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CN105086126A - Environmental-protection high-fire-retardant cable insulation material and preparation method thereof - Google Patents

Environmental-protection high-fire-retardant cable insulation material and preparation method thereof Download PDF

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Publication number
CN105086126A
CN105086126A CN201510548819.6A CN201510548819A CN105086126A CN 105086126 A CN105086126 A CN 105086126A CN 201510548819 A CN201510548819 A CN 201510548819A CN 105086126 A CN105086126 A CN 105086126A
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fire retardant
nitrogen phosphorus
mass parts
phosphorus fire
retardant
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Inventor
徐德生
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Wuxi Jiabang Electric Power Pipeline Factory
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Wuxi Jiabang Electric Power Pipeline Factory
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Priority to CN201510548819.6A priority Critical patent/CN105086126A/en
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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
    • 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 four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Insulated Conductors (AREA)

Abstract

The invention provides an environmental-protection high-fire-retardant cable insulation material, which comprises 30 to 50 parts of EVA (ethylene vinyl acetate) copolymer, 20 to 50 parts of methyl vinyl silicone rubber, 4 to 6 parts of glass powder, 10 to 15 parts of nitrogen-phosphorus flame retardant, 2 to 7 parts of compatilizer, 1 to 5 parts of antioxygen, 1 to 5 parts of vulcanizing agent and 1 to 5 parts of cross-linking agent in parts by mass, wherein the nitrogen-phosphorus flame retardant is the nitrogen-phosphorus flame retardant of which the surface is activated by silane or titanate. The cable insulation material provided by the invention avoids the use of the traditional organic halide flame retardant, does not contain halogen, has higher flame retardant property and is excellent in strength.

Description

A kind of environmental protection high flame-retardant cable insulating material and preparation method thereof
Technical field
The present invention relates to cable insulation material technical field, particularly relate to a kind of environmental protection high flame-retardant cable insulating material and preparation method thereof.
Background technology
In recent years, along with the develop rapidly of the relevant industries such as motor, electronic apparatus, automobile and irradiation crosslinking technological are in the widespread use of electric wire industry, cross-linking radiation electric wire is also in development trend faster.At present, cross-linking radiation electric wire is successfully applied to the industries such as motor, temperature-sensing element, high-power lamp decoration, the control of automobile low-voltage signal, all kinds of locomotive, track traffic, mineral exploration and exploitation, the percussion of X-ray high pressure and high power transmission.Wherein, what be most widely used is cross-linked polyolefin cable insulating material.
Cross-linked polyolefin cable insulating material, is adopt physical irradiation methods, facilitates polyolefine material to be cross-linked, thus form new more stable network molecular structure.Crosslinked polyolefin insulating material after irradiation has high temperature resistant, heat shock resistance, resistance to ozone, chemically-resistant solvent and good electrical insulation properties, and work-ing life of extending wire cable etc. advantage, be thus widely used.
Good cross-linked polyolefin cable insulating material needs to have higher flame retardant properties, meets environmental requirement simultaneously; But cross-linked polyolefin cable insulating material prepared by prior art, while having good flame-retardance energy, all containing halogen, can pollute environment, can not reach the requirement of environmental protection.
CN103333404A discloses a kind of environmental protection high flame retardant cross-linked polyolefin cable insulating material, comprising: EVA multipolymer 60 ~ 90 mass parts; Nitrogen phosphorus fire retardant 10 ~ 15 mass parts; Compatilizer 2 ~ 7 mass parts; Oxidation inhibitor 1 ~ 5 mass parts; Linking agent 1 ~ 5 mass parts; Described nitrogen phosphorus fire retardant is the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation.But the intensity of this cable insulation material is lower, and flame retardant properties need further raising.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of environmental protection high flame-retardant cable insulating material and preparation method thereof, and the cable insulation material of preparation has higher flame retardant properties, not halogen-containing, and mechanical property is better.
The invention provides a kind of environmental protection high flame-retardant cable insulating material, comprising:
EVA multipolymer 30 ~ 50 mass parts;
Methyl vinyl silicone rubber 20 ~ 50 mass parts;
Glass powder 4 ~ 6 mass parts;
Nitrogen phosphorus fire retardant 10 ~ 15 mass parts;
Compatilizer 2 ~ 7 mass parts;
Oxidation inhibitor 1 ~ 5 mass parts;
Vulcanizing agent 1 ~ 5 mass parts;
Linking agent 1 ~ 5 mass parts;
Described nitrogen phosphorus fire retardant is the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation.
EVA multipolymer containing 30 ~ 50 mass parts in cable insulation material provided by the invention, described EVA multipolymer can be 32 mass parts, 35 mass parts, 36 mass parts, 38 mass parts, 40 mass parts, 42 mass parts, 45 mass parts, 47 mass parts or 49 mass parts etc.; Methyl vinyl silicone rubber containing 20 ~ 50 mass parts, it can be 22 mass parts, 25 mass parts, 28 mass parts, 30 mass parts, 32 mass parts, 35 mass parts, 36 mass parts, 38 mass parts, 40 mass parts, 42 mass parts, 45 mass parts, 47 mass parts or 49 mass parts etc.; Glass powder containing 4 ~ 6 mass parts, it can be 4 mass parts, 5 mass parts or 6 mass parts etc.; Nitrogen phosphorus fire retardant containing 10 ~ 15 mass parts, it can be 12 mass parts, 13 mass parts, 14 mass parts or 15 mass parts etc.; Containing 2 ~ 7 mass parts compatilizers, it can be 3 mass parts, 4 mass parts, 5 mass parts, 6 mass parts or 7 mass parts etc.; Containing 1 ~ 5 mass parts oxidation inhibitor, it can be 2 mass parts, 3 mass parts, 4 mass parts or 5 mass parts etc.; Containing 1 ~ 5 mass parts vulcanizing agent, it can be 2 mass parts, 3 mass parts, 4 mass parts or 5 mass parts etc.; Containing 1 ~ 5 mass parts linking agent, it can be 2 mass parts, 3 mass parts, 4 mass parts or 5 mass parts etc.
Preferably, described EVA multipolymer is selected from the multipolymer of EVA and octene, propylene, butylene or amylene; Described compatilizer is maleic anhydride graft terpolymer EP rubber; Described oxidation inhibitor is antioxidant 1010, and described linking agent is propyl trimethoxy silicane; Described nitrogen phosphorus fire retardant is selected from nitrogen phosphorus fire retardant NPR, and described vulcanization system is DCP, TAIC, magnesium oxide and tetramethylolmethane.
Preferably, described environmental protection high flame-retardant cable insulating material also comprises the nano level polynite of 0.5 ~ 1.5 mass parts, as 0.6 mass parts, 0.7 mass parts, 0.8 mass parts, 0.9 mass parts, 1.0 mass parts, 1.1 mass parts, 1.2 mass parts, 1.3 mass parts or 1.4 mass parts etc.
Preferably, described nitrogen phosphorus fire retardant particle diameter is 5nm ~ 100nm, as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm or 90nm etc.
Present invention also offers a kind of preparation method of environmental protection high flame-retardant cable insulating material, comprising:
By EVA multipolymer, methyl vinyl silicone rubber, glass powder, nitrogen phosphorus fire retardant, compatilizer, oxidation inhibitor, vulcanizing agent and linking agent mixing, banburying, extrude, obtain cable insulation material.
Described nitrogen phosphorus fire retardant is the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation.
Preferably, described nitrogen phosphorus fire retardant is selected from nitrogen phosphorus fire retardant NPR; Described EVA multipolymer is selected from the multipolymer of EVA and octene, propylene, butylene or amylene; Described compatilizer is maleic anhydride graft terpolymer EP rubber; Described oxidation inhibitor is antioxidant 1010, and described linking agent is propyl trimethoxy silicane, and described vulcanization system is DCP, TAIC, magnesium oxide and tetramethylolmethane.
Preferably, the mass ratio of described EVA multipolymer, methyl vinyl silicone rubber, glass powder, nitrogen phosphorus fire retardant, compatilizer, oxidation inhibitor, vulcanizing agent and linking agent is (30 ~ 50): (20 ~ 50): (4 ~ 6): (10 ~ 15): (2 ~ 7): (1 ~ 5): (1 ~ 5): (1 ~ 5).
Preferably, nano level polynite is also comprised in described nitrogen phosphorus fire retardant.
Preferably, the massfraction that described nano level polynite accounts for described nitrogen phosphorus fire retardant is 5% ~ 10%, as 6%, 7%, 8%, 9% or 10% etc.
Preferably, the nitrogen phosphorus fire retardant of described surface after silane or titanic acid ester activation is prepared in accordance with the following methods:
Be scattered in solvent by nitrogen phosphorus fire retardant, heating, then adds silane coupling agent or titanate coupling agent reacts, and obtains the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation.
Compared with prior art, the invention provides a kind of environmental protection high flame retardant: cable insulation material, comprising: EVA multipolymer 30 ~ 50 mass parts; Methyl vinyl silicone rubber 20 ~ 50 mass parts; Glass powder 4 ~ 6 mass parts; Nitrogen phosphorus fire retardant 10 ~ 15 mass parts; Compatilizer 2 ~ 7 mass parts; Oxidation inhibitor 1 ~ 5 mass parts; Vulcanizing agent 1 ~ 5 mass parts; Linking agent 1 ~ 5 mass parts; Described nitrogen phosphorus fire retardant is the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation.The present invention adopts the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation as fire retardant, prepare cross-linked polyolefin cable insulating material, because the nitrogen phosphorus fire retardant surface after activation is with organic group, therefore, it is possible to disperse more uniformly in matrix resin, thus bring good flame retardant properties to product; Use traditional Organohalogen compounds fire retardant owing to avoiding simultaneously, and can not introduce halogens in the product, the cable insulation material therefore prepared has higher flame retardant properties, simultaneously not halogen-containing.
Carry out performance test to the cross-linked polyolefin cable insulating material of preparation, result shows, crosslinked polyolefin materials provided by the invention is not halogen-containing, and vertical combustion VW-1 is less than 10 seconds.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
The invention provides a kind of environmental protection high flame-retardant cable insulating material, comprising:
EVA multipolymer 30 ~ 50 mass parts;
Methyl vinyl silicone rubber 20 ~ 50 mass parts;
Glass powder 4 ~ 6 mass parts;
Nitrogen phosphorus fire retardant 10 ~ 15 mass parts;
Compatilizer 2 ~ 7 mass parts;
Oxidation inhibitor 1 ~ 5 mass parts;
Vulcanizing agent 1 ~ 5 mass parts;
Linking agent 1 ~ 5 mass parts;
Described nitrogen phosphorus fire retardant is the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation.
The present invention adopts the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation as fire retardant, prepare cable insulation material, because the nitrogen phosphorus fire retardant surface after activation is with organic group, therefore, it is possible to disperse more uniformly in matrix resin, thus bring good flame retardant properties to product; Use traditional Organohalogen compounds fire retardant owing to avoiding simultaneously, and can not introduce halogens in the product, the cable insulation material therefore prepared has higher flame retardant properties, simultaneously not halogen-containing.
Environmental protection high flame retardant cross-linked polyolefin cable insulating material provided by the invention, comprising:
EVA multipolymer, its content is preferably 30 ~ 50 mass parts; Described EVA multipolymer is preferably the multipolymer of EVA and octene, propylene, butylene or amylene; Be more preferably the multipolymer of EVA and octene or propylene.In the present invention, described EVA multipolymer is matrix resin, and the present invention there is no particular requirement to its preparation method, can be prepared according to the preparation method of EVA multipolymer well known to those skilled in the art, preferably, adopts following methods preparation:
EVA resin is mixed with alkene in Banbury mixer, after melting, adds linking agent and carry out melt blending, obtain EVA multipolymer.The present invention is preferred, and the weight ratio of described EVA and alkene is 1:(0.5 ~ 3), be more preferably 1:(0.8 ~ 2.5); Described linking agent is preferably linking agent PPF or linking agent PPCI; The mass ratio of described linking agent and EVA is preferably (0.2 ~ 0.5): 1; The temperature of described melt blending is preferably 120 DEG C ~ 150 DEG C, and the time of described melt blending is preferably 5min ~ 2h.
Cable insulation material provided by the invention not only has the EVA multipolymer of excellent insulation performance, and also containing methyl vinyl silicone rubber, its content is 20 ~ 50 weight parts.Experiment proves, the material insulation property that both combinations obtain is more excellent.
Containing glass powder in cable insulation material provided by the invention, its content is 4 ~ 6 mass parts, and effect is: when temperature is increased to glass powder softening temperature, and glass powder melting forms liquid phase, is filled between EVA multipolymer and methyl vinyl silicone rubber; Along with the prolongation of time, liquid phase infiltrates polymer network gradually, after cooling curing, plays bridging effect, reinforcing copolymer structure.
In the present invention, described environmental protection high flame-retardant cable insulating material also comprises nitrogen phosphorus fire retardant, and its content is preferably 10 ~ 15 mass parts, is more preferably 11 ~ 13 mass parts; Described nitrogen phosphorus fire retardant is preferably the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation, is more preferably the nitrogen phosphorus fire retardant NPR of surface after silane or titanic acid ester activation; Its particle diameter is preferably 5nm ~ 100nm, is more preferably 10nm ~ 50nm; The source of the present invention to described nitrogen phosphorus fire retardant NPR there is no particular requirement, can be generally commercially available, also can synthesize according to method well known to those skilled in the art, preferably prepares in accordance with the following methods:
By Ureaphil solution and urea mixing, pyroreaction, then carries out crystallisation by cooling by reaction system, filters and obtains nitrogen phosphorus fire retardant NPR; The mol ratio of described Ureaphil and urea is preferably 1:(1 ~ 3); Described Ureaphil solution is preferably the Ureaphil aqueous solution; The temperature of described pyroreaction is preferably 220 DEG C ~ 250 DEG C, and the reaction times is preferably 1h ~ 8h; The pressure of described reaction is preferably 0.005MPa ~ 0.01MPa; In the present invention, described pyroreaction is preferably carried out in the atmosphere of ammonia; Concrete, Ureaphil solution is mixed with urea, under constant agitation speed, be warming up to 220 DEG C ~ 250 DEG C react with the 6 DEG C/min ~ 10 DEG C/heat-up rate of min, after reaction terminates, reaction system is cooled, filtration obtains solid, by described solid drying, then pulverize, nitrogen phosphorus fire retardant NPR can be obtained.
The nitrogen phosphorus fire retardant of described surface after silane or titanic acid ester activation is preferably prepared in accordance with the following methods:
Be scattered in solvent by nitrogen phosphorus fire retardant, heating, then adds silane coupling agent or titanate coupling agent reacts, and obtains the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation.
Wherein, described solvent is preferably alcohol organic solvent or water, is more preferably water or ethanol; The temperature of described heating is preferably 30 DEG C ~ 50 DEG C, and the time of heating is preferably 3h ~ 5h; The mass ratio of described nitrogen phosphorus fire retardant and coupling agent is preferably 1 ~ 10:1, is more preferably 3 ~ 7:1; The consumption of the present invention to described solvent there is no particular requirement, nitrogen phosphorus fire retardant can be disperseed.
Environmental protection high flame-retardant cable insulating material provided by the invention also comprises compatilizer, and its content is preferably 2 ~ 7 mass parts, is more preferably 3 ~ 6 mass parts; Described compatilizer is preferably maleic anhydride graft terpolymer EP rubber; The present invention there is no particular requirement to its source, can be generally commercially available.
Described environmental protection high flame-retardant cable insulating material also comprises oxidation inhibitor, and its content is preferably 1 ~ 5 mass parts, is more preferably 2 ~ 4 mass parts; Described oxidation inhibitor is preferably antioxidant 1010; The present invention there is no particular requirement to its source, can be generally commercially available.
Described environmental protection high flame-retardant cable insulating material also comprises linking agent, and its content is preferably 1 ~ 5 mass parts, is more preferably 2 ~ 4 mass parts; Described linking agent is preferably propyl trimethoxy silicane; The present invention there is no particular requirement to its source, can be generally commercially available.
The present invention is preferred, and described environmental protection high flame-retardant cable insulating material also comprises nano level polynite, and its content is preferably 0.5 ~ 1.5 mass parts, is more preferably 0.6 ~ 1.2 mass parts; Be preferably (0.05 ~ 0.1) with the mass ratio of nitrogen phosphorus fire retardant: 1, be more preferably (0.06 ~ 0.08): 1; Described nano level polynite is preferably the nano level polynite after surface active, the preparation method of the present invention to the nano level polynite after described surface active there is no particular restriction, can be the activation method of polynite well known to those skilled in the art, preferably, adopt following methods:
Polynite mixed with acid solution and heats, obtaining the polynite of surface active; Described acid solution be preferably in hydrochloric acid soln, sulphuric acid soln and phosphoric acid solution any one or a few; Described acid solution is preferably aqueous acid, and mass content is preferably 40% ~ 80%, and its pH value is preferably 3 ~ 5; The temperature of described heating is preferably 50 DEG C ~ 70 DEG C, and the time of heating is preferably 30min ~ 2h.
The vulcanizing agent of environmental protection high flame-retardant cable insulating material provided by the invention also containing 1 ~ 5 mass parts, described vulcanizing agent is the mixture of DCP, TAIC, magnesium oxide and tetramethylolmethane.Described vulcanizing agent is used for making methyl vinyl silicone rubber and described EVA crosslinking copolymers.
Environmental protection high flame-retardant cable insulating material provided by the invention is without the need to adding Organohalogen compounds as fire retardant, while having compared with high flame resistance, not halogen-containing, has good environmental-protecting performance.Carry out performance test to the cross-linked polyolefin cable insulating material of preparation, result shows, crosslinked polyolefin materials provided by the invention is not halogen-containing, and vertical combustion VW-1 is less than 10 seconds.
Present invention also offers a kind of preparation method of environmental protection high flame-retardant cable insulating material, comprising:
By EVA multipolymer, methyl vinyl silicone rubber, glass powder, nitrogen phosphorus fire retardant, compatilizer, oxidation inhibitor, vulcanizing agent and linking agent mixing, banburying, extrude, obtain cable insulation material.
Described nitrogen phosphorus fire retardant is the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation.
The present invention for matrix resin, there is no particular requirement to the preparation method of described matrix resin with EVA multipolymer, can be prepared according to the preparation method of EVA multipolymer well known to those skilled in the art, preferably, adopts following methods preparation:
EVA resin is mixed with alkene in Banbury mixer, after melting, adds linking agent and carry out melt blending, obtain EVA multipolymer.The present invention is preferred, and the weight ratio of described EVA and alkene is 1:(0.5 ~ 3), be more preferably 1:(0.8 ~ 2.5); Described linking agent is preferably linking agent PPF or linking agent PPCI; The mass ratio of described linking agent and EVA is preferably (0.2 ~ 0.5): 1; The temperature of described melt blending is preferably 120 DEG C ~ 150 DEG C, and the time of described melt blending is preferably 5min ~ 2h.In the present invention, described EVA multipolymer is preferably the multipolymer of EVA and octene, propylene, butylene or amylene, is more preferably the multipolymer of EVA and octene or propylene.EVA is polymerized with alkene by the present invention, can improve the resistance to low temperature of EVA.
After obtaining EVA polymer matrices resin, it is mixed with nitrogen phosphorus fire retardant, compatilizer, oxidation inhibitor and linking agent, banburying, to extrude, cross-linked polyolefin cable insulating material can be obtained.
In the present invention, described nitrogen phosphorus fire retardant is preferably the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation; Its particle diameter is preferably 5nm ~ 100nm, is more preferably 10nm ~ 50nm; Described nitrogen phosphorus fire retardant is preferably nitrogen phosphorus fire retardant NPR; The source of the present invention to described nitrogen phosphorus fire retardant NPR there is no particular requirement, can be generally commercially available, also can synthesize according to method well known to those skilled in the art, preferably prepares in accordance with the following methods:
Ureaphil solution and urea are added reactor, pyroreaction, then reaction system is carried out crystallisation by cooling, filter and obtain nitrogen phosphorus fire retardant NPR; The mol ratio of described Ureaphil and urea is preferably 1:(1 ~ 3); Described Ureaphil solution is preferably the Ureaphil aqueous solution; The temperature of described pyroreaction is preferably 220 DEG C ~ 250 DEG C, and the reaction times is preferably 1h ~ 8h; The pressure of described reaction is preferably 0.005MPa ~ 0.01MPa; In the present invention, described pyroreaction is preferably carried out in the atmosphere of ammonia; Concrete, Ureaphil solution is mixed with urea, under constant agitation speed, be warming up to 220 DEG C ~ 250 DEG C react with the 6 DEG C/min ~ 10 DEG C/heat-up rate of min, after reaction terminates, reaction system is cooled, filtration obtains solid, by described solid drying, then pulverize, nitrogen phosphorus fire retardant NPR can be obtained.
In the present invention, the nitrogen phosphorus fire retardant of described surface after silane or titanic acid ester activation is preferably prepared in accordance with the following methods:
Be scattered in solvent by nitrogen phosphorus fire retardant, heating, then adds silane coupling agent or titanate coupling agent reacts, and obtains the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation.
Wherein, described solvent is preferably alcohol organic solvent or water, is more preferably water or ethanol; The temperature of described heating is preferably 30 DEG C ~ 50 DEG C, and the time of heating is preferably 3h ~ 5h; The mass ratio of described nitrogen phosphorus fire retardant and coupling agent is preferably 1 ~ 10:1, is more preferably 3 ~ 7:1; The consumption of the present invention to described solvent there is no particular requirement, nitrogen phosphorus fire retardant can be disperseed.First the present invention activates nitrogen phosphorus fire retardant surface, makes it with organic group, can avoid the reunion of nitrogen phosphorus fire retardant like this, simultaneously, because its surface is with organic group, can more even with EVA polymer matrices mixed with resin, make the product of preparation have excellent flame retardant properties.
The present invention is preferred, and described nitrogen phosphorus fire retardant also comprises nano level polynite, and the massfraction that described nano level polynite accounts for described nitrogen phosphorus fire retardant is preferably 5% ~ 10%, is more preferably 6% ~ 8%.The present invention is preferred, described polynite is the nano level polynite after surface active, and the preparation method of the present invention to the nano level polynite after described surface active there is no particular restriction, can be the activation method of polynite well known to those skilled in the art, preferably, following methods is adopted:
Polynite mixed with acid solution and heats, obtaining the polynite of surface active; Described acid solution be preferably in hydrochloric acid soln, sulphuric acid soln and phosphoric acid solution any one or a few; Described acid solution is preferably aqueous acid, and mass content is preferably 40% ~ 80%, and its pH value is preferably 3 ~ 5; The temperature of described heating is preferably 50 DEG C ~ 70 DEG C, and the time of heating is preferably 30min ~ 2h; Polynite, after acid activation, can better be scattered in fire retardant and matrix resin.The present invention adds polynite in fire retardant, can effectively reduce reaction heat release rate, and meanwhile, polynite can produce with fire retardant and act synergistically, and greatly improves the flame retardant properties of fire retardant, makes product have higher flame retardant properties.The source of the present invention to described polynite there is no particular requirement, can be generally commercially available.
In the present invention, described compatilizer is preferably maleic anhydride graft terpolymer EP rubber; Described oxidation inhibitor is preferably antioxidant 1010, and described linking agent is preferably propyl trimethoxy silicane; The source of the present invention to described compatilizer, oxidation inhibitor and linking agent there is no particular requirement, can be generally commercially available.The mass ratio of described EVA multipolymer, methyl vinyl silicone rubber, glass powder, nitrogen phosphorus fire retardant, compatilizer, oxidation inhibitor, vulcanizing agent and linking agent is preferably (30 ~ 50): (20 ~ 50): (4 ~ 6): (10 ~ 15): (2 ~ 7): (1 ~ 5): (1 ~ 5): (1 ~ 5).
Concrete, first EVA polymer matrices resin methyl vinyl silicone rubber is mixed according to a certain percentage with nitrogen phosphorus fire retardant, glass powder, compatilizer, oxidation inhibitor, vulcanizing agent and the linking agent of surface after silane or titanic acid ester activate, then carry out banburying, the temperature of described banburying is preferably 110 DEG C ~ 150 DEG C; After banburying to mixture melting, extrude, the present invention is preferred, adopts two rank twin screw extruder extruding pelletization, obtains cable insulation material.
The present invention adopts the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation as fire retardant, prepare cross-linked polyolefin cable insulating material, because the nitrogen phosphorus fire retardant surface after activation is with organic group, therefore, it is possible to disperse more uniformly in matrix resin, thus bring good flame retardant properties to product; Use traditional Organohalogen compounds fire retardant owing to avoiding simultaneously, and can not introduce halogens in the product, the cross-linked polyolefin cable insulating material therefore prepared has higher flame retardant properties, simultaneously not halogen-containing.
In order to further illustrate the present invention, below in conjunction with embodiment, environmental protection high flame retardant cross-linked polyolefin cable insulating material provided by the invention and preparation method thereof is described in detail.
Embodiment 1
Mixed in Banbury mixer with octene 110g by EVA resin 100g, after melting, add linking agent PPF10g, 130 DEG C are carried out melt blending 15min, obtain EVA and octene copolymer.
Embodiment 2
Mixed in Banbury mixer with propylene copolymer 105g by EVA resin 100g, after melting, add linking agent PPCI30g, 130 DEG C are carried out melt blending 15min, obtain EVA and propylene copolymer.
Embodiment 3
100g nitrogen phosphorus fire retardant NPR is scattered in 500mL water, 40 DEG C of heated and stirred, then adds silane coupling agent 70g and react, reaction terminate after, cross filter redundant solution, solid drying obtain surface activated after nitrogen phosphorus fire retardant.
Embodiment 4
Nitrogen phosphorus fire retardant 12g, the methyl vinyl silicone rubber 20g of surface after silane activates, glass powder 4g, maleic anhydride graft terpolymer EP rubber 5g, antioxidant 1010 5g, vulcanizing agent 5g and propyl trimethoxy silicane 5g prepared by EVA polymer matrices resin 50g and the embodiment 3 embodiment 1 prepared mix, then 130 DEG C are carried out banburying, to mixture melting, adopt two rank twin screw extruder extruding pelletization, obtain cross-linked polyolefin cable insulating material.
Carry out Performance Detection to the cross-linked polyolefin cable insulating material of preparation, result shows, it is not halogen-containing, and vertical combustion VW-1 is 4s, tensile strength:>=6N/mm 2; Elongation at break:>=250%; Heat extends :≤175%.
Embodiment 5
Nitrogen phosphorus fire retardant 10g, the methyl vinyl silicone rubber 50g of surface after silane activates, glass powder 6g, maleic anhydride graft terpolymer EP rubber 1g, antioxidant 1010 1g, vulcanizing agent 1g and propyl trimethoxy silicane 1g prepared by EVA polymer matrices resin 30g and the embodiment 3 embodiment 1 prepared mix, then 130 DEG C are carried out banburying, to mixture melting, adopt two rank twin screw extruder extruding pelletization, obtain cross-linked polyolefin cable insulating material.
Carry out Performance Detection to the cross-linked polyolefin cable insulating material of preparation, result shows, it is not halogen-containing, and vertical combustion VW-1 is 3s, tensile strength: >=6N/mm2; Elongation at break: >=250%; Heat extends :≤175%.
Embodiment 6
Nitrogen phosphorus fire retardant 12g, the methyl vinyl silicone rubber 35g of surface after silane activates, glass powder 5g, maleic anhydride graft terpolymer EP rubber 3g, antioxidant 1010 3g, vulcanizing agent 3g and propyl trimethoxy silicane 2g prepared by EVA polymer matrices resin 35g and the embodiment 3 embodiment 2 prepared mix, then 130 DEG C are carried out banburying, to mixture melting, adopt two rank twin screw extruder extruding pelletization, obtain cross-linked polyolefin cable insulating material.
Carry out Performance Detection to the cross-linked polyolefin cable insulating material of preparation, result shows, it is not halogen-containing, and vertical combustion VW-1 is 4s, tensile strength: >=6N/mm2; Elongation at break: >=250%; Heat extends :≤175%.
Embodiment 7
Nitrogen phosphorus fire retardant 12g, the methyl vinyl silicone rubber 35g of surface after silane activates, glass powder 5g, nano level polynite 1g, maleic anhydride graft terpolymer EP rubber 5g, antioxidant 1010 3g, vulcanizing agent 3g and propyl trimethoxy silicane 3g prepared by EVA polymer matrices resin 40g and the embodiment 3 embodiment 1 prepared mix, then 130 DEG C are carried out banburying, to mixture melting, adopt two rank twin screw extruder extruding pelletization, obtain cross-linked polyolefin cable insulating material.
Carry out Performance Detection to the cross-linked polyolefin cable insulating material of preparation, result shows, it is not halogen-containing, and vertical combustion VW-1 is 3s, tensile strength: >=6N/mm2; Elongation at break: >=250%; Heat extends :≤175%.
Embodiment 8
By the polynite of 1g nano level and 20mL60% combined, 60 DEG C of heating 1h, after reaction terminates, cross and filter unnecessary acid solution, by solid washed with water to neutral, dry, obtain the polynite of surface active.
Nitrogen phosphorus fire retardant 12g, the methyl vinyl silicone rubber 35g of surface after silane activates, glass powder 5g, maleic anhydride graft terpolymer EP rubber 5g, antioxidant 1010 3g, vulcanizing agent 3g and propyl trimethoxy silicane 2g prepared by EVA polymer matrices resin 35g, embodiment 2 that the polynite of getting surface active prepared by 1g is prepared with embodiment 3 mix, then 130 DEG C are carried out banburying, to mixture melting, adopt two rank twin screw extruder extruding pelletization, obtain cross-linked polyolefin cable insulating material.
Carry out Performance Detection to the cross-linked polyolefin cable insulating material of preparation, result shows, it is not halogen-containing, and vertical combustion VW-1 is 3s, tensile strength: >=6N/mm2; Elongation at break: >=250%; Heat extends :≤175%.
From above-described embodiment, the present invention adopts the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation, and the cable insulation material of preparation has higher flame retardant properties, simultaneously not halogen-containing.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.

Claims (10)

1. an environmental protection high flame-retardant cable insulating material, comprising:
EVA multipolymer 30 ~ 50 mass parts;
Methyl vinyl silicone rubber 20 ~ 50 mass parts;
Glass powder 4 ~ 6 mass parts;
Nitrogen phosphorus fire retardant 10 ~ 15 mass parts;
Compatilizer 2 ~ 7 mass parts;
Oxidation inhibitor 1 ~ 5 mass parts;
Linking agent 1 ~ 5 mass parts;
Vulcanizing agent 1 ~ 5 mass parts;
Described nitrogen phosphorus fire retardant is the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation.
2. environmental protection high flame-retardant cable insulating material according to claim 1, it is characterized in that, described EVA multipolymer is selected from the multipolymer of EVA and octene, propylene, butylene or amylene; Described compatilizer is maleic anhydride graft terpolymer EP rubber; Described oxidation inhibitor is antioxidant 1010, and described linking agent is propyl trimethoxy silicane; Described nitrogen phosphorus fire retardant is selected from nitrogen phosphorus fire retardant NPR, and described vulcanization system is DCP, TAIC, magnesium oxide and tetramethylolmethane.
3. environmental protection high flame-retardant cable insulating material according to claim 1 and 2, is characterized in that, also comprises the nano level polynite of 0.5 ~ 1.5 mass parts.
4. according to the environmental protection high flame retardant cross-linked polyolefin cable insulating material one of claim 1-3 Suo Shu, it is characterized in that, described nitrogen phosphorus fire retardant particle diameter is 5nm ~ 100nm.
5. a preparation method for environmental protection high flame retardant cross-linked polyolefin cable insulating material, comprising:
By EVA multipolymer, methyl vinyl silicone rubber, glass powder, nitrogen phosphorus fire retardant, compatilizer, oxidation inhibitor, vulcanizing agent and linking agent mixing, banburying, extrude, obtain cable insulation material;
Described nitrogen phosphorus fire retardant is the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation.
6. method according to claim 5, is characterized in that, described nitrogen phosphorus fire retardant is selected from nitrogen phosphorus fire retardant NPR; Described EVA multipolymer is selected from the multipolymer of EVA and octene, propylene, butylene or amylene; Described compatilizer is maleic anhydride graft terpolymer EP rubber; Described oxidation inhibitor is antioxidant 1010; Described linking agent is propyl trimethoxy silicane; Described vulcanization system is DCP, TAIC, magnesium oxide and tetramethylolmethane.
7. the method according to claim 5 or 6, it is characterized in that, the mass ratio of described EVA multipolymer, methyl vinyl silicone rubber, glass powder, nitrogen phosphorus fire retardant, compatilizer, oxidation inhibitor, vulcanizing agent and linking agent is (30 ~ 50): (20 ~ 50): (4 ~ 6): (10 ~ 15): (2 ~ 7): (1 ~ 5): (1 ~ 5): (1 ~ 5).
8. according to the method one of claim 5-7 Suo Shu, it is characterized in that, in described nitrogen phosphorus fire retardant, also comprise nano level polynite.
9. according to the method one of claim 5-8 Suo Shu, it is characterized in that, the massfraction that described nano level polynite accounts for described nitrogen phosphorus fire retardant is 5% ~ 10%.
10. according to the method one of claim 5-9 Suo Shu, it is characterized in that, the nitrogen phosphorus fire retardant of described surface after silane or titanic acid ester activation is prepared in accordance with the following methods:
Be scattered in solvent by nitrogen phosphorus fire retardant, heating, then adds silane coupling agent or titanate coupling agent reacts, and obtains the nitrogen phosphorus fire retardant of surface after silane or titanic acid ester activation.
CN201510548819.6A 2015-08-31 2015-08-31 Environmental-protection high-fire-retardant cable insulation material and preparation method thereof Pending CN105086126A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105482462A (en) * 2015-12-14 2016-04-13 湖南工业大学 High-temperature-resistant and low-smoke-zero-halogen cable material and preparing method
CN105860238A (en) * 2016-04-21 2016-08-17 安徽万泰电缆有限公司 Anti-impact flame-retardant cable material
CN106009095A (en) * 2016-06-20 2016-10-12 安徽海容电缆有限公司 Cold-resistant anti-cracking cable material
CN106065189A (en) * 2016-07-26 2016-11-02 潘明华 HVDC electric wire cable insulation material and preparation technology thereof
CN110105767A (en) * 2019-05-31 2019-08-09 昆山兆科电子材料有限公司 A kind of heat conductive flame-retarding insulating materials

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CN1333404A (en) * 2000-07-07 2002-01-30 国家淀粉及化学投资控股公司 Coating for paper products
CN103554648A (en) * 2013-11-11 2014-02-05 深圳市沃尔核材股份有限公司 Ceramic composite material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN1333404A (en) * 2000-07-07 2002-01-30 国家淀粉及化学投资控股公司 Coating for paper products
CN103554648A (en) * 2013-11-11 2014-02-05 深圳市沃尔核材股份有限公司 Ceramic composite material and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105482462A (en) * 2015-12-14 2016-04-13 湖南工业大学 High-temperature-resistant and low-smoke-zero-halogen cable material and preparing method
CN105482462B (en) * 2015-12-14 2019-04-09 湖南工业大学 A kind of high temperature resistant low smoke halogen free cable material and preparation method
CN105860238A (en) * 2016-04-21 2016-08-17 安徽万泰电缆有限公司 Anti-impact flame-retardant cable material
CN106009095A (en) * 2016-06-20 2016-10-12 安徽海容电缆有限公司 Cold-resistant anti-cracking cable material
CN106065189A (en) * 2016-07-26 2016-11-02 潘明华 HVDC electric wire cable insulation material and preparation technology thereof
CN110105767A (en) * 2019-05-31 2019-08-09 昆山兆科电子材料有限公司 A kind of heat conductive flame-retarding insulating materials

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Application publication date: 20151125