WO2023010495A1

WO2023010495A1 - Conductive flame-retardant polyvinyl chloride composite material and application thereof

Info

Publication number: WO2023010495A1
Application number: PCT/CN2021/111063
Authority: WO
Inventors: 熊圣东
Original assignee: 宁波先锋新材料股份有限公司
Priority date: 2021-08-06
Filing date: 2021-08-06
Publication date: 2023-02-09
Also published as: CN113785013A; CN113785013B

Abstract

The present invention relates to a conductive flame-retardant polyvinyl chloride composite material and an application thereof. The composite material comprises the following components in parts by weight: 70 parts of a polyvinyl chloride resin, 25-35 parts of chlorinated polyethylene, 3-5 parts of a stabilizer, 25-35 parts of a plasticizer, 5-8 parts of a flame retardant, 6-10 parts of a conductive filler, 10-15 parts of a modified resin, 0.2-0.4 part of a lubricant, and 0.6-1 part of other auxiliaries. The conductive filler is a mixture of silver-plated nano graphite microchips, nickel-coated copper powder, and single-arm carbon nanotubes. The composite material of the present invention has high conductivity, also has the characteristics of high flame retardance, high weather resistance, high mechanical property and good softness, has a wide application field, and can be widely applied to conductive coated wires and conductive woven fabrics.

Description

A conductive flame-resistant polyvinyl chloride composite material and its application

technical field

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.

Background technique

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.

In the prior art, 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. For example, 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. However, 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. In addition, in the preparation of conductive PVC composite materials, 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.

Contents of the invention

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.

The purpose of the present invention can be achieved through the following technical solutions: a conductive flame-resistant polyvinyl chloride composite material, the 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.

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 Ω.cm can be obtained, and the conductive composite material has good flame retardancy, weather resistance, and flow processability and mechanical properties.

In the above conductive and flame-resistant polyvinyl chloride composite material, the degree of polymerization of the polyvinyl chloride resin is 950-1700.

In the aforementioned conductive flame-resistant polyvinyl chloride composite material, 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. On the one hand, it reduces the amount of small molecules The effect of plasticizers on the conductivity of conductive fillers. On the other hand, 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. In addition, 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.

In the above-mentioned conductive flame-resistant polyvinyl chloride composite material, 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.

In the above conductive flame-resistant polyvinyl chloride composite material, 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.

In the above-mentioned conductive flame-resistant polyvinyl chloride composite material, 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. More importantly, during the high-temperature combustion process, 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. These 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 In the case of a flame retardant synergist, the purpose of high flame retardancy can be achieved, and the amount of flame retardant added is reduced.

In the above-mentioned conductive flame-resistant polyvinyl chloride composite material, 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. In the present invention, since the crystal structure of 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. When 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. When the single-walled carbon nanotubes of the present invention are embedded in a polymer material matrix, a three-dimensional strengthened conductive network can be formed to achieve high conductive properties. In addition, 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. On the one hand, 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. In addition, 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. When the conductive filler of the present invention is added to about 10 parts, 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.

In addition, 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. And 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. Within a certain range of addition, with the increase in the number of silver-plated nano-graphite microflakes and single-armed carbon nanotubes, the stronger the microcosmic bonding, the stronger the mechanical properties of the composite material. However, when the amount of electric filler added exceeds 10 parts, especially more than 15 parts, the silver-coated nanographite microflakes and single-armed carbon nanotubes that play a reinforcing role will appear agglomerated primary particles, and the defect points will increase, reducing the molecular weight of the composite material. Interaction forces reduce the ability to resist external destructive forces and reduce the mechanical properties of composite materials. Combined with the comprehensive judgment of the conductive performance, the dosage of the conductive filler in the present invention is controlled at 6-10 parts.

Preferably, 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).

Further preferably, 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.

In the above-mentioned conductive flame-resistant polyvinyl chloride composite material, the mass content of nickel in the nickel-clad copper powder is 10-35%.

Preferably, the mass content of nickel in the nickel-clad copper powder is 15-30%.

In the above-mentioned conductive flame-resistant polyvinyl chloride composite material, 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. In addition, 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.

Preferably, 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.

Preferably, 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.

In the above-mentioned conductive flame-resistant polyvinyl chloride composite material, the lubricant may be ethylene bisstearamide or oxidized polyethylene wax. In order to make PVC composites have good processing flow properties, especially with inorganic filling systems, 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. On the other hand, 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.

In the above conductive flame-resistant polyvinyl chloride composite material, the other additives include 0.3-0.5 part of antioxidant and 0.3-0.5 part of anti-ultraviolet agent.

Preferably, the antioxidant may be selected from one or both of hindered phenolic antioxidants and phosphite antioxidants.

Further preferably, the antioxidant can be selected from tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester, β-(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].

Preferably, the anti-ultraviolet agent is a benzophenone anti-ultraviolet agent.

Further preferably, 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. As a woven fabric for windows, 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:

Weigh 70 parts of polyvinyl chloride resin, 25-35 parts of chlorinated polyethylene, 3-5 parts of stabilizer, 25-35 parts of plasticizer, 5-8 parts of flame retardant, 0.2-0.4 parts of lubricant agent, 0.6-1 part of other additives, added to the high-speed mixer for mixing, when the temperature rises to 100-120 ° C, add 6-10 parts of conductive filler and 10-15 parts of modified resin by weight, Continue mixing in the high-speed mixer for 1 to 5 minutes, then add the mixed material to the cold mixer to cool to 40°C to 50°C, and then discharge it, and then add it to the twin-screw extruder to plasticize, melt, extrude and granulate. After pelletizing, pellets of conductive flame-resistant polyvinyl chloride composite material are obtained.

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.

Preferably, the surface of the conductive flame-resistant polyvinyl chloride composite material layer of the conductive covered wire further includes an electrostatic dust collector layer.

Preferably, 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.

Preferably, the electrostatic precipitant layer is formed by applying an electrostatic precipitant solution to the surface of the coated wire and then heating and curing. In parts by weight, 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.

Further preferably, 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.

Preferably, 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 .

Compared with prior art, the present invention has following advantage:

1. 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.

2. In 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.

3. 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.

4. 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.

Detailed ways

The following are specific examples of the present invention to further describe the technical solutions of the present invention, but the present invention is not limited to these examples.

Example 1

Take by weight 70 parts of polyvinyl chloride resins with a degree of polymerization of 1100, 30 parts of chlorinated high-density polyethylene with a chlorine content of 32%, 4 parts of calcium-zinc composite stabilizers, 30 parts of dioctyl terephthalate Plasticizer, 6 parts of flame retardant antimony trioxide, 0.3 part of ethylene bisstearamide, 0.4 part of antioxidant tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid ] Pentaerythritol ester and 0.4 parts of anti-ultraviolet agent 2-hydroxyl-4-n-octyloxybenzophenone are added to a high-speed mixer for mixing, and when the temperature rises to 110° C., add 8 parts by weight The ratio is 1:0.3:0.07 silver-plated nano-graphite microflakes, nickel-coated copper powder (the mass content of nickel is 30%), conductive filler of single-armed carbon nanotubes, and then add 6.5 parts of vinyl acetate with a content of 25% The mixture of ethylene-vinyl acetate copolymer resin and 6.5 parts of vinyl chloride-vinyl acetate copolymer resin with a vinyl acetate content of 15% continues high-speed stirring for 3 minutes before entering the cold mixer, cooling to 45°C and discharging, and then adding to the double The screw extruder is plasticized, melted, extruded and granulated, and pelletized to obtain conductive and flame-resistant polyvinyl chloride composite material pellets.

Example 2

Take by weight 70 parts of polyvinyl chloride resins with a degree of polymerization of 1100, 25 parts of chlorinated high-density polyethylene with a chlorine content of 32%, 4 parts of calcium-zinc composite stabilizers, 35 parts of dioctyl terephthalate Plasticizer, 6 parts of flame retardant antimony trioxide, 0.3 part of ethylene bisstearamide, 0.3 part of antioxidant β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid Eight-carbon alcohol ester and 0.3 parts of anti-ultraviolet agent 2-hydroxy-4-methoxybenzophenone are added to a high-speed mixer for mixing, and when the temperature rises to 110°C, add 8 parts by weight The ratio is 1:0.3:0.07 silver-plated nano-graphite microflakes, nickel-coated copper powder (the mass content of nickel is 30%), conductive filler of single-armed carbon nanotubes, and then add 6.5 parts of vinyl acetate with a content of 25% The mixture of ethylene-vinyl acetate copolymer resin and 6.5 parts of vinyl chloride-vinyl acetate copolymer resin with a vinyl acetate content of 15% continues high-speed stirring for 3 minutes before entering the cold mixer, cooling to 45°C and discharging, and then adding to the double The screw extruder is plasticized, melted, extruded and granulated, and pelletized to obtain conductive and flame-resistant polyvinyl chloride composite material pellets.

Example 3

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 4

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 5

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 6

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 7

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 8

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 9

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 10

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 11

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 12

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.

Comparative 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.

Comparative 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.

Comparative example 3

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.

Comparative example 4

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.

Comparative example 5

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.

Comparative example 6

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.

Comparative example 7

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.

Comparative example 8

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.

Comparative example 9

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.

Comparative example 10

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.

Application 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.

Application Example 2

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. In parts by weight, 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.

Application Example 3

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. In parts by weight, 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.

Application Example 4

A conductive woven fabric, the woven fabric is woven from the conductive covered wire in application example 1, and the porosity is 5%.

Application Example 5

A conductive woven fabric, the woven fabric is woven from the conductive covered wire in application example 2, and the porosity is 5%.

Application Example 6

A conductive braided fabric, which is braided by the conductive covered wire in application example 3, and has a porosity of 10%.

The properties of the conductive flame-resistant polyvinyl chloride composite materials prepared in Examples 1-12 of the present invention and Comparative Examples 1-10 were compared, and the comparison results are shown in Table 1.

Table 1

Note: 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; Shore hardness A test standard GBT 2411-2008.

The performances of the conductive covered wires prepared in Examples 1-6 of the present invention and the braided fabrics were compared, and the comparison results are shown in Table 2.

Table 2

Breaking strength test standard: GB/T3923.1-1997; tear strength test standard: GB/T3917.2-2009; light color fastness test standard: GB/T8427-2008

It can be seen from Table 1 that 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 Ω, and it has electrical conductivity, and the optimized formula system has better electrical conductivity. The Shore A hardness is around 92 and has softness.

It can be seen from the examples and comparative examples that as the content of the conductive filler that plays the main conductive characteristic in the conductive flame-resistant polyvinyl chloride composite material decreases, the resistance of the prepared coated wire increases, see Examples 1 and 3 and Comparative Example 3; but if the addition of conductive fillers is too high, the electrical conductivity of the composite material will decrease instead, and there will be obvious electrical percolation, see Example 1 and Comparative Example 4. In Comparative Example 1 of the polyvinyl chloride composite material without conductive filler, the prepared composite material was not conductive.

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. If the mass ratio of silver-plated nano-graphite microflakes, nickel-coated copper powder, and single-armed carbon nanotubes in the conductive filler is not within the range of 1:(0.2-0.6):(0.05-0.1), 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.

In the present invention, 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.

In the present invention, 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. However, if the addition of conductive fillers is too high, 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. Similarly, 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.

It can be seen from application examples 1 to 6 that 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.

The specific embodiments described herein are only to illustrate the spirit of the present invention. Those skilled in the art to which the present invention belongs can make various modifications or supplements to the described specific embodiments or adopt similar methods to replace them, but they will not deviate from the spirit of the present invention or go beyond the definition of the appended claims range.

Claims

A conductive polyvinyl chloride composite material, characterized in that the composite material comprises the following components in parts by weight: 70 parts of polyvinyl chloride resin (PVC), 25-35 parts of chlorinated polyethylene, 3-35 parts of stabilizer 5 parts, plasticizer 25-35 parts, flame retardant 5-8 parts, conductive filler 6-10 parts, modified resin 10-15 parts, lubricant 0.2-0.4 parts, other additives 0.6-1 part, all The conductive filler described above is a mixture of silver-plated nanographite microflakes, nickel-coated copper powder and single-arm carbon nanotubes.
Conductive polyvinyl chloride composite material according to claim 1, is characterized in that, in described conductive filler, the mass ratio of silver-plated nano-graphite microflakes, nickel-clad copper powder, and single-armed carbon nanotubes is 1:(0.2～ 0.6): (0.05～0.1).
Conductive polyvinyl chloride composite material according to claim 1, is characterized in that, in described conductive filler, the mass ratio of silver-plated nano-graphite microflakes, nickel-clad copper powder, and single-armed carbon nanotubes is 1:(0.2～ 0.4): (0.05～0.08).
The conductive polyvinyl chloride composite material according to claim 1, characterized in that 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 conductive polyvinyl chloride composite material according to claim 1 or 2 or 3 or 4, characterized in that the mass content of nickel in the nickel-coated copper powder is 10-35%.
The conductive polyvinyl chloride composite material according to claim 1, wherein the chlorinated polyethylene is a resin type chlorinated high-density polyethylene with a chlorine content of 20-35%.
The conductive polyvinyl chloride composite material according to claim 1, wherein the modified resin is a mixture of ethylene-vinyl acetate copolymer resin and vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin and chlorine The mass ratio of ethylene-vinyl acetate copolymer resin is 1:(0.5～1.6).
The conductive polyvinyl chloride composite material according to claim 7, wherein the content of vinyl acetate in the ethylene-vinyl acetate copolymer resin is 10% to 30%, and the content of vinyl acetate in the vinyl chloride-vinyl acetate copolymer resin is 10-30%.
A kind of application of conductive polyvinyl chloride composite material as claimed in claim 1 in conductive clad wire.
An application of the conductive polyvinyl chloride composite material as claimed in claim 1 in conductive woven fabrics.