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WO1994019423A1 - Method of protecting organic materials against breakdown - Google Patents

Method of protecting organic materials against breakdown Download PDF

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Publication number
WO1994019423A1
WO1994019423A1 PCT/SE1994/000148 SE9400148W WO9419423A1 WO 1994019423 A1 WO1994019423 A1 WO 1994019423A1 SE 9400148 W SE9400148 W SE 9400148W WO 9419423 A1 WO9419423 A1 WO 9419423A1
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Prior art keywords
carbon molecules
breakdown
molecules
carbon
polymer material
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Ceased
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PCT/SE1994/000148
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French (fr)
Inventor
Mats Dahlund
Lennart Johansson
Torsten Schütte
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ABB Research Ltd Switzerland
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ABB Research Ltd Switzerland
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Publication of WO1994019423A1 publication Critical patent/WO1994019423A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/045—Fullerenes
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08L23/06—Polyethene
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    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/02—Anti-oxidant compositions; Compositions inhibiting chemical change containing inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/02—Carbon; Graphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C10M2201/042—Carbon; Graphite; Carbon black halogenated, i.e. graphite fluoride
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/16—Dielectric; Insulating oil or insulators
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/17—Electric or magnetic purposes for electric contacts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/175—Pantographs, i.e. printing devices
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/18—Electric or magnetic purposes in connection with recordings on magnetic tape or disc
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/185—Magnetic fluids

Definitions

  • the invention relates to a method of protecting organic materials, such as polymer materials, fats and oils, against breakdown, preferably breakdown as a result of oxidation and/or partial discharge.
  • Organic materials such as polymeric materials, fats and oils are affected by external factors such as oxygen, heat or other radiation as well as electric or magnetic fields, whereby chemical changes such as crosslinking, chain scissoring, the occurrence of double bonds, gas evolution and oxidation arise.
  • organic materials are often stabilized by additives such as voltage stabilizers and antioxidation agents (antioxidants) .
  • Oxidative breakdown of organic materials can be initiated and propagate by means of radicals which are formed or supplied by the influence of the above-mentioned factors.
  • one or more antioxidants are added.
  • antioxidants, or radical scavengers are meant in this appli ⁇ cation additives which react with the radicals and thereby terminate the degrading chain reactions.
  • voltage stabilizers or energy scavengers
  • energy scavengers are meant in this application additives which protect organic materials against breakdown by capturing electrons, which function as carriers of energy in a field of force acting on the polymer.
  • Organic materials such as oils, fats and polymeric materials, which are exposed to oxidation or other degrading influence from external factors such a heat or other radiation as well as electric or magnetic fields, are protected against break ⁇ down by adding a counteracting agent in the form of anti ⁇ oxidants, voltage stabilizers, etc., to the material.
  • a greatly increased protection against breakdown of organic materials is obtained by adding globular or tubular carbon molecules, so-called fullerenes, or derivatives based on these carbon molecules, to the organic material.
  • the fullerene molecules are intermixed to a content amounting to between 0.01 and 15 per cent by weight, preferably to a content of between 0.1 and 7 per cent by weight.
  • the added carbon molecules prevent breakdown of the organic material by capturing and rendering harmless free radicals as well as electrons which, through the external influence, have been added or formed in the organic material.
  • the above-mentioned globular or tubular carbon molecules are mixed into an organic material such as an oil, a fat or into a polymer material to counteract breakdown in connection with thermal, electric, or magnetic load, or an external influence as a result of light or other radiation.
  • a polymer material which has been protected against breakdown by intermixing globular or tubular carbon molecules according to the invention is of great value as an insulator in elec ⁇ trical installations by constituting protection, in addition to the enhanced protection against breakdown by the above- mentioned carbon molecules capturing and taking care of free radicals and electrons, also against breakdown of 'the polymer material arising from electric breakdowns, so-called partial discharge.
  • the partial discharge resistance is obtained, during partial discharge, by carbon molecules included in the polymer material being exposed, whereby these carbon mole ⁇ cules, because of their lower resistivity and thermal conduc ⁇ tivity in relation to the polymer material, spread the elec ⁇ tric and thermal load from the partial discharge impulse over a large area such that the partial discharge is reduced in an effective way and the damage is limited instead of growing.
  • the above-mentioned globular or tubular carbon molecules are incorporated into a polymer material and chemically bonded to the polymer.
  • the protecting carbon molecules are retained in the polymer material and cannot migrate out of the same. If this is limited to one bond only between the carbon molecule and a polymer chain, the carbon molecule will terminate the chain.
  • the carbon molecule will be bonded into the polymer chain; if instead the two carbon atoms are each bonded to a polymer chain, the carbon molecule will bond these polymer chains together.
  • a transformer oil according to this example exhibits an increased resistance to oxidative breakdown and breakdown as a result of electric load.
  • C ⁇ o molecules were mixed to a content of 0.1 per cent by weight into toluene, whereby an insulator fluid was obtained which exhibits an increased resistance to oxidative breakdown and breakdown as a result of electric load.
  • An adduct was prepared by analogy with Example 1 based on C 60 molecules and dodecylamine and was mixed to a content of 0.5 per cent by weight into a lubricating grease consisting of mineral oil and a thickening agent in the form of a lithium soap.
  • a lubricating grease according to this Example exhibits an increased resistance to oxidative breakdown, especially at elevated temperature.
  • the C 6 o(OCH 2 CH 2 ⁇ H) n obtained was mixed in castor oil to a content of 5 per cent by weight. This mixture was reacted with a diisocyanate, methylene diphenyl isocyanate, whereby a crosslinked polyurethane with a fullerene content of 3.3 per cent by weight was obtained.
  • a crosslinked polyurethane according to this Example has the fullerene molecules incorporated in the polymer chains where- by isocyanate groups from a plurality of diisocyanate mole ⁇ cules are bonded to the same fullerene molecule. This cross- linking gives a very stiff polyurethane material.
  • Cgo molecules were mixed to a content of 5 per cent in an epoxy resin resin intended to be applied as an insulating layer onto an electric conductor.
  • An electrical insulation in the form of an insulating varnish according to the invention exhibits an increased resistance to oxidative breakdown as a result of electric load or other external factors.
  • a powder consisting of Cgo molecules was mixed with carbon black to a content of 6 per cent by weight.
  • the fullerene- containing carbon black mixture was mixed in HD polyethylene, was kneaded and rolled into a homogeneous compound with a composition of
  • a semiconducting polymer material with a positive temperature coefficient prepared according to this example exhibits an increased resistance to breakdown relative to conventional polymeric PTC materials.
  • a powder consisting of C 6 o molecules was mixed with carbon black to a content of 10 per cent by weight.
  • the fullerene- containing carbon black mixture was added to a copolymer of LD polyethylene, LD-PE, and ethylenebutyl acrylate, EBA, was kneaded and rolled into a homogeneous compound with a compo ⁇ sition of
  • a semiconducting copolymer prepared according to this Example and included as a screen in an insulating system around an electric conductor exhibits an increased resistance to oxida ⁇ tive breakdown as a result of electric load or other external factors.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Water Treatment By Sorption (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lubricants (AREA)
  • Insulated Conductors (AREA)

Abstract

A method of protecting organic materials such as oils, fats and polymeric materials, which are subjected to oxidation or other degrading influence from external factors such as heat or other radiation as well as electric or magnetic fields, whereby essentially globular or tubular carbon molecules, so-called fullerenes, or derivatives based on said carbon molecules, are added to the organic material.

Description

Method of protecting organic materials aσainst breakdown
TECHNICAL FIELD
The invention relates to a method of protecting organic materials, such as polymer materials, fats and oils, against breakdown, preferably breakdown as a result of oxidation and/or partial discharge.
BACKGROUND ART
Organic materials such as polymeric materials, fats and oils are affected by external factors such as oxygen, heat or other radiation as well as electric or magnetic fields, whereby chemical changes such as crosslinking, chain scissoring, the occurrence of double bonds, gas evolution and oxidation arise. To withstand these breakdown mechanisms, organic materials are often stabilized by additives such as voltage stabilizers and antioxidation agents (antioxidants) .
Oxidative breakdown of organic materials can be initiated and propagate by means of radicals which are formed or supplied by the influence of the above-mentioned factors. To counter¬ act this breakdown, one or more antioxidants are added. By antioxidants, or radical scavengers, are meant in this appli¬ cation additives which react with the radicals and thereby terminate the degrading chain reactions.
By voltage stabilizers, or energy scavengers, are meant in this application additives which protect organic materials against breakdown by capturing electrons, which function as carriers of energy in a field of force acting on the polymer. SUMMARY OF THE INVENTION
Organic materials such as oils, fats and polymeric materials, which are exposed to oxidation or other degrading influence from external factors such a heat or other radiation as well as electric or magnetic fields, are protected against break¬ down by adding a counteracting agent in the form of anti¬ oxidants, voltage stabilizers, etc., to the material.
According to the invention, a greatly increased protection against breakdown of organic materials is obtained by adding globular or tubular carbon molecules, so-called fullerenes, or derivatives based on these carbon molecules, to the organic material. According to the invention, the fullerene molecules are intermixed to a content amounting to between 0.01 and 15 per cent by weight, preferably to a content of between 0.1 and 7 per cent by weight.
The added carbon molecules prevent breakdown of the organic material by capturing and rendering harmless free radicals as well as electrons which, through the external influence, have been added or formed in the organic material.
In one embodiment of the invention, the above-mentioned globular or tubular carbon molecules are mixed into an organic material such as an oil, a fat or into a polymer material to counteract breakdown in connection with thermal, electric, or magnetic load, or an external influence as a result of light or other radiation.
A polymer material which has been protected against breakdown by intermixing globular or tubular carbon molecules according to the invention is of great value as an insulator in elec¬ trical installations by constituting protection, in addition to the enhanced protection against breakdown by the above- mentioned carbon molecules capturing and taking care of free radicals and electrons, also against breakdown of 'the polymer material arising from electric breakdowns, so-called partial discharge. The partial discharge resistance is obtained, during partial discharge, by carbon molecules included in the polymer material being exposed, whereby these carbon mole¬ cules, because of their lower resistivity and thermal conduc¬ tivity in relation to the polymer material, spread the elec¬ tric and thermal load from the partial discharge impulse over a large area such that the partial discharge is reduced in an effective way and the damage is limited instead of growing.
In another embodiment of the invention, the above-mentioned globular or tubular carbon molecules are incorporated into a polymer material and chemically bonded to the polymer. When these globular or tubular carbon molecules are incorporated and chemically bonded to a polymer material, the protecting carbon molecules are retained in the polymer material and cannot migrate out of the same. If this is limited to one bond only between the carbon molecule and a polymer chain, the carbon molecule will terminate the chain. When two carbon atoms included in the carbon molecule are bonded to a polymer chain, the carbon molecule will be bonded into the polymer chain; if instead the two carbon atoms are each bonded to a polymer chain, the carbon molecule will bond these polymer chains together.
By bonding more than one of the carbon atoms included in the carbon molecule to more than one polymer chain, a cross- linking is achieved which, in addition to increasing the breakdown resistance, connects the polymer molecules together into strong networks. These crosslinked networks change the polymer material and above all its mechanical properties, primarily in the form of an increase of the stiffness of the polymer material. EXAMPLE 1
Transformer oil
Essentially globular carbon molecules containing 60 carbon atoms, Ceo were mixed in a weight ratio of 1:50 with an excess of dodecylamine and were allowed to react under stirring and supply of heat. The adduct thus obtained was separated from the reactants and was mixed into a transformer oil to a content of 0.5 per cent by weight.
A transformer oil according to this example exhibits an increased resistance to oxidative breakdown and breakdown as a result of electric load.
EXAMPLE 2
Insulation fluid
Cδo molecules were mixed to a content of 0.1 per cent by weight into toluene, whereby an insulator fluid was obtained which exhibits an increased resistance to oxidative breakdown and breakdown as a result of electric load.
EXAMPLE 3
Lubricating grease
An adduct was prepared by analogy with Example 1 based on C60 molecules and dodecylamine and was mixed to a content of 0.5 per cent by weight into a lubricating grease consisting of mineral oil and a thickening agent in the form of a lithium soap. A lubricating grease according to this Example exhibits an increased resistance to oxidative breakdown, especially at elevated temperature.
EXAMPLE 4
Crosslinked polyurethane
C6o was reacted with a 10 per cent bromine solution in carbon disulphide at room temperature under stirring, whereby CβoBrβ was formed and was precipitated in the form of crystals. Bromine fullerene was separated from the reactants and was mixed with an excess of 1.2-ethane diol. This led to the formation of Cδo (OCH2CH2θH)n where n<8. Any remaining bromine substituents were removed by heating to 150°C.
The C6o(OCH2CH2θH)n obtained was mixed in castor oil to a content of 5 per cent by weight. This mixture was reacted with a diisocyanate, methylene diphenyl isocyanate, whereby a crosslinked polyurethane with a fullerene content of 3.3 per cent by weight was obtained.
A crosslinked polyurethane according to this Example has the fullerene molecules incorporated in the polymer chains where- by isocyanate groups from a plurality of diisocyanate mole¬ cules are bonded to the same fullerene molecule. This cross- linking gives a very stiff polyurethane material.
EXAMPLE 5
Insulating wire enamel
Cgo molecules were mixed to a content of 5 per cent in an epoxy resin resin intended to be applied as an insulating layer onto an electric conductor. An electrical insulation in the form of an insulating varnish according to the invention exhibits an increased resistance to oxidative breakdown as a result of electric load or other external factors.
EXAMPLE 6
Semiconducting polyethylene
A powder consisting of Cgo molecules was mixed with carbon black to a content of 6 per cent by weight. The fullerene- containing carbon black mixture was mixed in HD polyethylene, was kneaded and rolled into a homogeneous compound with a composition of
3 per cent by weight fullerene
47 per cent by weight carbon black
50 per cent by weight HD polyethylene
A semiconducting polymer material with a positive temperature coefficient prepared according to this example exhibits an increased resistance to breakdown relative to conventional polymeric PTC materials.
EXAMPLE 7
Semiconducting copolymers
A powder consisting of C6o molecules was mixed with carbon black to a content of 10 per cent by weight. The fullerene- containing carbon black mixture was added to a copolymer of LD polyethylene, LD-PE, and ethylenebutyl acrylate, EBA, was kneaded and rolled into a homogeneous compound with a compo¬ sition of
5 per cent by weight fullerene 45 per cent by weight carbon black
50 per cent by weight of a copolymer of LD-PE and EBA.
A semiconducting copolymer prepared according to this Example and included as a screen in an insulating system around an electric conductor exhibits an increased resistance to oxida¬ tive breakdown as a result of electric load or other external factors.

Claims

1. A method of protecting organic materials such as oils, fats and polymeric materials, which are subjected to oxida- tion or other degrading influence as a result of the influ¬ ence of external factors such as heat or other radiation as well as electric or magnetic fields, whereby means counter¬ acting the breakdown are added, characterized in that essentially globular or tubular carbon molecules, so-called fullerenes, or derivatives based on said carbon molecules are added to the organic material.
2. A method according to claim 1, characterized in that said essentially globular or tubular carbon molecules are mixed to a content of between 0.01 and 15 per cent by weight in an organic material to counteract the breakdown by- oxidation or other degrading influence.
3. A method according to claim 2, characterized in that said essentially globular or tubular carbon molecules are mixed to a content of between 0.1 and 7 per cent by weight.
4. A method according to claim 1, characterized in that said essentially globular or tubular carbon molecules are incorporated and bonded chemically to a polymer material.
5. A method according to claim 4, characterized in that said essentially globular or tubular carbon molecules are incorporated in the polymer material by incorporating two carbon atoms, included in the carbon molecule, into a polymer chain included in the polymer material.
6. A method according to claim 4, characterized in that said essentially globular or tubular carbon molecules are in- corporated into the polymer material by connecting together a plurality of carbon atoms, included in the carbon molecule, by a crosslinking reaction into a plurality of polymer chains to bond these together in a network.
PCT/SE1994/000148 1993-02-24 1994-02-23 Method of protecting organic materials against breakdown Ceased WO1994019423A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9300619A SE9300619L (en) 1993-02-24 1993-02-24 Methods of protecting organic materials such as oils, fats and polymeric materials from oxidation or other degradative action wherein fullerene or derivatives based thereon are added to the organic material
SE9300619-5 1993-02-24

Publications (1)

Publication Number Publication Date
WO1994019423A1 true WO1994019423A1 (en) 1994-09-01

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EP1245546A3 (en) * 2001-03-28 2002-12-11 Alcatel UV-curable optical fiber coating compositions including fullerenes
EP1272593A4 (en) * 2000-03-17 2004-12-08 Hyperion Catalysis Int Carbon nanotubes in fuels and lubricants
WO2015197842A1 (en) * 2014-06-27 2015-12-30 Borealis Ag Polyolefin composition for power cables
US20230041408A1 (en) * 2020-03-30 2023-02-09 Totai Co., Ltd. Method for producing fullerene-derivative-containing resin composition, fullerene-derivative-containing resin composition obtained from same, resin paint, resin coating, and enamel wire

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EP0544513A1 (en) * 1991-11-25 1993-06-02 Exxon Research And Engineering Company Fullerene-polymer compositions
DE4207246A1 (en) * 1992-03-07 1993-09-09 Basf Ag Low-wear thermoplastic moulding materials - contain thermoplastic polymer, fullerene, and opt. normal additives

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Title
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1272593A4 (en) * 2000-03-17 2004-12-08 Hyperion Catalysis Int Carbon nanotubes in fuels and lubricants
EP1245546A3 (en) * 2001-03-28 2002-12-11 Alcatel UV-curable optical fiber coating compositions including fullerenes
US6621970B2 (en) 2001-03-28 2003-09-16 Alcatel UV-curable optical fiber coating composition including fullerenes
WO2015197842A1 (en) * 2014-06-27 2015-12-30 Borealis Ag Polyolefin composition for power cables
CN106459479A (en) * 2014-06-27 2017-02-22 博里利斯股份公司 Polyolefin composition for power cables
US20170137595A1 (en) * 2014-06-27 2017-05-18 Borealis Ag Polyolefin composition for power cables
US20230041408A1 (en) * 2020-03-30 2023-02-09 Totai Co., Ltd. Method for producing fullerene-derivative-containing resin composition, fullerene-derivative-containing resin composition obtained from same, resin paint, resin coating, and enamel wire

Also Published As

Publication number Publication date
SE470404B (en) 1994-02-14
SE9300619L (en) 1994-02-14
SE9300619D0 (en) 1993-02-24

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