CN105237865A - Ultraviolet light cross-linking color low-smoke halogen-free flame-retardant cable material, cable product and preparation method of cable material - Google Patents
Ultraviolet light cross-linking color low-smoke halogen-free flame-retardant cable material, cable product and preparation method of cable material Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention provides an ultraviolet light cross-linking color low-smoke halogen-free flame-retardant cable material. The cable material comprises polyolefin, compatilizer, a flame-retardant agent, a flame-retardant synergist, color master, photoinitiator, assistant crosslinker, surfactant, antioxidant and a lubricating agent. The polyolefin is prepared from, by weight, 20-40 parts of ethylene-octene copolymer and 40-80 parts of poly (ethylene-co-vinyl acetate). The compatilizer is poly (ethylene-co-vinyl acetate) grafted by maleic anhydride. The cable material has various colors, the comprehensive mechanical performance of materials in different colors is excellent, flame-retardant performance is good, and cost performance is high.
Description
Technical field
The invention belongs to fireproofing cable material without halide field, be specifically related to the colored fireproofing cable material without halide of a kind of ultraviolet light cross-linking, cable goods and preparation method thereof.
Background technology
Halogen-free anti-flaming polyolefin material is widely used because of its excellent flame retardant properties, hypotoxicity and comprehensive mechanical performance etc. in electric wire field.In order to make halogen-free anti-flaming polyolefin cable material have higher life-time service temperature, corrosion-resistant, withstand voltage properties, physical strength etc., irradiation crosslinking technological is widely used in phosphorus flame retardant etc.
Wherein, ultraviolet light cross-linking technology is because of the advantage that its facility investment is little, energy consumption is low, easy to process, rate of crosslinking is fast, more and more come into one's own in the application in electric wire field, range of application is also in continuous expansion, expect that non-halogen flame-retardant cable all has from polyethylene insulation to relate to, and when being applied to non-halogen flame-retardant cable, because dissimilar cable needs distinct colors mark, this just needs the ultraviolet absorption wavelength solving different colours different, the problem that the shielding effect of UV-light is different.
Therefore, this area is in the urgent need to providing a kind of ultraviolet light cross-linking colored fireproofing cable material without halide.Colored fireproofing cable material without halide of ultraviolet light cross-linking of the present invention and preparation method thereof, solves those skilled in the art for a long time and thirsts for but the technical barrier of the colored fireproofing cable material without halide of the ultraviolet light cross-linking of always not capturing.
Summary of the invention
The first object of the present invention is that obtaining one overcomes the deficiencies in the prior art, can with ultraviolet light cross-linking, and flame retardant properties is good, the colored fireproofing cable material without halide of the ultraviolet light cross-linking that mechanical property is superior.
Another object of the present invention is the preparation method obtaining the colored fireproofing cable material without halide of a kind of above-mentioned ultraviolet light cross-linking.
Another object of the present invention is to obtain a kind of cable goods prepared according to the colored fireproofing cable material without halide of above-mentioned ultraviolet light cross-linking.
Can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking as a kind of of a first aspect of the present invention, it is characterized in that, describedly can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking to be prepared from by polyolefine, compatilizer, fire retardant, fire retarding synergist, look mother, light trigger, additional crosslinker, surface-modifying agent, oxidation inhibitor and lubricant, wherein, every 100 weight part polyolefine use the component of following weight part:
Wherein, described polyolefine contains ethylene-octene copolymer and ethylene-vinyl acetate copolymer, and by every 100 weight part polyolefine, the weight of ethylene-octene copolymer and ethylene-vinyl acetate copolymer is 20 ~ 40:40 ~ 80;
Described compatilizer is the ethylene-vinyl acetate copolymer with maleic anhydride graft;
Described fire retardant is magnesium hydroxide and aluminium hydroxide combination;
Described fire retarding synergist is one or more combinations of zinc borate, polydimethylsiloxane, red phosphorus and nano imvite.
In the present invention one preferred embodiment, the weight of described magnesium hydroxide and aluminium hydroxide is 1 ~ 3:1 ~ 3.
In the present invention one preferred embodiment, described fire retarding synergist is the mixture of nano imvite and red phosphorus, and weight is 1 ~ 4:2 ~ 7.。
In the present invention one preferred embodiment, the melting index of described ethylene-octene copolymer is 1 ~ 6g/10min, measures with GB/T3682-2000 method.
In the present invention one preferred embodiment, the melting index of described ethylene-vinyl acetate copolymer is 0.5 ~ 5g/10min, measures with GB/T3682-2000 method; And wherein the mass percentage of vinyl acetate is 10 ~ 40%, with the total weight of ethylene-vinyl acetate copolymer.
In the present invention one preferred embodiment, measure with GB/T3682-2000 method, the melting index of the ethylene-vinyl acetate copolymer of described maleic anhydride graft is 0.5 ~ 5g/10min; And its percentage of grafting is 0.5-5%, in the gross weight of the ethylene-vinyl acetate copolymer of maleic anhydride graft for benchmark.
In the present invention one preferred embodiment, the color of described look mother is the one in redness, blueness, yellow, black;
In the present invention one preferred embodiment, described light trigger is selected from benzophenone (BP), isopropyl thioxanthone (ITX), 4-dimethyl ethyl aminobenzoate (EDB), 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone (907), phenyl two (2, 4, 6-trimethylbenzoyl) phosphine oxide (819), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2, 4, 6,-trimethylbenzoy-dipheny phosphorus oxide (TPO), one or more mixture in 1-(4-morpholinyl phenyl)-2-(dimethyl amine)-2-benzyl-1-butanone (369) and benzoin derivatives (651), wherein, the CABLE MATERIALS of distinct colors adopts different photoinitiator systems.
In a preferred embodiment of the invention; when the color of described look mother is red; described light trigger be selected from 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), benzophenone (BP) and 1-hydroxycyclohexyl phenyl ketone (184) any one and 2; 4; 6; any one combination in-trimethylbenzoy-dipheny phosphorus oxide (TPO), 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone (907), the weight proportion of this combination described is 2 ~ 5:1 ~ 4.
In a preferred embodiment of the invention, when the color of described look mother is blue, described light trigger is selected from 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), isopropyl thioxanthone (ITX), any one or two kinds of mixtures and 2 in 4-dimethyl ethyl aminobenzoate (EDB), 4, 6,-trimethylbenzoy-dipheny phosphorus oxide (TPO), phenyl two (2, 4, 6-trimethylbenzoyl) any one combination in phosphine oxide (819), the weight proportion of this combination described is 1 ~ 4:3 ~ 6.
In a preferred embodiment of the invention, when the color of described look mother is yellow, described light trigger is selected from 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), isopropyl thioxanthone (ITX), any one or two kinds of mixtures in 4-dimethyl ethyl aminobenzoate (EDB) and 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone (907), any one combination in 1-(4-morpholinyl phenyl)-2-(dimethyl amine)-2-benzyl-1-butanone (369), the weight proportion of this combination described is 1 ~ 4:3 ~ 8.
In a preferred embodiment of the invention; when the color of described look mother is black; described light trigger is selected from one in 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) and 1-(4-morpholinyl phenyl)-2-(dimethyl amine)-2-benzyl-1-butanone (369), phenyl two (2; 4; 6-trimethylbenzoyl) any one combination in phosphine oxide (819), the weight proportion of this combination described is 1 ~ 4:3 ~ 8.
In the present invention one preferred embodiment, described additional crosslinker is selected from one or more the mixture in triallyl hydroxyl urea acid esters, cyanacrylate, trihydroxy methyl propane trimethyl acrylate and 1,2-polyhutadiene.
In the present invention one preferred embodiment, described surface-modifying agent is selected from one or more the mixture in silane coupling agent, titanate coupling agent, aluminate coupling agent and polyoxyethylene glycol.
In the present invention one preferred embodiment, described oxidation inhibitor is selected from four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, one or more mixture in two lauryl and three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester of thio-2 acid.
In the present invention one preferred embodiment, described lubricant is selected from one or more the combination in calcium stearate, Zinic stearas, Magnesium Stearate, polyethylene wax and silicone oil.
The present invention also provides a kind of method preparing the colored fireproofing cable material without halide of ultraviolet light cross-linking, and described method comprises:
By polyolefine, compatilizer, fire retardant, fire retarding synergist, look mother, light trigger, additional crosslinker, surface-modifying agent, oxidation inhibitor and lubricant by required weight part mixing, extruding pelletization, thus prepare described ultraviolet light cross-linking non-halogen flame-retardant cable.
In a specific embodiment of above-mentioned preparation method, adopt dual-screw pelletizer to carry out extruding pelletization, and four temperature sections in extruding pelletization process are: feeding section 85 ~ 95 DEG C, 95 ~ 105 DEG C, transportation section, melt zone 105 ~ 115 DEG C, head 110 ~ 120 DEG C; Screw speed is 50 ~ 400rpm.
The present invention also comprises cable goods, and described cable at least comprises the insulation layer or restrictive coating that adopt the colored fireproofing cable material without halide of ultraviolet light cross-linking of the present invention to prepare.
The present invention also comprises a kind of method preparing above-mentioned cable goods, and the method comprises:
(1) the colored non-halogen flame-retardant cable of ultraviolet light cross-linking is prepared: comprise polyolefine, compatilizer, fire retardant, fire retarding synergist, look mother, light trigger, additional crosslinker, surface-modifying agent, oxidation inhibitor and mix lubricant, then extruding pelletization;
(2) coated: the colored crosslinked halogen-free flame-retardant CABLE MATERIALS of UV-light step (1) prepared melt extrudes on conductive cable cores, the colored crosslinked halogen-free flame-retardant CABLE MATERIALS of the UV-light that encapsulation steps on conductive cable cores (1) is prepared becomes insulation layer or restrictive coating;
(3) ultraviolet light irradiation: the conductive cable cores of the colored crosslinked halogen-free flame-retardant CABLE MATERIALS of the UV-light coated step (1) of step (2) gained prepared is extruded the rear uv irradiation appts that directly enters and carried out ultraviolet light irradiation.
In the specific embodiment of method preparing cable goods, described in carry out ultraviolet light irradiation and refer to and adopt ultraviolet wavelength 200-400nm, light intensity 500-2500mW/cm
2ultraviolet source carry out ultraviolet light irradiation.
The colored fireproofing cable material without halide of ultraviolet light cross-linking of the present invention, color is wide in variety, superior comprehensive mechanical performance, and flame retardant properties is better.Crowded Wiring technology is simple, facility investment is little, comprehensive sexual valence is higher.
Embodiment
The present inventor is through extensive and deep research, and by improving formula, obtain one and can use ultraviolet light cross-linking, flame retardant properties is good, the colored fireproofing cable material without halide that mechanical property is superior.The present inventor finds in distinct colors system, use different light trigger combinations, the colored non-halogen flame-retardant cable of ultraviolet light cross-linking can be obtained, overcome the deficiency of existing crosslinking technological, make this material have excellent fire-retardancy and comprehensive mechanical performance, complete the present invention on this basis.
Below each component of colored non-halogen flame-retardant cable of the present invention is described in detail:
polyolefine
Be applicable to polyolefine of the present invention containing, for example lower component: ethylene-octene copolymer (POE) and ethylene-vinyl acetate copolymer (EVA), and both weight are 20 ~ 40:40 ~ 80, are preferably 25 ~ 35:50 ~ 80.
In the present invention one preferred embodiment, the melting index being applicable to ethylene-octene of the present invention (POE) multipolymer is 1 ~ 6g/10min, measures with GB/T3682-2000 method.
In the present invention one preferred embodiment, the melting index being applicable to ethylene-vinyl acetate of the present invention (EVA) multipolymer is 0.5 ~ 5g/10min, measures with GB/T3682-2000 method.Preferably, in described multipolymer, the mass percentage of vinyl acetate is 10 ~ 40%, and more preferably, the mass percentage of vinyl acetate is 20 ~ 30%, with the total weight of ethylene-vinyl acetate (EVA) multipolymer.
compatilizer
Compatilizer is used to improve fire retardant or other additives and polyolefinic consistency.In the present invention, use the ethylene-vinyl acetate copolymer of maleic anhydride graft as compatilizer.
In the present invention one preferred embodiment, the melting index of the ethylene-vinyl acetate copolymer of described maleic anhydride graft is 0.5-5g/10min (measuring with GB/T3682-2000 method), and percentage of grafting is 0.5-5%.Preferably, maleic anhydride grafting ratio is 1-3%, in the gross weight of the ethylene-vinyl acetate copolymer of maleic anhydride graft for benchmark.
Usually, in every 100 weight part polyolefine, use the compatilizer of 5 ~ 15 weight parts, preferably use the compatilizer of 6 ~ 12 weight parts.
fire retardant
Fire retardant of the present invention produces water molecules by decomposes and reaches flame retardant effect, and has certain smoke suppressing effect, and environmental protection LSZH.The fire retardant that the present invention selects is the combination of magnesium hydroxide and aluminium hydroxide; Commercially available magnesium hydroxide or aluminium hydroxide can be used to meet object of the present invention.
Usually, in every 100 weight part polyolefine, use the fire retardant of 80 ~ 150 weight parts, the weight of described magnesium hydroxide and aluminium hydroxide is 1 ~ 3:1 ~ 3.
fire retarding synergist
Fire retarding synergist is the known additive for improving fire retardant effect.For reaching optimization physicals, improving flame retardant effect, can fire retarding synergist be used.
Fire retarding synergist of the present invention is not specifically limited, various available fire retarding synergist can be adopted, only otherwise to goal of the invention of the present invention produce and limit.
Usually, in every 100 weight part polyolefine, use the fire retarding synergist of 5 ~ 15 weight parts, preferably use the fire retarding synergist of 6 ~ 14 weight parts, more preferably use the fire retarding synergist of 6 ~ 12 weight parts.
In example of the present invention, in every 100 weight part polyolefine, use the fire retarding synergist of 6 ~ 12 weight parts; And use the mixture of nano imvite and red phosphorus, wherein, by every 100 weight part polyolefine, the weight of nano imvite and red phosphorus is 1 ~ 4:2 ~ 7.
Look female
The female color of look of the present invention is selected from the one in redness, blueness, yellow, black, in every 100 weight part polyolefine, uses the look of 2 ~ 8 parts of weight female, preferably uses the look of 2-6 part weight female.
light trigger
Light trigger makes polyolefine material crosslinked under ultraviolet light irradiation.
Light trigger is selected from benzophenone (BP), isopropyl thioxanthone (ITX), 4-dimethyl ethyl aminobenzoate (EDB), 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone (907), phenyl two (2, 4, 6-trimethylbenzoyl) phosphine oxide (819), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2, 4, 6,-trimethylbenzoy-dipheny phosphorus oxide (TPO), one or more mixture in 1-(4-morpholinyl phenyl)-2-(dimethyl amine)-2-benzyl-1-butanone (369) and benzoin derivatives (651), wherein, the CABLE MATERIALS of distinct colors adopts different photoinitiator systems,
Wherein, the light trigger of red cable material be selected from 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), benzophenone (BP) and 1-hydroxycyclohexyl phenyl ketone (184) any one and 2; 4; 6; any one combination in-trimethylbenzoy-dipheny phosphorus oxide (TPO), 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone (907), the weight proportion of this combination described is 2 ~ 5:1 ~ 4.
The light trigger of yellow cable material is selected from any one or two kinds of mixtures and 2 in 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), isopropyl thioxanthone (ITX), 4-dimethyl ethyl aminobenzoate (EDB); 4; 6;-trimethylbenzoy-dipheny phosphorus oxide (TPO), phenyl two (2; 4; 6-trimethylbenzoyl) any one combination in phosphine oxide (819), the weight proportion of this combination described is 1 ~ 4:3 ~ 6.
The light trigger of blue cable material to be selected from any one or two kinds of mixtures in 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), isopropyl thioxanthone (ITX), 4-dimethyl ethyl aminobenzoate (EDB) and 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone (907), 1-(4-morpholinyl phenyl)-2-(dimethyl amine)-2-benzyl-1-butanone (369) any one combination, and the weight proportion of this combination described is 1 ~ 4:3 ~ 8.
The light trigger of balck cable material is selected from one in 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) and 1-(4-morpholinyl phenyl)-2-(dimethyl amine)-2-benzyl-1-butanone (369), phenyl two (2; 4; 6-trimethylbenzoyl) any one combination in phosphine oxide (819), the weight proportion of this combination described is 1 ~ 4:3 ~ 8.
additional crosslinker
Additional crosslinker effectively can improve the rate of crosslinking of ultraviolet light cross-linking, increases the degree of crosslinking of material, improves over-all properties.The additional crosslinker that the present invention uses comprises one or more the mixture in triallyl hydroxyl urea acid esters (TAC), cyanacrylate (TAIC), trihydroxy methyl propane trimethyl acrylate (TMPTMA), 1,2-polyhutadiene.
Usually, in every 100 weight part polyolefine, use the additional crosslinker of 0.5 ~ 5 weight part, preferably use the additional crosslinker of 1 ~ 3 weight part.
When using the mixture of two or more additional crosslinker, particular restriction be there is no to the weight proportion of additional crosslinker each in mixture.
surface-modifying agent
Surface-modifying agent can carry out surface treatment to fire retardant, increases itself and polyolefinic consistency, improves the over-all properties of CABLE MATERIALS.In example of the present invention, described surface-modifying agent is one or more the mixture in silane coupling agent, titanate coupling agent, aluminate coupling agent, polyoxyethylene glycol.
Usually, in every 100 weight part polyolefine, use the surface-modifying agent of 0.5 ~ 2 weight part, preferably use the surface-modifying agent of 0.8 ~ 1.5 weight part.
In a specific embodiment, the present invention uses ethenylmethoxy Ethoxysilane.
When using the mixture of two or more surface-modifying agent, particular restriction be there is no to the weight proportion of surface-modifying agent each in mixture.
oxidation inhibitor
The oxidation inhibitor that the present invention uses is not specifically limited, various commercially available available oxidation inhibitor can be adopted, only otherwise to goal of the invention of the present invention produce and limit.
In example of the present invention, described oxidation inhibitor is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester (1076) of propionic acid, the two lauryl (DLTP) of thio-2 acid, one or more mixture in three [2,4-di-tert-butyl-phenyl] phosphorous acid ester (168).
Usually, in every 100 weight part polyolefine, use the oxidation inhibitor of 0.5 ~ 3 weight part, preferably use the oxidation inhibitor of 0.5 ~ 2.0 weight part.
When using the mixture of two or more oxidation inhibitor, particular restriction be there is no to the weight proportion of oxidation inhibitor each in mixture.In a specific embodiment, the present invention uses four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester or β-(3,5-di-tert-butyl-hydroxy phenyl) mixture of the two lauryl of the positive octadecanol ester of propionic acid and thio-2 acid is as oxidation inhibitor, and both weight are 0.6 ~ 1.2:0.5 ~ 0.8.
lubricant
Lubricant is added to improve polyolefinic processability in the course of processing.The lubricant that the present invention uses is not specifically limited, and only otherwise to goal of the invention of the present invention produces and limits.
In example of the present invention, described lubricant is calcium stearate, Zinic stearas, Magnesium Stearate, polyethylene wax, one or more combination of silicone oil.
Usually, in every 100 weight part polyolefine, use the lubricant of 0.2 ~ 2 weight part, preferably use the lubricant of 0.2 ~ 0.8 weight part.
In the present invention's specific embodiment, use polyethylene wax as lubricant.
When using the mixture of two or more lubricant, particular restriction be there is no to the weight proportion of lubricant each in mixture.
cable goods
Present invention also offers a kind of cable goods adopting the colored non-halogen flame-retardant cable of ultraviolet light cross-linking of the present invention to prepare.Described cable goods colour is wide in variety, has excellent flame retardant properties and mechanical property.
preparation method
Present invention also offers a kind of preparation method preparing the colored non-halogen flame-retardant cable of ultraviolet light cross-linking of the present invention, described preparation method comprises polyolefine, compatilizer, fire retardant, fire retarding synergist, look mother, light trigger, additional crosslinker, surface-modifying agent, oxidation inhibitor and mix lubricant, then extruding pelletization, thus prepare the colored non-halogen flame-retardant cable of described ultraviolet light cross-linking.
In a specific embodiment, the method is by polyolefine, compatilizer, fire retardant, fire retarding synergist, look mother, light trigger, additional crosslinker, surface-modifying agent, oxidation inhibitor and mix lubricant and extruding pelletization;
Thus prepare the colored non-halogen flame-retardant cable of described ultraviolet light cross-linking.
In a specific embodiment of the present invention, adopt dual-screw pelletizer to carry out extruding pelletization in described preparation method, and four temperature sections in extruding pelletization process are: feeding section 85 ~ 95 DEG C, 95 ~ 105 DEG C, transportation section, melt zone 105 ~ 115 DEG C, head 110 ~ 120 DEG C; Screw speed is 50 ~ 400rpm.
The present invention also provides a kind of preparation method of cable goods, and the method comprises:
(1) the colored non-halogen flame-retardant cable of ultraviolet light cross-linking is prepared: comprise polyolefine, compatilizer, fire retardant, fire retarding synergist, look mother, light trigger, additional crosslinker, surface-modifying agent, oxidation inhibitor and mix lubricant, then extruding pelletization;
(2) coated: the colored non-halogen flame-retardant cable of ultraviolet light cross-linking step (1) prepared melt extrudes on conductive cable cores, makes this flame-proof material coated on conductive cable cores become insulation layer or restrictive coating;
(3) ultraviolet light irradiation: the conductive cable cores of this flame-proof material coated of step (2) gained is directly carried out ultraviolet light irradiation.
In a specific embodiment, wavelength 200-400nm, light intensity 500-2500mW/cm is adopted
2uV-light carry out ultraviolet light irradiation.
In the embodiment of method preparing cable, described method comprises:
By polyolefine, compatilizer, fire retardant, fire retarding synergist, look mother, light trigger, additional crosslinker, surface-modifying agent, oxidation inhibitor and mix lubricant, then extruding pelletization.
Should be understood that the composition of the polyolefine described in this part, compatilizer, fire retardant, fire retarding synergist, look mother, light trigger, additional crosslinker, surface-modifying agent, oxidation inhibitor and lubricant etc. and consumption as is described elsewhere herein.
The present invention also comprises and adopts coated insulation layer or restrictive coating on the conductive cable cores for preparing of aforesaid method.
The colored fireproofing cable material without halide of a kind of ultraviolet light cross-linking of the present invention and preparation method's tool have the following advantages:
1, adopt light trigger and additional crosslinker composite, the CABLE MATERIALS complete processing of preparation is simple, and facility investment is lower, and comprehensive cost performance is superior.
2, CABLE MATERIALS of the present invention has high flame retardant resistance, low cigarette characteristic and have multiple color optional.
In the present invention, term " contains " or " comprising " or " employing " represents that various composition can be applied in mixture of the present invention or composition together.Therefore, term " primarily of ... composition " and " by ... form " be included in term and " contain " or in " comprising " or " employing ".
Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.
As no specific instructions, various raw material of the present invention all can be obtained by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, measures according to national standard usually.If there is no corresponding national standard, then according to general international standard, normal condition or carry out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all numbers are weight part, and all per-cent is weight percentage, and described polymericular weight is number-average molecular weight.
Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1
Each ingredient names and each composition weight number of embodiment 1 formula are as shown in table 1:
Table 1
By poly alkene, compatilizer, fire retardant, fire retarding synergist, look mother, light trigger, additional crosslinker, surface-modifying agent, oxidation inhibitor, lubricant by proportioning extruding pelletization, obtain described UV-light and hand over colored connection fireproofing cable material without halide.Four temperature sections in extruding pelletization process are: feeding section 85 ~ 95 DEG C, 95 ~ 105 DEG C, transportation section, melt zone 105 ~ 115 DEG C, head 110 ~ 120 DEG C; Screw speed is 50 ~ 400rpm.
Then the colored CABLE MATERIALS obtained is melt extruded this flame-proof material coated on conductive cable cores and become insulation layer or restrictive coating, in ultraviolet light irradiation cross-linking apparatus, adopt ultraviolet wavelength 200-400nm, light intensity 500-2500mW/cm immediately
2ultraviolet source under carry out the ultraviolet light irradiation cross-linking of insulation layer or restrictive coating.
Carry out performance detection experiment to the product in embodiment 1, each performance value is as shown in PERFORMANCE EXAMPLES table 7.
Embodiment 2
Each ingredient names and each composition weight number of embodiment 2 formula are as shown in table 2:
Table 2
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Carry out performance detection experiment to the product in embodiment 2, each performance value is as shown in PERFORMANCE EXAMPLES table 7.
Embodiment 3
Each ingredient names and each composition weight number of embodiment 3 formula are as shown in table 3.
Table 3
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Carry out performance detection experiment to the product in embodiment 3, each performance value is as shown in PERFORMANCE EXAMPLES table 7.
Embodiment 4
Each ingredient names and each composition weight number of embodiment 4 formula are as shown in table 4.
Table 4
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Carry out performance detection experiment to the product in embodiment 4, each performance value is as shown in PERFORMANCE EXAMPLES table 7.
Embodiment 5
Each ingredient names and each composition weight number of embodiment 5 formula are as shown in table 5.
Table 5
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Carry out performance detection experiment to the product in embodiment 5, each performance value is as shown in PERFORMANCE EXAMPLES table 7.
Embodiment 6
Each ingredient names and each composition weight number of embodiment 6 formula are as shown in table 6.
Table 6
The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1.
Carry out performance detection experiment to the product in embodiment 6, each performance value is as shown in PERFORMANCE EXAMPLES table 7.
PERFORMANCE EXAMPLES
Carry out product performance test in the following manner:
(1) tensile property test:
According to the tensile property of GB/T1040-2008 standard testing non-halogen flame-retardant cable;
(2) vertical combustion test:
According to the flame retardant properties of UL94 standard testing non-halogen flame-retardant cable;
(3) hot elongation test
According to the heat extensibility energy of GB/T2951.21-2008 standard testing non-halogen flame-retardant cable.
Test result is as shown in table 7.
Table 7: embodiment product performance test result
Data as can be seen from table 7, adopt inorganic combustion inhibitor composite as main flame-retardant system and the UV-crosslinked colored non-halogen flame-retardant cable flame retardant properties adopting red phosphorus and nano montmorillonite flame-retardant synergist to prepare is good, mechanical property is superior.Distinct colors system, adopts different photoinitiator systems, simultaneously and additional crosslinker with CABLE MATERIALS can be made crosslinked under UV-irradiation, simply, product performance are stable, and cost performance is higher for production technique.
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read foregoing of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (21)
1. one kind can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, describedly can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking to be prepared from by polyolefine, compatilizer, fire retardant, fire retarding synergist, look mother, light trigger, additional crosslinker, surface-modifying agent, oxidation inhibitor and lubricant, wherein, every 100 weight part polyolefine use the component of following weight part:
Wherein, described polyolefine contains ethylene-octene copolymer and ethylene-vinyl acetate copolymer, and by every 100 weight part polyolefine, the weight of ethylene-octene copolymer and ethylene-vinyl acetate copolymer is 20 ~ 40:40 ~ 80;
Described compatilizer is the ethylene-vinyl acetate copolymer with maleic anhydride graft;
Described fire retardant is magnesium hydroxide and aluminium hydroxide combination;
Described fire retarding synergist is one or more combinations of zinc borate, polydimethylsiloxane, red phosphorus and nano imvite.
2. a kind of as claimed in claim 1 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, the weight of described magnesium hydroxide and aluminium hydroxide is 1 ~ 3:1 ~ 3.
3. a kind of as claimed in claim 1 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, described fire retarding synergist is the mixture of nano imvite and red phosphorus, and weight is 1 ~ 4:2 ~ 7.。
4. a kind of as claimed in claim 1 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, the melting index of described ethylene-octene copolymer is 1 ~ 6g/10min, measures with GB/T3682-2000 method.
5. a kind of as claimed in claim 1 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, the melting index of described ethylene-vinyl acetate copolymer is 0.5 ~ 5g/10min, measures with GB/T3682-2000 method; And wherein the mass percentage of vinyl acetate is 10 ~ 40%, with the total weight of ethylene-vinyl acetate copolymer.
6. a kind of as claimed in claim 1 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, measure with GB/T3682-2000 method, the melting index of the ethylene-vinyl acetate copolymer of described maleic anhydride graft is 0.5 ~ 5g/10min; And its percentage of grafting is 0.5-5%, in the gross weight of the ethylene-vinyl acetate copolymer of maleic anhydride graft for benchmark.
7. a kind of as claimed in claim 1 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, the color of described look mother is the one in red, blue, yellow, black.
8. a kind of as claimed in claim 1 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, described light trigger is selected from benzophenone, isopropyl thioxanthone, 4-dimethyl ethyl aminobenzoate, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone, phenyl two (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2, 4, 6,-trimethylbenzoy-dipheny phosphorus oxide, one or more mixture in 1-(4-morpholinyl phenyl)-2-(dimethyl amine)-2-benzyl-1-butanone and benzoin derivatives, wherein, the CABLE MATERIALS of distinct colors adopts different photoinitiator systems.
9. a kind of as claimed in claim 8 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking; it is characterized in that; when the color of described look mother is red; described light trigger be selected from 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzophenone and 1-hydroxycyclohexyl phenyl ketone any one and 2; 4; 6; any one combination in-trimethylbenzoy-dipheny phosphorus oxide, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone, the weight proportion of this combination described is 2 ~ 5:1 ~ 4.
10. a kind of as claimed in claim 8 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, when the color of described look mother is blue, described light trigger is selected from 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, isopropyl thioxanthone, any one or two kinds of mixtures and 2 in 4-dimethyl ethyl aminobenzoate, 4, 6,-trimethylbenzoy-dipheny phosphorus oxide, phenyl two (2, 4, 6-trimethylbenzoyl) any one combination in phosphine oxide, the weight proportion of this combination described is 1 ~ 4:3 ~ 6.
11. a kind of as claimed in claim 8 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, when the color of described look mother is yellow, described light trigger is selected from 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, isopropyl thioxanthone, any one or two kinds of mixtures in 4-dimethyl ethyl aminobenzoate and 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone, any one combination in 1-(4-morpholinyl phenyl)-2-(dimethyl amine)-2-benzyl-1-butanone, the weight proportion of this combination described is 1 ~ 4:3 ~ 8.
12. a kind of as claimed in claim 8 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking; it is characterized in that; when the color of described look mother is black; described light trigger is selected from one in 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 1-(4-morpholinyl phenyl)-2-(dimethyl amine)-2-benzyl-1-butanone, phenyl two (2; 4; 6-trimethylbenzoyl) any one combination in phosphine oxide, the weight proportion of this combination described is 1 ~ 4:3 ~ 8.
13. a kind of as claimed in claim 1 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, described additional crosslinker is selected from one or more the mixture in triallyl hydroxyl urea acid esters, cyanacrylate, trihydroxy methyl propane trimethyl acrylate and 1,2-polyhutadiene.
14. a kind of as claimed in claim 1 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, described surface-modifying agent is selected from one or more the mixture in silane coupling agent, titanate coupling agent, aluminate coupling agent and polyoxyethylene glycol.
15. a kind of as claimed in claim 1 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, described oxidation inhibitor is selected from four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, one or more mixture in two lauryl and three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester of thio-2 acid.
16. a kind of as claimed in claim 1 can the colored non-halogen flame-retardant cable of ultraviolet light cross-linking, it is characterized in that, described lubricant is selected from one or more the combination in calcium stearate, Zinic stearas, Magnesium Stearate, polyethylene wax and silicone oil.
17. 1 kinds of methods preparing the colored fireproofing cable material without halide of ultraviolet light cross-linking described in any one of claim 1 to 16 claim, it is characterized in that, described method comprises:
By polyolefine, compatilizer, fire retardant, fire retarding synergist, look mother, light trigger, additional crosslinker, surface-modifying agent, oxidation inhibitor and lubricant by required weight part mixing, extruding pelletization, thus prepare described ultraviolet light cross-linking non-halogen flame-retardant cable.
18. methods as claimed in claim 17, it is characterized in that, described extruding pelletization adopts dual-screw pelletizer to carry out extruding pelletization, and four temperature sections in extruding pelletization process are: feeding section 85 ~ 95 DEG C, 95 ~ 105 DEG C, transportation section, melt zone 105 ~ 115 DEG C, head 110 ~ 120 DEG C; Screw speed is 50 ~ 400rpm.
19. cable goods, is characterized in that, described cable goods at least comprise the insulation layer or restrictive coating that adopt the colored fireproofing cable material without halide of the ultraviolet light cross-linking described in any one of claim 1 to 16 claim to prepare.
20. 1 kinds of methods preparing cable goods according to claim 19, it is characterized in that, the method comprises:
(1) the colored non-halogen flame-retardant cable of ultraviolet light cross-linking is prepared: comprise polyolefine, compatilizer, fire retardant, fire retarding synergist, look mother, light trigger, additional crosslinker, surface-modifying agent, oxidation inhibitor and mix lubricant, then extruding pelletization;
(2) coated: the colored crosslinked halogen-free flame-retardant CABLE MATERIALS of UV-light step (1) prepared melt extrudes on conductive cable cores, the colored crosslinked halogen-free flame-retardant CABLE MATERIALS of the UV-light that encapsulation steps on conductive cable cores (1) is prepared becomes insulation layer or restrictive coating;
(3) ultraviolet light irradiation: the conductive cable cores of the colored crosslinked halogen-free flame-retardant CABLE MATERIALS of the UV-light coated step (1) of step (2) gained prepared is extruded the rear uv irradiation appts that directly enters and carried out ultraviolet light irradiation.
21. methods as claimed in claim 20, is characterized in that, described in carry out ultraviolet light irradiation and refer to and adopt ultraviolet wavelength 200-400nm, light intensity 500-2500mW/cm
2ultraviolet source carry out ultraviolet light irradiation.
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| CN201510694927.4A CN105237865A (en) | 2015-10-21 | 2015-10-21 | Ultraviolet light cross-linking color low-smoke halogen-free flame-retardant cable material, cable product and preparation method of cable material |
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| CN201510694927.4A CN105237865A (en) | 2015-10-21 | 2015-10-21 | Ultraviolet light cross-linking color low-smoke halogen-free flame-retardant cable material, cable product and preparation method of cable material |
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| CN110527178A (en) * | 2019-10-08 | 2019-12-03 | 安徽滁州德威新材料有限公司 | A kind of ultraviolet light cross-linking black low-smoke halogen-free cable sheath material and preparation method thereof |
| CN110922668A (en) * | 2019-10-29 | 2020-03-27 | 昆山勃盛电子有限公司 | Low-smoke halogen-free flame-retardant cable material and preparation method thereof |
| CN110951141A (en) * | 2019-12-11 | 2020-04-03 | 上海凯波特种电缆料厂有限公司 | Double-layer co-extrusion insulation LED ultraviolet light cross-linking color low-smoke halogen-free flame-retardant cable material and preparation method thereof |
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Application publication date: 20160113 |