EP2585514A1 - Method for producing fluid, colourless polyoctenamer by ring-opening, metathetic polymerization of cyclooctene - Google Patents

Method for producing fluid, colourless polyoctenamer by ring-opening, metathetic polymerization of cyclooctene

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Publication number
EP2585514A1
EP2585514A1 EP11722405.5A EP11722405A EP2585514A1 EP 2585514 A1 EP2585514 A1 EP 2585514A1 EP 11722405 A EP11722405 A EP 11722405A EP 2585514 A1 EP2585514 A1 EP 2585514A1
Authority
EP
European Patent Office
Prior art keywords
polyoctenamer
preparation
polymerization
cyclooctene
ring
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.)
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Application number
EP11722405.5A
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German (de)
French (fr)
Inventor
Peter Hannen
Norbert Wilczok
Manfred Thiery
Martin Roos
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Evonik Operations GmbH
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Evonik Degussa GmbH
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Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2585514A1 publication Critical patent/EP2585514A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • 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
    • C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F132/02—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F132/04—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3322—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from cyclooctene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/63—Viscosity

Definitions

  • catalyst systems are based on defined transition metal complexes.
  • the best known compounds include complexes based on ruthenium. 3 ' 4' A disadvantage here, however, in their high price and especially in the difficult separation of the reaction product. Residues of ruthenium lead to an often unacceptable coloration of the product. In these cases, the polymer has to be purified by complicated processes, such as reprecipitation, which precludes economical production.
  • Essential for the polymerization is the ability to adjust the properties of the resulting polymer. Besides the usual parameters such as temperature, concentration of monomer, catalyst concentration and reaction time, e.g. the
  • ROMP cyclooctene
  • ROMP cyclooctene
  • a polyoctenamer having an average molecular weight of> 100,000 g / mol For some applications, however, it is necessary for the polymer to be in a liquid state at room temperature.
  • An important application, for a polyoctenamer which is liquid and colorless at room temperature, is the barrier property with regard to oxygen, carbon dioxide, water, etc. in packaging films.
  • the object of producing a liquid and colorless polyoctene ester is achieved as described in the claims.
  • the object is achieved in that the reaction is stopped before or when the complete conversion becomes. Thereby, a cis / trans ratio in the specified range is obtained, resulting in a lower crystallinity of the polymer, whereby the melting point can be kept low.
  • An optionally incomplete conversion means no disadvantage, since unreacted cycloalkene can easily be separated off and recycled.
  • the reaction is stopped between 30 and 100%, preferably between 50 and 100% conversion.
  • the preferred catalyst system consists of a mixture of tungsten hexachloride (WC1 6 ) and ethylaluminum dichloride (EtAlCl 2 ).
  • the ratio of EtAlCl 2 to WC 1 6 is preferably one to six. Particularly preferred is a ratio of two to five.
  • acidic compounds such as alcohols can be used.
  • Ethylaluminiumdichlorid are also Ethylaluminiumsesquichlorid or mixtures of Ethylalummiumdichlorid with diethylaluminum chloride in different ratios.
  • the following quantities are used: Tungsten hexachloride> 0.1-0.04 mol%, particularly preferably 0.1-0.01 mol%. (related to cycloalkene)
  • the monomer may be in solution or in bulk.
  • the reaction is carried out in hexane or toluene. It is at a
  • the described method can be operated isothermally as well as adiabatically.
  • the temperature range is preferably between -20 and 120 ° C, depending on the monomers used and the solvent.
  • a particularly preferred temperature range is between 10 and 60 ° C.
  • the temperature can be determined by parameters such as, amount of catalyst, rate of addition, time of termination of the reaction, etc.
  • the preferred temperature range is 20-50 ° C.
  • regulators are added which limit the molecular weight increase.
  • This may be e.g. to acyclic alkenes having one or more non-conjugated double bonds, which may be terminal or internal and should bear no substituents act.
  • Such compounds are e.g. Pent-l-ene, hex-l-ene, hept-l-ene, oct-l-ene, pent-2-ene etc.
  • cyclic compounds can also be used which have a vinylic, allylic or have higher homologous double bond with low degree of substitution, such as
  • Vinylcyclohexene is used in amounts of 2-7 mol%; particularly preferably 3-6 mol% (based on starting material) is used.
  • cycloalkenes used in the process according to the invention are e.g. cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, 1,5-dimethylocta- 1, 5-diene, 1, 5, 9-tetramethyldodeca- 1, 5, 9-triene.
  • the average molecular weights achieved in the described process for the polyoctenamer according to the invention are between 10,000 and 50,000 g / mol.
  • Preferred is an average molecular weight of 10,000-30,000 g / mol. Particularly preferred is an average molecular weight of 15,000-20,000 g / mol. Stopper:
  • the polymerization is terminated after reaching the desired reaction time by inactivating the catalyst system.
  • a CH-acidic compound can be added.
  • Suitable for this purpose are e.g. Alcohols such as methanol, ethanol, propanol, etc. as well as carboxylic acids such as acetic acid.
  • Tungsten hexachloride in 44 mL of toluene is added to 1.05 mL (18 mmol) of ethanol.
  • the pre-catalyst solution obtained is added to the reactor and added dropwise via a cannula 8 mL of a 20% solution of ethylaluminum dichloride in hexane. If a temperature of 35 ° C is reached, the reaction is stopped by adding methanol. After distilling off all volatile constituents, a liquid polyoctenamer is obtained as product (yield 67% of theory).

Abstract

The invention relates to a polyoctenamer which at room temperature is fluid, colourless and clear and is produced by ring-opening, metathetic polymerization of cyclooctene.

Description

Verfahren zur Herstellung von flüssigem und farblosem Polyoctenamer durch ringöffnende, metathetische Polymerisation von Cycloocten  Process for the preparation of liquid and colorless polyoctenamer by ring-opening, metathetic polymerization of cyclooctene
Einleitung: Introduction:
Die Ring-öffnende, metathetische Polymerisation (ROMP = Ring Opening Metathesis Ring-opening, metathetic polymerization (ROMP = ring-opening metathesis
Polymerisation) von Cycloalkenen ist hinlänglich bekannt.1'' 2 Diese Reaktion wird durch eine Reihe von Übergangsmetallen katalysiert, wobei oft ein Co-Katalysator eingesetzt wird, der zusammen mit dem Übergangsmetallkomplex die eigentliche katalytisch aktive Spezies bildet. Als Co-Katalysatoren eigenen sich v. a. Aluminium- und Zinn-organyle. Polymerization) of cycloalkenes is well known. 1 ' ' 2 This reaction is catalyzed by a series of transition metals, often employing a co-catalyst that together with the transition-metal complex forms the actual catalytically active species. Particularly suitable cocatalysts are aluminum and tin organyls.
Andere Katalysatorsysteme basieren auf definierten Übergangsmetallkomplexen. Zu den bekanntesten Verbindungen gehören Komplexe auf Basis von Ruthenium.3 '4' Ein Nachteil besteht hier allerdings in ihrem hohen Preis und vor allem in der schwierigen Abtrennung vom Reaktionsprodukt. Reste an Ruthenium führen zu einer oft nicht zu akzeptierenden Färbung des Produktes. Das Polymer muss in diesen Fällen durch aufwändige Verfahren, wie z.B. Umfällen, gereinigt werden, was einer ökonomischen Herstellung entgegensteht. Other catalyst systems are based on defined transition metal complexes. The best known compounds include complexes based on ruthenium. 3 '4' A disadvantage here, however, in their high price and especially in the difficult separation of the reaction product. Residues of ruthenium lead to an often unacceptable coloration of the product. In these cases, the polymer has to be purified by complicated processes, such as reprecipitation, which precludes economical production.
Wesentlich für die Polymerisation ist die Möglichkeit zur Einstellung der Eigenschaften des resultierenden Polymers. Neben den üblichen Parametern wie Temperatur, Konzentration an Monomer, Katalysatorkonzentration und Reaktionszeit, lässt sich z.B. die Essential for the polymerization is the ability to adjust the properties of the resulting polymer. Besides the usual parameters such as temperature, concentration of monomer, catalyst concentration and reaction time, e.g. the
Molekulargewichtsverteilung über den Zusatz von Reglern steuern, deren Aufgabe die Controlling molecular weight distribution via the addition of regulators whose task is the
Terminierung der wachsenden Kette ist. Da es sich um einen statistischen Prozess handelt, verhält sich das Molekulargewicht in erster Näherung reziprok zur Konzentration an Regler. Eine Verbreiterung der Molekulargewichtsverteilung als Folge der Sekundärmetathese Termination of the growing chain is. Since this is a statistical process, the molecular weight in a first approximation is inversely related to the concentration of regulators. A broadening of the molecular weight distribution as a result of secondary metathesis
(Kettenübertragung bzw.,back-biting') ist hier nicht berücksichtigt. So lässt sich durch Zugabe von Reglern zwar das mittlere Molekulargewicht- hier als Mw angegeben-, nicht aber die Breite der Molekulargewichtsverteilung beeinflussen. Es kommt im weiteren Verlauf der Reaktion zu Sekundärmetathese, bei der das aktive Ende einer wachsenden Kette nicht ein weiteres (Chain transmission or 'back-biting') is not considered here. Thus, although the average molecular weight, in this case indicated as Mw, can be influenced by the addition of regulators, the width of the molecular weight distribution can not be influenced. In the further course of the reaction, secondary metathesis occurs, in which the active end of a growing chain is not yet another
Monomermolekül anlagert, sondern die Doppelbindung einer bereits bestehenden Polymerkette. Das Ergebnis ist eine Kettenübertragung, wodurch die Uneinheitlichkeit bzw. Polydispersität (ausgedrückt als (Mw/Mn)-1 bzw. Mw/Mn) zunimmt. Eine weitere Beobachtung bei fortschreitender Reaktion ist die Verschiebung des cisltrans- Verhältnisses zugunsten der transKonfiguration. Ein Effekt der sich ebenfalls auf die Sekundärmetathese zurückführen lässt. Um bestimmte Eigenschaften im Polymer einzustellen, bedarf es also der genauen Steuerung verschiedenster Verfahrensparameter. Monomolecule attached, but the double bond of an existing polymer chain. The result is a chain transfer, causing the polydispersity or polydispersity (expressed as (Mw / Mn) -1 or Mw / Mn) increases. Another observation as the reaction progresses is the shift of the cis / trans ratio in favor of the trans configuration. An effect that can also be attributed to secondary metathesis. In order to set certain properties in the polymer, it therefore requires the precise control of various process parameters.
Aufgabenstellung: Task:
Die Polymerisation von Cycloocten durch ROMP stellt ein wichtiges Verfahren zur Herstellung von Vestenamer® dar, einem Polyoctenamer mit einem mittleren Molekulargewichts von > 100.000 g/mol. Für manche Anwendungen ist es allerdings erforderlich, dass das Polymer in einem bei Raumtemperatur flüssigen Zustand vorliegt. Eine wichtige Anwendung, für ein bei Raumtemperatur flüssiges und dabei farbloses Polyoctenamer, ist die Barriereeigenschaft bezüglich Sauerstoff, Kohlendioxid, Wasser etc. in Verpackungsfolien.  The polymerization of cyclooctene by ROMP represents an important method for the preparation of Vestenamer®, a polyoctenamer having an average molecular weight of> 100,000 g / mol. For some applications, however, it is necessary for the polymer to be in a liquid state at room temperature. An important application, for a polyoctenamer which is liquid and colorless at room temperature, is the barrier property with regard to oxygen, carbon dioxide, water, etc. in packaging films.
Um diese Eigenschaften zu erreichen müssen die in Tabelle 1 angegebenen physikalischen Parameter eingestellt werden. To achieve these properties, the physical parameters given in Table 1 must be set.
Tabelle 1 : Physikalische Eigenschaften (bevorzugte Bereiche) des erfindungsgemäßen Table 1: Physical properties (preferred ranges) of the invention
Polyoctenamers: polyoctenamer:
Bestimmung der Viskositätszahl J nach ISO 1628-1 bei 23 °C: Determination of the viscosity number J according to ISO 1628-1 at 23 ° C:
10g Vestenamer in 11 Toluol lösen Dissolve 10 g of Vestenamer in 11 toluene
Messgerät Schott Visco System AVS 500  Measuring device Schott Visco System AVS 500
Kapillar-Typ Nr. 53713 von Fa. Schott  Capillary type No. 53713 from Schott
Lösung der Aufgabenstellung: Solution of the task:
Die Aufgabe zur Herstellung eines flüssigen und farblosen Polyoctenamers wird, wie in den Ansprüchen beschrieben, gelöst. In dem erfindungsgemäßen Verfahren wird die Aufgabe dadurch gelöst, dass die Reaktion vor bzw. bei Erreichen des vollständigen Umsatzes gestoppt wird. Dadurch wird ein cis/trans- Verhältnis im angegebenen Bereich erhalten, was eine geringere Kristallinität des Polymers zur Folge hat, wodurch der Schmelzpunkt niedrig gehalten werden kann. Ein gegebenenfalls unvollständiger Umsatz bedeutet keinen Nachteil, da nicht umgesetztes Cycloalken problemlos abgetrennt und rezykliert werden kann. Die Reaktion wird zwischen 30 und 100 %, bevorzugt zwischen 50 und 100 % Umsatzes gestoppt. The object of producing a liquid and colorless polyoctene ester is achieved as described in the claims. In the process of the invention, the object is achieved in that the reaction is stopped before or when the complete conversion becomes. Thereby, a cis / trans ratio in the specified range is obtained, resulting in a lower crystallinity of the polymer, whereby the melting point can be kept low. An optionally incomplete conversion means no disadvantage, since unreacted cycloalkene can easily be separated off and recycled. The reaction is stopped between 30 and 100%, preferably between 50 and 100% conversion.
Ein weiterer wesentlicher Aspekt des Verfahrens ist die Begrenzung des Molekulargewichts durch den Einsatz von Reglern, die, wie Eingangs erwähnt, den Kettenaufbau begrenzen. Another essential aspect of the process is the limitation of the molecular weight through the use of regulators, which, as mentioned in the introduction, limit the chain structure.
Neben der Reaktion in Lösung hat sich bei dem erfindungsgemäßen Verfahren besonders die Polymerisation in Substanz bewährt. Im Folgenden werden die Parameter beschrieben, die für das erfindungsgemäße Verfahren von Bedeutung sind. In addition to the reaction in solution, the polymerization in substance has proven particularly useful in the process according to the invention. The parameters which are important for the method according to the invention are described below.
Katalysatorsystem : Catalyst system:
Das bevorzugte Katalysatorsystem besteht aus einer Mischung von Wolframhexachlorid (WC16) und Ethylalummiumdichlorid (EtAlCl2). Das Verhältnis von EtAlCl2 zu WC16 ist bevorzugt eins bis sechs. Besonders bevorzugt ist ein Verhältnis von zwei bis fünf. Zur Aktivierung des Präkatalysators können acide Verbindungen wie Alkohole eingesetzt werden. Neben The preferred catalyst system consists of a mixture of tungsten hexachloride (WC1 6 ) and ethylaluminum dichloride (EtAlCl 2 ). The ratio of EtAlCl 2 to WC 1 6 is preferably one to six. Particularly preferred is a ratio of two to five. To activate the precatalyst, acidic compounds such as alcohols can be used. Next
Ethylalummiumdichlorid eignen sich auch Ethylaluminiumsesquichlorid bzw. Mischungen von Ethylalummiumdichlorid mit Diethylaluminiumchlorid in unterschiedlichen Verhältnissen. Eingesetzt werden folgende Mengen: Wolframhexachlorid > 0,1-0,04 mol-%, besonders bevorzugt 0,1-0,01 mol-%. (bezogen auf Cycloalken) Ethylaluminiumdichlorid are also Ethylaluminiumsesquichlorid or mixtures of Ethylalummiumdichlorid with diethylaluminum chloride in different ratios. The following quantities are used: Tungsten hexachloride> 0.1-0.04 mol%, particularly preferably 0.1-0.01 mol%. (related to cycloalkene)
Ethylalummiumdichlorid -> 0,2-0,08 mol-%>, besonders bevorzugt 0,2-0,02 mol-%>. (bezogen auf Cycloalken)  Ethylaluminum dichloride -> 0.2-0.08 mol%, more preferably 0.2-0.02 mol%>. (related to cycloalkene)
Lösungsmittel: Solvent:
Im erfindungsgemäßen Verfahren kann das Monomer in Lösung oder in Substanz vorliegen. Bevorzugt wird die Reaktion in Hexan oder Toluol ausgeführt. Dabei wird bei einer  In the process of the invention, the monomer may be in solution or in bulk. Preferably, the reaction is carried out in hexane or toluene. It is at a
Konzentration von 20-60 Gew.-% und besonders bevorzugt bei einer Konzentration von 40-60 Gew. -% .gearbeitet. Jedoch besonders bevorzugt wird die Polymerisation ohne Lösungsmittel durchgeführt. Temperatur: Concentration of 20-60 wt .-% and particularly preferably at a concentration of 40-60 wt -.% Worked. However, most preferably, the polymerization is carried out without a solvent. Temperature:
Das beschriebene Verfahren kann isotherm als auch adiabatisch betrieben werden.  The described method can be operated isothermally as well as adiabatically.
Der Temperaturbereich liegt vorzugsweise zwischen -20 und 120 °C, abhängig von den eingesetzten Monomeren und dem Lösungsmittel. Ein besonders bevorzugter Temperaturbereich liegt zwischen 10 und 60 °C. Bei adiabatischer Fahrweise kann die Temperatur über Parameter wie, Katalysatormenge, Geschwindigkeit der Zugabe, Zeitpunkt des Abbruchs der Reaktion etc. bestimmt werden. Hier liegt der bevorzugte Temperaturbereich bei 20-50 °C. The temperature range is preferably between -20 and 120 ° C, depending on the monomers used and the solvent. A particularly preferred temperature range is between 10 and 60 ° C. In adiabatic driving, the temperature can be determined by parameters such as, amount of catalyst, rate of addition, time of termination of the reaction, etc. Here the preferred temperature range is 20-50 ° C.
Regler: controller:
Wie beschrieben werden bei dem erfindungsgemäßen Verfahren Regler zugesetzt, die den Molekulargewichtsaufbau begrenzen. Dabei kann es sich z.B. um acyclische Alkene mit einer oder mehreren nichtkonjugierten Doppelbindungen, die end- oder innenständig liegen können und die keine Substituenten tragen sollten, handeln. Solche Verbindungen sind z.B. Pent-l-en, Hex-l-en, Hept-l-en, Oct-l-en, Pent-2-en usw. Des Weitern können aber auch cyclische Verbindungen eingesetzt werden, die in ihrer Seitenkette eine vinylische, allylische oder höher homologe Doppelbindung mit niedrigem Substitutionsgrad aufweisen, wie z.B.  As described, in the process according to the invention, regulators are added which limit the molecular weight increase. This may be e.g. to acyclic alkenes having one or more non-conjugated double bonds, which may be terminal or internal and should bear no substituents act. Such compounds are e.g. Pent-l-ene, hex-l-ene, hept-l-ene, oct-l-ene, pent-2-ene etc. However, cyclic compounds can also be used which have a vinylic, allylic or have higher homologous double bond with low degree of substitution, such as
Vinylcyclohexen. Vinylcyclohexen wird in Mengen von 2-7 mol-%; besonders bevorzugt 3-6 mol-% (bezogen auf Edukt) eingesetzt. Vinylcyclohexene. Vinylcyclohexene is used in amounts of 2-7 mol%; particularly preferably 3-6 mol% (based on starting material) is used.
Cycloalkene: cycloalkenes:
Bei den im erfindungsgemäßen Verfahren eingesetzten Cycloalkenen handelt es sich z.B. um Cyclobuten, Cyclopenten, Cyclohepten, Cycloocten, Cyclodecen, Cyclododecen, 1,5- Dimethylocta- 1 ,5-dien, 1 ,5 ,9-Tetramethyldodeca- 1 ,5 ,9-trien.  The cycloalkenes used in the process according to the invention are e.g. cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, 1,5-dimethylocta- 1, 5-diene, 1, 5, 9-tetramethyldodeca- 1, 5, 9-triene.
Molekulargewicht: Molecular weight:
Die bei dem beschriebenen Verfahren erreichten mittleren Molekulargewichte für das erfindungsgemäße Polyoctenamer liegen zwischen 10.000 und 50.000 g/mol.  The average molecular weights achieved in the described process for the polyoctenamer according to the invention are between 10,000 and 50,000 g / mol.
Bevorzugt ist ein mittleres Molekulargewicht von 10.000-30.000 g/mol. Besonders bevorzugt ist ein mittleres Molekulargewicht von 15.000-20.000 g/mol. Stopper: Preferred is an average molecular weight of 10,000-30,000 g / mol. Particularly preferred is an average molecular weight of 15,000-20,000 g / mol. Stopper:
Die Polymerisation wird nach Erreichen der gewünschten Reaktionszeit durch Inaktivierung des Katalysatorsystems beendet. Zu diesem Zweck kann z.B. eine CH-acide Verbindung zugesetzt werden. Hierzu eignen sich z.B. Alkohole wie Methanol, Ethanol, Propanol etc. als auch Carbonsäuren, wie Essigsäure.  The polymerization is terminated after reaching the desired reaction time by inactivating the catalyst system. For this purpose, e.g. a CH-acidic compound can be added. Suitable for this purpose are e.g. Alcohols such as methanol, ethanol, propanol, etc. as well as carboxylic acids such as acetic acid.
Beispiel: Example:
1,332 kg (12,09 mol) Cycloocten werden zusammen mit 0,065 kg (0,6 mol) 4-Vinyl-cyclohex-l- en in einem Reaktor unter Inertgas vorgelegt. Zu einer Lösung von 2,65 g (6,68 mmol)  1.332 kg (12.09 mol) of cyclooctene are charged together with 0.065 kg (0.6 mol) of 4-vinylcyclohex-1-ene in a reactor under inert gas. To a solution of 2.65 g (6.68 mmol)
Wolframhexachlorid in 44 mL Toluol werden 1,05 mL (18 mmol) Ethanol gegeben. Die erhaltene Präkatalysator-Lösung wird in den Reaktor gegeben und über eine Kanüle 8 mL einer 20%igen Lösung von Ethylaluminiumdichlorid in Hexan zugetropft. Ist eine Temperatur von 35 °C erreicht wird die Reaktion durch Zugabe von Methanol gestoppt. Nach Abdestillieren aller flüchtigen Bestandteile wird ein flüssiges Polyoctenamer als Produkt gewonnen (Ausbeute 67 % d.Th.). Das so hergestellte Polyoctenamer hat folgende Eigenschaften: J-Wert= 56; DSC= -2,6 °C (entspr. Schmelzbereich); cis/trans= 70/30. Tungsten hexachloride in 44 mL of toluene is added to 1.05 mL (18 mmol) of ethanol. The pre-catalyst solution obtained is added to the reactor and added dropwise via a cannula 8 mL of a 20% solution of ethylaluminum dichloride in hexane. If a temperature of 35 ° C is reached, the reaction is stopped by adding methanol. After distilling off all volatile constituents, a liquid polyoctenamer is obtained as product (yield 67% of theory). The polyoctenamer thus prepared has the following properties: J value = 56; DSC = -2.6 ° C (corresponding to melting range); cis / trans = 70/30.
J-Wert 23 °C nach ISO 1628-1 J value 23 ° C according to ISO 1628-1
DSC nach ISO 11357 und DIN 53765 DSC according to ISO 11357 and DIN 53765
Literaturstellen: , Olefine Metathesis and Metathesis Polymerization', K. J. Irvin, J. C. Mol, Academic Press 1997. References: "Olefins Metathesis and Metathesis Polymerization", K.J. Irvin, J.C. Mol, Academic Press 1997.
2 ,Handbook of Metathesis', Vol. 1-3, R. H. Grubbs, Wiley-VCH 2003. 2 , Handbook of Metathesis, Vol. 1-3, RH Grubbs, Wiley-VCH 2003.
3· ,Weskamp, T.; Kohl, F. J.; Herrmann, W. A. J. Organomet. Chem. 1999, 582, 362-365. Weskamp, T.; Kohl, F. j.; Hieringer, W.; Gleich, D.; Hermann, W. A. Angew. Chem. Int. Ed. 1999, 38, 2416-2419. 3 ·, Weskamp, T .; Kohl, F. J .; Herrmann, W.A. J. Organomet. Chem. 1999, 582, 362-365. Weskamp, T .; Kohl, F. j .; Hieringer, W .; Same, D .; Hermann, W.A. Angew. Chem. Int. Ed. 1999, 38, 2416-2419.
4· ,Nguyen, S. T.; Johnson, L. W.; Grubbs, R. H. ; Ziller, J. W. J. Am. Chem. Soc. 1992, 114, 3974-3975. Bielawski, C. W.; Grubbs, R. H. Angew. Chem. Int. Ed. 2000, 39, 2903-2906. 4 ·, Nguyen, ST; Johnson, LW; Grubbs, RH; Ziller, JWJ Am. Chem. Soc. 1992, 114, 3974-3975. Bielawski, CW; Grubbs, RH Angew. Chem. Int. Ed. 2000, 39, 2903-2906.

Claims

Patentansprüche: claims:
1. Po lyo ctenamer , 1. Po lyo ctenamer,
dadurch gekennzeichnet,  characterized,
dass es bei Raumtemperatur flüssig, farblos und klar ist.  that it is liquid, colorless and clear at room temperature.
2. Polyoctenamer nach Anspruch 1 , 2. Polyoctenamer according to claim 1,
dadurch gekennzeichnet,  characterized,
dass es ein mittleres Molekulargewicht zwischen 10.000 und 50.000 g/mol,  that it has an average molecular weight between 10,000 and 50,000 g / mol,
einen eis- Anteil zwischen 65 bis 70 %,  an egg percentage between 65 to 70%,
einen Schmelzpunkt von -10 bis 10 °C  a melting point of -10 to 10 ° C
und einen J-Wert nach ISO 1628-1 bei 23 °C zwischen 40 und 50 ml/g aufweist.  and a J value according to ISO 1628-1 at 23 ° C between 40 and 50 ml / g.
3. Verfahren zur Herstellung von Polyoctenamer nach Anspruch 1 und 2, 3. Process for the preparation of polyoctenamer according to claim 1 and 2,
dadurch gekennzeichnet,  characterized,
dass Cycloocten durch ringöffnende, metathetische Polymerisation in Gegenwart eines Katalysators und eines Reglers umgesetzt wird.  that cyclooctene is reacted by ring-opening, metathetic polymerization in the presence of a catalyst and a regulator.
4. Verfahren zur Herstellung von Polyoctenamer nach einem der vorhergehenden Ansprüch dadurch gekennzeichnet, 4. Process for the preparation of polyoctenamer according to one of the preceding claims characterized in that
dass Cycloocten durch ringöffnende, metathetische Polymerisation in Gegenwart eines Katalysatorsystems und eines Reglers umgesetzt wird, wobei die Reaktion bei einem Umsatz zwischen 30 und 100 % gestoppt wird.  that cyclooctene is reacted by ring-opening, metathetic polymerization in the presence of a catalyst system and a regulator, wherein the reaction is stopped at a conversion between 30 and 100%.
5. Verfahren zur Herstellung von Polyoctenamer nach einem der vorhergehenden Ansprüch dadurch gekennzeichnet, 5. Process for the preparation of polyoctenamer according to one of the preceding claims characterized in that
dass als Katalysatorsystem eine Mischung von Wolframhexachlorid (WC^) und Ethylaluminiumdichlorid (EtAlCl2) eingesetzt wird. in that the catalyst system used is a mixture of tungsten hexachloride (WC 1) and ethylaluminum dichloride (EtAlCl 2 ).
6. Verfahren zur Herstellung von Polyoctenamer nach einem der vorhergehenden Ansprüch dadurch gekennzeichnet, dass als Regler acyclische Alkene mit einer oder mehreren nichtkonjugierten Doppelbindungen, die end- oder innenständig liegen können und die keine Substituenten tragen oder cyclische Verbindungen, die in ihrer Seitenkette eine vinylische, allylische oder höher homologe Doppelbindung mit niedrigem Substitutionsgrad aufweisen, eingesetzt werden. 6. Process for the preparation of polyoctenamer according to one of the preceding claims characterized in that that acyclic alkenes having one or more non-conjugated double bonds, which may be terminal or internal, and which carry no substituents, or cyclic compounds which have a vinylic, allylic or higher homologous double bond with a low degree of substitution in their side chain, are used as regulators.
7. Verfahren zur Herstellung von Polyoctenamer nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, 7. Process for the preparation of polyoctenamer according to one of the preceding claims, characterized in that
dass die Polymerisation in einem Lösungsmittel durchgeführt wird.  that the polymerization is carried out in a solvent.
8. Verfahren zur Herstellung von Polyoctenamer nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, 8. Process for the preparation of polyoctenamer according to one of the preceding claims, characterized in that
dass die Polymerisation ohne Lösungsmittel durchgeführt wird.  the polymerization is carried out without solvent.
9. Verwendung von Polyoctenamer nach einem der vorhergehenden Ansprüche in 9. Use of Polyoctenamer according to any one of the preceding claims in
Verpackungsmaterialien.  Packaging materials.
EP11722405.5A 2010-06-25 2011-05-26 Method for producing fluid, colourless polyoctenamer by ring-opening, metathetic polymerization of cyclooctene Withdrawn EP2585514A1 (en)

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