CN100354383C - Process for producing self-extinguishing cables with low-level production of fumes, and flame-retardant compositions used therein - Google Patents
Process for producing self-extinguishing cables with low-level production of fumes, and flame-retardant compositions used therein Download PDFInfo
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- CN100354383C CN100354383C CNB2004100641100A CN200410064110A CN100354383C CN 100354383 C CN100354383 C CN 100354383C CN B2004100641100 A CNB2004100641100 A CN B2004100641100A CN 200410064110 A CN200410064110 A CN 200410064110A CN 100354383 C CN100354383 C CN 100354383C
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Abstract
Process for producing cables, in particular electrical cables for low-voltage power transmission or for telecommunications, which have self-extinguishing properties and produce a low level of fumes, in which the flame-retardant coating layer is obtained by extruding a flame-retardant composition comprising a polymer base, an inorganic flame-retardant filler and a dehydrating agent. The presence of the dehydrating agent makes it possible to obtain a smooth and uniform flame-retardant layer which is virtually free of pores.
Description
The present invention relates to a kind of cable, particularly low voltage power transmission or communication are with the manufacturing process of cable, and this class cable tool self-extinguishing and the amount of being fuming are low, and relate to wherein used fire-retardant combination.
The manufacture method of self extinguishing cable generally is, extrudes the flame retardant coating that one deck is made of polymer composition on cable core, and said composition is owing to added suitable additive thereby possessed flame retardant resistance.Such as being polyolefin compositions,, can contain halogen organic compound collocation ANTIMONY TRIOXIDE SB 203 99.8 PCT in this purpose available as flame-retardant additive such as based on polyethylene or ethylene/vinyl acetate copolymer.But, decompose because part can take place in polymer processing the halogenated flame-retarding additive, produce poisonous and the metal parts of polymer processing equipment had the halogen cigarette of corrosive nature to the workman, so a lot of shortcomings are arranged.In addition, if be placed directly in the flame, can burn produces a large amount of dense smoke that contains poison gas.During as matrix polymer, also run into same problem with the polyvinyl chloride (PVC) that is added with ANTIMONY TRIOXIDE SB 203 99.8 PCT.
Therefore, not halogen-containing compound, wherein polymeric matrix when making self extinguishing cable, have been begun to adopt in recent years, majority is a polyolefins, and with inorganic fire-retarded filler, majority is a metal, the particularly oxyhydroxide of aluminium or magnesium, hydrous oxide or salt hydrate, such as magnesium hydroxide or hibbsite or its mixture (such as referring to U.S.No.4,145,404, U.S.No.4,673,620, EP328,620 and EP 530,940) mix.
Mineral filler can directly be adopted or be coated with various types of hydrophobic substances, such as saturated or unsaturated fatty acids or its salt, especially oleic acid or stearic acid or corresponding oleate or stearate, or uses after organosilane or the titanic acid ester.
Such as, patent application WO 96/27885 has described a kind of fire-retardant combination that cable is used that is coated with, it comprises polypropylene as polymeric matrix, the polyethylene wax and the 100-200wt.% that add 1-20wt.% scribble the magnesium hydroxide (wt.% with respect to polyacrylic quality) of hydrophobic substance such as alkyl silane.It is said that this coating can improve the consistency between filler and the polymeric matrix and give flame retardant coating simultaneously with hydrophobicity, thereby avoided because of absorbing the insulation effect that moisture content reduces material.
Japanese patent application JP-07-161,230 (kokai) have described flame-retardant polymer composition, contain the brucite of the suitable grinding of surface through handling with respect to the lipid acid of quality 0.5～5wt.% consumption of oxyhydroxide or its salt or silane or titanic acid ester.Described according to this patent application, therefore surface-treated filler allegedly can reduce water-retaining capacity, can play to prevent from material to be applied certain expansion effect and destroy the effect of its appearance of cable that obtains at the water vapor that disengages in the filler in the process that composition is extruded on cable.
The applicant finds, when adopting described mineral filler to make self extinguishing cable, be coated with cloth filler with hydrophobizing agent and also be not enough to provide the gratifying result that can reappear by industrially scalable according to prior art is described, particularly in flowability and then processing characteristics in order to improve composition, in the hope of high rate of extrusion and therefore high productivity, and when at high temperature carrying out the expressing technique of fire-retardant combination.Particularly the applicant also often finds, no matter be coating or uncoated fire-retardant filler, and also (that is, the making but not synthetic by mineral) of especially natural product, can form the not too gratifying coating of outward appearance, the surface is unglazed and coarse.In addition, also be found in the inner hole that forms of flame-retardant layer in some cases, and then reduce the mechanical property of coating.
The applicant finds at present, if add dewatering agent in the composition that comprises polymeric matrix and inorganic fire-retarded filler, just might produce the self extinguishing cable that flame retardant coating is substantially free of hole and smooth outer surface homogeneous.Dewatering agent can mix (mix) step or directly add in fire-retardant combination in the upstream of forcing machine.
Therefore, first aspect present invention relates to the technology of the low self extinguishing cable of a kind of manufacturing amount of being fuming, and it comprises
(a) preparation comprises the fire-retardant combination of polymeric matrix and inorganic fire-retarded filler;
(b) on the optional lead that is coated with in advance with insulation layer, extrude described fire-retardant combination, obtain flame retardant coating;
It is characterized in that in described fire-retardant combination, adding dewatering agent.
According to the first embodiment of the present invention, in the preparation process (a) of fire-retardant combination, add dewatering agent.
In a preferred embodiment, composition mixes first step end with the water content in the reduction fire-retardant filler of one default period under preset temp after, in the preparation process (a) of fire-retardant combination, add dewatering agent.
Further embodiment according to the present invention is added dewatering agent in the extrusion step (b) of fire-retardant combination.
The invention further relates to a kind of fire-retardant combination that comprises polymeric matrix and inorganic fire-retarded filler, it is characterized in that it also comprises dewatering agent.
According to applicant's viewpoint, dewatering agent is brought into play its effect by institute's water content in the absorption fire-retardant filler, and these moisture content discharge in heat-processed when composition is extruded.Absorption mechanism is preferably irreversible, and perhaps dewatering agent can reversibly absorb moisture content but to discharge the speed of moisture content under extrusion temperature very low, thereby guarantees not exist fully in extrusion the moisture content of steam form.Can avoid whereby forming hole and/or occurring coarse phenomenon from the teeth outwards in flame retardant coating inside.The amount of release moisture content increases with the rising of extrusion temperature, consequently, when used extrusion temperature is higher relatively, generally is higher than 180 ℃, when preferably being higher than 200 ℃, more demonstrates the advantage that dewatering agent exists.
In addition the applicant finds, is adopting natural product fire-retardant filler, and during the magnesium hydroxide that obtains through grinding such as the brucite mineral, dewatering agent is obvious especially to the influence of the appearance of flame retardant coating and mechanical property thereof.Its reason is considered to natural product fire-retardant filler and contains a large amount of moisture content, surpasses the typical content in the synthesis type fire-retardant filler.Contained moisture content may be from initial mineral or to the grinding technics that these mineral carried out, or absorb from external environment.
Useful dewatering agent is the easy-to-use mineral compound that is easy to get, if they do not have disadvantageous effect to the mechanism of action of fire-retardant filler and are heated to high temperature or directly do not produce harmful product when flame is handled.Dewatering agent especially can be selected from: calcium oxide, calcium chloride, anhydrous alumina, zeolite, sal epsom, magnesium oxide, barium oxide, or its mixture.Preferred especially calcium oxide and zeolite or its mixture.
The addition of dewatering agent in fire-retardant combination will preestablish, and depends primarily on water content in material person's character and efficient and the fire-retardant filler.Generally speaking, it is believed that the quality with respect to fire-retardant filler, 0.5～15wt.%, the dewatering agent of preferred 1～10wt.% consumption just are enough to the effect that reaches satisfied.
General adoptable fire-retardant filler is a metal, the particularly oxyhydroxide of calcium, aluminium or magnesium, hydrous oxide, salt or salt hydrate, such as: magnesium hydroxide, hibbsite, hydrocarbonate of magnesia, magnesiumcarbonate, hydrated calcium magnesium carbonate, miemite or its mixture.Because one of its characteristic is a decomposition temperature be about 340 ℃ and thereby high extrusion temperature is used, so preferred especially magnesium hydroxide.Especially more preferably the natural product magnesium hydroxide that makes through grinding of magnesium hydroxide mineral such as brucite is described in the european patent application WO 99/05688 and Research Disclosure No.407 publication (in March, 1998) that submits on December 1st, 1997 as the applicant.
The general fire-retardant filler that adopts particulate forms can be unprocessed or surperficial saturated or unsaturated fatty acids or its metal-salt through 8～24 carbon atoms, such as oleic acid, palmitinic acid, stearic acid, Unimac 5680, lauric acid; Stearic acid or magnesium oleate or zinc were handled.In order to improve the consistency with polymeric matrix; fire-retardant filler also can carry out surface treatment such as organosilane or titanic acid ester such as vinyltriethoxysilane, vinyl triacetyl silane, titanium isopropylate, metatitanic acid tetra-n-butyl ester through suitable coupling agent.
Set the addition of fire-retardant filler in advance, can be so that obtain by the cable of common fire testing, such as the test of being undertaken by IEC 332-1 and IEC 332.3 A, B, C standard.Its amount generally is 10～90wt.%, and preferred 30～80wt.% is with respect to the total mass of fire-retardant combination.
Polymeric matrix generally can be selected from: multipolymer, polyester, polyethers, polyether/polyester multipolymer and its mixture of polyolefine, various olefin copolymer, alkene and alkene type unsaturated ester.
The example of polymkeric substance is: high density polyethylene(HDPE) (HDPE) (d=0.940-0.970g/cm
3), medium-density polyethylene (MDPE) (d=0.926-0.940g/cm
3), new LDPE (film grade) (d=0.910-0.926g/cm
3); The multipolymer, particularly linear low density polyethylene (LLDPE) of the alpha-olefin of ethene and 3～12 carbon atoms (such as 1-butylene, 1-hexene, 1-octene) and ultra-low density polyethylene (ULDPE) (d=0.860-0.910g/cm
3); Polypropylene (PP); The thermoplastic copolymer of propylene and other alkene, particularly ethene; Ethene and at least a multipolymer that is selected from alkyl acrylate, alkyl methacrylate and vinyl carboxylates, its neutral line or branched-alkyl can contain 1～8, preferred 1～4 carbon atom, linearity or branched carboxylic acids base then can contain 2～8, preferred 2～5 carbon atoms, particularly ethylene/vinyl acetate (EVA) multipolymer; Ethylene/ethyl acrylate multipolymer (EEA), ethylene/butylacrylate copolymer (EBA); Ethylene/alpha-olefin hydrocarbon rubbers, particularly ethylene/propylene rubber (EPR), ethylene/propylene/diene rubber (EPDM); Natural rubber; Isoprene-isobutylene rubber; And composition thereof.
Particularly preferred multipolymer is the alpha-olefin of ethene and at least a 3～12 carbon atoms, and optional and diene, obtains through copolyreaction under the existence of " single-point " catalyzer, particularly metalloscene catalyst or the limited catalyzer of geometrical shape.
These multipolymers is characterized in that density is 0.860～0.904g/cm
3, preferred 0.865～0.902g/cm
3, form distribution coefficient then greater than 45%, this coefficient is defined as the shared mass percent of copolymer molecule that alpha-olefin content is up to alpha-olefin population mean molar content 50%.Its preferred monomer of these multipolymers is composed as follows: 75-97mol.%, the ethene of preferred 90-95mol.%; 3-25mol.%, the alpha-olefin of preferred 5-10mol.%; 0-5mol.%, the diene of preferred 0-2mol.%. alpha-olefin is preferably selected from propylene, 1-butylene, 1-hexene, 1-octene.This commercially available series products is Du Pont-Dow Elastomers system Engage
With ExxonChemical system Exact
.
The ethylene copolymer that makes through single-point catalyst preferably with crystalline propylene homopolymer or multipolymer, such as described in the above-mentioned european patent application No.97121042.2, be 0.905～0.970g/cm perhaps with density
3, preferred 0.910～0.940g/cm
3Alathon or multipolymer mix to use, such as the european patent application No.98118194.4 that submits on September 25th, 1998 the applicant or also have U.S.No.5, described in 707,732.Polymeric matrix especially preferably comprises 5～60wt.%, more preferably above-mentioned propylene or Alathon or the multipolymer of 10～45wt.%, and 40～95wt.%, the more preferably ethylene copolymer that makes through single-point catalyst of 55～90wt.%, these per-cents are all with respect to polymeric components (a) and total mass (b).
Can in mixture, add and a kind ofly can strengthen interactional coupling agent between fire-retardant filler active group and the polymer chain, to improve the consistency between fire-retardant filler and the polymeric matrix.It is known that coupling agent can be selected from prior art, such as: saturation type silane compound or contain the silane compound of at least one alkene type unsaturated group; The epoxy compounds that contains an alkene type unsaturated group; With the monocarboxylic acid or the preferred di-carboxylic acid of at least one alkene type unsaturated group, or derivatives thereof, particularly acid anhydride or ester.
The silane compound example suitable in this purpose is: γ-methacryloxypropyl trimethoxy silane, allyltrimethoxysilanis, allyltriethoxysilane, allyl methyl dimethoxy silane, the allyl methyl diethoxy silane, Union carbide A-162, methyl three (2-methoxy ethoxy) silane, dimethyldiethoxysilane, vinyl three (2-methoxy ethoxy) silane, vinyltrimethoxy silane, the vinyl methyl dimethoxysilane, vinyltriethoxysilane, octyltri-ethoxysilane, the isobutyl-triethoxyl silane, isobutyl-Trimethoxy silane, or its mixture.
The epoxy compounds example that contains alkene type unsaturated group is: glycidyl acrylate, glycidyl methacrylate, methylene-succinic acid list glycidyl ester, toxilic acid glycidyl ester, vinyl glycidyl ether, glycidyl allyl ether, or its mixture.
Monocarboxylic acid or the di-carboxylic acid that can be used as coupling agent with at least one alkene type unsaturated group, or derivatives thereof is such as being: toxilic acid, maleic anhydride, fumaric acid, citraconic acid, methylene-succinic acid, vinylformic acid, methacrylic acid etc., and derive and the acid anhydrides or the ester that come, or its mixture from these acid.Preferred especially maleic anhydride.
Coupling agent can directly use or be grafted in advance by free radical reaction on the multipolymer of polyolefine such as polyethylene or ethene and alpha-olefin (such as referring to EP-530,940).The grafting amount of coupling agent is generally 0.05～5 weight part, and preferred 0.1～2 weight part is with respect to the polyolefine of 100 weight parts.The commercially available polyolefin products that is grafted with maleic anhydride is such as being Fusabond
(DuPont), Orevac
(Elf Atochem), Exxelor
(Exxon Chemical), Yparex
(DSM) etc.
In addition, the coupling agent of silane (such as the vinyltrimethoxy silane) type of above-mentioned carboxylic acid or epoxide (such as maleic anhydride) or band alkene type unsaturated group can combine with radical initiator and add to and go in the mixture, thereby compatilizer directly is grafted on the polymeric matrix.Such as adopting organo-peroxide to be used as initiator such as t-butylperoxyl benzoate, dicumyl peroxide, benzoyl peroxide and ditertiary butyl peroxide.The explanation that this method is done is such as referring to US-4, and 317,765, JP-62-58774 or also have above-mentioned european patent application No.97121042.2 and No.98118194.4.
The addition of coupling agent is variable in the mixture, depends primarily on the kind of used coupling agent and the addition of fire-retardant filler, and generally is 0.01～5%, and preferred 0.05～2wt.% is with respect to the total mass of matrix polymer mixture.
Also can add other common component in the composition of the present invention such as antioxidant, processing aid, lubricant, pigment and other filler etc.,
In the suitable common antioxidant of this purpose such as being: polymeric form trimethyldihydroquinoline, 4,4 '-thiobis (3-methyl-6-tert butyl) phenol; Tetramethylolmethane four-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2,2 '-sulfo-divinyl two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], or its mixture,
In other filler of available of the present invention such as comprising glass particle, glass fibre, calcined kaolin, talcum, or its mixture, the general processing aid that adds in polymeric matrix is such as being calcium stearate, Zinic stearas, stearic acid, petroleum wax, silicon rubber, or its mixture.
Fire-retardant combination of the present invention is preferably used its non-crosslinked form, obtaining the coating of tool thermoplastic characteristics, and then recycle in addition,
Fire-retardant combination of the present invention can pass through, contain the internal mixer of tangential rotors (Banbury) or interlocking rotors, altogether mediate (Buss) type or the double-screw type continuous mixer of rotation or retrograde rotation in the same way such as employing, the method of mixed polymer matrix, fire-retardant filler, dewatering agent and known addible other additive of prior art is prepared
Preferably introduce dewatering agent after first step of composition processing finishes, owing to the heat that hybrid technique produced, fire-retardant filler can lose a certain amount of moisture content that absorbs therebetween.Can avoid exhausting too early the water absorption capacity of dehydration property filler thus, require filler mainly just to be activated in extrusion step subsequently, the temperature of composition in this first mixing step is 100 ℃ at least, preferably at least 150 ℃, and the time length be at least 5min,
Can in the preparation process of fire-retardant combination, not add dewatering agent yet, but in extrusion, add, such as loading hopper via forcing machine.
Dewatering agent all adds in the fire-retardant combination with disintegrated (particle, powder) in both cases; optional utilization dispersion and protective material; be coated with it such as Microcrystalline Wax, lipid acid; in addition; in order to improve its deployment conditions in polymeric matrix, can be used in pre-dispersed dewatering agent in the polymer materials (such as the hemicrystalline ethylene/propylene rubber).
In extrusion; Can adopt the fire-retardant combination of above-mentioned preparation directly to be coated with wire; Perhaps form shell at the wire that scribbles in advance insulating barrier; When having two layers to exist; Can be divided into two independently step extrude; Send for the first time and out-of-dately extrude internal layer at wire and send for the second time and out-of-dately then extrude the second layer at internal layer; Coating process preferably can be finished through just once sending; Such as by " series connection " method; Two independently extruders by arranged in series have wherein been adopted; Perhaps also can give coextrusion via an extruder head
The extrusion temperature of fire-retardant combination can change in very wide scope and can determine in advance according to the rate of extrusion that will reach.In fact rate of extrusion depends on viscosity and then its temperature of molten state composition, and viscosity depends primarily on the kind of polymeric matrix and the kind and the consumption of used fire-retardant filler, the minimum extrusion temperature of composition generally is not less than the plasticization temperature of polymeric matrix, the highest extrusion temperature then needs to pre-determine, to avoid polymeric matrix and/or fire-retardant filler that degraded takes place or to decompose, therefore based on above-mentioned requirements, when fire-retardant combination during based on the mixture of polypropylene and above-mentioned ethylene/alpha-olefin copolymer, wherein with magnesium hydroxide as fire-retardant filler, the extrusion temperature of fire-retardant combination is generally 160 ℃～320 ℃, preferred 200 ℃～280 ℃
Though what this specification sheets was primarily aimed at is to make self extinguishing cable via expressing technique, but the use advantage that dewatering agent of the present invention brought is at common manufacturing rubber item, use the water absorbability filler during such as the cable concentrator of cable splice or terminal various extrude or moulding technology in also be tangible, particularly extruding or the flowability of moulding material and when needing high processing temperature in order to improve
For more clearly the present invention will be described, below will provide some embodiment examples, especially with reference to appendix:
Fig. 1 is the cross sectional representation of the self-extinguishing low voltage unidirectional cable made of the present invention,
" low voltage " speech generally refers to and is lower than 2kV, preferably is lower than the voltage of 1kV.
Cable among Fig. 1 comprises that a lead (1), one play the internal layer (2) of electrical insulator effect and a tool flame retardant resistance and the skin (3) that plays outer provide protection.
Internal layer (2) can be made of the crosslinked or non-crosslinked of tool electrical insulation capability, not halogen-containing polymer composition, can from known systems, select, such as: polyolefine (homopolymer of various alkene or multipolymer), alkene/alkene type unsaturated ester multipolymer, polyester, polyethers, polyether/polyester multipolymer and composition thereof, the example of these polymkeric substance is: polyethylene (PE), particularly linear low density polyethylene (LLDPE); Polypropylene (PP); The propylene/ethylene thermoplastic copolymer; Ethylene/propylene rubber (EPR) or ethylene/propylene/diene rubber (EPDM); Natural rubber; Isoprene-isobutylene rubber; Ethylene/vinyl acetate (EvA) multipolymer; Ethylene/methyl acrylate copolymer (EMA), ethylene/ethyl acrylate multipolymer (EEA), ethylene/butylacrylate copolymer (EBA); Ethylene/alpha-olefin copolymer.
In addition, the self extinguishing cable of manufacturing of the present invention can be made of the lead that directly scribbles fire-retardant combination, middle does not have any other insulation layer, and at this moment, flame retardant coating also plays the effect of electrical insulator.Play the polymer foil of antifriction medium effect, optional with suitable pigment mixes, with on the color being convenient to discern, add through the outside and can realize it.
The preparation of fire-retardant combination
It in the volume compactedness 95% closed Banbury mixing machine (mixing section volume: 1200cm
3) in the preparation fire-retardant combination, mix and to carry out in two steps, in the first step, the component of each except dewatering agent in the mixture is mixed together, reach about 200 ℃ up to temperature, guarantee each component energy good distribution and reduce water content in the filler.Keeping adding dewatering agent under the about 200 ℃ situation of mixing temperature then.
Mechanical property
The composition of above-mentioned preparation from being the forcing machine of 25 times of diameters, barrel diameter 120mm and length is extruded at red metal lead (cross section 2.5mm
2) on, with the preparation self extinguishing cable (final thickness of flame-retardant layer: 0.8mm). the temperature of composition in forcing machine keeps being about 250 ℃, rate of extrusion 900m/min.
Resulting flame retardant coating is pressed CEI standard 20-34 § 5.1 its mechanical tensile strengths of test, the results are shown in Table 1, randomly draws five samples and get its mean value from all cables of making.The cable of manufacturing has all passed through the flame retardant test test of IEC standard 332-1, and this test requirements document is grown the vertical sample of placing directly to handle 1min with the Bunsen lights flame at sample angle at 45 with 60cm.
Table 1
| |
1 | 2 | ?3 | ?4(*) | ?5 | ?6(*) |
| Engage 8003 | 85 | 85 | ?85 | ?85 | ?85 | ?85 |
| Moplen EP1X35HF | 15 | 15 | ?15 | ?15 | ?15 | ?15 |
| Hydrofy G1.5 | 210 | 210 | ?210 | ?210 | ?- | ?- |
| Hydrofy G1.5S | - | - | ?- | ?- | ?210 | ?210 |
| Peroximon DC40 | 0.4 | 0.4 | ?0.4 | ?0.4 | ?0.4 | ?0.4 |
| Silquest A-172 | 1.8 | 1.8 | ?1.8 | ?1.8 | ?1.8 | ?1.8 |
| Irganox 1010 | 0.8 | 0.8 | ?0.8 | ?0.8 | ?0.8 | ?0.8 |
| Irganox MD1024 | 0.3 | 0.3 | ?0.3 | ?0.3 | ?0.3 | ?0.3 |
| Stearic acid | 1.5 | 1.5 | ?1.5 | ?1.5 | ?1.5 | ?1.5 |
| Kezadol
|
2 | 6 | ?10 | ?- | ?6 | ?- |
| Its mechanical property of the cable that 900m/min extruded | ||||||
| Overall loading (MPa) | 14.0 | 13.8 | ?12.2 | ?14.2 | ?13.5 | ?13.0 |
| Elongation at break (%) | 122 | 140 | ?159 | ?90 | ?157 | ?105 |
(*) comparative example
Engage
The ethene that 8003-obtains through metallocene catalyst/1-octene copolymer: ethene/1-octene mass ratio=82/18 (the 1-octene of 5.5mol.%); D=0.885g/cm
3MFI=1.0g/10 ';
CDI＞70％；ΔH
2f＝55.6J/g；
Moplen
The crystallinity random copolymers of EP1X35HF-propylene/ethylene; D=0.900g/cm
3
MFI＝9.0g/10’；T
2f＝1?54℃；ΔH
2f＝90.6J/g；
Hydrofy
The natural product magnesium hydroxide that G1.5-makes through the grinding water magnesite, not surface treatment (SIMA company), specific surface area: 10.4m
2/ g,
Hydrofy
The natural product magnesium hydroxide that G1.5S-makes through the grinding water magnesite, (SIMA company), specific surface area: 10.4m were handled with stearic acid in the surface
2/ g.
Silquest
A-172-coupling agent: vinyl three (2-methoxy ethoxy) silane (VTMOEO);
Peroximon
DC40-peroxide initiator: dicumyl peroxide;
Irganox
1010-antioxidant: tetramethylolmethane four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] ester (Ciba-Geiy);
Irganox
The MD1024-metal inactivator: 1, two (3, the 5-di-t-butyl-4-hydroxybenzene propionyl) hydrazines (Ciba-Geiy) of 2-;
Kezadol
GR-is dispersed in the calcium oxide (CaO of 80wt.%) in the hemicrystalline EPR rubber in advance, is the particle (Kettlitz company) of mean diameter 6-7 μ m.
Table 1 is given result clearly illustrate that, makes cable in the presence of calcium oxide, the mechanical property excellence of flame retardant coating.On the contrary, do not add the dewatering agent manufacturing its poor mechanical properties of contrast cable and can't by this class cable the index request (overall loading generally will surpass 12.5MPa and elongation at break greater than 125%) that should reach.During range estimation, the contrast cable exists micropore owing to flame retardant coating inside thereby the surface is unglazed, but does not then have this class defective fully through the cable of manufacturing of the present invention.
Claims (12)
1. fire-retardant combination, it comprises:
(a) alpha-olefin of an ethene and an at least a 3-12 carbon atom, and the multipolymer of optional and diene, its density is 0.860～0.904g/cm
3Form distribution coefficient greater than 45%, this coefficient is defined as the mass percent that alpha-olefin content is up to the copolymer molecule of alpha-olefin population mean molar content 50%, wherein said ethene and at least a alpha-olefin, and the multipolymer of optional and diene obtains by single-point catalyst;
(b) brucite;
(c) dewatering agent.
2. the composition of claim 1, wherein dewatering agent is selected from: calcium oxide, calcium chloride, anhydrous alumina, zeolite, sal epsom, magnesium oxide, barium oxide or its mixture.
3. the composition of claim 2, wherein dewatering agent is selected from: calcium oxide, zeolite or its mixture.
4. any one composition of claim 1～3, wherein the content of dewatering agent is 0.5～15wt.%, with respect to the quality of fire-retardant filler.
5. the composition of claim 4, wherein the content of dewatering agent is 1～10wt.%, with respect to the quality of fire-retardant filler.
6. the composition of claim 1, therein ethylene and at least a alpha-olefin, and the multipolymer of optional and diene obtains by metalloscene catalyst.
7. the composition of claim 1, therein ethylene and at least a alpha-olefin, and the multipolymer of optional and diene obtains by the limited catalyzer of geometrical shape.
8. any one composition of claim 1-3 further comprises a kind of crystalline propylene homopolymer or multipolymer.
9. any one composition of claim 1-3, further comprising a kind of density is 0.905-0.970g/cm
3Alathon or multipolymer.
10. any one composition of claim 1-3 further comprises a kind of coupling agent to strengthen the consistency between fire-retardant filler and the polymeric matrix.
11. the composition of claim 10, wherein coupling agent is selected from: the saturation type silane compound; The silane compound that contains at least one alkene type unsaturated group; The epoxy compounds that contains an alkene type unsaturated group; With the monocarboxylic acid or the di-carboxylic acid of at least one alkene type unsaturated group, or derivatives thereof.
12. comprise the cable of a lead and at least one flame retardant coating, wherein said at least one flame retardant coating comprises the composition any according to claim 1-11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98124648 | 1998-12-24 | ||
| EP98124648.1 | 1998-12-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99815789 Division CN1184648C (en) | 1998-12-24 | 1999-12-20 | Process for producing self-extinguishing cables with low-level production of fumes and flame-retardant compositions used therein |
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| Publication Number | Publication Date |
|---|---|
| CN1594466A CN1594466A (en) | 2005-03-16 |
| CN100354383C true CN100354383C (en) | 2007-12-12 |
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| CN 99815789 Expired - Fee Related CN1184648C (en) | 1998-12-24 | 1999-12-20 | Process for producing self-extinguishing cables with low-level production of fumes and flame-retardant compositions used therein |
| CNB2004100641100A Expired - Fee Related CN100354383C (en) | 1998-12-24 | 1999-12-20 | Process for producing self-extinguishing cables with low-level production of fumes, and flame-retardant compositions used therein |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99815789 Expired - Fee Related CN1184648C (en) | 1998-12-24 | 1999-12-20 | Process for producing self-extinguishing cables with low-level production of fumes and flame-retardant compositions used therein |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JP2002533893A (en) |
| CN (2) | CN1184648C (en) |
| AR (1) | AR035309A1 (en) |
| AT (1) | ATE504927T1 (en) |
| BR (1) | BR9916586A (en) |
| DE (1) | DE69943340D1 (en) |
| ES (1) | ES2364028T3 (en) |
| HK (1) | HK1073321A1 (en) |
| RU (1) | RU2237078C2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8097809B2 (en) | 2005-10-27 | 2012-01-17 | Prysmian Cavi E Sistemi Energia S.R.L. | Low-smoke self-extinguishing cable and flame-retardant composition comprising natural magnesium hydroxide |
| US20080073627A1 (en) * | 2006-09-25 | 2008-03-27 | Goode Michael J | Flame resistance natural fiber-filled thermoplastics with improved properties |
| FR2913908B1 (en) * | 2007-03-19 | 2009-06-05 | Nexans Sa | PROCESS FOR PRODUCING A RETICULATED LAYER FOR ENERGY CABLE AND / OR TELECOMUNICATION |
| JP5324127B2 (en) | 2007-05-15 | 2013-10-23 | サンアロマー株式会社 | Flame retardant, flame retardant composition using the same, molded product thereof, and electric wire having coating |
| US8435427B2 (en) * | 2010-08-26 | 2013-05-07 | 3M Innovative Properties Company | Compositions having non-linear current-voltage characteristics |
| RU2460756C1 (en) * | 2011-03-10 | 2012-09-10 | Общество с ограниченной ответственностью "Ул. Полимер Композит" | Fire-resistant polymer composition for fabrication of items using extrusion, die casting and pressing methods |
| RU2542098C1 (en) * | 2012-11-30 | 2015-02-20 | Учреждение образования "Белорусский государственный университет транспорта" | Polymer composition for manufacturing electrohydroinsulating material |
| RU2548565C2 (en) * | 2013-05-23 | 2015-04-20 | Наиф Хасанович Салихов | Flexible fireproof self-extinguishing electric cable |
| RU2573517C2 (en) * | 2014-05-30 | 2016-01-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Национальный исследовательский Томский политехнический университет" | Method of making electric insulating composition |
| RU2617165C1 (en) * | 2016-03-10 | 2017-04-21 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | Method for producing electrical insulating compound |
| EP3499516A1 (en) * | 2017-12-12 | 2019-06-19 | Borealis AG | Flame retardant and fire resistant polyolefin composition |
| CN117423502B (en) * | 2023-12-18 | 2024-02-23 | 湖南华菱线缆股份有限公司 | Fireproof variable frequency cable |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1983004041A1 (en) * | 1982-05-07 | 1983-11-24 | A/S Norsk Kabelfabrik | Fire resistant material |
| EP0718388A2 (en) * | 1994-12-12 | 1996-06-26 | Erika Balle | Fire-protective substance and method for producing and depositing of a fire-protective substance |
-
1999
- 1999-12-20 JP JP2000591628A patent/JP2002533893A/en active Pending
- 1999-12-20 ES ES99965500T patent/ES2364028T3/en not_active Expired - Lifetime
- 1999-12-20 RU RU2001120719/04A patent/RU2237078C2/en active
- 1999-12-20 BR BR9916586-4A patent/BR9916586A/en not_active Application Discontinuation
- 1999-12-20 CN CN 99815789 patent/CN1184648C/en not_active Expired - Fee Related
- 1999-12-20 AT AT99965500T patent/ATE504927T1/en not_active IP Right Cessation
- 1999-12-20 DE DE69943340T patent/DE69943340D1/en not_active Expired - Lifetime
- 1999-12-20 CN CNB2004100641100A patent/CN100354383C/en not_active Expired - Fee Related
- 1999-12-23 AR ARP990106715 patent/AR035309A1/en active IP Right Grant
-
2005
- 2005-07-11 HK HK05105824.6A patent/HK1073321A1/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1983004041A1 (en) * | 1982-05-07 | 1983-11-24 | A/S Norsk Kabelfabrik | Fire resistant material |
| EP0718388A2 (en) * | 1994-12-12 | 1996-06-26 | Erika Balle | Fire-protective substance and method for producing and depositing of a fire-protective substance |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1073321A1 (en) | 2005-09-30 |
| ATE504927T1 (en) | 2011-04-15 |
| AR035309A1 (en) | 2004-05-12 |
| CN1371517A (en) | 2002-09-25 |
| CN1184648C (en) | 2005-01-12 |
| DE69943340D1 (en) | 2011-05-19 |
| BR9916586A (en) | 2001-09-25 |
| RU2237078C2 (en) | 2004-09-27 |
| JP2002533893A (en) | 2002-10-08 |
| CN1594466A (en) | 2005-03-16 |
| ES2364028T3 (en) | 2011-08-23 |
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