CN112538210A - Deformation-resistant low-eccentricity thermoplastic semiconductive shielding material and preparation method and application thereof - Google Patents
Deformation-resistant low-eccentricity thermoplastic semiconductive shielding material and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a deformation-resistant low-eccentricity thermoplastic semiconductive shielding material, a preparation method and application thereof, wherein the raw materials comprise: the composite material comprises a resin component, a layered additive with a three-dimensional layered structure, conductive carbon black, an antioxidant and a lubricating dispersant, wherein the resin component comprises polypropylene, bimodal linear low-density polyethylene and a thermoplastic polyolefin elastomer; the number of layers of the layered additive is more than or equal to 2, the distance between the layers is more than or equal to 20nm, and the layered additive is one or more selected from silicon-magnesium-aluminum powder, hydrotalcite and montmorillonite; preparation: mixing all raw materials except polypropylene according to a formula ratio, extruding and granulating to prepare a premix, and then mixing the premix with the polypropylene according to the formula ratio, extruding and granulating to prepare the polypropylene premix; the cable prepared from the semiconductive shielding material has low volume resistivity, excellent deformation resistance and low eccentricity, and stable product quality, and ensures good application of the material in preparation of power cables.
Description
Technical Field
The invention belongs to the technical field of semiconductive shielding layer materials, and particularly relates to a deformation-resistant low-eccentricity thermoplastic semiconductive shielding material, and a preparation method and application thereof.
Background
The power cable is composed of a metal conductor, an inner semi-conductive shielding layer, an insulating layer, an outer semi-conductive shielding layer, an outer protective material and the like. The semi-conductive shielding layer plays a role in homogenizing the surface electric field of the conductor, and the performance of the semi-conductive shielding layer greatly influences the performance of the cable. Due to the low cost and simple processing technology of the thermoplastic shielding material, the chemical crosslinking type polyolefin semiconductive shielding material is generally used as the conventional semiconductive shielding material, but the cable prepared by the method needs to be vulcanized through a vulcanization pipeline and needs to be degassed after vulcanization, the production period generally exceeds 15 days, and the energy consumption is huge. In view of these disadvantages, silane crosslinking type semiconductive shielding materials have been developed, for example, chinese patent CN110938274A, which discloses a silane crosslinking type semiconductive shielding material comprising a component a and a component B, wherein the mass ratio of the component a to the component B is 90-99.5: 10-0.5; wherein the component A comprises: silane crosslinked polyethylene, conductive carbon black and an ethylene-octene copolymer; the component B comprises: polyethylene and a silane crosslinking catalyst. The cable prepared by the method needs hot water cooking for crosslinking, and the process is complex.
In view of the above problems, non-crosslinked thermoplastic semiconductive shield materials have been recently studied. There is also currently proposed polypropylene as a resin component of a semiconductive shielding material for thermoplastic insulated cables, for example, CN110498964A, which discloses a thermoplastic semiconductive shielding material for high voltage cables, the material comprises the following components in parts by weight: 15-40 parts of polypropylene, 30-50 parts of polyolefin copolymer elastomer, 15-40 parts of conductive carbon black, 0.1-5.0 parts of composite conductive powder, 0.5-10 parts of lubricating dispersant and 0.5-5.0 parts of antioxidant; the composite conductive powder is MXene-graphene, MXene-carbon nano tube or graphene-carbon nano tube composite conductive powder.
However, although the semiconductive shielding materials in the above patents all reduce the volume resistivity of the materials and achieve a better uniform electric field effect, in the cable processing process, because the CCV (catenary production line) and VCV (vertical tower production line) technologies are commonly used at present, polypropylene is a crystalline polymer, and under the action of such gravity, the melt strength of the polypropylene is very low, the deformation resistance is very poor, and the roundness of the produced cable is unstable and the eccentricity is serious. This has become a problem to be solved for non-crosslinked thermoplastic cable shields.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an improved thermoplastic semiconductive shielding material, and a cable prepared from the semiconductive shielding material has low volume resistivity, excellent deformation resistance and low eccentricity, is stable in product quality, and ensures good application of the material in preparation of a power cable.
The invention also provides a preparation method of the thermoplastic semiconductive shielding material.
The invention also provides an application of the thermoplastic semiconductive shielding material in preparation of a power cable.
In order to achieve the purpose, the invention adopts a technical scheme that:
a thermoplastic semiconductive shield material, the semiconductive shield material comprising, from a feedstock: the conductive carbon black lubricating agent comprises a resin component, conductive carbon black, an antioxidant and a lubricating dispersant, wherein the resin component comprises polypropylene and a thermoplastic polyolefin elastomer; wherein the resin component also comprises bimodal linear low density polyethylene, and the feeding mass ratio of the polypropylene to the bimodal linear low density polyethylene to the thermoplastic polyolefin elastomer is 1: 0.05-0.5: 0.25-1.5; the raw materials also comprise layered additives with a three-dimensional layered structure, the number of layers of the layered additives is more than or equal to 2, the distance between the layers is more than or equal to 20nm, the layered additives are one or a combination of more than one of silicon-magnesium-aluminum powder, hydrotalcite and montmorillonite, and the feeding mass ratio of the layered additives to the resin component is 0.02-0.25: 1.
According to some preferred aspects of the present invention, the charge mass ratio of the polypropylene, the bimodal linear low density polyethylene and the thermoplastic polyolefin elastomer is 1: 0.2-0.5: 0.3-1.
According to some preferred aspects of the present invention, the charging mass ratio of the lamellar additive to the resin component is 0.05-0.1: 1.
According to some preferred aspects of the present invention, the polypropylene has a melt index of 0.3 to 5g/10 min.
According to some preferred aspects of the present invention, the bimodal linear low density polyethylene has a melt index of from 0.1 to 2g/10 min.
According to some preferred aspects of the present invention, the thermoplastic polyolefin elastomer is a POE resin (ethylene-octene copolymer) having a melt index of 0.1 to 5g/10 min.
According to some preferred aspects of the invention, the raw materials comprise, by mass, 40-80 parts of polypropylene, 5-20 parts of bimodal linear low density polyethylene, 20-50 parts of thermoplastic polyolefin elastomer, 5-15 parts of layered additive, 30-50 parts of conductive carbon black, 0.1-1.5 parts of antioxidant and 0.5-2 parts of lubricating dispersant.
According to some preferred and specific aspects of the present invention, the antioxidant is antioxidant 1010, antioxidant 300, antioxidant DLTDP, antioxidant DSTDP, or the like.
According to some preferred and specific aspects of the present invention, the lubricating dispersant is polyethylene wax, polypropylene wax, ethylene bis stearamide, or the like.
In the present invention, the layered additive of the present invention, such as attapulgite powder, hydrotalcite and montmorillonite, can be obtained commercially.
The invention provides another technical scheme that: a method for preparing the thermoplastic semiconductive shielding material, the method comprising the following steps:
(1) adding all raw materials except polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to prepare a premix; wherein the extrusion temperature of the extrusion granulation is 150-180 ℃;
(2) adding the premix obtained in the step (1) and polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to obtain the thermoplastic semiconductive shielding material; wherein the extrusion temperature of the extrusion granulation is 180-220 ℃.
The invention provides another technical scheme that: the application of the thermoplastic semiconductive shielding material in preparing a power cable is provided.
In the present invention, the melt index of polypropylene is measured at 230 ℃ under the test load of 2.16Kg in accordance with ASTM D1238, and the melt index of the other polymer is measured at 190 ℃ under the test load of 2.16Kg in accordance with ASTM D1238.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention creatively adds the bimodal linear low-density polyethylene into the semiconductive shielding material which adopts polypropylene as the main resin component, so that the bimodal linear low-density polyethylene is compounded with the polypropylene and the thermoplastic polyolefin elastomer, the melt strength of the material in a molten state can be improved, and the semiconductive shielding material has a preliminary anti-deformation effect The material has the advantages that the material has excessive eccentricity under the action of external force such as gravity, particularly, the melt viscosity of the material is more than 5000mPa.s at the processing temperature of 230 ℃, and the material can have excellent anti-deformation effect and low eccentricity effect in the processing process; in addition, the semiconductive shielding material disclosed by the invention has the advantages of lower volume resistivity, better mechanical property and the like, so that the semiconductive shielding material is suitable for preparing a power cable with stable quality.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art.
In the following examples, the melt index of polypropylene is 1.5g/10min, available from the smooth petrochemical under the EPS30R designation; the melt index of the bimodal linear low density polyethylene is 0.25g/10min, which is purchased from the Bolu chemical industry and has the brand number of FB 2235; the POE resin has a melt index of 3.6g/10min, is purchased from Mitsui Chemicals and has a mark of DF 840; the silicon-magnesium-aluminum powder is purchased from Liaoning essence new materials GmbH, and the trademark is silicon-magnesium-aluminum powder, the number of layers is 2, and the interlayer spacing is 25 nm; hydrotalcite is purchased from Nippon chemical, and has the mark of HT-P, 3 layers and 30nm interlayer spacing; montmorillonite is purchased from Nanocor, USA, and has a mark of I.44P, 2 layers and a layer spacing of 30 nm; conductive carbon black is available from U.S. cabot under the designation VCX 500; the antioxidant is antioxidant 1010; the lubricating dispersant is ethylene bis stearamide.
Example 1
The embodiment provides a thermoplastic semiconductive shielding material, which comprises the following raw materials in parts by mass: 60 parts of polypropylene, 20 parts of bimodal linear low-density polyethylene, 20 parts of thermoplastic polyolefin elastomer, 5 parts of silicon-magnesium-aluminum powder, 50 parts of conductive carbon black, 1 part of antioxidant and 1 part of lubricating dispersant.
The preparation method of the thermoplastic semiconductive shielding material comprises the following steps:
(1) adding all raw materials except polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to prepare a premix; wherein the extrusion temperature of the extrusion granulation is 165 +/-5 ℃;
(2) adding the premix obtained in the step (1) and polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to obtain the thermoplastic semiconductive shielding material; wherein the extrusion temperature of the extrusion granulation is 200 +/-5 ℃.
Example 2
The embodiment provides a thermoplastic semiconductive shielding material, which comprises the following raw materials in parts by mass: 60 parts of polypropylene, 20 parts of bimodal linear low-density polyethylene, 20 parts of thermoplastic polyolefin elastomer, 5 parts of hydrotalcite, 50 parts of conductive carbon black, 1 part of antioxidant and 1 part of lubricating dispersant.
The preparation method of the thermoplastic semiconductive shielding material comprises the following steps:
(1) adding all raw materials except polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to prepare a premix; wherein the extrusion temperature of the extrusion granulation is 165 +/-5 ℃;
(2) adding the premix obtained in the step (1) and polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to obtain the thermoplastic semiconductive shielding material; wherein the extrusion temperature of the extrusion granulation is 200 +/-5 ℃.
Example 3
The embodiment provides a thermoplastic semiconductive shielding material, which comprises the following raw materials in parts by mass: 60 parts of polypropylene, 20 parts of bimodal linear low-density polyethylene, 20 parts of thermoplastic polyolefin elastomer, 5 parts of montmorillonite, 50 parts of conductive carbon black, 1 part of antioxidant and 1 part of lubricating dispersant.
The preparation method of the thermoplastic semiconductive shielding material comprises the following steps:
(1) adding all raw materials except polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to prepare a premix; wherein the extrusion temperature of the extrusion granulation is 165 +/-5 ℃;
(2) adding the premix obtained in the step (1) and polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to obtain the thermoplastic semiconductive shielding material; wherein the extrusion temperature of the extrusion granulation is 200 +/-5 ℃.
Example 4
The embodiment provides a thermoplastic semiconductive shielding material, which comprises the following raw materials in parts by mass: 50 parts of polypropylene, 20 parts of bimodal linear low-density polyethylene, 30 parts of thermoplastic polyolefin elastomer, 10 parts of silicon-magnesium-aluminum powder, 45 parts of conductive carbon black, 1 part of antioxidant and 1 part of lubricating dispersant.
The preparation method of the thermoplastic semiconductive shielding material comprises the following steps:
(1) adding all raw materials except polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to prepare a premix; wherein the extrusion temperature of the extrusion granulation is 165 +/-5 ℃;
(2) adding the premix obtained in the step (1) and polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to obtain the thermoplastic semiconductive shielding material; wherein the extrusion temperature of the extrusion granulation is 200 +/-5 ℃.
Example 5
The embodiment provides a thermoplastic semiconductive shielding material, which comprises the following raw materials in parts by mass: 60 parts of polypropylene, 5 parts of bimodal linear low-density polyethylene, 35 parts of thermoplastic polyolefin elastomer, 10 parts of hydrotalcite, 45 parts of conductive carbon black, 1 part of antioxidant and 1 part of lubricating dispersant.
The preparation method of the thermoplastic semiconductive shielding material comprises the following steps:
(1) adding all raw materials except polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to prepare a premix; wherein the extrusion temperature of the extrusion granulation is 165 +/-5 ℃;
(2) adding the premix obtained in the step (1) and polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to obtain the thermoplastic semiconductive shielding material; wherein the extrusion temperature of the extrusion granulation is 200 +/-5 ℃.
Example 6
The embodiment provides a thermoplastic semiconductive shielding material, which comprises the following raw materials in parts by mass: 40 parts of polypropylene, 20 parts of bimodal linear low-density polyethylene, 40 parts of thermoplastic polyolefin elastomer, 5 parts of montmorillonite, 45 parts of conductive carbon black, 1 part of antioxidant and 1 part of lubricating dispersant.
The preparation method of the thermoplastic semiconductive shielding material comprises the following steps:
(1) adding all raw materials except polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to prepare a premix; wherein the extrusion temperature of the extrusion granulation is 165 +/-5 ℃;
(2) adding the premix obtained in the step (1) and polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to obtain the thermoplastic semiconductive shielding material; wherein the extrusion temperature of the extrusion granulation is 200 +/-5 ℃.
Comparative example 1
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: the bimodal linear low density polyethylene was not added and an equal amount of polypropylene was substituted.
Comparative example 2
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: silicon-magnesium-aluminum powder is not added.
Comparative example 3
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: the silicon-magnesium-aluminum powder is replaced by single-layer flake graphene (purchased from Shanghai Fubian Korea company, trademark FQ-23).
Performance testing
The thermoplastic semiconductive shield materials prepared in the above examples 1 to 6 and comparative examples 1 to 3 were subjected to the following performance tests, and the specific results are shown in table 1.
TABLE 1
In Table 1, the test standard for tensile strength is GB/T1040.3-2006;
the test standard of the elongation at break is GB/T1040.3-2006;
the test standard of the volume resistivity at 20 ℃ is GB/T3048.3-2007;
the test standard of the volume resistivity at 90 ℃ is GB/T3048.3-2007;
the test standard of the impact embrittlement temperature is GB/T5470-2008;
the test standard of the thermal aging test (130 ℃ multiplied by 168h) is GB/T2951.12-2008;
the test standard of the tensile strength change rate is GB/T1040.3-2006;
the test standard of the elongation at break change rate is GB/T1040.3-2006;
the test standard for melt viscosity at 230 ℃ is SY/T0520-.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A thermoplastic semiconductive shield material, the semiconductive shield material comprising, from a feedstock: the conductive carbon black-based composite material comprises a resin component, conductive carbon black, an antioxidant and a lubricating dispersant, wherein the resin component comprises polypropylene and a thermoplastic polyolefin elastomer, and is characterized in that the resin component also comprises bimodal linear low density polyethylene, and the feeding mass ratio of the polypropylene to the bimodal linear low density polyethylene to the thermoplastic polyolefin elastomer is 1: 0.05-0.5: 0.25-1.5; the raw materials also comprise layered additives with a three-dimensional layered structure, the number of layers of the layered additives is more than or equal to 2, the distance between the layers is more than or equal to 20nm, the layered additives are one or a combination of more than one of silicon-magnesium-aluminum powder, hydrotalcite and montmorillonite, and the feeding mass ratio of the layered additives to the resin component is 0.02-0.25: 1.
2. The thermoplastic semiconductive shield material of claim 1, wherein the polypropylene, the bimodal linear low density polyethylene, and the thermoplastic polyolefin elastomer are fed in a mass ratio of 1: 0.2-0.5: 0.3-1.
3. The thermoplastic semiconductive shield material of claim 1, wherein the charge mass ratio of the laminar additive to the resin component is 0.05-0.1: 1.
4. The thermoplastic semiconducting shield material of claim 1, wherein the polypropylene has a melt index of 0.3-5g/10 min.
5. The thermoplastic semiconductive shield material of claim 1, wherein the bimodal linear low density polyethylene has a melt index of 0.1-2g/10 min.
6. The thermoplastic semiconductive shield material of claim 1, wherein the thermoplastic polyolefin elastomer is a POE resin having a melt index of 0.1 to 5g/10 min.
7. The thermoplastic semiconductive shielding material according to claim 1, wherein the raw materials comprise, by mass, 40-80 parts of polypropylene, 5-20 parts of bimodal linear low density polyethylene, 20-50 parts of thermoplastic polyolefin elastomer, 5-15 parts of layered additive, 30-50 parts of conductive carbon black, 0.1-1.5 parts of antioxidant and 0.5-2 parts of lubricating dispersant.
8. The thermoplastic semiconductive shield material according to claim 1 or 7, wherein the antioxidant is a combination of one or more selected from antioxidant 1010, antioxidant 300, antioxidant DLTDP and antioxidant DSTDP; the lubricating dispersant is one or more of polyethylene wax, polypropylene wax and ethylene bisstearamide.
9. A method for preparing a thermoplastic semiconducting shield material according to any of claims 1-8, characterized in that the method comprises the steps of:
(1) adding all raw materials except polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to prepare a premix; wherein the extrusion temperature of the extrusion granulation is 150-180 ℃;
(2) adding the premix obtained in the step (1) and polypropylene into a double-screw extruder according to a formula ratio, and extruding and granulating to obtain the thermoplastic semiconductive shielding material; wherein the extrusion temperature of the extrusion granulation is 180-220 ℃.
10. Use of a thermoplastic semiconducting shield material according to any of claims 1-8 for the preparation of a power cable.
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