CN85101356A - Anti-flammability cross-linked composition and the anti-flammability cable that uses said composition to make - Google Patents
Anti-flammability cross-linked composition and the anti-flammability cable that uses said composition to make Download PDFInfo
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- CN85101356A CN85101356A CN198585101356A CN85101356A CN85101356A CN 85101356 A CN85101356 A CN 85101356A CN 198585101356 A CN198585101356 A CN 198585101356A CN 85101356 A CN85101356 A CN 85101356A CN 85101356 A CN85101356 A CN 85101356A
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Abstract
The anti-flammability cross-linked composition prepares by the following method: will be mixed and made into second compound with not halogen-containing silane grafted polyolefin resin by first compound that metal hydrate and not halogen-containing vistanex are formed; Then with crosslinked with silicane to make the anti-flammability cross-linked composition.Compare with traditional flame-retardant composition, this anti-flammability cross-linked composition has good anti-flammability, thermal endurance and mouldability, and cost is low in addition; And when burning, do not produce toxic gas as halogenation hydrogen or halogen and so on.Therefore, especially suitable crust and the insulating material of making fire-retardancy electric wire, cable etc. of this anti-flammability cross-linked composition.
Description
The invention relates to that fire-spreading property is little, the anti-flammability cross-linked composition of fine heat-resisting performance, and about manufacture the anti-flammability cable of crust with this composition.
Up to now, the known typical fire retardant resin composition that is used for electric wire and cable insulating material and crust, the antimony trioxide fire retardant is mixed with Corvic, neoprene, chlorosulfonated polyethylene rubber etc., perhaps methods such as antimony trioxide, chlorine fire retardant or bromine flame retardant are mixed with polyethylene, ethene-vinyl acetate copolymer, ethylene propylene monomer etc. are prepared.
In these compositions, primary resin or fire retardant contain halogen, so under hot conditions, these compositions will produce a large amount of toxic gases, for example hydrogen halides (hydrogen chloride, hydrogen bromide) and halogen gas (chlorine) exist serious problem on safety.Therefore, use in the place of using the product of these compositions to be unsuitable for safety is had high requirements, and for example is not suitable for using in places such as subterranean railway, building, boats and ships, nuclear power stations.Moreover, halogen gas and hydrogen halide also corrode conductor that closes on it or the like, and this is another shortcoming of known flame-retardant composition.
In order to improve the anti-flammability and the thermal endurance of the fire retardant resin composition that uses traditionally, with the primary resin of these compositions, for example polyethylene and ethylene propylene monomer are carried out crosslinked.When carrying out crosslinking Treatment, often adopt chemical crosslink technique and electron beam crosslinking method.Chemical crosslink technique is with water vapour or the like said composition to be heat-treated under HTHP, therefore needs to use special high-pressure-resistant vessel and firing equipment.On the other hand, the electron beam crosslinking method needs certain electron beam emission cavity and equipment.And in these two kinds of cross-linking methods, which kind of method all needs to use sizable cross-linking apparatus, has so improved equipment cost and maintenance cost greatly, thereby the production cost of said composition is increased.
For traditional cable, exist the another one serious problems.That is exactly some structural details of cable core inside, for example by polyethylene and the crosslinked made element of polyethylene, to melt in the time of under they are exposed to the flame that catches fire and dropwise flow on this cable surface, gasification and taking fire immediately under high-temperature atmosphere, thereby make this ignition of cable and the intensity of a fire is enlarged.In addition, use not halogen-containing rubber or the plastics cable as insulating material and crust, its anti-flammability is compared as the cable of insulating material and crust with the material that use contains halogen and halogen flame, and is poorer.To use the not anti-flammability of halogen containing material cable in order improving, in these materials, to mix a large amount of metal hydrates, but so but make its physical property and electric property variation.
When using peroxide and so on material to carry out the chemical crosslinking operation since under high-temperature and high-pressure conditions, carry out crosslinked, so may produce distortion near the material of desiring to carry out crosslinked part.For example, the inner core of cable may be owing to produce temperature distortion when crosslinked its crust.On the other hand, when carrying out electron beam crosslinking, electron beam is difficult to reach the desire bosom of crosslinked composition layer in addition.For example, at certain quite thick crust place, crosslinked action only results from its surface portion.The shortcoming of electron beam crosslinking method is that it is difficult to make the thick-layer composition crosslinked fully.
Therefore, one of purpose of the present invention is the anti-flammability cable that proposes a kind of anti-flammability cross-linked composition and use said composition to make.When this composition at high temperature burns, for example under ignition condition, do not produce poisonous and corrosive gas, do not smolder, thereby ensured safety, eliminated the gas that is generated and near metal and so on material has been produced the possibility of corrosion.
Second purpose of the present invention is to propose the anti-flammability cross-linked composition that a kind of thermal endurance is strong, Forming Quality is good, and the anti-flammability cable that uses said composition.
The 3rd purpose of the present invention is the anti-flammability cable that proposes a kind of anti-flammability cross-linked composition and use said composition, and the crosslinked operation of this composition does not need to use cross-linking apparatus, and its production cost is reduced.
Another object of the present invention is to propose a kind of anti-flammability cable with excellent flame retardancy structure.
In view of above-mentioned purpose and other purpose, one aspect of the present invention, be to propose a kind of anti-flammability cross-linked composition, its preparation method is as follows: make first compound of being made up of the hydrate of metal and not halogen-containing certain vistanex, mix with not halogen-containing silane grafted polyolefin resin, to make second compound; And, make this second compound crosslinked with silicane in order to make this anti-flammability cross-linked composition.Metal hydrate is mixed with vistanex and silane grafted polyolefin resin, and the mixing ratio of the two when calculating by weight is: polyolefin and silane grafted polyolefin resin about the metal hydrate about 50～200 parts/100 part; And the mixing ratio between vistanex and the silane grafted polyolefin resin is calculated by weight to approximately (100-X)/X, and wherein X value scope is the 80(part of about 20≤X≤approximately).
Anti-flammability cross-linked composition of the present invention does not produce the toxic gas of halogenation hydrogen or halogen gas and so on, and compares with the top conventional compositions of mentioning, and its anti-flammability, thermal endurance and Forming Quality are all good, also has the low advantage of production cost simultaneously.Therefore, anti-flammability cross-linked composition of the present invention is particularly suitable for insulating material and crust as electric wire, cable or the like.
In addition, another aspect of the present invention is to have proposed a kind of anti-flammability cable, and this cable has a sub-core at least, and this sub-core comprises the electric conductor that is coated with the electrical insulating material of being made by not halogen-containing material; And this cable crust of also having one deck to make by the anti-flammability cross-linked composition that proposes in first aspect of the present invention.
For the anti-flammability that improves anti-flammability cable of the present invention and the action effect of anti-flammability cross-linked composition, can between the fuse of this cable and crust, one deck flame barrier be set.
In the accompanying drawing, Fig. 1 is the sectional view of anti-flammability cable of the present invention.
Fig. 2 is the sectional view of a kind of modified model cable of cable among Fig. 1.
Fig. 3 is the sectional view of another modified model cable of cable among Fig. 1.
In the vistanex that the present invention uses, do not contain halogen. For example, operable polyolefin has in the present invention: polyethylene, ethene-alpha-olefin copolymer, ethylene-propylene copolymer, vinyl-vinyl acetate copolymer, tri poly ethylene-propylene rubber (EPDM), ethylene-methyl acrylate copolymer, PMA, polyethyl acrylate, polymethacrylates, ethylene acrylic rubber, HSBR and composition thereof.
In the present invention, can use aluminium hydroxide, magnesium hydroxide, basic magnesium carbonate, hydroxide Calcium or carried out surface-treated hydrate etc. with aliphatic acid, phosphate, silane coupler, titanate coupling agent is as metal hydrate. These metal hydrates are used for this resin of retardance and at high temperature burn with after polyolefin mixes. It is believed that this flame retarded reaction takes place in the following manner. When metal hydrate was heated to high temperature, the crystallization water wherein is free to be disengaged. The resin that mixes with this metal hydrate, since on fire and so on former thereby when being heated to high temperature, lose heat because of the free of this crystallization water, thereby make its drop in temperature, so that blocked the burning of this resin.
Although the use amount of metal hydrate, determined according to required anti-flammability size with factors such as miscibilty between the resin of wanting to be mixed, but the metal hydrate quantity of normal operation of the present invention, when calculating by weight be: with respect to about per 20～80 parts of polyolefin, use about 50～200 parts of metal hydrates, preferably use about 80～150 parts of metal hydrates. When the metal hydrate weight of using is less than about 50 parts, can not discharge the crystallization water of q.s, therefore can not produce gratifying anti-flammability. On the other hand, if the operating weight of metal hydrate during greater than 200 parts of left and right sides, then can make the Forming Quality variation of crosslinkable compound.
The vistanex of the Silane Grafted that uses among the present invention, like this some resins are for example arranged, this resin is to use organic peroxide, with vinyl alkoxy silane (for example VTES), γ-metering system oxygen propyl group-trimethoxy silane and vinyltrimethoxy silane etc. are grafted on above-mentioned certain vistanex and make, and have a lot of alkene main chains that are connected with the side chain of silanol functional on it, and with this vistanex good miscibilty is arranged preferably. The vistanex of Silane Grafted carries out crosslinked easily, and this cross-linking reaction is accelerated the space network structure that formation is three-dimensional in the presence of the materials such as moisture, catalyst. According to inferring, this crosslinked with silicane (water crosslinking) is the condensation reaction (condensa-tion reaction) of silanol side chain under the effect such as dehydration. According to the present invention, the use amount of the vistanex of Silane Grafted, each calculates by weight is about 20～80 parts generally speaking, and is (100-X) weight portion as the use amount of the vistanex of original copolymer, X is the Silane Grafted polyene in the formula The use amount of hydrocarbon resin. The use amount of the vistanex of Silane Grafted depends on the required degree of cross linking. When the use amount of Silane Grafted resin is less than about 20 weight portion, can not get the gratifying degree of cross linking, thereby make the product heat resistance variation of making. When the silane grafted polyolefin resin that uses greater than about 80 parts of weight, mix and forming process in the Forming Quality of said composition obviously descend, and it is also bad to make the outward appearance of product. The use amount X of the silane grafted polyolefin resin of preferentially selecting is calculated by weight to from about 20 to about 50 parts. An important feature of the present invention is, for the ease of processing anti-flammability cross-linked composition of the present invention, first compound (containing vistanex and metal hydrate) and the vistanex of Silane Grafted are wanted separate storage, when extrusion molding adds they are contacted with each other.
At the vistanex of Silane Grafted with after this anti-flammability compound mixes, make this cross-linking reaction acceleration by the method that the compound that mixed contact or make it to pass through under water with outside moisture, catalyst etc., therefore mainly due to the effect of silane grafted polyolefin resin, make in the product of making and produce cross-linked structure, thereby improved the heat resistance of product.
Red phosphorus combustion inhibitor and (perhaps) carbon dust (for example carbon black, thermally expandable graphite etc.) can be mixed in the anti-flammability compound. Sneak into after these materials of appropriate amount, be heated under the high temperature that produces carburization zone, these materials will speed up the carbonization of resinous principle. Therefore, except metal hydrate, also be mixed with this composition of red phosphorus combustion inhibitor and (perhaps) carbon dust, be heated under the high temperature, will prevent fusing and the drippage of said composition, thereby avoid spreading or reduce at least it and spreading of resin burning, therefore improved anti-flammability. It is believed that, red phosphorus combustion inhibitor is to the hastening phenomenon of this compound carbonization, because such reaction causes, namely because the oxidation under the high-temperature heating makes phosphorus obtain hydrogen from resin, become hydrophosphate etc., and between its main combustion period, carbon dust accelerates the carbonization of this resin, thereby by the hard carbide lamella of such generation, hinders the drippage of this molten resin.
In the present invention, with respect to the vistanex of per 100 parts of weight and the vistanex of Silane Grafted, when the vistanex gross weight that namely is equivalent to vistanex and Silane Grafted was 100 parts, the normal operation amount of carbon dust was about 5～70 parts of weight, and with about 10～40 parts of weight is for well. When about 5 parts of carbon dust shortage in weight, the hastening phenomenon of this resin carbonation effect shows insufficiently, thereby can not stop the drip phenomenon of this molten resin. On the other hand, when carbon dust weight is higher than about 70 parts, the obvious variation of the Forming Quality of said composition.
The red phosphorus combustion inhibitor that uses among the present invention can be red phosphorus or the fire retardant that contains red phosphorus. Red phosphorus combustion inhibitor use amount in the present invention with respect to the vistanex of per 100 parts of weight and the vistanex of Silane Grafted, should make the red phosphorus that wherein contains about 2～50 parts of weight, is preferably about 10～30 parts of weight red phosphorus. If red phosphorus content exceeds above-mentioned scope in the fire retardant, its effect of accelerating this resin carbonation is reduced significantly.
In order to make the series products of electrical insulating material, crust, when preparing this cross-linked composition, consider the Forming Quality of second compound, preferably prepare the vistanex of silane grafting separately according to the present invention, and it is sealed up for safekeeping in the aluminium foil laminated pouch, so that outside moisture can not be entered in the bag.On the other hand, when preparation first compound, metal hydrate be added in the vistanex, if necessary, in this vistanex, can also add antioxidant, catalyst, processing aid, and a kind of or two kinds of materials in red phosphorus combustion inhibitor and the carbon dust.Use roller mill, closed mixing machine, kneading machine etc. that these materials are evenly mixed, so as to making the anti-flammability compound, this anti-flammability compound is in addition airtight preservation also.This anti-flammability compound according to habitual mode moulding, is made needed shape, carry out crosslinked with silicane according to the method for having introduced then.
With reference to Fig. 1 to Fig. 3 in the accompanying drawing, three kinds of multicore anti-flammability cables in the present invention on the other hand are described, wherein each cable all has the crust of making according to described anti-flammability cross-linked composition in the first aspect present invention content.In the drawings, what reference number 11 was indicated is conductor, coat certain electrical insulating material 13 by traditional approach around conductor, this layer insulating material for example made by polyethylene, crosslinked polyethylene (XLPE made in following brief note), natural rubber, butyl rubber, silicone rubber, ethylene propylene monomer (EPR), tri poly ethylene-propylene rubber (EPDM), ethene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethene-alpha-olefin copolymer, ethylene acrylic rubber, HSBR or its mixture or the like.This insulating material 13 can perhaps add the mixture manufacturing that aforementioned not halogen-containing fire retardant is made by these flame-retardant materials by the mixture manufacturing of these halogen-free materials.Conductor 11 and insulating material 13 are formed insulator heart yearn 15.When insulating material 13 is when being made by XLPE, can adopt traditional chemical crosslink technique or electron beam crosslinking method to carry out crosslinked to polyethylene.In chemical crosslink technique, use certain organic peroxide, for example: the DCP(dicumyl peroxide), 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide alkynes) hexane, hydrogen peroxide cumene, tert-butyl hydroperoxide neopentanoic acid fat and silane coupler, for example: the VTMS(vinyltrimethoxy silane), vinyltriethoxysilane, γ-methylpropenyl propoxyl group trimethoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-methylpropenyl propoxyl group methyl dimethoxysilane.
By making the present invention's who had narrated anti-flammability cross-linked composition generation crosslinked with silicane effect, can make insulating material 13 moulding.
Forming cable core, inserts 17 comprises jute, paper, nonhygroscopic paper, anti-flammability paper, nonhygroscopic anti-flammability paper, polyethylene wire drawing, anti-flaming polypropylene (PP), polyacrylic fibres, Supreme Being's Telon (Tetoron) silk, polyethylene terephthalate thin film or the like with its tangle up for three sub-heart yearn 15 usefulness fillers 17.Around this cable core, but form the tape layer 19 of a carbonization, but the material that can be used for making the tape layer 19 of this carbonization has: brown paper, acrylic fiber cloth, viscose rayon cloth, native cellulose fibre and the above-mentioned material that is impregnated with silicone lacquer, alkyd resin coating and so on material.But the band of this carbonization is entangled in around this cable core, forms tape layer 19, and it can be carbonized when heating.But but the tape layer 19 of this carbonization also can save.
But around the tape layer 19 of this carbonization, form one deck flame barrier 21 or 23, this flame barrier protection insulating material 11 and filler 17 prevent that them from catching fire.In cable shown in Figure 1, this flame barrier 21 is to be entwined under overlapping 1/5～1/2 condition with one or several inorganic fire-resistant bands, and employed this fire-resistant band contains the material of pottery and so on, for example about 0.05～2 millimeter of its thickness.This inorganic fire-resistant band for example has: mica polyester film laminated tape, glass bonded mica band, mica-paper composites band, asbestos yarn, mica-paper laminated tape, glass tape, glass fibre and the aluminium-silicon fusion silk ribbon (for example composite band of alumina silicate synthetic fibers and ceramic fibre) that scribbles silicone lacquer or alkyd resin coating, aluminium-glass stack band or the like.This flame barrier also can adopt twine one or several mainly by oxygen index (Oxygen Index) be 35 or the method for the anti-flammability band made of higher organic material constitute.These anti-flammability bands for example have: scribble anti-flammability rubber cloth matter band and by polyether-ether-ketone (Polyetheretherketone) (PEEK), the band made of polyimide resin, polyether sulfone, Polyetherimide polysulfones, Merlon, phenolic plastics or aromatic polyester.When using these bands, be 1～5 this band of 0.05～0.2 millimeter, but be wrapped under 1/5～1/2 the condition of overlapping each other around the tape layer 19 of carbonization thickness.In cable shown in Figure 2, flame barrier 23 is a kind of or two kinds of sheet metal strips or contain the band of significant proportion metal with one or several, is entwined under 1/5 to 1/2 the condition of overlapping each other.The thickness of these bands is approximately 0.03～0.2 millimeter, includes copper strips, steel band, stainless steel (SUS) band, brass band, aluminium strip, aluminium-polyester film laminated tape or the like.In addition, in cable illustrated in fig. 3, this flame barrier 21,23 is made up of cable among Fig. 1 and Fig. 2 used the sort of inorganic tape layer and sheet metal strip layer respectively.Each layer all is under overlapping 1/5 to 1/2 condition, and the method for or several piece of tape of twining forms.This inorganic tape layer preferably is placed within the sheet metal strip layer.But, this inorganic band and metal tape, but also can be wrapped in by opposite mode around this carburization zone 19.Just as described above, but the tape layer 19 of carbonization and stopping in the belt 21,23, each layer all must with the mode that overlaps each other be wrapped in internal layer around.If adopt other canoe, then the combustibles of fusing and gasification may spray when cable fire internally.
Around the flame barrier 21,23 that forms like this, also can twine the barrier layer protected layer 27 that one deck is protected those flame barriers.The barrier layer protected layer 27 of this layer is to form with the method for twining certain band, and this band is made by composite material of for example asbestos, glass fibre, ceramic fibre, these materials or the like.
In addition, around barrier layer protected layer 27, form a crosslinked good crust 29.This crosslinked crust 29 is made by the sort of anti-flammability cross-linked composition described in the first aspect present invention.
In cable shown in Figure 1, this flame barrier 21 is to be made by the inorganic band that contains the vast scale pottery, and is therefore good from its essence thermal endurance.When barrier layer 21 is heated under ignition condition, survivable, therefore prevented effectively, thereby but be enough to protect cable core inside and make the carburization zone 19 that is in its inside that suitable carbonization take place to cable core internal delivery heat and air supply.Even cause insulating material 13 fusings in the cable core 15 owing to the cable internal temperature raises, but flame barrier 21 therein be carbonized under the common shielding action of carbonization belt 19 that the back forms a kind of hard sheet wall, stop the insulating material 13 of this fusing to flow to outside the cable effectively.
In cable shown in Figure 2, the flame barrier 23 by sheet metal strip forms except excellent heat resistance, also is better than flame barrier 21 aspect airtight quality, so it almost can stop the molten drop gasification back of this insulating material and so on material by it fully.From producing originally, preferably use the material of aluminium foil as flame barrier 23.
The sort of bilayer of inorganic layer 21 and strap layer 23 or the flame barrier of sandwich construction of including shown in Figure 3 with producing by the combination action effect that inorganic layer and metal level had, therefore can obtain better effect.
Be in flame barrier 21 or 23 barrier layer protected layer 27 all around, play a part mechanically to protect and reinforce flame barrier, with opposing external force.And, from this protective layer 27 of its performance poor thermal conductivity, play the fireproof heat protective effect, thereby prevent or reduce the temperature rising of crust 29 for flame barrier 21,23.
Crust 29 is made by the following method: the vistanex of silane grafting and the anti-flammability compound for preparing according to the described method of first aspect present invention are mixed; according to conventional method its extruding is attached to around barrier layer protected layer 27 then, makes each root cable.Insulation material layer 13 formation that can use the same method.
Though the present invention describes with regard to multicore cable, the present invention also is applicable to single-core cable.
When introducing embodiments of the invention in the above, but pointed out all have carburization zone, barrier layer and protective layer in these anti-flammability cables.But it is to be noted that these layers not necessarily must have, even they all save, still can obtain excellent flame-retardant performance in some applications, and can not produce toxic gas.
Embodiment 1-6
The silane grafted polyolefin resin A and the B of composition shown in the table 1 are to prepare according to following operating procedure respectively.In every kind of method of operation, all be that dicumyl peroxide (DCP) is dissolved among the vinyltrimethoxy silane, to wherein adding highdensity polyethylene powder, make paste shape compound then.This paste is evenly sneaked into by in Mitsui petro chemical industry Co., Ltd. (Mitsui Petrochemical Inc.Ltd.) manufacturing and the ethene-alpha-olefin copolymer with Japanese trade (brand) name " Tafmer A-4085 " sale, make mixture, using cylinder diameter then is traditional plastic extruding machine of 40 millimeters, in 200 ℃ of extrusion temperature and residence time is with this mixture extrusion moulding, so that make the silane grafted polyolefin resin A and the B of pellet type under the conditions such as 4～5 minutes.Resin A of making according to the method and B are sealed up for safekeeping respectively in the aluminium foil laminated pouch, and be isolated with outside moisture and so on material.
Table 1
| Parts by weight | ||
| Silane grafted polyolefin resin A | Silane grafted polyolefin resin B | |
| Ethene-alpha-olefin copolymer vinyltrimethoxy silane dicumyl peroxide (DCP) high density polyethylene (HDPE) * | 100 4 0.3 2 | 100 2 0.3 2 |
*Density is 0.95
In embodiment 1 to 6, use and have every batch materials of composition shown in the table 2, all according to following method of operation preparation.With aluminium hydroxide, magnesium hydroxide, red phosphorus combustion inhibitor, carbon black, as the stearic acid of lubricant, materials such as antioxidant, silane condensation catalyst and DCP commonly used, vistanex A and B with the silane grafting, according to the mixing formula shown in the table 2, add in the ethene-alpha-olefin copolymer, and mixed, made the anti-flammability compound (first compound) of partical.Condensation catalyst is dibutyl tin dilaurate (DBTDL).Under 160 ℃ or higher temperature, carry out this married operation with closed mixing machine.Then, every part of anti-flammability compound that according to said method prepares is sealed in the aluminium foil laminated tape that is stored in separately, isolated outside moisture and so on material prevents its intrusion.
Then, with silane grafted polyolefin resin A and the B that so makes, and every kind of anti-flammability compound among the embodiment 1 to 6, mix according to the mixture recipes shown in the table 2, make second compound, using common plastic extruding machine is 0.9 millimeter copper conductor outside with this second compound extrusion molding at diameter, so that make the insulated conductor of 2.8 to 3 millimeter coating layers for each embodiment.
To carry out thermal ageing test and heat distortion test by the insulated wire that this method is made, so that determine its characteristic.When doing thermal ageing test, every kind of insulated wire was being placed 7 days under 120 ℃ of temperature or after 100 ℃ are placed 10 days down, measured its tensile strength and elongation.When doing heat distortion test, with every kind of insulated wire 1 kilogram of load in addition, simultaneously 90 ℃ of heating 1 hour, according to IEC(International Electrotechnical Commission) method of 92-3 regulation measures the thermal deformation degree of every kind of insulated wire under this condition.In order to determine the anti-flammability of insulated wire outer tube among each embodiment, measure oxygen index according to the method for ASTM D-2863 regulation.For toxic gas and the etchant gas amount of determining to be produced, measure hydrogen halide according to the method for IEC-754 regulation.
Experimental result is listed in the table 2, as can be seen from Table 2, aspect the insulated wire among the embodiment 1～4 (row that belong to preferable range of the present invention), extrusion moulding and elongation before aging, all is better than the insulated wire in embodiment 5 and 6.
* handle through stearic acid on 1 surface;
* 2 contain 24(weight) conventional flame retardant of % red phosphorus;
* 3 antioxidants by Switzerland Ciba-Geigy company produce and market, brand name is " Irganox # 1076 ";
* 4 dicumyl peroxide curing agent;
* 5 under 90 ℃ and 1kg load-up condition according to IEC92-3 in specified standard measure;
* 6 according to the method mensuration of stipulating among the ASTMD-2863;
* 7 according to the method mensuration of stipulating among the IEC-754-1;
* 8 " * ", " * * " and " * * * " represent good, qualified and defective respectively.
Comparative example 1-5
According to the mixture recipes of listing in the table 3, use equipment and method of operation among the embodiment 1-6, for comparative example 1-4 has prepared four kinds of insulated wires.Compound in the comparative example 1 and 5 does not comprise the vistanex of silane grafting.In the comparative example 5, except that this compound contains DCP and carries out after extrusion molding the vapor crosslinking, all the other steps have been made another covering thread according to the similarity condition in the previous embodiment.To these insulated conductors, those tests among the embodiment 1-6 have also been done.
Result of the test is listed in table 3.Cross-linked composition in the comparative example 1 and 2, do not use the use amount of crosslinkable composition or crosslinkable composition to be lower than the lower limit of prescribed limit of the present invention, because they are obviously distortion and fusing or slight fusing in ageing test in heat distortion test, so these two kinds of compositions can not be satisfactory.Cross-linked composite in the comparative example 3 and 4, wherein the use amount of crosslinkable composition has surpassed the upper limit of prescribed limit of the present invention, and its extrusion moulding is poor, so can not be satisfactory.Cross-linked composite in the comparative example 5, it is crosslinked wherein to use DCP to carry out,
All demonstrate gratifying result in all test subjects, need use high temperature and high pressure equipment when still crosslinked.Using DCP that cable sheath is carried out in the crosslinked process, cable core may melt and stick together, and therefore adopts the cable of the crosslinked crust of DCP, and the material that uses at its core is had certain limitation.On the other hand, the silane cross-linking method that adopts among the present invention, without any need for cross-linking apparatus, the material to cable core uses does not have this restriction yet.
Embodiment 7-32
According to equipment and the operating performance among mixture recipes of listing in table 4 and the table 5 and the use embodiment 1～6, prepared the insulated conductor of each embodiment.Thus the data in two tables as can be seen, from extrusion moulding and other performance, the composition among embodiment 7～10 and the embodiment 20～23 is gratifying.Embodiment 7～19 has shown the various combinations between aluminium hydroxide composition and other fire retardant.Embodiment 20～32 has illustrated the various combinations between magnesium hydroxide composition and other fire retardant.
To these insulated conductors carry out with embodiment 1～6 in the identical test done, result of the test is also listed in table 4 and the table 5.
Cross-linked composition among embodiment 11～13 and the embodiment 24～26, because wherein the use amount of silane grafted polyolefin resin exceeded preferable range of the present invention, so indexs such as its extrusion molding formability before ageing test and elongation are poorer than the cross-linked composition among embodiment 7～10 and the embodiment 20～23 respectively.
Find out that by embodiment 14 and 27 anti-flammability compound wherein only contains metal hydrate as fire retardant, and its consumption exceeded preferable range of the present invention, so its extrusion modling variation.In fact, so the metal hydrate of high concentration causing themogenesis during the extrusion molding in plastic extruding machine, bubbles thereby cause in manufactured goods.In order to obtain high flame retardant, be suitable for when using metal hydrate, using the carbon black and the red phosphorus combustion inhibitor of appropriate amount.
Embodiment 33～54
For each embodiment, all prepared sample cable (shown in accompanying drawing 1～3) with three sub-heart yearns by following mode, it is 5.5mm that each sub-heart yearn all has a cross-sectional area
2Copper conductor.Insulating material squeezed be attached to every lead outside, use vapor crosslinking then, making diameter is the sub-heart yearn of 5.0mm.In embodiment 33～44, insulation material layer is to make with crosslinked polyethylene (XLPE), and coating thickness is 1.0mm; Insulating material among the embodiment 45-54, make by not halogen-containing cross-linked polyolefin anti-flammability compound, its coating thickness is 1.0mm, and this compound is by ethene-alpha-olefin copolymer (100 weight portion), magnesium hydroxide (80 weight portion), DCP(2 weight portion) and antioxidant (1 weight portion) formed.Use is as 90 μ m heavy kraft paper bands of inserts, and three sub-heart yearns with making as stated above are intertwined according to traditional approach, make cable core; But twine band, flame barrier strip and the barrier layer protected band of carbonization according to usual method on every side successively at this cable core then, these bands are as shown in table 6 with material.But the band of carbonization, flame barrier strip and barrier layer protected band are to twine in the mode of a lamination one deck.At last, be under 120～150 ℃ of conditions in extrusion temperature, the skin material shown in the table 6 squeezed be attached to around the cable core of making as stated above, make cable, then with it with water cooling be entangled on the cable axle.According to the IEEE(Institute of Electrical and Electronics) test method (vertically coiling flame assay, Vertical Tray Flame Test) of standard 383 checks these sample cables.And then measure hydrogen halide concentration that generates in this test and the visibility that sees through the smog that produces.
Listed the result of the test of this vertical dish flame assay in the table 7, and found from these results, whole results of these embodiment are very satisfactory.Result by embodiment 33-54 can also find that the hydrogen halide concentration of generation is zero, and the visibility that sees through the smog that produces is greater than 100 meters.Find out that from result of the test the cigarette amount that cable produced that belongs to the scope of the invention during burning is little, and does not generate hydrogen halide, also have enough big anti-flammability in addition.In addition, do not produce other toxic and corrosive gas yet.
* 9 mica-glass tapes that thickness is 0.13mm that under overlapping 1/4 condition, twine;
* the thickness of preparation is the anti-flammability cross-linked composition of 1.5mm among 10 embodiment 3;
* 11 thickness that twine under overlapping 1/3 condition are the ox-hide paper tape of 90 μ m;
* 12 thickness that twine under overlapping 1/4 condition are the glass tape of 0.13mm;
* 13 thickness that twine under overlapping 1/4 condition are an aluminium-polyester film laminated tape of 50 μ m;
* the thickness that uses among 14 embodiment 14 is the anti-flammability cross-linked composition of 1.5mm;
* 15 thickness that use in embodiment 31 are the anti-flammability cross-linked composition of 1.5mm;
* 16 thickness are the flame retardance poly vinyl chloride of 1.5mm;
* 17 thickness that use in embodiment 27 are the anti-flammability cross-linked composition of 1.5mm;
* 18 thickness that use in embodiment 10 are the anti-flammability cross-linked composition of 1.5mm.
Comparative example 6
For the ease of relatively, prepared certain sample cable in such a way.By conventional method Corvic is squeezed that to be attached to cross-sectional area be 5.5mm
2Copper conductor outside, making coating thickness is the sub-heart yearn of 1.0mm, this sub-core line diameter is 5.0mm.Three sub-heart yearns with making in this way are intertwined as filler with jute according to traditional approach, make cable core, squeeze attached flame retardance poly vinyl chloride then around this cable core, make the cable that skin thickness is 1.5mm.According to the same test method that in embodiment 33～54, adopts, this sample is tested.
The flame assay of vertical dish the results are shown in table 7, and these results are satisfactory.But can see that seeing through the visibility that produces smog is 1 meter, illustrate that therefore the amount of smoke of this cable generation is more much more than the cable among the embodiment 33-54.Can also find that the hydrogen halide that is generated is competed up to 530ppm, surpass the level of harm humans health, will produce corrosiveness near electricity contact equipment such as (electrical contacts).
Embodiment 55～62 and comparative example 7～9
In using embodiment 1～6 under the condition of equipment and operating performance, according to the mixture recipes of listing in the table 8 for each examples preparation flame-retardant composition.The oxygen index and the thermal deformation of these compositions have been measured.Experimental result is also listed in the table 8.
Embodiment 63-71
Basically the same way as among employing and the embodiment 33-44 has prepared the sample cable for each embodiment.That is, adopt with embodiment 33～44 in identical mode and identical materials make cable core, but twine carbonization zone as shown in table 9, flame barrier strip and barrier layer protected band all around at this cable core in the conventional mode then.Use equals 35 or the anti-flammability band made of the organic material of higher value by oxygen index (OI), as forming the whole or a part of flame barrier strip of each flame barrier.To these sample cables carry out with embodiment 33-44 in the same test done, its result of the test is listed in table 10.
Indicated as table 10, it is few to belong to the cigarette amount that the cable of the row of the scope of the invention produces, and does not produce for example toxic and corrosive gas of hydrogen chloride gas and so on.In addition, be also noted that this cable meter reveals enough anti-flammabilitys, and this crust is functional.
Claims (19)
1, a kind of anti-flammability cross-linked composition, its manufacturing step is:
(a) will be mixed with the vistanex of silane grafting by first compound that vistanex and metal hydrate are formed, make second compound, these two kinds of resins are all not halogen-containing,
(b) with this second compound of crosslinked with silicane, make the anti-flammability cross-linked composition,
(c) wherein, the combined amount of this metal hydrate is, the metal hydrate that mixes about 50～200 parts of weight in the vistanex of the vistanex of per 100 parts of common weight and silane grafting, and the combined amount of vistanex is calculated as approximately (100-X) part by weight, X is the vistanex consumption of silane grafting in the formula, 20≤X≤80 weight portions.
2, according to the anti-flammability cross-linked composition described in the claim 1, wherein first compound contains carbon dust, and its content is in the vistanex of the vistanex of per 100 parts of common weight and silane grafting, to contain about 5～70 parts of carbon dusts by weight.
3, according to the anti-flammability cross-linked composition described in the claim 2, wherein first compound also contains red phosphorus combustion inhibitor, and its content is, the vistanex of the vistanex of per 100 parts of common weight and silane grafting, in contain the red phosphorus of about 2～50 parts of weight.
4, according to the anti-flammability cross-linked composition described in claim 1,2 or 3, wherein this vistanex is the resin of selecting from one group of material that polyethylene, ethene-alpha-olefin copolymer, ethylene-propylene copolymer, ethene-vinyl acetate copolymer, ethylene propylene diene rubber, ethylene-methyl acrylate copolymer, polymethyl acrylate, polyethyl acrylate, polymetaacrylate, ethylene acrylic rubber, HSBR and composition thereof are formed.
5, according to the anti-flammability cross-linked composition described in the claim 4, wherein said metal hydrate is a kind of material that chooses from one group of material that aluminium hydroxide, magnesium hydroxide, calcium hydroxide and basic magnesium carbonate are formed.
6, according to the anti-flammability cross-linked composition described in the claim 5, wherein said metal hydrate carries out surface treatment with a kind of material in aliphatic acid, phosphate, silane coupler and the titanate coupling agent.
7, a kind of anti-flammability cable includes:
(a) cable core that a sub-heart yearn or a plurality of sub-heart yearn are intertwined and form, said sub-heart yearn has the lead that coats with electrical insulating material, and said insulating material is made by certain not halogen-containing material,
(b) at the crust of the peripheral parcel of cable core, said crust is made with the anti-flammability cross-linked composition, and the manufacture process of said composition comprises:
(c) will be mixed with the vistanex of silane grafting by first compound that vistanex and metal hydrate are formed, make second compound, said two kinds of resins are all not halogen-containing,
(d) with said second compound of crosslinked with silicane, make the anti-flammability cross-linked composition,
(e) said metal hydrate combined amount therein is, the metal hydrate that contains about 50 to 200 parts of weight in the vistanex of the vistanex of per 100 parts of common weight and silane grafting, the combined amount of the vistanex of Ji Suaning is about (100-X) by weight, X is the silane grafted polyolefin resin consumption in the formula, 20≤X≤80 weight portions.
8, according to claim 7 described anti-flammability cables, wherein first compound also contains carbon dust, and its content quite contains about 5 to 70 parts of weight carbon dusts in the vistanex of the vistanex of per 100 parts of common weight and silane grafting.
9, according to claim 8 described anti-flammability cables, wherein said first compound also contains red phosphorus combustion inhibitor, the consumption of said red phosphorus combustion inhibitor is equivalent to contain in the vistanex of the vistanex of per 100 parts of common weight and silane grafting the red phosphorus of about 2 to 50 parts of weight.
10, according to claim 7,8 or 9 described anti-flammability cables, wherein also comprise one deck and be placed on flame barrier between cable core and the crust, said flame barrier is to constitute by the incombustibility belt that overlapped way is wrapped in around the cable core.
11, according to claim 10 described anti-flammability cables, wherein said incombustibility belt is metal tape, contain a kind of among the composite band that the inorganic band of vast scale pottery and metal tape and inorganic band form.
12, according to claim 11 described anti-flammability cables, wherein said inorganic band, be mica-polyester laminated tape, glass bonded mica band, mica-paper composite band, mica-paper laminated tape, asbestos yarn, the glass tape that scribbles silicone, the glass tape that scribbles alkyd resin coating, alumina melt reel off raw silk from cocoons band, silicon dioxide melt reel off raw silk from cocoons band, with alumina melt reel off raw silk from cocoons composite band that fiber and glass fibre make, with reel off raw silk from cocoons a kind of among composite band that fiber and glass fibre make and the aluminium oxide-glass laminated tape of silicon dioxide melt.
13, according to claim 10 described anti-flammability cables, wherein said flame barrier be use by oxygen index be 35 or the anti-flammability band made of higher organic material constitute.
14, according to claim 10 described anti-flammability cables, but also include the carbonization belt between cable core and flame barrier, but but said carbonization belt is to utilize the method for twining carbonization zone around said cable core to make, but carbonization takes place in said carbonization zone when cable runs into high temperature.
15, according to claim 14 described anti-flammability cables, but wherein said carbonization zone, be from by brown paper, acrylic fiber cloth, adhesive fabric, native cellulose fibre and be impregnated with silicone lacquer or material group that these materials of alkyd resin coating are formed a kind of material of choosing make.
16, according to claim 14 described anti-flammability cables; also comprise the barrier layer protected layer that is used for said flame barrier is carried out mechanical protection and heat protection, said barrier layer protected layer is between said flame barrier and crust and be to constitute by twining at least one method of making band by asbestos, glass fibre or ceramic fibre.
17, according to claim 10 described anti-flammability cables; also comprise the barrier layer protected layer between flame barrier and crust; said barrier layer protected layer is used for said flame barrier is carried out mechanical protection and heat protection, and is to constitute by twining at least one method of making band by asbestos, glass fibre or ceramic fibre.
18, according to the anti-flammability cross-linked composition described in claim 7,8 or 9, wherein said metal hydrate is a kind of material that chooses from the material group that aluminium hydroxide, magnesium hydroxide, calcium hydroxide and basic magnesium carbonate are formed.
19, according to the anti-flammability cross-linked composition described in the claim 18, wherein said metal hydrate is with in addition surface treatment of a kind of material in aliphatic acid, phosphate, silane coupler and the titanate coupling agent.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59043138A JPS60189114A (en) | 1984-03-07 | 1984-03-07 | Flame resistant cable |
| CN85101356A CN85101356B (en) | 1984-03-07 | 1985-04-01 | Flame-retardant cross linking composite and flame-retardant cable thereby |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59043138A JPS60189114A (en) | 1984-03-07 | 1984-03-07 | Flame resistant cable |
| CN85101356A CN85101356B (en) | 1984-03-07 | 1985-04-01 | Flame-retardant cross linking composite and flame-retardant cable thereby |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101356A true CN85101356A (en) | 1987-01-10 |
| CN85101356B CN85101356B (en) | 1987-10-28 |
Family
ID=25741393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85101356A Expired CN85101356B (en) | 1984-03-07 | 1985-04-01 | Flame-retardant cross linking composite and flame-retardant cable thereby |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS60189114A (en) |
| CN (1) | CN85101356B (en) |
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| US8378009B2 (en) | 2007-05-31 | 2013-02-19 | Autonetworks Technologies, Ltd. | Process of producing flame-retardant silane-crosslinked olefin resin, insulated wire, and process of producing insulated wire |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN85101356B (en) | 1987-10-28 |
| JPS60189114A (en) | 1985-09-26 |
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