CN102492211B - Very-low density inflame-retarding halogen-free cable material and preparation method - Google Patents
Very-low density inflame-retarding halogen-free cable material and preparation method Download PDFInfo
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- CN102492211B CN102492211B CN2011103598371A CN201110359837A CN102492211B CN 102492211 B CN102492211 B CN 102492211B CN 2011103598371 A CN2011103598371 A CN 2011103598371A CN 201110359837 A CN201110359837 A CN 201110359837A CN 102492211 B CN102492211 B CN 102492211B
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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
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Abstract
The invention provides a very-low density inflame-retarding halogen-free cable material. Components of the cable material include, by weight parts, 100 parts of basic resin, 15 to 20 parts of inflame retardant A, 21 to 52 parts of inflame retardant B, 0.5 to 3 parts of oxidation inhibitor and 0.2 to 3 parts of lubricant. The basic resin includes the following components: ethylene-octene copolymer (POE) and ethylene- vinylacetate copolymer (EVA) according to the weight ratio of (20 to 35):(65 to 80). The inflame retardant A is magnesium hydroxide, the inflame retardant B is the mixture of ammonium polyphosphate (APP), pentaerythritol and melamine (M), the weight ratio of the ammonium polyphosphate (APP), the pentaerythritol (PT) and the melamine (M) is (10 to 25):(10 to 25):(1 to 5):(10 to 20). The invention further provides a preparation method of the low-smoke halogen-free inflame-retardant cable material which is very low in density, fine in inflame retardance and excellent in mechanical performance.
Description
Technical field
The present invention relates to a kind of Halogen CABLE MATERIALS and preparation method thereof, relate more specifically to the extremely low fire-retardant Halogen CABLE MATERIALS of a kind of density and preparation method.
Background technology
Low-smoke halogen-free inflaming-retarding cable partly is made up of metallic substance part and non-metallic material substantially, and under the situation of metallic substance partial fixing, the weight of unit length cable is determined by non-metallic part.The density of low-smoke halogen-free combustion-preventing cable insulation material and sheath material has directly determined the weight of cable.The low-smoke halogen-free inflaming-retarding cable that unit weight is low is laying, will bring great convenience in the transportation, installation process.
Cable is with fire retardant jacket or insulating material, and general selective polymer is as matrix resin.Material is in order to reach high fire-retardant, low cigarette, nontoxicity.In the manufacturing processed of material, usually add inorganic combustion inhibitors such as a large amount of magnesium hydroxides, aluminium hydroxide.High inorganic combustion inhibitor of filling though brought flame retardant effect preferably, has caused the density of cable material to increase considerably, and the mechanical property of fire retardant jacket material or insulating material descends.
In sum, this area lacks a kind of extremely low fire-retardant Halogen CABLE MATERIALS of density and preparation method that can satisfy above-mentioned over-all properties requirement.
For this reason, this area presses for a kind of the deficiencies in the prior art that overcome, and cable material density is extremely low, and flame retardant properties is good, the fireproofing cable material without halide that mechanical property is superior and preparation method.
Summary of the invention
First purpose of the present invention is to obtain a kind of the deficiencies in the prior art that overcome, and low-smoke halogen-free flame-proof cable material density is extremely low, and flame retardant properties is good, the CABLE MATERIALS that mechanical property is superior.
Second purpose of the present invention is to obtain a kind of the deficiencies in the prior art that overcome, and low-smoke halogen-free flame-proof cable material density is extremely low, and flame retardant properties is good, the cable that mechanical property is superior.
The 3rd purpose of the present invention is to obtain a kind of the deficiencies in the prior art that overcome, and low-smoke halogen-free flame-proof cable material density is extremely low, and flame retardant properties is good, the preparation method of the CABLE MATERIALS that mechanical property is superior.
In a first aspect of the present invention, provide a kind of density extremely low fire-retardant Halogen CABLE MATERIALS, each component and the parts by weight of described CABLE MATERIALS are as follows:
100 parts of base resins;
15～20 parts of fire retardant A;
21～52 parts of fire retardant B;
0.5～3 part in oxidation inhibitor;
0.2～3 part of lubricant;
Described base resin comprises following component: ethylene-octene copolymer (POE), ethylene-vinyl acetate copolymer (EVA), and both weight ratios are followed successively by (20～35): (65～80);
Described fire retardant A is magnesium hydroxide;
Described fire retardant B is the combination of polyphosphoric acid amine (APP), tetramethylolmethane, trimeric cyanamide (M), and the weight ratio of described polyphosphoric acid amine (APP), tetramethylolmethane (PT), trimeric cyanamide (M) is (10～25): (1～5): (10～20).
In a specific embodiment of the present invention, the melting index of described ethylene-octene (POE) multipolymer is: 1～6g/10min, measure with the GB/T3682-2000 method.
In a specific embodiment of the present invention, the melting index of described ethylene-vinyl acetate (EVA) multipolymer is: 0.5～5g/10min, wherein the quality percentage composition of vinyl acetate is: 10～30%, and in the gross weight of ethylene-vinyl acetate (EVA) multipolymer.
In a specific embodiment of the present invention, the median particle diameter of described magnesium hydroxide is 1.25-1.65 μ m, and specific surface area is 4-6m2/g.
In a specific embodiment of the present invention, described oxidation inhibitor is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), β, the combination of β '-sulfuration dipropionic acid SUNSOFT Q-182S (PS802).
In a specific embodiment of the present invention, described oxidation inhibitor is antioxidant 1010, β, the combination of β '-sulfuration dipropionic acid SUNSOFT Q-182S, and its weight ratio is (0.2～1): (0.2～1).
In a specific embodiment of the present invention, described lubricant is calcium stearate, Zinic stearas, Magnesium Stearate, polyethylene wax or its combination.
A second aspect of the present invention provides a kind of density of the present invention cable that extremely low fire-retardant Halogen CABLE MATERIALS makes.
A third aspect of the present invention provides the preparation method of the extremely low fire-retardant Halogen CABLE MATERIALS of a kind of density of the present invention, and described preparation method may further comprise the steps:
With fire retardant A, fire retardant B, lubricant, oxidation inhibitor according to described mixed to temperature to 90 ℃ ± 5 ℃, discharging is placed, with other components by the proportioning extruding pelletization, obtain the extremely low fire-retardant Halogen CABLE MATERIALS of described density.
In a specific embodiment of the present invention; adopt dual-screw pelletizer to carry out extruding pelletization among the described preparation method, and four temperature sections in the extruding pelletization process are: 115～125 ℃ of feeding sections, 125～135 ℃ of transportation sections; 135～145 ℃ of melt zones, 140～150 ℃ of heads.
Embodiment
The inventor is through extensive and deep research, and by improving prescription, it is extremely low to have obtained a kind of cable material density, and flame retardant properties is good, the fireproofing cable material without halide that mechanical property is superior and preparation method.Finished the present invention on this basis.
Among the present invention, term " contains " or the various compositions of " comprising " expression can be applied in mixture of the present invention or the composition together.Therefore, term " mainly by ... form " and " by ... composition " be included in that term " contains " or in " comprising ".
In this article, " density is extremely low " refers to: CABLE MATERIALS with respect to the density of water at 1.0-1.15.And in the prior art, the density of common fire-resistant cable material is 1.4-1.5, and the elongation at break of fire-resistant cable material is less than 300%.
Below describe in detail to various aspects of the present invention:
Specify as nothing, various raw materials of the present invention all can obtain by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
The extremely low fire-retardant Halogen CABLE MATERIALS of density
In a first aspect of the present invention, provide a kind of density extremely low fire-retardant Halogen CABLE MATERIALS, each component and the parts by weight of described CABLE MATERIALS are as follows:
100 parts of base resins;
15～20 parts of fire retardant A;
21～52 parts of fire retardant B;
0.5～3 part in oxidation inhibitor;
0.2～3 part of lubricant;
Described base resin comprises following component: ethylene-octene copolymer (POE), ethylene-vinyl acetate copolymer (EVA), and both weight ratios are followed successively by (20～35): (65～80);
Described fire retardant A is magnesium hydroxide;
Described fire retardant B is the combination of polyphosphoric acid amine (APP), tetramethylolmethane, trimeric cyanamide (M), and the weight ratio of described polyphosphoric acid amine (APP), tetramethylolmethane (PT), trimeric cyanamide (M) is (10～25): (1～5): (10～20).
Ethylene-octene (POE) multipolymer
In a specific embodiment of the present invention, the melting index of described ethylene-octene (POE) multipolymer is: 1～6g/10min, measure with the GB/T3682-2000 method.Be preferably: 2-4g/10min.
The ratio of described ethene and octene can determine that this is known for those skilled in the art according to melting index.
Ethylene-vinyl acetate (EVA) multipolymer
In a specific embodiment of the present invention, the melting index of described ethylene-vinyl acetate (EVA) multipolymer is: 0.5～5g/10min, wherein the quality percentage composition of vinyl acetate is: 10～30%, and in the gross weight of ethylene-vinyl acetate (EVA) multipolymer.Preferably, the quality percentage composition of vinyl acetate is: 18～28%, and in the gross weight of ethylene-vinyl acetate (EVA) multipolymer.
Magnesium hydroxide
In a specific embodiment of the present invention, the median particle diameter of described magnesium hydroxide is 1.25-1.65 μ m, and specific surface area is 4-6m
2/ g.
Oxidation inhibitor
Oxidation inhibitor of the present invention is not specifically limited, and can adopt various available oxidation inhibitor, only otherwise goal of the invention of the present invention is produced restriction to get final product.Hinered phenols antioxidant for example, the arylamine kind antioxidant.
In a specific embodiment of the present invention, described oxidation inhibitor is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), β, the combination of β '-sulfuration dipropionic acid SUNSOFT Q-182S (PS802).
In a specific embodiment of the present invention, described oxidation inhibitor is antioxidant 1010, β, the combination of β '-sulfuration dipropionic acid SUNSOFT Q-182S, and its weight ratio is (0.2～1): (0.2～1).The combination of above-mentioned oxidation inhibitor
Lubricant
Lubricant of the present invention is not specifically limited, and can adopt various available lubricants, only otherwise goal of the invention of the present invention is produced restriction to get final product.For example stearate, polyethylene wax, silicone resin.
In a specific embodiment of the present invention, described lubricant is calcium stearate, Zinic stearas, Magnesium Stearate, polyethylene wax or its combination.
Cable
A second aspect of the present invention provides a kind of density of the present invention cable that extremely low fire-retardant Halogen CABLE MATERIALS makes.
The preparation method of described cable can adopt the ordinary skill in the art.
The preparation method
A third aspect of the present invention provides the preparation method of the extremely low fire-retardant Halogen CABLE MATERIALS of a kind of density of the present invention, and described preparation method may further comprise the steps:
With fire retardant A, fire retardant B, lubricant, oxidation inhibitor according to described mixed to temperature to 90 ℃ ± 5 ℃, discharging is placed, with other components by the proportioning extruding pelletization, obtain the extremely low fire-retardant Halogen CABLE MATERIALS of described density.
In a specific embodiment of the present invention; adopt dual-screw pelletizer to carry out extruding pelletization among the described preparation method, and four temperature sections in the extruding pelletization process are: 115～125 ℃ of feeding sections, 125～135 ℃ of transportation sections; 135～145 ℃ of melt zones, 140～150 ℃ of heads.
Advantage
The extremely low fire-retardant Halogen CABLE MATERIALS of a kind of density of the present invention and preparation method have following advantage:
1. to adopt ethylene-octene copolymer (POE), ethylene-vinyl acetate (EVA) be matrix resin in the present invention, phosphorous, nitrogen compound is main fire retardant, magnesium hydroxide is synergistic flame retardant, and the CABLE MATERIALS of preparation has the extremely low characteristics of density (relative density is 1.023～1.150).
2. CABLE MATERIALS of the present invention has high flame retardant resistance, low cigarette characteristic.The CABLE MATERIALS vertical combustion can pass through the FV-0 level.
Other aspects of the present invention are because the disclosure of this paper is apparent to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is measured according to national standard usually.If there is not a corresponding national standard, then carry out according to general international standard, normal condition or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage, and described polymericular weight is number-average molecular weight.
Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
Embodiment 1.
Each component title and each composition weight umber are as follows:
The preparation method of foregoing invention, it comprises following processing step:
Polyphosphoric acid amine, tetramethylolmethane, trimeric cyanamide, Irganox 1010, Zinic stearas proportionally are mixed to temperature to 90 ℃ ± 5 ℃, and discharging is placed, with other components by the proportioning extruding pelletization.Four temperature sections in the extruding pelletization process are: 115～125 ℃ of feeding sections, 125～135 ℃ of transportation sections, 135～145 ℃ of melt zones, 140～150 ℃ of heads.
Product among the embodiment 1 is carried out the Performance Detection test, and each performance numerical value is shown in performance embodiment.
Embodiment 2
Each component title and each composition weight umber are as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1
Product among the embodiment 2 is carried out the Performance Detection test, and each performance numerical value is shown in performance embodiment.
Embodiment 3.
Each component title and each composition weight umber are as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Product among the embodiment 3 is carried out the Performance Detection test, and each performance numerical value is shown in performance embodiment
Embodiment 4.
Each component title and each composition weight umber are as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Product among the embodiment 4 is carried out the Performance Detection test, and each performance numerical value is shown in performance embodiment
Embodiment 5.
Each component title and each composition weight umber are as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Product among the embodiment 5 is carried out the Performance Detection test, and each performance numerical value is shown in performance embodiment
Embodiment 6
Each component title and each composition weight umber are as follows:
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1
Product among the embodiment 6 is carried out the Performance Detection test, and each performance numerical value is shown in performance embodiment.
Performance embodiment
Table 1 embodiment product performance test result
Conclusion
In the prior art, the density of common fire-resistant cable material is 1.4-1.5, and the elongation at break of fire-resistant cable material is less than 300%.And the present invention overcomes the deficiencies in the prior art, and density is extremely low, and flame retardant properties is good, and mechanical property is superior.
The above only is preferred embodiment of the present invention, be not in order to limit essence technology contents scope of the present invention, essence technology contents of the present invention is broadly to be defined in the claim scope of application, any technology entity or method that other people finish, if it is defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (7)
1. a density is extremely hanged down fire-retardant Halogen CABLE MATERIALS, it is characterized in that each component and the parts by weight of described CABLE MATERIALS are as follows:
100 parts of base resins;
15～20 parts of fire retardant A;
21～52 parts of fire retardant B;
0.5～3 part in oxidation inhibitor;
0.2～3 part of lubricant;
Described base resin comprises following component: ethylene-octene copolymer (POE), ethylene-vinyl acetate copolymer (EVA), and both weight ratios are followed successively by (20～35): (65～80);
Described fire retardant A is magnesium hydroxide;
Described fire retardant B is the combination of polyphosphoric acid amine (APP), tetramethylolmethane, trimeric cyanamide (M), and the weight ratio of described polyphosphoric acid amine (APP), tetramethylolmethane (PT), trimeric cyanamide (M) is (10～25): (1～5): (10～20);
Described CABLE MATERIALS with respect to the density of water at 1.0-1.15.
2. CABLE MATERIALS as claimed in claim 1 is characterized in that, described oxidation inhibitor is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), β, the combination of β '-sulfuration dipropionic acid SUNSOFT Q-182S (PS802).
3. CABLE MATERIALS as claimed in claim 1 is characterized in that, described oxidation inhibitor is antioxidant 1010, β, the combination of β '-sulfuration dipropionic acid SUNSOFT Q-182S, and its weight ratio is (0.2～1): (0.2～1).
4. CABLE MATERIALS as claimed in claim 1 is characterized in that, described lubricant is calcium stearate, Zinic stearas, Magnesium Stearate, polyethylene wax or its combination.
5. the cable that the extremely low fire-retardant Halogen CABLE MATERIALS of the described density of arbitrary claim makes in a kind as claimed in claim 1 1～4.
6. preparation method as the extremely low fire-retardant Halogen CABLE MATERIALS of the described density of arbitrary claim in the claim 1～4, it is characterized in that: described preparation method may further comprise the steps:
With fire retardant A, fire retardant B, lubricant, oxidation inhibitor according to the described mixed of claim 1 to temperature to 90 ℃ ± 5 ℃, discharging is placed, with other components by the proportioning extruding pelletization, obtain the extremely low fire-retardant Halogen CABLE MATERIALS of described density.
7. method as claimed in claim 6; it is characterized in that; adopt dual-screw pelletizer to carry out extruding pelletization among the described preparation method; and four temperature sections in the extruding pelletization process are: 115～125 ℃ of feeding sections; 125～135 ℃ of transportation sections; 135～145 ℃ of melt zones, 140～150 ℃ of heads.
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| CN2011103598371A CN102492211B (en) | 2011-11-14 | 2011-11-14 | Very-low density inflame-retarding halogen-free cable material and preparation method |
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| CN2011103598371A CN102492211B (en) | 2011-11-14 | 2011-11-14 | Very-low density inflame-retarding halogen-free cable material and preparation method |
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| CN102492211B true CN102492211B (en) | 2013-08-28 |
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| CN103093873B (en) * | 2012-12-28 | 2015-12-09 | 深圳市沃尔核材股份有限公司 | A kind of halogen-free high flame-retardant cable |
| CN103044759B (en) * | 2012-12-28 | 2015-04-22 | 上海至正道化高分子材料股份有限公司 | Low-smoke zero-halogen flame-retardant sheathing compound for round cable and preparation method thereof |
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| CN105037914A (en) * | 2015-08-24 | 2015-11-11 | 山东华凌电缆有限公司 | Low smoke and zero halogen flame retardant sheathing material with low temperature, oil and torsion resistance as well as preparation method and application |
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| CN112933557A (en) * | 2021-02-03 | 2021-06-11 | 天长市正牧铝业科技有限公司 | High-sealing-performance PU (polyurethane) veneered football with butyl liner and preparation process of football |
| CN113462067A (en) * | 2021-07-12 | 2021-10-01 | 潍坊亚星化学股份有限公司 | Halogen-free flame-retardant EVA cable material composite material and preparation method thereof |
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