CN111196886A - Environment-friendly high-temperature-resistant PVC (polyvinyl chloride) automobile insulated cable material composition and preparation method thereof - Google Patents
Environment-friendly high-temperature-resistant PVC (polyvinyl chloride) automobile insulated cable material composition and preparation method thereof Download PDFInfo
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- CN111196886A CN111196886A CN201811378243.3A CN201811378243A CN111196886A CN 111196886 A CN111196886 A CN 111196886A CN 201811378243 A CN201811378243 A CN 201811378243A CN 111196886 A CN111196886 A CN 111196886A
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- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004800 polyvinyl chloride Substances 0.000 title claims description 57
- 229920000915 polyvinyl chloride Polymers 0.000 title claims description 57
- 239000003381 stabilizer Substances 0.000 claims abstract description 23
- 239000004014 plasticizer Substances 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 24
- -1 fatty acid calcium salt Chemical class 0.000 claims description 19
- 235000021355 Stearic acid Nutrition 0.000 claims description 15
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 15
- 239000000194 fatty acid Substances 0.000 claims description 15
- 229930195729 fatty acid Natural products 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000008117 stearic acid Substances 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 150000003751 zinc Chemical class 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 159000000007 calcium salts Chemical class 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical class NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 claims description 5
- 229920001296 polysiloxane Polymers 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
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-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
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-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
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 239000005639 Lauric acid Substances 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
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-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
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- OMCYEZUIYGPHDJ-OQLLNIDSSA-N chembl354261 Chemical compound OC1=CC=CC=C1\C=N\NC(=O)C1=CC=CC=C1O OMCYEZUIYGPHDJ-OQLLNIDSSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 125000005591 trimellitate group Chemical group 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 3
- 235000010216 calcium carbonate Nutrition 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000002093 peripheral effect Effects 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 description 8
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 6
- 238000003889 chemical engineering Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- 239000012760 heat stabilizer Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004719 irradiation crosslinked polyethylene Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 2
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- XSXYESVZDBAKKT-UHFFFAOYSA-N 2-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1O XSXYESVZDBAKKT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- HIAAVKYLDRCDFQ-UHFFFAOYSA-L calcium;dodecanoate Chemical compound [Ca+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O HIAAVKYLDRCDFQ-UHFFFAOYSA-L 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- H01B3/443—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 vinylhalogenides or other halogenoethylenic compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention provides a high-temperature-resistant PVC automobile insulated cable material composition and a preparation method thereof. The insulated cable material composition comprises the following components in parts by weight: 100 parts of PVC resin; 30-80 parts of a plasticizer; stabilizer additive package: 2-6 parts; filling: 10-40 parts. The invention can be used for producing the automotive insulated cable with the temperature resistance of 125 ℃, is environment-friendly and nontoxic, has higher temperature resistance level and excellent surface effect, and can be used for preparing the high-temperature-resistant automotive engine peripheral cable.
Description
Technical Field
The invention belongs to the field of polymer blending and polymer molding processing, relates to a cable alloy material, and particularly relates to a high-temperature-resistant PVC automobile insulated cable material composition and a preparation method thereof.
Background
The automobile production and sales volume of China in 2017 breaks through 2800 ten thousand, the automobile production and sales volume of China in 1-6 months in 2018 is 1405 thousand and 1406 thousand respectively, the year-on-year increase is increased by 4.15% and 5.57%, and the automobile line of China is rapidly developed under the support and encouragement of domestic policies. As important parts for upgrading automobile upgrading, the requirements of the automobile industry on automobile cables are higher and higher, different countries and manufacturers set strict technical standards for automobile cable materials, and cable manufacturers must provide corresponding automobile cables according to different standard requirements.
At present, automobile cables which are required to be higher in temperature resistance of 125 ℃ in the market mainly comprise irradiation cross-linked polyethylene and thermoplastic polypropylene, but the irradiation cross-linked polyethylene and thermoplastic polypropylene cable materials are high in price, low in extrusion speed, complex in process and low in yield, particularly, cross-linked irradiation polyethylene can be applied only by an irradiation process after being manufactured into electric wires, and PVC cable materials have the advantages of wear resistance, light weight, easiness in processing, high cost performance and the like, are widely applied in the automobile field, and the 125 ℃ high-temperature resistant PVC automobile cable materials which meet the requirement of the automobile industry have huge market potential for replacing the cross-linked polyethylene and the thermoplastic polypropylene.
Patent CN103788531A adopts PVC resin, special plasticizer, stabilizer, lubricant and filler to prepare 125 ℃ resistant PVC cable material, wherein the stabilizer is mainly selected from common commercial calcium zinc stabilizer, the filler is selected from above 2000 mesh ultrafine filler, calcium zinc and organic tin type stabilizer has relatively high thermal stabilization effect on PVC, but pure use of calcium zinc type stabilizer requires relatively high addition amount to achieve relatively good stabilization effect, which easily causes the PVC cable material to have relatively low physical property and easy generation of pockmark, which affects the appearance and performance deterioration of the cable material, so it is necessary to develop a high cost performance environment-friendly 125 ℃ resistant automotive cable material by using low addition amount of special stabilizer.
Disclosure of Invention
Aiming at the problems existing in the current high-temperature-resistant cable material, the deep research finds that the PVC cable heat stabilizer prepared by utilizing the combination of the special additives has very excellent heat stabilization effect, can pass the high-temperature test at 125 ℃ by adding less than 6 parts of the stabilizer, has the advantages of high physical property, no pockmark on the surface and excellent extrusion performance, can replace the 125-DEG C-resistant automobile cable material of irradiation cross-linked polyethylene and thermoplastic polypropylene in the current market to be applied to automobile cables, and has very wide application prospect.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an environment-friendly high-temperature-resistant PVC (polyvinyl chloride) automobile insulated cable material composition comprises the following components in parts by mass:
100 parts of PVC resin, namely 100 parts of PVC resin,
plasticizer: 30 to 80 parts, preferably 35 to 65 parts,
stabilizer additive package: 2 to 6 parts, preferably 3 to 5 parts,
filling: 10 to 40 parts, preferably 15 to 25 parts,
wherein,
the stabilizer aid package comprises the following combinations of substances, in mass percent based on the stabilizer aid package:
fatty acid calcium salt: 25-65%, preferably 30% -60%, more preferably 35-50%,
zinc salts of fatty acids: 3 to 35%, preferably 5% to 30%, preferably 10 to 20%,
thiobis phenolic antioxidants: 15-35%, preferably 20% -30%, more preferably 22-28%,
metal ion passivator: 10-35%, preferably 15% -30%, more preferably 17-25%.
The calcium salt of the fatty acid in the stabilizer aid package is one or more of stearic acid, saturated fatty acid of C8-C16, calcium salt of oleic acid, preferably one or more of stearic acid or calcium salt of lauric acid, most preferably calcium salt of stearic acid. The zinc salt of the fatty acid is one or more of stearic acid, saturated fatty acid of C8-C16, zinc salt of oleic acid, preferably one or more of stearic acid or zinc salt of lauric acid, most preferably zinc salt of stearic acid.
The metal ion passivator in the stabilizer additive package is a hydrazide compound selected from one or more of N, N '-disubstituted oxalyl dihydrazide, N-salicylidene-N' salicyloyl hydrazide, 3-salicyloyl-1, 2, 4-triazole and oxalyl hydrazine, the hydrazide compound can be MD1024(N, N '-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine) of BASF Ciba Fine chemical industry, inhibitor OABH (oxalyl hydrazine) of Eastman Kodak company, CDA-1 (3-salicyloyl-1, 2, 4-triazole) of Asahi electro chemical industry Co., Ltd., CDA-6 (N-salicyloyl-N' salicyloyl hydrazide), and the metal ion passivator can form a stable complex with metal ions, the influence of residual metal ions in the resin and the influence of the metal wire core on the speed reduction and the aging of the PVC cable are effectively reduced.
Examples of the thiobisphenol antioxidant include BASF antioxidant 300 and Nanjing Kaikan chemical antioxidant 2246S.
The inventor surprisingly finds that the compounding of the four additives can play an excellent synergistic effect in PVC resin, and the excellent thermal stability effect can be played only by a small addition amount, so that the PVC cable material prepared by the special additive combination maintains the high physical property of PVC, and the prepared cable material has a smooth surface and is free of pockmarks. The three substances have a plurality of brands on the market, and the common brands on the market can be adopted.
Preferably, the PVC resin of the present invention is one or a combination of more than 1300 of ethylene-process PVC, preferably 1800 of ethylene-process PVC, most preferably 2000 of ethylene-process PVC, and the high molecular weight ethylene-process PVC resin has high physical properties and heat resistance, and the products of this kind are in wide variety on the market, such as HG-1800 and HG-2500 of Hanhua chemical Ningbo Co., Ltd, TH-2500 and TH-3000 of Tianjin chemical plant, S-80 and S-85 of Taihua Ningbo Industrial Co., Ltd, TK-2500P of Japan Xinyue Co., Ltd, and ONGROVIL-5070 of Wanhua-Bosu chemical.
Preferably, the plasticizer is one or a combination of more than two of polyester plasticizer and trimellitate plasticizer, preferably polyester plasticizer with molecular weight of 1500-6000, most preferably polyester plasticizer with molecular weight of 2000-4000, the loss degree of high-temperature volatilization of the polyester plasticizer with high molecular weight is low, and simultaneously the plasticizer has very excellent high and low temperature resistance, and typical brands on the market are UN-610 and UN-615 in Taiwan chemical engineering, PN850 in Taiwan chemical engineering, W-2050 and W-2340S in Japan ink chemical company.
The filler is a powdery inorganic filler with the fineness of 1500-5000 meshes, preferably one or more combinations of kaolin with the fineness of 2000-3500 meshes, calcium carbonate, talcum powder and barium sulfate, most preferably one or more combinations of kaolin with the fineness of more than 2000-3500 meshes and calcium carbonate, the high-fineness filler can effectively improve the physical property, heat resistance and processability of PVC, but the dispersion of the filler with the excessively high fineness is difficult, if the dispersion effect of the filler is not good, the physical property of a cable is reduced, the defects of pockmarks and the like are generated on the surface of the cable, and the fillers have a plurality of brands on the market, including new materials in Europe, Jiangxi Guangyuan, Fujian southeast and the like and can be applied to corresponding brands sold in the market.
The cable material can also be added with polyol auxiliary filler and auxiliary agent for dispersion, wherein the polyol is an alcohol with two or more hydroxyl groups in the molecule, and comprises pentaerythritol, propylene glycol, ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trihydroxypropane and glycerol; pentaerythritol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol, trimethylolpropane are preferred; pentaerythritol, dipropylene glycol and trimethylolpropane are most preferred. There are numerous commercial grades of such polyols, and common commercial grades can be used. The amount of the polyol based on 100 parts by mass of the PVC resin is in the range of 1 to 3 parts.
The cable material of the invention can also be added with one or more combinations of fatty acid esters, stearic acids, amides, olefins and organosilicon lubricants, preferably one or more combinations of stearic acids, olefins and organosilicon lubricants, most preferably one or more combinations of olefins and organosilicon lubricants, and the cable material has a plurality of brands on the market at present and can be used in common commercial brands. The amount of one or a combination of more of fatty acid esters, stearic acids, amides, olefins, and silicone lubricants is 1 to 2.5 parts per 100 parts by mass of the PVC resin.
The invention further relates to a preparation method of the environment-friendly high-temperature-resistant PVC automobile cable material composition, which comprises the following steps:
(1) hot mixing: mixing PVC resin, plasticizer, thiobisphenol antioxidant (heat stabilizer), fatty acid calcium salt and fatty acid zinc salt (lubricant), and metal ion deactivator at high temperature and high speed in high speed mixer at 80-120 deg.C (preferably 90-110 deg.C), preferably for 10-30min,
(2) cold mixing: adding filler into the hot-mixed raw material obtained in the step (1), carrying out high-speed cold mixing in a cold mixing device, wherein the mixing temperature is 40-60 ℃ (preferably 45-55 ℃), preferably, the mixing time is 5-8min,
(3) feeding the raw materials obtained by cold mixing into a single-screw or double-stage extruder through a feeding device for extrusion granulation to prepare the final finished product particles, wherein the extrusion temperature is 150-.
The invention also relates to application of the environment-friendly high-temperature-resistant PVC automobile cable material composition in preparation of PVC automobile insulating cable materials.
THE ADVANTAGES OF THE PRESENT INVENTION
The 125 ℃ resistant PVC cable material prepared by the combination of the special compound stabilizer, the PVC resin, the plasticizer and the filler can pass the test of various performance indexes required by ISO 6722T 3 line, has the advantages of high physical property, no pockmark on the surface, easy processing, high cost performance and the like, can replace irradiation crosslinking polyethylene and thermoplastic polypropylene resin to be widely applied to 125 ℃ resistant automobile cables, and has extremely high cost performance and wide market application prospect. The invention can be used for producing the automotive insulated cable with the temperature resistance of 125 ℃, is environment-friendly and nontoxic, has higher temperature resistance level and excellent surface effect, and can be used for preparing the high-temperature-resistant automotive engine peripheral cable.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The invention provides a preparation method of a high-temperature-resistant PVC cable material, which comprises the following steps:
(1) hot mixing: mixing PVC resin, plasticizer, heat stabilizer, lubricant and metal ion deactivator at high temperature and high speed in a high-speed mixer at 80-120 deg.C for 10-30min,
(2) cold mixing: adding filler into the hot mixed raw material obtained in the step (1) to perform high-speed cold mixing in cold mixing equipment, wherein the mixing temperature of a cold mixer is 40-60 ℃, the mixing time is 5-8min,
(3) and feeding the raw materials obtained by cold mixing into a double-stage extruder TSC65/D150 of Nanjing Ruia through feeding equipment for extrusion granulation to obtain final finished particles, wherein the extrusion temperature is 150-.
Raw materials and sources used in the examples
The PVC resin is HG-2500 and HG-1800 in Ningbo Hanhua, TK-2500P in Japan shin-Yue corporation, and ONGROVIL-5070 in Wanhua-Bosu chemical, wherein the polymerization degree of HG-2500 is 2500, the polymerization degree of HG-1800 is 1800, the polymerization degree of TK-2500P is 2500, and the polymerization degree of ONGROVIL-5070 is 1500.
The plasticizer is UN-615 in Taiwan integrated chemical engineering, PN-850 in Taiwan Changchun chemical engineering and W-2050 in Japanese ink chemical engineering, wherein the molecular weight of UN-615 is 2500-3500, the molecular weight of PN-850 is 2000-3500, and the molecular weight of Japanese ink chemical is 2500-3500.
The stabilizer additive package is combined according to the following raw materials and proportions:
the calcium stabilizer is calcium stearate of Shanghai Bei speciality chemical engineering Co., Ltd, calcium laurate of Jiangxi Hongyuan chemical engineering Co., Ltd, and the zinc stabilizer is zinc stearate of Shijiazhuang Hongda Zinc industry Co., Ltd, zinc laurate of Hubeixin Rundy chemical engineering Co., Ltd, antioxidant 300 of thiobisphenol antioxidant BASF, and antioxidant 2246S of Nanjing Jiatong chemical.
The metal ion passivator is MD1024(N, N '-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine) from BASF Ciba Fine chemical, CDA-1 (3-salicylamido-1, 2, 4-triazole) from Asahi Denka Kogyo, Japan, and CDA-6 (N-salicylidene-N' salicyloyl hydrazine).
The calcium-zinc stabilizer in the comparative example is XY-101 which is a calcium-zinc stabilizer for electric wires and cables of Asahi science and technology, and 619G which is a calcium-zinc stabilizer for electric wires and cables of Hongyuan chemical engineering in Jiangxi province.
The polyhydric alcohol is dipentaerythritol of Shandong Plus chemical Co., Ltd, and glycerol of Shandong Ruiwang chemical Co., Ltd.
The lubricant is polyethylene wax of Qingdao Sainuo chemical industry, high molecular weight silicone wax of Hangzhou Qianji plastic technology, and the filler is 2500 meshes of calcium carbonate of Europe, 2000 meshes of calcium carbonate of Jiangxi Guangyuan chemical industry.
All test methods of the present invention were tested according to the standard in ISO 6722T 3 cable.
The formulations of the examples and comparative examples are shown in table 1:
table 2 results of performance testing:
table 3 finished wire test results:
the comparison between the examples and the comparative examples shows that all indexes of the PVC cable material prepared by the special compounded heat stabilizer can meet the test requirement of ISO6722 on 125 ℃ resistance, and the prepared PVC cable material has high physical property, no pockmark on the extrusion surface and simple preparation method.
The above-described embodiments are illustrative, but not restrictive, of the spirit of the invention, and any modifications, equivalents, and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. An environment-friendly high-temperature-resistant PVC (polyvinyl chloride) automobile insulated cable material composition comprises the following components in parts by mass:
100 parts of PVC resin, namely 100 parts of PVC resin,
plasticizer: 30 to 80 parts, preferably 35 to 65 parts,
stabilizer additive package: 2 to 6 parts, preferably 3 to 5 parts,
filling: 10 to 40 parts, preferably 15 to 25 parts,
wherein the stabilizer aid package comprises the following combinations of substances in mass percent based on the stabilizer aid package:
fatty acid calcium salt: 25-65%, preferably 30% -60%, more preferably 35-50%,
zinc salts of fatty acids: 3 to 35%, preferably 5% to 30%, more preferably 10 to 20%,
thiobis phenolic antioxidants: 15-35%, preferably 20% -30%, more preferably 22-28%,
metal ion passivator: 10-35%, preferably 15% -30%, more preferably 17-25%.
2. The environment-friendly high-temperature-resistant PVC automobile insulated cable material composition according to claim 1, wherein the PVC resin is one or more of ethylene-process PVC with the polymerization degree of 1300 or more, preferably ethylene-process PVC with the polymerization degree of 1800 or more, and most preferably ethylene-process PVC with the polymerization degree of 2000 or more.
3. The environment-friendly high temperature resistant PVC automotive insulating cable material composition as claimed in claim 1 or 2, wherein the plasticizer is one or a combination of two or more of polyester plasticizer and trimellitate plasticizer, preferably polyester plasticizer with molecular weight of 1500-.
4. The environment friendly high temperature resistant PVC automotive insulation cable material composition according to any one of claims 1-3, wherein the calcium salt and zinc salt of fatty acid is one or more combination of stearic acid, saturated fatty acid of C8-C16, calcium salt of oleic acid, preferably one or more combination of stearic acid and calcium salt of lauric acid, most preferably calcium salt of stearic acid; the zinc salt of the fatty acid is one or more of stearic acid, saturated fatty acid of C8-C16 and zinc salt of oleic acid, preferably one or more of stearic acid and zinc salt of lauric acid, and most preferably zinc salt of stearic acid.
5. The environment-friendly high-temperature-resistant PVC automobile insulated cable material composition as claimed in any one of claims 1 to 4, wherein the metal ion passivating agent is a hydrazide compound, preferably one or more combinations selected from N, N '-disubstituted oxalyl dihydrazide, N-salicylidene-N' salicyloyl hydrazide, 3-salicyloylamino-1, 2, 4-triazole and oxalyl hydrazide.
6. The environment-friendly high temperature resistant PVC automobile insulation cable material composition as defined in any one of claims 1-5, wherein the filler is a powdered inorganic filler with fineness of 1500-5000 mesh, preferably one or more combinations of kaolin, calcium carbonate, talcum powder and barium sulfate with fineness of 2000-3500 mesh, most preferably one or more combinations of kaolin, calcium carbonate with fineness of 2000-3500 mesh.
7. The environment-friendly high temperature resistant PVC automotive insulation cable material composition according to any one of claims 1 to 6, further comprising a polyol substance for assisting dispersion thereof, wherein the polyol is an alcohol containing two or more hydroxyl groups in a molecule, and comprises one or more of pentaerythritol, propylene glycol, ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane and glycerol; preferably one or more of pentaerythritol, neopentyl glycol, 1,6 hexanediol, diethylene glycol, dipropylene glycol, and trimethylolpropane; most preferred are one or more of pentaerythritol, dipropylene glycol, and trimethylolpropane.
8. The environmentally friendly high temperature resistant PVC automotive insulated cable composition of any one of claims 1-7, further comprising one or more combinations of fatty acid esters, stearates, amides, olefins, silicone based lubricants, preferably one or more combinations of stearates, olefins, silicone based lubricants, most preferably one or more combinations of olefins, silicone based lubricants.
9. The preparation method of the environment-friendly high temperature-resistant PVC automotive insulated cable material composition according to any one of claims 1 to 8, characterized by comprising the following steps:
(1) hot mixing: mixing PVC resin, plasticizer, thiobisphenol antioxidant, fatty acid calcium salt, fatty acid zinc salt and metal ion passivator at high temperature and high speed in a high-speed mixer at 80-120 ℃,
(2) cold mixing: adding a filler into the hot mixed raw material obtained in the step (1), and then performing high-speed cold mixing in cold mixing equipment, wherein the mixing temperature is 40-60 ℃, and (3) feeding the raw material obtained by cold mixing into a single-screw or double-stage extruder through feeding equipment for extrusion granulation to obtain the final finished product particles, wherein the extrusion temperature is 150-.
10. Use of the environmentally friendly high temperature resistant PVC automotive insulated cable material composition according to any one of claims 1 to 8 for preparing automotive insulated cable materials.
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| CN103342868A (en) * | 2013-07-10 | 2013-10-09 | 江苏德威新材料股份有限公司 | Environment-friendly ethanol migration resistance elastomer sheathing compound and preparation method thereof |
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| CN113754967A (en) * | 2021-09-02 | 2021-12-07 | 安徽滁州德威新材料有限公司 | PVC composition capable of resisting temperature of 125 ℃ and preparation method and application thereof |
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