CN107778525B - A kind of stabiliser compositions of polyethylene wire and cable PP Pipe Compound - Google Patents
A kind of stabiliser compositions of polyethylene wire and cable PP Pipe Compound Download PDFInfo
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- CN107778525B CN107778525B CN201711063293.8A CN201711063293A CN107778525B CN 107778525 B CN107778525 B CN 107778525B CN 201711063293 A CN201711063293 A CN 201711063293A CN 107778525 B CN107778525 B CN 107778525B
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 122
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- -1 polyethylene Polymers 0.000 title claims abstract description 66
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 56
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 55
- 150000001875 compounds Chemical class 0.000 title claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 26
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 claims description 5
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N alpha-methylfuran Natural products CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 claims 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 2
- GQJDFTIOKVGUOF-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO Chemical class OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO GQJDFTIOKVGUOF-UHFFFAOYSA-N 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 abstract description 28
- 150000007970 thio esters Chemical class 0.000 abstract description 21
- 239000002250 absorbent Substances 0.000 abstract description 19
- 230000002745 absorbent Effects 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 15
- 230000003078 antioxidant effect Effects 0.000 abstract description 8
- 230000007812 deficiency Effects 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 description 19
- 238000007254 oxidation reaction Methods 0.000 description 16
- 230000006698 induction Effects 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 235000006708 antioxidants Nutrition 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 230000003026 anti-oxygenic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BLDFSDCBQJUWFG-UHFFFAOYSA-N 2-(methylamino)-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(NC)C(O)C1=CC=CC=C1 BLDFSDCBQJUWFG-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- WNKGQCYVYDRMAL-UHFFFAOYSA-N C1(=CC=CC=C1)O.CC=1C=CC(=CC1)C(C)(C)C Chemical compound C1(=CC=CC=C1)O.CC=1C=CC(=CC1)C(C)(C)C WNKGQCYVYDRMAL-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic 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
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention discloses a kind of stabiliser compositions of polyethylene wire and cable PP Pipe Compound.For the general deficiency of antioxidant effect that the dedicated material stabilizer of polyethylene wire and cable exists in the prior art, the stabiliser compositions carry out selection and the selection of mass ratio by the type to Hinered phenols stabilizer, phosphite-type stabilisers, thioesters stabilizer and acid absorbent, obtain a series of stabiliser compositions that can greatly improve polyethylene wire and cable PP Pipe Compound antioxygen stability.
Description
Technical field
The invention belongs to chemical technology fields, are related to fine chemistry industry, and in particular to a kind of polyethylene wire and cable PP Pipe Compound
Stabiliser compositions.
Background technique
Wire and cable product purpose is very extensive, is related to the industries such as electric power, communication, electrical equipment.Wire and cable PP Pipe Compound
It is raw materials used mainly to have PE and PVC.PVC is relatively unstable to light and heat, has environmentally friendly hidden danger, and the developed countries such as America and Europe exist already
Just forbid the beginning of the eighties using PVC insulated cable in pile and public place.China's relevant laws and regulations also want by explicit order
Important building is asked to be forbidden to use polyvinyl chloride electrical wire and cable, it is necessary to low smoke, zero halogen cross-linking polyolefin insulation electric wire cable is used, with
A large amount of dense smokes, chlorine, cause casualties when fire being avoided to occur.Communication cable generally also does insulating layer with HDPE, with LLDPE
Do restrictive coating；Optical cable mainly uses HDPE and MDPE as protective cover material.
The ultraviolet light in oxygen and sunlight in air causes plastic material that thermal oxide or photooxidation reaction occurs, and is used in
The polyolefine material physical mechanical property of wire and cable is deteriorated, and loses original function and use value in advance.The heat of wire and cable
Oxidation-stabilized performance can be used to judge the service life of cable and optical cable.Oxidation induction period (OIT) is stabilization material oxytolerant
Change the opposite measurement of the one kind decomposed, is a kind of evaluation to material settling outization level.By will be placed in added with the sample of stabilizer
The high purity oxygen gas of specific temperature flows down, and measures from logical oxygen to the time interval between oxidation reaction, to determine the OIT of material.
Antioxidant makes an addition in plastic material the thermal oxide speed that can effectively inhibit or reduce plastics macromolecular, significantly prolongs
The degradation of slow plastic material, ageing process, extend plastic products service life.The thermal oxide for testing electric wire and cable jacket material is steady
Qualitative energy is extremely important, and the oxidation induction period of electric wire and cable jacket material is exactly an important finger for reacting phase thermo oxidative stability energy
Mark identifies the service life of product and its quality of performance by the test of oxidation induction period.
The test equipment of oxidation induction period --- differential scanning calorimeter can accurately measure at a high speed the inoxidizability of material
Energy.The thermal stability of sample is determined by the length of oxidation induction period time, the time, more long then thermo oxidative stability can be just
Better.
In wire and cable PP Pipe Compound production process, on the one hand needs to select suitable plastics variety, on the other hand need
Suitable stabilizer is added, to improve its oxidation induction period and service life.
In realizing process of the present invention, inventor's discovery is had the following problems: although the prior art mentions electric wire electricity
Cable stabilizer, such as widely used stabiliser compositions antioxidant 215 of wire and cable manufacturer in the market, although also can be big
Amplitude improves antioxygenic property, at high cost, using effect general defect big but there are additive amounts.
Summary of the invention
In order to solve the deficiencies in the prior art, an object of the present invention is to provide a kind of polyethylene wire and cable PP Pipe Compound
Stabiliser compositions, the antioxygenic property of polyethylene wire and cable PP Pipe Compound can be greatly improved.
To achieve the goals above, the technical solution of the present invention is as follows:
A kind of stabiliser compositions of polyethylene wire and cable PP Pipe Compound are steady by Hinered phenols stabilizer, phosphorous acid esters
Determine agent and thioesters stabilizer composition；The Hinered phenols stabilizer is AO-1, AO-6, and the phosphite-type stabilisers are
PS-1, the thioesters stabilizer are TS-2；The mass ratio of described AO-1, AO-6, PS-1, TS-2 are 2~3:1:1:1~2.
A kind of stabiliser compositions of polyethylene wire and cable PP Pipe Compound are stablized by Hinered phenols stabilizer, thioesters
Agent and acid absorbent composition；The Hinered phenols stabilizer is AO-1, AO-7, and the thioesters stabilizer is TS-2, the suction
Sour agent is AC-1, AC-3 or AC-4；The mass ratio of described AO-1, TS-2 and AC-1 are the 3~12.5:1.5~4:1 or AO-
1, the mass ratio of TS-2 and AC-3 is 10:4:1 or the mass ratio of described AO-1, AO-7, TS-2 and AC-4 are 7.5:5:4:1.
A kind of stabiliser compositions of polyethylene wire and cable PP Pipe Compound are stablized by Hinered phenols stabilizer and thioesters
Agent composition or Hinered phenols stabilizer and acid absorbent composition；The Hinered phenols stabilizer is AO-1, AO-4, AO-6, the sulphur
It is TS-2 for esters stabilizer, the acid absorbent is AC-1；The mass ratio of the AO-4 and TS-2 be the 2:1 or AO-1,
The mass ratio of AO-4 and TS-2 is 1:1:1 or the mass ratio of described AO-1, AO-6 and AC-1 are 5:4:1.
A kind of stabiliser compositions of polyethylene wire and cable PP Pipe Compound are steady by Hinered phenols stabilizer, phosphorous acid esters
Determine agent, thioesters stabilizer and acid absorbent composition；The Hinered phenols stabilizer is AO-1, AO-8, the phosphorous acid esters
Stabilizer is PS-1, PS-2, and the thioesters stabilizer is TS-2, and the acid absorbent is AC-1, AC-3；Described AO-1, PS-
1, the mass ratio of TS-2 and AC-1 is 7.5:2.5:4:1 or the mass ratio of described AO-8, PS-1, TS-2 and AC-1 are 7.5:
The mass ratio of 2.5:4:1 or described AO-1, PS-1, TS-2 and AC-3 are 10:2.5:1.5:1 or described AO-1, PS-2, TS-2
Mass ratio with AC-3 is 10:2.5:1.5:1.
A kind of stabiliser compositions of polyethylene wire and cable PP Pipe Compound are steady by Hinered phenols stabilizer, phosphorous acid esters
Determine agent and acid absorbent composition；The Hinered phenols stabilizer is AO-1, AO-8 and AO-6, and the phosphite-type stabilisers are
PS-1, the acid absorbent are AC-3；The mass ratio of described AO-1, AO-8, AO-6, PS-1 and AC-3 are 5:5:2.5:1.5:1.
The composition that the existing common stabiliser compositions of polyethylene wire and cable are AO-1 and PS-1 mass ratio is 1:2,
Its inoxidizability that can increase polyethylene wire and cable, however the present inventor by many experiments confirm, AO-1 with
PS-1 mass ratio is that the secondary extrusion OIT parameter of the stabiliser compositions of 1:2 only has 9.3, and by Hinered phenols stabilizer,
The selection that phosphite-type stabilisers, thioesters stabilizer and acid absorbent are selected and matched finds the stabilization of specific proportion
Agent composition can greatly improve the secondary extrusion OIT parameter of stabiliser compositions, and the present invention is selected by many experiments
The stabiliser compositions of the polyethylene wire and cable PP Pipe Compound of above-mentioned specific proportion, the secondary extrusion of the composition of these stabilizers
OIT parameter 25 or more, enables to the antioxygenic property of polyethylene wire and cable to greatly improve.
The second object of the present invention is to provide a kind of polyethylene wire and cable PP Pipe Compound, including above stabilizer composition.
The invention has the benefit that
1. the present invention can protect melt index of polyethylene wire and cable PP Pipe Compound during repeated processing to stablize, instead
The multiple melt index squeezed out three times is larger, and variation is small, and showing can be mentioned using stabiliser compositions of the invention significantly
The processing stability of high density polyethylene wire and cable；And oxidation induction period is long, shows using stabiliser compositions of the invention
The service life of polyethylene wire and cable can be greatly improved.
2. stabiliser compositions property of the invention is stablized, safe and non-toxic, easy to use, polyethylene electric wire electricity can be improved
The stability of cable PP Pipe Compound in process extends its service life in use.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
Hinered phenols stabilizer described herein, i.e. Hinered phenols antioxidant, refer to space hindered structure
Phenolic compound.
Hinered phenols stabilizer is selected from following compound in the application:
Title: four [β-(the tertiary fourths of 3,5- bis-
Base -4- hydroxy phenyl) propionic acid] pentaerythritol ester (referred to as: AO-1)；
Title: two three second of contracting
Glycol bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic esters] (referred to as: AO-2)；
Title: β-(3,5- di-t-butyl -4- hydroxyl
Phenyl) propionic acid n-octadecyl alcohol ester (referred to as: AO-3)；
Title: 4,4' methylene bis (2,6 di t butyl phenol)
(referred to as: AO-4)；
Title: the bis- [3- (3,5- di-t-butyl -4- of N, N'-
Hydroxy phenyl) propionyl] hydrazine (referred to as: AO-5)；
Title: 2,2'- thiodiethyl
Bis- [3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic esters] (referred to as: AO-6)；
Title: 2,6- di-t-butyl -4- sylvan (referred to as: AO-7)；
Title: 4,4'- thiobis (6- tert-butyl -3- methylbenzene
Phenol) (referred to as: AO-8).
Phosphite ester antioxidant described herein is a kind of polymer hydrogen that will be generated in thermo-oxidative ageing chain reaction
Peroxide decomposes, and is allowed to generate deactivated compound, to terminate or delay the stabilizer of thermo-oxidative ageing.
The application phosphorous acid esters antioxidant is selected from following compound:
Title: phosphorous acid three (2,4- di-tert-butyl-phenyl) ester (referred to as: PS-1)；
Title: bis- two phosphorous of (2,4- di-tert-butyl-phenyl) pentaerythrite
Acid esters (referred to as: PS-2).
Thioesters stabilizer described herein, i.e. thioester antioxidant, thioesters stabilizer in the application
Selected from following compound:
Title: thiodipropionic acid bis-dodecanol ester (referred to as:
TS-1)；
Title: the double octadecyls of thio-2 acid (referred to as:
TS-2)；
Title: (the 3- lauryl sulphur of pentaerythrite four
For propionic ester) (referred to as: TS-3).
Acid absorbent in the application is selected from following compound: calcium stearate (referred to as: AC-1), zinc stearate is (referred to as: AC-
2), hydrotalcite (referred to as: AC-3), calcium carbonate (referred to as: AC-4), zinc oxide (referred to as: AC-5).
As background technique is introduced, the anti-oxidant of the dedicated material stabilizer of polyethylene wire and cable exists in the prior art
The general deficiency of effect, in order to solve technical problem as above, present applicant proposes a kind of polyethylene wire and cable PP Pipe Compounds
Stabiliser compositions.
A kind of exemplary embodiment of the application provides a kind of combination of stabilizers of polyethylene wire and cable PP Pipe Compound
Object is made of Hinered phenols stabilizer, phosphite-type stabilisers and thioesters stabilizer；The Hinered phenols stabilizer is
AO-1, AO-6, the phosphite-type stabilisers are PS-1, and the thioesters stabilizer is TS-2；The AO-1, AO-6,
The mass ratio of PS-1, TS-2 are 2~3:1:1:1~2.The stabiliser compositions of the proportion can greatly improve polyethylene electric wire
The oxidation induction period of cable, secondary extrusion OIT parameter is 25 or more.
Preferably, the mass ratio of described AO-1, AO-6, PS-1, TS-2 are 3:1:1:1.Polyethylene can be further increased
The oxidation induction period of wire and cable, secondary extrusion OIT parameter is up to 32.1.
Second of exemplary embodiment of the application provides a kind of combination of stabilizers of polyethylene wire and cable PP Pipe Compound
Object is made of Hinered phenols stabilizer, thioesters stabilizer and acid absorbent；The Hinered phenols stabilizer be AO-1, AO-7,
The thioesters stabilizer is TS-2, and the acid absorbent is AC-1, AC-3 or AC-4；The matter of described AO-1, TS-2 and AC-1
Amount than be 3~12.5:1.5~4:1 the mass ratio of described AO-1, TS-2 and AC-3 are 10:4:1 or the AO-1, AO-7,
The mass ratio of TS-2 and AC-4 is 7.5:5:4:1.The stabiliser compositions of the proportion can greatly improve polyethylene wire and cable
Oxidation induction period, secondary extrusion OIT parameter is 25 or more.
Preferably, the mass ratio of described AO-1, TS-2 and AC-1 are 10:4:1 or 12.5:1.5:1 or described AO-1, TS-
The mass ratio of 2 and AC-3 is 10:4:1 or the mass ratio of described AO-1, AO-7, TS-2 and AC-4 are 7.5:5:4:1.It can be into
One step improves the oxidation induction period of polyethylene wire and cable, and secondary extrusion OIT parameter is up to 30 or more.
The third exemplary embodiment of the application provides a kind of combination of stabilizers of polyethylene wire and cable PP Pipe Compound
Object, is made of Hinered phenols stabilizer and thioesters stabilizer or Hinered phenols stabilizer and acid absorbent form；It is described to be obstructed
Phenol stabilizer is AO-1, AO-4, AO-6, and the thioesters stabilizer is TS-2, and the acid absorbent is AC-1；The AO-4
Mass ratio with TS-2 is 2:1 or the mass ratio of described AO-1, AO-4 and TS-2 are 1:1:1 or described AO-1, AO-6 and AC-
1 mass ratio is 5:4:1.The stabiliser compositions of the proportion can greatly improve the oxidation induction period of polyethylene wire and cable,
Its secondary extrusion OIT parameter is 30 or more.
The 4th kind of exemplary embodiment of the application, provides a kind of combination of stabilizers of polyethylene wire and cable PP Pipe Compound
Object is made of Hinered phenols stabilizer, phosphite-type stabilisers, thioesters stabilizer and acid absorbent；The Hinered phenols
Stabilizer is AO-1, AO-8, and the phosphite-type stabilisers are PS-1, PS-2, and the thioesters stabilizer is TS-2, institute
Stating acid absorbent is AC-1, AC-3；The mass ratio of described AO-1, PS-1, TS-2 and AC-1 be the 7.5:2.5:4:1 or AO-8,
The mass ratio of PS-1, TS-2 and AC-1 are 7.5:2.5:4:1 or the mass ratio of described AO-1, PS-1, TS-2 and AC-3 are 10:
The mass ratio of 2.5:1.5:1 or described AO-1, PS-2, TS-2 and AC-3 are 10:2.5:1.5:1.The combination of stabilizers of the proportion
Object can greatly improve the oxidation induction period of polyethylene wire and cable, and secondary extrusion OIT parameter is 25 or more.
Preferably, the mass ratio of described AO-1, PS-1, TS-2 and AC-3 are 10:2.5:1.5:1 or described AO-1, PS-
2, the mass ratio of TS-2 and AC-3 is 10:2.5:1.5:1.The oxidation induction period of polyethylene wire and cable can be further increased,
Its secondary extrusion OIT parameter is up to 32 or more.
The 5th kind of exemplary embodiment of the application, provides a kind of combination of stabilizers of polyethylene wire and cable PP Pipe Compound
Object is made of Hinered phenols stabilizer, phosphite-type stabilisers and acid absorbent；The Hinered phenols stabilizer is AO-1, AO-
8 and AO-6, the phosphite-type stabilisers are PS-1, and the acid absorbent is AC-3；Described AO-1, AO-8, AO-6, PS-1 and
The mass ratio of AC-3 is 5:5:2.5:1.5:1.The stabiliser compositions of the proportion can greatly improve polyethylene wire and cable
Oxidation induction period, secondary extrusion OIT parameter is up to 34.1.
The composition that the existing common stabiliser compositions of polyethylene wire and cable are AO-1 and PS-1 mass ratio is 1:2,
Its inoxidizability that can increase polyethylene wire and cable, however the present inventor by many experiments confirm, AO-1 with
PS-1 mass ratio is that the secondary extrusion OIT parameter of the stabiliser compositions of 1:2 only has 9.3, and by Hinered phenols stabilizer,
The selection that phosphite-type stabilisers, thioesters stabilizer and acid absorbent are selected and matched finds the stabilization of specific proportion
Agent composition can greatly improve the secondary extrusion OIT parameter of stabiliser compositions, and the present invention is selected by many experiments
The stabiliser compositions of the polyethylene wire and cable PP Pipe Compound of above-mentioned specific proportion, the secondary extrusion of the composition of these stabilizers
OIT parameter 25 or more, enables to the antioxygenic property of polyethylene wire and cable to greatly improve.
Embodiment there is provided a kind of polyethylene wire and cable PP Pipe Compounds, including above stabilizer for the 6th kind of the application
Composition.
Preferably, the 0.2%~0.4% of the stabiliser compositions polyethylene quality.
It detects the method for stabilizer or stabiliser compositions stablizing effect and steps are as follows:
(1) above stabilizer composition is uniformly mixed with 500 grams of wire and cable base-materials (polyethylene)；
(2) extruding pelletization three times is carried out in double screw extruder, each extruding pelletization keeps sample about 50 grams；
(3) OIT, the melt index of each sample are tested respectively.
(4) OIT and melt index are analyzed.
The stabiliser compositions are as described above.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment and comparative example of body.
By the stabilizer of different formulations by certain additive amount (using wire and cable PP Pipe Compound base-material as the quality percentage of radix
Number, i.e., using polyethylene quality as the mass percent of radix) it is uniformly mixed with 500 grams of polyethylene powders, in double screw extruder
Extruding pelletization, each extruding pelletization keep sample about 50 grams three times for middle progress；OIT, the melt index of each sample, formula are tested respectively
It is as shown in table 1 with testing result, OIT and melt index are analyzed.
The OIT of the stabiliser compositions of 1 different formulations of table, melt index
By upper table 1 it is found that the secondary extrusion OIT parameter as conventional stabiliser compositions sample 1 only has 9.3, and match
Fang Butong, secondary extrusion OIT parameter improvement effect are different, wherein the secondary extrusion OIT of sample 7~8,12~14,16~25
Parameter can reach 25 or more, especially can achieve 30 with the secondary extrusion OIT parameter of sample 7~8,13,16~20,23~25
More than, the wherein secondary extrusion OIT parameter highest of sample 25, up to 34.1.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (9)
1. a kind of polyethylene wire and cable PP Pipe Compound, characterized in that including stabiliser compositions, the stabiliser compositions are
The mass ratio of AO-1, AO-6, PS-1, TS-2 are the composition of 2~3:1:1:1~2；
The AO-1 is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, and the AO-6 is 2,2'- sulphur
Bis- [3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic ester] for diethyl, the PS-1 is (2, the 4- di-tert-butyls of phosphorous acid three
Base) ester, the TS-2 is the double octadecyls of thio-2 acid.
2. polyethylene wire and cable PP Pipe Compound as described in claim 1, characterized in that described AO-1, AO-6, PS-1, TS-2
Mass ratio be 3:1:1:1.
3. a kind of polyethylene wire and cable PP Pipe Compound, characterized in that including stabiliser compositions, the stabiliser compositions are
The mass ratio of AO-1, TS-2 and AC-1 are that the mass ratio of 3~12.5:1.5~4:1 composition or AO-1, TS-2 and AC-3 are
The composition that the composition of 10:4:1 or the mass ratio of AO-1, AO-7, TS-2 and AC-4 are 7.5:5:4:1；
The AO-1 is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, and the AO-7 is 2,6- bis-
Tert-butyl -4- sylvan, the TS-2 are the double octadecyls of thio-2 acid, and the AC-1 is calcium stearate, and the AC-3 is
Hydrotalcite, the AC-4 are calcium carbonate.
4. polyethylene wire and cable PP Pipe Compound as claimed in claim 3, characterized in that the matter of described AO-1, TS-2 and AC-1
Amount is 10:4:1 or described AO-1, AO- than the mass ratio for being 10:4:1 or 12.5:1.5:1 or described AO-1, TS-2 and AC-3
7, the mass ratio of TS-2 and AC-4 is 7.5:5:4:1.
5. a kind of polyethylene wire and cable PP Pipe Compound, characterized in that including stabiliser compositions, the stabiliser compositions are
The composition that the mass ratio of composition or AO-1, AO-4 and TS-2 that the mass ratio of AO-4 and TS-2 is 2:1 is 1:1:1, or
The mass ratio of AO-1, AO-6 and AC-1 are the composition of 5:4:1；
The AO-1 is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, AO-4 4,4'- methylene
Bis- (2,6- DI-tert-butylphenol compounds), the AO-6 are the bis- [3- (3,5- di-t-butyl -4- hydroxyphenyl) third of 2,2'- thiodiethyl
Acid esters], the TS-2 is the double octadecyls of thio-2 acid, and the AC-1 is calcium stearate.
6. a kind of polyethylene wire and cable PP Pipe Compound, characterized in that including stabiliser compositions, the stabiliser compositions are
The mass ratio of AO-1, PS-1, TS-2 and AC-1 are the composition of 7.5:2.5:4:1 or the matter of AO-8, PS-1, TS-2 and AC-1
Amount is than the combination that the mass ratio of the composition or AO-1, PS-1, TS-2 and AC-3 that are 7.5:2.5:4:1 is 10:2.5:1.5:1
The mass ratio of object or AO-1, PS-2, TS-2 and AC-3 are the composition of 10:2.5:1.5:1；
The AO-1 is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, and the AO-8 is 4,4'- sulphur
Dai Shuan (6- tert-butyl -3- methylphenol), the PS-1 are phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, and the PS-2 is double
(2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, the TS-2 are the double octadecyls of thio-2 acid, the AC-1
For calcium stearate, the AC-3 is hydrotalcite.
7. polyethylene wire and cable PP Pipe Compound as claimed in claim 6, characterized in that described AO-1, PS-1, TS-2 and AC-3
Mass ratio be 10:2.5:1.5:1 or the mass ratio of described AO-1, PS-2, TS-2 and AC-3 are 10:2.5:1.5:1.
8. a kind of polyethylene wire and cable PP Pipe Compound, characterized in that including stabiliser compositions, the stabiliser compositions are
The mass ratio of AO-1, AO-8, AO-6, PS-1 and AC-3 are the composition of 5:5:1.5:2.5:1；
The AO-1 is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, and the AO-8 is 4,4'- sulphur
Dai Shuan (6- tert-butyl -3- methylphenol), the AO-6 are bis- [3- (3, the 5- di-t-butyl -4- oxybenzenes of 2,2'- thiodiethyl
Base) propionic ester], the PS-1 is phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, and the AC-3 is hydrotalcite.
9. the polyethylene wire and cable PP Pipe Compound as described in claim 1~8 is any, characterized in that the stabiliser compositions
It is the 0.2%~0.4% of polyethylene quality.
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| CN104419015A (en) * | 2013-09-03 | 2015-03-18 | 中国科学院化学研究所 | Composition with capability of providing thermal stability for polymer and application of composition |
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| WO2008055832A3 (en) * | 2006-11-09 | 2008-06-26 | Ciba Holding Inc | Process using liquid phenolic antioxidants |
| CN101824202A (en) * | 2010-04-29 | 2010-09-08 | 广州合成材料研究院有限公司 | Composite processing stabilizing agent for ABS (Acrylonitrile Butadiene Styrene) and HIPS (High Impact Polystyrene) resins |
| CN104419015A (en) * | 2013-09-03 | 2015-03-18 | 中国科学院化学研究所 | Composition with capability of providing thermal stability for polymer and application of composition |
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Denomination of invention: Stabilizer composition for polyethylene wire and cable special material Effective date of registration: 20210901 Granted publication date: 20190813 Pledgee: Qilu Bank Co.,Ltd. Linyi Hedong Branch Pledgor: SHANDONG LINYI SUNNY WEALTH CHEMICALS Co.,Ltd. Registration number: Y2021980008694 |
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