DE2437749C2 - Process for the production of a crosslinked insulation from ethylene homo- and copolymers - Google Patents

Process for the production of a crosslinked insulation from ethylene homo- and copolymers

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Publication number
DE2437749C2
DE2437749C2 DE2437749A DE2437749A DE2437749C2 DE 2437749 C2 DE2437749 C2 DE 2437749C2 DE 2437749 A DE2437749 A DE 2437749A DE 2437749 A DE2437749 A DE 2437749A DE 2437749 C2 DE2437749 C2 DE 2437749C2
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DE
Germany
Prior art keywords
copolymers
production
peroxide
ethylene homo
mixture
Prior art date
Legal status (The legal status 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 status listed.)
Expired
Application number
DE2437749A
Other languages
German (de)
Other versions
DE2437749A1 (en
Inventor
Hans A. Dipl.-Ing. 4330 Mülheim Mayer
Johann Dipl.-Chem. 3501 Vellmar Wartusch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kabel Rheydt AG
Licentia Patent Verwaltungs GmbH
Original Assignee
AEG Telefunken Kabelwerke AG
Licentia Patent Verwaltungs GmbH
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 AEG Telefunken Kabelwerke AG, Licentia Patent Verwaltungs GmbH filed Critical AEG Telefunken Kabelwerke AG
Priority to DE2437749A priority Critical patent/DE2437749C2/en
Publication of DE2437749A1 publication Critical patent/DE2437749A1/en
Application granted granted Critical
Publication of DE2437749C2 publication Critical patent/DE2437749C2/en
Expired legal-status Critical Current

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/29—Feeding the extrusion material to the extruder in liquid form
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/06—Rod-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
    • B29K2101/10—Thermosetting resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2301/00—Use of unspecified macromolecular compounds as reinforcement
    • B29K2301/10—Thermosetting resins
    • 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

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

Die vorliegende Erfindung bezieht sich auf ein Verfahren zur Herstellung einer vernetzten Isolierung aus Äthylen-Homo- und Copolymerisaten, insbesondere für Kabel und Leitungen, durch Extrudieren einer stabilisierten, vernetzbaren Mischung aus Äthylen-Homo- und Copolymerisaten mit Peroxid.The present invention relates to a method of making crosslinked insulation of ethylene homopolymers and copolymers, especially for cables and wires, by extruding a stabilized, crosslinkable mixture of ethylene homo- and copolymers with peroxide.

Bei dem vorgenannten Verfahren (DE-OS 22 20 147) werden feste Wärmestabilisatoren in einem flüssigen organischen Peroxid oder in einer Lösung eines organischen Peroxids beim Extrudieren dem Polyäthylen zur Wärmestabilisierung zugesetzt. Die Verwendung eines flüssigen Peroxids bringt die Gefahr der verhältnismäßig leichten Entzündbarkeit im Gemisch seines Dampfs mit Luft, da der Siedepunkt derartiger flüssiger Peroxide bereits unterhalb der Verarbeitungstemperatur liegt. Die Verwendung von Lösungsmitteln, wie z. B. Aceton, zum Auflösen eines festen Peroxids vermindert diese Gefahr ebenfalls nicht, da in diesem Fall das Lösungsmittel zu einem entzündbaren Gemisch führen kann, abgesehen von der Gefahr der Blasenbildung bei der Verarbeitung.In the aforementioned method (DE-OS 22 20 147) solid heat stabilizers are in a liquid organic peroxide or in a solution of an organic peroxide when extruding the polyethylene added for heat stabilization. The use of a liquid peroxide brings the risk of relatively easy flammability in a mixture of its vapor with air, since the boiling point is such liquid peroxides is already below the processing temperature. The use of solvents such as B. acetone, to dissolve a solid peroxide also does not reduce this risk, as in this If the solvent can lead to a flammable mixture, apart from the risk of bubble formation while processing.

Der Erfindung liegt die Aufgabe zugrunde, spannungstabilisierte, vernetzte Isolierungen herzustellen, die ohne technologische Schwierigkeiten und mit ausreichender Sicherheit zu einer Hochspannungsisolation verarbeitet v.erden können. Diese Aufgabe wird gemäß der Erfindung dadurch gelöst, daß zur Herstellung einer spannungsstabilisierten, vernetzten Isolierung dem Polymer während des Extrudierens eine Lösung zugesetzt wird, die aus einem flüssigen Spannungsstabilisator und einem darin gelösten Peroxid besteht.The invention is based on the object of producing voltage-stabilized, cross-linked insulation, which result in high-voltage insulation without technological difficulties and with sufficient security processed v. can be earthed. This object is achieved according to the invention in that for the production stress-stabilized, cross-linked insulation is applied to the polymer during extrusion Solution is added, which consists of a liquid tension stabilizer and a peroxide dissolved therein consists.

Vorteilhafte Ausgestaltungen der Erfindung sind den Unteransprüchen zu entnehmen.Advantageous embodiments of the invention can be found in the subclaims.

Für diesen Zweck hat sich insbesondere ein Gemisch als vorteilhaft erwiesen, das aus Mono- oder Bisperoxiden besteht, die in hocharomatischen Kohlenwasserstoffen auf Phenanthrenbasis gelöst sind. Als flüssige Stabilisatoren können neben hocharomatischen ölen auch Gemische aus diesen mit aromatischen Ketonen und/oder aromatischen Hydroxylverbindungen Anwendung Finden. Als solche kommen beispielsweise in Frage: Acetophenon bzw. Benzophenon und ähnliche Verbindungen, ferner Verbindungen wie Diisopropanolbenzol, 2-Phenylpropanal-2 oder gemischtsubstituierte Keto-Hydroxylverbindungen, wie z.B. 1-Aceto-3-isopropanolbenzol. Als Peroxide können an sich bekannte Verbindungen, wie Dicumylperoxid, oder Bisperoxide, wie Bis-(t-butylperoxiisopropyl)-benzol, verwendet werden.A mixture in particular has been used for this purpose Proven to be advantageous, which consists of mono- or bisperoxides, which in highly aromatic hydrocarbons based on phenanthrene are dissolved. As liquid stabilizers, in addition to highly aromatic oils Mixtures of these with aromatic ketones and / or aromatic hydroxyl compounds are also used Find. Examples of these are: acetophenone or benzophenone and the like Compounds, as well as compounds such as diisopropanolbenzene, 2-phenylpropanal-2 or mixed-substituted ones Keto-hydroxyl compounds such as 1-aceto-3-isopropanolbenzene. Compounds known per se, such as dicumyl peroxide, or bisperoxides, can be used as peroxides such as bis (t-butylperoxyisopropyl) benzene can be used.

Unter Polyäthylenen, die zu einer vernetzten Isolierung verarbeitet werden, sind in erster Linie Homopolymerisate, insbesondere Hochdruckpolyäthylene, ζ. B. vom Schmelzindex 1,5 g/10 min, zu verstehen. Ferner können auch Copolymerisate des Äthylens, wie Äthylen-Propylen-Copolymere oder -Terpolymere, wiePolyethylenes, which are processed into a cross-linked insulation, are primarily Homopolymers, especially high-pressure polyethylene, ζ. B. from the melt index 1.5 g / 10 min to understand. Furthermore, copolymers of ethylene, such as ethylene-propylene copolymers or terpolymers, such as

auch Mischpolymerisate aus Äthylen und Vinylacetat für diesen Zweck Anwendung finden.copolymers of ethylene and vinyl acetate are also used for this purpose.

Aus der JP-PS 39-5766 ist es bekannt, Polyolefinmassen zur Verbesserung der elektrischen Eigenschaften feste, hocharomatische Verbindungen zuzusetzen, ohne gleichzeitig eine Vernetzung herbeizuführen. Der Druckschrift ist kein Hinweis zu entnehmen, daß zur Vernetzung bei gleichzeitiger Spannungsstabilisierung ein Peroxid in einem flüssigen Stabilisator gelöst werden muß.From JP-PS 39-5766 it is known to use polyolefin compositions to improve the electrical properties add solid, highly aromatic compounds without causing crosslinking at the same time. Of the There is no reference to be found in the publication that cross-linking with simultaneous tension stabilization a peroxide must be dissolved in a liquid stabilizer.

Die Direktdosierung der Mischung aus Spannungsstabilisatoren und Peroxid kann vorteilhaft auch Anwendung finden bei der Verarbeitung von füllstoffhaltigen Mischungen der genannten Polymeren.
Bei der Herstellung von Vormischungen zum Extrudieren, z. B. bei der Einarbeitung von Füllstoffen und anderen Zusätzen, braucht dabei auf die gegebenenfalls auftretenden hohen Mischungstemperaturen keine Rücksicht genommen zu werden. Diese Maßnahme trifft insbesondere bei der Herstellung von hochgefüll-The direct metering of the mixture of tension stabilizers and peroxide can advantageously also be used in the processing of filler-containing mixtures of the polymers mentioned.
In the manufacture of premixes for extrusion, e.g. B. when incorporating fillers and other additives, no consideration needs to be given to the high mixing temperatures that may occur. This measure applies particularly to the production of highly filled

ten kautschukartigen Äthylen-Copolymerisaten zu.th rubber-like ethylene copolymers too.

Das Stabilisierungsmittel in Kombination mit dem Vernetzungsmittel wird in an sich bekannter Weise direkt in die Einzugszone eines Extruders zudosiert. Die Einarbeitung bzw. Homogenisierung der Stabilisator/ Peroxid-Mischung erfolgt in der Mischzone des Extruders bei Temperaturen zwischen 100—150°C, wobei bezüglich der Temperaturführung im wesentlichen auf das verwendete Peroxid Rücksicht zu nehmen ist, während der flüssige Spannungsstabilisator aufgrundThe stabilizing agent in combination with the crosslinking agent is used in a manner known per se metered directly into the feed zone of an extruder. The incorporation or homogenization of the stabilizer / Peroxide mixing takes place in the mixing zone of the extruder at temperatures between 100-150 ° C, with regard to the temperature control essentially taking into account the peroxide used is due to the liquid stress stabilizer

so seines geringen Dampfdruckes in thermischer Hinsicht keine besondere Rücksichtnahme erfordert. Damit ergibt sich auch die Möglichkeit, die Verarbeitung unter vermindertem Druck vorzunehmen (Trichterentgasung). so its low vapor pressure in thermal terms does not require any special consideration. This also gives the option of processing under reduced pressure (funnel degassing).

Das Verhältnis von Peroxid zu flüssigem Stabilisator kann in weiten Grenzen variiert werden, um den zu stellenden Anforderungen zu genügen, wobei eine Lösung im Verhältnis von Stabilisator : Peroxid =1:4 auf einfache Weise schon bei Raumtemperatur herge-The ratio of peroxide to liquid stabilizer can be varied within wide limits in order to achieve the to meet the requirements, with a solution in the ratio of stabilizer: peroxide = 1: 4 easily produced at room temperature

M) stellt werden kann; gegebenenfalls kann ein gelindes Erwärmen den Lösungsvorgang beschleunigen.M) can be provided; possibly a mild Warming up accelerates the dissolution process.

Durch Verwendung der flüssigen Stabilisatoren nach der Erfindung gelingt es, hochwertige Isolierungen für Hochspannungszwecke mit langer Lebensdauer undBy using the liquid stabilizers according to the invention, it is possible to obtain high-quality insulation for Long life and high voltage purposes

h"1 verbesserter Durchschlagsfestigkeit herzustellen.h " 1 to produce improved dielectric strength.

Claims (3)

Patentansprüche:Patent claims: 1. Verfahren zur Herstellung einer vernetzten Isolierung aus Äthylen-Homo- und Copolymerisaten, insbesondere für Kabel und Leitungen, durch Extrudieren einer stabilisierten, vernetzbaren Mischung aus Äthylen-Homo- und Copolymerisaten mit Peroxid, dadurch gekennzeichnet, daß zur Herstellung einer spannungsstabilisierten, vernetzten Isolierung dem Polymer während des Extrudierens eine Lösung zugesetzt wird, die aus einem flüssigen Spannungsstabilisator und einem darin gelösten Peroxid besteht.1. Process for the production of a cross-linked insulation from ethylene homo- and copolymers, especially for cables and wires, by extruding a stabilized, crosslinkable mixture of ethylene homo- and copolymers with peroxide, characterized in that for the production of a tension-stabilized, crosslinked Isolation a solution is added to the polymer during extrusion, which is made from a liquid tension stabilizer and a peroxide dissolved therein. 2. Verfahren zur Herstellung einer Isolierung nach Anspruch 1, dadurch gekennzeichnet, daß Mono- oder Bisperoxide, gelöst in einem Gemisch aus hocharomatischen Kohlenwasserstoffen auf Phenanthrenbasis, zugesetzt werden.2. A method for producing an insulation according to claim 1, characterized in that mono- or bisperoxides, dissolved in a mixture of highly aromatic hydrocarbons based on phenanthrene, can be added. 3. Verfahren zur Herstellung einer Isolierung nach Anspruch 2, dadurch gekennzeichnet, daß ein Gemisch aus einem hocharomatischen Kohlenwasserstoff mit Zusätzen von aromatischen Ketonen und/oder aromatischen Hydroxylverbindungen zugesetzt wird.3. A method for producing an insulation according to claim 2, characterized in that a Mixture of a highly aromatic hydrocarbon with the addition of aromatic ketones and / or aromatic hydroxyl compounds is added.
DE2437749A 1974-08-06 1974-08-06 Process for the production of a crosslinked insulation from ethylene homo- and copolymers Expired DE2437749C2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE2437749A DE2437749C2 (en) 1974-08-06 1974-08-06 Process for the production of a crosslinked insulation from ethylene homo- and copolymers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2437749A DE2437749C2 (en) 1974-08-06 1974-08-06 Process for the production of a crosslinked insulation from ethylene homo- and copolymers

Publications (2)

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DE2437749A1 DE2437749A1 (en) 1976-02-26
DE2437749C2 true DE2437749C2 (en) 1984-05-03

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE568576A (en) * 1958-08-20
DE1228802B (en) * 1964-09-10 1966-11-17 Siemens Ag Sunscreens for polyethylene
FR1464601A (en) * 1964-05-15 1967-01-06 Simplex Wire & Cable Co Dielectric composition, in particular for coating cables or the like, and cables or the like provided with an insulation conforming or similar to the preceding
BE687742A (en) * 1966-10-03 1967-04-03
JPS4837978A (en) * 1971-09-18 1973-06-04
DE2220147A1 (en) * 1972-04-25 1973-11-08 Basf Ag Stabilised cross-linked polyethylene prepn - by a simultaneous addn of polymer and stabiliser soln in peroxide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE568576A (en) * 1958-08-20
FR1464601A (en) * 1964-05-15 1967-01-06 Simplex Wire & Cable Co Dielectric composition, in particular for coating cables or the like, and cables or the like provided with an insulation conforming or similar to the preceding
DE1228802B (en) * 1964-09-10 1966-11-17 Siemens Ag Sunscreens for polyethylene
BE687742A (en) * 1966-10-03 1967-04-03
JPS4837978A (en) * 1971-09-18 1973-06-04
DE2220147A1 (en) * 1972-04-25 1973-11-08 Basf Ag Stabilised cross-linked polyethylene prepn - by a simultaneous addn of polymer and stabiliser soln in peroxide

Also Published As

Publication number Publication date
DE2437749A1 (en) 1976-02-26

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