Fire-resistant self-quenching cable or wire

FIELD: motor- and ship-building industries, mechanical and construction engineering, oil extraction, and oil-refining industry.

SUBSTANCE: proposed electric wire or cable has multicore copper conductor with core sectional area of 1.0 to 50 mm2 and rubber sheath, 0.4 to 7.0 mm thick, made of composite material based on rubber mixture incorporating mixture of high-molecular polymethylvinylsiloxane rubber and low-molecular polymethylvinylsiloxane rubber as polymeric matrix with molar mass of 20 000 to 70 000 in combination with probably stearic acid, fire-protective filler, dehydrating agent, silica powder, quartz crystal, anti-structuring agent (α, ω-dihydroxydimethylsiloxane), organic peroxide, and water repellant (silicone liquid). Composite material is applied by extrusion at a rate of 0.2-2 m/s and cured in radiation-chemistry curing mode under action of either vapor at pressure of 12-18 at or cobalt gun using gamma-ray source at dose rate of 2.5-20 Mrad, and/or by thermal curing. Electric cable or wire covered with such sheath is characterized in ability of self-quenching fire and can be used at temperatures ranging between -60 and +300 °C.

EFFECT: enhanced crack, oil, and gasoline resistance, flexibility, and electrophysical characteristics of cable or wire.

3 cl 1 tbl

 

The invention relates to the technology of polymeric materials used in electrical, chemical industry for production of polymeric materials, in particular in the manufacture of wires and cables.

Known cable with rubber protective shell composed of two layers: on top of the twisted insulated conductors impose a composition for formation of the inner layer of the shell, containing, by mass: ethylenepropylene rubber 100,0; bestratebadcreditloans of 6.5-7.5; sulfur is 0.04 to 0.6; dioxin 1,1-diacetylhydrazine 1,3-1,8; zinc white 4-6; dispersant 2,4-3,6; plasticizer 25-35; carbon 45-65; chalk natural 345-365, when the thickness of the inner layer of the shell provide equal 30-50% and vulcanization is carried out at a gauge pressure of 1.57 to 1.76 MPa and a temperature 193-196°WITH (EN 2024974).

A method of manufacturing such a cable is not practically feasible, because it foresees the use of high temperatures to the same cable does not have the necessary fire resistance.

Self-extinguishing cables, typically made by extrusion on top of the core cable fire retardant coating consisting of a polymer composition, which has a predetermined flame-retardant properties by adding appropriate additives. For this purpose, for instance, can be used songs to the Snov, polyolefins, for example, on the basis of polyethylene or copolymer of ethylene/vinyl acetate containing organic halide, in combination with antimony trioxide as a flame retardant additive. However, halogenated flame retardants have many drawbacks, since they partially decompose during processing of the polymer, leading to the separation of halogenated gases that are toxic to workers and corrosive to metal parts of equipment for processing of the polymer. In addition, when they get directly into the fire, their combustion leads to very large quantities of smoke containing toxic gases. Similar disadvantages occur when as a polymer base used polyvinyl chloride (PVC) with the addition of antimony.

Thus, in recent years is the use of halogen-free compounds in the production of self-extinguishing cables, in which the polymer base, as a rule, the type of polyolefin is mixed with inorganic flame retardant fillers, as a rule, hydroxides, hydrated oxides or hydrated salts of metals, in particular aluminum or magnesium, such as magnesium hydroxide or aluminum trihydrate, or mixtures thereof (see, for example, U.S. patent No. 4145404, 4673620, EP 328051 and EP 530940).

For these purposes, inorganic order the teli can be used insofar because they are covered with various hydrophobic substances, for example, saturated or unsaturated fatty acids or their salts, in particular oleic acid or stearic acid, or the corresponding oleates or stearates, or organosilane, or titanates.

For example, patent application WO 96/27885 describes a fire-retardant composition for coating electric cables containing polypropylene as the polymer matrix, supplemented 1-20 wt.% polyethylene wax and 100 to 200 wt.% of magnesium hydroxide coated with a hydrophobic product, such as alkylsilanes (wt.% in relation to the weight of the polypropylene). This coating, as mentioned, increases the compatibility between the filler and polymer matrix and at the same time imparting hydrophobic properties of fire-retardant coating, thus, prevents the absorption of moisture, which would reduce the efficiency of the insulating properties of the material.

The patent application of Japan Jp-07-161-230 (Kokai) describes polymer compositions with flame-retardant properties, containing appropriately crushed natural magnesium hydroxide, which is subjected to surface treatment with a fatty acid or a salt thereof, or using silane or titanate, in amounts in the range between 0.5 and 5 wt.% in relation to the weight of the hydroxide. As described in this behind the VCE patent surface treatment of the filler, as it is written, making it possible to reduce moisture, thus preventing the impact of water vapor released their filler during extrusion of the composition on the cable, in the form of some kind of expansion of the material and deterioration of the appearance of the surface of the thus obtained cable.

Known flexible electrical wire and method of its manufacture, which contains spaced rubber insulated wires and a two-layer shell. The inner layer of the shell is made of a polymer composition based on atactic polypropylene and rubber crumb in the ratio of 1:1-1,5. The outer layer is a solid rubber. As technological additives in the polymer composition is injected stearin, talc, light carbon black (SU 1305782, 1987). The main drawback of a wire is that used for the inner layer composition is combustible and therefore it cannot be used in many industries.

Known electric wire obtained in the following way (EN 1438501, 1996). On a conductive core sequentially carry out the imposition of a three-layer insulation first (adjacent to the vein, designed to align the electric field between the housing and the core insulation layer, which is made from a composition containing siloxane rubber, the flint is slightly filler, antistructuring additive, plasticizer, thermo stabilizer, low temperature and vysokotemperaturnoi organic peroxide, after applying it on mine extrusion is passed through the vulcanizing chamber, strengthen heat treatment in the regime of low-temperature curing organic peroxide at 120-140°With, also impose extrusion of the second layer of primary insulation, which is used as insulation containing low-density polyethylene, thermo stabilizer, an epoxy resin, a copolymer of ethylene with vinyl acetate, an activator and a high-temperature organic peroxide, cooled to 80-90°place the third layer, which is used as the first layer, pass through a vulcanizing chamber, strengthen heat treatment in the regime of low temperature vulcanization peroxide at atmospheric pressure, impose the lead or aluminium sheath is passed through the vulcanizing chamber and vulcanized mode vulcanization temperature of peroxide at 180-220°C.

However, the technology of receipt of such electrical wires complicated, involves the use of to obtain rubber insulation rubber mixture of complex composition, which does not provide the necessary high properties in heat resistance, cold resistance, fire resistance.

Most BL is skim to offer the technical essence is an electric wire, containing the conductors and rubber, in the manufacture of which is imposed isolation rubber type RTI-1 with the conductive screen of rubber type ER-2 with a specific electrical resistance of less than 0.8 Ohms. On twisted vein of superimposed two-layer shell on a twin-screw continuous vulcanization when the steam pressure 12-16 kgf/cm2. For the outer layer is applied rubber type RSN-1 based on chloroprene rubber, including zinc, captax, diphenylguanidine, burnt magnesia, stearin, paraffin wax and carbon black. For the inner layer is applied rubber stamps GSR-25 based on chloroprene rubber, including 2-mercaptobenzthiazole, diphenylguanidine, zinc white, burnt magnesia, phenyl-2-naphtylamine, stearin, paraffin, dibutyl phthalate, chalk and carbon black. The main drawback of a wire is the high cost, the use of scarce materials, including imported (chloroprene rubber), toxicity (EN 2028681 C1, 09.02.1995).

The technical objective of the claimed invention is the improvement of wear resistance, tear resistance, crack resistance, heat resistance, cold resistance, resistance to diesel fuel, malebestiality, improving electrical insulation properties, fire resistance, i.e. the production of an essentially self-extinguishing room is La and wires. The goal of the project is achieved in that the electric wire or cable with rubber insulation containing copper stranded wire and the sheath of vulcanized rubber insulation, contains copper stranded wire with a cross section of the conductors of 1.0-50 mm2the vulcanized rubber shell with an outer diameter of 0.4-7.0 mm, made of oil and petrol resistant composite material containing parts by weight of:

high-molecular methylvinylsiloxane rubber70-80
low-molecular methylvinylsiloxane rubber
with mol. weight 20-70 thousand20-30
Aerosil40-50
powdered quartz170-200
antistructure agent -
α,ω-dihydroxydiphenylsulfone8-10
organic peroxide1,5-2,0
water-repelling liquid
silicone1,8-8,0
stearic acid0-1,5
dehydrating agent0-3,0
fire-retardant filler0-30,0

struck the frame extrusion speed lines 0.2 to 2.0 m/sec and vulcanized on the treatment of radiation-chemical vulcanization under the action of cobalt gun m source γ radiation with a radiation dose of 2.5-20 Mrad, or by the method of combined radiation and chemical and thermal vulcanization or jointly under the action of steam at a pressure of from 12 to 18 atmospheres and method of thermal vulcanization.

Rubber insulation may be vulcanized by the method of two-stage thermal vulcanization, for example at 120-150°C for 15-30 min, then at 180-200°With speed lines, such as 0.2-0.3 m/sec.

Shell rubber insulation may be vulcanized by the method of combined radiation and thermal vulcanization, and at first by the method of radiation-chemical vulcanization using a cobalt gun placed in front of the vulcanizing chamber, and then one-step thermal vulcanization at 170-180°C.

As a polymer base for receiving a rubber isolation using high-molecular polymethylvinylsiloxane (methylvinylsiloxane) rubber, for example brands SKTV and SKTV-1, and low-molecular methylvinylsiloxane rubber, for example of the formula HO((CH3)SiO)m((CH3)(CH2CH)SiO)nH, where m, n is the molar content of units, and m+n=100 mole%; m=98,5-of 99.85 mol.%; n=0,15-1,5 mol.%, with a molecular mass of 20-70 tised

The use of this rubber compound for the composite material in the claimed invention, containing as p the polymer matrix (basis) mixture of high-molecular polymethylvinylsiloxane rubber and low molecular weight polymethylvinylsiloxane rubber with the specified molecular weight in combination with an organic peroxide, antistructuring agent of this structure, water repellent and fillers leads to formirovanie in the vulcanizate more perfect and dense patterns break the grid and, in addition, high concentrations of particulate silica in the mixture compared to traditional in combination with experimentally selected qualitative and quantitative composition of the entire mixture, the thickness of the rubber shell and conditions of vulcanization allows the complex to get cable or electric wire with good physico-mechanical properties, high resistance to gasoline, oils and organic solvents, and high electrical insulating properties and is virtually non-flammable - samozatuhaniya.

As Aerosil ispolzuemaya rubber mixture contains, for example, aerosol brands a-175, A-300 and other

As the organic peroxide compound may contain various organic peroxides, traditionally used for the rubber mixtures, such as, for example, benzoyl peroxide, peroxide 2,4-dichlorobenzoyl, peroxide Dicumyl, peroxide tert-butylperbenzoate and others. In most cases, as it is known the use of different peroxides in equivalent dosages allows to obtain rubber with similar physical-mechanical properties.

As the dehydrating agent to the positional material (cable or wire) contains the oxides of magnesium, calcium or barium, or aluminum, the zeolite.

As a flame retardant filler composite material may contain, for example, hydrated hydroxides of calcium, magnesium, aluminium, calcium carbonate, magnesium carbonate.

If the vulcanization is carried out by combining exposure and thermal obrabotki, after forming the rubber coating on the copper wire then carry out the vulcanization first by treatment with steam at a pressure of from 12 to 18 atmospheres, and then carry out thermal cure at 170-180°C.

As a water-repelling silicone fluid composite material contains, for example, polyethylene or polymethylhydrosiloxane liquid type NGL-94.

Imageresize cable according to the invention receives, for example, the following technologies:

(a) preparing a flame retardant composition comprising a polymer base, inorganic flame retardant filler; and other additives target;

(b) ekstragiruyut specified fire retardant composition on top of the electrical conductor, which is optional, is pre-coated with an insulating layer, the receiving layer of fire retardant coating rubber;

when the specified fire retardant composition may be added dehydrating agent.

A specific example of the preparation used compositio the aqueous material. In the mixer type M-1 with Z-shaped working blades and speed 20-28 per minute, cooled by water at a temperature of 20-30°With load and mixed 80 parts by weight of high molecular methylvinylsiloxane rubber, 40 parts by weight of Aerosil may stearic acid and 0.8 parts by weight, 8 parts by weight of antistructuring agent - product SU-8 pre-mixed 20 parts by weight of low-molecular methylvinylsiloxane rubber obsession to 0.72 mol. % methylvinylsiloxane units and a molecular mass of 55 thousand with 190 parts by weight of powdered quartz, dehydrating agent is calcium oxide to 1.0 parts by weight and Al(OH)3to 20.0 parts by weight of the Mixing is carried out to achieve uniformity of mass, then include the heating of the mixer. After the temperature reaches 170°the mixture is heated within 30-50 minutes. Then heating is stopped and the rubber mixture with stirring, cooled to room temperature. Cool rubber mixture injected silicone fluid - polyethylsiloxane to 1.5 parts by weight of organic peroxide - 2,4-dichlorobenzoyl. Next, the rubber mixture ekstragiruyut and put on a moving twisted vein thickness of 1.0-50 mm (stranded copper wire) with the speed of the line of 0.2-2 m/sec and the thickness of the shell 0.4 to 7.0 mm and down the line vulcanization, where they perform vulcanization or under the action of steam under pressure and from 12 to 18 atmospheres, or combined radiation and chemical using a cobalt gun (source γ-radiation), located in front of the camera thermal vulcanization and a radiation dose of 2.5 Mrad 10 Mrad and 20 Mrad, and then the wire is coated with rubber jacket arrives in the vulcanizing chamber (trumpet) and perform one-step thermal curing at a temperature of 170-180°C. If the vulcanization is carried out only heat, it is carried out usually in 2 stages, first by 120-150°C, pressure of not less than 3.5 MPa for 15-30 min, and then carry out a second stage at a temperature of 180-200°C for 6 hours.

As radiation-technical installation using cobalt installation type PB-1200, RUE-400, the AEG-500 etc.

Use when receiving an electric wire or cable of a specific rubber compound applied by extrusion on a conductive core of a certain thickness at a certain speed in combination with the subsequent vulcanization conditions allows to provide a uniform degree of vulcanization and to receive the wire with high performance properties, minimal toxicity, non-flammable.

Table 1 presents examples of composite material - rubber compound used in the preparation of rubber insulation cable or automotive wire according to the invention.

According to this invention have the cable or automotive wire with the thickness of the conductors 1.0 mm, 1.5 mm, 2.5 mm, 6.0 mm, 10 mm and 50 mm

The concept of automotive wire is conditional and does not limit the use of it.

This cable or wire can be used in the power industry, oil production and refining, construction, engineering, shipbuilding and automotive.

The cable or wire can withstand the operation mode from -68 to +320°; ogneuporami, nerasprostranenii flame (self-extinguishing), oil and petrol resistant, acid-alkali resistant, eliminates the risk of fire from short circuit protection, moisture-proof. The cable or wire, for example with the number of cores 19 has passed the test for resistance to punching shear 8 h at 180+3°on resistance mounting and operating curves at low temperature 2 h at -60°on resistance to exposure to elevated temperature for 96 h at 200°With; on resistance to heat shrinkage, malebestiality and resistance to diesel fuel, onthe proliferation of fire, a test voltage of 1000 V in (EI-1 according to GOST 23386-78)to determine the electrical insulation resistance: test results of the electrical resistance of the conductors is established that the resistance of the cable or wire with a length of 50 m was 0,882 Ohms, the resistance of the cable 10 m - 0,179 Ohms, which translated into 1 km of wire is 17.6 and 17.9 Ohms.

According to the results of IP is of itani isolation voltage 1000 V for 1 min set, the insulation of the cable or wire without breakdown withstood the test; after exposure to an open flame for 60 seconds, the burning wire is stopped, i.e. practically according to the invention receive self-extinguishing electrical wire or cable, which greatly expands the area of its use.

Tests for fire resistance of cables and wires is carried out in accordance with GOST 12176-89 (during the testing of single wire) on samples wires PRA, PHRA.

After removal of the burner flame goes out, on the surface of the wire (cable) there are no traces of soot, were not detected charring and damaged parts that confirms their non-Flammability, non-fire, samostojatelnosti them.

Additional samples of wires, the cable was maintained when exposed to flame for 3 to 10 minutes. When removing the burner flame goes out, the length of the undamaged section of the wires from 330 to 400 mm from the bottom edge to the top of the clip.

Table 1
The ingredients of the rubber compoundThe content of chemicals in rubber compounds, parts by weight, in examples No.
123456**K7**8**
You homomolecular methylvinylsiloxane 8080707075758570
Low-molecular methylvinylsiloxane rubber, (mol.% methylvinylsiloxane
0,15 mol.%, 20 tised-20------
to 0.72 mol.%, 55 production20-30-25--30
a 1.5 mol.%, 70 tised---30----
of 1.85 mol.%, 92 production-----25--
0,09 mol.%, 12 th ed------15-
Aerosil4050494540356040
Palevic the first quartz 190200180170190190150220
Antistructure agent89910910127
**Silicone fluid1,887521,0-9
Peroxide 2,4-DHB1,5-1,8-21,52,21,5
Precsion P-40-2-1,5---1,3
Dehydrating agent (calcium oxide-1,03,0-----
Fire-retardant filler-20,025,0-----
Stearic acid-0,81,5-----
** IP is result polyethylsiloxane liquid NGL-94

1. Electrical cable or wire with self-extinguishing rubber insulation containing copper stranded wire and the sheath of vulcanized rubber insulation, characterized in that it contains copper stranded wire with a cross section of the conductors with a diameter of 0.4÷7.0 mm, made of oil and petrol resistant rubber mixtures containing, parts by weight:

High-molecular methylvinylsiloxane
rubber70÷80
Low-molecular methylvinylsiloxane
rubber mol. wt. 20÷70 thousand20÷30
Aerosil40÷50
Powdered quartz170÷200
Antistructure agent -
α,ω-dihydroxydiphenylsulfone8÷10
Organic peroxide1,5÷2,0
Water-repelling
silicone fluid1,8÷8,0
Stearic acid0÷1,5
Dehydratase agent0÷3,0
Fire-retardant filler0

applied by extrusion with the speed of the line, 0,2÷2.0 m/s and vulcanized on the treatment of radiation-chemical vulcanization under the action of cobalt gun source γ-radiation with a radiation dose of 2.5÷20 Mrad, or by the method of combined radiation and chemical and thermal vulcanization, or under the action of steam at a pressure of from 12 to 18 ATM and method of thermal vulcanization.

2. Electrical cable or wire with rubber insulation according to claim 1, characterized in that the shell of vulcanized rubber isolation by the method of two-stage thermal vulcanization at 120÷150°C for 15÷30 minutes, then at 180÷200°C.

3. Electrical cable or wire with rubber insulation according to claim 1, characterized in that the shell of vulcanized rubber isolation according to the method of combined radiation and thermal vulcanization, and at first by the method of radiation-chemical vulcanization, and then one-step thermal vulcanization at 170÷180°C.



 

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