CN114106504A - Thermoplastic medium-voltage cable insulating material and preparation method thereof - Google Patents
Thermoplastic medium-voltage cable insulating material and preparation method thereof Download PDFInfo
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- CN114106504A CN114106504A CN202111039674.9A CN202111039674A CN114106504A CN 114106504 A CN114106504 A CN 114106504A CN 202111039674 A CN202111039674 A CN 202111039674A CN 114106504 A CN114106504 A CN 114106504A
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- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 50
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 50
- 239000011810 insulating material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 polypropylene Polymers 0.000 claims abstract description 159
- 239000004743 Polypropylene Substances 0.000 claims abstract description 148
- 229920001155 polypropylene Polymers 0.000 claims abstract description 148
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 85
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 38
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000007872 degassing Methods 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 83
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 39
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 38
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 34
- 239000005977 Ethylene Substances 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 28
- 238000009413 insulation Methods 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 11
- DZQLHCOVAAWDKG-UHFFFAOYSA-N NN.C(C)(C)(C)C=1C=C(C=C(C1O)C(C)(C)C)C(C(=O)O)C Chemical compound NN.C(C)(C)(C)C=1C=C(C=C(C1O)C(C)(C)C)C(C(=O)O)C DZQLHCOVAAWDKG-UHFFFAOYSA-N 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
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- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 9
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 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 claims description 7
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000001125 extrusion Methods 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 23
- 230000015556 catabolic process Effects 0.000 description 21
- 239000007789 gas Substances 0.000 description 14
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- 239000004703 cross-linked polyethylene Substances 0.000 description 11
- 239000008187 granular material Substances 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 8
- 239000003607 modifier Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011900 installation process Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
-
- 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
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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)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application discloses a thermoplastic medium voltage cable insulating material and a preparation method thereof, wherein the thermoplastic medium voltage cable insulating material comprises the following components in parts by weight: 100 parts of copolymerization modified polypropylene, 0.5-1 part of antioxidant and 0.5-1 part of copper inhibitor. According to the cable extrusion processing technology, the copolymerization modified polypropylene is adopted, is a thermoplastic environment-friendly material, is green and friendly, does not need crosslinking and degassing treatment in the cable extrusion process, greatly simplifies the process steps, reduces energy loss and carbon emission, and shortens the supply period of cables.
Description
Technical Field
The application relates to the field of novel power transmission and distribution equipment, in particular to a thermoplastic medium-voltage cable insulating material and a preparation method thereof.
Background
Crosslinked polyethylene (XLPE) has excellent mechanical properties and electrical properties, and is the main insulating material of the current extrusion-coated cable. However, since XLPE is a thermal fixing material and needs to be crosslinked by a crosslinking agent or chemical action, the insulating property of the cable is unstable and the service performance of the cable is affected due to the low-boiling-point micromolecule substances such as acetophenone, cumyl alcohol methane and water, which are byproducts generated in the crosslinking process. Meanwhile, the cross-linking and degassing processes are high in energy consumption and low in production efficiency, the retired insulating material is difficult to recycle, and the environment pollution is caused by burning or landfill, so that the existing concept of energy conservation and environmental protection and the target of double carbon are not met.
Content of application
The application provides a thermoplastic medium-voltage cable insulating material and a preparation method thereof, which can avoid crosslinking and degassing treatment in the cable extruding process, simplify the production process steps and promote the transition of the insulating material of a power cable to green environment-friendly type.
The following technical scheme is adopted in the application:
the application provides a thermoplastic medium-voltage cable insulating material which comprises the following components in parts by weight: 100 parts of copolymerization modified polypropylene, 0.5-1 part of antioxidant and 0.5-1 part of copper inhibitor.
Further, the co-modified polypropylene includes ethylene propylene co-modified polypropylene.
Further, the polypropylene in the ethylene-propylene copolymerization modified polypropylene is one of isotactic polypropylene or atactic polypropylene.
Furthermore, the content of ethylene and propylene in the ethylene and propylene copolymerization modified polypropylene is 10-20%.
Further, the melt index of the ethylene-propylene copolymerized modified polypropylene is 2 +/-0.5 g/10 min.
Further, the antioxidant comprises a primary antioxidant comprising 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid) hydrazine.
Further, the content of the main antioxidant in the antioxidant is more than or equal to 50 percent.
Furthermore, the antioxidant also comprises an auxiliary antioxidant, and the auxiliary antioxidant comprises one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite and 4, 4' -thiobis (6-tert-butyl-3-methylphenol).
Furthermore, the content of various auxiliary antioxidants in the antioxidant is 10-20%.
Further, the copper-resistant agent includes N-salicylamidophthalimide.
The application also provides a preparation method of the thermoplastic medium-voltage cable insulating material, which comprises the following steps: and (3) generating polypropylene in the first reactor, and feeding the polypropylene into the second reactor to be copolymerized with ethylene and propylene to generate ethylene-propylene copolymerization modified polypropylene. Feeding the ethylene-propylene copolymerization modified polypropylene into an extruder for mixing and granulation, and feeding the antioxidant and the copper inhibitor into the extruder to obtain the thermoplastic medium-voltage cable insulating material.
Further, the first reactor and the second reactor are both gas phase reactors.
Further, before feeding the ethylene propylene co-modified polypropylene into the extruder, the ethylene propylene co-modified polypropylene was fed into a bag filter to be separated from the gas.
Further, after feeding the ethylene propylene copolymerization modified polypropylene into a bag filter to be separated from gas, feeding the ethylene propylene copolymerization modified polypropylene into a degassing bin to be dried and remove the activity of the residual catalyst therein.
Further, the heating temperature of the extruder is 175-185 ℃.
The application also provides a thermoplastic medium-voltage cable, and the preparation raw materials comprise the thermoplastic medium-voltage cable insulating material or the thermoplastic medium-voltage cable insulating material prepared by the preparation method of the thermoplastic medium-voltage cable insulating material.
Compared with the prior art, the method has the following beneficial effects:
the modified polypropylene is a thermoplastic environment-friendly material, is green and friendly, does not need crosslinking and degassing treatment in the cable extrusion process, greatly simplifies the process steps, reduces the energy loss and carbon emission, and shortens the supply period of cables. This application adopts the direct production of petrochemical industry device to obtain thermoplasticity medium voltage cable insulating material, can directly get into cable factory and extrude the chain and carry out the cable extrusion process, need not secondary modification and additive and handles, prevents to pollute. The thermoplastic medium-voltage cable insulating material has excellent mechanical property and electrical property.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic flow diagram of a process for preparing thermoplastic medium voltage cable insulation in an embodiment of the present application.
Detailed description of the preferred embodiment
The technical method in the embodiments of the present application will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Based on the prior art, it is very important to develop an environment-friendly cable insulation material which satisfies mechanical and electrical properties. The modified thermoplastic polypropylene material has good electrical property, mechanical property and heat-resistant stability, and has the advantages of low energy consumption and short supply period in the production process, and can be used as an insulating material of medium-voltage power cables.
The application provides a thermoplastic medium-voltage cable insulating material which comprises the following components in parts by weight: 100 parts of ethylene-propylene copolymerization modified polypropylene, 0.5-1 part of antioxidant and 0.5-1 part of copper inhibitor. For the ethylene propylene copolymerization modified polypropylene, a modification method of random copolymerization is adopted, and ethylene and propylene chain segments are inserted into a polypropylene chain segment.
Wherein the polypropylene in the ethylene propylene copolymerization modified polypropylene is one of isotactic polypropylene or atactic polypropylene, the content of ethylene and propylene in the ethylene propylene copolymerization modified polypropylene is 10-20%, and the melt index of the ethylene propylene copolymerization modified polypropylene is 2 +/-0.5 g/10 min. The melt index for the ethylene propylene copolymerized modified polypropylene was 2. + -. 0.5g/10min, which was measured by applying a force of 2.16kg at 230 ℃.
The antioxidant comprises a main antioxidant, the main antioxidant comprises 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid) hydrazine, and the content of the main antioxidant in the antioxidant is more than or equal to 50%.
The antioxidant also comprises an auxiliary antioxidant, the auxiliary antioxidant comprises one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tri (2, 4-di-tert-butylphenyl) phosphite ester and 4, 4' -thiobis (6-tert-butyl-3-methylphenol), and the content of each auxiliary antioxidant in the antioxidant is 10-20%. The secondary antioxidant may not be added.
The copper-resistant agent comprises N-salicylamido phthalimide. For the copper resisting agent, the function of the copper resisting agent is to prevent the polypropylene material from contacting with the copper core of the cable to generate copper degradation.
Referring to fig. 1, the present application also provides a method for preparing a thermoplastic medium voltage cable insulation, comprising the steps of:
step one, generating polypropylene in a first reactor, and feeding the polypropylene into a second reactor to copolymerize with ethylene and propylene to generate ethylene-propylene copolymerization modified polypropylene.
In the first step, polypropylene is generated in the first reactor by adopting a gas-phase innoven process.
And introducing a catalyst, a modifier, ethylene and propylene into the first reactor. The catalyst comprises a main catalyst and a cocatalyst. The procatalyst may be Ziegler-Natta catalyzedAgent comprising TiCl4And supported on MgCl2The di-n-butyl titanate can be one of CD/CDI catalyst of Amoco company, NG/NA catalyst of Beijing chemical research institute and SAL catalyst of Beijing Orda catalyst company. The cocatalyst may be triethylaluminium. The modifier may be diisobutyldimethoxysilane. In addition, hydrogen is also introduced into the first reactor as a molecular weight regulator.
In the first reactor, the feed rate of propylene was 25kg/h and the flow ratio of ethylene to propylene was 1: 10. The flow ratio of the main catalyst to propylene was 1: 5000. The amounts of the main catalyst, the cocatalyst and the modifier meet the following conditions: Al/Mg (mol/mol) 12:1, Al/Si (mol/mol) 6: 1. The flow ratio of hydrogen to propylene was 1: 50000. The polymerization temperature is 70 ℃, the polymerization pressure is 3.20Mpa, and the retention time of the materials in the first reactor is 1.2 h. The flow rate is expressed in kg/h.
In the first step, in the second reactor, the polymer powder in the first reactor is copolymerized with ethylene and propylene to generate ethylene-propylene copolymerized modified polypropylene.
The second reactor is charged with the polymer powder, ethylene and propylene from the first reactor. In addition, hydrogen is also introduced into the second reactor as a molecular weight regulator.
In the second reactor, the mass ratio of propylene to ethylene was 1:4, the mass concentration of hydrogen was 0.25%, the copolymerization temperature was 65 ℃, the copolymerization pressure was 2.4MPa, and the copolymerization time was 1.3 hours.
In the first step, both the first reactor and the second reactor are gas phase reactors, specifically, both are horizontal stirred bed gas phase reactors.
Referring to fig. 1, in step one, both the catalyst and the modifier are located in a catalyst feed system from which they are fed to the first reactor of the first polymerization reaction unit. Ethylene and propylene are both located in the raw material purification unit and are fed from the raw material purification unit to the first reactor of the first polymerization reaction unit and the second reactor of the second polymerization reaction unit.
And step two, feeding the ethylene-propylene copolymerization modified polypropylene into an extruder for mixing and granulation, and feeding the antioxidant and the copper resisting agent into the extruder to obtain the thermoplastic medium-voltage cable insulating material.
And in the second step, before the ethylene-propylene copolymerization modified polypropylene is fed into the extruder, feeding the ethylene-propylene copolymerization modified polypropylene into a bag filter to be separated from gas.
And in the second step, after the ethylene-propylene copolymerization modified polypropylene is sent into a bag filter to be separated from gas, the ethylene-propylene copolymerization modified polypropylene is sent into a degassing bin to be dried and the activity of the residual catalyst is removed.
In the second step, the extruder is a twin-screw extruder. The heating temperature of the extruder is 175-185 ℃.
And in the second step, after granulation, the formed granules are sent to be uniformly mixed with the granules produced in the same batch, and the granules are sent to a storage tank for packaging after the uniformity of the granules is ensured.
Referring to FIG. 1, in step two, the copolymer powder in the second reactor is fed to a bag filter and a degassing bin of a powder degassing and drying unit. The deactivated and dried copolymer powder in the degassing bin is fed into an extruder in the pelletizing unit, the pellets extruded by the extruder are blended and homogenized and then fed into a storage tank in the pellet storage unit, and the pellets in the storage tank are sent to be packaged.
To sum up, the thermoplastic medium voltage cable insulating material of this application adopts petrochemical industry device to carry out catalytic synthesis-copolymerization modification-extrude granulation direct production and obtain, and antioxidant and anti copper agent also add petrochemical industry device at above-mentioned in-process simultaneously, and this pollution of having avoided secondary operation to cause has guaranteed the purity of insulating material, and the homogeneity and the stability of the ejection of compact can be guaranteed to petrochemical industry device simultaneously.
The application also provides a thermoplastic medium-voltage cable, and the preparation raw materials comprise the thermoplastic medium-voltage cable insulating material or the thermoplastic medium-voltage cable insulating material prepared by the preparation method of the thermoplastic medium-voltage cable insulating material.
The technical scheme and the beneficial effects of the application are further explained by combining the embodiment.
In each of the following examples, the first reactor was charged with the catalyst, modifier, ethylene and propylene. The catalyst comprises a main catalyst and a cocatalyst. The main catalyst is a Ziegler-Natta catalyst selected from the group consisting of the CD/CDI catalysts available from Amoco. The cocatalyst is triethyl aluminum. The modifier is diisobutyldimethoxysilane. In addition, hydrogen is also introduced into the first reactor as a molecular weight regulator.
In the first reactor, the feed rate of propylene was 25kg/h and the flow ratio of ethylene to propylene was 1: 10. The flow ratio of the main catalyst to propylene was 1: 5000. The amounts of the main catalyst, the cocatalyst and the modifier meet the following conditions: Al/Mg (mol/mol) 12:1, Al/Si (mol/mol) 6: 1. The flow ratio of hydrogen to propylene was 1: 50000. The polymerization temperature is 70 ℃, the polymerization pressure is 3.20Mpa, and the retention time of the materials in the first reactor is 1.2 h. The flow rate is expressed in kg/h.
The second reactor is charged with the polymer powder, ethylene and propylene from the first reactor. In addition, hydrogen is also introduced into the first reactor as a molecular weight regulator.
In the second reactor, the mass ratio of propylene to ethylene was 1:4, the mass concentration of hydrogen was 0.25%, the copolymerization temperature was 65 ℃, the copolymerization pressure was 2.4MPa, and the copolymerization time was 1.3 hours.
Example 1
And (2) generating polypropylene in the first reactor, and feeding the polypropylene into the second reactor to copolymerize with ethylene and propylene to generate ethylene-propylene copolymerization modified polypropylene, wherein the content of ethylene and propylene in the ethylene-propylene copolymerization modified polypropylene is 17%, and the melt index of the ethylene-propylene copolymerization modified polypropylene is 2.2g/10 min.
Feeding the ethylene propylene copolymerization modified polypropylene into a bag filter to be separated from gas, feeding the ethylene propylene copolymerization modified polypropylene into a degassing bin to be dried and remove the activity of the residual catalyst, feeding 100 parts of the ethylene propylene copolymerization modified polypropylene into a double-screw extruder to be mixed and granulated according to 100g of each part, and feeding 0.6 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine, 0.1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.1 part of tris (2.4-di-tert-butylphenyl) phosphite, 0.1 part of 4, 4' -thiobis (6-tert-butyl-3-methylphenol) and 0.5 part of N-salicylamido phthalimide into the double-screw extruder, the heating temperature of the double-screw extruder is 175 ℃, the formed granules are sent to be blended, homogenized and sent to a storage tank for packaging, and the thermoplastic medium-voltage cable insulating material is obtained.
Example 2
And (2) generating polypropylene in the first reactor, and feeding the polypropylene into the second reactor to copolymerize with ethylene and propylene to generate ethylene-propylene copolymerization modified polypropylene, wherein the content of ethylene and propylene in the ethylene-propylene copolymerization modified polypropylene is 10%, and the melt index of the ethylene-propylene copolymerization modified polypropylene is 1.5g/10 min.
Feeding the ethylene propylene copolymerization modified polypropylene into a bag filter to be separated from gas, feeding the ethylene propylene copolymerization modified polypropylene into a degassing bin to be dried and remove the activity of the residual catalyst, feeding 100 parts of the ethylene propylene copolymerization modified polypropylene into a double-screw extruder to be mixed and granulated, and feeding 0.5 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid) hydrazine, 0.2 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.2 part of tris (2.4-di-tert-butylphenyl) phosphite, 0.1 part of 4, 4' -thiobis (6-tert-butyl-3-methylphenol) and 0.7 part of N-salicylamido-phthalimide into the double-screw extruder, the heating temperature of the double-screw extruder is 180 ℃, the formed granules are sent to be blended, and then sent to a storage tank for packaging after being homogenized, and the thermoplastic medium-voltage cable insulating material is obtained.
Example 3
And (2) generating polypropylene in the first reactor, and feeding the polypropylene into the second reactor to copolymerize with ethylene and propylene to generate ethylene-propylene copolymerization modified polypropylene, wherein the content of ethylene and propylene in the ethylene-propylene copolymerization modified polypropylene is 20%, and the melt index of the ethylene-propylene copolymerization modified polypropylene is 2.5g/10 min.
Feeding the ethylene propylene copolymerization modified polypropylene into a bag filter to be separated from gas, feeding the ethylene propylene copolymerization modified polypropylene into a degassing bin to be dried and remove the activity of the residual catalyst, feeding 100 parts of the ethylene propylene copolymerization modified polypropylene into a double-screw extruder to be mixed and granulated according to 100g of each part, and feeding 0.25 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine, 0.05 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.1 part of tris (2.4-di-tert-butylphenyl) phosphite, 0.1 part of 4, 4' -thiobis (6-tert-butyl-3-methylphenol) and 1 part of N-salicylamido-phthalimide into the double-screw extruder, the heating temperature of the double-screw extruder is 185 ℃, the formed granules are sent to be blended, homogenized and sent to a storage tank for packaging, and the thermoplastic medium-voltage cable insulating material is obtained.
Example 4
And (2) generating polypropylene in the first reactor, and feeding the polypropylene into the second reactor to copolymerize with ethylene and propylene to generate ethylene-propylene copolymerization modified polypropylene, wherein the content of ethylene and propylene in the ethylene-propylene copolymerization modified polypropylene is 18%, and the melt index of the ethylene-propylene copolymerization modified polypropylene is 2.4g/10 min.
Feeding the ethylene propylene copolymerization modified polypropylene into a bag filter to be separated from gas, feeding the ethylene propylene copolymerization modified polypropylene into a degassing bin to be dried and remove the activity of the residual catalyst, feeding 100 parts of the ethylene propylene copolymerization modified polypropylene into a double-screw extruder to be mixed and granulated according to 100g of each part, and feeding 0.25 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine, 0.1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.05 part of tris (2.4-di-tert-butylphenyl) phosphite, 0.1 part of 4, 4' -thiobis (6-tert-butyl-3-methylphenol) and 0.8 part of N-salicylamido phthalimide into the double-screw extruder, the heating temperature of the double-screw extruder is 180 ℃, the formed granules are sent to be blended, and then sent to a storage tank for packaging after being homogenized, and the thermoplastic medium-voltage cable insulating material is obtained.
Example 5
And (2) generating polypropylene in the first reactor, and feeding the polypropylene into the second reactor to copolymerize with ethylene and propylene to generate ethylene-propylene copolymerization modified polypropylene, wherein the content of ethylene and propylene in the ethylene-propylene copolymerization modified polypropylene is 17%, and the melt index of the ethylene-propylene copolymerization modified polypropylene is 2.1g/10 min.
Feeding the ethylene propylene copolymerization modified polypropylene into a bag filter to be separated from gas, feeding the ethylene propylene copolymerization modified polypropylene into a degassing bin to be dried and remove the activity of the residual catalyst, feeding 100 parts of the ethylene propylene copolymerization modified polypropylene into a double-screw extruder according to 100g of each part, mixing and granulating, feeding 0.5 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine and 0.5 part of N-salicylamido phthalimide into the double-screw extruder, heating the double-screw extruder to 180 ℃, feeding the formed granules into blending, homogenizing, and then feeding the granules into a storage tank for packaging to obtain the thermoplastic medium-voltage cable insulating material.
Example 6
And (2) generating polypropylene in the first reactor, and feeding the polypropylene into the second reactor to copolymerize with ethylene and propylene to generate ethylene-propylene copolymerization modified polypropylene, wherein the content of ethylene and propylene in the ethylene-propylene copolymerization modified polypropylene is 20%, and the melt index of the ethylene-propylene copolymerization modified polypropylene is 2.5g/10 min.
Feeding the ethylene-propylene copolymerization modified polypropylene into a bag filter to be separated from gas, feeding the ethylene-propylene copolymerization modified polypropylene into a degassing bin to be dried and remove the activity of the residual catalyst, feeding 100 parts of the ethylene-propylene copolymerization modified polypropylene into a double-screw extruder according to 100g of each part for mixing and granulating, and 0.8 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid) hydrazine, 0.2 part of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of N-salicylamido phthalimide are fed into a twin-screw extruder, the heating temperature of the double-screw extruder is 185 ℃, the formed granules are sent to be blended, homogenized and sent to a storage tank for packaging, and the thermoplastic medium-voltage cable insulating material is obtained.
Example 7
And (2) generating polypropylene in the first reactor, and feeding the polypropylene into the second reactor to copolymerize with ethylene and propylene to generate ethylene-propylene copolymerization modified polypropylene, wherein the content of ethylene and propylene in the ethylene-propylene copolymerization modified polypropylene is 15%, and the melt index of the ethylene-propylene copolymerization modified polypropylene is 1.6g/10 min.
Feeding the ethylene propylene copolymerization modified polypropylene into a bag filter to be separated from gas, feeding the ethylene propylene copolymerization modified polypropylene into a degassing bin to be dried and remove the activity of the residual catalyst, feeding 100 parts of the ethylene propylene copolymerization modified polypropylene into a twin-screw extruder for mixing and granulation according to 100g of each part, feeding 0.7 part of 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenyl propionic acid) hydrazine, 0.1 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 0.1 part of 4, 4' -thiobis (6-tert-butyl-3-methylphenol) and 0.8 part of N-salicylamido phthalimide into the twin-screw extruder, wherein the heating temperature of the twin-screw extruder is 175 ℃, and the formed pellets are fed for blending, homogenizing, and packaging in a storage tank to obtain the thermoplastic medium-voltage cable insulating material.
The combination of properties of the crosslinked polyethylene used for commercial medium voltage crosslinked polyethylene insulated cables and the ethylene propylene copolymerized modified polypropylene used for the thermoplastic medium voltage cable insulation of examples 1-6 were examined and the results are shown in the following table:
semi-crystalline polymers are interpenetrating network structures composed of entangled amorphous and crystalline phase structures. Under large deformation, the molecular chains linking the amorphous regions of the basic morphological units undergo rotation parallel to the stretching direction. In the ethylene propylene copolymerization modified polypropylene, the ethylene chain segment with stronger chain segment movement capability is introduced into the polypropylene, so that the position adjustment of crystal form elements in the stretching process can be promoted, and the stretching performance of the polypropylene is improved. As can be seen from the data in the above table, the elongation at break of the ethylene-propylene copolymer modified polypropylene in example 1 reaches 680%, the elongation at break of the ethylene-propylene copolymer modified polypropylene in example 2 reaches 650%, the elongation at break of the ethylene-propylene copolymer modified polypropylene in example 3 reaches 712%, the elongation at break of the ethylene-propylene copolymer modified polypropylene in example 4 reaches 682%, the elongation at break of the ethylene-propylene copolymer modified polypropylene in example 5 reaches 682%, the elongation at break of the ethylene-propylene copolymer modified polypropylene in example 6 reaches 710%, and the elongation at break of the ethylene-propylene copolymer modified polypropylene in example 7 reaches 679%, which are all higher than the elongation at break of the crosslinked polyethylene 564%, that is, the ethylene-propylene copolymer modified polypropylene has a higher elongation at break, which is beneficial to reducing the construction difficulty of the medium-voltage polypropylene cable in the installation process.
As can be seen from the data in the above table, the shape parameter of the ethylene propylene co-modified polypropylene of the present application in the AC breakdown test is larger than that of the crosslinked polyethylene as a whole, and the dispersibility of the data is smaller, which is related to the uniform size distribution of the crystals in the ethylene propylene co-modified polypropylene. At normal temperature, the breakdown strength of the ethylene-propylene copolymer modified polypropylene in the embodiment 1 reaches 138.7kV/mm, the breakdown strength of the ethylene-propylene copolymer modified polypropylene in the embodiment 2 reaches 142.4kV/mm, the breakdown strength of the ethylene-propylene copolymer modified polypropylene in the embodiment 3 reaches 130.3kV/mm, the breakdown strength of the ethylene-propylene copolymer modified polypropylene in the embodiment 4 reaches 139.2kV/mm, the breakdown strength of the ethylene-propylene copolymer modified polypropylene in the embodiment 5 reaches 138.5kV/mm, the breakdown strength of the ethylene-propylene copolymer modified polypropylene in the embodiment 6 reaches 130.5kV/mm, and the breakdown strength of the ethylene-propylene copolymer modified polypropylene in the embodiment 7 reaches 134.8kV/mm, which are basically equivalent to that of crosslinked polyethylene. The temperature is increased to 90 ℃, the breakdown strength of the crosslinked polyethylene is 74.5kV/mm, which is reduced by 49.4% compared with the normal temperature, while the breakdown strength of the ethylene-propylene copolymer modified polypropylene of example 1 is 95.8kV/mm, which is reduced by 42.9% compared with the normal temperature, the breakdown strength of the ethylene-propylene copolymer modified polypropylene of example 2 is 100.3kV/mm, which is reduced by 42.1% compared with the normal temperature, the breakdown strength of the ethylene-propylene copolymer modified polypropylene of example 3 is 91.5kV/mm, which is reduced by 29.8% compared with the normal temperature, the breakdown strength of the ethylene-propylene copolymer modified polypropylene of example 4 is 95.4kV/mm, which is reduced by 43.8% compared with the normal temperature, the breakdown strength of the ethylene-propylene copolymer modified polypropylene of example 5 is 95.9kV/mm, which is reduced by 42.9% compared with the normal temperature, and the breakdown strength of the ethylene-propylene copolymer modified polypropylene of example 6 is 91.6kV/mm, compared with the normal temperature, the breakdown strength of the ethylene-propylene copolymerized modified polypropylene in the example 7 is reduced by 38.9 percent, the breakdown strength of the ethylene-propylene copolymerized modified polypropylene in the example 7 is reduced by 44.7 percent, and the breakdown strength is higher than that of the crosslinked polyethylene at 90 ℃. The reason is that the distribution size of the crystal in the ethylene propylene copolymerization modified polypropylene is more uniform, the melting point is higher, and the stability to temperature is better. Under normal operating temperature, higher breakdown strength is favorable for guaranteeing the normal operating of cable.
To sum up, the elongation at break of the ethylene propylene copolymerization modified polypropylene of the application is greatly improved, the elongation at break of the crosslinked polyethylene is already exceeded, the elastic modulus of the polyethylene is greatly reduced, the flexibility of the material is better, the laying of cables is facilitated, and the ethylene propylene copolymerization modified polypropylene has excellent mechanical properties. Meanwhile, the breakdown strength of the ethylene-propylene copolymerization modified polypropylene is higher, and the change along with the temperature is smaller.
The foregoing shows and describes the general principles, essential features, and advantages of the application. It will be understood by those skilled in the art that the present application is not limited to the embodiments described above, which are presented solely for purposes of illustrating the principles of the application, and that various changes and modifications may be made without departing from the spirit and scope of the application, which is defined by the appended claims, the specification, and equivalents thereof.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present application and not for limiting the protection scope of the present application, and although the present application 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 application without departing from the spirit and scope of the technical solutions of the present application.
Claims (16)
1. The thermoplastic medium-voltage cable insulating material is characterized by comprising the following components in parts by weight:
100 parts of copolymerization modified polypropylene, 0.5-1 part of antioxidant and 0.5-1 part of copper inhibitor.
2. The thermoplastic medium voltage cable insulation of claim 1,
the copolymerization modified polypropylene comprises ethylene propylene copolymerization modified polypropylene.
3. The thermoplastic medium voltage cable insulation of claim 2,
the polypropylene in the ethylene-propylene copolymerization modified polypropylene is one of isotactic polypropylene or atactic polypropylene.
4. The thermoplastic medium voltage cable insulation of claim 2,
the content of ethylene and propylene in the ethylene and propylene copolymerization modified polypropylene is 10-20%.
5. The thermoplastic medium voltage cable insulation of claim 2,
the melt index of the ethylene-propylene copolymerization modified polypropylene is 2 +/-0.5 g/10 min.
6. The thermoplastic medium voltage cable insulation of claim 1,
the antioxidant comprises a main antioxidant, and the main antioxidant comprises 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid) hydrazine.
7. Thermoplastic medium voltage cable insulation according to claim 6,
the content of the main antioxidant in the antioxidant is more than or equal to 50 percent.
8. Thermoplastic medium voltage cable insulation according to claim 6,
the antioxidant also comprises an auxiliary antioxidant, wherein the auxiliary antioxidant comprises one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite and 4, 4' -thiobis (6-tert-butyl-3-methylphenol).
9. The thermoplastic medium voltage cable insulation of claim 8,
the content of each auxiliary antioxidant in the antioxidant is 10-20%.
10. The thermoplastic medium voltage cable insulation of claim 1,
the copper resistant agent comprises N-salicylamido phthalimide.
11. A preparation method of a thermoplastic medium-voltage cable insulating material is characterized by comprising the following steps:
generating polypropylene in the first reactor, and feeding the polypropylene into the second reactor to copolymerize with ethylene and propylene to generate ethylene-propylene copolymerization modified polypropylene;
and feeding the ethylene-propylene copolymerization modified polypropylene into an extruder for mixing and granulation, and feeding an antioxidant and a copper resisting agent into the extruder to obtain the thermoplastic medium-voltage cable insulating material.
12. The method according to claim 11,
the first reactor and the second reactor are both gas phase reactors.
13. The method according to claim 12,
feeding the ethylene propylene co-modified polypropylene into a bag filter to be separated from gas before feeding the ethylene propylene co-modified polypropylene into an extruder.
14. The method according to claim 13, wherein the step of preparing the resin composition,
feeding the ethylene-propylene copolymerization modified polypropylene into a bag filter to be separated from gas, feeding the ethylene-propylene copolymerization modified polypropylene into a degassing bin to be dried, and removing the activity of the residual catalyst.
15. The method according to claim 11,
the heating temperature of the extruder is 175-185 ℃.
16. A thermoplastic medium voltage cable, characterized in that the raw materials for the preparation comprise the thermoplastic medium voltage cable insulation according to any one of claims 1 to 10 or the thermoplastic medium voltage cable insulation obtained by the method for the preparation of the thermoplastic medium voltage cable insulation according to any one of claims 11 to 15.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116589815A (en) * | 2023-05-04 | 2023-08-15 | 江苏上上电缆集团新材料有限公司 | Silane crosslinked polyethylene insulating material resistant to temperature of 150 ℃ and preparation method thereof |
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| CN103589105A (en) * | 2013-11-27 | 2014-02-19 | 天津市普立泰高分子科技有限公司 | Modified polypropylene insulation material and manufacturing method thereof |
| CN110498997A (en) * | 2019-07-22 | 2019-11-26 | 西安交通大学 | A kind of polypropylene-base high voltage direct current cable material and preparation method thereof |
| CN113248832A (en) * | 2021-02-03 | 2021-08-13 | 中国电力科学研究院有限公司 | High-voltage direct-current polypropylene cable material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103589105A (en) * | 2013-11-27 | 2014-02-19 | 天津市普立泰高分子科技有限公司 | Modified polypropylene insulation material and manufacturing method thereof |
| CN110498997A (en) * | 2019-07-22 | 2019-11-26 | 西安交通大学 | A kind of polypropylene-base high voltage direct current cable material and preparation method thereof |
| CN113248832A (en) * | 2021-02-03 | 2021-08-13 | 中国电力科学研究院有限公司 | High-voltage direct-current polypropylene cable material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116589815A (en) * | 2023-05-04 | 2023-08-15 | 江苏上上电缆集团新材料有限公司 | Silane crosslinked polyethylene insulating material resistant to temperature of 150 ℃ and preparation method thereof |
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