CN104558868B - Preparation method of corrosion-resistant flame-retardant cable rubber material - Google Patents
Preparation method of corrosion-resistant flame-retardant cable rubber material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a preparation method of a corrosion-resistant flame-retardant cable rubber material, belonging to the technical field of rubber materials. The method comprises the following steps: taking ethylene propylene diene monomer rubber, pulverizing, and implanting C ions with an ion implantation apparatus to obtain modified ethylene propylene diene monomer rubber; sequentially adding the modified ethylene propylene diene monomer rubber, natural rubber, chlorinated polypropylene, ethylene-vinyl acetate copolymer, polylactic acid-glycollic acid copolymer, polydimethylsiloxane, 1,2-polybutadiene, liquid paraffin, talcum powder, carbon black, bromide, antimony trioxide, hydrated magnesium silicate, vulcanizing agent, vulcanization accelerator, silicon dioxide, stearic acid, anti-aging agent and tackifier into an open mill, and compounding to obtain compounded rubber; and putting the compounded rubber on a flat vulcanizing machine, and vulcanizing to obtain the flame-retardant cable rubber material. The cable rubber composition has the advantages of favorable flame retardancy and excellent alkali/acid corrosion resistance.
Description
Technical field
The present invention discloses a kind of preparation method of corrosion resistant flame retardant cable elastomeric material, belongs to technical field of rubber material.
Background technology
The pernicious gas such as the chlorine containing substantial amounts of carbon monoxide and the burning generation of plastics chemical fibre, benzene in the smog producing after cable fire, flame also can cause respiratory tract to burn and laryngeal edema, and energy plunger passageway for fire apparatus, when therefore escaping in a fire, the impact of smog size is very big.In fire incident death toll, 80% does not directly burn to death, but smokes dead in eye produced by burning, poison, acid mist to cable.
Cable industry is accustomed to fire-retardant (fire retardant), low smoke, zero halogen (low smoke halogen free, lsoh) or low smoke and low halogen (low smoke fume
, lsf), fire resisting (fire resistant) etc. has the cable of certain fire protecting performance and is referred to as fire-retardant fireproof cable.Although halogen-free flame-retardant cable toxicity is low, smoke density is little, no acid mist, because it manufactures upper difficulty, its cost is significantly lifted.The base-material of bittern-free flame-proof material is that polyolefin pe and eva forms, and it is combustible material that its oxygen index (OI) is only 18 about.In order to reach fire-retardant purpose, the inorganic metal hydrate such as a considerable amount of magnesium hydroxides just must be mixed into.General ratio is 100:120-150(weight ratio), these particles are in turbid liquid state in organic polymer body, its particle conjugate gap its gap value bigger is also big, initially the amount of touching is also big to cause the ess-strain of composite, therefore makes its pliability, percentage elongation, tensile strength and infiltration defence degree severe exacerbation.
A kind of cn102875887b cable low-smoke halogen-free flame-retardant isolating material, including the weight portion of following component: base-material: 100.0；Inorganic combustion inhibitor: 100.0～200.0；Antioxidant: 0.1～8.0；Crosslinking sensitizer: 1.0～5.0；Anti-irradiation agent: 0.3～10.0；Described base-material at least contains polyethylene and ethylene-methacrylic acid copolymer.Cn102050971b discloses a kind of electric wire flame-retardant thermoset butyronitrile polyvinyl chloride rubber it is characterised in that it includes the raw material of following parts by weight: 50～70 parts of PNBR, 30～50 parts of pvc resin-oatmeal, 2～3 parts of vulcanizing agent, 2.5～4.5 parts of accelerator, 4～6 parts of zinc oxide, 2～3 parts of stearic acid, coumarone indene resin 1-3 part, 2～4 parts of age resistor, 20～40 parts of chlorinated paraffin, 7～10 parts of antimony oxide, 4～6 parts of Firebrake ZB, 50～70 parts of aluminium hydroxide, 40～70 parts of carbon black；The present invention, after exceeding uniform temperature, only can solidify, burn, and it is also possible to keep certain insulating properties, and intensity, stretch rate, fire resistance is all good than General Purpose Rubber and thermoplasticity butyronitrile polyvinyl chloride rubber.Although above-mentioned flame retardant rubber has certain fire resistance, its tensile property and decay resistance be not but good.
Content of the invention
The purpose of the present invention is: provides decay resistance and the fire resistance of cable rubber.
Technical scheme:
A kind of preparation method of corrosion resistant flame retardant cable elastomeric material, comprises the steps:
1st step, by weight, takes 80～120 parts of ethylene propylene diene rubber, after pulverizing, injects c(carbon with ion implantation apparatus to ethylene propylene diene rubber) ion, obtain modified EPT rubber；
2nd step, by modified EPT rubber, 15～30 parts of natural rubber, 5～10 parts of chlorinated polypropylene, 5～12 parts of ethylene-vinyl acetate copolymer, 3～4 parts of polylactic-co-glycolic acid, 5～10 parts of dimethyl silicone polymer, 1, 6～12 parts of 2- polybutadiene, 3～5 parts of atoleine, 5～15 parts of talcum powder, 20～30 parts of carbon black, 10～15 parts of bromide, 6～12 parts of antimony oxide, 3～5 parts of hydrated magnesium silicate, 5～10 parts of vulcanizing agent, 3～6 parts of vulcanization accelerator, 6～12 parts of silica, 7～15 parts of stearic acid, 5～7 parts of age resistor, 3～5 parts of tackifier sequentially add in mill, 10～20min is kneaded at 70～120 DEG C, obtain elastomeric compound；
3rd step, elastomeric compound is placed on vulcanizing press, vulcanizes 10～20min, prepared flame retardant cable elastomeric material at 140～200 DEG C.
In the 1st described step, c ion consumption is 1～3 part；Ion energy is 20～30kev；Beam current density scope is 0.5～0.8ma/ cm2；Using ion gun be the graphite that purity is more than 98%.
Described carbon black refers to carbon black n330.
In the 2nd described step, the chlorinty scope 28～32wt% of chlorinated polypropylene.
In the 2nd described step, bromide is one of deca-BDE, HBCD, ten tetrabromo two phenoxy group benzene or several mixtures.
Described vulcanizing agent is sulphur.
Described vulcanization accelerator is 2- benzothiazolyl mercaptan, the one of which in dibenzothiazyl disulfide or a combination thereof.
Described age resistor is antioxidant 4010 na or one kind of paraffin or a combination thereof.
Described tackifier are coumarone indene resin.
The specific surface area (bet method) of described silica is in 50～70 m2Between/g.
Described silica is to soak modified mistake in silane coupler；Described silane coupler is selected from one of kh-550, kh-560, kh-570 or several mixtures.
Beneficial effect
The cable rubber composition that the present invention prepares has good fire resistance, and alkaline-resisting, acid corrosion performance is also excellent.
Specific embodiment
Embodiment 1
1st step, take ethylene propylene diene rubber 80kg, after pulverizing, with ion implantation apparatus, c ion is injected to ethylene propylene diene rubber, obtain modified EPT rubber；C ion consumption is 1kg；Ion energy is 20kev；Beam current density scope is 0.5ma/ cm2；Using ion gun be the graphite that purity is more than 98%；
2nd step, by modified EPT rubber, natural rubber 30kg, chlorinated polypropylene 10kg (chlorinty 32wt%), ethylene-vinyl acetate copolymer 5kg, polylactic-co-glycolic acid 4kg, dimethyl silicone polymer 10kg, 1, 2- polybutadiene 12kg, atoleine 5kg, talcum powder 15kg, carbon black (carbon black n330) 20kg, bromide (deca-BDE) 10kg, antimony oxide 6kg, hydrated magnesium silicate 5kg, vulcanizing agent (sulphur) 10kg, vulcanization accelerator (2- benzothiazolyl mercaptan) 6kg, (specific surface area (bet method) is in 50～70 m for silica2Between/g) 12kg, stearic acid 15kg, age resistor (4010na) 5kg, tackifier (coumarone indene resin) 5kg sequentially add in mill, knead 10min, obtain elastomeric compound at 120 DEG C；
3rd step, elastomeric compound is placed on vulcanizing press, vulcanizes 10min, prepared flame retardant cable elastomeric material at 140 DEG C.
Embodiment 2
1st step, take ethylene propylene diene rubber 100kg, after pulverizing, with ion implantation apparatus, c ion is injected to ethylene propylene diene rubber, obtain modified EPT rubber；C ion consumption is 2kg；Ion energy is 25kev；Beam current density scope is 0.7ma/ cm2；Using ion gun be the graphite that purity is more than 98%；
2nd step, by modified EPT rubber, natural rubber 20kg, chlorinated polypropylene 7kg (chlorinty scope 30wt%), ethylene-vinyl acetate copolymer 10kg, polylactic-co-glycolic acid 3kg, dimethyl silicone polymer 7kg, 1, 2- polybutadiene 10kg, atoleine 4kg, talcum powder 10kg, carbon black (carbon black n330) 25kg, bromide (deca-BDE) 12kg, antimony oxide 10kg, hydrated magnesium silicate 4kg, vulcanizing agent (sulphur) 8kg, vulcanization accelerator (2- benzothiazolyl mercaptan) 5kg, (specific surface area (bet method) is in 50～70 m for silica2Between/g) 7kg, stearic acid 12kg, age resistor (4010na) 6kg, tackifier (coumarone indene resin) 4kg sequentially add in mill, knead 15min, obtain elastomeric compound at 9 DEG C；
3rd step, elastomeric compound is placed on vulcanizing press, vulcanizes 15min, prepared flame retardant cable elastomeric material at 160 DEG C.
Embodiment 3
Difference with embodiment 2 is: silica is that kh-570 immersion modification in 4 hours is crossed in silane coupler.
1st step, take ethylene propylene diene rubber 100kg, after pulverizing, with ion implantation apparatus, c ion is injected to ethylene propylene diene rubber, obtain modified EPT rubber；C ion consumption is 2kg；Ion energy is 25kev；Beam current density scope is 0.7ma/ cm2；Using ion gun be the graphite that purity is more than 98%；
2nd step, by modified EPT rubber, natural rubber 20kg, chlorinated polypropylene 7kg (chlorinty scope 30wt%), ethylene-vinyl acetate copolymer 10kg, polylactic-co-glycolic acid 3kg, dimethyl silicone polymer 7kg, 1, 2- polybutadiene 10kg, atoleine 4kg, talcum powder 10kg, carbon black (carbon black n330) 25kg, bromide (deca-BDE) 12kg, antimony oxide 10kg, hydrated magnesium silicate 4kg, vulcanizing agent (sulphur) 8kg, vulcanization accelerator (2- benzothiazolyl mercaptan) 5kg, (specific surface area (bet method) is in 50～70 m for improved silica2Between/g) 7kg, stearic acid 12kg, age resistor (4010na) 6kg, tackifier (coumarone indene resin) 4kg sequentially add in mill, knead 15min, obtain elastomeric compound at 9 DEG C；
3rd step, elastomeric compound is placed on vulcanizing press, vulcanizes 15min, prepared flame retardant cable elastomeric material at 160 DEG C.
Reference examples 1
Difference with embodiment 2 is: by c injection method, ethylene propylene diene rubber is modified.
1st step, by ethylene propylene diene rubber 100kg, natural rubber 20kg, chlorinated polypropylene 7kg (chlorinty scope 30wt%), ethylene-vinyl acetate copolymer 10kg, polylactic-co-glycolic acid 3kg, dimethyl silicone polymer 7kg, 1, 2- polybutadiene 10kg, atoleine 4kg, talcum powder 10kg, carbon black (carbon black n330) 25kg, bromide (deca-BDE) 12kg, antimony oxide 10kg, hydrated magnesium silicate 4kg, vulcanizing agent (sulphur) 8kg, vulcanization accelerator (2- benzothiazolyl mercaptan) 5kg, (specific surface area (bet method) is in 50～70 m for improved silica2Between/g) 7kg, stearic acid 12kg, age resistor (4010na) 6kg, tackifier (coumarone indene resin) 4kg sequentially add in mill, knead 15min, obtain elastomeric compound at 9 DEG C；
2nd step, elastomeric compound is placed on vulcanizing press, vulcanizes 15min, prepared flame retardant cable elastomeric material at 160 DEG C.
Reference examples 2
Difference with embodiment 2 is: does not add polylactic-co-glycolic acid in the 2nd step.
1st step, take ethylene propylene diene rubber 100kg, after pulverizing, with ion implantation apparatus, c ion is injected to ethylene propylene diene rubber, obtain modified EPT rubber；C ion consumption is 2kg；Ion energy is 25kev；Beam current density scope is 0.7ma/ cm2；Using ion gun be the graphite that purity is more than 98%；
2nd step, by modified EPT rubber, natural rubber 20kg, chlorinated polypropylene 7kg (chlorinty scope 30wt%), ethylene-vinyl acetate copolymer 10kg, dimethyl silicone polymer 7kg, 1,2- polybutadiene 10kg, atoleine 4kg, talcum powder 10kg, carbon black (carbon black n330) 25kg, bromide (deca-BDE) 12kg, antimony oxide 10kg, hydrated magnesium silicate 4kg, vulcanizing agent (sulphur) 8kg, vulcanization accelerator (2- benzothiazolyl mercaptan) 5kg, silica, (specific surface area (bet method) is in 50～70 m2Between/g) 7kg, stearic acid 12kg, age resistor (4010na) 6kg, tackifier (coumarone indene resin) 4kg sequentially add in mill, knead 15min, obtain elastomeric compound at 9 DEG C；
3rd step, elastomeric compound is placed on vulcanizing press, vulcanizes 15min, prepared flame retardant cable elastomeric material at 160 DEG C.
Reference examples 3
Difference with embodiment 2 is: does not add chlorinated polypropylene in the 2nd step.
1st step, take ethylene propylene diene rubber 100kg, after pulverizing, with ion implantation apparatus, c ion is injected to ethylene propylene diene rubber, obtain modified EPT rubber；C ion consumption is 2kg；Ion energy is 25kev；Beam current density scope is 0.7ma/ cm2；Using ion gun be the graphite that purity is more than 98%；
2nd step, by modified EPT rubber, natural rubber 20kg, ethylene-vinyl acetate copolymer 10kg, polylactic-co-glycolic acid 3kg, dimethyl silicone polymer 7kg, 1,2- polybutadiene 10kg, atoleine 4kg, talcum powder 10kg, carbon black (carbon black n330) 25kg, bromide (deca-BDE) 12kg, antimony oxide 10kg, hydrated magnesium silicate 4kg, vulcanizing agent (sulphur) 8kg, vulcanization accelerator (2- benzothiazolyl mercaptan) 5kg, silica, (specific surface area (bet method) is in 50～70 m2Between/g) 7kg, stearic acid 12kg, age resistor (4010na) 6kg, tackifier (coumarone indene resin) 4kg sequentially add in mill, knead 15min, obtain elastomeric compound at 9 DEG C；
3rd step, elastomeric compound is placed on vulcanizing press, vulcanizes 15min, prepared flame retardant cable elastomeric material at 160 DEG C.
Performance test
Oxygen index (OI) is tested by the method in gb/t 2406-2008 " plastics oxygen index method measures burning behavior "；Corresponding standard value is >=32 it is standard in jb/t10707-2007；
Tensile strength is tested according to the method for gb/t 1040-92 " plastic tensile method for testing performance "；Corresponding standard value >=9.0 are according to standard corresponding in jb/t 10707-2007；
Elongation at break is tested according to the method in gb/t 1040.2-92 " plastic tensile method for testing performance "；
The performance test results of above-described embodiment and reference examples are as follows:
As can be seen from the table, the flame-proof cable material that the present invention prepares has preferable mechanical strength, wherein, by embodiment 2 and embodiment 3 contrast as can be seen that by silica is carried out silane coupler modified after, its physical extension performance can be improved；Can be seen that by c ion implanting by reference examples 1 and embodiment, can be with improve tensile property；Can be seen that the addition by polylactic-co-glycolic acid by reference examples 2 and embodiment, oxygen index (OI) and elongation at break can be improved.
Above-mentioned sample is positioned over and takes out after soaking 7 days in 50 DEG C of hydrochloric acid, repeat above-mentioned test, result is as follows:
As can be seen from the table, due to not adding polylactic-co-glycolic acid in reference examples 2, result in after acid soak test, tensile strength and elongation at break are decreased obviously；Due to not adding chlorinated polypropylene in reference examples 3, result in after acid soak test, declining occur in oxygen index (OI) and tensile strength.
Claims (10)
1. a kind of preparation method of corrosion resistant flame retardant cable elastomeric material is it is characterised in that comprise the steps:
1st step, by weight, takes 80～120 parts of ethylene propylene diene rubber, after pulverizing, injects c ion with ion implantation apparatus to ethylene propylene diene rubber, obtains modified EPT rubber；
2nd step, by modified EPT rubber, 15～30 parts of natural rubber, 5～10 parts of chlorinated polypropylene, 5～12 parts of ethylene-vinyl acetate copolymer, 3～4 parts of polylactic-co-glycolic acid, 5～10 parts of dimethyl silicone polymer, 1, 6～12 parts of 2- polybutadiene, 3～5 parts of atoleine, 5～15 parts of talcum powder, 20～30 parts of carbon black, 10～15 parts of bromide, 6～12 parts of antimony oxide, 3～5 parts of hydrated magnesium silicate, 5～10 parts of vulcanizing agent, 3～6 parts of vulcanization accelerator, 6～12 parts of silica, 7～15 parts of stearic acid, 5～7 parts of age resistor, 3～5 parts of tackifier sequentially add in mill, 10～20min is kneaded at 70～120 DEG C, obtain elastomeric compound；
3rd step, elastomeric compound is placed on vulcanizing press, at 140～200 DEG C, vulcanizes 10～20min,
Prepared flame retardant cable elastomeric material.
2. corrosion resistant flame retardant cable elastomeric material according to claim 1 preparation method it is characterised in that: in the 1st described step, c ion consumption be 1～3 part；Ion energy is 20～30kev；Beam current density scope is 0.5～0.8ma/ cm2；Using ion gun be the graphite that purity is more than 98%.
3. corrosion resistant flame retardant cable elastomeric material according to claim 1 preparation method it is characterised in that: described carbon black refers to carbon black n330.
4. corrosion resistant flame retardant cable elastomeric material according to claim 1 preparation method it is characterised in that: in the 2nd described step, the chlorinty scope 28～32wt% of chlorinated polypropylene.
5. corrosion resistant flame retardant cable elastomeric material according to claim 1 preparation method it is characterised in that: in the 2nd described step, bromide is one of deca-BDE, HBCD, ten tetrabromo two phenoxy group benzene or several mixtures.
6. corrosion resistant flame retardant cable elastomeric material according to claim 1 preparation method it is characterised in that: described vulcanizing agent be sulphur.
7. corrosion resistant flame retardant cable elastomeric material according to claim 1 preparation method it is characterised in that: described vulcanization accelerator is 2- benzothiazolyl mercaptan, the one of which in dibenzothiazyl disulfide or a combination thereof.
8. corrosion resistant flame retardant cable elastomeric material according to claim 1 preparation method it is characterised in that: described age resistor is one kind or a combination thereof of antioxidant 4010 na or paraffin；Described tackifier are coumarone indene resin.
9. corrosion resistant flame retardant cable elastomeric material according to claim 1 preparation method it is characterised in that: the specific surface area of described silica according to bet method detect in 50～70 m2Between/g.
10. corrosion resistant flame retardant cable elastomeric material according to claim 1 preparation method it is characterised in that: described silica is to soak modified mistake in silane coupler；Described silane coupler is selected from one of kh-550, kh-560, kh-570 or several mixtures.
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| CN104558868A (en) | 2015-04-29 |
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