CN113583320B - Crosslinkable polyolefin composition, preparation method and application thereof, crosslinked polyolefin and application thereof - Google Patents

Crosslinkable polyolefin composition, preparation method and application thereof, crosslinked polyolefin and application thereof Download PDF

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CN113583320B
CN113583320B CN202010366193.8A CN202010366193A CN113583320B CN 113583320 B CN113583320 B CN 113583320B CN 202010366193 A CN202010366193 A CN 202010366193A CN 113583320 B CN113583320 B CN 113583320B
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tert
butyl
composition
antioxidant
thiobis
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CN113583320A (en
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任冬雪
孙小杰
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/375—Thiols containing six-membered aromatic rings
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

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Abstract

The invention relates to the field of polyolefin, and discloses a crosslinkable polyolefin composition, a preparation method and application thereof, and a crosslinked polyolefin and application thereof. The crosslinkable polyolefin composition comprises polyethylene, a crosslinking agent, an antioxidant A and an antioxidant B; the antioxidant A is thio hindered phenol; the antioxidant B is at least one selected from bisphenol monoacrylate, benzofuranone and allylphenol compounds; the amount of the crosslinking agent is 1 to 3 parts by weight, the amount of the antioxidant A is 0.1 to 3 parts by weight, and the amount of the antioxidant B is 0.01 to 2 parts by weight based on 100 parts by weight of polyethylene. The crosslinkable polyolefin composition has excellent direct current breakdown strength and volume resistivity, and can be used for a long period of time when the composition is used for preparing cables, particularly high-voltage insulated cables.

Description

Crosslinkable polyolefin composition, preparation method and application thereof, crosslinked polyolefin and application thereof
Technical Field
The invention relates to the field of polyolefin, in particular to a crosslinkable polyolefin composition, a preparation method and application thereof, and a crosslinked polyolefin and application thereof.
Background
The crosslinked polyethylene (XLPE) insulated cable has been widely used in power transmission and distribution systems in recent years due to the advantages of light weight, high working temperature, high transmission power, easy maintenance and the like. The high-voltage crosslinked polyethylene insulating material mainly comprises two preparation processes of direct blending and post-absorption, wherein the post-absorption process mainly aims at the high-voltage and ultra-high voltage cable insulating material with the voltage of more than 110 kV. For cable insulation materials with the voltage of 35kV and below, the preparation process comprises the steps of melting, blending, extruding and granulating all formula components such as matrix resin low-density polyethylene, an antioxidant and a crosslinking agent together to obtain the final XLPE insulation material. The method has high requirements on process control, is easy to generate pre-crosslinking in the production process, generates uneven gel impurities, and seriously affects the insulation performance of the XLPE insulation material.
CN104334630a discloses a crosslinked polyethylene composition with improved processability, comprising: 100 parts by weight of a polyethylene, 0.03-5 parts by weight of a crosslinking agent, 0.03-5 parts by weight of a crosslinking accelerator, and 0.01-1.5 parts by weight of a radical inhibitor, wherein the polyethylene is a copolymer and/or a homopolymer, contains at least 90% by weight of vinyl groups and at least one C3-C8 alpha-olefin group, and has a density of 0.920-0.970g/cm 3 The melt index is 2.5-17.5g/10min; the cross-linking agent is a peroxide cross-linking agent; the crosslinking accelerator is an organic matter containing maleimide group, (methyl) acrylate group and/or allyl group, and/or a polymer with vinyl content higher than 50%; the free radical inhibitor is an organic antioxidant, hydroquinone, and/or substituted hydroquinone. However, the composition is mainly concerned with improving the processability of XLPE, and it is not mentioned that this composition can improve the insulating properties of XLPE.
CN107698711a provides a grafted crosslinked polyethylene insulation layer for high voltage dc cable and a method for preparing the same. The preparation method comprises the steps of taking a thermoplastic polyethylene material as a matrix, preparing a polyethylene composition containing graftable polar groups according to the provided raw material ratio, carrying out chemical crosslinking through a crosslinking pipeline after the composition is subjected to melt extrusion in an extruder, and grafting small molecules (namely, chloroacetic acid propylene ester (CAAE)) with the polar groups on molecular chains of the polyethylene material while crosslinking the polyethylene material, wherein the grafted crosslinked polyethylene insulating layer prepared by the preparation method has higher direct current breakdown strength and lower conductivity. However, the cross-linking grafting reaction is difficult to control, and reaction residues are easy to occur, so that impurities are introduced to influence the uniformity of the material and the electrical performance of the material.
CN103396601a provides a high dielectric polyethylene composite. The composite material comprises: low density polyethylene and polyvinylcarbazole; the mass percentage of the antioxidant is 0.5%; wherein the mass percentage of the polyvinylcarbazole is 0.5% -3%; the antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]. According to the high-dielectric-property polyethylene composite material, a certain amount of polyvinylcarbazole is added into polyethylene, so that the material has higher breakdown strength. However, the electrical properties of the polyvinylcarbazole are improved only a limited amount, and the polyvinylcarbazole is difficult to uniformly mix with the low-density polyethylene at a very high processing temperature (about 250 ℃) to prepare a material with better performance consistency.
CN102532638A provides a polyolefin resin composition and a method for preparing the same. The polyolefin resin composition comprises polyolefin, antioxidant and crosslinking agent, wherein the size of impurities in the polyolefin resin composition is 100 μm or less, the tensile strength is 17MPa or more, and the volume resistivity is 1.0X10 15 Omega.m above; the antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the content of the main antioxidant is 0.1-5 parts by mass and the content of the auxiliary antioxidant is 0.04-2 parts by mass based on 100 parts by mass of polyolefin; the main antioxidant is selected from one or more of 4,4 '-thiobis (6-tertiary butyl m-cresol), 2, 6-di-tertiary butyl p-cresol and 2,2' -methylenebis- (4-methyl-6-tertiary butyl phenol); the auxiliary antioxidant is one or more selected from tri (2, 4-di-tert-butylphenyl) phosphite, dilauryl thiodipropionate and distearyl thiodipropionate; the content of the antioxidant is 0.1 to 3 parts by mass and the content of the crosslinking agent is 1 to 10 parts by mass based on 100 parts by mass of the polyolefin. However, the auxiliary antioxidant of the insulating material is selected from one or more of tris (2, 4-di-tert-butylphenyl) phosphite, dilauryl thiodipropionate and distearate thiodipropionate, and the preparation process of the composition is a two-step method, wherein the matrix resin and the antioxidant are mixed to obtain a mixed material, and the mixed material is mixed with DCP by a post-absorption process. The insulating property of the obtained final XLPE insulating material is still lower, and the requirements of high-voltage insulating cables cannot be met.
CN109370003a discloses a scorch-resistant high crosslinking degree chemical crosslinking polyethylene insulating material and a preparation method thereof, comprising the following raw materials in parts by weight: 80-120 parts of low-density polyethylene, 1.0-1.5 parts of cross-linking agent, 0.1-0.4 part of antioxidant and 0.2-0.4 part of auxiliary cross-linking agent. Wherein the auxiliary crosslinking agent is triallyl isocyanurate or triallyl isocyanurate, the antioxidant is hindered phenol antioxidant 4,4' -thiobis (6-tertiary butyl-3-methylphenol), and the crosslinking agent is dicumyl peroxide. The composition reduces the risk of pre-crosslinking and old glue during the insulation of extruded cables, but does not mention any improvement of the insulation properties of XLPE insulation.
Disclosure of Invention
The invention aims to solve the problem that the electrical insulation performance of XLPE insulation materials obtained by a one-step direct blending method cannot meet the requirement in the prior art, and provides a crosslinkable polyolefin composition, a preparation method and application thereof, and crosslinked polyolefin and application thereof.
In order to achieve the above object, the present invention provides in a first aspect a crosslinkable polyolefin composition, wherein the composition comprises a polyethylene, a crosslinking agent, an antioxidant a and an antioxidant B;
the antioxidant A is thio hindered phenol; the antioxidant B is at least one selected from bisphenol monoacrylate, benzofuranone and allylphenol compounds;
the amount of the crosslinking agent is 1 to 3 parts by weight, the amount of the antioxidant A is 0.1 to 3 parts by weight, and the amount of the antioxidant B is 0.01 to 2 parts by weight based on 100 parts by weight of polyethylene.
The second aspect of the present invention provides a process for preparing the crosslinkable polyolefin composition described above, wherein the process comprises the steps of:
mixing polyethylene, an antioxidant A, an antioxidant B and a crosslinking agent, extruding and granulating to obtain the crosslinkable polyolefin composition.
In a third aspect, the present invention provides a crosslinked polyolefin, wherein the crosslinked polyolefin is produced by crosslinking the crosslinkable polyolefin composition described above.
In a fourth aspect the present invention provides the use of a crosslinkable polyolefin composition as described above or a crosslinked polyolefin in a high voltage insulation cable.
Through the technical scheme, the crosslinkable polyolefin composition, the preparation method and the application thereof, the crosslinked polyolefin and the application thereof provided by the invention have the following beneficial effects:
according to the invention, by matching two specific antioxidants with the crosslinking agent, the direct-current breakdown strength and the volume resistivity of polyolefin, such as polyethylene, can be remarkably improved, and the crosslinkable polyolefin composition and the crosslinked polyolefin with excellent direct-current breakdown strength and volume resistivity can be obtained.
Further, when the crosslinkable polyolefin composition and the crosslinked polyolefin are used for cables, particularly high-voltage insulated cables, the performance of the insulated cables can be remarkably improved, and the service life of the insulated cables can be prolonged.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a crosslinkable polyolefin composition, wherein the composition comprises polyethylene, a crosslinking agent, an antioxidant a and an antioxidant B;
the antioxidant A is thio hindered phenol; the antioxidant B is at least one selected from bisphenol monoacrylate, benzofuranone and allylphenol compounds;
the amount of the crosslinking agent is 1 to 3 parts by weight, the amount of the antioxidant A is 0.1 to 3 parts by weight, and the amount of the antioxidant B is 0.01 to 2 parts by weight based on 100 parts by weight of polyethylene.
According to the invention, by matching two specific antioxidants with the crosslinking agent, the direct-current breakdown strength and the volume resistivity of polyolefin such as polyethylene can be remarkably improved, and the crosslinkable polyolefin composition with excellent direct-current breakdown strength and volume resistivity can be obtained.
According to the present invention, the crosslinking agent is used in an amount of 1 to 2.6 parts by weight, the antioxidant A is used in an amount of 0.1 to 2 parts by weight, and the antioxidant B is used in an amount of 0.01 to 1 part by weight, based on 100 parts by weight of polyethylene.
In the present invention, the inventors have found that when the weight ratio of the antioxidant A to the antioxidant B is 0.1 to 2:0.01 to 1, the crosslinkable polyolefin composition obtained has more excellent direct current breakdown strength and volume resistivity. In order to obtain a composition with more excellent comprehensive properties, the weight ratio of the antioxidant A to the antioxidant B is preferably 0.1-1:0.01-0.5.
In accordance with the present invention, the antioxidant A is selected from nonylphenol dichlorinated dithio copolymer, 1 '-thiobis (2-naphthol), 4' -thiobis (6-tertiary butyl-3-methylphenol), 2 '-thiobis (4-methyl-6-tert-butylphenol), and at least one of 4,4' - [ thiobis methylene ] bis [2, 6-bis (1, 1-dimethylethyl) phenol ], 4 '-thiobis (6-tert-butyl-2-methylphenol), 2' -thiobis (4-tert-octylphenol) and thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Further, the antioxidant A is at least one selected from the group consisting of 4,4' -thiobis (6-tert-butyl-3-methylphenol), 2' -thiobis (4-methyl-6-tert-butylphenol), 4' - [ thiobis methylene ] bis [2, 6-bis (1, 1-dimethylethyl) phenol ], 4' -thiobis (6-tert-butyl-2-methylphenol), 2' -thiobis (4-tert-octylphenol) and thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Still further, the antioxidant A is at least one selected from the group consisting of 4,4' -thiobis (6-tert-butyl-3-methylphenol), 2' -thiobis (4-methyl-6-tert-butylphenol), 4' - [ thiobis methylene ] bis [2, 6-bis (1, 1-dimethylethyl) phenol ], 4' -thiobis (6-tert-butyl-2-methylphenol) and 2,2' -thiobis (4-tert-octylphenol).
In the invention, the antioxidant A with the specific type is added into the polyolefin composition, so that the direct-current breakdown strength and the volume resistivity of the composition can be obviously improved, and the comprehensive performance of the composition is more excellent.
According to the present invention, the antioxidant B is selected from at least one of 2- (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-6-tert-butylphenylacrylate, 2- {1- [ 2-hydroxy-3, 5-bis (2-methylbutan-2-yl) phenyl ] ethyl } -4, 6-bis (2-methylbutan-2-yl) phenylacrylate, 2-tert-butyl-6- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -4-methylphenyl acrylate, 5, 6-dimethoxyisobenzofuran-1 (3H) -one, 4- (tert-butyl) -2- (5- (tert-butyl) -2-oxo-2, 3-dihydrobenzofuran-3-yl) phenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, 6-hydroxy-3-coumarone Ran Tong, allylphenol and 2-methoxy-4-allylphenol.
Further, the antioxidant B is at least one selected from the group consisting of 2- (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-6-tert-butylphenylacrylate, 2- {1- [ 2-hydroxy-3, 5-bis (2-methylbutan-2-yl) phenyl ] ethyl } -4, 6-bis (2-methylbutan-2-yl) phenylacrylate, 5, 6-dimethoxy isobenzofuran-1 (3H) -one, 4- (tert-butyl) -2- (5- (tert-butyl) -2-oxo-2, 3-dihydrobenzofuran-3-yl) phenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, allylphenol and 2-methoxy-4-allylphenol.
In the invention, the antioxidant B with the specific type is added into the polyolefin composition, so that the direct-current breakdown strength and the volume resistivity of the composition can be obviously improved, and the comprehensive performance of the composition is more excellent.
According to the invention, the polyethylene is selected from ethylene homopolymers and/or ethylene-C 4-8 An olefin copolymer;
according to the present invention, the polyethylene is at least one selected from the group consisting of polyethylene, low density polyethylene, high density polyethylene and linear low density polyethylene.
According to the invention, the polyethylene matrix resin has a density of 0.91-0.925g/cm 3 The melt index at 190℃and 2.16kg load is 1.9-2.2g/10min.
According to the invention, the crosslinking agent is a peroxide crosslinking agent.
According to the present invention, the peroxide crosslinking agent is at least one selected from the group consisting of 2, 5-dimethyl-2, 5-di-t-butylperoxy-3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butylperoxyisopropyl) benzene and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane.
In a second aspect, the present invention provides a process for preparing a crosslinkable polyolefin composition, wherein the process comprises the steps of:
mixing polyethylene, an antioxidant A, an antioxidant B and a crosslinking agent, extruding and granulating to obtain the crosslinkable polyolefin composition.
According to the invention, the extrusion is carried out in a twin-screw extruder.
According to the invention, the length-diameter ratio of the screw of the double-screw extruder is 10-100, and the extrusion temperature is 108-125 ℃.
The present invention provides in a third aspect a crosslinked polyolefin obtained by crosslinking the crosslinkable polyolefin composition as described above
According to the invention, the conditions of the crosslinking include: the crosslinking time is 3-300min at 150-240 ℃.
According to the invention, the gel content of the crosslinked polyolefin is 75-95%; the direct current breakdown strength is 345-410kV/mm; volume resistivity of 1X 10 18 -9.5×10 18 Ω·cm。
The crosslinked polyolefin has high direct current breakdown strength and low volume resistivity, and can obviously improve the insulating property of the cable and prolong the service life of the cable when being used for a high-voltage cable.
In a fourth aspect the present invention provides the use of the crosslinkable polyolefin composition described above or the crosslinked polyolefin described above in a high voltage insulated cable.
The present invention will be described in detail by examples.
DC breakdown strength
And (3) carrying out a direct current breakdown test on the insulating material by adopting a high-voltage complete test device, outputting a direct current voltage of 0-200kV, and selecting a ball-ball electrode with the diameter of 10mm, wherein the electrode material is brass. The film samples were tested in a continuous pressure rise mode with a diameter of 15cm and a thickness of (0.20.+ -. 0.02) mm, and at least 25 data points were measured for each sample. The electrical strength of the test sample is the ratio of the breakdown voltage to the thickness of the test sample, and the statistical data is analyzed by Weibull distribution. The direct current breakdown strength generally takes the corresponding breakdown electrical strength when the cumulative probability is 63.2%;
gel content
The xylene insoluble content was determined according to ASTM-D2765. Taking a certain amount of polyethylene resin scraps, wrapping the scraps in a 120-mesh copper net, putting the scraps into a conical flask with a reflux device, taking dimethylbenzene as a solvent, boiling and refluxing for at least 24 hours, drying the scraps to constant weight, and calculating the content of insoluble matters, namely gel content;
volume resistivity
According to national standard GB/T1410, taking a wafer with the diameter not smaller than 4.5mm and the thickness of 0.2mm as a sample, completing the test by using a high resistance meter 6517B, pressurizing 1kV, stabilizing the test for 5min, and then starting to record data, and taking an average value of 20 points.
LDPE (2220H) available from Shenghua Ulmin coal chemical Co., ltd, density of 0.920g/cm 3 Melt index of 2.0g/10min;
antioxidant I, 4' -thiobis (6-tert-butyl-3-methylphenol), purchased from Hubei Jusheng technology Co., ltd;
antioxidant II: thiodiethylene bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], available from Boschiza chemical industry development Co., ltd
Antioxidant III, 4- (tert-butyl) -2- (5- (tert-butyl) -2-oxo-2, 3-dihydrobenzofuran-3-yl) phenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, available from Shanghai QiTide engineering Co., ltd;
antioxidant IV, 2- (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-6-tert-butylphenyl acrylate, purchased from North America technology Co., ltd;
the other raw materials used in the examples and comparative examples are all commercially available.
Examples 1, 2 and comparative examples 1 to 4
Firstly, mixing polyethylene, an antioxidant A, an antioxidant B and a crosslinking simple ingredient, and carrying out melt blending, extrusion and granulation by a double-screw extruder to obtain the crosslinkable polyolefin composition. The formulation of the crosslinkable insulating polyolefin composition is shown in table 1.
The XLPE pellets were subjected to a crosslinking process in a flat-bed tablet press to give a sheet having a diameter of 15cm and a thickness of 0.2 mm. The sheet sample was degassed in an oven at 70℃for 24h to give the final plaques. Wherein the length-diameter ratio of the screw of the double-screw extruder is 20/1, the rotating speed of the screw is 100 revolutions per minute, and the blending temperature during screw extrusion is 150 ℃. The granulation process is completed in a thousand-level clean room. In the tabletting crosslinking process, the crosslinking temperature is 180 ℃ and the crosslinking time is 10min.
The obtained sample pieces were subjected to direct current breakdown strength test, gel content test and volume resistivity test, respectively, and the test results are shown in table 1.
TABLE 1
As can be seen from the results of Table 1, examples 1 to 4 employing the combination of the antioxidant A and the antioxidant B of the present invention have higher breakdown strength and volume resistivity, which are significantly better than comparative example 2 with only the antioxidant A or comparative examples 3 to 4 with only the antioxidant B, and are also better than comparative example 1 without any additives. The two antioxidants are used in a compounding way, so that a certain synergistic effect is achieved on improving the insulation performance of XLPE.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (44)

1. A crosslinkable polyolefin composition, wherein the composition comprises a polyethylene, a crosslinking agent, an antioxidant a and an antioxidant B;
the antioxidant A is thio hindered phenol; the antioxidant B is at least one selected from bisphenol monoacrylate, benzofuranone and allylphenol compounds;
based on 100 parts by weight of polyethylene, the amount of the cross-linking agent is 1-3 parts by weight, the amount of the antioxidant A is 0.1-3 parts by weight, and the amount of the antioxidant B is 0.01-2 parts by weight;
the weight ratio of the antioxidant A to the antioxidant B is 0.1-2:0.01-1.
2. The composition according to claim 1, wherein the crosslinking agent is used in an amount of 1 to 2.6 parts by weight, the antioxidant A is used in an amount of 0.1 to 2 parts by weight, and the antioxidant B is used in an amount of 0.01 to 1 part by weight, based on 100 parts by weight of polyethylene.
3. Composition according to claim 1 or 2, wherein the weight ratio of antioxidant a to antioxidant B is 0.1-1:0.01-0.5.
4. The composition according to claim 1 or 2, wherein, the antioxidant A is selected from nonylphenol dichlorinated dithio copolymer, 1 '-thiobis (2-naphthol), 4' -thiobis (6-tertiary butyl-3-methylphenol), 2 '-thiobis (4-methyl-6-tert-butylphenol), and at least one of 4,4' - [ thiobis methylene ] bis [2, 6-bis (1, 1-dimethylethyl) phenol ], 4 '-thiobis (6-tert-butyl-2-methylphenol), 2' -thiobis (4-tert-octylphenol) and thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
5. The composition of claim 4, wherein the antioxidant a is selected from at least one of 4,4' -thiobis (6-tert-butyl-3-methylphenol), 2' -thiobis (4-methyl-6-tert-butylphenol), 4' - [ thiobis methylene ] bis [2, 6-bis (1, 1-dimethylethyl) phenol ], 4' -thiobis (6-tert-butyl-2-methylphenol), 2' -thiobis (4-tert-octylphenol) and thiobis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
6. The composition of claim 5, wherein the antioxidant a is selected from at least one of 4,4' -thiobis (6-tert-butyl-3-methylphenol), 2' -thiobis (4-methyl-6-tert-butylphenol), 4' - [ thiobis methylene ] bis [2, 6-bis (1, 1-dimethylethyl) phenol ], 4' -thiobis (6-tert-butyl-2-methylphenol) and 2,2' -thiobis (4-tert-octylphenol).
7. The composition according to claim 3, wherein, the antioxidant A is selected from nonylphenol dichlorinated dithio copolymer, 1 '-thiobis (2-naphthol), 4' -thiobis (6-tertiary butyl-3-methylphenol), 2 '-thiobis (4-methyl-6-tert-butylphenol), and at least one of 4,4' - [ thiobis methylene ] bis [2, 6-bis (1, 1-dimethylethyl) phenol ], 4 '-thiobis (6-tert-butyl-2-methylphenol), 2' -thiobis (4-tert-octylphenol) and thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
8. The composition of claim 7, wherein the antioxidant a is selected from at least one of 4,4' -thiobis (6-tert-butyl-3-methylphenol), 2' -thiobis (4-methyl-6-tert-butylphenol), 4' - [ thiobis methylene ] bis [2, 6-bis (1, 1-dimethylethyl) phenol ], 4' -thiobis (6-tert-butyl-2-methylphenol), 2' -thiobis (4-tert-octylphenol) and thiobis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
9. The composition of claim 8, wherein the antioxidant a is selected from at least one of 4,4' -thiobis (6-tert-butyl-3-methylphenol), 2' -thiobis (4-methyl-6-tert-butylphenol), 4' - [ thiobis methylene ] bis [2, 6-bis (1, 1-dimethylethyl) phenol ], 4' -thiobis (6-tert-butyl-2-methylphenol) and 2,2' -thiobis (4-tert-octylphenol).
10. The composition of any of claims 1, 2 or 5-9, wherein the antioxidant B is selected from at least one of 2- (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-6-tert-butylphenylacrylate, 2- {1- [ 2-hydroxy-3, 5-bis (2-methylbutan-2-yl) phenyl ] ethyl } -4, 6-bis (2-methylbutan-2-yl) phenylacrylate, 2-tert-butyl-6- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -4-methylphenylacrylate, 5, 6-dimethoxyisobenzofuran-1 (3H) -one, 4- (tert-butyl) -2- (5- (tert-butyl) -2-oxo-2, 3-dihydrobenzofuran-3-yl) phenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, 6-hydroxy-3-coumarone Ran Tong, allylphenol and 2-methoxy-4-allylphenol.
11. The composition of claim 10, wherein the antioxidant B is selected from at least one of 2- (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-6-tert-butylphenylacrylate, 2- {1- [ 2-hydroxy-3, 5-bis (2-methylbutan-2-yl) phenyl ] ethyl } -4, 6-bis (2-methylbutan-2-yl) phenylacrylate, 5, 6-dimethoxyisobenzofuran-1 (3H) -one, 4- (tert-butyl) -2- (5- (tert-butyl) -2-oxo-2, 3-dihydrobenzofuran-3-yl) phenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, allylphenol, and 2-methoxy-4-allylphenol.
12. A composition according to claim 3, wherein the antioxidant B is selected from at least one of 2- (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-6-tert-butylphenylacrylate, 2- {1- [ 2-hydroxy-3, 5-bis (2-methylbutan-2-yl) phenyl ] ethyl } -4, 6-bis (2-methylbutan-2-yl) phenylacrylate, 2-tert-butyl-6- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -4-methylphenylacrylate, 5, 6-dimethoxyisobenzofuran-1 (3H) -one, 4- (tert-butyl) -2- (5- (tert-butyl) -2-oxo-2, 3-dihydrobenzofuran-3-yl) phenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, 6-hydroxy-3-tonka-bean Ran Tong, allylphenol and 2-methoxy-4-allylphenol.
13. The composition of claim 12, wherein the antioxidant B is selected from at least one of 2- (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-6-tert-butylphenylacrylate, 2- {1- [ 2-hydroxy-3, 5-bis (2-methylbutan-2-yl) phenyl ] ethyl } -4, 6-bis (2-methylbutan-2-yl) phenylacrylate, 5, 6-dimethoxyisobenzofuran-1 (3H) -one, 4- (tert-butyl) -2- (5- (tert-butyl) -2-oxo-2, 3-dihydrobenzofuran-3-yl) phenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, allylphenol, and 2-methoxy-4-allylphenol.
14. The composition of claim 4, wherein the antioxidant B is selected from at least one of 2- (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-6-tert-butylphenylacrylate, 2- {1- [ 2-hydroxy-3, 5-bis (2-methylbutan-2-yl) phenyl ] ethyl } -4, 6-bis (2-methylbutan-2-yl) phenylacrylate, 2-tert-butyl-6- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -4-methylphenylacrylate, 5, 6-dimethoxyisobenzofuran-1 (3H) -one, 4- (tert-butyl) -2- (5- (tert-butyl) -2-oxo-2, 3-dihydrobenzofuran-3-yl) phenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, 6-hydroxy-3-coumarone Ran Tong, allylphenol and 2-methoxy-4-allylphenol.
15. The composition of claim 14, wherein the antioxidant B is selected from at least one of 2- (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methyl-6-tert-butylphenylacrylate, 2- {1- [ 2-hydroxy-3, 5-bis (2-methylbutan-2-yl) phenyl ] ethyl } -4, 6-bis (2-methylbutan-2-yl) phenylacrylate, 5, 6-dimethoxyisobenzofuran-1 (3H) -one, 4- (tert-butyl) -2- (5- (tert-butyl) -2-oxo-2, 3-dihydrobenzofuran-3-yl) phenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, allylphenol, and 2-methoxy-4-allylphenol.
16. The composition of any of claims 1, 2, 5-9 or 11-15, wherein the polyethylene is selected from ethylene homopolymers and/or ethylene-C 4-8 An olefin copolymer.
17. The composition of claim 16, wherein the polyethylene is selected from at least one of polyethylene, low density polyethylene, high density polyethylene, and linear low density polyethylene.
18. The composition of claim 17, wherein the polyethylene matrix resin has a density of 0.91-0.925g/cm 3 At 190℃andThe melt index under a load of 2.16kg is 1.9-2.2g/10min.
19. A composition according to claim 3, wherein the polyethylene is selected from ethylene homopolymers and/or ethylene-C 4-8 An olefin copolymer.
20. The composition of claim 19, wherein the polyethylene is selected from at least one of polyethylene, low density polyethylene, high density polyethylene, and linear low density polyethylene.
21. The composition of claim 20, wherein the polyethylene matrix resin has a density of 0.91-0.925g/cm 3 The melt index at 190℃and 2.16kg load is 1.9-2.2g/10min.
22. The composition according to claim 4, wherein the polyethylene is selected from ethylene homopolymers and/or ethylene-C 4-8 An olefin copolymer.
23. The composition of claim 22, wherein the polyethylene is selected from at least one of polyethylene, low density polyethylene, high density polyethylene, and linear low density polyethylene.
24. The composition of claim 23, wherein the polyethylene matrix resin has a density of 0.91-0.925g/cm 3 The melt index at 190℃and 2.16kg load is 1.9-2.2g/10min.
25. Composition according to claim 10, wherein the polyethylene is selected from ethylene homopolymers and/or ethylene-C 4-8 An olefin copolymer.
26. The composition of claim 25, wherein the polyethylene is selected from at least one of polyethylene, low density polyethylene, high density polyethylene, and linear low density polyethylene.
27. The composition of claim 26, wherein the polyethylene matrix resin has a density of 0.91-0.925g/cm 3 The melt index at 190℃and 2.16kg load is 1.9-2.2g/10min.
28. The composition of any one of claims 1, 2, 5-9, 11-15, or 17-27, wherein the crosslinking agent is a peroxide crosslinking agent.
29. The composition of claim 28, wherein the peroxide crosslinking agent is selected from at least one of 2, 5-dimethyl-2, 5-di-t-butylperoxy-3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butylperoxyisopropyl) benzene, and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane.
30. A composition according to claim 3, wherein the cross-linking agent is a peroxide cross-linking agent.
31. The composition of claim 30, wherein the peroxide crosslinking agent is selected from at least one of 2, 5-dimethyl-2, 5-di-t-butylperoxy-3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butylperoxyisopropyl) benzene, and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane.
32. The composition of claim 4, wherein the crosslinking agent is a peroxide crosslinking agent.
33. The composition of claim 32, wherein the peroxide crosslinking agent is selected from at least one of 2, 5-dimethyl-2, 5-di-t-butylperoxy-3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butylperoxyisopropyl) benzene, and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane.
34. The composition of claim 10, wherein the crosslinking agent is a peroxide crosslinking agent.
35. The composition of claim 34, wherein the peroxide crosslinking agent is selected from at least one of 2, 5-dimethyl-2, 5-di-t-butylperoxy-3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butylperoxyisopropyl) benzene, and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane.
36. The composition of claim 16, wherein the crosslinking agent is a peroxide crosslinking agent.
37. The composition of claim 36, wherein the peroxide crosslinking agent is selected from at least one of 2, 5-dimethyl-2, 5-di-t-butylperoxy-3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butylperoxyisopropyl) benzene, and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane.
38. A process for preparing the crosslinkable polyolefin composition of any of claims 1-37, wherein the process comprises the steps of:
mixing polyethylene, an antioxidant A, an antioxidant B and a crosslinking agent, extruding and granulating to obtain the crosslinkable polyolefin composition.
39. The method of claim 38, wherein the extruding is performed in a twin screw extruder.
40. The process according to claim 39, wherein the twin-screw extruder has a screw aspect ratio of 10 to 100 and an extrusion temperature of 108 to 125 ℃.
41. A crosslinked polyolefin, wherein the crosslinked polyolefin is produced by crosslinking the crosslinkable polyolefin composition of any one of claims 1-37.
42. The crosslinked polyolefin of claim 41, wherein the crosslinking conditions comprise: the cross-linking temperature is 150-240 ℃ and the cross-linking time is 3-300min.
43. The crosslinked polyolefin of claim 41 or 42, wherein the crosslinked polyolefin has a gel content of 75-95%; the direct current breakdown strength is 345-410kV/mm; volume resistivity of 1X 10 18 -9.5×10 18 Ω·cm。
44. Use of the crosslinkable polyolefin composition of any of claims 1-37 or the crosslinked polyolefin of any of claims 41-43 in a high voltage insulation cable.
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