WO1999062690A1 - Method for producing a cross-linked, extruded polymer product - Google Patents

Method for producing a cross-linked, extruded polymer product Download PDF

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Publication number
WO1999062690A1
WO1999062690A1 PCT/EP1999/003795 EP9903795W WO9962690A1 WO 1999062690 A1 WO1999062690 A1 WO 1999062690A1 EP 9903795 W EP9903795 W EP 9903795W WO 9962690 A1 WO9962690 A1 WO 9962690A1
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Prior art keywords
carrier material
temperature
antioxidant
catalyst
grafting
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PCT/EP1999/003795
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German (de)
French (fr)
Inventor
Werner Kempter
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Werner Kempter
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Publication of WO1999062690A1 publication Critical patent/WO1999062690A1/en

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    • 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
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • 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
    • 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
    • B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the invention relates to a method for producing a crosslinked, extruded polymer product according to the preamble of patent claim 1
  • a polymer base material is crosslinked by adding a hydrolyzable unsaturated silane, a free radical generator and a catalyst and an antioxidant in a silane condensation reaction in an extruder. All components of the reaction mixture are mechanically linked mixed with one another before they reach the extruder.
  • a method of this type is also known from EP-A-0 695 320.
  • the silane-containing additive is preferably added in a liquid state.
  • the catalyst and the antioxidant can be bound in a carrier material which is in the form of solid granules It is also known to add the catalyst and the antioxidant directly to the reaction mixture without using a carrier material
  • the invention is therefore based on the object of developing a method of the type mentioned at the outset in such a way that optimal processing of the polymer is ensured without undesirable side reactions
  • Carrier material ensures that the catalyst bound in the carrier material and the antioxidant are not yet released during the grafting on of the silane.
  • the temperature of the melt during the grafting must be set below the melting point of the carrier material. Due to the higher melting point of the carrier material, deposits are formed tools are graft cleaned and the catalyst and antioxidant have no effect on the chemical grafting reaction
  • the carrier material is used, so to speak, as a "Trojan horse", which is "filled” with the aggressive reaction participants, such as a catalyst and / or antioxidant. Only during the melt does the "Trojan horse” open at a higher melting temperature than that of the base material and only then grip the aggressive "inhabitants" of the "Trojan Horse” in the reaction
  • the temperature of the melt is increased at least up to the melting temperature of the carrier material after the grafting
  • a high molecular weight polymer is preferably used as the carrier material, which consists of the same material as the base polymer, but with a melting point that is higher than this
  • the catalyst and the antioxidant in the carrier material are mechanically mixed, compounded and granulated with the carrier material, and added to the polymer base material in the form of these granules.
  • Color pigments can also be added
  • the grafting is preferably carried out at a melt temperature of 160 ° C. to 180 ° C., the melting point of the base polymer also being in this range
  • the melt temperature is increased to 200 ° C. to 220 ° C. This corresponds to the melting temperature of the carrier material, so that the catalyst and the antioxidant are only released when this melting temperature of the carrier material is reached
  • the additive is preferably added in liquid form, it also being possible for the additive to contain a peroxide
  • the same starting material is preferably used as the polymer base material and carrier material, in the example a polyetylene.
  • the materials must differ significantly in their melting point
  • Figure 1 is a schematic representation of a device for
  • FIG. 2 shows a schematic representation of the process flow
  • the device comprises a screw extruder 2 with a screw 10, a feed hopper 3 arranged above the extruder 2 for the polymer base material and the carrier material, which feed hopper 3 is located in between the
  • Feed hopper 3 and the extruder mixer 4 opens.
  • a feed line 6 for an additive (here: silane compound and peroxide) coming from a metering pump unit 5 also opens into this mixer 4 via an injection nozzle 7 into the interior of the mixer 4.
  • an agitator 8 which is driven by a motor 9 is, and ensures a good mechanical mixing of the added components.
  • the extruder 2 After the components have been mixed, they pass into the extruder 2, in which the silane is grafted on at a predetermined starting temperature. In the further course, the temperature of the melt is increased so that the melting point of the carrier material is reached and the reaction products contained therein are released.
  • FIG. 2 schematically shows the process sequence for producing a crosslinked, extruded polymer product.
  • a catalyst 11 an antioxidant 13 and a carrier material
  • the base polymer 17, here a polyethylene, is already in granular form and is mechanically mixed in the mixer 4 (FIG. 1) with the carrier material additive, cf. Step 19.
  • An additive 18 containing a silane compound and a peroxide is also added to the mixture.
  • the amount added for the base polymer 17 is 93.5% in the example, 5% for the carrier material additive and 1.5% for the additive.
  • the melting point of the base polymer 17 is, for example, 160 ° C. to 180 ° C., whereas a melting point of, for example, 200 ° C. to 220 ° C. is selected for the carrier material 12.
  • the extrusion step 20 takes place, which takes place first at a temperature of 160 ° C. to 180 ° C. corresponding to the melting point of the base polymer 17, step 21.
  • the silane is grafted on.
  • the process temperature is increased to a value from 200 ° C. to 220 ° C., corresponding to the melting point of the carrier material 12.
  • the catalyst 11 and the antioxidant 13 are only now released from the carrier material 12 and have them thus no influence on the chemical reaction during the grafting. Any undesirable reaction products and deposits are avoided.
  • Extrusion device screw extruder feed hopper mixer dosing pump unit feed line injector stirrer motor screw catalyst carrier material antioxidant process step process step process step polyethylene (base polymer) silane + peroxide (additive) process step process step process step process step process step

Abstract

The invention relates to a method for producing a cross-linked, extruded polymer product. According to the inventive method, a polymer base material, a supporting material for a catalyst, an antioxidant and an additive containing a hydrolisable, unsaturated silane are, in a common manner, mechanically mixed and fed to an extruder. In said extruder, the temperature of the mixture is increased to a value at which a grafting reaction of the silane occurs. The invention is characterized in that a supporting material is used whose melting temperature is higher than the melting temperature of the polymer base material. As a result, the substances bound in the supporting material are not released and are not active during grafting.

Description

Verfahren zur Herstellung eines vernetzten, extrudierten Polymerproduktes Process for producing a cross-linked, extruded polymer product
Die Erfindung betrifft ein Verfahren zur Herstellung eines vernetzten, extrudierten Polymerproduktes nach dem Oberbegriff des Patentanspruches 1The invention relates to a method for producing a crosslinked, extruded polymer product according to the preamble of patent claim 1
Ein derartiges Verfahren ist aus der DE-OS-25 54 525 bekannt Hierbei wird ein Polymer-Basismaterial durch Zugabe eines hydrolisierbaren ungesättigten Silans, eines freien Radikalbildners sowie eines Katalysators und eines Antioxidants in einer Silankondensationsreaktion in einem Extruder vernetzt Dabei werden sämtliche Bestandteile des Reaktionsgemisches mechanisch miteinander vermischt, bevor sie in den Extruder gelangen Auch aus der die EP-A-0 695 320 ist ein derartiges Verfahren bekannt Vorzugsweise wird das silanhaltige Additiv in flussigem Zustand zugegeben Der Katalysator und das Antioxidant können in einem Tragermaterial gebunden sein, das als festes Granulat zugegeben wird Es ist auch bekannt, den Katalysator und das Antioxidant ohne Verwendung eines Tragermateπals direkt dem Reaktionsgemisch zuzugebenSuch a method is known from DE-OS-25 54 525. Here, a polymer base material is crosslinked by adding a hydrolyzable unsaturated silane, a free radical generator and a catalyst and an antioxidant in a silane condensation reaction in an extruder. All components of the reaction mixture are mechanically linked mixed with one another before they reach the extruder A method of this type is also known from EP-A-0 695 320. The silane-containing additive is preferably added in a liquid state. The catalyst and the antioxidant can be bound in a carrier material which is in the form of solid granules It is also known to add the catalyst and the antioxidant directly to the reaction mixture without using a carrier material
Es hat sich gezeigt, daß es bei bestimmten Mischungsverhaltnissen zu unerwünschten Ablagerungen auf der Schnecke des Extruders und in den Folgewerkzeugen kommen kann Dies rührt daher, daß wahrend der chemischen Aufpfropfung der Silangruppen das Antioxidant und der Katalysator in dieser Phase unkontrollierte Reaktionen verursachen können, die den Prozess und damit das Verfahren ungunstig beeinflussen, so daß es zu diesen unerwünschten Ablagerungen auf den Werkzeugen kommen kannIt has been shown that, with certain mixing ratios, undesirable deposits can occur on the screw of the extruder and in the subsequent dies.This is due to the fact that during the chemical grafting of the silane groups, the antioxidant and the catalyst in this phase can cause uncontrolled reactions, which Process and thus adversely affect the process so that it can lead to these undesirable deposits on the tools
Der Erfindung liegt deshalb die Aufgabe zugrunde, ein Verfahren der eingangs genannten Art so weiterzubilden, daß ein optimale Verarbeitung des Polymers ohne unerwünschte Nebenreaktionen gewährleistet wirdThe invention is therefore based on the object of developing a method of the type mentioned at the outset in such a way that optimal processing of the polymer is ensured without undesirable side reactions
Diese Aufgabe wird durch die kennzeichnende Merkmale des Patentanspruchs 1 gelost Die Erfindung beruht darauf, daß ein Tragermatenal verwendet wird, dessen Schmelztemperatur hoher ist als die Schmelztemperatur des Polymer- BasismateπalsThis object is achieved by the characterizing features of patent claim 1 The invention is based on the use of a carrier material whose melting temperature is higher than the melting temperature of the polymer base material
Durch den gegenüber dem Basismateπal erhöhten Schmelzpunkt desDue to the increased melting point of the base material
Tragermaterials wird erreicht, daß der im Tragermatenal gebundenen Katalysator und das Antioxidant wahrend der Aufpfropfung des Silans noch nicht freigesetzt werden Dabei muß natürlich die Temperatur der Schmelze wahrend der Aufpfropfuπg unterhalb des Schmelzpunkts des Tragermaterials eingestellt werden Durch den höheren Schmelzpunkt des Tragermatenals werden eventuell entstehende Ablagerungen an den Werkzeugen bei der Aufpfropfung gereinigt und der Katalysator und das Antioxidant haben keinen Einfluß auf die chemische AufpfropfungsreaktionCarrier material ensures that the catalyst bound in the carrier material and the antioxidant are not yet released during the grafting on of the silane. Of course, the temperature of the melt during the grafting must be set below the melting point of the carrier material. Due to the higher melting point of the carrier material, deposits are formed tools are graft cleaned and the catalyst and antioxidant have no effect on the chemical grafting reaction
Das Tragermatenal wird sozusagen als „Trojanisches Pferd" verwendet, welches mit den aggressiven Reaktionsteilnehmem, wie Katalysator und/oder Antioxidant „gefüllt" ist Erst wahrend der Schmelze wird bei einer höheren Schmelztemperatur als diejenige des Grundmaterials das „Trojanische Pferd" geöffnet und erst dann greifen die aggressiven „Bewohner" des „Trojanischen Pferdes" in das Reaktionsgeschehen einThe carrier material is used, so to speak, as a "Trojan horse", which is "filled" with the aggressive reaction participants, such as a catalyst and / or antioxidant. Only during the melt does the "Trojan horse" open at a higher melting temperature than that of the base material and only then grip the aggressive "inhabitants" of the "Trojan Horse" in the reaction
Um den Katalysator und das Antioxidant freizusetzen, wird nach der Aufpfropfung die Temperatur der Schmelze mindestens bis auf die Schmelztemperatur des Tragermatenals erhöhtIn order to release the catalyst and the antioxidant, the temperature of the melt is increased at least up to the melting temperature of the carrier material after the grafting
Als Tragermatenal wird vorzugsweise ein hochmolekulares Polymer verwendet, welches aus dem gleichen Mateπal besteht wie das Basispolymer, jedoch mit einem gegenüber diesem erhöhten SchmelzpunktA high molecular weight polymer is preferably used as the carrier material, which consists of the same material as the base polymer, but with a melting point that is higher than this
Um den Katalysator und das Antioxidant im Tragermaterial zu binden, werden diese mit dem Tragermaterial mechanisch vermischt, compoundiert und granuliert, und in Form dieses Granulats dem Polymer-Basismateπal zugegeben Es können noch zusätzlich auch Farbpigmente zugesetzt werden Die Aufpfropfung erfolgt vorzugsweise bei einer Temperatur der Schmelze von 160°C bis 180°C, wobei auch der Schmelzpunkt des Basispolymers in diesem Bereich liegtIn order to bind the catalyst and the antioxidant in the carrier material, these are mechanically mixed, compounded and granulated with the carrier material, and added to the polymer base material in the form of these granules. Color pigments can also be added The grafting is preferably carried out at a melt temperature of 160 ° C. to 180 ° C., the melting point of the base polymer also being in this range
Die Schmelzetemperatur wird nach dem Aufpfropfen auf 200°C bis 220°C erhöht Dies entspricht der Schmelztemperatur des Tragermaterials, so daß der Katalysator und das Antioxidant erst bei Erreichen dieser Schmelztemperatur des Tragermatenals freigegeben werdenAfter the grafting, the melt temperature is increased to 200 ° C. to 220 ° C. This corresponds to the melting temperature of the carrier material, so that the catalyst and the antioxidant are only released when this melting temperature of the carrier material is reached
Das Additiv wird vorzugsweise in flussiger Form zugegeben, wobei das Additiv auch ein Peroxid enthalten kannThe additive is preferably added in liquid form, it also being possible for the additive to contain a peroxide
Als Polymer-Basismaterial und Tragermaterial wird vorzugsweise das gleiche Ausgangsmateπal verwendet, im Beispiel ein Polyetylen Die Materialien müssen sich jedoch im ihrem Schmelzpunkt deutlich unterscheidenThe same starting material is preferably used as the polymer base material and carrier material, in the example a polyetylene. However, the materials must differ significantly in their melting point
Der Erfindungsgegenstand der vorliegenden Neuerung ergibt sich nicht nur aus dem Gegenstand der einzelnen Schutzanspruche, sondern auch aus der Kombination der einzelnen Schutzanspruche untereinander Alle Unterlagen, einschließlich der Zusammenfassung, offenbarten Angaben und Merkmale, insbesondere die in den Zeichnungen dargestellte räumliche Ausbildung werden als erfindungswesenthch beansprucht, soweit sie einzeln oder in Kombination gegenüber dem Stand der Technik neu sindThe subject matter of the present innovation results not only from the subject of the individual claims for protection, but also from the combination of the individual claims for protection among one another. All documents, including the summary, disclosed details and features, in particular the spatial design shown in the drawings, are claimed as essential to the invention, as far as they are new compared to the prior art, individually or in combination
Im folgenden wird die Erfindung anhand eines Ausfuhrungsbeispiels unterIn the following, the invention is described using an exemplary embodiment
Bezugnahme auf die Zeichnungsfiguren naher erläutert Hierbei gehen aus den Zeichnungen und ihrer Beschreibung weitere Merkmale und Vorteile der Erfindung hervor Es zeigenReference to the drawing figures explained in more detail. From the drawings and their description, further features and advantages of the invention are shown
Figur 1 eine schematische Darstellung einer Vorrichtung zurFigure 1 is a schematic representation of a device for
Herstellung eines vernetzten extrudierten Polymerproduktes,Production of a cross-linked extruded polymer product,
Figur 2 schematische Darstellung des Verfahrensablaufs In Figur 1 ist schematisch der Aufbau einer Extrudiervorrichtung 1 dargestellt, wie sie zur Durchführung des Verfahrens verwendet werden kann. Die Vorrichtung umfasst einen Schneckenextruder 2 mit Schnecke 10, einem oberhalb des Extruders 2 angeordneten Aufgabetrichter 3 für das Polymer-Basismaterial und das Trägermaterial, welcher Aufgabetrichter 3 in den zwischen demFigure 2 shows a schematic representation of the process flow In Figure 1, the structure of an extrusion device 1 is shown schematically, as it can be used to carry out the method. The device comprises a screw extruder 2 with a screw 10, a feed hopper 3 arranged above the extruder 2 for the polymer base material and the carrier material, which feed hopper 3 is located in between the
Aufgabetrichter 3 und dem Extruder angeordneten Mischer 4 mündet. In diesen Mischer 4 mündet ferner eine von einer Dosierpumpeneinheit 5 kommende Zuführleitung 6 für ein Additiv (hier: Silanverbindung und Peroxid) über eine Einspritzdüse 7 in das Innere des Mischers 4. Im Mischer selbst befindet sich ein Rührwerk 8, welches durch einen Motor 9 angetrieben wird, und für eine gute mechanische Durchmischung der zugegebenen Komponenten sorgt. Nach dem Durchmischen der Komponenten gelangen diese in den Extruder 2, in welchem bei einer vorgegebenen Anfangstemperatur die Aufpfropfung des Silans erfolgt. Im weiteren Verlauf wird die Temperatur der Schmelze erhöht, so daß der Schmelzpunkt des Trägermaterials erreicht wird, und die darin enthaltenen Reaktionsprodukte freigegeben werden.Feed hopper 3 and the extruder mixer 4 opens. A feed line 6 for an additive (here: silane compound and peroxide) coming from a metering pump unit 5 also opens into this mixer 4 via an injection nozzle 7 into the interior of the mixer 4. In the mixer itself there is an agitator 8 which is driven by a motor 9 is, and ensures a good mechanical mixing of the added components. After the components have been mixed, they pass into the extruder 2, in which the silane is grafted on at a predetermined starting temperature. In the further course, the temperature of the melt is increased so that the melting point of the carrier material is reached and the reaction products contained therein are released.
In Figur 2 ist schematisch der Verfahrensablauf zur Herstellung eines vernetzten, extrudierten Polymerproduktes dargestellt. Zunächst werden ein Katalysator 11 , ein Antioxidant 13 und ein TrägermaterialFIG. 2 schematically shows the process sequence for producing a crosslinked, extruded polymer product. First, a catalyst 11, an antioxidant 13 and a carrier material
12, z.B. Polyethylen, in einem ersten Verfahrensschritt 14 mechanisch miteinander vermischt. Danach wird die Mischung in einem nächsten Schritt 15 zu einer homogenen Masse compoundiert, die dann in einem weiteren Schritt 16 granuliert wird. Durch das Compoundieren werden der Katalysator 11 und das Antioxidant 13 im Trägermaterial 12 gebunden.12, e.g. Polyethylene, mechanically mixed together in a first process step 14. The mixture is then compounded in a next step 15 to a homogeneous mass, which is then granulated in a further step 16. The catalyst 11 and the antioxidant 13 are bound in the carrier material 12 by the compounding.
Das Basispolymer 17, hier ein Polyethylen, liegt bereits in granulärer Form vor, und wird im Mischer 4 (Figur 1 ) mit dem Trägermaterialzusatz mechanisch gemischt, vgl. Schritt 19. Ferner wird der Mischung ein Additiv 18 zugegeben, das eine Silanverbindung und ein Peroxid enthält. Der zugegebenen Mengenanteil für das Basispolymer 17 beträgt im Beispiel 93,5%, für den Trägermaterialzusatz 5% und für das Additiv 1 ,5%. Diese Mengenangaben können natürlich variiert werden.The base polymer 17, here a polyethylene, is already in granular form and is mechanically mixed in the mixer 4 (FIG. 1) with the carrier material additive, cf. Step 19. An additive 18 containing a silane compound and a peroxide is also added to the mixture. The amount added for the base polymer 17 is 93.5% in the example, 5% for the carrier material additive and 1.5% for the additive. These quantities can of course be varied.
Der Schmelzpunkt des Basispolymers 17 beträgt dabei z.B. 160°C bis 180°C wogegen für das Trägermaterial 12 ein Schmelzpunkt von z.B. 200°C bis 220°C gewählt wird. Nach einer gründlichen Durchmischung der Reaktionsbestandteile erfolgt der Extrusionsschritt 20, der zunächst bei einer Temperatur von 160°C bis 180°C entsprechend dem Schmelzpunkt des Basispolymers 17 erfolgt, Schritt 21. Dabei erfolgt die Aufpfropfung des Silans.The melting point of the base polymer 17 is, for example, 160 ° C. to 180 ° C., whereas a melting point of, for example, 200 ° C. to 220 ° C. is selected for the carrier material 12. After thorough mixing of the reaction components, the extrusion step 20 takes place, which takes place first at a temperature of 160 ° C. to 180 ° C. corresponding to the melting point of the base polymer 17, step 21. The silane is grafted on.
Im Verlauf der Extrusion wird im nächsten Schritt 22 die Prozesstemperatur in auf einen Wert von 200°C bis 220°C erhöht, entsprechend dem Schmelzpunkt des Trägermateriais 12. Damit werden erst jetzt der Katalysator 11 und das Antioxidant 13 aus dem Trägermaterial 12 freigesetzt und haben somit keinen Einfluß auf die chemische Reaktion während der Aufpfropfung. Ein Entstehen eventueller unerwünschter Reaktionsprodukte und Ablagerungen wird vermieden. In the course of the extrusion, in the next step 22 the process temperature is increased to a value from 200 ° C. to 220 ° C., corresponding to the melting point of the carrier material 12. The catalyst 11 and the antioxidant 13 are only now released from the carrier material 12 and have them thus no influence on the chemical reaction during the grafting. Any undesirable reaction products and deposits are avoided.
ZeichnungslegendeDrawing legend
Extrudiervorrichtung Schneckenextruder Aufgabetrichter Mischer Dosierpumpeneinheit Zuführleitung Einspritzdüse Rührwerk Motor Schnecke Katalysator Trägermaterial Antioxidant Verfahrensschritt Verfahrensschritt Verfahrensschritt Polyethylen (Basispolymer) Silan + Peroxid (Additiv) Verfahrensschritt Verfahrensschritt Verfahrensschritt Verfahrensschritt Extrusion device screw extruder feed hopper mixer dosing pump unit feed line injector stirrer motor screw catalyst carrier material antioxidant process step process step process step polyethylene (base polymer) silane + peroxide (additive) process step process step process step process step

Claims

Patentansprüche claims
1. Verfahren zur Herstellung eines vernetzten, extrudierten Polymerproduktes, wobei ein Polymer-Basismaterial, ein Trägermaterial für einen Katalysator und ein Antioxidant und ein ein hydrolisierbares, ungesättigtes Silan enthaltendes Additiv mechanisch zusammengemischt und einem Extruder zugeführt werden, und darin die Temperatur der Mischung auf einen Wert erhöht wird, bei dem eine Aufpfropfungsreaktion des Silans eintritt; dadurch gekennzeichnet, daß ein Trägermaterial verwendet wird, dessen Schmelztemperatur höher ist als die Schmelztemperatur des Polymer-Basismaterials.1. A process for producing a crosslinked, extruded polymer product, wherein a polymer base material, a support material for a catalyst and an antioxidant and an additive containing a hydrolyzable, unsaturated silane are mechanically mixed together and fed to an extruder, and therein the temperature of the mixture to one Value is increased at which a grafting reaction of the silane occurs; characterized in that a carrier material is used, the melting temperature of which is higher than the melting temperature of the polymer base material.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß nach der Aufpfropfung der Silangruppen die Temperatur der Schmelze mindestens bis auf die Schmelztemperatur des Trägermaterials erhöht wird.2. The method according to claim 1, characterized in that after the grafting of the silane groups, the temperature of the melt is increased at least up to the melting temperature of the carrier material.
3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß als Trägermaterial ein hochmolekulares Polymer verwendet wird.3. The method according to any one of claims 1 or 2, characterized in that a high molecular weight polymer is used as the carrier material.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Trägermaterial mit dem Katalysator und dem Antioxidant vermischt, compoundiert und granuliert wird, und in Form dieses Granulats dem Polymer-Basismaterial zugegeben wird.4. The method according to any one of claims 1 to 3, characterized in that the carrier material is mixed with the catalyst and the antioxidant, compounded and granulated, and is added to the polymer base material in the form of these granules.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Aufpfropfung bei einer Temperatur der Schmelze von 160°C bis 180°C erfolgt.5. The method according to any one of claims 1 to 4, characterized in that the grafting is carried out at a melt temperature of 160 ° C to 180 ° C.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Schmelzetemperatur nach dem Aufpfropfen auf 200°C bis 220°C erhöht wird.6. The method according to any one of claims 1 to 5, characterized in that the melt temperature is increased to 200 ° C to 220 ° C after grafting.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Katalysator und das Antioxidant erst bei Erreichen der Schmelztemperatur des Trägermaterials freigegeben werden. 7. The method according to any one of claims 1 to 6, characterized in that the catalyst and the antioxidant are only released when the melting temperature of the support material is reached.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Additiv in flüssiger Form zugegeben wird8. The method according to any one of claims 1 to 7, characterized in that the additive is added in liquid form
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß dem Additiv ein Peroxid zugegeben ist.9. The method according to any one of claims 1 to 8, characterized in that a peroxide is added to the additive.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß als Polymer-Basismaterial ein Polyetylen verwendet wird. 10. The method according to any one of claims 1 to 9, characterized in that a polyetylene is used as the polymer base material.
PCT/EP1999/003795 1998-06-03 1999-06-01 Method for producing a cross-linked, extruded polymer product WO1999062690A1 (en)

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US8183328B2 (en) 2007-03-30 2012-05-22 Exxonmobil Chemical Patents Inc. Compositions comprising grafted and crosslinked LLDPE's, Methods for making same, and articles made therefrom
US8211985B2 (en) 2007-03-30 2012-07-03 Exxonmobil Chemical Patents Inc. Silicon-containing ethylene-based polymer blends, methods for making same, and articles made therefrom
CN105448433A (en) * 2015-05-28 2016-03-30 天津市安正电力高分子材料有限公司 Post-grafting device used for silane crosslinking cable production line

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EP0019661A1 (en) * 1979-04-21 1980-12-10 Kabel- und Metallwerke Gutehoffnungshütte Aktiengesellschaft Process and device for manufacturing elongated material from polymers cross-linkable under the influence of moisture
DE3150808A1 (en) * 1981-12-22 1983-06-30 Dipox Kurt Schulze KG, 4190 Kleve Free-flowing crosslinking additive for crosslinkable organic polymers, and a process for crosslinking crosslinkable organic polymers
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Cited By (4)

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Publication number Priority date Publication date Assignee Title
US8183328B2 (en) 2007-03-30 2012-05-22 Exxonmobil Chemical Patents Inc. Compositions comprising grafted and crosslinked LLDPE's, Methods for making same, and articles made therefrom
US8211985B2 (en) 2007-03-30 2012-07-03 Exxonmobil Chemical Patents Inc. Silicon-containing ethylene-based polymer blends, methods for making same, and articles made therefrom
CN105448433A (en) * 2015-05-28 2016-03-30 天津市安正电力高分子材料有限公司 Post-grafting device used for silane crosslinking cable production line
CN105448433B (en) * 2015-05-28 2017-07-21 安正（天津）新材料股份有限公司 A kind of rear grafting device of silanes crosslinked cable production line

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DE19824958A1 (en) 1999-12-09

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