CN115216082B - Semiconductive shielding material with improved peeling strength, preparation method, product and cable - Google Patents
Semiconductive shielding material with improved peeling strength, preparation method, product and cable Download PDFInfo
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- CN115216082B CN115216082B CN202211049408.9A CN202211049408A CN115216082B CN 115216082 B CN115216082 B CN 115216082B CN 202211049408 A CN202211049408 A CN 202211049408A CN 115216082 B CN115216082 B CN 115216082B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims abstract description 42
- 239000011159 matrix material Substances 0.000 claims abstract description 29
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- 239000002994 raw material Substances 0.000 claims abstract description 24
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- 238000000034 method Methods 0.000 claims description 12
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- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 8
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- 238000004519 manufacturing process Methods 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 5
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- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 12
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 3
- DEKVAWHRMRNKMI-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1OOC(C)(C)C DEKVAWHRMRNKMI-UHFFFAOYSA-N 0.000 description 2
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
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- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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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
Abstract
The invention relates to a semiconductive shielding material with improved peeling strength, a preparation method, a product and a cable. The raw materials of the semiconductive shielding material with the improved peeling strength comprise 58-68 parts of matrix resin, 27-34 parts of conductive carbon black, 1-5 parts of maleic anhydride grafted polyethylene and 0.4-2.2 parts of cross-linking agent in parts by weight, the low-density polyethylene resin and ethylene-acrylic resin in the matrix resin have good interfacial compatibility under the proportion of the raw materials, and the conductive carbon black has good dispersibility in the resin. When the semiconductive shielding material is applied to the cable for preparing the semiconductive shielding layer, the adhesive force between the semiconductive shielding layer and the insulating layer can be effectively improved, the peeling strength between the semiconductive shielding layer and the insulating layer is improved, and the service life of the cable is prolonged.
Description
Technical Field
The invention relates to the technical field of high-voltage cables, in particular to a semiconductive shielding material with improved peeling strength, a preparation method, a product and a cable.
Background
With the development of the power industry, the demand for high-voltage power cables is increasing. In the construction of high voltage cables, the semiconductive shield is an important component that primarily serves to prevent electrical discharge at the interface between the insulating layer and the conductor, as well as to reduce the strength of the electrical stress in the insulating layer. Meanwhile, the semi-conductive shielding layer provides more uniform electric field distribution for the insulating layer by reducing the potential gradient between the stranded conductor and the metal shielding, and improves the initial corona discharge performance of the cable. Compared with a medium-low voltage cable, the high-voltage cable has higher requirements on the quality and reliability of the semiconductor shielding layer.
Adhesion of the semiconductive shield to the insulating layer is a relatively important contributor in improving the performance of high voltage cables. If the adhesive force is small, the semi-conductive shielding layer and the insulating layer are easy to peel, a gap is likely to appear between the semi-conductive shielding layer and the insulating layer due to factors such as stretching in the cable laying process, and a gap is also likely to be generated between the semi-conductive shielding layer and the insulating layer due to factors such as temperature in long-term use. After the gap between the semiconductive shielding layer and the insulating layer occurs, the partial discharge amount may be increased continuously, and even the insulating layer may be broken down in severe cases, resulting in damage to the cable.
Disclosure of Invention
Based on this, it is necessary to provide a semiconductive shield composition having improved peel strength, a method of making, an article of manufacture, and a cable. The semiconductive shielding material can effectively improve the adhesive force between the semiconductive shielding layer and the insulating layer, improve the peeling strength between the semiconductive shielding layer and the insulating layer and prolong the service life of the cable.
In order to solve the above technical problems, the technical solution of an embodiment of the present invention is as follows:
The semiconductive shielding material with improved peeling strength comprises the following raw materials in parts by weight: 58-68 parts of matrix resin, 27-34 parts of conductive carbon black, 1-5 parts of maleic anhydride grafted polyethylene and 0.4-2.2 parts of cross-linking agent; wherein the matrix resin is formed by compounding low-density polyethylene resin and ethylene-acrylic ester resin; the ethylene-acrylic ester resin is one or two of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin.
In one embodiment, the maleic anhydride grafted polyethylene has a grafting ratio of 0.8% to 1.2%.
In one embodiment, the melt index of the maleic anhydride grafted polyethylene is from 2g/10min to 4g/10min.
In one embodiment, the mass ratio of the low-density polyethylene resin to the ethylene-acrylate resin is 1:4 to 4:1.
In one embodiment, the low density polyethylene resin has a melt index of 0.25g/10min to 2g/10min.
In one embodiment, the low density polyethylene resin has a density of 0.918g/cm 3～0.932g/cm3.
In one embodiment, the ethylene-acrylate resin has a melt index of 10g/min or less at 190℃and 2.16 kg.
In one embodiment, the ethylene-acrylate resin has an elongation at break of greater than or equal to 700%.
In one embodiment, the conductive carbon black has an oil absorption value of 150ml/100g to 170ml/100g.
In one embodiment, the conductive carbon black has an ash content of 0.2% or less.
In one embodiment, the conductive carbon black has a 325 mesh screen residue content of 8ppm or less.
In one embodiment, the conductive carbon black is free of sulfur impurities and silicon impurities.
In one embodiment, the cross-linking agent is one or more of bis-t-butylperoxyisopropyl benzene, dicumyl peroxide, and bis 25.
In one embodiment, the feedstock further comprises a processing aid.
In one embodiment, the processing aid includes a dispersant in an amount of 0.6 parts to 2.5 parts by mass.
In one embodiment, the processing aid comprises a coupling agent, wherein the mass portion of the coupling agent is 1-2.
In one embodiment, the processing aid includes a lubricant in an amount of 1 to 2 parts by mass.
In one embodiment, the processing aid comprises 0.3 to 0.7 parts by weight of an antioxidant.
The method for preparing the peel strength improvement type semiconductive shielding material according to any one of the above embodiments, comprising the steps of:
Mixing the low-density polyethylene resin, the ethylene-acrylic ester resin, the conductive carbon black and the maleic anhydride grafted polyethylene to obtain a mixture;
extruding and granulating the mixture to obtain granules;
mixing the chopped granules with the cross-linking agent to obtain a preform;
and heating the preform.
In one embodiment, the temperature of the mixing treatment is 45-50 ℃.
In one embodiment, the rotational speed of the mixing process is 150rpm to 250rpm.
In one embodiment, the extrusion temperature is 150℃to 200 ℃.
In one embodiment, the host rotational speed of the extrusion is 100rpm to 150rpm.
In one embodiment, the temperature of the heating treatment is 50 ℃ to 70 ℃.
In one embodiment, the heating treatment is performed for a period of time ranging from 5 hours to 15 hours.
A semiconductive shield composition comprising the peel strength-improved semiconductive shield composition described in any one of the above embodiments or the peel strength-improved semiconductive shield composition prepared by the method described in any one of the above embodiments.
A cable comprising a conductor, an insulating layer and a semiconductive shield; the conductor is positioned on the inner side of the insulating layer, and the semi-conductive shielding layer is positioned on at least one surface of the insulating layer; the semiconductive shield layer is made of the peel strength-improved semiconductive shield composition described in any one of the above embodiments or the peel strength-improved semiconductive shield composition prepared by the preparation method described in any one of the above embodiments.
The raw materials of the semiconductive shielding material with improved peeling strength comprise 58-68 parts of matrix resin, 27-34 parts of conductive carbon black, 1-5 parts of maleic anhydride grafted polyethylene and 0.4-2.2 parts of cross-linking agent in parts by weight, wherein the low-density polyethylene resin and ethylene-acrylic ester resin in the matrix resin have good interfacial compatibility under the proportion of the raw materials, and the conductive carbon black has good dispersibility in the resin. When the semiconductive shielding material is applied to the cable for preparing the semiconductive shielding layer, the adhesive force between the semiconductive shielding layer and the insulating layer can be effectively improved, the peeling strength between the semiconductive shielding layer and the insulating layer is improved, and the service life of the cable is prolonged.
Further, in the semiconductive shielding material with improved peeling strength, the problems that the mechanical properties of the semiconductive shielding material are restricted by the low-density polyethylene resin and the ethylene-acrylic ester resin due to polarity difference are well solved by the proportion of 58-68 parts by mass, 27-34 parts by mass, 1-5 parts by mass and 0.4-2.2 parts by mass of the matrix resin, the conductive carbon black, the maleic anhydride grafted polyethylene and the crosslinking agent, so that the semiconductive shielding material has good mechanical properties while improving peeling strength.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
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. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
An embodiment of the invention provides a semiconductive shielding material with improved peeling strength. The semiconductive shielding material with improved peeling strength comprises the following raw materials in parts by weight: 58-68 parts of matrix resin, 27-34 parts of conductive carbon black, 1-5 parts of maleic anhydride grafted polyethylene and 0.4-2.2 parts of cross-linking agent; wherein, the matrix resin is compounded by low-density polyethylene resin and ethylene-acrylic ester resin; the ethylene-acrylic ester resin is one or two of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin. In the proportion of the raw materials in the embodiment, the low-density polyethylene resin and the ethylene-acrylic ester resin in the matrix resin have good interfacial compatibility, and the conductive carbon black has good dispersibility in the resin. When the semiconductive shielding material is applied to the cable for preparing the semiconductive shielding layer, the adhesive force between the semiconductive shielding layer and the insulating layer can be effectively improved, the peeling strength between the semiconductive shielding layer and the insulating layer is improved, and the service life of the cable is prolonged.
It will be appreciated that the low density polyethylene resin is a non-polar molecule and the ethylene-acrylate resin is a polar molecule, and that the difference in polarity between the two may adversely affect the mechanical properties such as tensile strength and elongation at break of the product made from the semi-conductive shielding material. In the embodiment, the problems that the mechanical properties of the semiconductive shielding material are restricted by the low-density polyethylene resin and the ethylene-acrylic ester resin due to polarity difference are well solved by the proportion of 58-68 parts by mass of matrix resin, 27-34 parts by mass of conductive carbon black, 1-5 parts by mass of maleic anhydride grafted polyethylene and 0.4-2.2 parts by mass of cross-linking agent, so that the semiconductive shielding material has good mechanical properties. In addition, through the use of the low-density polyethylene resin in the embodiment, the volume resistivity of the semiconductive shielding material at 23 ℃ and 90 ℃ can be effectively reduced, and the electrical property of the semiconductive shielding material is improved.
In yet another embodiment of the present invention, a peel strength improved semiconductive shield composition is provided. The semiconductive shielding material with improved peeling strength comprises the following raw materials in parts by weight: 58-68 parts of matrix resin, 27-34 parts of conductive carbon black, 1-5 parts of maleic anhydride grafted polyethylene and 0.4-2.2 parts of cross-linking agent; wherein, the matrix resin is compounded by low-density polyethylene resin and ethylene-acrylic ester resin; the ethylene-acrylic ester resin is one or two of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin. In the embodiment, 58-68 parts of matrix resin, 27-34 parts of conductive carbon black, 1-5 parts of maleic anhydride grafted polyethylene and 0.4-2.2 parts of cross-linking agent are used as raw materials, and the semiconductive shielding material with good peeling strength and mechanical property can be obtained.
It is understood that, in the raw materials of the peel strength improving type semiconductive shield composition, the mass parts of the matrix resin may be selected from 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, and the like. It will also be appreciated that other suitable selections may be made in the range of 58 parts to 68 parts by mass of the matrix resin.
It is understood that, in the raw materials of the peel strength improving type semiconductive shielding material, the mass part of the conductive carbon black may be selected from 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, and the like. It will also be appreciated that other suitable selections may be made in the range of 27 parts to 34 parts by mass of conductive carbon black.
It is understood that the mass part of the maleic anhydride grafted polyethylene in the raw material of the peel strength improving type semiconductive shielding material may be selected from 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc. It will also be appreciated that other suitable selections may be made in the range of 1 part to 5 parts by mass of maleic anhydride grafted polyethylene.
It is understood that the cross-linking agent may be selected from 0.4 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, etc. in the raw materials of the peel strength improving type semiconductive shielding material. It will also be appreciated that other suitable selections may be made with the mass fraction of crosslinker in the range of 0.4 parts to 2.2 parts.
In a specific example, the low density polyethylene resin has a melting point higher than that of the ethylene-acrylate resin. At this time, the melt expansion of the ethylene-acrylic acid ester resin can be suppressed better by the low-density polyethylene resin, which is advantageous for fixing the conductive network.
In a specific example, the grafting ratio of the maleic anhydride grafted polyethylene is 0.8% to 1.2%. For example, the grafting ratio of the maleic anhydride-grafted polyethylene may be, but not limited to, 0.8%, 0.9%, 1%, 1.1%, 1.2%, etc. It will be appreciated that the grafting ratio of the maleic anhydride grafted polyethylene may be selected in the range of 0.8% to 1.2%.
In a specific example, the melt index of the maleic anhydride grafted polyethylene is from 2g/10min to 4g/10min. Alternatively, the melt index of the maleic anhydride grafted polyethylene is 2g/10min, 2.5g/10min, 3g/10min, 3.5g/10min, 4g/10min, etc. Further alternatively, the melt index of the maleic anhydride-grafted polyethylene may be selected in the range of 2g/10min to 4g/10min.
In the matrix resin, as an example of the amount of the low-density polyethylene resin and the ethylene-acrylic acid ester resin, the mass ratio of the low-density polyethylene resin to the ethylene-acrylic acid ester resin is 1:4 to 4:1. For example, the mass ratio of the low density polyethylene resin to the ethylene-acrylate resin is 1:4, 3:7, 2:3, 1:1, 2:1, 3:1, etc. It will be appreciated that the mass ratio of the low density polyethylene resin to the ethylene-acrylate resin may be selected in the range of 1:4 to 4:1 as well as other suitable choices.
As an example of the parameters of the low-density polyethylene resin, the melt index of the low-density polyethylene resin is 0.25g/10min to 2g/10min. For example, the low-density polyethylene resin has a melt index of 0.5g/10min, 0.6g/10min, 0.8g/10min, 1g/10min, 1.5g/10min, 1.8g/10min, 2g/10min, or the like. It will be appreciated that the melt index of the low density polyethylene resin may be selected in the range of 0.25g/10min to 2g/10min.
Alternatively, the low density polyethylene resin has a density of 0.918g/cm 3～0.932g/cm3. For example, the density of the low-density polyethylene resin is 0.918g/cm 3、0.92g/cm3、0.925g/cm3、0.928g/cm3、0.93g/cm3 or the like. It will be appreciated that the density of the low density polyethylene resin may be selected within the range of 0.918g/cm 3～0.932g/cm3 as well as other suitable options.
In a specific example, the ethylene-acrylate resin has a melt index of 10g/min or less at 190℃and 2.16 kg. For example, the melt index of the ethylene-acrylic acid ester resin is less than or equal to 9g/min at 190 ℃ and 2.16 kg; the melt index of the ethylene-acrylic ester resin is less than or equal to 8g/min at 190 ℃ and 2.16 kg; the melt index of the ethylene-acrylic ester resin is less than or equal to 5g/min at 190 ℃ and 2.16 kg. Further, the elongation at break of the ethylene-acrylic ester resin is more than or equal to 700 percent. Alternatively, the elongation at break of the ethylene-acrylate resin is greater than or equal to 800%; the elongation at break of the ethylene-acrylic ester resin is more than or equal to 900 percent, etc.
Further, the mass percentage of acrylic ester in the ethylene-acrylic ester resin is 15-20%. Alternatively, the mass percent of acrylate in the ethylene-acrylate resin is 15%, 16%, 17%, 18%, 19%, 20%, etc. Further alternatively, the mass percentage of acrylic acid ester in the ethylene-acrylic acid ester resin may be selected within a range of 15% to 20%.
It is understood that the ethylene-acrylate resin is one or both of an ethylene-ethyl acrylate resin and an ethylene-butyl acrylate resin. At this time, the mass percentage of ethyl acrylate in the ethylene-ethyl acrylate resin is 15% -20%. The mass percentage of the butyl acrylate in the ethylene-butyl acrylate resin is 15-20%.
In a specific example, the conductive carbon black has an oil absorption value of 150ml/100g to 170ml/100g. For example, the oil absorption value of the conductive carbon black is 150ml/100g, 160ml/100g, 170ml/100g, etc. It will be appreciated that the oil absorption value of the conductive carbon black may be selected in the range of 150ml/100g to 170ml/100g.
Further, the conductive carbon black is a high purity conductive carbon black. Specifically, the ash content of the conductive carbon black is less than or equal to 0.2 percent. Optionally, the ash content of the conductive carbon black is less than or equal to 0.1%. Further alternatively, the conductive carbon black has an ash content of 0.05% or less. The content of the 325 mesh screen residue of the conductive carbon black is less than or equal to 8ppm. Optionally, the 325 mesh screen residue content of the conductive carbon black is less than or equal to 7ppm. Further alternatively, the conductive carbon black has a 325 mesh screen residue content of 5ppm or less. In a further alternative, the conductive carbon black has a 325 mesh screen residue content of 3ppm or less. Still further, the conductive carbon black is free of sulfur impurities and silicon impurities.
In one specific example, the crosslinking agent is one or more of bis-t-butylperoxyisopropyl benzene (BIPB), dicumyl peroxide (DCP), and bis 25.
In a specific example, the raw material of the peel strength improving type semiconductive shield material further includes a processing aid. The processing property of the semiconductive shielding material can be improved by adding the processing aid, and the comprehensive performance of the semiconductive shielding material is further improved.
Optionally, the processing aid comprises a dispersing agent, wherein the mass part of the dispersing agent is 0.6-2.5 parts. For example, the mass part of the dispersant may be, but is not limited to, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.2 part, 1.5 part, 1.6 part, 1.8 part, 2 parts, 2.2 parts, 2.5 parts, etc. It will be appreciated that the mass fraction of dispersant may be in the range of 0.6 to 2.5 parts, as well as other suitable choices. Specifically, the dispersing agent is one or more of Ethylene Bis Stearamide (EBS), white oil and oleamide.
Optionally, the processing aid comprises a coupling agent, wherein the mass part of the coupling agent is 1-2 parts. For example, the coupling agent is 1 part, 1.3 parts, 1.5 parts, 1.8 parts, 2 parts, etc. by mass. It will be appreciated that the mass fraction of coupling agent may be selected within the range of 1 to 2 parts as appropriate. Specifically, the coupling agent is a silane coupling agent. More specifically. The silane coupling agent may be KH550.
Optionally, the processing aid comprises a lubricant, wherein the mass part of the lubricant is 1-2 parts. For example, the lubricant is 1 part, 1.3 parts, 1.5 parts, 1.8 parts, 2 parts, etc. by mass. It will be appreciated that the parts by weight of the lubricant may be selected within the range of 1 part to 2 parts as appropriate. Specifically, the lubricant is at least one of zinc stearate and paraffin wax.
Optionally, the processing aid comprises an antioxidant, wherein the weight portion of the antioxidant is 0.3 to 0.7 portion. For example, the antioxidant is 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, etc. It will be appreciated that the parts by weight of the antioxidant may be selected within the range of 0.3 to 0.7 parts by weight. Specifically, the antioxidant is one or more of antioxidant 1010, antioxidant 168 and antioxidant 300. More specifically, the antioxidant can be formed by mixing an antioxidant 1010 and an antioxidant 300 according to a mass ratio of 1:1.
In one specific example, the processing aid is formed by mixing a dispersant, a coupling agent, a lubricant, and an antioxidant.
In a specific example, the peel strength improved semiconductive shielding material comprises the following raw materials in parts by weight: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, 1 to 5 parts of maleic anhydride grafted polyethylene, 0.4 to 2.2 parts of cross-linking agent, 0.6 to 2.5 parts of dispersing agent, 1 to 2 parts of coupling agent, 1 to 2 parts of lubricant and 0.3 to 0.7 part of antioxidant; wherein, the matrix resin is compounded by low-density polyethylene resin and ethylene-acrylic ester resin; the ethylene-acrylic ester resin is one or two of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin.
In a specific example, the peel strength improved semiconductive shielding material comprises the following raw materials in parts by weight: 58 to 68 parts of matrix resin, 27 to 34 parts of conductive carbon black, 1 to 5 parts of maleic anhydride grafted polyethylene, 0.4 to 2.2 parts of cross-linking agent, 0.6 to 2.5 parts of dispersing agent, 1 to 2 parts of coupling agent, 1 to 2 parts of lubricant and 0.3 to 0.7 part of antioxidant; wherein, the matrix resin is compounded by low-density polyethylene resin and ethylene-acrylic ester resin; the ethylene-acrylic ester resin is one or two of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin.
In still another embodiment of the present invention, a method for preparing the above-mentioned semiconductive shielding material with improved peel strength is provided. The preparation method comprises the following steps: mixing low-density polyethylene resin, ethylene-acrylic ester resin, conductive carbon black and maleic anhydride grafted polyethylene to obtain a mixture; extruding and granulating the mixture to obtain cut granules; mixing the cut particles with a cross-linking agent to obtain a preform; and heating the preform.
In a specific example, the temperature of the compounding process is 45 ℃ to 50 ℃. For example, the temperature of the mixing treatment may be 45℃at 46℃at 47℃at 48℃at 49℃at 50 ℃. The rotational speed of the mixing treatment is 150 rpm-250 rpm. For example, the rotational speed of the mixing treatment is 150rpm, 180rpm, 200rpm, 250rpm, etc. It will be appreciated that the compounding process may be carried out in a blender.
In one specific example, the temperature of extrusion is 150 ℃ to 200 ℃; for example, the extrusion temperature may be 150 ℃, 160 ℃, 180 ℃, 190 ℃, 200 ℃, etc. The rotation speed of the extruded host machine is 100 rpm-150 rpm; for example, the host rotation speed for extrusion is 100rpm, 110rpm, 120rpm, 130rpm, 140rpm, 150rpm, etc. It is understood that extrusion may be performed in an extruder. Alternatively, the extruder may be a twin screw extruder.
In one specific example, the temperature of the heat treatment is 50 ℃ to 70 ℃; alternatively, the temperature of the heat treatment is 50 ℃, 55 ℃,60 ℃,65 ℃, 70 ℃, or the like. Further, the heating treatment time is 5-15 h. Alternatively, the time of the heat treatment is 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, or the like. By the heat treatment, the cross-linking agent can be fully absorbed by the cut particles, so that the performance of the semiconductive shielding material is improved.
Before mixing the chopped pellets with the cross-linking agent, the method further comprises the steps of: and (3) preserving the temperature of the chopped granules at 50-70 ℃. Alternatively, the incubation temperature is 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, etc. Further, the heat preservation time is 3-6 h. Optionally, the incubation time is 3h, 4h, 5h, 6h, etc.
Before mixing the chopped pellets with the cross-linking agent, the method further comprises the steps of: the crosslinking agent is subjected to grinding treatment. The grinding time is 8 min-20 min. Specifically, the grinding time is 8min, 10min, 15min or 20min, etc. It will be appreciated that the milling may be carried out in a mill.
It is understood that in preparing the peel strength improved semiconductive shielding material, the following steps are further included before the low density polyethylene resin, the ethylene-acrylic acid ester resin, the conductive carbon black and the maleic anhydride grafted polyethylene are mixed: the low-density polyethylene resin, the ethylene-acrylic ester resin, the conductive carbon black, the maleic anhydride grafted polyethylene and the cross-linking agent are dried to remove the moisture in each raw material. Further, when a processing aid is included, the low density polyethylene resin, the ethylene-acrylate resin, the conductive carbon black, the maleic anhydride grafted polyethylene, the crosslinking agent, and the processing aid are dried to remove moisture in each raw material.
Yet another embodiment of the present invention provides a semiconductive shielding article. The preparation raw materials of the product comprise the peel strength improved semi-conductive shielding material or the peel strength improved semi-conductive shielding material prepared by the preparation method. Alternatively, the semiconductive shield composition is extruded from a feedstock comprising the semiconductive shield composition described above. Further alternatively, the semiconductive shielding article is a semiconductive shielding can. Alternatively, the semiconductive shielding article is a high voltage cable semiconductive shielding article.
In a specific example, the semiconductive shielding article may further comprise an insulating material in the raw material from which the semiconductive shielding article is prepared. The semiconductive shielding product is prepared by extrusion molding of raw materials comprising the semiconductive shielding material and the insulating material.
A further embodiment of the present invention provides a cable comprising a conductor, an insulating layer, and a semiconductive shield; the conductor is positioned on the inner side of the insulating layer, and the semi-conductive shielding layer is positioned on at least one surface of the insulating layer; the semiconductive shielding layer is made of the semiconductive shielding material with improved peeling strength or the semiconductive shielding material with improved peeling strength prepared by the preparation method.
In one specific example, the semiconductive shield is positioned on both surfaces of the insulating layer. At this time, the cable comprises a conductor, an inner shielding layer, an insulating layer and an outer shielding layer which are sequentially arranged from inside to outside, wherein the inner shielding layer and the outer shielding layer are semiconductive shielding layers.
The following are specific examples.
Example 1
The preparation raw materials of the semiconductive shielding material with improved peeling strength in the embodiment are as follows: 62.5 parts of matrix resin, 30 parts of conductive carbon black, 1 part of maleic anhydride grafted polyethylene, 2 parts of dispersing agent, 2 parts of coupling agent, 1 part of lubricant, 0.5 part of antioxidant and 1 part of crosslinking agent.
Wherein the matrix resin is low-density polyethylene resin and ethylene-ethyl acrylate resin, and the mass ratio of the low-density polyethylene resin to the ethylene-ethyl acrylate resin is 3:7. The melt index of the low-density polyethylene resin was 0.5g/10min, and the density of the low-density polyethylene resin was 0.918g/cm 3. The mass percent of the ethyl acrylate in the ethylene-ethyl acrylate resin is 17%, the melt index of the ethylene-ethyl acrylate resin at 190 ℃ and 2.16kg is 8.5g/min, and the elongation at break of the ethylene-ethyl acrylate resin is 900%.
The oil absorption value of the conductive carbon black is 158ml/100g, the ash content is less than 0.2%, the content of 325 mesh screen residue is 5ppm, and the conductive carbon black does not contain sulfur impurities and silicon impurities.
The grafting ratio of the maleic anhydride grafted polyethylene is 1.2%, and the melt index of the maleic anhydride grafted polyethylene is 2.5g/10min.
The dispersing agent is ethylene bis stearamide. The coupling agent is silane coupling agent KH550. The lubricant is zinc stearate. The antioxidant is formed by mixing an antioxidant 1010 and an antioxidant 300 according to a mass ratio of 1:1.
The preparation method of the semiconductive shielding material with improved peeling strength in the embodiment comprises the following steps:
S101: drying the low-density polyethylene resin, the ethylene-ethyl acrylate resin, the conductive carbon black, the maleic anhydride grafted polyethylene, the cross-linking agent, the dispersing agent, the coupling agent, the lubricant and the antioxidant to remove water in each raw material.
S102: mixing the low-density polyethylene resin, ethylene-ethyl acrylate resin, conductive carbon black, maleic anhydride grafted polyethylene, a dispersing agent, a coupling agent, a lubricant and an antioxidant in a mixer to obtain a mixture. The temperature of the mixing treatment is 45 ℃, and the rotating speed of the mixing treatment is 160rpm.
S103: extruding the mixture in a double-screw extruder, and granulating to obtain the cut granules. The extrusion temperature was 180℃and the host rotation speed of the extrusion was 120rpm.
S104: the cut pellets were incubated at 65℃for 3h.
S105: the cross-linking agent was milled in a mill for 10min.
S106: mixing the cut pellets after heat preservation with the cross-linking agent after grinding to obtain a preform.
S107: the preform was heated at 65℃for 10h.
After heating, the peel strength-improved semiconductive shield composition in this example was obtained.
Example 2
Example 2 differs from example 1 in that the mass fraction of maleic anhydride-grafted polyethylene is 2 parts.
Example 3
Example 3 differs from example 1 in that the mass fraction of maleic anhydride-grafted polyethylene is 3 parts.
Comparative example 1
Comparative example 1 is different from example 1 in that the base resin is an ethylene-ethyl acrylate resin and the mass part of the maleic anhydride-grafted polyethylene is 0 part.
Comparative example 2
Comparative example 2 is different from example 1 in that the matrix resin is a low density polyethylene resin and the mass part of the maleic anhydride-grafted polyethylene is 0 part.
Comparative example 3
Comparative example 3 differs from example 1 in that the mass fraction of maleic anhydride-grafted polyethylene is 0 parts.
Performance testing
The shields obtained in examples and comparative examples were each pressed to prepare test boards having a thickness of 1 mm. The test panels were then tested for tensile strength, elongation at break, room temperature volume resistivity, 90 ℃ volume resistivity, and glass strength, respectively. The test results are shown in Table 1.
TABLE 1
It can be seen from examples 1 to 3 and comparative example 3 that the mechanical properties of the test boards are effectively improved with the increase of the maleic anhydride grafted polyethylene, and the peeling strength is enhanced from 46N/2cm to be non-peelable, thereby meeting the requirement that the high-voltage cable insulating layer and the semiconductive shielding layer are not peelable. The use of the maleic anhydride grafted polyethylene improves the electrical performance of the test board to a certain extent, probably because the maleic anhydride grafted polyethylene plays roles of a compatilizer, a dispersing agent and a binder, so that the dispersibility of the conductive carbon black in matrix resin is improved, and the adhesiveness of the semiconductive shielding layer and the insulating layer is improved.
As is apparent from comparative examples 1 and 3, the use of the low-density polyethylene resin and the ethylene-ethyl acrylate resin as the matrix resin can effectively improve the peel strength of the semiconductive shield layer and the insulation layer, probably because the low-density polyethylene resin used is a high-voltage ac cable insulation material base material, which has excellent interface matching properties with the insulation layer, so that the peel strength thereof is increased. Further, after the low-density polyethylene resin and the ethylene-ethyl acrylate resin are compounded, the electrical performance of the semiconductive shielding layer is more excellent, but the mechanical performance of the semiconductive shielding layer is reduced, probably because the ethylene-ethyl acrylate resin is a polar molecule, the low-density polyethylene resin is a nonpolar polymer, the compatibility of the low-density polyethylene resin and the ethylene-ethyl acrylate resin is poor, and the tensile strength and the elongation at break of the semiconductive shielding material are reduced during high-proportion compounding. In comparative example 2, a low-density polyethylene resin was used as the matrix resin, but the mechanical properties were poor although the electrical properties and peel strength were good.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is, therefore, indicated by the appended claims, and the description may be intended to interpret the contents of the claims.
Claims (10)
1. The semiconductive shielding material with improved peeling strength is characterized by comprising the following raw materials in parts by weight: 58-68 parts of matrix resin, 27-34 parts of conductive carbon black, 2-5 parts of maleic anhydride grafted polyethylene and 0.4-2.2 parts of cross-linking agent;
Wherein the matrix resin is formed by compounding low-density polyethylene resin and ethylene-acrylic ester resin; the melt index of the low-density polyethylene resin is 0.25g/10 min-2 g/10min; the ethylene-acrylic ester resin is one or two of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin; the melt index of the ethylene-acrylic ester resin is less than or equal to 10g/min at 190 ℃ and 2.16 kg; the elongation at break of the ethylene-acrylic ester resin is more than or equal to 700%;
The grafting rate of the maleic anhydride grafted polyethylene is 0.8% -1.2%; the melt index of the maleic anhydride grafted polyethylene is 2g/10 min-4 g/10min;
The cross-linking agent is one or more of di-tert-butyl peroxyisopropyl benzene, dicumyl peroxide and bis 25.
2. The peel strength improving semiconductive shield composition according to claim 1, wherein the mass ratio of the low-density polyethylene resin to the ethylene-acrylic acid ester resin is 1:4 to 4:1.
3. The peel strength improved semiconductive shield composition of claim 1, comprising one or more of the following features:
(1) The density of the low-density polyethylene resin is 0.918g/cm 3~0.932g/cm3;
(2) The oil absorption value of the conductive carbon black is 150ml/100 g-170 ml/100g;
(3) The ash content of the conductive carbon black is less than or equal to 0.2%;
(4) The content of the 325 mesh screen residue of the conductive carbon black is less than or equal to 8ppm;
(5) The conductive carbon black is free of sulfur impurities and silicon impurities.
4. The peel strength improved semiconductive shield composition of any one of claims 1-3, wherein the feedstock further comprises a processing aid that meets one or more of the following characteristics:
(1) The processing aid comprises 0.6-2.5 parts of dispersing agent by mass;
(2) The processing aid comprises a coupling agent, wherein the mass part of the coupling agent is 1-2;
(3) The processing aid comprises 1-2 parts of lubricant in parts by weight;
(4) The processing aid comprises 0.3-0.7 part of antioxidant by mass.
5. A method for preparing the peel strength improved semiconductive shielding material according to any one of claims 1 to 4, comprising the steps of:
Mixing the low-density polyethylene resin, the ethylene-acrylic ester resin, the conductive carbon black and the maleic anhydride grafted polyethylene to obtain a mixture;
extruding and granulating the mixture to obtain granules;
mixing the chopped granules with the cross-linking agent to obtain a preform;
and heating the preform.
6. The method of preparing a peel strength improved semiconductive shield composition according to claim 5, wherein the compounding treatment meets one or more of the following characteristics:
(1) The temperature of the mixing treatment is 45-50 ℃;
(2) The rotational speed of the mixing treatment is 150 rpm-250 rpm.
7. The method of preparing a peel strength improved semiconductive shield according to claim 5, wherein the extrusion meets one or more of the following characteristics:
(1) The extrusion temperature is 150-200 ℃;
(2) The rotation speed of the extruded host machine is 100 rpm-150 rpm.
8. The method for producing a peel strength-improved semiconductive shield composition according to any one of claims 5 to 7, wherein the heat treatment satisfies one or more of the following characteristics:
(1) The temperature of the heating treatment is 50-70 ℃;
(2) The heating treatment time is 5-15 h.
9. A semiconductive shield composition comprising the peel strength-improved semiconductive shield composition according to any one of claims 1 to 4 or the peel strength-improved semiconductive shield composition according to any one of claims 5 to 8.
10. A cable comprising a conductor, an insulating layer, and a semiconductive shield; the conductor is positioned on the inner side of the insulating layer, and the semi-conductive shielding layer is positioned on at least one surface of the insulating layer; the semiconductive shield layer is made of the peel strength-improved semiconductive shield composition according to any one of claims 1 to 4 or the peel strength-improved semiconductive shield composition prepared by the preparation method according to any one of claims 5 to 8.
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| CN202211049408.9A CN115216082B (en) | 2022-08-30 | 2022-08-30 | Semiconductive shielding material with improved peeling strength, preparation method, product and cable |
| PCT/CN2022/130994 WO2024045340A1 (en) | 2022-08-30 | 2022-11-10 | Peel strength-improved semi-conductive shielding material, preparation method, article, and cable |
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| CN115322472B (en) * | 2022-08-30 | 2023-09-12 | 深圳供电局有限公司 | Semiconductive shielding material based on compound resin and preparation method and application thereof |
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| US3951871A (en) * | 1974-05-16 | 1976-04-20 | Union Carbide Corporation | Deformation resistant shielding composition |
| CN102875883A (en) * | 2006-02-06 | 2013-01-16 | 陶氏环球技术有限责任公司 | Semiconductive compositions |
| FR3090985A1 (en) * | 2018-12-21 | 2020-06-26 | Nexans | Cable comprising an easily peelable semiconductor layer |
| CN113930005A (en) * | 2020-07-14 | 2022-01-14 | 浙江万马高分子材料集团有限公司 | Semiconductive shielding material and preparation method and application thereof |
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| US7767299B2 (en) * | 2005-04-29 | 2010-08-03 | General Cable Technologies Corporation | Strippable cable shield compositions |
| CN102492199A (en) * | 2011-11-24 | 2012-06-13 | 无锡江南电缆有限公司 | Cable semi-conductive shielding material |
| CN107129625A (en) * | 2017-05-09 | 2017-09-05 | 上海贝恩科电缆有限公司 | A kind of elevator cable semi-conductive screen CABLE MATERIALS and preparation method thereof |
| US11017918B2 (en) * | 2017-12-07 | 2021-05-25 | Dym Solution Co., Ltd. | Semi-conductive composition for power cable |
| CN113943454A (en) * | 2021-09-16 | 2022-01-18 | 江苏上上电缆集团新材料有限公司 | Graphene and carbon nanotube synergistic high-electrical-property semiconductive shielding material and preparation method thereof |
| CN115216082B (en) * | 2022-08-30 | 2024-04-16 | 南方电网科学研究院有限责任公司 | Semiconductive shielding material with improved peeling strength, preparation method, product and cable |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3951871A (en) * | 1974-05-16 | 1976-04-20 | Union Carbide Corporation | Deformation resistant shielding composition |
| CN102875883A (en) * | 2006-02-06 | 2013-01-16 | 陶氏环球技术有限责任公司 | Semiconductive compositions |
| FR3090985A1 (en) * | 2018-12-21 | 2020-06-26 | Nexans | Cable comprising an easily peelable semiconductor layer |
| CN113930005A (en) * | 2020-07-14 | 2022-01-14 | 浙江万马高分子材料集团有限公司 | Semiconductive shielding material and preparation method and application thereof |
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