop planting, poultry, heating meal bags, waistcoats back, silica gel heating plates, heating water pipes, new energy automobile battery heat preservation, petroleum conveying pipelines, wind power host heating and the like, the cushions comprise airplane cushions, train cushions, high-speed railway cushions, automobile cushions and bus cushions, and the cushions comprise airplane cushions, train cushions, high-speed railway cushions, automobile cushions and bus cushions, so that the aim of safe intelligent temperature control function is fulfilled.
Drawings
Fig. 1 is a graph showing a change in heat generation power versus temperature of the electric heating wire rod of example 17 of the present application at 220V.
Fig. 2 is a graph showing the change of the resistance and temperature of the electric heating wire in example 17 of the present application.
Fig. 3 is a graph showing the change of the heating power and the temperature of the electric heating wire in example 32 of the present application at 72V.
Fig. 4 is a graph showing the change of the resistance and temperature of the electric heating wire in example 32 of the present application.
Fig. 5 is a graph showing the change of the heating power and the temperature of the electric heating wire at 36V in example 33 of the present application.
Fig. 6 is a graph showing the change of the resistance and temperature of the electric heating wire in example 33 of the present application.
Fig. 7 is a graph showing the heat generation power versus temperature of the electric heating wire rods of example 41 and example 54 in the present application.
Fig. 8 is a graph showing the comparison of the resistance versus temperature of the electric heating wire in example 41 and example 54 of the present application.
Fig. 9 is a graph showing the variation of the heating power with temperature of the electric heating wire at 36V in example 50 of the present application.
Fig. 10 is a graph showing the change of the resistance and temperature of the electric heating wire in example 50 of the present application.
Fig. 11 is a graph showing the change of the heating power with temperature of the electric heating wire in example 51 of the present application at 36V.
Fig. 12 is a graph showing the change of the resistance and temperature of the electric heating wire in example 51 of the present application.
Fig. 13 is a graph showing a change in heat generation power versus temperature of the electric heating wire rod of comparative example 42 in the present application at 220V.
Fig. 14 is a graph showing the change in resistance versus temperature of the electric heating wire in comparative example 42 in the present application.
Fig. 15 is a graph showing a change in heat generation power versus temperature of the electric heating wire rod of comparative example 43 in the present application at 36V.
Fig. 16 is a graph showing the change in resistance versus temperature of the electric heating wire in comparative example 43 in the present application.
Detailed Description
The present application is described in further detail below in conjunction with comparative examples and examples.
Preparation example
Preparation example 1
The TPU resin in the electric heating wire rod is mainly prepared from the following raw materials: isocyanate composition, chain extender, polyol, catalyst and assistant. The ratio of the sum of the molar amounts of hydroxyl groups in the polyol and chain extender to the molar amount of-NCO-in the isocyanate composition is 1 (0.985-0.998). The hard segment content in the TPU resin is controlled to be 45-52wt%. The hard segment content of the TPU resin in this preparation example was controlled at 46.1%.
The catalyst is organic bismuth or organic tin, specifically bismuth octodecanoate, and the mass of the catalyst is 0.01% -0.1% of the total mass of the isocyanate composition, the chain extender and the polyalcohol.
The auxiliary agent consists of an antioxidant 1024, an antioxidant 168, an ultraviolet absorber UV-531, a flame retardant, a lubricant PE wax and a mold release agent zinc stearate. The flame retardant is composed of graphene, nano magnesium hydroxide and ammonium polyphosphate in a mass ratio of 1:1:1.
The isocyanate composition is composed of HDI and MDI, the mole ratio of the MDI and the HDI is (0.2-0.35): (0.65-0.80).
The chain extender is composed of at least two of 3 methyl-1, 5-pentanediol, 1,4 butanediol, 1,6 hexanediol, ethylenediamine, hydrazine hydrate, 1, 4-butanediamine and 1,6 hexamethylenediamine and at least one of 2, 6-toluenediamine and diethyl toluenediamine.
The polyol mainly comprises polycarbonate diol with molecular weight of 1000-4000, propylene glycol polyether with molecular weight of 1000-4000 and polytetrahydrofuran diol with molecular weight of 1000-4000.
The total molar weight of the propylene glycol polyether with the molecular weight of 1000-4000 and the polytetrahydrofuran glycol with the molecular weight of 1000-4000 accounts for 60-80% of the total molar weight of the polyol. Propylene glycol polyether with molecular weight of 1000-4000 and polytetrahydrofuran glycol with molecular weight of 1000-4000 in the molar ratio of 1 (0.5-2).
The polyol mainly comprises polycarbonate diol with molecular weight of 1000-4000 and polytetrahydrofuran diol with molecular weight of 1000-4000, wherein the polytetrahydrofuran diol with molecular weight of 1000-4000 accounts for 60-80% of the total mole weight of the polyol.
The TPU resin comprises the following specific formula: 127.57g of HDI, 60g of MDI, 29.54g of 3-methyl-1, 5-pentanediol, 31.73g of 1, 4-butanediamine, 42.8g of diethyltoluenediamine, 120g of polycarbonate diol with a molecular weight of 3000 (UBE-mixed polyglycol PH series PH-300), 100g of propylene glycol polyether PPG2000 with a molecular weight of 2000 (Mitsui chemical (Shandong)), 120g of polytetrahydrofurandiol with a molecular weight of 2000 (BASF Basex polytetrahydrofuran ether PTMEG 2000), 0.5g of bismuth octodecanoate, 5g of antioxidant 1024, 1.2g of antioxidant 168, 4.87g of ultraviolet absorber UV-531, 6.2g of graphene (CAS: 7782-42-5), 6.2g of nano magnesium hydroxide (CAS: 1309-42-8), 6.2g of ammonium polyphosphate (model: TMR-F208; brand is robust), 3g of lubricant PE, 5g of film remover-zinc stearate.
The preparation method of the TPU resin comprises the following steps:
step one, 29.54g of 3 methyl-1, 5-pentanediol, 31.73g of 1, 4-butanediamine and 42.8g of diethyltoluenediamine which are accurately metered are put into a first trough of a double-screw extruder; simultaneously, 120g of polycarbonate diol with the molecular weight of 3000, 100g of propylene glycol polyether with the molecular weight of 2000 and 120g of polytetrahydrofuran diol with the molecular weight of 2000 which are accurately metered are put into a second material groove of a double-screw extruder; 127.57g of HDI, 60g of MDI, 0.5g of bismuth octodecanoate of g g, 5g of antioxidant 1024, 1.2g of antioxidant 168, 4.87g of ultraviolet absorbent UV-531, 6.2g of graphene, 6.2g of nano magnesium hydroxide, 6.2g of ammonium polyphosphate, 3g of lubricant PE wax and 5g of mold release agent-zinc stearate are stirred uniformly and then put into a third trough of a double-screw extruder; extruding and granulating, wherein the temperature interval of a metering section in the double-screw extruder is 185-188 ℃, the temperature interval of a compression section is 175+/-0.5 ℃, the temperature interval of a feeding section is 180+/-0.5 ℃, the temperature of a die head is 190.5 ℃, the rotating speed of a screw is 30rpm, discharging the material from the double-screw extruder by using a gear pump, and performing water cooling and granulating to obtain semi-finished TPU granules;
And thirdly, placing the prepared semi-finished TPU granules at the temperature of 85.0 ℃, drying until the moisture content is lower than 0.02%, and then placing the semi-finished TPU granules at the temperature of 80 ℃ for 24 hours for heat treatment to obtain the finished TPU resin, wherein the test Shore hardness of the finished TPU resin is 73A.
Preparation example 2
Preparation 2 differs from preparation 1 in that: the hard segment content of the TPU resin in this preparation example was controlled at 49.1%. The TPU resin comprises the following specific formula: 127.57g of HDI, 60g of MDI, 33.1g of 3-methyl-1, 5-pentanediol, 30.24g of 1, 4-butanediamine, 42.8g of diethyltoluenediamine, 90g of polycarbonate diol with a molecular weight of 3000, 110g of propylene glycol polyether with a molecular weight of 2000, 104g of polytetrahydrofuran diol with a molecular weight of 2000, 0.5g of bismuth octodecanoate, 4.7g of antioxidant 1024, 1.2g of antioxidant 168, 4.7g of ultraviolet absorber UV-531, 5.85g of graphene, 5.85g of nano magnesium hydroxide, 5.85g of ammonium polyphosphate, 3g of lubricant PE wax, 4.7g of remover-zinc stearate. The test shore hardness of the finished TPU resin was 85A.
Preparation example 3
Preparation 3 differs from preparation 1 in that: the hard segment content in the TPU resin in this preparation example was controlled to be 51.9%. The TPU resin comprises the following specific formula: 127.57g of HDI, 60g of MDI, 29.54g of 3-methyl-1, 5-pentanediol, 23.80g of 1, 4-butanediamine, 63.11g of diethyltoluenediamine, 90g of polycarbonate diol with a molecular weight of 3000, 108g of propylene glycol polyether with a molecular weight of 2000, 84g of polytetrahydrofuran diol with a molecular weight of 2000, 0.5g of bismuth octodecanoate, 4.5g of antioxidant 1024, 1.1g of antioxidant 168, 4.5g of ultraviolet absorber UV-531, 5.65g of graphene, 5.65g of nano magnesium hydroxide, 5.65g of ammonium polyphosphate, 2.8g of lubricant PE wax, 4.5g of remover-zinc stearate. The finished TPU resin has a test Shore hardness of 93A.
Preparation example 4
Preparation example 4 differs from preparation example 1 in that: the hard segment content of the TPU resin in this preparation example was controlled at 41.1%. The TPU resin comprises the following specific formula: 127.57g of HDI, 60g of MDI, 33.56g of 3-methyl-1, 5-pentanediol, 29.97g of 1, 4-butanediamine, 35.66g of diethyltoluenediamine, 174g of polycarbonate diol with a molecular weight of 3000, 144g of propylene glycol polyether with a molecular weight of 2000, 92g of polytetrahydrofuran diol with a molecular weight of 2000, 0.5g of bismuth octodecanoate, 5.5g of antioxidant 1024, 1.4g of antioxidant 168, 5.5g of ultraviolet absorber UV-531, 6.85g of graphene, 6.85g of nano magnesium hydroxide, 6.85g of ammonium polyphosphate, 3.4g of lubricant PE wax, 5.5g of parting agent zinc stearate. The finished TPU resin tested had a shore hardness of 62A.
Preparation example 5
Preparation 5 differs from preparation 1 in that: the hard segment content in the TPU resin in this preparation example was controlled to be 53.9%. The TPU resin comprises the following specific formula: 127.57g of HDI, 60g of MDI, 28.72g of 3-methyl-1, 5-pentanediol, 19.39g of 1, 4-butanediamine, 74.88g of diethyltoluenediamine, 96g of polycarbonate diol with a molecular weight of 3000, 90g of propylene glycol polyether with a molecular weight of 2000, 80g of polytetrahydrofuran diol with a molecular weight of 2000, 0.5g of bismuth octodecanoate, 4.36g of antioxidant 1024, 1.09g of antioxidant 168, 4.36g of ultraviolet absorber UV-531, 5.45g of graphene, 5.45g of nano magnesium hydroxide, 5.45g of ammonium polyphosphate, 2.73g of lubricant PE wax, 4.36g of release agent zinc stearate. The test shore hardness of the finished TPU resin was 96A.
Preparation example 6
Preparation example 6 differs from preparation example 1 in that: the TPU resin comprises the following specific formula: 127.57g of HDI, 60g of MDI, 29.54g of 3-methyl-1, 5-pentanediol, 31.73g of 1, 4-butanediamine, 42.8g of diethyltoluenediamine, 120g of polycarbonate diol with a molecular weight of 3000, 100g of propylene glycol polyether with a molecular weight of 2000, 120g of polytetrahydrofuran diol with a molecular weight of 2000, 0.5g of bismuth octodecanoate, 5g of antioxidant 1024, 1.2g of antioxidant 168, 4.87g of ultraviolet absorber UV-3, 9.3g of nano magnesium hydroxide, 9.3g of ammonium polyphosphate, 3g of lubricant PE wax, 5g of mold release agent zinc stearate. The finished TPU resin has a test Shore hardness of 72A.
Preparation example 7
Preparation 7 differs from preparation 1 in that: the hard segment content of the TPU resin in this preparation example was controlled at 46.1%.
The TPU resin comprises the following specific formula: 127.57g of HDI, 60g of MDI, 35.45g of 3-methyl-1, 5-pentanediol, 26.68g of 1, 4-butanediol, 44.93g of diethyltoluenediamine, 120g of polycarbonate diol with a molecular weight of 3000, 124g of propylene glycol polyether with a molecular weight of 2000, 100g of polytetrahydrofuran diol with a molecular weight of 2000, 0.5g of bismuth octodecanoate, 5g of antioxidant 1024, 1.25g of antioxidant 168, 5g of ultraviolet absorber UV-531, 6.25g of graphene, 6.25g of nano magnesium hydroxide, 6.25g of ammonium polyphosphate, 3.2g of lubricant PE wax, 5.0g of mold release agent zinc stearate. The test shore hardness of the finished TPU resin was 75A.
Preparation example 8
Preparation 8 differs from preparation 1 in that:
the hard segment content of the TPU resin in this preparation example was controlled at 46.1%.
The TPU resin comprises the following specific formula: 127.57g of HDI, 60g of MDI, 35.45g of 3-methyl-1, 5-pentanediol, 27.04g of 1, 4-butanediol, 30.37g of 1, 6-hexanediol, 123g of polycarbonate diol with a molecular weight of 3000, 104g of propylene glycol polyether with a molecular weight of 2000, 100g of polytetrahydrofuran diol with a molecular weight of 2000, 0.5g of bismuth octodecanoate, 4.75g of antioxidant 1024, 1.2g of antioxidant 168, 4.76g of ultraviolet absorber UV-531, 5.95g of graphene, 5.95g of nano magnesium hydroxide, 5.95g of ammonium polyphosphate, 3.0g of lubricant PE wax, 4.76g of release agent zinc stearate. The finished TPU resin tested had a shore hardness of 58A.
Table 1 shows the parameters of the TPU's of preparation examples 1 to 8
As can be seen in connection with preparation examples 1-8 and in connection with Table 1, preparation examples 1-3 are compared with preparation examples 4-8: the TPU prepared in the application has relatively good cohesiveness and mechanical properties, and is suitable for electric heating wires. And the TPU in preparation example 1 had a limiting oxygen index LOI of 30.4% and the TPU in preparation example 6 had a limiting oxygen index LOI of 27.6%, therefore graphene was used: nano magnesium hydroxide: ammonium polyphosphate in mass ratio = 1:1: the compound flame retardant prepared by the method 1 can play a better role in flame retardance.
Preparation example 9
The TPU resin in the electrothermal film material is mainly prepared from the following raw materials: isocyanate composition, chain extender, polyol, catalyst and assistant. The ratio of the sum of the molar amounts of hydroxyl groups in the polyol and chain extender to the molar amount of-NCO-in the isocyanate composition is 1 (0.985-0.998). The hard segment content in the TPU resin is controlled to be 40-46wt%. The hard segment content in the TPU resin in this preparation example was controlled to be 40.2wt%
The catalyst is organic bismuth or organic tin, specifically bismuth octodecanoate, and the mass of the catalyst is 0.01% -0.1% of the total mass of the isocyanate composition, the chain extender and the polyalcohol.
The auxiliary agent consists of an antioxidant 1024, an antioxidant 168, an ultraviolet absorber UV-531, a flame retardant, a lubricant PE wax and a mold release agent zinc stearate. The flame retardant is composed of graphene, nano magnesium hydroxide and ammonium polyphosphate in a mass ratio of 1:1:1.
The isocyanate composition is composed of HDI and MDI, the mole ratio of the MDI and the HDI is (0.01-0.1): (0.9-0.99).
The chain extender is composed of at least one of 3 methyl-1, 5-pentanediol, 1,4 butanediol, 1,6 hexanediol, glycerol, ethylene glycol and 1,3 propanediol, and at least one of ethylenediamine, hydrazine hydrate, 1, 4-butanediamine, 1,6 hexamethylenediamine, 2, 6-toluenediamine and diethyl toluenediamine.
The polyol mainly comprises polycarbonate diol with molecular weight of 1000-4000, polytetrahydrofuran diol with molecular weight of 1000-4000 and double-end diamine reactive silicone with molecular weight of 5000-10000, wherein the double-end diamine reactive silicone with molecular weight of 5000-10000 accounts for 5-10% of the total mole weight of the polyol.
The specific formula is as follows: the TPU resin comprises the following specific formula: 154.43g of HDI, 20g of MDI, 31.91g of 3-methyl-1, 5-pentanediol, 44.91g of 1, 6-hexanediol, 24..43g of 2, 6-toluenediamine, 150g of polycarbonate diol with a molecular weight of 3000, 160g of polytetrahydrofuran diol with a molecular weight of 2000, 100g of a double-ended diamine reactive silicone FM3321 (JNC), 0.55g of bismuth octodecanoate, 5.5g of antioxidant 1024, 1.4g of antioxidant 168, 5.5g of ultraviolet absorber UV-531, 6.86g of graphene, 6.86g of nano magnesium hydroxide, 6.86g of ammonium polyphosphate, 3.4g of lubricant PE wax, 5.5g of mold release agent zinc stearate.
The preparation method of the TPU resin comprises the following steps:
step one, 31.91g of 3 methyl-1, 5-pentanediol, 44.91g of 1, 4-butanediol and 24.43 g of 1, 6-hexanediol with accurate measurement are put into a first trough of a double-screw extruder; simultaneously, 150g of polycarbonate diol with a molecular weight of 3000, 160g of polytetrahydrofuran diol with a molecular weight of 2000 and 100g of double-end diamine reactive silicone FM3321 with a molecular weight of 5000, which are accurately metered, are put into a second material groove of a double-screw extruder; 154.43g of HDI, 20g of MDI, 0.55g of bismuth octodecanoate, 5.5g of antioxidant 1024, 1.4g of antioxidant 168, 5.5g of ultraviolet absorbent UV-531, 6.86g of graphene, 6.86g of nano magnesium hydroxide, 6.86g of ammonium polyphosphate, 3.4g of lubricant PE wax and 5.5g of mold release agent-zinc stearate are uniformly stirred and then put into a third trough of a double-screw extruder;
Extruding and granulating, wherein the temperature interval of a metering section in the double-screw extruder is 185-188 ℃, the temperature interval of a compression section is 175+/-0.5 ℃, the temperature interval of a feeding section is 180+/-0.5 ℃, the temperature of a die head is 190.5 ℃, the rotating speed of a screw is 30rpm, discharging the material from the double-screw extruder by using a gear pump, and performing water cooling and granulating to obtain semi-finished TPU granules;
and thirdly, placing the prepared semi-finished TPU granules at the temperature of 85.0 ℃, drying until the moisture content is lower than 0.02%, and then placing the semi-finished TPU granules at the temperature of 80 ℃ for 24 hours for heat treatment to obtain the finished TPU resin, wherein the test Shore hardness of the finished TPU resin is 52A.
Preparation example 10
Preparation 10 differs from preparation 9 in that: the hard segment content in the TPU resin in this preparation example was controlled to 43.3wt%. The TPU resin comprises the following specific formula: the TPU resin comprises the following specific formula: 154.43g of HDI, 20g of MDI, 34.86g of 3-methyl-1, 5-pentanediol, 44.91g of 1, 6-hexanediol, 24..43g of 2, 6-toluenediamine, 150g of polycarbonate diol with a molecular weight of 3000, 140g of polytetrahydrofuran diol with a molecular weight of 2000, 75g of a double-ended diamine reactive silicone FM3321 (JNC, japan) with a molecular weight of 5000, 0.52g of bismuth octodecanoate, 5.16g of antioxidant 1024, 1.3g of antioxidant 168, 5.16g of ultraviolet absorber UV-531, 6.45g of graphene, 6.45g of nano magnesium hydroxide, 6.45g of ammonium polyphosphate, 3.23g of lubricant PE wax, 5.2g of mold release agent zinc stearate. The finished TPU resin tested had a shore hardness of 58A.
PREPARATION EXAMPLE 11
Preparation 11 differs from preparation 9 in that: the hard segment content in the TPU resin in this preparation example was controlled to 45.8wt%. The TPU resin comprises the following specific formula: 154.43g of HDI, 20g of MDI, 35.1g of 3-methyl-1, 5-pentanediol, 40.18g of 1, 6-hexanediol, 29.57g of 2, 6-toluenediamine, 120g of polycarbonate diol with a molecular weight of 3000, 130g of polytetrahydrofuran diol with a molecular weight of 2000, 80g of a double-ended diamine reactive silicone FM3321 (JNC, japan) with a molecular weight of 5000, 0.49g of bismuth octodecanoate, 4.88g of antioxidant 1024, 1.22g of antioxidant 168, 4.88g of ultraviolet absorber UV-531, 6.1g of graphene, 6.1g of nano magnesium hydroxide, 6.1g of ammonium polyphosphate, 3.05g of lubricant PE wax, 4.88g of release agent zinc stearate. The finished TPU resin was tested for a Shore hardness of 67A.
Preparation example 12
Preparation 12 differs from preparation 9 in that: the hard segment content in the TPU resin in this preparation example was controlled at 40.5 wt.%, and the double-terminal diamine type reactive silicone was adopted as the double-terminal diamine type reactive silicone FM3325 having a molecular weight of 10000.
The TPU resin comprises the following specific formula: 154.43g of HDI, 20g of MDI, 35.1g of 3-methyl-1, 5-pentanediol, 40.18g of 1, 6-hexanediol, 29.57g of 2, 6-toluenediamine, 120g of polycarbonate diol with a molecular weight of 3000, 130g of polytetrahydrofuran diol with a molecular weight of 2000, 160g of a double-end diamine reactive silicone FM3325 (JNC, japan), 0.55g of bismuth octodecanoate, 5.52g of antioxidant 1024, 1.38g of antioxidant 168, 5.52g of ultraviolet absorber UV-531, 6.9g of graphene, 6.9g of nano magnesium hydroxide, 6.9g of ammonium polyphosphate, 3.45g of lubricant PE wax, 5.52g of release agent zinc stearate. The finished TPU resin has a test Shore hardness of 51A.
Preparation example 13
Preparation 13 differs from preparation 9 in that: the hard segment content in the TPU resin in this preparation example was controlled at 38% by weight. The TPU resin comprises the following specific formula: 154.43g of HDI, 20g of MDI, 33.8g of 3-methyl-1, 5-pentanediol, 40.18g of 1, 6-hexanediol, 26.88g of 2, 6-toluenediamine, 153g of polycarbonate diol with a molecular weight of 3000, 146g of polytetrahydrofuran diol with a molecular weight of 2000, 150g of a double-ended diamine reactive silicone FM3325 (JNC, japan) with a molecular weight of 5000, 0.58g of bismuth octodecanoate, 5.8g of antioxidant 1024, 1.45g of antioxidant 168, 5.8g of ultraviolet absorber UV-531, 7.25g of graphene, 7.25g of nano magnesium hydroxide, 7.25g of ammonium polyphosphate, 3.63g of lubricant PE wax, 5.8g of release agent zinc stearate. The finished TPU resin has a test Shore hardness of 47A.
PREPARATION EXAMPLE 14
Preparation 14 differs from preparation 9 in that: the hard segment content in the TPU resin in this preparation example was controlled to 48.1wt%. The TPU resin comprises the following specific formula: 154.43g of HDI, 20g of MDI, 35.57g of 3-methyl-1, 5-pentanediol, 40.89g of 1, 6-hexanediol, 29.57g of 2, 6-toluenediamine, 108g of polycarbonate diol with a molecular weight of 3000, 120g of polytetrahydrofuran diol with a molecular weight of 2000, 75g of a double-ended diamine reactive silicone FM3325 (JNC, japan) with a molecular weight of 5000, 0.48g of bismuth octodecanoate, 4.76g of antioxidant 1024, 1.45g of antioxidant 168, 4.76g of ultraviolet absorber UV-531, 6g of graphene, 6g of nano magnesium hydroxide, 6g of ammonium polyphosphate, 3.0g of lubricant PE wax, 4.76g of a mold release agent zinc stearate. The finished TPU resin has a test Shore hardness of 76A.
Preparation example 15
Preparation 15 differs from preparation 9 in that:
the hard segment content in the TPU resin in this preparation example was controlled to 40.1wt%.
The TPU resin comprises the following specific formula: 154.43g of HDI, 20g of MDI, 76.81g of 3-methyl-1, 5-pentanediol, 23.63g of 1, 6-hexanediol, 150g of polycarbonate diol with a molecular weight of 3000, 160g of polytetrahydrofuran diol with a molecular weight of 2000, 100g of double-end diamine reactive silicone FM3321 with a molecular weight of 5000 (JNC, japan), 0.56g of bismuth octodecanoate, 5.6g of antioxidant 1024, 1.4g of antioxidant 168, 5.6g of ultraviolet absorber UV-531, 6.95g of graphene, 6.95g of nano magnesium hydroxide, 6.95g of ammonium polyphosphate, 3.5g of lubricant PE wax, 5.6g of release agent zinc stearate. The test shore hardness of the finished TPU resin was 46A.
PREPARATION EXAMPLE 16
Preparation 16 differs from preparation 9 in that:
the hard segment content in the TPU resin in this preparation example was controlled to 40.2wt%.
The TPU resin comprises the following specific formula: 154.43g of HDI, 20g of MDI, 31.91g of 3-methyl-1, 5-pentanediol, 41.95g of 1, 6-hexanediol, 24.43g of 2, 6-toluenediamine, 165g of polycarbonate diol with a molecular weight of 3000, 240g of polytetrahydrofuran diol with a molecular weight of 2000, 0.54g of bismuth octodecanoate, 5.42g of antioxidant 1024, 1.36g of antioxidant 168, 5.42g of UV absorber UV-531, 6.78g of graphene, 6.78g of nano magnesium hydroxide, 6.78g of ammonium polyphosphate, 3.4g of lubricant PE wax, 5.42g of mold release agent zinc stearate. The test shore hardness of the finished TPU resin was 55A.
Table 2 shows the parameters of the TPU in preparation examples 9 to 16
As can be seen in connection with preparation examples 9-16 and in connection with Table 2, preparation examples 9-12 are compared with preparation examples 13-16: the TPU prepared in the application has relatively good cohesiveness and flexibility, and is suitable for electrothermal film materials.
As can be seen in connection with preparation examples 9-16 and in connection with Table 2, preparation examples 9-12 are compared with preparation examples 13-16: the addition of the double-end glycol type reactive silicone can improve the integral mechanical strength and flexibility of the application, and is suitable for electrothermal film materials, namely the prepared electrothermal film materials have better tensile fracture rate and flexibility and are convenient for the composite processing of the electrothermal film and electrode materials in the later period.
Examples
The application discloses an electric heating material with intelligent temperature control function is mainly prepared from the following raw materials in percentage by mass: 15.0-20.0% of conductive composition, 5.0-10.0% of auxiliary synergistic auxiliary agent, 1.2-1.8% of antioxidant composition, 0.2-0.4% of ultraviolet resistance auxiliary agent, 0.10-0.50% of dispersing agent and the balance of matrix resin.
The matrix resin mainly comprises PP resin, HDPE resin and compatilizer.
The mass ratio of the PP resin, the HDPE resin and the compatilizer is controlled to be (750-800): 380-440): 180-250. The compatilizer is at least one of EAA resin, EVA resin, TPU resin and PCTG resin.
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. Preferably, the conductive composition mainly comprises nano titanium diboride, nano carbon black, nano carbon fiber, nano graphite powder and titanium nitride whisker. Wherein the average grain diameter of the nano titanium diboride is 0.05-3 microns, the hexagonal crystal form is hexagonal crystal form, the nano graphite powder is scaly graphite powder, the average grain diameter is 0.2-1.0 micron, and the mass ratio of the nano titanium diboride, the nano carbon black, the nano carbon fiber, the nano graphite powder and the titanium nitride whisker is controlled to be (5-10): 60-80): 5-20): 10-40): 0.5-5.
The auxiliary synergistic auxiliary agent 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 nanosheet and boron nitride whisker. Preferably, the auxiliary synergistic auxiliary agent mainly comprises nano zinc oxide, nano zirconium oxide, titanium tin carbide superfine micropowder and boron nitride nanosheets, wherein the mass ratio of the nano zinc oxide, the nano zirconium oxide, the titanium tin carbide superfine micropowder to the boron nitride nanosheets is controlled to be (55-90): (5-20): (5-20): (0.5-5). The dispersing agent is at least one of stearate and a coupling agent.
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. Preferably, the antioxidant composition mainly comprises 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): (5-40).
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, wherein the organic ultraviolet resistance reagent mainly comprises at least one of UV-531 and UV-234 matched with at least one of UV622, UV-770, UV-944 and UV-783. 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 electrothermal material with the intelligent temperature control function is prepared into the electrothermal film material with the intelligent temperature control function through a tape casting or calendaring process, and the mass ratio of the PP resin to the HDPE resin to the compatilizer is controlled to be (790-800): 400-420): 220-250. The compatilizer consists of EAA resin and TPU resin; the mass ratio of the EAA resin to the TPU resin is (15-30) to (70-85). The shore hardness of TPU resin in the electrothermal film material is controlled to be 30-70A. The EAA resin is preferably DuPont Surlyn EAA1702, U.S.A. The TPU resin is preferably the TPU resin pellets prepared in preparation examples 9 to 12.
The preparation method for preparing the electrothermal film material with the intelligent temperature control function by using the electrothermal material with the intelligent temperature control function through a tape casting or calendaring process comprises the following steps of:
s1, placing the dried matrix resin, the conductive composition, the auxiliary synergistic additive, the antioxidant composition, the ultraviolet resistance additive and the dispersing agent which are accurately measured into an internal mixer, and mixing uniformly, wherein the internal mixing temperature is 160-168 ℃ and the time is 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 film-making master batch with the thickness of 1.0-2.0mm, and drying until the moisture is lower than 0.1%;
S3, placing the film-making master batch in the S3 into a double-screw extruder, extruding the film-making master batch in a 140-185 ℃ melting environment, wherein the S3 double-screw extruder is provided with five temperature areas, the first temperature area is 135+/-2 ℃, the second temperature area is 150+/-2 ℃, the third temperature area is 175+/-2 ℃, the fourth temperature area is 178-180 ℃, the fifth temperature area is 178-180 ℃, the screw speed is 35-60r/min, the die head temperature is 175-180 ℃, and the molten material flowing out of an extrusion die head is cast to obtain a semi-finished film material, and carrying out heat treatment, cooling and rolling to obtain the finished electrothermal film material.
The electric heating material with the intelligent temperature control function is prepared into the electric heating wire rod with the intelligent temperature control function through a masterbatch spinning process, and the mass ratio of the PP resin to the HDPE resin to the compatilizer is controlled to be 790-800:420-430:180-200. The compatilizer consists of EAA resin, TPU resin and PCTG resin, wherein the mass ratio of the EAA resin to the TPU resin to the PCTG resin is (10-20): 55-80): 10-25.
The shore hardness of the TPU resin in the electric heating wire is controlled to be 60-95A. The EAA resin is preferably DuPont EAA2002. The TPU resin is preferably the TPU resin pellets prepared in 1 to 3. The PCTG resin is preferably model YF300 of the SK complex chemical ECOZEN PCTG of korea or plastic TX1501HF of the islman chemical PCTG.
The preparation method for preparing the electric heating wire rod with the intelligent temperature control function by using the electric heating material masterbatch spinning process with the intelligent temperature control function comprises the following steps of:
s1, placing the dried matrix resin, the conductive composition, the auxiliary synergistic additive, the antioxidant composition, the ultraviolet resistance additive and the dispersing agent which are accurately measured into an internal mixer, and mixing uniformly, wherein the internal mixing temperature is 160-168 ℃ and the time is 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%;
s3, taking the graphene wire or the carbon fiber 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 carrying out water cooling, heat treatment and drying to obtain the finished product heating wire.
Example 1
An electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g of PP resin (Yangzi petrochemical K8003), 420g of HDPE resin (bench plastic HDPE 8001), 185g of EVA resin (bench plastic EVA 7340M, VA content: 28 wt%), 292g of carbon black (Bote conductive carbon black VVC 72), 8g of titanium diboride (planetary ball milling to an average particle size of 0.5-1 micrometer, hexagonal crystal form), 160g of nano zinc oxide (average particle size 500nm, spherical crystal form), 20g of antioxidant 1024, 13g of antioxidant 697, 3g of nano zirconium carbide (average particle size 200nm, cubic crystal form), 0.87g of nano silicon nitride (average particle size 800nm, face-centered cubic crystal form), 2.9g of UV-531, 2.03g of UV-622, 4g of zinc stearate.
The preparation method of the electrothermal material comprises the following steps: the method comprises the following steps:
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, 20g of antioxidant 1024, 13g of antioxidant 697, 3g of nano zirconium carbide, 1.8g of nano titanium carbide, 0.87g of nano silicon nitride, 2.9g of UV-531, 2.03g of UV-622 and 4g of zinc stearate in an internal mixer uniformly, and banburying 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 five heating temperature areas are formed, 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 electric heating material with the intelligent temperature control function is obtained through wiredrawing, water cooling and granulating, and the electric heating material is dried until the water content is lower than 0.1%.
Example 2
Example 2 differs from example 1 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 750g of PP resin, 380g of HDPE resin, 180g of EVA resin, 292g of carbon black (Bott conductive carbon black VVC 72), 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, 4g of zinc stearate.
Example 3
Example 3 differs from example 1 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 800g of PP resin, 440g of HDPE resin, 250g of EVA resin, 292g of carbon black (Bott conductive carbon black VCC 72), 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, 4g of zinc stearate.
Example 4
Example 4 differs from example 1 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 790g of PP resin, 420g of HDPE resin, 180g of EVA resin, 292g of carbon black (Bott conductive carbon black VVC 72), 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, 4g of zinc stearate.
Example 5
Example 5 differs from example 1 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 800g of PP resin, 430g of HDPE resin, 200g of EVA resin, 292g of carbon black (Bott conductive carbon black VCC 72), 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, 4g of zinc stearate.
Example 6
Example 6 differs from example 1 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 790g of PP resin, 400g of HDPE resin, 220g of EVA resin, 292g of carbon black (Bott conductive carbon black VVC 72), 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, 4g of zinc stearate.
Example 7
Example 7 differs from example 1 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 800g of PP resin, 420g of HDPE resin, 250g of EVA resin, 292g of carbon black (Bott conductive carbon black VCC 72), 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, 4g of zinc stearate.
Example 8
Example 8 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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, 18g antioxidant 1024, 10.8g antioxidant 697, 3.6g antioxidant DBHQ, 1.8g nano zirconium carbide, 1.8g nano titanium carbide (average particle size 200nm, cubic crystal form), 0.29g nano titanium nitride (average particle size 700nm, cubic crystal form, SW-TiN-003), 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Example 9
Example 9 differs from example 1 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 405g HDPE resin, 230g EVA resin, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10.8g antioxidant 697, 3.6g antioxidant DBHQ, 1.8g nano zirconium carbide, 1.8g nano titanium carbide (average particle size 200nm, cubic crystal form), 0.29g nano titanium nitride (average particle size 700nm, cubic crystal form, SW-TiN-003), 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Example 10
Example 10 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 11
Example 11 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 12
Example 12 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 13
Example 13 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 14
Example 14 differs from example 1 in that: and (3) controlling the banburying temperature in the step S1 at 160 ℃ for 350S.
Example 15
Example 15 differs from example 1 in that: and (3) controlling the banburying temperature in the step S1 at 165 ℃ for 320S.
Example 16
Example 16 differs from example 1 in that: and (3) controlling the banburying temperature in the step S1 at 168 ℃ for 280S.
Example 17
Example 17 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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.
The electric heating material masterbatch spinning process with the intelligent temperature control function prepares the electric heating wire rod with the intelligent temperature control function, wherein the adopted core wire is a commercially available cotton yarn and 100 long-staple cotton yarn (Yubang spinning).
An electric heating material masterbatch spinning process with an intelligent temperature control function is used for preparing an electric heating wire rod with the intelligent temperature control function, and the process comprises the following steps:
S1, drying PP resin, HDPE resin and EVA resin until the moisture is lower than 0.1% for later use;
mixing dried 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 in an internal mixer uniformly, and banburying at 166 ℃ 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 electric heating material with an intelligent temperature control function is obtained by wire drawing, water cooling and granulating, and the electric heating material is dried until the moisture is lower than 0.1%;
s3, taking 100 cotton threads as core wires, placing spinning master batches into a double-screw extruder, wherein the extrusion temperature is 175-195 ℃, and specifically five heating temperature areas are divided, 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 192.8 ℃, the obtained extrusion molten materials are attached to the outer surface of the core wires, the traction speed is 10.0cm/S, and the water cooling and the 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 the finished electric heating wire rod of 800D.
Example 18
Example 18 differs from example 1 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g of PP resin, 405g of HDPE resin, 230g 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 S1 is controlled to be 162 ℃ and banburying is performed for 320S.
The preparation method of the electrothermal film material with the intelligent temperature control function comprises the following steps:
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, 405g of HDPE resin and 230g of EVA resin which are dried uniformly with 1024 g of antioxidant, 697 g of antioxidant, 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 in an internal mixer, and banburying at 162 ℃ for 320s;
S2, placing the banburying material obtained in the S1 into a double-screw extruder for melt extrusion, wherein the extrusion temperature is 135-180 ℃, and particularly the banburying material is divided into five heating temperature areas, wherein the first temperature area is 135+/-0.5 ℃, the second temperature area is 150+/-0.5 ℃, the third temperature area is 175+/-0.5 ℃, the fourth temperature area is 180+/-0.5 ℃, the fifth temperature area is 180+/-0.5 ℃, the screw speed is 40r/min, the die head temperature is 178.9 ℃, and the electric heating material with the intelligent temperature control function is obtained by wire drawing, water cooling and granulating, and the electric heating material is dried until the moisture is lower than 0.1%;
s3, placing the film-making master batch in the S3 into a double-screw extruder, extruding in a melting environment of 135-180 ℃, specifically dividing into five heating temperature areas, wherein the first temperature area is 135 ℃ +/-0.5 ℃, the second temperature area is 150 ℃ +/-0.5 ℃, the third temperature area is 175 ℃ +/-0.5 ℃, the fourth temperature area is 180 ℃ +/-0.5 ℃, the fifth temperature area is 180 ℃ +/-0.5 ℃, the screw speed is 40r/min, the die head temperature is 178.9 ℃, and the molten material flowing out of an extrusion die head is cast to obtain a semi-finished film material, the traction speed is 6cm/S, and the heat treatment is carried out: placing the film in a 50 ℃ oven for 3.6m in a range of 5.4m in a 75 ℃ oven, placing the film in a 50 ℃ oven for 3.6m in a range of 5.4m in a room temperature air-cooled range, and cooling and rolling to obtain the finished product of the electrothermal film with the intelligent temperature control function.
Example 19
Example 19 differs from example 18 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g of PP resin, 405g of HDPE resin, 57.5g of EAA resin (Surlyn EAA 1702, duPont, U.S.), 172.5g of TPU resin pellets in preparation example 9, 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, 4g of zinc stearate.
Example 20
Example 20 differs from example 18 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 405g HDPE resin, 57.5g EAA resin, 172.5g TPU resin pellets of preparation 10, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Example 21
Example 21 differs from example 18 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 405g HDPE resin, 57.5g EAA resin, 172.5g TPU resin pellets of preparation 11, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Example 22
Example 22 differs from example 18 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 405g HDPE resin, 57.5g EAA resin, 172.5g TPU resin pellets of preparation 12, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Example 23
Example 23 differs from example 18 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 405g HDPE resin, 34.5g EAA resin, 195.5g TPU resin pellets of preparation example 9, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Example 24
Example 24 differs from example 18 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 405g HDPE resin, 69g EAA resin, 161g TPU resin pellets of preparation example 9, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Example 25
Example 25 differs from example 18 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 405g HDPE resin, 50.6g EAA resin, 179.4g TPU resin pellets of preparation 11, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Example 26
Example 26 differs from example 17 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 27.8g of EAA resin (DuPont EAA2002 in U.S.), 129.4g of TPU resin pellets in preparation example 1, 27.8g of PTCG resin (ECOZEN PCTG model YF300 in Korea, comprehensive chemical, SK), 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, 4g of zinc stearate.
Example 27
Example 27 differs from example 17 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 27.8g of EAA resin, 129.4g of TPU resin pellets in preparation example 2, 27.8g of PTCG 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, 4g of zinc stearate.
Example 28
Example 28 differs from example 17 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 27.8g of EAA resin, 129.4g of TPU resin pellets in preparation example 3, 27.8g of PTCG 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, 4g of zinc stearate.
Example 29
Example 29 differs from example 17 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 420g HDPE resin, 18.5g EAA resin, 148g TPU resin pellets of preparation example 1, 18.5g PTCG resin, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Example 30
Example 30 differs from example 17 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 37g of EAA resin, 108.8g of TPU resin pellets of preparation example 1, 46.2g of PTCG 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, 4g of zinc stearate.
Example 31
Example 31 differs from example 17 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 27.8g of EAA resin, 120.2g of TPU resin pellets in preparation example 1, 37g of PTCG 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, 4g of zinc stearate.
Example 32
Example 32 differs from example 17 in that: the electric heating material masterbatch spinning process with the intelligent temperature control function is used for preparing the electric heating wire rod with the intelligent temperature control function, wherein the core wire is a graphene wire (manufactured by using a new graphene material) with the commercial 300D technology.
Example 33
Example 33 differs from example 17 in that: the electric heating material masterbatch spinning process with the intelligent temperature control function is used for preparing the electric heating wire rod with the intelligent temperature control function, wherein the adopted core wire is a commercially available 300D carbon fiber wire (Dongli T300K customization).
Example 34
Example 34 differs from example 33 in that: 160g of nano zinc oxide is replaced by 145g of nano zinc oxide and 15g of nano zirconium oxide.
Example 35
Example 35 differs from example 33 in that: 160g of nano zinc oxide is replaced by 145g of nano zinc oxide and 15g of titanium tin carbide superfine powder.
Example 36
Example 36 differs from example 33 in that: 160g of nano zinc oxide is replaced by 145g of nano zinc oxide, 10g of nano zirconium oxide and 5g of titanium tin carbide superfine powder.
Example 37
Example 37 differs from example 33 in that: 160g of nano zinc oxide is replaced by 143g of nano zinc oxide, 10g of nano zirconium oxide, 5g of titanium tin carbide superfine powder and 2g of boron nitride nano tube.
Example 38
Example 38 differs from example 33 in that: 160g of nano zinc oxide is replaced by 143g of nano zinc oxide, 10g of nano zirconium oxide, 5g of titanium tin carbide superfine powder and 2g of boron nitride whisker.
Example 39
Example 39 differs from example 33 in that: 160g of nano zinc oxide is replaced by 105.6g of nano zinc oxide, 16g of nano zirconium oxide, 32g of titanium tin carbide superfine powder and 6.4g of boron nitride nano tube.
Example 40
Example 40 differs from example 33 in that: 160g of nano zinc oxide is replaced by 140.8g of nano zinc oxide, 8g of nano zirconium oxide, 8g of titanium tin carbide superfine micropowder and 3.2g of boron nitride nanotube.
Example 41
Example 41 differs from example 33 in that: 160g of nano zinc oxide is replaced by 124.8g of nano zinc oxide, 12.8g of nano zirconium oxide, 19.2g of titanium tin carbide superfine micropowder and 3.2g of boron nitride nanotube.
Example 42
Example 42 differs from example 41 in that: 292g of carbon black, 8g of titanium diboride are replaced by 270g of carbon black, 8g of titanium diboride, 22g of carbon nanofibers.
Example 43
Example 43 differs from example 41 in that: 292g of carbon black, 8g of titanium diboride replaced by 270g of carbon black, 8g of titanium diboride and 22g of nano graphite powder.
Example 44
Example 44 differs from example 41 in that: 292g of carbon black, 8g of titanium diboride replaced by 270g of carbon black, 8g of titanium diboride, 20g of nano graphite powder and 2g of titanium nitride whisker.
Example 45
Example 45 differs from example 41 in that: 292g of carbon black, 8g of titanium diboride replaced with 270g of carbon black, 8g of titanium diboride, 17g of graphene, 5g of carbon nanotubes.
Example 46
Example 46 differs from example 41 in that: 292g of carbon black, 8g of titanium diboride replaced by 270g of carbon black, 8g of titanium diboride, 2g of titanium nitride whisker, 15g of graphene, 5g of carbon nanotube.
Example 47
Example 47 differs from example 41 in that: 292g of carbon black, 8g of titanium diboride are replaced by 270g of carbon black, 8g of titanium diboride, 12g of carbon nanofiber, 10g of graphite nanopowder and 2g of titanium nitride whiskers.
Example 48
Example 48 differs from example 41 in that: 292g of carbon black, 8g of titanium diboride are replaced by 180g of carbon black, 15g of titanium diboride, 45g of carbon nanofiber, 54g of graphite nanopowder and 6g of titanium nitride whiskers.
Example 49
Example 49 differs from example 41 in that: 292g of carbon black, 8g of titanium diboride replaced by 234g of carbon black, 15g of titanium diboride, 15g of carbon nanofiber, 30g of graphite nanopowder and 6g of titanium nitride whiskers.
Example 50
Example 50 differs from example 41 in that: 292g of carbon black, 8g of titanium diboride replaced by 210g of carbon black, 18g of titanium diboride, 36g of carbon nanofibers, 30g of graphite nanopowder and 6g of titanium nitride whiskers.
Example 51
Example 51 differs from example 41 in that: 292g of carbon black, 8g of titanium diboride replaced by 186g of carbon black, 20g of titanium diboride, 45g of carbon nanofiber, 30g of graphite nanopowder, 4g of titanium nitride whiskers and 15g of graphene.
Example 52
Example 52 differs from example 41 in that: the carbon black was selected from Japanese, ECP 600JD.
Example 53
Example 53 differs from example 41 in that: the carbon black was selected as Czech AC-80 (type B).
Example 54
Example 54 differs from example 41 in that: 4g of zinc stearate was replaced with 2.5g of zinc stearate, 5g of KH570, and the remaining composition was unchanged. The preparation method of the electric heating wire with the intelligent temperature control function is different in that: s1, drying PP resin, HDPE resin and EVA resin until the moisture is lower than 0.1% for later use;
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;
the dried 795g of PP resin, 420g of HDPE resin and 185g of EVA resin are placed into an internal mixer to be uniformly mixed 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, and then the internal mixing is carried out at the temperature of 165 ℃ for 300s.
Comparative example
Comparative example 1 differs from example 1 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 160g 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.
Comparative example 2 differs from example 1 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 260g 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, 4g of zinc stearate.
Comparative example 3 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 4 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 5 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 6 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 7 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 8 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 9 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 10 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 11 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 12 differs from example 1 in that: an electrothermal material with intelligent temperature control function 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 13 differs from example 1 in that: and (3) controlling the banburying temperature in the step S1 at 160 ℃ for 400S.
Comparative example 14 differs from example 1 in that: and (3) controlling the banburying temperature in the step S1 at 168 ℃ for 250S.
Comparative example 15 differs from example 1 in that: and (3) controlling the banburying temperature in the step S1 to 158 ℃, and banburying for 420S.
Comparative example 16 differs from example 32 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, 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 are placed in an air cooling stroke of 5.4m in a room temperature air duct, so as to obtain the finished electric heating wire.
Comparative example 17 differs from example 19 in that: the TPU resin pellets in preparation example 9 were replaced with commercially available Pasteur 560A P TSGTPU resin with a Shore 50A.
Comparative example 18 differs from example 19 in that: the TPU resin pellets in preparation example 9 replace the TPU resin pellets in preparation example 13.
Comparative example 19 differs from example 19 in that: the TPU resin pellets in preparation example 9 replace the TPU resin pellets in preparation example 14.
Comparative example 20 differs from example 19 in that: the TPU resin pellets in preparation example 9 replaced the TPU resin pellets in preparation example 15.
Comparative example 21 differs from example 19 in that: the TPU resin pellets in preparation example 9 replace the TPU resin pellets in preparation example 16.
Comparative example 22 differs from example 19 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 405g HDPE resin, 230g TPU resin pellets of preparation example 9, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Comparative example 23 differs from example 19 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 405g HDPE resin, 230g EAA resin, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate
Comparative example 24 differs from example 19 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 405g HDPE resin, 23g EAA resin, 207g TPU resin pellets of preparation example 9, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Comparative example 25 differs from example 19 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 405g HDPE resin, 92g EAA resin, 138g TPU resin pellets of preparation example 9, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Comparative example 26 differs from example 26 in that: the TPU resin pellets in preparation example 1 were replaced with a commercially available Pasteur 1180A10 TPU resin having a Shore 80A.
Comparative example 27 differs from example 26 in that: the TPU resin pellets in preparation example 1 replace the TPU resin pellets in preparation example 4.
Comparative example 28 differs from example 26 in that: the TPU resin pellets in preparation example 1 replace the TPU resin pellets in preparation example 5.
Comparative example 29 differs from example 26 in that: the TPU resin pellets in preparation example 1 replace the TPU resin pellets in preparation example 6.
Comparative example 30 differs from example 26 in that: the TPU resin pellets in preparation example 1 replace the TPU resin pellets in preparation example 7.
Comparative example 31 differs from example 26 in that: the TPU resin pellets in preparation example 1 replace the TPU resin pellets in preparation example 8.
Comparative example 32 differs from example 26 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 420g HDPE resin, 185g EAA resin, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Comparative example 33 differs from example 26 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 420g HDPE resin, 185g TPU resin pellets of preparation example 1, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Comparative example 34 differs from example 26 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 185g of PTCG 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.
The preparation method of the electric heating material with the intelligent temperature control function comprises the following steps:
S1, drying PP resin, HDPE resin and PTCG resin until the moisture is lower than 0.1% for later use;
mixing 795g of PP resin, 420g of HDPE resin, 185g of PTCG 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 in an internal mixer uniformly, and banburying at 168 ℃ for 320s;
s2, placing the banburying material obtained in the S1 into a double-screw extruder for melt extrusion, wherein the extrusion temperature is 180-200 ℃, and specifically, the banburying material is divided into five heating temperature areas, wherein the first temperature area is 180+/-0.5 ℃, the second temperature area is 190+/-0.5 ℃, the third temperature area is 195+/-0.5 ℃, the fourth temperature area is 200+/-0.5 ℃, the fifth temperature area is 200+/-0.5 ℃, the screw speed is 30r/min, the die head temperature is 199.6 ℃, and the electric heating material with the intelligent temperature control function is obtained by wire drawing, water cooling and granulating, and the electric heating material is dried until the moisture is lower than 0.1%;
S3, taking 100 cotton threads as core wires, placing spinning master batches into a double-screw extruder, wherein the extrusion temperature is 180-200 ℃, and specifically five heating temperature areas are divided, wherein the first temperature area is 180+/-0.5 ℃, the second temperature area is 190+/-0.5 ℃, the third temperature area is 195+/-0.5 ℃, the fourth temperature area is 200+/-0.5 ℃, the fifth temperature area is 200+/-0.5 ℃, the screw speed is 30r/min, the die head temperature is 199.6 ℃, the obtained extruded molten materials are attached to the outer surface of the core wires, the traction speed is 10.0cm/S, and the water cooling and the 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 the finished electric heating wire rod of 800D.
Comparative example 35 differs from example 26 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 420g HDPE resin, 92.5g EAA resin, 92.5g PTCG resin, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Comparative example 36 differs from example 26 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 420g HDPE resin, 92.5g EAA resin, 92.5g TPU resin pellets of preparation example 1, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Comparative example 37 differs from example 26 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g of PP resin, 420g of HDPE resin, 9.3g of EAA resin, 13.87g of TPU resin pellets in preparation example 1, 37g of PTCG 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, 4g of zinc stearate.
Comparative example 38 differs from example 26 in that: an electrothermal material with intelligent temperature control function is prepared from the following raw materials in percentage by mass: 795g PP resin, 420g HDPE resin, 55.5g EAA resin, 92.5g TPU resin pellets of preparation example 1, 37g PTCG resin, 292g carbon black, 8g titanium diboride, 160g nano zinc oxide, 18g antioxidant 1024, 10g antioxidant 697, 3.0g antioxidant DBHQ, 2.2g nano zirconium carbide, 2.9g nano titanium carbide, 0.29g nano titanium nitride, 0.58g nano silicon nitride, 2.9g UV-234, 1.16g UV-622, 0.87g UV-770, 4g zinc stearate.
Comparative example 39 differs from example 33 in that: an electrothermal material with intelligent temperature control function 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 40 differs from example 33 in that: an electrothermal material with intelligent temperature control function 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 41 differs from example 41 in that: an electrothermal material with intelligent temperature control function 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 42
The electric 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 100 cotton threads as connection yarns, extruding spinning master batches at 160-170 ℃, adhering extruded molten materials to the outer surfaces of polyester yarns, water-cooling, and drying to obtain finished product electric heating wires.
Comparative example 43
Comparative example 43 differs from comparative example 42 in that: 100 cotton threads are replaced by Dongli T300K carbon fiber threads.
Performance test
Detection method/test method
1. Mechanical strength test of TPU: tensile strength test the tensile test was carried out according to the GB1040-79 plastic tensile test method. Tensile failure test the tensile test was carried out according to the GB1040-79 plastic tensile test method.
2. The softening points Tm of the TPU of preparations 1-16 were tested using a DSC differential scanning calorimeter.
3. The method for testing the mechanical properties of the electrothermal material comprises the following steps: tested according to SO 527-1-2019/-2-2012.
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 strength and the elongation at break.
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 ℃; the test piece is placed in an ultraviolet aging box (in order to ensure sufficient radiation of the test piece, two test pieces are placed in each test piece plate at most), ultraviolet radiation and condensation are alternately carried out every 4 hours, the total radiation time is 1000 hours, and the tensile strength and the elongation at break are tested.
4. The impact strength testing method of the electrothermal material comprises the following steps: the test is carried out according to a method for testing the notch impact of the simple beam at 23 ℃ and the notch impact of the simple beam at-30 ℃.
Notched impact of a simply supported beam at 23 ℃): ISO179-1eA-2010 sample size 80mm x 10mm x 4mm; a type A notch; pendulum energy 4.0J; impact speed 2.9m/s; span: 62mm.
The notched impact test of a simply supported beam at-30℃was tested in accordance with ISO179-1 eA-2010. Sample size 80mm x 10mm x 4mm; a type A notch; pendulum energy 2.0J; impact speed 2.9m/s; span: 62mm; low temperature treatment conditions: 4 hours-30 ℃.
5. Power test of the heating wire at different temperatures: the resistance is the test condition: -40 ℃ to 85 ℃,65% rh; the power supply voltage is 36-220V (test voltage is selected according to the requirement); the test length is 12-50cm (the test length is selected according to the requirement), copper wires are used for connecting the two ends of the heating wire, and the resistance of the connected copper wires is 0.1 omega. And (3) power test: the test was performed using a multichannel power analyzer 8962A1 meter using a green 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 continuously electrified for testing, and the change conditions of the resistance and the power of the electric heating wire at different temperatures are recorded.
Data analysis
Table 3 is a table of conventional test parameters for the electric heating materials of examples 1 to 7 and comparative examples 1 to 2
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Table 4 is a table showing the weather resistance test parameters of the electric heating materials of examples 1 to 7 and comparative examples 1 to 2
As can be seen in combination with examples 1-7 and comparative examples 1-2 and in combination with tables 3-4, examples 1-6 are compared with comparative examples 1-2: the mass ratio of PP resin, HDPE resin and compatilizer EVA is controlled to be (750-800): (380-440): (180-250), and the prepared electrothermal material has relatively good mechanical property and flexibility. The lower the EVA content of the compatilizer, the lower the tensile strength, the slightly improved elongation at break, the lower the overall mechanical strength and the lower the impact resistance. The lower EVA content of the compatilizer leads to the reduction of the integral mechanical strength and the reduction of the shock resistance due to the deviation of the blending effect of the PP resin and the HDPE resin. In addition, in the preparation process of the electric heating wire rod, the lower dosage of the compatilizer EVA can cause incapability of adhering to the core wire and processing the electric heating wire rod, so that quality adjustment of PP resin, HDPE resin and compatilizer EVA is one of key influencing factors of a formula.
As can be seen in combination with examples 1-7 and comparative examples 1-2 and in combination with tables 3-4, a comparison between examples 1-6 shows that: the mass ratio of PP resin, HDPE resin and compatilizer EVA in the application is controlled to be (790-800) (420-430) (180-200) to obtain the electric heating material with intelligent temperature control function, and the tensile strength is relatively better, so that the electric heating material is suitable for being used as an electric heating wire; the mass ratio of PP resin, HDPE resin and compatilizer EVA in the application is controlled to be (790-800) (400-420) (220-250), and the obtained electrothermal material with intelligent temperature control function has relatively good elongation at break and impact resistance, and is suitable for being used as electrothermal film materials.
As can be seen in combination with examples 1-7 and comparative examples 1-2 and in combination with tables 3-4, a comparison between examples 1-6 shows that: as the electric heating wire, the mass ratio of PP resin, HDPE resin and compatilizer EVA is controlled at 795:420:185. As electrothermal film material, the mass ratio of PP resin, HDPE resin and compatilizer EVA is controlled at 795:420 (230-235) is most suitable.
Table 5 shows conventional test parameter tables for the electric heating materials of examples 8 to 18 and comparative examples 3 to 16
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Table 6 shows the weather-resistant test parameters of the electric heating materials of examples 8 to 18 and comparative examples 3 to 16
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As can be seen in combination with examples 8-18 and comparative examples 3-16 and in combination with tables 5-6, example 8 compares with comparative examples 3-7 to see: the mechanical property, impact resistance and weather resistance of the electric heating material in the embodiment 8 are superior to those of the electric heating material prepared by compounding the antioxidant composition and the ultraviolet-resistant auxiliary agent provided by the application, namely the mechanical property of the electric heating material 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 electric heating wire prepared by compounding the antioxidant composition and the ultraviolet resistance auxiliary agent has good mechanical strength, weather resistance and impact resistance.
As can be seen in combination with examples 8-18 and comparative examples 3-16 and in combination with tables 5-6, example 8 compares with comparative examples 8-12 to see: the mechanical properties, impact resistance and weather resistance of the heating wire in example 8 are superior to those of comparative examples 8-12, namely the mechanical properties of the 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.
As can be seen from the combination of examples 8 to 18 and comparative examples 3 to 16 and the combination of tables 5 to 6, when example 8 is compared with examples 10 to 13, as the electric heating wire, the ultraviolet resistance 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 electrothermal material prepared in (5-40) has excellent mechanical strength, impact resistance and flexibility. The preferred embodiment of the electrothermal wire is embodiment 17, and the preferred embodiment of the electrothermal film is embodiment 18.
As can be seen from the combination of examples 8-18 and comparative examples 3-16 and the combination of tables 5-6, 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, the formula is combined and considered, the mechanical property, the impact resistance and the weather resistance of the electric heating material prepared by banburying at 165 ℃ in S1 and 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 or the electric heating film material of the product, ensure that the mechanical property and the impact resistance of the electric heating material of the final finished product are relatively obviously optimized, and further optimize the formula of the electric heating wire based on the mechanical property and the impact resistance.
Table 7 shows conventional test parameter tables for the electric heating materials of examples 18 to 25 and comparative examples 17 to 25
Table 8 shows the weather-resistant test parameters of the electric heating materials of examples 18 to 25 and comparative examples 17 to 25
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Combining examples 18-25 and comparative examples 17-25 and combining tables 7-8, as electrothermal film materials, the compatilizer is composed of EAA resin and TPU resin; and the mass ratio of the EAA resin to the TPU resin is (15-30), and the electrothermal film material granules prepared by (70-85) have relatively good elongation at break, weather resistance and impact strength. Preferably, as the electrothermal film material, the compatilizer consists of EAA resin and TPU resin according to the weight ratio of 22:78, and the prepared electrothermal film material has relatively good comprehensive performance. In the test process, the electrothermal film materials prepared by adopting the conventional TPU resin to replace EVA resin are compared with comparative example 17, and the electrothermal film material granules prepared by adopting the EAA resin and the TPU resin in the mass ratio of (15-30) are better in mechanical property and impact resistance.
Examples 19-22 are compared to comparative examples 18-21 as follows in conjunction with examples 18-25 and comparative examples 17-25 and with tables 7-8: the electrothermal film material prepared by adopting the special TPU resin in the preparation examples 9-12 has better mechanical property and shock resistance, and the electrothermal film material prepared by the polyol in the TPU resin which consists of polycarbonate diol with the molecular weight of 3000, polytetrahydrofuran diol with the molecular weight of 2000 and double-end diol type reactive silicone with the molecular weight of 5000-10000 has better mechanical property and shock resistance.
By combining examples 18 to 25 and comparative examples 17 to 25 and combining tables 7 to 8, as the electrothermal film material, the TPU resin in the electrothermal film material is preferably controlled to have a Shore hardness of 30 to 70A, preferably 50 to 70A; the TPU resins employed in preparation examples 11-12 of this application are superior to commercially available conventional TPU resins. Specifically, the self-made TPU resin in the application has relatively better bonding performance, is easier to mix the filler and the matrix resin uniformly, and improves the mechanical property, weather resistance and impact toughness of the integral electrothermal film.
Table 9 is a table of conventional test parameters for the electric heating materials of examples 26 to 31 and comparative examples 26 to 38
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Table 10 shows the weathering test parameters of the electric heating materials of examples 26 to 31 and comparative examples 26 to 38
As can be seen from the combination of examples 26 to 33 and comparative examples 26 to 38 and the combination of tables 9 to 10, example 17 has the effect of reinforcing mechanical properties and flexibility by improving the tensile strength, tensile fracture rate and impact strength of the electric heating material using EAA resin, TPU resin and TCPG resin as the compatibilizers as compared with example 26.
As can be seen from a combination of examples 26-33 and comparative examples 26-38 and from a combination of tables 9-10, example 26 shows that the TPU resin in the compatibilizer has better overall properties than the TPU resin of preparation 1 of the present application.
As can be seen from a combination of examples 26-33 and comparative examples 26-38 and from Table 9-10, examples 26-28 provide better overall performance of the electrocaloric materials prepared from TPU resins of examples 1-3 in this application as compared to comparative examples 27-31.
As can be seen from the combination of examples 26 to 33 and comparative examples 26 to 38 and tables 9 to 10, the use of EAA resin, TPU resin, TCPG resin as the compatibilizing agent improves the tensile strength, tensile failure rate and impact strength of the electrocaloric material, and serves to reinforce mechanical properties and flexibility, as compared with comparative examples 32 to 36. Further, as can be seen from the comparison of examples 26, 29-31 and comparative examples 35-38 with comparative examples 27-31, the mass ratio of EAA resin, TPU resin and TCPG resin is (10-20): 55-80): 10-25. The compatibility agent formed by compounding can improve the mechanical properties and flexibility of the electric heating material. Preferably, the mass ratio of EAA resin, TPU resin and TCPG resin is 15:65:20.
As can be seen from the combination of examples 26-33 and comparative examples 26-38 and tables 9-10, as the electric heating wire, the TPU resin in the compatibilizer is preferably controlled to have a Shore hardness of 60-95A, preferably 70-90A. The TPU resins used in preparation examples 2-3 in this application are superior to commercially available conventional TPU. Specifically, the self-made TPU resin in the application has relatively better bonding performance and mechanical strength, is easier to mix the filler and the matrix resin uniformly, can improve the overall tensile strength, and improves the mechanical property, weather resistance and impact toughness of the overall electrothermal film.
Table 11 shows the weather-resistant test parameters of the electric heating materials of examples 31 to 54 and comparative examples 39 to 42
Remarks: the wire resistance test is performed after the electric heating wire is prepared.
Table 12 shows the weather-resistant test parameters of the electric heating materials of examples 31, 34 to 53 and comparative examples 39 to 42
As can be seen in combination with examples 31-54 and comparative examples 39-42 and in combination with tables 11-12, the comparison of example 31 with comparative examples 39-40 shows that: the electric heating wire rod prepared by controlling the average grain diameter of the adopted nano zinc oxide to be 20-500nm has relatively good mechanical property and impact resistance.
As can be seen by combining examples 31-54 and comparative examples 39-42 and combining tables 11-12, the auxiliary synergistic additive is composed of nano zinc oxide, nano zirconium oxide, titanium tin carbide superfine powder and boron nitride nanotubes, the mass ratio of nano zinc oxide, nano zirconium oxide, titanium tin carbide superfine powder and boron nitride nanotubes is controlled to be (55-90): 5-20): 0.5-5, and the prepared electric heating wire has better mechanical strength and weather resistance, preferably, the mass ratio of nano zinc oxide, nano zirconium oxide, titanium tin carbide superfine powder and boron nitride nanotubes is controlled to be (78-88): 5-8): 5-12): 2.
It can be seen from the combination of examples 31 to 54 and comparative examples 39 to 42 and the combination of tables 11 to 12 that the addition of the nano titanium diboride and the carbon black can improve the overall conductivity of the electric heating wire rod and simultaneously improve the mechanical strength, flexibility and weather resistance of the electric heating wire rod.
As can be seen from the combination of examples 31 to 54 and comparative examples 39 to 42 and tables 11 to 12, the electric heating wire prepared from the conductive composition composed 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 conductivity of the finished 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 31-54 and comparative examples 39-42 and with tables 11-12, during the actual test it was found that: 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 by adopting the conductive material, the conductive performance, mechanical strength, flexibility and weather resistance can be improved well, and the stability of the quality of the finished product can be regulated well.
Table 13 is a table for detecting intelligent control performance of the electric heating wire in example 17
Remarks: the test voltage was 220V, and the resistance of the wire (25 ℃,65% rh)) of the electric heating wire in example 17 was 2.64×10 4 Omega.m, test length was 8.0cm.
As is clear from table 13, the core wire of the electric heating wire is a cotton wire, the electric heating wire has a large resistance as a whole, and the electric heating wire is reduced in resistance by shortening the length of the electric heating wire, thereby improving the heating power as a whole. The voltage of the electric heating wire rod is required to be 220V, and when the voltage is smaller, the heating power is lower, so that the practical performance is deviated.
Table 14 shows the intelligent control performance test chart of the electric heating wire in example 32
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Remarks: the test voltage was 72V, and the resistance of the wire (25 ℃,65% rh)) of the electric heating wire in example 32 was 1.268×10 3 Omega.m, test length was 18.0cm.
As can be seen from Table 14, the core wire of the electric heating wire is a 300D graphene wire (the new graphene material is customized), the overall resistance of the electric heating wire in the embodiment 32 is obviously reduced compared with that of the embodiment 17, the heating power of the electric heating wire at the voltage of 72V is similar to that of the electric heating wire at the voltage of 220V in the embodiment 17, the use safety is obviously improved, the use range is also greatly improved, and meanwhile, the problem of poor use performance of the graphene wire produced by the carbon slurry process is solved.
Table 15 shows the intelligent control performance test chart of the electric heating wire in example 33
Remarks: the test voltage was 36V, the resistance of the wire (10 ℃,65% rh)) of the electric heating wire in example 33 was 418.4 Ω×m, and the test length was 32.0cm.
As can be seen from Table 15, the core wire of the electric heating wire is 1K carbon fiber wire (DONGLIT 300 1K), the electric resistance of the whole electric heating wire in the embodiment 33 is obviously reduced compared with that in the embodiment 17, and the electric resistance of the electric heating wire in the embodiment 32 is obviously reduced compared with that in the embodiment 32, and the electric heating wire has similar heating power at the voltage of 220V in the embodiment 17 and heating power at the voltage of 72V in the embodiment 32 at the voltage of 36V, so that the use safety is obviously improved, and the use range is also greatly improved. It should be noted that: the heating wire of example 33 is more expensive to produce than the heating wire of example 32.
Table 16 shows intelligent control performance test tables of the electric heating wires in examples 41 and 54
Remarks: the test voltage was 36V, the resistance of the wire (10 ℃,65% rh)) of the electric heating wire in example 41 was 418.2 Ω×m, and the test length was 32.0cm.
As can be seen from tables 15-16, the intelligent temperature control effect of the electric heating wire in example 41 is improved to a certain extent compared with that of the electric heating wire in example 33, and the formulation of example 41 is relatively good.
It can be seen from the combination of examples 41 and 54, the combination of tables 11 to 12 and 16 and the combination of fig. 7 to 8 that the mechanical strength of the electric heating wire is obviously enhanced by adding the coupling agent, but the intelligent temperature control performance of the electric heating wire is reduced along with the addition of the coupling agent, and the electric heating wire is beneficial and disadvantageous, and is customized according to the actual demands of customers. The electric heating wire product added with the coupling agent for improvement is suitable for scene application with high requirements on mechanical properties of wires and intelligent temperature control performance, such as novel covering materials in a third major class, a seventh minor class and a novel textile material in the prior development field of national torch plan.
Table 17 shows the intelligent control performance test chart of the electric heating wire in example 50
Remarks: the test voltage was 36V, the resistance of the wire (10 ℃,65% rh)) of the electric heating wire in example 50 was 408.1 Ω×m, and the test length was 32.0cm.
Table 18 shows the intelligent control performance test chart of the electric heating wire in example 51
Remarks: the test voltage was 36V, the resistance of the wire (10 ℃,65% rh)) of the electric heating wire in example 51 was 410.3 Ω×m, and the test length was 32.0cm.
As can be seen from tables 15-18, the intelligent temperature control effect of the electric heating wires in examples 50-51 is slightly improved compared with the intelligent temperature control effect of the electric heating wires in example 41, and the intelligent temperature control effect of the electric heating wires in example 41 is improved to a certain extent compared with the intelligent temperature control effect of the electric heating wires in example 33, and the formulation of examples 50-51 is relatively better.
Table 19 is an intelligent control performance test chart of the electric heating wire in comparative example 42
Remarks: the test voltage was 220V, and the resistance of the electric heating wire (25 ℃,65% rh)) in comparative example 42 was 4.02×10 4 Omega.m, test length was 8.0cm.
Table 20 is an intelligent control performance test chart of the electric heating wire in comparative example 43
Remarks: the test voltage was 36V, and the resistance of the electric heating wire rod in comparative example 43 (25 ℃,65% rh)) was 5.04×10 2 Omega.m, test length was 32.0cm.
As can be seen from the combination of examples 17, examples 32-33, example 41, examples 50-51, examples 54 and comparative examples 42-43 and the combination of tables 13-20 and the combination of FIGS. 1-16, the electrothermal material provided in the application has better heat conduction performance and intelligent temperature control effect, improved mechanical properties, impact resistance and weather resistance, and better market prospect.
In summary, the electric heating material in the application can be prepared into the electric heating film and the electric heating wire, has relatively excellent mechanical strength, flexibility, electric conduction performance and weather resistance compared with the existing electric heating material, has wider application field, is applied to the fields of carpets, ground mats, mattresses, yoga mats, physiotherapy mats, cushions, back cushions, clothes fillers and the like, realizes the purpose of safe intelligent temperature control function, and has better market prospect. And the heating module component prepared by adopting the electrothermal film and the heating wire in the application has wide application, can replace the existing heat tracing belt and PTC heating wire products, has excellent physical and chemical properties, can be applied to a plurality of fields, fully plays an intelligent temperature control function, and improves the competitiveness of the products.
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 (14)

1. An electric heating material with intelligent temperature control function, which is characterized in that: the electrothermal material with the intelligent temperature control function is mainly prepared from the following raw materials: the material is mainly prepared from the following raw materials in percentage by mass: 15.0-20.0% of conductive composition, 5.0-10.0% of auxiliary synergistic auxiliary agent, 1.2-1.8% of antioxidant composition, 0.2-0.4% of uvioresistant auxiliary agent, 0.10-0.50% of dispersing agent and the balance of matrix resin; the matrix resin mainly comprises PP resin, HDPE resin and a compatilizer; the mass ratio of the PP resin to the HDPE resin to the compatilizer is controlled to be (750-800): 380-440): 180-250; the compatilizer is at least one of EAA resin, EVA resin, TPU resin and PCTG resin; 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 auxiliary synergistic agent is at least one of nano zinc oxide, nano zirconium oxide, nano aluminum nitride, nano aluminum oxide, titanium tin carbide superfine micropowder, boron nitride nanosheet and boron nitride whisker; the electrothermal material with the intelligent temperature control function is used for preparing an electrothermal film material with the intelligent temperature control function through a tape casting or calendaring process; or the electric heating material master batch spinning process with the intelligent temperature control function prepares the electric heating wire rod with the intelligent temperature control function; the dispersing agent is at least one of stearate and a coupling agent.
2. The electric heating material with intelligent temperature control function according to claim 1, wherein: when the electric heating material master batch spinning process with the intelligent temperature control function is used for preparing the electric heating wire rod with the intelligent temperature control function, the mass ratio of the PP resin to the HDPE resin to the compatilizer is controlled to be (790-800): 420-430): 180-200; the compatilizer consists of (10-20): 55-80): 10-25 by mass ratio of EAA resin, TPU resin and PCTG resin; the shore hardness of the TPU resin in the electric heating wire is controlled to be 65-95A.
3. The electric heating material with intelligent temperature control function according to claim 1, wherein: when the electrothermal material with the intelligent temperature control function is prepared into the electrothermal film material with the intelligent temperature control function through a tape casting or calendaring process, the mass ratio of the PP resin to the HDPE resin to the compatilizer is controlled to be (790-800): 400-420): 220-250; the compatilizer consists of EAA resin and TPU resin; the mass ratio of the EAA resin to the TPU resin is (15-30) to (70-85); the shore hardness of TPU resin in the electrothermal film material is controlled to be 30-70A.
4. The electric heating material with intelligent temperature control function according to claim 1, wherein: the TPU resin in the electric heating wire rod is mainly prepared from the following raw materials: isocyanate composition, chain extender, polyol, catalyst and auxiliary agent; the auxiliary agent comprises at least one of a leveling agent, an antioxidant, an ultraviolet absorber, a flame retardant, a lubricant and a mold release agent; the catalyst is organic bismuth or organic tin; the mass of the catalyst is 0.01% -0.1% of the total mass of the isocyanate composition, the chain extender and the polyol; the isocyanate composition is composed of HDI and MDI; the molar ratio of MDI to HDI is (0.2-0.35): (0.65-0.80); the chain extender is composed of at least two of 3 methyl-1, 5-pentanediol, 1,4 butanediol, 1,6 hexanediol, ethylenediamine, hydrazine hydrate, 1, 4-butanediamine and 1,6 hexamethylenediamine and at least one of 2, 6-toluenediamine and diethyltoluenediamine; the polyalcohol mainly comprises polycarbonate diol with molecular weight of 1000-4000, propylene glycol polyether with molecular weight of 1000-4000 and polytetrahydrofuran diol with molecular weight of 1000-4000; the total mole of the propylene glycol polyether with the molecular weight of 1000-4000 and the polytetrahydrofuran glycol with the molecular weight of 1000-4000 accounts for 60-80% of the total mole of the polyol; the molar ratio of the propylene glycol polyether with the molecular weight of 1000-4000 to the polytetrahydrofuran glycol with the molecular weight of 1000-4000 is 1 (0.5-2); the ratio of the sum of the molar amounts of hydroxyl groups in the polyol and chain extender to the molar amount of-NCO-in the isocyanate composition is 1 (0.985-0.998); the hard segment content in the TPU resin is controlled to be 45-52wt%.
5. An electric heating material with intelligent temperature control function according to claim 2, characterized in that: the TPU resin in the electrothermal film material is mainly prepared from the following raw materials: isocyanate composition, chain extender, polyol, catalyst and auxiliary agent; the auxiliary agent comprises at least one of a leveling agent, an antioxidant, an ultraviolet absorber, a flame retardant, a lubricant and a mold release agent; the catalyst is organic bismuth or organic tin; the mass of the catalyst is 0.01% -0.1% of the total mass of the isocyanate composition, the chain extender and the polyol; the isocyanate composition is composed of HDI and MDI; the molar ratio of MDI to HDI is (0.01-0.1): (0.9-0.99); the chain extender is composed of at least one of 3 methyl-1, 5-pentanediol, 1,4 butanediol, 1,6 hexanediol, glycerol, ethylene glycol and 1,3 propanediol, and at least one of ethylenediamine, hydrazine hydrate, 1, 4-butanediamine, 1,6 hexamethylenediamine, 2, 6-toluenediamine and diethyltoluenediamine; the polyalcohol mainly comprises polycarbonate diol with molecular weight of 1000-4000, polytetrahydrofuran diol with molecular weight of 1000-4000 and double-end diamine type reactive silicone with molecular weight of 5000-10000; the double-end diamine reactive silicone with the molecular weight of 5000-10000 accounts for 5-10% of the total mole of the polyol; the ratio of the sum of the molar amounts of hydroxyl groups in the polyol and chain extender to the molar amount of-NCO-in the isocyanate composition is 1 (0.985-0.998); the hard segment content in the TPU resin is controlled to be 40-46wt%.
6. An electrothermal material having an intelligent temperature control function according to claim 1 or 2, characterized in that: 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.
7. An electrothermal material having an intelligent temperature control function according to claim 2 or 3, wherein: the auxiliary synergistic auxiliary agent 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 powder to the boron nitride nanosheets is controlled to be (55-90)/(5-20)/(0.5-5).
8. The electric heating material with intelligent temperature control function according to claim 7, wherein: 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.
9. The electric heating material with intelligent temperature control function according to claim 8, wherein: 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).
10. The electric heating material with intelligent temperature control function according to claim 7, wherein: 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.
11. The electric heating material with intelligent temperature control function according to claim 10, wherein: 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).
12. A method for preparing an electrothermal material with intelligent temperature control function as claimed in any one of claims 1 to 11, characterized in that: an electric heating material masterbatch spinning process with an intelligent temperature control function is used for preparing an electric heating wire rod with the intelligent temperature control function, and the process comprises the following steps:
s1, placing the dried matrix resin, the conductive composition, the auxiliary synergistic additive, the antioxidant composition, the ultraviolet resistance additive and the dispersing agent which are accurately measured into an internal mixer, and mixing uniformly, wherein the internal mixing temperature is 160-168 ℃ and the time is 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%;
s3, taking the graphene wire or the carbon fiber 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 carrying out water cooling, heat treatment and drying to obtain the finished product heating wire.
13. A method for preparing an electrothermal material with intelligent temperature control function as claimed in any one of claims 1 to 11, characterized in that: the electrothermal material with the intelligent temperature control function is prepared into the electrothermal film material with the intelligent temperature control function through a tape casting or calendaring process, and the method comprises the following steps of:
S1, placing the dried matrix resin, the conductive composition, the auxiliary synergistic additive, the antioxidant composition, the ultraviolet resistance additive and the dispersing agent which are accurately measured into an internal mixer, and mixing uniformly, wherein the internal mixing temperature is 160-168 ℃ and the time is 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 film-making master batch with the thickness of 1.0-2.0mm, and drying until the moisture is lower than 0.1%;
s3, placing the film-making master batch in the S3 into a double-screw extruder, extruding in a 140-185 ℃ melting environment, and carrying out tape casting on a melting material flowing out of an extrusion die head to obtain a semi-finished film material, and carrying out heat treatment, cooling and winding to obtain the finished electrothermal film material.
14. The method for preparing the electric heating material with the intelligent temperature control function as claimed in claim 13, wherein the method comprises the following steps: the S3 double-screw extruder is provided with five temperature areas, wherein the first temperature area is 135+/-2 ℃, the second temperature area is 150+/-2 ℃, the third temperature area is 175+/-2 ℃, the fourth temperature area is 178-180 ℃, the fifth temperature area is 178-180 ℃, the screw rotating speed is 35-60r/min, and the die head temperature is 175-180 ℃.
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