EP2265652A1 - Oxymethylene polymers, method for the production thereof, and use of same - Google Patents

Oxymethylene polymers, method for the production thereof, and use of same

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Publication number
EP2265652A1
EP2265652A1 EP09732684A EP09732684A EP2265652A1 EP 2265652 A1 EP2265652 A1 EP 2265652A1 EP 09732684 A EP09732684 A EP 09732684A EP 09732684 A EP09732684 A EP 09732684A EP 2265652 A1 EP2265652 A1 EP 2265652A1
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EP
European Patent Office
Prior art keywords
oxymethylene
molecular weight
oxymethylene polymers
polymers
low molecular
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
EP09732684A
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German (de)
French (fr)
Inventor
Michael Haubs
Michael Hoffmockel
Jürgen LINGNAU
Horst Roeschert
Robert Gronner
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Ticona GmbH
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Ticona GmbH
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Publication date
Application filed by Ticona GmbH filed Critical Ticona GmbH
Publication of EP2265652A1 publication Critical patent/EP2265652A1/en
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    • 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
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/04—Polymerisation by using compounds which act upon the molecular weight, e.g. chain-transferring agents
    • 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
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/18—Copolymerisation of aldehydes or ketones
    • C08G2/24—Copolymerisation of aldehydes or ketones with acetals
    • 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
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/30—Chemical modification by after-treatment
    • C08G2/34—Chemical modification by after-treatment by etherification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/02—Polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/04—Copolyoxymethylenes

Definitions

  • Oxymethylene polymers process for their preparation and their use
  • the present invention relates to novel oxymethylene polymers for producing moldings having excellent low-temperature impact strength and high elastic modulus, their use and processes for producing the oxymethylene polymers.
  • Oxymethylene polymers are accessible by the anionic polymerization of formaldehyde.
  • the polymers thus obtained are capped by stable end groups, for example by introduction of ether or ester end groups. Examples of this can be found in DE-AS-1, 158,709, US Pat.
  • Ester-capped oxymethylene polymers are degraded at elevated temperatures or in basic environments
  • Ether end groups masked oxymethylene polymers by higher chemical stability.
  • the processes proposed so far for the preparation of these polymers comprise a separate step in capping the polymers (see, for example, US-A-3,161,616), and the high molecular weights required for practical applications are not achieved in this way.
  • this polymer-analogous reaction is not quantitative, resulting in low yields and / or a product with still increased degradation rate.
  • stable oxymethylene polymers can be prepared by cationically copolymerizing formaldehyde-unit-forming monomers, preferably trioxane, with small amounts of comonomers and thereby incorporating largely random amounts of oxyalkylene units into the chain.
  • the molecular weight control is carried out by transmitter, usually
  • Dialkylformale By degradation of the unstable ends to the first oxyalkylene unit in the alkaline (hydrolysis) so copolymers are obtained which have stable hydroxyalkyl (from the comonomer) and alkyl end groups (from the carrier).
  • oxymethylene polymers which in addition to oxymethylene units contain small amounts of other oxyalkylene units, in particular on oxyethylene units, and which have a low content of formyl end groups.
  • the proportion of the other oxyalkylene units, based on the proportion of Oxymethylenein units, is 0.07 to 0.5 mol%. Falling below the specified content of oxyalkylene units produce polymers with insufficient heat resistance and hot water resistance.
  • Polymers are prepared in the presence of a selected amount of a perfluoroalkylsulfonic acid (derivative) as a catalyst and low-water and low-acid monomers are used.
  • the deactivation of the polymerization mixture is carried out by addition of selected crystalline basic adsorbents, for example of oxides or of hydroxides of alkali metal or alkaline earth metals. Accordingly, it is also possible to prepare copolymers having a higher content of oxyalkylene units.
  • the polymer formed precipitates already in the early phase of the polymerization - regardless of whether one carries out a bulk polymerization, a polymerization in the presence of an inert solvent or a suspension polymerization.
  • the mass fraction of the low molecular weight fraction is between 5 and 15%.
  • the low molecular weight fraction can be determined by means of gel permeation chromatography (GPC). These significant amounts of the low molecular weight fraction have a not inconsiderable influence on the mechanical properties of the polymer.
  • oxymethylene polymers with unimodal molecular weight distribution are also known from cationic polymerization of trioxane (EP 0 716 105 A1), which are distinguished by improved impact strength and flexural modulus of elasticity. The improvement is achieved by adjusting a unimodal molecular weight distribution, a comonomer content of 0.3 to 0.9 mol% and a
  • the preparation of these polymers is carried out by polymerization in a homogeneous phase at elevated temperature. As a result, increased side reactions occur and the polymer yield in the production is limited.
  • oxymethylene polymers are known, which are prepared by admixing linear low molecular weight Oxymethylenan former to conventionally prepared by cationic polymerization Oxymethylenpolymeren (US 6,388,049 B1). This admixture takes place in the range of 1 to 500 parts per 100
  • the present invention relates to oxymethylene polymers which are homopolymers or copolymers in which the molar ratio of comonomer units to oxymethylene units is less than 0.008, which have an at least bimodal molecular weight distribution and in which the proportion of low molecular weight oxymethylene polymers having molecular weights below
  • the molar ratio of comonomer units to oxymethylene units is between 0.0004 and 0.005.
  • the oxymethylene polymers according to the invention particularly preferably have a
  • the low molecular weight fraction preferably consists of more than 50% by weight, particularly preferably more than 80% by weight, of cyclic polyoxymethylenes.
  • the distinction between linear and cyclic components can be determined by MALDI-TOF-MS (Matrix Assisted Laser Desorption Ionization -
  • the oxymethylene polymers according to the invention have an at least bimodal molecular weight distribution. It is preferably a bimodal distribution, but it may also be higher modal distributions.
  • the oxyalkylene unit is particularly preferably -O- (CH 2) 2-
  • the molecular weights, characterized as volume melt index MVR, of these polymers can be adjusted within wide ranges.
  • Typical MVR values are from 0.1 to 100 g / 10 min, preferably 1 to 80 g / 10 min, particularly preferably 2 to 20 g / 10 min, measured according to EN ISO 1133 at 190 0 C under a load of 2.16 kg ,
  • Products according to the invention can be prepared, for example, by mixing a mixture of the monomers (preferably trioxane and dioxolane) and
  • Molecular weight regulator (preferably methylal) are added at temperatures above 65 0 C in a gas-tight polymerization reactor with a cationic initiator.
  • the crystallization heat of the precipitated polymer heats the reaction mixture.
  • further heat can be supplied so that a predetermined temperature profile (polymerization temperature as
  • T f (t)
  • T f (t)
  • T f (t)
  • the temperature profile can be adjusted so that the reaction mixture becomes homogeneous again at the end of the polymerization.
  • a basic component for example triethylamine
  • the polymerization is stopped. Since the low molecular weight fraction forms at the beginning of the precipitation polymerization and disappears again in the polymerization-active melt, the content of the low molecular weight fraction can be deliberately between 1% by weight and 5 by the time of addition of the basic component or by the temperature profile of the polymerization Adjust% by weight.
  • the crude polymer is worked up, any existing unstable hemiacetal end groups are degraded by hydrolysis, compounded and formulated.
  • branching agents can be used. Usually, the amount of branching agent is not more than 1% by weight based on the total amount of the monomer used for producing the oxymethylene polymers, preferably not more than 0.3% by weight.
  • preferred Branches are polyfunctional epoxides, polyfunctional glycidyl ethers or polyfunctional cyclic formals.
  • Preferred chain transfer agents are compounds of the formula I.
  • R 1 and R 2 independently of one another are linear or branched alkyl radicals, in particular CrC ⁇ -alkyl radicals, which are preferably straight-chain.
  • R 1 and R 2 are more preferably independently of one another methyl, ethyl, propyl or butyl, in particular methyl.
  • r is an integer and can be from 1 to 9.
  • OH end groups in the polymer and chain transfer agents can be used, which transfer protons. Examples of these
  • the chain transfer agents are usually used in amounts of up to 20,000 ppm by weight, preferably from 100 to 5,000 ppm, more preferably from 200 to 2,000 ppm, based on the monomer mixture.
  • protic acids such as fluorinated or chlorinated alkyl and arylsulfonic acids
  • strong protic acids such as fluorinated or chlorinated alkyl and arylsulfonic acids
  • Trifluoromethanesulfonic acid or derivatives thereof such as esters or anhydrides of protic acids, in particular trifluoromethanesulfonic anhydride or Trifluormethansulfonklareester, such as the alkyl esters.
  • perchloric acid and its esters are also suitable.
  • initiators are those compounds which start polymerization in concentrations of ⁇ 10 -4 mol%.
  • Lewis acids such. B. BF 3 or BF 3 ethers as initiators, but in somewhat higher concentrations, use.
  • the polymers according to the invention can be prepared by mixing unimodally distributed and conventional bi- or higher modal distributed
  • Oxymethylene polymers containing 5 to 15 mass percent of low molecular weight fraction are prepared. Unimodal distributed polyoxymethylene polymers are described in EP 0716 105. In the context of this description, unimodally distributed oxymethylene polymers are understood as meaning those polymers which have only one peak in the molecular weight distribution, this peak being above 10,000 daltons, preferably between 30,000 and 200,000 daltons.
  • the molded articles produced from the oxymethylene polymers obtained in this way have excellent low-temperature notched-bar impact strengths and high moduli of elasticity combined with good chemical resistance.
  • the shaping can be carried out by known molding methods, for example by blow molding or by injection molding.
  • the invention also relates to the use of the above-described oxymethylene polymers for the production of molded articles with good
  • Example 1 (Inventive)
  • the starting compounds were metered by means of HPLC pumps and mixed efficiently in the premixing zone by means of static mixing elements before they reached the extruder for polymerization.
  • the deactivator used was a mixture of 0.2% by weight of triethylamine in 1,3-dioxolane. This solution was metered in between zones 5 and 6 at a delivery rate of 40 g / h.
  • the residence time in the extruder was about 1 min.
  • DMAc dimethylacetamide
  • the oxymethylene polymer of Example 1 of EP 716,105 was readjusted.
  • the oxymethylene polymer of Comparative Example 3 was prepared as follows: a mixture of 100 g of 1, 3,5-trioxane and 0.7 g of 1,3-dioxolane was stirred at 100 ° C. with 0.1 ml of a solution of trifluoromethanesulfonic acid (200 ppm) Methylal added with stirring. After a reaction time of about 5 min solid reaction product was dissolved in DMAc in the boiling heat and boiled for 1 h reflux to remove unstable chain ends. The precipitated after cooling polymer was boiled twice in methanol, filtered and dried.
  • Example 5 Separation of the low molecular weight constituents from oxymethylene polymers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Polyethers (AREA)

Abstract

The invention relates to oxymethylene polymers which are distributed bimodally or higher and have a target low-molecular part of between 1 and 5 mass percent. Moulded bodies consisting of said polymers are characterised by high low-temperature impact strength combined with a high elasticity modululus.

Description

Beschreibung description
Oxymethylenpolymere, Verfahren zu deren Herstellung und deren VerwendungOxymethylene polymers, process for their preparation and their use
Die vorliegende Erfindung betrifft neue Oxymethylenpolymere zur Herstellung von Formkörpern mit ausgezeichneter Tieftemperaturkerbschlagzähigkeit und hohem Elastizitätsmodul, deren Verwendung und Verfahren zur Herstellung der Oxymethylenpolymeren.The present invention relates to novel oxymethylene polymers for producing moldings having excellent low-temperature impact strength and high elastic modulus, their use and processes for producing the oxymethylene polymers.
Oxymethylen-Polymere sind durch die anionische Polymerisation von Formaldehyd zugänglich. Um die für eine praktische Anwendung erforderliche thermische Stabilität des Polymeren zu gewährleisten, werden die so erhaltenen Polymeren durch stabile Endgruppen verkappt, beispielsweise durch Einführung von Ether- oder Ester-Endgruppen. Beispiele dafür finden sich in den DE-AS-1 ,158,709, US-A-Oxymethylene polymers are accessible by the anionic polymerization of formaldehyde. In order to ensure the thermal stability of the polymer required for a practical application, the polymers thus obtained are capped by stable end groups, for example by introduction of ether or ester end groups. Examples of this can be found in DE-AS-1, 158,709, US Pat.
3,998,791 , US-A-3,393,179, DE-A-1 ,445,255, DE-AS-1 , 158,709, US-A-4,097,453 und US-A-3,161 ,616.3,998,791, US-A-3,393,179, DE-A-1, 445,255, DE-AS-1, 158,709, US-A-4,097,453 and US-A-3,161,616.
Während mit Ester-Endgruppen verkappte Oxymethylen-Polymere bei erhöhten Temperaturen oder in basischen Umgebungen abgebaut werden, zeichnen sich mitEster-capped oxymethylene polymers are degraded at elevated temperatures or in basic environments
Ether-Endgruppen verkappte Oxymethylen-Polymere durch eine höhere chemische Stabilität aus. Die bisher vorgeschlagenen Verfahren zur Herstellung dieser Polymeren umfassen jedoch einen separaten Schritt zur Verkappung der Polymeren (vergl. z.B. US-A-3,161 ,616), die für praktische Anwendungen erforderlichen hohen Molekulargewichte werden auf diesem Wege nicht erreicht. Zudem verläuft diese polymeranaloge Reaktion nicht quantitativ, was zu niedrigen Ausbeuten und/oder einem Produkt mit immer noch erhöhter Abbaurate führt.Ether end groups masked oxymethylene polymers by higher chemical stability. However, the processes proposed so far for the preparation of these polymers comprise a separate step in capping the polymers (see, for example, US-A-3,161,616), and the high molecular weights required for practical applications are not achieved in this way. In addition, this polymer-analogous reaction is not quantitative, resulting in low yields and / or a product with still increased degradation rate.
Die so durch anionische Polymerisation von Formaldehyd erhaltenen Homopolymeren weisen eine unimodale Molekulargewichtsverteilung auf (PolymerThe homopolymers thus obtained by anionic polymerization of formaldehyde have a unimodal molecular weight distribution (Polymer
Degradation and Stability, 92 (2007) 2181-2189). Alternativ lassen sich stabile Oxymethylenpolymere dadurch herstellen, daß man Formaldehyd-Einheiten bildende Monomere, bevorzugt Trioxan, mit geringen Mengen von Comonomeren kationisch copolymerisiert und dadurch in geringen Mengen Oxyalkyleneinheiten weitgehend statistisch in die Kette einbaut. Die Molekulargewichtsregelung erfolgt dabei durch Überträger, in der RegelDegradation and Stability, 92 (2007) 2181-2189). Alternatively, stable oxymethylene polymers can be prepared by cationically copolymerizing formaldehyde-unit-forming monomers, preferably trioxane, with small amounts of comonomers and thereby incorporating largely random amounts of oxyalkylene units into the chain. The molecular weight control is carried out by transmitter, usually
Dialkylformale. Durch Abbau der instabilen Enden bis zur ersten Oxyalkyleneinheit im Alkalischen (Hydrolyse) werden so Copolymere erhalten, die stabile Hydroxyalkyl- (aus dem Comonomer) und Alkyl-Endgruppen (aus dem Überträger) aufweisen. So sind z.B. aus der EP-A-504,405 Oxymethylen-Polymere bekannt, die neben Oxymethyleneinheiten geringe Anteile an anderen Oxyalkyleneinheiten, insbesondere an Oxyethyleneinheiten enthalten, und die einen geringen Gehalt an Formylendgruppen aufweisen. Der Anteil der anderen Oxyalkyleneinheiten, bezogen auf den Anteil der Oxymethylenein-heiten, beträgt 0,07 bis 0,5 Mol%. Bei Unterschreiten des angegebenen Gehaltes an Oxyalkyleneinheiten entstehen Polymere mit unzureichender Hitzebeständigkeit und Heisswasserbeständigkeit. DieDialkylformale. By degradation of the unstable ends to the first oxyalkylene unit in the alkaline (hydrolysis) so copolymers are obtained which have stable hydroxyalkyl (from the comonomer) and alkyl end groups (from the carrier). Thus, e.g. From EP-A-504,405 oxymethylene polymers are known, which in addition to oxymethylene units contain small amounts of other oxyalkylene units, in particular on oxyethylene units, and which have a low content of formyl end groups. The proportion of the other oxyalkylene units, based on the proportion of Oxymethylenein units, is 0.07 to 0.5 mol%. Falling below the specified content of oxyalkylene units produce polymers with insufficient heat resistance and hot water resistance. The
Polymeren werden in Gegenwart einer ausgewählten Menge eines Perfluoralkylsulfonsäure(derivats) als Katalysator hergestellt und es kommen wasser- und ameisensäurearme Monomere zum Einsatz. Die Deaktivierung des Polymerisationsgemisches erfolgt durch Zugabe von ausgewählten kristallinen basischen Adsorbentien, beispielsweise von Oxiden oder von Hydroxiden von Alkalioder Erdalkali-metallen. Entsprechend lassen sich auch Copolymere mit einem höheren Gehalt an Oxyalkyleneinheiten herstellen.Polymers are prepared in the presence of a selected amount of a perfluoroalkylsulfonic acid (derivative) as a catalyst and low-water and low-acid monomers are used. The deactivation of the polymerization mixture is carried out by addition of selected crystalline basic adsorbents, for example of oxides or of hydroxides of alkali metal or alkaline earth metals. Accordingly, it is also possible to prepare copolymers having a higher content of oxyalkylene units.
Unter den genannten Polymerisationsbedingungen fällt das gebildete Polymer bereits in der frühen Phase der Polymerisation aus - unabhängig davon, ob man eine Substanzpolymerisation, eine Polymerisation in Gegenwart eines inerten Lösemittels oder eine Suspensionspolymerisation durchführt. Dies führt in der Folge immer zu einer bimodalen Molekulargewichtsverteilung: Ein Maximum in der Kurve der Molekulargewichtsverteilung befindet sich dabei typischerweise bei vergleichsweise niedrigen Molekulargewichten, beispielsweise bei 2.000 bis 5.000Under the said polymerization conditions, the polymer formed precipitates already in the early phase of the polymerization - regardless of whether one carries out a bulk polymerization, a polymerization in the presence of an inert solvent or a suspension polymerization. This always leads to a bimodal molecular weight distribution: a maximum in the curve of the molecular weight distribution is typically at comparatively low molecular weights, for example 2,000 to 5,000
Dalton; ein weiteres Maximum in der Kurve der Molekulargewichtsverteilung befindet sich dabei typischerweise bei vergleichsweise hohen Molekulargewichten, beispielsweise bei 50.000 - 100.000 Dalton. Der Massenanteil des niedermolekularen Anteils liegt zwischen 5 und 15%. Der niedermolekulare Anteil lässt sich mittels Gelpermeationschromatographie (GPC) bestimmen. Diese signifikanten Mengen des niedermolekularen Anteils haben einen nicht unerheblichen Einfluß auf die mechanischen Eigenschaften des Polymeren.Dalton; another maximum in the curve of the molecular weight distribution is typically at comparatively high molecular weights, for example 50,000-100,000 daltons. The mass fraction of the low molecular weight fraction is between 5 and 15%. The low molecular weight fraction can be determined by means of gel permeation chromatography (GPC). These significant amounts of the low molecular weight fraction have a not inconsiderable influence on the mechanical properties of the polymer.
Auch aus kationischer Polymerisation des Trioxan sind andererseits Oxymethylenpolymere mit unimodaler Molekulargewichtsverteilung bekannt (EP 0 716 105 A1), die sich durch verbesserte Schlagzähigkeit und Biege-E-Modul auszeichnen. Die Verbesserung wird durch Einstellung einer unimodalen Molmassenverteilung, eines Comonomergehaltes von 0,3 bis 0,9 mol% und einesOn the other hand, oxymethylene polymers with unimodal molecular weight distribution are also known from cationic polymerization of trioxane (EP 0 716 105 A1), which are distinguished by improved impact strength and flexural modulus of elasticity. The improvement is achieved by adjusting a unimodal molecular weight distribution, a comonomer content of 0.3 to 0.9 mol% and a
Schmelzindexes von 1 bis 5 g/10 min erzielt.Melt index of 1 to 5 g / 10 min achieved.
Die Herstellung dieser Polymere erfolgt durch Polymerisation in homogener Phase bei erhöhter Temperatur. Dadurch treten verstärkt Nebenreaktionen auf und die Polymerausbeute bei der Herstellung ist begrenzt.The preparation of these polymers is carried out by polymerization in a homogeneous phase at elevated temperature. As a result, increased side reactions occur and the polymer yield in the production is limited.
Schließlich sind Oxymethylenpolymere bekannt, die durch Zumischung von linearen niedermolekularen Oxymethylenanteilen zu konventionell durch kationische Polymerisation hergestellten Oxymethylenpolymeren hergestellt werden (US 6,388,049 B1 ). Diese Zumischung erfolgt im Bereich von 1 bis 500 Teile auf 100Finally, oxymethylene polymers are known, which are prepared by admixing linear low molecular weight Oxymethylenanteilen to conventionally prepared by cationic polymerization Oxymethylenpolymeren (US 6,388,049 B1). This admixture takes place in the range of 1 to 500 parts per 100
Teile konventionell hergestelltem Oxymethylenpolymer. Ausgehend von mindestens 5% niedermolekularem Anteil im Basispolymer wird somit ein Oxymethylenpolymer mit einem niedermolekularem Anteil im Bereich von mindestens 6% bis 84% im Polymer beschrieben. Zum größten Teil handelt es sich bei diesem niedermolekularen Anteil um lineare Polymere.Parts of conventionally produced oxymethylene polymer. Starting from at least 5% low molecular weight fraction in the base polymer, an oxymethylene polymer having a low molecular weight fraction in the range of at least 6% to 84% in the polymer is thus described. For the most part, this low molecular weight fraction is linear polymers.
Aufgabe der vorliegenden Erfindung ist die Bereitstellung von ausgewählten Oxymethylenpolymeren, die sich mittels an sich bekannter Formgebungs-verfahren zu Formkörpern verarbeiten lassen, welche sich durch eine sehr hohe Tieftemperaturkerbschlagzähigkeit und weiter erhöhtem Elastizitäts-modul auszeichnen. Die vorliegende Erfindung betrifft Oxymethylenpolymere, die Homopolymere oder Copolymere sind, bei denen das molare Verhältnis von Comonomer-einheiten zu Oxymethyleneinheiten kleiner als 0,008 ist, die eine mindestens bimodale Molekulargewichtsverteilung aufweisen und bei denen der Anteil von niedermolekularen Oxymethylenpolymeren mit Molekulargewichten unterhalb vonIt is an object of the present invention to provide selected oxymethylene polymers which can be processed into shaped articles by means of shaping processes known per se, which are distinguished by a very high low-temperature impact strength and a further increased modulus of elasticity. The present invention relates to oxymethylene polymers which are homopolymers or copolymers in which the molar ratio of comonomer units to oxymethylene units is less than 0.008, which have an at least bimodal molecular weight distribution and in which the proportion of low molecular weight oxymethylene polymers having molecular weights below
10.000 Dalton zwischen 1 und 5 Gew. %, bezogen auf die Gesamtmasse der Oxymethylenpolymeren, beträgt. Bevorzugt liegt das molare Verhältnis von Comonomereinheiten zu Oxymethyleneinheiten zwischen 0,0004 und 0,005.10,000 daltons between 1 and 5 wt.%, Based on the total mass of the oxymethylene polymers is. Preferably, the molar ratio of comonomer units to oxymethylene units is between 0.0004 and 0.005.
Besonders bevorzugt weisen die erfindungsgemäßen Oxymethylenpolymeren einenThe oxymethylene polymers according to the invention particularly preferably have a
Anteil an Alkyletherendgruppen, bezogen auf alle Endgruppen, von mindestens 70 % auf.Proportion of alkyl ether end groups, based on all end groups, of at least 70%.
Der Anteil von niedermolekularen Oxymethylenpolymeren mit Molekular-gewichten unterhalb von 10.000 Dalton beträgt bei den erfindungsgemäßenThe proportion of low molecular weight oxymethylene polymers with molecular weights below 10,000 daltons is in the inventive
Oxymethylenpolymeren 1 bis 5 Gew. %, bezogen auf die Gesamtmasse der Oxymethylenpolymeren. Der niedermolekulare Anteil besteht bevorzugt zu mehr als 50 Gew.%, besonders bevorzugt zu mehr als 80 Gew.%, aus zyklischen Polyoxymethylenen. Die Unterscheidung zwischen linearem und zyklischem Anteil lässt sich mittels MALDI-TOF-MS (Matrix Assisted Laser Desorption Ionisation -Oxymethylene polymers 1 to 5 wt.%, Based on the total mass of the oxymethylene polymers. The low molecular weight fraction preferably consists of more than 50% by weight, particularly preferably more than 80% by weight, of cyclic polyoxymethylenes. The distinction between linear and cyclic components can be determined by MALDI-TOF-MS (Matrix Assisted Laser Desorption Ionization -
Time of Flight Mass Sprectrometry) vornehmen.Time of Flight Mass Sprectrometry).
Die erfindungsgemäßen Oxymethylenpolymeren weisen eine mindestens bimodale Molekulargewichtsverteilung auf. Dabei handelt es sich vorzugsweise um eine bimodale Verteilung, es kann sich aber auch um höhermodale Verteilungen handeln.The oxymethylene polymers according to the invention have an at least bimodal molecular weight distribution. It is preferably a bimodal distribution, but it may also be higher modal distributions.
In einer bevorzugten Ausführungsform enthält das Produkt 0,04 bis 0,5 mol%, bezogen auf Oxymethyleneinheiten, der Struktur In a preferred embodiment, the product contains from 0.04 to 0.5 mol%, based on oxymethylene units, of the structure
worin x eine ganze Zahl von 2 bis 8 bedeutet. Besonders bevorzugt ist die Oxyalkyleneinheit -O-(CH2)2--where x is an integer from 2 to 8. The oxyalkylene unit is particularly preferably -O- (CH 2) 2-
Die Molekulargewichte, charakterisiert als Volumenschmelzindex MVR, dieser Polymeren können innerhalb weiter Bereiche eingestellt werden. Typische MVR- Werte betragen 0,1 bis 100 g/10 min, bevorzugt 1 bis 80 g/10min, besonders bevorzugt 2 bis 20 g/10 min, gemessen nach EN ISO 1133 bei 190 0C bei einer Belastung von 2,16 kg.The molecular weights, characterized as volume melt index MVR, of these polymers can be adjusted within wide ranges. Typical MVR values are from 0.1 to 100 g / 10 min, preferably 1 to 80 g / 10 min, particularly preferably 2 to 20 g / 10 min, measured according to EN ISO 1133 at 190 0 C under a load of 2.16 kg ,
Erfindungsgemäße Produkte können beispielsweise hergestellt werden, indem eine Mischung der Monomere (vorzugsweise Trioxan und Dioxolan) undProducts according to the invention can be prepared, for example, by mixing a mixture of the monomers (preferably trioxane and dioxolane) and
Molekulargewichtsregler (vorzugsweise Methylal) bei Temperaturen oberhalb von 650C in einem gasdichten Polymerisationsreaktor mit einem kationischen Initiator versetzt werden. Durch die Kristallisationwärme des ausfallenden Polymers erwärmt sich das Reaktionsgemisch. Gegebenfalls kann weitere Wärme zugeführt werden, so dass sich ein vorgegebenes Temperaturprofil (Polymerisationstemperatur alsMolecular weight regulator (preferably methylal) are added at temperatures above 65 0 C in a gas-tight polymerization reactor with a cationic initiator. The crystallization heat of the precipitated polymer heats the reaction mixture. Optionally, further heat can be supplied so that a predetermined temperature profile (polymerization temperature as
Funktion der Polymerisationszeit) T = f(t)) einstellen lässt. Das Temperaturprofil lässt sich so einstellen, daß das Reaktionsgemisch zum Ende der Polymerisation wieder homogen wird. Durch Zusatz einer basischen Komponente (beispielsweise Triethylamin) in die homogene Schmelze wird die Polymerisation abgebrochen. Da sich der niedermolekulare Anteil zu Beginn der Fällungspolymerisation bildet und in der polymerisationsaktiven Schmelze wieder verschwindet, lässt sich durch den Zeitpunkt der Zugabe der basischen Komponente oder durch das Temperatur-profil der Polymerisation der Gehalt des niedermolekularen Anteils gezielt zwischen 1 Gew.-% und 5 Gew.-% einstellen. Im Anschluss wird das Rohpolymer aufgearbeitet, eventuell vorhandene instabile Halbacetalendgruppen durch Hydrolyse abgebaut, compoundiert und konfektioniert. Diese Verfahrensschritte sind dem Fachmann bekannt.Function of the polymerization time) T = f (t)) can be set. The temperature profile can be adjusted so that the reaction mixture becomes homogeneous again at the end of the polymerization. By addition of a basic component (for example triethylamine) in the homogeneous melt, the polymerization is stopped. Since the low molecular weight fraction forms at the beginning of the precipitation polymerization and disappears again in the polymerization-active melt, the content of the low molecular weight fraction can be deliberately between 1% by weight and 5 by the time of addition of the basic component or by the temperature profile of the polymerization Adjust% by weight. Subsequently, the crude polymer is worked up, any existing unstable hemiacetal end groups are degraded by hydrolysis, compounded and formulated. These process steps are known to the person skilled in the art.
Gewünschtenfalls können geringe Mengen von Verzweigern eingesetzt werden. Üblicherweise beträgt die Menge an Verzweigern nicht mehr als 1 Gew. %, bezogen auf die zur Herstellung der Oxymethylen-Polymeren verwendeten Gesamtmonomermenge, vorzugsweise nicht mehr als 0,3 Gew. %. Bevorzugte Verzweiger sind mehrfach funktionelle Epoxide, mehrfach funktionelle Glycidylether oder mehrfach funktionelle cyclische Formale.If desired, small amounts of branching agents can be used. Usually, the amount of branching agent is not more than 1% by weight based on the total amount of the monomer used for producing the oxymethylene polymers, preferably not more than 0.3% by weight. preferred Branches are polyfunctional epoxides, polyfunctional glycidyl ethers or polyfunctional cyclic formals.
Bevorzugte Kettenüberträger (Regler) sind Verbindungen der Formel IPreferred chain transfer agents (regulators) are compounds of the formula I.
R1 -(0-CH2JrO-R2 (I),R 1 - (O-CH 2 JrO-R 2 (I),
worin R1 und R2 unabhängig voneinander lineare oder verzweigte Alkylreste, insbesondere CrCβ-Alkylreste, die bevorzugt geradkettig sind, bedeuten.wherein R 1 and R 2 independently of one another are linear or branched alkyl radicals, in particular CrCβ-alkyl radicals, which are preferably straight-chain.
Besonders bevorzugt sind R1 und R2 unabhängig voneinander Methyl, Ethyl, Propyl oder Butyl, insbesondere Methyl.R 1 and R 2 are more preferably independently of one another methyl, ethyl, propyl or butyl, in particular methyl.
r bedeutet eine ganze Zahl und kann die Werte von 1 bis 9 annehmen.r is an integer and can be from 1 to 9.
Besonders bevorzugte Kettenüberträger sind Verbindungen der Formel I, worin r=1 ist, ganz besonders bevorzugt Methylal.Particularly preferred chain transfer agents are compounds of the formula I in which r = 1, very particularly preferably methylal.
Zur gezielten Erzeugung von OH-Endgruppen im Polymeren können auch Kettenüberträger eingesetzt werden, die Protonen übertragen. Beispiele für dieseFor targeted generation of OH end groups in the polymer and chain transfer agents can be used, which transfer protons. Examples of these
Gruppe sind Wasser, Ameisensäure, einfache und mehrfache Alkohole wie Methanol, Ethanol, Ethylenglykol, Butandiol, Glycerin oder 1 ,1 ,1-Trimethylolpropan. Durch Einsatz dieser protischen Überträger werden zum einem gewissen Anteil instablile Halbacetal-Endgruppen erzeugt, die in der anschließenden Hydrolyse zu stabilen Alkylen-OH Endgruppen führen. Bevorzugte Überträger sind mehrfacheGroup are water, formic acid, simple and multiple alcohols such as methanol, ethanol, ethylene glycol, butanediol, glycerol or 1, 1, 1-trimethylolpropane. The use of these protic transfer agents produces, to a certain extent, instable hemiacetal end groups which lead to stable alkylene-OH end groups in the subsequent hydrolysis. Preferred carriers are multiple
Alkohole.Alcohols.
Die Kettenüberträger werden üblicherweise in Mengen von bis zu 20.000 Gewichts- ppm, vorzugsweise von 100 bis 5.000 ppm, besonders bevorzugt 200 bis 2000 ppm bezogen auf das Monomergemisch, eingesetzt.The chain transfer agents are usually used in amounts of up to 20,000 ppm by weight, preferably from 100 to 5,000 ppm, more preferably from 200 to 2,000 ppm, based on the monomer mixture.
Als Initiatoren können insbesondere starke Protonensäuren, wie fluorierte oder chlorierte Alkyl- und Arylsulfonsäuren verwendet werden. Beispiele dafür sind Trifluormethansulfonsäure oder deren Derivate, wie Ester oder Anhydride von Protonensäuren, insbesondere Trifluormethansulfonsäureanhydrid oder Trifluormethansulfonsäureester, wie die Alkylester. Ebenfalls geeignet sind Perchlorsäure und deren Ester. Erfindungsgemäß sind Initiatoren solche Verbindungen, die in Konzentrationen von < 10~4 Mol% die Polymerisation starten.In particular, strong protic acids, such as fluorinated or chlorinated alkyl and arylsulfonic acids, can be used as initiators. Examples are Trifluoromethanesulfonic acid or derivatives thereof, such as esters or anhydrides of protic acids, in particular trifluoromethanesulfonic anhydride or Trifluormethansulfonsäureester, such as the alkyl esters. Also suitable are perchloric acid and its esters. According to the invention, initiators are those compounds which start polymerization in concentrations of <10 -4 mol%.
Grundsätzlich lassen sich auch Lewis-Säuren wie z. B. BF3 oder BF3-Etherate als Initiatoren, allerdings in etwas höheren Konzentrationen, einsetzen.In principle, Lewis acids such. B. BF 3 or BF 3 ethers as initiators, but in somewhat higher concentrations, use.
Alternativ können die erfindungsgemäßen Polymere durch Mischung von unimodal verteilten und konventionellen bi- oder höhermodal verteiltenAlternatively, the polymers according to the invention can be prepared by mixing unimodally distributed and conventional bi- or higher modal distributed
Oxymethylenpolymeren, die 5 bis 15 Massenprozent niedermolekularen Anteil enthalten, hergestellt werden. Unimodal verteilte Polyoxymethylenpolymere sind in EP 0716 105 beschrieben. Unter unimodal verteilten Oxymethylen-polymeren werden im Rahmen dieser Beschreibung solche Polymere ver-standen, die nur einen Peak in der Molekulargewichtsverteilung aufweisen, wobei dieser Peak oberhalb von 10.000 Dalton, bevorzugt zwischen 30.000 und 200.000 Dalton, liegt.Oxymethylene polymers containing 5 to 15 mass percent of low molecular weight fraction are prepared. Unimodal distributed polyoxymethylene polymers are described in EP 0716 105. In the context of this description, unimodally distributed oxymethylene polymers are understood as meaning those polymers which have only one peak in the molecular weight distribution, this peak being above 10,000 daltons, preferably between 30,000 and 200,000 daltons.
Auch ist es möglich zu den erfindungsgemäßen Polymeren zu gelangen, indem man bei bi- oder höhermodal verteilten Polymeren den niedermolekularen Anteil durch Fraktionierung abtrennt.It is also possible to arrive at the polymers of the invention by separating the low molecular weight fraction by fractionation in bi- or higher modal distributed polymers.
Die aus so erhaltenen erfindungsgemäßen Oxymethylen-Polymere herge-stellten Formkörper weisen hervorragende Tieftemperatur Kerbschlag-zähigkeiten und hohe Elastizitätsmodule bei gleichzeitig guter chemischer Beständigkeit auf.The molded articles produced from the oxymethylene polymers obtained in this way have excellent low-temperature notched-bar impact strengths and high moduli of elasticity combined with good chemical resistance.
Die Formgebung kann nach bekannten Formverfahren erfolgen, beispielsweise durch Blasformen oder durch Spritzguss.The shaping can be carried out by known molding methods, for example by blow molding or by injection molding.
Die Erfindung betrifft auch die Verwendung der oben beschriebenen Oxymethylenpolymeren zur Herstellung von Formkörpern mit guterThe invention also relates to the use of the above-described oxymethylene polymers for the production of molded articles with good
Tieftemperaturkerbschlagzähigkeit.Low-temperature impact strength.
Die folgenden Beispiele erläutern die Erfindung ohne diese zu begrenzen. Beispiel 1 (erfindunqsqemäß)The following examples illustrate the invention without limiting it. Example 1 (Inventive)
Die Polymerisation wurde in einem gasdichten, druckstabilen Zweischnecken- extruder mit 7 etwa gleich langen, separat einstellbaren Heizstufen (= Zonen 1 bis 7) durchgeführt. Die Ausgangsverbindungen wurden mittels HPLC-Pumpen zudosiert und in der Vormischzone effizient durch statische Mischelemente gemischt, bevor sie zur Polymerisation in den Extruder gelangten. Als Deaktivator wurde eine Mischung aus 0,2 Gewichts% Triethylamin in 1 ,3-Dioxolan verwendet. Diese Lösung wurde zwischen Zone 5 und 6 mit einer Förderrate von 40 g/h zudosiert.The polymerization was carried out in a gas-tight, pressure-stable twin-screw extruder with 7 approximately equal length, separately adjustable heating stages (= zones 1 to 7). The starting compounds were metered by means of HPLC pumps and mixed efficiently in the premixing zone by means of static mixing elements before they reached the extruder for polymerization. The deactivator used was a mixture of 0.2% by weight of triethylamine in 1,3-dioxolane. This solution was metered in between zones 5 and 6 at a delivery rate of 40 g / h.
4 kg/h auf 800C vorerwärmtes Trioxan und 4 g/h Methylal, in dem 300 ppm Trifluormethansulfonsäure und 600 ppm Triethylammoniumhydrogentriflat gelöst waren, wurden in den Extruder bei einer Wellenumdrehungszahl von 120 U/min gepumpt. Der Druck wurde durch ein Druckhalteventil am Ende des Extruders konstant bei 18 bar gehalten. Die Temperaturen für die einzelnen Heizzonen waren wie folgt:4 kg / h preheated to 80 0 C trioxane and 4 g / h methylal in which 300 ppm of trifluoromethanesulfonic acid and 600 ppm Triethylammoniumhydrogentriflat were dissolved, were pumped into the extruder at a shaft revolution number of 120 rev / min. The pressure was kept constant at 18 bar by a pressure holding valve at the end of the extruder. The temperatures for the individual heating zones were as follows:
Zone: 1 2 3 4 5 6 7 Temperatur in 0C: 110 120 135 150 160 170 170Zone: 1 2 3 4 5 6 7 Temperature in 0 C: 110 120 135 150 160 170 170
Die Verweilzeit im Extruder betrug ca. 1 min. Die Polymere wurden als Schmelze ausgetragen und in einem Vorlagegefäß aufgefangen. Nach dem Abkühlen wurden Polymerproben in Dimethylacetamid (= DMAc) in der Siedehitze gelöst, für etwa 1 h gekocht, um instabile Kettenenden zu entfernen. Die nach dem Abkühlen ausgefallenen Polymere wurden 2 mal in Methanol aufgekocht, filtriert und getrocknet. Die Molekular-gewichtsverteilung des Polymeren wies einen niedermolekularen Anteil von 3 Gew.% auf.The residence time in the extruder was about 1 min. The polymers were discharged as a melt and collected in a receiver. After cooling, polymer samples were dissolved in dimethylacetamide (= DMAc) at boiling heat, boiled for about 1 h to remove unstable chain ends. The precipitated after cooling polymers were boiled twice in methanol, filtered and dried. The molecular weight distribution of the polymer had a low molecular weight content of 3% by weight.
Vergleichsbeispiele 2 bis 4Comparative Examples 2 to 4
Als Vergleichsbeispiel 2 wurde das Oxymethylenpolymer des Beispiels 1 von EP 716,105 nachgestellt. Das Oxymethylenpolymer von Vergleichsbeispiel 3 wurde folgendermaßen hergestellt: eine Mischung aus 100 g 1 ,3,5-Trioxan und 0,7 g 1 ,3-Dioxolan wurde bei 100 0C mit 0,1 ml einer Lösung von Trifluormethansulfonsäure (200 ppm) in Methylal unter Rühren versetzt. Das nach einer Reaktionszeit von ca. 5 min feste Reaktionsprodukt wurde in DMAc in der Siedehitze gelöst und 1 h Rückfluß gekocht, um instabile Kettenenden zu entfernen. Das nach dem Abkühlen ausgefallene Polymere wurde 2 mal in Methanol aufgekocht, filtriert und getrocknet.As Comparative Example 2, the oxymethylene polymer of Example 1 of EP 716,105 was readjusted. The oxymethylene polymer of Comparative Example 3 was prepared as follows: a mixture of 100 g of 1, 3,5-trioxane and 0.7 g of 1,3-dioxolane was stirred at 100 ° C. with 0.1 ml of a solution of trifluoromethanesulfonic acid (200 ppm) Methylal added with stirring. After a reaction time of about 5 min solid reaction product was dissolved in DMAc in the boiling heat and boiled for 1 h reflux to remove unstable chain ends. The precipitated after cooling polymer was boiled twice in methanol, filtered and dried.
Als Vergleichsbeispiel 4 wurde das kommerzielle Produkt Delrin® 100P eingesetzt und charakterisiert.As Comparative Example 4, the commercial product Delrin® 100P was used and characterized.
Einzelheiten der untersuchten Proben sind in der nachstehenden Tabelle zu finden.Details of the samples tested are given in the table below.
(*): der niedermolekulare Anteil in Gew.% wurde aus dem Verhältnis der Peakflächen der entsprechenden GPC-Kurven berechnet. Die GPC-Messungen wurden in Hexafluorisopropanol vorgenommen und PMMA als Standard verwendet.(*): The low molecular weight content in% by weight was calculated from the ratio of the peak areas of the corresponding GPC curves. GPC measurements were made in hexafluoroisopropanol and PMMA was used as standard.
Beispiel 5: Abtrennen der niedermolekularen Bestandteile aus Oxymethylen- polymerenExample 5: Separation of the low molecular weight constituents from oxymethylene polymers
4 g Oxymethylenpolymer mit einem Schmelzeindex MVR von 2,5 ml/10 min und einem Anteil von niedermolekularen Anteilen von 10 Gew.%, wurden in 40 g eines4 g of oxymethylene polymer having a melt index MVR of 2.5 ml / 10 min and a proportion of low molecular weight fractions of 10 wt.% Was dissolved in 40 g of a
Gemisches aus 85 Gew.% Methanol, 15 Gew. % Wasser und 500 ppm Triethylamin für 10 min in einem Autoklaven unter Rühren auf 1700C erhitzt. Nach dem Erkalten auf Raumtemperatur (ohne Rühren) wurde die über-stehende trübe Flüssigkeit von den am Boden liegenden groben Polymer-teilchen durch einfaches Dekantieren getrennt. Die groben Polymerteilchen hatten nach dem Trocknen ein Gewicht von 3,4 g und wiesen einen nieder-molekularen Anteil von 5 Gew. % auf. Mixture of 85 wt.% Methanol, 15 wt.% Water and 500 ppm of triethylamine for 10 min in an autoclave with stirring to 170 0 C heated. After cooling to room temperature (without stirring), the supernatant turbid liquid from the bottom coarse polymer particles was simply decanted separated. The coarse polymer particles had a weight of 3.4 g after drying and had a low molecular weight content of 5% by weight.

Claims

Patentansprüche claims
1. Oxymethylenpolymere, die Homopolymere oder Copolymere sind, bei denen das molare Verhältnis von Comonomereinheiten zu Oxymethylen-einheiten kleiner als 0,008 ist, und die eine mindestens bimodale Molekulargewichtsverteilung aufweisen, dadurch gekennzeichnet, dass der Anteil von niedermolekularen1. oxymethylene polymers, which are homopolymers or copolymers in which the molar ratio of comonomer units to oxymethylene units is less than 0.008, and which have an at least bimodal molecular weight distribution, characterized in that the proportion of low molecular weight
Oxymethylenpolymeren mit Molekulargewichten unterhalb von 10.000 Dalton zwischen 1 und 5 Gew. %, bezogen auf die Gesamtmasse der Oxymethylenpolymeren, beträgt.Oxymethylene polymers having molecular weights below 10,000 daltons between 1 and 5 wt.%, Based on the total mass of Oxymethylenpolymeren.
2. Oxymethylenpolymere nach Anspruch 1 , dadurch gekennzeichnet, dass das molare Verhältnis von Comonomereinheiten zu Oxymethyleneinheiten zwischen 0,0004 und 0,005 liegt.2. oxymethylene polymers according to claim 1, characterized in that the molar ratio of comonomer units to oxymethylene units is between 0.0004 and 0.005.
3. Oxymethylenpolymere nach den Ansprüchen 1 bis 2, dadurch gekennzeichnet, dass diese einen Anteil an Alkyletherendgruppen, bezogen auf alle Endgruppen, von mindestens 70 % aufweisen.3. oxymethylene polymers according to claims 1 to 2, characterized in that they have a proportion of Alkyletherendgruppen, based on all end groups, of at least 70%.
4. Oxymethylenpolymere nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, dass diese mindestens 70 % an Polymeren der allgemeinen Formel4. oxymethylene polymers according to claims 1 to 3, characterized in that these at least 70% of polymers of the general formula
R-O-(CH2O)p-(CsH2sO)q-R'RO- (CH 2 O) p- (C s H 2 SO) q -R '
enthalten, wobei R und R' Alkylreste darstellen, s eine ganze Zahl von 2 bis 10 bedeutet und p und q für gemittelte statistische Anteile der Comono-meren stehen, wobei q/p kleiner als 0,008 ist, wobei die Oxymethylen-polymeren eine mindestens bimodale Molekulargewichtsverteilung aufweisen, bei welcher der Anteil von niedermolekularen Oxymethylen-polymeren mit einem Molekulargewicht von unter 10.000 Dalton zwischen 1 und 5 Gew.%, bezogen auf die Gesamtmasse der Oxymethylenpolymeren, liegt.s, wherein R and R 'represent alkyl radicals, s is an integer from 2 to 10 and p and q are averaged statistical proportions of the comonomers, wherein q / p is less than 0.008, wherein the oxymethylene polymers have an at least bimodal Have molecular weight distribution, in which the proportion of low molecular weight oxymethylene polymers having a molecular weight of less than 10,000 daltons between 1 and 5 wt.%, Based on the total mass of the oxymethylene polymers is.
5. Oxymethylenpolymere nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die niedermolekularen Bestandteile zu mehr als 50 Massenprozent aus zyklischen Oxymethylenpolymeren bestehen. 5. oxymethylene polymers according to any one of claims 1 to 4, characterized in that the low molecular weight constituents consist of more than 50 percent by mass of cyclic oxymethylene polymers.
6. Oxymethylenpolymere nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die niedermolekularen Bestandteile zu mehr als 80 Massenprozent aus zyklischen Oxymethylenpolymeren bestehen.6. oxymethylene polymers according to any one of claims 1 to 5, characterized in that the low molecular weight constituents consist of more than 80 percent by mass of cyclic Oxymethylenpolymeren.
7. Oxymethylenpolymere nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Molekulargewichtsverteilung der niedermolekularen Oxymethylenpolymeren mit Molekulargewichten unterhalb von 10.000 Dalton eine Polydispersität MJMn von < 1 ,5, bevorzugt von < 1 ,2 aufweisen.7. oxymethylene polymers according to any one of claims 1 to 6, characterized in that the molecular weight distribution of the low molecular weight oxymethylene polymers having molecular weights below 10,000 daltons a polydispersity MJM n of <1, 5, preferably of <1, 2 have.
8. Oxymethylenpolymere nach einem der Anprüche 1 bis 7, dadurch gekennzeichnet, dass die Oxyalkyleneinheiten -O-(CH2)2- sind.8. oxymethylene polymers according to any one of claims 1 to 7, characterized in that the oxyalkylene units -O- (CH 2 ) 2 - are.
9. Verfahren zur Herstellung von Oxymethylenpolymeren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß ein Formaldehyd-Einheiten bildendes Monomeres, bevorzugt Trioxan, gegebenenfalls zusammen mit einem C-C-Einheiten bildenden Comonomeren, zusammen mit einem Kettenüberträger und einem Initiator der kationischen Polymerisation so polymerisiert werden, daß zunächst eine Fällungspolymerisation erfolgt, die Polymerisation aber in der Endphase homogen erfolgt und durch Zugabe einer basischen Verbindung abgebrochen wird, wobei das Temperaturprofil und die Polymerisationsdauer so eingestellt werden, daß Oxymethylenpolymere mit einem Gehalt an niedermolekularen Bestandteilen zwischen 1 und 5 Gew. % entstehen.9. A process for the preparation of oxymethylene polymers according to any one of claims 1 to 8, characterized in that a formaldehyde units forming monomer, preferably trioxane, optionally together with a CC units forming comonomer, together with a chain transfer agent and an initiator of the cationic polymerization so be polymerized, that initially a precipitation polymerization takes place, but the polymerization takes place homogeneously in the final phase and is terminated by addition of a basic compound, wherein the temperature profile and the polymerization time are adjusted so that oxymethylene polymers having a content of low molecular weight components between 1 and 5 wt. % arise.
10. Verfahren zur Herstellung von Oxymethylenpolymeren nach einem der10. A process for the preparation of oxymethylene polymers according to one of
Ansprüche 1 bis 8, dadurch gekennzeichnet, dass ein Oxymethylenpolymer mit einem Anteil von niedermolekularen Oxymethylenpolymeren mit Molekulargewichten unterhalb von 10.000 Dalton von mehr als 5 Gew. %, bezogen auf die Gesamtmasse der Oxymethylenpolymeren, durch fraktionierte Fällung in ein Oxymethylenpolymer mit einem Anteil an niedermolekularenClaims 1 to 8, characterized in that an oxymethylene polymer with a proportion of low molecular weight oxymethylene polymers having molecular weights below 10,000 Dalton of more than 5 wt.%, Based on the total mass of the oxymethylene polymers, by fractional precipitation into an oxymethylene polymer with a proportion of low molecular weight
Oxymethylenpolymeren von weniger als 5 Gew. % übergeführt wird. Oxymethylene polymers of less than 5 wt.% Is converted.
11. Verfahren zur Herstellung von Oxymethylenpolymeren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass ein Oxymethylenpolymer mit einem Anteil von niedermolekularen Oxymethylenpolymeren mit Molekulargewichten unterhalb von 10.000 Dalton von mehr als 5 Gew. %, bezogen auf die Gesamtmasse der Oxymethylenpolymeren, und ein unimodal verteiltes Oxymethylenpolymer miteinander gemischt werden.11. A process for the preparation of oxymethylene polymers according to any one of claims 1 to 8, characterized in that an oxymethylene polymer with a proportion of low molecular weight oxymethylene polymers having molecular weights below 10,000 daltons of more than 5 wt.%, Based on the total mass of Oxymethylenpolymeren, and a unimodally distributed oxymethylene polymer are mixed together.
12. Verwendung der Oxymethylenpolymeren nach einem der Ansprüche 1 bis 8 zur Herstellung von Formkörpern mit guter Tieftemperaturkerbschlag-zähigkeit. 12. Use of the oxymethylene polymers according to any one of claims 1 to 8 for the production of moldings with good low temperature impact strength.
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