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WO1999062690A1 - Procede de realisation d'un produit polymere reticule extrude - Google Patents

Procede de realisation d'un produit polymere reticule extrude 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
Authority
WO
WIPO (PCT)
Prior art keywords
carrier material
temperature
antioxidant
catalyst
grafting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1999/003795
Other languages
German (de)
English (en)
Inventor
Werner Kempter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of WO1999062690A1 publication Critical patent/WO1999062690A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de réalisation d'un produit polymère réticulé extrudé. Selon ledit procédé, un matériau de base polymère, un matériau support destiné à un catalyseur, un antioxydant et un additif contenant un silane insaturé hydrolysable sont mélangés mécaniquement et conduits à une extrudeuse. Dans l'extrudeuse, la température du mélange est élevée à une valeur à laquelle se produit une réaction de greffe du silane. L'invention se caractérise en ce que l'on utilise un matériau support dont la température de fusion est supérieure à celle du matériau de base polymère. Grâce à cela, les substances liées dans le matériau support ne sont pas libérées et ne deviennent pas actives pendant la greffe.
PCT/EP1999/003795 1998-06-03 1999-06-01 Procede de realisation d'un produit polymere reticule extrude Ceased WO1999062690A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19824958A DE19824958B4 (de) 1998-06-03 1998-06-03 Verfahren zur Herstellung eines vernetzten, extrudierten Polymerproduktes
DE19824958.6 1998-06-03

Publications (1)

Publication Number Publication Date
WO1999062690A1 true WO1999062690A1 (fr) 1999-12-09

Family

ID=7869879

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/003795 Ceased WO1999062690A1 (fr) 1998-06-03 1999-06-01 Procede de realisation d'un produit polymere reticule extrude

Country Status (2)

Country Link
DE (1) DE19824958B4 (fr)
WO (1) WO1999062690A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
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 (zh) * 2015-05-28 2016-03-30 天津市安正电力高分子材料有限公司 一种硅烷交联电缆生产线用后接枝装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2554525A1 (de) * 1974-12-06 1976-06-16 Bicc Ltd Verfahren zur herstellung von stranggepressten produkten
EP0019661A1 (fr) * 1979-04-21 1980-12-10 Kabel- und Metallwerke Gutehoffnungshütte Aktiengesellschaft Procédé et dispositif pour la fabrication d'objets de forme allongée en polymère réticulable en présence d'humidité
DE3150808A1 (de) * 1981-12-22 1983-06-30 Dipox Kurt Schulze KG, 4190 Kleve Rieselfaehiges vernetzungsadditiv fuer vernetzungsfaehige organische polymere und verfahren zum vernetzen von vernetzungsfaehigen organischen polymeren
EP0695320A1 (fr) * 1993-04-23 1996-02-07 Bernhard Rustige Gmbh Und Co K Procede et dispositif permettant de realiser un produit polymere extrude reticule

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3327149A1 (de) * 1983-07-28 1985-04-04 Dynamit Nobel Ag, 5210 Troisdorf Verfahren zum herstellen von halbzeugen bzw. formteilen aus polypropylen
JP2996903B2 (ja) * 1995-09-29 2000-01-11 住友ベークライト株式会社 シラン架橋ポリオレフィンの製造方法
KR100455476B1 (ko) * 1995-12-27 2005-01-15 스미또모 베이크라이트 가부시키가이샤 난연성실란-가교결합폴리올레핀의제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2554525A1 (de) * 1974-12-06 1976-06-16 Bicc Ltd Verfahren zur herstellung von stranggepressten produkten
EP0019661A1 (fr) * 1979-04-21 1980-12-10 Kabel- und Metallwerke Gutehoffnungshütte Aktiengesellschaft Procédé et dispositif pour la fabrication d'objets de forme allongée en polymère réticulable en présence d'humidité
DE3150808A1 (de) * 1981-12-22 1983-06-30 Dipox Kurt Schulze KG, 4190 Kleve Rieselfaehiges vernetzungsadditiv fuer vernetzungsfaehige organische polymere und verfahren zum vernetzen von vernetzungsfaehigen organischen polymeren
EP0695320A1 (fr) * 1993-04-23 1996-02-07 Bernhard Rustige Gmbh Und Co K Procede et dispositif permettant de realiser un produit polymere extrude reticule

Cited By (4)

* Cited by examiner, † Cited by third party
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 (zh) * 2015-05-28 2016-03-30 天津市安正电力高分子材料有限公司 一种硅烷交联电缆生产线用后接枝装置
CN105448433B (zh) * 2015-05-28 2017-07-21 安正（天津）新材料股份有限公司 一种硅烷交联电缆生产线用后接枝装置

Also Published As

Publication number Publication date
DE19824958A1 (de) 1999-12-09
DE19824958B4 (de) 2004-02-05

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