CN100425645C - Low-smoke fireproofing cable material without halide and its preparation method - Google Patents
Low-smoke fireproofing cable material without halide and its preparation method Download PDFInfo
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- CN100425645C CN100425645C CNB2006100488237A CN200610048823A CN100425645C CN 100425645 C CN100425645 C CN 100425645C CN B2006100488237 A CNB2006100488237 A CN B2006100488237A CN 200610048823 A CN200610048823 A CN 200610048823A CN 100425645 C CN100425645 C CN 100425645C
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Abstract
The invention discloses a low-smoke flame-proof non-halogen cable material and preparing method, which comprises the following steps: blending polyphosphoric ammonia and zinc boride evenly; spraying and cladding the composite material through coupler; adding middle-density polyethylene, copolymer, functional nylon, compatible agent, anti-oxidant and lubricant to stir evenly; transmitting composite material into concurrent twin-screw extruder to fuse; graining after winding to obtain the product.
Description
Technical field
The invention belongs to cable protective material technology field, be specifically related to a kind of low cigarette, Halogen, fire-retardant CABLE MATERIALS.Simultaneously, the invention still further relates to a kind of preparation method of described CABLE MATERIALS.
Background technology
Electric wire is widely used in the transmission of energy and information, traditional covering material of cable is made by inflammable high molecular synthetic material, not only aging easily, work-ing life is shorter, and is and very easily excessive or outside temperature is too high burns because of line load in its use, thereby initiation fire.Simultaneously, its burning can produce a large amount of smog and poison gas, can cause the inhaler to have difficulty in breathing, faint even causes death the serious harm people's the security of the lives and property.Continuous enhancing along with people's safety, environmental consciousness, low cigarette, Halogen, fire-retardant electric wire are subjected to human consumer's favor just gradually, and this series products is with a wide range of applications at aspects such as Nuclear power plants, shipbuilding, mine, Highrise buildings, subterranean tunnel and subway works.But existing CABLE MATERIALS product uses mostly with AL (OH)
3, Mg (OH)
2Be main inorganic filled-type fire retardant, need to add a large amount of inorganic components in the prescription,, make that the processing of material and mechanical property are still undesirable because the consistency of high molecular synthetic material and inorganic component is bad.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of novel cable material is provided, on the basis of realizing low cigarette, Halogen, fire-retardant requirement, the mechanical property of strengthening material overcomes the technical barrier of inorganic materials and organic materials consistency difference.
The present invention also aims to provide a kind of method for preparing above-mentioned CABLE MATERIALS.
Purpose of the present invention is achieved by following technical scheme.
CABLE MATERIALS of the present invention is made by the raw material of following weight parts:
Medium-density polyethylene (MDPE) 70~90
Copolymer 1 0~30
Ammonium polyphosphate (APP) 30~45
Functionalized nylon 10~15
Trimeric cyanamide (MEL) 1.0~1.5
Zinc borate (ZB) 5~10
Compatilizer 5~10
Coupling agent 0.4~0.60
Antioxidant 1010 0.3
Lubricant 0.2~0.4
Wherein, described multipolymer is ethylene-vinyl acetate copolymer (EVA), and this moment, compatilizer was an ethylene-vinyl acetate copolymer grafted maleic anhydride multipolymer;
Described multipolymer can also be ethylene-octene elastomer copolymer (POE), and this moment, compatilizer was an ethylene-octene elastomer copolymer grafted maleic anhydride multipolymer;
The polymerization degree of described ammonium polyphosphate (APP) is preferably more than and equals 500;
Described functionalized nylon is selected from a kind of in molten nylon of trivalent alcohol or the ternary copolycondensation nylon;
Described coupling agent is selected from a kind of among titanate coupling agent qq127, the silane coupling agent KH550;
Described lubricant is selected from a kind of in Magnesium Stearate, the calcium stearate;
Described ammonium polyphosphate (APP) requires to answer≤25um with the particle diameter of zinc borate (ZB).
The method for preparing CABLE MATERIALS of the present invention is made up of following steps:
1. take by weighing each raw material for standby by above-mentioned weight part;
2. ammonium polyphosphate (APP), trimeric cyanamide (MEL) and zinc borate (ZB) are placed high-speed mixer, mix, with coupling agent to mixed powder spray coat to handle after, add all the other components again, be stirred to evenly;
3. step (2) gained mixture is sent into carry out in the parallel dual-screw extruding machine mixing, the processing temperature of each section of twin screw extruder is set at respectively: 140~155 ℃ of first section 110~115 ℃, second section 115~120 ℃, the 3rd section 120~125 ℃, the 4th section 125~130 ℃, the 5th section 130~135 ℃, the 6th section 130~135 ℃, the 7th section 135~140 ℃, die head temperature, and after air-cooled granulation promptly obtains required fireproofing cable material without halide.
The present invention has the following advantages compared with the prior art:
1, the expansion type flame-retarding system of being made up of ammonium polyphosphate (APP), functionalized nylon and trimeric cyanamide (MEL) has advantages such as addition is few, flame retarding efficiency is high, no molten drop.Overcome existing expansion type phosphor nitrogen combustion inhibitor easily in substrate surface " frost " phenomenon, the fireproofing cable material without halide of preparation gained has excellent water tolerance energy and electrical insulation capability.
2, the use of compatilizer has improved inorganic and shortcoming organic materials consistency difference, makes the uniform dispersing and mixing of various components, and the CABLE MATERIALS of preparation gained has the good mechanical performance, tensile strength 〉=12MPa, elongation at break 〉=400%.
3, the use of zinc borate has significantly improved and has pressed down cigarette and fire-retardant effect.
4, not halogen-containing and other environmentally hazardous material during raw material is formed, clean environment firendly.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but they are not limitation of the invention.
Embodiment 1
Take by weighing 70 parts of medium-density polyethylenes (MDPE), 30 parts of ethylene-octene elastomer copolymers (POE), 45 parts of the ammonium polyphosphates of the polymerization degree 500, particle diameter 25um (APP), 15 parts of the molten nylon of trivalent alcohol, 1.5 parts of trimeric cyanamides (MEL), 5 parts of the zinc borates of particle diameter 25um (ZB), 0 part of ethylene-octene elastomer copolymer grafted maleic anhydride copolymer 1,0.6 part of titanate coupling agent (qq127), (1010) 0.3 parts in oxidation inhibitor and 0.2 part of Magnesium Stearate are standby.With ammonium polyphosphate (APP), trimeric cyanamide (MEL) and zinc borate (ZB) place high-speed mixer, mix, with qq127 mixed powder was sprayed the coating processing after 5 minutes, add medium-density polyethylene (MDPE), ethylene-octene elastomer copolymer (POE), the molten nylon of trivalent alcohol, ethylene-octene elastomer copolymer grafted maleic anhydride multipolymer, antioxidant 1010 and Magnesium Stearate again, be stirred to evenly; With the gained mixture send into carry out in the parallel dual-screw extruding machine mixing, the processing temperature of each section of twin screw extruder is set at respectively: 140~155 ℃ of first section 110~115 ℃, second section 115~120 ℃, the 3rd section 120~125 ℃, the 4th section 125~130 ℃, the 5th section 130~135 ℃, the 6th section 130~135 ℃, the 7th section 135~140 ℃, die head temperature, and after air-cooled granulation promptly obtains required CABLE MATERIALS.After testing, every index is as shown in table 1.
Embodiment 2
Repeat embodiment 1, following difference is arranged: the weight part of each raw material consists of 80 parts of medium-density polyethylenes (MDPE), 20 parts of ethylene-octene elastomer copolymers (POE), 40 parts of the ammonium polyphosphates (APP) of the polymerization degree 600, particle diameter 20um; 0.4 part of (1010) 0.3 parts of 5 parts of the zinc borates (ZB) of 15 parts of the molten nylon of trivalent alcohol, 1.5 parts of trimeric cyanamides (MEL), particle diameter 20um, 0 part of ethylene-octene elastomer copolymer grafted maleic anhydride copolymer 1,0.4 part of titanate coupling agent (qq127), oxidation inhibitor and Magnesium Stearate.After testing, every index is as shown in table 1.
Embodiment 3
Repeat embodiment 1, following difference is arranged: the weight part of each raw material consists of 90 parts of medium-density polyethylenes (MDPE), 10 parts of ethylene-vinyl acetate copolymers (EVA), 30 parts of the ammonium polyphosphates (APP) of the polymerization degree 700, particle diameter 15um; 0.2 part of 10 parts of the zinc borates (ZB) of 10 parts of the molten nylon of trivalent alcohol, 1 part of trimeric cyanamide (MEL), particle diameter 15um, 5 parts of ethylene-vinyl acetate copolymer grafted maleic anhydride multipolymers, 0.4 part of titanate coupling agent (qq127) and (1010) 0.3 parts in oxidation inhibitor and calcium stearate.After testing, every index is as shown in table 1.
Embodiment 4
Repeat embodiment 1, following difference is arranged: the weight part of each raw material consists of 70 parts of medium-density polyethylenes (MDPE), 30 parts of ethylene-vinyl acetate copolymers (EVA), 45 parts of the ammonium polyphosphates (APP) of the polymerization degree 800, particle diameter 10um; 0.4 part of (1010) 0.3 parts of 5 parts of the zinc borates (ZB) of 12.5 parts of ternary copolycondensation nylon, 1.5 parts of trimeric cyanamides (MEL), particle diameter 10um, 0 part of ethylene-vinyl acetate copolymer grafted maleic anhydride copolymer 1,0.6 part of titanate coupling agent (qq127), oxidation inhibitor and calcium stearate.After testing, every index is as shown in table 1.
Embodiment 5
Repeat embodiment 1, following difference is arranged: replace titanate coupling agent qq127 with silane coupling agent KH550.After testing, every index is as shown in table 1.
Embodiment 6
Repeat embodiment 1, following difference is arranged: it is 40 parts of 1000 ammonium polyphosphates (APP) that the weight part of each raw material consists of 80 parts of medium-density polyethylenes (MDPE), 20 parts of ethylene-vinyl acetate copolymers (EVA), the polymerization degree; 0.4 part of (1010) 0.3 parts of 10 parts of ternary copolycondensation nylon, 1.5 parts of trimeric cyanamides (MEL), 10 parts of zinc borates (ZB), 7.5 parts of ethylene-vinyl acetate copolymer grafted maleic anhydride multipolymers, 0.6 part of titanate coupling agent (qq127), oxidation inhibitor and Magnesium Stearate.After testing, every index is as shown in table 1.
Table one
Performance | Unit | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
Breaking tenacity | Mpa | 13.2 | 12.8 | 14.1 | 13.1 | 12.6 | 12.4 |
Elongation at break | % | 440 | 430 | 460 | 420 | 420 | 410 |
Limiting oxygen index(LOI) | % | 30 | 32 | 34 | 33 | 30 | 33 |
Vertical combustion | FV-0 | FV-0 | FV-0 | FV-0 | FV-0 | FV-0 | |
Smoke density (nonflame) | 95 | 88 | 76 | 90 | 87 | 82 | |
Volume specific resistance | Ω.cm | 8.66 ×10 15 | 7.53× 10 15 | 1.85× 10 16 | 4.67× 10 16 | 5.37× 10 16 | 2.26× 10 16 |
Dielectric strength | Kv/mm | 32.2 | 30.4 | 35.2 | 33.9 | 32.8 | 34.1 |
Claims (8)
1, a kind of fireproofing cable material without halide, make by the raw material that the one-tenth with following weight parts is grouped into:
Medium-density polyethylene 70~90
Ethylene-vinyl acetate copolymer 10~30
Ammonium polyphosphate 30~45
Functionalized nylon 10~15
Trimeric cyanamide 1.0~1.5
Zinc borate 5~10
Ethylene-vinyl acetate copolymer grafted maleic anhydride multipolymer 5~10
Coupling agent 0.4~0.60
Antioxidant 1010 0.3
Lubricant 0.2~0.4
Wherein said functionalized nylon is selected from a kind of in molten nylon of trivalent alcohol or the ternary copolycondensation nylon; Described coupling agent is selected from a kind of among titanate coupling agent qq127, the silane coupling agent KH550.
2, a kind of fireproofing cable material without halide, make by the raw material that the one-tenth with following weight parts is grouped into:
Medium-density polyethylene 70~90
Ethylene-octene elastomer copolymer 10~30
Ammonium polyphosphate 30~45
Functionalized nylon 10~15
Trimeric cyanamide 1.0~1.5
Zinc borate 5~10
Ethylene-octene elastomer copolymer grafted maleic anhydride multipolymer 5~10
Coupling agent 0.4~0.60
Antioxidant 1010 0.3
Lubricant 0.2~0.4
Wherein said functionalized nylon is selected from a kind of in molten nylon of trivalent alcohol or the ternary copolycondensation nylon; Described coupling agent is selected from a kind of among titanate coupling agent qq127, the silane coupling agent KH550.
3, a kind of fireproofing cable material without halide according to claim 1 and 2 is characterized in that: the polymerization degree of described ammonium polyphosphate is more than or equal to 500.
4, a kind of fireproofing cable material without halide according to claim 1 and 2 is characterized in that: described lubricant is selected from a kind of in Magnesium Stearate, the calcium stearate.
5, a kind of fireproofing cable material without halide according to claim 1 and 2 is characterized in that: the particle diameter of described ammonium polyphosphate is smaller or equal to 25 μ m.
6, a kind of fireproofing cable material without halide according to claim 1 and 2 is characterized in that: the particle diameter of described zinc borate is smaller or equal to 25 μ m.
7, the preparation method of claim 1 or 2 described CABLE MATERIALS, this method is made up of following steps:
1. take by weighing each raw material for standby by described weight part;
2. ammonium polyphosphate, trimeric cyanamide and zinc borate are placed high-speed mixer, mix, with coupling agent to mixed powder spray coat to handle after, add all the other components again, be stirred to evenly;
3. with step 2. the gained mixture send into carry out in the parallel dual-screw extruding machine mixing, the processing temperature of each section of twin screw extruder is set at respectively: 140~155 ℃ of first section 110~115 ℃, second section 115~120 ℃, the 3rd section 120~125 ℃, the 4th section 125~130 ℃, the 5th section 130~135 ℃, the 6th section 130~135 ℃, the 7th section 135~140 ℃, die head temperature, and after air-cooled granulation promptly obtains required covering material of cable.
8, CABLE MATERIALS preparation method according to claim 7 is characterized in that: the polymerization degree of described ammonium polyphosphate is more than or equal to 500.
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CN100425645C true CN100425645C (en) | 2008-10-15 |
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KR101840574B1 (en) * | 2008-02-08 | 2018-03-20 | 유니온 카바이드 케미칼즈 앤드 플라스틱스 테크날러지 엘엘씨 | Flame-retardant polyolefin/thermoplastic polyurethane composition |
CN102492201A (en) * | 2011-12-02 | 2012-06-13 | 江苏七宝光电集团有限公司 | Low-smoke zero-halogen flame-retarding optical cable sheath material |
CN102719088A (en) * | 2012-06-15 | 2012-10-10 | 苏州宇度医疗器械有限责任公司 | Preparation method of bisphenol A type organic phosphate modified nylon alloy material |
CN104045856A (en) * | 2014-06-06 | 2014-09-17 | 浙江农林大学 | Catalytic-expansion-type alcohol-soluble nylon modified flame retardant and preparation method thereof |
CN104356476A (en) * | 2014-10-30 | 2015-02-18 | 安徽电信器材贸易工业有限责任公司 | Low-smoke halogen-free flame-retardant polyethylene cable material and preparation method thereof |
KR102499963B1 (en) * | 2015-02-20 | 2023-02-16 | 다우 글로벌 테크놀로지스 엘엘씨 | Cable jacket with designed microstructure and manufacturing method of cable jacket with designed microstructure |
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CN111710469B (en) * | 2020-06-28 | 2021-12-07 | 四川天邑康和通信股份有限公司 | Low-smoke halogen-free wear-resistant indoor photoelectric hybrid cable and manufacturing method thereof |
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CN1335334A (en) * | 2000-07-22 | 2002-02-13 | 中国科学技术大学 | Prepn of fireproofing cable material without halide |
CN1506398A (en) * | 2002-12-12 | 2004-06-23 | 中国科学技术大学 | Prepn of halogen-free fireproof polypropylene cable material |
WO2006003421A1 (en) * | 2004-07-02 | 2006-01-12 | University Of Strathclyde | Fire retarded flexible nanocomposite polyurethane foams |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH06128430A (en) * | 1992-10-19 | 1994-05-10 | Toshiba Corp | Flame-retardant polypropylene resin composition |
CN1335334A (en) * | 2000-07-22 | 2002-02-13 | 中国科学技术大学 | Prepn of fireproofing cable material without halide |
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WO2006003421A1 (en) * | 2004-07-02 | 2006-01-12 | University Of Strathclyde | Fire retarded flexible nanocomposite polyurethane foams |
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