CN1371517A - 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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- CN1371517A CN1371517A CN 99815789 CN99815789A CN1371517A CN 1371517 A CN1371517 A CN 1371517A CN 99815789 CN99815789 CN 99815789 CN 99815789 A CN99815789 A CN 99815789A CN 1371517 A CN1371517 A CN 1371517A
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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-extinguishment 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 proper additive thereby possessed anti-flammability.In this purpose can with such as being polyolefin composition, such as based on polyethylene or ethylene/vinyl acetate copolymer, can contain halogen organic compound collocation antimony trioxide as flame-retardant additive.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 corrosiveness 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.
Therefore, not halogen-containing compound, wherein polymeric matrix when making self extinguishing cable, have been begun to adopt in recent years, majority is a TPO, and with inorganic fire-retarded filler, majority is a metal, the particularly hydroxide of aluminium or magnesium, hydrous oxide or hydrated salt, 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.
Inorganic filler can directly be adopted or be coated with various types of hydrophobic substances, such as saturated or unrighted acid or its salt, especially oleic acid or stearic acid or corresponding oleate or stearate, or uses after organosilan or the titanate esters.
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 Tissuemat E 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 compatibility 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 aliphatic acid of quality 0.5～5wt.% consumption of hydroxide or its salt or silane or titanate esters.Described according to this patent application, therefore surface-treated filler allegedly can reduce water absorbing 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 vapour that disengages in the filler in the process that composition is extruded on cable.
The applicant finds, when adopting described inorganic filler to make self extinguishing cable, be coated with cloth filler with water-repelling 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 production rate, 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 performance of coating.
The applicant finds at present, if add dehydrating 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.Dehydrating agent can mix (mix) step or directly add in fire-retardant combination in the upstream of extruder.
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 the fire-retardant combination that (a) preparation comprises polymeric matrix and inorganic fire-retarded filler; (b) on the optional lead that is coated with in advance with insulating barrier, extrude described fire-retardant combination, obtain flame retardant coating; It is characterized in that in described fire-retardant combination, adding dehydrating agent.
According to the first embodiment of the present invention, in the preparation process (a) of fire-retardant combination, add dehydrating 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 temperature after, in the preparation process (a) of fire-retardant combination, add dehydrating agent.
Further embodiment according to the present invention is added dehydrating 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 dehydrating agent.
According to applicant's viewpoint, dehydrating agent is brought into play its effect by institute's water content in the absorption fire-retardant filler, and these moisture content discharge in heating process when composition is extruded.Absorption mechanism is preferably irreversible, and perhaps dehydrating 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 dehydrating 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 mineral such as shepardites, dehydrating agent is obvious especially to the influence of the appearance of flame retardant coating and mechanical performance 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 dehydrating agent is the easy-to-use inorganic compound that is easy to get, if they do not have adverse 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.Dehydrating agent especially can be selected from: calcium oxide, calcium chloride, anhydrous alumina, zeolite, magnesium sulfate, magnesium oxide, barium monoxide etc., or its mixture.Preferred especially calcium oxide and zeolite or its mixture.
The addition of dehydrating 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 dehydrating 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 hydroxide of calcium, aluminium or magnesium, hydrous oxide, salt or hydrated salt, such as: magnesium hydroxide, hibbsite, hydrocarbonate of magnesia, magnesium carbonate, 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 such as magnesium hydroxide mineral such as shepardite is described in the european patent application No.97121042.2 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 unrighted acid or its slaine through 8～24 carbon atoms, such as oleic acid, palmitic acid, stearic acid, isostearic acid, laurate; Stearic acid or magnesium oleate or zinc; Or the like handled.In order to improve the compatibility with polymeric matrix; fire-retardant filler also can carry out surface treatment such as organosilan or titanate esters such as vinyltriethoxysilane, vinyl triacetyl silane, tetraisopropyl titanate, metatitanic acid tetra-n-butyl ester etc. through suitable coupling agent.
Set the addition of fire-retardant filler in advance, can be so that obtain by the cable of common fire resistance test, 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 gross mass of fire-retardant combination.
Polymeric matrix generally can be selected from: copolymer, polyester, polyethers, polyether/polyester copolymer and its mixture of polyolefin, various olefin copolymer, alkene and alkene type beta-unsaturated esters.
The example of polymer is: high density polyethylene (HDPE) (HDPE) (d=0.940-0.970g/cm
3), medium density polyethylene (MDPE) (d=0.926-0.940g/cm
3), low density polyethylene (LDPE) (d=0.910-0.926g/cm
3); Copolymer, particularly LLDPE (LLDPE) and ultra-low density polyethylene (the ULDPE) (d=0.860-0.910g/cm of the alpha-olefin of ethene and 3～12 carbon atoms (such as 1-butylene, 1-hexene, 1-octene etc.)
3); Polypropylene (PP); The thermoplastic copolymer of propylene and other alkene, particularly ethene; Ethene and at least a copolymer 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) copolymer; Ethylene/ethyl acrylate copolymer (EEA), ethylene/butylacrylate copolymer (EBA); Ethylene/alpha-olefin hydrocarbon rubbers, particularly ethylene/propylene rubber (EPR), ethylene/propylene/diene rubber (EPDM); Natural rubber; Butyl rubber; And composition thereof.
Particularly preferred copolymer 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 " catalyst, particularly metalloscene catalyst or the limited catalyst of geometry.
These copolymers is characterized in that density is 0.860～0.904g/cm
3, preferred 0.865～0.902g/cm
3, form breadth 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 copolymers 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 etc.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 copolymer, 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 copolymer 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 copolymer of 10～45wt.%, and 40～95wt.%, the more preferably ethylene copolymer that makes through single-point catalyst of 55～90wt.%, these percentages are all with respect to polymeric components (a) and gross 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 compatibility 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 dicarboxylic acids 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, methyl triethoxysilane, methyl three (2-methoxy ethoxy) silane, dimethyldiethoxysilane, vinyl three (2-methoxy ethoxy) silane, vinyltrimethoxy silane, the vinyl methyl dimethoxysilane, vinyltriethoxysilane, octyltri-ethoxysilane, the isobutyl group triethoxysilane, isobutyl group trimethoxy silane etc., or its mixture.
The epoxy compounds example that contains alkene type unsaturated group is: glycidyl acrylate, glycidyl methacrylate, itaconic acid list ethylene oxidic ester, maleic acid ethylene oxidic ester, vinyl glycidyl ether, allyl glycidyl ether etc., or its mixture.
Monocarboxylic acid or the dicarboxylic acids that can be used as coupling agent with at least one alkene type unsaturated group, or derivatives thereof is such as being: maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, acrylic 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 radical reaction on the copolymer of polyolefin 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 portion, and preferred 0.1～2 weight portion is with respect to the polyolefin of 100 weight portions.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 epoxides (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.Be used as initator such as organic peroxides such as can adopting t-butyl perbenzoate, dicumyl peroxide, benzoyl peroxide and di-tert-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 gross 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; Pentaerythrite 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] etc., or its mixture.
In the present invention can with other filler such as comprising glass particle, glass fibre, calcined kaolin, talcum etc., or its mixture.The general processing aid that adds in polymeric matrix is such as being calcium stearate, zinc stearate, stearic acid, pertroleum wax, silicon rubber etc., 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 can be recycling in addition.
Fire-retardant combination of the present invention can pass through, contain the internal mixture of tangential rotors (Banbury) or interlocking rotors, altogether mediate (Buss) type or the double-screw type continuous mixer of rotation or counter-rotating in the same way such as employing, the method for mixed polymer matrix, fire-retardant filler, dehydrating agent and known addible other additive of prior art is prepared.
Preferably introduce dehydrating 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 in extrusion step subsequently, just to be activated.The temperature of composition in this first blend step is 100 ℃ at least, preferably at least 150 ℃, and the duration be at least 5min.
Can in the preparation process of fire-retardant combination, not add dehydrating agent yet, but in extrusion, add, such as loading hopper via extruder.
Dehydrating agent all adds in the fire-retardant combination with comminution (particle, powder) in both cases, optional utilization dispersion and protective agent, such as coatings such as microwax, aliphatic acid.In addition, in order to improve its deployment conditions in polymeric matrix, can be used in pre-dispersed dehydrating agent in the polymeric material (such as the hemicrystalline ethylene/propylene rubber).
In extrusion, can adopt the fire-retardant combination of above-mentioned preparation directly to be coated with lead, perhaps on the lead that scribbles insulating barrier in advance, form shell.When two layers exist, can be divided into two independent step and extrude, send for the first time and out-of-dately send for the second time the out-of-date second layer of then on internal layer, extruding extruding internal layer on the lead.Coating process preferably can be finished through just once sending, and such as by " series connection " method, had wherein adopted two independently extruders by arranged in series, 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, and 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 was primarily aimed at is to make self extinguishing cable via expressing technique, but the use advantage that dehydrating agent of the present invention brought is at common manufacturing rubber, use the moisture absorption filler during such as the cable concentrator of cable joint or terminal various extrude or moulding technology in also be significantly, 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-extinguishment 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 anti-flammability and the skin (3) that plays outer protective effect.
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: polyolefin (homopolymers of various alkene or copolymer), alkene/alkene type beta-unsaturated esters copolymer, polyester, polyethers, polyether/polyester copolymer and composition thereof.The example of these polymer is: polyethylene (PE), particularly LLDPE (LLDPE); Polypropylene (PP); The propylene/ethylene thermoplastic copolymer; Ethylene/propylene rubber (EPR) or ethylene/propylene/diene rubber (EPDM); Natural rubber; Butyl rubber; Ethylene/vinyl acetate (EVA) copolymer; Ethylene/methyl acrylate copolymer (EMA), ethylene/ethyl acrylate copolymer (EEA), ethylene/butylacrylate copolymer (EBA); Ethylene/alpha-olefin copolymer etc.
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 insulating barrier.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 mixer (mixing chamber volume: 1200cm
3) middle preparation fire-retardant combination.Mix and carry out in two steps.In the first step, the component of each except dehydrating agent in the mixture is mixed together, reaches about 200 ℃, guarantee that each component can fine dispersion and reduce water content in the filler up to temperature.Keeping adding dehydrating agent under the about 200 ℃ situation of mixing temperature then.Mechanical performance
The composition of above-mentioned preparation from being the extruder 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 extruder 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, from all cables of making, randomly draw five samples and get its mean value.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
(*) 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 '; CD I＞70%; Δ H
2f=55.6J/g; Moplen
The crystallinity random copolymer of EP1 * 35HF-propylene/ethylene; D=0.900g/cm
3MFI=9.0g/10 '; T
2f=154 ℃; Δ H
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 area: 10.4m
2/ g.Hydrofy
The natural product magnesium hydroxide that G1.5S-makes through the grinding water magnesite, (SIMA company), specific 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: pentaerythrite 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-hydroxy benzenes propiono) 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 average diameter 6-7 μ m.
| Embodiment | 1 | ?2 | 3 | 4(*) | 5 | 6(*) |
| Engage 8003 | 85 | 85 | 85 | 85 | 85 | 85 |
| Moplen EP1×35HF | 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 performance of the cable that 900m/min extruded | ||||||
| Maximum load (MPa) | 14.0 | 13.8 | 12.2 | 14.2 | 13.5 | 13.0 |
| Elongation at break (%) | 122 | 140 | 159 | 90 | 157 | 105 |
Table 1 is given result clearly illustrate that, makes cable in the presence of calcium oxide, the mechanical performance excellence of flame retardant coating.On the contrary, do not add the dehydrating agent manufacturing its poor mechanical properties of contrast cable and can't by this class cable the index request (maximum load 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 (26)
1. the manufacturing process of the self extinguishing cable that the amount of being fuming is low, 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 insulating barrier, extrude described fire-retardant combination, obtain flame retardant coating;
It is sharp to it is characterized in that adding dehydration in described fire-retardant combination.
2. the technology of claim 1 is wherein added dehydrating agent in the preparation process (a) of fire-retardant combination.
3. the technology of claim 2 wherein composition mixes first step end with the water content in the reduction fire-retardant filler of one default period under preset temperature after, is added dehydrating agent in the preparation process (a) of fire-retardant combination.
4. the technology of claim 1 is wherein added dehydrating agent in the extrusion step (b) of fire-retardant combination.
5. any one technology of aforementioned claim, the wherein dehydrating agent of interpolation comminution in fire-retardant combination.
6. any one technology of aforementioned claim wherein is dispersed in dehydrating agent in the polymeric material in advance and then adds in the fire-retardant combination and go.
7. any one technology of aforementioned claim is wherein extruded this fire-retardant combination under the preset temperature relevant with resulting rate of extrusion.
8. the technology of claim 7, wherein the extrusion temperature of fire-retardant combination is 160～320 ℃.
9. the technology of claim 8, wherein the extrusion temperature of fire-retardant combination is 200～280 ℃.
10. any one technology of aforementioned claim, wherein dehydrating agent is selected from: calcium oxide, calcium chloride, anhydrous alumina, zeolite, magnesium sulfate, magnesium oxide, barium monoxide etc. or its mixture.
11. the technology of claim 10, wherein dehydrating agent is selected from: calcium oxide, zeolite or its mixture.
12. the technology that aforementioned claim is any one, wherein the addition of dehydrating agent in fire-retardant combination is 0.5～15wt.%, with respect to the quality of fire-retardant filler.
13. the technology of claim 12, wherein the addition of dehydrating agent in fire-retardant combination is 1～10wt.%, with respect to the quality of fire-retardant filler.
14. the technology that aforementioned claim is any one, wherein fire-retardant filler is selected from: the hydroxide of metal, hydrous oxide, salt or hydrated salt.
15. the technology of claim 14, wherein fire-retardant filler is selected from: magnesium hydroxide, hibbsite, hydrocarbonate of magnesia, magnesium carbonate, hydrated calcium magnesium carbonate, miemite or its mixture.
16. the technology of claim 15, wherein fire-retardant filler is a magnesium hydroxide.
17. the technology of claim 15, wherein fire-retardant filler is natural product magnesium hydroxide.
18. a fire-retardant combination that comprises polymeric matrix and inorganic fire-retarded filler is characterized in that also comprising dehydrating agent.
19. the composition of claim 18, wherein dehydrating agent is selected from: calcium oxide, calcium chloride, anhydrous alumina, zeolite, magnesium sulfate, magnesium oxide, barium monoxide etc. or its mixture.
20. the composition of claim 19, wherein dehydrating agent is selected from: calcium oxide, zeolite or its mixture.
21. the composition that claim 18～20 is any, wherein the content of dehydrating agent is 0.5～15wt.%, with respect to the quality of fire-retardant filler.
22. the composition of claim 21, wherein the content of dehydrating agent is 1～10wt.%, with respect to the quality of fire-retardant filler.
23. the composition that claim 18～22 is any, wherein fire-retardant filler is selected from: the hydroxide of metal, hydrous oxide, salt or hydrated salt.
24. the composition of claim 23, wherein fire-retardant filler is selected from: magnesium hydroxide, hibbsite, hydrocarbonate of magnesia, magnesium carbonate, hydrated calcium magnesium carbonate, miemite or its mixture.
25. the composition of claim 24, wherein fire-retardant filler is a magnesium hydroxide.
26. the composition of claim 25, wherein fire-retardant filler is natural product magnesium hydroxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98124648 | 1998-12-24 | ||
| EP98124648.1 | 1998-12-24 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100641100A Division 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1371517A true CN1371517A (en) | 2002-09-25 |
| CN1184648C CN1184648C (en) | 2005-01-12 |
Family
ID=8233243
Family Applications (2)
| 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 |
| 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 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679870A (en) * | 2007-05-15 | 2010-03-24 | 胜亚诺盟股份有限公司 | Flame retardant, flame-retardant composition using the same, molded article of the composition, and coated electric wire |
| CN101295565B (en) * | 2007-03-19 | 2012-07-18 | 尼克桑斯公司 | Method of manufacturing a cross-linked layer for a power and/or telecommunications cable, and the cable |
| CN117423502A (en) * | 2023-12-18 | 2024-01-19 | 湖南华菱线缆股份有限公司 | Fireproof variable frequency cable |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2386169T3 (en) | 2005-10-27 | 2012-08-10 | Prysmian S.P.A. | Self-extinguishing cable with low smoke formation 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 |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0109408B2 (en) * | 1982-05-07 | 1992-08-19 | A/S Norsk Kabelfabrik | Fire resistant material |
| JPH08165468A (en) * | 1994-12-12 | 1996-06-25 | Erika Balle | Fireproofing substance,production of fire-proofing substanceand method of adhering fireproofing substance |
-
1999
- 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 AT AT99965500T patent/ATE504927T1/en not_active IP Right Cessation
- 1999-12-20 ES ES99965500T patent/ES2364028T3/en not_active Expired - Lifetime
- 1999-12-20 CN CN 99815789 patent/CN1184648C/en not_active Expired - Fee Related
- 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
- 1999-12-20 JP JP2000591628A patent/JP2002533893A/en active Pending
- 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
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101295565B (en) * | 2007-03-19 | 2012-07-18 | 尼克桑斯公司 | Method of manufacturing a cross-linked layer for a power and/or telecommunications cable, and the cable |
| CN101679870A (en) * | 2007-05-15 | 2010-03-24 | 胜亚诺盟股份有限公司 | Flame retardant, flame-retardant composition using the same, molded article of the composition, and coated electric wire |
| CN101679870B (en) * | 2007-05-15 | 2013-11-06 | 胜亚诺盟股份有限公司 | Flame retardant, flame-retardant composition using the same, molded article of the composition, and coated electric wire |
| US8617437B2 (en) | 2007-05-15 | 2013-12-31 | Sun Allomer Ltd. | Flame retardant and flame retardant composition using same, molded article thereof, and electric wire with coating |
| CN117423502A (en) * | 2023-12-18 | 2024-01-19 | 湖南华菱线缆股份有限公司 | Fireproof variable frequency cable |
| CN117423502B (en) * | 2023-12-18 | 2024-02-23 | 湖南华菱线缆股份有限公司 | Fireproof variable frequency cable |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1594466A (en) | 2005-03-16 |
| CN100354383C (en) | 2007-12-12 |
| CN1184648C (en) | 2005-01-12 |
| AR035309A1 (en) | 2004-05-12 |
| ATE504927T1 (en) | 2011-04-15 |
| ES2364028T3 (en) | 2011-08-23 |
| RU2237078C2 (en) | 2004-09-27 |
| HK1073321A1 (en) | 2005-09-30 |
| BR9916586A (en) | 2001-09-25 |
| DE69943340D1 (en) | 2011-05-19 |
| JP2002533893A (en) | 2002-10-08 |
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