PL77354B1 - Thermoplastic moulding compositions based on polyoxymethylenes[gb1382472a] - Google Patents

Abstract

1382472 Polyoxymethylene compositions HOECHST AG 17 Jan 1972 [15 Jan 1971 7 Oct 1971] 2235/72 Heading C3P A moulding composition comprises 99À999- 90% of a linear polyoxymethylene and 0À001-10% by wt. of a branched or cross-linked polyoxymethylene. The components, each optionally containing a stabilizer, may be mixed in powder form then melted, homogenized, extruded and granulated. The linear polymer may be a homopolymer of formaldehyde or trioxan or a copolymer of trioxan with a monofunctional comonomer such as a cyclic ether, cyclic acetal or linear polyacetal: exemplified comonomers are ethylene oxide and 1,3- dioxolane. The branched or cross-linked polymer may be prepared (a) by copolymerizing trioxan with a polyfunctional comonomer and optionally a monofunctional comonomer: copolymers of trioxan with ethylene oxide or dioxolane and dicyclopentadiene oxide, methyl glycidyl formal, 1,4-butanediol diglycidyl ether, 1,2,6-hexanertiol formal, or oligomeric formals of 1,2,6-hexanetriol and 1,6-hexanediol or polyethylene glycol are exemplified; (b) by crosslinking a copolymer of trioxas, a polyfunctional monomer of which only one functionality is copolymerizable and optionally a monofunctional comonomer such as ethylene oxide or dioxolane by means appropriate to the residual function(s) of the polyfunctional monomer; in the examples copolymers in which the latter is p-glycidoxybenzaldehyde are cross-linked by reaction with hydrazine, adipic acid bishydrazide or ethylene diamine or by heating, a copolymer of methyl p-glycidoxycinnamate is cross-linked by U.V. irradiation, and copolymers of p-glycidoxynitrobenzene or epichlorohydrin are cross-linked by reaction with 4,41-diisocyanatodiphenylmethane after conversion of the nitro and chloro groups to amino and hydroxy respectively; (c) by polymerizing trioxan and optionally a monofunctional comonomer in the presence of a branched or cross-linked polyether, or by reacting a linear polyoxymethylene with such a polyether, in the examples trioxan and dioxolane are copolymerized in the presence of polyethers derived from tetrahydrofuran, ethylene glycol and 1,4-butanediol diglycidyl ether or 2,9-dioxa-dispiro [3.2.3.2] duodecane, and a trioxan-dioxolane copolymer is reacted with 1,4-butanediol diglycidyl ether in the presence of BF 3 .Bu 2 O. Either of the polymer components may be treated, e.g. by heating with an alcohol in the presence of an amine, to remove unstable end-groups. [GB1382472A]

Description

Patent holder: Farbwerke Hoechst Akitiengesellschaft vormals Meister Lucius u. Brilning, Frankfurt am Main, (Federal Republic of Germany) Polyoxymethylene-based thermoplastic molding compounds. The invention relates to polyoxymethylene-based thermoplastic molding compounds. It is known that polyacetals, e.g. polyoxymethylenes (POM) have a marked tendency to crystallize. Even with a slight overcooling of their alloy, a rapid growth of spherulites is observed, which are usually much larger than the length of the light waves and which make the material highly opaque. Moreover, as a consequence of the crystallization process in the interior and on the surface of the material, numerous microscopic small cracks as well as internal stresses appear. These cracks and internal stresses cause unfavorable changes in the mechanical properties of moldings, for example polyoxymethylene injection moldings. The above-mentioned disadvantages are more pronounced the larger the individual spherulites are. It is also known that by adding 0.0001-0.5% by weight of talc to the high molecular weight polyoxymethylene and uniformly distributing this inorganic additive in the organic material. the crystalline structure of the injection moldings can be made uniform and thus one can move from a coarse spherulite structure with an average spherulite diameter of 100 microns to homogeneous structures with spherulite diameters of 4 to 8 microns (cf. British Patent Specification No. 1,133,490). Since these are injection specimens, the above-mentioned sizes are for formulations which crystallize under pressure at 50 ° -100 ° C. It is further known that the size of polyoxymethylene spherulites can be reduced if the polyoxymethylenes are mixed before melting. with certain, organic nucleating agents that are either not or only slightly soluble in the polyoxymethylene melt, for example imidazole or pyrazine derivatives containing hydroxyl groups (see US Pat. No. 1,193,708). Moreover, it is known that the crystalline structure of thermoplastic crystallizable high-molecular polymers, e.g. olefinic polymers, can be modified upon cooling. melt the polymer by means of nucleating agents that are chemically stable above the melting point of the polymer crystallites (cf. US Patent No. 3,367,926). In addition to the large number of various chemical compounds, polyoxymethylene is also mentioned as a nucleating agent, but no data is available as to whether polyoxymethylenes are suitable as a nucleus nucleating agent for other polyoxymethylenes. However, if one tries to seed the known linear homo- or copolymers of formaldehyde or trioxane by adding the same or a different linear homo- or copolymer of hib trioxane formaldehyde or copolymer, no grafting effect is obtained. 773 577 354 3 The invention therefore relates to thermoplastic masses. for molding, which consist of a mixture of 99.999-90% by weight of linear polyoxymethylene and 0.001-10% by weight of branched or cross-linked polyoxymethylene. The linear polyoxymethylenes used in the molding compositions according to the invention are obtained by known methods and they are homopolymers of formaldehyde or trioxane, or copolymers of trioxane with at least one monofunctionally reacting compound that can be copolymerizable with trioxane. can be polymerized with a trioxane reactive polyfunctional compound and optionally with at least one monofunctional reactive compound that can be copolymerizable with trioxane, or by additionally carrying out linear or cross-functional chain disaggregating reactions on the linear polyoxymethylene, or or by copolymer The variation of trioxane with at least one compound that can be copolymerized with trioxane reacting monofunctionally and with a branched or cross-linked polyether, or by reacting a linear polyoxymethylene with a branched or cross-linked polyether. The polyoxymethylene content of the polyoxymethylene is non-linear by mass for the invention. , 99-95% by weight, while the branched or cross-linked polyoxymethylene content is preferably 0.01-5% by weight. Particularly good properties are shown by the molding compositions which consist of 99.9 to 98% by weight of a linear polymer and 0.1 to 2% by weight of a branched or cross-linked polymer obtained by the first and second of the mentioned processes. The inventive molding compositions of the branched or cross-linked polyoxymethylenes of the invention preferably contain 99.9 to 95% by weight of linear polyoxymethylene and 0.1 to 5% by weight of branched or cross-linked polyoxymethylene. Particularly good properties are shown by those molding compositions according to the invention with branched or cross-linked polyoxymethylenes obtained which contain 99.5 to 96% by weight of linear polyoxymethylene and 0.5 to 3% by weight of branched or cross-linked polyoxymethylene. In the case of branched or cross-linked polyoxymethylenes with a low flow index, smaller amounts are generally sufficient for satisfactory seeding with embryos than in the case of polyoxymethylenes with a higher flow index. Formaldehyde or trioxane homopolymers are understood to mean those homopolymers of formaldehyde or trioxane trioxane groups, The hydroxyls are chemically stabilized, for example by esterification or etherification, against degradation. When linear trioxane copolymers are used as trioxane comonomers, cyclic ethers with 3-5, preferably 3 ring members, are used as trioxane comonomers, and when trioxane is used, ¬ nu different cyclic acetals by 5-1 1, preferably 5-8 ring members and linear polyacetals, each in amounts of 0.1-20, preferably 0.5-10% by weight. Copolymers consisting of 99-95% by weight of trioxane and 1-5% by weight of one of the above-mentioned constituents are best suited. The compounds of formula I are used as cyclic ethers and cyclic acetals in which R1 and R2 are identical. They are either a hydrogen atom, an aliphatic alkyl residue with 1 to 6, preferably 1 to 3, carbon atoms, which may contain 1 to 3 halogen atoms, preferably chlorine atoms, or represent a phenyl residue, x is either an integer 1-3, ay is zero, or x is zero and y is an integer 1-3 and z is 2 or x is zero, y is 1 and z is an integer of 3-6, preferably 3 or 4, or w wherein R 1 is an alkoxymethyl residue with 2 to 6, preferably 2 to 4, carbon atoms or a phenoxymethyl residue, where x is equal to 1 and y equal to zero and R 2 has the above meaning. In particular, the compounds are cyclic ethers and cyclic acetals. of Formula 2 wherein R 25 is hydrogen, aliphatic res the alkyl group with 1 to 6, preferably 1 to 3, carbon atoms, which may contain 1 to 3 halogen atoms, preferably chlorine atoms, or represents a phenyl residue, x is either an integer of 1 to 3, and y is equal to zero 30 or x is zero, y is an integer of 1-3, z is 2, or x is zero, y is equal to 1, and z is an integer of 3-6, preferably 3 or 4, or where R is an alkoxymethyl residue of 2 to 6, preferably 2 to 4, carbon atoms or a phenoxymethyl residue, where x is equal to 1 and y is equal to zero. Compounds of formula III are preferably used as cyclic ethers and cyclic acetals, where x is an integer 1 - 3, and y is zero, 40 or x is zero, y is an integer 1-3, and z is 2, or where x is zero, y is 1 and z is an integer 3-6, preferably 3 or 4. Suitable cyclic ethers are, above all, those with 3-membered rings, for example ethylene oxide, styrene oxide, propylene oxide and epichlorohydrin. Dryin and phenylglycidyl ether. As cyclic acetals, the cyclic forms of aliphatic and cycloaliphatic alpha, omega-diols with 2-8, preferably 2-4 carbon atoms, the carbon chain of which can be at intervals of 2 carbon atoms, are particularly suitable interrupted with an oxygen atom, e.g. glycol formal, i.e. 1,3-dioxolane, butanediol form, i.e. 1,3-dioxepane, and diglycol formal 55 i.e. 1,3,6-trioxocane, and 4-chloromethyl -1,3-dioxolane and hexanediol formal, i.e. 1,3-dioxanane. As linear polyacetals, both homo- or copolymers of the above-defined cyclic acetals as well as linear condensates of aliphatic or cycloaliphatic alpha, omega-diols with aliphatic aldehydes or thioaldehydes, preferably with formaldehyde. In particular, homopolymers of linear alpha aliphatic formals, omega-65 diols with 2 to 8, preferably 2 to 4, carbon atoms are used, e.g. 5 pblidioxolane, poly (1,3-propanediol formal) and poly (1-butanediol formal) 4). The reduced specific viscosity values of the polyoxymethylenes used according to the invention, determined in butyrolactone containing 2% by weight of diphenylamine, at a temperature of 140 ° C at a concentration of 0.5 g / 100 ml, are 0.07-2.50 dl. . g_1, preferably 0.14-1.20 dL. g-1. The melting points of polyoxymethylene crystallites are within the range of 140 ° C to 180 ° C, and their densities, determined according to DIN 53479, are in the range of 1.38-1.45 g.ml-1. Linear, preferably two - or ternary trioxane copolymers are prepared in a known manner by polymerizing the monomers in the presence of cationic catalysts at a temperature of 0 ° -100 ° C, preferably 50 ° -90 ° C (see British Patent Specification No. 903 668). The catalysts used are Lewis acids, for example boron trifluoride and antimony pentafluoride, and complex compounds of Lewis acids, preferably with ethers, for example a complex of boron trifluoride with diethyl ether and boron trifluoride with two-tier ether. butyl. Moreover, protic acids, for example perchloric acid, and compounds of the salt type, for example triphenylmethyl hexafluorophosphate, triethyloxonium tetrafluoroborate or acetyl perchlorate, are suitable. The polymerization can be carried out in bulk, in suspension or in solution. In order to remove unstable fractions, the copolymers are preferably thermally or hydrolytically degraded partially into primary alcohol end groups (cf. British Patents Nos. 926 903, 951 272 and 986 925). The homopolymers used according to the invention are Maldehyde or trioxane are also produced in a known manner by catalysed polymerization of a monomer (cf. United States Patent No. 2,768,994 and British Patent No. 877,820). In the preparation of the branched or cross-linked polyoximeters used in the present invention, According to the first of the above-mentioned methods, polyfunctional compounds are used, in general amounts of 0.01, by copolymerization of trioxane with at least one co-polymerizable with trioxane multifunctionally reacting compound and possibly with at least one compound which reacts monofunctionally with trioxane. -5, preferably 0.05-2% by weight, a monofunctional compounds generally in amounts of 0.1-10, preferably 1-5%, by weight. As monofunctional reactants, the cyclic ethers, cyclic acetals and polyacetals already mentioned in the preparation of the linear trioxane copolymers used according to the invention are used. As polyfunctional reacting compounds, monomeric or oligomeric compounds are used which contain at least one of the above-mentioned monofunctional cyclic ether or cyclic acetal groups and no one or more linear acetal groups, the total number of the reactive groups mentioned above being cyclic ether, cyclic acetal and linear acetal are, however, CO 2 at least 2. Preferably, alkylglycidyl formalals, polyglycol-glycidyl ethers, alkanediol-diglycidyl ethers and bis (alkanetriol) -triumformals are used. The term alkylglycidylformals is understood to mean the compounds of formula IV in which R is an aliphatic residue with 1 to 10, preferably 1 to 5, carbon atoms. Alkylglycidylformals of the formula above, where R is and linear, lower aliphatic alkyl residues, for example, methylglycidylformal, ethylglycidylformal, propylglycidylformal and butylglycidylformal, are particularly well suited. As polyglycolylglycidylformals are denoted by the formula 5 total number 15 2-5. Particularly suitable are polyglycol diglycidyl ethers of the above formula in which n is 2 or 3, for example diethylene glycol dglycidyl ether and triethylene glycol diglycidyl ether. The compounds of formula 6 in which w is an integer from 2 to 6, preferably 2 to 4, are known as alkane di glycidyl ethers. Butanediol diglycidyl ether is especially suitable. Bis (alkanotriol) -triformal is understood to mean 25 compounds with one linear and two cyclic formal groups, in particular compounds of formula 7, where pi and q are in each case an integer of 3 to 9, preferably 3. or 4. Above all, bis (alkanetriol) -triformals of the above formula are suitable, wherein p and q are the same numbers, for example bis (pentanetriol-1,2,5) -triformal, preferably bis- (hexanetriol-1,2,6) -triformal. As multifunctional reacting compounds in the preparation of the branches used according to the invention. of cross-linked or cross-linked polyoxymethylenes, it is also possible to use oligomeric forms, which are obtained by reacting 1 mole of 1,2- (5-11) triol with 0-1 mole of alpha, omega-diol in the molecular weight of 62-1000.0 —1 mole of monovalent alcohol with 1-11 carbon atoms and 1 mole of formaldehyde for every 2 moles of OH groups of the reaction mixture (cf. British Patent Specification No. 1,171,107). Copolymerizations of trioxane with the mentioned 45 multifunctional and monofunctional compounds are carried out in a method already known for the preparation of linear trioxane copolymers. The degradation of the unstable end segments of the chain can in principle take place according to methods known for stabilizing the end groups of trioxane copolymers. However, it is also possible to use branched or cross-linked polyoxymethylenes without further treatment in finely ground form directly as nucleating agents. ; A further possibility for the preparation of these branched or cross-linked polyoxymethylenes consists in reacting linear polyoxymethylenes with the above-mentioned multifunctional compounds with cationic catalysts and preferably with inert diluting agents, e.g. cyclohexane, n-hexane or methylene chloride oxymethylene. branched or cross-linked according to the second of the above-mentioned methods, they are obtained by copper-molecular reaction of linear polyoxyme-77354 * tylenes with side or chain functional groups, optionally after chemical conversion of these groups into other functional groups and optionally in the presence of difunctional crosslinkers. The above-mentioned polyoxymethylenes with side or chain functional groups are prepared by polymerization of mixtures of 99.9-60, preferably 99.7-80% by weight of trioxane, 0- 20, preferably 0.1-10% by weight of cyclic with an ether of 3-5 ring members or a cyclic acetal different from trioxane with 5-11 ring members or a linear polyacetal and 0.1-20, preferably 0.2-10% by weight of at least one copolymerizable with multifunctional trioxane. Particularly good results are obtained when 1 to 5% by weight of mono-functional compounds and 1 to 5% by weight of polyfunctional compounds are used. For the preparation of linear functional polyoxymethylenes, polyfunctional monomer compounds are used as polyfunctional compounds which are on the one hand they have a functional group which is reactive under the polymerization conditions, and on the other hand they have at least one functional group which does not react under the polymerization conditions. In particular, saturated cyclic ethers or acetals with aromatic or aliphatic substituents which for their part contain at least one such non-reacting functional group or at least once unsaturated cyclic ethers or acetals are suitable. epoxy compounds containing aldehyde, hydroxyl, nitro or ester groups or halogen atoms, e.g., o-, m- and p-glycidoxybenzaldehyde, 3-methyl-4-glycidoxybenzaldehyde, 3-methoxy-4-glycidoxybenzaldehyde, p- glycidoxynitrobenzene, 2,4-dinitro-1-glycidoxyCenen, 1,6-dihitro-2-glycidoxy-naphthalene, p-glycidoxybenzoic acid methyl ester, epoxy-methacrylic acid methyl ester, methyl ester β-glycidoxy-cinnamic acid and epichlorohydrin The unsaturated cyclic acetals are, in particular, monounsaturated cyclic formals with more than 6, preferably 7 to 8 ring members, such as, for example, 1,3-dioxacyclohepten-5 or cyclical fo Rmals with non-ring double bonds and 5-11, preferably 5-8 ring members, such as, for example, 4-vinyl-1,3-dioxolane and 5-vinyl-1,3-dioxacyclohexane. Unsaturated cyclic ethers are in particular cyclic ethers with 3-5 ring members with a non-standing double bond in the ring, for example butadiene oxide, dicyclopentadiene oxide and vinylcyclohexene oxide, i.e. 1-vinyl-3,4-epoxy cyclohexane. Polymerizations are carried out in a known manner by polymerizing the monomers in the presence of cationic catalysts at a temperature of 0 ° -100 ° C, preferably 50 ° -90 ° C (see British Patents No. No. 1146 649, 1 179 260, 1179 576, 1 031 705 and 1 039 936). The degradation of the unstable end segments of the chain can in principle be carried out by methods known for the stabilization of the end groups of trioxane copolymers. The conversion of linear polyoxymethylenes with side or chain functional groups into branched or cross-linked polyoxymethylenes is optionally converted into change of functional groups, either by direct reactions of the functional groups between themselves or by reactions with bifunctional crosslinking agents. The conversion is carried out in solution, in suspension or preferably in the melt. Solvents used are inert polar solvents, for example benzyl alcohol, chlorobenzene, dimethylformamide and gamma-butyrolactone. Suitable suspending agents are inert, aliphatic, cycloaliphatic or aromatic hydrocarbons having 6-8 to 18 carbon atoms, for example hexane, cyclohexane and toluene. Crosslinking is initiated at 0-230 ° C. Preferably, the temperature is in the solution: 110-170 ° C, in suspension 50-170 ° C and in the melt 150-0-230 ° C. Chemically induced reactions by radiation can also be used (see British Patents 863 176 and 1155 863). Polyoxymethylenes containing aldehyde groups are preferably combined by condensation with difunctional crosslinking agents, in particular with hydrazine, terephthalic acid. , semicarbazide, dicyanediamide, urea, thiourea, thioacetamide, ammonia, acetone, aliphatic and aromatic diamines, e.g. hexamethylenediamine and phenylenediamine, and diisocyanates, e.g. 4,4'-diisocyanate! e.g. British Patent 1,156,045). The presence of basic catalysts, for example piperidine, is optionally advantageous. The pendant nitro polyoxymethylenes are then converted in a known manner into rolling amino polyoxymethylenes. By combining these amino groups with suitable difunctional reagents, such as bicaldehyde - hybrids (e.g. terephthalic dialdehyde, glyoxal-, glutaraldehyde), diisocyanates (e.g. 1,6-diisocyanato-hexane, toluene diisocyanate, 1,5-naphthalene diisocyanate and 4,4'-diisocyanato-diisocyanate) <5 diphenylmethane) or dicarboxylic acid anhydrides (eg, maleic acid anhydride, succinic acid anhydride, phthalic acid anhydride) give branched or cross-linked polyoxymethylenes. 50 Polyoxymethylenes with pendant ester groups, after conversion of the ester groups to free carboxyl groups (see British Patent No. 1 191 505), are bound together by bifunctional crosslinkers, 55 in particular they are reacted with diisocyanates, diamines, eg, phenylenediamine, hexomethylenediamine, diols, eg, 1,4-butanediol, hydrazine or with dihydrazides; It is also possible to react directly unsaponified ester groups with diols, for example with 1,4-butanediol, preferably in the presence of basic transesterification catalysts, for example sodium hydroxide, as well as polyoxymethylenes with pendant hydroxyl groups obtained for example, by copolymerization of 77,354 l of trioxane with epichlorohydrin and the exchange of chlorine atoms into hydroxyl groups by reaction of polymers with alkali metal hydroxide solutions at elevated temperatures, they are bonded with each other by bifunctional crosslinking agents, e.g. polyoxymethylenes with side halogen atoms, preferably chlorine atoms, are converted into branched or cross-linked polyoxymethylenes by direct reaction of the side halogen atoms with salts of alkali metals and organic compounds with at least two weakly reacting group per molecule, preferably with bis-phenols, such as, for example, 4,4'-dihydroxy-diphenyl-dimethyl-methane or 4,4'-dihydroxy-diphenylmethane. Linear polyoxymethylenes in the lancet or The side double bonds are converted into branched or cross-linked polyoxymethylenes, e.g. by reaction with sulfur and 2-mercaptobenzothiazole, preferably in the molten state. Subsequently, polyoxymethylenes with different reactive groups can be obtained to obtain cross-linked products react with each other, for example those containing aldehyde groups with amino groups. The production of the branched or cross-linked polyoxymethylenes used in the invention consists in the polymerization of trioxane with branched or cross-linked polyethers, optionally in the presence of at least one compound known to copolymerization with trioxane. Mixtures of 99.99-50, preferably 99.8-70% by weight of trioxane and 0-20, preferably 0.1-10% by weight of at least one known compound are used for the polymerization. for copolymerization with trioxane and from 0.01 to 30, preferably 0.1 to 20% by weight of branched or cross-linked polyether. The best results are obtained with 98.5-85% by weight of trioxane, 1-5% by weight of at least one compound known to be copolymerized with trioxane and 0.5-10% by weight of branched or cross-linked polyether. branched or cross-linked polyethers, copolymers of at least one, preferably 2, monofunctionally reacting cyclic ethers with 3-5 ring members with a bifunctionally reacting cyclic ether, i.e. an aliphatic or cycloaliphatic compound, which contain two ring-ether groups, are used. and has 3 to 5, preferably 3 or 4 ring members. For this, the compounds of formula VIII are preferably used as monofunctional cyclic ethers in which R and R 'are the same or different and each represent a hydrogen atom, an aliphatic alkyl residue with 1 to 6, preferably 1 to 3 carbon atoms, which may contain 1 to 4 halogen atoms, preferably chlorine atoms, or represent a fcyl residue, x = 0 or 1 or 2. Oxygen should be mentioned as an example k ethylene, propylene oxide, isobutylene oxide, epichlorohydrin, oxacyclobutane, 3,3-bis (chloromethyl) oxacyclobutane and tetrahydrofuran. As bifunctional cyclic ethers, in particular dicycidyl ethers alpha, omega-diols, preferably with 2 to 8 2-4 carbon atoms, the carbon chain of which can be separated in increments of 2 carbon atoms with an oxygen atom, or bisphenol diglycidyl ethers, or doubly substituted oxacyclobutyl residue, aliphatic or cycloaliphatic hydrocarbons with 1-6 carbon atoms. 1,3-propanediol diglycidyl ether, 1,4-butanediol-1,4-diglycidyl ether, glycol-diglycidyl ether, diglycol diglycidyl ether, triglycol diglycidyl ether, 4,4 (-double- (glycydoxyphenyl) -dimethyl, l-dimethyl) 2-di (3-oxacyclobutyl) -ethane, 1,4-di- (3-oxacyclobutyl) -butane and 2,9-dioxa-dispiro- - [3,2,3,2] -dodecane. The cyclic ethers are generally 99.99-98, preferably. 99.95-99% by weight, while the proportion of bifunctional cyclic ethers is 0.01-2, preferably 0.05-1% by weight. The production of branched or cross-linked polyethers is generally carried out in a known manner by copolymerization of monomers with cationic or anionic initiators. However, polyethers can also be obtained by subsequent grafting or condensation of linear polyethers. Copolymerization of trioxane with the described branched or cross-linked polyethers and possibly with at least one compound known for copolymerization with trioxane takes place in the manner already stated in the preparation of linear trioxane copolymers. It is also possible to achieve incorporation of branched or cross-linked polyethers into linear polyoxymethylenes by mixing the polyethers and polyoxymethylenes with one another, preferably in the presence of a solvent for the polyether, e.g. cyclohexane or methylene chloride, and using cationic active substances. The catalysts are reacted at a temperature of 0-100 ° C, preferably 50-90 ° C. The removal of unstable fractions or the chemical stabilization of the hydroxyl end groups is expediently carried out in the manner described above. The branched or cross-linked polyoxymethylenes used according to the invention have a flow index of 0 to 50 g / 10 minutes, preferably 0 to 10 g. 10 minutes, determined according to DIN 53 735 at a temperature of 190 ° C and a load of 2.16 kg. Giving the lower limit i2 equal to zero means that above a certain degree of cross-linking, the polyoxymethylenes used according to the invention are no longer either meltable or soluble, so that it is not possible to characterize them by flow indicators or by the value of the reduced intrinsic viscosity. Branched or cross-linked polyoxymethylenes with a flow index of 0.1-5 g / 10 minutes are quite particularly suitable. According to the invention, the molding compounds can be stabilized against vein, high temperature, oxygen and light changes. ¬ assess with stabilizers and then homogenize in the molten state. Polyamides, polycarboxylic acid amides, amidines, hydrazines, ureas and polyH-N-vinyl lactames, for example, are suitable as hydrophilic stabilizers. Phenols, in particular bis-phenols and aromatic amirias, are used as anti-oxidation stabilizers, and alpha-hydroxybenzophenone and benzotriazole derivatives as light stabilizers, these stabilizers being used in total amounts of 0.1-10, preferably 0.5 - 5% by weight, based on the total amount of the mixture. In order to prepare the molding compositions according to the invention, the components are mixed together in the form of powder or granules, and then homogenized in the melt. Branched or cross-linked polyoxymethylenes with flow index values below 0.1 g / 10 minutes are preferably used with a grain size of less than 1 micron. The mixing and homogenization of the molding compounds according to the invention takes place on any , heated mixing devices, for example, "rolling mills, calenders, crushers and extruders. The mixing temperatures are preferably above the crystallite melting point of the components and are 150-250 ° C, preferably 170-200 ° C. Probably due to the presence of branched or cross-linked polyoxymethylenes in the molding masses according to the invention, in the preparation of the molds of them, grafting with germs occurs, which is evidenced by a reduction in the size of the spherulites and an improvement in the mechanical properties of the molds. elongation stress, tear strength and torsional stiffness (at twisting) compared to unmodified linear polyoxymethylenes. A further consequence of seeding with embryos is an increase in the rate of crystallization, which enables an increase in the processing speed. This faster processability is particularly evident in the shorter operating cycles of injection molding and the tighter tolerances of the injection moldings. The use of branched or cross-linked polyxymethylenes as nucleating agents for linear polyoxymethylenes according to the invention is particularly advantageous because of the same quality, without the need for special purification of the product, which is, for example, necessary for naturally occurring materials which are suitable as an excipient. Alkali generally seeding with linear polyoxymethylenes is possible by adding small amounts of polyoxymethylenes branched or cross-linked. The molding compositions according to the invention can be reduced mechanically, e.g. by cutting or milling, into granules, walls, flakes or powders. They can be thermoplastic processed e.g. by injection or extrusion. They are suitable for the production of shapes which are used as blanks or finished parts, e.g. blocks, bars, plates, sheets, tapes, dishes and pipes. They are particularly suited to the manufacture of precision machine parts, such as gear wheels, bearing parts and controls. 10 15 20 25 30 35 40 45 50 55 65 12 Examples I-VI. Linear copolymer consisting of 98% by weight of trioxane and 2% by weight of ethylene oxide with a density of 1.41 g.ml-1, a reduced specific viscosity of 0.75 dl.g_1 and a crystallite melting point of 166 °. C is mixed in powdered form with 0.5% by weight of di- "(2-hydroxy-3-III-thirin-bu (tyla-5-methyl-phenya) -methane) and 0.1% by weight of di-cyanediamide, with respect to the amount of linear polyoxymethylene, and with different amounts, in each case in relation to the amount of the mixture, previously stabilized in the same way, cross-linked terpolymer in the form of granules, consisting of 98% by weight of trioxane, 1.8% by weight % by weight of ethylene oxide and 0.2% by weight of 1,4-butanediol diglycidyl ether with a flow index of i2 = 0.2 g / 10 minutes and homogenized on a single-screw extruder at a temperature of 200 ° C. the cylinder of the extruder is about 4 minutes. The mixture of polyoxymethylenes obtained in each case is subjected to granules after leaving the extruder. In the obtained products, the size of spherulites is measured, producing 10 microns thick pellets or pellets by melting between two glass plates at 180 ° C and subsequent crystallization at 150 ° C under atmospheric pressure, then The slabs are examined under a microscope. In addition, 60 x 60 x 2 mm plates are injection molded from the obtained molding compounds at a mass temperature of 200 ° C and a mold temperature of 80 ° C, which is used to determine the hardness by the pressing method. balls according to VDE 0302 (loading time 10 seconds). Elongation stress and tensile strength are each determined on injection tensile rods 1 mm thick (1/4 proportional rod) according to DIN 53 455. The torsional stiffness is measured on test rods made of pressed boards, 2 mm thick according to DIN 53477 at a temperature of 20 ° C and a load time of 60 seconds. Size of spherulites and mechanical properties of the The molding compositions according to the invention are given in Table 1. For comparison, the respective sizes are given for non-seeded linear polyoxymethylenes. Examples VII-XI. Linear copolymer consisting of 97% by weight of trioxane and 3% by weight of dioxolane. having a density of 1.41 g-ml-1, a reduced specific viscosity of 0.72 dl g-1 and a crystallite melting point of 166 ° C, is mixed in powdered form with the stabilizers mentioned in Examples 1-6 in similar amounts , and each 0.5% by weight of the powdered terpolymers listed in Table 2 consisting of trioxane, 2% by weight of ethylene oxide and varying amounts of 1,4-butanediol diglycidyl ether, and then homogenized. Table 2 shows the flow rates of the 12 used terpolymers and the size of spherulites in the shapes obtained from mixtures of linear and cross-linked polyoxymethylene. 13 ms4 Table 1 14 Example I II III IV V VI Amount of terpolymer% by weight - 0.08 0.06 0, 04 0.02 0.01 0.005 Size of spherulites in microns 350 32 38 40 45 55 65 Ball pressure hardness kg / cm2 1560 1600 1590 1590 1580 1580 1575 Elongation stress kg / cm2 650 690 685 680 680 670 670 Tear strength kg / cm2 506 560 560 550 545 540 530 Torsional stiffness kg / cm2 7600 8180 8160 8000 8030 7950 7950 Example b VII VIII IX X XI Table 2 Terpolymer composed of Trioxane ° / weight 97.8 97.4 97.0 96.0 95.0 Ethylene oxide% by weight - 2 2 2 2 2 Butanediol diglycidyl ether% by weight 0.2 0.6 1.0 2.0 3.0 Flow rate g / 10 minutes - 0.06 0.01 0 0 0 spherulites microns 530 17 13 15 11 9 Examples XII-XVIII. Linear copolymer consisting of 98% by weight of trioxane and 2% by weight of ethylene oxide with a density of 1.41 g.ml-1, a reduced specific viscosity of 0.73 dl g-1 and a crystallite melting point 166 ° C is mixed in powdered form with 0.5% by weight of di (2-hydroxy-3-tertiary-butyl-5-methyl-phenyl) -methane and 0.1% by weight of di-cyanediamide in a hundred relative to the amount of linear polyoxymethylene, and with different amounts of a previously stabilized cross-linked terpolymer in the form of granules consisting of 98% by weight of trioxane, 1.95% by weight of ethylene oxide and 0.05% by weight of ether. 1,4-butanediol diglycidyl with a flow index of i2 = 1.0 g / 10 minutes and homogenized on a single screw extruder at a temperature of 200 ° C. The residence time of the mass in the barrel of the extruder is about 4 minutes. The size of the spherulites and the mechanical properties of the piston shapes according to the invention are given in Table 3. For comparison, the corresponding data for uninoculated linear polyoxymethylene are given. Table 3 Example c. XII XIII. XIV XV XVI XVII xviii Amount of terpolymer% - 0.5 1.0 2.0 3.0 4.0 5.0 8.0 Size of spherulites in microns 230 16 14 13 12 11 9 9 Ball indentation hardness kg / cm2 1570 1585 1590 1600 1610 1625 1615 1610 Elongation stress kg / cm2 652 706 716 720 726 726 729 728 Tear strength kg / cm2 516 564 562 566 567 552 575 560 Torsion stiffness kg / cm2 7600 8180 8160 8140 8260 8300 8430 845015 ?? 354 Examples XIX to XXIII. Linear copolymer consisting of 96% by weight of trioxane and 4% by weight of dioxolane with a density of 1.40 g.ml-1, a reduced specific viscosity of 0.68 dl g-1 and a crystallite melting point of 164 ° C is mixed in powder form with the stabilizers mentioned in Examples XII-XVIII, and 16 in each case with 1% by weight of the powdered terpolymers mentioned in Table 4 and homogenized as in Examples XII-XVIII. The terpolymers used are those consisting of trioxane, 2% by weight of ethylene oxide and variable amounts of 1,4-butanediol diglycidyl ether. The size of the spherulites is measured in the products obtained. Table 4 Example d XIX XX XXI XXII XXIII Terpolymer with the composition Trioxane% by weight 97.9 97.5 97.0 96.0 93.0 Ethylene oxide% by weight - 2 2 2 2 2 Butanediol diglycidyl ether wt.% 0.1 0.5 1.0 2.0 5.0 Spherulite size microns 592 8 14 15 21 17 Examples XXIV-XXVIII. Linear copolymer consisting of 98% by weight of trioxane and 2% by weight of ethylene oxide with a density of 1.41 g.ml-1, a reduced specific viscosity of 0.71 dl g-1 and a crystallite melting point of 166 ° C in powder form with the amounts of the stabilizers mentioned in Examples 1-6, and in each case 1% by weight of the terpolymers listed in Table 5, consisting of trioxane, ethylene oxide (AO) or dioxolane (DO) and multifunctional compound are mixed and homogenized according to Examples 40 I to VI. The multifunctionally reacting compounds are dicyclopentadiene dioxide (I), methylglycidylformal (II), hexanetriol-1,2,6 formal and polyglycol with a molecular weight of 1000 (III), hexanetriol-1,2,6 (IV) formal and formal from hexane-triol-1,2,6 and hexanediol-1,6 (V). Table 5 gives the flow rates and 2 terpolymers of cross-linked polymers and the size of spherulites in the shapes obtained from the molding compounds according to the invention, and: hardness method of ball indentation and elongation stress Table 5 Example XXIV xxv XXVI XXVII XXVIII Terpolymer composed of Trioxan ° / o by weight and 97.9 97.9 95.0 97.9 97.0 AO or DÓ% by weight - 2 AO 2 AO 2 DO 2 DO 2 DO Multifunctional compound% by weight 0.1 I 0.1 II 3.0 III 0.1 IV 1.0 V Flow index - 0 0.08 0.05 0 0 Size of spherulites microns 387 9 21 19 16 8 Ball pressure hardness (strain relief) kg / cm2 1545/620 1675/660 1585/640 1615/645 1615/645 1660/660 Examples XXIX — XXXVIII. A linear copolymer consisting of 98% by weight of trioxane and 2% by weight of ethylene oxide with a density of 1.41 g.ml-1, a crystallite melting point of 166 ° C and a reduced specific viscosity of 0.73l g-1 is mixed with the stabilizers given in Examples 1-6 in the amounts indicated therein, as well as with varying amounts of the following, finely ground, cross-linked polyoxymethylenes (POM i-VIII) and extruded on a single-screw extruder at a cylinder temperature of 190 ° C and a head temperature of 180 ° C and at a screw speed of 60 revolutions / minute, and then granulated. The residence time of the mass in the extruder barrel is 4 minutes. Table 6 shows the mixing ratio of linear and cross-linked polyoxymethylenes, as well as 17 773 * 4 18 size of spherulites and the hardness of the ball interference method of the shapes obtained from the molding compounds according to the invention. POM polyoxymethylene I. A mixture of 1000 g of trioxane, 20 g of ethylene oxide and 30 g of p-glycidoxy-cinnamic acid methyl ester is mixed with 35 ml of a catalyst solution consisting of 1 part by volume of a BFj complex with dibutyl ether in 40 parts by volume of cyclohexane. is polymerized in a closed vessel in a 0.8 cm thick layer on a thermostated bath at 70 ° C. The polymerization time is 30 minutes. The resulting polymer block is ground and treated to remove unstable semi-acetal end groups and residual monomers with benzyl alcohol containing 1 part by weight of triethanolamine for 30 minutes at 150 ° C. After cooling, the polymer is filtered off, boiled several times with methanol and dried under reduced pressure at a temperature of 50-70 ° C. The yield of the polymer is 670 g, the reduced specific viscosity of the polymer is 0.78 dl g_1, and the flow index i2 1.27 g / 10 minutes. Then the obtained product is ground and exposed to a 10-hour xenon lamp. After this, the reduced specific viscosity can no longer be measured, because too little polymer dissolves in butyrolactone. The flow index 12 is 0.77 g / 10 minutes. Polyoxymethylene POM II. A mixture of 85 g of trioxane, 5 g of dioxolane and 10 g of p-glycidoxybenzaldehyde is mixed with 1.5 ml of a catalyst solution consisting of 1 part by volume of a BF3 complex with dibutyl ether in 10 parts by volume of cyclohexane. The mixture is polymerized in a closed vessel in a thermostatic bath at 70 ° C. The polymer block obtained is kept for a further 60 minutes at 70 ° C. and then worked up in benzyl alcohol as described in the preparation of POM I, washed and dried. 79 g of a white powder are obtained, having a reduced specific viscosity of 0.34 dl. G-1. The polymer is kneaded in 10 minutes with 0.5% by weight of two (2-hydroxy-3-III) of rt-butyl-5-methyl-phenyl) -methane and 0.1% by weight of the dicyandiamide in a Brabender plastograph at 195 ° C. under nitrogen. The obtained product no longer dissolves in butyrolactone and its flow index i2 is 0.15 g / 10 minutes. Polyoxymethylene POM III. 10 g of a copolymer consisting of 1000 g of trioxane, 20 g of ethylene oxide and 50 g of p-glycidoxybenzaclehydrate are treated in 350 ml of benzyl alcohol for 30 minutes at 120 ° C 0.3 ml of an 80% water solution. - hydrazine knitting. The flow rate of the polymer thus changes from i * = 156 g / 10 minutes to ij = 1.0 g / 10 minutes. Polyoxymethylene POM IV. 5 g of a copolymer consisting of 1000 g of trioxane, 20 g of ethylene oxide and 50 g of p-glycidobenzaldehyde are mixed with 40 mg of adipic acid dihydrazide and additionally stabilized with 35 mg of bis (2-hydroxy-3-tertiary). butyl-5-methyl-phenyl) -metahu. After a melting period of 40 minutes at 190 ° C, the flow index i * is immeasurably low compared to 156 g / 10 minutes before the reaction. Polyoxymethylene POM V. A mixture of 95 g of trioxane and 5 g of p-glycidaxynitrobenzene is added to 0.7 ml a catalyst solution consisting of 1 part by volume of a BF * complex with dibutyl ether in 40 parts by volume of cyclohexane as a catalyst and, as described in the preparation of POM I, is polymerized and processed, with the difference, however, that the polymerization time is 60 minutes The washed and dried polymer powder is dissolved at 120 ° -130 ° C in 2 X 1 benzyl alcohol, to which 50 ml of 80% by weight aqueous hydrazine hydrate solution has been added, and after dissolving it is given a trace amount of Ranney's nickel . The reaction mixture is kept at 120 ° -130 ° C for 30 minutes. After cooling, the polymer is filtered off, boiled with methanol and dried in vacuo at 50 ° -70 ° C. The yield of the amine-containing polymer is 77 g, its flow rate is 15.7 g / 10 minutes. 25 g of this polymer is melted, as described in the preparation of POM II, with 200 mg of 1,4-dibasic [2,2,2] octane at 190 ° C. 300 mg of diphenylmethane 4,4'-diisocyanate are added in small portions within 3 minutes. The melt viscosity increases very strongly. After a further 3 minutes the reaction is complete. Measurement of the reduced intrinsic viscosity is no longer possible due to the high degree of cross-linking. The i * flow rate is 0.5 g / 10 minutes. Polyoxymethylene POM II. A mixture of 9 parts by weight of trioxane and 1 part by weight of epichlorohydrin is polymerized as described in the preparation of POM I with 0.05 parts by weight of a mixture of 20 parts by volume of cyclohexane and 1 part by weight of a BFj complex with cfc-n-butyl ether. . The resulting block of polymer is ground and the powder is boiled in methanol for 30 minutes. After filtration and drying at 50 ° C. under nitrogen, a polymer powder is obtained with a reduced specific viscosity of 0.64 dLg-1 and a chlorine content of 4.1% by weight. 1 part by weight of this polymer is mixed with 1 part by weight of potassium hydroxide, 17 parts by weight of water and 33 parts by weight of methanol in an autoclave under nitrogen for 2 hours at 155 ° C. The mass remaining after cooling down is ground and boiled several times in methanol. After drying at 50 ° C., 0.6 parts by weight of a faint yellowish powder remain in a nitrogen stream, the infrared spectrum of which shows clearly bands corresponding to the hydroxyl groups. 25 g of this hydroxyl-containing polymer is melted together with 125 mg of di (2-hydroxy-3-tertiary-butyl-5-methyl-phenyl) -methane and 25 mg of di-cyanediamide at 190 ° C under nitrogen. in Brabender's plastograph. After the addition of 200 mg of 1,4-dibasicyclo [2,2,2] octane, a total of 500 mg of 4,4'-diisocyanate diphenylmethane was metered in small portions. The viscosity of the molten mass increases at this strongly at the same time. - After a further 5 minutes, the mass cools down. The value of the flow index i is 0.1 g / 10 minutes, the measurement of the viscosity is not possible due to the polymer insolubility in butyrolactone. POM VII polyoxymethylene. 25 g of polymer obtained according to the preparation of POM II from 88 parts by weight of trioxane, 2 parts by weight of ethylene oxide and 10 parts by weight of p-glycidoxybenzaldehyde are melted with 125 mg of bis (2-hydroxy-3-tertiary butyl). 5-methyl-phenyl) -methane at 190 ° C under nitrogen in a Brabender plastograph. A total of 370 mg of ethylene diamine is added in small portions within 15 minutes. After this time, the alloy has largely solidified. Measurement of the -I2-value is not. more possible.Polyoxymethylene POM VIII. 10 g of a powdered copolymer consisting of 98% by weight of trioxane and 2% by weight of dioxolane with a flow index of i. 9.0 g / 10 minutes are dispersed in 100 ml of dried over lithium aluminum hydride and distilled cyclohexane and mixed with 1.0 ml of 1,4-butanediol glycidyl ether and 0.15 g of BF3 complex with di-n-butyl ether. The mixture is kept under nitrogen for 40 minutes at 45.degree. C. and treated with benzyl alcohol as described in the preparation of POM I, washed and dried. The value of the polymer flow index is not measurable. Example f XXIX xxx XXXI XXXII XXXIII * XXXIV xxxv XXXVI XXXVII XXXVIII POM linear ° / weight 100 99 99 97 99 99 99 99 99.95 99 97 Table 6 / POM branched or cross-linked • / weight • 1 POM I 1 POM II 3 POM II 1 POM III 1 POM IV 1 POM V 1 POM VI 0.05 POM VII 1 POM VII 3 POM VIII Size of spherulites microns 550 15 7 6 10 12 25 10 30 25 16 Hardness ball pressure method kg / cm2 1545 1635 1615 1645 1610 1615 1600 1615 1600 1605 1610 Example XXXIX. Linear formaldehyde homopolymer with acetate end groups, density 1.43 g.ml-1, reduced specific viscosity 0.70 dl g-1 and crystalline melting point 174 ° C, is mixed with those mentioned in Examples I - VI stabilizers in the amounts indicated therein and 2% by weight of POM IV used in example XXXIII and, as indicated in Examples XXIX-XXXVIII, homogenize and granulate. Table 7 shows the size of spherulites and hardness method of ball insertion of the shapes obtained from the molding compounds according to the invention compared to the unmodified homopolymer Table 7 Example g XXXIX POM linear% by weight 100 MU-FOM branched or cross-linked% by weight - 2 POM IV Spherulites size microns 482 27 Hardness ball pressure method kg / cm2 1740 1790 Examples XL — XLI. Linear copolymer consisting of 98% by weight of yttrioxane and 2% by weight of ethylene oxide with a density of 1.41 g.ml-1, a crystallite melting point of 166 ° C. and a reduced specific viscosity of 0.73 dl .g-1 is mixed with the stabilizers given in Examples 1-6 in the amounts indicated therein, and in each case of 100% by weight of POM IX and POM X described below, and homogenized and granulated as indicated in Examples XXIX-XXXVIII. Table 8 shows the size of the spherolites of the shapes obtained from the molding compositions according to the invention. POM IX polyoxymethylene. 100 g of a mixture consisting of 96.75 parts by weight of trioxane, 2 parts by weight of dioxolane and 1.25 parts by weight of a polyether consisting of tetrahydrofuran, ethylene oxide and 2.9-dioxa-dioxane [3, 2,3,2] -dodecane in a weight ratio of 50: 50 = 0.05, 0.3 ml of a catalyst solution consisting of 1 part by volume of BF3 complex with dibutyl ether in 20 parts by volume of cyclohexane is added and polymerized at 70 ° C. for 30 minutes. The said polyether is prepared by polymerization of 100 g of monomer mixture each time with 150 mg of triphenylmethyl hexafluorophosphate as a catalyst in aluminum tubes at 20 ° C. The polymerization time is 24 hours, the work-up is carried out by steam distillation. The resulting polyoxymethylene is cooled to 0 ° C and immediately ground to a fine powder. The powder in a concentration of 50 g of polymer / 1000 ml of a solution methanol: water: triethylamine in a ratio of 66: 34: 0.1 (parts by volume) is subjected to a degradation treatment under nitrogen at 150 ° C. for 30 minutes. It is then washed thoroughly with acetone and dried at 70 ° C. in a nitrogen stream. The obtained product has a flow index of i2 = 2.8 g / 10 minutes. Polyoxymethylene POM I. The production is carried out as in the case of POM IX, but the polyester is a terpolymer of tetrahydrofuran, ethylene oxide and 1,4-butanediol diglycidyl ether in the ratio by weight 50: 50: 0.5. The obtained block polymer has a flow index of i2 - 4.1 g / 10 minutes. Table 8 Example h XL XLI POM linear • w / w 100 99 99 POM branched or cross-linked by weight ”- 1 POM IX 1 POM X Size , micron spherulites 493 20 25 PL PL

Claims (5)

1. Claims 1. Polyoxymethylene-based thermoplastic molding compositions, characterized in that they consist of a mixture of 99.9-90% by weight of linear polyoxymethylene and 0.1-10% by weight of branched polyoxymethylene or cross-linked. 2. Polyoxymethylene-based thermoplastic molding compositions, characterized in that they consist of a mixture of 99.999-90% by weight of linear polyoxymethylene and 0.001-10% by weight of branched or cross-linked polyoxymethylene. 3. Thermoplastic molding compositions according to claim 1, A process as claimed in claim 1, characterized in that as branched or cross-linked polyoxymethylenes they comprise copolymers of trioxane with a multifunctionally reactive compound that can be copolymerized with a trioxane and, optionally, copolymerized with a monofunctional reactive compound with trioxane. 4. Thermoplastic molding compositions according to claim 1 2. The method of claim 2, wherein the branched or cross-linked polyoxymethylenes contain additionally branched or cross-linked linear polyoxymethylenes with 6 side or chain functional groups. 5. Thermoplastic molding compositions according to claim 1 The process of claim 2, wherein as branched or cross-linked polyoxymethylenes they comprise copolymers of trioxane with a trioxane copolymerizable compound that reacts monofunctionally and with a branched or cross-linked polyether. 39b *, 37/02 77354 MKP C08g 37/02 CH2- [CRtH] x- [0- (CR2 ^] y — O Formula I ch2- [crh] - [o- (ch2) z] —o Formula 2 CH2 - [cH2] - [0— (CH2)] - 0 Formula 3 R- O-CH - O— CH — CH — CK, C 2 v / Z \ / O Formula 4 CH, - CH- CHrO- (CHr CHrO ) ,, -CHr CH-CM O ° Formula 5 CH2-CH- CH, -O-fCHj-O-CH, - CH -CH ^ YO Formula 6 CH2-CH- (CH2L- O-CH2-0- (CH2 ) q-CH-CH2 II II 0 0 0 0 \ / X / CH2 OHe Pattern 7 CH ^ -CRR'— (CH2) - O Pattern 8 Krak, Graph Ass., Plant No. 3, order 262/75 Price 10 zl / PL PL