CN114230940A - Modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material, preparation method and cable - Google Patents
Modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material, preparation method and cable Download PDFInfo
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- CN114230940A CN114230940A CN202111463272.1A CN202111463272A CN114230940A CN 114230940 A CN114230940 A CN 114230940A CN 202111463272 A CN202111463272 A CN 202111463272A CN 114230940 A CN114230940 A CN 114230940A
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003063 flame retardant Substances 0.000 title claims abstract description 76
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 66
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 66
- 238000005452 bending Methods 0.000 title claims abstract description 59
- 229920001971 elastomer Polymers 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 28
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 28
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 239000004014 plasticizer Substances 0.000 claims abstract description 26
- 239000003381 stabilizer Substances 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 229920001897 terpolymer Polymers 0.000 claims abstract description 22
- 239000000314 lubricant Substances 0.000 claims abstract description 20
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 7
- 239000012964 benzotriazole Substances 0.000 claims description 7
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 7
- 230000002195 synergetic effect Effects 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008240 homogeneous mixture Substances 0.000 claims description 4
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical group CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 238000010408 sweeping Methods 0.000 claims description 3
- WGKLIJDVPACLGG-UHFFFAOYSA-N trizinc diborate hydrate Chemical compound O.[Zn++].[Zn++].[Zn++].[O-]B([O-])[O-].[O-]B([O-])[O-] WGKLIJDVPACLGG-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of insulating rubber materials, in particular to a modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material, a preparation method and a cable, wherein the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material comprises the following components in parts by weight: 90-100 parts of SG0 type polyvinyl chloride resin, 70-90 parts of environment-friendly plasticizer, 20-30 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 10-15 parts of dioctyl maleate, 15-25 parts of modified polymer, 8-15 parts of composite flame retardant, 20-30 parts of magnesium hydroxide, 8-10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1-2 parts of lubricant. The modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material obtained by the formula and the process has the characteristics of high tensile strength and high elongation at break, also meets the temperature resistance grade of-40-105 ℃ and the combustion grade of VW-1, simultaneously meets the bending-resistant requirements of oil resistance of 1000 ten thousand times and UL 60 ℃ of a drag chain line, and solves the problem that the industrial drag chain line is difficult to meet the wide temperature-resistant range and the high bending-resistant times.
Description
Technical Field
The invention relates to the technical field of insulating rubber materials, in particular to a modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material and a preparation method thereof.
Background
The industrial drag chain line is a composite cable, can prevent the electric wire from being entangled, abraded, pulled off, hung and scattered when the equipment unit moves back and forth, protects the electric wire, and can also move back and forth along with the drag chain. To accommodate the back and forth movement following the tow chain, such wires typically require a wire jacket with high flexibility and good wear resistance.
The industrial drag chain line PVC sheath material on the market generally meets the bending resistance times of 200 ten thousand and the temperature resistance level of minus 40-80 ℃, or meets the bending resistance times of 200 ten thousand and the temperature resistance level of minus 20-105 ℃. However, with the wider and more extreme application range of cables and the more and more extreme application environment, the rubber material in the market is difficult to meet the requirements of bending resistance times of 1000 ten thousand times, wide temperature resistance range of-40-105 ℃ and UL 60 ℃ oil resistance, so that a sheath rubber material meeting the performance conditions needs to be developed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material which comprises the following components in parts by weight: 90-100 parts of SG0 type polyvinyl chloride resin, 70-90 parts of environment-friendly plasticizer, 20-30 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 10-15 parts of dioctyl maleate, 15-25 parts of modified polymer, 8-15 parts of composite flame retardant, 20-30 parts of magnesium hydroxide, 8-10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1-2 parts of lubricant;
wherein the modified polymer comprises 30-40 parts of styrene-butadiene-styrene block copolymer, 10-15 parts of high styrene rubber, 8-15 parts of benzotriazole, 5-8 parts of beta-diketone synergistic stabilizer and 8-15 parts of triallyl isocyanurate;
the composite flame retardant comprises 5-8 parts of antimony trioxide, 3-5 parts of aluminum hydroxide and 2-3 parts of 3.5 parts of zinc borate hydrate.
Preferably, the preparation process of the modified polymer comprises the steps of adding the styrene-butadiene-styrene block copolymer and the high styrene rubber into a high-speed kneading machine, running at a high speed of 1000-1500r/min for 2-5min, adding the benzotriazole, the beta-diketone synergistic stabilizer and the triallyl isocyanurate, running at a low speed of 100-300r/min for 8-15min, and cooling the materials in a cold mixer to room temperature for later use.
Preferably, the environment-friendly plasticizer is trioctyl trimellitate.
Preferably, the lubricant comprises a polyethylene wax.
Preferably, 100 parts of SG0 type polyvinyl chloride resin, 80 parts of environment-friendly plasticizer, 20 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 10 parts of dioctyl maleate, 15 parts of modified polymer, 8 parts of composite flame retardant, 20 parts of magnesium hydroxide, 10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1 part of lubricant.
A preparation method of the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material comprises the following steps:
s1, weighing and mixing SG0 type polyvinyl chloride resin, ethylene-n-butyl acrylate-carbonyl terpolymer, modified polymer, composite flame retardant, magnesium hydroxide, efficient environment-friendly calcium-zinc stabilizer and lubricant according to the mass parts of the component proportion, putting the mixture into a high-speed kneader, and uniformly mixing at a low speed of 250r/min at the rotation speed of 150-; simultaneously preheating dioctyl maleate and an environment-friendly plasticizer to 50-60 ℃;
s2, adding dioctyl maleate and an environment-friendly plasticizer when the material temperature in the kneader reaches 60-70 ℃, uniformly mixing at a high speed, wherein the rotating speed is 500-800r/min, and stopping when the material temperature reaches 100 +/-5 ℃ and the dioctyl maleate is completely absorbed to form a homogeneous mixture;
s3, putting the mixture obtained in the S2 into an internal mixer for internal mixing, and once sweeping the internal mixer when the internal mixing temperature reaches 130 ℃;
and S4, when the banburying temperature reaches 165 ℃, conveying the mixture obtained by blending to a double-screw extruder for extrusion granulation to obtain the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material.
On the other hand, the application provides a cable which is prepared by adopting the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material prepared by the preparation method.
On the other hand, the application provides a cable, which is prepared by adopting the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material.
From the above, the following beneficial effects can be obtained by applying the invention: the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material obtained by the formula and the process has the characteristics of high tensile strength and high elongation at break, and simultaneously meets the temperature resistance of-40-105 ℃ and the combustion performance of VW-1, and the temperature resistance of 105 ℃ is reached by selecting SG0 type PVC resin; the combustion performance requirement of VW-1 is met by adjusting the using amounts and the proportion of the composite flame retardant and the magnesium hydroxide; the requirements of temperature resistance grade at minus 40 ℃ and oil resistance at 60 ℃ are met by selecting a proper amount of ethylene-n-butyl acrylate-carbonyl terpolymer; the bending resistance of 1000 ten thousand times is achieved by adjusting the ratio of the modified polymer to the dioctyl maleate.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments of the present application or the prior art will be briefly described below. It should be apparent that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained by those skilled in the art without inventive exercise.
FIG. 1 is a flow chart of a preparation method of a modified polyvinyl chloride flame-retardant bending-resistant sheath rubber compound in the embodiment of the application.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In order to solve the technical problems, the embodiment provides a modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material, which comprises the following components in parts by weight: 90-100 parts of SG0 type polyvinyl chloride resin, 70-90 parts of environment-friendly plasticizer, 20-30 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 10-15 parts of dioctyl maleate, 15-25 parts of modified polymer, 8-15 parts of composite flame retardant, 20-30 parts of magnesium hydroxide, 8-10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1-2 parts of lubricant;
wherein the modified polymer comprises 30 parts of styrene-butadiene-styrene block copolymer, 15 parts of high styrene rubber, 10 parts of benzotriazole, 5 parts of beta-diketone synergistic stabilizer and 8 parts of triallyl isocyanurate; in the modified polymer, beta-diketone synergistic stabilizer obviously improves the initial coloring of polyvinyl chloride products, and benzotriazole is a high molecular stabilizer and has the performances of lubrication, ultraviolet absorption and the like. The triallyl isocyanurate is used as an auxiliary crosslinking agent for free radical reaction crosslinking, the heat resistance, flame retardance, solvent resistance, mechanical strength and the like of a sizing material product can be obviously improved after crosslinking, the strength of polyvinyl chloride at higher temperature can be improved, and by matching with high styrene rubber and styrene-butadiene-styrene block copolymer, the rubber vulcanization time can be obviously shortened, the strength, the wear resistance, the solvent resistance and the corrosion resistance are improved, the bending resistance of the sizing material product is improved, and the requirement that the bending resistance times reach 1000 ten thousand times is met.
The composite flame retardant comprises 5 parts of antimony trioxide, 3 parts of aluminum hydroxide and 2 parts of 3.5 parts of zinc borate hydrate, effectively reduces agglomeration of flame-retardant powder in the processing process, enables the flame-retardant powder to be dispersed in polyvinyl chloride more uniformly, improves the flame-retardant efficiency, and simultaneously improves the low-temperature performance.
Wherein the environment-friendly plasticizer is trioctyl trimellitate, and the lubricant is polyethylene wax.
The dioctyl maleate can couple polar groups of the PVC resin, so that the intermolecular polar effect is weakened, the dioctyl maleate is inserted into macromolecules to increase the distance between the macromolecules, the mobility and the flexibility of molecular chains of the PVC resin are improved, and the shaping of the PVC resin is increased.
In order to meet the requirement of 105 ℃, SG0 type PVC resin is selected as the raw material in the formula, so that the polymerization degree is high, and the mechanical property and the temperature resistance grade are improved. In order to meet the requirements of minus 40 ℃ and 60 ℃ on oil resistance, a low-temperature modifier ethylene-n-butyl acrylate-carbonyl terpolymer is selected.
In order to meet the VW-1, the composite flame retardant and the magnesium hydroxide are added, and because the plasticizer has high weight, the composite flame retardant and the magnesium hydroxide are required to meet the requirement of flame retardant performance. Further, the lubricant is a low molecular organic substance, which lowers the flame retardant property, and the amount thereof should be controlled.
Specifically, the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material of the embodiment comprises the following components in parts by weight: 100 parts of SG0 type polyvinyl chloride resin, 80 parts of environment-friendly plasticizer, 20 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 10 parts of dioctyl maleate, 15 parts of modified polymer, 8 parts of composite flame retardant, 20 parts of magnesium hydroxide, 10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1 part of lubricant.
The preparation process of the modified polymer comprises the steps of adding styrene-butadiene-styrene block copolymer and high styrene rubber into a high-speed kneading machine, running at high speed for 2-5min at the rotation speed of 1000-1500r/min, adding benzotriazole, beta-diketone synergistic stabilizer and triallyl isocyanurate, running at low speed at the rotation speed of 100-300r/min for 8-15min, and cooling the materials in a cold mixer to room temperature for later use.
The application provides a preparation method of a modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material, as shown in figure 1, comprising the following steps:
s1, weighing and mixing SG0 type polyvinyl chloride resin, ethylene-n-butyl acrylate-carbonyl terpolymer, modified polymer, composite flame retardant, magnesium hydroxide, efficient environment-friendly calcium-zinc stabilizer and lubricant according to the mass parts of the component proportion, putting the mixture into a high-speed kneader, and uniformly mixing at a low speed of 250r/min at the rotation speed of 150-; simultaneously preheating dioctyl maleate and an environment-friendly plasticizer to 50-60 ℃;
preferably, the low speed rotation speed in this step is 200r/min, and the preheating temperature of the dioctyl maleate and the environmentally friendly plasticizer is 50 ℃.
S2, adding dioctyl maleate and an environment-friendly plasticizer when the material temperature in the kneader reaches 60-70 ℃, uniformly mixing at a high speed, wherein the rotating speed is 500-800r/min, and stopping when the material temperature reaches 100 +/-5 ℃ and the dioctyl maleate is completely absorbed to form a homogeneous mixture;
preferably, in the step, when the material temperature in the kneader reaches 60 ℃, dioctyl maleate and environment-friendly plasticizer are added, the high-speed rotation speed is 600r/min, when the material temperature reaches 100 ℃, dioctyl maleate is completely absorbed, and a homogeneous mixture is formed after mixing is stopped,
s3, putting the mixture obtained in the S2 into an internal mixer for internal mixing, and once sweeping the internal mixer when the internal mixing temperature reaches 130 ℃;
the internal rubber mixer plasticates and mixes the polymer material intermittently under a closed state with adjustable temperature and pressure.
And S4, when the banburying temperature reaches 165 ℃, conveying the mixture obtained by blending to a double-screw extruder for extrusion granulation to obtain the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material.
On the other hand, the application provides a cable which is prepared by adopting the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material prepared by the preparation method. After the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material is obtained by the preparation method, the obtained modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material particles are extruded into cable wires by an extruder. The industrial requirements of temperature resistance of-40 ℃ to 105 ℃ and bending resistance of 1000 ten thousand times are met simultaneously.
Example 2
100 parts of SG0 type polyvinyl chloride resin, 80 parts of environment-friendly plasticizer, 20 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 5 parts of dioctyl maleate, 5 parts of modified polymer, 8 parts of composite flame retardant, 20 parts of magnesium hydroxide, 10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1 part of lubricant.
The preparation method comprises the same steps as example 1, and the obtained modified polyvinyl chloride flame-retardant bending-resistant sheath rubber particles are extruded into cable wires by an extruder.
Example 3
100 parts of SG0 type polyvinyl chloride resin, 90 parts of environment-friendly plasticizer, 20 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 15 parts of dioctyl maleate, 25 parts of modified polymer, 5 parts of composite flame retardant, 20 parts of magnesium hydroxide, 10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1 part of lubricant.
The preparation method comprises the same steps as example 1, and the obtained modified polyvinyl chloride flame-retardant bending-resistant sheath rubber particles are extruded into cable wires by an extruder.
Example 4
100 parts of SG0 type polyvinyl chloride resin, 80 parts of environment-friendly plasticizer, 30 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 5 parts of dioctyl maleate, 10 parts of modified polymer, 8 parts of composite flame retardant, 20 parts of magnesium hydroxide, 10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1 part of lubricant.
The preparation method comprises the same steps as example 1, and the obtained modified polyvinyl chloride flame-retardant bending-resistant sheath rubber particles are extruded into cable wires by an extruder.
Example 5
100 parts of SG0 type polyvinyl chloride resin, 80 parts of environment-friendly plasticizer, 30 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 5 parts of dioctyl maleate, 15 parts of modified polymer, 8 parts of composite flame retardant, 20 parts of magnesium hydroxide, 10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1 part of lubricant.
The preparation method comprises the same steps as example 1, and the obtained modified polyvinyl chloride flame-retardant bending-resistant sheath rubber particles are extruded into cable wires by an extruder.
Example 6
100 parts of SG0 type polyvinyl chloride resin, 80 parts of environment-friendly plasticizer, 20 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 10 parts of dioctyl maleate, 15 parts of modified polymer, 3 parts of composite flame retardant, 10 parts of magnesium hydroxide, 10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1 part of lubricant.
The preparation method comprises the same steps as example 1, and the obtained modified polyvinyl chloride flame-retardant bending-resistant sheath rubber particles are extruded into cable wires by an extruder.
Example 7
100 parts of SG0 type polyvinyl chloride resin, 80 parts of environment-friendly plasticizer, 15 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 5 parts of dioctyl maleate, 15 parts of modified polymer, 8 parts of composite flame retardant, 30 parts of magnesium hydroxide, 10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1 part of lubricant.
The preparation method comprises the same steps as example 1, and the obtained modified polyvinyl chloride flame-retardant bending-resistant sheath rubber particles are extruded into cable wires by an extruder.
TABLE 1
Table 1 shows the raw material formulas of the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber materials of examples 1 to 7
TABLE 2
As shown in Table 2, the results of the performance test of the cable prepared from the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber compound of examples 1-7 are shown.
As can be seen from comparison of test results of examples 1, 2 and 3, when the amount of the environmentally-friendly plasticizer trioctyl trimellitate reaches 90 parts, the oxygen index is reduced in the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material, so that the VW-1 cannot be combusted satisfactorily; and when the parts of the modified polymer and the dioctyl maleate are low, the hardness of the rubber material is higher, the rubber material is unqualified by cold bending at the temperature of-40 ℃, and the bending resistance times are greatly reduced. As the amount of the modified polymer and the dioctyl maleate is increased, the bending resistance times are increased, the elongation is better, and when the amount of the modified polymer and the dioctyl maleate is larger, the tensile strength is unqualified, cracks are generated in an oil resistance test at 60 ℃, and the flame retardant property of VW-1 can be influenced. Therefore, the amount of the modified polymer and dioctyl maleate is increased to improve the bending resistance, but a proper amount is required.
As can be seen from comparison of the test results of examples 1, 4, 5 and 7, the bending resistance was decreased when the amount of the ethylene-n-butyl acrylate-carbonyl terpolymer was increased to 30 parts; when the weight of the ethylene-n-butyl acrylate-carbonyl terpolymer is reduced to 15 parts, the cold bending performance at the temperature of minus 40 ℃ is not qualified, and when the weight is reduced to 10 parts, the cold bending performance at the temperature of minus 40 ℃ and the oil resistance performance at the temperature of 60 ℃ are not qualified.
As can be seen from comparison of test results of examples 1, 3, 6 and 7, the flame retardant performance can be better improved by matching the composite flame retardant and the magnesium hydroxide, when the parts of the composite flame retardant and the magnesium hydroxide are low, the VW-1 flame retardant test is unqualified, and when the parts of the magnesium hydroxide are high, the flame retardant performance is obviously improved.
Wherein, although the flame retardant property can be improved by the magnesium hydroxide, the low temperature resistance can be reduced by adding too much magnesium hydroxide, and the magnesium hydroxide cannot be qualified by cold bending at minus 40 ℃ when the weight of the magnesium hydroxide reaches 30 parts; when the amount is reduced to 10 parts, the flame retardant property of the system is unqualified, and the combustion time of the VW-1 exceeds 60 s. The proportions of modified polymer, magnesium hydroxide, dioctyl maleate and ethylene-n-butyl acrylate-carbonyl terpolymer are therefore related to the cold-bending properties at-40 ℃.
According to the comparison, the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material obtained by the formula and the process disclosed by the invention not only has the characteristics of high tensile strength and high elongation at break, but also meets the temperature resistance of-40-105 ℃ and the combustion performance of VW-1, and the temperature resistance of 105 ℃ is reached by selecting SG0 type PVC resin; the combustion performance requirement of VW-1 is met by adjusting the using amounts and the proportion of the composite flame retardant and the magnesium hydroxide; the requirements of temperature resistance grade at minus 40 ℃ and oil resistance at 60 ℃ are met by selecting a proper amount of ethylene-n-butyl acrylate-carbonyl terpolymer; the bending resistance of 1000 ten thousand times is achieved by adjusting the ratio of the modified polymer to the dioctyl maleate.
The above-described embodiments do not limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the above-described embodiments should be included in the protection scope of the technical solution.
Claims (8)
1. The modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material is characterized in that: comprises the following components in parts by mass: 90-100 parts of SG0 type polyvinyl chloride resin, 70-90 parts of environment-friendly plasticizer, 20-30 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 10-15 parts of dioctyl maleate, 15-25 parts of modified polymer, 8-15 parts of composite flame retardant, 20-30 parts of magnesium hydroxide, 8-10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1-2 parts of lubricant;
wherein the modified polymer comprises 30-40 parts of styrene-butadiene-styrene block copolymer, 10-15 parts of high styrene rubber, 8-15 parts of benzotriazole, 5-8 parts of beta-diketone synergistic stabilizer and 8-15 parts of triallyl isocyanurate;
the composite flame retardant comprises 5-8 parts of antimony trioxide, 3-5 parts of aluminum hydroxide and 2-3 parts of 3.5 parts of zinc borate hydrate.
2. The modified polyvinyl chloride flame-retardant bending-resistant sheath rubber compound according to claim 1, characterized in that: the preparation process of the modified polymer comprises the steps of adding styrene-butadiene-styrene block copolymer and high styrene rubber into a high-speed kneading machine, running at high speed for 2-5min at the rotation speed of 1000-1500r/min, adding benzotriazole, beta-diketone synergistic stabilizer and triallyl isocyanurate, running at low speed at the rotation speed of 100-300r/min for 8-15min, and cooling the materials in a cold mixer to room temperature for later use.
3. The modified polyvinyl chloride flame-retardant bending-resistant sheath rubber compound according to claim 1, characterized in that: the environment-friendly plasticizer is trioctyl trimellitate.
4. The modified polyvinyl chloride flame-retardant bending-resistant sheath rubber compound according to claim 1, characterized in that: the lubricant comprises polyethylene wax.
5. The modified polyvinyl chloride flame-retardant bending-resistant sheath rubber compound according to claim 1, characterized in that: 100 parts of SG0 type polyvinyl chloride resin, 80 parts of environment-friendly plasticizer, 20 parts of ethylene-n-butyl acrylate-carbonyl terpolymer, 10 parts of dioctyl maleate, 15 parts of modified polymer, 8 parts of composite flame retardant, 20 parts of magnesium hydroxide, 10 parts of high-efficiency environment-friendly calcium-zinc stabilizer and 1 part of lubricant.
6. A preparation method of the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber compound used in any one of claims 1 to 5 is characterized by comprising the following steps: the method comprises the following steps:
s1, weighing and mixing SG0 type polyvinyl chloride resin, ethylene-n-butyl acrylate-carbonyl terpolymer, modified polymer, composite flame retardant, magnesium hydroxide, efficient environment-friendly calcium-zinc stabilizer and lubricant according to the mass portion ratio, putting the mixture into a high-speed kneader, and uniformly mixing at a low speed of 250 r/min; simultaneously preheating dioctyl maleate and an environment-friendly plasticizer to 50-60 ℃;
s2, adding dioctyl maleate and an environment-friendly plasticizer when the material temperature in the kneader reaches 60-70 ℃, uniformly mixing at a high speed, wherein the rotating speed is 500-800r/min, and stopping when the material temperature reaches 100 +/-5 ℃ and the dioctyl maleate is completely absorbed to form a homogeneous mixture;
s3, putting the mixture obtained in the S2 into an internal mixer for internal mixing, and once sweeping the internal mixer when the internal mixing temperature reaches 130 ℃;
and S4, when the banburying temperature reaches 165 ℃, conveying the mixture obtained by blending to a double-screw extruder for extrusion granulation to obtain the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber material.
7. A cable, characterized by: the modified polyvinyl chloride flame-retardant bending-resistant sheath rubber compound prepared by the preparation method of claim 6 is prepared.
8. A cable, characterized by: the flame-retardant and bending-resistant modified polyvinyl chloride sheath rubber compound is prepared by adopting the flame-retardant and bending-resistant modified polyvinyl chloride sheath rubber compound of any one of claims 1 to 5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115785589A (en) * | 2022-11-30 | 2023-03-14 | 广东鑫达新材料科技有限公司 | Vinyl chloride-based resin composition |
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| CN104312038A (en) * | 2014-10-09 | 2015-01-28 | 深圳市帝源新材料科技有限公司 | Super-heat-resistant oil-resistant polyvinyl chloride cable material as well as preparation method and cable |
| CN108250632A (en) * | 2018-04-02 | 2018-07-06 | 合肥市闵葵电力工程有限公司 | A kind of high rigidity fire-resistant cable material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103205070A (en) * | 2013-04-12 | 2013-07-17 | 江苏领瑞新材料科技有限公司 | Cold-resistant oilproof flame-retardant PVC (Polyvinyl Chloride) cable material and preparation method thereof |
| CN104312038A (en) * | 2014-10-09 | 2015-01-28 | 深圳市帝源新材料科技有限公司 | Super-heat-resistant oil-resistant polyvinyl chloride cable material as well as preparation method and cable |
| CN108250632A (en) * | 2018-04-02 | 2018-07-06 | 合肥市闵葵电力工程有限公司 | A kind of high rigidity fire-resistant cable material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115785589A (en) * | 2022-11-30 | 2023-03-14 | 广东鑫达新材料科技有限公司 | Vinyl chloride-based resin composition |
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