CN1102611C - Halide-free smokeless flame-resistant thermoplatstic polyolefine composition and preparation thereof - Google Patents
Halide-free smokeless flame-resistant thermoplatstic polyolefine composition and preparation thereof Download PDFInfo
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- CN1102611C CN1102611C CN98113205A CN98113205A CN1102611C CN 1102611 C CN1102611 C CN 1102611C CN 98113205 A CN98113205 A CN 98113205A CN 98113205 A CN98113205 A CN 98113205A CN 1102611 C CN1102611 C CN 1102611C
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Abstract
The present invention provides a halogen-free smokeless fire-retardant thermoplatstic polyolefin composite used as a sheathing material for electric wires and cables, and a preparation method thereof. The composite is prepared from thermoplastic polyolefin, modified thermoplastic polyolefin, a fire retardant, a synergistic agent, a coupling agent, an auxiliary processing agent, a colorant, etc. by a process of double screw rod extrusion. The composite has the advantages of fine performances of fire retardance and smoke prevention, excellent performances of processing and shaping and fine performance of carbon formation, and nicely keeps the mechanical properties of a base material. The process of double screw rod extrusion, which is used for preparing the halogen-free smokeless fire-retardant thermoplatstic polyolefin composite, has the advantages of simple and continuous preparation procedures, high production efficiency and stable quality of products.
Description
The present invention relates to a kind of flame-proofed thermoplastic polyolefin complex that is used as the electric wire and cable jacket material and preparation method thereof, particularly halide-free smokeless flame-resistant thermoplatstic polyolefine composition and preparation method thereof.
The conventional electric wire and cable jacket material overwhelming majority is a pvc material, though at developed country's pvc material also in occupation of more than 70% of wire cable material.Pvc material the time produces a large amount of deleterious CO (carbon monoxide converter) gas and corrosive hydrogenchloride smog in burning, makes in fire failure the hazardness that causes because of these gases and smog be far longer than naked light.Can generate 2 liters during the burning of 1 kilogram of polyvinyl chloride has the concentrated hydrochloric acid of strong corrosion to human body and metal, makes zinc chloride pollution concentration that the zinc-base electric wire produces up to 900 μ g/cm
3, surpass arm's length standard (2 μ g/cm
3) 450 times, the smog of generation can fill the air 500m
3The space.In fire failure, the personnel death of the overwhelming majority is caused by these toxic gases and smog.Therefore, the electric wire and cable material of the low cigarette of development, few halogen even halogen-free flameproof becomes countries in the world, particularly the key subjects of developed country.
In the seventies later stage, the success of the cross-linked wire and cable material development of first-generation Halogen, its base polymer is terpolymer EP rubber, ethylene-propylene rubber(EPR), ethylene/vinyl acetate multipolymer.The inflammableness of this analog copolymer itself is lower than homopolymer polyethylene, polypropylene, the more important thing is that these multipolymers have good filler consistency.After filling a large amount of fire-retardant things of mineral, discharge carbonic acid gas and moisture during this base polymer burning.With this base polymer serves as that the electric wire that the basis produces is well suited for chemically-resistant and oil-proofness occasion, on ship and offshore platform.
The eighties mid-term, the thermoplastics of halogen-free flameproof is succeeded in developing.Such material is the mixture of new LDPE (film grade), linear low density polyethylene and ethylene/vinyl acetate multipolymer.This class material has characteristics such as low cigarette, Halogen, good flame retardation effect and thermoplasticity, but machine-shaping property is very poor.When the moulding of large-scale electric wire, this class material exists that torque is big, processing difficulties, production efficiency is low and defective such as scrap rate height.
Purpose of the present invention is exactly that a kind of new low cigarette, Halogen, fire-retardant, TPO mixture that machine-shaping property is good are provided for the shortcoming that overcomes current material.
According to the designed halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention, its feature is formed (weight %): TPO 35～45, modified thermoplastic polyolefin hydrocarbon 4～18, fire retardant 40～55, synergistic agent 1.5～10, coupling agent 0.4～1.5, process auxiliaries 1～4 and tinting material 0～1.6.
The preparation method of halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention is: with the every other component except that (part) fire retardant in the mixture after high-speed stirring is mixed, send in the screw rod by the feeder of delicate metering, after the thing fusing to be mixed, (residue) fire retardant successively segmentation by one and/or a plurality of side direction feeder is sent into screw rod and by the high speed homodisperse, through head extrude, tie rod, air-cooled, pelletizing and packing.
TPO can be the mixture of olefinic copolymer and/or these multipolymers in the halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention, and these multipolymers comprise terpolymer EP rubber (EPDM), ethylene-propylene rubber(EPR) (EPR) and ethylene/vinyl acetate multipolymer (EVA).These TPO have constituted the basis of whole material.
The modified thermoplastic polyolefin hydrocarbon can be new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE) and the modifier of polypropylene (PP) and/or the mixture of these modified compounds in the halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention.The existence of these modified thermoplastic polyolefin hydrocarbon has improved the mechanical property of the caused body material of a large amount of filling inorganic mineral fire retardants and the deterioration of machine-shaping property significantly, has guaranteed halide-free smokeless flame-resistant thermoplatstic polyolefine composition excellent comprehensive performances of the present invention.
Fire retardant must be not halogen-containing in the halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention, inorganic mineral based flame retardant preferably, and this comprises the mixture of aluminium hydroxide, magnesium hydroxide, zinc borate, magnesiumcarbonate and/or these materials.These fire retardants reduce thermal value and flame temperature, the dilution combustion air in beginning thermal endothermic decomposition dehydration more than 200 ℃; Decompose the charring layer of the metal oxide of generation, play adiabatic protective effect, help the formation of charcoal, suppress burning, reduce the amount of being fuming in material surface formation one deck firm compact.
Synergistic agent can be those more significant other fire retardants of fire retardation that can make fire retardant of the present invention in the halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention, the mixture that comprises phosphorus, phosphoric acid ester, silicon fire retardant and/or these compounds is as red phosphorus, diphenyl 2 ethylhexyl phosphate, tricresyl phosphate (dimethylbenzene) ester, trioctyl phosphate and SFR-100 etc.
Coupling agent can be the coupling agent of coupling TPO well and inorganic mineral fire retardant in the halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention, and this comprises the mixture of titanate coupling agent, silane coupling agent, aluminic acid compound and/or these compounds.Specifically can be A-189, A-172, Cavco Mod S, DL-411-D, QG-50, OL-T951, TC-1, TTDPP-385 and TTS etc.
Process auxiliaries is to help can effectively improve when material produce and moulding each component dispersiveness, the harmful chemical substance that rubs, reduces the interface adhesion, improves machine-shaping property of minimizing in the halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention, and this comprises the mixture of some fatty acid, fatty acid amide and/or these compounds.Specifically can be solid paraffin, whiteruss, low-molecular-weight polypropylene, stearic amide, methylene bis stearic amide and N, N '-ethylene bis stearic acid amide etc.
Tinting material can be various face (look) material that excellent compatibility is arranged with TPO in the halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention, and the most frequently used is carbon black.
Halide-free smokeless flame-resistant thermoplatstic polyolefine composition preparation method of the present invention adopts the twin screw expressing technique.Traditional electric wire and cable jacket material manufacturing technique is out smelting method and banburying method, and these method technologies are loaded down with trivial details, processing condition are wayward, constant product quality, production technique are interrupted, production efficiency is low.According to the characteristics of halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention, the present invention adopts efficiently, cleaning and processing condition can accurately be controlled and serialization is produced twin screw expressing technique method.This method be with the every other component except that (part) fire retardant in the halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention after high-speed stirring is mixed, send in the screw rod by the feeder of delicate metering, after the thing fusing to be mixed, (residue) fire retardant successively segmentation by one and/or a plurality of side direction feeder is sent into screw rod and by the high speed homodisperse, through head extrude, tie rod, air-cooled, pelletizing and packing.
Halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention is compared with traditional Halogen fire retardant material, the not containing halide element, the thermal endothermic decomposition reaction of dependence inorganic mineral fire retardant under high temperature (burning) environment generates harmless carbon dioxide and plays the moisture of cooling diluting effect and the metal oxide that energy covering material surface takes blocking effect.Owing on prescription, adopted aforesaid particular design, halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention not only has the characteristics on the performances such as low cigarette, Halogen, fire-retardant and thermoplasticity, and the moulding processability when adopting mixture of the present invention to make electric wire is good, and product surface is smooth.
Specific embodiments of the present invention is provided by embodiment.
Example formulations sees attached list 1, and its concrete operations step is basic identical, and promptly the first step mixes components such as TPO, modified thermoplastic polyolefin hydrocarbon, synergistic agent, coupling agent, process auxiliaries and tinting material in mixer; Second step was that said mixture is sent in the dual-screw-stem machine through the feeder of delicate metering, after the thing fusing to be mixed, according to the fire retardant consumption what successively segmentation by one and/or a plurality of side direction feeder is sent into screw rod and by the high speed homodisperse, through head extrude, tie rod, air-cooled, pelletizing, pack at last.
The length that is applied to the twin screw extruder among the preparation method of the present invention is through than being at least 36, more preferably greater than 40; Has a cover side direction feeding device at least; Have precise dose control and vacuum-pumping equipment.
Each section extruder temperature among the preparation method of the present invention should be controlled between 120～190 ℃, is preferably between 130～180 ℃.
Also can sneak into a part of fire retardant earlier in the above-mentioned the first step, concrete consumption is decided on the viscosity flow of used base-material and consumption what and the concrete state of arts of fire retardant.
The performance perameter of halide-free smokeless flame-resistant thermoplatstic polyolefine composition of the present invention sees attached list 2.
Subordinate list 1
Embodiment component one two three four five TPO ethylene-propylene copolymers 10 19 20 10 ternary ethylene-propylene copolymers 10 20.2 20 16.2 ethylene vinyl acetate copolymers 18 20 10 20 modified thermoplastic polyolefin hydrocarbon-modified low-density polyethylenes 3 4.7 5 modifying linear low-density polyethylenes 5 10 7.5 5 modified polypropenes 7 fire retardant aluminium hydroxides 40 25 25 30 magnesium hydroxides 45 24.2 Firebrake ZBs 8 14.2 magnesium carbonate 10 synergist red phosphorus 5 diphenyl 2 ethylhexyl phosphates 0.8 1.6 1 tricresyl phosphates 132 SFR-100 5 coupling agent A-189 0.6 0.2 0.4 0.5 A-172 0.3 TC-1 0.4 DL-411-D 0.2 process auxiliaries solid paraffin 1 1.5 1.5 stearic amides 31 stearic acid 1.5 0.5 1 methylene bis stearic amides 1 colouring agent carbon black 0.8 0.8 0.8 0.8 0.8
Subordinate list 2 Interventions Requested unit testing method performance indications hot strength MPa GB1040 〉=10.0 elongation at break % GB1040 〉=100 ℃ * 168h of 150.0 heat aging performances GB9344 tensile strength rate of change %≤± 25 elongation at break rate of change %≤± 25 high temperature pressures (80 ℃) %＜40 impact brittle temperature (25 ℃) GB1843 by resisting environmental stress and cracking (96h) pH value 〉=4.3 electrical conductivity μ S/mm≤23 ℃/h of 10 water absorption rates %≤0.5 proportion g/cm, 1.4 poison exponent %≤5.0 oxygen index (OI) % 〉=33 humidity index % 〉=280 smoke densitys (the smokelessly)＜150HCI content mg/g 0 that do not ftracture
Claims (1)
1, a kind of halide-free smokeless flame-resistant thermoplatstic polyolefine composition that is prepared from by TPO, modified thermoplastic polyolefin hydrocarbon, fire retardant, synergistic agent, coupling agent, process auxiliaries and colorant set lease making twin screw expressing technique, the composition of this mixture (weight %) is: TPO is terpolymer EP rubber, ethylene-propylene rubber(EPR) and ethylene/vinyl acetate multipolymer three's a mixture 35～45; The modified thermoplastic polyolefin hydrocarbon is the mixture 4～18 of new LDPE (film grade), linear low density polyethylene and MODIFICATION OF POLYPROPYLENE thing and/or these modified compounds; Fire retardant is the mixture 40～55 of aluminium hydroxide, magnesium hydroxide, zinc borate, magnesiumcarbonate and/or these compounds; Synergistic agent is phosphoric acid ester and/or silicon fire retardant 1.5～10; Coupling agent is an aluminic acid compound 0.4～1.5; Process auxiliaries is a low-molecular-weight polypropylene 1～4; Tinting material 0～1.6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113205A CN1102611C (en) | 1998-05-12 | 1998-05-12 | Halide-free smokeless flame-resistant thermoplatstic polyolefine composition and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113205A CN1102611C (en) | 1998-05-12 | 1998-05-12 | Halide-free smokeless flame-resistant thermoplatstic polyolefine composition and preparation thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1235175A CN1235175A (en) | 1999-11-17 |
| CN1102611C true CN1102611C (en) | 2003-03-05 |
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| CN98113205A Expired - Fee Related CN1102611C (en) | 1998-05-12 | 1998-05-12 | Halide-free smokeless flame-resistant thermoplatstic polyolefine composition and preparation thereof |
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| CN1709953B (en) * | 2005-07-01 | 2011-05-04 | 马顺发 | Silicon-series five-retardant and producing method thereof |
| CN100447192C (en) * | 2005-08-05 | 2008-12-31 | 东莞银禧塑胶有限公司 | High flame retardance low smoke no-halogen cable sheath material and its production process |
| US8618215B2 (en) | 2006-02-03 | 2013-12-31 | Sunallomer Ltd. | Modified polypropylene-based polymer and composition comprising it |
| CN100465220C (en) * | 2007-02-08 | 2009-03-04 | 北京化工大学 | Halogen-free flame-proof cable sheath material |
| CN101157789B (en) * | 2007-09-30 | 2010-09-08 | 上海金发科技发展有限公司 | Non-bittern flame-proof elastomer composite material and method for making same |
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| CN106519403A (en) * | 2012-12-04 | 2017-03-22 | 苏州亨利通信材料有限公司 | Low-smoke halogen-free flame-retardant polyolefin cable material |
| CN103214824B (en) * | 2013-03-26 | 2015-10-21 | 安徽瑞之星电缆集团有限公司 | A kind of Isotactic polypropylene insulation radiation-crosslinkecable cable material and preparation method thereof |
| CN105504482B (en) * | 2013-09-29 | 2020-08-04 | 江苏理工学院 | Halogen-free flame-retardant linear low-density polyethylene material |
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| CN103540064B (en) * | 2013-10-29 | 2015-12-30 | 绿宝电缆（集团）有限公司 | The flame-retardant modified polyvinyl chloride cable sheathing compound of a kind of oil resistant |
| CN103739931A (en) * | 2014-01-20 | 2014-04-23 | 苏州新区华士达工程塑胶有限公司 | Modified EVA resin plastic |
| CN104292579B (en) * | 2014-09-24 | 2016-09-07 | 苏州博利迈新材料科技有限公司 | A kind of halogen-free flameproof LDPE/PC composite and preparation method thereof |
| CN104629199A (en) * | 2015-01-27 | 2015-05-20 | 安徽德源电缆集团有限公司 | High-performance modified cable sheath material |
| CN105061854A (en) * | 2015-08-03 | 2015-11-18 | 上海科悦高分子材料有限公司 | Halogen-free flame retardation polyolefin material and use thereof |
| CN106065124A (en) * | 2016-06-12 | 2016-11-02 | 芜湖航飞科技股份有限公司 | A kind of low-smoke halogen-free inflaming-retarding cable sheath material peculiar to vessel and preparation method thereof |
| CN106046683B (en) * | 2016-07-07 | 2018-05-15 | 西华大学 | Low-smoke and flame retardant polymer composite and preparation method thereof |
| CN107602923A (en) * | 2017-09-08 | 2018-01-19 | 宣城市聚源精细化工有限公司 | A kind of fire retardant with extremely strong suppression cigarette effect |
| CN108623905A (en) * | 2018-04-04 | 2018-10-09 | 长兴天晟能源科技有限公司 | A kind of preparation method of ABS modified materials |
| BR112020021937B1 (en) * | 2018-04-27 | 2023-11-14 | Dow Global Technologies Llc | COMPOSITION, CROSS-CUT COMPOSITION, ARTICLE, PROCESS FOR MEASURING THE PHOSPHORUS CONTENT OF A COMPOSITION AND PROCESS FOR MEASURING THE PHOSPHORUS CONTENT OF A CROSS-CROSS COMPOSITION |
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| CN1059533A (en) * | 1991-10-30 | 1992-03-18 | 北京化工学院 | Thermoplastic ethylene-propylene rubber/polyolefine elastomer and preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1059533A (en) * | 1991-10-30 | 1992-03-18 | 北京化工学院 | Thermoplastic ethylene-propylene rubber/polyolefine elastomer and preparation method |
| CN1074454A (en) * | 1991-12-10 | 1993-07-21 | 日本石油化学株式会社 | Abrasion-resistant flame-retardant composition |
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| CN1235175A (en) | 1999-11-17 |
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