EP2265652A1 - Oxymethylenpolymere, verfahren zu deren herstellung und deren verwendung - Google Patents

Oxymethylenpolymere, verfahren zu deren herstellung und deren verwendung

Info

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
Authority
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.)
Withdrawn
Application number
EP09732684A
Other languages
German (de)
English (en)
French (fr)
Inventor
Michael Haubs
Michael Hoffmockel
Jürgen LINGNAU
Horst Roeschert
Robert Gronner
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.)
Ticona GmbH
Original Assignee
Ticona GmbH
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 Ticona GmbH filed Critical Ticona GmbH
Publication of EP2265652A1 publication Critical patent/EP2265652A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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

Landscapes

  • 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)
EP09732684A 2008-04-16 2009-04-14 Oxymethylenpolymere, verfahren zu deren herstellung und deren verwendung Withdrawn EP2265652A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US4532408P 2008-04-16 2008-04-16
DE102008018967A DE102008018967A1 (de) 2008-04-16 2008-04-16 Oxymethylenpolymere, Verfahren zu deren Herstellung und deren Verwendung
PCT/EP2009/002715 WO2009127388A1 (de) 2008-04-16 2009-04-14 Oxymethylenpolymere, verfahren zu deren herstellung und deren verwendung

Publications (1)

Publication Number Publication Date
EP2265652A1 true EP2265652A1 (de) 2010-12-29

Family

ID=41078553

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09732684A Withdrawn EP2265652A1 (de) 2008-04-16 2009-04-14 Oxymethylenpolymere, verfahren zu deren herstellung und deren verwendung

Country Status (6)

Country Link
US (2) US8188211B2 (enExample)
EP (1) EP2265652A1 (enExample)
JP (1) JP5709060B2 (enExample)
CN (1) CN102037036B (enExample)
DE (1) DE102008018967A1 (enExample)
WO (1) WO2009127388A1 (enExample)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7902324B2 (en) 2006-09-26 2011-03-08 Ticona Gmbh Initiator
DE102008018968A1 (de) * 2008-04-16 2009-10-22 Ticona Gmbh Polyoxymethylen-Formmassen und Formkörper und deren Verwendung
CN102079801A (zh) 2009-09-25 2011-06-01 提克纳有限公司 氧亚甲基聚合物及其制备方法
US9051476B2 (en) * 2010-12-30 2015-06-09 Ticona Llc Powder containing a polyoxymethylene polymer for coating metallic substrates
WO2015002147A1 (ja) * 2013-07-01 2015-01-08 三菱瓦斯化学株式会社 オキシメチレン共重合体の製造方法
US11981772B2 (en) 2018-09-14 2024-05-14 Asahi Kasei Kabushiki Kaisha Polyoxymethylene and method of producing same

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US8188211B2 (en) 2012-05-29
DE102008018967A1 (de) 2009-10-22
CN102037036A (zh) 2011-04-27
US20120232246A1 (en) 2012-09-13
CN102037036B (zh) 2013-07-10
WO2009127388A1 (de) 2009-10-22
US8742065B2 (en) 2014-06-03
US20090270587A1 (en) 2009-10-29
JP2011516705A (ja) 2011-05-26
JP5709060B2 (ja) 2015-04-30

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