CN114085454A - Environment-friendly high-voltage cable thermoplastic shielding material and preparation method thereof - Google Patents
Environment-friendly high-voltage cable thermoplastic shielding material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 36
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004743 Polypropylene Substances 0.000 claims abstract description 27
- 229920001155 polypropylene Polymers 0.000 claims abstract description 25
- -1 polypropylene Polymers 0.000 claims abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920001971 elastomer Polymers 0.000 claims abstract description 16
- 239000000806 elastomer Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- 239000004698 Polyethylene Substances 0.000 claims abstract description 4
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005977 Ethylene Substances 0.000 claims abstract description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000155 melt Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 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 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 12
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- 239000004703 cross-linked polyethylene Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 4
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- 239000006229 carbon black Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
Abstract
The invention belongs to the technical field of shielding materials, and discloses an environment-friendly high-voltage cable thermoplastic shielding material and a preparation method thereof, which aim to solve the technical problem that the shielding material in the prior art is difficult to simultaneously meet the requirements of mechanical property and thermal stability. The thermoplastic shielding material of the present invention comprises the following components: polypropylene, conductive carbon black, an elastomer, a compatilizer, a dispersant and an antioxidant; the compatilizer is at least one of maleic anhydride grafted PP, maleic anhydride grafted POE, maleic anhydride grafted polyethylene PE, glycidyl methacrylate grafted ethylene and vinyl acetate copolymer. The thermoplastic shielding material disclosed by the invention is designed with a formula system, so that the polypropylene does not need a crosslinking reaction during preparation, has excellent physical and mechanical properties on the basis of ensuring the conductive property of the shielding material only through a grafting reaction, can simplify the production process, effectively saves the production cost, and is suitable for the field of 110, 220 and 500 kV high-voltage alternating current or direct current cables.
Description
Technical Field
The invention relates to the technical field of shielding materials, in particular to an environment-friendly high-voltage cable thermoplastic shielding material and a preparation method thereof.
Background
The power cable is an important matching industry for economic construction in China and has an extremely important position in national economy. In the prior art, cross-linked polyethylene (XLPE) insulated cables are generally adopted, but the XLPE material has higher equipment cost, low yield and large energy consumption in the preparation process; and XLPE is a thermosetting material, is difficult to recover, and not only can bring serious pollution but also wastes a large amount of resources when the XLPE reaches the service life.
In order to improve the compatibility of the material and the environment, polypropylene (PP) is used as a green environment-friendly recyclable non-crosslinked thermoplastic cable insulating material for replacing XLPE insulation, and the development trend is met, and the low-carbon environment-friendly guide of the current society is met. The research on the matched thermoplastic shielding material also has very important significance.
At present, the shielding material for polypropylene cables is prepared by melt blending, such as polypropylene and elastomer as matrix, and Carbon Black (CB) as conductive filler. However, the compatibility and adhesion between the matrix resin and the conductive filler are poor, so that the prepared shielding material has good electrical properties, but the requirements of mechanical properties and thermal stability are difficult to meet at the same time.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an environment-friendly high-voltage cable thermoplastic shielding material and a preparation method thereof so as to overcome the technical problem that the shielding material in the prior art is difficult to meet the requirements of mechanical property and thermal stability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides an environment-friendly thermoplastic shielding material for high-voltage cables, which comprises the following components in parts by weight:
40-60 parts of polypropylene, 10-25 parts of conductive carbon black, 30-60 parts of elastomer, 5-10 parts of compatilizer, 0.5-1 part of dispersant and 0.5-1 part of antioxidant;
the compatilizer is at least one of maleic anhydride grafted PP, maleic anhydride grafted POE, maleic anhydride grafted polyethylene PE, glycidyl methacrylate grafted ethylene and vinyl acetate copolymer.
According to the invention, through the design of a formula system, the electrical and mechanical properties of the shielding material can be considered without crosslinking, the production process can be simplified, and the production cost can be effectively saved. According to the invention, the grafted polymer compatilizer is introduced, and the components of the grafted polymer compatilizer enable the matrix resin molecules and the matrix resin to be combined with the conductive filler, so that the cohesiveness and compatibility among the polypropylene, the elastomer and the conductive carbon black are improved, the dispersity of the conductive carbon black and the elastomer in the polypropylene is improved, the thermal stability of the shielding material is further improved, and the electrical property (volume resistivity) of the shielding material is improved.
As a preferred embodiment of the environment-friendly high-voltage cable thermoplastic shielding material, the melt index of the polypropylene is 2-5 g/10 min.
As a preferred embodiment of the environment-friendly high-voltage cable thermoplastic shielding material, the particle size of the conductive carbon black is 20-30 nm, and the specific surface area is 200-1400 m2/g。
As a preferable embodiment of the environment-friendly high-voltage cable thermoplastic shielding material, the elastomer is at least one of ethylene-octene copolymer, polyethylene, ethylene-vinyl acetate copolymer and ethylene-propylene rubber, so as to improve the impact strength by cooperating with other components.
As a preferred embodiment of the environment-friendly high-voltage cable thermoplastic shielding material, the grafting ratio of the compatilizer is 0.4-1.5%, and the melt index is 1-100 g/10 min.
As a preferred embodiment of the environment-friendly high-voltage cable thermoplastic shielding material, the dispersing agent is a silane or titanate coupling agent, so as to synergistically promote filler dispersion with other components, reduce mixing energy consumption, improve rubber material fluidity, improve product appearance and have the effect of a mold release agent.
As a preferred embodiment of the environment-friendly high-voltage cable thermoplastic shielding material, the antioxidant is at least one of antioxidant 1010, antioxidant 1024 and antioxidant 300; so as to stabilize the volume resistivity of the shielding material in cooperation with other components, and prolong the service life of the shielding material to a certain extent.
In a second aspect, the invention provides a preparation method of the environment-friendly high-voltage cable thermoplastic shielding material, which comprises the following steps:
(1) fully mixing the conductive carbon black and a dispersing agent to obtain pretreated conductive carbon black;
(2) fully mixing polypropylene, elastomer, compatilizer and antioxidant to obtain a mixture;
(3) mixing the mixture with the pretreated conductive carbon black, extruding and granulating to obtain the product.
As a preferred embodiment of the preparation method of the environment-friendly high-voltage cable thermoplastic shielding material, the screw rotation speed is 30-70 r/min during extrusion; the temperature is as follows: the charging section is 175 +/-10 ℃, the mixing section is 185 +/-10 ℃, the extrusion granulation section is 195 +/-10 ℃, and the head section is 170 +/-10 ℃.
By setting and optimizing the working parameters of the extruder, the dispersibility of the conductive filler in the shielding material is improved in the extrusion process, the volume resistivity of the shielding material is reduced, and the electrical property of the shielding material is improved.
In a third aspect, the invention applies the environment-friendly high-voltage cable thermoplastic shielding material to 110, 220 and 500 kV high-voltage alternating current or direct current cables.
Compared with the prior art, the invention has the beneficial effects that:
the environment-friendly high-voltage cable thermoplastic shielding material disclosed by the invention is designed according to a formula system, so that the polypropylene does not need a crosslinking reaction during preparation, has excellent physical and mechanical properties on the basis of ensuring the conductive performance of the shielding material only through a grafting reaction, can simplify the production process, and effectively saves the production cost.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified.
The following examples and comparative examples illustrate the raw materials but are not limited to these materials:
polypropylene 1, No. K8303, melt index 2.5g/10min, purchased from Yanshan petrochemical;
polypropylene 2, brand T30S, melt index 3.4g/10min, purchased from the metallocene petrochemical industry;
conductive carbon black 1 with the mark of Vxc-72, the particle diameter of 30nm and the specific surface area of 254m2Per g, from cabot;
conductive carbon black 2 with the mark of EC-600JD, particle size of 21nm and specific surface area of 1400m2Per g, from Japanese lion king；
Conductive carbon black 3 with the mark of TYT-5, the particle diameter of 50nm and the specific surface area of 63m2(iv)/g, available from Tianyi chemical industry;
elastomer 1, POE8450, available from Dow, USA;
elastomer 2, EPDM3720, available from dow, usa;
1, maleic anhydride grafted PP (polypropylene), with the mark of SWJ-1B, the grafting rate of 0.6-0.8 percent and the melt index of 100g/10 min;
the compatilizer 2 is maleic anhydride grafted POE (polyolefin elastomer) with the mark of PO-1020, the grafting rate of 1.0-1.3 percent and the melt index of 2.6g/10 min;
the compatilizer 3 is maleic anhydride grafted polyethylene PE with the mark of 1040, the grafting rate of 0.4-1 percent and the melt index of 1-4 g/10 min;
the melt index of the polypropylene and the compatibilizer is measured according to GB/T3682-2000 determination of melt mass flow rate and melt volume flow rate of thermoplastic plastics, and the melt index is measured at 230 ℃ and under the load of 2.16 Kg.
Dispersant, trade name KH550, commercially available;
antioxidant 1010, commercially available;
antioxidant 300, commercially available.
Examples and comparative examples:
1. preparation of thermoplastic Shielding Material
(1) The components are weighed according to the weight portion ratio in the table 1.
TABLE 1 formulation of the components of the thermoplastic screen of the examples and comparative examples
(2) Conducting carbon black pretreatment: firstly, mixing conductive carbon black and a dispersing agent at 70 +/-5 ℃ at a low speed for 2-3 min, and then mixing at a high speed for 3-5 min;
preparation of modified matrix resin: adding polypropylene, elastomer, compatilizer and antioxidant into a mixer for fully mixing, controlling the temperature to be 70 +/-5 ℃, mixing for 2-3 min, and stirring at the speed of 40-50 rpm to uniformly disperse all the powder;
preparing a semiconductive shielding material: mixing polypropylene, elastomer, compatilizer and antioxidant, and then adding the mixture into the main feed; and adding the mixture of the conductive carbon black and the dispersing agent which are stirred at a high speed into a side feed, extruding the mixture in a feeding, extruding, granulating and mixing type double-screw extruding granulator, and granulating and drying the mixture underwater to prepare the particles of the environment-friendly power cable semiconductive shielding material.
Wherein, the twin-screw process parameters are as follows: the rotating speed of the screw is 30-70 r/min, and the temperature of the double-screw extruder is as follows: the charging section is 175 +/-10 ℃, the mixing section is 185 +/-10 ℃, the extrusion granulation section is 195 +/-10 ℃, and the head section is 170 +/-10 ℃.
2. Detection of electrical and mechanical properties
(1) Detection standard
The resistivity is detected according to the GB3048.3 standard, the detection condition is that the volume resistivity test utilizes an oven, a testing device is placed in the oven, the testing device is a BD400H type semi-conductive rubber resistivity tester, and the volume resistivity of the test sample at 30 ℃ is measured. Testing the current size to be 1mA, and placing the sample in an oven for at least 15min before testing;
the elongation at break is determined according to the GB/T13022-91 standard under the condition that the samples are dumbbell-shaped samples with the national standard of 4 multiplied by 75mm, the samples are grouped into one group according to each test direction, and each group of the samples comprises 5 samples. The control mode adopted by the test is displacement control, and the test speed is 250 mm/min;
the aging treatment is detected according to GB/T2951.12-2008 standard, and the test condition is 135 ℃ and 168 h.
(2) The results of testing the thermoplastic shields of the examples and comparative examples are shown in table 2.
TABLE 2 thermoplastic Shielding Material Properties
The thermoplastic shielding materials prepared in examples 1, 2, 3 and 4 have higher elongation at break, have lower elongation at break degradation rate after aging test, have no influence on electrical properties basically, and meet the requirements of cable operation.
In conclusion, the embodiment of the invention designs the formula system, so that the polypropylene generates a grafting reaction in the extruder, and the polypropylene has excellent physical and mechanical properties on the basis of ensuring the conductive performance of the shielding material without crosslinking, thereby simplifying the production process and effectively saving the production cost.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The environment-friendly thermoplastic shielding material for the high-voltage cable is characterized by comprising the following components in parts by weight:
40-60 parts of polypropylene, 10-25 parts of conductive carbon black, 30-60 parts of elastomer, 5-10 parts of compatilizer, 0.5-1 part of dispersant and 0.5-1 part of antioxidant;
the compatilizer is at least one of maleic anhydride grafted PP, maleic anhydride grafted POE, maleic anhydride grafted polyethylene PE, glycidyl methacrylate grafted ethylene and vinyl acetate copolymer.
2. The environment-friendly high-voltage cable thermoplastic shielding material as claimed in claim 1, wherein the melt index of the polypropylene is 2-5 g/10 min.
3. The environment-friendly high-voltage cable thermoplastic shielding material as claimed in claim 1, wherein the conductive carbon black has a particle size of 20-30 nm and a specific surface area of 200-1400 m2/g。
4. The environmentally friendly high voltage cable thermoplastic shielding material of claim 1, wherein the elastomer is at least one of ethylene-octene copolymer, polyethylene, ethylene-vinyl acetate copolymer, and ethylene-propylene rubber.
5. The environment-friendly high-voltage cable thermoplastic shielding material as claimed in claim 1, wherein the compatibilizer has a grafting ratio of 0.4-1.5% and a melt index of 1-100 g/10 min.
6. The environment-friendly high-voltage cable thermoplastic shielding material as claimed in claim 1, wherein the dispersant is a silane or titanate coupling agent.
7. The environment-friendly high-voltage cable thermoplastic shielding material as claimed in claim 1, wherein the antioxidant is at least one of an antioxidant 1010, an antioxidant 1024 and an antioxidant 300.
8. The preparation method of the environment-friendly high-voltage cable thermoplastic shielding material as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
(1) fully mixing the conductive carbon black and a dispersing agent to obtain pretreated conductive carbon black;
(2) fully mixing polypropylene, elastomer, compatilizer and antioxidant to obtain a mixture;
(3) mixing the mixture with the pretreated conductive carbon black, extruding and granulating to obtain the product.
9. The method for preparing the environment-friendly high-voltage cable thermoplastic shielding material according to claim 8, wherein during extrusion, the screw rotation speed is 30-70 r/min; the temperature is as follows: the charging section is 175 +/-10 ℃, the mixing section is 185 +/-10 ℃, the extrusion granulation section is 195 +/-10 ℃, and the head section is 170 +/-10 ℃.
10. Use of the environmentally friendly high voltage cable thermoplastic shielding material of any one of claims 1 to 7 in 110, 220, 500 kv high voltage ac or dc cables.
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|---|---|---|---|---|
| CN114891295A (en) * | 2022-06-01 | 2022-08-12 | 青岛科技大学 | High-voltage direct-current cable and polypropylene semi-conductive shielding material and preparation method thereof |
| CN114891295B (en) * | 2022-06-01 | 2023-11-17 | 青岛科技大学 | High-voltage direct-current cable, polypropylene semi-conductive shielding material thereof and preparation method |
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Application publication date: 20220225 |