CN111019269A - PVC cable material and preparation method thereof - Google Patents
PVC cable material and preparation method thereof Download PDFInfo
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- CN111019269A CN111019269A CN201911383810.9A CN201911383810A CN111019269A CN 111019269 A CN111019269 A CN 111019269A CN 201911383810 A CN201911383810 A CN 201911383810A CN 111019269 A CN111019269 A CN 111019269A
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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
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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Abstract
The invention provides a PVC cable material and a preparation method thereof. The PVC cable material comprises the following components in parts by weight: 90-110 parts of PVC resin, 30-50 parts of dioctyl terephthalate, 5-20 parts of epoxidized soybean oil, 10-20 parts of filler, 1-10 parts of organic flame retardant, 1-10 parts of inorganic flame retardant, 3-6 parts of main antioxidant, 3-6 parts of auxiliary antioxidant, 1-5 parts of lubricant and 1-5 parts of stabilizer. The PVC cable material has the advantages that the components are matched with each other, the synergy is realized, the smoke suppression flame retardance of the cable material is effectively improved, the mechanical strength of the cable material can be improved, the mechanical damage is effectively reduced, and the service life of the cable is prolonged.
Description
Technical Field
The invention belongs to the technical field of cable materials, and particularly relates to a PVC cable material and a preparation method thereof.
Background
The wire and cable products bring great convenience and improvement to human life and work, wherein the PVC cable has low price and excellent performance and occupies an important position in the wire and cable insulation protective material for a long time. However, the flame retardant performance of PVC wires and cables is always puzzled, the flame retardant material of the current wires and cables contains more halogen, when the wires and cables are on fire, the problems of delayed combustion, dripping, generation of a large amount of toxic smoke and the like exist, how to reduce smoke toxicity caused by plastic combustion and secondary damage caused by dripping combustion are very important, the research on the flame retardant performance of the current domestic wire and cable sheathing materials mainly focuses on organic phosphorus nitrogen and inorganic hydrate, but the current research results still have the problems of poor flame retardant effect, poor heat insulation and temperature insulation effect and the like.
CN107619560A discloses a high-temperature-resistant flame-retardant PVC cable material, which is composed of the following components in parts by weight: 120 parts of polyvinyl chloride, 5-10 parts of magnesium aluminum alloy, 50-100 parts of flame retardant, 20-50 parts of dispersant and 5.2-10 parts of composite flame retardant synergist. The flame retardant accounts for 25-31% of the raw materials by 50-100 parts, the flame retardant performance of the material is improved by increasing the dosage of the flame retardant, but the problems of the reduction of the mechanical property, low temperature resistance and other properties of the material and the like are caused by increasing the addition amount of the flame retardant.
CN102911460A discloses a halogen-free flame-retardant polyvinyl chloride pipe and a preparation process thereof, which is prepared from the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 0.1-10.0 parts of heat stabilizer, 1-20 parts of flexibilizer, 10-80 parts of metal hydroxide flame retardant, 1-20 parts of metal compound flame retardant synergist, 0.5-3.0 parts of processing aid, 1.1-5 parts of lubricant, 0.01-5 parts of antioxidant, 0.03-5 parts of colorant and 0.1-5 parts of ultraviolet absorber. The flame retardant performance of the polyvinyl chloride pipe is improved by increasing the using amount of the flame retardant, although the flame retardant performance is better, the corrosion resistance is poor, the impact resistance of the polyvinyl chloride pipe is poorer, and the brittleness is higher.
CN105482296A discloses a light heat-resistant flame-retardant modified PVC resin compound cable material, which is prepared from the following raw materials in parts by weight: 55-65 parts of PVC resin, 30-40 parts of ethylene-vinyl acetate copolymer, 0.01-0.02 part of tourmaline, 10-15 parts of expandable graphite, 5-8 parts of polytetramethylene glycol ether, 15-22 parts of aluminum silicate, 3-4 parts of eleostearic acid, 3-4 parts of hexamethyl-dinitrogen silane and the like; although the cable material has good flame retardant property, more expandable graphite is added, and the expandable graphite serving as a conductor is added into the cable material as a filler, so that the insulation property of the cable material is greatly reduced, the occurrence of dangers such as electric leakage, electric shock and the like is caused, and great potential safety hazards are generated.
Therefore, the development of a PVC cable material with a small addition amount of flame retardant and a good flame retardant effect is the focus of current research in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a PVC cable material and a preparation method thereof, wherein the components in the PVC cable material are matched with each other to realize synergistic interaction, so that the smoke suppression and flame retardance of the cable material are effectively improved, the mechanical strength of the cable material is improved, the mechanical damage is effectively reduced, and the service life of the cable is prolonged.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention discloses a PVC cable material, which comprises the following components in parts by weight: 90-110 parts of PVC resin, 30-50 parts of dioctyl terephthalate, 5-20 parts of epoxidized soybean oil, 10-20 parts of filler, 1-10 parts of organic flame retardant, 1-10 parts of inorganic flame retardant, 5-10 parts of main antioxidant, 5-10 parts of auxiliary antioxidant, 1-5 parts of lubricant and 1-5 parts of stabilizer.
In the present invention, the PVC resin is 90 to 110 parts by weight, for example, 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, 99 parts, 100 parts, 112 parts, 114 parts, 116 parts, 118 parts, and 120 parts.
In the invention, the weight portion of the dioctyl terephthalate is 30-50 parts, such as 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 parts and 50 parts.
In the present invention, the epoxidized soybean oil is 5 to 20 parts by weight, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts.
In the present invention, the weight part of the composite filler is 10 to 20 parts, and may be, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, or 20 parts.
In the present invention, the organic flame retardant is 1 to 10 parts by weight, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts.
In the present invention, the inorganic flame retardant may be used in an amount of 1 to 10 parts by weight, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts.
In the present invention, the weight portion of the main antioxidant is 3 to 6, for example, 3, 4, 5, 6.
In the invention, the auxiliary antioxidant is 3-6 parts by weight, for example, 3 parts, 4 parts, 5 parts and 6 parts.
In the present invention, the lubricant is 1 to 5 parts by weight, for example, 1 part, 2 parts, 3 parts, 4 parts, and 5 parts.
In the present invention, the weight part of the stabilizer is 1 to 5 parts, and may be, for example, 1 part, 2 parts, 3 parts, 4 parts, or 5 parts.
In the invention, dioctyl terephthalate (DOTP) and epoxidized soybean oil are cooperatively used as plasticizers of PVC resin, and are combined with PVC molecules by hydrogen bonds or Van der Waals force, so that the plasticity and the flow property of the PVC resin are improved during processing and molding, and the flexibility of a finished product is further improved. After the plasticization of DOTP and epoxidized soybean oil, the laminated structure of the PVC resin is separated, more free DOTP and epoxidized soybean oil areas exist between PVC resin layers, and a relatively complete reticular structure exists in the PVC resin.
According to the invention, after the PVC cable material is heated, the composite filler, the composite flame retardant, the main antioxidant and the auxiliary antioxidant are matched with each other, so that a synergistic effect is achieved, a covering layer is formed on the surface of PVC resin in a melting mode, and the covering layer becomes a barrier between a condensed phase and flame, so that oxygen can be isolated, the diffusion of combustible gas can be prevented, heat conduction and heat radiation can be blocked, the heat fed back to the PVC resin can be reduced, the thermal cracking and combustion reaction can be inhibited, the temperature of the surface of the PVC resin material and a flame zone can be reduced, the thermal cracking reaction speed can be slowed down, and the generation of the combustible gas and smoke. In the invention, the antioxidant is divided into a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant can react with free radicals to interrupt the growth of active chains, and the auxiliary antioxidant can inhibit and delay the generation of the free radicals in the initiation process, decompose hydroperoxide and passivate metal ions remained in resin.
Preferably, the degree of polymerization of the PVC resin is 1700-1800, and may be 1700, 1710, 1720, 1730, 1740, 1750, 1760, 1780, 1790, 1800, for example.
In the invention, the polymerization degree of the PVC resin is 1700-1800, the PVC resin has long molecular chain and large crimpability in the range, the entanglement points among molecular chains are increased, the crystallinity is high, the acting force among the molecular chains is enhanced, and the slippage among the molecular chains is difficult; meanwhile, the plasticizer can absorb more plasticizer, so that the function of the plasticizer can be exerted to the maximum. If the polymerization degree of the PVC resin is too small, the acting force among molecular chains is small, so that the strength, heat resistance, rebound resilience, wear resistance, cold resistance and other properties of the product are reduced, and if the polymerization degree of the PVC resin is too large, the distance among PVC macromolecules is increased too much, so that the processing rheological property is reduced.
Preferably, the filler comprises any one of or a combination of at least two of organically modified montmorillonite, mesoporous silica, nano active calcium carbonate, halloysite nanotubes, bentonite or diatomite.
In the invention, the organic modified montmorillonite and the mesoporous silica are preferably used as composite fillers to be blended with the PVC resin and uniformly distributed in the PVC resin master batch, so that the thermal stability of the PVC resin can be effectively improved, the degradation of the PVC resin is delayed, the aim of synergistic flame retardance is fulfilled, and the strength, the rigidity and the toughness of the PVC resin are obviously improved. The organic modified montmorillonite is structurally used for extremely high surface area and high length-width ratio, so that the PVC resin has good barrier property, and PVC resin molecules enter among mesoporous silica particles, so that the movement of PVC resin molecule chain segments is limited under the combined action of the organic modified montmorillonite and the mesoporous silica, and the heat resistance of the PVC cable material and the dimensional stability of the material are obviously improved.
Preferably, the organic modified montmorillonite comprises glycidyl methacrylate modified montmorillonite, betaine modified montmorillonite, octadecyl dimethyl benzyl ammonium chloride modified montmorillonite and octadecyl trimethyl ammonium bromide modified montmorillonite;
preferably, the particle size of the mesoporous silica is 80 to 100 μm, and may be, for example, 80 μm, 82 μm, 84 μm, 86 μm, 88 μm, 90 μm, 92 μm, 94 μm, 96 μm, 98 μm, 100 μm.
Preferably, the mesoporous silica has a specific surface area of 500-600m2G, may be, for example, 500m2/g、510m2/g、520m2/g、530m2/g、540m2/g、550m2/g、560m2/g、570m2/g、580m2/g、590m2/g、600m2/g、。
Preferably, the mass ratio of the organic flame retardant to the inorganic flame retardant is (2-4):1, and may be, for example, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4: 1.
According to the invention, the organic flame retardant and the inorganic flame retardant are matched with each other in a specific proportion, and have a synergistic effect, so that the dispersibility of the flame retardant in PVC resin can be ensured, the composite flame retardant can be rapidly formed into a stable covering layer at high temperature, oxygen is isolated, the combustible gas is prevented from escaping outwards, a cross-linked solid substance or a carbonized layer with a more stable structure is generated, and meanwhile, the composite flame retardant has a diluting effect on the oxygen concentration in a combustion area, and the combustion is prevented from continuing, thereby achieving the efficient flame retardant effect.
Preferably, the organic flame retardant comprises any one of or a combination of at least two of diphenylisooctyl phosphite, tris (nonylphenyl) phosphite, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate or tris (dichloropropyl) phosphate.
Preferably, the inorganic flame retardant is a phosphate flame retardant.
Preferably, the phosphate comprises any one of diammonium phosphate, ammonium pyrophosphate, aluminum hypophosphite or ammonium polyphosphate, or a combination of at least two thereof.
Preferably, the primary antioxidant is a hindered phenolic antioxidant.
Preferably, the hindered phenolic antioxidant comprises one or a mixture of at least two of 2, 6-tributyl-4-methylphenol, bis (3, 5-tributyl-4-hydroxyphenyl) sulfide or pentaerythrityl tetrakis [ β - (3, 5-tributyl-4-hydroxyphenyl) propionate ].
Preferably, the secondary antioxidant is a combination of thioester-based antioxidants.
Preferably, the thioester antioxidant comprises any one of, or a combination of at least two of, dilauryl thiodipropionate, stearyl thiodipropionate, ditridecyl thiodipropionate, or dimyristyl thiodipropionate.
Preferably, the lubricant comprises any one or a combination of at least two of magnesium stearate, calcium stearate, zinc stearate, polyethylene wax, montan wax, or paraffin wax;
preferably, the stabilizer comprises any one of dibutyltin dilaurate, isooctyl di-n-octyltin dimercaptoacetate, tin methyl mercaptide, tin butyl mercaptide, tin dibutyl dichloride or tin octyl mercaptide or a combination of at least two of the same.
Preferably, the PVC cable material further comprises an ultraviolet absorber.
Preferably, the weight part of the ultraviolet absorber in the PVC cable material is 0.5-2 parts, for example, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 part, 1.2 part, 1.3 part, 1.4 part, 1.5 part, 1.6 part, 1.7 part, 1.8 part, 1.9 part, 2 parts.
Preferably, the ultraviolet absorber includes any one or a combination of at least two of 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, or 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole.
Preferably, the PVC cable material further comprises a colorant.
Preferably, the colorant is present in the PVC cable material in an amount of 0.5 to 1 part by weight, and may be, for example, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part.
Preferably, the colorant comprises any one of titanium dioxide, carbon black or toner or a combination of at least two thereof.
In a second aspect, the present invention provides a method for preparing the PVC cable material according to the first aspect, the method comprising the steps of:
(1) mixing and stirring PVC resin, dioctyl terephthalate and epoxy soybean oil according to the formula amount to obtain mixed slurry;
(2) adding a composite filler, a composite flame retardant, a main antioxidant, an auxiliary antioxidant, a lubricant and a stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material;
(3) and (3) extruding and dicing the mixed material obtained in the step (2) to obtain the PVC cable material.
Preferably, the mixing and stirring in step (1) is carried out in a high-speed mixer.
Preferably, the mixing and stirring in step (1) are carried out under a vapor pressure of 0.15 to 0.25MPa, for example, the vapor pressure may be 0.15MPa, 0.16MPa, 0.17MPa, 0.18MPa, 0.19MPa, 0.2MPa, 0.21MPa, 0.22MPa, 0.23MPa, 0.24MPa or 0.25 MPa.
Preferably, the mixing and stirring temperature in step (1) is 70-80 deg.C, such as 70 deg.C, 71 deg.C, 72 deg.C, 73 deg.C, 74 deg.C, 75 deg.C, 76 deg.C, 77 deg.C, 78 deg.C, 79 deg.C, 80 deg.C.
Preferably, the mixing and stirring time in step (1) is 3-5min, such as 3min, 3.2min, 3.4min, 3.6min, 3.8min, 4min, 4.2min, 4.4min, 4.6min, 4.8min, 5 min.
Preferably, the rotation speed of the mixing and stirring in the step (1) is 600-800r/min, such as 600r/min, 620r/min, 640r/min, 680r/min, 700r/min, 720r/min, 740r/min, 760r/min, 780r/min and 800 r/min.
Preferably, the mixing and stirring in step (2) is: firstly stirring at a high speed and then stirring at a low speed.
Preferably, the high speed stirring temperature is 110-.
Preferably, the high speed stirring time is 5-10min, such as 5min, 6min, 7min, 8min, 9min, 10 min.
Preferably, the rotation speed of the high-speed stirring is 1500-.
Preferably, the low speed stirring temperature is 40-50 ℃, for example, can be 40 degrees, 41 degrees, 42 degrees, 43 degrees, 44 degrees, 45 degrees, 46 degrees, 47 degrees, 48 degrees, 49 degrees, 50 degrees.
Preferably, the time of the low-speed stirring is 10-20min, for example, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20 min.
Preferably, the rotation speed of the low-speed stirring is 100-200r/min, such as 100r/min, 110r/min, 120r/min, 130r/min, 140r/min, 150r/min, 160r/min, 170r/min, 180r/min, 190r/min, 200 r/min.
Preferably, the extrusion of step (3) is carried out in a first-order twin-screw extruder.
Preferably, the upper twin-screw processing temperature of the first-order twin-screw extruder is 140 ℃ to 175 ℃, and may be 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃ to 175 ℃.
Preferably, the lower stage single screw temperature of the first-stage twin-screw extruder is 130-165 ℃, for example 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃.
Preferably, the first-order twin-screw extruder comprises a first zone, a second zone, a third zone, a fourth zone and a head die which are connected in sequence.
Preferably, the first zone has an operating temperature of 175-, (e.g., 175 ℃, 176 ℃, 177 ℃, 178 ℃, 179 ℃, 180 ℃, 181 ℃, 182 ℃, 183 ℃, 184 ℃, 185 ℃), the second zone has an operating temperature of 180-, (e.g., 180 ℃, 181 ℃, 182 ℃, 183 ℃, 184 ℃, 185 ℃, 186 ℃, 187 ℃, 188 ℃, 189 ℃, 190 ℃), the third zone has an operating temperature of 185-, (e.g., 185 ℃, 186 ℃, 187 ℃, 188 ℃, 189 ℃, 190 ℃, 191 ℃, 192 ℃, 193 ℃, 194 ℃, 195 ℃), the fourth zone has an operating temperature of 185-, (e.g., 185 ℃, 186 ℃, 187 ℃, 189 ℃, 190 ℃, 191 ℃, 192 ℃, 193 ℃, 194 ℃), and the handpiece mold has an operating temperature of 185-, (e.g., 185 ℃, 186 ℃, 187 ℃; 187 ℃.) (e.g., 185 ℃., 195 ℃) 188 deg.C, 189 deg.C, 190 deg.C, 191 deg.C, 192 deg.C, 193 deg.C, 194 deg.C, 195 deg.C).
Preferably, the pelletizing in the step (3) adopts an air-cooling ground surface hot pelletizing mode
Compared with the prior art, the invention has the following beneficial effects:
(1) the components in the PVC cable material are matched with each other, and the synergistic effect is achieved, so that the smoke suppression and flame retardance of the cable material are effectively improved, the cable material has good mechanical strength, thermal aging performance, wear resistance and traction resistance, and the service life of the cable in severe environment is prolonged.
(2) The building wire and cable material provided by the invention has the tensile strength of more than 16MPa, the elongation at break of more than 200%, the oxygen index of more than 32%, the electrolyte strength of more than 20MV/m, and single vertical combustion passes through the material.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a PVC cable material, which comprises the following components in parts by weight: 100 parts of PVC resin (with the polymerization degree of 1700), 40 parts of dioctyl terephthalate, 10 parts of epoxidized soybean oil, 10 parts of octadecyl dimethyl benzyl ammonium chloride modified montmorillonite and mesoporous silica (with the particle size of 80 mu m and the specific surface area of 600 m)2Per gram) 5 parts, diisooctyl diphenyl phosphite 6 parts, diammonium hydrogen phosphate 2 parts, 2, 6-tributyl-4-methylphenol 6 parts, dilauryl thiodipropionate 5 parts, calcium stearate 2 parts, dibutyltin dilaurate 1 part, 2-hydroxy-4-methoxybenzophenone 0.5 part, and carbon black 0.5 part.
The preparation method of the PVC cable material comprises the following steps:
(1) adding PVC resin, dioctyl terephthalate and epoxy soybean oil into a high-speed mixer according to the formula amount, introducing 0.15MPa of vapor pressure, heating to 70 ℃, and mixing and stirring for 3min at the rotating speed of 800r/min to obtain mixed slurry;
(2) adding octadecyl dimethyl benzyl ammonium chloride modified montmorillonite, mesoporous silica, diisooctyl diphenyl phosphite, diammonium hydrogen phosphate, 2, 6-tributyl-4-methylphenol, dilauryl thiodipropionate, calcium stearate, dibutyltin dilaurate, 2-hydroxy-4-methoxybenzophenone and carbon black into the mixed slurry obtained in the step (1), firstly stirring at a high speed of 1500r/min for 5min at 120 ℃, and then stirring at a low speed of 100r/min for 10min at 50 ℃ to obtain a mixed material;
(3) adding the mixed material obtained in the step (2) into a first-order double-screw extruder for extrusion, wherein the processing temperature of an upper-order double screw of the first-order double-screw extruder is 140 ℃, the temperature of a lower-order single screw of the first-order double-screw extruder is 130 ℃, the working temperature of a first area is 175 ℃, the working temperature of a second area is 180 ℃, the working temperature of a third area is 185 ℃, the working temperature of a fourth area is 185 ℃, and the working temperature of a head die is 185 ℃; and (3) adopting an air-cooled ground surface hot granulating mode, and enabling the granules to enter a storage bin through a cyclone separator and a vibrating screen to obtain the PVC cable material.
Example 2
The embodiment provides a PVC cable material, which comprises the following components in parts by weight: 110 parts of PVC resin (with the polymerization degree of 1800), 50 parts of dioctyl terephthalate, 20 parts of epoxidized soybean oil, 7.5 parts of octadecyl trimethyl ammonium bromide modified montmorillonite and mesoporous silica (with the particle size of 100 mu m and the specific surface area of 500 m)2/g)2.5 parts, 8 parts of tris (nonylphenyl) phosphite, 2 parts of ammonium polyphosphate, 5 parts of 2, 6-tributyl-4-methylphenol, 6 parts of stearyl thiodipropionate, 4 parts of zinc stearate, 2 parts of dibutyltin dilaurate, 1 part of 2-hydroxy-4-n-octoxybenzophenone and 1 part of titanium dioxide.
The preparation method of the PVC cable material comprises the following steps:
(1) adding PVC resin, dioctyl terephthalate and epoxy soybean oil into a high-speed mixer according to the formula amount, introducing a vapor pressure of 0.2MPa, heating to 80 ℃, and mixing and stirring for 5min at a rotating speed of 600r/min to obtain mixed slurry;
(2) adding octadecyl trimethyl ammonium bromide modified montmorillonite, mesoporous silica, tris (nonylphenyl) phosphite, diammonium hydrogen phosphate, 2, 6-tributyl-4-methylphenol, stearyl thiodipropionate, zinc stearate, dibutyltin dilaurate, 2-hydroxy-4-n-octoxybenzophenone and titanium dioxide into the mixed slurry obtained in the step (1), firstly stirring at a high speed of 2000r/min at 110 ℃ for 10min, and then stirring at a low speed of 200r/min at 40 ℃ for 20min to obtain a mixed material;
(3) adding the mixed material obtained in the step (2) into a first-order double-screw extruder for extrusion, wherein the processing temperature of an upper-order double screw of the first-order double-screw extruder is 175 ℃, the temperature of a lower-order single screw of the first-order double-screw extruder is 165 ℃, the working temperature of a first area is 185 ℃, the working temperature of a second area is 190 ℃, the working temperature of a third area is 195 ℃, the working temperature of a fourth area is 195 ℃, and the working temperature of a machine head die is 195 ℃; and (3) adopting an air-cooled ground surface hot granulating mode, and enabling the granules to enter a storage bin through a cyclone separator and a vibrating screen to obtain the PVC cable material.
Example 3
The embodiment provides a PVC cable material, which comprises the following components in parts by weight: 80 parts of PVC resin (polymerization degree of 1750), 30 parts of dioctyl terephthalate, 10 parts of epoxidized soybean oil, 5 parts of glycidyl methacrylate modified montmorillonite, and mesoporous silica (particle size of 100 mu m and specific surface area of 500 m)2Per gram) 5 parts, 6 parts of tris (nonylphenyl) phosphite, 3 parts of ammonium pyrophosphate, 5 parts of bis (3, 5-tributyl-4-hydroxyphenyl) sulfide, 5 parts of lauryl stearyl thiodipropionate, 2 parts of paraffin and 2 parts of tin methyl mercaptide.
The preparation method of the PVC cable material comprises the following steps:
(1) adding PVC resin, dioctyl terephthalate and epoxy soybean oil into a high-speed mixer according to the formula amount, introducing 0.25MPa of vapor pressure, heating to 80 ℃, and mixing and stirring for 3min at the rotating speed of 600r/min to obtain mixed slurry;
(2) adding glycidyl methacrylate modified montmorillonite, mesoporous silica, tris (nonylphenyl) phosphite, diammonium hydrogen phosphate, bis (3, 5-tributyl-4-hydroxyphenyl) sulfide, stearyl thiodipropionate, paraffin and tin methyl mercaptide into the mixed slurry obtained in the step (1), firstly stirring at a high speed of 2000r/min at 110 ℃ for 10min, and then stirring at a low speed of 200r/min at 40 ℃ for 20min to obtain a mixed material;
(3) adding the mixed material obtained in the step (2) into a first-order double-screw extruder for extrusion, wherein the processing temperature of an upper-order double screw of the first-order double-screw extruder is 175 ℃, the temperature of a lower-order single screw of the first-order double-screw extruder is 165 ℃, the working temperature of a first area is 185 ℃, the working temperature of a second area is 190 ℃, the working temperature of a third area is 195 ℃, the working temperature of a fourth area is 195 ℃, and the working temperature of a machine head die is 195 ℃; and (3) adopting an air-cooled ground surface hot granulating mode, and enabling the granules to enter a storage bin through a cyclone separator and a vibrating screen to obtain the PVC cable material.
Example 4
This example provides a PVC cable material, which is different from example 1 only in that 4 parts of diisooctyl diphenyl phosphite and 4 parts of diammonium hydrogen phosphate, and the contents of other components and the preparation method are the same as example 1.
Example 5
This example provides a PVC cable material, which is different from example 1 only in that 7 parts of diisooctyl diphenyl phosphite and 1 part of diammonium hydrogen phosphate, and the contents of other components and the preparation method are the same as example 1.
Example 6
This example provides a PVC cable material, which differs from example 1 only in that: the filler does not contain octadecyl dimethyl benzyl ammonium chloride modified montmorillonite, only contains 15 parts of mesoporous silica, and the contents of other components and the preparation method are the same as those in example 1.
Example 7
This example provides a PVC cable material, which differs from example 1 only in that: the filler does not contain mesoporous silica, and only contains 15 parts of octadecyl dimethyl benzyl ammonium chloride modified montmorillonite, and the contents of other components and the preparation method are the same as those in example 1.
Example 8
This example provides a PVC cable material, which differs from example 1 only in that: the polymerization degree of the PVC resin is 1500, and the contents of other components and the preparation method are the same as those of the example 1.
Example 9
This example provides a PVC cable material, which differs from example 1 only in that: the polymerization degree of the PVC resin is 2000, and the contents of other components and the preparation method are the same as those of the example 1.
Comparative example 1
This comparative example provides a PVC cable material which differs from example 1 only in that: the PVC cable material does not contain dioctyl terephthalate, 50 parts of epoxidized soybean oil is added, and the contents of other components and the preparation method are the same as those in example 1.
Comparative example 2
This comparative example provides a PVC cable material which differs from example 1 only in that: the PVC cable material does not contain epoxidized soybean oil, 50 parts of dioctyl terephthalate is added, and the contents of other components and the preparation method are the same as those of example 1.
Comparative example 3
This comparative example provides a PVC cable material which differs from example 1 only in that: the weight of dioctyl terephthalate is 10 parts, the weight of epoxidized soybean oil is 30 parts, and the contents of other components and the preparation method are the same as those in example 1.
Comparative example 4
This comparative example provides a PVC cable material which differs from example 1 only in that: the PVC cable material does not contain dilauryl thiodipropionate (auxiliary antioxidant), 11 parts of 2, 6-tributyl-4-methylphenol (main antioxidant), and the contents of other components and the preparation method are the same as those in example 1.
Comparative example 5
This comparative example provides a PVC cable material which differs from example 1 only in that: the PVC cable material does not contain 2, 6-tributyl-4-methylphenol (main antioxidant), dilauryl thiodipropionate (auxiliary antioxidant) is added into 11 parts, and the contents of other components and the preparation method are the same as those in example 1.
Comparative example 6
Compared with the example 1, the PVC cable material is only different in that the flame retardant does not contain the organic flame retardant of diisooctyl diphenylphosphite, only contains 8 parts of diammonium hydrogen phosphate, and has the same contents of other components and preparation method as the example 1.
Comparative example 7
Compared with the example 1, the PVC cable material is only different in that the flame retardant does not contain the inorganic flame retardant diammonium hydrogen phosphate, only contains 8 parts of diphenyl isooctyl phosphite, and has the same contents of other components and the preparation method as the example 1.
Test example 1
The cable materials provided in examples 1 to 9 and comparative examples 1 to 7 above were tested for their performance, and the test criteria included: tensile strength, elongation at break: GB/T2951; oxygen index (oxygen index refers to the minimum oxygen concentration required for a material to undergo flaming combustion in a stream of oxygen-nitrogen mixture under specified conditions, expressed as a percentage by volume of oxygen. ISO 4586, single vertical combustion: GB/T18380-2008, electrolyte strength, measured by an electrolyte analyzer (PL1000A), the specific test results are shown in Table 1:
TABLE 1
From the above test results, it can be seen that the PVC cable materials prepared in examples 1 to 9 have a tensile strength of 16MPa or more, an elongation at break of 200% or more, an oxygen index of 32% or more, and an electrolyte strength of 20MV/m or more, which fully indicates that the components in the PVC cable material of the present invention cooperate with each other to achieve synergistic effects, thereby not only effectively improving the smoke suppression and flame retardancy of the cable material, but also enabling the cable material to have good mechanical strength and electrical properties.
Test example 2
The cable materials provided in examples 1 to 9 and comparative examples 1 to 7 were tested for temperature resistance according to the JB/T10436 standard, and the thermal aging test method was performed by heating to (135 ± 2) ° c and maintaining for 240 hours, and then testing the tensile strength, elongation at break, and quality after aging of the insulation and sheath, and calculating the tensile change rate of the insulation and sheath, and the elongation at break of the insulation and sheath; mass loss after aging: low temperature bending test method: cooling temperature (-40 +/-2) DEG C, time 16h, test bar diameter of 4-5 times of cable external diameter, winding for 3-4 circles, no visible cracks on the surface after test, and specific test results are shown in Table 2.
TABLE 2
From the test results, the tensile change rate of the PVC cable materials prepared in examples 1 to 9 after the thermal aging test is below 20%, the elongation at break change rate is below 20%, and the mass loss rate after aging is below 18%, which fully indicates that the components in the PVC cable material of the present invention cooperate with each other to achieve synergistic interaction, thereby not only effectively improving the smoke suppression and flame retardancy of the cable material, but also improving the strength of the cable, effectively reducing mechanical damage, and prolonging the service life of the cable. The cable material also has excellent wear resistance, corrosion resistance, thermal aging resistance and low-temperature performance.
The applicant states that the present invention is illustrated by the above examples to describe the PVC cable material and the preparation method thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must rely on the above examples to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The PVC cable material is characterized by comprising the following components in parts by weight: 90-110 parts of PVC resin, 30-50 parts of dioctyl terephthalate, 5-20 parts of epoxidized soybean oil, 10-20 parts of filler, 1-10 parts of organic flame retardant, 1-10 parts of inorganic flame retardant, 3-6 parts of main antioxidant, 3-6 parts of auxiliary antioxidant, 1-5 parts of lubricant and 1-5 parts of stabilizer.
2. The PVC cable material as claimed in claim 1, wherein the degree of polymerization of the PVC resin is 1700-1800.
3. The PVC cable material according to claim 1 or 2, wherein the filler comprises any one or a combination of at least two of organically modified montmorillonite, mesoporous silica, nano-active calcium carbonate, halloysite nanotubes, bentonite or diatomite, preferably organically modified montmorillonite and/or mesoporous silica;
preferably, the organic modified montmorillonite comprises glycidyl methacrylate modified montmorillonite, betaine modified montmorillonite, octadecyl dimethyl benzyl ammonium chloride modified montmorillonite and octadecyl trimethyl ammonium bromide modified montmorillonite;
preferably, the particle size of the mesoporous silica is 80-100 μm;
preferably, the mesoporous silica has a specific surface area of 500-600m2/g。
4. PVC cable material according to any of claims 1 to 3, characterized in that the mass ratio of organic flame retardant to inorganic flame retardant is (2-4) 1;
preferably, the organic flame retardant comprises any one of or a combination of at least two of diphenylisooctyl phosphite, tris (nonylphenyl) phosphite, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate or tris (dichloropropyl) phosphate;
preferably, the inorganic flame retardant is a phosphate flame retardant;
preferably, the phosphate comprises any one of diammonium phosphate, ammonium pyrophosphate, aluminum hypophosphite or ammonium polyphosphate, or a combination of at least two thereof.
5. PVC cable material according to any of claims 1 to 4, characterized in that the primary antioxidant is a hindered phenolic antioxidant;
preferably, the hindered phenolic antioxidant comprises one or a mixture of at least two of 2, 6-tributyl-4-methylphenol, bis (3, 5-tributyl-4-hydroxyphenyl) sulfide or pentaerythrityl tetrakis [ β - (3, 5-tributyl-4-hydroxyphenyl) propionate ];
preferably, the secondary antioxidant is a combination of thioester antioxidants;
preferably, the thioester antioxidant comprises any one of, or a combination of at least two of, dilauryl thiodipropionate, stearyl thiodipropionate, ditridecyl thiodipropionate, or dimyristyl thiodipropionate.
6. The PVC cable material according to any one of claims 1 to 5, wherein the lubricant comprises any one or a combination of at least two of magnesium stearate, calcium stearate, zinc stearate, polyethylene wax, montan wax, or paraffin wax;
preferably, the stabilizer comprises any one of dibutyltin dilaurate, isooctyl di-n-octyltin dimercaptoacetate, tin methyl mercaptide, tin butyl mercaptide, tin dibutyl dichloride or tin octyl mercaptide or a combination of at least two of the same;
preferably, the PVC cable material further comprises an ultraviolet absorber;
preferably, the weight part of the ultraviolet absorbent in the PVC cable material is 0.5-2 parts;
preferably, the ultraviolet absorber comprises any one or a combination of at least two of 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone or 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole;
preferably, the PVC cable material further comprises a colorant;
preferably, the weight part of the colorant in the PVC cable material is 0.5-1 part;
preferably, the colorant comprises any one of titanium dioxide, carbon black or toner or a combination of at least two thereof.
7. Process for the preparation of the PVC cable material according to any one of claims 1 to 6, characterized in that it comprises the following steps:
(1) mixing and stirring PVC resin, dioctyl terephthalate and epoxy soybean oil according to the formula amount to obtain mixed slurry;
(2) adding a filler, an organic flame retardant, an inorganic flame retardant, a main antioxidant, an auxiliary antioxidant, a lubricant and a stabilizer into the mixed slurry obtained in the step (1), and mixing and stirring to obtain a mixed material;
(3) and (3) extruding and dicing the mixed material obtained in the step (2) to obtain the PVC cable material.
8. The production method according to claim 7, wherein the mixing stirring in the step (1) is performed in a high-speed mixer;
preferably, the mixing and stirring in the step (1) are carried out under the condition of introducing 0.15-0.25MPa of steam pressure;
preferably, the temperature of the mixing and stirring in the step (1) is 70-80 ℃;
preferably, the mixing and stirring time of the step (1) is 3-5 min;
preferably, the rotation speed of the mixing and stirring in the step (1) is 600-800 r/min.
9. The production method according to claim 7 or 8, wherein the mixing and stirring in the step (2) is: firstly, high-speed stirring is carried out, and then low-speed stirring is carried out;
preferably, the temperature of the high-speed stirring is 110-120 ℃;
preferably, the high-speed stirring time is 5-10 min;
preferably, the rotating speed of the high-speed stirring is 1500-;
preferably, the temperature of the low-speed stirring is 40-50 ℃;
preferably, the low-speed stirring time is 10-20 min;
preferably, the rotation speed of the low-speed stirring is 100-200 r/min.
10. The production method according to any one of claims 7 to 9, wherein the extrusion of step (3) is carried out in a first-order twin-screw extruder;
preferably, the upper-stage twin-screw processing temperature of the first-stage twin-screw extruder is 140-175 ℃;
preferably, the lower stage single screw temperature of the first stage twin screw extruder is 130-165 ℃;
preferably, the first-order twin-screw extruder comprises a first zone, a second zone, a third zone, a fourth zone and a head die which are connected in sequence;
preferably, the working temperature of the first zone is 175-185 ℃, the working temperature of the second zone is 180-190 ℃, the working temperature of the third zone is 185-195 ℃, the working temperature of the fourth zone is 185-195 ℃, and the working temperature of the handpiece mold is 185-195 ℃;
preferably, the pelletizing in the step (3) adopts an air-cooled ground surface hot pelletizing mode.
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