CN106397962A - Flame-resistant PE composite cable material, and preparation method thereof - Google Patents
Flame-resistant PE composite cable material, and preparation method thereof Download PDFInfo
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- CN106397962A CN106397962A CN201610842060.7A CN201610842060A CN106397962A CN 106397962 A CN106397962 A CN 106397962A CN 201610842060 A CN201610842060 A CN 201610842060A CN 106397962 A CN106397962 A CN 106397962A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- C08K2201/011—Nanostructured additives
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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
- 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
- C08L2205/02—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
Abstract
The invention provides a flame-resistant PE composite cable material. The flame-resistant PE composite cable material is prepared from, by weight, 100 parts of PE, 0.4 to 0.9 part of a lubricating agent, 2 to 4 parts of a cross-linking agent, 1 to 1.5 parts of an antioxidant, 20 to 25 parts of a filler, 0.5 to 1 part of a coupling reagent, 0.1 to 0.6 part of an ultraviolet light absorber, 10 to 15 parts of an elastomer, and 9 to 14 parts of a phosphorus boron silicon composite flame retardant. The invention also discloses a preparation method of the flame-resistant PE composite cable material. The flame-resistant PE composite cable material is relatively excellent in flame resistance.
Description
Technical field
The present invention relates to a kind of CABLE MATERIALS, more particularly to a kind of fire-retardant PE composite cable material and preparation method thereof.
Background technology
PE is the English abbreviation of polyethylene, is a kind of aggregated thermoplastic resin of ethylene, odorless, nontoxic, feel
Ceraceous, has excellent resistance to low temperature (minimum use temperature is up to -70 to -100 DEG C), chemical stability is good, is resistant to mostly
The corrosion (acid intolerant to having oxidizing property) of number soda acid, does not dissolve in common solvent under room temperature, water absorption is little, and electrical insulation capability is excellent
Good, it is therefore the preferable raw material making CABLE MATERIALS.But, PE is inflammable and may proceed to burn after fire, in burning intermittent fever release speed
Rate is big, and calorific value is high, flame propagation speed, is therefore difficult to extinguish.
Publication No. CN103214712B, publication date are 2015.09.09, apply for that artificial Anhui double honor appliance cord is limited
The Chinese patent of company discloses " a kind of Cold-tolerant polyethylene cable material and preparation method thereof ", and the weight portion of its constitutive material is：
Hi-fax 1802：95-105, Tissuemat E：0.04-0.06, ethylene glycol：0.04-0.06, antioxidant 1010：0.09-
0.11st, ethylene bis stearic acid amide：0.02-0.04, rheological agent PPA：0.07-0.09, antioxidant MB：0.01-0.03, modified tree
Wood ash cinder：0.3-0.5, Firebrake ZB：0.008-0.012 and antioxidant 1024：0.04-0.06；This invention adopts Hi-fax
1802 as the present invention basic material, increased adjuvant Tissuemat E, ethylene glycol, modified tree ash, age resistor, boron simultaneously
Sour zinc and multiple antioxidant, solve cable material and can not meet the use situation that works under cold-resistant environment, and have good
Good wear-resisting, oil resistant, insulation electrical, physical mechanical and the characteristic of softness.However, similarly there is resistance in this poly-ethylene cable material
Poor, the inflammable defect of combustion property.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of fire-retardant PE composite cable material, and its anti-flammability is stronger.
For solving above-mentioned technical problem, the technical scheme is that：
A kind of fire-retardant PE composite cable material, its weight portion component is：100 parts of PE, 0.4～0.9 part of lubricant, cross-linking agent 2
～4 parts, 1～1.5 part of antioxidant, 20～25 parts of filler, 0.5～1 part of coupling agent, 0.1～0.6 part of UV absorbent, elasticity
10～15 parts of body, 9～14 parts of phosphorus borosilicate composite flame-retardant agent.
Preferably, PE of the present invention is LLDPE.
Preferably, lubricant of the present invention is vinyl bis-stearamides.
Preferably, cross-linking agent of the present invention is Triallyl isocyanurate.
Preferably, antioxidant of the present invention is the mixture of antioxidant 1024 and antioxidant 1010.
Preferably, filler of the present invention is nanoclay.
Preferably, coupling agent of the present invention is silane coupler.
Preferably, UV absorbent of the present invention is UV-531.
Preferably, elastomer of the present invention is POE.
The invention solves the problems that another technical problem be the preparation method that above-mentioned fire-retardant PE composite cable material is provided.
For solving above-mentioned technical problem, technical scheme is：
A kind of preparation method of fire-retardant PE composite cable material, its step is as follows：
(1) stoichiometric proportion pressing P and B is 1:1 weighs diammonium phosphate, ammonium borate, adds in deionized water and is heated to
After 65 DEG C, stirring in water bath overnight, is placed in after becoming pasty state and is dried 3 hours at 110 DEG C in thermostatic drying chamber, proceed to after moisture evaporation
At 550 DEG C in Muffle furnace, roasting obtains presoma in 5 hours, crosses 40 mesh sieves, be then charged in reduction furnace, hydrogen after presoma is pulverized
Atmosphere is warming up to after 600 DEG C with 1 DEG C/minute of speed under enclosing and is incubated 5 hours, naturally cools to room temperature post-passivation 10 hours, grinds
After obtain phosphorus boron compound；
(2) by 1:The tetraethyl orthosilicate of 3 weight ratios, dehydrated alcohol add in flask, add dilute hydrochloric acid to adjust ph value for after 8
Stir 4 hours after being heated to 75 DEG C, obtain the Ludox of clear homogeneous, Ludox is added in the deionized water of 2 times of volumes, stirs
Obtain silicon sol solution after mixing uniformly, phosphorus boron compound is added in the dehydrated alcohol of 5 times of weight, after being heated to 90 DEG C, stir 1
Hour, then ultrasonic disperse obtains uniform phosphorus boron compound solution for 30 minutes；
(3) stoichiometric proportion pressing Si and B is 1:1, by silicon sol solution, the mixing of phosphorus boron compound solution, is placed in 55 DEG C
In water-bath, the mixing speed stirring with 400 revs/min obtains uniform mixed liquor in 2 hours, and mixed liquor spray-dried instrument is sprayed
Mist is dried to obtain mix precursor, mix precursor is put into roasting 6 hours at 900 DEG C in Muffle furnace, cools to the furnace
Take out after room temperature, cross 40 mesh sieves after grinding and obtain phosphorus borosilicate composite flame-retardant agent；
(4) weigh each component by weight, each component is put into high-speed mixer and mixing 15 minutes, is mixed after discharge
Material, compound input double screw extruder extruding pelletization is obtained pellet, the extrusion temperature of double screw extruder is 120～190
DEG C, pellet is placed in hot wind flow at 85～90 DEG C in air drier and is dried 2 hours, obtain fire-retardant PE composite cable material.
Compared with prior art, the invention has the advantages that：
Phosphorus and boron are environmental-protection flame-retardant elements, and the present invention is with diammonium phosphate as phosphorus source, led to successively with ammonium borate for boron source
Cross dissolving, evaporation, roasting, heating reduction have been obtained phosphorus boron compound, the excellent in flame retardance of phosphorus boron compound, but stability,
Dispersibility is not good, and therefore phosphorus boron compound and Ludox are obtained presoma by spray drying method by the present invention, by roasting
Prepared phosphorus borosilicate composite flame-retardant agent, the form of the element silicon in phosphorus borosilicate composite flame-retardant agent is silicon dioxide, and it has well
Stability and dispersibility, but also there is preferable suppression cigarette and become charcoal, fall within environmental-protection flame-retardant element, therefore can carry further
The anti-flammability of high phosphorus borosilicate composite flame-retardant agent, when being blended with PE, phosphorus borosilicate composite flame-retardant agent can be uniformly dispersed in PE matrix, makes
The anti-flammability obtaining PE composite cable material is significantly enhanced.
Specific embodiment
To describe the present invention, the illustrative examples of the here present invention and explanation below in conjunction with specific embodiment in detail
It is used for explaining the present invention, but not as a limitation of the invention.
Embodiment 1
Fire-retardant PE composite cable material, its weight portion component is：100 parts of LLDPE, 0.4 part of vinyl bis-stearamides, three
4 parts of allyl iso cyanurate, 1.4 parts of the mixture of antioxidant 1024 and antioxidant 1010,21 parts of nanoclay, silane coupled
0.7 part of agent, 11 parts of 0.2 part of UV-531, POE, 13 parts of phosphorus borosilicate composite flame-retardant agent.
The step of its preparation method is as follows：
(1) stoichiometric proportion pressing P and B is 1:1 weighs diammonium phosphate, ammonium borate, adds in deionized water and is heated to
After 65 DEG C, stirring in water bath overnight, is placed in after becoming pasty state and is dried 3 hours at 110 DEG C in thermostatic drying chamber, proceed to after moisture evaporation
At 550 DEG C in Muffle furnace, roasting obtains presoma in 5 hours, crosses 40 mesh sieves, be then charged in reduction furnace, hydrogen after presoma is pulverized
Atmosphere is warming up to after 600 DEG C with 1 DEG C/minute of speed under enclosing and is incubated 5 hours, naturally cools to room temperature post-passivation 10 hours, grinds
After obtain phosphorus boron compound；
(2) by 1:The tetraethyl orthosilicate of 3 weight ratios, dehydrated alcohol add in flask, add dilute hydrochloric acid to adjust ph value for after 8
Stir 4 hours after being heated to 75 DEG C, obtain the Ludox of clear homogeneous, Ludox is added in the deionized water of 2 times of volumes, stirs
Obtain silicon sol solution after mixing uniformly, phosphorus boron compound is added in the dehydrated alcohol of 5 times of weight, after being heated to 90 DEG C, stir 1
Hour, then ultrasonic disperse obtains uniform phosphorus boron compound solution for 30 minutes；
(3) stoichiometric proportion pressing Si and B is 1:1, by silicon sol solution, the mixing of phosphorus boron compound solution, is placed in 55 DEG C
In water-bath, the mixing speed stirring with 400 revs/min obtains uniform mixed liquor in 2 hours, and mixed liquor spray-dried instrument is sprayed
Mist is dried to obtain mix precursor, mix precursor is put into roasting 6 hours at 900 DEG C in Muffle furnace, cools to the furnace
Take out after room temperature, cross 40 mesh sieves after grinding and obtain phosphorus borosilicate composite flame-retardant agent；
(4) weigh each component by weight, each component is put into high-speed mixer and mixing 15 minutes, is mixed after discharge
Material, compound input double screw extruder extruding pelletization is obtained pellet, the extrusion temperature of double screw extruder is 120～190
DEG C, pellet is placed in hot wind flow at 85～90 DEG C in air drier and is dried 2 hours, obtain fire-retardant PE composite cable material.Real
Apply example 2
Fire-retardant PE composite cable material, its weight portion component is：100 parts of LLDPE, 0.6 part of vinyl bis-stearamides, three
2.5 parts of allyl iso cyanurate, 1.2 parts of the mixture of antioxidant 1024 and antioxidant 1010,23 parts of nanoclay, silane is even
0.5 part of agent of connection, 13 parts of 0.6 part of UV-531, POE, 11 parts of phosphorus borosilicate composite flame-retardant agent.
Its preparation method is in the same manner as in Example 1.
Embodiment 3
Fire-retardant PE composite cable material, its weight portion component is：100 parts of LLDPE, 0.8 part of vinyl bis-stearamides, three
3 parts of allyl iso cyanurate, 1 part of the mixture of antioxidant 1024 and antioxidant 1010,25 parts of nanoclay, silane coupler
0.9 part, 15 parts of 0.4 part of UV-531, POE, 9 parts of phosphorus borosilicate composite flame-retardant agent.
Its preparation method is in the same manner as in Example 1.
Embodiment 4
Fire-retardant PE composite cable material, its weight portion component is：100 parts of LLDPE, 0.5 part of vinyl bis-stearamides, three
3.5 parts of allyl iso cyanurate, 1.5 parts of the mixture of antioxidant 1024 and antioxidant 1010,20 parts of nanoclay, silane is even
0.8 part of agent of connection, 10 parts of 0.5 part of UV-531, POE, 14 parts of phosphorus borosilicate composite flame-retardant agent.
Its preparation method is in the same manner as in Example 1.
Embodiment 5
Fire-retardant PE composite cable material, its weight portion component is：100 parts of LLDPE, 0.7 part of vinyl bis-stearamides, three
2.2 parts of allyl iso cyanurate, 1.3 parts of the mixture of antioxidant 1024 and antioxidant 1010,22 parts of nanoclay, silane is even
1 part of agent of connection, 12 parts of 0.1 part of UV-531, POE, 12 parts of phosphorus borosilicate composite flame-retardant agent.
Its preparation method is in the same manner as in Example 1.
Embodiment 6
Fire-retardant PE composite cable material, its weight portion component is：100 parts of LLDPE, 0.9 part of vinyl bis-stearamides, three
2 parts of allyl iso cyanurate, 1.1 parts of the mixture of antioxidant 1024 and antioxidant 1010,24 parts of nanoclay, silane coupled
0.6 part of agent, 14 parts of 0.3 part of UV-531, POE, 10 parts of phosphorus borosilicate composite flame-retardant agent.
Its preparation method is in the same manner as in Example 1.
The fire resistance of embodiment 1-6 and comparative example is tested respectively, wherein,
Comparative example is the Chinese patent of Publication No. CN103214712B；
Fire resistance is tested in terms of limited oxygen index and vertical combustion performance two, and limited oxygen index is with reference to GB/T 2406-
2008 standard testings, then with reference to UL-94 standard testing, limited oxygen index is higher, UL-94 lower grade shows vertical combustion performance
Anti-flammability is stronger.
Test result is as shown in the table：
Can find out from upper table, the limited oxygen index of embodiment 1-6 is higher than that comparative example is a lot, and it is right that UL-94 grade is then less than
Ratio, shows there is stronger anti-flammability.
Above-described embodiment only principle of the illustrative present invention and its effect, not for the restriction present invention.Any ripe
The personage knowing this technology all can carry out modifications and changes without prejudice under the spirit and the scope of the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
All equivalent modifications becoming or change, must be covered by the claim of the present invention.
Claims (10)
1. a kind of fire-retardant PE composite cable material is it is characterised in that its weight portion component is：PE100 part, lubricant 0.4～0.9
Part, 2～4 parts of cross-linking agent, 1～1.5 part of antioxidant, 20～25 parts of filler, 0.5～1 part of coupling agent, UV absorbent 0.1～
0.6 part, 10～15 parts of elastomer, 9～14 parts of phosphorus borosilicate composite flame-retardant agent.
2. a kind of fire-retardant PE composite cable material according to claim 1 it is characterised in that：Described PE is LLDPE.
3. a kind of fire-retardant PE composite cable material according to claim 2 it is characterised in that：Described lubricant is that vinyl is double
Stearmide.
4. a kind of fire-retardant PE composite cable material according to claim 3 it is characterised in that：Described cross-linking agent is triallyl
Isocyanuric acid ester.
5. a kind of fire-retardant PE composite cable material according to claim 4 it is characterised in that：Described antioxidant is antioxidant
1024 and the mixture of antioxidant 1010.
6. a kind of fire-retardant PE composite cable material according to claim 5 it is characterised in that：Described filler is nanoclay.
7. a kind of fire-retardant PE composite cable material according to claim 6 it is characterised in that：Described coupling agent is silane coupled
Agent.
8. a kind of fire-retardant PE composite cable material according to claim 7 it is characterised in that：Described UV absorbent is
UV-531.
9. a kind of fire-retardant PE composite cable material according to claim 8 it is characterised in that：Described elastomer is POE.
10. the preparation method of a kind of fire-retardant PE composite cable material according to claim 1～9 any one, its feature exists
In its step is as follows：
(1) stoichiometric proportion pressing P and B is 1:1 weighs diammonium phosphate, ammonium borate, adds in deionized water and is heated to 65 DEG C
Stirring in water bath overnight, is placed in after becoming pasty state and is dried 3 hours at 110 DEG C in thermostatic drying chamber, proceed to Muffle after moisture evaporation afterwards
At 550 DEG C in stove, roasting obtains presoma in 5 hours, crosses 40 mesh sieves, be then charged in reduction furnace, nitrogen atmosphere after presoma is pulverized
It is warming up to after 600 DEG C with 1 DEG C/minute of speed under enclosing and is incubated 5 hours, naturally cool to room temperature post-passivation 10 hours, after grinding
To phosphorus boron compound；
(2) by 1:The tetraethyl orthosilicate of 3 weight ratios, dehydrated alcohol add in flask, and adding dilute hydrochloric acid to adjust ph value is 8 post-heating
Stir 4 hours to after 75 DEG C, obtain the Ludox of clear homogeneous, Ludox is added in the deionized water of 2 times of volumes, stirring is all
Obtain silicon sol solution after even, phosphorus boron compound added in the dehydrated alcohol of 5 times of weight, stirs 1 hour after being heated to 90 DEG C,
Then ultrasonic disperse obtains uniform phosphorus boron compound solution for 30 minutes；
(3) stoichiometric proportion pressing Si and B is 1:1, by silicon sol solution, the mixing of phosphorus boron compound solution, is placed in 55 DEG C of water-bath
In pot, the mixing speed stirring with 400 revs/min obtains uniform mixed liquor in 2 hours, by mixed liquor spray-dried instrument spray dried
Dry obtain mix precursor, mix precursor is put into roasting 6 hours at 900 DEG C in Muffle furnace, cools to room temperature with the furnace
After take out, after grinding cross 40 mesh sieves obtain phosphorus borosilicate composite flame-retardant agent；
(4) weigh each component by weight, each component is put into high-speed mixer and mixing 15 minutes, after discharge, obtains compound, will
Compound puts into double screw extruder extruding pelletization and obtains pellet, and the extrusion temperature of double screw extruder is 120～190 DEG C, will
Pellet is placed in hot wind flow at 85～90 DEG C in air drier and is dried 2 hours, obtains fire-retardant PE composite cable material.
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| WO2019115723A1 (en) * | 2017-12-15 | 2019-06-20 | Byk-Chemie Gmbh | Thermoplastic composition having improved flame retardant properties |
| CN111154273A (en) * | 2020-01-10 | 2020-05-15 | 何先鹏 | Flexible high-temperature-resistant wire and cable material and processing method thereof |
| CN111925605A (en) * | 2020-07-23 | 2020-11-13 | 安徽嘉阳新材料科技有限公司 | PVC hard floor film and processing technology thereof |
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| CN111154273A (en) * | 2020-01-10 | 2020-05-15 | 何先鹏 | Flexible high-temperature-resistant wire and cable material and processing method thereof |
| CN111925605A (en) * | 2020-07-23 | 2020-11-13 | 安徽嘉阳新材料科技有限公司 | PVC hard floor film and processing technology thereof |
| CN111925605B (en) * | 2020-07-23 | 2022-05-27 | 安徽嘉阳新材料科技有限公司 | PVC hard floor film and processing technology thereof |
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Application publication date: 20170215 |