WO2023010495A1 - Matériau composite conducteur de polychlorure de vinyle ignifuge et application associée - Google Patents

Matériau composite conducteur de polychlorure de vinyle ignifuge et application associée Download PDF

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WO2023010495A1
WO2023010495A1 PCT/CN2021/111063 CN2021111063W WO2023010495A1 WO 2023010495 A1 WO2023010495 A1 WO 2023010495A1 CN 2021111063 W CN2021111063 W CN 2021111063W WO 2023010495 A1 WO2023010495 A1 WO 2023010495A1
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conductive
parts
composite material
polyvinyl chloride
vinyl acetate
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PCT/CN2021/111063
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English (en)
Chinese (zh)
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熊圣东
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宁波先锋新材料股份有限公司
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Priority to PCT/CN2021/111063 priority Critical patent/WO2023010495A1/fr
Priority to CN202180002370.7A priority patent/CN113785013B/zh
Publication of WO2023010495A1 publication Critical patent/WO2023010495A1/fr

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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
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0862—Nickel
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

Definitions

  • the invention belongs to the technical field of polymer materials, and in particular relates to a conductive and flame-resistant polyvinyl chloride composite material and its application.
  • Conductive composite materials are functional polymer materials that are processed by mixing matrix resin and conductive substances and processing them in the same way as resin materials. It is mainly used in the fields of electronics, electromagnetic wave shielding, and integrated circuit packaging, and has broad application prospects in light-emitting diodes, mobile phones, solar cells, miniature TV screens, and even life science research.
  • the method of compounding is often used when preparing conductive resin materials, that is, the polymer resin is used as the matrix, and it is made by cooperating with conductive fillers, modified polymers or antistatic agents, and the conductive fillers are often used in large quantities.
  • Carbon black or metal powder, etc. the Chinese patent application (CN201911284896.X) relates to a polyvinyl chloride elastomer conductive composite material and its preparation method. The mechanical properties and processability of the material are greatly reduced due to the addition of a large amount of conductive carbon black.
  • Another example is the Chinese patent application (CN201410812623.9), which relates to a high-strength PVC conductive composite material and its preparation method.
  • This technology also adds a large amount (15% to 18%) of carbon black and traditional metal substances as conductive fillers.
  • the material has certain conductivity, but the material obtained by this method is a hard PVC material, which has poor processability, poor flame retardancy, weather resistance and other properties, which limit the application of the material.
  • Another example is the Chinese patent application (CN111234410A), which relates to a polyvinyl chloride conductive material and its preparation method.
  • the conductive composite material obtained by this technology has a certain flexibility, but the conventional conductive carbon black used is added in an amount of 10% to 13%.
  • the amount of filler calcium carbonate added is 7% to 10%, the mechanical properties of the material are poor, and it does not have good flame retardant properties, which limits the application of the material.
  • PVC materials with certain softness are widely used in fields such as films, cables, and packaging materials.
  • PVC materials with softness generally contain plasticizers.
  • the addition of plasticizers improves the processability of the material and gives the material softness, but on the other hand, it also improves the flame retardancy, weather resistance, mechanical properties and Self-cleaning performance is reduced.
  • the addition of low molecular weight plasticizers will also greatly reduce the conductive effect of traditional conductive fillers (such as carbon black or metal powder, etc.). Therefore, developing a high-conductivity flame-resistant polyvinyl chloride composite material with flame retardancy, weather resistance, excellent mechanical properties and a certain degree of softness is a technical difficulty in the current research on polyvinyl chloride composite materials.
  • the purpose of the present invention is to solve the above-mentioned problems in the prior art, and propose a conductive flame-resistant polyvinyl chloride composite material with good electrical conductivity, weather resistance, flame retardancy, softness and excellent mechanical properties.
  • a conductive flame-resistant polyvinyl chloride composite material includes the following components in parts by weight: 70 parts of polyvinyl chloride resin (PVC), chlorinated polyvinyl chloride 25-35 parts of ethylene, 3-5 parts of stabilizer, 25-35 parts of plasticizer, 5-8 parts of flame retardant, 6-10 parts of conductive filler, 10-15 parts of modified resin, 0.2-0.4 parts of lubricant , 0.6-1 part of other additives, the conductive filler is a mixture of silver-plated nano-graphite microflakes, nickel-coated copper powder, and single-armed carbon nanotubes.
  • PVC polyvinyl chloride resin
  • chlorinated polyvinyl chloride 25-35 parts of ethylene
  • stabilizer 25-35 parts of plasticizer
  • plasticizer 25-35 parts of plasticizer
  • flame retardant 6-10 parts
  • 6-10 parts of conductive filler 10-15 parts of modified resin
  • 0.2-0.4 parts of lubricant 0.6-1 part of other additives
  • the conductive filler is
  • the amount of conductive filler added in the composite material of the present invention is 4.2% to 5.6%, and a conductive composite material with a volume resistivity within 10 3 ⁇ .cm can be obtained, and the conductive composite material has good flame retardancy, weather resistance, and flow processability and mechanical properties.
  • the degree of polymerization of the polyvinyl chloride resin is 950-1700.
  • the chlorinated polyethylene is a resin-type chlorinated high-density polyethylene with a chlorine content of 20-35%.
  • the chlorinated high-density polyethylene used in the present invention is a high-molecular material obtained by chlorination substitution reaction of high-density polyethylene. It has excellent weather resistance, ozone resistance, chemical resistance and oil resistance, and has good properties with PVC. compatibility. Blending with PVC can significantly improve the mechanical and weather resistance properties of PVC materials. In addition, it can also play the role of plasticizing PVC, thereby reducing the amount of plasticizers used in conductive flame-resistant PVC composite materials.
  • plasticizers are flammable substances, and the reduction of plasticizer dosage can also improve the flame retardancy of materials. Furthermore, the reduction of the amount of plasticizer also reduces the risk of plasticizer precipitation in the composite material and improves the easy-cleaning performance of the material.
  • chlorinated high-density polyethylene contains a large number of polar chlorine atoms. The existence of this polar component increases the compatibility and combination of the matrix polymer material with conductive fillers and inorganic flame retardants, making the composite material uniform Enhanced, the conductivity, flame retardancy, weather resistance and mechanical properties of the material are perfectly presented.
  • the stabilizer is a calcium-zinc composite stabilizer.
  • Calcium-zinc composite stabilizer can inhibit the decomposition reaction of polyvinyl chloride under light and heat environment.
  • the plasticizer includes dioctyl terephthalate, diisooctyl adipate, dioctyl sebacate, tri-n-butyl citrate, acetyl lemon One or more of tributyl citrate, triethyl citrate, butyl epoxy stearate, and trioctyl trimellitate.
  • the present invention adds a certain amount of plasticizer to the conductive flame-resistant polyvinyl chloride composite material, and the molecules of the plasticizer can be inserted between the PVC molecular chains to increase the mobility of the PVC molecular chains and reduce the crystallinity of the PVC molecular chains, thereby Increase the plasticity and flexibility of PVC.
  • the use of plasticizers together with chlorinated high-density polyethylene can significantly improve the flow processing performance of PVC and endow PVC composites with good flexibility.
  • the flame retardant is antimony trioxide.
  • Antimony trioxide is an additive flame retardant, which itself has no obvious flame retardant effect, but it will show a synergistic effect in the presence of halides.
  • the main resin materials in the system of the present invention are polyvinyl chloride resin and chlorinated high-density polyethylene resin with a chlorine content of 20 to 35%, both of which have a large amount of chlorine elements in their molecular structures, and the presence of these chlorine elements makes the matrix
  • the resin material itself has a certain flame retardant performance.
  • chlorine elements in polyvinyl chloride resin and chlorinated high-density polyethylene resin will react to generate high concentrations of hydrochloric acid or free chlorine, which will React with antimony trioxide to produce antimony chloride substances such as antimony trichloride or antimony pentachloride.
  • antimony compounds can reduce the contact between combustibles and oxygen, so that the carbon coating is formed, and it can also capture the combustion process in the gaseous state Free radicals, so as to achieve the purpose of low flame retardant addition to achieve high flame retardancy, and endow the final composite with good flame retardancy and mechanical properties.
  • the chlorinated polyethylene in the present invention plays plasticizing effect on the one hand and reduces the usage amount of plasticizer;
  • the compatibility between polymer resins, and more importantly, its high chlorine content combined with antimony trioxide has played a synergistic role in flame retardancy, so that the present invention only uses traditional antimony trioxide flame retardants without other
  • a flame retardant synergist the purpose of high flame retardancy can be achieved, and the amount of flame retardant added is reduced.
  • the conductive filler is silver-plated nano-graphite microflakes, nickel-coated copper powder, and single-armed carbon nanotubes in a mass ratio of 1:(0.2 ⁇ 0.6):(0.05 ⁇ 0.1) Mixed mixture.
  • the conductive and flame-resistant polyvinyl chloride composite material of the present invention adopts silver-plated nano-graphite microflakes as the main conductive filler.
  • Graphite has a small specific gravity, and can be used in a small amount under the same volume, and its chemical stability is also relatively high; nickel-clad copper powder not only has good electrical conductivity but also has excellent electromagnetic shielding performance.
  • the present invention has good electrical conductivity.
  • Single-armed carbon nanotubes are a supplement to the conductivity of silver-plated nano-graphite microsheets, which have ultra-high electrical conductivity and good mechanical and mechanical properties.
  • One of the most important characteristics of conductive polymer composites is that the more conductive particles in the contact state, the denser the network, and the smaller the gap between conductive particles, the higher the conductivity of the composite material.
  • silver-plated nano-graphite microflakes, nickel-clad copper powder and single-arm carbon nanotubes is different from that of matrix resin, silver-plated nano-graphite microflakes, nickel-clad copper powder and single-arm carbon nanotubes are used as Conductive particles can only stay inlaid on the grain boundaries with relatively loose structure in the matrix.
  • the volume fraction of conductive filler particles reaches a certain critical value, that is, when the conductive particles embedded in the grain boundaries are in contact with each other or the gap is small, the potential barrier of the conductive filler particles is continuously reduced, and an electrical percolation network is formed. A part of the tunnel current channel with strong conductivity will be formed in the phase, so as to realize the conductive function.
  • a three-dimensional strengthened conductive network can be formed to achieve high conductive properties.
  • the silver-coated nano-graphite microflakes as the main conductive particles are microscopically a nano-scale sheet structure, which is conducive to the formation of conductive pathways in the polymer, which can greatly reduce the conductive percolation of the composite material system. Threshold, so as to achieve low conductive filler addition and obtain high conductive characteristics.
  • the addition of low-conductivity fillers reduces the cost of conductive composite materials, and on the other hand, it also greatly retains the high flow processability and good mechanical properties of the material, increasing its application fields.
  • the silver-plated nano-graphite microflakes are used as the main conductive particles, and the different conductive particles are in ohmic contact.
  • the migration rate in that improves the electrical conductivity of the composite.
  • the electrical conductivity of the composite material reaches a certain value, and does not change significantly with the increase of the amount of conductive filler, and has obvious electrical percolation just like the traditional conductive polymer composite material. Phenomenon.
  • silver-coated nano-graphite microflakes and single-armed carbon nanotubes can be combined with PVC and chlorinated polyvinyl acetate under the coupling action of the vinyl acetate polar groups of the modified resin ethylene-vinyl acetate copolymer resin and vinyl chloride-vinyl acetate copolymer resin.
  • the polar groups in ethylene are combined to form a strong micro-interface between the components. This strong micro-interface enables the composite material to effectively transmit the destructive force to the silver-coated nano-graphite microflakes when it is damaged by an external force.
  • single-arm carbon nanotubes so that the mechanical properties of the composite material such as tensile resistance and impact are greatly improved, and the mechanical properties are reinforced.
  • the dosage of the conductive filler in the present invention is controlled at 6-10 parts.
  • the conductive filler is a mixture of silver-plated nano-graphite flakes, nickel-coated copper powder, and single-armed carbon nanotubes in a mass ratio of 1:(0.2-0.4):(0.05-0.08).
  • the mass ratio of silver-plated nano-graphite microflakes, nickel-coated copper powder, and single-armed carbon nanotubes in the conductive filler is 1:0.3:0.07.
  • the mass content of nickel in the nickel-clad copper powder is 10-35%.
  • the mass content of nickel in the nickel-clad copper powder is 15-30%.
  • the modified resin is a mixture of ethylene-vinyl acetate copolymer resin and vinyl chloride-vinyl acetate copolymer resin, and ethylene-vinyl acetate copolymer resin and vinyl chloride-vinyl acetate copolymer resin
  • the mass ratio is 1:(0.5 ⁇ 1.6).
  • Ethylene-vinyl acetate copolymer resin is obtained by copolymerizing ethylene and vinyl acetate; vinyl chloride-vinyl acetate copolymer resin is a polymer obtained by copolymerizing vinyl chloride (VC) and vinyl acetate (VAC) monomers. Both copolymer resins have polar and nonpolar groups.
  • the conductive filler and antimony trioxide used in the present invention have poor compatibility with polyvinyl chloride resin. If these additives cannot be uniformly dispersed in the continuous phase of polyvinyl chloride resin, it will directly affect the conductivity and flame retardancy of the composite material. And processing fluidity and mechanical properties.
  • Ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin and polyvinyl chloride resin have good compatibility, and the vinyl acetate polar groups they contain can have chemical properties with conductive fillers of the present invention and inorganic additives such as antimony trioxide. Coupling effect, so as to play a compatible role on the matrix polyvinyl chloride resin and various inorganic additives, can improve the flexibility, toughness and processing flow performance of the composite material, and make the composite material system more uniform and reasonable.
  • the vinyl acetate group in ethylene-vinyl acetate copolymer resin and vinyl chloride-vinyl acetate copolymer has good self-adhesive properties, so that the polyvinyl chloride composite material of the present invention has good thermal bonding properties.
  • the coated wire woven fabric is then heat-set to improve the smoothness and firmness of the structure.
  • the modified resin is a mixture of ethylene-vinyl acetate copolymer resin and vinyl chloride-vinyl acetate copolymer resin in a mass ratio of 1:1.
  • the content of vinyl acetate in the ethylene-vinyl acetate copolymer resin is 10-30%, and the content of vinyl acetate in the vinyl chloride-vinyl acetate copolymer resin is 10-30%. If the content of polar vinyl acetate in the modified resin is too small, it will not achieve the effect of compatibility modification; if the content is too large, it will reduce the overall performance of the composite material in terms of mechanics, electrical conductivity and heat resistance.
  • the lubricant may be ethylene bisstearamide or oxidized polyethylene wax.
  • lubricants are a commonly used additive.
  • the lubricant used in the invention increases the lubricating performance of the composite material and the metal processing equipment on the one hand, and prevents the polyvinyl chloride composite material from sticking to the processing equipment.
  • After melting it melts into the interior of the PVC melt, lubricates the molecules in the melt, and properly reduces friction, which is convenient for processing and molding.
  • the other additives include 0.3-0.5 part of antioxidant and 0.3-0.5 part of anti-ultraviolet agent.
  • the antioxidant may be selected from one or both of hindered phenolic antioxidants and phosphite antioxidants.
  • the antioxidant can be selected from tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester, ⁇ -(3,5-di-tert-butyl-4- n-octadecyl hydroxyphenyl)propionate, tris(2,4-di-tert-butylphenyl)phosphite, or 2,2'-thiobis[3-(3,5-di-tert-butyl One or more of ethyl-4-hydroxyphenyl) propionate].
  • the anti-ultraviolet agent is a benzophenone anti-ultraviolet agent.
  • the anti-ultraviolet agent includes 2-hydroxyl-4-n-octyloxybenzophenone, 2-hydroxyl-4-octyloxybenzophenone, 2-hydroxyl-4-methoxybenzophenone One or more of ketone or 4-dihydroxybenzophenone.
  • the weather resistance of the fabric must be good.
  • PVC itself is easy to decompose and age, and it has a more sensitive chemical reaction to ultraviolet rays. Under the irradiation of outdoor ultraviolet rays, polyvinyl chloride is prone to chemical decomposition reactions.
  • the antioxidant added in the invention can effectively inhibit the oxidative decomposition effect of oxygen in the air on the PVC composite material, and improve the retention of physical properties of the composite material after heating in aerobic air.
  • the use of the anti-ultraviolet agent in the present invention can absorb the ultraviolet rays irradiated on the product so as to effectively inhibit the chemical decomposition reaction between the ultraviolet rays and the PVC composite material, so as to ensure the high weather resistance and ultraviolet resistance of the composite material.
  • the present invention also provides a method for preparing the conductive flame-resistant polyvinyl chloride composite material as described above, comprising the following steps:
  • the present invention also provides an application of the conductive and flame-resistant polyvinyl chloride composite material in conductive coated wires.
  • the conductive covered wire includes a fiber layer and a conductive flame-resistant polyvinyl chloride composite material coating layer made of conductive flame-resistant polyvinyl chloride composite material.
  • the surface of the conductive flame-resistant polyvinyl chloride composite material layer of the conductive covered wire further includes an electrostatic dust collector layer.
  • the fiber may be any fiber, such as one or more selected from polyester fiber, glass fiber, acrylic fiber, polypropylene fiber, aramid fiber, spandex fiber and polyethylene fiber.
  • the electrostatic precipitant layer is formed by applying an electrostatic precipitant solution to the surface of the coated wire and then heating and curing.
  • the electrostatic precipitant solution includes the following components: electrostatic precipitator 8 ⁇ 12 parts, 10-15 parts of vinyl chloride-vinyl acetate copolymer resin, 0.1-0.2 parts of dispersant, 50-70 parts of butyl acetate.
  • the electrostatic cleaner is a mixture of calcium sulfide, ferric oxide, zinc stannate, and magnesium hydroxide, and the mass percentages of calcium sulfide, ferric oxide, zinc stannate, and magnesium hydroxide in the mixture are respectively It is 15-30%, 15-30%, 15-30%, 15-30%. The effect is best when the quality of calcium sulfide, ferric oxide, zinc stannate, and magnesium hydroxide is the same. Therefore, it is further preferred that the mass ratios of calcium sulfide, ferric oxide, zinc stannate and magnesium hydroxide in the electrostatic cleaner are all 25%.
  • the inorganic electrostatic dust collector used in the present invention has poor compatibility with the polymer resin material, and it is difficult to have better compatibility with the PVC material layer in the covered wire.
  • the present invention is by introducing vinyl chloride-vinyl acetate copolymer resin in electrostatic precipitator solution, and it has good compatibility with electrostatic precipitator (calcium sulfide, ferric oxide, zinc stannate, magnesium hydroxide) used in the present invention Compatible coupling effect, and also has good compatibility with PVC, so that the electrostatic dust collector coating can be well integrated with the PVC composite material, and solves the problem of the conductive package between the electrostatic dust collector coating and the PVC substrate.
  • the compatibility of the covered wire is poor, and the electrostatic effect gradually weakens with time, so that the conductive covered wire of the present invention has a long-term electrostatic adsorption effect.
  • the present invention also provides an application of the conductive and flame-resistant polyvinyl chloride composite material in conductive woven fabrics.
  • the conductive braided fabric is woven from conductive covered wires, and the conductive covered wires include a fiber layer and a conductive flame-resistant polyvinyl chloride composite material coating layer made of conductive flame-resistant polyvinyl chloride composite material .
  • the surface of the conductive flame-resistant polyvinyl chloride composite material layer of the conductive covered wire further includes an electrostatic dust collector layer.
  • the present invention has following advantage:
  • Conductive and flame-resistant polyvinyl chloride composite material of the present invention is compounded by silver-plated nano-graphite microflakes, nickel-coated copper powder, and single-arm carbon nanotubes, and is combined with polyvinyl chloride resin, chlorinated polyethylene, and plasticized
  • the synergistic effect of additives, modified resins, flame retardants and other components makes the composite material not only have high electrical conductivity, but also have high flame retardancy, high weather resistance, high mechanical properties and good softness characteristics.
  • the conductive and flame-resistant polyvinyl chloride composite material of the present invention due to the rational use of the synergistic effect of each system, the addition of conductive fillers and flame retardants can obtain good conductivity and flame-retardant effects within 10 parts.
  • the machinable fluidity and mechanical property retention of the material are greatly improved, making it have a wide range of applications.
  • the conductive flame-resistant polyvinyl chloride composite material of the present invention has good processability and flexibility, and can be widely used in conductive coated wires and conductive woven fabrics.
  • the conductive coated wire/conductive braided fabric of the present invention has a conductive flame-resistant polyvinyl chloride composite material coating layer, which has excellent mechanical properties, is easy to clean, has excellent weather resistance, and has a very long service life.
  • the surface of the conductive coated wire/conductive woven fabric contains an electrostatic dust collector coating.
  • the dust collector uses the principle of static electricity to effectively absorb tiny particles such as dust in the air. Since the conductive coated wire of the present invention contains an electrostatic dust collector coating on its surface, it can absorb a certain amount of PM2.5 even when it is not electrified. The electrostatic dust-absorbing agent coating on the surface will not fall off gradually over time, so that the conductive coated wire/conductive woven fabric of the present invention has a long-term electrostatic adsorption effect.
  • Example 1 The only difference with Example 1 is that 10 parts of silver-plated nano-graphite microflakes, nickel-clad copper powder (the mass content of nickel is 30%), single-arm carbon Conductive fillers for nanotubes. Others are the same as in Example 1 and will not be repeated here.
  • Example 1 The only difference from Example 1 is that 8 parts of flame retardant antimony trioxide are added in this example, and the others are the same as in Example 1, and will not be repeated here.
  • Example 1 The difference with Example 1 is only that the chlorine content in the chlorinated high-density polyethylene added in this example is 20%, and the others are the same as Example 1, so they are no longer repeated here.
  • Example 1 The difference with Example 1 is only that adding 5 parts of ethylene-vinyl acetate copolymer resins with a vinyl acetate content of 25% and 5 parts of vinyl chloride-vinyl acetate copolymer resins with a vinyl acetate content of 15% by weight in this embodiment Mixture, other is identical with embodiment 1, repeats no more here.
  • Example 1 The difference between this embodiment and Example 1 is that the conductive filler in this embodiment is added by weight in 8 parts by weight and is 1:0.2:0.05 silver-plated nano-graphite microflakes, nickel-coated copper powder (the mass content of nickel 30%), the conductive filler of single-armed carbon nanotubes, the others are the same as in Example 1, and will not be repeated here.
  • Example 1 The difference between this embodiment and Example 1 is that the conductive filler in this embodiment adds 8 parts by weight of silver-plated nano-graphite microflakes, nickel-coated copper powder (the mass content of nickel is 1:0.6:0.1) 30%), the conductive filler of single-armed carbon nanotubes, the others are the same as in Example 1, and will not be repeated here.
  • Example 1 The difference between this comparative example and Example 1 is only that, in this comparative example, adding 8 parts by weight of silver-plated nano-graphite microflakes and nickel-coated copper powder (the mass content of nickel is 5 parts by weight) with a mass ratio of 1:0.3:0.07 %), conductive filler of single-armed carbon nanotubes. Others are the same as in Example 1.
  • Example 1 The only difference with Example 1 is that in this example, 8 parts by weight of silver-plated nano-graphite microflakes and nickel-coated copper powder (the mass content of nickel is 40%) are added in 8 parts by weight in a mass ratio of 1:0.3:0.07. , Conductive filler of single-armed carbon nanotubes. Others are the same as in Example 1.
  • Example 1 The difference with Example 1 is only that, in this embodiment, adding 6.5 parts of vinyl acetate content is the mixture of 5% ethylene-vinyl acetate copolymer resin and 6.5 parts of vinyl acetate content of 5% vinyl chloride-vinyl acetate copolymer resin. Others are the same as in Example 1.
  • Example 1 The difference with Example 1 is only that, in this embodiment, adding 6.5 parts of vinyl acetate content is 35% ethylene-vinyl acetate copolymer resin and 6.5 parts of vinyl acetate content is the mixture of 35% vinyl chloride-vinyl acetate copolymer resin. Others are the same as in Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that no conductive filler is added in this comparative example. Others are the same as in Example 1.
  • Example 2 The only difference between this comparative example and Example 2 is that the conductive filler in this comparative example is 8 parts of conductive carbon black. Others are identical with embodiment 2.
  • Example 1 The only difference between this comparative example and Example 1 is that in this comparative example, 4 parts by weight of silver-plated nano-graphite microflakes and nickel-coated copper powder (the mass content of nickel is 30% by weight) are added in a mass ratio of 1:0.3:0.07. %), conductive filler of single-armed carbon nanotubes. Others are the same as in Example 1.
  • Example 1 The difference between this comparative example and Example 1 is that in this comparative example, 15 parts by weight of silver-plated nano-graphite microflakes and nickel-coated copper powder (the mass content of nickel is 30% by weight) are added in a mass ratio of 1:0.3:0.07. %), conductive filler of single-armed carbon nanotubes. Others are the same as in Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that in this comparative example, 8 parts by weight of silver-plated nano-graphite microflakes and nickel-coated copper powder (the mass content of nickel is 30% by weight) are added in a mass ratio of 5:3:0.7. %), conductive filler of single-armed carbon nanotubes. Others are the same as in Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that in this comparative example, adding 8 parts by weight is silver-plated nano-graphite microchips and nickel-coated copper powder with a mass ratio of 1:0.3 (the mass content of nickel is 30% ) conductive filler. Others are the same as in Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that in this comparative example, 30 parts of chlorinated high-density polyethylene with a chlorine content of 32% are replaced by 30 parts of high-density polyethylene. Others are the same as in Example 1.
  • Example 1 The difference between this comparative example and Example 1 is that in this comparative example, 2.5 parts of ethylene-vinyl acetate copolymer resin with a vinyl acetate content of 25% and 2.5 parts of ethylene-vinyl acetate copolymer resin with a vinyl acetate content of 15% are added in parts by weight in this example.
  • the mixture of vinyl chloride-vinyl acetate copolymer resin, others are identical with embodiment 1, repeat no more here.
  • Example 1 The only difference between this comparative example and Example 1 is that in this comparative example, 3 parts of flame retardant antimony trioxide are added in parts by weight. Others are the same as in Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that in this comparative example, 8 parts by weight of silver-plated nano-graphite microflakes and nickel-coated copper powder (the mass content of nickel is 30% by weight) are added in a mass ratio of 1:1:0.02. %), conductive filler of single-armed carbon nanotubes. Others are the same as in Example 1.
  • a conductive sheathed wire with a diameter of 0.33mm which includes a polyester fiber layer with a specification of 220D from the inside to the outside, and a conductive flame-resistant polyvinyl chloride made of the conductive flame-resistant polyvinyl chloride composite material obtained in Example 1. Composite layer.
  • a conductive coated wire with a diameter of 0.35mm including a 220D polyester fiber layer and a conductive flame-resistant polyvinyl chloride composite material layer made of the conductive flame-resistant polyvinyl chloride composite material in Example 1 from the inside to the outside and the electrostatic dust collector layer, wherein the electrostatic dust collector layer is formed by applying the electrostatic dust collector solution to the surface of the coated wire and then heating and curing.
  • the electrostatic dust collector solution includes the following components: electrostatic dust collector 10 parts of dusting agent, 12 parts of vinyl chloride-vinyl acetate copolymer resin, 0.15 parts of dispersant BYK-110, 60 parts of butyl acetate, 2.5 parts of calcium sulfide, 2.5 parts of ferric oxide, 2.5 parts of stannic acid A mixture of zinc, 2.5 parts magnesium hydroxide.
  • a conductive coated wire with a diameter of 0.35 mm which sequentially includes a 300D glass fiber layer from the inside to the outside, and a conductive flame-resistant polyvinyl chloride composite material layer made of the conductive flame-resistant polyvinyl chloride composite material in Example 1 and the electrostatic dust collector layer, wherein the electrostatic dust collector layer is formed by applying the electrostatic dust collector solution to the surface of the coated wire and then heating and curing.
  • the electrostatic dust collector solution includes the following components: electrostatic dust collector 8 parts of dust agent, 15 parts of vinyl chloride-vinyl acetate copolymer resin, 0.1 parts of dispersant BYK-111, 70 parts of butyl acetate, 2 parts of calcium sulfide, 2 parts of ferric oxide, 2 parts of hydroxide Magnesium mixture.
  • a conductive woven fabric is woven from the conductive covered wire in application example 1, and the porosity is 5%.
  • a conductive woven fabric is woven from the conductive covered wire in application example 2, and the porosity is 5%.
  • a conductive braided fabric which is braided by the conductive covered wire in application example 3, and has a porosity of 10%.
  • Oxygen index test standard GB/T5454-1997
  • Light color fastness test standard GB/T8427-2008
  • Volume resistivity test standard GB/T1410-2006
  • Impact strength test standard GB/T 1843-2008
  • Tensile strength test standard GB/T 16421-1996
  • Breaking strength test standard GB/T3923.1-1997; tear strength test standard: GB/T3917.2-2009; light color fastness test standard: GB/T8427-2008
  • the conductive flame-resistant polyvinyl chloride composite material prepared in the embodiment of the present invention has good mechanical properties and weather resistance. Has good flame retardant properties.
  • the volume resistivity of the composite material is in the range of 10 3 ⁇ , and it has electrical conductivity, and the optimized formula system has better electrical conductivity.
  • the Shore A hardness is around 92 and has softness.
  • the ethylene-vinyl acetate copolymer resin and vinyl chloride-vinyl acetate copolymer resin with coupling dispersion effect play a positive role in the dispersion uniformity between the inorganic metal filler and the polyvinyl chloride resin in the conductive composite system, so that The functions of conductivity and flame retardancy are fully exerted. If the content of the two in the formula is reduced, the dispersion uniformity of the inorganic metal filler in PVC is poor, which increases the resistance of the material and weakens the flame retardant performance, see Examples 1, 6 and Comparative Example 8. If the content of polar vinyl acetate in the modified resin is not within the preferred range, the overall mechanical, electrical and thermal properties of the composite material obtained will be reduced, see examples 1, 11 and 12.
  • the conductive filler used in the present invention is a mass ratio of 1:(0.2 ⁇ 0.6):(0.05 ⁇ 0.1) a mixture of silver-plated nano-graphite microflakes, nickel-clad copper powder, single-armed carbon nanotubes, as preferably, the The mass ratio of silver-plated nano-graphite microflakes, nickel-coated copper powder, and single-arm carbon nanotubes in the conductive filler is 1:0.3:0.07.
  • the conductive filler optimized formula system has better conductivity, see Examples 1, 7, and 8.
  • the conductivity of the composite material obtained will change significantly. Poor, see embodiment 1 and comparative examples 5,10. If the conductive filler of the present invention is replaced by common conductive carbon black in equal parts, the conductivity of the resulting conductive material will be significantly weakened, as shown in Example 2 and Comparative Example 2. If the conductive filler does not contain single-armed carbon nanotubes, the conductivity of the resulting conductive material is also significantly weakened, see Example 1 and Comparative Example 6.
  • the mass content of nickel in the nickel-clad copper powder is 10 to 35%. If the mass content of nickel in the nickel-clad copper powder used is too small, the conductivity of the composite material will decrease due to the reduction of the volume fraction of the conductive particles. See embodiment 1, embodiment 9. If the mass content of nickel in the nickel-clad copper powder used is too large, it will also affect the conductivity of the composite material, see Example 1 and Example 10.
  • the silver-plated nano-graphite microflakes and single-armed carbon nanotubes not only play the role of conduction, but also play the role of reinforcement.
  • the mechanical properties of the composite material increase with the increase of the content of the two within a certain range. See Embodiment 1,3 and comparative example 1,3,5,6.
  • the silver-plated nano-graphite microflakes and single-armed carbon nanotubes that play a reinforcing role will appear agglomerated primary particles, and the defect points will increase, reducing the intermolecular force in the composite material, resulting in resistance.
  • the ability of external destructive force is reduced, and the mechanical properties of the composite material are reduced, see Example 1 and Comparative Example 4.
  • the Shore A hardness of the composite material obtained in the present invention is about 92, and the hardness of the composite material is mainly determined by the content of the plasticizer and the compatibility of each system, and the amount of the filler also affects the hardness of the material. If the plasticizer content increases, its hardness will decrease appropriately, see Examples 1 and 2; if the content of inorganic or metal fillers decreases, its hardness will decrease appropriately, see Example 1 and Comparative Examples 1, 3, and 9; if the system As the filler content increases, the hardness will increase, see Example 1 and Comparative Example 4. In addition, if the compatibility of the system is poor, the dispersion of the filler will be uneven, and the hardness of the obtained composite material will also increase, see Example 1, Example 11 and Comparative Example 8.
  • the flame retardant performance of the composite material of the present invention is good, and the flame retardant performance increases with the increase of the added amount of the flame retardant within a certain range, see Examples 1, 4 and Comparative Example 9.
  • the flame retardant performance of the material is also related to the dispersion uniformity of the system. If the compatibility of the system is poor, the dispersion of the filler will be uneven, and the flame retardant performance of the obtained composite material will be reduced. See Example 1, Example 11 and Comparative Example 8 .
  • the polar chlorine element in the chlorinated high-density polyethylene used in the present invention provides a high flame-retardant synergistic effect on the one hand, and on the other hand can also increase the compatibility of inorganic and metal fillers with polymer resins. If the chlorine used If the chlorine content in the high-density polyethylene is low, or does not contain chlorine, the overall properties of the material such as flame retardancy, electrical conductivity and mechanical properties are all reduced, see Examples 1, 5 and Comparative Example 7.
  • the conductive flame-resistant polyvinyl chloride composite material of the present invention can be successfully applied to conductive flame-resistant coated wires and braids thereof, and the mechanical properties, flame retardancy and weather resistance of the obtained products are good, It also has conductive properties.

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Abstract

La présente invention concerne un matériau composite conducteur de polychlorure de vinyle ignifuge et une application associée. Le matériau composite comprend les constituants suivants, en parties en poids, à savoir : 70 parties d'une résine de polychlorure de vinyle, de 25 à 35 parties de polyéthylène chloré, de 3 à 5 parties d'un stabilisateur, de 25 à 35 parties d'un plastifiant, de 5 à 8 parties d'un retardateur de flamme, de 6 à 10 parties d'une charge conductrice, de 10 à 15 parties d'une résine modifiée, de 0,2 à 0,4 partie d'un lubrifiant et de 0,6 à 1 partie d'autres auxiliaires. La charge conductrice est un mélange de micropuces en nanographite plaqué d'argent, de poudre de cuivre revêtue de nickel et de nanotubes de carbone à un seul bras. Le matériau composite de la présente invention présente une haute conductivité, présente également les caractéristiques d'un retard de flamme élevé, d'une haute résistance aux intempéries, d'une propriété mécanique élevée et d'une bonne souplesse, présente un large champ d'application et peut être largement appliqué sur des fils revêtus conducteurs et des tissus tissés conducteurs.
PCT/CN2021/111063 2021-08-06 2021-08-06 Matériau composite conducteur de polychlorure de vinyle ignifuge et application associée WO2023010495A1 (fr)

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