CN103724759B - A kind of halogen-free flame-retardant organosilane self crosslinking polyolefin cable material and preparation method thereof - Google Patents
A kind of halogen-free flame-retardant organosilane self crosslinking polyolefin cable material and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
- B29C48/385—Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in separate barrels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
Abstract
The invention provides a kind of halogen-free flame-retardant organosilane self crosslinking polyolefin cable material, this cable material is expected by A, B expects and C expects to form, the weight ratio between three is 80 ~ 85:3 ~ 5:10 ~ 17.Wherein A material is prepared from by polyolefin resin, softening agent, halogen-free flame retardants, saturated fatty acid, linking agent, initiator, oxidation inhibitor; By polyolefin resin, effective catalyst, oxidation inhibitor, Metal Ion Inhibitor, metal oxide, B, B material expects that processing aid is prepared from, C material is prepared from by polyolefin resin, halogen-free flame retardants, coupling agent, oxidation inhibitor.The invention also discloses the preparation method of halogen-free flame-retardant organosilane self crosslinking polyolefin cable material.Halogen-free flame-retardant organosilane self-crosslinking cable material provided by the invention environmental protection, have good flame retardant resistance, thermotolerance, aging resistance and good processability, preparation technology is simple, energy consumption is low, has good economic benefit.
Description
Technical field
The present invention relates to a kind of halogen-free flame-retardant organosilane self crosslinking polyolefin cable material and preparation method thereof, be mainly used in the flexible cable series products such as transmission line, belong to the production technique field of CABLE MATERIALS.
Background technology
Polyolefin cable material itself has excellent mechanical property and processing characteristics, but the inflammable material of polyolefine material own, when electric energy is subject to internal fault or outside burning things which may cause a fire disaster in cable transportation, cable is easy to initiation fire, in order to reduce fire losses, need to add fire retardant in the material to realize the flame retardant effect of electric wire.
Electric wire and cable material can improve the high thermal resistance of material, resistance to cracking energy, mechanical property and flame retardant properties after crosslinked.Current polyethylene crosslinking main method has three kinds: irradiation crosslinking, peroxide crosslinking method and silane grafting and crosslinking method.The crosslinked polyethylene purity that cross-linking radiation is produced is high, and production technique is simple, but apparatus expensive, has radiation pollution, the more difficult control of production technique; To processing temperature control overflow accurately, accurately, the performance change of manufacturing process slightly deviation product is comparatively large, and the loss caused is huge for peroxide crosslinking method.Organosilane crosslinked polyethylene introduces crosslinkable group by grafting or copolymerization in Polyethylene Chain, and then isomorphism hydrolysis makes it be cross-linked, and does not need specific equipment, and conventional extruder just can processing, and technique is simple.
Traditional two-step approach organosilane crosslinked polyethylene is: first the first step adopts twin screw extruder by Silane Grafted on polyethylene molecular chain, forms A material, secondly catalyzer and polyethylene is expected at twin screw extruder mixing formation B.Second step is extruded after A material and the mixing by a certain percentage of B material, and shaping product is hydrolyzed crosslinked under hot water bath or water vapour.
Existing crosslinked with silicane low smoke and zero halogen product is mostly poach or vapor crosslinking reaction, and the time-consuming power consumption of this process, poach also can affect electric property and the flame retardant properties of material.Chinese patent CN102093625B discloses natural-crosslinked cable material of polyolefin of low smoke and zero halogen one-step method silanes and preparation method thereof, extrude in the single screw extrusion machine of cable in cable producer when the method shortcoming is the graft reaction of silane and occur, require very high for the extrusion equipment of client and expressing technique, if graft reaction controls bad, especially easily there is situation that is not crosslinked or precrosslink.Chinese patent CN101245169B discloses water cooking preventing low-smoke non-halogen flame-proof silicone hydride crosslinked polyolefin composition and preparation method thereof, the method adopts two-step approach to prepare silane natural cross-linking low smoke halogen-free polyolefin flame-retardant material, but its base material A just adds initiator and silane in mixer mixing process, the preparation of this process flame-proof composite material and the Silane Grafted of resin react and carry out simultaneously, absorb after the combination solution that the final step prepared in base material A also adds initiator and silane carries out, in cable extrusion process, still have side reaction produce, quality product is wayward.
Summary of the invention
Object of the present invention mainly solves the above-mentioned problems in the prior art, provides silane natural-crosslinked fire retardant polyolefin cable material of a kind of low smoke and zero halogen and preparation method thereof.
The cable insulation material environmental protection that this production method is produced, there is good flame retardant resistance, thermotolerance, aging resistance and good processability, preparation technology is simple, energy consumption is low, has good economic benefit, is mainly used in the production of 10KV and following power cable insulation layer, during processing cable, extruded velocity is fast, the cable surface made is smooth, and soft, over-all properties is better.
Silane natural cross-linking low smoke halogen-free flame retardant polyolefin cable material of the present invention, is expected by the fire-retardant blend A of Silane Grafted material, catalyzer flame-retardant master batch B expects and highly effective flame-retardant masterbatch C expects to form by weight 80 ~ 85:3 ~ 5:10 ~ 17.
Technical scheme of the present invention is: a kind of halogen-free flame-retardant organosilane self crosslinking polyolefin cable material, is expected, B expects and C expects to form by A;
Composition and the parts by weight of described A material are:
Component and the parts by weight of described B material are:
Component and the parts by weight of described C material are:
Polyolefin resin in described A material, B material and C material selects one or more the mixing in Low Density Polyethylene, ultra-low density polyethylene, linear low density polyethylene, metallocene linear low density polyethylene.
Halogen-free flame retardants in described A material, C material selects one or more the mixing in red phosphorus, aluminium hydroxide, magnesium hydroxide, zinc borate, the agent of phosphorus nitrogen fire-retardant.
In described A material, the one of vinyltrimethoxy silane, vinyltriethoxysilane or vinyl three (2-methoxyethoxy) silane selected by linking agent.
The one in dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide selected by initiator in described A material;
One or more the mixing in 1010,1135,300,168,1076 selected by oxidation inhibitor in described A material, B material and C material.
Effective catalyst in described B material selects one or more the mixing in positive tetrabutyl zirconate, dioctyl dibutyl tin, dibutyltin diacetate, dibutyl tin laurate.
One or more the mixing in ethylene vinyl acetate, ethylene ethyl acrylate, maleic anhydride graft acetic acid ethylene copolymer selected by softening agent in described A material.
Processing aid in described B material selects one or more the mixing of polyethylene with lubricator in amine hydroxybenzene, polyethylene wax, Poly Propylene Wax.
Metal Ion Inhibitor in described B material selects one or more the mixing in oxalic acid diamide, salicylic amide, hydrazine two acyl.
Metal oxide in described B material is one or more the mixing in zinc oxide, aluminum oxide, stannic oxide.
Coupling agent in described B material is solid-state titanate coupling agent or the molecular weight solid-state aluminate coupling agent that is greater than 800 that molecular weight is greater than 800.
Saturated fatty acid in described A material is: stearic acid, lauric acid, sad in one or more mixing.
The preparation method of halogen-free flame-retardant organosilane self crosslinking polyolefin CABLE MATERIALS of the present invention, is characterized in that, comprise the following steps:
(1) preparation of A material;
After A being expected each component weighs, twin screw machine barrel one district that polyolefine and softening agent claim feed system to enter two steps type twin-screw extrusion unit through weightlessness after compounding getting well; Initiator and oxidation inhibitor incorporate linking agent completely, make composite silane, then are squeezed into twin screw machine barrel two district of two steps type twin-screw extrusion unit by filling gun through liquid weightlessness title feed system; Halogen-free flameproof and saturated fatty acid enter twin screw machine barrel six district of two steps type twin-screw extrusion unit after compounding through the side feed system feeding of two steps type twin-screw extrusion unit, the plasticization temperature of machine barrel entirety controls at 130 ~ 190 DEG C, and the Silane Grafted A obtaining having certain flame retardant resistance expects particle;
(2) preparation of B material
Expect to pour in high mixer after raw material weight proportioning is extracted to mix 5 ~ 10 minutes according to above-mentioned B, then compound is extruded through twin screw extruder mixing plasticizing under 140 ~ 190 DEG C of plasticization temperatures, carry out stretching and granulation after extruding, obtain B and expect particulate material;
(3) preparation of C material
Expect to pour in high mixer after raw material weight proportioning is extracted to mix 5 ~ 10 minutes according to above-mentioned C, then compound is extruded through twin screw extruder mixing plasticizing under 140 ~ 190 DEG C of plasticization temperatures, carry out stretching and granulation after extruding, obtain C and expect particulate material;
(4) halogen-free flame-retardant organosilane self crosslinking polyolefin CABLE MATERIALS preparation
The B that fire-retardant grafting A expects particle, prepared by step (2) step (1) prepared expects that highly effective flame-retardant C prepared by particle and step (3) expects that particle is 80 ~ 85:3 ~ 5:10 ~ 17 according to weight ratio, carry out dispersing and mixing, extrude at the temperature of 140 ~ 190 DEG C and obtain halogen-free flame-retardant organosilane self crosslinking polyolefin CABLE MATERIALS.
The macromolecular material of polarity is used in B material of the present invention, i.e. promotor, greatly can accelerate the velocity of diffusion of water molecules, greatly improve the speed of response of hydrolytic crosslinking, add polyethylene rheological agent, i.e. processing aid, greatly strengthen the mobility that grafting A expects, make this complete processing flexibly very convenient, operate simpler.Metal Ion Inhibitor can effectively suppress the catalysis of cable copper core cupric ion to insulation aging, can extend the work-ing life of cable.
Embodiment
Below implementing is further illustrate of the present invention, instead of limits the scope of the invention.
Embodiment 1:
A kind of halogen-free flame-retardant organosilane self crosslinking polyolefin CABLE MATERIALS, is expected by A, B expects and C expects to form;
Composition and the parts by weight of A material are:
Composition and the parts by weight of B material are:
Composition and the parts by weight of C material are:
The preparation method of a kind of halogen-free flame-retardant organosilane self crosslinking polyolefin cable material of this embodiment, comprises the steps:
(1) preparation of A material
After linear low density polyethylene, high density polyethylene(HDPE), ethylene vinyl acetate and maleic anhydride graft acetic acid ethylene copolymer polyolefin resin feedstock are weighed by proportioning, pour in high mixer and stir 5 ~ 10 minutes, carry out feeding through the weightless feed system that claims by the main feed system of two steps type twin-screw extrusion unit again after even after mixed, enter twin screw machine barrel one district of two steps type twin-screw extrusion unit; Dicumyl peroxide, di-tert-butyl peroxide, antioxidant 1010 initiator and oxidation inhibitor 1135 incorporate in vinyltriethoxysilane silane crosslinker completely, make composite silane after mixing, then squeezed into twin screw machine barrel two district of two steps type twin-screw extrusion unit by filling gun through liquid weightlessness title feed system; Red phosphorus, aluminium hydroxide halogen-free flame retardants and stearic acid saturated fatty acid claim feed system through the side feed system feeding of two steps type twin-screw extrusion unit by weightlessness after compounding, enter twin screw machine barrel six district of two steps type twin-screw extrusion unit, the plasticization temperature of machine barrel entirety controls at 130 ~ 190 DEG C.After material plasticizing grafting in singe screw extruding pelletization, the Silane Grafted A obtaining having certain flame retardant resistance expects particle.
(2) B material preparation
Expect to pour in high mixer after raw material weight proportioning is extracted to mix 5 ~ 10 minutes according to above-mentioned B, then compound is extruded through twin screw extruder mixing plasticizing under 140 ~ 190 DEG C of plasticization temperatures, carry out stretching and granulation after extruding, obtain B and expect particulate material;
(3) C material preparation
Expect to pour in high mixer after raw material weight proportioning is extracted to mix 5 ~ 10 minutes according to above-mentioned C, then compound is extruded through twin screw extruder mixing plasticizing under 140 ~ 190 DEG C of plasticization temperatures, carry out stretching and granulation after extruding, obtain C and expect particulate material;
Above-mentioned fire-retardant grafting A is expected particle, B expect that particle and highly effective flame-retardant C expect that particle is according to the part by weight dispersing and mixing of 80:3:17, extrudes and obtains halogen-free flame-retardant organosilane self crosslinking polyolefin CABLE MATERIALS at the temperature of 140 ~ 190 DEG C.
Embodiment 2:
A kind of halogen-free flame-retardant organosilane self crosslinking polyolefin cable material, is expected by A, B expects and C expects to form.Wherein A material component and parts by weight be:
Composition and the parts by weight of A material are:
Composition and the parts by weight of B material are:
Composition and the parts by weight of C material are:
The preparation method of the halogen-free flame-retardant organosilane self crosslinking polyolefin cable material of this embodiment, comprises the steps:
(1) preparation of A material
Linear low density polyethylene, high density polyethylene(HDPE), ethylene vinyl acetate and maleic anhydride graft acetic acid ethylene copolymer polyolefin resin feedstock are after weighing and proportioning, pour in high mixer and stir 5 ~ 10 minutes, carry out feeding through the weightless feed system that claims by the main feed system of two steps type twin-screw extrusion unit again after even after mixed, enter twin screw machine barrel one district of two steps type twin-screw extrusion unit; Dicumyl peroxide, di-tert-butyl peroxide, antioxidant 1010 initiator and antioxidant 300 incorporate in vinyltriethoxysilane silane crosslinker completely, make composite silane after mixing, then squeezed into twin screw machine barrel two district of two steps type twin-screw extrusion unit by filling gun through liquid weightlessness title feed system; Red phosphorus, aluminium hydroxide halogen-free flame retardants and lauric acid saturated fatty acid claim feed system through the side feed system feeding of two steps type twin-screw extrusion unit by weightlessness after compounding, enter twin screw machine barrel six district of two steps type twin-screw extrusion unit, the plasticization temperature of machine barrel entirety controls at 130 ~ 190 DEG C.After material plasticizing grafting in singe screw extruding pelletization, the Silane Grafted A obtaining having certain flame retardant resistance expects particle.
(2) B material preparation
Expect to pour in high mixer after raw material weight proportioning is extracted to mix 5 ~ 10 minutes according to above-mentioned B, then compound is extruded through twin screw extruder mixing plasticizing under 140 ~ 190 DEG C of plasticization temperatures, carry out stretching and granulation after extruding, obtain B and expect particulate material;
(3) C material preparation
Expect to pour in high mixer after raw material weight proportioning is extracted to mix 5 ~ 10 minutes according to above-mentioned C, then compound is extruded through twin screw extruder mixing plasticizing under 140 ~ 190 DEG C of plasticization temperatures, carry out stretching and granulation after extruding, obtain C and expect particulate material;
Above-mentioned fire-retardant grafting A is expected particle, B expect that particle and highly effective flame-retardant C expect that particle is according to the part by weight dispersing and mixing of 82:4:15, extrudes and obtains halogen-free flame-retardant organosilane self crosslinking polyolefin CABLE MATERIALS at the temperature of 140 ~ 190 DEG C.
Embodiment 3:
A kind of halogen-free flame-retardant organosilane self crosslinking polyolefin cable material, is expected by A, B expects and C expects to form.Wherein A material component and parts by weight be:
Composition and the parts by weight of A material are:
Composition and the parts by weight of B material are:
Composition and the parts by weight of C material are:
The preparation method of this embodiment halogen-free flame-retardant organosilane self crosslinking polyolefin cable material, comprises the steps:
(1) preparation of A material
Linear low density polyethylene, high density polyethylene(HDPE), ethylene vinyl acetate and maleic anhydride graft acetic acid ethylene copolymer polyolefin resin feedstock are after weighing and proportioning, pour in high mixer and stir 5 ~ 10 minutes, carry out feeding through the weightless feed system that claims by the main feed system of two steps type twin-screw extrusion unit again after even after mixed, enter twin screw machine barrel one district of two steps type twin-screw extrusion unit; Dicumyl peroxide, di-tert-butyl peroxide, antioxidant 300 initiator and antioxidant 1076 incorporate in vinyltriethoxysilane silane crosslinker completely, make composite silane after mixing, then squeezed into twin screw machine barrel two district of two steps type twin-screw extrusion unit by filling gun through liquid weightlessness title feed system; Red phosphorus, aluminium hydroxide halogen-free flame retardants and lauric acid saturated fatty acid claim feed system through the side feed system feeding of two steps type twin-screw extrusion unit by weightlessness after compounding, enter twin screw machine barrel six district of two steps type twin-screw extrusion unit, the plasticization temperature of machine barrel entirety controls at 130 ~ 190 DEG C.After material plasticizing grafting in singe screw extruding pelletization, the Silane Grafted A obtaining having certain flame retardant resistance expects particle.
(2) B material preparation
Expect to pour in high mixer after raw material weight proportioning is extracted to mix 5 ~ 10 minutes according to above-mentioned B, then compound is extruded through twin screw extruder mixing plasticizing under 140 ~ 190 DEG C of plasticization temperatures, carry out stretching and granulation after extruding, obtain B and expect particulate material;
(3) C material preparation
Expect to pour in high mixer after raw material weight proportioning is extracted to mix 5 ~ 10 minutes according to above-mentioned C, then compound is extruded through twin screw extruder mixing plasticizing under 140 ~ 190 DEG C of plasticization temperatures, carry out stretching and granulation after extruding, obtain C and expect particulate material;
Above-mentioned fire-retardant grafting A is expected particle, B expect that particle and highly effective flame-retardant C expect that particle is according to the part by weight dispersing and mixing of 85:5:10, extrudes and obtains halogen-free flame-retardant organosilane self crosslinking polyolefin CABLE MATERIALS at the temperature of 140 ~ 190 DEG C.
Above three examples adopt JB/T10436-2004 standard to detect, and the results are shown in Table 1.
Table 1 example the performance test results:
The halogen-free flame-retardant organosilane self crosslinking polyolefin cable material that above three examples are prepared into, payingoff speed is fast, and cable surface is smooth, cable extrude after (thickness 1mm), 23 DEG C, place under 65% humidity condition and can complete crosslinked in 2 ~ 3 days.
Claims (8)
1. a halogen-free flame-retardant organosilane self crosslinking polyolefin cable material, is characterized in that, is expected, B expects and C expects to form by A; Wherein A material, B expect that the weight ratio between C material is 80 ~ 85:3 ~ 5:10 ~ 17;
Composition and the parts by weight of described A material are:
Component and the parts by weight of described B material are:
Component and the parts by weight of described C material are:
Metal Ion Inhibitor in described B material selects one or both the mixing in oxalic acid diamide, salicylic amide;
Metal oxide in described B material is one or more the mixing in zinc oxide, aluminum oxide, stannic oxide;
Processing aid in described B material selects one or more the mixing of polyethylene with lubricator in amine hydroxybenzene, polyethylene wax, Poly Propylene Wax;
Effective catalyst in described B material selects one or more the mixing in positive tetrabutyl zirconate, dibutyltin diacetate, dibutyl tin laurate;
Polyolefin resin in described A material, B material and C material selects one or more the mixing in Low Density Polyethylene, ultra-low density polyethylene, linear low density polyethylene, metallocene linear low density polyethylene;
Halogen-free flame retardants in described A material, C material selects one or more the mixing in red phosphorus, aluminium hydroxide, magnesium hydroxide, zinc borate.
2. halogen-free flame-retardant organosilane self crosslinking polyolefin cable material as claimed in claim 1, it is characterized in that, in described A material, the one of vinyltrimethoxy silane, vinyltriethoxysilane or vinyl three (2-methoxyethoxy) silane selected by linking agent.
3. halogen-free flame-retardant organosilane self crosslinking polyolefin cable material as claimed in claim 1, is characterized in that, the one in dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide selected by the initiator in described A material.
4. halogen-free flame-retardant organosilane self crosslinking polyolefin cable material as claimed in claim 1, is characterized in that, one or more the mixing in 1010,1135,300,168,1076 selected by the oxidation inhibitor in described A material, B material and C material.
5. halogen-free flame-retardant organosilane self crosslinking polyolefin cable material as claimed in claim 1, it is characterized in that, one or more the mixing in ethylene vinyl acetate, ethylene ethyl acrylate copolymer, maleic anhydride graft acetic acid ethylene copolymer selected by the softening agent in described A material.
6. halogen-free flame-retardant organosilane self crosslinking polyolefin cable material as claimed in claim 1, is characterized in that, the coupling agent in described C material is solid-state titanate coupling agent or the molecular weight solid-state aluminate coupling agent that is greater than 800 that molecular weight is greater than 800.
7. halogen-free flame-retardant organosilane self crosslinking polyolefin cable material as claimed in claim 1, is characterized in that, the saturated fatty acid in described A material is: stearic acid, lauric acid, sad in one or more mixing.
8. the preparation method of the halogen-free flame-retardant organosilane self crosslinking polyolefin CABLE MATERIALS described in any one of claim 1 to 7 claim, is characterized in that, comprise the following steps:
(1) preparation of A material;
After A being expected each component weighs, twin screw machine barrel one district that polyolefine and softening agent claim feed system to enter two steps type twin-screw extrusion unit through weightlessness after compounding getting well; Initiator and oxidation inhibitor incorporate linking agent completely, make composite silane, then are squeezed into twin screw machine barrel two district of two steps type twin-screw extrusion unit by filling gun through liquid weightlessness title feed system; Halogen-free flame retardants and saturated fatty acid enter twin screw machine barrel six district of two steps type twin-screw extrusion unit after compounding through the side feed system feeding of two steps type twin-screw extrusion unit, the plasticization temperature of machine barrel entirety controls at 130 ~ 190 DEG C, and the Silane Grafted A obtaining having certain flame retardant resistance expects particle;
(2) preparation of B material
Expect to pour in high mixer after raw material weight number takes to mix 5 ~ 10 minutes according to B, then compound is extruded through twin screw extruder mixing plasticizing under 140 ~ 190 DEG C of plasticization temperatures, carry out stretching and granulation after extruding, obtain B and expect particulate material;
(3) preparation of C material
Expect to pour in high mixer after raw material weight number takes to mix 5 ~ 10 minutes according to C, then compound is extruded through twin screw extruder mixing plasticizing under 140 ~ 190 DEG C of plasticization temperatures, carry out stretching and granulation after extruding, obtain C and expect particulate material;
(4) halogen-free flame-retardant organosilane self crosslinking polyolefin CABLE MATERIALS preparation
The B that fire-retardant grafting A expects particle, prepared by step (2) step (1) prepared expects that highly effective flame-retardant C prepared by particle and step (3) expects that particle is 80 ~ 85:3 ~ 5:10 ~ 17 according to weight ratio, carry out dispersing and mixing, extrude at the temperature of 140 ~ 190 DEG C and obtain halogen-free flame-retardant organosilane self crosslinking polyolefin CABLE MATERIALS.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923879A (en) * | 2006-09-19 | 2007-03-07 | 上海电缆研究所 | Silicane crosslinking flame retardant polyolefin cable material with low smoke halogen and preparation technology thereof |
| CN101245169A (en) * | 2008-03-21 | 2008-08-20 | 江苏德威新材料股份有限公司 | Water cooking preventing low-smoke non-halogen flame-proof silicone hydride crosslinked polyolefin composition and method of producing the same |
| CN101781419A (en) * | 2010-01-30 | 2010-07-21 | 江苏上上电缆集团有限公司 | Organosilane crosslinked polyethylene insulation material for 20kV cable and preparation method thereof |
| CN102010538A (en) * | 2010-11-08 | 2011-04-13 | 湖北乐源新材科技有限公司 | Method for preparing natural cross-linking halogen-free flame-retardant polyolefin thermal conductive foam |
| CN102093625A (en) * | 2010-12-17 | 2011-06-15 | 苏州三角洲新材料研发有限公司 | Low smoke non-halogen one-stage process silane naturally crosslinked polyolefin cable material and preparation method thereof |
| CN102532664A (en) * | 2011-12-31 | 2012-07-04 | 上海至正道化高分子材料有限公司 | Silane cross-linked polyethylene insulating material and production method thereof |
| CN103013021A (en) * | 2012-12-31 | 2013-04-03 | 上海至正道化高分子材料有限公司 | Preparation method of silane crosslinked halogen-free flame-retardant polyolefin cable material |
| CN103013020A (en) * | 2012-12-25 | 2013-04-03 | 上海新上化高分子材料有限公司 | Natural silane cross-linking LSOH (Low Smoke Zero Halogen) flame-retardant polyolefin cable material and preparation method thereof |
| CN103087379A (en) * | 2013-02-06 | 2013-05-08 | 上海驰程化工工贸有限公司 | Room-temperature silane cross-linked polyolefin and its preparation method |
-
2013
- 2013-12-05 CN CN201310654906.0A patent/CN103724759B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923879A (en) * | 2006-09-19 | 2007-03-07 | 上海电缆研究所 | Silicane crosslinking flame retardant polyolefin cable material with low smoke halogen and preparation technology thereof |
| CN101245169A (en) * | 2008-03-21 | 2008-08-20 | 江苏德威新材料股份有限公司 | Water cooking preventing low-smoke non-halogen flame-proof silicone hydride crosslinked polyolefin composition and method of producing the same |
| CN101781419A (en) * | 2010-01-30 | 2010-07-21 | 江苏上上电缆集团有限公司 | Organosilane crosslinked polyethylene insulation material for 20kV cable and preparation method thereof |
| CN102010538A (en) * | 2010-11-08 | 2011-04-13 | 湖北乐源新材科技有限公司 | Method for preparing natural cross-linking halogen-free flame-retardant polyolefin thermal conductive foam |
| CN102093625A (en) * | 2010-12-17 | 2011-06-15 | 苏州三角洲新材料研发有限公司 | Low smoke non-halogen one-stage process silane naturally crosslinked polyolefin cable material and preparation method thereof |
| CN102532664A (en) * | 2011-12-31 | 2012-07-04 | 上海至正道化高分子材料有限公司 | Silane cross-linked polyethylene insulating material and production method thereof |
| CN103013020A (en) * | 2012-12-25 | 2013-04-03 | 上海新上化高分子材料有限公司 | Natural silane cross-linking LSOH (Low Smoke Zero Halogen) flame-retardant polyolefin cable material and preparation method thereof |
| CN103013021A (en) * | 2012-12-31 | 2013-04-03 | 上海至正道化高分子材料有限公司 | Preparation method of silane crosslinked halogen-free flame-retardant polyolefin cable material |
| CN103087379A (en) * | 2013-02-06 | 2013-05-08 | 上海驰程化工工贸有限公司 | Room-temperature silane cross-linked polyolefin and its preparation method |
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