CN109627565A - 150 DEG C of heatproof of low-smoke zero-halogen cable material formula and preparation method - Google Patents
150 DEG C of heatproof of low-smoke zero-halogen cable material formula and preparation method Download PDFInfo
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- CN109627565A CN109627565A CN201811592199.6A CN201811592199A CN109627565A CN 109627565 A CN109627565 A CN 109627565A CN 201811592199 A CN201811592199 A CN 201811592199A CN 109627565 A CN109627565 A CN 109627565A
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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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
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- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2461/04, C08J2461/18, and C08J2461/20
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Abstract
The invention discloses a kind of 150 DEG C of heatproof of low-smoke zero-halogen cable material formula and preparation methods.It includes: 100 parts of base resins that each component is calculated based on parts by weight；5-20 parts of benzoxazine resins；65-90 parts of composite flame-retardant agents；16-20 parts of compatilizers；0.5-0.8 parts of antioxidant；1.0-1.5 parts of lubricants；6-8 parts of crosslinking sensitizers.
Description
Technical field
The present invention relates to a kind of electric cable material with low smoke and halogen free formula and preparation methods, and in particular to a kind of 150 DEG C of heatproof irradiation
Cross-linking low smoke halogen-free flame retardant CABLE MATERIALS and preparation method.
Background technique
Wire and cable can generate heat under load current, and the temperature of cable is high, is at this time just easy to cause
Fire.Therefore general CABLE MATERIALS requires anti-flammability and thermal conductivity.Traditional CABLE MATERIALS mostly uses halogen fire proofing, although
Its flame retardant effect is outstanding, but can discharge a large amount of toxic smogs when its burning, and very big injury can be caused to human body and equipment.With
Environmental regulation it is stringent, halogen CABLE MATERIALS is gradually replaced fireproofing cable material without halide.Fireproofing cable material without halide
In order to meet fire-retardant and Halogen requirement, the design being generally formulated uses polyolefin for substrate, a large amount of inorganic fire retardants is added
To obtain the flame retardant effect of requirement.On the one hand research in relation to wire and cable improves the pyroconductivity of material, reduces the temperature of material
It rises and improves its durability, on the other hand when wire cable material reaches certain temperature, it is necessary to which material has certain heat-resisting
When performance, even electric wire and cable material normal use temperature are 150 DEG C, due to being chronically at high temperature, it is easy to happen aging embrittlement,
Material can lose-protective value, it is therefore desirable to take measures to find electric wire and cable material heating conduction, flame retardant property and mechanical property
The equalization point of energy.
Inorganic fire retardants is added in electric wire and cable material, and flame retardant property can be improved and improves material to a certain extent
Pyroconductivity, but the disadvantage is that mechanical properties decrease, reduces the crosslink density of resin material, heat resistance reduces.
Such as be directed to wire and cable it is thermally conductive in terms of, done some researchs both at home and abroad in recent years, low thermal resistance material can be bright
The aobvious current-carrying capacity for improving wire and cable.High heat conductive insulating rubber mass and preparation side of the CN108659355A for ship deperming cable
Mentioned in method, add resin quality 50% 2 microns of boron nitride BN/30 nano aluminum nitride AlN granulate mixtures (mass ratio 3:
1) thermal conductivity of cable material, can be improved, but its additive amount is high, and since inorganic filler is rigidly strong, is easy cracking.
Inorganic fire retardants in the low-smoke zero-halogen cable material formula and preparation method that CN103739927B temperature resistant grade is 150 DEG C
For the 130%-150% of resin, resistance to cracking is poor, and tensile strength needs to be further increased in 11-13Mpa.
Therefore there is an urgent need in the art to reduce inorganic resistance under the premise of meeting or improving electric wire and cable material flame-retardancy requirements
The additive amount for firing agent to improve the mechanical properties such as tensile strength, elongation at break, and improves the crosslink density of resin and heat-resisting
Property, that is, develop a kind of anti-flammability and mechanical property is good, low-smoke zero-halogen cable material resistant to high temperature.
Summary of the invention
The present invention is intended to provide a kind of 150 DEG C of irradiated crosslinking low-smoke and halogen-free flame retardant CABLE MATERIALSs of heatproof, temperature resistant grade is high, fire-retardant
Excellent, and keep excellent mechanical performances.
The second object of the present invention is to provide a kind of preparation of 150 DEG C of irradiated crosslinking low-smoke and halogen-free flame retardant CABLE MATERIALSs of heatproof
Method.
In the first aspect of the present invention, a kind of 150 DEG C of heatproof of low-smoke zero-halogen cable material, each component are provided
Include: based on parts by weight
100 parts of base resin；
The base resin is ethylene-vinyl acetate (EVA), high density polyethylene (HDPE) (HDPE) and ethylene-octene copolymerization
The mixture of object (POE)；
5-20 parts of benzoxazine resin；
The benzoxazine resin is prepared by the mixture of bisphenol-A, allyl amine and paraformaldehyde, bisphenol-A, alkene
The molar ratio of propyl amine and paraformaldehyde is (1-2): (2-4): (3-5)；
65-90 parts of composite flame-retardant agent；
The composite flame-retardant agent includes:
In another preferred example, the low-smoke zero-halogen cable material each component is calculated based on parts by weight by such as the following group
It is grouped as:
100 parts of base resin；
The base resin is ethylene-vinyl acetate (EVA), high density polyethylene (HDPE) (HDPE) and ethylene-octene copolymerization
The mixture of object (POE)；
5-20 parts of benzoxazine resin；
The benzoxazine resin is prepared by the mixture of bisphenol-A, allyl amine and paraformaldehyde, bisphenol-A, alkene
The molar ratio of propyl amine and paraformaldehyde is (1-2): (2-4): (3-5)；
65-90 parts of composite flame-retardant agent；
The composite flame-retardant agent includes:
In another preferred example, the base resin includes:
50-80 parts of ethylene-vinyl acetate (EVA)；
10-30 parts of high density polyethylene (HDPE) (HDPE)；
10-30 parts of ethylene-octene copolymer (POE).
In another preferred example, the benzoxazine resin softening point is 70 DEG C -80 DEG C.
In another preferred example, the benzoxazine resin be make bisphenol-A, allyl amine and paraformaldehyde mixing after
100 ± 5 DEG C of reactions obtain for 4-6 hours.
In another preferred example, in the low-smoke zero-halogen cable material,
The VA content of ethylene-vinyl acetate (EVA) is 30-35%, with the calculating of ethylene-vinyl acetate total weight, is melted
Body index is 0.5-2.5g/10min；
The melt index of high density polyethylene (HDPE) (HDPE) are as follows: 0.5-1.5g/10min；
The melt index of ethylene-octene copolymer (POE) are as follows: 1.0-1.5g/10min, density 0.860-0.865g/
cm3。
In another preferred example, the compatilizer is ethylene-vinyl acetate grafted maleic anhydride copolymer (EVA-g-
MAH), grafting rate 0.5-5%, melt index (MI) 0.5-2.5g/10min (measurement of GB/T3682-2000 method).
In another preferred example, the antioxidant is six [β-(3,5- di-t-butyl -4- hydroxy-pheny) propionamide phenyl]
Ring triphosphine nitrile (HACP).
In another preferred example, the lubricant is selected from following a combination of one or more: organosilicon lubrication is female
Grain, silicone powder, zinc stearate, PE wax.
In another preferred example, organosilicon lubrication master batch is dimethyl silicone polymer raw rubber and polyacrylic mixing,
Dimethyl silicone polymer raw rubber and polyacrylic molar ratio are 1:1.
In another preferred example, the crosslinking sensitizer is trimethylol-propane trimethacrylate (TMPTMA) SR-
350 and three (2- ethoxy) isocyanuric acid triacrylate SR-368 mixing.
In another preferred example, trimethylol-propane trimethacrylate (TMPTMA) SR-350 and three (2- hydroxyls
Ethyl) isocyanuric acid triacrylate SR-368 mass ratio be 1:1.
In the second aspect of the present invention, a kind of 150 DEG C of heatproof of cross-linking radiation provided present invention as described above is provided
The preparation method of electric cable material with low smoke and halogen free, described to comprise the following steps that repeatedly:
The CABLE MATERIALS each component provided present invention as described above is provided；
Each component is sequentially added into mixer, mixing mixing discharging；
Using dual-screw pelletizer extruding pelletization, 150 DEG C of heatproof of the irradiation provided present invention as described above is handed over
Join electric cable material with low smoke and halogen free.
In another preferred example, the benzoxazine resin be make bisphenol-A, allyl amine and paraformaldehyde mixing after
100 ± 5 DEG C of reactions obtain for 4-6 hours；
The composite flame-retardant agent is to mix magnesium hydroxide, aluminium hydroxide and hypo-aluminum orthophosphate to 95 ± 5 DEG C, stirs 10-15
Minute and obtain.
In another preferred example, four temperature sections during the extruding pelletization are as follows: 115-120 DEG C of feeding section, conveying
115-120 DEG C, 130-140 DEG C of melt zone, 135-140 DEG C of head of section.
In the third aspect of the present invention, a kind of benzoxazine resin is provided, the benzoxazine resin contains following structures
Unit:
In another preferred example, the benzoxazine resin softening point is 70 DEG C -80 DEG C.
In the fourth aspect of the present invention, a kind of preparation side of benzoxazine resin provided present invention as described above is provided
Method, the method includes the steps: be prepared by bisphenol-A, allyl amine and paraformaldehyde, the bisphenol-A, allyl amine and
The molar ratio of paraformaldehyde is (1-2): (2-4): (3-5).
In another preferred example, the method includes the steps: be in molar ratio by bisphenol-A, allyl amine and paraformaldehyde
(1-2): (2-4): the benzo provided present invention as described above for 4-6 hours is provided after (3-5) mixing at 100 ± 5 DEG C and is disliked
Piperazine resin.
In the fifth aspect of the invention, a kind of use of benzoxazine resin provided present invention as described above is provided
On the way, the purposes includes the low-smoke zero-halogen cable material and its product for 150 DEG C of heatproof；Or it is used to prepare heatproof
150 DEG C of low-smoke zero-halogen cable material and its product.
Accordingly, the present invention provides a kind of anti-flammability and mechanical property are good, irradiated crosslinking low-smoke and halogen-free cable resistant to high temperature
Material.
Specific embodiment
The present inventor after extensive and in-depth study, by improving formula and preparation process, obtains anti-flammability and power
It is good to learn performance, and low-smoke halogen-free flame-retardant sheath material resistant to high temperature and preparation method thereof.The present invention is completed on this basis.
Specifically, the present invention has synthesized a kind of specific benzoxazine resin, and good toughness, heat-resisting height, crosslink density are high,
It is used cooperatively simultaneously by it with composite flame-retardant agent and obtains a kind of 150 DEG C of irradiated crosslinking low-smoke and halogen-free flame retardant CABLE MATERIALSs of heatproof, solved
Existing low-smoke zero-halogen cable material of having determined is easy out due to adding a large amount of filled-type inorganic fire retardants, long-time service
Hot rate of release and the problem of cigarette rate of release when splitting, while reducing low-smoke zero-halogen cable material burning, so as to subtract
Small fire is damaged caused by personnel and property.
In the present invention, term " containing " or " comprising " indicate that various composition can be applied to mixture or group of the invention together
It closes in object.Therefore, term " mainly by ... form " and " consist of " are included in term " containing " or " comprising ".
It is described in detail to various aspects of the present invention below:
The low-smoke zero-halogen cable material that 150 DEG C of heatproof
The present invention provides a kind of 150 DEG C of heatproof of low-smoke zero-halogen cable material, each component includes:
Base resin
The content of each ingredient is the basic tree in terms of 100 parts by weight are by the base resin contained in CABLE MATERIALS of the present invention
Rouge includes being blended by ethene-vinyl acetate copolymer (EVA), high density polyethylene (HDPE) (HDPE) and ethylene-octene copolymer (POE)
And it obtains.The blend method is not specifically limited, can be using conventional blend method, this is for those skilled in the art
It is known.
In a preferred example, the base resin is the mixture of the component of following parts by weight: ethane-acetic acid ethyenyl is total
50-80 parts of polymers (EVA), 10-30 parts of high density polyethylene (HDPE) (HDPE), 10-30 parts of ethylene-octene copolymer (POE).
In a preferred example, ethene-vinyl acetate copolymer (EVA) melt index (MI) is 0.5-2.5g/10min, is surveyed
Strip part are as follows: temperature is 190 DEG C, load 2.16KG, with the total weight of copolymer, vinyl acetate content 30-35%.
In a preferred embodiment, high density polyethylene (HDPE) (HDPE) melt index (MI) is 0.5-1.5g/10min, test
Condition are as follows: temperature is 190 DEG C, load 2.16KG.
In a preferred example, ethylene-octene copolymer (POE) density is 0.860-0.865g/cm3, melt index (MI)
1.0-l.5g/10min, test condition are as follows: temperature is 190 DEG C, and load 2.16KG, with the total weight of copolymer, octene contains
Amount is 28-40%.
Benzoxazine resin
Contain 5-20 parts by weight benzoxazine resin in CABLE MATERIALS of the present invention, the raw material of the benzoxazine resin includes double
Phenol A, allyl amine and paraformaldehyde.
In a preferred example, 10-20 Patent Law benzoxazine resin is contained in CABLE MATERIALS of the present invention.
In a preferred example, the raw material group of the benzoxazine resin becomes rubbing for bisphenol-A, allyl amine and paraformaldehyde
You are than being (1-2): (2-4): (3-5).
In one embodiment, the benzoxazine resin appearance is yellowish-brown powder, and softening point is 70 DEG C -80 DEG C, is surveyed
Method for testing " GB/T 4507-2014 asphalt softening point measuring method ring and ball method ".
In a preferred example, the benzoxazine resin flame retardant rating V-1, is tested, Residual carbon is reachable through TGA thermal weight loss
56% or more, 400 DEG C of initial temperature of thermal decomposition or more.
In a preferred example, contain following formula in the benzoxazine resin structure:
In one embodiment, the benzoxazine resin is prepared by following step:
Bisphenol-A, allyl amine and paraformaldehyde are (1-2) by the first step in molar ratio: (2-4): (3-5) is 100 ± 5
It is reacted 4-6 hours at DEG C；
Second step crushes after cooling, obtains benzoxazine resin.
Composite flame-retardant agent
The present invention contains 65-90 parts by weight composite flame-retardant agent, and the composite flame-retardant agent is by the fire-retardant of following parts by weight
Agent composition: 50-60 parts of aluminium hydroxide, 10-20 parts of magnesium hydroxide and 5-10 parts of hypo-aluminum orthophosphate.
Antioxidant
The present invention contains 0.5-0.8 parts by weight antioxidant, and the antioxidant is six [β-(3,5- di-t-butyl -4- hydroxyls
Base-phenyl) propionamide phenyl] ring triphosphine nitrile (HACP), four [β (3.5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites
Ester (antioxidant 1010), 2'2- oxalyl amido-bis--[ethyl -3- (3,5- di-t-butyl -4- hydroxyphenyl)] propionic ester (antioxidant
One or more of 697) combination.
Lubricant
The present invention contains 1.0-1.5 parts by weight lubricant, and the lubricant is that organosilicon lubricates master batch, silicone powder, hard
One of resin acid zinc, PE wax or any two or more mixing.
In a preferred example, dimethyl silicone polymer raw rubber and polypropylene molar ratio are 1 in the organosilicon lubrication master batch:
1。
Compatilizer
The present invention contains 16-20 parts by weight of compatible agent, and the compatilizer is ethene-vinyl acetate vinegar grafted maleic anhydride
Copolymer (EVA-g-MAH).
In a preferred example, the grafting rate of EVA-g-MAH is 0.5-5%, melt index (MI) 0.5-2.5g/10min, test-strips
Part are as follows: temperature is 190 DEG C, load 2.16KG.
Crosslinking sensitizer
The present invention contains 6-8 parts by weight crosslinking sensitizer, and the crosslinking sensitizer is trimethylol propane trimethyl third
Olefin(e) acid ester (TMPTMA) SR-350 and three (2- ethoxy) isocyanuric acid triacrylate SR-368 composition (mass ratio 1:
1)。
It is 150 DEG C that product of the invention, which is able to satisfy using warm grade, and has splendid flame retardant property and processing performance,
Many environment special occasions are able to satisfy to use.
More specifically show:
1, compared with prior art, the present invention 150 DEG C of low-smoke zero-halogen cable material tools of the modified heatproof of benzoxazine
The features such as having resistance to cracking good, flame retardant property is good, electrothermal calefactive rate and fuming rate are lower in combustion process.The benzo used is disliked
Piperazine resin has the excellent characteristic such as high heat resistance, low moisture absorption, high hardness and corrosion resistance, lower shrinkage, fire-retardant, electrical isolation, with second
After alkene-vinyl acetate copolymer (EVA), high density polyethylene (HDPE) (HDPE), ethylene-octene copolymer (POE) melt blending, in electricity
It can play the role of improving heat-resisting, enhancing mechanical property in the frame structure of cable material.
2, the benzoxazine resin used has certain flame-retarding characteristic, plays with the hypo-aluminum orthophosphate in composite flame-retardant agent
The Residual carbon of cooperative flame retardant effect, benzoxazine resin is high, and finer and close carburization zone can be formed under the action of hypo-aluminum orthophosphate, because
The anti-flammability of CABLE MATERIALS can be improved using the modified 150 DEG C of low-smoke zero-halogen cable materials of heatproof of benzoxazine in this.In addition,
The cooperative flame retardant acts on the dosage that can reduce the such inorganic fire retardants of aluminium hydroxide, improves resistance to cracking and mechanical property (stretches
Intensity, elongation at break).
3, the benzoxazine resin used has the characteristic of high-intensity high heat-resistance, is modified the low cigarette of 150 DEG C of cross-linking radiations with this
The heat-resisting and mechanical property of CABLE MATERIALS can be improved in halogen-free cable material.
Preparation method
The second aspect of the present invention provides a kind of 150 DEG C of heatproof as described in the present invention of irradiated crosslinking low-smoke and halogen-free cable
The preparation method of material, comprises the following steps that:
The first step provides CABLE MATERIALS each component as described in the present invention；
Second step, base resin, benzoxazine resin, composite flame-retardant agent, lubricant, antioxidant, compatilizer, crosslinking is quick
Agent sequentially adds mixer, mixing mixing discharging；
Third step obtains the low cigarette of the modified 150 DEG C of cross-linking radiations of heatproof of benzoxazine using dual-screw pelletizer extruding pelletization
Halogen-free cable material.
In one embodiment of the invention, it is prepared what the present invention used by foregoing manner in the above-mentioned first step
Benzoxazine resin.
In one embodiment of the invention, composite flame-retardant agent is prepared by following step in the above-mentioned first step: will hindered
Combustion agent is proportionally mixed to temperature to 95 ± 5 DEG C, is stirred 10-15 minutes and is discharged.
In one embodiment of the invention, four temperature sections during the extruding pelletization of above-mentioned third step are as follows: add
115-120 DEG C of section of material, 115-120 DEG C of conveying section, 130-140 DEG C of melt zone, 135-140 DEG C of head.
Unless specific instructions, raw material of the invention can be by being commercially available；Or the conventional method system according to this field
It is standby to obtain.Unless otherwise defined or described herein, all professional and scientific terms used herein and the skilled people of art technology
Meaning known to member is identical.Furthermore any method similar to or equal to what is recorded and material all can be applied to the present invention
In method.
Other aspects of the present invention are apparent to those skilled in the art due to this disclosure
's.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually marks according to country
Quasi- measurement.If being built without corresponding national standard according to general international standard, normal condition or according to manufacturer
The condition of view carries out.Unless otherwise stated, otherwise all number is parts by weight, and all percentage is weight percentage, institute
The polymer molecular weight stated is number-average molecular weight.
Unless otherwise defined or described herein, all professional and scientific terms used herein and the skilled people of art technology
Meaning known to member is identical.Furthermore any method similar to or equal to what is recorded and material all can be applied to the present invention
In method.
Embodiment
Below in conjunction with specific embodiment, the present invention is furture elucidated.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Referring to table 1, each raw material dosage unit is gram for embodiment 1-6 and the composition of raw materials of comparative example；The performance of products obtained therefrom
Test result is shown in Table 2.
Benzoxazine resin used in embodiment 1-6 the preparation method is as follows:
In molar ratio (1-2) by bisphenol-A, allyl amine and paraformaldehyde: (2-4): (3-5) reacts 5 small at 100 DEG C
When, it is made after cooling through crushing, appearance is yellowish-brown powder, and softening point is 80 DEG C.
Crosslinking sensitizer used in embodiment 1-6 and comparative example is trimethylol-propane trimethacrylate
(TMPTMA) composition (mass ratio 1:1) of SR-350 and three (2- ethoxy) isocyanuric acid triacrylate SR-368.
Performance test standard:
1, tensile strength: " the measurement second part of GBT 1040.2-2006 plastic tensile performance: molding and extrusion molding plastics
Experiment condition "
2, elongation at break: " the measurement second part of GBT 1040.2-2006 plastic tensile performance: molding and extrusion molding modeling
The experiment condition of material "
3, oxygen index (OI): " GBT 2406.2-2009 plastics oxygen index method measures burning behavior part 2 room temperature and tests "
4, heat release rate peak value: " GB/T 31248-2014 cable or optical cable propagation of flame heat under the conditions of by fire discharge
With the test method for producing cigarette characteristic "；" GB/T 8323.1-2008 plastics cigarette generates part 1: smoke density test method directive/guide "
5, smoke density: " the smoke density measurement the 1st that GB/T 17651.1-1998 cable or optical cable burn under given conditions
Part: experimental rig "
6, hardness Shore A: the sclerometer " survey of GB/T 6031-2017 vulcanized rubber or thermoplastic elastomer hardness is used
It is fixed "
Table 1
Table 2
The result shows that CABLE MATERIALS intensity height provided by the invention, good flame retardation effect, smoke density are low, heat release rate peak value
It is low, it is that a kind of anti-flammability and mechanical property are good, low-smoke zero-halogen cable material resistant to high temperature.
The foregoing is merely illustrative of the preferred embodiments of the present invention, the substantial technological content model being not intended to limit the invention
It encloses, substantial technological content of the invention is broadly defined in the scope of the claims of application, any technology that other people complete
Entity or method also or a kind of equivalent change, will if identical with defined in the scope of the claims of application
It is considered as being covered by among the scope of the claims.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, those skilled in the art can be right after having read above content of the invention
The present invention makes various changes or modifications, and these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (19)
1. a kind of 150 DEG C of heatproof of low-smoke zero-halogen cable material, each component include: based on parts by weight
100 parts of base resin；
The base resin is ethylene-vinyl acetate (EVA), high density polyethylene (HDPE) (HDPE) and ethylene-octene copolymer
(POE) mixture；
5-20 parts of benzoxazine resin；
The benzoxazine resin is prepared by the mixture of bisphenol-A, allyl amine and paraformaldehyde, bisphenol-A, allyl
The molar ratio of amine and paraformaldehyde is (1-2): (2-4): (3-5)；
65-90 parts of composite flame-retardant agent；
The composite flame-retardant agent includes:
2. low-smoke zero-halogen cable material as described in claim 1, wherein its each component is calculated based on parts by weight by such as
The following group is grouped as:
100 parts of base resin；
The base resin is ethylene-vinyl acetate (EVA), high density polyethylene (HDPE) (HDPE) and ethylene-octene copolymer
(POE) mixture；
5-20 parts of benzoxazine resin；
The benzoxazine resin is prepared by the mixture of bisphenol-A, allyl amine and paraformaldehyde, bisphenol-A, allyl
The molar ratio of amine and paraformaldehyde is (1-2): (2-4): (3-5)；
65-90 parts of composite flame-retardant agent；
The composite flame-retardant agent includes:
3. low-smoke zero-halogen cable material as described in claim 1, which is characterized in that the base resin includes:
50-80 parts of ethylene-vinyl acetate (EVA)；
10-30 parts of high density polyethylene (HDPE) (HDPE)；
10-30 parts of ethylene-octene copolymer (POE).
4. low-smoke zero-halogen cable material as described in claim 1, which is characterized in that the benzoxazine resin softening
Point is 70 DEG C -80 DEG C.
5. low-smoke zero-halogen cable material as described in claim 1, which is characterized in that the benzoxazine resin is to make
It is obtained within 4-6 hours after bisphenol-A, allyl amine and paraformaldehyde mixing in 100 ± 5 DEG C of reactions.
6. low-smoke zero-halogen cable material as described in claim 1, wherein
The VA content of ethylene-vinyl acetate (EVA) is 30-35%, and with the calculating of ethylene-vinyl acetate total weight, melt refers to
Number is 0.5-2.5g/10min；
The melt index of high density polyethylene (HDPE) (HDPE) are as follows: 0.5-1.5g/10min；
The melt index of ethylene-octene copolymer (POE) are as follows: 1.0-1.5g/10min, density 0.860-0.865g/cm3。
7. low-smoke zero-halogen cable material as described in claim 1, which is characterized in that the compatilizer is ethylene-vinegar
Vinyl acetate grafted maleic anhydride copolymer (EVA-g-MAH), grafting rate 0.5-5%, melt index (MI) 0.5-2.5g/10min
(measurement of GB/T3682-2000 method).
8. low-smoke zero-halogen cable material as described in claim 1, which is characterized in that the antioxidant be six [β-(3,
5- di-t-butyl -4- hydroxy-pheny) propionamide phenyl] ring triphosphine nitrile (HACP).
9. low-smoke zero-halogen cable material as described in claim 1, which is characterized in that the lubricant is selected from following
A combination of one or more: organosilicon lubricates master batch, silicone powder, zinc stearate, PE wax.
10. low-smoke zero-halogen cable material as claimed in claim 9, which is characterized in that the organosilicon lubricates master batch
It is dimethyl silicone polymer raw rubber and polyacrylic mixing, dimethyl silicone polymer raw rubber and polyacrylic molar ratio are 1:1.
11. low-smoke zero-halogen cable material as described in claim 1, which is characterized in that the crosslinking sensitizer is three
Methylolpropane trimethacrylate (TMPTMA) SR-350 and three (2- ethoxy) isocyanuric acid triacrylate SR-368
Mixing.
12. a kind of preparation of such as low-smoke zero-halogen cable material of 150 DEG C of the described in any item heatproofs of claim 1-11
Method, which is characterized in that described to comprise the following steps that repeatedly:
Such as the described in any item CABLE MATERIALS each components of claim 1-11 are provided；
Each component is sequentially added into mixer, mixing mixing discharging；
Using dual-screw pelletizer extruding pelletization, obtains 150 DEG C of the described in any item heatproofs of claim 1-11 of irradiation such as and hand over
Join electric cable material with low smoke and halogen free.
13. preparation method as claimed in claim 13, which is characterized in that the benzoxazine resin is to make bisphenol-A, allyl
It is obtained within 4-6 hours after amine and paraformaldehyde mixing in 100 ± 5 DEG C of reactions；
The composite flame-retardant agent is to mix magnesium hydroxide, aluminium hydroxide and hypo-aluminum orthophosphate to 95 ± 5 DEG C, is stirred 10-15 minutes
And it obtains.
14. preparation method as claimed in claim 13, which is characterized in that four temperature sections during the extruding pelletization
Are as follows: 115-120 DEG C of feeding section, 115-120 DEG C of conveying section, 130-140 DEG C of melt zone, 135-140 DEG C of head.
15. a kind of benzoxazine resin, which is characterized in that the benzoxazine resin contains following structural units:
16. benzoxazine resin as claimed in claim 15, which is characterized in that the benzoxazine resin softening point is 70
℃-80℃。
17. a kind of preparation method of the benzoxazine resin as described in claim 15 or 16, which is characterized in that the method packet
It includes step: being prepared by bisphenol-A, allyl amine and paraformaldehyde, the bisphenol-A, allyl amine and paraformaldehyde rub
You are than being (1-2): (2-4): (3-5).
18. preparation method as claimed in claim 17, which is characterized in that the method includes the steps: by bisphenol-A, allyl
Amine and paraformaldehyde are (1-2) in molar ratio: (2-4): being obtained such as right within 4-6 hours after (3-5) mixing in 100 ± 5 DEG C of reactions
It is required that benzoxazine resin described in 15 or 16.
19. a kind of benzoxazine resin as described in claim 15 or 16 is used for 150 DEG C of heatproof of irradiated crosslinking low-smoke and halogen-free
CABLE MATERIALS and its product；Or the application in 150 DEG C of heatproof of preparation of low-smoke zero-halogen cable material and its product.
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