WO2005012380A1 - Alcools utilises comme cocatalyseurs dans la production de polyoxymethylenes - Google Patents

Alcools utilises comme cocatalyseurs dans la production de polyoxymethylenes Download PDF

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Publication number
WO2005012380A1
WO2005012380A1 PCT/EP2004/007865 EP2004007865W WO2005012380A1 WO 2005012380 A1 WO2005012380 A1 WO 2005012380A1 EP 2004007865 W EP2004007865 W EP 2004007865W WO 2005012380 A1 WO2005012380 A1 WO 2005012380A1
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Prior art keywords
polymerization
cocatalyst
process according
acid
alcohols
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PCT/EP2004/007865
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German (de)
English (en)
Inventor
Burkhardt Dames
Johannes Heinemann
Original Assignee
Basf Aktiengesellschaft
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.)
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO2005012380A1 publication Critical patent/WO2005012380A1/fr

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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
    • C08G2/06—Catalysts
    • 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
    • C08G2/10—Polymerisation of cyclic oligomers of formaldehyde

Definitions

  • the invention relates to an improved process for the preparation of polyoxymethylene.
  • oxymethylene polymers can be prepared by continuous bulk polymerization of the monomers in the presence of cationically active initiators. This polymerization is often carried out in kneaders or extruders. The temperature can be controlled so that the resulting oxymethylene polymer is either in solid form (DE-A 1 161 421, DE-A 1 495228, DE-A 1 720358, DE-A 3 018898) or as a melt (DE-A 3 147309) occurs.
  • the processing of the polymer obtained in solid form is known, see: DE-A 3147309, DE-A 3628561, EP-A 678535, EP-A 699965 and DE-A 4423617.
  • the production by means of suspension or precipitation polymerization with cationic initiators is generally known.
  • the resulting polymer should not be soluble in the solvent used here, so that it can be separated more easily.
  • the catalysts used are not soluble in these reaction media and must be used in larger amounts and over a longer period of time. This has a disadvantageous effect on the stability of the resulting polymer, which is degraded by such acids. It is therefore essential that as little catalyst as possible is used, but at the same time the reaction time is not significantly extended.
  • the object of the present invention was therefore to provide an improved method for
  • the process can be carried out on any reactor with a high mixing action, such as, for example, trays, ploughshare mixers, tubular reactors, list reactors, kneaders, stirred reactors.
  • these polymers have at least 50 mol% of recurring units - CH 2 O - in the main polymer chain.
  • the homopolymers are generally prepared by polymerizing monomers a), such as formaldehyde or trioxane, preferably in the presence of suitable catalysts.
  • polyoxymethylene copolymers are preferred, in particular those which, in addition to the repeating units —CH 2 O—, up to 50, preferably 0.1 to 20, in particular 0.3 to 10 mol% and very particularly preferably 2 to 6 mol -% of recurring units.
  • R 1 to R 4 independently of one another are a hydrogen atom, a C to C alkyl group or a halogen-substituted alkyl group having 1 to 4 C atoms and R 5 is a - CH 2 -, -CH 2 O -, a C to C 4 -Alkyl- or C to C 4 -haloalkyl substituted methylene group or a corresponding oxymethylene group and n has a value in the range from 0 to 3.
  • these groups can ring opening from cyclic ethers are introduced into the copolymers.
  • Preferred cyclic ethers are those of the formula
  • R 1 to R 5 and n have the meaning given above.
  • ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,3-dioxane, 1,3-dioxoxane and 1,3-dioxepane may be mentioned as cyclic ethers and linear oligo- or polyformals such as polydioxolane or polydioxepane as comonomers.
  • oxymethylene terpolymers for example by reacting trioxane, one of the cyclic ethers described above, with a third monomer, preferably bifunctional compounds of the formula
  • Preferred monomers of this type are ethylene diglycide, diglycidyl ether and diether from glycidylene and formaldehyde, dioxane or trioxane in a molar ratio of 2: 1 and diether from 2 mol of glycidyl compound and 1 mol of an aliphatic diol with 2 to 8 carbon atoms, such as, for example, the diglycidyl ether of ethylene glycol, 1 , 4-butanediol, 1,3-butanediol, cyclobutane-1,3-diol, 1,2-propanediol and cyclohexane-1,4-diol, to name just a few examples.
  • End group-stabilized polyoxymethylene polymers which have CC or -O-CH 3 bonds at the chain ends are particularly preferred.
  • the preferred polyoxymethylene copolymers have melting points of at least 150 ° C. and molecular weights (weight average) M w in the range from 5,000 to 300,000, preferably from 7,000 to 250,000.
  • POM copolymers with a non-uniformity (M w / M n ) from 2 to 15, preferably from 3 to 12, particularly preferably from 4 to 9 are particularly preferred.
  • the measurements are generally carried out using (GPC) SEC (size exclusion chromatography) ,
  • the M n value number average molecular weight
  • Particularly preferred POM copolymers have a bimodal molecular weight distribution, the low molecular weight fraction having a molecular weight of 500 to 20,000, preferably 1,000 to 15,000 and in area proportions of 1 to 15, preferably 8 to 10% in the case of the distribution graph w (log M) versus log M is present.
  • the crude polyoxymethylenes obtainable by the process according to the invention preferably have a residual formaldehyde content according to VDA 275 in the granulate of a maximum of 3%, preferably a maximum of 1%, preferably a maximum of 0.05%.
  • the average particle size (d 5 o value) (grain size) of the POM polymers is preferably from 0.5 mm to 20, preferably from 0.75 mm to 15 mm and in particular 1 to 7
  • a d 50 value is generally understood by the person skilled in the art to mean the particle size value, in which 50% of the particles have a smaller particle size and 50% have a larger particle size. This is to be understood accordingly for the stated dio and dgo values.
  • the d-io value is preferably less than 1 mm, in particular 0.75 mm and very particularly preferably less than 0.5 mm.
  • Preferred d 90 values are less than 30 mm and in particular less than 20 mm and very particularly preferably less than 10 mm.
  • the particle size distribution was divided into different sieve fractions using a standard sieve set (test sieves according to DIN 4188) and these were weighed out.
  • d 50 1 mm means that 50% by weight of the sample has a particle size of less than or equal to 1 mm.
  • the process according to the invention is preferably used for the homo- and copolymerization of trioxane. Basically, however, any monomer described above, for example also tetroxane or (para) formaldehyde, can be used as monomer a).
  • the monomers for example trioxane, are preferably metered in in the molten state, generally at temperatures from 60 to 120 ° C.
  • the temperature of the reaction mixture at the dosage is preferably 62 to 114 ° C., in particular 70 to 90 ° C.
  • the molecular weights of the polymer can, if appropriate, be adjusted to the desired values by the regulators d) customary in (trioxane) polymerization.
  • Possible regulators are acetals or formals of monohydric alcohols, the alcohols themselves and the small amounts of water which act as chain transfer agents, the presence of which can generally never be completely avoided.
  • the regulators are used in amounts of 10 to 10,000 ppm, preferably 100 to 1,000 ppm.
  • Initiators b) are the cationic initiators customary in (trioxane) polymerization.
  • Protonic acids such as fluorinated or chlorinated alkyl and arylsulfonic acids, e.g. Perchloric acid, trifluoromethanesulfonic acid or Lewis acids, e.g. Tin tetrachloride, arsenic pentafluoride, phosphoric acid pentafluoride and boron trifluoride as well as their complex compounds and salt-like compounds, e.g. Boron trifluoride etherates and triphenylmethylene hexafluorophosphate.
  • fluorinated or chlorinated alkyl and arylsulfonic acids e.g. Perchloric acid, trifluoromethanesulfonic acid or Lewis acids, e.g. Tin tetrachloride, arsenic pentafluoride, phosphoric acid pentafluoride and
  • the catalysts are used in amounts of about 0.01 to 1,000 ppm, preferably 0.01 to 500 ppm and in particular from 0.01 to 200 ppm. In general, it is advisable to add the catalyst in dilute form, preferably in concentrations of 0.005 to 5% by weight.
  • Inert compounds such as aliphatic, cycloaliphatic hydrocarbons, e.g. Cyclohexane, halogenated aliphatic hydrocarbons, glycol ethers, etc. can be used.
  • Triglyme is particularly preferred as the solvent (triethylene glycol dimethyl ether).
  • Monomers a), initiators b), cocatalyst c) and optionally regulator d) can be premixed in any manner or can be added to the polymerization reactor separately.
  • Components a), b) and / or c) can furthermore contain sterically hindered phenols for stabilization, as described in EP-A 129369 or EP-A 128739. In order to minimize the proportion of unstable end groups, it has proven to be advantageous to dissolve the initiator b) in the regulator d) before it is added to the monomer a) and, if appropriate, comonomer a).
  • the polymerization is carried out as precipitation polymerization (depending on the degree of solubility of the individual components, also known as suspension polymerization) in a solvent in which the resulting polyoxyethylene homo- or copolymer is largely insoluble.
  • the term “largely insoluble” should be understood to mean that the polymer precipitates from a degree of polymerization of at least 4.
  • Inert compounds are used in particular as solvents, for example aliphatic hydrocarbons such as propane, butane, pentane, iso-octane, n-hexanes, n-heptane, n-octane, iso-octane and cycloaliphatic hydrocarbons such as cyclohexane or cycloheptane and cyclopentane, which may optionally be heteroatoms can wear as substituents.
  • aliphatic hydrocarbons such as propane, butane, pentane, iso-octane, n-hexanes, n-heptane, n-octane, iso-octane and cycloaliphatic hydrocarbons such as cyclohexane or cycloheptane and cyclopentane, which may optionally be heteroatoms can wear as substituents.
  • Suitable aromatic hydrocarbons are those which have at least 6 to 30 carbon atoms, with nitrobenzene, toluene and benzene being preferred.
  • Dichloromethane, chloroform, dichloroethane and trichloroethane may be mentioned as further suitable halogenated hydrocarbons.
  • ethers such as dioxane or THF and triglyme (triethylene glycol dimethyl ether) are suitable as inert solvents.
  • the solvent preferably has temperatures of 50 to 250 ° C., preferably 55 to 130 and in particular 60 to 120 ° C. at the start of the reaction (metering in).
  • the cocatalyst c) is preferably metered in after the addition of the monomers a) or before the addition of the catalyst b).
  • the reaction is carried out under inert gas conditions, preferably under N 2 , at pressures of up to 5, preferably up to 2, bar abs.
  • Alcohols of any kind are used as cocatalysts according to the invention.
  • Some preferred types 1. aliphatic alcohols with 1 to 20 carbon atoms, t-amyl alcohol, methanol, ethanol, propanol, butanol, pentanol, hexanol etc. being preferred,
  • alcohols c) are glycols of all kinds, diethylene glycol and triethylene glycol being particularly preferred,
  • aliphatic dihydroxy compounds are diols with 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol. 1,4-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof are preferred.
  • the residence time for the polymerization in the solvent is preferably 0.1 to 240 min, in particular 5 to 120 min.
  • the polymerization is preferably carried out up to a conversion of at least 30%, in particular more than 60%. Under favorable conditions, sales of 90% and above can also be achieved, quantitative sales of up to 100% are easily reproducible.
  • the polymerization mixture is preferably deactivated immediately after the polymerization, preferably without a phase change taking place.
  • the deactivation e) of the catalyst residues is generally carried out by adding deactivators e) to the polymerization melt.
  • deactivators are e.g. Ammonia, aliphatic and aromatic amines, basic salts such as soda and borax. These are usually added to the polymers in amounts of preferably up to 1% by weight.
  • the organic compounds of the (earth) alkali metals include the corresponding salts of (cyclo) aliphatic, araliphatic or aromatic carboxylic acids with preferably up to 30 C atoms and preferably 1 to 4 carboxyl groups.
  • Examples include: alkali metal salts of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, caprylic acid, stearic acid, cyclohexane carboxylic acid, succinic acid, adipic acid, suberic acid, 1,10-decanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, terephthalic acid, 1,2,3- Propane tricarboxylic acid, 1,3,5-cyclohexane tricarboxylic acid, trimellitic acid, 1,2,3,4-cyclopentanetetra- carboxylic acid, pyromellitic acid, benzoic acid, substituted benzoic acids, dimer acid and trimer acid as well as neutral and partially neutral montan wax salts or montan wax ester salts (montanates).
  • Salts with different types of acid residues such as, for example, alkali-paraffin, alkali-olefin and alkali-aryl sulfonates or also phenolates and alcoholates, such as, for example, methanolates, ethanolates, glycolates, can be used according to the invention.
  • Sodium salts of mono- and polycarboxylic acids in particular the aliphatic mono- and polycarboxylic acids, preferably those having 2 to 18 carbon atoms, in particular having 2 to 6 carbon atoms and up to four, preferably up to two, carboxyl groups, and sodium alcoholates are preferred 2 to 15, in particular 2 to 8 carbon atoms used.
  • particularly preferred representatives are sodium acetate, sodium propionate, sodium butyrate, sodium oxalate, sodium immalonate, sodium succinate, sodium methoxide, sodium ethanolate, sodium glyconate.
  • Sodium methoxide is very particularly preferred, which is used particularly advantageously in an amount of 1-5 times equimolar to component b) used. Mixtures of different (earth) alkali metal compounds can also be used.
  • alkaline earth alkyls are preferred as deactivators e) which have 2 to 30 carbon atoms in the alkyl radical.
  • Li, Mg and Na may be mentioned as particularly preferred metals, n-butyllithium being particularly preferred.
  • the resulting polymer can then be washed with inert solvents, for example acetone or cyclohexane, and separated from the solvent using suitable devices, and optionally cooled.
  • inert solvents for example acetone or cyclohexane
  • the polyoxymethylene obtainable by the process according to the invention has a low residual cyclic ether content (trioxane) and a high degree of uniformity with regard to the granule particle size distribution and the molecular weight across the discharged polyoxymethylene.
  • the corresponding polyoxymethylene polymer can then be processed further in the usual manner with conventional additives such as stabilizers, rubbers, fillers, etc. Examples
  • the comonomer (BuFo) was then metered in (3.6% by weight, based on trioxane). If desired, a regulator (MTBE) or co-catalyst / accelerator and the catalyst were metered in over a fixed time (1 min to 30 min).
  • the starting temperature was 80 ° C to 110 ° C, a nitrogen pressure of 2 bar was set before the polymerization. After cat. Dosing, a temperature increase of 5 to 20 ° C was observed in most polymerizations. The pressure in the boiler rose up to 7 bar.

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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)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne un procédé permettant de produire des polyoxyméthylènes par polymérisation par précipitation de monomères a) en présence d'initiateurs à action cationique ; b) et de cocatalyseurs ; c) ainsi qu'éventuellement en présence de régulateurs d) : le polymère est éventuellement désactivé, puis séparé. Ledit procédé se caractérise en ce qu'on utilise des alcools comme cocatalyseurs.
PCT/EP2004/007865 2003-08-04 2004-07-15 Alcools utilises comme cocatalyseurs dans la production de polyoxymethylenes WO2005012380A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10335959.1 2003-08-04
DE2003135959 DE10335959A1 (de) 2003-08-04 2003-08-04 Alkohole als Cokatalysatoren bei der POM-Herstellung

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006097487A1 (fr) * 2005-03-16 2006-09-21 Basf Aktiengesellschaft Procede de fabrication de polyoxymethylenes
WO2007009925A1 (fr) * 2005-07-20 2007-01-25 Basf Aktiengesellschaft Procede de production de polyoxymethylenes
WO2009127388A1 (fr) * 2008-04-16 2009-10-22 Ticona Gmbh Polymères d'oxyméthylène, leur procédé de production et leur utilisation
US8133966B2 (en) 2008-04-16 2012-03-13 Ticona Gmbh Oxymethylene copolymers and the use thereof and process for the preparation of oxymethylene copolymers
US8263716B2 (en) 2004-02-04 2012-09-11 Basf Aktiengesellschaft Fluid polyester molding masses
US8278381B2 (en) 2004-10-13 2012-10-02 Basf Se Flowable thermoplastics with halogen flame retardancy system
US8293823B2 (en) 2004-10-08 2012-10-23 Basf Se Flowable thermoplastic materials with halogen-free flame protection
US8354495B2 (en) 2008-04-16 2013-01-15 Ticona Gmbh Process for the preparation of oxymethylene polymers and apparatus suitable for this purpose
US8362146B2 (en) 2004-08-10 2013-01-29 Basf Se Impact-modified polyesters with hyperbranched polyesters/polycarbonates
US8362136B2 (en) 2004-08-10 2013-01-29 Basf Se Flowable polyester molding compositions with ASA/ABS and SAN
US8410227B2 (en) 2004-02-04 2013-04-02 Basf Se Fluid polyester moulding masses
US8445576B2 (en) 2004-07-21 2013-05-21 Basf Se Continuous process for preparing polyalkylene arylates with hyperbranched polyesters and/or polycarbonates
US8445107B2 (en) 2005-06-14 2013-05-21 Basf Se Multicomponent molding with polyester layers
US8501845B2 (en) 2005-01-14 2013-08-06 Basf Se Flowable polyesters with hydrolysis resistance
US8530568B2 (en) 2004-10-20 2013-09-10 Basf Se Flowable polyamides with hyperbranched polyesters/polycarbonates
US8840976B2 (en) 2010-10-14 2014-09-23 Ticona Llc VOC or compressed gas containment device made from a polyoxymethylene polymer
US8968858B2 (en) 2011-12-30 2015-03-03 Ticona Llc Printable molded articles made from a polyoxymethylene polymer composition
US9005515B2 (en) 2011-04-01 2015-04-14 Ticona Gmbh High impact resistant polyoxymethylene for extrusion blow molding
US9745467B2 (en) 2012-12-27 2017-08-29 Ticona, Llc Impact modified polyoxymethylene composition and articles made therefrom that are stable when exposed to ultraviolet light

Citations (3)

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Publication number Priority date Publication date Assignee Title
US4024105A (en) * 1974-02-22 1977-05-17 Hoechst Aktiengesellschaft Process for preparing a stabilized oxymethylene copolymer
US20030018104A1 (en) * 2000-02-10 2003-01-23 Marian Mours Method for production of polyoxymethylenes
EP1418190A1 (fr) * 2002-11-05 2004-05-12 Ticona GmbH Copolymères de polyoxyméthylène, leur préparation et leur utilisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4024105A (en) * 1974-02-22 1977-05-17 Hoechst Aktiengesellschaft Process for preparing a stabilized oxymethylene copolymer
US20030018104A1 (en) * 2000-02-10 2003-01-23 Marian Mours Method for production of polyoxymethylenes
EP1418190A1 (fr) * 2002-11-05 2004-05-12 Ticona GmbH Copolymères de polyoxyméthylène, leur préparation et leur utilisation

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8263716B2 (en) 2004-02-04 2012-09-11 Basf Aktiengesellschaft Fluid polyester molding masses
US8410227B2 (en) 2004-02-04 2013-04-02 Basf Se Fluid polyester moulding masses
US8445576B2 (en) 2004-07-21 2013-05-21 Basf Se Continuous process for preparing polyalkylene arylates with hyperbranched polyesters and/or polycarbonates
US8362136B2 (en) 2004-08-10 2013-01-29 Basf Se Flowable polyester molding compositions with ASA/ABS and SAN
US8362146B2 (en) 2004-08-10 2013-01-29 Basf Se Impact-modified polyesters with hyperbranched polyesters/polycarbonates
US8293823B2 (en) 2004-10-08 2012-10-23 Basf Se Flowable thermoplastic materials with halogen-free flame protection
US8278381B2 (en) 2004-10-13 2012-10-02 Basf Se Flowable thermoplastics with halogen flame retardancy system
US8530568B2 (en) 2004-10-20 2013-09-10 Basf Se Flowable polyamides with hyperbranched polyesters/polycarbonates
US8501845B2 (en) 2005-01-14 2013-08-06 Basf Se Flowable polyesters with hydrolysis resistance
WO2006097487A1 (fr) * 2005-03-16 2006-09-21 Basf Aktiengesellschaft Procede de fabrication de polyoxymethylenes
CN101142248B (zh) * 2005-03-16 2012-02-01 巴斯福股份公司 生产聚甲醛的方法
US8445107B2 (en) 2005-06-14 2013-05-21 Basf Se Multicomponent molding with polyester layers
US7906609B2 (en) 2005-07-20 2011-03-15 Basf Ag Method for producing polyoxymethlenes
WO2007009925A1 (fr) * 2005-07-20 2007-01-25 Basf Aktiengesellschaft Procede de production de polyoxymethylenes
KR101301818B1 (ko) * 2005-07-20 2013-08-29 바스프 에스이 폴리옥시메틸렌의 제조 방법
WO2009127388A1 (fr) * 2008-04-16 2009-10-22 Ticona Gmbh Polymères d'oxyméthylène, leur procédé de production et leur utilisation
US8188211B2 (en) 2008-04-16 2012-05-29 Ticona Gmbh Oxymethylene polymers, process for the preparation thereof and use thereof
US8354495B2 (en) 2008-04-16 2013-01-15 Ticona Gmbh Process for the preparation of oxymethylene polymers and apparatus suitable for this purpose
US8133966B2 (en) 2008-04-16 2012-03-13 Ticona Gmbh Oxymethylene copolymers and the use thereof and process for the preparation of oxymethylene copolymers
US8742065B2 (en) 2008-04-16 2014-06-03 Ticona Gmbh Oxymethylene polymers, process for the preparation thereof and use thereof
US8840976B2 (en) 2010-10-14 2014-09-23 Ticona Llc VOC or compressed gas containment device made from a polyoxymethylene polymer
US9005515B2 (en) 2011-04-01 2015-04-14 Ticona Gmbh High impact resistant polyoxymethylene for extrusion blow molding
US8968858B2 (en) 2011-12-30 2015-03-03 Ticona Llc Printable molded articles made from a polyoxymethylene polymer composition
US9745467B2 (en) 2012-12-27 2017-08-29 Ticona, Llc Impact modified polyoxymethylene composition and articles made therefrom that are stable when exposed to ultraviolet light

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