CN109651691B - Low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material and preparation method and application thereof - Google Patents
Low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material and preparation method and application thereof Download PDFInfo
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0853—Ethene vinyl acetate copolymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/2224—Magnesium hydroxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material which is characterized by comprising the following components in parts by weight: 30-60 parts of ethylene vinyl acetate rubber (EVM); 20-40 parts of ethylene-acrylate copolymer; 15-30 parts of SEBS elastomer; 10-15 parts of compatilizer; 80-140 parts of flame retardant; 4-14 parts of flame retardant synergist; 0.5-2 parts of auxiliary crosslinking agent; 0.5-1.5% of antioxidant; 0.2-1.5 of lubricant. The invention also discloses a preparation method and application thereof. The wind energy cable sheath material disclosed by the invention is excellent in various performances and can meet the oil-resistant requirement in the technical indexes of wind energy cables; the torsion resistance is good, and the torsion resistance can withstand torsion tests of 2 ten thousand times at normal temperature and 2000 times at low temperature (-55 ℃); low smoke, no halogen, flame retarding and high mechanical performance. The material is soft, the processability is good, and the cost performance is high.
Description
Technical Field
The invention relates to the field of low-smoke halogen-free flame-retardant cable materials, in particular to a low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material and a preparation method and application thereof.
Background
In recent years, non-renewable energy sources such as petroleum and coal are becoming increasingly more and more concerned about environmental problems such as climate warming and carbon emission. The low-carbon and green clean energy gradually replaces high-carbon and high-pollution non-clean energy, and is a necessary choice for reasonably coping with climate change, effectively protecting ecological environment and guaranteeing energy supply safety in all countries around the world. Wind power is used as a main component of clean energy, has the advantages of inexhaustibility, no pollution, no resource consumption, wide distribution and the like, and is vigorously developed in recent years. The demand for wind power cables as the main component of wind power plants is also greatly increasing. Because of the requirements of laying environment and use, the wind energy cable is required to have the characteristics of torque resistance, cold resistance, oil resistance and the like.
The current wind energy cable material mainly comprises PVC, chloroprene rubber and the like, and has the following defects:
1. the requirements of-55 low-temperature torsion resistance are difficult to meet;
2. belongs to halogen-containing materials, is harmful to the bodies of operators in the production process, can release a large amount of halogen-containing gas during combustion, and is dangerous to health.
Therefore, some cable manufacturers gradually replace halogen-containing materials such as PVC with low-smoke halogen-free materials at present, but the materials produced by domestic material manufacturers have a certain problem in low-temperature torque resistance, and thus a solution is needed.
Therefore, the low-temperature resistant, oil resistant, torsion resistant, low-smoke, halogen-free and flame retardant wind energy cable sheath material is urgently needed to be provided in the field.
Disclosure of Invention
In order to overcome the defects in the prior art, one of the purposes of the invention is to provide a low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material, which solves the problems of good flame retardant property and excellent torsion resistance when the cable sheath material is used for a long time under an ultralow temperature condition.
The invention also aims to provide a preparation method of the low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material.
The invention also aims to provide the application of the low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material.
In order to realize one of the purposes of the invention, the adopted technical scheme is as follows: the low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material comprises the following components in parts by weight:
in a preferred embodiment of the invention, the ethylene vinyl acetate rubber (EVM) has an acrylate content of 50 to 80% and a Mooney viscosity ML (1+4) at 100 ℃ of 20 to 30.
In a preferred embodiment of the present invention, the ethylene-acrylate copolymer is one or a mixture of any two or more of ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA) and ethylene-butyl acrylate copolymer (EBA), wherein the acrylic acid content is 20-30%.
In a preferred embodiment of the present invention, the SEBS elastomer is a linear polymer having a 25-35% styrene content and a viscosity of 1300-2900 cps measured at 25 ℃ in a 20 wt% toluene solution.
In a preferred embodiment of the invention, the compatibilizer is any one or a mixture of more than two of ethylene-acrylate copolymer grafted maleic anhydride, SEBS grafted maleic anhydride and ethylene vinyl acetate grafted maleic anhydride, wherein the maleic anhydride grafting rate of the material is 0.5-5%.
In a preferred embodiment of the invention, the flame retardant is a combination of magnesium hydroxide, aluminum hydroxide and hydromagnesite, and the weight ratio of the magnesium hydroxide, the aluminum hydroxide and the hydromagnesite is 2:2:1-1:1: 1.
In a preferred embodiment of the present invention, the flame retardant synergist is a combination of zinc borate, hydrotalcite and nano montmorillonite, wherein the weight ratio of zinc borate to hydrotalcite to nano montmorillonite is: (2-6): (1-4): (1-4).
In a preferred embodiment of the present invention, the auxiliary crosslinking agent is any one or a mixture of two or more of triallyl hydroxyureate (TAC), triallyl isocyanurate (TAIC), trimethylolpropane trimethacrylate (TMPTMA), and 1, 2-polybutadiene.
In a preferred embodiment of the present invention, the antioxidant is any one or a mixture of two or more of pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076), dilauryl thiodipropionate (DLTP), and tris [2, 4-di-tert-butylphenyl ] phosphite (168).
In a preferred embodiment of the present invention, the lubricant is one or a mixture of two or more of calcium stearate, zinc stearate, polyethylene wax, silicone oil, and silicone master batch.
In order to realize the second purpose of the invention, the adopted technical scheme is as follows: a preparation method of a low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material comprises the following steps:
mixing a flame retardant, a flame-retardant synergist, an auxiliary crosslinking agent, an antioxidant, a lubricant and the like according to a ratio, mixing the mixed flame retardant with ethylene vinyl acetate rubber (EVM), an ethylene-acrylate copolymer, an SEBS elastomer and a compatilizer, and extruding and granulating, wherein four temperature sections in the extruding and granulating process are as follows: the feeding section is 120-130 ℃, the conveying section is 130-140 ℃, the melting section is 140-150 ℃, and the machine head is 150-160 ℃.
In order to achieve the third purpose of the invention, the adopted technical scheme is that the low-temperature-resistant, oil-resistant and torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material is used for preparing the low-temperature-resistant, oil-resistant and torsion-resistant low-smoke halogen-free flame-retardant wind energy cable.
The invention has the beneficial effects that:
the wind energy cable sheath material disclosed by the invention is excellent in various performances and can meet the oil-resistant requirement in the technical indexes of wind energy cables; the torsion resistance is good, and the torsion resistance can withstand torsion tests of 2 ten thousand times at normal temperature and 2000 times at low temperature (-55 ℃); low smoke, no halogen, flame retarding and high mechanical performance.
The material is soft, the processability is good, and the cost performance is high.
Detailed Description
The inventor obtains a radiation crosslinking cable which can meet the oil-resistant requirement in the technical index of the wind energy cable by improving the formula through extensive and intensive research; the torsion resistance is good, and the torsion resistance can withstand torsion tests of 2 ten thousand times at normal temperature and 2000 times at low temperature (-55 ℃); the low-smoke halogen-free flame-retardant wind energy cable sheath material has the advantages of low smoke halogen-free flame retardance, good mechanical property and excellent processing property. The invention discloses a low-smoke halogen-free flame-retardant wind energy cable sheath material, which overcomes the defects of the traditional automobile cable material, so that the material has excellent low-temperature resistance, oil resistance, torsion resistance, flame retardance and comprehensive mechanical properties, and the invention is completed on the basis.
The components of the low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material are described in detail as follows:
ethylene vinyl acetate rubber (EVM)
The ethylene vinyl acetate rubber has excellent oil resistance, flame retardant property, low temperature deflection resistance and weather resistance. The introduction of the vinyl acetate side chain endows the EVM with certain oil resistance, and simultaneously destroys the regularity of the main chain, so that the EVM has good low-temperature flexibility, and the nonpolar methylene structure in the main chain endows the EVM with good low-temperature flex resistance and polar solvent resistance. The content of acrylic ester in ethylene vinyl acetate rubber (EVM) is 50-80%, and the Mooney viscosity ML (1+4) is 20-30 at 100 deg.C.
Ethylene-acrylic ester copolymer
The ethylene-acrylate copolymer has excellent low temperature resistance, oil resistance and thermal stability. The ethylene-acrylic ester copolymer is at least one of ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA) and ethylene butyl acrylate copolymer (EBA); the content of acrylic ester is 20-30%.
SEBS elastomer
The SEBS elastomer has excellent low-temperature deflection resistance, good heat resistance and high mechanical strength. The SEBS elastomer is a linear polymer, has a styrene content of 25-35%, and has a viscosity of 1300-2900 cps measured in a 20 wt% toluene solution at 25 ℃.
Compatilizer
The compatibilizer may improve the compatibility of the flame retardant or other component with the elastomer. The compatilizer is at least one of ethylene-acrylate copolymer grafted maleic anhydride, SEBS grafted maleic anhydride and ethylene vinyl acetate grafted maleic anhydride, and the maleic anhydride grafting rate of the material is 0.5-5%. Preferably, the maleic anhydride graft ratio is 1-3%, based on the total weight of the maleic anhydride grafted material.
Flame retardant
The flame retardant disclosed by the invention achieves a flame retardant effect by generating water molecules through thermal decomposition, has a certain smoke suppression effect, and is environment-friendly, low-smoke and non-toxic. The flame retardant is a combination of magnesium hydroxide, aluminum hydroxide and hydromagnesite, and the weight ratio of the magnesium hydroxide to the aluminum hydroxide to the hydromagnesite is 2:2:1 to 1:1: 1.
Flame-retardant synergist
Flame retardant synergists are known additives for improving the flame retardant effect of flame retardants.
The flame-retardant synergist is a combination of zinc borate, hydrotalcite and nano montmorillonite, wherein the weight ratio of the zinc borate to the hydrotalcite to the nano montmorillonite is as follows: (2-6): (1-4): (1-4).
Auxiliary crosslinking agent
The crosslinking assistant can be added into the irradiation crosslinking elastomer cable material to promote the further irradiation crosslinking of the material, the crosslinking agent added into the irradiation crosslinking elastomer cable material is not particularly limited, and various commercially available crosslinking assistants can be adopted as long as the purpose of the invention is not limited.
The auxiliary crosslinking agent is one or a mixture of more than two of triallyl hydroxyureate (TAC), triallyl isocyanurate (TAIC), trimethylolpropane trimethacrylate (TMPTMA) and 1, 2-polybutadiene.
Antioxidant agent
Antioxidants refer to agents that prevent or inhibit factors such as oxygen, heat, light, ozone, mechanical stress, heavy metal ions, etc., from degrading the performance of the article and extending the shelf-life and service life of the article. The antioxidant to be used in the present invention is not particularly limited, and various commercially available antioxidants can be used as long as they do not limit the object of the present invention.
The antioxidant is one or a mixture of more than two of pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076), dilauryl thiodipropionate (DLTP) and tris [2, 4-di-tert-butylphenyl ] phosphite (168).
Lubricant agent
Lubricants are added during processing to improve the processability of the polyolefin. The lubricant used in the present invention is not particularly limited as long as it does not limit the object of the present invention.
In one embodiment of the present invention, the lubricant is one or a combination of two or more of calcium stearate, zinc stearate, polyethylene wax, silicone oil, and silicone master batch.
Cable product
The invention relates to a low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable product.
The cable product has excellent low temperature resistance, oil resistance, torsion resistance, flame retardance and comprehensive mechanical properties.
Preparation method
A preparation method of a low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material comprises the following steps:
mixing a flame retardant, a flame retardant synergist, an auxiliary crosslinking agent, an antioxidant, a lubricant and the like according to the proportion of claim 1, mixing the mixed flame retardant with ethylene vinyl acetate rubber (EVM), ethylene-acrylate copolymer, SEBS elastomer, a compatilizer and the like, extruding and granulating, wherein four temperature sections in the extruding and granulating process are as follows: the feeding section is 120-130 ℃, the conveying section is 130-140 ℃, the melting section is 140-150 ℃, and the machine head is 150-160 ℃.
It should be understood that, in this section: the ingredients and amounts of ethylene vinyl acetate rubber (EVM), ethylene-acrylate copolymer, SEBS elastomer, compatibilizer, flame retardant synergist, co-crosslinking agent, antioxidant, lubricant, and the like are as described elsewhere herein.
The low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material and the preparation method thereof have the following advantages:
1. by compounding the EVM, the ethylene acrylate copolymer and the SEBS, the prepared cable material is simple in processing technology, high in extrusion speed, low in equipment investment and excellent in comprehensive cost performance.
2. The elastomer cable material disclosed by the invention has excellent low-temperature resistance, oil resistance, torsion resistance, flame retardance and comprehensive mechanical properties.
Other aspects of the invention will be apparent to those skilled in the art in view of the disclosure herein.
Unless otherwise specified, various starting materials of the present invention are commercially available; or prepared according to conventional methods in the art. Unless defined or stated 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. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. Other aspects of the invention will be apparent to those skilled in the art in view of the disclosure herein.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer. Unless otherwise indicated, all parts are parts by weight, all percentages are percentages by weight, and the molecular weight of the polymer is the number average molecular weight.
Unless defined or stated 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. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
Example 1
The names and parts by weight of the components of the formulation of example 1 are shown in table 1:
TABLE 1
Mixing a flame retardant, a flame-retardant synergist, an auxiliary crosslinking agent, an antioxidant, a lubricant and the like in proportion, mixing the mixed flame retardant with ethylene vinyl acetate rubber (EVM), an ethylene-acrylate copolymer, an SEBS (styrene-ethylene-butadiene-styrene) elastomer, a compatilizer and the like, extruding and granulating, wherein four temperature sections in the extruding and granulating process are as follows: the feeding section is 120-130 ℃, the conveying section is 130-140 ℃, the melting section is 140-150 ℃, and the machine head is 150-160 ℃.
Then the obtained cable material is melted and extruded on a cable conductive wire core to coat the flame retardant material to form a sheath, and then irradiation crosslinking is carried out in an electron accelerator by adopting the dose of 12-18 Mrad.
The product of example 1 was tested for property detection and the values of each property are shown in table 7 for the property examples.
Example 2
The names and parts by weight of the components of the formulation of example 2 are shown in table 2:
TABLE 2
The preparation method of the cable material is the same as that of the embodiment 2.
The product of example 2 was tested for property detection and the values of each property are shown in table 7 for the performance examples.
Example 3
The names and parts by weight of the components of the formulation of example 3 are shown in table 3:
TABLE 3
The preparation method of the cable material is the same as that of example 3.
The product of example 3 was tested for property detection and the values of each property are shown in table 7 for the performance examples.
Example 4
The names and parts by weight of the components of the formulation of example 4 are shown in table 4:
TABLE 4
The preparation method of the cable material is the same as that of example 4.
The product of example 4 was tested for property detection and the values of each property are shown in table 7 for the performance examples.
Example 5
The names and parts by weight of the components of the formulation of example 5 are shown in table 5:
TABLE 5
The preparation method of the cable material is the same as that of example 5.
The product of example 5 was tested for property detection and the values of each property are shown in table 7 for the performance examples.
Example 6
The names and parts by weight of the components of the formulation of example 6 are shown in table 6:
TABLE 6
The preparation method of the cable material is the same as that of example 6.
The product of example 6 was tested for property detection and the values of each property are shown in table 7 for the performance examples.
Comparative example 1
The names and parts by weight of the components of the formulation of comparative example 1 are shown in table 7:
TABLE 7
The preparation method of the cable material is the same as that of comparative example 1.
The product of comparative example 1 was subjected to a performance test, and the respective performance values are shown in table 7 of performance examples.
Performance testing
The product performance was tested as follows:
(1) and (3) testing tensile property:
testing the tensile property according to the GB/T1040-2008 standard;
(2) and (3) oxygen index test:
testing the flame retardant property according to the GB/T2406.1-2008 standard;
(3) smoke Density test
Testing the smoke density performance according to the GB/T17651.2-1998 standard;
(3) hot elongation test
The hot elongation properties were tested according to the GB/T2951.21-2008 standard.
(4) Hardness of
The Shore hardness A is tested according to the GB/T2411-2008 standard.
(5) Oil resistance
And testing the mineral oil resistance according to the GB/T2951.21-2008 standard.
(6) Torque resistance test
And testing the torque resistance according to the GB/T33606-2017 standard. The test results are shown in table 8.
TABLE 8
As can be seen from the data in Table 7, the wind energy cable sheath material disclosed by the invention is excellent in various performances and can meet the oil-resistant requirement in the technical indexes of wind energy cables; the torsion resistance is good, and the torsion resistance can withstand torsion tests of 2 ten thousand times at normal temperature and 2000 times at low temperature (-55 ℃); low smoke, no halogen, flame retarding and high mechanical performance. The material is soft, the processability is good, the cost performance is high, and the market prospect is wide.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the scope of the invention, which is defined by the claims appended hereto, and any other technical entity or method that is encompassed by the claims as broadly defined herein, or equivalent variations thereof, is contemplated as being encompassed by the claims. All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the above disclosure, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (3)
1. The low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material is characterized by comprising the following components in parts by weight:
the flame retardant is a combination of magnesium hydroxide, aluminum hydroxide and hydromagnesite, and the weight ratio of the magnesium hydroxide to the aluminum hydroxide to the hydromagnesite is 2:2:1-1:1: 1;
the flame-retardant synergist is a combination of zinc borate, hydrotalcite and nano-montmorillonite, wherein the weight ratio of the zinc borate to the hydrotalcite to the nano-montmorillonite is as follows: (2-6): (1-4): (1-4);
the auxiliary crosslinking agent is any one of triallyl hydroxyureate (TAC), triallyl isocyanurate (TAIC), trimethylolpropane trimethacrylate (TMPTMA) and 1, 2-polybutadiene;
the content of acrylic ester of the ethylene vinyl acetate rubber (EVM) is 50-80%, and the Mooney viscosity ML (1+4) is 20-30 at 100 ℃;
the ethylene-acrylate copolymer is any one of ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA) and ethylene butyl acrylate copolymer (EBA), wherein the acrylic acid content is 20-30%;
the SEBS elastomer is a linear polymer, wherein the content of the benzene and the olefin is 25-35%, and the viscosity measured in a 20 wt% toluene solution at 25 ℃ is 1300-2900 cps;
the compatilizer is any one of ethylene-acrylate copolymer grafted maleic anhydride, SEBS grafted maleic anhydride and ethylene vinyl acetate grafted maleic anhydride, wherein the maleic anhydride grafting rate of the material is 0.5-5%
The antioxidant is any one of pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076)
The lubricant is any one of zinc stearate, polyethylene wax and silicone oil.
2. The preparation method of the low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material as claimed in claim 1, characterized by comprising the following steps:
mixing a flame retardant, a flame-retardant synergist, an auxiliary crosslinking agent, an antioxidant, a lubricant and the like according to a ratio, mixing the mixed flame retardant with ethylene vinyl acetate rubber (EVM), an ethylene-acrylate copolymer, an SEBS elastomer and a compatilizer, and extruding and granulating, wherein four temperature sections in the extruding and granulating process are as follows: the feeding section is 120-130 ℃, the conveying section is 130-140 ℃, the melting section is 140-150 ℃, and the machine head is 150-160 ℃.
3. The use of the low temperature resistant, oil resistant, torsion resistant low smoke zero halogen flame retardant wind energy cable sheathing material according to claim 1, characterized in that it is used for preparing low temperature resistant, oil resistant, torsion resistant low smoke zero halogen flame retardant wind energy cable.
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| CN201811475874.7A CN109651691B (en) | 2018-12-04 | 2018-12-04 | Low-temperature-resistant oil-resistant torsion-resistant low-smoke halogen-free flame-retardant wind energy cable sheath material and preparation method and application thereof |
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