CN102875887A - 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, relate in particular to a kind of cable low-smoke halogen-free flame-retardant isolating material, belong to the new insulation material technical field.
Background technology
The insulating material for cable general requirement must have that good anti-long term heat ageing performance, anti-irradiation, electric property are stable, flame retardant properties and the excellent characteristics of insulating property.The base-material of insulating material for cable commonly used is the materials such as polyethylene, polyvinyl chloride, ethylene-propylene rubber(EPR) at present, and still, 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, compare with Halogen base-materials such as adopting polyolefine, adopt the polyvinyl chloride base-material when burning, can produce poisonous hydrogen chloride gas and a large amount of smog, the people is poisoned and suffocate, hinder people from fire, to withdraw carrying out with fire-fighting work, caused the loss of life and property.Therefore, existing Insulation Material is to adopt the halogen-free flame-retardant cable Insulation Material basically, and this Insulation Material is normally added inorganic combustion inhibitor in the organic polymer base-material, such as aluminium hydroxide, and magnesium hydroxide etc.The inorganic fire-retarded thing itself that adds does not burn, and about 300 ℃, begin to decompose, decompose the metal oxide that produces and be attached to the organism surface, can stop the organism base-material further to burn, and decomposition course itself will absorb a large amount of heat, has reduced the temperature of burning, in addition, decompose the water vapour that produces and to absorb certain smog again, have preferably flame retardant effect.But, because the inorganic combustion inhibitor itself that adds has higher water absorbing properties, easily attract moisture when in use soaking, and water itself is a kind of medium of conduction, thereby existing insulating material for cable electrical insulation capability in the process of soaking is descended, and does not reach preferably 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 mixingly, extrude the shortcoming of processing difficulties.
Disclose a kind of insulation material for nuclear power plant cable such as Chinese patent (Granted publication number: CN101456992B, Granted publication day: on 03 06th, 2011), 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, the high density polyethylene(HDPE), must contain ethylene-methacrylic acid copolymer in the base-material; Described fire retardant is one or more mixing in aluminium hydroxide, magnesium hydroxide, the 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 mixes with norbide.Above-mentioned Insulation Material has preferably flame retardant properties, and still, owing to adopting a large amount of inorganic combustion inhibitors such as aluminium hydroxide to have stronger water-absorbent, the water molecules of absorption has electroconductibility, thus the shortcoming that the insulating property of this Insulation Material under wet-out conditions are reduced; And adopt the consistency of a large amount of aluminium hydroxide inorganic combustion inhibitors and organic base-material bad, have mixing, as to extrude processing difficulties shortcoming.
Summary of the invention
The present invention is directed to the defective that exists in the above prior art, a kind of cable low-smoke halogen-free flame-retardant isolating material is provided, one of problem that solves is to solve existing insulating material for cable because having stronger water absorbing properties, thereby make the poor shortcoming of electrical insulation capability under the wet-out conditions, can realize simultaneously that flame retardant resistance and electrical insulation capability are good, and the effect that stable, the used inorganic combustion inhibitor of electrical insulation capability and base-material have better consistency under the wet-out conditions.
The objective 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 contains polyethylene and ethylene-methacrylic acid copolymer at least; Described inorganic combustion inhibitor contains aluminium hydroxide and kaolin at least; Described anti-irradiation agent is selected from ferrocene, the p-p-methoxy-phenyl of 2-amino-5-()-1,3, one or more of 4-thiadiazoles lanthanum title complex, 6-benzyl aminopurine copper complex.
Cable of the present invention has preferably characteristic with the low-smoke halogen-free flame-retardant isolating material take ethylene-methacrylic acid copolymer and polyethylene as main base-material, and has preferably consistency between each composition in the Insulation Material of the present invention.Described base-material can also comprise one or more in polyolefin compound, ethylene-octene copolymer, the vinyl-vinyl acetate copolymer.By with kaolin as of the present invention must inorganic combustion inhibitor, can increase the insulating property of insulating material for cable, has synergy between described kaolin and the aluminium hydroxide, not only can play multiple flame retardant effect, and it is poor that kaolin itself has water-absorbent, can reduce the water-absorbent of insulating material for cable, thereby realize improving the insulating property of insulating material for cable when realizing improving flame retardant properties.In addition, the anti-irradiation agent that the present invention selects not only can improve anti-irradiation 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, realizes having the effect of low cigarette; And, anti-irradiation agent and fire retardant that the present invention selects have synergy equally, described anti-irradiation agent can be wrapped in the surface of fire retardant, especially can be wrapped in the surface of the bibulous fire retardants such as aluminium hydroxide, reduced the water-absorbent of inorganic combustion inhibitor (such as aluminium hydroxide), thereby existing defective when solving the easy inorganic combustion inhibitors that absorbs water such as adopting aluminium hydroxide as fire retardant, realize improving insulating property and the flame retardant properties of insulating material for cable, and Insulation Material still has preferably insulating property, stable insulation under wet-out conditions.By adding oxidation inhibitor and crosslinking sensitizer in Insulation Material, and have equally preferably synergy between each composition of the present invention, realize improving product ageing resistance and work-ing life.
Above-mentioned cable with the low-smoke halogen-free flame-retardant isolating material in, described inorganic combustion inhibitor also comprises one or both in zinc borate, the calcium carbonate.Decomposition reaction can occur in the calcium carbonate that adds when high temperature, the calcium oxide that produces is attached to base-material (such as base-materials such as polyethylene) top layer, realize stoping the effect of cable fire, and decomposing the carbonic acid gas atmosphere that produces can stop cable to contact with air, thereby the burning that can realize stoping material in the environment can be played fire-retardant effect equally to the effect that cable transmits.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.
Above-mentioned cable with the low-smoke halogen-free flame-retardant isolating material in, the particle diameter of described inorganic combustion inhibitor is 1.0～5.0 microns.The particle diameter of control inorganic combustion inhibitor can improve dispersing uniformity between fire retardant and the base-material, prevents that fire retardant from tying granular gathering in base-material.If fire retardant is tied quality that granular gathering can reduce insulating material for cable greatly and anti ageing property, anti-be full of cracks performance.
Above-mentioned cable with the low-smoke halogen-free flame-retardant isolating material in, 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 lanthanum title complex: 0.1～5.0;
Ferrocene: 0.2～10.0;
6-benzyl aminopurine copper complex: 0～5.0.The adding of ferrocene has preferably anti-radiation performance and fire extinguishing function.Ferrocene is a kind of orange crystal or faint yellow powder, and fusing point is 172 ℃～174 ℃, has the thermostability of height, does not decompose with interior 400 ℃ temperature.In addition; ferrocene has the ultraviolet effect of strong absorption; on chemical structure; 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 the sandwich biscuit structure; and two cyclopentadienyls different energy levels in the different positions correspondence in space; when the illumination of UV-light and other wavelength is mapped to ferrocene; light is absorbed; make ferrocene from an energy level transition to another energy level; thereby can realize stoping the fracture of C-C in the polymer; stoped the Degradation of light to base-material, thereby ferrocene has the Degradation of the base-materials such as protection polyethylene and other multipolymer, be equivalent to play protectant effect.The 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 the smoke elimination effect, realizes the effect of low cigarette.And the auxiliary anti-irradiation agent 6-benzyl aminopurine copper complex that adds is to be used as first the anti-irradiation agent of insulating material for cable, and can improve the ageing-resistant and radiation-resistant property of insulating material for cable.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 lanthanum title complex: 1.0～3.0;
Ferrocene: 2.0～8.0;
6-benzyl aminopurine copper complex: 0.2～4.0.
Above-mentioned cable with the low-smoke halogen-free flame-retardant isolating material in, described Insulation Material comprises that also weight part is 2.5～7.0 lubricant.Owing to adding a large amount of inorganic combustion inhibitors, because the problem of consistency makes that Insulation Material is mixing in processing, extrusion difficulty, be unfavorable for the problem that the processing of technique, particularly extrusion pressure are large.Can better realize consistency between inorganic combustion inhibitor and base-material and other compositions for addressing this problem the present invention by the lubricant that adds, thus solve mixing, extrude hard problem.As preferably, described lubricant is selected from one or more in silicone grease, silicone oil, the 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.Compare and adopt merely paraffin to make lubricant in the existing Insulation Material, have the low effect of better flame retardant effect and smoke density, it tests transmittance up to (the IEC standard: transmittance 〉=60% is qualified) more than 93% at the 27cm3 smoke-box test demonstration.As further preferred, described lubricant is comprised of the weight part of following composition:
Silicone grease: 0～3.0; Silicone oil: 0.5～5.0; Paraffin: 1.0～6.0.
Above-mentioned cable with the low-smoke halogen-free flame-retardant isolating material in, described oxidation inhibitor is selected from 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), Tyox B, 7-hydroxyl-6, one or more in the 8-dimethoxy benzo pyran-2-one.The present invention adopts oxidation inhibitor 4,4 '-the existing oxidation inhibitor β-(3 of thiobis-(the 6-tertiary butyl-3-methylphenol) (being also referred to as antioxidant 300) replacement, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester can have the dual-use function of free radical terminator and hydrogen peroxide decomposition agent simultaneously; Described 7-hydroxyl-6,8-dimethoxy benzo pyran-2-one can absorb the fluorescent that pale blue is sent in ultraviolet ray, thereby the energy of ultraviolet light degradation C-C bond is scattered with the form of fluorescent, realize stoping the effect of carbon radicals generation, the anti-irradiation agent of described oxidation inhibitor and the present invention shares, have good synergistic effect, further improve CABLE MATERIALS in the performance of the aspects such as ageing resistance and electrical insulating property.As preferably, described oxidation inhibitor is comprised 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, above-mentioned cable with the low-smoke halogen-free flame-retardant isolating material in, described oxidation inhibitor is comprised 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.
Above-mentioned cable with the low-smoke halogen-free flame-retardant isolating material in, described crosslinking sensitizer is selected from a kind of in cyanacrylate, the trimethylammonium vinylformic acid trishydroxymethyl propyl ester.
Above-mentioned cable with the low-smoke halogen-free flame-retardant isolating material in, described base-material is comprised 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 base-material ethylene-methacrylic acid copolymer has preferably insulating property and acid-proof alkaline equally.
In sum, the present invention compared with prior art has the following advantages:
1. cable of the present invention low-smoke halogen-free flame-retardant isolating material, do not need to add the halogen-containing base-materials such as halogen-containing polyvinyl chloride, just can realize preferably flame retardant effect, and by the synergy between each composition, reduced the water absorbing properties of Insulation Material, simultaneously, in conjunction with the kaoline fire-resistant agent that adds, realize the high electric insulation effect when realizing the high flame retardant effect and under wet-out conditions Insulation Material still have preferably electrical isolation stability, and base-material of the present invention, oxidation inhibitor, inorganic combustion inhibitor, crosslinking sensitizer, all has preferably synergy between lubricant and the anti-irradiation agent, improved the over-all properties of Insulation Material, and the effect that also has smoke elimination, the effect that realizes hanging down cigarette.
2. cable of the present invention low-smoke halogen-free flame-retardant isolating material, under realizing flame retardant properties and electrical insulation capability and wet-out conditions electrical insulation capability stable in, still have higher mechanical property and ageing resistance, such as tensile strength performance, advantage that elongation at break properties is high.
3. cable of the present invention low-smoke halogen-free flame-retardant isolating material, by adding lubricant, further improved the performance of Insulation Material, the problems such as Insulation Material mixing difficulty, extrusion pressure in the course of processing be large have been solved, simplify production technique, reduced the requirement to equipment, the effect that realization reduces production costs is conducive to the purpose 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 embodiment.
Cable of the present invention low-smoke halogen-free flame-retardant isolating material adopts the method preparation of this area routine get final product, and as preferably, the cable described in following examples prepares with low-smoke halogen-free flame-retardant isolating material employing following methods:
Namely choose raw material according to the weight part of each composition among the corresponding embodiment in the following table 1～table 3; join in the mixing machine; heat up; and control temperature under normal temperature condition fully mixing 2～7 minutes; then; put into again two rank double-screw extruding pelletizing machine (model: the Nanjing CM-80/150 of sincere alliance type) under 145 ℃～175 ℃ condition, carry out extruding pelletization, make cable of the present invention low-smoke halogen-free flame-retardant isolating material.
Table 1 be in the embodiments of the invention 1～4 cable with the weight part of each composition of low-smoke halogen-free flame-retardant isolating material:
Table 2 be in the embodiments of the invention 5～8 cable with the weight part of each composition of low-smoke halogen-free flame-retardant isolating material:
Table 3 be in the embodiments of the invention 9～12 cable with the weight part of each composition of low-smoke halogen-free flame-retardant isolating material:
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, and 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, the auxiliary antioxidant Tyox B, be 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, and the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles lanthanum title 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 comprised of the weight part of following composition: silicone grease: 0.1 part, and 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, and 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, and 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, the auxiliary antioxidant Tyox B, be 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, and the p-p-methoxy-phenyl of 2-amino-5-()-1,3,1.0 parts of 4-thiadiazoles lanthanum title complexs, 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, and 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, and 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 become to be grouped into by following weight part: aluminium hydroxide: 100.0 parts, and 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, and the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles lanthanum title 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 comprised of the weight part of following composition: silicone grease: 0.5 part, and 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, and 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 become to be grouped into by following weight part: aluminium hydroxide: 100.0 parts, and 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, the auxiliary antioxidant Tyox B, be 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, and 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 comprised of the weight part of following composition: silicone grease: 0.5 part, and 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, and 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, the auxiliary antioxidant Tyox B, be 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, and the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles lanthanum title 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 comprised of the weight part of following composition: silicone grease: 0.5 part, and 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, and 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, the auxiliary antioxidant Tyox B, be 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, and the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles lanthanum title 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, and 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 become to be grouped into by following weight part: aluminium hydroxide: 100.0 parts, and 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, and the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles lanthanum title complex: 1.0 parts;
Crosslinking sensitizer is cyanacrylate described in above-mentioned table 2 embodiment 7;
Lubricant described in above-mentioned table 2 embodiment 7 is comprised of the weight part of following composition: silicone grease: 0.5 part, and 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, and 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 become to be grouped into by following weight part: aluminium hydroxide: 105.0 parts, and 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, and 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 comprised of the weight part of following composition: silicone oil: 3.0 parts, and paraffin: 3.0 parts.
Table 3:
"-" is illustrated in and do not add this composition among the corresponding embodiment in the above-mentioned table 3.
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, and kaolin: 50.0 parts; Calcium carbonate: 10.0 parts;
Oxidation inhibitor described in above-mentioned table 3 embodiment 9 be oxidation inhibitor 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol);
Anti-irradiation agent described in above-mentioned table 3 embodiment 9 is the 6-benzyl aminopurine copper complex;
Crosslinking sensitizer described in above-mentioned table 3 embodiment 9 is trimethylammonium vinylformic 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, and 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 lanthanum title 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 become to be grouped into by following weight part: aluminium hydroxide: 68.0 parts, and 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, and the p-p-methoxy-phenyl of 2-amino-5-()-1,3,4-thiadiazoles lanthanum title 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, and 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 become to be grouped into by following weight part: aluminium hydroxide: 50.0 parts, and 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, and 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 that prepared by embodiment 1-12 with low-smoke halogen-free flame-retardant isolating material sample, extrude and make the cable insulation layer.Then insulation layer is crosslinked by electron accelerator irradiation, the concrete technology of cross-linking radiation is: after electric wire is extruded dish, the one end is drawn, delivered to by transmission mechanism under the electron beam of rumbatron and shine, behind the irradiation certain hour, sent by transmission mechanism, coil at the other end.By to electronic beam current (mA) and energy (Mev), transmission speed is controlled, the control irradiation dose, thus realize the control crosslinking degree.Behind the cross-linking radiation its insulation layer is carried out performance test, average test the results are shown in shown in the following table 4.
Table 4: Insulation Material of the present invention is used for the average test performance of cable
Comparative Examples 1
Be insulation material for nuclear power plant cable according to patent name, Granted publication number: CN101456992B, Granted publication day: the Insulation Material described on 03 06th, 2011 the patent document embodiment 1 prepares corresponding Insulation Material:
Weight part composition and the preparation method of the composition of concrete Insulation Material are 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 stearyl alcohol ester: 4 weight parts; The two hard ester alcohol esters 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.
Weight part according to each composition in the above-mentioned reference examples 1 is chosen; join together in the mixing machine under 25 ℃ ± 5 ℃ the temperature condition fully mixing 5～8 minutes; then; (model: the Nanjing CM-80/150 of sincere alliance type) the control temperature is carried out extruding pelletization under 120 ℃～180 ℃ condition, makes corresponding Insulation Material to put into two rank double-screw extruding pelletizing machine again.
Choose the Insulation Material sample for preparing in the above-mentioned Comparative Examples 1, extrude and make the cable insulation layer.Then insulation layer is crosslinked by electron accelerator irradiation, the concrete technology of cross-linking radiation is: after electric wire is extruded dish, the one end is drawn, delivered to by transmission mechanism under the electron beam of rumbatron and shine, behind the irradiation certain hour, sent by transmission mechanism, coil at the other end.By to electronic beam current (mA) and energy (Mev), transmission speed is controlled, the control irradiation dose, thus realize the control crosslinking degree.Behind the cross-linking radiation its insulation layer is carried out performance test, average test the results are shown in shown in the following table 5.
Table 5: the Insulation Material in the Comparative Examples 1 is used for the average test performance of cable
The testing method of the lead in above-mentioned table 4 and the table 5 in the 1-6 item, cadmium, mercury, sexavalent chrome, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers is according to detecting six kinds of restricted substances content detection standards in the I EC62321-2008 electric product " in corresponding method test; Corresponding standard value≤1000 are the standard in the ROSH of the European Union instruction;
The method that wherein oxygen index is pressed among the GB/T 2406-2008 " Plastics Combustion method for testing performance oxygen index method " in table 4 and the table 5 is tested; Corresponding standard value be 〉=32 to be the standard among the JB/T10707-2007;
Wherein smoke density has the flame test according to the method among the GB83232-2008 " plastics-cigarette generates the second part: the single chamber method is measured the smoke density test method(s) " in table 4 and the table 5; Corresponding standard value≤100 are the standard of JB/T 10707-2007;
Wherein tensile strength is tested according to the method for GB/T 1040.2-92 " plastic tensile method for testing performance " in table 4 and the table 5; Corresponding standard value 〉=9.0 are according to corresponding standard among the JB/T10707-2007;
Wherein table 4 and table 5 Fracture elongation is tested according to the method among the GB/T 1040.2-92 " plastic tensile method for testing performance ";
Wherein 20 ℃ of volume specific resistances are tested according to the method among the GB/T1410-2007 " solid insulating material volume specific resistance and surface resistivity test methods test method " in table 4 and the table 5;
Wherein the tensile strength retention rate in table 4 and the table 5 and extension at break retention rate are according to corresponding method test in " GB/T11026.1-2003 insulating material thermotolerance the 1st part: the evaluation of aging program and test-results ".
Can find out from above-mentioned table 4 and table 5, by the insulating material for cable that Insulation Material among the embodiments of the invention 1-12 that chooses at random makes, not only anti-long term heat ageing performance is good, and tensile strength is high; And anti-irradiation and electric property are stable, and flame retardant properties is good and have the characteristics of halide-free smokeless, and the insulating property of Insulation Material are still fine after using, and has well solved the defective that causes electrical insulating property reduction in the use procedure because of existing fire retardant suction.Insulation Material of the present invention only need be by rumbatron at normal temperature when the preparation cable is used insulation layer in addition, cross-linking radiation under the 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 has been filled kaolin in a large number, thereby the antiacid effect of this CABLE MATERIALS is stronger, and electrical insulation capability is stable under the hygrometric state condition, and the electrical isolation stability under the hygrometric state condition is higher than the electrical isolation stability of the Insulation Material in the reference examples 1 far away.The electric wire of Insulation Material preparation of the present invention can be used for the demanding places of fire-protection rating such as subway, boats and ships, Nuclear power plants, computer house, Highrise buildings, is with a wide range of applications.
Specific embodiment described in the present invention only is to the explanation for example of the present invention's spirit.Those skilled in the art can make various modifications or replenish or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made a detailed description and has quoted as proof some specific embodiments, to those skilled in the art, only otherwise it is obvious leaving that the spirit and scope of the present invention can make various changes or revise.
Claims (10)
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 contains polyethylene and ethylene-methacrylic acid copolymer at least; Described inorganic combustion inhibitor contains aluminium hydroxide and kaolin at least; Described anti-irradiation agent is selected from ferrocene, the p-p-methoxy-phenyl of 2-amino-5-()-1,3, one or more of 4-thiadiazoles lanthanum title complex, 6-benzyl aminopurine copper complex.
2. cable according to claim 1 low-smoke halogen-free flame-retardant isolating material is characterized in that, 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.
3. cable according to claim 1 low-smoke halogen-free flame-retardant isolating material is characterized in that, 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 lanthanum title complex: 0.1～5.0;
Ferrocene: 0.2～10.0;
6-benzyl aminopurine copper complex: 0～5.0.
4. cable according to claim 1 low-smoke halogen-free flame-retardant isolating material is characterized in that, comprises that also weight part is 2.5～7.0 lubricant.
5. cable according to claim 4 low-smoke halogen-free flame-retardant isolating material is characterized in that, described lubricant is selected from one or more in silicone grease, silicone oil, the paraffin.
6. according to claim 4 or 5 described cable low-smoke halogen-free flame-retardant isolating material, it is characterized in that, described lubricant is comprised of the weight part of following composition:
Silicone grease: 0～3.0; Silicone oil: 0.5～5.0; Paraffin: 1.0～6.0.
7. the selected cable of any one low-smoke halogen-free flame-retardant isolating material according to claim 1-5, it is characterized in that, described oxidation inhibitor is selected from 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), Tyox B, 7-hydroxyl-6, one or more in the 8-dimethoxy benzo pyran-2-one.
8. cable according to claim 6 low-smoke halogen-free flame-retardant isolating material is characterized in that, described oxidation inhibitor is comprised 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.
9. the described cable of any one low-smoke halogen-free flame-retardant isolating material is characterized in that according to claim 1-5, and described crosslinking sensitizer is selected from a kind of in cyanacrylate, the trimethylammonium vinylformic acid trishydroxymethyl propyl ester.
10. the described cable of any one low-smoke halogen-free flame-retardant isolating material according to claim 1-5, described base-material is comprised 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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| CN104558868A (en) * | 2015-02-21 | 2015-04-29 | 刘平 | Preparation method of corrosion-resistant flame-retardant cable rubber material |
| CN105185454A (en) * | 2015-09-28 | 2015-12-23 | 张翔 | Fireproof cable for aerospace |
| CN105989914A (en) * | 2015-02-05 | 2016-10-05 | 上海朗达电缆（集团）有限公司 | Environment-friendly type flexible fireproof cable |
| CN106340344A (en) * | 2016-11-12 | 2017-01-18 | 河南开启电力实业有限公司 | Aging-resistant insulated cable and preparation method thereof |
| CN106373641A (en) * | 2016-11-12 | 2017-02-01 | 河南开启电力实业有限公司 | Double-capacity electric cable and manufacture method therefor |
| 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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| CN1752129A (en) * | 2004-09-20 | 2006-03-29 | 三星Total株式会社 | Incombustible polyolefin resin composition |
| CN101456992A (en) * | 2008-12-25 | 2009-06-17 | 临海市亚东特种电缆料厂 | Insulation material for nuclear power plant cable |
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| CN1752129A (en) * | 2004-09-20 | 2006-03-29 | 三星Total株式会社 | Incombustible polyolefin resin composition |
| CN101456992A (en) * | 2008-12-25 | 2009-06-17 | 临海市亚东特种电缆料厂 | Insulation material for nuclear power plant cable |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105989914A (en) * | 2015-02-05 | 2016-10-05 | 上海朗达电缆（集团）有限公司 | Environment-friendly type flexible fireproof cable |
| 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 |
| CN104558868A (en) * | 2015-02-21 | 2015-04-29 | 刘平 | Preparation method of corrosion-resistant flame-retardant cable rubber material |
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| CN105185454A (en) * | 2015-09-28 | 2015-12-23 | 张翔 | Fireproof cable for aerospace |
| CN106340344A (en) * | 2016-11-12 | 2017-01-18 | 河南开启电力实业有限公司 | Aging-resistant insulated cable and preparation method thereof |
| CN106373641A (en) * | 2016-11-12 | 2017-02-01 | 河南开启电力实业有限公司 | Double-capacity electric cable and manufacture method therefor |
| 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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| CN102875887B (en) | 2015-01-28 |
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