CN103819758A - Flame-retardant fire-resistant rubber composition and preparation method thereof, and flame-retardant fire-resistant rubber wrapping tape - Google Patents
Flame-retardant fire-resistant rubber composition and preparation method thereof, and flame-retardant fire-resistant rubber wrapping tape Download PDFInfo
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Abstract
The invention provides a flame-retardant fire-resistant rubber composition and a preparation method thereof, and a flame-retardant fire-resistant rubber wrapping tape. The flame-retardant fire-resistant rubber composition is prepared from the following components in parts by mass: 50-120 parts of an organic polymer, 10-100 parts of a reinforcing filler, 20-80 parts of a non-reinforcing filler, 5-120 parts of a flame-retardant agent, 0.1-5 parts of a coupling agent, 1-30 parts of a liquid operation oil, and 1-10 parts of a curing agent. The flame-retardant fire-resistant rubber composition and the preparation method thereof and the flame-retardant fire-resistant rubber wrapping tape have the advantages of excellent flame-retardant fire-resistant performance, good elasticity, good flexibility, simple and safe use and lower cost.
Description
Technical field
The present invention relates to flame-retardant material technology field, particularly a kind of flame-retardant rubber combination, preparation method and fire resistant flame retardant rubber band.
Background technology
The flame retardant resistance of material of construction and under fire condition, keep supply of electric power and communication unimpeded, to resident safety with effectively fire-fighting is extremely important.Therefore many countries have worked out the safety standards of material of construction under fire condition. there is BS6387CWZ for flame resistant cable, DIN4102, UL2196, EN50200, IEC60331-11, NFC32070CR1, the standards such as GB12666.6.
At present, flame resistant cable mainly adopts mica tape and magnesium oxide mineral insulation to realize the function of flame-retardant.There is following defect in mica tape insulated flame-resistant cable: one, mica tape products of combustion powder of detached under fire condition, be difficult to the severe scene of fire environment such as tolerance vibration and spray, and therefore its fire resistance rating is not high; Two, mica tape is short in the memory cycle, can absorb airborne moisture, reduces its electrical property, even can cause delamination to affect it and normally use.Magnesium oxide mineral insulated cable fire performance excellence, but its tooling cost is high, needs Special complete equipment, it is installed, lays and also have particular requirement simultaneously.Therefore,, in the urgent need to a flame-retardant excellent performance, reasonable price, and the material of easy handling, to meet the requirement of modern cable industry to flame resistant cable.
Summary of the invention
The object of the invention is to propose a kind of flame-retardant rubber combination, preparation method and fire resistant flame retardant rubber band, both had good flame-retardant performance, have again good elasticity and flexibility, and use simple and safely, cost is lower.
For achieving the above object, the present invention proposes a kind of flame-retardant rubber combination, it is formulated by mass parts by following composition:
Organic polymer 50-120 part, reinforcement filler 10-100 part, non-reinforcement filler 20-80 part, fire retardant 5-120 part, coupling agent 0.1-5 part, fluid operated oily 1-30 part and solidifying agent 1-10 part.
Further, in above-mentioned flame-retardant rubber combination, described organic polymer is one or more in natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), terpolymer EP rubber, isoprene-isobutylene rubber, ethylene-vinyl acetate copolymer, methyl vinyl silicone rubber, methyl silicone rubber, phenyl siloxane rubber, penylene base silicon rubber.
Further, in above-mentioned flame-retardant rubber combination, described reinforcement filler is that carbon black, the specific surface area that particle diameter is less than 40 nanometers is greater than 50m
2one or more in the precipitated silica of/g, thermal silica, modified white carbon black.
Further, in above-mentioned flame-retardant rubber combination, described non-reinforcement filler is silicates glass powder, borate family glass powder, phosphate-based glass powder, one or more in calcium carbonate, potter's clay, mica powder, silica powder, wilkinite, vermiculite, diatomite, Calucium Silicate powder, zirconium silicate, zeolite, ferric oxide, zinc oxide, magnesium oxide, aluminum oxide, cerium oxide, titanium oxide.
Further, in above-mentioned flame-retardant rubber combination, described fire retardant is one or more in aluminium hydroxide, magnesium hydroxide, zinc borate, platinum fire retardant, silicone flame retardant.
Further, in above-mentioned flame-retardant rubber combination, described coupling agent is one or more in vinyltriethoxysilane, methyltriethoxy silane oxygen, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane.
Further, in above-mentioned flame-retardant rubber combination, described fluid operated oil is one or more in paraffin oil, naphthenic oil, methyl-silicone oil, hydroxy silicon oil, dimethyldiethoxysilane.
Further, in above-mentioned flame-retardant rubber combination, described solidifying agent is sulfocompound, 1, two (the di-t-butyl peroxies)-3 of 1-, 3,5-trimethyl-cyclohexane, 2,5-dimethyl-2,5-bis-(benzoyl peroxy) hexane, 1,4-dual-tert-butyl peroxide diisopropyl benzene, the tertiary fourth fat of benzoyl hydroperoxide, diisopropylbenzyl superoxide, tert butyl isopropyl benzene peroxide, 2,5-dimethyl-2,5-bis-(t-butylperoxy)-3-hexin, 2, one or more in 4-dichlorobenzoperoxide (two two, four).
The present invention also provides a kind of preparation method of above-mentioned flame-retardant rubber combination, comprises the following steps:
Organic polymer in above-mentioned flame-retardant rubber combination, reinforcement filler, non-reinforcement filler, fire retardant, coupling agent, fluid operated oil are carried out at not higher than 180 ℃ in rubber mixing machine mixing evenly, obtain dough composition, described dough composition is placed cooling at least 2 hours;
Cooled doughy mix is opened to refining in mill, then by the slitting shape of mixture of opening after refining;
Above-mentioned strip mixture is filtered on rubber strainer;
The solidifying agent appropriate according to the different choice of described organic polymer, is added into this solidifying agent in the mixture after filtration, to carry out mixingly by mill, obtains described flame-retardant rubber combination.
The present invention also provides a kind of fire resistant flame retardant rubber band, comprise flame-retardant fabric, this flame-retardant fabric coating or be stained with above-mentioned flame-retardant rubber combination, described flame-retardant fabric is one or more of carbon fibre fabric, glasscloth, ceramic fiber fabric and organic fabrix.
Flame-retardant rubber combination of the present invention, preparation method and fire resistant flame retardant rubber band had both had good flame-retardant performance, had again good elasticity and flexibility, and used simple and safely, and cost is lower.
Embodiment
Below in conjunction with describing the preferred embodiments of the present invention in detail.
The invention provides a kind of flame-retardant rubber combination, it is formulated by mass parts by following composition:
Organic polymer 50-120 part, reinforcement filler 10-100 part, non-reinforcement filler 20-80 part, fire retardant 5-120 part, coupling agent 0.1-5 part, fluid operated oily 1-30 part and solidifying agent 1-10 part.
The each composition quality ratio of above-mentioned flame-retardant rubber combination is preferably: 100 parts of organic polymers, 40 parts of reinforcement fillers, 60 parts of non-reinforcement fillers, 70 parts of fire retardants, 2 parts of coupling agents, 8 parts, fluid operated oily 10 parts and solidifying agent.
Wherein, described organic polymer is one or more in natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), terpolymer EP rubber, isoprene-isobutylene rubber, ethylene-vinyl acetate copolymer (EVA), methyl vinyl silicone rubber, methyl silicone rubber, phenyl siloxane rubber, penylene base silicon rubber.
Described reinforcement filler is that carbon black, the specific surface area that particle diameter is less than 40 nanometers is greater than 50m
2one or more in the precipitated silica of/g, thermal silica, modified white carbon black.
Described non-reinforcement filler is silicates glass powder, borate family glass powder, phosphate-based glass powder, one or more in calcium carbonate, potter's clay, mica powder, silica powder, wilkinite, vermiculite, diatomite, Calucium Silicate powder, zirconium silicate, zeolite, ferric oxide, zinc oxide, magnesium oxide, aluminum oxide, cerium oxide, titanium oxide.
Described fire retardant is one or more in aluminium hydroxide, magnesium hydroxide, zinc borate, platinum fire retardant, silicone flame retardant.
Described coupling agent is one or more in vinyltriethoxysilane, methyltriethoxy silane oxygen, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane.
Described fluid operated oil is one or more in paraffin oil, naphthenic oil, methyl-silicone oil, hydroxy silicon oil, dimethyldiethoxysilane.
Described solidifying agent is sulfocompound, 1, two (the di-t-butyl peroxies)-3 of 1-, 3,5-trimethyl-cyclohexane, 2,5-dimethyl-2,5-bis-(benzoyl peroxy) hexane, 1,4-dual-tert-butyl peroxide diisopropyl benzene, the tertiary fourth fat of benzoyl hydroperoxide, diisopropylbenzyl superoxide, tert butyl isopropyl benzene peroxide, 2,5-dimethyl-2,5-bis-(t-butylperoxy)-3-hexin, 2, one or more in 4-dichlorobenzoperoxide (two two, four).
Flame-retardant rubber combination of the present invention is to be cross-linked formulated by the multiple material with excellent flame retardancy energy, it is at aerobic, has and in flame and/or anaerobic, aphlogistic situation, form fire-retardant, fire insulation, heat insulation mineral inorganic salt composition, said composition not only has the mechanical property that elastomerics is good, the tensile strength for example improving, also show excellent good electrical property, volume specific resistance can reach 2 × 10
15Ω cm, voltage breakdown is greater than 22KV/mm, in the time of fire, forms by burning, high temperature the duricrust shape body that has good electrical insulating property and have physical strength.
The present invention also provides a kind of preparation method of above-mentioned flame-retardant rubber combination, and it comprises the following steps:
Organic polymer in above-mentioned flame-retardant rubber combination, reinforcement filler, non-reinforcement filler, fire retardant, coupling agent, fluid operated oil are carried out at not higher than 180 ℃ in rubber mixing machine mixing evenly, obtain dough composition, described dough composition is placed cooling at least 2 hours;
Cooled doughy mix is opened to refining in mill, then by the slitting shape of mixture of opening after refining;
Above-mentioned strip mixture is filtered on rubber strainer;
The solidifying agent appropriate according to the different choice of described organic polymer, is added into this solidifying agent in the mixture after filtration, to carry out mixingly by mill, obtains described flame-retardant rubber combination.
The present invention also provides a kind of fire resistant flame retardant rubber band, and it comprises flame-retardant fabric, this flame-retardant fabric coating or be stained with above-mentioned flame-retardant rubber combination.
Described flame-retardant fabric is one or more of carbon fibre fabric, glasscloth, ceramic fiber fabric and organic fabrix, and described flame-retardant fabric is the fiber mixed fabrics that comprises mentioned component.
While preparing this fire resistant flame retardant rubber band, above-mentioned flame-retardant rubber combination can be applied or sticks on this flame-retardant fabric and be heating and curing, again the flame-retardant fabric after solidifying is cut, form the fire resistant flame retardant rubber band with good fire resistant flame retardant performance.
The present invention also provides the purposes of above-mentioned flame-retardant rubber combination or fire resistant flame retardant rubber band, and its purposes includes but not limited to following aspect:
1, as insulation layer, flame retardant coating and the restrictive coating material of electric wire, the material of this layer contains flame-retardant rubber combination.In the time manufacturing electric wire, can adopt forcing machine to extrude insulation moulding, before extruding, add above-mentioned solidifying agent;
2, as insulation layer, flame retardant coating and the restrictive coating material of electric wire, material contains flame-retardant rubber combination or fire resistant flame retardant rubber band.Manufacturing when electric wire, can adopt forcing machine to extrude insulation moulding or wrapping machine is wrapped on electric wire.
By above-mentioned flame-retardant rubber combination by extruding on electric wire, or by coated on electric wire above-mentioned fire resistant flame retardant rubber band, it is greater than under 320 ℃ of environment and can be converted into inorganic housing shape thing by elastomerics state in temperature, the flame-retardant and fire-resistant wire and cable of producing can pass through A level fire-retardant fireproof refractory standard, also can meet at present the most harsh external spray, the CWZ level fire-retardant fireproof refractory standard of vibrations simultaneously; This composition of while is nontoxic, harmless, heavy metal free, and the flue gas after burning is nontoxic, harmless to human body, can reach organism highest level ZA1 grade standard, and transmittance can reach more than 80%.
Above-mentioned flame-retardant rubber combination or fire resistant flame retardant rubber band are as the material of electric wire, and the fire-resistant wire and cable making according to the method described above, requires to conform to through test result and the RoHS Directive 2002/95/EC of SGS test; Through national fire-proof construction material Quality Supervision and Inspection Center to flue gas toxity assay be, judge according to GB/T20285, this material flue gas toxity reaches accurate safe one-level (ZA1); By the fire-resistant test of 90min, meet GB GB/T12666.6; Meet the standard-required of BS6387.
Than prior art, flame-retardant rubber combination of the present invention, preparation method and fire resistant flame retardant rubber band are a kind of novel polymer composites, be easy to processing, production cost is low, nontoxic at normal temperatures, tasteless, there is good flexibility and elasticity, possesses the characteristic of General Purpose Rubber and rubber band, can be under 330-3000 ℃ of high temperature that has flame or a nonflame, through being converted to shelly body in 90-180min and above time, rather than quilt is burnt till powdery ashes, this shelly body forms the hard protective layer of one deck, this protective layer stops burning away of flame, play the effect of isolated extraneous flame, thereby electric wire or protected object that protection is burnt are not damaged.Moreover, the minute mist that flame-retardant rubber combination of the present invention and the fire resistant flame retardant rubber band that contains said composition produced within 1-2 minute ablation initial stage, detecting through third party is also nontoxic, halogen, heavy metal free, and giving up smoking completely after burning 2～3 minutes, and in the process that stops flame, itself also no longer produces smog, is a kind of fire-retardant, fire-resistant macromolecular material with excellent oxygen index, smoke density and electrical insulation capability.
To sum up, flame-retardant rubber combination of the present invention, preparation method and fire resistant flame retardant rubber band had both had good flame-retardant performance, had again good elasticity and flexibility, and used simple and safely, and cost is lower.
Below in conjunction with specific embodiment, flame-retardant rubber combination preparation method of the present invention (umber of composition unless otherwise indicated, is all in mass parts) is described:
Embodiment 1
Get 100 parts of natural rubbers, 50 parts of particle diameters are less than the carbon black of 40 nanometers, 1 part of vinyltriethoxysilane, 60 parts of silicate glass powder, 70 parts of aluminium hydroxides, 5 parts of methyl-silicone oils and 8 parts of sulfocompounds, make according to the preparation method of above-mentioned flame-retardant rubber combination.
After testing, the material performance of this flame-retardant rubber combination is as follows:
Tensile strength: 15MPa;
Elongation at break: 450%;
Disruptive strength: 14.5KV/mm;
Volume specific resistance: 1.2E+15;
Oxygen index: 29.
Embodiment 2
Get 100 parts of methyl vinyl silicone rubbers, 50 parts of thermal silicas, 5 parts of hydroxy silicon oils, 1 part of vinyltrimethoxy silane, 20 parts of borate glass powder, 90 parts of aluminium hydroxide and 3 part 2,4-dichlorobenzoperoxide (two two, four), make according to the preparation method of above-mentioned flame-retardant rubber combination.
After testing, the material performance of this flame-retardant rubber combination is as follows:
Tensile strength: 6.4MPa;
Elongation at break: 185%;
Disruptive strength: 20KV/mm;
Volume specific resistance: 5.12E+14;
Oxygen index: 35.
Embodiment 3
Get 100 parts of ethylene-vinyl acetate copolymers (EVA), 10 parts of specific surface areas are greater than 50m
2the precipitated silica of/g, 10 parts of methyl-silicone oils, 1 part of vinyl three ('beta '-methoxy oxyethyl group) silane, 100 parts of magnesium hydroxides, 50 parts of phosphate-based glass powder, 1 part of sulfocompound, make according to the preparation method of above-mentioned flame-retardant rubber combination.
After testing, the material performance of this flame-retardant rubber combination is as follows:
Tensile strength: 9.5MPa;
Elongation at break: 170%;
Disruptive strength: 13.5KV/mm;
Volume specific resistance: 1.15E+12;
Oxygen index: 37.
Embodiment 4
Get 100 parts of terpolymer EP rubbers, 50 modified white carbon blacks, 100 parts of aluminium hydroxides, 10 parts of paraffin oils, 1 part of vinyl three ('beta '-methoxy oxyethyl group) silane, 60 parts of borate glass powder and 5 parts of diisopropylbenzyl superoxide, make according to the preparation method of above-mentioned flame-retardant rubber combination.
After testing, the material performance of this flame-retardant rubber combination is as follows:
Tensile strength: 11.5MPa;
Elongation at break: 245%;
Disruptive strength: 15KV/mm;
Volume specific resistance: 1.56E+14;
Oxygen index: 36.
Embodiment 5
Get 50 parts of methyl silicone rubbers, 50 parts of modified white carbon blacks, 120 parts of zinc borates, 30 parts of naphthenic oil, 0.1 part of vinyltrimethoxy silane, 80 parts of borate glass powder and 10 parts of diisopropylbenzyl superoxide, make according to the preparation method of above-mentioned flame-retardant rubber combination.
Embodiment 6
Get 120 parts of cis-1,4-polybutadiene rubbers, 50 modified white carbon blacks, 5 parts of aluminium hydroxides, 1 part of hydroxy silicon oil, 5 parts of vinyl three ('beta '-methoxy oxyethyl group) silane, 60 parts of borate glass powder and 8 parts of diisopropylbenzyl superoxide, make according to the preparation method of above-mentioned flame-retardant rubber combination.
Above-mentioned flame-retardant rubber combination applied or sticks on this flame-retardant fabric and be heating and curing, then the flame-retardant fabric after solidifying is cut, can prepare the fire resistant flame retardant rubber band with good fire resistant flame retardant performance.
Here description of the invention and application is illustrative, not wants scope of the present invention to limit in the above-described embodiments.Here the distortion of disclosed embodiment and change is possible, and for those those of ordinary skill in the art, the various parts of the replacement of embodiment and equivalence are known.Those skilled in the art are noted that in the situation that not departing from spirit of the present invention or essential characteristic, and the present invention can be with other form, structure, layout, ratio, and realize with other assembly, material and parts.In the situation that not departing from the scope of the invention and spirit, can carry out other distortion and change to disclosed embodiment here.
Claims (10)
1. a flame-retardant rubber combination, is characterized in that, it is formulated by mass parts by following composition:
Organic polymer 50-120 part, reinforcement filler 10-100 part, non-reinforcement filler 20-80 part, fire retardant 5-120 part, coupling agent 0.1-5 part, fluid operated oily 1-30 part and solidifying agent 1-10 part.
2. flame-retardant rubber combination according to claim 1, it is characterized in that, described organic polymer is one or more in natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), terpolymer EP rubber, isoprene-isobutylene rubber, ethylene-vinyl acetate copolymer, methyl vinyl silicone rubber, methyl silicone rubber, phenyl siloxane rubber, penylene base silicon rubber.
3. flame-retardant rubber combination according to claim 1, is characterized in that, described reinforcement filler is that carbon black, the specific surface area that particle diameter is less than 40 nanometers is greater than 50m
2one or more in the precipitated silica of/g, thermal silica, modified white carbon black.
4. flame-retardant rubber combination according to claim 1, it is characterized in that, described non-reinforcement filler is silicates glass powder, borate family glass powder, phosphate-based glass powder, one or more in calcium carbonate, potter's clay, mica powder, silica powder, wilkinite, vermiculite, diatomite, Calucium Silicate powder, zirconium silicate, zeolite, ferric oxide, zinc oxide, magnesium oxide, aluminum oxide, cerium oxide, titanium oxide.
5. flame-retardant rubber combination according to claim 1, is characterized in that, described fire retardant is one or more in aluminium hydroxide, magnesium hydroxide, zinc borate, platinum fire retardant, silicone flame retardant.
6. flame-retardant rubber combination according to claim 1, it is characterized in that, described coupling agent is one or more in vinyltriethoxysilane, methyltriethoxy silane oxygen, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane.
7. flame-retardant rubber combination according to claim 1, is characterized in that, described fluid operated oil is one or more in paraffin oil, naphthenic oil, methyl-silicone oil, hydroxy silicon oil, dimethyldiethoxysilane.
8. flame-retardant rubber combination according to claim 1, it is characterized in that, described solidifying agent is sulfocompound, 1, two (the di-t-butyl peroxies)-3 of 1-, 3, 5-trimethyl-cyclohexane, 2, 5-dimethyl-2, 5-bis-(benzoyl peroxy) hexane, 1, 4-dual-tert-butyl peroxide diisopropyl benzene, the tertiary fourth fat of benzoyl hydroperoxide, diisopropylbenzyl superoxide, tert butyl isopropyl benzene peroxide, 2, 5-dimethyl-2, 5-bis-(t-butylperoxy)-3-hexin, 2, 4-dichlorobenzoperoxide (two two, four) one or more in.
9. a preparation method for the flame-retardant rubber combination as described in claim 1～8 any one, is characterized in that, said method comprising the steps of:
Organic polymer in above-mentioned flame-retardant rubber combination, reinforcement filler, non-reinforcement filler, fire retardant, coupling agent, fluid operated oil are carried out at not higher than 180 ℃ in rubber mixing machine mixing evenly, obtain dough composition, described dough composition is placed cooling at least 2 hours;
Cooled doughy mix is opened to refining in mill, then by the slitting shape of mixture of opening after refining;
Above-mentioned strip mixture is filtered on rubber strainer;
The solidifying agent appropriate according to the different choice of described organic polymer, is added into this solidifying agent in the mixture after filtration, to carry out mixingly by mill, obtains described flame-retardant rubber combination.
10. a fire resistant flame retardant rubber band, it is characterized in that, it comprises flame-retardant fabric, this flame-retardant fabric coating or be stained with the flame-retardant rubber combination as described in claim 1～8 any one, described flame-retardant fabric is one or more of carbon fibre fabric, glasscloth, ceramic fiber fabric and organic fabrix.
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