CN105924757A - Halogen-free and high-flame-retardancy cable material and preparation method thereof - Google Patents
Halogen-free and high-flame-retardancy cable material and preparation method thereof Download PDFInfo
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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
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- 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
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Abstract
The invention discloses a halogen-free and high-flame-retardancy cable material which is prepared from the following raw materials in parts by weight: 116 to 130 parts of ethylene-vinyl acetate copolymer, 12 to 16 parts of kieselguhr, 8 to 13 parts of sulfur, 8 to 12 parts of white carbon black, 9 to 15 parts of calcium lignosulphonate, 5 to 10 parts of epoxy soybean oil, 7 to 13 parts of sodium carboxymethylcellulose, 14 to 20 parts of magnesium hydroxide, 6 to 10 parts of rectorite, 6 to 13 parts of zinc borate, 9 to 14 parts of a rare earth stabilizer, 12 to 17 parts of dioctyl phthalate and 7 to 12 parts of an antioxidant 1010. The oxygen index of the halogen-free and high-flame-retardancy cable material disclosed by the invention is obviously increased, and the halogen-free and high-flame-retardancy cable material is low-smoke and non-toxic; on the premise of guaranteeing the toughness and the flame retardancy, the mechanical properties such as the tensile strength, the mechanical strength, the impact resistance performance, the abrasion resistance performance and the tear strength of a product are improved; the halogen-free and high-flame-retardancy cable material has toughness and mechanical properties, and is applicable to various types of cables.
Description
Technical field
The present invention relates to CABLE MATERIALS field, especially relate to a kind of halogen-free high flame-retardant cable material and preparation method thereof.
Background technology
Wire cable insulating and sheath plastics are commonly called as CABLE MATERIALS, which includes the multiple product such as rubber, plastics, nylon
Kind.CABLE MATERIALS manufacturing enterprise is with cable manufacturing enterprise as user, as long as live wire cabling requirements just has the market of CABLE MATERIALS.Electricity
Cable is the modern people life indispensable ingredient of each side, along with the frequent generation of electrical fire accident, electric wire
Fire-retardant problem gradually cause the attention of countries in the world.Owing to the material of cable insulation is usually macromolecular material, having can
Combustion property, in order to prevent cable to catch fire, it is necessary to improves the fire resistance of CABLE MATERIALS, is usually and adds necessarily in macromolecular material
Fire retardant.The fire retardant great majority being currently used for TPO are halogen flame system, good flame retardation effect, cost performance height,
But discharge a large amount of smog and poisonous, corrosive gas during its burning, environment is caused serious injury with human body, fire
During easily cause the danger that suffocates of people occur.In electric wire product in addition to the bare wire product such as steel-cored aluminium strand, electromagnetic wire
Nearly all need insulating barrier mouth.Nearly 5000 of live wire cable manufacturing enterprise of China at present, has again upgrading urban and rural power grids, western part big
Exploitation and the communications facility large area upgrading great demand to electric wire product, thus from the point of view of a period of time, cable
Material has market development prospect widely in China.
Fast development along with industries such as China's metallurgy, electric power, electronics, automatization and informatization and networks so that join therewith
The consumption of electric wire particularly flame-retardant electric wire and cable of set sharply increases, including power cable, control cable, signal cable,
Instrument and meter cable, computer cable etc..In recent years, CABLE MATERIALS manufacturing enterprise of China has a great development, and particularly one
A little private enterprises, comply with the market demand in production scale, product restructuring and new product development, improve a lot.
In existing non-halogen flame-retardant cable, publication number CN 103756171 A(application number 201410012593.3) special
Profit discloses a kind of Halogen-free cable material with high flame retardancy, and it is to be prepared by the raw material of following weight parts: chlorinated polyethylene 100-110,
Poly(4-methyl-1-pentene) 8-12, polysiloxanes 1-2, sodium tripolyphosphate 1.2-2.5, CP resin 4-6, trimellitic acid three monooctyl ester
1-2, epoxy soybean oil 1-2, modified montmorillonoid 45-58, dibutyl tin laurate 0.5-0.8, tributyl citrate 0.1-
0.2, magnesium oxide 1-2, calcium stearate 0.9-1.5；The preparation method of modified montmorillonoid is: (1) first, takes montmorillonite in flash burning kiln
The flash burning 3-5 second at middle 700-800 DEG C, add in deionized water, 1600-1900r/min centrifugal treating 20-25min, it is dried；
(2) hydrochloric acid solution that concentration is 4-8%, at 50-55 DEG C, 1000-1800r/min are put in step (1) dried montmorillonite
Centrifugal treating 5-10min, deionized water wash, drying；(3) montmorillonite after step (2) processes adds to be equivalent to it heavy
After the irgasfos 168 of silane coupler KH792,2-4% of amount 1-2% and suitable quantity of water stir, in 60-65 DEG C time, insulation
10-18 minute, add the adipate ester being equivalent to montmorillonite weight 1-2%, stir, be cooled to 40-50 DEG C, be incubated 10-
18 minutes, take out, be dried, pulverize last, to obtain final product.Publication number CN 105504478 A(application number 201610030270.6)
Patent disclose a kind of fireproofing cable material without halide, including the raw material of following weight portion: base material: 100 parts, lubricant: 1-4
Part, inorganic combustion inhibitor: 60-80 part, fire retarding synergist: 5-10 part, antioxidant: 1-3 part, coupling agent: 0.5-4 part, compatilizer: 2-
10 parts, described base material contains ethylene-vinyl acetate copolymer and linear low density polyethylene.Publication number CN 103571010 A
The patent of (application number 201310464745.9) discloses a kind of fireproofing cable material without halide, by the raw material system of following weight portion
Become: polyethylene 20-30, polystyrene 20-25, butadiene-styrene rubber 10-15, Tissuemat E 3-6, rare-earth stabilizer 5-8, hydroxide
Magnesium 20-30, zinc hydroxide 20-30, APP 10-20, MTMS 1-2, antioxidant 1010 1-4, zinc oxide
4-5, compatilizer ST-32-4, nano aluminum nitride 0.1-0.3, polyvinyl alcohol 1-2, modified filler 10-12.
The production the most very imperfection of CABLE MATERIALS at present, fire resistance is poor, and tensile strength is weak, easily causes aging, impact
Cable uses, and needs often to change, is unfavorable for that use and cost are huge.
Summary of the invention
For the deficiency of existing a kind of halogen-free high flame-retardant cable material, an object of the present invention is to provide a kind of Halogen high
Fire-resistant cable material, oxygen index (OI) significantly improves, LSZH, on the premise of ensureing pliability and fire resistance, improves product
Hot strength, mechanical property, shock resistance, anti-wear performance, the mechanical performance such as tear resistance, have pliability and machinery concurrently
Performance, it is adaptable to various types of cables.Another object is just to provide the preparation method of above-mentioned halogen-free high flame-retardant cable material.
The above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of halogen-free high flame-retardant cable material, takes off and states the raw material of weight proportion and be prepared from: vinyl-vinyl acetate copolymer
116-130 part, kieselguhr 12-16 part, sulfur 8-13 part, white carbon 8-12 part, calcium lignosulfonate 9-15 part, epoxy soybean oil
5-10 part, sodium carboxymethyl cellulose 7-13 part, magnesium hydroxide 14-20 part, rectorite 6-10 part, Firebrake ZB 6-13 part, rare earth are steady
Determine agent 9-14 part, dioctyl phthalate 12-17 part, antioxidant 1010 7-12 part.
A kind of halogen-free high flame-retardant cable material, preferred scheme is, takes off and states the raw material of weight proportion and be prepared from: ethylene-
Vinyl acetate copolymer 120-125 part, kieselguhr 13-15 part, sulfur 10-12 part, white carbon 9-11 part, calcium lignosulfonate
11-13 part, epoxy soybean oil 7-9 part, sodium carboxymethyl cellulose 9-11 part, magnesium hydroxide 16-18 part, rectorite 7-9 part, boric acid
Zinc 9-11 part, rare-earth stabilizer 11-13 part, dioctyl phthalate 14-16 part, antioxidant 1010 9-11 part.
A kind of halogen-free high flame-retardant cable material, scheme more preferably is, takes off and states the raw material of weight proportion and be prepared from: second
Alkene-vinyl acetate copolymer 123 parts, 14 parts of kieselguhr, 11 parts of sulfur, white carbon 10 parts, calcium lignosulfonate 12 parts, epoxy
Soybean oil 8 parts, sodium carboxymethyl cellulose 10 parts, 17 parts of magnesium hydroxide, rectorite 8 parts, Firebrake ZB 10 parts, rare-earth stabilizer 12
Part, dioctyl phthalate 15 parts, antioxidant 1010 10 parts.
The preparation method of above-mentioned a kind of halogen-free high flame-retardant cable material, step is as follows:
(1) rectorite is placed in calcining furnace, high-temperature calcination 3-5 hour, takes out, be placed in anticorrosion container, be slowly added to 3%-5%
Sodium hydroxide solution, grind 50-70 minute, filter, add 15%-19% hydrochloric acid solution, regulation pH is 6.8-7.2, addition
Sodium carboxymethyl cellulose, mix homogeneously, dry, pulverize, cross 80-100 mesh sieve；
(2) kieselguhr is placed in firing, the high temperature flash burning 8-12 second, adds the deionized water of 4-6 times of quality, stand 2-4 hour,
It is centrifuged processing 30-40 minute with the speed of 1400-1800 r/min, deionized water, washing, dries, pulverize；
(3) magnesium hydroxide is placed in three-roll grinder, adds vinyl-vinyl acetate copolymer, impregnate 4-6 hour, grind
30-40 minute, it is sequentially added into sulfur, calcium lignosulfonate and antioxidant 1010, adds deionized water, stir, grind 40-
60 minutes, making slurry granularity was 0.034-0.039mm, is heated to isothermal holding 3-4 hour when 145-165 DEG C, is cooled to room temperature,
Standby；
(4) step (3) products therefrom is heated to when temperature reaches 68-75 DEG C being slowly added to white carbon, phthalic acid two pungent
Ester and step (1) products therefrom, mix homogeneously, join in high-speed kneading machine, adds epoxy soybean oil and step (2) gained produces
Thing, high-speed stirred 35-46 minute, fully mediate, when material is in expansion loose powder, transfer to low speed in cooling and stirring machine stir
Mix 8-12 minute；
(5) step (4) products therefrom is placed in banbury, falls floating weight mixing 1-2 minute, mention floating weight, add boron
Acid zinc and rare-earth stabilizer, fall floating weight mixing 4-5 minute, discharging when banburying becomes bulk fritter, mixing, pelletize, is dried place
Reason, screening, packaging.
The preparation method of above-mentioned halogen-free high flame-retardant cable material, preferred scheme is: step (1) preferable temperature is 520-
580 DEG C, more preferably temperature is 560 DEG C.
The preparation method of above-mentioned halogen-free high flame-retardant cable material, preferred scheme is: step (1) preferably sodium hydroxide solution
2-4 times that consumption is rectorite quality, the more preferably consumption of sodium hydroxide solution is 3 times of rectorite quality.
The preparation method of above-mentioned halogen-free high flame-retardant cable material, preferred scheme is: step (2) preferable temperature is 750-
820 DEG C, more preferably temperature is 790 DEG C.
The preparation method of above-mentioned halogen-free high flame-retardant cable material, preferred scheme is: the use of step (3) preferably deionized water
Amount be 8-12 times of magnesium hydroxide quality, the more preferably consumption of deionized water be 10 times of magnesium hydroxide quality.
The preparation method of above-mentioned halogen-free high flame-retardant cable material, preferred scheme is: preferably turn during step (4) high-speed stirred
Speed is 840-940 rev/min, and more preferably rotating speed is 890 revs/min.
The preparation method of above-mentioned halogen-free high flame-retardant cable material, preferred scheme is: preferably turn during step (4) stirring at low speed
Speed is 140-180 rev/min, and more preferably rotating speed is 160 revs/min.
Non-halogen flame-retardant cable of the present invention, with vinyl-vinyl acetate copolymer as major ingredient, is aided with kieselguhr, sulfomethylated lignin
Acid calcium, sodium carboxymethyl cellulose, magnesium hydroxide etc., on the premise of ensureing product pliability and fire resistance, improve product
Hot strength, mechanical property, shock resistance, anti-wear performance, the mechanical performance such as tear resistance.
The beneficial effects are mainly as follows:
1, halogen-free high flame-retardant cable material of the present invention is on the premise of ensureing pliability and fire resistance, and the stretching that improve product is strong
The mechanical performances such as degree, mechanical property, and smoke density is low, and oxygen index (OI) is high, and dielectric strength is high, and poison exponent is low.
2, the physical and mechanical properties of halogen-free high flame-retardant cable material of the present invention and electrical insulating property, elasticity, resistance to ag(e)ing, corrosion-resistant
The performance of each side such as property, wearability, oil resistivity has increased significantly.Non-halogen flame-retardant cable of the present invention has pliability concurrently
And mechanical performance, it is adaptable to various types of cables.
3, halogen-free high flame-retardant cable material oxygen index (OI) of the present invention significantly improves, and LSZH has higher weatherability, resistance
Shape, to base-layer contraction and craze and transfiguration strong adaptability, antiacid alkali so that cable and wire can make under rugged environment requiring very much
With.
4, halogen-free high flame-retardant cable material of the present invention effectively reduces production cost, economizes on resources, and protects environment, has higher
Economic benefit, social benefit and environmental benefit, have broad application prospects, and is suitable for marketing.
Detailed description of the invention
Describe technical scheme in detail below in conjunction with embodiment and experimental example, but protection domain is not limited by this.
Primary raw material brief introduction is as follows:
Vinyl-vinyl acetate copolymer: i.e. EVA, is solid under room temperature, and heating is molten to uniform temperature and becomes flowing, and
There is the liquid of certain viscosity.EVA hot-melt adhesive after Rong Rong, in light brown or white.EVA hot-melt adhesive by basic resin, viscosifier,
Viscosity modifier becomes to be grouped into antioxidant etc..There is good flexibility, the elasticity as rubber, at-50 DEG C, it still is able to tool
Having preferable pliability, the transparency and lustrous surface property are good, environmental stress crack resistance, the advantage that against weather is good, aging resistance
Good with resistance to ozone intensity, good with the miscibility of filler, coloring and molding processibility are good.Applicable industrial material has power cord exhausted
Edge suitcase, household electrical appliance accessory, window encapsulant etc..
Kieselguhr: be a kind of siliceous rock, be a kind of biogenic silicastone, mainly by the remains of diatom in ancient times
Being formed, chemical composition is mainly SiO2, containing a small amount of Al2O3、Fe2O3, CaO, MgO etc. and organic.Industrial it is commonly used to
As insulation material, filtering material, filler, grinding-material, waterglass raw material, decolorising agent and super-cell, catalyst carries
Body etc..
Sulfur: crystallize or powder for faint yellow fragility, water insoluble, it is slightly soluble in ethanol, ether, is soluble in Carbon bisulfide.Main
It is used for manufacturing dyestuff, pesticide, match, gunpowder, rubber, artificial silk etc..
White carbon: be white powder X-ray amorphous silicic acid and the general name of silicate product.High temperature resistant, do not fire, nothing
Taste is odorless, have good electrical insulating property.Specific surface area is big, and superficial attractive forces is strong, and surface can be big, and chemical purity is high, dispersibility
The aspects such as energy good, thermal resistance, resistance have special performance.It is widely used in every profession and trade as additive, catalyst carrier, oil
Work, decolorising agent, delustering agent, rubber reinforcing filler, plastics filler, ink thickeners, the soft buffing compound of metal, insulation and thermal insulation is filled
Agent, the various fields such as high-grade daily-use cosmetics filler and sprayed on material, medicine, environmental protection.
Calcium lignosulfonate: be called for short wood calcium, for light yellow to dark brown powder, slightly aromatic odor, is a kind of multicomponent
High molecular polymer anion surfactant, has the strongest dispersibility, caking property, sequestering.From acid polishing (or claim
For sulfite pulping) cooking waste liquor, spray-dried form.
Epoxy soybean oil: for thick pale yellow oily liquids, be the oneization prepared after oxidation processes with soybean oil
Chemical product, is that one uses nontoxic polyvinyl chloride plasticizer widely to hold concurrently stabilizer: good with the polyvinyl chloride resin compatibility, volatility is low,
Animal migration is little.There is excellent heat stability and light stability, resistance to water and oil resistivity the best, the machinery that goods are good can be given
Intensity, weatherability and electrical property.It is commonly used for the plasticizer of epoxy resin, PVC, neoprene, nitrile rubber etc..
Sodium carboxymethyl cellulose: for white or milky fibrous powder or granule, odorless, tasteless, have hygroscopicity, insoluble
In organic solvent, for the sodium salt of carboxymethyl cellulose ether, belong to anionic cellulose ether.Purposes: be used as thickening in food industry
Agent, is used as pharmaceutical carrier in medical industry, be used as adhesive, resist the most dignified dose in daily chemical industry.Printing and dyeing industry is used as
Sizing agent and the protecting colloid etc. of printing gum, can be as oil recovery fracturing fluid composition in petrochemical industry.Production method is by fibre
Dimension element and sodium hydroxide react generation alkali cellulose, then carry out carboxy methylation with chloroacetic acid and prepare.
Magnesium hydroxide: for colourless hexagonal prism crystal or white powder, can be used as fire retardant or fire-retardant filler joins poly-second
In alkene, polypropylene, polystyrene and ABS resin, there is good fire-retardant and smoke elimination effect, particularly mining ventilating duct is coated
Cloth, PVC whole core conveyer belt, flame-retardant aluminum plastic plate, fire-retardant tarpaulin, PVC cable material, mine cable sheath, the resistance of cable accessory
Combustion, smoke elimination antistatic, can replace aluminium hydroxide, have excellent flame retardant effect.
Rectorite: be a kind of to there are special construction, the rarest clay of laminar silicate mineral, by class Muscovitum elementary layer
Alternately pile up regularly under special natural condition with class montmorillonite elementary layer, but be not the simple combination of the two.By sixteen
The regular interstratified mineral that face body paragonite elementary layer and dioctahedron ca-montmorillonite elementary layer alternately pile up composition with 1: 1 rule glues scholar
Mineral, containing Ca between montmorillonite layer2+、Mg2+、K+And Na+Deng exchangeable cation, wherein with Ca2+It is main, accounts for cation total amount
50%.There is the strongest absorbability and cation exchange capacity (CEC), by ion-exchange reactions, organic cation can be made to insert
To rectorite interlayer, making interlayer structure and character that corresponding change to occur, the compatibility with high polymer strengthens.
Firebrake ZB: for white anorthic crystal or amorphous powder, be slightly soluble in water, is mainly used as mineral-type additive, nontoxic
Fire retardant, can be effectively improved fire resistance as the multifunctional synergistic additive of stibium oxide or other halogen flame,
The generation of smog when reducing burning, it is possible to the chemistry of regulation Plastic Rubber Products, machinery, the performance of the aspects such as electricity.Be usually used in plastics,
The industries such as rubber, weaving, coating.
Rare-earth stabilizer: for white or pale yellow powder shape, carboxylate or soap by rare earth element are main group
Divide and synthesize, containing appropriate rare earth metal composition, there is goodish heat stability, light stability and the transparency and coloring
Power.Purchased from Zibo Huaxing Additives Co., Ltd., use used as stabilizers in the present invention.
Dioctyl phthalate: for colourless transparent liquid, be a kind of organic esters, water insoluble, it is dissolved in second
Most of organic solvents such as alcohol, ether, mineral oil.It is a kind of important universal plasticizer, is mainly used in Corvic
Processing, it may also be used for the processing of the high polymers such as chemical fibre resin, acetate resin, ABS resin and rubber is it can also be used to make paint, dye
Material, dispersant etc..This product has good combination property, good mixing property, and plasticizing efficiency is high, and volatility is relatively low, and low temperature is soft
Property preferable, water-fast extraction, electric property is high, and thermostability and weatherability are good.Make plasticizer in the present invention to use.
Antioxidant 1010: for white crystalline powder, chemistry is entitled: four [β-(3,5-di-tert-butyl-hydroxy phenyls) third
Acid] pentaerythritol ester, chemical property is stable.Can be widely applied to general-purpose plastics, engineering plastics, synthetic rubber, fiber, hot melt
Glue, resin, oil product, ink, in the industry such as coating.Antioxidant 1010 used by the present invention is by tetramethylolmethane and β-(3,5-bis-
Tert-butyl-hydroxy phenyl) methyl propionate, under the catalysis of Feldalat NM, carry out what ester exchange reaction obtained in 100-140 DEG C.
It is used as antioxidant in the present invention.
1 one kinds of halogen-free high flame-retardant cable materials of embodiment, take off and state raw material and be prepared from (every part takes 24kg): ethylene-acetate
Vinyl ester copolymers 116 parts, 12 parts of kieselguhr, 8 parts of sulfur, white carbon 8 parts, calcium lignosulfonate 9 parts, epoxy soybean oil 5 parts,
Sodium carboxymethyl cellulose 7 parts, 14 parts of magnesium hydroxide, rectorite 6 parts, Firebrake ZB 6 parts, rare-earth stabilizer 9 parts, phthalic acid two
Monooctyl ester 12 parts, antioxidant 1010 7 parts.
A kind of halogen-free high flame-retardant cable material preparation process is as follows:
(1) being placed in calcining furnace by rectorite, high temperature (520 DEG C) is calcined 3 hours, takes out, is placed in anticorrosion container, is slowly added to
The sodium hydroxide solution of 3% 2 times of rectorite quality (consumption be), grinds 50 minutes, filters, add the hydrochloric acid solution of 15%, adjust
Joint pH is 6.8, adds sodium carboxymethyl cellulose, mix homogeneously, dries, pulverize, crosses 80 mesh sieves；
(2) kieselguhr is placed in firing, high temperature (750 DEG C) flash burning 8 seconds, adds the deionized water of 4 times of quality, stand 2 hours,
It is centrifuged processing 30 minutes with the speed of 1400r/min, deionized water, washing, dries, pulverize；
(3) magnesium hydroxide is placed in three-roll grinder, adds vinyl-vinyl acetate copolymer, impregnate 4 hours, grind 30
Minute, it is sequentially added into sulfur, calcium lignosulfonate and antioxidant 1010, (consumption is the 8 of magnesium hydroxide quality to add deionized water
Times), stir, grind 40 minutes, making slurry granularity is 0.034mm, is heated to isothermal holding 3 hours when 145 DEG C, is cooled to
Room temperature, standby；
(4) be heated to step (3) products therefrom when temperature reaches 68 DEG C being slowly added to white carbon, dioctyl phthalate and
Step (1) products therefrom, mix homogeneously, join in high-speed kneading machine, add epoxy soybean oil and step (2) products therefrom,
(rotating speed is 840 revs/min) stirs 35 minutes at a high speed, fully mediates, and transfers to cooling and stir when material is in expansion loose powder
Mix low speed in machine (rotating speed is 140 revs/min) to stir 8 minutes；
(5) step (4) products therefrom is placed in banbury, falls floating weight mixing 1 minute, mention floating weight, add boric acid
Zinc and rare-earth stabilizer, fall floating weight mixing 4 minutes, discharging when banburying becomes bulk fritter, mixing, pelletize, dried, sieve
Choosing, packaging.
2 one kinds of halogen-free high flame-retardant cable materials of embodiment, take off and state raw material and be prepared from (every part takes 13kg): ethylene-acetate
Vinyl ester copolymers 130 parts, 16 parts of kieselguhr, 13 parts of sulfur, white carbon 12 parts, calcium lignosulfonate 15 parts, epoxy soybean oil
10 parts, sodium carboxymethyl cellulose 13 parts, 20 parts of magnesium hydroxide, rectorite 10 parts, Firebrake ZB 13 parts, rare-earth stabilizer 14 parts, adjacent
Dioctyl phthalate 17 parts, antioxidant 1010 12 parts.
A kind of halogen-free high flame-retardant cable material preparation process is as follows:
(1) being placed in calcining furnace by rectorite, high temperature (580 DEG C) is calcined 5 hours, takes out, is placed in anticorrosion container, is slowly added to
The sodium hydroxide solution of 5% 4 times of rectorite quality (consumption be), grinds 70 minutes, filters, add the hydrochloric acid solution of 19%, adjust
Joint pH is 7.2, adds sodium carboxymethyl cellulose, mix homogeneously, dries, pulverize, crosses 100 mesh sieves；
(2) kieselguhr is placed in firing, high temperature (820 DEG C) flash burning 12 seconds, adds the deionized water of 6 times of quality, stand 4 little
Time, it is centrifuged processing 40 minutes with the speed of 1800 r/min, deionized water, washing, dries, pulverize；
(3) magnesium hydroxide is placed in three-roll grinder, adds vinyl-vinyl acetate copolymer, impregnate 6 hours, grind 40
Minute, it is sequentially added into sulfur, calcium lignosulfonate and antioxidant 1010, (consumption is magnesium hydroxide quality to add deionized water
12 times), stir, grind 60 minutes, making slurry granularity is 0.039mm, is heated to isothermal holding 4 hours when 165 DEG C, cooling
To room temperature, standby；
(4) be heated to step (3) products therefrom when temperature reaches 75 DEG C being slowly added to white carbon, dioctyl phthalate and
Step (1) products therefrom, mix homogeneously, join in high-speed kneading machine, add epoxy soybean oil and step (2) products therefrom,
(rotating speed is 940 revs/min) stirs 46 minutes at a high speed, fully mediates, and transfers to cooling and stir when material is in expansion loose powder
Mix low speed in machine (rotating speed is 180 revs/min) to stir 12 minutes；
(5) step (4) products therefrom is placed in banbury, falls floating weight mixing 2 minutes, mention floating weight, add boric acid
Zinc and rare-earth stabilizer, fall floating weight mixing 5 minutes, discharging when banburying becomes bulk fritter, mixing, pelletize, dried, sieve
Choosing, packaging.
3 one kinds of halogen-free high flame-retardant cable materials of embodiment, take off and state raw material and be prepared from (every part takes 15kg): ethylene-acetate
Vinyl ester copolymers 120 parts, 13 parts of kieselguhr, 10 parts of sulfur, white carbon 9 parts, calcium lignosulfonate 11 parts, epoxy soybean oil 7
Part, sodium carboxymethyl cellulose 9 parts, 16 parts of magnesium hydroxide, rectorite 7 parts, Firebrake ZB 9 parts, rare-earth stabilizer 11 parts, O-phthalic
Dioctyl phthalate 14 parts, antioxidant 1010 9 parts.
A kind of halogen-free high flame-retardant cable material preparation process is as follows:
(1) being placed in calcining furnace by rectorite, high temperature (540 DEG C) is calcined 3 hours, takes out, is placed in anticorrosion container, is slowly added to
The sodium hydroxide solution of 3% 2 times of rectorite quality (consumption be), grinds 55 minutes, filters, add the hydrochloric acid solution of 16%, adjust
Joint pH is 6.9, adds sodium carboxymethyl cellulose, mix homogeneously, dries, pulverize, crosses 80 mesh sieves；
(2) kieselguhr is placed in firing, high temperature (770 DEG C) flash burning 9 seconds, adds the deionized water of 4 times of quality, stand 2 hours,
It is centrifuged processing 33 minutes with the speed of 1500 r/min, deionized water, washing, dries, pulverize；
(3) magnesium hydroxide is placed in three-roll grinder, adds vinyl-vinyl acetate copolymer, impregnate 4 hours, grind 33
Minute, it is sequentially added into sulfur, calcium lignosulfonate and antioxidant 1010, (consumption is the 9 of magnesium hydroxide quality to add deionized water
Times), stir, grind 45 minutes, making slurry granularity is 0.036mm, is heated to isothermal holding 3 hours when 149 DEG C, is cooled to
Room temperature, standby；
(4) be heated to step (3) products therefrom when temperature reaches 70 DEG C being slowly added to white carbon, dioctyl phthalate and
Step (1) products therefrom, mix homogeneously, join in high-speed kneading machine, add epoxy soybean oil and step (2) products therefrom,
(rotating speed is 870 revs/min) stirs 38 minutes at a high speed, fully mediates, and transfers to cooling and stir when material is in expansion loose powder
Mix low speed in machine (rotating speed is 150 revs/min) to stir 9 minutes；
(5) step (4) products therefrom is placed in banbury, falls floating weight mixing 1 minute, mention floating weight, add boric acid
Zinc and rare-earth stabilizer, fall floating weight mixing 4 minutes, discharging when banburying becomes bulk fritter, mixing, pelletize, dried, sieve
Choosing, packaging.
4 one kinds of halogen-free high flame-retardant cable materials of embodiment, take off and state raw material and be prepared from (every part takes 17kg): ethylene-acetate
Vinyl ester copolymers 125 parts, 15 parts of kieselguhr, 12 parts of sulfur, white carbon 11 parts, calcium lignosulfonate 13 parts, epoxy soybean oil 9
Part, sodium carboxymethyl cellulose 11 parts, 18 parts of magnesium hydroxide, rectorite 9 parts, Firebrake ZB 11 parts, rare-earth stabilizer 13 parts, adjacent benzene two
Formic acid dioctyl ester 16 parts, antioxidant 1010 11 parts.
A kind of halogen-free high flame-retardant cable material preparation process is as follows:
(1) being placed in calcining furnace by rectorite, high temperature (570 DEG C) is calcined 5 hours, takes out, is placed in anticorrosion container, is slowly added to
The sodium hydroxide solution of 5% 4 times of rectorite quality (consumption be), grinds 65 minutes, filters, add the hydrochloric acid solution of 18%, adjust
Joint pH is 7.1, adds sodium carboxymethyl cellulose, mix homogeneously, dries, pulverize, crosses 100 mesh sieves；
(2) kieselguhr is placed in firing, high temperature (800 DEG C) flash burning 11 seconds, adds the deionized water of 6 times of quality, stand 4 little
Time, it is centrifuged processing 37 minutes with the speed of 1700 r/min, deionized water, washing, dries, pulverize；
(3) magnesium hydroxide is placed in three-roll grinder, adds vinyl-vinyl acetate copolymer, impregnate 6 hours, grind 37
Minute, it is sequentially added into sulfur, calcium lignosulfonate and antioxidant 1010, (consumption is magnesium hydroxide quality to add deionized water
11 times), stir, grind 55 minutes, making slurry granularity is 0.037mm, is heated to isothermal holding 4 hours when 162 DEG C, cooling
To room temperature, standby；
(4) be heated to step (3) products therefrom when temperature reaches 73 DEG C being slowly added to white carbon, dioctyl phthalate and
Step (1) products therefrom, mix homogeneously, join in high-speed kneading machine, add epoxy soybean oil and step (2) products therefrom,
(rotating speed is 910 revs/min) stirs 43 minutes at a high speed, fully mediates, and transfers to cooling and stir when material is in expansion loose powder
Mix low speed in machine (rotating speed is 170 revs/min) to stir 11 minutes；
(5) step (4) products therefrom is placed in banbury, falls floating weight mixing 2 minutes, mention floating weight, add boric acid
Zinc and rare-earth stabilizer, fall floating weight mixing 5 minutes, discharging when banburying becomes bulk fritter, mixing, pelletize, dried, sieve
Choosing, packaging.
5 one kinds of halogen-free high flame-retardant cable materials of embodiment, take off and state raw material and be prepared from (every part takes 23kg): ethylene-acetate
Vinyl ester copolymers 123 parts, 14 parts of kieselguhr, 11 parts of sulfur, white carbon 10 parts, calcium lignosulfonate 12 parts, epoxy soybean oil 8
Part, sodium carboxymethyl cellulose 10 parts, 17 parts of magnesium hydroxide, rectorite 8 parts, Firebrake ZB 10 parts, rare-earth stabilizer 12 parts, adjacent benzene two
Formic acid dioctyl ester 15 parts, antioxidant 1010 10 parts.
A kind of halogen-free high flame-retardant cable material preparation process is as follows:
(1) being placed in calcining furnace by rectorite, high temperature (560 DEG C) is calcined 4 hours, takes out, is placed in anticorrosion container, is slowly added to
The sodium hydroxide solution of 4% 3 times of rectorite quality (consumption be), grinds 60 minutes, filters, add the hydrochloric acid solution of 17%, adjust
Joint pH is 7.0, adds sodium carboxymethyl cellulose, mix homogeneously, dries, pulverize, crosses 90 mesh sieves；
(2) kieselguhr is placed in firing, high temperature (790 DEG C) flash burning 10 seconds, adds the deionized water of 5 times of quality, stand 3 little
Time, it is centrifuged processing 35 minutes with the speed of 1600 r/min, deionized water, washing, dries, pulverize；
(3) magnesium hydroxide is placed in three-roll grinder, adds vinyl-vinyl acetate copolymer, impregnate 5 hours, grind 35
Minute, it is sequentially added into sulfur, calcium lignosulfonate and antioxidant 1010, (consumption is magnesium hydroxide quality to add deionized water
10 times), stir, grind 50 minutes, making slurry granularity is 0.036mm, is heated to isothermal holding 3.5 hours when 155 DEG C, cold
But to room temperature, standby；
(4) be heated to step (3) products therefrom when temperature reaches 72 DEG C being slowly added to white carbon, dioctyl phthalate and
Step (1) products therefrom, mix homogeneously, join in high-speed kneading machine, add epoxy soybean oil and step (2) products therefrom,
(rotating speed is 890 revs/min) stirs 41 minutes at a high speed, fully mediates, and transfers to cooling and stir when material is in expansion loose powder
Mix low speed in machine (rotating speed is 160 revs/min) to stir 10 minutes；
(5) step (4) products therefrom is placed in banbury, falls floating weight mixing 2 minutes, mention floating weight, add boric acid
Zinc and rare-earth stabilizer, fall floating weight mixing 5 minutes, discharging when banburying becomes bulk fritter, mixing, pelletize, dried, sieve
Choosing, packaging.
Test example: in order to verify the performance of one halogen-free high flame-retardant cable material (embodiment 1-5) of the present invention, the present invention is real
Execute example (1-5) gained halogen-free high flame-retardant cable material and other CABLE MATERIALS (purchased from Sheng Er plasthetics company limited of Hebei province, product
Entitled polyvinyl chloride cable material) carry out performance test, (with GB/T8627-2007, " construction material burns to measure smoke density respectively
Or decompose smoke density test method " method be measured), oxygen index (OI) (fire-retardant to test under room temperature with GB/T 2406 method
The oxygen index (OI) of CABLE MATERIALS), dielectric strength, poison exponent (use NES 713, i.e. eudiometry detect), hot strength, disconnected
Split the performance indications such as percentage elongation, aging after-drawing intensity, aging rear elongation at break, wherein, measure aging after-drawing intensity and
During aging rear elongation at break be through 100 DEG C × 168h aging after, then measure hot strength and elongation at break.Measure each
During performance indications, equal replication is averaged for 20 times again, concrete data such as table 1 below:
Table 1 each performance indications concrete condition
From the point of view of the result of this test example, the performance indications of products obtained therefrom of the present invention compared with the performance indications of other CABLE MATERIALS,
Smoke density is low, and oxygen index (OI) is significantly higher, and poison exponent is the most on the low side；Hot strength and elongation at break before aging are the brightest
Aobvious higher, and the product of the present invention through 100 DEG C × 168h aging after, its hot strength and elongation at break are without substantially becoming
Change, more higher than the hot strength of other CABLE MATERIALS and elongation at break, there is physically better mechanical performance, can meet not
The demand of synthermal environmental change, has broad application prospects, and is suitable for marketing.
Finally it should be noted that embodiment is the optimum detailed description of the invention of the present invention, be not limited to this
Invention, although being described in detail the present invention with reference to previous embodiment, for a person skilled in the art, it depends on
So the technical scheme described in foregoing embodiments can be modified, or wherein portion of techniques feature is carried out equivalent replace
Change.All within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included in the present invention
Protection domain within.
Claims (10)
1. a halogen-free high flame-retardant cable material, is characterized in that, takes off and states the raw material of weight proportion and be prepared from: ethylene-acetate second
Enoate copolymer 116-130 part, kieselguhr 12-16 part, sulfur 8-13 part, white carbon 8-12 part, calcium lignosulfonate 9-15 part,
Epoxy soybean oil 5-10 part, sodium carboxymethyl cellulose 7-13 part, magnesium hydroxide 14-20 part, rectorite 6-10 part, Firebrake ZB 6-13
Part, rare-earth stabilizer 9-14 part, dioctyl phthalate 12-17 part, antioxidant 1010 7-12 part.
Halogen-free high flame-retardant cable material the most according to claim 1, is characterized in that, take off state weight proportion raw material preparation and
Become: vinyl-vinyl acetate copolymer 120-125 part, kieselguhr 13-15 part, sulfur 10-12 part, white carbon 9-11 part, wooden
Element sulfoacid calcium 11-13 part, epoxy soybean oil 7-9 part, sodium carboxymethyl cellulose 9-11 part, magnesium hydroxide 16-18 part, rectorite 7-
9 parts, Firebrake ZB 9-11 part, rare-earth stabilizer 11-13 part, dioctyl phthalate 14-16 part, antioxidant 1010 9-11 part.
Halogen-free high flame-retardant cable material the most according to claim 1, is characterized in that, take off state weight proportion raw material preparation and
Become: vinyl-vinyl acetate copolymer 123 parts, 14 parts of kieselguhr, 11 parts of sulfur, white carbon 10 parts, calcium lignosulfonate 12
Part, epoxy soybean oil 8 parts, sodium carboxymethyl cellulose 10 parts, 17 parts of magnesium hydroxide, rectorite 8 parts, Firebrake ZB 10 parts, rare earth are steady
Determine agent 12 parts, dioctyl phthalate 15 parts, antioxidant 1010 10 parts.
4. according to the preparation method of the arbitrary described halogen-free high flame-retardant cable material of claim 1-3, it is characterized in that, step is as follows:
(1) rectorite is placed in calcining furnace, high-temperature calcination 3-5 hour, takes out, be placed in anticorrosion container, be slowly added to 3%-5%
Sodium hydroxide solution, grind 50-70 minute, filter, add 15%-19% hydrochloric acid solution, regulation pH is 6.8-7.2, addition
Sodium carboxymethyl cellulose, mix homogeneously, dry, pulverize, cross 80-100 mesh sieve；
(2) kieselguhr is placed in firing, the high temperature flash burning 8-12 second, adds the deionized water of 4-6 times of quality, stand 2-4 hour,
It is centrifuged processing 30-40 minute with the speed of 1400-1800 r/min, deionized water, washing, dries, pulverize；
(3) magnesium hydroxide is placed in three-roll grinder, adds vinyl-vinyl acetate copolymer, impregnate 4-6 hour, grind
30-40 minute, it is sequentially added into sulfur, calcium lignosulfonate and antioxidant 1010, adds deionized water, stir, grind 40-
60 minutes, making slurry granularity was 0.034-0.039mm, is heated to isothermal holding 3-4 hour when 145-165 DEG C, is cooled to room temperature,
Standby；
(4) step (3) products therefrom is heated to when temperature reaches 68-75 DEG C being slowly added to white carbon, phthalic acid two pungent
Ester and step (1) products therefrom, mix homogeneously, join in high-speed kneading machine, adds epoxy soybean oil and step (2) gained produces
Thing, high-speed stirred 35-46 minute, fully mediate, when material is in expansion loose powder, transfer to low speed in cooling and stirring machine stir
Mix 8-12 minute；
(5) step (4) products therefrom is placed in banbury, falls floating weight mixing 1-2 minute, mention floating weight, add boron
Acid zinc and rare-earth stabilizer, fall floating weight mixing 4-5 minute, discharging when banburying becomes bulk fritter, mixing, pelletize, is dried place
Reason, screening, packaging.
Preparation method the most according to claim 4, is characterized in that: step (1) preferable temperature is 520-580 DEG C, more excellent
Selecting temperature is 560 DEG C.
Preparation method the most according to claim 4, is characterized in that: the consumption of step (1) preferably sodium hydroxide solution is tired
2-4 times of torr stone quality, the more preferably consumption of sodium hydroxide solution are 3 times of rectorite quality.
Preparation method the most according to claim 4, is characterized in that: step (2) preferable temperature is 750-820 DEG C, more excellent
Selecting temperature is 790 DEG C.
Preparation method the most according to claim 4, is characterized in that: the consumption of step (3) preferably deionized water is hydroxide
The consumption of 8-12 times of magnesia amount, more preferably deionized water is 10 times of magnesium hydroxide quality.
Preparation method the most according to claim 4, is characterized in that: during step (4) high-speed stirred, preferred rotating speed is 840-940
Rev/min, more preferably rotating speed is 890 revs/min.
Preparation method the most according to claim 4, is characterized in that: during step (4) stirring at low speed, preferred rotating speed is 140-
180 revs/min, more preferably rotating speed is 160 revs/min.
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| CN201610371536.3A CN105924757A (en) | 2016-05-31 | 2016-05-31 | Halogen-free and high-flame-retardancy cable material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106543725A (en) * | 2016-10-17 | 2017-03-29 | 安徽省绿环电气股份有限公司 | A kind of flame-proof silicon rubber cable material |
| CN107353391A (en) * | 2017-07-18 | 2017-11-17 | 合肥广能新材料科技有限公司 | Halogen-free flameproof rigid polyurethane foam and preparation method thereof |
| CN110527139A (en) * | 2019-02-25 | 2019-12-03 | 福建师范大学 | A kind of zinc borate, anti-flammability composite material and its preparation method |
| CN111171465A (en) * | 2019-12-02 | 2020-05-19 | 东莞福川精密工业股份有限公司 | Photovoltaic cable and preparation method thereof |
| CN111662495A (en) * | 2020-07-04 | 2020-09-15 | 上海方之德新材料有限公司 | Scratch-resistant low-smoke halogen-free flame-retardant polyolefin cable material |
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| CN106543725A (en) * | 2016-10-17 | 2017-03-29 | 安徽省绿环电气股份有限公司 | A kind of flame-proof silicon rubber cable material |
| CN107353391A (en) * | 2017-07-18 | 2017-11-17 | 合肥广能新材料科技有限公司 | Halogen-free flameproof rigid polyurethane foam and preparation method thereof |
| CN110527139A (en) * | 2019-02-25 | 2019-12-03 | 福建师范大学 | A kind of zinc borate, anti-flammability composite material and its preparation method |
| CN110527139B (en) * | 2019-02-25 | 2022-04-22 | 福建师范大学 | Zinc borate, flame-retardant composite material and preparation method thereof |
| CN111171465A (en) * | 2019-12-02 | 2020-05-19 | 东莞福川精密工业股份有限公司 | Photovoltaic cable and preparation method thereof |
| CN111662495A (en) * | 2020-07-04 | 2020-09-15 | 上海方之德新材料有限公司 | Scratch-resistant low-smoke halogen-free flame-retardant polyolefin cable material |
| CN112321954A (en) * | 2020-12-01 | 2021-02-05 | 扬州市缆讯电气技术服务有限公司 | Jet flame and hydrocarbon flame resistant sheath rubber and jet flame and hydrocarbon flame resistant low-voltage cable for marine oil and gas |
| CN112321954B (en) * | 2020-12-01 | 2023-04-04 | 扬州市缆讯电气技术服务有限公司 | Jet flame and hydrocarbon flame resistant sheath rubber and jet flame and hydrocarbon flame resistant low-voltage cable for marine oil and gas |
| CN115160674A (en) * | 2022-07-25 | 2022-10-11 | 巢湖市金鸿电缆有限公司 | Processing method of environment-friendly cable insulating material |
| CN116731453A (en) * | 2023-07-18 | 2023-09-12 | 四川安费尔高分子材料科技有限公司 | Anti-cracking low-smoke flame-retardant polyolefin cable material and preparation method thereof |
| CN116731453B (en) * | 2023-07-18 | 2024-03-19 | 四川安费尔高分子材料科技有限公司 | Anti-cracking low-smoke flame-retardant polyolefin cable material and preparation method thereof |
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Address after: 561000 Guizhou province Xixiu District of Anshun City Zhonghua Road No. 45 Huaxia District 1 building 1-502 Applicant after: Li Xiaotao Address before: 250000 Ji'nan, China Hi tech Zone, Shandong Chong Hua Road, No. 1586 Applicant before: Li Xiaotao |
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Application publication date: 20160907 |