WO1999057190A1 - Compositions stabilisantes pour isolants polymeres - Google Patents

Compositions stabilisantes pour isolants polymeres Download PDF

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Publication number
WO1999057190A1
WO1999057190A1 PCT/US1999/008573 US9908573W WO9957190A1 WO 1999057190 A1 WO1999057190 A1 WO 1999057190A1 US 9908573 W US9908573 W US 9908573W WO 9957190 A1 WO9957190 A1 WO 9957190A1
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WO
WIPO (PCT)
Prior art keywords
polymer
composition
zinc
polyethylene
further contains
Prior art date
Application number
PCT/US1999/008573
Other languages
English (en)
Inventor
Richard A. Suhoza
Original Assignee
R.T. Vanderbilt Company, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by R.T. Vanderbilt Company, Inc. filed Critical R.T. Vanderbilt Company, Inc.
Publication of WO1999057190A1 publication Critical patent/WO1999057190A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • 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
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • 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
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene

Definitions

  • the present invention concerns stabilizer systems for curable and cured polyolefin polymers.
  • the invention relates to stabilization of electrical polyolefin insulation against oxidation and thermal aging. Cables, electrical wires and other electrical conductors are protected against exposure to extreme temperature variations, moisture and oil or chemical leaks by polymeric insulation.
  • polymeric insulation used for electrical insulation must be durable and substantially retain its physical properties for effective and safe, long term performance.
  • Polyolefins are the base resins used for many electrical insulations. The most commonly used are polyethylene based resins. Polyethylenes are subject to oxidative degradation which is detrimental to the physical properties of the polymer causing embrittlement and cracking. The rate of oxidation degradation is greatly accelerated at elevated temperatures which are associated with electrical conductors. The oxidative degradation is called "heat aging" when oxidation is accelerated or intensified by increased temperature.
  • U.S. Pat. No. 4,260,661 discloses antioxidant combinations of zinc salt of mercaptoimidazole compounds, sterically hindered di-tert-butylphenol, and optionally zinc stearate, which are particularly useful for stabilizing peroxide crosslinked polyolefins.
  • polyethylene is crosslinked with high energy radiation such as electron beam or x-rays.
  • the crosslink during irradiation occurs at low temperature and thus, produces crosslinked structures of a different nature than peroxide cures. Therefore, the radiation crosslinked polyethylenes require particular heat aging stabilizers.
  • synergistic compositions of antioxidants prevent heat aging in polyethylene based resins, when radiation crosslinking is applied as well as during peroxide crosslinking.
  • polyethylene based compositions stabilized against heat aging with a stabilizing amount of a synergistic stabilizer consisting of zinc 2-mercaptotoluimidazole, zinc dibutyldithiocarbamate and tetrakis (methylene (3,5-
  • a synergistic stabilizer consisting of zinc 2- mercaptotoluimidazole, zinc dibutyldithiocarbamate and tetrakis(methylene(3,5-di-t-butyl- 4-hydroxyhydrocinnamate)) and optionally, a flame retardant and a yellow pigment or a filler.
  • Another object of the invention relates to a method of producing electrical conductors insulated with a polyethylene based compound by incorporating about 1 to 10 percent by weight a synergistic stabilizer described hereinabove and about 40 to 50 percent by weight of a flame retardant and a yellow pigment or a filler and crosslinking by radiation or peroxide-curing.
  • the electrical insulations of the invention comprise ethylene based polymers, including homopolymers of ethylene and copolymers of ethylene with other polymerizable materials.
  • the copolymers include, among others, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, ethylene-vinyl acetate, ethylene-ethyl acrylate and ethylene-methyl acrylate copolymers.
  • the polymers may be high, medium or low density.
  • the insulations can be prepared from blends of such polymers and blends of polyethylene polymers with halogenated polyethylene polymers.
  • the synergistic stabilizer of the invention is composed of commercially available materials.
  • the zinc 2-mercaptotoluimidazole is manufactured under the trade name VANOX®ZMTI and the zinc dibutyldithiocarbamate ingredient under the trade name BUTYL ZIMATE® by R.T. Vanderbilt Company, Inc.
  • the tetrakis (methylene(3,5-di-t- butyl-4-hydroxyhydrocinnamate)) is manufactured under the trade name Irganox® 1010 by Ciba Specialty Chemicals Corp.
  • the three component system displays synergistic stabilizing function when the components are present in the weight ratio of the imidazole to the dithiocarbamate to the cinnamate from about 3.1:2.7:3.1 to about 3.9:3.3:3.9, the preferred ratio being about 3.5:3.0:3.5.
  • the stabilizer of the invention may be incorporated in the polyethylene resin in an amount effective to produce the desired long range stability. Typically, an amount from
  • the polyethylene insulation is commonly cured by peroxide crosslinking.
  • Common curing agents are dicumyl peroxide and tertiary diperoxides such as 2,5- dimethyl-2,5-di(t-butyl-peroxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5- dimethyl-2,5-di(t-butylperoxy)-hexyne-3, n-butyl-4,4-bis(t-butylperoxy)valerate and the like.
  • Peroxide curing is generally limited to low density polyethylene.
  • the stabilizers of the invention provide good heat aging properties to peroxide-cured polyethylenes.
  • polyethylenes are crosslinked by high energy radiation such as electron o beam or x-rays.
  • high energy radiation such as electron o beam or x-rays.
  • the advantage of radiation crosslinking is that it eliminates handling of peroxides. Additionally, the only by-products produced during curing in an inert atmosphere are hydrogen and low molecular weight hydrocarbons.
  • the crosslinking during irradiation normally occurs at low temperature below the melting point of the polymer, while peroxide cured systems are crosslinked in the molten state. Ionizing radiation curing can be conducted with the use of triallyl cyanurate or ethylene dimethacrylate coagents.
  • the stabilizer system of the invention is particularly compatible with polyethylene based resins that are radiation cured at about 20 to 100°C. Alternately the stabilizers can be used in uncured polyethylene based resins.
  • the synergistic stabilizers of the invention are useful in polyethylene based formulations that contain yellow pigment concentrates.
  • the yellow pigment concentrates usually contain chrome yellow and organic yellow pigments of the azo or non-azo type. Yellow pigment concentrates are incompatible with polyethylene based compounds and are known to exacerbate the deterioration of the polyethylene after crosslinking.
  • the synergistic stabilizers counteract the negative action of the yellow pigment and increase the overall stability of the composition.
  • Other applications include polyethyl based formulations that contain fillers.
  • the fillers may be selected from carbon blacks such as furnace and thermal blacks and mineral fillers such as clay, calcium carbonate, talc, and silica. The fillers may contribute to viscosity control, thermal conductivity and control of thermal expansion of the insulation.
  • the stabilizers of the invention are compatible with conventional flame retardants.
  • Typical flame retardants are halogen containing organic compounds and antimony compounds. Halogen containing compounds can be present up to 70 percent by weight per
  • Antimony oxide compounds can be present from about 35 to 70 parts by weight per hundred parts of polyethylene polymer.
  • Particularly preferred flame retardants are aluminum hydroxide and alumina trihydrate, which display good arc and track resistance.
  • the solventless resins compounded with fillers, hardeners and other additives are used to encapsulate electronic components, insulate electrical cables, wires and conductors by casting, extruding and impregnation techniques.
  • EXAMPLE 1 Static oven stability tests were conducted with crosslinked and non-crosslinked ethylene-vinyl acetate copolymer based resin (EVA) composition.
  • test samples were formulated with aluminum hydroxide flame retardant, yellow pigment concentrate containing chrome yellow and diarylide yellow (Yellow 420 EVA, manufactured by Breen Color Concentrates, Inc.).
  • Test sample 1 served as a control.
  • test samples 2 to 4 and 7 to 9 contained the individual components of the present synergistic stabilizer and test samples 5 and 10 contained the three component stabilizer: zinc 2-mercaptotoluimidazole (hereinafter ZMTI), zinc dibutyldithiocarbamate (hereinafter ZDTC) and tetrakis (methylene (3,5-di-t-butyl-4- hydroxyhydrocinnamate)) (hereinafter cinnamate) in the weight ratio of 3.5:3.0:3.5.
  • ZMTI zinc 2-mercaptotoluimidazole
  • ZDTC zinc dibutyldithiocarbamate
  • tetrakis methylene (3,5-di-t-butyl-4- hydroxyhydrocinnamate
  • test ingredients were weighed and thoroughly blended before milling at 99 to 102°C for 5 to 10 minutes. After milling, 3 x 5 x 0.003 inch specimens were cut and placed on aluminum foil. The specimens were placed in a forced air circulating oven that was preheated to 204°C. Samples were taken until total degradation occurred as evidenced by dark brown or black color of the aged specimen.
  • EXAMPLE 2 The stability of non-crosslinked polyethylene (PE) based resin composition was tested by determining the oxygen induction time by differential scanning calorimetry.
  • test samples were formulated with carbon black filler.
  • Test sample 11 served as a control.
  • test samples 12 to 14 contained the individual components for the present stabilizer described in Example 1 above.
  • Test samples 15 and 16 contained the three component stabilizer.
  • test sample sheets were placed into a tared aluminum sample pan, weighed and loaded into Differential Scanning Calorimeter, (DSC) TA Instruments Model 2910 along with an empty pan as reference.
  • DSC Differential Scanning Calorimeter
  • the cell of DSC was purged isothermally with nitrogen for 5 minutes.
  • the cell was heated at a programmed ramped rate of 20° min. to 230°C.
  • oxygen was introduced and the test was run at 230°C until onset point time (OIT) is reached, i.e., point value time signal is obtained.
  • OIT onset point time

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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)

Abstract

L'invention concerne des compositions à base de polyéthylène, possédant un stabiliseur synergétique, comprenant 2-mercaptotoluimidazole zincique, dibutyldithiocarbamate zincique et tétrakis (méthylène(3,5-di-butyl-4-hydroxyhydrocinnamate) dans des rapport critiques, améliorant la résistance à l'oxydation et le vieillissement à la chaleur. Les compositions de polyéthylène peuvent contenir des retardateurs de flamme, des pigments jaunes et des charges. Les compositions de polyéthylène peuvent être réticulées par rayonnement ou par des peroxydes, de façon à obtenir une isolation de conducteurs électriques.
PCT/US1999/008573 1998-05-04 1999-04-19 Compositions stabilisantes pour isolants polymeres WO1999057190A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7205998A 1998-05-04 1998-05-04
US09/072,059 1998-05-04

Publications (1)

Publication Number Publication Date
WO1999057190A1 true WO1999057190A1 (fr) 1999-11-11

Family

ID=22105308

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/008573 WO1999057190A1 (fr) 1998-05-04 1999-04-19 Compositions stabilisantes pour isolants polymeres

Country Status (1)

Country Link
WO (1) WO1999057190A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6653380B2 (en) 2001-07-18 2003-11-25 R. T. Vanderbilt Company, Inc. Latex film compound with improved tear resistance
US7048977B2 (en) 2001-07-18 2006-05-23 R.T. Vanderbilt Company, Inc. Latex film compound with improved tear resistance
EP1870955A2 (fr) 2006-05-22 2007-12-26 Andrew Corporation Isolant polymère thermoconducteur de dispositif RF coaxial et son procédé de fabrication
US8287765B2 (en) 2008-06-17 2012-10-16 R.T. Vanderbilt Company, Inc. Systems and compositions for color stabilization of polymer
EP3401929A1 (fr) 2017-05-09 2018-11-14 Borealis AG Isolation des câbles
US10679768B2 (en) 2016-06-21 2020-06-09 Borealis Ag Cable and composition
US10886034B2 (en) 2016-06-21 2021-01-05 Borealis Ag Cable with advantageous electrical properties
US11613633B2 (en) 2016-06-21 2023-03-28 Borealis Ag Polymer composition for wire and cable applications with advantageous thermomechanical behaviour and electrical properties

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4260661A (en) * 1980-01-23 1981-04-07 General Electric Company Polyolefin compounds having improved heat curing stability, method of improving heat aging stability therein, an electrical conductor insulated therewith and method of forming
US4382112A (en) * 1981-07-07 1983-05-03 General Electric Company Flexible insulation with improved discoloration and heat age resistance
EP0206413A2 (fr) * 1985-06-19 1986-12-30 BOZZETTO INDUSTRIE CHIMICHE S.p.A. Compositions de polymères stabilisées et systèmes de stabilisants appropriés
EP0254010A2 (fr) * 1986-06-10 1988-01-27 Sumitomo Chemical Company, Limited Procédé pour la préparation de caoutchouc réticulé
EP0513699A2 (fr) * 1991-05-16 1992-11-19 Montell North America Inc. Sels de zinc de certains composés thioliques comme antioxydants pour vieillissement à hautes températures d'élastomères thermoplastiques
EP0530641A1 (fr) * 1991-08-31 1993-03-10 Montell North America Inc. Elastomères thermoplastiques à base de polyoléfines ayant une stabilité au vieillissement thermique amélioré à l'aide de sels de zinc de certains composés thioliques et phénols présentant un empêchement stérique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4260661A (en) * 1980-01-23 1981-04-07 General Electric Company Polyolefin compounds having improved heat curing stability, method of improving heat aging stability therein, an electrical conductor insulated therewith and method of forming
US4382112A (en) * 1981-07-07 1983-05-03 General Electric Company Flexible insulation with improved discoloration and heat age resistance
EP0206413A2 (fr) * 1985-06-19 1986-12-30 BOZZETTO INDUSTRIE CHIMICHE S.p.A. Compositions de polymères stabilisées et systèmes de stabilisants appropriés
EP0254010A2 (fr) * 1986-06-10 1988-01-27 Sumitomo Chemical Company, Limited Procédé pour la préparation de caoutchouc réticulé
EP0513699A2 (fr) * 1991-05-16 1992-11-19 Montell North America Inc. Sels de zinc de certains composés thioliques comme antioxydants pour vieillissement à hautes températures d'élastomères thermoplastiques
EP0530641A1 (fr) * 1991-08-31 1993-03-10 Montell North America Inc. Elastomères thermoplastiques à base de polyoléfines ayant une stabilité au vieillissement thermique amélioré à l'aide de sels de zinc de certains composés thioliques et phénols présentant un empêchement stérique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Derwent World Patents Index; Class A17, AN 70-04345R, XP002111210 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6653380B2 (en) 2001-07-18 2003-11-25 R. T. Vanderbilt Company, Inc. Latex film compound with improved tear resistance
US7048977B2 (en) 2001-07-18 2006-05-23 R.T. Vanderbilt Company, Inc. Latex film compound with improved tear resistance
EP1870955A2 (fr) 2006-05-22 2007-12-26 Andrew Corporation Isolant polymère thermoconducteur de dispositif RF coaxial et son procédé de fabrication
EP1870955A3 (fr) * 2006-05-22 2008-07-23 Andrew Corporation Isolant polymère thermoconducteur de dispositif RF coaxial et son procédé de fabrication
US7705238B2 (en) 2006-05-22 2010-04-27 Andrew Llc Coaxial RF device thermally conductive polymer insulator and method of manufacture
US8287765B2 (en) 2008-06-17 2012-10-16 R.T. Vanderbilt Company, Inc. Systems and compositions for color stabilization of polymer
US10679768B2 (en) 2016-06-21 2020-06-09 Borealis Ag Cable and composition
US10886034B2 (en) 2016-06-21 2021-01-05 Borealis Ag Cable with advantageous electrical properties
US11613633B2 (en) 2016-06-21 2023-03-28 Borealis Ag Polymer composition for wire and cable applications with advantageous thermomechanical behaviour and electrical properties
EP3401929A1 (fr) 2017-05-09 2018-11-14 Borealis AG Isolation des câbles
WO2018206580A1 (fr) 2017-05-09 2018-11-15 Borealis Ag Isolation de câble

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