EP1063655A1 - Carriers bearing functionalised organoorganooxysilanes in cable compositions - Google Patents

Carriers bearing functionalised organoorganooxysilanes in cable compositions Download PDF

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Publication number
EP1063655A1
EP1063655A1 EP00109631A EP00109631A EP1063655A1 EP 1063655 A1 EP1063655 A1 EP 1063655A1 EP 00109631 A EP00109631 A EP 00109631A EP 00109631 A EP00109631 A EP 00109631A EP 1063655 A1 EP1063655 A1 EP 1063655A1
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EP
European Patent Office
Prior art keywords
functional
carrier
use according
organylorganyloxysilane
liquid
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EP00109631A
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German (de)
French (fr)
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EP1063655B1 (en
Inventor
Helmut Dr. Mack
Dieter Barfurth
Roland Edelmann
Albert-Johannes Dr. Frings
Michael Dr. Horn
Peter Dr. Jenkner
Ralf Dr. Laven
Jaroslaw Dr. Monkiewicz
Burkhard Dr. Standke
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Evonik Operations GmbH
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Degussa GmbH
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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
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31801—Of wax or waxy material
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • the invention relates to the use of functional Organylorganyloxysilanen on carriers in cable compounds, the contain certain thermoplastic base polymers and fillers.
  • the invention further relates to the cable compounds as such and cables Envelopes from these cable compounds.
  • Cable compounds are mixtures of substances that are a base polymer as well as mineral (or inorganic) reinforcing, stretching or contain flame retardant fillers and used to make metallic To wrap the conductor in an electrically insulating manner. It is known that an addition of functional organylorganyloxysilanes dispersing the filler in the Base polymer facilitates and the adhesion between base polymer and filler improved. Functional organylorganyloxysilanes are in this Relationship of such silanes that attach one to the carbon atom Silicon atom bound organic residue, which in turn has a contains functional group. The easier dispersion and the better Adhesion is likely to result in the water repellency caused by the silane Surface of the filler particles can be attributed. The better liability leads to better mechanical properties of the cable sheathing.
  • EP 0 518 057 B1 contains liquid vinyl groups Mixtures of chain and cyclic siloxanes or siloxane oligomers and their use as crosslinking agents, e.g. B. for High pressure polyethylene, known in cable masses.
  • liquid additives are problematic for users in that the usual facilities for Weighing and dosing small amounts of additives for solids only are designed. Liquid small components must therefore be manually be weighed and dosed. This is usually at a higher cost connected and represents an additional source of error.
  • reinforcing additives composed of oligomeric and / or polymeric sulfur-containing organylorganyloxysilanes and semi-active, active and / or highly active carbon blacks as a carrier, which are suitable for use in rubber mixtures or compositions and in plastic mixtures, are not mentioned in either of the cited documents 0 428 073 B1 discloses a process in which (i) a base polymer, (ii) a sponge-like polymer or a swellable polymer are mixed with a (meth) acryloxy-functional organosilane contained therein and (iii) a free radical-donating substance and the The mixture melts and homogenizes.
  • WO 97/07165 states that the solid mixtures of functional organosilanes and certain large-area silicas with low surface energy described therein can be used, inter alia, for the insulation of wires and cables.
  • One of the objects of the present invention is the use (1) a liquid functional bound to a carrier Organylorganyloxysilans or one bound to a carrier liquid (co) condensate of a functional organylorganyloxysilane for Manufacture of cable compounds containing one (2) thermoplastic, polar functional group-bearing base polymer and (3) a reinforcing one or stretching mineral filler.
  • Another object of the invention are cable compounds, which (1) a a carrier-bound liquid functional organylorganyloxysilane or a liquid (co) condensate bound to a carrier functional organylorganyloxysilane, (2) a thermoplastic, polar functional group-bearing base polymer and (3) a reinforcing, stretching or flame retardant mineral filler.
  • Another object of the invention are cables, their metallic conductors are covered with such a cable compound.
  • Functional organylorganyloxysilanes in the sense of the invention contain at least one organic radical bonded to a silicon atom via a carbon atom (organyl radical), for. B. a straight-chain or branched alkylene radical having 2 to 6 carbon atoms, which carries at least one functional group.
  • the functional group can e.g. B.
  • X x a hydroxyl, nitrile, carbonyl, carboxyl, acyl, acyloxy, carboalkoxy, mercapto, sulfane (X x ), epoxy or one optionally substituted by one or two hydrocarbon radicals having 1 to 6 carbon atoms Amino group and a halogen atom, in particular a chlorine atom or an olefinic double or a CC triple bond.
  • the organic radical can also contain several identical or different functional groups, e.g. B. two amino groups or an acyl radical with olefinic double bond, such as the (meth) acryloxy radical.
  • the functional organylorganyloxysilanes on the other hand contain at least one hydrolyzable radical, preferably three hydrolyzable radicals, e.g. B. one or more alkoxy or alkoxyalkoxy radicals each having 1 to 6 carbon atoms.
  • the functional organylorganyloxysilanes can further contain one or two further, non-functional and non-hydrolyzable radicals, e.g. B. a hydrocarbon radical with up to 8 carbon atoms, such as methyl, propyl or n-hexyl.
  • suitable functional organylorganyloxysilanes are Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-methacryloxypropyl-triethoxysilane, 3-methacryloxypropyl-trimethoxysilane and 3-methacryloxypropyl tris (2-methoxy-ethoxy) silane.
  • Preferred functional organylorganyloxysilanes are optionally by 1 or 2 alkyl radicals each having 1 to 6 carbon atoms N-substituted aminoorganylorganyloxysilane because the coatings from the corresponding compounds outstanding mechanical properties (such as Tensile strength, elongation at break, tensile strength and modulus of elasticity) and electrical Properties (such as electrical loss factor, dielectric constant) exhibit.
  • mechanical properties such as Tensile strength, elongation at break, tensile strength and modulus of elasticity
  • electrical Properties such as electrical loss factor, dielectric constant
  • the (co) condensates are z. B. in known Way by hydrolysis or cohydrolysis of the silanes with limited amounts Water and subsequent condensation of the silanols. In the Cocondensates should be the proportion of (amino) functional Organylorganyloxysilane at least 10 wt .-%, advantageously at least 50% by weight.
  • the base polymer of the Cable compounds is thermoplastic and carries polar groups.
  • Such Base polymers result in e.g. B. Improved fire behavior (i.e. lower Flammability and smoke density) and increase the filler absorption capacity.
  • Polar groups are e.g. B. hydroxyl, nitrile, carbonyl, Carboxyl, acyl, acyloxy, carboalkoxy groups or amino groups and Halogen atoms, especially chlorine atoms. Olefinic are not polar Double bonds or C-C triple bonds.
  • Suitable polymers are in addition to polyvinyl chloride copolymers of one or more olefins and one or more comonomers containing polar groups, e.g. B.
  • the polar groups are generally found in copolymers in amounts of 0.1 to 50 mol%, preferably from 5 to 30 mol%, based on the Polyolefin building blocks.
  • Suitable base polymers are ethylene-vinyl acetate copolymers. For example, contains a suitable commercial one Copolymer 19 mole% vinyl acetate and 81 mole% ethylene building blocks.
  • the fillers are mineral (or inorganic) and can be reinforcing or just stretching. At least they wear on their surfaces Groups associated with the organyloxy groups of the functional Organylorganyloxysilans react. The result is that Silicon atom with the attached functional organyl residue on the Surface chemically fixed. Such groups on the surface of the filler are especially hydroxyl groups.
  • Preferred fillers are accordingly, metal hydroxides with a stoichiometric proportion or, in their different drainage levels, with substoichiometric proportion Hydroxyl groups to oxides with comparatively few remaining but hydroxyl groups detectable by DRIFT-IR spectroscopy. Examples of suitable fillers are aluminum trihydroxide (ATH), Alumina hydrate (AlOOH), magnesium hydroxide, brucite, huntite, Hydromagnesite, mica and montmorillonite.
  • the proportion of the filler depends on its type, the respective base polymer and the stresses to which the compounds are subjected are exposed to the intended use. Generally the Filler in an amount of 5 to 80% by weight, advantageously 50 to 70% by weight, based on the compound applied.
  • the amount of the functional organylorganyloxysilane must be such that that the surface of the filler is sufficiently covered and hydrophobized.
  • the cable compounds according to the invention can be the usual compounds Contain additives in the usual amounts.
  • additives include UV and heat stabilizers, lubricants, Extrusion aids and peroxides called. Your share of the compound is generally less than 5% by weight.
  • the cable compounds are made by mixing the components in the Melt produced, expediently with exclusion of moisture. Therefore are the usual heatable homogenizers, z. B. kneader or, advantageous in continuous operation, extruder, in particular Twin screw extruder.
  • the components are, each for themselves or in Partial mixtures, in the specified quantity ratio heat a temperature above the melting point of the base polymer Extruder fed. Expediently, the temperature is allowed to Rise the screw end to set a lower viscosity and thereby enabling an intimate mixing.
  • the extrudates can still liquid a device for sheathing electrical conductors be fed. Alternatively, you can freeze them and then open them to shred appropriate particle sizes.
  • Example 1 Dry Liquid "from 3-aminopropyl-triethoxysilane and Flame silica
  • Example 2- Dry Liquid "from precipitated silica and N-aminoethyl-3-aminopropyl-trimethoxysilane
  • a cylindrical vessel with an outer diameter of 20 cm and one Length of 35 cm is 800 g of precipitated silica (ULTRASIL® VN3 from DEGUSSA-HÜLS AG).
  • the filling is made with dry nitrogen overlaid and the vessel closed.
  • the Batch heated to 60 ° C for 1 h.
  • the heated vessel is opened and the Content with 1,200 g N-aminoethyl-3-aminopropyltrimethoxysilane (DYNASYLAN® DAMO from DEGUSSA-HÜLS AG).
  • the vessel will be back closed and then in rotation on a roller device for 30 min transferred.
  • the product obtained in this way is superficially dry and free-flowing. It is filled into opaque containers under dry nitrogen.
  • the table shows that the silane is almost completely reversible the carrier is bound.
  • halogen-free cable compounds with flame-retardant properties Halogen Free Flame Retardant "[HFFR] Compounds
  • component quantity Aluminum hydroxide (ATH) 160 pieces Ethylene-vinyl acetate copolymer (EVA, 19% VA) 100 parts IRGANOX® 1010 (UV stabilizer) 1st chapter
  • the base polymer EVA is dried in a forced air oven at 60 ° C for one hour. When using liquid silane, this is added to the dried EVA and absorbed within one hour. Is the silane considered Dry Liquid "is used to mix the EVA.
  • the stabilizer is mixed with the ATH. EVA / silane on the one hand and ATH / stabilizer on the other hand are gravimetrically metered into the extruder.
  • the extruder temperature rises from 135 to the end of the screw 170 ° C.
  • the residence time is a maximum of 150 seconds. Bands are extruded from which test specimens are produced.

Abstract

Cable composition (I) comprises: (A) a liquid functional organylorganyloxysilane or a corresponding (co)condensate bonded to a support material, (B) a thermoplastic, polar functional group containing base polymer and (C) a reinforcing or extending mineral filler. An Independent claim is included for a cable comprising a metallic conductor sheathed in (I).

Description

Die Erfindung betrifft die Verwendung von funktionellen Organylorganyloxysilanen auf Trägerstoffen in Kabelcompounds, die bestimmte thermoplastische Basispolymere sowie Füllstoffe enthalten. Die Erfindung betrifft weiterhin die Kabelcompounds als solche sowie Kabel mit Umhüllungen aus diesen Kabelcompounds.The invention relates to the use of functional Organylorganyloxysilanen on carriers in cable compounds, the contain certain thermoplastic base polymers and fillers. The The invention further relates to the cable compounds as such and cables Envelopes from these cable compounds.

Stand der TechnikState of the art

Unter Kabelcompounds versteht man Stoffmischungen, die ein Basispolymer sowie mineralische (oder anorganische) verstärkende, streckende oder flammschützende Füllstoffe enthalten und verwendet werden, um metallische Leiter elektrisch isolierend zu umhüllen. Es ist bekannt, daß ein Zusatz von funktionellen Organylorganyloxysilanen das Dispergieren des Füllstoffs im Basispolymer erleichtert und die Haftung zwischen Basispolymer und Füllstoff verbessert. Funktionelle Organylorganyloxysilane sind in diesem Zusammenhang solche Silane, die einen über ein Kohlenstoffatom an das Siliciumatom gebundenen organischen Rest tragen, der seinerseits eine funktionelle Gruppe enthält. Die leichtere Dispergierung und die bessere Haftung dürften auf eine durch das Silan bewirkte Hydrophobierung der Oberfläche der Füllstoffteilchen zurückzuführen sein. Die bessere Haftung führt zu besseren mechanischen Eigenschaften der Kabelumhüllung.Cable compounds are mixtures of substances that are a base polymer as well as mineral (or inorganic) reinforcing, stretching or contain flame retardant fillers and used to make metallic To wrap the conductor in an electrically insulating manner. It is known that an addition of functional organylorganyloxysilanes dispersing the filler in the Base polymer facilitates and the adhesion between base polymer and filler improved. Functional organylorganyloxysilanes are in this Relationship of such silanes that attach one to the carbon atom Silicon atom bound organic residue, which in turn has a contains functional group. The easier dispersion and the better Adhesion is likely to result in the water repellency caused by the silane Surface of the filler particles can be attributed. The better liability leads to better mechanical properties of the cable sheathing.

Beispielsweise sind aus EP 0 518 057 B1 flüssige, vinylgruppenhaltige Gemische aus kettenförmigen und cyclischen Siloxanen bzw. Siloxan-Oligomeren und deren Verwendung als Vernetzungsmittel, z. B. für Hochdruckpolyethylen, in Kabelmassen bekannt. Flüssige Additive sind jedoch für die Verwender insofern problematisch, als die üblichen Einrichtungen zum Wiegen und Dosieren kleiner Mengen von Additiven nur für Feststoffe ausgelegt sind. Flüssige Kleinkomponenten müssen deshalb manuell verwogen und dosiert werden. Dies ist in der Regel mit höheren Kosten verbunden und stellt eine zusätzliche Fehlerquelle dar.For example, EP 0 518 057 B1 contains liquid vinyl groups Mixtures of chain and cyclic siloxanes or siloxane oligomers and their use as crosslinking agents, e.g. B. for High pressure polyethylene, known in cable masses. However, liquid additives are problematic for users in that the usual facilities for Weighing and dosing small amounts of additives for solids only are designed. Liquid small components must therefore be manually be weighed and dosed. This is usually at a higher cost connected and represents an additional source of error.

Eine bekannte Lösung dieses Problems besteht darin, flüssige funktionelle Organosilane an hochadsorbierende oder -absorbierende Feststoffe zu binden, die dann als

Figure 00020001
trockene Flüssigkeiten" (oder Dry Liquids") mit den üblichen Einrichtungen ohne weiteres gewogen und zudosiert werden können. So beschreibt DE 195 03 779 A1 eine Kombination aus Kieselsäure und trans-Polyoctenamer als Trägerstoff für flüssige Kautschukchemikalien, darunter Vinyl- und Mercaptosilane sowie Schwefelsilane. In DE 44 35 311 A1 werden sogenannte Verstärkungsadditive aus oligomeren und/oder polymeren schwefelhaltigen Organylorganyloxysilanen und halbaktiven, aktiven und/oder hochaktiven Rußen als Trägerstoff beschrieben, die sich zur Verwendung in Kautschukmischungen oder -massen sowie in Kunststoffmischungen eignen. In beiden genannten Schriften werden allerdings Kabelcompounds nicht erwähnt. EP 0 428 073 B1 offenbart ein Verfahren, bei dem man (i) ein Basispolymer, (ii) ein schwammartiges Polymer oder ein quellbares Polymer mit einem darin enthaltenen (Meth)acryloxy-funktionellen Organosilan und (iii) einen freie Radikale liefernden Stoff mischt und die Mischung aufschmilzt und homogenisiert. Auch dieses Verfahren ist nicht auf die Verwendung der homogenisierten Mischungen für Kabelcompounds gerichtet. Dagegen heißt es in WO 97/07165, daß die dort beschriebenen festen Mischungen aus funktionellen Organosilanen und bestimmten großoberflächigen Kieselsäuren mit niedriger Oberflächenenergie u. a. bei der Isolierung von Drähten und Kabeln eingesetzt werden können.A known solution to this problem is to bind liquid functional organosilanes to highly adsorbing or absorbing solids, which are then used as
Figure 00020001
dry liquids "(or Dry liquids ") can be easily weighed and metered in with the usual equipment. Thus, DE 195 03 779 A1 describes a combination of silica and trans-polyoctenamer as a carrier for liquid rubber chemicals, including vinyl and mercaptosilanes and sulfur silanes. In DE 44 35 311 A1, so-called reinforcing additives composed of oligomeric and / or polymeric sulfur-containing organylorganyloxysilanes and semi-active, active and / or highly active carbon blacks as a carrier, which are suitable for use in rubber mixtures or compositions and in plastic mixtures, are not mentioned in either of the cited documents 0 428 073 B1 discloses a process in which (i) a base polymer, (ii) a sponge-like polymer or a swellable polymer are mixed with a (meth) acryloxy-functional organosilane contained therein and (iii) a free radical-donating substance and the The mixture melts and homogenizes. This method is also not aimed at using the homogenized mixtures for cable compounds. In contrast, WO 97/07165 states that the solid mixtures of functional organosilanes and certain large-area silicas with low surface energy described therein can be used, inter alia, for the insulation of wires and cables.

Einer der Gegenstände der gegenwärtigen Erfindung ist die Verwendung (1) eines an einen Trägerstoff gebundenen flüssigen funktionellen Organylorganyloxysilans oder eines an einen Trägerstoff gebundenen flüssigen (Co)kondensats eines funktionellen Organylorganyloxysilans zur Herstellung von Kabelcompounds, die ein (2) thermoplastisches, polare funktionelle Gruppen tragendes Basispolymer und (3) einen verstärkenden oder streckenden mineralischen Füllstoff enthalten.One of the objects of the present invention is the use (1) a liquid functional bound to a carrier Organylorganyloxysilans or one bound to a carrier liquid (co) condensate of a functional organylorganyloxysilane for Manufacture of cable compounds containing one (2) thermoplastic, polar functional group-bearing base polymer and (3) a reinforcing one or stretching mineral filler.

Ein anderer Gegenstand der Erfindung sind Kabelcompounds, die (1) ein an einen Trägerstoff gebundenes flüssiges funktionelles Organylorganyloxysilan oder ein an einen Trägerstoff gebundenes flüssiges (Co)kondensat eines funktionellen Organylorganyloxysilans, (2) ein thermoplastisches, polare funktionelle Gruppen tragendes Basispolymer und (3) einen verstärkenden, streckenden oder flammschützenden mineralischen Füllstoff enthalten.Another object of the invention are cable compounds, which (1) a a carrier-bound liquid functional organylorganyloxysilane or a liquid (co) condensate bound to a carrier functional organylorganyloxysilane, (2) a thermoplastic, polar functional group-bearing base polymer and (3) a reinforcing, stretching or flame retardant mineral filler.

Ein weiterer Gegenstand der Erfindung sind Kabel, deren metallische Leiter mit einem solchen Kabelcompound umhüllt sind.Another object of the invention are cables, their metallic conductors are covered with such a cable compound.

Funktionelle OrganylorganyloxysilaneFunctional organylorganyloxysilanes

Funktionelle Organylorganyloxysilane im Sinne der Erfindung enthalten mindestens einen über ein Kohlenstoffatom an ein Siliciumatom gebundenen organischen Rest (Organylrest), z. B. einen geradkettigen oder verzweigten Alkylenrest mit 2 bis 6 Kohlenstoffatomen, der mindestens eine funktionelle Gruppe trägt. Die funktionelle Gruppe kann z. B. eine Hydroxyl-, Nitril-, Carbonyl-, Carboxyl-, Acyl-, Acyloxy-, Carboalkoxy-, Mercapto-, Sulfan- (Xx), Epoxy- oder eine gegebenfalls durch ein oder zwei Kohlenwasserstoffreste mit 1 bis 6 Kohlenstoffatomen substituierte Aminogruppe sowie ein Halogenatom, insbesondere ein Chloratom oder eine olefinische Doppel- oder eine C-C-Dreifachbindung sein. Der organische Rest kann auch mehrere gleiche oder verschiedene funktionelle Gruppen enthalten, z. B. zwei Aminogruppen oder einen Acylrest mit olefinischer Doppelbindung, wie den (Meth)acryloxyrest. Die funktionellen Organylorganyloxysilane enthalten andererseits mindestens einen hydrolysierbaren Rest, vorzugsweise drei hydrolysierbare Reste, z. B. einen oder mehrere Alkoxy- oder Alkoxyalkoxyreste mit jeweils 1 bis 6 Kohlenstoffatomen. Die funktionellen Organylorganyloxysilane können weiterhin ein oder zwei weitere, nichtfunktionelle und nichthydrolysierbare Reste enthalten, z. B. einen Kohlenwasserstoffrest mit bis zu 8 Kohlenstoffatomen, wie Methyl, Propyl oder n-Hexyl.Functional organylorganyloxysilanes in the sense of the invention contain at least one organic radical bonded to a silicon atom via a carbon atom (organyl radical), for. B. a straight-chain or branched alkylene radical having 2 to 6 carbon atoms, which carries at least one functional group. The functional group can e.g. B. a hydroxyl, nitrile, carbonyl, carboxyl, acyl, acyloxy, carboalkoxy, mercapto, sulfane (X x ), epoxy or one optionally substituted by one or two hydrocarbon radicals having 1 to 6 carbon atoms Amino group and a halogen atom, in particular a chlorine atom or an olefinic double or a CC triple bond. The organic radical can also contain several identical or different functional groups, e.g. B. two amino groups or an acyl radical with olefinic double bond, such as the (meth) acryloxy radical. The functional organylorganyloxysilanes on the other hand contain at least one hydrolyzable radical, preferably three hydrolyzable radicals, e.g. B. one or more alkoxy or alkoxyalkoxy radicals each having 1 to 6 carbon atoms. The functional organylorganyloxysilanes can further contain one or two further, non-functional and non-hydrolyzable radicals, e.g. B. a hydrocarbon radical with up to 8 carbon atoms, such as methyl, propyl or n-hexyl.

Beispiele für geeignete funktionelle Organylorganyloxysilane sind Vinyltrimethoxysilan, Vinyltriethoxysilan, Vinyltris(2-methoxy-ethoxy)silan, 3-Mercaptopropyl-trimethoxysilan, 3-Glycidyloxypropyl-trimethoxysilan, 3-Glycidyloxypropyltriethoxysilan, 3-Methacryloxypropyl-triethoxysilan, 3-Methacryloxypropyl-trimethoxysilan und 3-Methacryloxypropyltris(2-methoxy-ethoxy)silan. Bevorzugte funktionelle Organylorganyloxysilane sind gegebenfalls durch 1 oder 2 Alkylreste mit jeweils 1 bis 6 Kohlenstoffatomen N-substituierte Aminoorganylorganyloxysilane, weil die Umhüllungen aus den entsprechenden Compounds herausragende mechanische Eigenschaften (wie Zugfestigkeit, Bruchdehnung, Reißfestigkeit und E-Modul) und elektrische Eigenschaften (wie elektrischer Verlustfaktor, Dielektrizitätskonstante) aufweisen. Von den geeigneten Aminoorganylorganyloxysilanen seien z. B. 3-Aminopropyl-trimethoxysilan, 3-Aminopropyltriethoxysilan, 3-Aminopropyl-methyl-diethoxysilan, N-Aminoethyl-3-aminopropyltrimethoxysilan, triamino-funktionelles Propyltrimethoxysilan (N-Trimethoxysilylpropyl-diethylentriamin, auch als DYNASYLAN® TRIAMO bezeichnet) und (N'-Aminoethyl)-N-aminoethyl-3-aminopropylsilan genannt.Examples of suitable functional organylorganyloxysilanes are Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-methacryloxypropyl-triethoxysilane, 3-methacryloxypropyl-trimethoxysilane and 3-methacryloxypropyl tris (2-methoxy-ethoxy) silane. Preferred functional organylorganyloxysilanes are optionally by 1 or 2 alkyl radicals each having 1 to 6 carbon atoms N-substituted aminoorganylorganyloxysilane because the coatings from the corresponding compounds outstanding mechanical properties (such as Tensile strength, elongation at break, tensile strength and modulus of elasticity) and electrical Properties (such as electrical loss factor, dielectric constant) exhibit. Of the suitable aminoorganylorganyloxysilanes z. B. 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyl-diethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, triamino-functional Propyltrimethoxysilane (N-trimethoxysilylpropyl-diethylenetriamine, also called DYNASYLAN® TRIAMO) and (N'-aminoethyl) -N-aminoethyl-3-aminopropylsilane called.

Anstelle eines funktionellen Organylorganyloxysilans kann man auch ein Gemisch aus einem oder mehreren dieser Stoffe einsetzen. Weiterhin lassen sich mit gleichem Erfolg (Co)kondensate der funktionellen Organylorganyloxysilane mit gewichtsdurchschnittlichen Molgewichten bis zu etwa 10.000 erfindungsgemäß verwenden. Hierunter werden Kondensate (oder Oligomere) der funktionellen Organylorganyloxysilane bzw. Cokondensate dieser Stoffe mit anderen, nichtfunktionellen Organylorganyloxysilanen oder Organyloxysilanen verstanden. Von diesen seien beispielsweise Methyltrimethoxysilan, Methyltriethoxysilan, n-Propyltrimethoxysilan, n-Propyltriethoxysilan, i-Butyltrimethoxysilan, i-Butyltriethoxysilan, Octyltriethoxysilan, Hexadecyltrimethoxysilan und Tetraethoxysilan genannt. Man stellt die (Co)kondensate z. B. in bekannter Weise durch Hydrolyse bzw. Cohydrolyse der Silane mit begrenzten Mengen Wasser und anschließender Kondensation der Silanole her. In den Cokondensaten sollte der Anteil der (Amino)-funktionellen Organylorganyloxysilane mindestens 10 Gew.-%, vorteilhaft mindestens 50 Gew.-% betragen.Instead of a functional organylorganyloxysilane you can also use a Use a mixture of one or more of these substances. Continue to leave with the same success (co) condensate the functional Organylorganyloxysilane with weight average molecular weights up to use about 10,000 according to the invention. This includes condensates (or oligomers) of the functional organylorganyloxysilanes or Cocondensates of these substances with other, non-functional Organylorganyloxysilanen understood or Organyloxysilanen. Of these Examples include methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-butyltrimethoxysilane, i-butyltriethoxysilane, Octyltriethoxysilane, hexadecyltrimethoxysilane and Called tetraethoxysilane. The (co) condensates are z. B. in known Way by hydrolysis or cohydrolysis of the silanes with limited amounts Water and subsequent condensation of the silanols. In the Cocondensates should be the proportion of (amino) functional Organylorganyloxysilane at least 10 wt .-%, advantageously at least 50% by weight.

Weiterhin ist es möglich, statt eines Cokondensats das funktionelle Organylorganyloxysilan zusammen mit einem nichtfunktionellen Organylorganyloxysilan oder Organyloxysilan in dem für die Cokondensate angegebenen Mengenverhältnis einzu setzen.It is also possible to use the functional one instead of a cocondensate Organylorganyloxysilan together with a non-functional Organylorganyloxysilan or Organyloxysilan in the for the cocondensates to use the specified ratio.

Wenn in der Folge vereinfachend von funktionellen Organylorganyloxysilanen gesprochen wird, sind immer bei Raumtemperatur flüssige Stoffe gemeint, wobei die erwähnten (Co)kondensate eingeschlossen sind.If in the following simplifying from functional organylorganyloxysilanes spoken are always liquids at room temperature, the (co) condensates mentioned being included.

Trägerstoffe für die funktionellen OrganylorganyloxysilaneCarriers for the functional organylorganyloxysilanes

Als Trägerstoffe eignen sich eine Vielzahl von an sich als Trägerstoffe bekannten Materialien. Im einzelnen seien erwähnt:

  • Flammkieselsäure, die im großtechnischen Maßstab durch kontinuierliche Hydrolyse von Siliciumtetrachlorid in einer Knallgasflamme hergestellt wird. Dabei wird das Siliciumtetrachlorid verdampft und reagiert anschließend innerhalb der Flamme mit dem aus der Knallgasreaktion stammenden Wasser spontan und quantitativ. Die Flammkieselsäure ist eine amorphe Modifikation des Siliciumdioxids in Form eines lockeren, bläulichen Pulvers. Die Teilchengröße liegt im Bereich von wenigen Nanometern, die spezifische Oberfläche ist daher groß und beträgt im allgemeinen 50 bis 600 m2/g. Die Teilchen sind nicht porös, die Aufnahme der funktionellen Organylorganyloxysilane beruht allein auf Adsorption.
  • Fällungskieselsäuren werden im allgemeinen aus Natronwasserglas-Lösungen durch Neutralisation mit anorganischen Säuren unter kontrollierten Bedingungen hergestellt. Nach Abtrennung von der flüssigen Phase, Auswaschen und Trocknen wird das Rohprodukt feingemahlen, z. B. in Dampfstrahlmühlen. Auch Fällungskieselsäure ist ein amorphes Siliciumdioxid, das aber in der Regel eine kleinere spezifische Oberfläche hat, meist im Bereich von 50 bis 150 m2/g. Fällungskieselsäure weist im Gegensatz zur Flammkieselsäure eine gewisse Porosität auf (ca. 10 %). Die Aufnahme der funktionellen Organylorganyloxysilane erfolgt daher sowohl durch Adsorption an der Oberfläche als auch durch Absorption in den Poren.
  • Calciumsilikat wird technisch durch Zusammenschmelzen von Quarz oder Kieselgur mit Calciumcarbonat bzw. -oxid oder durch Fällung von wäßrigen Natriummetasilikat-Lösungen mit wasserlöslichen Calciumverbindungen hergestefit. Das sorgfältig getrocknete Produkt ist porös und kann Wasser oder Öle bis zur fünffachen Gewichtsmenge aufnehmen.
  • Poröses Polyethylen wird durch spezielle Polymerisationstechniken und -verfahren hergestellt und z. B. von AKZO und DSM in technischen Mengen angeboten. Die Teilchengrößen liegen zwischen 3 und <1 mm, die Porosität beträgt über 50 %, so daß die Produkte große Mengen an funktionellen Organylorganyloxysilanen zu absorbieren vermögen, ohne ihre Freifließ-Eigenschaften zu verlieren.
  • Als Wachse eignen sich insbesondere Polyolefinwachse auf Basis von LDPE (verzweigt, mit langen Seitenketten). Der Schmelz- und Erstarrungspunkt liegt in der Regel zwischen 90 und 120 °C. Die Wachse lassen sich in der niedrigviskosen Schmelze gut mit den funktionellen Organylorganyloxysilanen mischen. Die erstarrte Mischung ist hinreichend hart, so daß sie granuliert werden kann.
  • Ruß in seinen verschiedenen Handelsformen eignet sich z. B. zur Herstellung von schwarzen Kabelummantelungen. Ruß wird hauptsächlich in Verbindung mit schwefelhaltigen Silanen verwendet.
A variety of materials known per se as carriers are suitable as carriers. The following should be mentioned in detail:
  • Flame silica , which is produced on an industrial scale by the continuous hydrolysis of silicon tetrachloride in a detonating gas flame. The silicon tetrachloride is vaporized and then reacts spontaneously and quantitatively within the flame with the water from the detonating gas reaction. Flame silica is an amorphous modification of the silica in the form of a loose, bluish powder. The particle size is in the range of a few nanometers, the specific surface is therefore large and is generally 50 to 600 m 2 / g. The particles are not porous, the absorption of the functional organylorganyloxysilanes is based solely on adsorption.
  • Precipitated silicas are generally produced from sodium silicate solutions by neutralization with inorganic acids under controlled conditions. After separation from the liquid phase, washing and drying, the crude product is finely ground, e.g. B. in steam mills. Precipitated silica is also an amorphous silicon dioxide, but it usually has a smaller specific surface, usually in the range from 50 to 150 m 2 / g. In contrast to flame silica, precipitated silica has a certain porosity (approx. 10%). The functional organylorganyloxysilanes are therefore taken up both by adsorption on the surface and by absorption in the pores.
  • Calcium silicate is manufactured industrially by melting quartz or diatomaceous earth with calcium carbonate or oxide or by precipitation of aqueous sodium metasilicate solutions with water-soluble calcium compounds. The carefully dried product is porous and can absorb water or oils up to five times the amount by weight.
  • Porous polyethylene is produced by special polymerization techniques and processes and z. B. offered by AKZO and DSM in technical quantities. The particle sizes are between 3 and <1 mm, the porosity is over 50%, so that the products are able to absorb large amounts of functional organylorganyloxysilanes without losing their free-flowing properties.
  • Polyolefin waxes based on LDPE (branched, with long side chains) are particularly suitable as waxes . The melting and solidification point is usually between 90 and 120 ° C. The waxes can be mixed well with the functional organylorganyloxysilanes in the low-viscosity melt. The solidified mixture is sufficiently hard that it can be granulated.
  • Soot in its various forms of trade is suitable for. B. for the production of black cable sheaths. Carbon black is mainly used in connection with sulfur-containing silanes.

Herstellung der
Figure 00070001
Dry Liquids" aus funktionellen Organylorganyloxysilanen und Trägerstoffen Manufacturing the
Figure 00070001
Dry Liquids "from functional organylorganyloxysilanes and carriers

Zur Herstellung der Dry Liquids" stehen unter anderem folgende Methoden zur Verfügung:

  • Mineralische Träger oder poröse Polymere werden vorgewärmt, z. B. in einem Wärmeschrank auf 60 °C, und in einen zylindrischen Behälter gegeben, der mit trockenem Stickstoff gespült und gefüllt wurde. Anschließend wird das funktionelle Organylorganyloxysilan zugegeben und der Behälter in eine Rollvorrichtung gelegt, durch die er ca. 30 min lang in Rotation versetzt wird. Nach dieser Zeit hat sich aus dem Trägerstoff und dem flüssigen funktionellen Organylorganyloxysilan ein rieselfähiges, oberflächlich trockenes Granulat gebildet, das zweckmäßig unter Stickstoff in lichtundurchlässigen Behältern gelagert wird. Alternativ kann man den erwärmten Trägerstoff in einen mit trockenem Stickstoff gespülten und gefüllten Mischer, z. B. einen Pflugscharmischer vom Typ LÖDIGE oder einen Propellermischer vom Typ HENSCHEL. Das Mischwerk wird in Betrieb genommen und das funktionelle Organylorganyloxysilan nach Erreichen der maximalen Mischleistung □ ber eine Düse eingesprüht. Nach beendeter Zugabe wird noch ca. 30 min homogenisiert und danach das Produkt, z. B. mittels einer mit trockenem Stickstoff betriebenen pneumatischen Förderung, in lichtundurchlässige, mit Stickstoff gefüllte Behälter abgefüllt.
  • Wachs/Polyethylenwachs in pelletierter Form mit einem Schmelzpunkt von 90 bis 120 °C wird in einem beheizbaren Gefäß mit Rührer, Rückflußkühler und Flüssigkeitszugabevorrichtung portionsweise aufgeschmolzen und im schmelzflüssigen Zustand gehalten. Während des gesamten Herstellprozesses wird trockener Stickstoff durch die Apparatur geleitet. Über die Flüssigkeitszugabevorrichtung wird nach und nach das flüssige funktionelle Organylorganyloxysilan in die Schmelze gegeben und durch intensives Rühren mit dem Wachs vermischt. Danach wird die Schmelze zum Erstarren in Formen abgelassen, und das erstarrte Produkt wird granuliert. Alternativ kann man die Schmelze auf ein gekühltes Formband auftropfen lassen, auf dem sie in gebrauchsfreundlicher Pastillenform erstarrt.
To make the Dry Liquids "include the following methods:
  • Mineral carriers or porous polymers are preheated, e.g. B. in an oven at 60 ° C, and placed in a cylindrical container which was flushed with dry nitrogen and filled. The functional organylorganyloxysilane is then added and the container placed in a rolling device, by means of which it is rotated for about 30 minutes. After this time, a free-flowing, superficially dry granulate has formed from the carrier substance and the liquid functional organylorganyloxysilane, which is expediently stored under nitrogen in opaque containers. Alternatively, the heated carrier can be flushed and filled with dry nitrogen in a mixer, e.g. B. a ploughshare mixer type LÖDIGE or a propeller mixer type HENSCHEL. The mixer is put into operation and the functional organylorganyloxysilane is sprayed through a nozzle after reaching the maximum mixing capacity. After the addition is complete, the mixture is homogenized for about 30 minutes and then the product, for. B. by means of a pneumatic nitrogen operated operated, filled in opaque, filled with nitrogen containers.
  • Wax / polyethylene wax in pelletized form with a melting point of 90 to 120 ° C. is melted in portions in a heatable vessel with stirrer, reflux condenser and liquid addition device and kept in the molten state. Dry nitrogen is passed through the apparatus throughout the manufacturing process. The liquid functional organylorganyloxysilane is gradually added to the melt via the liquid addition device and mixed with the wax by intensive stirring. The melt is then discharged into molds for solidification and the solidified product is granulated. Alternatively, you can let the melt drip onto a cooled forming belt, on which it solidifies in a user-friendly pastille shape.

BasispolymereBase polymers

Es ist ein wichtiges Merkmal der Erfindung, daß das Basispolymer der Kabelcompounds thermoplastisch ist und polare Gruppen trägt. Derartige Basispolymere ergeben z. B. ein verbessertes Brandverhalten (d. h. geringere Entflammbarkeit und Rauchgasdichte) und erhöhen das Füllstoffaufnahmevermögen. Polare Gruppen sind z. B. Hydroxyl-, Nitril-, Carbonyl-, Carboxyl-, Acyl-, Acyloxy-, Carboalkoxygruppen oder Aminogruppen sowie Halogenatome, insbesondere Chloratome. Nicht polar sind olefinische Doppelbindungen oder C-C-Dreifachbindungen. Geeignete Polymere sind neben Polyvinylchlorid Copolymere aus einem oder mehreren Olefinen und einem oder mehreren Comonomeren, die polare Gruppen enthalten, z. B. Vinylacetat, Vinylpropionat, (Meth)acrylsäure, (Meth)acrylsäuremethylester, (Meth)acrylsäureethylester, (Meth)acrylsäurebutylester, Acrylnitril. In den Copolymeren finden sich die polaren Gruppen im allgemeinen in Mengen von 0,1 bis 50 Mol-%, vorzugsweise von 5 bis 30 Mol-%, bezogen auf die Polyolefinbausteine. Gut geeignete Basispolymere sind Ethylen-Vinylacetat-Copolymere. Beispielsweise enthält ein geeignetes handelsübliches Copolymer 19 Mol-% Vinylacetat- und 81 Mol-% Ethylenbausteine.It is an important feature of the invention that the base polymer of the Cable compounds is thermoplastic and carries polar groups. Such Base polymers result in e.g. B. Improved fire behavior (i.e. lower Flammability and smoke density) and increase the filler absorption capacity. Polar groups are e.g. B. hydroxyl, nitrile, carbonyl, Carboxyl, acyl, acyloxy, carboalkoxy groups or amino groups and Halogen atoms, especially chlorine atoms. Olefinic are not polar Double bonds or C-C triple bonds. Suitable polymers are in addition to polyvinyl chloride copolymers of one or more olefins and one or more comonomers containing polar groups, e.g. B. Vinyl acetate, vinyl propionate, (meth) acrylic acid, (meth) acrylic acid methyl ester, (Meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, acrylonitrile. In the The polar groups are generally found in copolymers in amounts of 0.1 to 50 mol%, preferably from 5 to 30 mol%, based on the Polyolefin building blocks. Suitable base polymers are ethylene-vinyl acetate copolymers. For example, contains a suitable commercial one Copolymer 19 mole% vinyl acetate and 81 mole% ethylene building blocks.

FüllstoffeFillers

Die Füllstoffe sind mineralisch (oder anorganisch) und können verstärkend oder lediglich streckend sein. Sie tragen zumindest auf ihren Oberflächen Gruppen, die mit den Organyloxygruppen des funktionellen Organylorganyloxysilans reagieren. Im Ergebnis wird dadurch das Siliciumatom mit dem daran gebundenen funktionellen Organylrest auf der Oberfläche chemisch fixiert. Solche Gruppen auf der Oberfläche des Füllstoffs sind insbesondere Hydroxylgruppen. Bevorzugte Füllstoffe sind dementsprechend Metallhydroxide mit stöchiometrischem Anteil oder, in ihren unterschiedlichen Entwässerungsstufen, mit substöchiometrischem Anteil an Hydroxylgruppen bis hin zu Oxiden mit vergleichsweise wenigen restlichen, aber durch DRIFT-IR-Spektroskopie nachweisbaren Hydroxylgruppen. Beispiele für geeignete Füllstoffe sind Aluminiumtrihydroxid (ATH), Aluminiumoxidhydrat (AlOOH), Magnesiumhydroxid, Brucit, Huntit, Hydromagnesit, Glimmer und Montmorillonit.The fillers are mineral (or inorganic) and can be reinforcing or just stretching. At least they wear on their surfaces Groups associated with the organyloxy groups of the functional Organylorganyloxysilans react. The result is that Silicon atom with the attached functional organyl residue on the Surface chemically fixed. Such groups on the surface of the filler are especially hydroxyl groups. Preferred fillers are accordingly, metal hydroxides with a stoichiometric proportion or, in their different drainage levels, with substoichiometric proportion Hydroxyl groups to oxides with comparatively few remaining but hydroxyl groups detectable by DRIFT-IR spectroscopy. Examples of suitable fillers are aluminum trihydroxide (ATH), Alumina hydrate (AlOOH), magnesium hydroxide, brucite, huntite, Hydromagnesite, mica and montmorillonite.

Mengenverhältnisse der verschiedenen Komponenten in den KabelcompoundsQuantity ratios of the various components in the cable compounds

Das Mengenverhältnis von funktionellem Organylorganyloxysilan zu Trägerstoff kann, je nach der Art und dem Aufnahmevermögen des Trägerstoffs und abhängig von dem jeweiligen Silan, in weiten Grenzen schwanken. Durch orientierende Versuche läßt sich unschwer ermitteln, welche Mengen an dem gewünschten funktionellen Organylorganyloxysilan ein bestimm ter Trägerstoff aufzunehmen vermag, ohne seine freifließenden Eigenschaften zu verlieren. Im allgemeinen wendet man 20 bis 80 Gew.-% funktionelles Organylorganyloxysilan, bezogen auf den Trägerstoff, an.The quantitative ratio of functional organylorganyloxysilane to Depending on the type and the absorption capacity of the Carrier and depending on the particular silane, within wide limits vary. It is easy to determine by means of orientation tests what amounts of the desired functional organylorganyloxysilane a certain carrier is able to absorb without its free flowing Properties to lose. In general, 20 to 80% by weight is used. functional organylorganyloxysilane, based on the carrier.

Der Anteil des Füllstoffs hängt von dessen Art, dem jeweiligen Basispolymer und den Beanspruchungen ab, denen die Compounds bei bestimmungsgemäßer Verwendung ausgesetzt sind. Im allgemeinen wird der Füllstoff in einer Menge von 5 bis 80 Gew.-%, vorteilhaft von 50 bis 70 Gew.-%, bezogen auf das Compound, angewandt.The proportion of the filler depends on its type, the respective base polymer and the stresses to which the compounds are subjected are exposed to the intended use. Generally the Filler in an amount of 5 to 80% by weight, advantageously 50 to 70% by weight, based on the compound applied.

Die Menge des funktionellen Organylorganyloxysilans muß so bemessen sein, daß die Oberfläche des Füllstoffs hinreichend belegt und hydrophobiert wird. The amount of the functional organylorganyloxysilane must be such that that the surface of the filler is sufficiently covered and hydrophobized.

Dazu genügen verhältnismäßig kleine Mengen. Im allgemeinen setzt man 0,1 bis 5 Gew.-% und zweckmäßig 0,5 bis 2 Gew.-% funktionelles Organylorganyloxysilan, bezogen auf den Füllstoff, ein.Relatively small amounts are sufficient for this. Generally 0.1 is used up to 5 wt .-% and expediently 0.5 to 2 wt .-% functional Organylorganyloxysilan, based on the filler.

Für alle genannten Mengenverhältnisse gilt, daß sich die optimalen Werte für einen gegebenen Verwendungszweck und gegebene Komponenten durch orientierende Versuch unschwer ermitteln lassen.For all quantitative ratios mentioned, the optimal values for given use and components easy to find an orientation test.

Weitere Komponenten in den KabelcompoundsOther components in the cable compounds

Die Kabelcompounds nach der Erfindung können die für Compounds üblichen Zusatzstoffe in den üblichen Mengen enthalten. Von diesen Zusatzstoffen seien beispielsweise UV- und Hitzestabilisatoren, Gleitmittel, Extrudierhilfsmittel und Peroxide genannt. Ihr Anteil an dem Compound liegt im allgemeinen unter 5 Gew.%.The cable compounds according to the invention can be the usual compounds Contain additives in the usual amounts. Of these additives Examples include UV and heat stabilizers, lubricants, Extrusion aids and peroxides called. Your share of the compound is generally less than 5% by weight.

Herstellung der Kabelcompounds aus Basispolymer, Füllstoff undManufacture of cable compounds from base polymer, filler and Dry Liquid"Dry Liquid"

Die Kabelcompounds werden durch Mischen der Komponenten in der Schmelze hergestellt, zweckmäßig unter Feuchtigkeitsausschluß. Dafür eignen sich die üblichen heizbaren Homogenisierapparate, z. B. Kneter oder, vorteilhaft bei kontinuierlichem Betrieb, Extruder, insbesondere Doppelschneckenextruder. Die Komponenten werden, jeweils für sich oder in Teilmischungen, in dem vorgegebenen Mengenverhältnis laufend dem auf eine Temperatur oberhalb des Schmelzpunkts des Basispolymers erhitzen Extruder zugeführt. Zweckmäßig läßt man die Temperatur zum Schneckenende hin ansteigen, um eine niedrigere Viskosität einzustellen und dadurch eine innige Durchmischung zu ermöglichen. Die Extrudate können noch flüssig einer Vorrichtung zur Ummantelung von elektrischen Leitern zugeführt werden. Alternativ kann man sie erstarren lassen, um sie dann auf zweckentsprechende Teilchengrößen zu zerkleinern. The cable compounds are made by mixing the components in the Melt produced, expediently with exclusion of moisture. Therefore are the usual heatable homogenizers, z. B. kneader or, advantageous in continuous operation, extruder, in particular Twin screw extruder. The components are, each for themselves or in Partial mixtures, in the specified quantity ratio heat a temperature above the melting point of the base polymer Extruder fed. Expediently, the temperature is allowed to Rise the screw end to set a lower viscosity and thereby enabling an intimate mixing. The extrudates can still liquid a device for sheathing electrical conductors be fed. Alternatively, you can freeze them and then open them to shred appropriate particle sizes.

Die folgenden Beispiele sollen die Erfindung weiter erläutern, nicht aber ihren Anwendungsbereich begrenzen, wie er in den Patentansprüchen dargelegt ist.The following examples are intended to explain the invention further, but not its Limit the scope as set out in the claims.

Beispiel 1 -Example 1 - Dry Liquid" aus 3-Aminopropyl-triethoxysilan und FlammkieselsäureDry Liquid "from 3-aminopropyl-triethoxysilane and Flame silica

In einen Labormischer vom Typ HENSCHEL FM/A 10 mit einem Fassungsvermögen von ca. 9 Liter werden 500 g Flammkieselsäure (AEROSIL® 200) gegeben, und der Mischer wird in Gang gesetzt. Die Drehzahl des Mischwerkzeugs wird auf 400 U/min eingestellt. Man ersetzt zunächst über die Dosiervorrichtung die Luft durch trockenen Stickstoff. Danach wird die Flammkieselsäure über den Doppelmantel des Mischgefäßes mittels Thermostat und Wärmeträgeröl auf 50 °C temperiert. Nach ca. 30 min wird über die Dosiervorrichtung des Mischers 3-Aminopropyl-triethoxysilan (DYNASYLAN® AMEO von DEGUSSA-HÜLS AG) zudosiert, und zwar 50 g/min, insgesamt 1.500 g. Nach Beendigung der Zugabe wird die Wärmezufuhr eingestellt und das Mischgut noch 30 min gemischt. Danach wird das Mischgut, das Dry Liquid", dem Mischer entnommen und unter Stickstoff in lichtundurchlässige Behälter abgefüllt.In a laboratory mixer of the type HENSCHEL FM / A 10 with a capacity of approx. 9 liters, 500 g of flame silicic acid (AEROSIL® 200) are placed and the mixer is started. The speed of the mixing tool is set to 400 rpm. The air is first replaced by dry nitrogen via the metering device. The flame silica is then heated to 50 ° C via the double jacket of the mixing vessel using a thermostat and thermal oil. After approx. 30 min, 3-aminopropyl-triethoxysilane (DYNASYLAN® AMEO from DEGUSSA-HÜLS AG) is metered in via the metering device of the mixer, namely 50 g / min, a total of 1,500 g. After the addition has ended, the supply of heat is stopped and the material to be mixed is mixed for a further 30 min. After that, the mix that Dry Liquid ", taken from the mixer and filled into opaque containers under nitrogen.

Beispiel 2-Example 2- Dry Liquid" aus Fällungskieselsäure und N-Aminoethyl-3-aminopropyl-trimethoxysilanDry Liquid "from precipitated silica and N-aminoethyl-3-aminopropyl-trimethoxysilane

In ein zylindrisches Gefäß mit einem Außendurchmesser von 20 cm und einer Länge von 35 cm werden 800 g Fällungskieselsäure (ULTRASIL® VN3 von DEGUSSA-HÜLS AG) eingefüllt. Die Füllung wird mit trockenem Stickstoff überlagert und das Gefäß verschlossen. In einem Wärmeschrank wird der Ansatz 1 h auf 60 °C erwärmt. Das erwärmte Gefäß wird geöffnet und der Inhalt mit 1.200 g N-Aminoethyl-3-aminpropyl-trimethoxysilan (DYNASYLAN® DAMO von DEGUSSA-HÜLS AG) versetzt. Das Gefäß wird wieder geschlossen und anschließend auf einer Walzenvorrichtung 30 min in Rotation versetzt. Das so erhaltene Produkt ist oberflächlich trocken und rieselfähig. Es wird unter trockenem Stickstoff in lichtundurchlässige Behälter abgefüllt. In a cylindrical vessel with an outer diameter of 20 cm and one Length of 35 cm is 800 g of precipitated silica (ULTRASIL® VN3 from DEGUSSA-HÜLS AG). The filling is made with dry nitrogen overlaid and the vessel closed. In a heating cabinet, the Batch heated to 60 ° C for 1 h. The heated vessel is opened and the Content with 1,200 g N-aminoethyl-3-aminopropyltrimethoxysilane (DYNASYLAN® DAMO from DEGUSSA-HÜLS AG). The vessel will be back closed and then in rotation on a roller device for 30 min transferred. The product obtained in this way is superficially dry and free-flowing. It is filled into opaque containers under dry nitrogen.

Beispiel 3 - Bestimmung des extrahierbaren Anteils einesExample 3 - Determination of the extractable fraction of a Dry Liquids"Dry liquids "

In die Extraktionshülse einer 100-ml-Soxhlet-Extraktionsapparatur werden jeweils 30 g des Dry Liquid" gegeben, und in den Kolben werden 180 ml trockenes, analysenreines Methylethylketon gefüllt. Das Methylethylketon wird zum Sieden erhitzt und das Dry Liquid" über 2 h extrahiert. Die Extraktionshülse mit dem Extraktionsrückstand wird getrocknet und gewogen. Der Gewichtsverlust wird als extrahierbares Silan" berechnet. Die Ergebnisse gehen aus der folgenden Tabelle 1 hervor. Dry Liquid" Silan-Gehalt im Dry Liquid" Extraktionsrückstand Extrahierbares Silan" [%] [g/30 g] [g/30 g] [g/30 g] [%] Beispiel 1 75 22,5 7,9 22,1 98,2 Beispiel 2 60 18,0 12,8 17,2 95,6 In the extraction sleeve of a 100 ml Soxhlet extraction apparatus, 30 g of the Dry Liquid "and 180 ml of dry, analytically pure methyl ethyl ketone are filled into the flask. The methyl ethyl ketone is heated to boiling and the Dry Liquid "extracted over 2 h. The extraction thimble with the extraction residue is dried and weighed. The weight loss is considered extractable silane ". The results are shown in Table 1 below. Dry Liquid " Silane content in Dry Liquid " Extraction residue Extractable silane " [%] [g / 30 g] [g / 30 g] [g / 30 g] [%] example 1 75 22.5 7.9 22.1 98.2 Example 2 60 18.0 12.8 17.2 95.6

Aus der Tabelle geht hervor, daß das Silan praktisch vollständig reversibel an den Trägerstoff gebunden ist.The table shows that the silane is almost completely reversible the carrier is bound.

Beispiel 4 - Verarbeitung vonExample 4 - Processing of Dry Liquids" zu Kabelcompounds / Vergleich von Flüssigsilan mit Silan auf TrägerstoffDry Liquids "for cable compounds / Comparison of liquid silane with silane on carrier

Zur Herstellung von halogenfreien Kabelcompounds mit flammwidrigen Eigenschaften ( Halogen-Free Flame-Retardant" [HFFR] Compounds) wurden die folgenden Komponenten verwendet: Komponente Menge Aluminiumhydroxid (ATH) 160 Teile Ethylen-Vinylacetat-Copolymer (EVA, 19 % VA) 100 Teile IRGANOX® 1010 (UV-Stabilisator) 1 Teil For the production of halogen-free cable compounds with flame-retardant properties ( Halogen Free Flame Retardant "[HFFR] Compounds) the following components were used: component quantity Aluminum hydroxide (ATH) 160 pieces Ethylene-vinyl acetate copolymer (EVA, 19% VA) 100 parts IRGANOX® 1010 (UV stabilizer) 1st chapter

Funktionelle Organylorganyloxysilane:Functional organylorganyloxysilanes:

  • (1) 3-Aminopropyltriethoxysilan (DYNASYLAN® AMEO)(1) 3-aminopropyltriethoxysilane (DYNASYLAN® AMEO)
  • (2) N-Ethylamino-3-aminopropyl-trimethoxysilan (DYNASYLAN® DAMO)(2) N-ethylamino-3-aminopropyltrimethoxysilane (DYNASYLAN® DAMO)
  • (3) DYNASYLAN® 1291 (Mischung aus 3-Aminopropyl-trimethoxysilan und Methyltriethoxysilan im Gewichtsverhältnis 2 : 1)(3) DYNASYLAN® 1291 (mixture of 3-aminopropyltrimethoxysilane and Methyltriethoxysilane in a weight ratio of 2: 1)
    • - als Flüssigkeit- as a liquid lt. Tabelleaccording to table - als Dry Liquid" mit Fällungskieselsäure (ULTRASIL® VN3) als Trägerstoff- as Dry Liquid "with precipitated silica (ULTRASIL® VN3) as a carrier lt. Tabelleaccording to table

    Die Compoundierung wird in einem Zweischnecken-Extruder, Typ ZE 25, Fa. Berstorff, Hannover, DE, vorgenommen (L/D-Verhältnis = 33, Schneckendurchmesser 25 mm, 125 U/min). Zunächst wird das Basispolymer EVA in einem Umluftofen bei 60 °C eine Stunde getrocknet. Bei Verwendung von flüssigem Silan wird dieses auf das getrocknete EVA gegeben und darin innerhalb einer Stunde absorbiert. Wird das Silan als Dry Liquid" eingesetzt, so wird das EVA damit vermischt. Der Stabilisator wird mit dem ATH vermischt. EVA/Silan einerseits und ATH/Stablisator andererseits werden gravimetrisch in den Extruder dosiert. Die Extruder-Temperatur steigt von der Zugabe bis zum Schneckenende von 135 auf 170 °C. Die Verweilzeit beträgt maximal 150 sec. Es werden Bänder extrudiert, aus denen Prüfkörper hergestellt werden.The compounding is carried out in a twin-screw extruder, type ZE 25, from Berstorff, Hanover, DE (L / D ratio = 33, screw diameter 25 mm, 125 rpm). First, the base polymer EVA is dried in a forced air oven at 60 ° C for one hour. When using liquid silane, this is added to the dried EVA and absorbed within one hour. Is the silane considered Dry Liquid "is used to mix the EVA. The stabilizer is mixed with the ATH. EVA / silane on the one hand and ATH / stabilizer on the other hand are gravimetrically metered into the extruder. The extruder temperature rises from 135 to the end of the screw 170 ° C. The residence time is a maximum of 150 seconds. Bands are extruded from which test specimens are produced.

    An den Prüfkörpern wurden folgende Werte nach folgenden Vorschriften ermittelt: Zugfestigkeit [N/mm], bestimmt nach EN ISO 527 Bruchdehnung [%], bestimmt nach EN ISO 527 Reißfestigkeit [N/mm], bestimmt nach EN ISO 527 Wasseraufnahme [mg/cm2], bestimmt durch Wägung The following values were determined on the test specimens in accordance with the following regulations: tensile strenght [N / mm], determined after EN ISO 527 Elongation at break [%], determined after EN ISO 527 Tensile strength [N / mm], determined after EN ISO 527 Water absorption [mg / cm 2 ], determined by Weighing

    Die folgende Tabelle 2 zeigt die Mengenverhältnisse und die erhaltenen Ergebnisse. Die Teile sind Gewichtsteile. Dry Liquid" Testergebnisse Silan flüss. [Tle.] Silangehalt [%] Menge [Tle.] Zugfestigkeit [N/mm] Bruchdehnung [%] Reißfestigkeit [N/mm] Wasseraufnahme [mg/cm2] (1) 1,5 - - 16,3 210 10,2 4,02 (1) - 75 2 16,5 215 10,0 3,96 (2) 1,5 - - 17,3 220 10,9 3,85 (2) - 60 2,5 17,7 215 10,5 3,81 (3) 1,5 - - 16,6 226 12,4 3,40 (3) - 75 2 16,8 222 12,7 3,34 The following Table 2 shows the proportions and the results obtained. The parts are parts by weight. Dry Liquid " Test results Silane fluent [Tle.] Silane content [%] Amount [parts] Tensile strength [N / mm] Elongation at break [%] Tensile strength [N / mm] Water absorption [mg / cm 2 ] (1) 1.5 - - 16.3 210 10.2 4.02 (1) - 75 2nd 16.5 215 10.0 3.96 (2) 1.5 - - 17.3 220 10.9 3.85 (2) - 60 2.5 17.7 215 10.5 3.81 (3) 1.5 - - 16.6 226 12.4 3.40 (3) - 75 2nd 16.8 222 12.7 3.34

    Die mit flüssigem Silan erhaltenen Werte und die Werte mit Silan auf Trägerstoff sind vergleichbar. Der Vorteil der leichteren Handhabung der Dry Liquids" wird also nicht mit schlechteren Eigenschaften der Kabelcompounds erkauft.The values obtained with liquid silane and the values with silane on a carrier are comparable. The advantage of easier handling of the Dry Liquids "is not bought with the poorer properties of the cable compounds.

    Claims (12)

    Verwendung (1) eines an einen Trägerstoff gebundenen flüssigen funktionellen Organylorganyloxysilans oder eines an einen Trägerstoff gebundenen flüssigen (Co)kondensats eines funktionellen Organylorganyloxysilans zur Herstellung von Kabelcompounds, die (2) ein thermoplastisches, polare funktionelle Gruppen tragendes Basispolymer und (3) einen verstärkenden oder streckenden mineralischen Füllstoff enthalten.Use (1) of a liquid bound to a carrier functional organylorganyloxysilane or one to a carrier bound liquid (co) condensate of a functional Organylorganyloxysilans for the production of cable compounds which (2) a thermoplastic bearing polar functional groups Base polymer and (3) a reinforcing or stretching contain mineral filler. Verwendung nach Anspruch 1,
    dadurch gekennzeichnet,
    daß der Trägerstoff Flammkieselsäure ist.    Use according to claim 1,
    characterized,
    that the carrier is flame silica.         Verwendung nach Anspruch 1,
    dadurch gekennzeichnet,
    daß der Trägerstoff gefällte Kieselsäure ist.    Use according to claim 1,
    characterized,
    that the carrier is precipitated silica.         Verwendung nach Anspruch 1,
    dadurch gekennzeichnet,
    daß der Trägerstoff Calciumsilikat ist.    Use according to claim 1,
    characterized,
    that the carrier is calcium silicate.         Verwendung nach Anspruch 1,
    dadurch gekennzeichnet,
    daß der Trägerstoff ein Wachs ist.    Use according to claim 1,
    characterized,
    that the carrier is a wax.         Verwendung nach Anspruch 5,
    dadurch gekennzeichnet,
    daß das Wachs ein Polyolefinwachs auf Basis LDPE ist.     Use according to claim 5,
    characterized,
    that the wax is a polyolefin wax based on LDPE.         Verwendung nach einem der Ansprüche 1 bis 6,
    dadurch gekennzeichnet,
    daß das funktionelle Organylorganyloxysilan ein gegebenfalls durch 1 oder 2 Alkylreste mit jeweils 1 bis 6 Kohlenstoffatomen N-substituiertes Aminoorganylorganyloxysilan ist.    Use according to one of claims 1 to 6,
    characterized,
    that the functional organylorganyloxysilane is an amino-organylorganyloxysilane which is optionally substituted by 1 or 2 alkyl radicals each having 1 to 6 carbon atoms.         Verwendung nach Anspruch 7,
    dadurch gekennzeichnet,
    daß das funktionelle Organylorganyloxysilan in Form eines (Co)kondensats mit nichtfunktionellen Organylorganyloxysilanen mit einem gewichtsdurchschnittlichen Molgewicht bis zu etwa 10.000 verwendet wird.    Use according to claim 7,
    characterized,
    that the functional organylorganyloxysilane is used in the form of a (co) condensate with nonfunctional organylorganyloxysilanes with a weight average molecular weight up to about 10,000.         Verwendung nach einem der Ansprüche 1 bis 8,
    dadurch gekennzeichnet,
    daß das Basispolymer Polyvinylchlorid oder ein Copolymer aus einem oder mehreren Olefinen und einem oder mehreren Comonomeren ist, die polare Gruppen enthalten.    Use according to one of claims 1 to 8,
    characterized,
    that the base polymer is polyvinyl chloride or a copolymer of one or more olefins and one or more comonomers containing polar groups.         Verwendung nach einem der Ansprüche 1 bis 8,
    dadurch gekennzeichnet,
    daß der mineralische Füllstoff ein Metallhydroxid mit stöchiometrischem oder substöchiometrischem Anteil an Hydroxylgruppen oder ein Metalloxid mit restlichen Hydroxylgruppen ist.    Use according to one of claims 1 to 8,
    characterized,
    that the mineral filler is a metal hydroxide with a stoichiometric or substoichiometric proportion of hydroxyl groups or a metal oxide with residual hydroxyl groups.         Kabelcompounds, die (1) ein an einen Trägerstoff gebundenes flüssiges funktionelles Organylorganyloxysilan oder ein an einen Trägerstoff gebundenes flüssiges (Co)kondensat eines funktionellen Organylorganyloxysilans, (2) ein thermoplastisches, polare funktionelle Gruppen tragendes Basispolymer und (3) einen verstärkenden oder streckenden mineralischen Füllstoff enthalten. Cable compounds, which (1) a liquid bound to a carrier functional organylorganyloxysilane or one attached to a carrier bound liquid (co) condensate of a functional Organylorganyloxysilans, (2) a thermoplastic, polar functional Group bearing base polymer and (3) a reinforcing or stretching mineral filler included. Kabel, deren metallische Leiter mit einem Kabelcompound nach Anspruch 11 umhüllt sind.Cables whose metallic conductors are followed by a cable compound Claim 11 are enveloped.
    EP00109631A 1999-06-25 2000-05-05 Carriers bearing functionalised organoorganooxysilanes in cable compositions Expired - Lifetime EP1063655B1 (en)

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    US6500883B1 (en) 1999-12-22 2002-12-31 Degussa Ag Organosilane-and/or organosiloxane-containing agent for filled polyamide
    EP1318526A2 (en) 2001-12-06 2003-06-11 Degussa AG Use of liquid unsaturated organosilane (mixtures) or unsaturated organosilane mixtures applied to a carrier for producing moisture-crosslinked and filled cablecompounds

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    JP2001057109A (en) 2001-02-27
    DE19929021A1 (en) 2000-12-28
    ATE320657T1 (en) 2006-04-15
    EP1063655B1 (en) 2006-03-15
    US6403228B1 (en) 2002-06-11
    DE50012392D1 (en) 2006-05-11

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