CN113736183B - Anti-seismic low-smoke halogen-free flame-retardant cable sheath material and preparation method and application thereof - Google Patents
Anti-seismic low-smoke halogen-free flame-retardant cable sheath material and preparation method and application thereof Download PDFInfo
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- 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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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
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- 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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
Abstract
The invention provides an anti-seismic low-smoke halogen-free flame-retardant cable sheath material and a preparation method and application thereof, and the cable sheath material comprises, by mass, 40-50% of ethylene propylene diene monomer, 1-5% of unsaturated acid, 5-10% of a high-molecular compatilizer, 30-50% of a flame retardant, 1-2% of a vulcanizing agent, 0.5-1% of a vulcanization accelerator, 0.2-0.4% of an antioxidant, 5-10% of white carbon black and 0.5-0.8% of an anti-aging agent. According to the invention, through chemical crosslinking and the ion coordination of metal cations and anion groups such as carboxyl, phosphate radical and the like in an inorganic flame retardant, the cable material with an ion-covalent double crosslinking network structure is constructed in a system, wherein the covalent crosslinking network ensures the stability of the material structure, and the energy generated by vibration can be consumed by the dissociation and combination between cations and anions in the ionic crosslinking structure and the dynamic exchange characteristic between ions, so that the cable material has the characteristics of stable structure, no cracking, good size stability and the like under the working condition of forced vibration.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an anti-seismic low-smoke halogen-free flame-retardant cable sheath material as well as a preparation method and application thereof.
Background
The cable for the high-speed motor train unit is the basis and guarantee for the stable operation of the high-speed train, and the requirements on the stability and the safety of the operation of the cable for the high-speed motor train unit are continuously improved along with the continuous speed increase of the high-speed rail. In order to ensure the continuous and stable power or signal transmission of the cable for the train in the high-speed operation process of the locomotive, special performance requirements are put on the sheath material of the cable. On one hand, the cable sheath material needs to meet basic performance requirements of halogen-free flame retardance, high strength, bending resistance, wear resistance, tear resistance, high dimensional stability and the like, and on the other hand, the cable sheath material also needs to keep stable structure and size and no cracking under the vibration working condition of high-speed train operation, so that guarantee is provided for stable structure and stable operation of the cable and the high-speed train.
Regarding the research and development of the low-smoke halogen-free flame-retardant high-speed train cable sheath material for the high-speed train, related invention patents have been disclosed so far, wherein the patent with the publication number of CN 103214749A prepares a thermoplastic polyurethane elastomer cable material by compounding modified sulfonated polyethylene, maleic anhydride grafted polyolefin elastomer, thermoplastic polyurethane elastomer, flame retardant and other auxiliary agents, and the cable material can work at high temperature and has good flame retardant property and mechanical property.
However, the cable materials reported in these patents do not relate to the design of the structural stability and shock resistance of the cable sheath material during the forced vibration of the cable.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide an anti-seismic low-smoke halogen-free flame-retardant cable sheath material and a preparation method thereof, wherein an ion-covalent double cross-linked network structure is constructed in a system through the ion coordination effect of metal cations and anion groups such as carboxyl, phosphate radical and the like in an inorganic flame retardant, the covalent cross-linked network ensures the stability of the material structure, and the energy generated by vibration can be consumed by the dissociation and combination of anions and cations in the ionic cross-linked structure and the dynamic exchange characteristic between ions, so that the cable sheath material has the characteristics of stable material structure, no cracking, good dimensional stability and the like under the working condition of forced vibration.
In order to achieve the above objects and other objects, the present invention provides an anti-seismic low-smoke halogen-free flame-retardant cable sheath material, which comprises the following components by mass:
preferably, the third monomer of the ethylene propylene diene monomer is ethylidene norbornene, and the mass percentage of the ethylidene norbornene is 0.5-9.0% of the ethylene propylene diene monomer.
Preferably, the unsaturated acid comprises one or more of acrylic acid and derivatives thereof, itaconic acid and derivatives thereof, and unsaturated phosphoric acid and derivatives thereof.
Preferably, the polymer compatilizer comprises one or two of ethylene propylene diene monomer grafted glycidyl methacrylate compatilizers and ethylene propylene diene monomer grafted maleic anhydride compatilizers; the grafting rate of the macromolecular compatilizer is 1.0-3.5 wt%.
Preferably, the flame retardant comprises an inorganic flame retardant and a synergistic flame retardant; the inorganic flame retardant comprises magnesium hydroxide and aluminum hydroxide; the synergistic flame retardant comprises a metal borate; the average particle diameter D50 of the flame retardant is 0.5-3 μm.
Preferably, the vulcanizing agent comprises one or more of sulphur, a sulphur-containing compound, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
Preferably, the vulcanization accelerator comprises one or more of a metal oxide, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate.
Preferably, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, and the mass ratio of the main antioxidant to the auxiliary antioxidant is 1: 1-2.
The invention also provides a preparation method of the anti-seismic low-smoke halogen-free flame-retardant cable sheath material, which comprises the following steps:
premixing a flame retardant, an antioxidant, white carbon black and an anti-aging agent for 2-4 min at the rotating speed of 1000-2500 rpm to obtain primary mixed filler;
adding unsaturated acid into the primary mixed filler, and dispersing and mixing for 5-8min at the rotating speed of 1500-2500 rpm to obtain a modified mixed filler;
and mixing the modified mixed filler, the ethylene propylene diene monomer rubber and the high polymer compatilizer for 10-15min, then adding a vulcanizing agent and a vulcanization accelerator, and continuously mixing for 5-8min at the mixing temperature of 80-120 ℃ to obtain the cable sheath material.
In addition, the invention also provides application of the anti-seismic low-smoke halogen-free flame-retardant cable sheath material in preparation of a high-speed train cable sheath.
As mentioned above, the anti-seismic low-smoke halogen-free flame-retardant cable sheath material disclosed by the invention has the following beneficial effects:
the cable sheath material of the invention introduces unsaturated acid, the double bond in the unsaturated acid and the polymer matrix generate chemical crosslinking action, and the anion group such as carboxyl in the unsaturated acid and the like and the metal cation of the inorganic flame retardant form ion coordination action, thereby constructing an ion-covalent crosslinking network coexisting structure in the material and improving the interface compatibility between the inorganic flame retardant hydroxide and the polymer matrix. On one hand, the covalent cross-linked network ensures the stability of the structure; on the other hand, the dissociation and combination between the anions and cations in the ionic crosslinking structure and the dynamic exchange characteristic between the ions can consume energy generated by vibration, so that the prepared cable sheath material is suitable for preparing a high-speed train cable sheath under the vibration working condition, and provides guarantee for the stable operation of a high-speed train. Meanwhile, the tensile strength of the cable sheath material reaches 40 +/-2 MPa, the limiting oxygen index LOI% reaches more than 35, and the cable sheath material has the performances of oil resistance, aging resistance, environmental stress cracking resistance and the like.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
Note that "%" and "part(s)" shown in the description herein mean "% by mass" and "part(s) by mass", respectively, unless otherwise specified.
The invention provides an anti-seismic low-smoke halogen-free flame-retardant cable sheath material which comprises, by mass, 40-50% of ethylene propylene diene monomer, 1-5% of unsaturated acid, 5-10% of a high-molecular compatilizer, 30-50% of a flame retardant, 1-2% of a vulcanizing agent, 0.5-1% of a vulcanization accelerator, 0.2-0.4% of an antioxidant, 5-10% of white carbon black and 0.5-0.8% of an anti-aging agent.
In a specific embodiment, the third monomer of the ethylene-propylene-diene monomer can be ethylidene norbornene, and the content of ethylidene norbornene is, for example, 0.5-9.0% by mass, for example, 0.5%, 1.0%, 3.0%, 9.0% and the like of the ethylene-propylene-diene monomer. The ethylidene norbornene is used as a third monomer, so that the vulcanization speed of the ethylene propylene diene monomer can be increased, and the ethylene propylene diene monomer has the performances of ozone resistance, chemical medicine resistance (solvent, acid, alkali and the like), discharge resistance, steam resistance and the like, so that the cable sheath material can be suitable for a harsher environment.
In one embodiment, the unsaturated acid may include one or more of acrylic acid and its derivatives, itaconic acid and its derivatives, and unsaturated phosphoric acid and its derivatives, for example, acrylic acid, such as itaconic acid, and unsaturated phosphoric acid, such as vinyl phosphoric acid.
In a particular embodiment, the flame retardant may include an inorganic flame retardant and a synergistic flame retardant; the inorganic flame retardant may include, for example, magnesium hydroxide and aluminum hydroxide; the synergistic flame retardant includes, for example, metal borates; the average particle diameter D50 of the flame retardant may be 0.5 to 3 μm, for example, 0.5 μm, 1.0 μm, 2.0 μm, or the like.
On one hand, the double bond in the unsaturated acid can form a chemical crosslinking structure with the polymer matrix; on the other hand, the unsaturated acid such as carboxyl group and phosphate group in acrylic acid or vinylphosphoric acid can react with metal cation such as Mg in inorganic flame retardant such as magnesium hydroxide and aluminum hydroxide2+、Al3+And ion coordination is formed, so that an ion-covalent cross-linked network coexisting structure is constructed in the material.
In one embodiment, the polymer compatibilizer may include one or two of epdm grafted glycidyl methacrylate compatilizers and epdm grafted maleic anhydride compatilizers. Specifically, for example, ethylene propylene diene monomer rubber is grafted with maleic anhydride, and the maleic anhydride grafted compatilizer enables the material to have high polarity and reactivity by introducing a strong polar reactive group, so that the compatibility of the composite material and the dispersibility of the filler can be greatly improved, and the mechanical strength of the composite material is improved. The graft ratio of the polymeric compatibilizer may be 1.0 to 3.5wt%, for example, 1.0 wt%, 1.5 wt%, 2.0 wt%, 3.0 wt%, 3.5 wt%. The melt index of the polymeric compatibilizer can be 2.0-6.0g/10min (test conditions, 190 ℃/2.16kg), such as 2.0g/10min, 4.0g/10min, 6.0g/10 min; the density of the polymeric compatibilizer may be from 0.80 to 1.10g/cm3For example, 0.8g/cm3、0.9g/cm3、1.0g/cm3、1.1g/cm3。
In one embodiment, the vulcanizing agent may be selected from one or more of sulfur, sulfur-containing compounds, dicumyl peroxide, and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, such as sulfur, dicumyl peroxide, and mixtures of dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane. The vulcanization accelerator may be selected from one or more of metal oxides, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate, such as triallyl cyanurate, such as triallyl isocyanurate, and also mixtures of metal oxides, triallyl cyanurate, triallyl isocyanurate.
In one embodiment, the antioxidant may include a primary antioxidant such as pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and a secondary antioxidant such as tris (2, 4-di-tert-butylphenyl) phosphite. Further, the mass ratio of the primary antioxidant to the secondary antioxidant may be 1:1 to 2, specifically 1:1, 1: 2.
In a specific embodiment, the white carbon black may be, for example, fumed hydrophobic white carbon black, and the average particle size D50 may be 0.9 to 2 μm, such as 0.9 μm, 1.1 μm, 1.5 μm, 2 μm, and the like. The fumed silica is commonly called as 'nano silica', has high chemical purity, good dispersion performance, high temperature resistance and good electrical insulation, and can be used in the cable sheath material to well reinforce the mechanical performance of the material and simultaneously improve the flame retardance and the insulation performance of the material.
In a specific embodiment, the antioxidant is, for example, a hindered phenol type antioxidant, specifically, one or a mixture of two of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl). More specifically, for example, a mixture of N, N' -bis- (3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and 1,3, 5-tris (4-t-butyl-3-hydroxy-2, 6-dimethylbenzyl) in a mass ratio of 1:1 is exemplified.
In addition, the invention also provides a preparation method of the anti-seismic low-smoke halogen-free flame-retardant cable sheath material, which comprises the following steps:
s1, premixing the flame retardant, the antioxidant, the white carbon black and the anti-aging agent for 2-4 min at the rotating speed of 1000-2500 rpm to obtain primary mixed filler;
s2, adding unsaturated acid into the primary mixed filler, and dispersing and mixing for 5-8min at the rotating speed of 1500-2500 rpm to obtain a modified mixed filler;
s3, mixing the modified mixed filler, the ethylene propylene diene monomer rubber and the high polymer compatilizer for 10-15min, then adding the vulcanizing agent and the vulcanization accelerator, and continuing mixing for 5-8min at the mixing temperature of 80-120 ℃ to obtain the anti-seismic low-smoke halogen-free flame-retardant cable sheath material.
In one embodiment, the process of premixing the materials in step S1 is performed in a high speed mixer. In step S2, the unsaturated acid is uniformly added dropwise to the primary mixed filler by means of dropwise addition. The mixing in step S3 is performed in an internal mixer.
The present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited to these examples.
The raw materials used in the examples are described below:
the weight fraction of a third monomer Ethylidene Norbornene (ENB) in the ethylene propylene diene monomer is 0.5 wt%, and the Mooney viscosity [ ML 1+4125 ℃ C ] is 20;
the melt index of the ethylene propylene diene monomer grafted maleic anhydride is 15-25g/10min under the test condition of 280 ℃/2.16kg, the Shore A hardness is 55-90, and the density is 0.80-1.10g/cm3；
In the flame retardant, the inorganic flame retardant is magnesium hydroxide and aluminum hydroxide, the synergistic flame retardant is zinc borate, and the average particle size D50 of the flame retardant is 0.5-3 μm.
The vulcanizing agent is dicumyl peroxide (DCP); the vulcanization accelerator triallyl isocyanurate (TAIC);
in the antioxidants, the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite ester, which are mixed according to the mass ratio of 1: 1;
the white carbon black is gas-phase hydrophobic white carbon black with the fineness of 5000 meshes and the specific surface area of 200 m/g.
The anti-aging agent is N, N' -bis- (3- (3, 5-di-tert-butyl-4 hydroxyphenyl) propionyl) hexanediamine and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) which are mixed according to the mass ratio of 1: 1;
example 1
(1) Weighing the raw materials according to the gram weight of each component listed in the table 1, putting flame retardants magnesium hydroxide, aluminum hydroxide, zinc borate, antioxidant pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, white carbon black, antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) into a high-speed mixer, and premixing for 3min at the rotating speed of 2000rpm to obtain a primary mixed filler.
(2) And uniformly dropwise adding 1g of acrylic acid into the primary mixed filler, and continuously mixing for 5min at the rotating speed of 2000rpm to ensure that the acrylic acid and the inorganic flame retardant generate sufficient ion coordination, thereby obtaining the modified mixed filler.
(3) Setting the mixing temperature of an internal mixer to be 100 ℃, placing the modified mixed filler, the ethylene propylene diene monomer rubber and the high-molecular compatilizer ethylene propylene diene monomer rubber grafted maleic anhydride into the internal mixer, mixing for 10-15min, adding a vulcanizing agent dicumyl peroxide (DCP) and a vulcanization accelerator triallyl isocyanurate (TAIC), and continuously mixing for 5-8min to obtain the cable sheath material.
In order to test the performance of the cable sheath material, the prepared cable sheath material is subjected to hot-pressing vulcanization on a parallel plate vulcanizer, the hot-pressing pressure is 10MPa, the temperature is 180 ℃, and the vulcanization time is 20min, so that a sample strip for testing is obtained.
Example 2
(1) Weighing the raw materials according to the gram weight of each component listed in the table 1, putting flame retardants magnesium hydroxide, aluminum hydroxide, zinc borate, antioxidant pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, white carbon black, antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) into a high-speed mixer, and premixing for 3min at the rotating speed of 2000rpm to obtain a primary mixed filler.
(2) And (3) uniformly dropwise adding 3g of acrylic acid into the primary mixed filler, and continuously mixing for 5min at the rotating speed of 2000rpm, so that the acrylic acid and the inorganic flame retardant generate sufficient ion coordination, and the modified mixed filler is obtained.
(3) Setting the mixing temperature of an internal mixer to be 100 ℃, placing the modified mixed filler, the ethylene propylene diene monomer rubber and the high-molecular compatilizer ethylene propylene diene monomer rubber grafted maleic anhydride into the internal mixer, mixing for 10-15min, adding a vulcanizing agent dicumyl peroxide (DCP) and a vulcanization accelerator triallyl isocyanurate (TAIC), and continuously mixing for 5-8min to obtain the cable sheath material.
In order to test the performance of the cable sheath material, the prepared cable sheath material is subjected to hot-pressing vulcanization on a parallel plate vulcanizer, the hot-pressing pressure is 10MPa, the temperature is 180 ℃, and the vulcanization time is 20min, so that a sample strip for testing is obtained.
Example 3
(1) Weighing the raw materials according to the gram weight of each component listed in the table 1, putting flame retardants magnesium hydroxide, aluminum hydroxide, zinc borate, antioxidant pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, white carbon black, antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) into a high-speed mixer, and premixing for 3min at the rotating speed of 2000rpm to obtain a primary mixed filler.
(2) 1g of vinyl phosphoric acid is uniformly dripped into the primary mixed filler, and the materials are continuously mixed for 5min at the rotating speed of 2000rpm, so that the vinyl phosphoric acid and the inorganic flame retardant generate sufficient ion coordination, and the modified mixed filler is obtained.
(3) Setting the mixing temperature of an internal mixer to be 100 ℃, placing the modified mixed filler, the ethylene propylene diene monomer rubber and the high-molecular compatilizer ethylene propylene diene monomer rubber grafted maleic anhydride into the internal mixer, mixing for 10-15min, adding a vulcanizing agent dicumyl peroxide (DCP) and a vulcanization accelerator triallyl isocyanurate (TAIC), and continuously mixing for 5-8min to obtain the cable sheath material.
In order to test the performance of the cable sheath material, the prepared cable sheath material is subjected to hot-pressing vulcanization on a parallel plate vulcanizer, the hot-pressing pressure is 10MPa, the temperature is 180 ℃, and the vulcanization time is 20min, so that a sample strip for testing is obtained.
Example 4
(1) Weighing the raw materials according to the gram weight of each component listed in the table 1, putting flame retardants magnesium hydroxide, aluminum hydroxide, zinc borate, antioxidant pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, white carbon black, antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) into a high-speed mixer, and premixing for 3min at the rotating speed of 2000rpm to obtain a primary mixed filler.
(2) 3g of vinyl phosphoric acid is uniformly dripped into the primary mixed filler, and the materials are continuously mixed for 5min at the rotating speed of 2000rpm, so that the vinyl phosphoric acid and the inorganic flame retardant generate sufficient ion coordination, and the modified mixed filler is obtained.
(3) Setting the mixing temperature of an internal mixer to be 100 ℃, placing the modified mixed filler, the ethylene propylene diene monomer rubber and the high-molecular compatilizer ethylene propylene diene monomer rubber grafted maleic anhydride into the internal mixer, mixing for 10-15min, adding a vulcanizing agent dicumyl peroxide (DCP) and a vulcanization accelerator triallyl isocyanurate (TAIC), and continuously mixing for 5-8min to obtain the cable sheath material.
In order to test the performance of the cable sheath material, the prepared cable sheath material is subjected to hot-pressing vulcanization on a parallel plate vulcanizer, the hot-pressing pressure is 10MPa, the temperature is 180 ℃, and the vulcanization time is 20min, so that a sample strip for testing is obtained.
Comparative example
(1) Weighing the raw materials according to the gram weight of each component listed in the table 1, putting flame retardants magnesium hydroxide, aluminum hydroxide, zinc borate, antioxidant pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, white carbon black, antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) into a high-speed mixer, and premixing for 3min at the rotating speed of 2000rpm to obtain a primary mixed filler.
(3) Setting the mixing temperature of an internal mixer to be 100 ℃, placing the primary mixed filler, the ethylene propylene diene monomer rubber and the high molecular compatilizer ethylene propylene diene monomer rubber grafted maleic anhydride into the internal mixer, mixing for 10-15min, adding a vulcanizing agent dicumyl peroxide (DCP) and a vulcanization accelerator triallyl isocyanurate (TAIC), and continuously mixing for 5-8min to obtain the cable sheath material.
In order to test the performance of the cable sheath material, the prepared cable sheath material is subjected to hot-pressing vulcanization on a parallel plate vulcanizer, the hot-pressing pressure is 10MPa, the temperature is 180 ℃, and the vulcanization time is 20min, so that a sample strip for testing is obtained.
TABLE 1 composition of raw materials (unit: g) of examples 1 to 4 and comparative example
Performance testing
The main properties of the cable sheath materials prepared in examples 1 to 4 and comparative example are shown in table 1.
TABLE 1 Main Properties of Cable sheath materials of examples 1-4 and comparative examples
It can be found by comparing the properties of examples 1-4 of table 2 with the comparative examples: unsaturated acid is introduced into the material, and a covalent crosslinking structure formed by ion coordination of metal cations and anion groups such as carboxyl, phosphate radical and the like in the inorganic flame retardant and chemical crosslinking is adopted to construct the cable material with an ion-covalent double crosslinking network structure in a system, so that the compatibility between the flame retardant and ethylene propylene diene monomer is remarkably improved, the mechanical property and the oil resistance of the material are improved, the flame retardant effect of the hydroxide flame retardant is improved, and the halogen-free flame retardant property of the cable sheath material is enhanced. Because the inorganic mineral filler has the characteristics of high heat resistance, gas barrier, electric insulation and the like, after the inorganic mineral filler is introduced into the material, the volume resistivity of the material is further improved, so that the insulating property is improved. In addition, the energy generated in forced vibration is dissipated by the dynamic exchange of cross-linking formed by the ionic cross-linking structure in the material, so that a foundation and a guarantee are provided for the structural stability of the material and the dimensional stability of the sheath, the cable sheath prepared from the material has the characteristics of no cracking, good dimensional stability and the like under the vibration working condition of high-speed train operation, and the guarantee is provided for the stable operation of the high-speed train.
The above examples are intended to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.
Claims (9)
1. The anti-seismic low-smoke halogen-free flame-retardant cable sheath material is characterized by comprising the following components in percentage by mass:
40-50 percent of ethylene propylene diene monomer
1 to 5 percent of unsaturated acid
5-10% of macromolecular compatilizer
30 to 50 percent of flame retardant
1 to 2 percent of vulcanizing agent
0.5 to 1 percent of vulcanization accelerator
0.2 to 0.4 percent of antioxidant
5 to 10 percent of white carbon black
0.5 to 0.8 percent of anti-aging agent;
wherein the unsaturated acid comprises one or more of unsaturated phosphoric acid and derivatives thereof; the flame retardant comprises an inorganic flame retardant and a synergistic flame retardant; the inorganic flame retardant comprises magnesium hydroxide and aluminum hydroxide; the synergistic flame retardant includes a metal borate.
2. The anti-seismic low-smoke halogen-free flame-retardant cable sheath material as claimed in claim 1, wherein a third monomer of the ethylene propylene diene monomer is ethylidene norbornene, and the mass percentage of the ethylidene norbornene is 0.5-9.0% of the ethylene propylene diene monomer.
3. The anti-seismic low-smoke halogen-free flame-retardant cable sheath material as claimed in claim 1, wherein the polymer compatilizer comprises one or two of ethylene propylene diene monomer grafted glycidyl methacrylate compatilizer and ethylene propylene diene monomer grafted maleic anhydride compatilizer; the grafting rate of the macromolecular compatilizer is 1.0-3.5 wt%.
4. The anti-seismic low-smoke halogen-free flame-retardant cable sheath material as claimed in claim 1, wherein the average particle size D50 of the flame retardant is 0.5-3 μm.
5. The aseismatic low smoke zero halogen flame retardant cable sheathing compound as claimed in claim 1, wherein the vulcanizing agent comprises one or more of sulfur, a sulfur-containing compound, dicumyl peroxide, 2, 5-dimethyl-2, 5 bis (t-butylperoxy) hexane.
6. The anti-seismic low-smoke zero-halogen flame-retardant cable sheath material as claimed in claim 1, wherein the vulcanization accelerator comprises one or more of metal oxide, triallyl cyanurate, triallyl isocyanurate, and trimethylolpropane triacrylate.
7. The anti-seismic low-smoke halogen-free flame-retardant cable sheath material as claimed in claim 1, wherein the antioxidant comprises a main antioxidant and an auxiliary antioxidant, and the mass ratio of the main antioxidant to the auxiliary antioxidant is 1: 1-2.
8. A preparation method of the anti-seismic low-smoke halogen-free flame-retardant cable sheath material of claim 1 is characterized by comprising the following steps:
premixing a flame retardant, an antioxidant, white carbon black and an anti-aging agent for 2-4 min at the rotating speed of 1000-2500 rpm to obtain primary mixed filler;
adding unsaturated acid into the primary mixed filler, and dispersing and mixing for 5-8min at the rotating speed of 1500-2500 rpm to obtain a modified mixed filler;
and mixing the modified mixed filler, the ethylene propylene diene monomer rubber and the high polymer compatilizer for 10-15min, adding a vulcanizing agent and a vulcanization accelerator, and continuously mixing for 5-8min at the mixing temperature of 80-120 ℃ to obtain the cable sheath material.
9. The use of the aseismatic low smoke zero halogen flame retardant cable sheath material according to any one of claims 1 to 7 in the preparation of a cable sheath for a high speed train.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003147087A (en) * | 2002-11-22 | 2003-05-21 | Sony Corp | Flame retardant resin and method for producing the same |
| CN106554547A (en) * | 2015-09-28 | 2017-04-05 | 上海凯波特种电缆料厂有限公司 | A kind of EMUs cable cross-linking radiation grease-proof low-smoke halogen-free fire proofing and preparation method thereof |
| CN108102207A (en) * | 2018-01-12 | 2018-06-01 | 合肥工业大学 | A kind of halogen-free flameproof thin-walled oil resistant cable insulating manufactured by multiple cross-linked technique and sheath and its manufacturing method and application |
| CN109206820A (en) * | 2018-08-13 | 2019-01-15 | 中铁二院工程集团有限责任公司 | A kind of ageing-resistant EPT rubber packing material and preparation method thereof |
| CN109575418A (en) * | 2018-12-10 | 2019-04-05 | 中广核三角洲（苏州）高聚物有限公司 | 105 DEG C of oil-resisting type irradiated crosslinking low-smoke and halogen-free flame retardant CABLE MATERIALSs and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101918755B1 (en) * | 2017-09-07 | 2018-11-14 | 주식회사 경신전선 | Irradiation crosslinking EPDM composite and cable making by of that |
-
2021
- 2021-10-20 CN CN202111220866.XA patent/CN113736183B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003147087A (en) * | 2002-11-22 | 2003-05-21 | Sony Corp | Flame retardant resin and method for producing the same |
| CN106554547A (en) * | 2015-09-28 | 2017-04-05 | 上海凯波特种电缆料厂有限公司 | A kind of EMUs cable cross-linking radiation grease-proof low-smoke halogen-free fire proofing and preparation method thereof |
| CN108102207A (en) * | 2018-01-12 | 2018-06-01 | 合肥工业大学 | A kind of halogen-free flameproof thin-walled oil resistant cable insulating manufactured by multiple cross-linked technique and sheath and its manufacturing method and application |
| CN109206820A (en) * | 2018-08-13 | 2019-01-15 | 中铁二院工程集团有限责任公司 | A kind of ageing-resistant EPT rubber packing material and preparation method thereof |
| CN109575418A (en) * | 2018-12-10 | 2019-04-05 | 中广核三角洲（苏州）高聚物有限公司 | 105 DEG C of oil-resisting type irradiated crosslinking low-smoke and halogen-free flame retardant CABLE MATERIALSs and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Effect of imidazolium phosphate and multiwalled carbon nanotubes on thermal stability and flame retardancy of polylactide;Hu, YD等;《Composites Part A-Applied Science and Manufacturing》;20150702;第77卷;第147-153页 * |
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