CN102875887B - Low-smoke halogen-free flame-retardant electric insulation material for cables - Google Patents
Low-smoke halogen-free flame-retardant electric insulation material for cables Download PDFInfo
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Abstract
The invention relates to a low-smoke halogen-free flame-retardant electric insulation material for cables, belonging to the technical field of novel electric insulation materials. In order to solve the problem of poor electric insulation property of the existing electric insulation material under moist conditions, the invention provides a low-smoke halogen-free flame-retardant electric insulation material for cables, which comprises the following components in parts by weight: 100.0 parts of base material, 100.0-200.0 parts of inorganic flame retardant, 0.1-8.0 parts of antioxidant, 1.0-5.0 parts of cross-linking sensitizer and 0.3-10.0 parts of anti-irradiation agent, wherein the base material at least contains polyethylene and ethylene-methacrylic acid copolymer; the inorganic flame retardant at least contains aluminum hydroxide and kaolin; and the anti-irradiation agent is selected from one or more of ferrocene, 2-amino-5-(p-methoxyphenyl)-1,3,4-thiadiazole lanthanum complex and 6-benzylaminopurine copper. The low-smoke halogen-free flame-retardant electric insulation material for cables has the advantages of favorable synergistic action, stable flame retardancy, stable electric insulation property, favorable mechanical properties and high aging resistance.
Description
Technical field
The present invention relates to a kind of Insulation Material, particularly relate to a kind of cable low-smoke halogen-free flame-retardant isolating material, belong to new insulation material technical field.
Background technology
Insulating material for cable general requirement must have that excellent resistance to long term heat ageing performance, resistance to irradiation, electric property are stable, flame retardant properties and the excellent feature of insulating property.The base-material of insulating material for cable conventional is at present the materials such as polyethylene, polyvinyl chloride, ethylene-propylene rubber(EPR), but the main drawback of these base-materials is that easy ignition causes fire.And adopt halogen-containing flame-proof polyvinyl chloride, although have certain fire retardation, but, compared with Halogen base-material such as employing polyolefine etc., adopt polyvinyl chloride base-material can produce poisonous hydrogen chloride gas and a large amount of smog when burning, make people poisoning and suffocate, hinder people from fire, withdraw the carrying out with fire-fighting work, cause the loss of life and property.Therefore, existing Insulation Material is adopt halogen-free flame-retardant cable Insulation Material substantially, and this Insulation Material normally adds inorganic combustion inhibitor in organic polymer base-material, as aluminium hydroxide, and magnesium hydroxide etc.The inorganic fire-retarded thing itself added does not burn, and start to decompose at about 300 DEG C, decompose the metal oxide produced and be attached to organism surface, organism base-material can be stoped to burn further, and decomposition course itself will absorb a large amount of heat, reduce the temperature of burning, in addition, decompose the water vapour smog that Absorbable rod is certain again produced, there is good flame retardant effect.But, because the inorganic combustion inhibitor itself added has higher water absorbing properties, easily moisture is attracted when in use soaking, and water itself is a kind of medium of conduction, thus existing insulating material for cable electrical insulation capability in wetting process is declined, do not reach good insulation effect, also can make the shortcomings such as tensile strength variation, and adopt existing inorganic combustion inhibitor and organic base-material consistency bad, cause mixing, extrude the shortcoming of processing difficulties.
As Chinese patent (Authorization Notice No.: CN101456992B, authorized announcement date: on 03 06th, 2011) discloses a kind of insulation material for nuclear power plant cable, this Insulation Material comprises the component of following weight part: base-material: 100.0 parts; Fire retardant: 100.0 ~ 200.0 parts; Oxidation inhibitor: 2.0 ~ 8.0 parts; Anti-irradiation agent: 2.0 ~ 20.0 parts; Crosslinking sensitizer: 1.0 ~ 10.0 parts, wherein, described base-material is one or more mixing in ethylene-methacrylic acid copolymer, ethylene-octene copolymer, high density polyethylene(HDPE), must contain ethylene-methacrylic acid copolymer in base-material; Described fire retardant is one or more mixing in aluminium hydroxide, magnesium hydroxide, zinc borate, and fire retardant must contain aluminium hydroxide; Described anti-irradiation agent is the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles organolanthanide complexes mix with norbide.Above-mentioned Insulation Material has good flame retardant properties, but owing to adopting the inorganic combustion inhibitors such as a large amount of aluminium hydroxide to have stronger water-absorbent, the water molecules of absorption has electroconductibility, thus makes the shortcoming that the insulating property of this Insulation Material under wet-out conditions reduce; And adopt the consistency of a large amount of aluminium hydroxide inorganic combustion inhibitors and organic base-material bad, there is mixing, to extrude processing difficulties shortcoming.
Summary of the invention
The present invention is directed to the defect existed in above prior art, a kind of cable low-smoke halogen-free flame-retardant isolating material is provided, one of problem solved solves existing insulating material for cable because having stronger water absorbing properties, thus the shortcoming of electrical insulation capability difference under making wet-out conditions, flame retardant resistance can be realized and electrical insulation capability is good simultaneously, and the effect that under wet-out conditions, electrical insulation capability is stablized, inorganic combustion inhibitor used and base-material have better consistency.
The object of the invention is to be achieved by the following technical programs, a kind of cable low-smoke halogen-free flame-retardant isolating material, this Insulation Material comprises the weight part of following composition:
Base-material: 100.0; Inorganic combustion inhibitor: 100.0 ~ 200.0;
Oxidation inhibitor: 0.1 ~ 8.0; Crosslinking sensitizer: 1.0 ~ 5.0;
Anti-irradiation agent: 0.3 ~ 10.0; Wherein, described base-material is at least containing polyethylene and ethylene-methacrylic acid copolymer; Described inorganic combustion inhibitor is at least containing aluminium hydroxide and kaolin; Described anti-irradiation agent is selected from ferrocene, the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles Lanthanide complex, 6-benzyl aminopurine copper complex one or more.
Cable low-smoke halogen-free flame-retardant isolating material of the present invention with ethylene-methacrylic acid copolymer and polyethylene for main base has good characteristic, and between each composition, there is good consistency in Insulation Material of the present invention.Described base-material can also comprise one or more in polyolefin compound, ethylene-octene copolymer, vinyl-vinyl acetate copolymer.By using kaolin as of the present invention must inorganic combustion inhibitor, the insulating property of insulating material for cable can be increased, between described kaolin and aluminium hydroxide, there is synergy, multiple flame retardant effect can not only be played, and kaolin itself has water-absorbent difference, the water-absorbent of insulating material for cable can be reduced, thus realize the insulating property improving insulating material for cable while realizing improving flame retardant properties.In addition, the anti-irradiation agent that the present invention selects can not only improve Flouride-resistani acid phesphatase and the ageing-resistant performance of Insulation Material, can also reduce the smoke density of insulating material for cable in flaming combustion and flameless combustion experiment, realize the effect with low cigarette; And, the anti-irradiation agent that the present invention selects is same with fire retardant has synergy, described anti-irradiation agent can be wrapped in the surface of fire retardant, especially the surface of the bibulous fire retardants such as aluminium hydroxide can be wrapped in, reduce the water-absorbent of inorganic combustion inhibitor (as aluminium hydroxide), thus solve the easy inorganic combustion inhibitors absorbed water such as adopting aluminium hydroxide as defect existing during fire retardant, realize the insulating property and the flame retardant properties that improve insulating material for cable, and Insulation Material still has good insulating property under wet-out conditions, stable insulation.By adding oxidation inhibitor and crosslinking sensitizer in Insulation Material, same with between each composition of the present invention have good synergy, realizes improving product ageing resistance and work-ing life.
In above-mentioned cable low-smoke halogen-free flame-retardant isolating material, described inorganic combustion inhibitor also comprise in zinc borate, calcium carbonate one or both.Can decomposition reaction be there is in the calcium carbonate added when high temperature, the calcium oxide produced is attached to base-material (as base-materials such as polyethylene) top layer, realize the effect stoping cable fire, and the carbonic acid gas atmosphere of decomposing generation can stop cable to contact with air, thus the effect that the burning that can realize material in prevention environment is transmitted to cable, fire-retardant effect can be played equally.As preferably, described inorganic combustion inhibitor is grouped into by the one-tenth of following weight part:
Aluminium hydroxide: 60.0 ~ 100.0; Kaolin: 40.0 ~ 60.0;
Zinc borate: 0 ~ 20.0; Calcium carbonate: 0 ~ 30.0.
As further preferred, described inorganic combustion inhibitor is grouped into by the one-tenth of following weight part:
Aluminium hydroxide: 70.0 ~ 90.0; Kaolin: 45.0 ~ 55.0;
Zinc borate: 2.0 ~ 8.0; Calcium carbonate: 5.0 ~ 15.0.
In above-mentioned cable low-smoke halogen-free flame-retardant isolating material, the particle diameter of described inorganic combustion inhibitor is 1.0 ~ 5.0 microns.The particle diameter of control inorganic combustion inhibitor can improve the dispersing uniformity between fire retardant and base-material, prevents fire retardant from base-material, tying granular gathering.If fire retardant ties quality and anti ageing property, anti-be full of cracks performance that granular gathering can reduce insulating material for cable greatly.
In above-mentioned cable low-smoke halogen-free flame-retardant isolating material, as preferably, described anti-irradiation agent is grouped into by the one-tenth of following weight part:
The p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles Lanthanide complex: 0.1 ~ 5.0;
Ferrocene: 0.2 ~ 10.0;
6-benzyl aminopurine copper complex: 0 ~ 5.0.Adding of ferrocene has good anti-radiation performance and fire extinguishing function.Ferrocene is a kind of orange crystal or faint yellow powder, and fusing point is 172 DEG C ~ 174 DEG C, has the thermostability of height, does not decompose within the temperature of 400 DEG C.In addition, ferrocene has the ultraviolet effect of strong absorption, chemically structure is seen, ferrocene is the title complex of cyclopentadiene and iron molecule, two cyclopentadienide anions lay respectively at the two sides of ferrous ion, whole molecule presents sandwich biscuit structure, and two cyclopentadienyls correspond to different energy levels at the different positions in space, when UV-light is mapped to ferrocene with the illumination of other wavelength, light is absorbed, make ferrocene from an energy level transition to another energy level, thus the fracture stoping C-C in polymer can be realized, prevent light to the Degradation of base-material, thus ferrocene has the Degradation of base-material such as protection polyethylene and other multipolymer etc., be equivalent to play protectant effect.Adding of the anti-irradiation agent such as ferrocene can also reduce the smoke density of Insulation Material in flaming combustion experiment and flameless combustion experiment, plays smoke elimination effect, realizes the effect of low cigarette.And the auxiliary anti-irradiation agent 6-benzyl aminopurine copper complex added is the anti-irradiation agent being used as insulating material for cable first, and the ageing-resistant of insulating material for cable and radiation-resistant property can be improved.As further preferred, described anti-irradiation agent is grouped into by the one-tenth of following weight part:
The p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles Lanthanide complex: 1.0 ~ 3.0;
Ferrocene: 2.0 ~ 8.0;
6-benzyl aminopurine copper complex: 0.2 ~ 4.0.
In above-mentioned cable low-smoke halogen-free flame-retardant isolating material, described Insulation Material also comprises the lubricant that weight part is 2.5 ~ 7.0.Owing to adding a large amount of inorganic combustion inhibitors, the problem because of consistency make Insulation Material processing mixing, extrusion is more difficult, is unfavorable for the problem that the processing of technique, particularly extrusion pressure are large.For solving the consistency that the present invention of this problem can better realize between inorganic combustion inhibitor and base-material and other compositions by the lubricant added, thus solve mixing, to extrude difficulty problem.As preferably, described lubricant is selected from one or more in silicone grease, silicone oil, paraffin.Silicone oil is a kind of organo-siloxane of different polymerization degree chain-like structure, and silicone oil has remarkable thermotolerance and electrical insulation capability.To compare in existing Insulation Material the simple paraffin that adopts and make lubricant, there is better flame retardant effect and the low effect of smoke density, test display its at 27cm3 smoke-box test transmittance up to more than 93% (IEC standard: transmittance >=60% is qualified).As further preferred, described lubricant is made up of the weight part of following composition:
Silicone grease: 0 ~ 3.0; Silicone oil: 0.5 ~ 5.0; Paraffin: 1.0 ~ 6.0.
In above-mentioned cable low-smoke halogen-free flame-retardant isolating material, described oxidation inhibitor is selected from 4, one or more in 4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), Tyox B, 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one.The present invention adopts oxidation inhibitor 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol) (also referred to as antioxidant 300) replaces existing oxidation inhibitor β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl, the dual-use function of free radical terminator and hydrogen peroxide decomposition agent can be had simultaneously; Described 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one can absorb the fluorescent that ultraviolet sends pale blue, thus the energy of ultraviolet light degradation C-C bond is scattered with the form of fluorescent, realize the effect stoping carbon radicals to produce, described oxidation inhibitor and anti-irradiation agent of the present invention share, there is good synergistic effect, improve the performance of CABLE MATERIALS in ageing resistance and electrical insulating property etc. further.As preferably, described oxidation inhibitor is made up of the weight part of following composition:
4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 2.0 ~ 6.0;
Tyox B: 0 ~ 5.0;
7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 0 ~ 2.0.
As further preferred, in above-mentioned cable low-smoke halogen-free flame-retardant isolating material, described oxidation inhibitor is made up of the weight part of following composition:
4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 3.0 ~ 5.0;
Tyox B: 1.0 ~ 3.0;
7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 0.5 ~ 1.0.
In above-mentioned cable low-smoke halogen-free flame-retardant isolating material, described crosslinking sensitizer is selected from the one in cyanacrylate, trimethacrylate acid trishydroxymethyl propyl ester.
In above-mentioned cable low-smoke halogen-free flame-retardant isolating material, described base-material is made up of the weight part of following composition:
Ethylene-methacrylic acid copolymer: 60.0 ~ 90.0;
Vinyl-vinyl acetate copolymer: 5.0 ~ 10.0;
Polyethylene: 15.0 ~ 20.0.Described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5.Polyethylene has the advantages such as good thermotolerance, winter hardiness, dielectricity and chemical resistance, and main basic vinyl-Sipacril 2739OF has good insulating property and acid-proof alkaline equally.
In sum, the present invention compared with prior art, has the following advantages:
1. cable low-smoke halogen-free flame-retardant isolating material of the present invention, do not need to add the halogen-containing base-materials such as halogen-containing polyvinyl chloride, just can realize good flame retardant effect, and by the synergy between each composition, reduce the water absorbing properties of Insulation Material, simultaneously, in conjunction with the kaoline fire-resistant agent added, high electric insulation effect is realized and Insulation Material still has good electrical isolation stability under wet-out conditions while realizing high flame retardant effect, and base-material of the present invention, oxidation inhibitor, inorganic combustion inhibitor, crosslinking sensitizer, between lubricant and anti-irradiation agent, all there is good synergy, improve the over-all properties of Insulation Material, and also there is the effect of smoke elimination, realize the effect of low cigarette.
2. cable low-smoke halogen-free flame-retardant isolating material of the present invention, realize electrical insulation capability under flame retardant properties and electrical insulation capability and wet-out conditions stable while, still there is higher mechanical property and ageing resistance, as tensile strength performance, advantage that elongation at break properties is high.
3. cable low-smoke halogen-free flame-retardant isolating material of the present invention, by adding lubricant, further increase the performance of Insulation Material, solve the problems such as Insulation Material mixing difficulty, extrusion pressure in the course of processing be large, simplify production technique, reduce requirement to equipment, realize the effect reducing production cost, be conducive to the object of suitability for industrialized production.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail, but the present invention is not limited to these embodiments.
Cable low-smoke halogen-free flame-retardant isolating material of the present invention, adopts the method for this area routine to prepare, and as preferably, the cable low-smoke halogen-free flame-retardant isolating material employing following methods described in following examples prepares:
Namely raw material is chosen according to the weight part of each composition in embodiment corresponding in following table 1 ~ table 3; join in mixing machine; heat up; and control temperature under normal temperature condition fully mixing 2 ~ 7 minutes; then; put into two rank double-screw extruding pelletizing machine (model: Nanjing sincere alliance CM-80/150 type) again and carry out extruding pelletization under the condition of 145 DEG C ~ 175 DEG C, make cable low-smoke halogen-free flame-retardant isolating material of the present invention.
Table 1 is the weight part of each composition of cable low-smoke halogen-free flame-retardant isolating material in embodiments of the invention 1 ~ 4:
Table 2 is weight parts of each composition of cable low-smoke halogen-free flame-retardant isolating material in embodiments of the invention 5 ~ 8:
Table 3 is weight parts of each composition of cable low-smoke halogen-free flame-retardant isolating material in embodiments of the invention 9 ~ 12:
Table 1:
Base-material described in above-mentioned table 1 embodiment 1 is grouped into by the one-tenth of following weight part; Ethylene-methacrylic acid copolymer: 90.0 parts, polyethylene: 10.0 parts; Described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5;
Fire retardant described in above-mentioned table 1 embodiment 1 is grouped into by the one-tenth of following weight part: aluminium hydroxide: 60.0 parts, kaolin: 48.0 parts, zinc borate: 2.0 parts;
Oxidation inhibitor described in above-mentioned table 1 embodiment 1 is grouped into by the one-tenth of following weight part: primary antioxidant 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 3.0 parts, auxiliary antioxidant Tyox B, i.e. anti-oxidant DLTP: 4.0 parts, 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 1.0 parts;
Anti-irradiation agent described in above-mentioned table 1 embodiment 1 is grouped into by the one-tenth of following weight part: ferrocene: 0.4 part, the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles Lanthanide complex: 0.1 part, 6-benzyl aminopurine copper complex: 0.1 part;
Crosslinking sensitizer described in above-mentioned table 1 embodiment 1 is cyanacrylate;
Lubricant described in above-mentioned table 1 embodiment 1 is made up of the weight part of following composition: silicone grease: 0.1 part, silicone oil: 1.0 parts, paraffin: 1.4 parts.
Base-material described in above-mentioned table 1 embodiment 2 is grouped into by the one-tenth of following weight part: ethylene-methacrylic acid copolymer: 90.0 parts, polyethylene: 10.0 parts; Described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5;
Fire retardant described in above-mentioned table 1 embodiment 2 is grouped into by the one-tenth of following weight part: aluminium hydroxide: 80.0 parts, kaolin: 20.0 parts, calcium carbonate: 10.0 parts;
Oxidation inhibitor described in above-mentioned table 1 embodiment 2 is grouped into by the one-tenth of following weight part: 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 0.6 part, auxiliary antioxidant Tyox B, i.e. anti-oxidant DLTP: 0.5 part, 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 0.1 part;
Anti-irradiation agent described in above-mentioned table 1 embodiment 2 is grouped into by the one-tenth of following weight part: ferrocene: 1.4 parts, the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles Lanthanide complex 1.0 parts, 6-benzyl aminopurine copper complex: 0.1 part;
Crosslinking sensitizer described in above-mentioned table 1 embodiment 2 is cyanacrylate;
Lubricant described in above-mentioned table 1 embodiment 2 is grouped into by the one-tenth of following weight part: silicone grease: 0.1 part, silicone oil: 1.0 parts, paraffin: 1.7 parts;
Base-material described in above-mentioned table 1 embodiment 3 is grouped into by the one-tenth of following weight part: ethylene-methacrylic acid copolymer: 70.0 parts, ethylene-octene copolymer: 10.0 parts, polyethylene: 20.0 parts; Described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5;
Fire retardant described in above-mentioned table 1 embodiment 3 is made up of following parts by weight ingredient: aluminium hydroxide: 100.0 parts, kaolin: 37.0 parts, zinc borate: 3.0 parts, calcium carbonate: 10.0 parts;
Oxidation inhibitor described in above-mentioned table 1 embodiment 3 is grouped into by the one-tenth of following weight part: 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 0.35 part; Auxiliary antioxidant Tyox B, i.e. anti-oxidant DLTP: 0.35 part; 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 0.1 part;
Anti-irradiation agent described in above-mentioned table 1 embodiment 3 is grouped into by the one-tenth of following weight part: ferrocene: 1.0 parts, the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles Lanthanide complex: 0.9 part, 6-benzyl aminopurine copper complex: 0.1 part;
Crosslinking sensitizer described in above-mentioned table 1 embodiment 3 is cyanacrylate;
Lubricant described in above-mentioned table 1 embodiment 3 is made up of the weight part of following composition: silicone grease: 0.5 part, silicone oil: 2.0 parts, paraffin: 1.0 parts;
Base-material described in above-mentioned table 1 embodiment 4 is grouped into by the one-tenth of following weight part: ethylene-methacrylic acid copolymer: 70.0 parts, ethylene-octene copolymer: 10.0 parts, polyethylene: 20.0 parts; Described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5;
Fire retardant described in above-mentioned table 1 embodiment 4 is made up of following parts by weight ingredient: aluminium hydroxide: 100.0 parts, kaolin: 30.0 parts, calcium carbonate: 30.0 parts;
Oxidation inhibitor described in above-mentioned table 1 embodiment 4 is grouped into by the one-tenth of following weight part: 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 0.4 part, auxiliary antioxidant Tyox B, i.e. anti-oxidant DLTP: 0.3 part, 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 0.1 part;
Anti-irradiation agent described in above-mentioned table 1 embodiment 4 is grouped into by the one-tenth of following weight part: ferrocene: 2.0 parts, 6-benzyl aminopurine copper complex: 0.5 part;
Crosslinking sensitizer described in above-mentioned table 1 embodiment 4 is cyanacrylate;
Lubricant described in above-mentioned table 1 embodiment 4 is made up of the weight part of following composition: silicone grease: 0.5 part, silicone oil: 2.5 parts, paraffin: 2.0 parts.
Table 2:
Base-material described in above-mentioned table 2 embodiment 5 is grouped into by the one-tenth of following weight part; Ethylene-methacrylic acid copolymer: 70.0 parts, vinyl-vinyl acetate copolymer: 10.0 parts, polyethylene: 20.0 parts, described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5;
Fire retardant described in above-mentioned table 2 embodiment 5 is grouped into by the one-tenth of following weight part: aluminium hydroxide: 70.0 parts, kaolin: 60.0 parts;
Oxidation inhibitor described in above-mentioned table 2 embodiment 5 is grouped into by the one-tenth of following weight part: primary antioxidant 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 0.2 part, auxiliary antioxidant Tyox B, i.e. anti-oxidant DLTP: 0.2 part, 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 0.1 part;
Anti-irradiation agent described in above-mentioned table 2 embodiment 5 is grouped into by the one-tenth of following weight part: ferrocene: 0.2 part, the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles Lanthanide complex: 0.5 part, 6-benzyl aminopurine copper complex: 0.5 part;
Crosslinking sensitizer described in above-mentioned table 2 embodiment 5 is cyanacrylate;
Lubricant described in above-mentioned table 2 embodiment 5 is made up of the weight part of following composition: silicone grease: 0.5 part, silicone oil: 1.3 parts, paraffin: 2.2 parts.
Base-material described in above-mentioned table 2 embodiment 6 is grouped into by the one-tenth of following weight part: ethylene-methacrylic acid copolymer: 90.0 parts, vinyl-vinyl acetate copolymer: 5.0 parts, polyethylene: 5.0 parts, described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5;
Fire retardant described in above-mentioned table 2 embodiment 6 is grouped into by the one-tenth of following weight part: aluminium hydroxide: 47.0 parts, kaolin: 30.0 parts, zinc borate: 8.0 parts, calcium carbonate: 15.0 parts;
Oxidation inhibitor described in above-mentioned table 2 embodiment 6 is grouped into by the one-tenth of following weight part: 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 4.0 parts, auxiliary antioxidant Tyox B, i.e. anti-oxidant DLTP: 3.0 parts, 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 1.0 parts;
Anti-irradiation agent described in above-mentioned table 2 embodiment 6 is grouped into by the one-tenth of following weight part: ferrocene: 0.23 part, the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles Lanthanide complex: 0.07 part;
Crosslinking sensitizer described in above-mentioned table 2 embodiment 6 is cyanacrylate;
Lubricant described in above-mentioned table 2 embodiment 6 is grouped into by the one-tenth of following weight part: silicone grease: 0.5 part, silicone oil: 2.0 parts, paraffin: 2.5 parts.
Base-material described in above-mentioned table 2 embodiment 7 is grouped into by the one-tenth of following weight part: ethylene-methacrylic acid copolymer: 75.0 parts, vinyl-vinyl acetate copolymer: 5.0 parts, polyethylene: 20.0 parts, described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5;
Fire retardant described in above-mentioned table 2 embodiment 7 is made up of following parts by weight ingredient: aluminium hydroxide: 100.0 parts, kaolin: 60.0 parts, zinc borate: 5.0 parts, calcium carbonate: 15.0 parts;
Oxidation inhibitor described in above-mentioned table 2 embodiment 7 is grouped into by the one-tenth of following weight part: 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 4.5 parts; Auxiliary antioxidant Tyox B, i.e. anti-oxidant DLTP: 0.75 part; 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 0.75 part;
Anti-irradiation agent described in above-mentioned table 2 embodiment 7 is grouped into by the one-tenth of following weight part: ferrocene: 7.0 parts, the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles Lanthanide complex: 1.0 parts;
Described in above-mentioned table 2 embodiment 7, crosslinking sensitizer is cyanacrylate;
Lubricant described in above-mentioned table 2 embodiment 7 is made up of the weight part of following composition: silicone grease: 0.5 part, silicone oil: 4.5 parts, paraffin: 2.0 parts.
Base-material described in above-mentioned table 2 embodiment 8 is grouped into by the one-tenth of following weight part: ethylene-methacrylic acid copolymer: 70.0 parts, ethylene-octene copolymer: 15.0 parts, polyethylene: 15.0 parts; Described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5;
Fire retardant described in above-mentioned table 2 embodiment 8 is made up of following parts by weight ingredient: aluminium hydroxide: 105.0 parts, kaolin: 82.5 parts, zinc borate: 15.0 parts, calcium carbonate: 7.5 parts;
Oxidation inhibitor described in above-mentioned table 2 embodiment 8 is grouped into by the one-tenth of following weight part: 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 0.7 part, 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 0.3 part;
Anti-irradiation agent described in above-mentioned table 2 embodiment 8 is grouped into by the one-tenth of following weight part: ferrocene: 7.0 parts, 6-benzyl aminopurine copper complex: 3.0 parts;
Crosslinking sensitizer described in above-mentioned table 2 embodiment 8 is cyanacrylate;
Lubricant described in above-mentioned table 2 embodiment 8 is made up of the weight part of following composition: silicone oil: 3.0 parts, paraffin: 3.0 parts.
Table 3:
In above-mentioned table 3, "-" expression does not add this composition in corresponding embodiment.
Base-material described in above-mentioned table 3 embodiment 9 is grouped into by the one-tenth of following weight part; Ethylene-methacrylic acid copolymer: 70.0 parts, vinyl-vinyl acetate copolymer: 10.0 parts, polyethylene: 20.0 parts, described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5;
Fire retardant described in above-mentioned table 3 embodiment 9 is grouped into by the one-tenth of following weight part: aluminium hydroxide: 60.0 parts, kaolin: 50.0 parts; Calcium carbonate: 10.0 parts;
Oxidation inhibitor described in above-mentioned table 3 embodiment 9 is oxidation inhibitor 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol);
Anti-irradiation agent described in above-mentioned table 3 embodiment 9 is 6-benzyl aminopurine copper complex;
Crosslinking sensitizer described in above-mentioned table 3 embodiment 9 is trimethacrylate acid trishydroxymethyl propyl ester;
Lubricant described in above-mentioned table 3 embodiment 9 is silicone oil.
Base-material described in above-mentioned table 3 embodiment 10 is grouped into by the one-tenth of following weight part: ethylene-methacrylic acid copolymer: 65.0 parts, vinyl-vinyl acetate copolymer: 5.0 parts, polyethylene: 30.0 parts, described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5;
Fire retardant described in above-mentioned table 3 embodiment 10 is grouped into by the one-tenth of following weight part: aluminium hydroxide: 60.0 parts, kaolin: 25.0 parts, zinc borate: 5.0 parts, calcium carbonate: 15.0 parts;
Oxidation inhibitor described in above-mentioned table 3 embodiment 10 is 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one;
Anti-irradiation agent described in above-mentioned table 3 embodiment 10 is the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles Lanthanide complex;
Crosslinking sensitizer described in above-mentioned table 3 embodiment 10 is cyanacrylate.
Base-material described in above-mentioned table 3 embodiment 11 is grouped into by the one-tenth of following weight part: ethylene-methacrylic acid copolymer: 60.0 parts, ethylene-octene copolymer: 20.0 parts, polyethylene: 20.0 parts, described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5;
Fire retardant described in above-mentioned table 3 embodiment 11 is made up of following parts by weight ingredient: aluminium hydroxide: 68.0 parts, kaolin: 41.0 parts, calcium carbonate: 21.0 parts;
Oxidation inhibitor described in above-mentioned table 3 embodiment 11 is grouped into by the one-tenth of following weight part: 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 0.7 part; 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 0.8 part;
Anti-irradiation agent described in above-mentioned table 3 embodiment 11 is grouped into by the one-tenth of following weight part: ferrocene: 2.0 parts, the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles Lanthanide complex: 1.5 parts;
Crosslinking sensitizer described in above-mentioned table 3 embodiment 11 is cyanacrylate;
Lubricant described in above-mentioned table 3 embodiment 11 is silicone grease.
Base-material described in above-mentioned table 3 embodiment 12 is grouped into by the one-tenth of following weight part: ethylene-methacrylic acid copolymer: 70.0 parts, ethylene-octene copolymer: 15.0 parts, polyethylene: 15.0 parts; Described polyethylene is high density polyethylene(HDPE), and melting index is 1.5 ~ 2.5;
Fire retardant described in above-mentioned table 3 embodiment 12 is made up of following parts by weight ingredient: aluminium hydroxide: 50.0 parts, kaolin: 50.0 parts, zinc borate: 5.0 parts, calcium carbonate: 10.0 parts;
Oxidation inhibitor described in above-mentioned table 3 embodiment 12 is grouped into by the one-tenth of following weight part: 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 2.0 parts, 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 1.0 parts;
Anti-irradiation agent described in above-mentioned table 3 embodiment 12 is grouped into by the one-tenth of following weight part: ferrocene: 4.0 parts, 6-benzyl aminopurine copper complex: 2.0 parts;
Crosslinking sensitizer described in above-mentioned table 3 embodiment 12 is cyanacrylate.
Application Example
Randomly draw the cable low-smoke halogen-free flame-retardant isolating material sample prepared by embodiment 1-12, extrude and make cable insulation layer.Then be cross-linked by electron accelerator irradiation by insulation layer, the concrete technology of cross-linking radiation is: after electric wire extrudes dish, is drawn its one end, irradiate delivered to the electron beam of rumbatron by transmission mechanism under, after irradiating certain hour, sent by transmission mechanism, coil on an opposite end.By to electronic beam current (mA) and energy (Mev), transmission speed controls, and controls irradiation dose, thus realizes controlling crosslinking degree.Carry out performance test to its insulation layer after cross-linking radiation, average test the results are shown in shown in following table 4.
Table 4: Insulation Material of the present invention is used for the average test performance of cable
Comparative example 1
Be insulation material for nuclear power plant cable according to patent name, Authorization Notice No.: CN101456992B, authorized announcement date: the Insulation Material described in patent document embodiment 1 of on 03 06th, 2011 prepares corresponding Insulation Material:
The composition of concrete Insulation Material weight part composition and preparation method as follows;
Base-material: 100.0 weight parts; Fire retardant: 110.0 weight parts; Oxidation inhibitor: 6.0 weight parts; Anti-irradiation agent: 8.0 weight parts; Crosslinking sensitizer: 8.0 weight parts; Mould inhibitor 0.2 weight part; Lubricant: 1.0 weight parts;
Wherein, described base-material is grouped into by the one-tenth of following weight part: ethylene-methacrylic acid copolymer: 100.0 weight parts;
Described fire retardant is grouped into by the one-tenth of following weight part: aluminium hydroxide: 110.0 weight parts;
Described oxidation inhibitor is grouped into by the one-tenth of following weight part: primary antioxidant β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl: 4 weight parts; The two hard ester alcohol ester of auxiliary antioxidant thio-2 acid: 2.0 weight parts;
Described anti-irradiation agent is grouped into by the one-tenth of following weight part: 2-amino-5-(p-p-methoxy-phenyl-1,3,4-thiadiazoles organolanthanide complexes: 4.0 weight parts; Norbide: 4.0 weight parts;
Described crosslinking sensitizer is cyanacrylate;
Described mould inhibitor is 10, the two phenoxazine arsenic of 10 '-oxygen;
Described lubricant is microcrystalline wax.
Choose according to the weight part of each composition in above-mentioned reference examples 1; under joining the temperature condition of in mixing machine 25 DEG C ± 5 DEG C together fully mixing 5 ~ 8 minutes; then; put into two rank double-screw extruding pelletizing machine (model: Nanjing sincere alliance CM-80/150 type) control temperature again and carry out extruding pelletization under the condition of 120 DEG C ~ 180 DEG C, make corresponding Insulation Material.
Choose the Insulation Material sample prepared in above-mentioned comparative example 1, extrude and make cable insulation layer.Then be cross-linked by electron accelerator irradiation by insulation layer, the concrete technology of cross-linking radiation is: after electric wire extrudes dish, is drawn its one end, irradiate delivered to the electron beam of rumbatron by transmission mechanism under, after irradiating certain hour, sent by transmission mechanism, coil on an opposite end.By to electronic beam current (mA) and energy (Mev), transmission speed controls, and controls irradiation dose, thus realizes controlling crosslinking degree.Carry out performance test to its insulation layer after cross-linking radiation, average test the results are shown in shown in following table 5.
Table 5: the Insulation Material in comparative example 1 is used for the average test performance of cable
The testing method of lead, cadmium, mercury, sexavalent chrome, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers in above-mentioned table 4 and table 5 in 1-6 item detects six kinds of restricted substances content detection standards according in I EC62321-2008 electric product " in corresponding method test; Corresponding standard value≤1000 are the standard in European Union ROSH instruction;
Wherein in table 4 and table 5, oxygen index presses the method test in GB/T 2406-2008 " Plastics Combustion method for testing performance oxygen index method "; The corresponding standard value standard that to be >=32 be in JB/T10707-2007;
Wherein in table 4 and table 5, smoke density carries out having flame to test according to the method in GB83232-2008 " plastics-cigarette generates the second part: single chamber method measures smoke density test method(s) "; Corresponding standard value≤100 are the standard of JB/T 10707-2007;
Wherein in table 4 and table 5, tensile strength is tested according to the method for GB/T 1040.2-92 " plastic tensile method for testing performance "; Corresponding standard value >=9.0 are according to standard corresponding in JB/T10707-2007;
Wherein table 4 and table 5 Fracture elongation are according to the method test in GB/T 1040.2-92 " plastic tensile method for testing performance ";
Wherein in table 4 and table 5 20 DEG C of volume specific resistances according to the method test in GB/T1410-2007 " solid insulating material volume specific resistance and surface resistivity test methods test method ";
Tensile strength retention rate wherein in table 4 and table 5 and extension at break retention rate are according to method test corresponding in " GB/T11026.1-2003 insulating material thermotolerance the 1st part: the evaluation of aging procedure and test-results ".
As can be seen from above-mentioned table 4 and table 5, by the insulating material for cable that Insulation Material in the embodiments of the invention 1-12 of random selecting is obtained, not only resistance to long term heat ageing performance is good, and tensile strength is high; And resistance to irradiation and electric property are stablized, flame retardant properties is good and have the feature of halide-free smokeless, and after using, the insulating property of Insulation Material are still fine, well solve and cause because existing fire retardant water suction the defect that in use procedure, electrical insulating property reduces.In addition Insulation Material of the present invention only need by rumbatron at normal temperature when preparing cable insulation layer, cross-linking radiation under condition of normal pressure, and production technique is simple, and required equipment is less, greatly reduces production cost.On the other hand, because fire retardant is filled with kaolin in a large number, thus the antiacid effect of this CABLE MATERIALS is comparatively strong, and under hygrometric state condition, electrical insulation capability is stablized, and the electrical isolation stability under hygrometric state condition is far away higher than the electrical isolation stability of the Insulation Material in reference examples 1.Electric wire prepared by Insulation Material of the present invention can be used for the fire-protection ratings such as subway, boats and ships, Nuclear power plants, computer house, Highrise buildings and requires high place, is with a wide range of applications.
Specific embodiment described in the present invention is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment, but can't depart from spirit of the present invention or surmount the scope that appended claims defines.
Although made a detailed description the present invention and quoted some specific embodiments as proof, to those skilled in the art, only otherwise it is obvious for leaving that the spirit and scope of the present invention can make various changes or revise.
Claims (9)
1. a cable low-smoke halogen-free flame-retardant isolating material, is characterized in that, this Insulation Material comprises the weight part of following composition:
Base-material: 100.0; Inorganic combustion inhibitor: 100.0 ~ 200.0;
Oxidation inhibitor: 0.1 ~ 8.0; Crosslinking sensitizer: 1.0 ~ 5.0;
Anti-irradiation agent: 0.3 ~ 10;
Wherein, described base-material is at least containing polyethylene and ethylene-methacrylic acid copolymer; Described inorganic combustion inhibitor is at least containing aluminium hydroxide and kaolin; Described anti-irradiation agent be selected from ferrocene, 2-amino-5-(p-p-methoxy-phenyl)-1,3,4-thiadiazoles Lanthanide complex, 6-benzyl aminopurine copper complex one or more;
Described inorganic combustion inhibitor is grouped into by the one-tenth of following weight part:
Aluminium hydroxide: 60.0 ~ 100.0; Kaolin: 40.0 ~ 60.0;
Zinc borate: 0 ~ 20; Calcium carbonate: 0 ~ 30.
2. cable low-smoke halogen-free flame-retardant isolating material according to claim 1, it is characterized in that, described anti-irradiation agent is grouped into by the one-tenth of following weight part:
2-amino-5-(p-p-methoxy-phenyl)-1,3,4-thiadiazoles Lanthanide complex: 0.1 ~ 5.0;
Ferrocene: 0.2 ~ 10.0;
6-benzyl aminopurine copper complex: 0 ~ 5.0.
3. cable low-smoke halogen-free flame-retardant isolating material according to claim 1, is characterized in that, also comprises the lubricant that weight part is 2.5 ~ 7.0.
4. cable low-smoke halogen-free flame-retardant isolating material according to claim 3, it is characterized in that, described lubricant is selected from one or more in silicone grease, silicone oil, paraffin.
5. the low-smoke halogen-free flame-retardant isolating material of the cable according to claim 3 or 4, is characterized in that, described lubricant is made up of the weight part of following composition:
Silicone grease: 0 ~ 3.0; Silicone oil: 0.5 ~ 5.0; Paraffin: 1.0 ~ 6.0.
6. the cable low-smoke halogen-free flame-retardant isolating material selected by claim 1-4 any one, it is characterized in that, described oxidation inhibitor is selected from 4, one or more in 4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), Tyox B, 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one.
7. cable low-smoke halogen-free flame-retardant isolating material according to claim 5, it is characterized in that, described oxidation inhibitor is made up of the weight part of following composition:
4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol): 2.0 ~ 6.0;
Tyox B: 0 ~ 5.0;
7-hydroxyl-6,8-dimethoxy benzo pyran-2-one: 0 ~ 2.0.
8. the low-smoke halogen-free flame-retardant isolating material of the cable according to claim 1-4 any one, is characterized in that, described crosslinking sensitizer is selected from the one in cyanacrylate, trimethacrylate acid trishydroxymethyl propyl ester.
9. the low-smoke halogen-free flame-retardant isolating material of the cable according to claim 1-4 any one, described base-material is made up of the weight part of following composition:
Ethylene-methacrylic acid copolymer: 60.0 ~ 90.0;
Vinyl-vinyl acetate copolymer: 5.0 ~ 10.0;
Polyethylene: 10.0 ~ 30.0.
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| CN201210419150.7A CN102875887B (en) | 2012-10-26 | 2012-10-26 | Low-smoke halogen-free flame-retardant electric insulation material for cables |
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| CN105989914B (en) * | 2015-02-05 | 2018-10-30 | 上海朗达电缆（集团）有限公司 | A kind of environment-friendly type flexible fire-proof cable |
| CN104558868B (en) * | 2015-02-21 | 2017-01-25 | 江苏兴华胶带股份有限公司 | Preparation method of corrosion-resistant flame-retardant cable rubber material |
| CN105185454A (en) * | 2015-09-28 | 2015-12-23 | 张翔 | Fireproof cable for aerospace |
| CN106340344B (en) * | 2016-11-12 | 2017-12-01 | 河南开启电力实业有限公司 | Non-aging insulation cable and preparation method thereof |
| CN106373641B (en) * | 2016-11-12 | 2017-12-05 | 河南开启电力实业有限公司 | Times bulky cables and preparation method thereof |
| CN112226004A (en) * | 2020-10-13 | 2021-01-15 | 远东电缆有限公司 | Cross-linked insulating material and preparation method thereof |
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| KR100561556B1 (en) * | 2004-09-20 | 2006-03-17 | 삼성토탈 주식회사 | Incombustible polyolefin resin composition |
| CN101456992B (en) * | 2008-12-25 | 2011-03-16 | 临海市亚东特种电缆料厂 | Insulation material for nuclear power plant cable |
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