CN104592648B - Flame-retardant ethylene propylene diene monomer for cable and preparation method of flame-retardant ethylene propylene diene monomer - Google Patents
Flame-retardant ethylene propylene diene monomer for cable and preparation method of flame-retardant ethylene propylene diene monomer 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
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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
- C08L2312/00—Crosslinking
Abstract
The invention discloses a flame-retardant ethylene propylene diene monomer for a cable and a preparation method of the flame-retardant ethylene propylene diene monomer. The preparation method comprises the following steps: a, mixing the ethylene propylene diene monomer, fumedsilica, chlorinated paraffin, aluminum hydroxide, hexabromocyclododecane, boehmite and sodium molybdate together to form a rubber master batch; b, mixing a vulcanizingagent with the rubber master batch and performing first vulcanizing treatment; c, performing secondary vulcanizing on the primarily vulcanized rubber master batch in a drying oven to form the flame-retardant ethylene propylene diene monomer for the cable. The flame-retardant ethylene propylene diene monomer for the cable has excellent flame retardance.
Description
Technical field
The present invention relates to rubber, in particular it relates to a kind of cable fire retardant trielement ethylene-propylene rubber.
Background technology
The cushion of cable is made up of rubber mostly, and existing cushion rubber layer is merely capable of playing buffering and makees
With, in the case of the most on fire, rubber then can at high temperature be decomposed into flammable lower-molecular substance.Can
Combustion property lower-molecular substance carries out violent oxidation reaction with oxygen with then interrogating speed, and oxidation reaction is released a large amount of
Heat then can promote the decomposition of rubber, the product such as low mass molecule alcohol, aldehyde in simultaneous oxidation reaction further
Also oxidation reaction can be carried out with oxygen until rubber burnouts.
Summary of the invention
It is an object of the invention to provide a kind of cable fire retardant trielement ethylene-propylene rubber and preparation method thereof, pass through
The cable fire retardant trielement ethylene-propylene rubber that the method prepares has the anti-flammability of excellence.
To achieve these goals, the invention provides the preparation of a kind of cable fire retardant trielement ethylene-propylene rubber
Method, described preparation method includes:
A, by ethylene propylene diene rubber, fume colloidal silica, chlorinated paraffin, aluminium hydroxide, hexabromo ring ten
Dioxane, boehmite and sodium molybdate are mixing makes rubber master batch；
B, by vulcanizing agent and described milling maternal rubber to carry out primary vulcanization process；
C, the described rubber master batch after primary vulcanization is carried out in an oven second time vulcanize to make cable and use
Fire retardant trielement ethylene-propylene rubber.
Present invention also offers and additionally provide a kind of cable fire retardant trielement ethylene-propylene rubber, described cable hinders
Combustion ethylene propylene diene rubber is prepared from by above-mentioned method.
By technique scheme, the cable that the present invention provides fire retardant trielement ethylene-propylene rubber passes through ternary second
Third rubber, fume colloidal silica, chlorinated paraffin, aluminium hydroxide, HBCD, boehmite, sulfur
Agent and the synergism of sodium molybdate so that this cable fire retardant trielement ethylene-propylene rubber is in the case of burning
Can interrogate and decompose water outlet, fire-retardant gas (such as nitrogen), the fast and life at rubber surface formation sintering fastly
Become halogen radical thus effectively stop the carrying out of combustion reaction.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides the preparation method of a kind of cable fire retardant trielement ethylene-propylene rubber, described preparation method
Including:
A, by ethylene propylene diene rubber, fume colloidal silica, chlorinated paraffin, aluminium hydroxide, hexabromo ring ten
Dioxane, boehmite and sodium molybdate are mixing makes rubber master batch；
B, by vulcanizing agent and described milling maternal rubber to carry out primary vulcanization process；
C, the described rubber master batch after primary vulcanization is carried out in an oven second time vulcanize to make cable and use
Fire retardant trielement ethylene-propylene rubber.
In step a of the present invention, the consumption of each raw material can select in wide scope, but in order to
The cable fire retardant trielement ethylene-propylene rubber prepared is made to have more excellent anti-flammability, it is preferable that in step
In a, relative to the described ethylene propylene diene rubber of 100 weight portions, the consumption of described fume colloidal silica is
160-190 weight portion, the consumption of described chlorinated paraffin is 3-7 weight portion, the consumption of described aluminium hydroxide
For 35-55 weight portion, the consumption of described HBCD is 4-8 weight portion, the use of described boehmite
Amount is 7-10 weight portion, and the consumption of described sodium molybdate is 0.3-1.2 weight portion.
In step b of the present invention, the consumption of each raw material can select in wide scope, but in order to
The cable fire retardant trielement ethylene-propylene rubber prepared is made to have more excellent anti-flammability, it is preferable that in step
In b, relative to the described rubber master batch of 100 weight portions, the consumption of described vulcanizing agent is 0.2-0.8 weight portion.
In the present invention, described chlorinated paraffin can be one-component can also be various ingredients mixing and
Become, but so that the cable fire retardant trielement ethylene-propylene rubber prepared has more excellent anti-flammability, excellent
Selection of land, described chlorinated paraffin is selected from chlorinated paraffin-50 and chlorinated paraffin-70.Prepared in order to improve further
Cable fire retardant trielement ethylene-propylene rubber there is more excellent anti-flammability, it is highly preferred that described chlorinated paraffin
-50 is 1:1.5-2 with the weight ratio of described chlorinated paraffin-70.
In the present invention, the concrete component of described vulcanizing agent can select in wide scope, but in order to
The cable fire retardant trielement ethylene-propylene rubber prepared is made to have more excellent anti-flammability, it is preferable that described sulfur
Agent is selected from dual-tert-butyl cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide and 2,4-
One or more in dichloride benzoyl peroxide.In order to improve prepared cable further with fire-retardant three
Unit's EP rubbers has more excellent anti-flammability, it is highly preferred that described vulcanizing agent contains described dual-tert-butyl
Cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide and 2,4-dichloride benzoyl peroxide
Formyl；Further, relative to the described dual-tert-butyl cumene hydroperoxide of 1 weight portion, described peroxidating
The consumption of diisopropyl benzene is 0.5-0.6 weight portion, and the consumption of described benzoyl peroxide is 0.1-0.2 weight
Amount part, the consumption of described 2,4-dichloride benzoyl peroxide is 0.2-0.4 weight portion.
In the present invention, the actual conditions of primary vulcanization can select in wide scope, but in order to
The cable fire retardant trielement ethylene-propylene rubber prepared is made to have more excellent anti-flammability, it is preferable that described
Once sulfuration meets following condition: curing temperature is 120-170 DEG C, and cure time is 15-20min, sulfur
Change pressure is 10-12Mpa.
In the present invention, the actual conditions of second time sulfuration can select in wide scope, but in order to
The cable fire retardant trielement ethylene-propylene rubber prepared is made to have more excellent anti-flammability, it is preferable that described
Post-cure meets following condition: curing temperature is 210-220 DEG C, and cure time is 3-5h.
Present invention also offers a kind of cable fire retardant trielement ethylene-propylene rubber, described cable is by fire-retardant ternary second
Third rubber is prepared from by above-mentioned method.
Hereinafter will be described the present invention by embodiment.In following example, the self-extinguishment time
Parameter is recorded by the method for UL-94, and oxygen index (OI) parameter is recorded by the method for GB/T10707-89.
Embodiment 1
A, it is the vapor phase method Linesless charcoal of A200 by ethylene propylene diene rubber 100kg that the trade mark is 4770R, the trade mark
Black 180kg, 5kg chlorinated paraffin-50, aluminium hydroxide 45kg, HBCD 6kg, boehmite 9kg
Mixing with sodium molybdate 0.8kg make rubber master batch；
B, under 150 DEG C and 11Mpa, by dual-tert-butyl cumene hydroperoxide 0.5kg and above-mentioned mother
The mixing 17min of glue 100kg carries out primary vulcanization process；
C, at 215 DEG C, the described rubber master batch after primary vulcanization is carried out in an oven second time vulcanize
4h is to make cable fire retardant trielement ethylene-propylene rubber A1.
The fire resistance parameter of this cable fire retardant trielement ethylene-propylene rubber is shown in Table 1.
Embodiment 2
A, it is the vapor phase method Linesless charcoal of A200 by ethylene propylene diene rubber 100kg that the trade mark is 4770R, the trade mark
Black 190kg, 7kg chlorinated paraffin-50, aluminium hydroxide 55kg, HBCD 8kg, boehmite 10kg
Mixing with sodium molybdate 1.2kg make rubber master batch；
B, under 170 DEG C and 12Mpa, by dual-tert-butyl cumene hydroperoxide 0.8kg and above-mentioned mother
The mixing 20min of glue 100kg carries out primary vulcanization process；
C, at 220 DEG C, the described rubber master batch after primary vulcanization is carried out in an oven second time vulcanize
5h is to make cable fire retardant trielement ethylene-propylene rubber A2.
The fire resistance parameter of this cable fire retardant trielement ethylene-propylene rubber is shown in Table 1.
Embodiment 3
A, it is the vapor phase method Linesless charcoal of A200 by ethylene propylene diene rubber 100kg that the trade mark is 4770R, the trade mark
Black 160kg, 3kg chlorinated paraffin-50, aluminium hydroxide 35kg, HBCD 4kg, boehmite 7kg
Mixing with sodium molybdate 0.3kg make rubber master batch；
B, under 120 DEG C and 10Mpa, by dual-tert-butyl cumene hydroperoxide 0.2kg and above-mentioned mother
The mixing 15min of glue 100kg carries out primary vulcanization process；
C, at 210 DEG C, the described rubber master batch after primary vulcanization is carried out in an oven second time vulcanize
3h is to make cable fire retardant trielement ethylene-propylene rubber A3.
The fire resistance parameter of this cable fire retardant trielement ethylene-propylene rubber is shown in Table 1.
Embodiment 4
According to the method for embodiment 1 carry out prepare cable fire retardant trielement ethylene-propylene rubber A4, except for the difference that,
Chlorinated paraffin-50 is changed into chlorinated paraffin-50 and chlorinated paraffin-70 (weight ratio of the two is 1:1.7).
The fire resistance parameter of this cable fire retardant trielement ethylene-propylene rubber is shown in Table 1.
Comparative example 5
According to the method for embodiment 1 carry out prepare cable fire retardant trielement ethylene-propylene rubber A5, except for the difference that,
Change dual-tert-butyl cumene hydroperoxide into dual-tert-butyl cumene hydroperoxide, diisopropyl peroxide
Benzene, benzoyl peroxide and 2,4-dichloride benzoyl peroxide (weight ratio of four is 1:
0.5:0.15:0.3).The fire resistance parameter of this cable fire retardant trielement ethylene-propylene rubber is shown in Table 1.
Comparative example 1
According to the method for embodiment 1 carry out prepare cable fire retardant trielement ethylene-propylene rubber B1, except for the difference that,
Without chlorinated paraffin.The fire resistance parameter of this cable fire retardant trielement ethylene-propylene rubber is shown in Table 1.
Comparative example 2
According to the method for embodiment 1 carry out prepare cable fire retardant trielement ethylene-propylene rubber B2, except for the difference that,
Without boehmite.The fire resistance parameter of this cable fire retardant trielement ethylene-propylene rubber is shown in Table 1.
Comparative example 3
According to the method for embodiment 1 carry out prepare cable fire retardant trielement ethylene-propylene rubber B3, except for the difference that,
Without sodium molybdate.The fire resistance parameter of this cable fire retardant trielement ethylene-propylene rubber is shown in Table 1.
Comparative example 4
According to the method for embodiment 1 carry out prepare cable fire retardant trielement ethylene-propylene rubber B4, except for the difference that,
Without aluminium hydroxide.The fire resistance parameter of this cable fire retardant trielement ethylene-propylene rubber is shown in Table 1.
Table 1
| A1 | A2 | A3 | A4 | A5 | B1 | B2 | B3 | B4 | |
| Self-extinguishment time/s | 6 | 4 | 5 | 3 | 2 | 25 | 20 | 31 | 28 |
| Limited oxygen index/% | 26 | 27 | 25 | 29 | 30 | 17 | 20 | 19 | 18 |
From above-described embodiment and comparative example, the cable fire retardant trielement ethylene-propylene rubber that the present invention provides has
There is the flame retardant effect of excellence.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (8)
1. the preparation method of a cable fire retardant trielement ethylene-propylene rubber, it is characterised in that described preparation
Method includes:
A, by ethylene propylene diene rubber, fume colloidal silica, chlorinated paraffin, aluminium hydroxide, hexabromo ring ten
Dioxane, boehmite and sodium molybdate are mixing makes rubber master batch；
B, by vulcanizing agent and described milling maternal rubber to carry out primary vulcanization process；
C, the described rubber master batch after primary vulcanization is carried out in an oven second time vulcanize to make cable and use
Fire retardant trielement ethylene-propylene rubber；
Wherein, in step a, relative to the described ethylene propylene diene rubber of 100 weight portions, described gas phase
The consumption of method white carbon is 160-190 weight portion, and the consumption of described chlorinated paraffin is 3-7 weight portion, institute
The consumption stating aluminium hydroxide is 35-55 weight portion, and the consumption of described HBCD is 4-8 weight portion,
The consumption of described boehmite is 7-10 weight portion, and the consumption of described sodium molybdate is 0.3-1.2 weight portion；?
In step b, relative to the described rubber master batch of 100 weight portions, the consumption of described vulcanizing agent is 0.2-0.8 weight
Amount part.
Preparation method the most according to claim 1, wherein, described chlorinated paraffin is selected from chlorination stone
Wax-50 and chlorinated paraffin-70.
Preparation method the most according to claim 2, wherein, described chlorinated paraffin-50 and described chlorine
The weight ratio of fossil waxes-70 is 1:1.5-2.
4. according to the preparation method described in any one in claim 1-3, wherein, described vulcanizing agent
Selected from dual-tert-butyl cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide and 2,4-bis-
One or more in chlorination benzoyl peroxide.
Preparation method the most according to claim 4, wherein, described vulcanizing agent contains described couple of uncle
Butyl peroxy cumene, dicumyl peroxide, benzoyl peroxide and 2,4-dichloride peroxide
Change benzoyl；Further, relative to the described dual-tert-butyl cumene hydroperoxide of 1 weight portion, described mistake
The consumption of oxidation diisopropyl benzene is 0.5-0.6 weight portion, and the consumption of described benzoyl peroxide is 0.1-0.2
Weight portion, the consumption of described 2,4-dichloride benzoyl peroxide is 0.2-0.4 weight portion.
6. according to the preparation method described in any one in claim 1-3, wherein, described first time
Sulfuration meets following condition: curing temperature is 120-170 DEG C, and cure time is 15-20min, sulfuration pressure
Power is 10-12Mpa.
Preparation method the most according to claim 6, wherein, described second time vulcanizes below satisfied
Condition: curing temperature is 210-220 DEG C, cure time is 3-5h.
8. a cable fire retardant trielement ethylene-propylene rubber, it is characterised in that the fire-retardant ternary of described cable
EP rubbers is prepared from by the method described in any one in claim 1-7.
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| CN201510011683.5A CN104592648B (en) | 2015-01-09 | 2015-01-09 | Flame-retardant ethylene propylene diene monomer for cable and preparation method of flame-retardant ethylene propylene diene monomer |
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| CN105419035A (en) * | 2016-01-12 | 2016-03-23 | 芜湖航天特种电缆厂股份有限公司 | Stretch-resisting cable rubber sleeve and preparing method thereof |
| CN106496679B (en) * | 2016-11-02 | 2019-01-22 | 芜湖瑞德机械科技有限公司 | Modified flame-retardant butadiene rubber and preparation method thereof |
| CN107501948A (en) * | 2017-09-12 | 2017-12-22 | 芜湖航天特种电缆厂股份有限公司 | Rocket engine high temperature-resistant cable sheet material and preparation method thereof |
| JP7329383B2 (en) * | 2019-07-31 | 2023-08-18 | 住友理工株式会社 | Flame-retardant anti-vibration rubber composition and flame-retardant anti-vibration rubber member |
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| CN103509257A (en) * | 2013-08-30 | 2014-01-15 | 安徽天民电气科技有限公司 | 105 DEG C low-smoke zero-halogen flame-retardant ethylene-propylene-diene monomer cable material and preparation method thereof |
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Address after: 241000 Wuhu high tech Development Zone, Anhui, No. 15 Zhanghe Road Applicant after: WUHU SPACEFLIGHT SPECIAL CABLE FACTORY CO., LTD. Address before: 241000 Wuhu high tech Development Zone, Anhui, No. 15 Zhanghe Road Applicant before: Wuhu Aerospace Special Cable Factory |
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