CN118084702A - Antioxidant and application thereof in high-voltage cable insulating material - Google Patents
Antioxidant and application thereof in high-voltage cable insulating material Download PDFInfo
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- CN118084702A CN118084702A CN202211428735.5A CN202211428735A CN118084702A CN 118084702 A CN118084702 A CN 118084702A CN 202211428735 A CN202211428735 A CN 202211428735A CN 118084702 A CN118084702 A CN 118084702A
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 81
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 71
- 239000011810 insulating material Substances 0.000 title abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 19
- 239000003431 cross linking reagent Substances 0.000 claims description 17
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 16
- 229920003020 cross-linked polyethylene Polymers 0.000 claims description 16
- 239000004703 cross-linked polyethylene Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 229920001684 low density polyethylene Polymers 0.000 claims description 15
- 239000004702 low-density polyethylene Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- -1 styrene-ethylene-butylene-styrene Chemical class 0.000 claims description 12
- 150000001491 aromatic compounds Chemical class 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 10
- LYNCRGYDKRNBAB-UHFFFAOYSA-N 8-chlorooct-1-ene Chemical compound ClCCCCCCC=C LYNCRGYDKRNBAB-UHFFFAOYSA-N 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 240000005572 Syzygium cordatum Species 0.000 claims description 8
- 235000006650 Syzygium cordatum Nutrition 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 claims description 4
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- ALYNCZNDIQEVRV-PZFLKRBQSA-N 4-amino-3,5-ditritiobenzoic acid Chemical compound [3H]c1cc(cc([3H])c1N)C(O)=O ALYNCZNDIQEVRV-PZFLKRBQSA-N 0.000 claims description 2
- AJJUMRVAJYRSME-UHFFFAOYSA-N 7-bromooct-1-ene Chemical compound CC(Br)CCCCC=C AJJUMRVAJYRSME-UHFFFAOYSA-N 0.000 claims description 2
- ASCJDBOFQQSNSS-UHFFFAOYSA-N 7-chlorooct-1-ene Chemical compound CC(Cl)CCCCC=C ASCJDBOFQQSNSS-UHFFFAOYSA-N 0.000 claims description 2
- SNMOMUYLFLGQQS-UHFFFAOYSA-N 8-bromooct-1-ene Chemical compound BrCCCCCCC=C SNMOMUYLFLGQQS-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 238000001556 precipitation Methods 0.000 abstract description 4
- 230000003679 aging effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000012774 insulation material Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- WYLQRHZSKIDFEP-UHFFFAOYSA-N benzene-1,4-dithiol Chemical compound SC1=CC=C(S)C=C1 WYLQRHZSKIDFEP-UHFFFAOYSA-N 0.000 description 3
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical group C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- AXGUBXVWZBFQGA-UHFFFAOYSA-N chloropropylate Chemical compound C=1C=C(Cl)C=CC=1C(O)(C(=O)OC(C)C)C1=CC=C(Cl)C=C1 AXGUBXVWZBFQGA-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003696 structure analysis method Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an antioxidant, which has the following structure:
Description
Technical Field
The invention relates to the field of antioxidants and high-voltage insulating materials thereof, in particular to a preparation method of a high-voltage cable insulating material composition, which comprises an antioxidant capable of obviously improving precipitation problems.
Background
Currently, along with the development of the powerful construction of infrastructure, the power network is in a high-speed development stage, and renewable energy sources such as wind energy, solar energy and tidal energy are increasingly applied, so that a higher long-distance large-capacity power transmission technology is also required. Crosslinked polyethylene is a currently mainstream polymer insulation material, has excellent electrical properties such as high breakdown strength, low dielectric loss and the like, and simultaneously has excellent thermal properties and mechanical properties, and has gradually replaced the traditional impregnated paper insulation and self-contained oil-filled insulation. However, the antioxidant commonly used in the cross-linked polyethylene insulating material industry at present has good ageing resistance and scorch resistance, but has poor compatibility with matrix resin, and the problem of 'frosting' afflicts the industry for many years.
The most commonly used antioxidant in the cable insulation material at present is a thiobisphenol antioxidant which can stop free radicals and decompose hydroperoxides, and meanwhile, the excellent scorch resistance of the antioxidant contributes to the current almost irreplaceable application position. CN103154113B reports that antioxidants for cable insulation are selected from phenols having two substituents each containing a sulfur atom and optionally other substituents. CN105829424B reports a polymer composition comprising a polyolefin, a peroxide and a sulfur-containing antioxidant for high voltage insulated power cables. CN107709443B reports that the antioxidants used in the cable insulation composition include a sulfur-containing first antioxidant having at least one-S (CH 2) 2CO2R group and a sulfur-containing second antioxidant that is free of-S (CH 2) 2CO2R groups. In recent years, excellent effects of secondary amine antioxidants in cable insulation materials are reported, and CN100741446B reports the application of 2, 6-tetramethyl-piperidinyl as a light stabilizer in cable insulation materials.
However, the currently used antioxidants have a disadvantage of poor compatibility with the insulation matrix resin, uneven antioxidant distribution and "bloom" problems which plague the industry for many years.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a novel antioxidant comprising a secondary amino group, a thio group or an ester group together with a long-chain hydrocarbon group and an unsaturated double bond. The secondary amino and the sulfur group have the function of a main antioxidant, so that the thermal stability of the material in the process of storage and use is ensured; the double bond has the function of an auxiliary antioxidant and has thermal stability in the processing process. Meanwhile, long-chain hydrocarbon groups enable the compatibility of the material and matrix resin to be better, and the problem of 'frosting' is avoided. In the processing process, compared with a polyethylene macromolecular chain, free radicals can react with double bonds of a micromolecular antioxidant preferentially. And the designed small molecule has a large conjugated structure, so that the structure is more stable, the energy of free radicals can be buffered better, and the possibility of attacking a polyethylene molecular chain is reduced.
In order to achieve the aim of the invention, the invention adopts the following specific technical scheme:
in one aspect, the present invention provides an antioxidant having the structure:
wherein R1 is selected from-NH-or-S-; r2 is selected from-COO-or-S-.
On the other hand, the invention also provides a preparation method of the antioxidant, which comprises the following steps:
the antioxidant is prepared by mixing an aromatic compound, halogenated olefin and an alkaline catalyst, and reacting in an alkaline solvent.
In the step of the invention, the aromatic compound is selected from 4-aminobenzoic acid, 4-mercaptobenzoic acid, 4-mercaptoaniline or p-dimercaptobenzene;
The halogenated olefin is selected from any one or a combination of at least two of 8-chloro-1-octene, 8-bromo-1-octene, 7-chloro-1-octene and 7-bromo-1-octene, and is preferably 8-chloro-1-octene;
the alkaline catalyst is selected from any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, preferably sodium hydroxide and/or potassium hydroxide;
The alkaline solvent is selected from organic amine solvents, preferably any one or a combination of at least two of triethylamine, ethylenediamine, triethanolamine and ethanolamine, more preferably triethylamine and/or ethylenediamine;
preferably, the molar ratio of aromatic compound to halogenated olefin is from 1:1 to 1:5, preferably from 1:2 to 1:3, such as 1:1, 1:2, 1:2.1, 1:2.3, 1:2.5, 1:3, 1:4, 1:5;
Preferably, the molar ratio of aromatic compound to basic catalyst is from 1:1 to 1:5, preferably from 1:1 to 1:2, such as 1:1, 1:1.1, 1:1.3, 1:1.5, 1:1.8, 1:2, 1:3, 1:4, 1:5;
Preferably, the mass ratio of the aromatic compound to the basic solvent is 1:10 to 1:40, preferably 1:20 to 1:30, such as 1:10, 1:20, 1:25, 1:30, 1:40.
In the present invention, the reaction temperature is 50 to 150 ℃, preferably 100 to 150 ℃, such as 50 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃; the reaction time is 2-24h, preferably 2-12h, such as 2h, 4h, 8h, 10h, 12h, 24h;
Preferably, after the reaction is finished, the method further comprises conventional post-treatment processes such as separation, washing, drying and the like, for example, the product is separated out by cooling, the product is filtered and washed with water, and the surface impurities are washed off, and then the antioxidant is obtained by drying in a vacuum drying oven.
In another aspect, the present invention also provides a polymer composition comprising a polyolefin compound, a cross-linking agent, an antioxidant and optionally a water tree retardant additive, a lubricant, wherein the antioxidant is selected from antioxidants having the structure above.
The polymer composition has a lower surface residue content, and the surface residue content of the polymer composition containing the antioxidant is detected by an alcohol washing surface residue method, and the detected residue content is lower than 1800ppm.
In the invention, the polyolefin compound is low-density polyethylene, the density range is 0.91-0.93g/cm 3, preferably 0.920-0.925g/cm 3, and the polyolefin compound is selected from any one or a combination of at least two of Yangbuck 2220H, shenhua Xinjiang 2420H, shanghai petrochemical J182A, yanshan petrochemical LD9202W, preferably Yangbuck 2220H and/or Shanghai petrochemical J182A;
In the present invention, the crosslinking agent is selected from any one or a combination of at least two of dicumyl peroxide (DCP), benzoyl Peroxide (BPO) and di-tert-butyl peroxide (DTBP), preferably dicumyl peroxide (DCP);
In the invention, the water tree retardant additive is selected from any one or a combination of at least two of polyethylene glycol (PEG), ethylene-vinyl acetate copolymer (EVA), styrene-ethylene-butylene-styrene block copolymer (SEBS) and sorbitol, preferably ethylene-vinyl acetate copolymer and/or sorbitol;
in the invention, the lubricant is selected from any one or a combination of at least two of stearic acid, butyl stearate, oleic acid, oleamide and ethylene bis stearamide, and is preferably stearic acid and/or oleic acid.
Preferably, the crosslinked polyethylene high-voltage insulation composite material comprises the following raw materials in percentage by mass:
89.0 to 99.8%, preferably 96.0 to 99.8%, such as 80.0%, 85.0%, 90.0%, 91.1%, 93.5%, 94.0%, 95.0%, 96.5%, 97.5%, 98%, 99.3% of low density polyethylene;
0.5 to 5.0%, preferably 1.0 to 2.0%, such as 0.5%, 1.0%, 1.5%, 2.0%, 3.0%, 4.0%, 5.0% of a crosslinking agent;
the antioxidant shown in formula (1) is 0.1-1.0%, preferably 0.2-0.4%, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.6%, 0.8%, 1.0%;
Optionally, the water tree retardant additive is 0-5.0%, preferably 1.0-3.0%, such as 0%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 4.0%, 5.0%;
Optionally, the lubricant is 0-3.0%, preferably 0.1-1.0%, such as 0%, 0.1%, 0.5%, 1.0%, 2.0%, 3.0%.
Finally, the invention provides a preparation method of the crosslinked polyethylene high-voltage insulation composite material, which comprises the steps of adding an antioxidant of a high-voltage cable insulation material shown in a formula 1, and optionally a water tree delay additive and a lubricant into low-density polyethylene LDPE, firstly mixing and granulating by a reciprocating single-screw extruder, and adding a crosslinking agent into a shaking tank to perform crosslinking agent absorption;
the mixing temperature is 110-190 ℃, preferably 120-180 ℃;
The post-absorption temperature is 40-100deg.C, preferably 50-80deg.C; the time is 8-48 hours, preferably 12-24 hours.
Compared with the prior art, the invention has the following advantages:
The crosslinked polyethylene high-voltage insulation composite material prepared by the novel antioxidant can obviously improve the compatibility of an LDPE matrix and the antioxidant and effectively solve the problem of 'frosting' on the basis of guaranteeing the antioxidation of the material, including the processing process, long-term use and scorch resistance.
Detailed Description
The invention is further described in connection with the following examples, but the scope of the invention is not limited to the examples, but is intended to include any other known modifications within the scope of the claims.
The main raw material sources of the examples are as follows:
Low density polyethylene: yangbuck 2220H with a melt index of 2.0g/10min (190 ℃,2.16 kg) and a density of 0.922g/cm 3;
crosslinking agent: dicumyl peroxide DCP, acciaierie, with a purity of 99.0%;
an antioxidant: antioxidant 300, very easy company, purity 99.0%;
An antioxidant: antioxidant DSTDP: very easy Co., purity 99.0%
An antioxidant: antioxidant 5057: li Anlong, purity 99.0%
And (3) a lubricant: butyl stearate: neutralization chemistry, purity 99.0%
4-Aminobenzoic acid: TCI company, purity 99.0%;
4-mercaptobenzoic acid: alatine with purity of 90%;
4-mercaptoaniline: a gem reagent, 95%;
p-dimercaptobenzene: heng Jing Rui chemical Co., ltd., 98%
8-Chloro-1-octene: the purity of Shanghai source leaf biotechnology company is 97.0%;
triethylamine: shanghai (national medicine) company with purity of 99.5%;
all other materials are commercially available common materials unless otherwise specified.
The blending materials prepared in the following examples were tested for oxidation resistance, mechanical properties, electrical properties, scorch resistance, while the compatibility of the antioxidant and matrix LDPE was characterized by testing the methanol wash out content of the material:
Antioxidant precipitation performance: detecting the precipitation amount of the antioxidant by an alcohol washing residue method, wherein the specific operation is QGDW 11883.1-2018;
oxidation resistance: the oxidation induction period test was performed by a differential scanning calorimeter (METTLER, DSC) at a temperature of 215 ℃.
Mechanical properties: the mechanical property test is carried out on the sample by adopting a stretcher (INSTRON 5966), the sample bar preparation method is a mould pressing method, and the specific test conditions are according to the standard ISO 527.
Scorch preventing performance: the test (alpha, MDR) was carried out by a rotor-free vulcanizer at 160℃with an oscillation angle of 0.5 ℃.
Thermal elongation properties: the test was performed by a combination of equipment in an oven at a temperature of 200℃for a period of 14 minutes.
Conductivity: the test was performed using a high resistance meter (Keithley) according to GB/T1410.
Breakdown strength: a Hafford breakdown strength tester is adopted, and specific testing standards are according to GB/T1408.1.
The product structure analysis method comprises the following steps: 1 H-NMR was performed using an AM 400Bruker Spect rospin instrument with a deuterated solvent of CCl 3 COOD.
Example 1
Preparation of antioxidant (1):
1) 15.0g (0.11 mol) of 4-aminobenzoic acid and 48.2g (0.33 mol) of 8-chloro-1-octene were added to a round bottom flask, then 4.8g (0.12 mol) of sodium hydroxide and 364g (500 ml) of triethylamine were added to carry out reflux reaction at 110℃for 4 hours, the product was precipitated by cooling, filtered and washed with water to remove surface impurities, and then dried in a vacuum oven at 60℃for 12 hours to give 37.3g of substance (1) in a yield of 95%, the structure of which was as follows:
NMR[H,CDCl3]：1.29(m,10H),1.43(m,2H),1.63(m,2H),1.80(m,2H),2.18(m,6H),3.35(t,2H),4.02(s,H),4.30(t,2H),5.00～5.09(m,4H),5.82～5.90(m,2H),6.71(d,2H),7.68(d,2H)
Example 2
Preparation of novel antioxidant (2):
1) 17.0g (0.11 mol) of 4-mercaptobenzoic acid and 48.2g (0.33 mol) of 8-chloro-1-octene were charged into a round-bottomed flask, then 4.8g (0.12 mol) of sodium hydroxide, 364g (500 ml) of triethylamine were added, the reaction was refluxed at 110℃for 4 hours, the product was precipitated by cooling, filtered off with water, surface impurities were washed off, and then dried in a vacuum oven at 60℃for 12 hours to give 38.3g of substance (2) in 93% yield, which had the following structure:
NMR[H,CDCl3]：1.29(m,8H),1.42(m,4H),1.60(m,2H),1.80(m,2H),2.18(m,4H),2.94(t,2H),4.30(t,2H),5.00～5.09(m,4H),5.82(m,2H),7.50(d,2H),7.95(d,2H)
Example 3
Preparation of novel antioxidant (3):
1) 13.8g (0.11 mol) of 4-mercaptoaniline and 48.2g (0.33 mol) of 8-chloro-1-octene were charged into a round bottom flask, then 4.8g (0.12 mol) of sodium hydroxide and 364g (500 ml) of triethylamine were added to carry out reflux reaction at 110℃for 4 hours, the product was precipitated by cooling, filtered and washed with water to remove surface impurities, and then dried in a vacuum oven at 60℃for 12 hours to give 36.5g of substance (3) in 96% yield, which had the following structure:
NMR[H,CDCl3]：1.29(m,10H),1.40～1.45(m,2H),1.60～1.65(m,4H),2.18(t,4H),2.94(t,2H),3.35(t,2H),4.02(s,1H),5.00～5.09(m,4H),5.82(m,2H),6.50(d,2H),7.64(d,2H)
Example 4
Preparation of novel antioxidant (4):
1) 15.4g (0.11 mol) of p-dimercaptobenzene and 48.2g (0.33 mol) of 8-chloro-1-octene were charged into a round bottom flask, then 4.8g (0.12 mol) of sodium hydroxide and 364g (500 ml) of triethylamine were added to carry out reflux reaction at 110℃for 4 hours, the product was precipitated by cooling, filtered and washed with water to remove surface impurities, and then dried in a vacuum oven at 60℃for 12 hours to give 36.5g of substance (3) in 96% yield, which had the following structure:
NMR[H,CDCl3]：1.29(m,8H),1.42(m,4H),1.60(m,4H),2.18(t,4H),2.94(t,4H),5.00～5.09(m,4H),5.82(m,2H),7.29(d,4H)
Example 5
Preparing a crosslinked polyethylene high-voltage insulation composite material:
99.8% of LDPE Yangbuck 2220H as a base material and 0.2% of the antioxidant prepared in the example 1 are accurately weighed, extruded and mixed in a reciprocating single screw extruder, and the extrusion temperature is 120-150-180 ℃. Granulating, then, adding the mixture into a rotary drum for post-absorption, wherein the amount of the added cross-linking agent DCP is 2%, the post-absorption temperature is 80 ℃, and the time is 16 hours, so that the cross-linked polyethylene high-voltage insulation composite material sample is obtained.
The prepared samples were subjected to the above-mentioned correlation property measurement.
Example 6
Preparing a crosslinked polyethylene high-voltage insulation composite material:
99.8% of base LDPE Yangba 2220H and 0.2% of antioxidant prepared in example 2 are accurately weighed, extruded and mixed in a reciprocating single screw extruder, and the extrusion temperature is 120-150-180 ℃. Granulating, then, adding the mixture into a rotary drum for post-absorption, wherein the amount of the added cross-linking agent DCP is 2%, the post-absorption temperature is 80 ℃, and the time is 16 hours, so that the cross-linked polyethylene high-voltage insulation composite material sample is obtained.
The prepared samples were subjected to the above-mentioned correlation property measurement.
Example 7
Preparing a crosslinked polyethylene high-voltage insulation composite material:
99.8% of base LDPE Yangba 2220H and 0.2% of antioxidant prepared in example 3 are accurately weighed, extruded and mixed in a reciprocating single screw extruder, and the extrusion temperature is 120-150-180 ℃. Granulating, then, adding the mixture into a rotary drum for post-absorption, wherein the amount of the added cross-linking agent DCP is 2%, the post-absorption temperature is 80 ℃, and the time is 16 hours, so that the cross-linked polyethylene high-voltage insulation composite material sample is obtained.
The prepared samples were subjected to the above-mentioned correlation property measurement.
Example 8
Preparing a crosslinked polyethylene high-voltage insulation composite material:
99.8% of base LDPE Yangba 2220H and 0.2% of antioxidant prepared in example 3 are accurately weighed, extruded and mixed in a reciprocating single screw extruder, and the extrusion temperature is 120-150-180 ℃. Granulating, then, adding the mixture into a rotary drum for post-absorption, wherein the amount of the added cross-linking agent DCP is 2%, the post-absorption temperature is 80 ℃, and the time is 16 hours, so that the cross-linked polyethylene high-voltage insulation composite material sample is obtained.
The prepared samples were subjected to the above-mentioned correlation property measurement.
Example 9
99.7% Of LDPE Yangbuck 2220H as base material and 0.3% of antioxidant prepared in example 1 are accurately weighed, extruded and mixed in a reciprocating single screw extruder, and the extrusion temperature is 120-150-180 ℃. Granulating, then, adding the mixture into a rotary drum for post-absorption, wherein the amount of the added cross-linking agent DCP is 1.5%, the post-absorption temperature is 80 ℃, and the time is 12 hours, so that the cross-linked polyethylene high-voltage insulation composite material sample is obtained.
The prepared samples were subjected to the above-mentioned correlation property measurement.
Example 10
99.7% Of base material Shanghai petrochemical J182A and 0.2% of antioxidant prepared in example 4 and 0.1% of lubricant butyl stearate are accurately weighed, extruded and mixed in a reciprocating single screw extruder, and the extrusion temperature is 120-150-180 ℃. Granulating, then, adding the mixture into a rotary drum for post-absorption, wherein the amount of the added cross-linking agent DCP is 1.8%, the post-absorption temperature is 70 ℃, and the time is 24 hours, so that the cross-linked polyethylene high-voltage insulation composite material sample is obtained.
The prepared samples were subjected to the above-mentioned correlation property measurement.
Comparative example 1
Preparing a polyethylene composite material:
the preparation method is described with reference to example 5, the only difference being that: no 0.2% of the antioxidant (1) prepared in example 1 was added to obtain a polyethylene composite sample.
The prepared samples were subjected to the above-described correlation property test.
Comparative example 2
Preparing a polyethylene composite material:
The preparation method is described with reference to example 5, the only difference being that: 0.2% of the antioxidant (1) prepared in example 1 was replaced with 0.2% of the antioxidant 300 to obtain a polyethylene composite sample.
The prepared samples were subjected to the above-described correlation property test.
Comparative example 3
Preparing a polyethylene composite material:
The preparation method is described with reference to example 5, the only difference being that: 0.2% of the antioxidant (1) prepared in example 1 was replaced with 0.2% of distearyl 3,3' -thiodipropionate DSTDP to obtain a polyethylene composite sample.
The prepared samples were subjected to the above-described correlation property test.
Comparative example 4
Preparing a polyethylene composite material:
the preparation method is described with reference to example 5, the only difference being that: 0.2% of the antioxidant (1) prepared in example 1 was replaced with 0.2% of amine antioxidant 5057 to obtain a polyethylene composite sample.
The prepared samples were subjected to the above-described correlation property test. The results of the performance tests of the examples and comparative examples are shown in Table 1:
TABLE 1 summary of sample Performance test results
Comparing the performance data of the different samples in the above table, it can be found that the comparative example 1 without antioxidant has a smaller amount of alcohol-washed precipitate, which indicates that the source of the alcohol-washed precipitate is mainly an antioxidant, whereas in the examples of the antioxidant prepared by the invention, the level of the alcohol-washed precipitate is significantly lower than that of the existing antioxidant after the addition. When thermal elongation data and MH are observed, the addition of an antioxidant can reduce the crosslinking degree due to the reaction with a crosslinking agent, and the novel antioxidant in the invention has obviously weaker inhibition effect on crosslinking than the traditional antioxidant. The tensile strength and the elongation at break are not obviously affected by different antioxidants, but the tensile strength and the elongation at break performance are obviously improved after the antioxidants are added, so that the antioxidant has a better antioxidant effect. The same conclusion can be obtained by comparing OIT data. Compared with TS1 data, the novel antioxidant has better scorch resistance. Comparing the breakdown strength data can find that the novel antioxidant has less influence on the insulating property of the product.
The above embodiments are only for describing the preferred embodiments of the present invention, not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit of the invention as defined in the appended claims.
Claims (10)
1. An antioxidant having the structure:
wherein R1 is selected from-NH-or-S-; r2 is selected from-COO-or-S-.
2. The method for preparing an antioxidant according to claim 1, wherein the method comprises the steps of:
the antioxidant is prepared by mixing an aromatic compound, halogenated olefin and an alkaline catalyst, and reacting in an alkaline solvent.
3. The method of claim 2, wherein the aromatic compound is selected from the group consisting of 4-aminobenzoic acid, 4-mercaptobenzoic acid, and 4-mercaptoaniline; and/or the halogenated olefin is selected from any one or a combination of at least two of 8-chloro-1-octene, 8-bromo-1-octene, 7-chloro-1-octene, 7-bromo-1-octene, preferably 8-chloro-1-octene; and/or the alkaline catalyst is selected from any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, preferably sodium hydroxide and/or potassium hydroxide; and/or the basic solvent is selected from organic amine solvents, preferably any one or a combination of at least two of triethylamine, ethylenediamine, triethanolamine and ethanolamine, more preferably triethylamine and/or ethylenediamine.
4. A process according to claim 2 or 3, wherein the molar ratio of aromatic compound to halogenated olefin is from 1:1 to 1:5, preferably from 1:2 to 1:3; and/or the molar ratio of the aromatic compound to the basic catalyst is from 1:1 to 1:5, preferably from 1:1 to 1:2; and/or the mass ratio of the aromatic compound to the alkaline solvent is 1:10-1:40, preferably 1:20-1:30.
5. The preparation process according to any one of claims 2 to 4, wherein the reaction temperature is 50 to 150 ℃, preferably 100 to 150 ℃; the reaction time is 2 to 24 hours, preferably 2 to 12 hours.
6. A polymer composition comprising a polyolefin compound, a cross-linking agent, an antioxidant and optionally a water tree retardant additive, a lubricant, wherein the antioxidant is selected from the group of antioxidants as claimed in claim 1 or the antioxidants prepared by the preparation process as claimed in any of claims 2-5.
7. The polymer composition of claim 6, wherein the polyolefin compound is a low density polyethylene having a density in the range of 0.91-0.93g/cm 3, preferably 0.920-0.925g/cm 3; and/or the cross-linking agent is selected from any one or a combination of at least two of dicumyl peroxide (DCP), benzoyl Peroxide (BPO) and di-tert-butyl peroxide (DTBP), and is preferably dicumyl peroxide (DCP); and/or the water tree retardant additive is selected from any one or a combination of at least two of polyethylene glycol (PEG), ethylene-vinyl acetate copolymer (EVA), styrene-ethylene-butylene-styrene block copolymer (SEBS) and sorbitol, preferably ethylene-vinyl acetate copolymer and/or sorbitol; and/or the lubricant is selected from any one or a combination of at least two of stearic acid, butyl stearate, oleic acid, oleamide and ethylene bis stearamide, and is preferably stearic acid and/or oleic acid.
8. The polymer composition according to claim 6 or 7, wherein the crosslinked polyethylene high-voltage insulation composite material comprises the following raw materials in percentage by mass:
89.0 to 99.8%, preferably 96.0 to 99.8% of low density polyethylene; and/or, a crosslinking agent of 0.5 to 5.0%, preferably 1.0 to 2.0%; and/or, antioxidants 0.1 to 1.0%, preferably 0.2 to 0.4%; and/or, water tree retardant additives 0-5.0%, preferably 1.0-3.0%; and/or, the lubricant is 0-3.0%, preferably 0.1-1.0%.
9. A process for the preparation of a polymer composition according to any one of claims 6 to 8, comprising the steps of: adding antioxidant, optional water tree retardant additive and lubricant into LDPE, mixing with reciprocating single screw extruder, granulating, adding cross-linking agent into shaking tank, and absorbing.
10. The method of preparation according to claim 9, wherein the mixing temperature is 110-190 ℃, preferably 120-180 ℃; and/or, said post-absorption, at a temperature of 40-100 ℃, preferably 50-80 ℃; the time is 8-48 hours, preferably 12-24 hours.
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