Classifications

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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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  • 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
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  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • 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
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  • 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
  • C08K5/14—Peroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
  • C08K5/372—Sulfides, e.g. R-(S)x-R'
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
  • C08K5/375—Thiols containing six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
• • 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
  • C08L23/08—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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • 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
• • 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
  • H01B3/447—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 acrylic compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
  • H01B3/448—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 other vinyl compounds
• • 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
  • H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
  • H01B7/2813—Protection against damage caused by electrical, chemical or water tree deterioration
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2423/04—Homopolymers or copolymers of ethene
  • C08J2423/08—Copolymers of ethene
• • 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
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/06—Properties of polyethylene
  • C08L2207/066—LDPE (radical process)
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making
  • Y10T29/49227—Insulator making

Definitions

• the present invention relates to a masterbatch consisting essentially of a copolymer (A) of ethylene and at least one ethylenic comonomer having at least one polar group, an organic peroxide (B) and an antioxidant (C), its method of preparation and its uses for the manufacture of insulating layers for electric cables and for limiting or preventing the water tree phenomenon of electric cables.
• A copolymer
• B organic peroxide
• C antioxidant
• An electric wire or an electrical cable is generally made of a conductive material coated with one or more layers of polymeric materials.
• the nature and thickness of the different layers depend on the type of electrical cable, eg medium voltage cable (1-35 kV), high voltage cable (36-132 kV) or very high voltage cable (> 132 kV).
• At least one layer is generally an insulating layer which provides electrical insulation of the conductive part of the cable.
• Crosslinked low density polyethylene or XLPE for "Cross-Linked PolyEthylene"
• XLPE Crosslinked low density polyethylene
• Water treeing is a phenomenon of deterioration of solid insulators which is manifested by the appearance, inside or on the surface of the insulation, of channels or furrows. water more or less fine having a tree shape. The water tree has the effect of causing electrical breakdown and thus reduce the life of the cables.
• the first technique is physical protection, which consists of protecting the cable with an aluminum "sheath" that acts as a barrier to water and moisture. This process is widely used for high and very high voltage cables.
• the second technique consists in using additives within the polyethylene insulating layer, typically silane compounds. This technique is generally used for medium voltage cables.
• the third method consists in incorporating an ethylene / acrylate copolymer into the polyethylene insulating layer.
• This third method of incorporating a copolymer into a polyethylene matrix presents difficulties of implementation. To make such insulating layers, it is necessary to implement several steps, for example:
• Another possible method consists of:
• DPI direct peroxide injection
• DPI units are manufactured by the companies INOEX and LICO and are mentioned in the patent applications EP 0 472 949 and EP 1 221 702.
• the Applicant has set itself the objective of proposing a method for producing a layer insulation having anti-tree water properties, which is advantageously simpler, faster to implement, and less expensive than known methods and which, in particular, does not require the use of very specific and expensive devices.
• the present invention thus relates to a masterbatch consisting essentially of:
• the total weight of the copolymer (A), the peroxide (B) and the antioxidant (C) representing at least 90% of the weight of the masterbatch;
• the organic peroxide (B) representing from 0.2 to 100 parts by weight, per 100 parts by weight of the copolymer (A)
• the antioxidant (C) representing from 0.02 to 50 parts by weight, per 100 parts by weight; weight of the copolymer (A).
• the invention also relates to a process for the preparation of said masterbatch.
• the process for preparing the masterbatch comprises the steps of:
• the process for preparing the masterbatch comprises the steps of:
• the process for preparing the masterbatch comprises the steps of:
• This masterbatch is intended to be incorporated into a crosslinkable polymer matrix, and may be used to limit or prevent the tree phenomenon of water electric cables.
• the present invention therefore also relates to the use of said masterbatch for the manufacture of insulating layers on electrical cables.
• the method of manufacturing an insulating layer on electrical cables comprising the steps of:
• the term "essentially consisting of” means that the total weight of copolymer (A), peroxide (B) and antioxidant (C) is at least 90% of the weight of the mixture. master. Any components of the masterbatch other than the copolymer (A), the peroxide (B) and the antioxidant (C) therefore represent at most 10% of the weight of the masterbatch. These other components may be chosen from compounds conventionally present in an insulating layer of electrical cable, for example stabilizers, technical adjuvants, premature vulcanization retarders, crosslinking accelerators, flame retardants, acid scavengers or loads.
• the presence of components other than the copolymer (A), the peroxide (B) and the antioxidant (C) in the masterbatch may not be desirable when said masterbatch is used to make insulating layers. water tree on medium or high voltage electrical cables. Indeed, the presence of other components can create inhomogeneities in the polymer, which can promote the risk of electrical breakdown.
• the optional components of the masterbatch other than the copolymer (A), the peroxide (B) and one antioxidant (C) thus represent more than 5% / more preferably at most 1%, and even more preferred at most 0.1%, of the weight of the masterbatch.
• the masterbatch which is the subject of the present invention consists solely of the copolymer (A), the peroxide (B) and the antioxidant (C).
• A copolymer
• B peroxide
• C antioxidant
• the copolymer (A) comprises an ethylene comonomer and at least one ethylenic comonomer having at least one polar group.
• the copolymer (A) may optionally comprise other comonomer (s).
• the ethylenic comonomer having at least one polar group may be chosen from the group consisting of:
• vinyl esters such as vinyl acetate and vinyl pivalate
• acrylates and methacrylates of alkyl and hydroxyalkyls such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate;
• unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid;
• acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylic amide and methacrylic amide
• vinyl ethers such as methyl vinyl ether and vinyl phenyl ether.
• alkyl acrylates or methacrylates having 1 to 4 carbon atoms are preferred.
• Particularly preferred comonomers are n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, methyl methacrylate and the like. ethyl methacrylate.
• the copolymer (A) consists of an ethylene comonomer and an ethylenic comonomer having at least one polar group.
• the copolymer (A) comprises from 10 to 60%, preferably from 15 to 25% by weight of ethylenic comonomer having at least one polar group, relative to the total weight of the copolymer.
• the organic peroxide (B) included in the masterbatch of the present invention has the following formula (I):
• n is an integer equal to 1, 2, 3 or 4;
• R 1 and R 1 are each, independently of each other, an oxygen atom, a linear or branched, saturated or partially unsaturated C 1 to C 5 divalent hydrocarbon radical, and preferably a linear C 1 -C 4 alkylene chain; unsubstituted C5,
• R 2 , R 2 ', R 3 and R 3' are each, independently of each other, a linear or branched, saturated or partially unsaturated C 1 -C 5 hydrocarbon-based radical, and preferably a linear C 1 -C 5 linear alkyl group; substituted
• R 4 and R 4 ' are each, independently of each other, a hydrogen atom, a linear or branched, saturated or partially unsaturated C 1 -C 5 hydrocarbon-based radical, and preferably a linear C 1 -C 4 alkyl group; unsubstituted C5.
• R 1 and R 1 ' are each, independently of one another, an alkylene chain of formula - (C3 ⁇ 4) - or - (CH 2 -CH 2) -;
• R 2 , R 2 ', R 3 and R 3' are each, independently of one another, selected from the group consisting of methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl and tert-butyl, preferably methyl ;
• R 4 and R 4 ' are each, independently of one another, selected from the group consisting of the hydrogen atom, methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl and tert-butyl, preferably the hydrogen atom.
• the organic peroxide (B) is selected from the group consisting of dimethyl-2,5-di- (tert-butylperoxy) hexane, di-tert-amyl peroxide, di-tert-butyl peroxide and tert-butylcumyl peroxide.
• These organic peroxides are available on the market from ARKEMA under the trade name Luperox® 101, Luperox® DTA, Luperox® DI, Luperox® DC, Luperox® DCP and Luperox® 801.
• the organic peroxide (B) is 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane of formula (II):
• the organic peroxide (B) is tert-butyl cumyl peroxide of formula (III):
• organic peroxide (B) is dicumyl peroxide of formula (IV):
• n 1;
• R 4 and R 4 ' together form a carbocycle or a heterocycle comprising from 3 to 14 carbon atoms and optionally 1 to 4 heteroatoms selected from 0, N, P, S and Si.
• an organic peroxide (B) of this type is 3, 6, 9-triethyl-3, 6, 9-trimethyl-1,4,7-triperoxonane of (V) form:
• This organic peroxide is available on the market from the company AKZO NOBEL under the trade name Trigonox® 301.
• the organic peroxide (B) may be an organic peroxide as described above, or a mixture of several of said organic peroxides.
• the organic peroxide (B) is from 0.2 to 100 parts by weight, per 100 parts by weight of the copolymer (A). More preferably, the organic peroxide (B) is from 2 to 50 parts by weight, per 100 parts by weight of the copolymer (A). Even more preferably, the organic peroxide (B) represents from 9 to 15 parts by weight, per 100 parts by weight of the copolymer (A).
• the antioxidant (C) may be chosen from those conventionally used in polymer matrices, in particular from hindered or semi-congested phenols. sterically, optionally substituted by one or more functional groups, aromatic amines, sterically hindered aliphatic amines, organic phosphates and thio compounds.
• antioxidants are commercially available from BASF under the trade name Irganox® 1035 and Irganox® PS802.
• the antioxidant (C) may be an antioxidant or a mixture of several antioxidants.
• the antioxidant (C) is from 0.02 to 50 parts by weight per 100 parts by weight of the copolymer (A). More preferably, the antioxidant (C) is 0.1 to 10 parts by weight per 100 parts by weight of the copolymer (A). Even more preferably, the antioxidant (C) is from 1 to 3 parts by weight per 100 parts by weight of the copolymer (A).
• the invention also relates to a process for preparing the masterbatch according to the invention. According to a first embodiment, this method comprises the steps of:
• the homogeneous liquid mixture of the organic peroxide (B) and the antioxidant (C) can be produced in different ways depending on the nature of the compounds. If the organic peroxide (B) is in liquid form, the mixture can be obtained by adding the antioxidant (C), itself in liquid or solid form, into the organic peroxide (B) and mixing with the aid of magnetic or mechanical agitation. If the organic peroxide (B) is in solid form, the homogeneous liquid mixture can be obtained by preheating the organic peroxide (B) above its melting point, then adding the antioxidant (C) and mixing . The heating can be achieved for example using a water bath.
• an additional step of heating for example with the aid of a water bath, the mixture can to be implemented.
• the temperature of the heating may be between 30 ° C and 80 ° C, preferably between 40 ° C and 70 ° C.
• the nature and the relative amounts of the organic peroxide (B) and the antioxidant (C) are chosen so that their liquid mixture is homogeneous, that is to say they are totally miscible together with the naked eye.
• the homogeneous liquid mixture between the organic peroxide (B) and the antioxidant (C) can be obtained by dissolving the organic peroxide (B) and the antioxidant (C), these two compounds possibly being in liquid form or solid, in a suitable solvent.
• the solvent may preferably be removed in a subsequent step of preparing the masterbatch, preferably by evaporation.
• the choice of the solvent can be made by the skilled person depending on the solubility of the various components and depending on the boiling temperature of the solvent.
• the organic peroxide (B) and the antioxidant (C) are preferably selected from low volatility compounds so that they are not removed together with the solvent.
• the resulting liquid mixture is contacted with the copolymer (A).
• the copolymer (A) is preferably in the form of granules.
• the contacting is carried out so that the liquid mixture is absorbed by the copolymer (A).
• the absorption of the liquid mixture by the copolymer (A) may be complete or not.
• the liquid mixture can be brought into contact with the copolymer (A) by quenching, with or without stirring.
• the liquid mixture can be brought into contact with the copolymer (A) at ambient temperature (approximately 25 ° C.) or with heating.
• the use of heating is advantageous if, in particular, the liquid mixture is homogeneous only at a temperature above room temperature.
• the contacting step can therefore be carried out at a temperature of between 40 ° C. and 80 ° C., preferably between 50 ° C. and 70 ° C.
• the copolymer (A) and the liquid mixture are introduced into a mixer.
• a mechanical stirring is carried out, so that the copolymer (A) is impregnated with the liquid mixture.
• the mechanical stirring is interrupted and quenching is continued until the liquid mixture has been completely absorbed by the copolymer (A).
• the duration of the contacting step may be adapted by those skilled in the art depending on the speed with which the liquid mixture is absorbed by the copolymer (A). This step may for example take between 5 minutes and 12 hours.
• copolymer (A) may be contact with components other than peroxide (B) and antioxidant (C).
• these other components which have been described above, can be added to the homogeneous liquid mixture, before or after its formation, or be brought into contact with the copolymer (A), independently, before, during or after the step contacting the liquid mixture.
• the copolymer (A) impregnated with the peroxide (B) and the antioxidant (C) is recovered.
• the relative proportions of copolymer (A), organic peroxide (B), antioxidant (C), and optionally other components are chosen so that the organic peroxide (B) represents from 0.2 to 100 parts by weight, per 100 parts by weight of the copolymer (A), and the antioxidant (C) is from 0.02 to 50 parts by weight, per 100 parts by weight of the copolymer (A).
• these proportions can be adapted according to whether the absorption of the liquid mixture by the copolymer (A) is complete or not.
• the process for preparing the masterbatch comprises the steps of:
• the extrusion of the copolymer (A) with the antioxidant (C) can be carried out according to the techniques known to those skilled in the art, for example by means of a single screw or twin screw extruder.
• the antioxidant (C) may be in liquid form or in solid form.
• the temperature of the extrusion is adapted, as known to those skilled in the art, to the melting temperature of the copolymer (A).
• the extrudate is preferably recovered in the form of granules.
• Said extrudate is then brought into contact with the organic peroxide (B) once it is at a sufficiently low temperature not to trigger the thermal decomposition of the peroxide.
• the extrudate can be actively cooled, or it can be allowed to cool freely.
• the contact with the organic peroxide (B) can be carried out as described above for the first embodiment of the process for preparing the masterbatch. In particular, if the organic peroxide (B) is not liquid at room temperature, it can be heated.
• the process for preparing the masterbatch comprises the steps of:
• the extrusion of the copolymer (A) with the antioxidant (C) can be carried out as described above for the second embodiment of the process for preparing the masterbatch.
• the extrudate is then extruded a second time with the organic peroxide (B).
• the temperature of the extrusion is adapted, as known to those skilled in the art, to the melting temperature of the copolymer (A), so as to allow extrusion.
• the temperature of this second extrusion is adjusted so that the temperature is low enough not to trigger the thermal decomposition of the peroxide.
• the adjustment of the extrusion temperature is part of the know-how of the person skilled in the art.
• the masterbatch thus obtained is stable over time.
• the contents of organic peroxide (B) and antioxidant (C) do not vary significantly after storage under usual conditions of 12 months at room temperature, that is to say below 30 ° C.
• These master batches can be transported in bags or drums from the production center to the processing center.
• the electrical cable may be in particular a medium voltage cable (1-35 kV) or a high voltage cable (36-132 kV).
• the present invention also relates to a method of manufacturing an insulating layer on electrical cables comprising the steps of: diluting the masterbatch described above in a crosslinkable polymer matrix to obtain a polymeric composition;
• the dilution step can be carried out by means of any device conventionally used in the plastics industry, in particular using internal mixers, or mixers or roll mills (bi- or tri-cylindrical).
• the dilution step may also consist of introducing the compounds into the hopper of an extruder using gravimetric feeders, for example. It is also possible to carry out this dilution using a lateral extruder.
• the crosslinkable polymer matrix preferably consists of polyethylene, more preferably low density polyethylene (or LDPE for "Low Density PolyEthylene"). It is preferably in the form of granules.
• the masterbatch and the crosslinkable polymer matrix are introduced into the feed hopper of the extruder without adding any other component.
• the dilution ratio by weight of the masterbatch in the crosslinkable polymer matrix may be between 0.1 / 99.9 and 60/40, preferably between 5/95 and 30. / 70, and even more preferably between 10/90 and 20/80. This rate may vary depending on the composition of the masterbatch.
• the masterbatch and the crosslinkable polymer matrix are introduced into the feed hopper of the extruder, with additionally an additional amount of copolymer (A).
• this dilution step makes it possible to obtain a polymeric composition.
• a polymeric composition comprising the crosslinkable polymer, the copolymer (A), the organic peroxide (B) and the antioxidant (C).
• Other components may optionally be present, such as, for example, stabilizers, technical adjuvants, premature vulcanization retarders, crosslinking accelerators, flame retardants, acid traps or fillers. These optional components may come from the masterbatch or be added during the dilution of the masterbatch in the crosslinkable polymer matrix.
• the copolymer (A) is from 0.2% to 50% by weight, more preferably from 5% to 20% by weight, and even more preferably from 10 to 15% by weight, of the composition. polymer.
• the organic peroxide (B) is preferably from 0.1 to 100 parts by weight, and more preferably from 0.5 to 2 parts by weight, per 100 parts of the total weight of the crosslinkable polymer and the copolymer. (AT) .
• the antioxidant (C) is preferably 0.01 to 1 part by weight, and more preferably 0.2 0.3 part by weight, per 100 parts of the total weight of the crosslinkable polymer and the copolymer (A).
• the polymeric composition obtained is shaped by extrusion so as to form a layer around an electric cable.
• the extrusion may be simple or consist of coextrusion with other polymeric compositions.
• the extrusion can be made directly on the conductive material forming the electrical cable.
• Other layers may conventionally be arranged between the conductive material and the insulating layer, for example an internal semiconducting layer.
• the extruded polymeric composition is then subjected to a crosslinking step.
• the organic peroxide (B) present in the polymeric composition allows crosslinking of the crosslinkable polymer.
• the crosslinking step may vary depending on the nature of the materials used and the size of the electric cable.
• this step comprises subjecting the extruded polymeric composition to an elevated temperature, preferably from 100 ° C to 450 ° C, more preferably from 110 ° C to 400 ° C.
• the insulating layer obtained on the electric cable has a thickness advantageously between 1 millimeter and 5 centimeters.
• the thickness of the insulating layer may be about 5 millimeters.
• the thickness of the insulating layer may be several centimeters.
• the crosslinked polymeric composition constitutes an insulating layer on the electrical cable.
• the use of the masterbatch according to the invention makes it easy to manufacture this insulating layer, without using several extrusion devices or specific equipment such as a unit for direct injection of peroxides.
• the crosslinking density obtained with the masterbatch according to the present invention is comparable to that obtained with a masterbatch containing no antioxidant (C).
• the presence of the antioxidant (C) in the masterbatch does not therefore alter the crosslinking density of the insulating layer.
• Peroxide (B) and then the antioxidant (C) were added to a flask.
• the flask was placed in a water bath at a temperature of 57 ° C and the peroxide and antioxidant mixture was stirred with a magnet bar to obtain a homogeneous liquid mixture.
• the granular copolymer (A) was introduced into a 250 ml Schott® glass bottle.
• the homogeneous liquid mixture of peroxide and antioxidant was warmed in a water bath at 60 ° C and then the desired amount was removed and introduced into the vial containing the copolymer (A).
• the flask was placed in apparatus allowing continuous agitation and the temperature was maintained at 60 ° C until the homogeneous liquid mixture of peroxide and antioxidant was fully absorbed by the copolymer (A).
• the liquid mixture was absorbed in 3 hours.
• the liquid mixture was absorbed in 6 hours.
• copolymer granules (A) originally translucent, became opaque white after adsorption.
• the 2 masterbatches prepared are therefore stable over time.
• Table 4 The values of MH-ML (dNm) are directly correlable to the crosslinking density.
• the values obtained for the crosslinked polymer compositions of LDPE prepared with masterbatches 1 and 2 show that these compositions have a correct crosslinking density.
• the T90 values represent the time required to reach 90% of the maximum crosslinking density.
• the values of Ts2 represent the time of pre-crosslinking, or roasting, of the mixture studied.
• the T90 and TsO2 values obtained at 180 ° C for the crosslinked polymer compositions of LDPE prepared with master batches 1 and 2 are as expected.

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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)
• Processes Of Treating Macromolecular Substances (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Insulating Materials (AREA)
• Processes Specially Adapted For Manufacturing Cables (AREA)

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• 2011
  • 2011-10-24 FR FR1159597A patent/FR2981655B1/fr not_active Expired - Fee Related
• 2012
  • 2012-10-19 CN CN201280052032.5A patent/CN103890077A/zh active Pending
  • 2012-10-19 WO PCT/FR2012/052389 patent/WO2013060969A1/fr active Application Filing
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