CN1261716A - Radiation-crosslinked low smoke no halide flame retaining thermal shrinking electric cable fitting - Google Patents
Radiation-crosslinked low smoke no halide flame retaining thermal shrinking electric cable fitting Download PDFInfo
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- CN1261716A CN1261716A CN 99125747 CN99125747A CN1261716A CN 1261716 A CN1261716 A CN 1261716A CN 99125747 CN99125747 CN 99125747 CN 99125747 A CN99125747 A CN 99125747A CN 1261716 A CN1261716 A CN 1261716A
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Abstract
The power cable fitting consists of radiation-crosslinked low-smoke no-halide flame-retarding thermal shrinking insulating material thermal shrinking no-halide stress pipe material, low-smoke no-halide flame-retarding thermal shrinking branch casing material, filling glue and sealing glue. It is suitable for use as insulating and protecting part of terminal and intermediate connection of 35 KV and below power cable.
Description
The present invention relates to a kind of thermal shrinking electric cable fitting and preparation method of crosslinking with radiation, have low cigarette, Halogen and fire-retardant premium properties.
As everyone knows, heat-shrinkage material is to be base material with high molecule plastic or rubber, it is promptly crosslinked to make the linear molecule chain of polymer become network structure through radiation or chemical method, obtain " elastic memory " and be expanded to specific dimensions through heating, suitable heating can retract to the preceding size of expansion voluntarily during use.Power cable thermal contraction annex is to reach filling glue matching used with it, fluid sealant coated terminals and the joint that is installed on the cable of heat shrink at the scene with all kinds of heat shrinkage insulations (full skirt) pipe, stress tube, branch spider thermal contraction parts such as (sheaths).The heat shrinkage insulation that existing market is just being used (full skirt) material and stress tube material adopt the Halogen fire proofing, and divide spider (sheath) material to adopt common polyolefine material (heat-shrinkage material limited company of Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences product description), Shenzhen oval new material Co., Ltd development flame retardant type thermal contraction electronic cables annex, the heat shrinkage insulation of its use (full skirt) material, stress tube material and branch joint (sheath) material all adopts Halogen fire proofing (building, fire-retardant, the fire-resisting cable symposium, electric wire Professional Committee of China Institute of Electrical Engineering Technology, 1999,1,12).Only stipulate that in DL413-91 power industry standard power cable thermal contraction annex the heat shrinkage insulation material uses fire proofing, other thermal contraction device all adopts common polyolefine material.
The object of the invention provides a kind of radiation-crosslinked low smoke no halide flame retaining thermal shrinking electric cable fitting, wherein adopt radiation-crosslinked low smoke no halide flame retaining heat shrinkage insulation (full skirt) material, branch joint (sheath) material that thermal contraction Halogen stress tube material and the fire-retardant heat shrinkage insulation material of low-smoke non-halogen flame-retardant thermal contraction branch joint (sheath) material substitution tradition Halogen, Halogen thermal shrinkage stress tube material, common polyolefin or Halogen flame retardant polyolefine material are formed.
Purpose of the present invention also provides a kind of method for preparing radiation-crosslinked low smoke no halide flame retaining thermal shrinking electric cable fitting.
Another purpose of the present invention provides the purposes of above-mentioned thermal shrinking electric cable fitting.
Radiation-crosslinked low smoke no halide flame retaining thermal shrinking electric cable fitting of the present invention comprises heat shrinkage insulation (full skirt) pipe, stress tube, branch joint (sheath) and matching used filling glue and fluid sealant, described heat shrinkage insulation pipe (full skirt), stress tube and branched pipe (sheath) are made up of following each weight ratio material respectively: the heat shrinkage insulation material: low density polyethylene (LDPE) (LDPE) 10-30, ethylene-vinyl acetate copolymer (EVA) 50-70, ethylene propylene diene rubber (EPDM) 10-30, methyl vinyl silicone rubber (PDMVS) 2-10, amines antioxidants 0.5-1.5, divalence or trivalent metal stearate lubricant 2-4, efficient halogen-free anti-inflaming agent (trade name MRP) 5-10, melamine complex compound (MCA) 10-20, superfine active Halogenless composite fire retardant 40-80, Benzophenone class light stabilizer 0-1, color masterbatch 0-8, acrylate cross linked dose of 1-3 of polyfunctional group (methyl).
Thermal shrinkage stress tube material: low density polyethylene (LDPE) (LDPE) 30-50, ethylene propylene diene rubber (EPDM) 50-70, amines antioxidants 1-3, high-k filler barium titanate 30-70, carbon black 15-40, the stearate lubricant 1-3 of divalence or trivalent metal.
Thermal contraction branch joint (sheath) material: low density polyethylene (LDPE) (LDPE) 30～50, ethylene-vinyl acetate copolymer (EVA) 50～70, ester kind antioxidant 0.1～1.0, efficient halogen-free anti-inflaming agent (MRP) 5～15, melamine complex compound (MCA) 10～20, superfine active Halogenless composite fire retardant 50～100, divalence or trivalent metal stearate 1～3, color masterbatch 0～5, polyfunctional group (methyl) acrylate 1～3.
In order to reach application purpose and to be convenient to processing, in aforesaid heat shrinkage insulation material and the heat-shrinkable tube material, described LDPE recommends to use melt index MI≤0.5g/10min, and the LDPE in thermal contraction branched pipe (sheath) material recommends MI≤2g/min.
In above-mentioned material, recommend to use the EVA of melt index MI=2-5g/min, wherein vinyl acetate content is 14-18%.
In the described heat shrinkage insulation material, can add color masterbatch, generally be pigment, with the conversion shades of colour, is convenient to distinguish and uses.Usually addition is the 3-8 of relative weight ratio.When using out of doors, can suitably add light stabilizer, as Benzophenone class light stabilizer, recommending addition is the 0.2-1 of relative weight ratio.
In the above-mentioned thermal shrinkage stress tube material, described carbon black can be high abrasion carbon black and conductive acetylene carbon black, recommends the relative weight ratio to be followed successively by 2-3: 1-2.
Ester kind antioxidant described in the present invention can be β-propionic acid stearyl (antioxidant 1076), four seasons Doutrate (antioxidant 1010), dilauryl thiodipropionate (antioxidant DLDP), thio-2 acid stearyl (antioxidant DSTP), β-cyclohexyl propionate (antioxidant 121), thio-2 acid two (myristyl ester) (antioxidant DMTDP), thio-2 acid tricosyl ester (antioxidant 711), lauryl-thio-2 acid octadecyl ester admixture (antioxidant 1212), 1,3,5-triisocyanate (antioxidant 3114) or trilauryl trithiophosphite (age resistor TLTTP) etc.
Described amine antioxidants (age resistor) can be N, N '-two-p-phenylenediamine (PPD) (age resistor 4030), N, N '-di-sec-butyl-p-phenyl enediamine (antioxidant D BPP), N, N '-two-betanaphthyl-p-phenylenediamine (PPD) (antioxidant DNP), N-phenyl-N '-cyclohexyl p-phenylenediamine (PPD) (antioxidant 4010) or N-phenyl-N '-isopropyl p-phenylenediamine (PPD) (antioxidant 4010NA) etc.
The acrylate cross linked auxiliary agent of described polyfunctional group (methyl) can be the monomer of trimethylolpropane triacrylate (TMPTA), trimethylol-propane trimethacrylate (TMPTMA) or tri (propylene glycol) diacrylate (TPGDA) or pentaerythritol triacrylate (PETA) etc.
Described Benzophenone class light stabilizer can be 2-2 '-dihydroxy-4-oxy-octyl benzophenone (UV-314), 2-hydroxyl-4-dodecyloxy benzophenone (DOPB), 2-hydroxyl-4-n-octyl benzophenone (UV-531) or 2-hydroxyl-4-(2 '-hydroxyl-3 '-the acryloxy propoxyl group) benzophenone (UV-342) etc.
The method for preparing radiation-crosslinked low smoke no halide flame retaining thermal shrinking electric cable fitting of the present invention is mixed following weight respectively than component:
(1) LDPE 10-30, EVA 50-70, EPDM 10-30, PDMVS 2-10, amines antioxidants 0.5-1.5, lubricant 2-4, MRP 5-10, MCA 10-20, superfine active Halogenless composite fire retardant 40-80, light stabilizer 0-1, color masterbatch 0-8, the acrylate cross linked auxiliary agent 1-3 of polyfunctional group (methyl);
(2) LDPE 30-50, EPDM50-70, amines antioxidants 1-3, barium titanate 30-70, carbon black 15-40, divalence or trivalent metal stearate lubricant 1-3;
(3) LDPE 30-50, EVA50-70, ester kind antioxidant 0.1-1.0, MRP 5-15, MCA 10-20, superfine active Halogenless composite fire retardant 50-100, lubricant 1-3, color masterbatch 0-5, the acrylate cross linked auxiliary agent 1-3 of polyfunctional group (methyl).
The high speed kneader can be at room temperature used in this mixing, mixes during rotating speed 750-1500r/min.Extruding pelletization and extrusion molding respectively then recommends to use double screw extruder each interval mixing to extrude wire drawing, air-cooled, pelletizing at 100～180 ℃.
Above-mentioned three kinds of master batches are adopted extrude, injection moulding or hot-press method plasticizing forming, with gamma-rays or electron ray irradiation, cumulative dose be 80-180KGY respectively behind crosslinking with radiation, become three-dimensional netted high molecular products by linear polymeric.The resilient, crosslinked high molecular products is expanded and be drawn into to above-mentioned three kinds of goods at 80-160 ℃, becomes low-smoke non-halogen flame-retardant heat shrinkage insulation pipe (full skirt), thermal contraction Halogen stress tube and low-smoke non-halogen flame-retardant thermal contraction branch joint (sheath) respectively through cooling and shaping again.
Radiation-crosslinked low smoke no halide flame retaining thermal shrinking electric cable fitting of the present invention meet national sector standard DL413-91's " 35KV and following power cable thermal contraction type attachment technique condition ".Material smoke density performance≤150 (ASTME62), hydrogen halide content performance≤5mg/g[IEC (754-1)] standard.Anti-flammability oxygen index (OI) 〉=30.Owing to adopt radiation-crosslinked low smoke no halide flame retaining heat shrinkage insulation (full skirt) material, crosslinking with radiation Halogen thermal shrinkage stress tube material and radiation-crosslinked low smoke no halide flame retaining thermal contraction branched pipe (sheath) material are made, can produce the poisonous hydrogen halide of macro-corrosion when having solved existing inflammable and crosslinking with radiation thermal shrinking electric cable fitting that the Halogen fire proofing is made burning substantially, cause serious secondary disaster, harm casualties and property loss, the a large amount of cigarette amounts that produce hinder the problem of rescue and pollutant atmosphere, are a kind of non-harmful cleaning articles of low-smoke non-halogen flame-retardant of environment-friendly type.And raw material is easy to get all commercially availablely, and the preparation method is simple and easy, is suitable for suitability for industrialized production.
The present invention will be helped to understand by following embodiment, but content of the present invention can not be limited.
Embodiment 1
The LDPE 10-30kg of MI≤0.5g/10min, MI is 2-5g/min, the EVA 50-70kg of vinyl acetate content 14-18%, EPDM 10-30kg, PDMVS 2-10kg, amines antioxidants 4030 or 4010 0.5-1.5kg, the stearate of divalence or trivalent metal (as zinc stearate etc.) lubricant 2-4kg, MRP 5-10kg, MCA10-20kg, superfine active Halogenless composite fire retardant (FR-2～6) 40-80kg, Benzophenone class light stabilizer UV-314 or 342 0.2-1kg, pigment 3-8kg, polyfunctional group (methyl) acrylate TMPTA or PETA 1-3kg, at room temperature use high speed kneader (rotating speed 750-1500r/min) to mix, extrude wire drawing 100～180 ℃ of interval mixing with double screw extruder, air-cooled, pelletizing.
Above-mentioned master batch 100-200 ℃ with extruder extrude, injection moulding or hot pressing, plasticizing forming, be the linear polymeric goods, then with gamma-rays or electron ray crosslinking with radiation, cumulative dose 80-180KGY becomes cross-linked polymer goods (small size), 80～160 ℃ of heating, expand 0.5-5 doubly with dilator or stretching-machine, cooling and shaping.This radiation-crosslinked low smoke no halide flame retaining heat-shrinkage material heat shrink in use reverts back to the undersized goods of cross-linked polymer again.
Embodiment 2
Respectively following two groups of components (weight ratio) material is mixed by embodiment 1 method, extrude, granulation, crosslinking with radiation, expansion, cooling and shaping.Make crosslinking with radiation Halogen thermal shrinkage stress tube material and radiation-crosslinked low smoke no halide flame retaining thermal contraction branch joint (sheath) material respectively:
(1) LDPE (30-50kg of MI≤0.5g/10min), EPDM50-70kg, amines antioxidants 4030 or DBPP1-3kg, barium titanate 30-70kg, high abrasion carbon black 10-30kg, conductive acetylene carbon black 5-10kg, divalence or trivalent metal stearate 1-3kg;
(2) LDPE (30-50kg of MI≤2g/10min), EVA (MI=2-5g/min, vinylacetate 14～8%) 50-70kg, commodity are by name 1010, DLDP or 1212 ester kind antioxidant 0.1-1.0kg, efficient halogen-free anti-inflaming agent MRP 5-15kg, MCA10-20kg, the superfine active Halogenless composite fire retardant 50-100kg of trade name FR-2～6, divalence or trivalent metal stearate 1-3kg, carbon black (color masterbatch) 0-5kg, the acrylate cross linked auxiliary agent of polyfunctional group (methyl) (commodity TMPTA by name or TMPTMA) 1-3kg.
Embodiment 3
The heat-shrinkage material of implementing 1 and 2 is tested, " 35KV and the following power cable thermal contraction type accessory application technical conditions " that meet national sector standard DL413-91, material smoke density performance≤150 (ASTME662), hydrogen halide content≤5mg/g (IEC 754-1) standard, anti-flammability oxygen index (OI) 〉=30.
Claims (10)
1, a kind of radiation-crosslinked low smoke no halide flame retaining thermal shrinking electric cable fitting, comprise heat shrinkage insulation (full skirt) pipe, stress tube, branch spider (sheath) and matching used filling glue, fluid sealant, it is characterized in that described heat shrinkage insulation material, thermal shrinkage stress tube material and thermal contraction branch joint (sheath) material be made up of the component of following each weight ratio respectively:
Heat shrinkage insulation (full skirt) material: low density polyethylene (LDPE) 10-30, ethylene-vinyl acetate copolymer 50-70, ethylene propylene diene rubber 10-30, methyl vinyl silicone rubber 2-10, amines antioxidants 0.5-1.5 divalence or trivalent metal stearate 2-4, efficient halogen-free anti-inflaming agent MRP 5-10, melamine complex compound 10-20, superfine active Halogenless composite fire retardant 40-80, Benzophenone class light stabilizer 0-1, color masterbatch 0-8, acrylate cross linked dose of 1-3 of polyfunctional group (methyl);
Thermal shrinkage stress tube material: low density polyethylene (LDPE) 30-50, ethylene propylene diene rubber 50-70, amines antioxidants 1-3, barium titanate 30-70, carbon black 15-40, the stearate 1-3 of divalence or trivalent metal;
Thermal contraction branch joint (sheath) material: low density polyethylene (LDPE) 30-50, ethylene-vinyl acetate copolymer 50-70, ester kind antioxidant 0.1-1.0, the efficient halogen-free anti-inflaming agent 5-15 of commodity MRP by name, melamine complex compound 10-20, superfine active Halogenless composite fire retardant 50-100, divalence or trivalent metal stearate 1-3, color masterbatch 0-5, acrylate cross linked dose of 1-3 of polyfunctional group (methyl).
2, thermal shrinking electric cable fitting as claimed in claim 1 is characterized in that in described heat shrinkage insulation material and the heat-shrinkable tube material melt index MI≤0.5g/10min of low density polyethylene (LDPE).
3, thermal shrinking electric cable fitting as claimed in claim 1 is characterized in that in described thermal contraction branched pipe (sheath) material low density polyethylene (LDPE) melt index MI≤2g/min.
4, thermal shrinking electric cable fitting as claimed in claim 1 is characterized in that described ethylene-vinyl acetate copolymer melt index MI 2-5g/min, and wherein vinyl acetate content is 14-18%.
5, thermal shrinking electric cable fitting as claimed in claim 1 is characterized in that in the described heat shrinkage insulation material that the relative weight ratio of light stabilizer and color masterbatch is respectively 0.2-1 and 3-8.
6, thermal shrinking electric cable fitting as claimed in claim 1 is characterized in that in the described thermal shrinkage stress tube material, carbon black is made up of high abrasion carbon black and conductive acetylene carbon black, and the relative weight ratio is respectively 2-3: 1-2.
7, thermal shrinking electric cable fitting as claimed in claim 1 is characterized in that described ester kind antioxidant is β-propionic acid stearyl, four seasons Doutrate, dilauryl thiodipropionate, thio-2 acid stearyl, β-cyclohexyl propionate, thio-2 acid two (myristyl ester), thio-2 acid two (tridecyl) ester, lauryl-thio-2 acid octadecyl ester admixture, 1,3,5-triisocyanate or trilauryl trithiophosphite; Described amine antioxidants is N, N '-two-p-phenylenediamine (PPD), N, N '-di-sec-butyl-p-phenyl enediamine, N, N '-two-betanaphthyl-p-phenylenediamine (PPD) or N-phenyl-N '-cyclohexyl p-phenylenediamine (PPD) or N-phenyl-N '-isopropyl p-phenylenediamine (PPD); The acrylate cross linked auxiliary agent of described polyfunctional group (methyl) is trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, tri (propylene glycol) diacrylate or pentaerythritol triacrylate; Described Benzophenone class light stabilizer be 2-2 '-dihydroxy-4-oxy-octyl benzophenone, 2-hydroxyl-4-dodecyloxy benzophenone, UV-531 or 2-hydroxyl-4-(2 '-hydroxyl-3 '-the acryloyl-oxy propoxyl group) benzophenone.
8, a kind of preparation method as claim 1,2,3,4,5 and 6 described radiation-crosslinked low smoke no halide flame retaining thermal shrinking electric cable fittings, it is characterized in that the mixed respectively granulation of component separately of described heat shrinkage insulation material, thermal shrinkage stress tube material and thermal contraction branched pipe material, extrude again, the plasticizing forming of injection moulding or hot pressing, through gamma-rays or electron ray crosslinking with radiation, cumulative dose is 80-180KGY, carrying out dilator or stretching-machine at 80-160 ℃ expands or stretches cooling and shaping.
9, preparation method as claimed in claim 7, it is characterized in that described mixed be to be to mix under 750-1500r/min and the room temperature at high speed kneader medium speed.
10, preparation method as claimed in claim 7 is characterized in that described extruding, and is to extrude 100-180 ℃ of interval the mixing with twin-screw to extrude.
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| CN 99125747 CN1091296C (en) | 1999-12-24 | 1999-12-24 | Radiation-crosslinked low smoke no halide flame retaining thermal shrinking electric cable fitting |
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|---|---|---|---|
| CN 99125747 CN1091296C (en) | 1999-12-24 | 1999-12-24 | Radiation-crosslinked low smoke no halide flame retaining thermal shrinking electric cable fitting |
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| CN1261716A true CN1261716A (en) | 2000-08-02 |
| CN1091296C CN1091296C (en) | 2002-09-18 |
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| AT411261B (en) * | 2002-03-19 | 2003-11-25 | Intumex Gmbh | INTUMESCENT ELECTRICAL INSTALLATION SYSTEMS CONTAINING A COMBINATION OF POLYIMIDES AND VERMICULAR GRAPHITE AND THEIR PRODUCTION THEREOF |
| CN100354989C (en) * | 2005-09-01 | 2007-12-12 | 赵成刚 | Environmental protection type fire retardant thermal shrinkage tube without halogen |
| CN100487820C (en) * | 2006-12-25 | 2009-05-13 | 金友友 | Low-smoke halogen-free combustion-preventing cable insulation and jacket material for nuclear power plant |
| CN1969007B (en) * | 2004-06-15 | 2010-05-12 | Lg电线有限公司 | Resin composition resistant to thermal deformation and cut-through and the insulation material and the cable using the same |
| CN101308714B (en) * | 2007-05-17 | 2010-11-10 | 上海长顺电梯电缆有限公司 | Preparing method of low-smoke non-halogen fire-retarding elevator cable |
| CN101613506B (en) * | 2009-07-25 | 2011-07-20 | 四川明星电缆股份有限公司 | High temperature resistance non halogen flame retardant cable sheath material and preparation method thereof |
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- 1999-12-24 CN CN 99125747 patent/CN1091296C/en not_active Expired - Fee Related
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| AT411261B (en) * | 2002-03-19 | 2003-11-25 | Intumex Gmbh | INTUMESCENT ELECTRICAL INSTALLATION SYSTEMS CONTAINING A COMBINATION OF POLYIMIDES AND VERMICULAR GRAPHITE AND THEIR PRODUCTION THEREOF |
| US7521495B2 (en) | 2002-03-19 | 2009-04-21 | Intumex Gmbh | Intumescent electrical installation systems and processes for their production |
| CN1969007B (en) * | 2004-06-15 | 2010-05-12 | Lg电线有限公司 | Resin composition resistant to thermal deformation and cut-through and the insulation material and the cable using the same |
| CN100354989C (en) * | 2005-09-01 | 2007-12-12 | 赵成刚 | Environmental protection type fire retardant thermal shrinkage tube without halogen |
| CN100487820C (en) * | 2006-12-25 | 2009-05-13 | 金友友 | Low-smoke halogen-free combustion-preventing cable insulation and jacket material for nuclear power plant |
| CN101308714B (en) * | 2007-05-17 | 2010-11-10 | 上海长顺电梯电缆有限公司 | Preparing method of low-smoke non-halogen fire-retarding elevator cable |
| CN101613506B (en) * | 2009-07-25 | 2011-07-20 | 四川明星电缆股份有限公司 | High temperature resistance non halogen flame retardant cable sheath material and preparation method thereof |
| CN102219972B (en) * | 2010-04-19 | 2013-07-10 | 李梅 | Preparation method of durable ultrahigh temperature resisting acrylic rubber |
| CN102219972A (en) * | 2010-04-19 | 2011-10-19 | 李梅 | Preparation method of durable ultrahigh temperature resisting acrylic rubber |
| CN103183865A (en) * | 2011-12-29 | 2013-07-03 | 深圳市宏商材料科技股份有限公司 | Chemical crosslinking umbrella skirt and production technology |
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| CN102977605A (en) * | 2012-11-05 | 2013-03-20 | 安徽金桥电缆有限公司 | Silicon rubber cross-linked flame-retardant cable material and its preparation method |
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| CN106217917A (en) * | 2016-08-25 | 2016-12-14 | 苏州泰斯拓伟机电设备有限公司 | A kind of Making method of environment-friendlyflame flame retardant polyolefin hot pyrocondensation pipe |
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