CN107383576B - Low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material and preparation method and application thereof - Google Patents

Low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material and preparation method and application thereof Download PDF

Info

Publication number
CN107383576B
CN107383576B CN201710642756.XA CN201710642756A CN107383576B CN 107383576 B CN107383576 B CN 107383576B CN 201710642756 A CN201710642756 A CN 201710642756A CN 107383576 B CN107383576 B CN 107383576B
Authority
CN
China
Prior art keywords
weight ratio
parts
low
powder
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710642756.XA
Other languages
Chinese (zh)
Other versions
CN107383576A (en
Inventor
李同兵
刘方达
钟荣栋
苏俐娇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Antop Polymer Technology Co ltd
Original Assignee
Guangdong Antopu Polymer Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Antopu Polymer Technology Co ltd filed Critical Guangdong Antopu Polymer Technology Co ltd
Priority to CN201710642756.XA priority Critical patent/CN107383576B/en
Publication of CN107383576A publication Critical patent/CN107383576A/en
Application granted granted Critical
Publication of CN107383576B publication Critical patent/CN107383576B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • 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
    • H01B3/441—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 alkenes
    • 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
    • H01B3/442—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 aromatic vinyl 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention relates to the technical field of polyolefin elastomers, in particular to a low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material, a preparation method and application thereof, wherein the low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following raw materials in parts by weight: 20-80 parts of thermoplastic polyolefin, 2-10 parts of EVA resin, 2-10 parts of ethylene propylene rubber, 20-70 parts of halogen-free flame retardant, 1-10 parts of smoke suppressant, 20-80 parts of ceramic powder, 0.5-5 parts of compatilizer and 0.02-0.1 part of antioxidant. The thermoplastic polyolefin elastomer composite material has the advantages of excellent flame retardant effect, low smoke density, high strength, good flexibility and high elongation at break; and a compact ceramic product can be formed within the range of 600-1000 ℃, the ceramic forming temperature is low, the ceramic forming is compact, and the formed ceramic product has good high-temperature strength and thermal current impact resistance.

Description

Low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of polyolefin elastomers, in particular to a low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material and a preparation method and application thereof.
Background
With the continuous progress of social development, the requirements of people on safety protection are continuously improved. In the field of electric wires and cables, people have higher and higher requirements on the continuous power supply capacity of fire-resistant power cables in fire disasters, and the insulation performance of the fire-resistant power cables has an important influence on the continuous power supply capacity of the fire-resistant power cables in fire disasters.
The ceramic high molecular composite material is a novel heat-proof material, and is prepared by adding a ceramic additive into polymer/resin and performing melt blending. The ceramic polymer composite material has excellent high and low temperature resistance, electric insulation, ozone resistance, weather resistance and arc resistance, and can form a hard ceramic-based protective layer when subjected to high-temperature flame ablation, so that a protected object is not damaged. Specifically, the ceramizable polymer composite material has the excellent characteristics of the common polymer composite material at normal temperature; in the middle and low temperature stage, the heat is prevented by the ablation resistance of the ablation-resistant high polymer material; however, at high temperature, after the environmental temperature exceeds the ceramic temperature point of the material, the composite material is subjected to ceramic conversion to form a ceramic protective layer, the ceramic material has high heat resistance to play a role in thermal protection, and the composite material has certain strength and can bear certain heat flow scouring, so that the interior of the material can be protected from being damaged by high temperature. The ceramic polymer composite material is a novel fireproof, flame-retardant and thermal protection material.
Chinese patent CN1973019A discloses a fire-resistant ceramifying composition comprising a mineral silicate, at least one inorganic phosphate forming a liquid phase at a temperature not exceeding 800 ℃, a polymer-based composition comprising at least 50% by weight of an organic polymer. The fireproof ceramic composition is used for manufacturing fire-resistant cables, polyurethane foams and the like. The disadvantage of this patent is that the resulting ceramic is of poor strength and requires high temperatures for ceramic formation.
Chinese patent CN1320556C discloses a fire resistant cable comprising at least one conductor and at least one fire resistant coating, wherein the fire resistant coating comprises at least one organic polymer having a burning temperature in the range between a minimum temperature T1 and a maximum temperature T2; (at least one glass frit; at least one inert compound; wherein the inert compound has a softening or melting temperature of not less than 1000 ℃; the temperature range is selected so that the glass flows onto the inert compound and the burned organic polymer to form a solid carbon refractory coating.
Chinese patent 101404189B discloses a fast ceramic fire-resistant cable material and a preparation method thereof, wherein the fire-resistant cable material is prepared by blending and extruding ethylene-vinyl acetate copolymer EVA, linear low-density polyethylene LLDPE, ceramic filler, flame retardant, antioxidant, lubricant and coupling agent, the cable material can be vitrified within 10 minutes at 750 ℃ and higher, and the vitrified material can ensure that the line normally runs for more than 90 minutes at 750 ℃ and 950 ℃. The defects of the patent are that the formed ceramic has poor strength, the temperature required by ceramic formation is high, and the mechanical property of the cable material is poor.
Chinese patent CN104650441A discloses a flame-retardant polymer composite material capable of being ceramized based on polyolefin or based on thermoplastic polyurethane elastomer, which comprises the following components in parts by weight: 30-40 parts of polyolefin resin or thermoplastic polyurethane elastomer, 25-45 parts of porcelain forming filler, 20-30 parts of halogen-free flame retardant, 1-5 parts of synergistic flame retardant, 1-3 parts of plasticizer, 0.5-2 parts of antioxidant and 0.02-0.15 part of cross-linking agent, wherein the porcelain forming filler comprises low-softening-point glass powder and silicate mineral filler. This patent suffers from the following disadvantages: the addition of a large amount of porcelain forming filler leads to the remarkable reduction of the tensile strength, the tearing strength and the elongation at break of the composite material, and can not meet the mechanical property requirements of cables and optical cables on insulating or sheathing materials. The composite material disclosed by the patent can generate large toxic smoke during combustion, and is extremely not beneficial to escape of people in case of fire; the existing cable and optical cable usually have flame retardant property, and the flame retardant property can only prevent the cable from becoming a fire source inducing fire due to short circuit and the like. However, when a fire occurs and the high-temperature flame is ablated, the insulation and sheath materials of the cable and the optical cable still have combustion reaction. When the polyolefin elastomer is burnt, a large amount of toxic smoke is released, so that people are hindered from escaping or poisoned and died directly. Another hazard of the cable and the optical cable being ablated by flame is that after the cable, the insulating layer and the outer sheath of the optical cable are ablated by fire, the exposed lead can be disconnected due to the ablation of the flame, thereby causing the interruption of power supply and communication, the failure of various alarm devices and fire fighting devices in the building and the extinction of light, thus being extremely not beneficial to people to escape and rescue the disaster. The existing insulation and sheath materials for cables and optical cables only have a flame retardant function, and a few materials have low smoke characteristics. Insulating and sheathing materials for ceramifiable cables and optical cables have also become a hot point of research and development. However, materials which have flame retardant, low smoke and ceramic functions and can comprehensively overcome the negative influence on escape of people caused by burning of cables and optical cables have not been provided, and reports are rarely made. Therefore, a composite material integrating flame retardant, low smoke and ceramic functions is urgently needed to be developed.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material which has the advantages of excellent flame-retardant effect, low smoke density, high strength, good flexibility and high elongation at break; and a compact ceramic product can be formed within the range of 600-1000 ℃, the ceramic forming temperature is low, the ceramic forming is compact, and the formed ceramic product has good high-temperature strength and thermal current impact resistance.
The invention also aims to provide a preparation method of the low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material, which has the advantages of simple process, convenient operation and control, stable quality, high production efficiency and low production cost, and can be used for large-scale industrial production.
The invention also aims to provide application of the low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material in flame-retardant wires, cables and optical cables.
The purpose of the invention is realized by the following technical scheme: a low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following raw materials in parts by weight:
20-80 parts of thermoplastic polyolefin elastomer
EVA resin 2-10 weight portions
2-10 parts of ethylene propylene rubber
5-15 parts of polyester staple fiber
20-70 parts of halogen-free flame retardant
1-10 parts of smoke suppressant
20-80 parts of porcelainized powder
0.5 to 5 portions of compatilizer
0.02-0.1 part of antioxidant.
By adopting the raw materials and strictly controlling the weight ratio of the raw materials, the thermoplastic polyolefin elastomer composite material has the advantages of excellent flame retardant effect, low smoke density, high strength, good flexibility and high elongation at break; and a compact ceramic product can be formed within the range of 600-1000 ℃, the ceramic forming temperature is low, the ceramic forming is compact, and the formed ceramic product has good high-temperature strength and thermal current impact resistance.
The inventor finds that the addition of the polyester short fiber can obviously inhibit the reduction effect of mechanical properties caused by the addition of a large amount of inorganic substances and can also improve the high-temperature resistance of the material.
Preferably, the thermoplastic polyolefin elastomer is at least one of ethylene-octene copolymer and polystyrene elastomer; the polystyrene elastomer is at least one of styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer and styrene-ethylene-propylene-styrene type block copolymer.
More preferably, the thermoplastic polyolefin is a mixture of an ethylene-octene copolymer and a styrene-ethylene-butene-styrene block copolymer in a weight ratio of 1:0.4 to 0.8.
By adopting the thermoplastic polyolefin, the invention has the characteristics of small density, large bending, high low-temperature impact resistance, easy processing, reusability and the like.
Preferably, the halogen-free flame retardant is at least one of ammonium phosphate, ammonium polyphosphate, modified ammonium polyphosphate, aluminum hypophosphite, melamine and compounds thereof, zinc borate, montmorillonite, clay, metal hydroxide, an organic phosphate ester compound, an organic hypophosphite compound and polyol.
The modified ammonium polyphosphate is at least one of piperazine modified ammonium polyphosphate, ethylenediamine modified ammonium polyphosphate, diethylenetriamine modified ammonium polyphosphate and hydroxyethyl ethylenediamine modified ammonium polyphosphate.
The melamine and the compound thereof are at least one of melamine, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine hypophosphite, melamine phosphite, melamine cyanurate and melamine salt of 2-carboxyethyl phenyl phosphinic acid.
The metal hydroxide is aluminum hydroxide and/or magnesium hydroxide.
The organic phosphate compound is at least one of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-chloroethyl) phosphate, tris (2, 3-dichloropropyl) phosphate, tris (2, 3-dibromopropyl) phosphate, toluene-diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, and 2-ethylhexyl-diphenyl phosphate.
The organic hypophosphite compound is at least one of trimethyl hypophosphite, triethyl hypophosphite, tripropyl hypophosphite and tributyl hypophosphite.
The polyol is at least one of polyester polyol, polyether polyol and phosphorus-containing polyol.
More preferably, the halogen-free flame retardant is a mixture of polycyanurate cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite in a weight ratio of 1-2:0.8-1.2:1: 0.4-0.8.
The halogen-free flame retardant is adopted, so that the flame retardance of the material can be improved, the use safety of the material is greatly improved, and in addition, the flame retardant is free of halogen, so that the material has the characteristics of environmental protection and no toxicity.
Preferably, the smoke suppressant is at least one of a molybdenum compound, an iron compound, a metal oxide, a magnesium-zinc complex and a zinc compound.
Wherein the molybdenum compound is molybdenum trioxide and/or ammonium octamolybdate. The iron compound is ferrocene. The metal oxide is at least one of magnesium oxide, zinc oxide, nickel oxide, zirconium oxide, antimony trioxide and antimony pentoxide. The magnesium-zinc compound is a magnesium oxide and zinc oxide compound. The zinc compound is at least one of zinc borate, zinc aluminate and zinc stannate.
More preferably, the smoke suppressant is a mixture of ferrocene, antimony trioxide and zinc borate in a weight ratio of 0.5-1.5:1.5-2.5: 1.
By adopting the smoke suppressant, the smoke suppressant has good smoke suppression effect and can reduce toxic gas and smoke generated by the thermoplastic polyolefin elastomer during combustion.
Preferably, the ceramic powder is composed of at least one of boron compound, low-softening-point glass powder and glass fiber and mineral filler; the mineral filler is at least one of attapulgite, bentonite, kaolin, montmorillonite, argil, clay, mica powder, talcum powder, feldspar powder, brucite powder, ludwigite powder, forsterite powder, silico-calcium-boron stone powder, chlorite powder, pyrophyllite powder, montmorillonite powder, calcite powder, limestone powder, potassium feldspar powder, wollastonite powder, spodumene powder and dilithite powder; the boron compound is at least one of boric anhydride, borax, ammonium borate, zinc borate and boron frit; the low-softening-point glass powder is at least one of lead oxide glass powder, calcium oxide glass powder, bismuth oxide glass powder, phosphate glass powder, silicate glass powder and borate glass powder; the glass fiber is alkali-free chopped glass fiber with monofilament diameter of 0.1-5 μm and length of 5-60 μm.
Wherein the dosage of the mineral filler is 20-50%, the melting point of the mineral filler is 800-1500 ℃, and the softening point of the low-softening-point glass powder is 300-500 ℃.
More preferably, the ceramic powder is a mixture of a boron compound, a low softening point glass powder, glass fibers and a mineral filler in a weight ratio of 0.8-1.2:1:0.4-0.8: 0.5-1.5.
The boron compound is a mixture of borax, ammonium borate and zinc borate in a weight ratio of 0.5-1.5:1: 0.4-0.8.
The softening point glass powder is a mixture of bismuth oxide glass powder, phosphate glass powder, silicate glass powder and borate glass powder in a weight ratio of 0.4-0.8:0.8-1.2:1: 0.5-1.5.
The mineral filler is a mixture of talcum powder, mica powder and wollastonite powder in a weight ratio of 1:0.3-0.7: 0.8-1.2.
The ceramic powder is compounded by at least one of boron compound, low-softening-point glass powder and glass fiber and mineral filler, the ceramizable flame-retardant polymer composite material can form a compact ceramized product within the temperature range of 600-1000 ℃, and the formed ceramized product has good high-temperature strength and thermal current impact resistance and good mechanical property at normal temperature.
Preferably, the ceramic powder is subjected to surface treatment by using a high molecular polymer, and the high molecular polymer is at least one of polyvinyl alcohol, isomeric alcohol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, trimethyl nonanol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene sorbitol fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene hardened castor oil fatty acid ester and polyoxyethylene modified organopolysiloxane. More preferably, the high molecular polymer is a mixture of polyvinyl alcohol, trimethyl nonyl alcohol polyoxyethylene ether and polyoxyethylene sorbitol fatty acid ester in a weight ratio of 1:0.8-1.2: 0.4-0.8.
The invention can improve the compatibility of ceramic powder and organic resin, improve the tensile strength and tearing strength of the composite material, improve the processing rheological property and improve the surface smoothness by adopting the high molecular polymer to treat the surface of the ceramic powder.
Preferably, the compatibilizer is maleic anhydride grafted SEBS, maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, maleic anhydride grafted styrene, maleic anhydride grafted polyolefin, hydrogenated thermoplastic styrene-butadiene rubber-maleic anhydride graft, hydrogenated thermoplastic styrene-butadiene rubber-polyurethane graft, thermoplastic styrene-butadiene rubber-maleic anhydride graft, hydrogenated thermoplastic styrene-butadiene rubber-thermoplastic polyurethane copolymer, thermoplastic styrene-butadiene rubber-methyl methacrylate graft, ethylene-octene copolymer grafted maleic anhydride polymer, styrene-butadiene-styrene block copolymer grafted maleic anhydride polymer, ethylene propylene diene monomer rubber grafted maleic anhydride polymer, divinyltetramethyldisiloxane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (beta-methoxyethoxy) silane, maleic anhydride grafted polyethylene, maleic anhydride grafted styrene-maleic anhydride grafted copolymer, hydrogenated thermoplastic styrene-butadiene rubber-maleic anhydride graft, styrene-maleic anhydride grafted copolymer, thermoplastic polyurethane copolymer, thermoplastic, At least one of gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyl-trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl-methyl-trimethoxysilane, gamma-chloropropyl-trimethoxysilane, gamma-mercaptopropyl-trimethoxysilane, gamma-aminopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, and N- (beta-aminoethyl) -gamma-aminopropyl-trimethoxysilane. More preferably, the compatilizer is prepared by mixing maleic anhydride grafted polyolefin, ethylene propylene diene monomer grafted maleic anhydride polymer and gamma-aminopropyltriethoxysilane in a weight ratio of 1-2: 0.5-1.5:1, in a mixture of the components.
By adopting the compatilizer, the compatibility of the inorganic filler and the organic resin can be improved, the tensile strength and the tearing strength of the composite material are improved, high filling is realized, the resin consumption is reduced, the processing rheological property is improved, the surface smoothness is improved, and the scratch whitening is prevented.
Preferably, the antioxidant is at least one of tetrakis [ methylene-3, 5- (di-tert-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester, N' -bis [ [3- (3,5) -di-tert-butyl-4-hydroxyphenyl ] propionyl ] hexanediamine, tris [2, 4-di-tert-butylphenyl ] phosphite, pentaerythritol distearate and N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate. More preferably, the antioxidant is a mixture of tetrakis [ methylene-3, 5- (di-t-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester, tris [2, 4-di-t-butylphenyl ] phosphite and n-octadecyl beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate in a weight ratio of 1:0.2-0.6: 0.4-0.8.
The antioxidant can delay or inhibit the oxidation process of the material, thereby preventing the aging of the material and prolonging the service life of the material.
Preferably, the anti-ultraviolet radiation agent also comprises 0.2 to 1.0 part of anti-ultraviolet radiation agent and 0.5 to 1.5 parts of lubricant.
The ultraviolet resistant agent is at least one of phenyl salicylate, ultraviolet absorbent UV-P, ultraviolet absorbent UV-O, ultraviolet absorbent UV-9, ultraviolet absorbent UV-531, ultraviolet absorbent UVP-327, ultraviolet absorbent RMB, light stabilizer AM-101, light stabilizer 744, light stabilizer HPT and 2,4, 6-tri (2' n-butoxyphenyl) -1,3, 5-triazine. More preferably, the ultraviolet absorber is a mixture of an ultraviolet absorber UV-531, an ultraviolet absorber RMB and a light stabilizer 744 in a weight ratio of 0.8-1.2:0.5-1.5: 1.
The ultraviolet resistant agent can strongly absorb ultraviolet rays and has excellent synergistic effect when being compounded and used.
The lubricant is at least one of liquid paraffin, solid paraffin, natural paraffin, microcrystalline paraffin, chlorinated paraffin, polyethylene wax, oxidized polyethylene wax, fatty acid, butyl stearate, glyceryl monostearate, ethylene bis stearamide, oleamide, pentaerythritol stearate, N-ethylene bis stearamide and N, N-ethylene bis ricinoleate. More preferably, the lubricant is a mixture of oxidized polyethylene wax, pentaerythritol stearate and amine N, N-ethylene bisricinoleate in a weight ratio of 2-4:0.5-1.5: 1.
The lubricant is adopted, so that the fluidity of the material and the demoulding performance of a product can be improved in the processing process of the material, and the processing performance of the material is improved.
The other purpose of the invention is realized by the following technical scheme: a preparation method of a low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following steps:
(1) weighing the raw materials according to the weight ratio, mixing, and putting into a high-speed blender for uniformly mixing to obtain a mixture;
(2) extruding and granulating the mixture through a double-screw extruder to prepare the low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material;
wherein the screw temperature of the double-screw extruder is 180-240 ℃, and the screw rotating speed is 200-600 r/min.
The low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material with good flame retardant property and low smoke property is prepared by selecting a reasonable formula and proper screw temperature and rotating speed and through the working procedures of mixing, extruding, granulating and the like, and the composite material is simple in process and low in cost.
The invention also aims to realize the following technical scheme: an application of low-smoke halogen-free flame-retardant ceramic thermoplastic polyolefin elastomer composite material in flame-retardant wires, cables and optical cables.
The invention has the beneficial effects that: the thermoplastic polyolefin elastomer composite material has the advantages of excellent flame retardant effect, low smoke density, high strength, good flexibility and high elongation at break; and a compact ceramic product can be formed within the range of 600-1000 ℃, the ceramic forming temperature is low, the ceramic forming is compact, and the formed ceramic product has good high-temperature strength and thermal current impact resistance.
The preparation method has the advantages of simple process, convenient operation and control, stable quality, high production efficiency and low production cost, and can be used for large-scale industrial production.
The low-smoke halogen-free flame-retardant ceramic thermoplastic polyolefin elastomer composite material disclosed by the invention is applied to flame-retardant wires, cables and optical cables, has low smoke and no toxic gas released during combustion, and has good flame retardant property and mechanical property; and can form hard protective housing when burning, the protective housing can prevent that flame from further extending to cable inside, plays the effect of isolated external flame to the protection is located the insulating sinle silk of ceramic fire-resistant intraformational and is not damaged, ensures the normal use function of electric wire, cable and optical cable.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following raw materials in parts by weight:
thermoplastic polyolefin elastomer 20 parts
EVA resin 2 parts
Ethylene propylene rubber 2 parts
5 parts of polyester staple fiber
20 portions of halogen-free flame retardant
1 part of smoke suppressant
20 portions of porcelainized powder
0.5 part of compatilizer
0.02 part of antioxidant.
The thermoplastic polyolefin elastomer is at least one of ethylene-octene copolymer and polystyrene elastomer; the polystyrene elastomer is a styrene-butadiene-styrene block copolymer.
The halogen-free flame retardant is ammonium phosphate, ammonium polyphosphate, modified ammonium polyphosphate or aluminum hypophosphite.
The smoke suppressant is a molybdenum compound.
The ceramic powder is composed of at least one of boron compound, low-softening-point glass powder and glass fiber and mineral filler; the mineral filler is attapulgite, bentonite, kaolin, montmorillonite, argil or clay; the boron compound is boric anhydride; the low softening point glass powder is lead oxide glass powder; the glass fiber is alkali-free chopped glass fiber with monofilament diameter of 0.1 μm and length of 5 μm.
The compatilizer is maleic anhydride grafted SEBS, maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, maleic anhydride grafted styrene or maleic anhydride grafted polyolefin.
The antioxidant is tetra [ methylene-3, 5- (di-tert-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester.
Also comprises 0.2 part of anti-ultraviolet agent and 0.5 part of lubricant.
A preparation method of a low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following steps:
(1) weighing the raw materials according to the weight ratio, mixing, and putting into a high-speed blender for uniformly mixing to obtain a mixture;
(2) extruding and granulating the mixture through a double-screw extruder to prepare the low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material;
wherein the screw temperature of the double-screw extruder is 180 ℃, and the screw rotating speed is 200 r/min.
An application of low-smoke halogen-free flame-retardant ceramic thermoplastic polyolefin elastomer composite material in flame-retardant wires, cables and optical cables.
Example 2
A low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following raw materials in parts by weight:
thermoplastic polyolefin elastomer 5 parts
EVA resin 4 parts
4 parts of ethylene propylene rubber
Polyester staple fiber 8 parts
30 portions of halogen-free flame retardant
3 portions of smoke suppressant
40 portions of ceramic powder
2 portions of compatilizer
0.04 part of antioxidant.
The thermoplastic polyolefin elastomer is at least one of ethylene-octene copolymer and polystyrene elastomer; the polystyrene elastomer is a styrene-isoprene-styrene block copolymer.
The halogen-free flame retardant is melamine and compounds thereof.
The smoke suppressant is an iron compound.
The ceramic powder is composed of at least one of boron compound, low-softening-point glass powder and glass fiber and mineral filler; the mineral filler is mica powder, talcum powder, feldspar powder or brucite powder; the boron compound is borax; the low softening point glass powder is calcium oxide glass powder or bismuth oxide glass powder; the glass fiber is alkali-free chopped glass fiber with monofilament diameter of 2 μm and length of 15 μm.
The compatilizer is a hydrogenated thermoplastic styrene-butadiene rubber-maleic anhydride graft, a hydrogenated thermoplastic styrene-butadiene rubber-polyurethane graft, a thermoplastic styrene-butadiene rubber-maleic anhydride graft, a hydrogenated thermoplastic styrene-butadiene rubber-thermoplastic polyurethane copolymer or a thermoplastic styrene-butadiene rubber-methyl methacrylate graft.
The antioxidant is N, N' -bis [ [3- (3,5) -di-tert-butyl-4-hydroxyphenyl ] propionyl ] hexanediamine.
Also comprises 0.4 part of anti-ultraviolet agent and 0.8 part of lubricant.
A preparation method of a low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following steps:
(1) weighing the raw materials according to the weight ratio, mixing, and putting into a high-speed blender for uniformly mixing to obtain a mixture;
(2) extruding and granulating the mixture through a double-screw extruder to prepare the low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material;
wherein the screw temperature of the double-screw extruder is 200 ℃, and the screw rotating speed is 300 r/min.
An application of low-smoke halogen-free flame-retardant ceramic thermoplastic polyolefin elastomer composite material in flame-retardant wires, cables and optical cables.
Example 3
A low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following raw materials in parts by weight:
50 parts of thermoplastic polyolefin elastomer
EVA resin 6 parts
Ethylene propylene rubber 6 parts
Polyester staple fiber 10 parts
45 parts of halogen-free flame retardant
5 portions of smoke suppressant
50 portions of ceramic powder
Compatilizer 3 parts
0.06 part of antioxidant.
The thermoplastic polyolefin elastomer is at least one of ethylene-octene copolymer and polystyrene elastomer; the polystyrene elastomer is a styrene-ethylene-butylene-styrene block copolymer.
The halogen-free flame retardant is zinc borate, montmorillonite or clay.
The smoke suppressant is a metal oxide.
The ceramic powder is composed of at least one of boron compound, low-softening-point glass powder and glass fiber and mineral filler; the mineral filler is boron-magnesium stone powder, forsterite powder, silico-calcium-boron stone powder, chlorite powder or pyrophyllite powder; the boron compound is ammonium borate; the low-softening-point glass powder is phosphate glass powder; the glass fiber is alkali-free chopped glass fiber with monofilament diameter of 3 μm and length of 30 μm.
The compatilizer is an ethylene-octene copolymer grafted maleic anhydride polymer, a styrene-butadiene-styrene block copolymer grafted maleic anhydride polymer or an ethylene propylene diene monomer grafted maleic anhydride polymer.
The antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite.
Also comprises 0.6 part of anti-ultraviolet agent and 1 part of lubricant.
A preparation method of a low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following steps:
(1) weighing the raw materials according to the weight ratio, mixing, and putting into a high-speed blender for uniformly mixing to obtain a mixture;
(2) extruding and granulating the mixture through a double-screw extruder to prepare the low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material;
wherein the screw temperature of the double-screw extruder is 210 ℃, and the screw rotating speed is 400 r/min.
An application of low-smoke halogen-free flame-retardant ceramic thermoplastic polyolefin elastomer composite material in flame-retardant wires, cables and optical cables.
Example 4
A low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following raw materials in parts by weight:
65 parts of thermoplastic polyolefin elastomer
EVA resin 8 parts
Ethylene propylene rubber 8 parts
Polyester staple fiber 12 parts
60 parts of halogen-free flame retardant
8 portions of smoke suppressant
60 portions of ceramic powder
4 portions of compatilizer
0.08 part of antioxidant.
The thermoplastic polyolefin elastomer is at least one of ethylene-octene copolymer and polystyrene elastomer; the polystyrene elastomer is a styrene-ethylene-propylene-styrene block copolymer.
The halogen-free flame retardant is a metal hydroxide or an organic phosphate compound.
The smoke suppressant is a magnesium-zinc compound.
The ceramic powder is composed of at least one of boron compound, low-softening-point glass powder and glass fiber and mineral filler; the mineral filler is montmorillonite powder, calcite powder, limestone powder or potassium feldspar powder; the boron compound is zinc borate; the low-softening-point glass powder is silicate glass powder; the glass fiber is alkali-free chopped glass fiber with monofilament diameter of 4 μm and length of 45 μm.
The compatilizer is divinyl tetramethyl disiloxane, vinyl triethoxy siloxane, vinyl trichlorosilane, vinyl tri (beta-methoxyethoxy) silane, gamma-glycidyl ether oxypropyl trimethoxysilane, gamma-methacryloxypropyl-trimethoxysilane or N- (beta-aminoethyl) -gamma-aminopropyl-methyl-trimethoxysilane.
The antioxidant is pentaerythritol diphosphite stearyl alcohol ester.
Also comprises 0.8 part of anti-ultraviolet agent and 1.2 parts of lubricant.
A preparation method of a low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following steps:
(1) weighing the raw materials according to the weight ratio, mixing, and putting into a high-speed blender for uniformly mixing to obtain a mixture;
(2) extruding and granulating the mixture through a double-screw extruder to prepare the low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material;
wherein the screw temperature of the double-screw extruder is 220 ℃, and the screw rotating speed is 500 r/min.
An application of low-smoke halogen-free flame-retardant ceramic thermoplastic polyolefin elastomer composite material in flame-retardant wires, cables and optical cables.
Example 5
A low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following raw materials in parts by weight:
80 parts of thermoplastic polyolefin elastomer
10 portions of EVA resin
10 portions of ethylene propylene rubber
Polyester staple fiber 15 parts
70 portions of halogen-free flame retardant
10 portions of smoke suppressant
80 portions of ceramic powder
5 portions of compatilizer
0.1 part of antioxidant.
The thermoplastic polyolefin elastomer is at least one of ethylene-octene copolymer and polystyrene elastomer; the polystyrene elastomer is a styrene-butadiene-styrene block copolymer.
The halogen-free flame retardant is an organic hypophosphite compound or polyhydric alcohol.
The smoke suppressant is a zinc compound.
The ceramic powder is composed of at least one of boron compound, low-softening-point glass powder and glass fiber and mineral filler; the mineral filler is wollastonite powder, spodumene powder or diopside powder; the boron compound is boron frit; the low-softening-point glass powder is borate glass powder; the glass fiber is alkali-free chopped glass fiber with monofilament diameter of 5 μm and length of 60 μm.
The compatilizer is gamma-chloropropyl-trimethoxy silicon, gamma-mercaptopropyl-trimethoxy silane, gamma-aminopropyl triethoxy silane, 3-isocyanatopropyl triethoxy silane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane or N- (beta-aminoethyl) -gamma-aminopropyl-trimethoxy silane.
The antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate.
Also comprises 1.0 part of uvioresistant agent and 1.5 parts of lubricant.
A preparation method of a low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material comprises the following steps:
(1) weighing the raw materials according to the weight ratio, mixing, and putting into a high-speed blender for uniformly mixing to obtain a mixture;
(2) extruding and granulating the mixture through a double-screw extruder to prepare the low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material;
wherein the screw temperature of the double-screw extruder is 240 ℃, and the screw rotating speed is 600 r/min.
An application of low-smoke halogen-free flame-retardant ceramic thermoplastic polyolefin elastomer composite material in flame-retardant wires, cables and optical cables.
Example 6
This embodiment is different from embodiment 1 described above in that:
the thermoplastic polyolefin is a mixture of an ethylene-octene copolymer and a styrene-ethylene-butene-styrene block copolymer in a weight ratio of 1: 0.4.
The halogen-free flame retardant is a mixture of polycyanurate cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite in a weight ratio of 1:0.8:1: 0.4.
The smoke suppressant is a mixture of ferrocene, antimony trioxide and zinc borate in a weight ratio of 0.5:1.5: 1.
The ceramic powder is a mixture of a boron compound, low-softening-point glass powder, glass fibers and a mineral filler in a weight ratio of 0.8:1:0.4: 0.5.
The boron compound is a mixture of borax, ammonium borate and zinc borate in a weight ratio of 0.5-1.5:1: 0.4-0.8.
The softening point glass powder is a mixture of bismuth oxide glass powder, phosphate glass powder, silicate glass powder and borate glass powder in a weight ratio of 0.4:0.8:1: 0.5.
The mineral filler is a mixture of talcum powder, mica powder and wollastonite powder in a weight ratio of 1:0.3: 0.8.
The compatilizer is prepared by grafting maleic anhydride to polyolefin, ethylene propylene diene monomer to maleic anhydride polymer and gamma-aminopropyltriethoxysilane according to the weight ratio of 1:0.5:1, in a mixture of the components.
The antioxidant is a mixture of tetra [ methylene-3, 5- (di-tert-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester, tris [2, 4-di-tert-butylphenyl ] phosphite and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate in a weight ratio of 1:0.2: 0.4.
The ultraviolet absorbent is a mixture of an ultraviolet absorbent UV-531, an ultraviolet absorbent RMB and a light stabilizer 744 in a weight ratio of 0.8:0.5: 1.
The lubricant is a mixture consisting of oxidized polyethylene wax, pentaerythritol stearate and amine N, N-ethylene bisricinoleate in a weight ratio of 2:0.5: 1.
The ceramic powder is subjected to surface treatment by a high molecular polymer, and the high molecular polymer is a mixture of polyvinyl alcohol, trimethyl nonanol polyoxyethylene ether and polyoxyethylene sorbitol fatty acid ester in a weight ratio of 1:0.8: 0.4.
Example 7
This embodiment is different from embodiment 2 described above in that:
the thermoplastic polyolefin is a mixture of an ethylene-octene copolymer and a styrene-ethylene-butene-styrene block copolymer in a weight ratio of 1: 0.5.
The halogen-free flame retardant is a mixture of polycyanurate cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite in a weight ratio of 1.2:0.9:1: 0.5.
The smoke suppressant is a mixture of ferrocene, antimony trioxide and zinc borate in a weight ratio of 0.8:1.8: 1.
The ceramic powder is a mixture of a boron compound, low-softening-point glass powder, glass fibers and a mineral filler in a weight ratio of 0.9:1:0.5: 0.8.
The boron compound is a mixture of borax, ammonium borate and zinc borate in a weight ratio of 0.8:1: 0.5.
The softening point glass powder is a mixture of bismuth oxide glass powder, phosphate glass powder, silicate glass powder and borate glass powder in a weight ratio of 0.5:0.9:1: 0.8.
The mineral filler is a mixture of talcum powder, mica powder and wollastonite powder in a weight ratio of 1:0.4: 0.9.
The compatilizer is prepared by mixing maleic anhydride grafted polyolefin, ethylene propylene diene monomer grafted maleic anhydride polymer and gamma-aminopropyltriethoxysilane in a weight ratio of 1.5: 0.8:1, in a mixture of the components.
The antioxidant is a mixture of tetra [ methylene-3, 5- (di-tert-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester, tris [2, 4-di-tert-butylphenyl ] phosphite and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate in a weight ratio of 1:0.3: 0.5.
The ultraviolet absorbent is a mixture of an ultraviolet absorbent UV-531, an ultraviolet absorbent RMB and a light stabilizer 744 in a weight ratio of 0.9:0.8: 1.
The lubricant is a mixture consisting of oxidized polyethylene wax, pentaerythritol stearate and amine N, N-ethylene bisricinoleate in a weight ratio of 2.5:0.8: 1.
The ceramic powder is subjected to surface treatment by a high molecular polymer, and the high molecular polymer is a mixture of polyvinyl alcohol, trimethyl nonanol polyoxyethylene ether and polyoxyethylene sorbitol fatty acid ester in a weight ratio of 1:0.9: 0.5.
Example 8
This embodiment is different from embodiment 3 described above in that:
the thermoplastic polyolefin is a mixture of an ethylene-octene copolymer and a styrene-ethylene-butene-styrene block copolymer in a weight ratio of 1: 0.6.
The halogen-free flame retardant is a mixture of polycyanurate cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite in a weight ratio of 1.5:1:1: 0.6.
The smoke suppressant is a mixture of ferrocene, antimony trioxide and zinc borate in a weight ratio of 1:2: 1.
The ceramic powder is a mixture of a boron compound, low-softening-point glass powder, glass fibers and a mineral filler in a weight ratio of 1:1:0.6: 1.
The boron compound is a mixture of borax, ammonium borate and zinc borate in a weight ratio of 1:1: 0.6.
The softening point glass powder is a mixture of bismuth oxide glass powder, phosphate glass powder, silicate glass powder and borate glass powder in a weight ratio of 0.6:1:1: 1.
The mineral filler is a mixture of talcum powder, mica powder and wollastonite powder in a weight ratio of 1:0.5: 1.
The compatilizer is prepared by mixing maleic anhydride grafted polyolefin, ethylene propylene diene monomer grafted maleic anhydride polymer and gamma-aminopropyltriethoxysilane in a weight ratio of 1.5:1:1, in a mixture of the components.
The antioxidant is a mixture of tetra [ methylene-3, 5- (di-tert-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester, tris [2, 4-di-tert-butylphenyl ] phosphite and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate in a weight ratio of 1:0.4: 0.6.
The ultraviolet absorbent is a mixture of an ultraviolet absorbent UV-531, an ultraviolet absorbent RMB and a light stabilizer 744 in a weight ratio of 1:1:1.
The lubricant is a mixture of oxidized polyethylene wax, pentaerythritol stearate and N, N-ethylene bisricinoleate in a weight ratio of 3:1: 1.
The ceramic powder is subjected to surface treatment by a high molecular polymer, and the high molecular polymer is a mixture of polyvinyl alcohol, trimethyl nonanol polyoxyethylene ether and polyoxyethylene sorbitol fatty acid ester in a weight ratio of 1:1: 0.6.
Example 9
This embodiment is different from embodiment 4 described above in that:
the thermoplastic polyolefin is a mixture of an ethylene-octene copolymer and a styrene-ethylene-butene-styrene block copolymer in a weight ratio of 1: 0.7.
The halogen-free flame retardant is a mixture of polycyanurate cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite in a weight ratio of 1.8:1.1:1: 0.7.
The smoke suppressant is a mixture of ferrocene, antimony trioxide and zinc borate in a weight ratio of 1.2:2.2: 1.
The ceramic powder is a mixture of a boron compound, low-softening-point glass powder, glass fibers and a mineral filler in a weight ratio of 1.1:1:0.7: 1.2.
The boron compound is a mixture of borax, ammonium borate and zinc borate in a weight ratio of 1.2:1: 0.7.
The softening point glass powder is a mixture of bismuth oxide glass powder, phosphate glass powder, silicate glass powder and borate glass powder in a weight ratio of 0.7:1.1:1: 1.2.
The mineral filler is a mixture of talcum powder, mica powder and wollastonite powder in a weight ratio of 1:0.6: 1.1.
The compatilizer is prepared by mixing maleic anhydride grafted polyolefin, ethylene propylene diene monomer grafted maleic anhydride polymer and gamma-aminopropyltriethoxysilane in a weight ratio of 1.8: 1.2:1, in a mixture of the components.
The antioxidant is a mixture of tetra [ methylene-3, 5- (di-tert-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester, tris [2, 4-di-tert-butylphenyl ] phosphite and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate in a weight ratio of 1:0.5: 0.7.
The ultraviolet absorbent is a mixture consisting of an ultraviolet absorbent UV-531, an ultraviolet absorbent RMB and a light stabilizer 744 in a weight ratio of 1.1:1.2: 1.
The lubricant is a mixture consisting of oxidized polyethylene wax, pentaerythritol stearate and amine N, N-ethylene bisricinoleate in a weight ratio of 3.5:1.2: 1.
The ceramic powder is subjected to surface treatment by a high molecular polymer, and the high molecular polymer is a mixture of polyvinyl alcohol, trimethyl nonanol polyoxyethylene ether and polyoxyethylene sorbitol fatty acid ester in a weight ratio of 1:1.1: 0.7.
Example 10
This embodiment is different from embodiment 5 described above in that:
the thermoplastic polyolefin is a mixture of an ethylene-octene copolymer and a styrene-ethylene-butene-styrene block copolymer in a weight ratio of 1: 0.8.
The halogen-free flame retardant is a mixture of polycyanurate cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite in a weight ratio of 2:1.2:1: 0.8.
The smoke suppressant is a mixture of ferrocene, antimony trioxide and zinc borate in a weight ratio of 1.5:2.5: 1.
The ceramic powder is a mixture of a boron compound, low-softening-point glass powder, glass fibers and a mineral filler in a weight ratio of 1.2:1:0.8: 1.5.
The boron compound is a mixture of borax, ammonium borate and zinc borate in a weight ratio of 1.5:1: 0.8.
The softening point glass powder is a mixture of bismuth oxide glass powder, phosphate glass powder, silicate glass powder and borate glass powder in a weight ratio of 0.8:1.2:1: 1.5.
The mineral filler is a mixture of talcum powder, mica powder and wollastonite powder in a weight ratio of 1:0.7: 1.2.
The compatilizer is prepared by mixing maleic anhydride grafted polyolefin, ethylene propylene diene monomer grafted maleic anhydride polymer and gamma-aminopropyltriethoxysilane in a weight ratio of 2:1.5:1, in a mixture of the components.
The antioxidant is a mixture of tetra [ methylene-3, 5- (di-tert-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester, tris [2, 4-di-tert-butylphenyl ] phosphite and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate in a weight ratio of 1:0.6: 0.8.
The ultraviolet absorbent is a mixture of an ultraviolet absorbent UV-531, an ultraviolet absorbent RMB and a light stabilizer 744 in a weight ratio of 1.2:1.5: 1.
The lubricant is a mixture consisting of oxidized polyethylene wax, pentaerythritol stearate and amine N, N-ethylene bisricinoleate in a weight ratio of 4:1.5: 1.
The ceramic powder is subjected to surface treatment by a high molecular polymer, and the high molecular polymer is a mixture of polyvinyl alcohol, trimethyl nonanol polyoxyethylene ether and polyoxyethylene sorbitol fatty acid ester in a weight ratio of 1:1.2: 0.8.
Comparative example 1
The Chinese patent application No. 201510113925.1, inventive example 39, was used as comparative example 34, and the formulation of the raw materials was as follows: linear low density polyethylene LDPE/HDPE (70/30): 40 parts of low-softening-point glass powder: 15 parts, mica: 15 parts, flame retardant MP: 29 parts, LDH: 1 part, antioxidant MB: 1 part, plasticizer DINP: 2.5 parts of a cross-linking agent DCP: 0.05 part.
Comparative example 2
The Chinese patent application No. 201510113925.1, inventive example 40, was used as comparative example 35, and the formulation of the raw materials was as follows: polyolefin elastomer POE: 30 parts of low-softening-point glass powder: 22.5 parts, mica: 22.5 parts, flame retardant MyPA: 20 parts, OMMT: 5 parts, antioxidant DNP: 1 part, plasticizer DINP: 2.5 parts of a cross-linking agent DCP: 0.05 part.
The low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite materials prepared in examples 1 to 10 and the ceramizable flame-retardant polymer composite materials prepared in comparative examples 1 to 2 were respectively tested, the flame retardancy was tested according to IEC 60332.1.2 standard, the fire retardancy was tested according to EN50575 standard (classified into Aca, B1ca, B2ca, Cca, Dca, Eca and Fca7 grades, and the Aca fire retardancy was the best), the smoke density was tested according to IEC61034 standard (required light transmittance not less than 60%), and the test results are shown in the following table:
test items Tensile strength (Mpa) Elongation at Break (%) Flame retardancy test Fire test Smoke Density test
Example 1 18.3 420 By passing Cca The light transmittance is 71 percent
Example 2 19.8 440 By passing Cca The light transmittance is 72%
Example 3 20.6 480 By passing Cca Light transmittance of 73%
Example 4 20.1 470 By passing Cca The light transmittance is 72%
Example 5 19.3 460 By passing Cca The light transmittance is 71 percent
Example 6 20.3 450 By passing Cca The light transmittance is 72%
Example 7 20.2 470 By passing Cca Transmittance of 74%
Example 8 21.5 490 By passing Cca The light transmittance is 75 percent
Example 9 20.7 480 By passing Cca The light transmittance is 75 percent
Example 10 19.9 460 By passing Cca Light transmittance of 73%
Comparative example 1 13.8 350 Do not pass through Eca Transmittance is 46%
Comparative example 2 14.1 360 Do not pass through Eca The light transmittance is 47%
From the table, the flame retardant performance of the low-smoke halogen-free flame retardant ceramizable thermoplastic polyolefin elastomer composite material prepared by the invention meets the VW-1 international cable combustion standard of UL1581 and the IEC 60332.1.2 European Union cable single combustion test standard, the light transmittance after combustion can reach more than 70%, the smoke density meets the international IEC61034 cable combustion smoke density test standard, and compared with the existing low-smoke halogen-free flame retardant material, the low-smoke halogen-free flame retardant ceramizable thermoplastic polyolefin elastomer composite material has better mechanical performance.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.

Claims (3)

1. A low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material is characterized in that: the feed comprises the following raw materials in parts by weight:
50-65 parts of thermoplastic polyolefin elastomer
EVA resin 2-10 weight portions
2-10 parts of ethylene propylene rubber
5-15 parts of polyester staple fiber
45-60 parts of halogen-free flame retardant
1-10 parts of smoke suppressant
50-60 parts of vitrified powder
0.5 to 5 portions of compatilizer
0.02-0.1 part of antioxidant
0.2 to 1.0 portion of anti-ultraviolet agent
0.5-1.5 parts of a lubricant;
the thermoplastic polyolefin is a mixture of an ethylene-octene copolymer and a styrene-ethylene-butene-styrene block copolymer in a weight ratio of 1: 0.4-0.8;
the halogen-free flame retardant is a mixture consisting of melamine cyanurate, triphenyl phosphate, magnesium hydroxide and montmorillonite in a weight ratio of 1-2:0.8-1.2:1: 0.4-0.8;
the smoke suppressant is a mixture consisting of ferrocene, antimony trioxide and zinc borate in a weight ratio of 0.5-1.5:1.5-2.5: 1;
the ceramic powder is a mixture consisting of a boron compound, low-softening-point glass powder, glass fibers and mineral fillers in a weight ratio of 0.8-1.2:1:0.4-0.8: 0.5-1.5; the boron compound is a mixture of borax, ammonium borate and zinc borate in a weight ratio of 0.5-1.5:1: 0.4-0.8; the low-softening-point glass powder is a mixture consisting of bismuth oxide glass powder, phosphate glass powder, silicate glass powder and borate glass powder in a weight ratio of 0.4-0.8:0.8-1.2:1: 0.5-1.5; the mineral filler is a mixture consisting of talcum powder, mica powder and wollastonite powder in a weight ratio of 1:0.3-0.7: 0.8-1.2;
the glass fiber is alkali-free chopped glass fiber with monofilament diameter of 0.1-5 μm and length of 5-60 μm;
the compatilizer is prepared by grafting maleic anhydride to polyolefin, ethylene propylene diene monomer to maleic anhydride polymer and gamma-aminopropyltriethoxysilane according to the weight ratio of 1-2: 0.5-1.5: 1;
the antioxidant is a mixture of tetra [ methylene-3, 5- (di-tert-butyl-4-hydroxy-phenyl) propionate ] pentaerythritol ester, tris [2, 4-di-tert-butylphenyl ] phosphite and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate in a weight ratio of 1:0.2-0.6: 0.4-0.8;
the anti-ultraviolet agent is a mixture consisting of an ultraviolet absorbent UV-531, an ultraviolet absorbent RMB and a light stabilizer 744 in a weight ratio of 0.8-1.2:0.5-1.5: 1;
the lubricant is a mixture of oxidized polyethylene wax, pentaerythritol stearate and N, N-ethylene bisricinoleate in a weight ratio of 2-4:0.5-1.5: 1.
2. The preparation method of the low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material according to claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps:
(1) weighing the raw materials according to the weight ratio, mixing, and putting into a high-speed blender for uniformly mixing to obtain a mixture;
(2) extruding and granulating the mixture through a double-screw extruder to prepare the low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material;
wherein the screw temperature of the double-screw extruder is 180-240 ℃, and the screw rotating speed is 200-600 r/min.
3. The use of a low smoke, zero halogen, flame retardant ceramifiable thermoplastic polyolefin elastomer composite as claimed in claim 1 in flame retardant wire, cable and cable applications.
CN201710642756.XA 2017-07-31 2017-07-31 Low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material and preparation method and application thereof Active CN107383576B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710642756.XA CN107383576B (en) 2017-07-31 2017-07-31 Low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710642756.XA CN107383576B (en) 2017-07-31 2017-07-31 Low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN107383576A CN107383576A (en) 2017-11-24
CN107383576B true CN107383576B (en) 2021-01-15

Family

ID=60343230

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710642756.XA Active CN107383576B (en) 2017-07-31 2017-07-31 Low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN107383576B (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11472926B2 (en) * 2017-10-10 2022-10-18 Nano And Advanced Materials Institute Limited Impact protection material and method of making the same
CN109810371A (en) * 2017-11-22 2019-05-28 宝胜科技创新股份有限公司 A kind of thermoplastic halogen-free and low-smoke flame-retardant can ceramic polyolefin oxygen barrier material
CN108003411A (en) * 2017-12-21 2018-05-08 扬州市金鑫电缆有限公司 Can be into porcelain low-smoke halogen-free polyolefin cable material and preparation method thereof
CN108456429A (en) * 2018-01-15 2018-08-28 东莞市安拓普塑胶聚合物科技有限公司 A kind of thermoplastic elastomer (TPE) and its preparation method and application that Applicable temperature range is wide
CN108395729A (en) * 2018-02-01 2018-08-14 天津科创复兴科技咨询有限公司 A kind of high temperature resistant TPE material and its preparation method and application
CN110240797A (en) * 2018-03-09 2019-09-17 中国石油化工股份有限公司 3D printing composition and its preparation method and application
JP7429972B2 (en) * 2018-05-08 2024-02-09 積水フーラー株式会社 Synthetic resin compositions, fireproof materials, sealants, adhesives and joint structures
CN109627745A (en) * 2018-12-27 2019-04-16 武汉德航联合科技有限公司 A kind of filler particles and preparation method thereof for runway
CN112552584A (en) * 2019-09-26 2021-03-26 合肥杰事杰新材料股份有限公司 Novel flame-retardant polypropylene composite material capable of being ceramized and preparation method thereof
CN111540521B (en) * 2020-05-12 2022-01-07 陕西西特电缆有限公司 Anti-pressure anti-interference flame-retardant composite cable
CN113004638B (en) * 2021-03-11 2023-03-28 西华大学 Flame-retardant cable material and preparation method thereof
CN113563663B (en) * 2021-07-22 2023-09-12 广东聚石化学股份有限公司 Fireproof low-smoke halogen-free soft material and preparation method thereof
CN113462068B (en) * 2021-07-22 2023-01-06 广东聚石化学股份有限公司 Flame-retardant oxygen-barrier layer material and preparation method thereof
CN115141459A (en) * 2022-08-03 2022-10-04 江苏卡续曼新材料科技有限公司 Flame retardant method based on blending modification of thermoplastic high polymer material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104497404A (en) * 2014-12-31 2015-04-08 深圳市沃尔核材股份有限公司 Porcelainized polyolefin composite material and preparation method thereof
CN104650441A (en) * 2015-03-16 2015-05-27 四川大学 Ceramic bovine flame retardant polymer composite material and application thereof
CN106336563A (en) * 2016-08-23 2017-01-18 江苏上上电缆集团有限公司 Ceramic polyolefin cable material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104497404A (en) * 2014-12-31 2015-04-08 深圳市沃尔核材股份有限公司 Porcelainized polyolefin composite material and preparation method thereof
CN104650441A (en) * 2015-03-16 2015-05-27 四川大学 Ceramic bovine flame retardant polymer composite material and application thereof
CN106336563A (en) * 2016-08-23 2017-01-18 江苏上上电缆集团有限公司 Ceramic polyolefin cable material and preparation method thereof

Also Published As

Publication number Publication date
CN107383576A (en) 2017-11-24

Similar Documents

Publication Publication Date Title
CN107383576B (en) Low-smoke halogen-free flame-retardant ceramizable thermoplastic polyolefin elastomer composite material and preparation method and application thereof
CN107286637B (en) Low-smoke halogen-free flame-retardant ceramic thermoplastic polyurethane elastomer composite material and preparation method and application thereof
CN107286636B (en) Low-smoke flame-retardant ceramic thermoplastic polyurethane elastomer composite material and preparation method and application thereof
CN107236238A (en) A kind of low-smoke and flame retardant can ceramifiable thermoplastic's polyolefin elastic composite material and its preparation method and application
CN107286518A (en) A kind of low-smoke and flame retardant can ceramic PVC material and its preparation method and application
JP7198361B2 (en) Flame retardant mixtures, flame retardant polymer compositions, cables provided therewith and uses thereof
US7851559B2 (en) Soft zero halogen flame retardant thermoplastic elastomers
CN104650441B (en) One kind can ceramic flame-retardant high-molecular composite and application
JP5425774B2 (en) Halogen-free flame retardant
AU2007242059B2 (en) Fire resistant compositions
CN107254135A (en) A kind of low-smoke halogen-free flame-retardant thermoplastic polyolefin elastomer and its preparation method and application
US20060089444A1 (en) Flame retardant polymer compositions comprising a particulate clay mineral
CN108250726A (en) A kind of fire-retardant TPU cable jacket materials with electro-magnetic screen function and preparation method thereof
MX2010010227A (en) Low-smoke, fire-resistant and water-resistant cable coating.
CN104231409A (en) EVA/MLLDPE (ethylene-vinyl acetate/metallocene linear low-density polyethylene) component-type low-smoke halogen-free irradiation-crosslinked wire cable material, and preparation method and application thereof
CN104403181A (en) Low-smoke halogen-free high-flame-retardant crosslinked polyethylene wire and cable material and preparation method thereof
US11031152B2 (en) Flame- retardant electrical cable
CN105308102A (en) Heat-resistant silane crosslinked resin molded article and method for manufacturing same, and heat-resistant product equipped with heat-resistant silane crosslinked resin molded article
CN111303619A (en) Low-smoke halogen-free ceramic flame-retardant thermoplastic polyurethane elastomer composite material and preparation method thereof
CN103525075A (en) High-flame-retardation highly-heatproof halogen-free flame-retardant thermoplastic cable material
JP7130137B2 (en) Flame-retardant mixture, flame-retardant polymer composition, cable with same and use thereof
KR100688643B1 (en) Composition for production flame retardant insulating material of halogen free type
KR100688642B1 (en) Composition for production flame retardant insulating material of halogen free type
WO2023279660A1 (en) Flame-retardant polyolefin composite material, and preparation method therefor and use thereof
KR20120050096A (en) Polypropylene resin composition containing non-halogen frame retardant for electric cable

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 523127 Dongcheng District Tongsha Science and Technology Park Guanghui Industrial Zone, Dongguan City, Guangdong Province

Applicant after: Guangdong Antopu Polymer Technology Co.,Ltd.

Address before: 523000 Area B and E, Building 2, Guanghui Industrial Zone, Tongsha Science Park, Dongcheng District, Dongguan City, Guangdong Province

Applicant before: ADVANCED THERMOPLASTIC POLYMER TECHNOLOGY Co.,Ltd.

CB02 Change of applicant information
CB02 Change of applicant information

Address after: 523000 Dongcheng Street Tongsha Science Park Guanghui Industrial Zone, Dongguan City, Guangdong Province

Applicant after: Guangdong Antopu Polymer Technology Co.,Ltd.

Address before: 523127 Dongcheng District Tongsha Science and Technology Park Guanghui Industrial Zone, Dongguan City, Guangdong Province

Applicant before: Guangdong Antopu Polymer Technology Co.,Ltd.

GR01 Patent grant
GR01 Patent grant
CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: 523000 area B2, D and E2, building 2, Guanghui Industrial Zone, Tongsha Science Park, Dongcheng Street, Dongguan City, Guangdong Province

Patentee after: Guangdong Antop Polymer Technology Co.,Ltd.

Address before: 523000 area B2, D and E2, building 2, Guanghui Industrial Zone, Tongsha Science Park, Dongcheng Street, Dongguan City, Guangdong Province

Patentee before: Guangdong Antopu Polymer Technology Co.,Ltd.