CN1091296C - 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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- CN1091296C CN1091296C CN 99125747 CN99125747A CN1091296C CN 1091296 C CN1091296 C CN 1091296C CN 99125747 CN99125747 CN 99125747 CN 99125747 A CN99125747 A CN 99125747A CN 1091296 C CN1091296 C CN 1091296C
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Abstract
The present invention relates to an accessory of a radiation crosslinking power cable with low smoke, no halogen, flame retardance and thermal shrinkage, which adopts radiation crosslinking insulation (parachute skirt) materials with low smoke, no halogen, flame retardance and thermal shrinkage, stress tube materials with thermal shrinkage and no halogen, branch joint (sheath) materials with low smoke, no halogen, flame retardance and thermal shrinkage, filling glue and sealing glue, wherein the filling glue and the sealing glue are matched with the branch joint (sheath) materials with low smoke, no halogen, flame retardance and thermal shrinkage. The present invention has the advantage of easy raw material obtainment and simple and convenient preparation method. Therefore, the present invention is suitable for cable terminals of a 35KV voltage level and less than a 35KV voltage level, and the insulation protection of intermediate connection.
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 (hereinafter referred to as the heat shrinkage insulation pipe), stress tube, branch joint (sheath) thermal contraction parts such as (being designated hereinafter simply as branch joint).Heat shrinkage insulation tube material that existing market is just being used and stress tube material adopt the Halogen fire proofing, and the branch joint material adopts 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 tube material of its use, stress tube material and branch joint material all adopt 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 tube material, the branch joint material that thermal contraction Halogen stress tube material and the fire-retardant heat shrinkage insulation tube material of low-smoke non-halogen flame-retardant thermal contraction branch joint 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 the heat shrinkage insulation pipe, stress tube, branch joint and matching used filling glue and fluid sealant, described heat shrinkage insulation pipe, stress tube and branch joint are made up of following each ratio of weight and number material respectively: the heat shrinkage insulation tube 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, multi-functional acrylate's crosslinking agent 1-3.
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 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, the multi-functional 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 the thermal contraction branch joint 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 portion rate.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 portion rate.
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 portion rate 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 two (tridecyl) 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.
Described multi-functional acrylate's crosslinking coagent 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 will be that following portions by weight is mixed respectively than component:
(1) LDPE10-30, EVA50-70, EPDM10-30, PDMVS2-10, amines antioxidants 0.5-1.5, lubricant 2-4, MRP5-10, MCA10-20, superfine active Halogenless composite fire retardant 40-80, light stabilizer 0-1, color masterbatch 0-8, multi-functional acrylate's crosslinking coagent 1-3;
(2) LDPE30-50, EPDM50-70, amines antioxidants 1-3, barium titanate 30-70, carbon black 15-40, divalence or trivalent metal stearate lubricant 1-3;
(3) LDPE30-50, EVA50-70, ester kind antioxidant 0.1-1.0, MRP5-15, MCA10-20, superfine active Halogenless composite fire retardant 50-100, lubricant 1-3, color masterbatch 0-5, multi-functional acrylate's crosslinking coagent 1-3.
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 to extrude wire drawing, air-cooled, pelletizing 100～180 ℃ of interval mixing.
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, form 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, thermal contraction Halogen stress tube and low-smoke non-halogen flame-retardant thermal contraction branch joint 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 tube material, crosslinking with radiation Halogen thermal shrinkage stress tube material and radiation-crosslinked low smoke no halide flame retaining thermal contraction branch joint 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 LDPE10-30kg of MI≤0.5g/10min, MI is 2-5g/min, the EVA50-70kg of vinyl acetate content 14-18%, EPDM10-30kg, PDMVS2-10kg, amines antioxidants 4030 or 4010 0.5-1.5kg, the stearate of divalence or trivalent metal (as zinc stearate etc.) lubricant 2-4kg, MRP5-10kg, 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 PETA1-3kg, 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 (ratio of weight and number) 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 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 MRP5-15kg, 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, multi-functional acrylate's crosslinking coagent (commodity TMPTA by name or TMPTMA) 1-3kg.
The heat-shrinkage material of enforcement 1 and embodiment 2 is tested, the result meet national sector standard DL413-91's " 35KV and following power cable thermal contraction type accessory application technical conditions ", material smoke density performance≤150 (ASTME662), hydrogen halide content≤5mg/g (IEC754-1) 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 pipe, stress tube, branch joint and matching used filling glue, fluid sealant, it is characterized in that described heat shrinkage insulation tube material, thermal shrinkage stress tube material and thermal contraction branch joint material be made up of the component of following each ratio of weight and number respectively:
Heat shrinkage insulation 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 MRP5-10, melamine complex compound 10-20, superfine active Halogenless composite fire retardant 40-80, Benzophenone class light stabilizer 0-1, color masterbatch 0-8, multi-functional acrylate's crosslinking agent 1-3;
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 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, multi-functional acrylate's crosslinking agent 1-3.
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 the described thermal contraction branched pipe 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 MI2-5g/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, the relative weight portion rate 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 portion rate is respectively 2-3: 1-2.
7, thermal shrinking electric cable fitting as claimed in claim 1, it 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); Described multi-functional acrylate's crosslinking coagent 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 tube material, thermal shrinkage stress tube material and thermal contraction branch joint 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, the preparation method of thermal shrinking electric cable fitting 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, the preparation method of thermal shrinking electric cable fitting as claimed in claim 7 is characterized in that described extruding, and is to extrude 100-180 ℃ of interval the mixing with double screw extruder.
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| Application Number | Priority Date | Filing Date | Title |
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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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| Application Number | Priority Date | Filing Date | Title |
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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 CN1261716A (en) | 2000-08-02 |
| CN1091296C true CN1091296C (en) | 2002-09-18 |
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Cited By (1)
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| CN101404396B (en) * | 2008-04-24 | 2010-07-28 | 上海长园电子材料有限公司 | Double-layer thermal contraction casing tube |
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1999
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101404396B (en) * | 2008-04-24 | 2010-07-28 | 上海长园电子材料有限公司 | Double-layer thermal contraction casing tube |
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