DE102005022641A1 - Improved process for residual monomer removal from polyoxyethylene - Google Patents

Abstract

Process for the removal of unreacted residual monomers from polyoxymethylene homopolymers or copolymers (POM) by degassing in a degassing device and subsequent mixing in a mixing device, characterized in that the residence time of the POM between the discharge from the degassing device and the entry into the mixing device is a maximum of 60 sec is.

Description

The The invention relates to a process for removing unreacted Residual monomers of polyoxymethylene homopolymers or copolymers (POM) Degassing in a degasser and then mixing in a mixing device, characterized in that the residence time the POM between the discharge from the degassing and the Entry into the mixing device is a maximum of 60 sec.

It also concerns the invention the use of said method during the or following the preparation of polyoxymethylene homo- or copolymers, and a process for the preparation of polyoxymethylene homo- or copolymers, characterized in that first in a monomer plant produces or stores suitable monomers, then the monomers in a polymerization reactor to the mentioned Polymer polymerized, and while or after this polymerization, those contained in the polymers Residual monomers removed by the former method.

Finally, concerns the invention the polyoxymethylene homopolymers or copolymers obtainable according to latter method.

polyoxymethylene (POM, also called polyacetals) are by homo- or copolymerization 1,3,5-trioxane (trioxane for short), formaldehyde or another Formaldehyde source obtained. The conversion is usually not completely, rather contains the POM crude still up to 40% unreacted monomers. Such residual monomers are, for example, trioxane and formaldehyde, and optionally co-used comonomers such as 1,3-dioxolane, 1,3-butanediol formal or ethylene oxide. In summary, POM stands for homo- and copolymers.

The Residual monomers are made by workup by degassing from the Removed raw polymers. According to the state Technically, POM becomes at atmospheric pressure or degassed negative pressure and then optionally mixed with additives.

The EP-A 638 599 describes a process for the preparation of polyacetals, in which the residual monomers in a degassing by pressure reduction be evaporated. Thereafter, customary additives are used in a confectioning extruder mixed.

In EP-A 999 224 describes the preparation of polyacetal copolymers described without the addition of deactivators. It falls the raw POM leaving the polymerization reactor is unspecified by a "drop shaft" Length in a "mixing unit "(e.g., extruder) and is mixed there with additives, the unreacted Monomers are removed before or in the mixing unit by "reduced pressure".

The DE-A 31 47 309 discloses the preparation of oxymethylene polymers in the melt, in a degassing and confectioning reactor removed the unreacted monomers and mixed in conventional additives become.

The not pre-published German patent application Az. 102005002413.0 dated 18.01.05 describes a Process for the removal of residual monomers from POM, in which a heated POM melt under pressure is degassed. Before, while and / or after degassing the POM can be placed in an extruder or another mixing device provided with conventional additives.

In the not previously published German patent application Az. 102005012480.1 dated 16.03.05 is also discloses a process for removing residual monomers from POM, wherein a heated POM melt degassed in a strand degasser becomes. Preference is given to degassing twice (degassing pot with downstream Extrudate). Also according to this You can script the POM before, while and / or after degassing in an extruder or another Mixing device with usual Provided additives.

None The mentioned documents provide information on the spatial or temporal distance residual monomer removal (degassing) and addition of additives, or the residence time of the POM between degassing and additive addition. In particular, a maximum residence time of 60 sec is between Discharge from the degassing and entry in the mixing device, or even an arrangement of the degassing directly on the mixing device, not revealed.

The Embodiments described in said prior art Degassing and additive mixing are for demanding applications the POM is not always satisfactory. Polyoxymethylenes may be added thermal stress and shear stress, as with the degassing and additive mixing, undergoing unwanted degradation reactions, see, e.g. Michailow et al., Plastics and Rubber 1974, 653-655. Thereby can increase the formaldehyde residual content in the polymer, and The polymer can be an undesirable Show own color and / or worse mechanical properties.

It The task was to remedy the disadvantages described, and to further improve degassing and additive addition. Especially a process should be provided which comprises polyoxymethylene Degas in a particularly gentle way and provided with additives to let.

Accordingly, became the initially defined method for removing the residual monomers found. Furthermore was the mentioned use of this method, the mentioned method for the preparation of the POM polymers and after the latter Method available POM polymers, found. Preferred embodiments of the invention are the dependent claims refer to. All pressures are absolute pressures, if not stated otherwise.

polyoxymethylene and copolymers

The Polyoxymethylene homopolymers or copolymers (POM) are known as such and commercially available. The homopolymers are prepared by polymerization of formaldehyde or, preferably, trioxane produced; in the preparation of the copolymers also become comonomers concomitantly.

enthalten, wobei R¹ bis R⁴ unabhängig voneinander ein Wasserstoffatom, eine C₁-bis C₄-Alkylgruppe oder eine halogensubstituierte Alkylgruppe mit 1 bis 4 C-Atomen und R⁵ eine -CH₂-, -CH₂O-, eine C₁- bis C₄-Alkyl- oder C₁- bis C₄-Haloalkyl substituierte Methylengruppe oder eine entsprechende Oxymethylengruppe darstellen und n einen Wert im Bereich von 0 bis 3 hat. Vorteilhafterweise können diese Gruppen durch Ringöffnung von cyclischen Ethern in die Copolymere eingeführt werden. Bevorzugte cyclische Ether sind solche der Formel

wobei R¹ bis R⁵ und n die oben genannte Bedeutung haben. Nur beispielsweise seien Ethylenoxid, 1,2-Propylenoxid, 1,2-Butylenoxid, 1,3-Butylenoxid, 1,3-Dioxan, 1,3-Di oxolan und 1,3-Dioxepan (= Butandiolformal, BUFO) als cyclische Ether genannt sowie lineare Oligo- oder Polyformale wie Polydioxolan oder Polydioxepan als Comonomere genannt.In general, such POM polymers have at least 50 mole percent of recurring units -CH ₂ O- in the polymer backbone. Polyoxymethylene copolymers are preferred, in particular those which, in addition to the repeating units -CH ₂ O-, have up to 50, preferably 0.01 to 20, in particular 0.1 to 10 mol% and very particularly preferably 0.5 to 6 mol%. at recurring units

wherein R ¹ to R ^{4 are} independently a hydrogen atom, a C _{1 to} C ₄ alkyl group or a halogen-substituted alkyl group having 1 to 4 carbon atoms and R ^{5 is} a -CH ₂ -, -CH ₂ O-, a C ₁ to C ₄ alkyl or C ₁ to C ₄ haloalkyl substituted methylene group or a corresponding oxymethylene group and n has a value in the range of 0 to 3. Advantageously, these groups can be introduced into the copolymers by ring opening of cyclic ethers. Preferred cyclic ethers are those of the formula

wherein R ¹ to R ⁵ and n have the abovementioned meaning. For example, ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,3-dioxane, 1,3-di oxolane and 1,3-dioxepane (= butanediol, BUFO) as cyclic ethers mentioned as well as linear oligo- or polyformals such as polydioxolane or polydioxepan called comonomers.

wobei Z eine chemische Bindung, -O-, -ORO- (R gleich C₁- bis C₈-Alkylen oder C₃- bis C₈-Cycloalkylen) ist, hergestellt werden.Also suitable are Oxymethylenterpolymerisate, for example, by reacting trioxane, one of the cyclic ethers described above with a third monomer, preferably bifunctional compounds of the formula

wherein Z is a chemical bond, -O-, -ORO- (R is C ₁ - to C ₈ -alkylene or C ₃ - to C ₈ -cycloalkylene) are prepared.

preferred Monomers of this type are ethylene diglycidyl, diglycidyl ether and diether from glycidylene and formaldehyde, dioxane or trioxane in the molar ratio 2: 1 and diether from 2 mol glycidyl compound and 1 mol of an aliphatic Diols with 2 to 8 carbon atoms such as the diglycidyl ethers 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 to call.

End-group-stabilized polyoxymethylene polymers which have predominantly C-C 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 weight average molecular weights M _w in the range of 5,000 to 300,000, preferably 7,000 to 250,000. Particular preference is given to POM copolymers having a nonuniformity (M _w / M _n ) of from 2 to 15, preferably from 2.5 to 12, particularly preferably 3 to 9. The measurements are generally carried out by gel permeation chromatography (GPC) / SEC (size exclusion chromatography), the M _n value (number average molecular weight) is generally determined by GPC / SEC.

The If appropriate, molecular weights of the polymer can be determined by customary in trioxane polymerization Regulator, as well as by the reaction temperature and residence time the desired values are set. As regulators come acetals or Formal monohydric alcohols, the alcohols themselves and acting as chain transfer agents small amounts of water whose presence usually never completely avoid leaves, in question. The regulators are used in quantities of 10 to 10,000 ppm, preferably from 20 to 5,000 ppm.

When Initiators (also called catalysts) are used in the Trioxane polymerization usual cationic Starter used. Proton acids such as fluorinated or chlorinated are suitable Alkyl and arylsulfonic acids, e.g. perchloric acid, trifluoromethanesulfonic or Lewis acids, such as. Tin tetrachloride, arsenic pentafluoride, phosphoric pentafluoride and boron trifluoride and their complex compounds and salt-like Compounds, e.g. Boron trifluoride etherates and triphenylmethylene hexafluorophosphate. The initiators (catalysts) are used in amounts of about 0.01 to 1,000 ppm, preferably 0.01 to 500 ppm and in particular 0.01 used up to 200 ppm. In general, it is recommended that the initiator in dilute Add form, preferably in concentrations of 0.005 to 5 Wt .-%. As a solvent therefor can inert compounds such as aliphatic or cycloaliphatic hydrocarbons e.g. Cyclohexane, halogenated aliphatic hydrocarbons, glycol ethers, cyclic carbonates, lactones, etc. can be used. Especially preferred solvent are triglyme (triethylene glycol dimethyl ether), 1,4-dioxane, propylene carbonate or gamma-butyrolactone.

In addition to the initiators can Cocatalysts are used. They are all alcohols Kind, e.g. aliphatic alcohols having 2 to 20 C atoms, such as t-amyl alcohol, Methanol, ethanol, propanol, butanol, pentanol, hexanol; aromatic Alcohols having 2 to 30 C atoms, such as hydroquinone; halogenated alcohols with 2 to 20 carbon atoms, such as hexafluoroisopropanol; very particular preference is given to glycols of any kind, especially diethylene glycol and triethylene glycol; and aliphatic dihydroxy compounds, in particular diols with 2 to 6 carbon atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol.

monomers Initiators, cocatalyst and optionally regulators can any way premixed or separated from each other the polymerization reactor be added.

Further can the components for stabilizing sterically hindered phenols as described in EP-A 129369 or EP-A 128739.

Preferably will be followed directly the polymerization mixture deactivates the polymerization mixture, preferably without a phase change takes place. The deactivation the initiator residues (catalyst residues) are usually carried out by Addition of deactivators (demulsifiers) to the polymerization melt. Suitable deactivators are e.g. Ammonia as well as primary, secondary or tertiary, aliphatic and aromatic amines, e.g. Trialkylamines such as triethylamine, or triacetone diamine. Furthermore Also suitable are basic salts, such as soda and borax the carbonates and hydroxides of the alkali and alkaline earth metals, as well as Alcoholates, such as sodium ethanolate. Furthermore, alkali or Erdalkalialkyle preferred as deactivators which have 2 to 30 C atoms in the alkyl radical exhibit. As particularly preferred metals are Li, Mg and Na named, with n-butyl lithium being particularly preferred.

The Deactivators usually become the polymers in amounts of preferably 0.01 ppmw up to 2 wt .-% added, either as such or dissolved or suspended in water, Methanol, other alcohols or other organic solvents.

POM from formaldehyde are in common Manner by polymerization in the gas phase, in solution, by precipitation polymerization or in mass (substance) to produce. POM from trioxane will be in usually obtained by bulk polymerization, including any Reactors with high mixing effect can use. The reaction can be homogeneous, e.g. in a melt, or heterogeneous, e.g. as polymerization to a solid or solid granules. For example, shell reactors, plowshare mixers, Tubular reactors, list reactors, kneaders (e.g., Buss kneaders), extruders with, for example, one or two screws, and stirred reactors, the reactors having static or dynamic mixers can.

at a bulk polymerization, e.g. in an extruder, can through melted polymer a so-called. Melt seal for extruder feed be generated, which volatile Components remain in the extruder. You dose the above Monomers in the present in the extruder polymer melt, together or separately from the initiators (catalysts), in a preferred Temperature of the reaction mixture from 62 to 114 ° C. Also preferred are the Monomers (trioxane) dosed in the molten state, e.g. at 60 up to 120 ° C.

The Melt polymerization usually takes place at 1.5 to 500 bar and 130 to 300 ° C, and the residence time of the polymerization mixture in the reactor is usually 0.1 to 20, preferably 0.4 to 5 min. Preferably, one leads the polymerization to a conversion above 30%, e.g. 60 to 90%.

you receives in each case, a raw POM, as mentioned, considerable shares, for example contains up to 40% of unreacted residual monomers, in particular Trioxane and formaldehyde. It can also formaldehyde in the crude POM then exist when only trioxane was used as the monomer since it can arise as a degradation product of trioxane. Besides, too other oligomers of formaldehyde, e.g. the tetramer Tetroxane.

Prefers is used for the preparation of POM trioxane as a monomer, which is why also contain the residual monomers trioxane, also usually still 0.5 to 10 Wt .-% tetroxane and 0.1 to 75 wt .-% formaldehyde.

The inventive method to remove the residual monomers may be discontinuous or preferred be operated continuously.

degasing

The Crude POM is degassed in a degasser. As degassing devices Degassing pots are suitable (Flash pots) Degassing extruder with one or more screws, film extruder, Thin film evaporator, spray dryer, Strand degasser and other common ones Degassing. Degassing extruders are preferably used or degassing pots. The latter are particularly preferred.

The Degassing can be single-stage (in a single degassing device) respectively. Likewise, it can be multi-level - for example, two-stage - in several Degassing devices take place behind each other and / or in parallel are arranged. Preferably, the series-connected arrangement.

at the multi-stage degassing can the degassing devices the same or different in type and size be. For example, you can two equal Entgasungstöpfe one behind the other operate, or two different sized degassing pots in a row, or two equal degassing extruders, or two different sized ones Degassing extruder, or a degassing and behind a Degassing extruder, or a vented extruder and behind a Degassing. The variant with two (same or different) devolatilization vessels is preferred. Particularly preferred to use two different degassing pots one behind the other, the second pot having a smaller volume.

at a single-stage degassing is the pressure in the degassing usually at 0.1 mbar to 10 bar, preferably 1 mbar to 2 bar and especially preferably 5 mbar to 800 mbar, and the temperature usually at 100 to 260, preferably 115 to 230 and in particular 150 to 210 ° C.

at a two-stage degassing is the pressure in the first Stage preferably 0.1 mbar to 10 bar, in particular 0.5 mbar to 8 bar and more preferably 1 mbar to 7 bar, and in the second Step preferably 0.1 mbar to 5 bar, in particular 0.5 mbar to 2 bar and more preferably 1 mbar to 1.5 bar. The temperature is different in a two-stage degassing usually not essential from the for the single-stage degassing temperatures mentioned.

The Temperature control of the polymer is carried out in the usual way by heat exchangers, Double jacket, tempered static mixers, internal heat exchangers or other suitable devices. The setting of the pressure one also takes in a conventional manner, e.g. by means of Pressure control valves. The polymer may be in the degassing device molten or fixed.

The Residence time of the polymer in the degassing device is in the Usually 0.1 sec to 30 min, preferably 0.1 sec to 20 min. At a Multi-stage degassing, these times refer to a single one Step. additional Residence time can be introduced by connecting pipes. For damages of the polymer due to thermal stresses to minimize, this is additional Residence time through connecting pipes preferably not more than 10 minute

The in the degassing released residual monomers are called vapor stream separated. Independently of the design of the degassing (single or multi-stage, degassing or extruder, etc.), the residual monomers are usually selected from Trioxane, formaldehyde, tetroxane, 1,3-dioxolane, 1,3-dioxepane, ethylene oxide and oligomers of formaldehyde.

The with the method according to the invention separated residual monomers (vapor stream) become commonplace Deducted manner. You can condensed and recycled to the polymerization. The ratio of Trioxane and formaldehyde in the vapor stream can be varied by setting appropriate pressures and temperatures become. The higher the pressure is the greater the formaldehyde content in the vapor stream.

Mix

To degassing in the degassing device, the POM in a Mixing device mixed. It is preferred in the mixing device the POM with usual Additives mixed, which are described below. Also Preferably, the mixing device also serves a further degassing, see below.

When Mixers are, for example, mixers, kneaders or - preferably - extruder. The mixing device is preferably operated continuously and is possibly tempered, where usually a part of the heat energy already generated by the shear associated with the mixing process is, and the remaining part by heating the mixing device supplied becomes.

When Mixers are particularly suitable for mixers with moving tools, e.g. Spiral mixer, double spiral mixer, paddle mixer, Ploughshare mixer, paddle mixer, agitator mixer (also agitator planetary mixer) or rolling mills.

When Extruders are all common Screw machines into consideration, in particular single-screw and twin-screw extruder (for example, type ZSK from Coperion or Werner & Pfleiderer), co-kneaders, Kombiplast machines, MPC kneading mixer, FCM mixer, KEX kneading screw extruder or shear roller extruder.

The Mixing device and its design, in particular the nature and Speed of the mixing tool and the quantities supplied and the throughput the mixing device are chosen in a known manner such that the POM in the desired Way mixed or the additives in the desired Be incorporated into the POM or the POM further degassed becomes.

At the Extruders can for example, speed, length, Temperature profile along the screw (s), diameter and design the extruder screw (s), for example, number of gears and depth, slope, Use and sequence of promotional (e.g., thrust edge), recirculating, jamming, kneading and / or mixing elements along the screw, be varied accordingly. Preference is given to twin-screw extruders, especially those with co-rotating screws.

At the Mixing is usually the temperature at 160 to 260, preferably 180 to 240 and in particular 200 to 220 ° C and is with usual Heater set. For heavily shearing mixers can a cooling be necessary to the warming of the polymer.

Of the Pressure during mixing hangs et al from the mixing device and the operating conditions. He is generally not critical and is for example 1 to 80, preferably 5 to 50 bar.

In a preferred embodiment be the mixing device and their operating conditions in chosen in a known manner, that further degassing takes place in the mixing device, i. Mixing in the mixing device becomes the residual monomer content the POM lowered again. For this purpose one can use the mixing device with usual Provided degassing. For example, an extruder used, the degassing having. these can optionally at negative pressure, e.g. 50 to 800 mbar (absolute), operated, to improve the degassing effect, and may have restraint devices, which prevent the escape of polymer.

Out the mixing device, the polymer by conventional conveying elements, for example Pumps, in particular melt pumps, screw conveyors or the like deducted so far the mixing device is not self-promoting (extruder). Subsequently, will the discharged melt usually chilled and granulated.

dwell between degassing and mixing

According to the invention, the residence time the POM between the discharge from the degassing and the Entry into the mixing device for a maximum of 60 seconds, preferably a maximum 30 sec and more preferably not more than 10 sec. With residence time meant the mean residence time, and in a multi-stage degassing is with degassing the last degassing before the mixing device meant.

In an embodiment A of the invention, the polymer with a pipe and / or conventional Austragsorganen withdrawn from the degassing and into the mixing device encouraged if necessary, also collecting container or valves interposed could be. Suitable delivery devices are e.g. Pumps (melt pumps, gear pumps, etc.), screw conveyors and others for promoting melt common Conveyors. The residence time of POM in pipelines, conveyors, storage tanks and Valves is taken together a maximum of 60, preferably a maximum of 30 and preferably maximum 10 sec.

In a particularly preferred embodiment B falls the discharge of the degassing device with the entry of the mixing device together, i. the said residence time is zero sec. In this case is the discharge of the degassing directly and without intermediate tanks, Pipelines, pumps, screw conveyors, Valves or other conveying organs or control devices mounted on the entry of the mixing device.

In the embodiment B, one can see the mixing device as the Austragsorgan which the POM is removed from the degassing device. This will be a separate one Discharge organ for the degassing saved, which the investment sum and reduces the space required by the plant and the economy improved.

of apparatus Advantageously, the degassing device is arranged above the mixing device so that the polymer follows gravity from the degassing falls into the mixing device.

As mentioned, a degassing pot is preferred as the degassing device, and as a mixing device preferably an extruder used. In this case, embodiment B can be realized, for example, by removing the bottom of the degassing pot and mounting the downwardly open degassing pot directly onto the entry dome of the extruder. As a result, the extruder is the bottom of the Entga sungsstopfs, and the extruder acts as a Austragsorgan the Entgasungstopfs by pulling the POM from the pot. Accordingly, in this realization, the polymer is not first collected in the degassing pot, then discharged by a pump or other conveying member and conveyed through a pipe into the extruder. Rather, the degassing is arranged on the extruder and emptied directly into the extruder.

additives

The Polyoxymethylene molding compounds can, as mentioned, optionally contain other additives in the mixing device mixed and described below under 1) to 11). The quantities given are preferred quantities in the event that the concerned Additive at all is used.

1)

Talc, a hydrated magnesium silicate of the composition Mg ₃ [(OH) ₂ / Si ₄ O ₁₀ ] or 3 MgO.4 SiO ₂ .H ₂ O. These so-called three-layer phyllosilicates have a triclinic, monoclinic or rhombic crystal structure with a platelet-like appearance. On further trace elements Mn, Ti, Cr, Ni, Na and K may be present, wherein the OH group may be partially replaced by fluoride.

talc will - if co-used - preferably in amounts of from 0.01 to 2% by weight, preferably 0.02 to 0.8% by weight and in particular 0.03 to 0.4 wt .-%, based on the finished POM.

Especially talc is preferably used whose particle sizes are 100% less than 20 μm is. The particle size distribution becomes common determined by sedimentation analysis and is preferably: <20 .mu.m: 100 wt .-%, <10 .mu.m: 99 wt .-%, <5 .mu.m: 85 wt .-%, <3 .mu.m: 60 wt .-%, <2 microns : 43% by weight. such Products are commercially available as Micro-Talc I.T. extra (Norwegian company Talc Minerals).

2)

polyamides, especially semicrystalline or amorphous resins, as e.g. in the Encyclopedia of Polymer Science and Engineering, Vol. 11, p. 315-489, John Wiley & Sons, Inc., 1988. As a rule, the melting point is of the polyamide below 225 ° C, preferably below 215 ° C.

Examples therefor are polyhexamethyleneazelaic acid amide, polyhexamethylenesebacamide, polyhexamethylenedodecanediamide, Poly-11-aminoundecansäureamid and bis- (p-aminocyclohexyl) -methane-dodecansediamide or by ring-opening of Lactams, e.g. Caprolactam or polylaurolactam obtained products. Also polyamides based on terephthalic or isophthalic acid as acid component and / or trimethylhexamethylenediamine or bis (p-aminocyclohexyl) -propane as a diamine component and polyamide base resins by copolymerization two or more of the aforementioned polymers or their components have been prepared are suitable.

Particularly suitable polyamides 2) which may be mentioned are mixed polyamides based on caprolactam, hexamethylenediamine, p, p'-diaminodicyclohexylmethane and adipic acid, which may additionally contain monofunctionally polymerizing compounds such as propionic acid or triacetonediamine as molecular weight-regulating components. Examples of this are Ultramid ^® 1C or Ultramid ^® C31 by BASF Aktiengesellschaft.

Other suitable polyamides are marketed by Du Pont Company under the name Elvamides ^®.

The Preparation of these polyamides is also in the aforementioned Scripture described. The relationship from terminal Amino groups to terminal acid groups can by varying the molar ratio the starting compounds, or by the amount of said monofunctional polymerizing compounds are controlled.

Of the Proportion of polyamides 2) in the finished POM - if used - is usually 0.001 to 2% by weight, preferably 0.005 to 1.99% by weight, preferably 0.01 to 0.08 wt .-%.

By the concomitant use of a polycondensation product of 2,2-di- (4-hydroxyphenyl) propane (Bisphenol A) and epichlorohydrin can be improved in some cases, the dispersibility of the polyamides used.

Such condensation products of epichlorohydrin and bisphenol A are commercially available. Processes for their preparation are also known to the person skilled in the art. Trade names of the polycondensates are Phenoxy ^® (Union Carbide Corporation) or Epikote ^® (Shell). The molecular weight of the polycondensates can vary within wide limits; In principle, the commercially available types are all suitable.

3)

alkaline earth and / or alkaline earth glycerophosphates, if commonly used in amounts of 0.002 to 2.0 wt .-%, preferably 0.005 to 0.5 wt .-% and in particular 0.01 to 0.3 wt .-%, based on the finished POM.

As alkaline earth metals for the formation of silicates and glycerophosphates preferably calcium and especially magnesium have proven. Expediently calcium glycerophosphate and preferably magnesium glycerophosphate and / or calcium silicate and preferably magnesium silicate, being preferred as alkaline earth silicates, especially those which are represented by the formula Me · x SiO ₂ · n H ₂ O be described in the mean
Me an alkaline earth metal, preferably calcium or magnesium in particular,
x is a number from 1.4 to 10, preferably 1.4 to 6 and
n is a number equal to or greater than 0, preferably 0 to 8.

The Erdalkalisilikate or -glycerophospahte 3) are advantageously used in finely ground form. Products with an average Particle size of smaller as 100 μm, preferably less than 50 microns are particularly suitable.

• Calcium- bzw.- Magnesiumsilikat:
• Gehalt an CaO bzw. MgO: 4 bis 32 Gew.-%, vorzugsweise 8 bis 30 Gew.-% und insbesondere 12 bis 25 Gew.-%,
• Verhältnis SiO₂: CaO bzw. SiO₂: MgO (mol/mol): 1,4 bis 10, vorzugsweise 1,4 bis 6 und insbesondere 1,5 bis 4,
• Schüttdichte: 10 bis 80 g/100 ml, vorzugsweise 10 bis 40 g/100 ml,
• durchschnittliche Korngröße: kleiner als 100 μm, vorzugsweise kleiner als 50 μm;
• Calcium- bzw. Magnesiumglycerophosphate:
• Gehalt an CaO bzw. MgO: größer als 70 Gew.-%, vorzugsweise größer als 80 Gew.-%,
• Glührückstand: 45 bis 65 Gew.-%,
• Schmelzpunkt: größer als 300°C und
• durchschnittliche Korngröße: kleiner als 100 μm, vorzugsweise kleiner als 50 μm.

Preferably used are calcium and magnesium silicates and / or calcium and magnesium glycerophosphates. For example, they can be specified by the following characteristics:

• Calcium or magnesium silicate:
• Content of CaO or MgO: 4 to 32 wt.%, Preferably 8 to 30 wt.% And in particular 12 to 25 wt.
• SiO ₂ ratio: CaO or SiO ₂ : MgO (mol / mol): 1.4 to 10, preferably 1.4 to 6 and in particular 1.5 to 4,
• Bulk density: 10 to 80 g / 100 ml, preferably 10 to 40 g / 100 ml,
• average grain size: less than 100 μm, preferably less than 50 μm;
• Calcium or magnesium glycerophosphates:
• Content of CaO or MgO: greater than 70% by weight, preferably greater than 80% by weight,
• Incineration residue: 45 to 65% by weight,
• Melting point: greater than 300 ° C and
• average grain size: less than 100 μm, preferably less than 50 μm.

4)

• a) ester or amide saturated or unsaturated aliphatic carboxylic acids with 10 to 40 C atoms, preferably 16 to 22 C atoms, with polyols or aliphatic saturated Alcohols or amines having 2 to 40 carbon atoms, preferably 2 to 6 carbon atoms, or b) ethers derived from alcohols and ethylene oxide.

The Amount of these esters, amides or ethers - if used - is usually 0.01 to 5, preferably from 0.09 to 2 and especially from 0.1 to 0.7 wt .-%, based on the finished POM.

The carboxylic acids can be monovalent or divalent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid as well as montanic acid (Mixture of fatty acids with 30 to 40 carbon atoms).

The aliphatic alcohols can be monovalent to tetravalent. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, glycerol and penta erythritol are preferred.

The aliphatic amines can be one to three valued. Examples of these are stearylamine, ethylenediamine, Propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, wherein Ethylenediamine and hexamethylenediamine are particularly preferred. preferred Esters or amides are according to glycerol distearate, glycerol tristearate, Ethylene diamine distearate, glycerol monopalmitate, glycerol trilacate, Glycerol monobehenate and pentaerythritol tetrastearate.

It can also mixtures of different esters or amides or esters with amides be used in combination, the mixing ratio arbitrary is.

Also suitable are polyether polyols or polyester polyols which are esterified or etherified with mono- or polybasic carboxylic acids, preferably fatty acids. Suitable products are commercially available for example as Loxiol ^® EP 728 from Henkel KGaA.

Preferred ethers 4) b), which are derived from alcohols and ethylene oxide, have the general formula RO (CH ₂ CH ₂ O) _n H, in which R is an alkyl group having 6 to 40 carbon atoms and n is an integer greater than or equal to 1 means.

Particularly preferred for R is a saturated C _16-18 fatty alcohol with n 50, which as Lutensol ^® AT BASF is commercially available 50th

5)

• non-polar polypropylene waxes, i. Polypropylene with waxy Character, which accordingly have a low molecular weight.

The Amount of these polypropylene waxes - if used - is usually 0.05 to 10, preferably from 0.1 to 5 wt .-%, based on the finished POM.

Waxes 5) have a weight average molecular weight M _{w of} from 2,000 to 60,000 (by GPC and standard polystyrene), preferably from 5,000 to 50,000, and more preferably from 10,000 to 45,000. Their softening point is preferably at least 140 ° C, preferably at least 150 ° C, determined according to DIN EN 1427 (ring-and-ball method), their viscosity generally from 10 to 5000 mPas, preferably from 100 to 3000 mPas at 170 ° C. according to DIN 53018 and their density usually from 0.87 to 0.92 g / cm ³ , preferably from 0.88 to 0.91 g / cm ³ according to DIN 53479.

Preferred waxes 5) have the form of so-called micropowders whose d ₅₀ value is from 1 to 50 μm, preferably from 5 to 30 μm.

Under Non-polar polypropylene waxes in the context of the invention are understood according to Ullmann's Encyclopedia of Industrial Chemistry, 6th edition Keyword 6.1.5 Polar polyolefin Waxes, Verlag Chemie, 2000, waxes without the incorporation of polar groups (in particular of carboxyl and / or ester groups).

The Production of waxes 5) can be done in stirred high pressure autoclave or in high-pressure tube reactors using regulators. The preparation in stirred High pressure autoclave is preferred. The high-pressure stirred autoclave are a description can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996. Behaves with them predominantly The relationship Length / diameter in Intervals of 5: 1 to 30: 1, preferably 10: 1 to 20: 1. The same applicable high-pressure tube reactors can also be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996th

When Another method of preparation is according to Ullmann (see above) the depolymerization of polypropylenes having higher molecular weights usual.

The commercially available Waxes 5) are translucent, colorless to white powder products which are clear Melting and soluble in nonpolar solvents.

Preferred products are Licowax PP ^{® ®} particular Licowax PP 230, and PP 220 and Licowax ^® VP PP grades from Clariant and Ceridust ^® VP 6071 and the LC 525 N, LC 502 N, LC 502 NC, LC 503 N, LC 503 NC types from Hana Corporation, Korea.

6)

nucleating agents, if used usually in amounts of from 0.0001 to 1% by weight, preferably 0.001 to 0.8 wt .-% and in particular 0.01 to 0.3 Wt .-%, based on the finished POM.

As a nucleating agent, all known compounds are suitable, for example melamine cyanurate, boron compounds such as boron nitride, silica, talc, 2,3-Dioxychinoxalin, branched and crosslinked acetal, Acetalblockcopolymere and pigments such as Heliogen ^® (copper phthalocyanine pigment) from BASF Aktiengesellschaft, also melamine-formaldehyde condensates.

7)

fillers, if used usually in amounts of up to 50 wt .-%, preferably 5 to 40 wt .-% based on the finished POM.

Suitable For example, potassium titanate whiskers, carbon and, preferably, are Glass fibers, the glass fibers e.g. in the form of glass fabrics, mats, nonwovens and / or glass silk rovings or cut glass silk from low-alkali E glass with a diameter of 5 to 200 microns, preferably 8 to 50 μm can be used. fiber-shaped fillers after incorporation, they preferably have an average length of 0.05 to 1 mm, in particular 0.1 to 0.5 mm.

Other suitable fillers For example, calcium carbonate or glass beads are preferred in ground form or mixtures of these fillers.

8th)

• impact modifying polymers (hereinafter also referred to as rubber-elastic Polymers or elastomers), if commonly used in amounts up to 50, preferably 0 to 40 wt .-%, based on the finished POM.

preferred Types of such elastomers are the so-called ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers. EPM rubbers have in general, virtually no double bonds, while EPDM rubbers 1 to 20 double bonds / 100 carbon atoms may have.

When Diene monomers for EPDM rubbers 8) are, for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes of 5 to 25 C atoms such as Penta-1,4-diene, Hexa-1,4-diene, hexa-1,5-diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene and alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyltricyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof. Preferred are hexa-1,5-diene, 5-ethylidene-norbornene and dicyclopentadiene. The diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber.

The EPDM rubbers can also be grafted with other monomers, e.g. with glycidyl (meth) acrylates, acrylsäureestern (meth) and (meth) acrylamides.

wobei R⁶ bis R¹⁰ Wasserstoff oder Alkylgruppen mit 1 bis 6 C-Atomen darstellen und m eine ganze Zahl von 0 bis 20, g eine ganze Zahl von 0 bis 10 und p eine ganze Zahl von 0 bis 5 ist.Another group of preferred rubbers 8) are copolymers of ethylene with esters of (meth) acrylic acid. In addition, the rubbers may still contain epoxy group-containing monomers. These epoxy group-containing monomers are preferably incorporated into the rubber by adding epoxy group-containing monomers of the general formulas I or II to the monomer mixture

wherein R ⁶ to R ^{10 are} hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 0 to 5.

The radicals R ⁶ to R ⁸ preferably denote hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are allyl glycidyl ether and vinyl glycidyl ether.

preferred Compounds of formula II are epoxy group-containing esters of Acrylic acid and / or methacrylic acid, such as glycidyl acrylate and glycidyl methacrylate.

Advantageous The copolymers consist of 50 to 98 wt .-% of ethylene, 0 to 20 Wt .-% epoxy-containing monomers and the remaining Amount of (meth) acrylic esters.

• – 50 bis 98, insbesondere 55 bis 95 Gew.-% Ethylen,
• – 0,1 bis 40, insbesondere 0,3 bis 20 Gew.-% Glycidylacrylat und/oder Glycidylmethacrylat, (Meth)acrylsäure und/oder Maleinsäureanhydrid und
• – 1 bis 50, insbesondere 10 bis 40 Gew.-% n-Butylacrylat und/oder 2-Ethylhexylacrylat.

Particularly preferred are copolymers of

• From 50 to 98, in particular from 55 to 95,% by weight of ethylene,
• - 0.1 to 40, in particular 0.3 to 20 wt .-% glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride and
• - 1 to 50, especially 10 to 40 wt .-% n-butyl acrylate and / or 2-ethylhexyl acrylate.

Further preferred esters of acrylic and / or methacrylic acid are the methyl, ethyl, Propyl and i- or t-butyl ester. In addition, vinyl esters and vinyl ethers can also be used be used as comonomers.

The The above-described ethylene copolymers 8) can be known per se Process are prepared, preferably by random copolymerization under high pressure and elevated Temperature. Corresponding methods are generally known.

preferred Elastomers 8) are also emulsion polymers, their preparation e.g. at Blackley in the monograph "Emulsion Polymerization". The emulsifiers and catalysts which can be used are known per se.

Basically, can be homogeneous constructed elastomers or those used with a shell structure become. The shell-like structure is u.a. by the order of addition the individual monomers determined; also the morphology of the polymers is influenced by this order of addition.

Just are representative here as monomers for the preparation of the rubber part the elastomers acrylates such as e.g. n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof called. These monomers can with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, Methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.

The Soft or rubber phase (with a glass transition temperature of below 0 ° C) the Elastomers may be the core, the outer shell or a middle shell (for elastomers with more than two-shell construction) group; in multi-shell elastomers can also be several shells a rubber phase.

are in addition to the rubber phase, one or more hard components (with glass transition temperatures of more than 20 ° C) involved in the construction of the elastomer, so these are in general by polymerization of styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, acrylic esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as major monomers produced. In addition, you can Here, too, lower proportions of other comonomers are used.

eingeführt werden können,
wobei die Substituenten folgende Bedeutung haben können:
R¹⁵ Wasserstoff oder eine C₁- bis C₄-Alkylgruppe,
R¹⁶ Wasserstoff, eine C₁- bis C₈-Alkylgruppe oder eine Arylgruppe, insbesondere Phenyl,
R¹⁷ Wasserstoff, eine C₁- bis C₁₀-Alkyl-, eine C₆- bis C₁₂-Arylgruppe oder -OR¹⁸
R¹⁸ eine C₁- bis C₈-Alkyl- oder C₆- bis C₁₂-Arylgruppe, die gegebenenfalls mit O- oder N-haltigen Gruppen substituiert sein können,
X eine chemische Bindung, eine C₁- bis C₁₀-Alkylen- oder C₆-C₁₂-Arylengruppe oder

Y OZ oder NH-Z und
Z eine C₁ bis C₁₀-Alkylen- oder C₆ bis C₁₂-Arylengruppe.In some cases it has been found to be advantageous to use emulsion polymers 8) which have reactive groups on the surface. Such groups include, for example, epoxy, amino or amide groups and functional groups obtained by concomitant use of monomers of the general formula

can be introduced
where the substituents may have the following meanings:
R ^{15 is} hydrogen or a C ₁ - to C ₄ -alkyl group,
R ^{16 is} hydrogen, a C ₁ - to C ₈ -alkyl group or an aryl group, in particular phenyl,
R ^{17 is} hydrogen, a C ₁ - to C ₁₀ -alkyl, a C ₆ - to C ₁₂ -aryl group or -OR ¹⁸
R ^{18 is} a C ₁ - to C ₈ -alkyl or C ₆ - to C ₁₂ -aryl group which may optionally be substituted by O- or N-containing groups,
X is a chemical bond, a C ₁ - to C ₁₀ -alkylene or C ₆ -C ₁₂ -arylene group or

Y OZ or NH-Z and
Z is a C ₁ to C ₁₀ alkylene or C ₆ to C ₁₂ arylene group.

Also the graft monomers described in EP-A 208 187 are more reactive for introduction Groups on the surface suitable. As further examples may be acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (N-t-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N, N-diethylamino) ethyl acrylate.

Farther can the particles of the rubber phase also be crosslinked. As a crosslinker acting monomers are, for example, buta-1,3-diene, divinylbenzene, Diallyl phthalate, butanediol diacrylate and dihydrodicyclopentadienyl acrylate as well as the compounds described in EP-A 50 265.

Further can also so-called graftlinking monomers be used, i. Monomers with two or more polymerisable Double bonds, which in the polymerization with different Speeds respond.

Preferably Such compounds are used in which at least one reactive Group at about the same speed as the other monomers polymerized while the other reactive group (or reactive groups) e.g. clear polymerized more slowly (polymerize). The different ones Polymerization rates bring a certain proportion in unsaturated Double bonds in rubber with it. Will then open grafted such a rubber another phase, so react the double bonds present in the rubber at least partially with the grafting monomers forming chemical bonds, i.e. the grafted phase is at least partially chemical Bindings linked to the grafting base.

Examples for such graftlinking monomers are allyl group-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids, such as Allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids. Besides There are a variety of other suitable graftlinking monomers; for details For example, reference is made here to US Pat. No. 4,148,846.

in the general amounts the proportion of these crosslinking monomers in the component 8) to to 5 wt .-%, preferably not more than 3 wt .-%, based on the Elastomers 8).

preferred Emulsion polymers 8) have a core of buta-1,3-diene, isoprene, n-butyl acrylate, ethylhexyl acrylate or mixtures thereof, if necessary together with crosslinking monomers, and at least one outer shell of styrene, acrylonitrile, (Meth) acrylates or mixtures thereof, optionally with reactive Groups as described herein.

Instead of of graft polymers having a multi-shell construction can also homogeneous, i. single-shell elastomers of buta-1,3-diene, isoprene and n-butyl acrylate or their copolymers are used. Also these products can by concomitant use of crosslinking monomers or monomers with reactive Groups are produced.

The described elastomers 8) also after other usual Method, e.g. by suspension polymerization.

When other suitable elastomers 8) are thermoplastic polyurethanes called, which e.g. in EP-A 115 846, EP-A 115 847 and EP-A 117 664 are described.

Of course you can too Mixtures of the abovementioned Rubber types are used.

9)

• more usual Additives and processing aids, in particular flame retardants, Plasticizers, adhesion promoters, dyes and pigments. The amount such additives is - if co-used - in general in the range of 0.001 to 5 wt .-%, based on the finished POM.

10)

Formaldehyde scavengers. suitable Formaldehyde scavenger 10) are listed below under 10a), 10b), 10c) and 10d). The under 10a), 10b) and 10c), if used, in amounts of 0.001 to 3, preferably 0.01 to 2 and in particular 0.1 to 1 wt .-%, based on the finished POM used. The amount the compounds 10d) is mentioned below.

10a)

Amine group-containing compounds. Preferably used amine-substituted triazine compounds such as melamine (1,3,5-triazine-2,4,6-triamine). The amine groups may be unsubstituted (-NH ₂ ) or substituted with substituents R (-NHR or -NR ₂ ).

genannt, worin R₁, R₂ und R₃ gleich oder unterschiedlich sind und jeweils Wasserstoffatome, Halogenatome, eine Hydroxylgruppe, eine Alkylgruppe, eine Alkoxygruppe, eine Arylgruppe, eine Arylalkyloxygruppe oder eine substituierte oder unsubstituierte Amingruppe mit der Maßgabe bedeuten, dass mindestens einer der Reste R₁, R₂ und R₃ eine substituierte oder unsubstituierte Amingruppe ist und mindestens ein Rest R₁, R₂ und R₃ aus einer aromatischen C₅-C₂₀-Gruppe, welche gegebenenfalls substituiert sein kann, aufgebaut ist.Very particular preference is given to amine-substituted triazine compounds which additionally have at least one aromatic group. Preferred triazine compounds are compounds of the general formula

wherein R ₁ , R ₂ and R _{3 are the} same or different and each represent hydrogen atoms, halogen atoms, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an arylalkyloxy group or a substituted or unsubstituted amine group with the proviso that at least one of R ₁ , R ₂ and R _{3 is} a substituted or unsubstituted amine group and at least one radical R ₁ , R ₂ and R ₃ from a C ₅ -C ₂₀ aromatic group, which may be optionally substituted, is constructed.

The Halogen atom is, for example, chlorine or bromine, preferably chlorine. examples for the alkyl group are those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of alkoxy groups are those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.

When Aryl group preferred are the phenyl group, naphthyl group and fluorenyl group. As arylalkyloxy groups are phenylalkyloxy groups, in particular Benzyloxy or Phenylethyloxy groups, preferred.

Examples of substituents on the substituted amino group include lower alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, butyl or hexyl groups, phenyl groups, lower alkenyl groups having 3 to 6 carbon atoms such as allyl or hexenyl groups, hydroxyalkyl groups having 1 or 2 carbons atoms such as hydroxymethyl or hydroxyethyl groups, and cyanoalkyl groups having 3 to 6 carbon atoms such as cyanoethyl or cyanobutyl groups.

Examples for amine-substituted and aromatically substituted triazine compounds include 2,4-diamino-6 (o, p, m) chlorophenyl triazine, 2-amino-4-chloro-6-phenyltriazine, 2-amino-4,6-diphenyltriazine, 2,4-diamino-6-naphthyltriazine, 2,4-diamino-6-fluorenyl triazine, 2,4-diamino-6 (o, m, p) alkylphenyl triazines, where the methyl radical is preferred as a substituent, 2,4-diamino-6 (o, m, p) methoxyphenyltriazine and 2,4-diamino-6 (o, m, p) carboxy-phenyltriazine, N-phenylmelamine, N, N'-Diphenylmelamin, benzoguanamine, i. 2,4-diamino-6-phenyl-sym.-triazine, 2,4-diamino-6-benzyloxy-sym.-triazine are particularly preferred.

Particularly preferred triazine compounds contain at least two radicals R ₁ , R ₂ or R ₃ , which are composed of (un) substituted amino groups and / or in which the aromatic radical R ₁ , R ₂ or R ₃ consists of at least one phenyl ring.

All particularly preferred as the triazine compound are the guanamines, in particular Benzoguanamine.

10b)

• inorganic, formaldehyde-binding compounds. It can the binding of formaldehyde chemically or preferably physically take place, e.g. by adsorption.

Preference is given to using zeolites, ie crystalline aluminosilicates with ordered channel and cage structures. The network of such zeolites is composed of SiO ₄ ^- and AlO ₄ ^- tetrahedra which are connected via common oxygen bridges. An overview of the known structures can be found, for example, in MW Meier, DH Olson, Ch. Baerlocher "Atlas of Zeolite Structure Types", 5th revised edition, Elsevier, London, 2001. Another listing is available on the Internet at the URL http: // /topaz.ethz.ch/IZA-SC/SearchRef.htm, where among others the following structures are described: ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX , AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AWO, AWW, BCT, BEA, BEC, BIK, BOG, BPH, BRE, CAN, CAS, CDO, CFI , CGF, CGS, CHA, CHI, CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EPI, ERI, ESV, ETR, EUO, FAU, FER, FRA, GIS , GIU, GME, GON, GOO, HEU, IFR, ISV, ITE, ITH, ITW, IWR, IWW, JBW, KFI, LAU, LEV, LIO, LOT, LOV, LTA, LTL, LTN, MAR, MAZ, MEI , MEL, MEP, MER, MMFI, MFS, MON, MOR, MSO, MTF, MTN, MTT, MTW, MWW, NAB, NAT, NEES, NON, NPO, OBW, OFF, OSI, OSO, PAR, PAU, PHI , PON, RHO, RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAO, SAS, SAT, SAV, SBE, SBS, SBT, SFE, SFF, SFG, SFH, SFN SFO, SGT, SOD, SSY, STF, STI, STT, TER, THO, TON, TSC, UEI, UFI, UOZ, USI, UTL, VET , VFI, VNI, VSV, WEI, WEN, YUG or ZON.

Prefers are the structures BEA, FER, FAU, LTA, MEL, MFI or MOR, as well To name mixed structures of two or more of these types, such as a zeolitic material with MEL / MFI mixed structure. Amongst other things particularly preferred is an LTA-type zeolite. Most notably preferred are zeolites which are essentially 8-ring channels (and essentially no 10- and / or 12-ring channels).

To the Compensation of negative electrovalence caused by the installation of Al (III) is formed in the Si (IV) silicate lattice found in zeolitic ones Materials interchangeable Cations. In particular, it may be - depending on the manufacturing process of the zeolitic material - for example to act cations of sodium, potassium, lithium, rubidium or cesium. Also ammonium ions can be contained as cations in the zeolitic material. Replacing one these cations against protons, for example by an ion exchange, so receives the corresponding materials in the so-called acid form, the H-shape. Preferably, at least 75 wt .-% of the zeolite are not in the H form, more preferably at least 97 wt%.

Prefers the pore diameter of the zeolites is in the range of 0.3 to 0.5 nm, in particular 0.37 to 0.43 nm, determined according to DIN 66134 and DIN 66135.

The particle size of the zeolites is preferably in the range of 3 to 7 .mu.m, in particular 4 to 6 .mu.m, determined according to ISO 13320 in the version of 1999-11-01. As a dispersant for determining the particle size, demineralized (VE) water was used. The apparatus used was a Malvern Mastersizer 2000 (Module Hydro 2000G). The preparation of the samples was carried out at a solids content of 1 to 2 wt .-% in water and subsequent stirring with a magnetic stirrer, stirring for 1 min. When Particle size, the size of the particles was set at a passage of 50%.

All Particularly preferably, the zeolite has a pore diameter in Range of 0.37 to 0.43 nm and a particle size in the range of 4.0 to 6.0 microns.

The zeolite may in principle have any molar ratio Si: Al, calculated as molar ratio SiO ₂ : Al ₂ O ₃ . Preferably, the Si: Al ratio, calculated as the molar ratio SiO ₂ : Al ₂ O ₃ , in the range of up to 5: 1, in particular 0.9: 1 to 5: 1, more preferably about 1: 1.

Furthermore zeolites are also suitable whose structures are different from the ones above mentioned, or their pore diameter and / or particle sizes and / or Si: Al ratios and / or H-form portions, outside the areas mentioned lie.

10c)

• the following compounds or their derivatives (ie those compounds which contain the following compounds as the main body): allantoin (5-ureidohydantoin); Aminopyridines, especially 2-, 3- and 4-aminopyridine; Poly-beta-alanine; polyacrylamides; Ethyl-para-aminobenzoate; Polyethylene vinyl alcohols; Urea derivatives; 2-amino-2-methyl-1,3-propanediol; 1,2,3-benzotriazole; anthranilamide; sterically hindered amines (monomeric or oligomeric), eg the compound with CAS no. 152261-33-1, commercially available as Uvinul ^® 5050 H from BASF; soy protein isolate; Distearyl pentaerythritol diphosphite; Casseine; and 4-aminobenzoic acid.

10d)

Polyethyleneimines. This is understood to mean both homopolymers and copolymers which contain the grouping -CH ₂ -CH ₂ -NH-. They are, for example, according to the methods in Ullmann's Encyclopedia of Industrial Chemistry as the 6th edition, 1999 Electronic Release, Verlag VCH Weinheim, and as the 6th edition, 2000 Electronic Release, Verlag Wiley-VCH, each keyword "Aziridines", Chap. 6 "Uses", available, or according to WO-A 94/12560 available.

Prefers If one uses the polyethyleneimines 10d) - if used - in one such that the POM is 0.01 to 500 ppmw, in particular 0.1 to 200 ppmw, more preferably 0.1 to 50 ppmw and most especially preferably contains 0.5 to 10 ppmw of the polyethyleneimine. you can also use several polyethylenimines; in this case the amounts mentioned are based on the sum of all polyethyleneimines.

The ethyleneimine homopolymers are generally obtainable by polymerization of ethyleneimine (aziridine) in aqueous or organic solution in the presence of acid-releasing compounds, acids or Lewis acids. Such homopolymers are linear or preferably branched polymers. The latter generally have primary, secondary and tertiary amino groups in the ratio of, for example, about 1: 1: 0.7. The distribution of the amino groups can be determined, for example, by means of ¹³ C-NMR spectroscopy.

When Comonomers are preferably used compounds which at least have two amino functions. As suitable comonomers are, for example Alkylenediamines having 2 to 10 carbon atoms in the Alkyenrest mentioned, wherein Ethylenediamine and propylenediamine are preferred. Furthermore suitable Comonomers are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.

In addition, crosslinked polyethylene amines obtained by the reaction of polyethyleneimines are obtainable with bi- or polyfunctional crosslinkers which have as a functional group at least one halohydrin, glycidyl, aziridine, isocyanate unit or a halogen atom. Examples include its epichlorohydrin or bischlorohydrin of polyalkylene glycols having 2 to 100 ethylene oxide and / or propylene oxide units and in DE-A 19 93 17 20 and US 4,144,123 called compounds listed. Processes for the preparation of crosslinked polyethyleneimines are known inter alia from the abovementioned publications and EP-A 895 521 and EP-A 25 515.

Farther are grafted polyethyleneimines suitable as a grafting agent all Connections can be used which react with the amino or imino groups of the polyethyleneimines can. Suitable grafting agents and process for the preparation of grafted Polyethyleneimines can be found, for example, in EP-A 675 914.

As well Suitable polyethylenimines are amidated polymers, which are usually by reaction of polyethyleneimines with carboxylic acids whose Esters or anhydrides, carboxylic acid amides or carboxylic acid halides available are. Depending on the proportion of amidated nitrogen atoms in the Polyethyleniminkette the amidated polymers later be crosslinked with the crosslinkers mentioned. Preferably in this case up to 30% of the amino functions amidated, thus for a subsequent crosslinking reaction still enough primary and / or secondary Nitrogen atoms available stand.

Also suitable alkoxylated polyethyleneimines, for example, by reaction polyethyleneimine with ethylene oxide and / or propylene oxide. Such aloxylated polymers are also crosslinkable.

When Further suitable polyethyleneimines are hydroxyl-containing Polyethyleneimines and amphoteric polyethyleneimines (incorporation of anionic Groups) as well as lipophilic polyethyleneimines, which are usually by incorporation of long-chain hydrocarbon radicals in the polymer chain to be obtained. Process for the preparation of such polyethyleneimines are known in the art, so that no further details on this.

• – Homopolymeren des Ethylenimins,
• – Copolymeren aus Ethylenimin und Aminen mit mindestens zwei Aminogruppen,
• – vernetzten Polyethyleniminen,
• – gepfropften Polyethyleniminen,
• – amidierten Polymerisaten erhältlich durch Umsetzung von Polyethyleniminen mit Carbonsäuren oder Carbonsäureestern, -anhydriden, -amiden oder -halogeniden,
• – alkoxylierten Polyethyleniminen,
• – hydroxylgruppenhaltigen Polyethyleniminen,
• – amphoteren Polyethyleniminen, und
• – lipophilen Polyethyleniminen.

Accordingly, the polyethyleneimines 10d) are preferably selected from

• Homopolymers of ethyleneimine,
• Copolymers of ethyleneimine and amines having at least two amino groups,
• Crosslinked polyethyleneimines,
• Grafted polyethyleneimines,
• Amidated polymers obtainable by reaction of polyethyleneimines with carboxylic acids or carboxylic acid esters, anhydrides, amides or halides,
• Alkoxylated polyethyleneimines,
• Hydroxyl-containing polyethyleneimines,
• Amphoteric polyethylenimines, and
• - lipophilic polyethylenimines.

suitable Polyethyleneimines usually have a weight average molecular weight of 100 to 3,000,000, preferably from 200 to 1,000,000, and more preferably 500 to 500,000 g / mol as determined by light scattering or gel permeation chromatography (GPC).

The Polyethyleneimines 10d) can as such ("anhydrous") or as a solution or Suspension are used, with water being the preferred solvent. The viscosity of the "anhydrous" polyethyleneimines - their water content according to DIN 53715 according to Karl Fischer maximum about 1 wt .-% - is generally in the range from 100 to> 200,000 mPa · s, preferably in the range from 500 to> 200,000 mPa.s, determined according to DIN EN ISO 2555 (Brookfield RVT, 20 ° C, Spindle 6, 20 rpm).

suitable aqueous solutions The polyethyleneimines generally have a water content (according to DIN 53715 according to Karl Fischer) from 20 to 99, preferably from 40 to 80% by weight; the viscosity of these solutions according to DIN EN ISO 2555 (Brookfield RVT, 20 ° C, Spindle 5, 20 rpm) is usually 50 to 100,000, preferably 200 to 50,000 mPa · s.

Prefers one uses polyethyleneimines with a maximum water content 5% by weight, e.g. about 0.5 to 1 wt .-%, according to DIN 53715 after Karl Fischer.

In a preferred embodiment, the polyethyleneimines are hyperbranched or hyperbranched. Under In the context of this invention, highly branched or hyperbranched polyethyleneimines are understood as meaning uncrosslinked macromolecules having --NH groups which are structurally as well as molecularly nonuniform. They can be constructed either from a central molecule analogous to dendrimers, but with uneven chain length of the branches. However, they can also be constructed linearly with functional side groups or, as a combination of the two extremes, have linear and branched molecular moieties. For the definition of dendrimeric and hyperbranched polymers see also PJ Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499.

wobei T die Anzahl der terminalen Monomereinheiten, Z die Anzahl der verzweigten Monomereinheiten, und L die Anzahl der linearen Monomereinheiten, bedeutet. Diese Anzahlen können mittels ¹³C-Kernresonanzspektren als primäre (ergibt T), tertiäre (ergibt Z) sowie sekundäre (ergibt L) Aminogruppen bestimmt werden. Unter „dendrimer" wird im Zusammenhang mit der vorliegenden Erfindung verstanden, dass der Verzweigungsgrad 99,9 bis 100% beträgt. Zur Definition des Degree of Branching siehe auch H. Frey et al., Acta Polym. 1997, 48, 30.The degree of branching (DB) is defined as

where T is the number of terminal monomer units, Z is the number of branched monomer units, and L is the number of linear monomer units. These numbers can be determined by ¹³ C nuclear magnetic resonance spectra as primary (gives T), tertiary (gives Z) and secondary (gives L) amino groups. In the context of the present invention, "dendrimer" is understood to mean that the degree of branching is 99.9 to 100% For the definition of the degree of branching, see also H. Frey et al., Acta Polym., 1997, 48, 30.

Of the Branching degree of the inventively preferred hyperbranched or hyperbranched Polyethyleneimines is usually 40 to 100, preferably 50 to 80 and in particular 55 up to 70%.

Suitable polyethyleneimines are also commercially available, such as Lupasol ^® from BASF. In particular, Lupasol ^® WF, an anhydrous (water content max. 1 wt .-%, in accordance with DIN 53715 by Karl Fischer), hochverzeigtes polyethyleneimine with a specific means GPC weight average molecular weight of about 25,000 g / mol, a viscosity of> 200,000 mPa.s (Brookfield RVT, 20 ° C, spindle 6, 20 rpm) and a dynamic viscosity of about 15,000 mPa · s (ISO 2555, 50 ° C), is well suited.

method for the preparation of said formaldehyde scavengers 10a) to 10d) are the Known specialist or the compounds are commercially available, which is why further details on this are unnecessary. You can have one or several different Formaldehydfänger 10) use.

11)

antioxidants if used in amounts of 0.01 to 3, preferably 0.05 to 2 and in particular 0.1 to 1 wt .-%, based on the finished POM. Suitable antioxidants 11) are below 11a), 11b) and 11c).

11a)

in Betracht, in der bedeuten:
R¹ und R² eine Alkylgruppe, eine substituierte Alkylgruppe oder eine substituierte Triazolgruppe, wobei die Reste R¹ und R² gleich oder verschieden sein können und R³ eine Alkylgruppe, eine substituierte Alkylgruppe, eine Alkoxigruppe oder eine substituierte Aminogruppe.Stabilizers against thermo-oxidative degradation of POM, in particular all compounds with phenolic structure, which have at least one sterically demanding group on the phenolic ring. Preferably, for example, compounds of the formula

into consideration, in which mean:
R ¹ and R ^{2 are} an alkyl group, a substituted alkyl group or a substituted triazole group, wherein the radicals R ¹ and R ^{2 may be the} same or different and R ^{3 is} an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.

antioxidants of the type mentioned, for example, in DE-A 27 02 661 (US-A 4 360 617).

Another group of preferred sterically hindered phenols IV) is derived from substituted Ben from zolcarbonsäuren, in particular substituted benzene propionic acids.

wobei R⁴, R⁵, R⁷ und R⁸ unabhängig voneinander C₁-C₈-Alkylgruppen, die ihrerseits substituiert sein können (mindestens eine davon ist eine sterisch anspruchsvolle Gruppe) und R⁶ einen zweiwertigen aliphatischen Rest mit 1 bis 10 C-Atomen, der in der Hauptkette auch C-O-Bindungen aufweisen kann.Particularly preferred compounds of this class are compounds of the formula

where R ⁴ , R ⁵ , R ⁷ and R ⁸ independently of one another are C ₁ -C ₈ -alkyl groups which in turn may be substituted (at least one of which is a sterically demanding group) and R ^{6 is} a divalent aliphatic radical having 1 to 10 C- Atoms, which may also have CO bonds in the main chain.

im Handel erhältlich als Irganox^®245 der Firma Ciba-Geigy, und

ein Handelsprodukt Irganox^®259 der Firma Ciba-Geigy.Preferred compounds corresponding to this formula are

commercially available as Irganox ^® 245 from Ciba-Geigy, and

a commercial product Irganox ^® 259 from Ciba-Geigy.

Further examples of suitable antioxidants 11a) are:
4,4'-butylidene-bis (6-tert-butyl-3-methyl-phenol),
2,2'-methylene-bis (4-methyl-6-tert-butyl-phenol),
N, N'-hexamethylene-bis (3,5-di-tert-butyl-4-hydroxyhydrozinnamid)
1,6-hexamethylene-bis (3,5-di-tert-butyl-4-hydroxyhydrozinnamat)
N, N'-bis (3,5-di-tert-butyl-4-hydroxyhydrozinnamoyl) hydrazine,
Tetrakis methylene (3,5-di-tert-butyl-4-hydroxyhydrozinnamat) methane,
1,8- (3,6-oxa-octamethylene) -bis (3-methyl-5-tert-butyl-4-hydroxyhydrozinnamate),
1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
Pentaerythril-tetrakis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
Distiaryl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
2,6,7-trioxa-1-phosphabicyclo- [2.2.2] oct-4-yl-methyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate,
3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearyl-thiotriazylamin,
2- (2'-hydroxy-3'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole,
2,6-di-tert-butyl-4-hydroxymethylphenol,
1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene,
4,4'-methylene-bis- (2,6-di-tert-butylphenol),
3,5-di-tert-butyl-4-hydroxybenzyl-dimethylamine, and
N, N'-hexamethylene-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide).

Have proven to be particularly effective and therefore preferably be used
2,2'-methylenebis (4-methyl-6-tert-butylphenyl)
1,6-hexanediol-bis- (3,5-di-tert-butyl-4-hydroxyphenyl] propionate (Irganox ^® 259),
Pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and
the above-described Irganox ^® 245 from Ciba Geigy, which is particularly well suited.

In some cases have sterically hindered phenols with no more than one sterically hindered group ortho to the phenolic hydroxy group proved to be particularly advantageous; especially for improvement the color stability when stored in diffused light over longer Periods.

When Antioxidants 11a) are also useful sulfur compounds.

11b)

• i) Benzophenonderivate wie 2,4-Dihydroxybenzophenon, 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-alkoxybenzophenone mit n-Octyl, iso-Octyl und Dodecyl als Alkylgruppe, 2,2'-Dihydroxy-4-methoxybenzophenon, 2,2'-Dihydroxy-4,4'-dimethoxybenzophenon, 2-Hydroxy-4-methoxy-5-sulphobenzophenone und 2-Hydroxy-4-oxybenzylbenzophenon,
• ii) Benzotriazolderivate, wie sie unter der Bezeichnung Tinuvin^® von Ciba Geigy erhältlich sind, beispielsweise 2-(2'-Hydroxy-5'-methylphenyl)benzotriazol, 2-(2'-Hydroxy-5'-tert.octylphenyl)benzotriazol, 2-(2'-Hydroxy-3',5'-di-tert.-amyl-phenyl)-benzotriazol, 2-(2'-Hydroxy-3',5'-di-{2''-phenyl}iso-propyl-phenyl)benzotriazol, 2-(2'-Hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazol, 2-(2'-Hydroxy-3'-methyl-5'-tert-butyl-phenyl)-5-chlorobenzotriazol, 2-(2-Hydroxy-5-methylphenyl)-benzotriazol, 2-(2-Hydroxy-3,5di-tert-butylphenyl)-benzotriazol, 2-(3,5-Di-tert-amyl-hydroxyphenyl)-benzotriazol, 2-(2-Hydroxy-3',5'-diisoamylphenyl)-benzotriazol, 2-(2'-Hydroxy-4-octoxyphenyl)benzotriazol, 2-(2H)-Benzotriazol-2-yl)-4,6-bis-(1,1-dimethylpropyl)-phenol und 2-(2H-Benzotriazol-2-yl)-4-(1,1-dimethylpropyl)-6-(1-methylpropyl)-phenol, wobei 2-(2'Hydroxy-3'5'- bis (1,1 Dimethylbenzyl)phenyl)-benzotriazol besonders bevorzugt ist.
• iii) 2-Ethylhexyl-2-cyano-3,3'-diphenylacrylat,
• iv) Benzoate wie p-tert-Butylphenylsalicylat, p-Octylphenylsalicilat, n-Hexadecyl-3,5-di-tertiär butyl-4-hydroxybenzoat,
• v) Oxanilide wie N-(2-ethylphenyl)-N'-(2-ethoxy-5-tertiär butylphenyl)-oxalamid, oder 2-Ethyl-2'-ethoxyoxanilid,
• vi) UV-absorbierende Pigmente, vor allem Ruß, aber auch TiO₂ wirken ebenfalls gegen Lichteinwirkung stabilisierend, bei ausreichender Dosierung auch in Gegenwart von Buntpigmenten.

Stabilizers against photo-oxidative degradation of POM, which act as UV absorbers, for example

• i) Benzophenone derivatives such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-alkoxybenzophenones with n-octyl, iso-octyl and dodecyl as alkyl group, 2,2'-dihydroxy-4-methoxybenzophenone, 2 '2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulphobenzophenone and 2-hydroxy-4-oxybenzylbenzophenone,
• ii) benzotriazole derivatives, such as are available under the name Tinuvin ^® from Ciba Geigy, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3', 5'-di- {2''-phenyl} iso -propyl-phenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-methyl-5'- tert -butyl-phenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-methylphenyl) -benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -benzotriazole, 2- (3,5- Di-tert-amylhydroxyphenyl) benzotriazole, 2- (2-hydroxy-3 ', 5'-diisoamylphenyl) benzotriazole, 2- (2'-hydroxy-4-octoxyphenyl) benzotriazole, 2- (2H) -benzotriazole -2-yl) -4,6-bis (1,1-dimethylpropyl) phenol and 2- (2H-benzotriazol-2-yl) -4- (1,1-dimethylpropyl) -6- (1-methylpropyl ) -phenol, with 2- (2'-hydroxy-3'5'-bis (1,1-dimethylbenzyl) phenyl) benzotriazole being particularly preferred.
• iii) 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate,
• iv) benzoates such as p-tert-butylphenyl salicylate, p-octylphenylsalicilate, n-hexadecyl-3,5-di-tertiary-butyl-4-hydroxybenzoate,
• v) oxanilides such as N- (2-ethylphenyl) -N '- (2-ethoxy-5-tertiary butylphenyl) oxalamide, or 2-ethyl-2'-ethoxyoxanilide,
• vi) UV-absorbing pigments, especially carbon black, but also TiO _{2 also} act to stabilize the action of light, with sufficient dosage even in the presence of colored pigments.

11c)

in Betracht, wobei
R gleiche oder verschiedene Alkylreste
R' Wasserstoff oder einen Alkylrest und
A eine gegebenenfalls substituierte 2- oder 3-gliedrige Alkylenkette, bedeutet.Stabilizers against photooxidative degradation of POM, which are hindered amine light stabilizers (HALS). Suitable HALS are in particular compounds of the formula

into consideration, where
R is the same or different alkyl radicals
R 'is hydrogen or an alkyl radical and
A represents an optionally substituted 2- or 3-membered alkylene chain.

Preferred HALS are derivatives of 2,2,6,6-tetramethylpiperidine such as
4-acetoxy-2,2,6,6-tetramethylpiperidine,
4-stearoyloxy-2,2,6,6-tetramethylpiperidine,
4-aryloyloxy-2,2,6,6-tetramethylpiperidine,
4-methoxy-2,2,6,6-tetramethylpiperidine,
4-benzoyloxy-2,2,6,6-tetramethylpiperidine,
4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine,
4-phenoxy-2,2,6,6-6-tetramethylpiperidine,
4-benzoxy-2,2,6,6-tetramethylpiperidine, and
4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine.

Further suitable are:
Bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate,
Bis (2,2,6,6-tetramethyl-4-piperidyl) succinate,
Bis (2,2,6,6-tetramethyl-4-piperidyl) malonate,
Bis (2,2,6,6-tetramethyl-4-piperidyl) adipate,
Bis (1,2,2,6,6-pentamethyl-piperidyl) sebacate,
Bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate,
1,2-bis (2,2,6,6-tetramethyl-4-piperidyloxy) ethane,
Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1,6-dicarbamate,
Bis (1-methyl-2,2,6,6-tetramethyl-4-diperidyl) adipate, and
Tris (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate.

Furthermore preferred are higher molecular weight Piperidine derivatives, e.g. the polymer of dimethyl butanedioate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol or poly-6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl (2,2,6,6-tetramethyl-4-piperidinyl) imino-1, 6-hexanediyl (2,2,6,6-tetramethyl-14-piperidinyl) imino, and polycondensates of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine suitable, which such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebazate particularly are well suited.

Such compounds are available under the name Tinuvin ^® or Chimasorb® ^® by Ciba-Geigy.

As another particularly preferred HALS antioxidant 11c) Uvinul ^® was named 4049 H from BASF:

Further details and other suitable antioxidants are Gächter / Müller (ed.), Plastics Additives, 4th edition 1993, Reprint Nov. 1996, Hanser-Verlag Munich, on pages 40 to 48 and 205 to 213, as well as Bottenbruch (Ed.), Plastics Handbook, Volume 3/1 Polycarbonates Polyacetals Polyester Cellulose ester, Hanser Verlag Munich 1993, on pages 320 to 323.

method for the preparation of said antioxidants are known in the art or the compounds are commercially available, which is why more Details on this are unnecessary. One or more different antioxidants 11) can be used.

process product and use of the process in POM production

When Product of the process according to the invention for residual monomer removal (hereinafter "degassing process" for short) is a degassed, Restmonomerenarmes POM received. As a rule, the residual monomer content is POM 0.0001 to 0.02 wt .-%, in particular 0.0001 to 0.01 wt .-% and particularly preferably 0.0001 to 0.001 wt .-%.

The Degassing process according to the invention allows to degas polyoxymethylenes in a particularly gentle way and to be provided with additives. The obtained POM does not stand out only by a low residual monomer content, but also by a low intrinsic color and good mechanical properties.

Another The invention relates to the use of the above-described Degassing during or subsequent to the production of polyoxymethylene homo- or copolymers.

at The production of POM will become common first in a so-called monomer plant, suitable monomers are prepared, e.g. Trioxane from aqueous Formaldehyde solution, and / or suitable monomers stored. Thereafter, the monomers transferred from the monomer plant in a polymerization reactor and there polymerized to POM, as already described above. You get this describes a crude POM from which the unreacted residual monomers with the degassing process according to the invention be separated. Likewise, one can already during the polymerization for POM, remove residual monomers by the degassing process according to the invention, or you lead this residual monomer separation according to the invention both during as well as after the polymerization.

Another The subject of the invention is therefore also a process (hereinafter "POM process") for the production of polyoxymethylene homopolymers or copolymers, characterized that one first in a monomer plant produces or stores suitable monomers, then the monomers in a polymerization reactor to the mentioned Polymer polymerized, and while or after this polymerization, those contained in the polymers Remaining monomers removed by the above degassing. Of course you can the residual monomers also during and remove after polymerization.

The POM method according to the invention As a process step, therefore, the degassing process according to the invention is included.

It is preferred, also the residence time between the individual steps the POM procedure to minimize. For example, you can set the residence time between Polymerization rector or demolition zone and the degassing minimize, and / or the residence time between the mixing device and minimize the granulator.

As mentioned, can the remainder monomers removed by the degassing process again used in POM production as starting materials, ie in the POM process according to the invention recycled (recycled) become. In this case, one can reach the destination of this return of the production plant to adjust. For example, one can use the residual monomers directly in return the polymerization or in its feed, or return them to the monomer plant.

consequently the POM method is preferably characterized in that the removed residual monomers in the polymerization reactor or in the Monomer plant be returned. Naturally You can also combine these two variants.

Inventive subject matter are finally also the polyoxymethylene homo- or copolymers, obtainable according to the described POM method.

A Monomer mixture consisting of 95% by weight of trioxane, 3% by weight of dioxolane and 0.005 wt% of methylal was added at a flow rate of 5 kg / hr continuously metered into a polymerization reactor. The reactor was a tube reactor equipped with static mixers and became at 155 ° C and operated at 30 bar.

As an initiator, 0.1 ppmw of perchloric acid was mixed into the monomer stream, using a 0.01% by weight solution of 70% by weight aqueous perchloric acid in gamma-butyrolactone. After a polymerization time (residence time) of 2 minutes, triacetonediamine (as a 0.1% strength by weight solution in 1,3-dioxolane) was metered into the polymer melt as deactivator and mixed in so that the deactivator was present in 10-fold molar excess to the initiator , The residence time in the deactivation zone was 3 min.

The Polymer melt was withdrawn through a pipeline and over Control valve relaxed in a first degassing, the with a Exhaust pipe was provided. The temperature of the degassing pot was 190 ° C and the pressure was 3 bar.

Out the first pot, the melt was withdrawn through a pipe and over a control valve in a second Entgasungstopf relaxed with the an exhaust pipe was provided. The temperature of the degassing pot was 190 ° C and the pressure was ambient pressure. The pot had no bottom and was directly on the feed dome of a twin-screw extruder ZSK 30 from Werner & Pfleiderer mounted so that the degassed polymer from the pot directly to the Extruder screws fell.

The extruder was operated at 190 ° C and with a screw speed of 150 rpm and was provided with vent openings, which were operated at 500 mbar. He also had a feed opening for additives, through which 0.5 kg / h of the antioxidant Irganox ^® 245 (see formula under 11a) above) were metered from Messrs. Ciba. The product was discharged in a conventional manner, cooled and granulated.

Claims (13)

Process for the removal of unreacted residual monomers from polyoxymethylene homopolymers or copolymers (POM) by degassing in a degassing device and subsequent mixing in a mixing device, characterized in that the residence time of the POM between the discharge from the degassing device and the entry into the mixing device is a maximum of 60 sec is. Method according to claim 1, characterized in that that the residence time is a maximum of 30 seconds. Process according to claims 1 to 2, characterized that the degassing device is a degassing pot. Process according to claims 1 to 3, characterized that the mixing device is an extruder. Process according to claims 1 to 4, characterized that the discharge of the degassing device with the entry of the mixing device coincides. Process according to claims 1 to 5, characterized that the Entgasungstopf is arranged on the extruder and emptied directly into the extruder. Process according to claims 1 to 6, characterized that the residual monomers are selected from trioxane, formaldehyde, tetroxane, 1,3-dioxolane, 1,3-dioxepane, Ethylene oxide and oligomers of formaldehyde. Process according to claims 1 to 7, characterized that mixed in the mixing device, the POM with conventional additives becomes. Process according to claims 1 to 8, characterized in that a further degassing takes place in the mixing device. Use of the method according to claims 1 to 9 during the or following the preparation of polyoxymethylene homo- or copolymers. Process for the preparation of polyoxymethylene homo- or copolymers, characterized in that first in a monomer plant produces or stores suitable monomers, then the monomers in a Polymerisati onsreaktor to said Polymer polymerized, and while or after this polymerization, those contained in the polymers Residual monomers removed by the process according to claims 1 to 9. Method according to claim 11, characterized in that that the removed residual monomers in the polymerization reactor or returned to the monomer plant. Polyoxymethylene homo- or copolymers obtainable according to the method according to claims 11 to 12th