CN102492211A - 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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- CN102492211A CN102492211A CN2011103598371A CN201110359837A CN102492211A CN 102492211 A CN102492211 A CN 102492211A CN 2011103598371 A CN2011103598371 A CN 2011103598371A CN 201110359837 A CN201110359837 A CN 201110359837A CN 102492211 A CN102492211 A CN 102492211A
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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 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 basically, 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 property, nontoxicity.In the manufacturing processed of material, usually add inorganic combustion inhibitors such as a large amount of Marinco Hs, white lake.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 deficiency that overcomes prior art, and cable material density is extremely low, and flame retardant properties is good, 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 deficiency that overcomes prior art, 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 deficiency that overcomes prior art, 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 deficiency that overcomes prior art, 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 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 said CABLE MATERIALS are following:
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;
Said 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 a Marinco H;
Described fire retardant B is the combination of polyphosphoric acid amine (APP), tetramethylolmethane, trimeric cyanamide (M), and the weight ratio of said polyphosphoric acid amine (APP), tetramethylolmethane (PT), trimeric cyanamide (M) is (10～25): (1～5): (10～20).
In an embodiment of the present invention, the melting index of said ethylene-octene (POE) multipolymer is: 1～6g/10min, measure with the GB/T3682-2000 method.
In an embodiment of the present invention; The melting index of said 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 an embodiment of the present invention, the median particle diameter of described Marinco H is 1.25-1.65 μ m, and specific surface area is 4-6m2/g.
In an embodiment of the present invention, said oxidation inhibitor is four [3-(3, the 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 an embodiment of the present invention, said 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 an embodiment of the present invention, described lubricant is calcium stearate, Zinic stearas, Magnesium Stearate, polyethylene wax or its combination.
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 third aspect of the 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:
According to described mixed to temperature to 90 ℃ ± 5 ℃, discharging is placed with fire retardant A, fire retardant B, lubricant, oxidation inhibitor, with other components by the proportioning extruding pelletization, obtain the extremely low fire-retardant Halogen CABLE MATERIALS of described density.
In an 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 through improving prescription, it is extremely low to have obtained a kind of cable material density, and flame retardant properties is good, fireproofing cable material without halide that mechanical property is superior and preparation method.Accomplished 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 compsn together.Therefore, term " mainly by ... form " be included in " by ... composition " that term " contains " or in " comprising ".
In this article, " density is extremely low " is meant: 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 detail to various aspects of the present invention:
Specify like nothing, various raw materials of the present invention all can obtain through commercially available; Or prepare according to the ordinary method of this area.Only if definition or explanation are arranged in addition, the same meaning that all specialties used herein and scientific words and those skilled in the art are familiar with.Any in addition with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.
The extremely low fire-retardant Halogen CABLE MATERIALS of density
In 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 said CABLE MATERIALS are following:
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;
Said 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 a Marinco H;
Described fire retardant B is the combination of polyphosphoric acid amine (APP), tetramethylolmethane, trimeric cyanamide (M), and the weight ratio of said polyphosphoric acid amine (APP), tetramethylolmethane (PT), trimeric cyanamide (M) is (10～25): (1～5): (10～20).
Ethylene-octene (POE) multipolymer
In an embodiment of the present invention, the melting index of said ethylene-octene (POE) multipolymer is: 1～6g/10min, measure with the GB/T3682-2000 method.Be preferably: 2-4g/10min.
The ratio of said ethene and octene can confirm that this is known to those skilled in the art according to melting index.
Ethylene-vinyl acetate (EVA) multipolymer
In an embodiment of the present invention; The melting index of said 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.
Marinco H
In an embodiment of the present invention, the median particle diameter of described Marinco H is 1.25-1.65 μ m, and specific surface area is 4-6m
2/ g.
Oxidation inhibitor
The not concrete restriction of oxidation inhibitor of the present invention can be adopted 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 an embodiment of the present invention, said oxidation inhibitor is four [3-(3, the 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 an embodiment of the present invention, said 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
The not concrete restriction of lubricant of the present invention can be adopted 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 an embodiment of the present invention, described lubricant is calcium stearate, Zinic stearas, Magnesium Stearate, polyethylene wax or its combination.
Cable
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 said cable can adopt the ordinary skill in the art.
The preparation method
The third aspect of the 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:
According to described mixed to temperature to 90 ℃ ± 5 ℃, discharging is placed with fire retardant A, fire retardant B, lubricant, oxidation inhibitor, with other components by the proportioning extruding pelletization, obtain the extremely low fire-retardant Halogen CABLE MATERIALS of described density.
In an 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
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; Marinco H is a synergistic flame retardant, and the CABLE MATERIALS of preparation has the extremely low characteristics of density (specific 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 conspicuous 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 to the present invention is described and be not used in the restriction scope of the present 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 standards, 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 a number-average molecular weight.
Only if definition or explanation are arranged in addition, the same meaning that all specialties used herein and scientific words and those skilled in the art are familiar with.Any in addition with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.
Embodiment 1.
Each component title and each composition weight umber are following:
The preparation method of foregoing invention, it comprises following process 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 following:
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 following:
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 following:
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 following:
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 following:
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 deficiency of prior art, and density is extremely low, and flame retardant properties is good, and mechanical property is superior.
The above is merely 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, and if any technological entity or method that other people accomplish are defined identical with the claim scope of application; Also or a kind of change of equivalence, all will be regarded as and be covered by among this claim scope.
All documents in that the present invention mentions are all quoted as a reference in this application, are just quoted such as a reference separately as each piece document.Should be understood that in addition that after having read foregoing of the present invention those skilled in the art can do various changes or modification to the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
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 said CABLE MATERIALS are following:
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;
Said 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 a Marinco H;
Described fire retardant B is the combination of polyphosphoric acid amine (APP), tetramethylolmethane, trimeric cyanamide (M), and the weight ratio of said polyphosphoric acid amine (APP), tetramethylolmethane (PT), trimeric cyanamide (M) is (10～25): (1～5): (10～20).
2. CABLE MATERIALS as claimed in claim 1 is characterized in that, the melting index of said ethylene-octene (POE) multipolymer is: 1～6g/10min, measure with the GB/T3682-2000 method.
3. CABLE MATERIALS as claimed in claim 1; It is characterized in that; The melting index of said ethylene-vinyl acetate (EVA) multipolymer is: 0.5～5g/10min, and wherein the quality percentage composition of vinyl acetate is: 10～30%, in the gross weight of ethylene-vinyl acetate (EVA) multipolymer.
4. CABLE MATERIALS as claimed in claim 1 is characterized in that, the median particle diameter of described Marinco H is 1.25-1.65 μ m, and specific surface area is 4-6m
2/ g.
5. CABLE MATERIALS as claimed in claim 1 is characterized in that, said oxidation inhibitor is four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), β, the combination of β '-sulfuration dipropionic acid SUNSOFT Q-182S (PS802).
6. CABLE MATERIALS as claimed in claim 5 is characterized in that, said 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).
7. 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.
8. 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 1～7.
9. preparation method like the extremely low fire-retardant Halogen CABLE MATERIALS of the described density of arbitrary claim in the claim 1～7, it is characterized in that: described preparation method may further comprise the steps:
According to the described mixed of claim 1 to temperature to 90 ℃ ± 5 ℃, discharging is placed with fire retardant A, fire retardant B, lubricant, oxidation inhibitor, with other components by the proportioning extruding pelletization, obtain the extremely low fire-retardant Halogen CABLE MATERIALS of described density.
10. method as claimed in claim 9; 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 CN102492211B (en) | 2013-08-28 |
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| CN103044759A (en) * | 2012-12-28 | 2013-04-17 | 上海至正道化高分子材料有限公司 | Low-smoke zero-halogen flame-retardant sheathing compound for round cable and preparation method thereof |
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| CN103627074A (en) * | 2013-12-05 | 2014-03-12 | 上海至正道化高分子材料有限公司 | Low-smoke, halogen-free, high-flame-retardance, oil-resistant and cold-resistant cable material, preparation method thereof and cable |
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| CN103627074B (en) * | 2013-12-05 | 2016-02-10 | 上海至正道化高分子材料股份有限公司 | A kind of low-smoke bittern-free highly fire-proof Oil-resistant cold-resistant CABLE MATERIALS and preparation method and cable |
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| CN105801992A (en) * | 2014-12-30 | 2016-07-27 | 上海凯波特种电缆料厂有限公司 | Low-smoke halogen-free heat-insulating fireproof cable material used for fire-resistant cable, and preparation method and application 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 |
| CN108178864A (en) * | 2017-11-24 | 2018-06-19 | 中广核拓普（四川）新材料有限公司 | Height knot carbon type low smoke halogen-free fire retardant polyolefin cable material |
| 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 |
| CN112933559A (en) * | 2021-02-03 | 2021-06-11 | 天长市正牧铝业科技有限公司 | Dry manufacturing process of PU (polyurethane) leather-covered volleyball |
| 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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