Flame retardant preparation and composition and thermoplastic molding compound containing the flame retardant preparation

Abstract

The present invention relates to a flame retardant preparation containing A) a cyclic phosphazene according to formula (1), where R is identical or different and in each case represents - C1- to C8-alkyl, preferably methyl, ethyl, propyl or butyl, - C1- to C8-alkoxy, preferably methoxy, ethoxy, propoxy or butoxy, - optionally C5- to C6-cycloalkyl substituted by alkyl, preferably C1-C4-alkyl, - optionally C6- to C20-aryloxy, preferably phenoxy, naphthyloxy, substituted by alkyl, preferably C1-C4-alkyl and / or hydroxy, - optionally C7- to C12-aralkyl, preferably phenyl-C1-C4-alkyl, substituted by alkyl, preferably C1-C4-alkyl, or - an OH group, and k represents 0 or an integer from 1 to 15, preferably a number from 1 to 10, B) a polymer containing structural units containing Brønsted acid groups, wherein the content of structural units containing Brønsted acid groups in component B is at least 50 wt. % and wherein at least some of the Brønsted acidic groups are deprotonated. The invention also relates to a composition containing the flame retardant mixture and a polymer, to use of the flame retardant mixture for reducing the burning drip of polymers in a flame retardant test, to a thermoplastic molding compound produced from the composition, and to molded bodies containing the composition or obtained from the thermoplastic molding compound.

Description

[0001] 2024PF30096-Abroad

[0002] - 1 -

[0003] Flame retardant preparation as well as composition and thermoplastic molding compound containing the flame retardant preparation

[0004] The present invention relates to a flame retardant preparation, a composition containing a polymer and this flame retardant preparation, a thermoplastic molding compound obtained from such a composition, and the use of the flame retardant preparation for reducing burning dripping during a flame retardant test of the polymer.

[0005] Thermoplastic polymers are used in countless applications today. However, these applications often require the polymers to be treated with flame retardant additives (also called flame retardants) to reduce their inherent flammability and meet regulatory requirements. But it's not just the flame-retardant properties that a material must possess for a specific application that are regulated. Increasingly, the flame retardants themselves are also being critically examined, and their use is being regulated or even prohibited.

[0006] For example, halogenated flame retardants can release environmentally harmful and toxic combustion gases in the event of a fire. Therefore, the use of such flame retardants is restricted in many countries.

[0007] When assessing the fire properties of a material according to the widely used UL 94 V standard, various criteria are considered. One relevant factor is the afterburn time, i.e., the time a sample continues to burn once ignited until it self-extinguishes. Furthermore, any dripping of burning material leads to a downgrade of the achieved classification.

[0008] To prevent this burning dripping, polytetrafluoroethylene (PTFE) has long been added to many thermoplastic polymers, such as polycarbonate, as an effective anti-drip agent. PTFE and the surfactants used in its production belong to the class of polyfluoroalkyl substances (PFAS), many of which are classified as substances of very high concern under the European chemicals regulation REACH. For such substances of very high concern, special reporting obligations apply under the REACH regulation, and a strict restriction of permitted uses is to be expected. Therefore, the development of alternative, PFAS-free flame retardants or flame retardant preparations is of great interest for improving the dripping behavior of polymers.

[0009] WO 2008 / 051120 Al discloses a flame-retardant additive for polymers, wherein the additive is a polyacrylate in combination with a) at least one zinc borate, b) at least one silicone resin 2024PF30096-Abroad

[0010] - 2 - and c) aluminum oxide trihydrate or magnesium hydroxide or a mixture thereof, wherein the additive is free of halogens, antimony oxide and phosphorus-containing substances.

[0011] However, no tests are described in which no dripping of molten material occurred during the fire test.

[0012] However, avoiding burning dripping is necessary to achieve a very good flame retardant classification (UL94 V-0 or UL94 Vl), so that the use of PFAS can be avoided.

[0013] WO2017 / 222448 discloses a halogen-free flame retardant additive for polymers containing a) a phosphorus-nitrogen-containing component containing amine and / or ammonium groups and b) a (meth)acrylic acid-containing homo- or copolymer selected from the group consisting of partially or fully neutralized salts of poly(meth)acrylic acid, a partially or fully neutralized salt of a partially cross-linked poly(meth)acrylic acid, a partially or fully neutralized salt of a copolymer consisting of olefin and (meth)acrylic acid and combinations of the aforementioned polymers.

[0014] In WO2017 / 222448 Al, a mechanism for the effect of amine-containing phosphorus compounds in conjunction with carboxyl groups is also postulated.

[0015] US 2012 / 190781 A1 discloses a thermoplastic molding compound consisting of a) 30 to 95 wt.% of at least one aliphatic polyamide or copolyamide as component A, b) 1 to 30 wt.% of at least one cyclic phenoxyphosphazene with at least 3 phenoxyphosphazene units as component B, c) 1 to 15 wt.% of red phosphorus as component C, d) 0.1 to 20 wt.% of at least one impact-modifying polymer as component D, e) 0 to 50 wt.% of glass fibers as component E, and f) 0 to 30 wt.% of other additives as component F.

[0016] US 2024 / 287306 discloses thermoplastic compositions based on aromatic polycarbonate with a high CTI (Comparative Tracking Index), good flame retardancy, and high heat resistance. The compositions contain a combination of PMMI, a phosphorus-containing flame retardant, and a fluorinated anti-drip agent.

[0017] Besides the actual flame-retardant effect, other criteria are important when selecting suitable flame-retardant additives. The flame-retardant additive should also complement other properties of the polymer compositions (hereinafter also referred to simply as compositions) or the thermoplastic molding compounds produced from them in which the additive is to be used, in particular their mechanical characteristics such as toughness. 2024PF30096-Abroad

[0018] - 3 - as well as how thermal stability and stability against the influence of moisture should be affected as little as possible. Insufficient thermal stability can result in a decrease in molecular weight, even to the point of the release of low-molecular-weight fragments (degradation products). For example, the release of bisphenol A from polycarbonates must be avoided because the amount of this substance in polycarbonate molding compounds and the resulting molded parts is also to be restricted by currently discussed regulatory measures.

[0019] It was therefore desirable to provide a flame retardant preparation that reduces the burning dripping of polymer compositions and thermoplastic molding compounds produced therefrom, as well as of molded parts produced therefrom, during flame retardancy testing according to UL 94 V, wherein the flame retardant preparation does not include any intentionally added polyfluoroalkyl substances (PFAS), in particular no polytetrafluoroethylene (PTFE), and preferably also no intentionally added chlorine- and / or bromine-containing substances. Furthermore, it was desirable that molded parts produced from the molding compounds exhibit high toughness. It was even more desirable that molding compounds containing the thermoplastic polymer and the flame retardant preparation exhibit high thermal stability, i.e.,The polymers should exhibit high integrity of the polymer molecular weight and a low tendency to form low-molecular-weight or oligomeric components due to thermally induced back-cleavage. In the case of compositions and thermoplastic molding compounds containing condensation polymers, it was also desirable for them to exhibit low hydrolysis susceptibility.

[0020] Surprisingly, it was found that a flame retardant preparation containing

[0021] A) a cyclic phosphazene according to formula (1) where

[0022] R are the same or different and each for

[0023] - CI - to C8 alkyl, preferably methyl, ethyl, propyl or butyl,

[0024] - CI - to C8- Alkoxy, preferably Methoxy, Ethoxy, Propoxy or Butoxy, 2024PF30096-Abroad

[0025] - 4 -

[0026] - optionally substituted by alkyl, preferably Cl-C4-alkyl, C5- to C6-cyclo-alkyl,

[0027] - optionally by alkyl, preferably Cl-C4-alkyl and / or hydroxy-substituted, C6- to C20-aryloxy, preferably phenoxy, naphthyloxy,

[0028] - optionally substituted by alkyl, preferably Cl-C4-alkyl, C7- to C12-aralkyl, preferably phenyl-Cl-C4-alkyl, or

[0029] - an OH residue and k represents 0 or an integer from 1 to 15, preferably a number from 1 to 10, B) a polymer containing structural units containing Bronsted acid groups, wherein the content of structural units containing Bronsted acid groups in component B is at least 50 wt. %, and wherein at least some of the Bronsted acid groups are deprotonated, which solves the problem according to the invention.

[0030] Bronsted acidic groups, as defined in the present invention, are groups which, in reaction with water, are able to lower the pH value by transferring a proton.

[0031] The release of a proton from a Brønsted acidic group is called deprotonation. If the Brønsted acidic group can release multiple protons, then "deprotonated" refers to the release of at least one of the protons.

[0032] The term "preparation" as used in this application does not include any restrictions regarding the method for its manufacture. In this sense, a "preparation" within the scope of this application is generally understood to be any composition containing components A and B, without requiring it to have undergone any specific, i.e., more precisely defined, preparation or mixing process steps. In a preferred embodiment, however, the flame retardant preparation is an intimate, i.e., largely homogeneous, mixture of its components. For example, and preferably, this can be produced from powdered components A and B in a container mixer manufactured by Mixaco Dr. Herfeld GmbH & Co. KG (Neuenrade, Germany) or in comparable high-energy mixing units from other manufacturers.

[0033] The flame retardant formulation contains no intentionally added halogens and therefore no polyfluoroalkyl substances (PFAS), yet burning dripping in the flame retardant test according to UL94V can be significantly reduced or even completely avoided. Compared to a flame retardant mixture known from the prior art, furthermore 2024PF30096-Ausland

[0034] - 5 - improves the toughness, thermal stability and hydrolysis stability of flame-retardant polymer compositions and thermoplastic molding compounds obtained therefrom.

[0035] The flame retardant mixture preferably contains

[0036] 60 to 99.5 parts by weight, more preferably 70 to 99 parts by weight, most preferably 80 to 98 parts by weight, each based on a total of 100 parts by weight of components A and B, of component A and

[0037] 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, most preferably 2 to 20 parts by weight, each based on a total of 100 parts by weight of components A and B, of component B.

[0038] A further object of the present invention is a composition comprising components A and B of the aforementioned flame retardant preparation and a polymer, preferably a thermoplastic polymer, as component C. The thermoplastic polymer is preferably selected from the group consisting of polycarbonates, polyester carbonates, polyesters, polyolefins, vinyl (co)polymers and polyamides, as well as mixtures thereof.

[0039] The term "a cyclic phosphazene" for component A of the flame retardant preparation also includes mixtures of various compounds falling under the definition of component A. "A cyclic phosphazene" is therefore to be understood as "at least one cyclic phosphazene". This applies analogously to component B used in the flame retardant preparation according to the invention, as well as to the components in the polymer composition according to the invention and their monomer Z structural units.

[0040] The composition preferably contains

[0041] 1 to 40 parts by weight, more preferably 3 to 30 parts by weight, particularly preferably 5 to 20 parts by weight, each based on a total of 100 parts by weight of polymer and flame retardant preparation, the flame retardant preparation consisting of components A and B and

[0042] 60 to 99 parts by weight, more preferably 70 to 97 parts by weight, particularly preferably 80 to 95 parts by weight, each based on a total of 100 parts by weight of polymer and flame retardant preparation, of the polymer according to component C.

[0043] Optionally, the composition contains as component D a polymer additive as described below. Preferably, component D, if used, is present in an amount of 0.01 to 30 parts by weight, more preferably in an amount of 0.05 to 10 parts by weight, and most preferably in an amount of 0.1 to 5 parts by weight, based on a total of 100 parts by weight of components A to C. 2024PF30096-Abroad

[0044] Compositions consisting of at least 98 wt.%, and further preferably at least 99 wt.%, of the components named herein are preferred. Particularly preferred are compositions consisting of the components named herein, i.e., the flame retardant preparations A and B, polymer C, and polymer additives D.

[0045] Another object of the present invention is the use of a flame retardant preparation containing

[0046] A) a cyclic phosphazene according to formula (1)

[0047] (1)

[0048] R are the same or different and each for

[0049] - CI - to C8 alkyl, preferably methyl, ethyl, propyl or butyl,

[0050] - CI - to C8- Alkoxy, preferably Methoxy, Ethoxy, Propoxy or Butoxy,

[0051] - optionally substituted by alkyl, preferably Cl-C4-alkyl, C5- to C6-cyclo-alkyl,

[0052] - optionally by alkyl, preferably Cl-C4-alkyl and / or hydroxy-substituted, C6- to C20-aryloxy, preferably phenoxy, naphthyloxy,

[0053] - optionally substituted by alkyl, preferably Cl-C4-alkyl, C7- to C12-aralkyl, preferably phenyl-Cl-C4-alkyl, or

[0054] - an OH residue and k represents 0 or an integer from 1 to 15, preferably a number from 1 to 10,

[0055] B) a polymer containing structural units containing Bronsted acid groups, wherein the content of structural units containing Bronsted acid groups in component B is at least 50 wt.%, wherein at least some of the Bronsted acid groups are deprotonated, for reducing the burning dripping of a polymer, preferably a thermoplastic polymer, in a flame retardancy test, preferably according to UL 94 V, further preferably for achieving a Vl or VO rating in this flame retardancy test, further preferably for achieving a V-0 rating, preferably at a thickness of 3.0 mm. 2024PF30096-Abroad

[0056] The preferred embodiments for the components of the flame retardant preparation and the thermoplastic polymer mentioned within the scope of this invention also apply to the composition according to the invention, the use according to the invention, as well as the molding compound and the molded bodies according to the invention mentioned below.

[0057] Component A

[0058] Component A in the flame retardant preparation is a cyclic phosphazene according to formula 1. where

[0059] R are the same or different and each for

[0060] - C to Cg-alkyl, preferably methyl, ethyl, propyl or butyl,

[0061] - Cp to Cg- alkoxy, preferably methoxy, ethoxy, propoxy or butoxy,

[0062] - optionally substituted by alkyl, preferably CpCpAlkyl, C5- to Cg-cycloalkyl,

[0063] - optionally substituted by alkyl, preferably CpCpAlkyl and / or hydroxy-substituted, Cp to CpQ-aryloxy. Preferably phenoxy, naphthyloxy,

[0064] - optionally substituted by alkyl, preferably CpCpalkyl, C7- to C12-aralkyl, preferably Phcnyl-CpCpalkyl. or

[0065] - an OH residue and k represents 0 or an integer from 1 to 15, preferably a number from 1 to 10.

[0066] Although generally undesirable, it is sometimes unavoidable due to the manufacturing process that certain proportions of the phosphazene according to formula (1) on the phosphorus are (partially) halogen-, in particular chlorine-substituted, since the phosphazenes according to the invention are often produced from halogen-, in particular chlorine-substituted phosphazenes by nucleophilic substitution and the completeness of this substitution cannot always be ensured. 2024PF30096-Abroad

[0067] - 8 - can. In this respect, phosphazenes according to the invention can also include residual amounts of halogen, in particular chlorine, resulting from the process. In these phosphazenes, the proportion of halogen, in particular chlorine, is preferably less than 1000 ppm by weight, more preferably less than 500 ppm by weight, particularly less than 100 ppm by weight, and most preferably less than 50 ppm by weight.

[0068] In a further preferred embodiment, only phosphazenes with the same R are used.

[0069] Preferred substances are propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene and

[0070] In the compounds shown above, k = 1, 2, or 3.

[0071] Cyclic phosphazenes according to formula (1) with a proportion of oligomers with k = 1 (trimers) of 60 to 99.99 mol%, and more preferably of 70 to 99.5 mol%, are particularly preferred. Phosphazenes according to formula (2), in which all R groups are phenoxy groups, are also further preferred: 2024PF30096-Ausland

[0072] Preferably, component A is a phenoxyphosphazene according to formula (2), with a trimere fraction (k=l) of 65 to 99.9 mol%, a tetramer fraction (k=2) of 0.1 to 35 mol%, a fraction of higher oligomeric phosphazenes (k=3,4,5,6 and 7) of 0 to 20 mol% and a fraction of phosphazene oligomers with k>= 8 of 0 to 2 mol%, each based on component A.

[0073] Phosphazenes and their production are described, for example, in EP-A 728 811, DE-A 1 961668 and WO 97 / 40092.

[0074] Suitable phosphazenes include, for example, Rabitle™ FP 110 (Fushimi, Japan) or HPCTP (hexaphenoxycyclotriphosphazene) from Weihai Jinwei Chemical Industry Co. Ltd.

[0075] The oligomer compositions of the phosphazenes in the respective thermoplastic samples can also be determined after compounding using 31 P NMR detect and quantify (chemical shift; 5 trimer: 6.5 to 10.0 ppm; 5 tetramer: -10 to -13.5 ppm; 5 higher oligomers: -16.5 to -25.0 ppm).

[0076] Component B

[0077] Component B of the inventive flame retardant preparation contains a polymer containing structural units containing Bronsted acid groups, wherein the content of structural units containing Bronsted acid groups in component B is at least 50 wt.% and wherein at least some of the Bronsted acid groups are deprotonated.

[0078] Preferably, not all Bronsted acidic groups of component B are deprotonated, but only a portion of them.

[0079] The stated 50 wt% refers to all structural units containing Brønsted acid groups, regardless of whether the Brønsted acid group in the respective structural unit is protonated (i.e., with a bound hydrogen atom) or deprotonated after reaction with a basic reagent. 2024PF30096-Abroad

[0080] - 10 -

[0081] In the case that component B is a mixture of several such polymers, the content of structural units containing Bronsted acid groups in each of these polymers is at least 50 wt. %, with at least a part of the acid groups being deprotonated in each case.

[0082] The Brønsted acidic groups can be, for example, carboxylic acid groups and / or sulfonic acid groups. Preferably, the Brønsted acidic groups are carboxylic acid groups, and accordingly, component B is a polymer containing structural units derived from a carboxylic acid, wherein at least some of the acidic groups are deprotonated.

[0083] Containing structural units “derived from a carboxylic acid” means, in the context of this invention, that a carboxylic acid is used in the production of component B. In addition to the carboxyl groups remaining in the polymer, the carboxylic acid has further polymerizable groups and / or carbon-carbon double bonds and is then covalently incorporated into the polymer chain.

[0084] Preferably, the carboxylic acid is an unsaturated carboxylic acid, meaning it contains carbon-carbon double bonds.

[0085] Preferred carboxylic acids are acrylic acid, methacrylic acid, maleic acid, fumaric acid, cinnamic acid, sorbic acid, itaconic acid and crotonic acid, further preferred are acrylic acid and methacrylic acid, and most preferred is acrylic acid.

[0086] Copolymers containing both carboxyl groups and sulfonic acid groups can therefore be used, as is the case, for example, with the copolymer of 4-styrenesulfonic acid and maleic acid.

[0087] It is also possible to use a polymeric organic compound containing carboxylic acid groups as substituents as component B. An example of this is cellulose containing carboxyl groups, preferably carboxymethylcellulose, where at least some of the acid groups are deprotonated.

[0088] It is also possible to use a copolymer as component B containing structural units derived from several monomers, wherein at least one of the monomers contains at least one Brønsted acid group and wherein the content of structural units containing Brønsted acid groups in component B is at least 50 wt.%, with at least some of the acid groups being deprotonated. Furthermore, structural units from a monomer that does not contain Brønsted acid groups may also be included. 2024PF30096-Abroad

[0089] - 11 -

[0090] This additional monomer can, for example, be an olefin. Preferred olefins as components of the copolymers are α-olefins and particularly preferably have between 2 and 10 carbon atoms and can be unsubstituted or substituted with one or more aliphatic, cycloaliphatic, or aromatic groups.

[0091] Particularly preferred olefins are selected from the group comprising ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 3-methyl-1-pentene. Especially preferred olefins are ethene and propene, with ethene being particularly preferred. Mixtures of the olefins described are also suitable.

[0092] Likewise, the other monomer can be a vinyl monomer selected from the group consisting of (meth)acrylic acid (Ci to Cs) alkyl esters (such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate), carboxylic acid anhydrides, vinyl aromatics (such as styrene, α-methyl styrene) and vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile).

[0093] Preferably, however, no other monomer besides the monomer(s) containing the Brønsted acid groups is used. If several monomers containing Brønsted acid groups are used, these monomers can all contain the same Brønsted acid groups, preferably all carboxyl groups. The different monomers can also contain different types of Brønsted acid groups. Examples include copolymers of a monomer containing carboxyl groups and a monomer containing sulfonic acid groups. Preferably, copolymers are selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, cinnamic acid, sorbic acid, itaconic acid, and crotonic acid, preferably acrylic acid, methacrylic acid, and maleic acid, most preferably maleic acid, and from the group of sulfonic acid-substituted vinyl monomers, preferably 4-styrenesulfonic acid.

[0094] The Brønsted acid groups, preferably the carboxylic acid groups, of the polymers are at least partially deprotonated. These are preferably salts in which the deprotonation is effected by cation-containing bases, preferably selected from sodium and zinc, particularly preferably sodium. Compounds containing deprotonated acid groups are also referred to as ionomers. The proportion of deprotonated carboxylic acid groups can range from 5 to 100% and is preferably 10 to 70%. If the metal cation has a valence of two, such as the zinc cation, one metal cation can deprotonate two monovalent Brønsted acid groups originating from two polymer chains. This allows for ionic bonding of these chains via the metal cation. Commercially, such copolymers containing carboxylic acid groups partially deprotonated with metal cations are available under the trade names Surlyn™ (DuPont) or Ionia™ ​​(SK Functional Polymer).2024PF30096-Abroad.

[0095] - 12 -

[0096] Component B is particularly preferably polyacrylic acid or polymethacrylic acid in which the acid group is at least partially deprotonated, or mixtures of the aforementioned components.

[0097] At least partially deprotonated polyacrylic acid is most preferred.

[0098] It is also possible for component B to be used in the form of a masterbatch. In this case, component B is dispersed in a thermoplastic, such as a polyolefin, and optionally with other additives, and used as such a mixture. The proportion of component B in the masterbatch is preferably 5 to 95 wt.%, more preferably 40 to 90 wt.%. The proportion of component B in the flame retardant mixture specified above refers to pure component B, i.e., without considering the other components of the masterbatch.

[0099] Component C: Polymer

[0100] The flame retardant preparation is suitable for improving the flame-retardant properties of polymers that can exhibit both thermoplastic and thermoset properties. The flame retardant preparation is preferably used to improve the flame-retardant properties of thermoplastic polymers as well as single-phase or multi-phase blends of several (thermoplastic) polymers.

[0101] Examples of thermoplastic polymers according to component C include polycarbonates, polyesters, polyester carbonates, polyacetals (such as polyoxymethylene and polyphenylene ethers), polyamides, polyolefins, polyimides, thermoplastic polyurethanes, polysulfones, polyarylates, polyaryl ethers, and optionally rubber-modified vinyl(co)polymers including acrylonitrile butadiene styrene, polyacrylates, polyarylsulfones, polyaryl sulfides, polyethersulfones, polyetheramides, polyphenylene sulfide, polyetherketones, polyamide imides, polyether imides and polyester imides.

[0102] The polymer is preferably selected from the group consisting of polycarbonates, polyester carbonates, polyesters, polyolefins, vinyl(co)polymers and polyamides.

[0103] Thermoplastic polymers containing aromatic groups are particularly preferred.

[0104] The polymer is more preferably selected from the group consisting of polycarbonates, polyester carbonates and polyesters, even more preferably selected from the group consisting of polycarbonates and polyester carbonates, and particularly preferably selected from the group of polycarbonates.

[0105] Suitable polycarbonates and / or polyester carbonates according to component C are known from the literature or can be produced using methods known from the literature (for the production of 2024PF30096-Abroad).

[0106] - 13 -

[0107] For polycarbonates, see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, as well as DE-AS 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A

[0108] 2 714 544, DE-A 3 000 610, DE-A 3 832 396; for the production of polyester carbonates, e.g. DE-A

[0109] 3 007 934).

[0110] The production of polycarbonates suitable as component C according to the invention is carried out, for example, by reacting dihydroxyaryl compounds (also referred to as aromatic diols, diphenols, or bisphenols) and / or aliphatic diols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, by the interface process, optionally using chain terminators, for example, monophenols, and optionally using trifunctional or more than trifunctional branchers, for example, trihydroxyaryl or tetrahydroxyaryl compounds. Likewise, production via a melt polymerization process by reacting dihydroxyaryl compounds and / or aliphatic diols with carbonic acid stems, for example, diphenyl carbonate, is possible.

[0111] For the production of the polycarbonates suitable as component C according to the invention and / or for the production of the polyester carbonates suitable as component C according to the invention, dihydroxyaryl compounds of structure (4) are preferably used.

[0112] (4)

[0113] A a single bond, Ci to Cs-alkylene, C2 to Cs-alkylidene, Cs to Ce-cycloalkylidene, -O- , -SO- , -CO- , -S- , -SO2- , Ce to Cn-arylene, to which further aromatic rings, optionally containing heteroatoms, may be fused, or a residue of the structure (5) or (6) 2024PF30096-Abroad

[0114] - 14 -

[0115] B each Ci to Cn-alkyl, preferably methyl, halogen, preferably chlorine and / or bromine x each independently 0, 1 or 2, p 1 or 0 are, and

[0116] R 5 and R 6 for each X 1Individually selectable, independently of each other hydrogen or Ci to Ce-

[0117] Alkyl, preferably hydrogen, methyl or ethyl,

[0118] XI carbon and m an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X 1 , R 5 and R 6 are simultaneously alkyl.

[0119] Preferred dihydroxyaryl compounds used are hydroquinone, resorcinol, dihydroxydiphenyls, bis-(hydroxyphenyl)alkanes, bis-(hydroxyphenyl)cycloalkanes, bis-(hydroxyphenyl)sulfides, bis-(hydroxyphenyl)ethers, bis-(hydroxyphenyl)ketones, bis-(hydroxyphenyl)sulfones, bis-(hydroxyphenyl)sulfoxides, α-α'-bis-(hydroxyphenyl)diisopropylbenzenes, phthalimidines derived from isatin or phenolphthalein derivatives, and their kemalkylated, kemarylated, and kemhalogenated compounds.

[0120] Other preferred dihydroxyaryl compounds used are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3-methyl-4-hydroxyphenyl)propane, dimethyl bisphenol A, bis-(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)propane, bis-(3,5-dimethyl-4-hydroxyphenyl)sulfone, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene and 1,1-Bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and dihydroxyaryl compounds (I) to (III) 2024PF30096-Abroad

[0121] - 15 -

[0122] These and other suitable dihydroxyaryl compounds are, for example, in US 3 028 635 A, US 2 999 835 A, US 3 148 172 A, US 2 991 273 A, US 3 271 367 A, US 4 982 014 A and US 2 999 846 A, in DE 1 570 703 A, DE 2063 050 A, DE 2 036 052 A, DE 2 211 956 A and DE 3 832 396 A, in FR 1 561 518 A, in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" as well as in JP 62039 / 1986 A, JP 62040 / 1986 A and JP 105550 / 1986 A described.

[0123] These dihydroxyaryl compounds can be used individually or in any mixture. The dihydroxyaryl compounds are known from the literature or can be obtained by methods known from the literature.

[0124] Suitable aliphatic diols are selected from the group consisting of 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxycyclohexyl)propane, tetrahydro-2,5-furandimethanol, 2-butyl-2-ethyl-1,3-propanediol, 2-(2-hydroxyethoxy)ethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethylpropane-1,3-diol, and cyclobutane-1,1-diyldimethanol. 8-(Hydroxymethyl)-3-tricyclo[5.2.1.02,6]decanyl]methanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, isosorbide and any mixtures thereof.

[0125] Suitable chain termination compounds for the production of polycarbonates include, for example, phenol, p-chlorophenol, p-tert-butylphenol, or 2,4,6-tribromophenol, but also long-chain alkylphenols such as 4-[2-(2,4,4-trimethylpentyl)]phenol, 4-(1,3-tetramethylbutyl)phenol according to DE-A 2 842 005, or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol, and 2-(3,5-dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol. The amount of chain terminators to be used is generally between 0.5 mol% and 10 mol%, based on the total molar content of the dihydroxyaryl compounds used.

[0126] The thermoplastic aromatic polycarbonates have medium molecular weights (average weight M). w) preferably 15 to 50 kg / mol, further preferably 18 to 35 kg / mol, particularly preferably 24 to 32 kg / mol, measured by GPC (gel permeation chromatography) using dichloromethane as solvent, calibration with linear polycarbonates (from bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany, calibration according to method 2301-0257502-09D (from 2009 in German) of Currenta GmbH & Co. OHG, Leverkusen. The eluent is 2024PF30096-Ausland

[0127] - 16 -

[0128] Dichloromethane. Column combination made of cross-linked styrene-divinylbenzene resins. Diameter of analytical columns: 7.5 mm; length: 300 mm. Particle size of column material: 3 pm to 20 pm. Solution concentration: 0.2 wt%. Flow rate: 1.0 ml / min, solution temperature: 30°C. Use of UV and / or RI detection.

[0129] The polycarbonates can be branched in a known manner, preferably by the incorporation of 0.05 to 2.0 mol%, based on the total number of dihydroxyaryl compounds used, of trifunctional or more than trifunctional compounds, for example, those with three or more phenolic groups. Linear polycarbonates are preferred, and linear polycarbonates based exclusively on bisphenol A are even more preferred.

[0130] Both homopolycarbonates and copolycarbonates are suitable. For the production of copolycarbonates according to the invention as described in component C, 1 to 25 wt.%, preferably 2.5 to 25 wt.%, based on the total amount of dihydroxyaryl compounds to be used, of polydiorganosiloxanes with hydroxyaryloxy end groups can also be employed. These are known (US 3,419,634) and can be prepared according to methods known from the literature. The preparation of the polydiorganosiloxane-containing copolycarbonates obtained in this way is described, for example, in DE-A 3 334 782 and W02015 / 052106 A2.

[0131] Copolycarbonates produced using diphenols of general formula (6a) are also preferred:

[0132] (6a)

[0133] R 5 for hydrogen or Ci- to C4-alkyl, Ci- to Cs-alkoxy, preferably for hydrogen;

[0134] Methoxy or methyl, stands,

[0135] R 6 , R7 , R 8 and R 9 each independently of each other stand for Ci- to C4-alkyl or Ce- to Cn-aryl, preferably for methyl or phenyl, 2024PF30096-Abroad

[0136] - 17 -

[0137] Y represents a single bond, SO2-, -S-, -CO-, -O-, Ci- to Ce-alkylene, C2- to Ce-alkylidene, Ce- to Ci2-arylene, which may optionally be condensed with aromatic rings containing further heteroatoms, or a C5- to Ce-cycloalkylidene residue which may be substituted once or several times with Ci- to C4-alkyl, preferably a single bond, -O-, isopropylidene or a C5- to Ce-cycloalkylidene residue which may be substituted once or several times with Ci- to C4-alkyl.

[0138] V represents oxygen, C2- to Ce-alkylenes or C3- to Ce-alkylidenes, preferably oxygen or Cs-alkylenes; p, q and r each independently represent 0 or 1 when q = 0; W represents a single bond when q = 1 and r = 0; W represents oxygen, C2- to Ce-alkylenes or C3- to Ce-alkylidenes, preferably oxygen or Cs-alkylenes when q = 1 and r = 1; W and V each independently represent C2- to Ce-alkylenes or Cs- to Ce-alkylidenes, preferably Cs-alkylenes.

[0139] Z represents a Ci to Ce alkylene, preferably a Cs alkylene, o represents an average number of repeating units of 10 to 500, preferably 10 to 100, and m represents an average number of repeating units of 1 to 10, preferably 1 to 6, more preferably 1.5 to 5. It is also possible to use diphenols in which two or more siloxane blocks of general formula (6a) are linked to one another via terephthalic acid and / or isophthalic acid to form ester groups.

[0140] Particularly preferred are (poly)siloxanes of formulas (7) and (8) 2024PF30096-Abroad

[0141] - 18 - where RI stands for hydrogen, Ci to C4 alkyl, preferably for hydrogen or methyl, and particularly preferably for hydrogen,

[0142] R2 independently represents aryl or alkyl, preferably methyl, X represents a single bond, -SO2-, -CO-, -O-, -S-, Ci- to Ce -alkylenes, C2- to Cs-alkylidenes or Ce- to Cn-arylene, which may optionally be condensed with further aromatic rings containing heteroatoms,

[0143] X preferably represents a single bond, Ci- to Cs-alkylenes, C2- to Cs-alkylidenes, Cs- to C12-cycloalkylidenes, -O-, -SO-, -CO-, -S-, -SO2-, particularly preferably X represents a single bond, isopropylidenes, Cs- to Cn-cycloalkylidenes or oxygen, and most preferably

[0144] isopropylidene, n an average number of 10 to 400, preferably 10 and 100, particularly preferably 15 to

[0145] 50 means and m stands for an average number of 1 to 10, preferably 1 to 6 and particularly preferably 1.5 to 5.

[0146] The siloxane block can also preferably be derived from the following structure. (10), preferably (10a) 2024PF30096-Abroad

[0147] - 19 - where a in formula (9), (10), (10a) and (11) represents an average number of 10 to 400, preferably 10 to 100 and particularly preferably 15 to 50.

[0148] It is also preferred that at least two identical or different siloxane blocks of the general formulas (9), (10), (10a) or (11) are linked together via terephthalic acid and / or isophthalic acid to form ester groups.

[0149] Likewise, it is preferred if in formula (6a) p = 0, V stands for Cs-alkylene, r = 1, Z stands for Cs-alkylene, R 8 and R 9 where q = 1 represents methyl, W represents Cs-alkylene, m = 1 represents R 5 R stands for hydrogen or Ci to C4 alkyl, preferably for hydrogen or methyl. 6 and R 7each independently of each other stands for Ci - to C4 alkyl, preferably for methyl and o stands for 10 to 500.

[0150] Copolycarbonates with monomer units of formula (6a) and in particular their preparation are described in WO 2015 / 052106 A2.

[0151] Copolycarbonates with monomer units of formula (9) and in particular their preparation are described in WO 2015 / 052106 A2.

[0152] Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid, and naphthalene-2,6-dicarboxylic acid. Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20:1 are particularly preferred. In the production of polyester carbonates, a carbonic acid halide, preferably phosgene, is additionally used as a bifunctional acid derivative.

[0153] In addition to the monophenols already mentioned, the ketene terminators used for the production of aromatic polyester carbonates include their chlorocarbonate esters and the acid chlorides of aromatic monocarboxylic acids, which may be modified by Ci to C22 alkyl groups or by 2024PF30096-Abroad

[0154] - 20 -

[0155] Halogen atoms may be substituted, as well as aliphatic C2 to C22 monocarboxylic acid chlorides.

[0156] The amount of chain terminators is 0.1 to 10 mol% in each case, based on moles of diphenol in the case of phenolic chain terminators and on moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators.

[0157] In the production of aromatic polyester carbonates, one or more aromatic hydroxycarboxylic acids can also be used.

[0158] The aromatic polyester carbonates can be either linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934), but linear polyester carbonates are preferred.

[0159] Branching agents can include, for example, tri- or multi-functional carboxylic acid chlorides such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-,4,4'-benzophenone tetracarboxylic acid tetrachloride, 1,4,5,8-napthalin tetracarboxylic acid tetrachloride, or pyromellitic acid tetrachloride, or tri- or multi-functional phenols such as phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)hept-2-ene, 4,6-dimethyl-2,4-6-tri-(4-hydroxyphenyl)heptane, 1,3,5-tri-(4-hydroxyphenyl)benzene, 1,1,1-tri-(4-hydroxyphenyl)ethane, tri-(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenylj-cyclohexyl]-propane, 2,4-Bis(4-hydroxyphenyl-isopropyl)-phenol, Tetra-(4-hydroxyphenyl)-methane, 2,6-Bis(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, Tetra-(4-[4-hydroxyphenyl-isopropyl]-phenoxyyl-methane, 1,4-Bis[4,4'-dihydroxytri-phenyl]-methyl]-benzene, in amounts of 0.01 to 1.0 mol% based on the diphenols used.Phenolic branching agents can be introduced with the diphenols. Acid chloride branching agents can be introduced together with the acid dichlorides.

[0160] In thermoplastic aromatic polyester carbonates, the proportion of carbonate structural units can vary as desired. Preferably, the proportion of carbonate groups is up to 99.9 mol%, particularly up to 80 mol%, and most preferably up to 50 mol%, based on the sum of ester and carbonate groups. Both the ester and carbonate components of the aromatic polyester carbonates can be present in the form of blocks or statistically distributed within the polycondensate.

[0161] Suitable polyesters are aromatic in preferred embodiments; more preferably, they are polyalkylene terephthalates. Particularly preferred is 2024PF30096-Ausland.

[0162] - 21 -

[0163] Form of application for reaction products from aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols, as well as mixtures of these reaction products.

[0164] Particularly preferred aromatic polyalkylene terephthalates contain at least 80 wt.%, preferably at least 90 wt.%, based on the dicarboxylic acid component terephthalic acid residues and at least 80 wt.%, preferably at least 90 wt.%, based on the diol component ethylene glycol and / or butanediol-1,4 residues.

[0165] The preferred aromatic polyalkylene terephthalates may contain, in addition to terephthalic acid residues up to 20 mol%, preferably up to 10 mol%, residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, mezzotinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanedioacetic acid.

[0166] The preferred aromatic polyalkylene terephthalates may contain, in addition to ethylene glycol or butanediol-1,4 residues up to 20 mol%, preferably up to 10 mol%, other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms, e.g., residues of propanediol-1,3, 2-ethylpropanediol-1,3, neopentyl glycol, pentanediol-1,5, hexanediol-1,6, cyclohexane-dimethanol-1,4, 3-ethylpentanediol-2,4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3, 2-ethylhexanediol-1,3, 2,2-diethylpropanediol-1,3, hexanediol-2,5, 1,4-di-(β-hydroxyethoxy)benzene. 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1, 1,3,3-tetramethyl-cyclobutane, 2,2-bis-(4-ß-hydroxyethoxy-phenyl)-propane and 2,2-bis-(4-hydroxypropoxyphenyl)-propane (DE-A 2 407 674, 2 407 776, 2,715,932).

[0167] Aromatic polyalkylene terephthalates prepared solely from terephthalic acid and its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol and / or butanediol-1,4 are particularly preferred, as are mixtures of these polyalkylene terephthalates.

[0168] Preferred mixtures of aromatic polyalkylene terephthalates contain 1 to 50 wt.%, preferably 1 to 30 wt.%, polyethylene terephthalate and 50 to 99 wt.%, preferably 70 to 99 wt.%, polybutylene terephthalate.

[0169] Aromatic polyalkylene terephthalates can be produced using known methods (see, for example, Kunststoff-Handbuch [Plastics Handbook], Volume VIII, pp. 695 ff., Carl Hanser Verlag, Munich 1973). 2024PF30096-Ausland

[0170] - 22 -

[0171] The polymer could also be a polyolefin.

[0172] Polyolefins are produced by ketene polymerization, for example, by radical or anionic polymerization. Alkenes are used as monomers. An alternative name for alkenes is olefins. The monomers can be polymerized individually or as a mixture of different monomers.

[0173] Preferred monomers are ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-heptene, 1-octene and 4-methyl-1-pentene.

[0174] The polyolefins can contain < 50 wt.%, more preferably up to 30 wt.%, one or more different vinylic comonomers, for example styrene, acrylonitrile, glycidyl methacrylate, maleic anhydride, acrylic acid and methacrylic acid, as well as methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate, wherein methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate are preferred.

[0175] Polyolefins are mostly semi-crystalline and can be linear or branched. The production of polyolefins has long been known to experts.

[0176] The polymerization can be carried out, for example, at pressures of 1 to 3000 bar and temperatures between 20°C and 300°C, optionally using a catalyst system. Suitable catalysts include mixtures of titanium and aluminum compounds as well as metallocenes.

[0177] By changing the polymerization conditions and the catalyst system, the number of branches, the crystallinity, and the density of the polyolefins can be varied over a wide range. These measures are also familiar to those skilled in the art.

[0178] The vinyl(co)polymer suitable as a thermoplastic polymer according to component C can be rubber-free or rubber-modified. Likewise, it can contain both rubber-modified vinyl(co)polymer and rubber-free vinyl(co)polymer, meaning vinyl(co)polymer that is not chemically bonded to or embedded in rubber.

[0179] The rubber-modified vinyl(co)polymer is preferably a graft polymer of

[0180] 20 to 95 wt.% of at least one vinyl monomer on

[0181] 5 to 80 wt.% of one or more rubber-like, preferably particulate, graft bases, preferably with glass transition temperatures < 10 °C, more preferably < 0 °C, particularly preferably < -20 °C, wherein the polymer chains formed from the vinyl monomers are, at least partially, chemically bonded to the surface of the graft base as a graft shell or are enclosed in the volume of the graft base in such a way that they are not lost during the production and processing of the inventive 2024PF30096-Ausland

[0182] - 23 -

[0183] The compositions do not leach from this graft base. Furthermore, due to the manufacturing process, the graft polymers may contain (co)polymers from the vinyl monomers that are neither covalently bound to the graft base nor enclosed within it (so-called "free" (co)polymer). This fraction of the free (co)polymer can be extracted in suitable solvents, such as toluene or acetone, and can therefore be quantified by gravimetric analysis of the soluble residue using a mass balance.

[0184] The glass transition temperature is determined by differential scanning calorimetry (DSC) according to DIN EN ISO 11357-1-6 (version of 2016) at a heating rate of 10 K / min with definition of Tg as the midpoint temperature (tangent method).

[0185] The preferred particulate graft bases generally have a mean particle size (d50 value) of 0.05 to 10 pm, preferably 0.1 to 5 pm, particularly preferably 0.2 to 1.5 pm.

[0186] The mean particle size d50 is the diameter above and below which 50 wt.% of the particles lie. It can be determined by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).

[0187] The vinyl monomers are preferably mixtures of

[0188] 50 to 99 wt.%, preferably 65 to 85 wt.%, preferably 70 to 80 wt.%, in each case based on the totality of the monomers of the graft shell, vinyl aromatics and / or nucleo-substituted vinyl aromatics (such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (meth)acrylic acid (Cl-C8) alkyl esters, such as methyl methacrylate, ethyl methacrylate and butyl acrylate, and

[0189] 1 to 50 wt.%, preferably 15 to 35 wt.%, particularly preferably 20 to 30 wt.%, each based on the totality of the monomers of the vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth)acrylic acid (Cl-C8) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl maleimide.

[0190] Preferred are mixtures of at least one of the monomers styrene, α-methylstyrene and methyl methacrylate with at least one of the monomers acrylonitrile, n-butyl acrylate, maleic anhydride and methyl methacrylate.

[0191] Particularly preferred are mixtures of styrene and acrylonitrile. Methyl methacrylate, or mixtures of methyl methacrylate and styrene, are also preferred.

[0192] Suitable graft bases for the graft polymers include, for example, diene rubbers, EP(D)M rubbers, i.e., those based on ethylene / propylene and possibly diene, acrylate, 2024PF30096-Abroad

[0193] - 24 -

[0194] Polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers, as well as silicone / acrylate composite rubbers.

[0195] Preferred graft bases are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers.

[0196] Pure polybutadiene rubber is particularly preferred as a grafting base.

[0197] Particularly preferred graft polymers are, for example, ABS polymers, as described in DE-OS 2 035 390 (=US PS 3 644 574) or in DE-OS 2 248 242 (=GB-PS 1 409 275) or in Ullmanns, Encyclopedia of Technical Chemistry, Vol. 19 (1980), p. 280 ff.

[0198] The graft copolymers are produced by radical polymerization, e.g. by emulsion, suspension, solution or bulk polymerization.

[0199] Rubber-free vinyl (co)polymers are (co)polymers of at least one vinyl monomer, preferably selected from the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth)acrylic acid (Cl to C8) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids.

[0200] (Co)polymers made from are particularly suitable

[0201] 50 to 99 wt.%, preferably 65 to 85 wt.%, particularly preferably 70 to 80 wt.%, based on the (co)polymer, of at least one monomer selected from the group of vinyl aromatics (such as styrene, α-methylstyrene), keme-substituted vinyl aromatics (such as p-methylstyrene, p-chlorostyrene) and (meth)acrylic acid (Cl-C8) alkyl esters (such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and

[0202] 1 to 50 wt.%, preferably 15 to 35 wt.%, particularly preferably 20 to 30 wt.%, based on the (co)polymer, of at least one monomer selected from the group of vinyl cyanides (such as unsaturated nitriles like acrylonitrile and methacrylonitrile), (meth)acrylic acid (Cl-C8) alkyl esters (such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate), unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids (for example, maleic anhydride and N-phenyl maleimide).

[0203] Suitable polymers also include amorphous and / or semi-crystalline polyamides. Suitable polyamides are, for example, aliphatic polyamides such as PA-6, PA-11, PA-12, PA-4.6, PA-4.8, PA-4.10, PA-4.12, PA-6.6, PA-6.9, PA-6.10, PA-6.12, PA-10.10, PA-12.12, PA-6 / 6.6-copolyamide, PA-6 / 12-copolyamide, PA-6 / 11-copolyamide, PA-6.6 / 11-copolyamide, PA-6.6 / 12-2024PF30096-Ausland

[0204] - 25 -

[0205] Copolyamide, PA-6 / 6,10-copolyamide, PA-6,6 / 6,10-copolyamide, PA-4,6 / 6-copolyamide, PA-6 / 6,6 / 6,10-terpolyamide, and copolyamide of 1,4-cyclohexanedicarboxylic acid and 2,2,4- and 2,4,4-trimethylhexamethylenediamine, aromatic polyamides, for example PA-6,1, PA-6,1 / 6,6-copolyamide, PA-6,T, PA-6,T / 6-copolyamide, PA-6,176,6-copolyamide, PA-6,1 / 6,T-copolyamide, PA-6,6 / 6,176,1-copolyamide, PA-6,T / 2-MPMDT-copolyamide (2-MPMDT = 2-

[0206] Methylpentamethylenediamine), PA-9,T, copolyamide of terephthalic acid, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, copolyamide of isophthalic acid, laurinlactam and 3,5-dimethyl-4,4-diaminodicyclohexylmethane, copolyamide of isophthalic acid, azelaic acid and / or sebacic acid and 4,4-diaminodicyclohexylmethane, copolyamide of caprolactam, isophthalic acid and / or terephthalic acid and 4,4-diaminodicyclohexylmethane, copolyamide of caprolactam, isophthalic acid and / or terephthalic acid and isophoronediamine, copolyamide of isophthalic acid and / or terephthalic acid and / or other aromatic or aliphatic dicarboxylic acids, optionally alkyl-substituted hexamethylenediamine and alkyl-substituted 4,4-diaminodicyclohexylamine or their copolyamides, and mixtures thereof The aforementioned polyamides. In a further embodiment of the present invention, semicrystalline polyamides are used as component C, which exhibit advantageous thermal properties.Semi-crystalline polyamides are used, which have a melting point of at least 200 °C, preferably at least 220 °C, more preferably at least 240 °C, and even more preferably at least 260 °C. The higher the melting point of the semi-crystalline polyamides, the more advantageous the thermal behavior of the compositions according to the invention. The melting point is determined by DSC.

[0207] Preferred semi-crystalline polyamides are selected from the group containing PA-6, PA-6, 6, PA-6, 10, PA-4,6, PA-11, PA-12, PA-12,12, PA-6,1, PA-6,T, PA-6,T / 6,6-copolyamide, PA-6,T / 6-copolyamide, PA-6 / 6,6-copolyamide, PA-6, 6 / 6, T / 6,1-copolyamide, PA-6,T / 2-MPMDT-copolyamide, PA-9,T, PA-4,6 / 6-copolyamide and their mixtures or copolyamides.

[0208] Other preferred semi-crystalline polyamides are PA-6,1, PA-6,T, PA-6, 6, PA-6,6 / 6T, PA- 6, 6 / 6, T / 6,1 -copolyamide, PA-6,T / 2-MPMDT-copolyamide, PA-9,T, PA-4,6 and their mixtures or copolyamides.

[0209] The component C used most preferably comprises a polycarbonate, more preferably an aromatic polycarbonate, more preferably an aromatic polycarbonate containing structural units derived from bisphenol-A, and more preferably an aromatic polycarbonate based exclusively on bisphenol-A as the diol component. Most preferably, the component C consists of the polycarbonate mentioned in this paragraph.

[0210] Furthermore, the component C used is preferably a mixture containing a first polymer selected from the group consisting of a polycarbonate, further preferably an aromatic 2024PF30096-Ausland

[0211] - 26 -

[0212] Polycarbonate, particularly preferably an aromatic polycarbonate containing structural units derived from bisphenol-A and most preferably an aromatic polycarbonate based exclusively on bisphenol-A as the diol component, and a second polymer selected from the group consisting of polyester carbonates, polyesters, vinyl (co)polymers, polyolefins, and olefin copolymers. Furthermore preferably, the component C used is a mixture consisting of a first polymer selected from the group consisting of a polycarbonate, more preferably an aromatic polycarbonate, particularly preferably an aromatic polycarbonate containing structural units derived from bisphenol-A and most preferably an aromatic polycarbonate based exclusively on bisphenol-A as the diol component, and a second polymer selected from the group consisting of polyester carbonates, polyesters, vinyl (co)polymers, polyolefins, and olefin copolymers.

[0213] Polymer additives (Component D)

[0214] In the composition according to the invention, one or more polymer additives can be used as component D, preferably selected from the group consisting of further flame retardants, flame retardant synergists, smoke inhibitors, lubricants and demolding agents, nucleating agents, conductivity additives, stabilizers (e.g. hydrolysis, heat aging and UV stabilizers as well as transesterification inhibitors), fillers and reinforcing agents as well as dyes and pigments.

[0215] In a preferred embodiment, at least one polymer additive selected from the group consisting of lubricants and demolding agents, stabilizers, dyes, and pigments is used. In a preferred embodiment, at least one stabilizer selected from the group consisting of sterically hindered phenols, organic phosphites, and sulfur-based co-stabilizers is used.

[0216] Production of molding compounds and molded parts

[0217] Thermoplastic molding compounds according to the invention can be produced from the compositions according to the invention, comprising the flame retardant preparation according to the invention or its components A and B, polymer according to component C, provided that this is thermoplastic, and optionally polymer additives according to component D.

[0218] The thermoplastic molding compounds can be produced, for example, by melting and mixing the respective components of the compositions in a known manner a) preferably at a temperature in the range of 100°C to 400°C, particularly preferably at 200°C to 350°C, and most preferably at 230°C to 300°C, and b) subsequently solidifying the composition by cooling the melt composition. 2024PF30096-Abroad

[0219] - 27 -

[0220] This process is preferably carried out in conventional units such as internal kneaders, extruders, and twin-screw extruders. This process is generally referred to as (melt) compounding or (melt) extrusion.

[0221] Thermoplastic molding compound is therefore understood to be the product that is obtained when the components of the thermoplastic composition are melt-compounded and melt-extruded.

[0222] The mixing of the individual components of the compositions can be carried out in a known manner, both successively and simultaneously, at approximately 20°C (room temperature) as well as at higher temperatures. This means, for example, that some of the components can be metered via the main feed of an extruder, while the remaining components can be added later in the compounding process via a side extruder.

[0223] The components of the flame retardant preparation can also be added separately to the compounding process during the production of the thermoplastic molding compounds according to the invention; i.e., it is not necessary to first produce a flame retardant preparation according to the invention from components A and B and add it to the compounding process as such.

[0224] Another object of the present invention is therefore a thermoplastic molding compound produced from a composition according to the invention containing the components A, B, thermoplastic polymer C and optionally D.

[0225] The molding compounds according to the invention can be used to produce molded bodies of any kind. These can be produced, for example, by injection molding, extrusion, and blow molding processes, and are a further aspect of the present invention. Another processing method is the production of molded bodies by deep drawing from previously produced sheets or films.

[0226] It is also possible to dose the components of the compositions directly into an injection molding machine or an extrusion unit and process them into molded bodies.

[0227] Examples of such molded bodies that can be produced from the inventive compositions and molding compounds are films, profiles, molded parts of all kinds, e.g. for the transport sector, especially the automotive industry, the electrical / electronics application area, the construction sector, for household appliances and medical technology.

[0228] Such shaped bodies are also an object of the present invention.

[0229] Further embodiments of the present invention are described below: 2024PF30096-Abroad

[0230] - 28 -

[0231] 1. Flame retardant preparation containing

[0232] A) a cyclic phosphazene according to formula (1)

[0233] (1)

[0234] R are the same or different and each for

[0235] - CI - to C8 alkyl, preferably methyl, ethyl, propyl or butyl,

[0236] - CI - to C8- Alkoxy, preferably Methoxy, Ethoxy, Propoxy or Butoxy,

[0237] - optionally substituted by alkyl, preferably Cl-C4-alkyl, C5- to C6-cycloalkyl,

[0238] - optionally by alkyl, preferably Cl-C4-alkyl and / or hydroxy-substituted, C6- to C20-aryloxy, preferably phenoxy, naphthyloxy,

[0239] - optionally substituted by alkyl, preferably Cl-C4-alkyl, C7- to C12-aralkyl, preferably phenyl-Cl-C4-alkyl, or

[0240] - an OH residue and k represents 0 or an integer from 1 to 15, preferably a number from 1 to 10, B) a polymer containing structural units containing Bronsted acid groups, wherein the content of structural units containing Bronsted acid groups in component B is at least 50 wt. % and wherein at least some of the Bronsted acid groups are deprotonated.

[0241] 2. Flame retardant preparation according to embodiment 1, characterized in that all residues R in component A are the same.

[0242] 3. Flame retardant preparation according to embodiment 2, characterized in that all residues R in component A are phenoxy residues.

[0243] 4. Flame retardant preparation according to one of the embodiments 1 to 3, characterized in that the trimerene content (k=l) is 60 to 100 mol-%, based on component A.

[0244] 5. Flame retardant preparation according to one of the preceding embodiments, characterized in that component B contains carboxyl groups, wherein at least some of the carboxyl groups are deprotonated.

[0245] 6. Flame retardant preparation according to one of the preceding embodiments, characterized in that component B contains structural units derived from a monomer 2024PF30096-Abroad

[0246] - 29 - selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, wherein at least part of the Bronsted acidic groups are deprotonated.

[0247] 7. Flame retardant preparation according to one of the preceding embodiments, characterized in that component B contains a sodium salt of a carboxyl group.

[0248] 8. Flame retardant preparation according to one of the preceding embodiments, characterized in that component B contains or consists of polyacrylic acid and / or polymethacrylic acid, wherein at least a part of the Bronsted acidic groups are deprotonated in each case.

[0249] 9. Flame retardant preparation according to one of the preceding embodiments, characterized in that component B contains or consists of a sodium salt of polyacrylic acid or polymethacrylic acid.

[0250] 10. Flame retardant preparation comprising one of the preceding formulations

[0251] 60 to 99.5 parts by weight, based on a total of 100 parts by weight of components A and B, of component A and

[0252] 0.5 to 40 parts by weight, based on a total of 100 parts by weight of components A and B, of component B.

[0253] 11. Flame retardant preparation comprising one of the preceding formulations

[0254] 80 to 98 parts by weight, based on a total of 100 parts by weight of components A and B, of component A and

[0255] 2 to 20 parts by weight, each based on a total of 100 parts by weight of components A and B, of component B.

[0256] 12. Flame retardant preparation according to one of the preceding embodiments, characterized in that neither component A nor component B intentionally contains halogen.

[0257] 13. Composition comprising a flame retardant preparation or its components according to any of the preceding embodiments and at least one polymer according to component C.

[0258] 14. Composition according to formulation 13, comprising a total of 1 to 40 parts by weight of components A and B and 60 to 99 parts by weight of component C, each based on a total of 100 parts by weight of components A to C.

[0259] 15. Composition according to formulation 13, comprising a total of 3 to 30 parts by weight of components A and B and 70 to 97 parts by weight of component C, each based on a total of 100 parts by weight of components A to C.

[0260] 16. Composition according to version 13, containing a total of 5 to 20 parts by weight of components A and B and 80 to 95 parts by weight of component C, each based on a total of 100 parts by weight of components A to C. 2024PF30096-Foreign

[0261] - 30 -

[0262] 17. Composition according to one of the embodiments 13 to 16, containing components A and B in the proportions specified in one of the embodiments 10 and 11.

[0263] 18. Composition according to one of the embodiments 13 to 17, wherein the polymer according to component C is a thermoplastic polymer.

[0264] 19. Composition according to embodiment 18, characterized in that the thermoplastic polymer according to component C is selected from the group consisting of polycarbonates, polyester carbonates, polyesters, polyolefins, vinyl(co)polymers and polyamides as well as mixtures thereof.

[0265] 20. Composition according to embodiment 19, characterized in that the thermoplastic polymer according to component C is selected from the group consisting of polycarbonates, polyester carbonates and polyesters.

[0266] 21. Composition according to one of the embodiments 13 to 20, characterized in that the composition contains as component D 0.01 to 30 parts by weight, based on a total of 100 parts by weight of components A to C, at least one polymer additive different from components A to C.

[0267] 22. Composition according to implementation form 21, consisting of components A to D.

[0268] 23. Composition according to one of the embodiments 13 to 22, characterized in that the composition is free of polyfluorinated alkyl substances (PFAS).

[0269] 24. Composition according to one of the embodiments 13 to 23, characterized in that the composition is free of intentionally halogen-containing components.

[0270] 25. Use of a flame retardant preparation containing

[0271] A) a cyclic phosphazene according to formula (1) where

[0272] R are the same or different and each for

[0273] - CI - to C8 alkyl, preferably methyl, ethyl, propyl or butyl,

[0274] - CI - to C8- Alkoxy, preferably Methoxy, Ethoxy, Propoxy or Butoxy,

[0275] - optionally substituted by alkyl, preferably Cl-C4-alkyl, C5- to C6-cyclo-alkyl,

[0276] - optionally by alkyl, preferably Cl-C4-alkyl and / or hydroxy-substituted, C6- to C20-aryloxy, preferably phenoxy, naphthyloxy, 2024PF30096-Abroad

[0277] - 31 -

[0278] - optionally substituted by alkyl, preferably Cl-C4-alkyl, C7- to C12-aralkyl, preferably phenyl-Cl-C4-alkyl, or

[0279] - an OH residue and k represents 0 or an integer from 1 to 15, preferably a number from 1 to 10

[0280] B) a polymer containing structural units containing Bronsted acid groups, wherein the content of structural units containing Bronsted acid groups in component B is at least 50 wt.% and wherein at least some of the Bronsted acid groups are deprotonated, for reducing the burning dripping of a polymer in a flame retardancy test.

[0281] 26. Use according to embodiment 25, wherein the polymer is a thermoplastic polymer selected from the group consisting of polycarbonates, polyester carbonates, polyesters, polyolefins, vinyl(co)polymers and polyamides, as well as mixtures thereof.

[0282] 27. Use according to one of embodiments 25 or 26, wherein a flame retardant preparation according to one of embodiments 2 to 12 is used.

[0283] 28. Use in accordance with one of the embodiments 25 to 27, wherein the flame retardant preparation is used in a flame retardant test according to UL94 V, achieving a rating of V1 or V-0 with a test specimen thickness of 3.2 mm or with a test specimen thickness less than 3.2 mm.

[0284] 29. Thermoplastic molding compound produced from a composition according to one of embodiments 13 to 24.

[0285] 30. Molded body containing a composition according to one of embodiments 13 to 24 or obtained from a thermoplastic molding compound according to embodiment 29.

[0286] Examples

[0287] Composition of the flame retardant mixture

[0288] Component Al (not according to the invention)

[0289] Ammonium polyphosphate with an acid number of 1 mg KOH / g determined according to ISO 2114, a water solubility of 0.4% (25 °C, 10% suspension, gravimetry after filtration) and a particle size of < 100 pm (Exolit AP 422, Clariant, Germany).

[0290] Component A-2 (according to design):

[0291] Phenoxycyclophosphazene of formula (2) with a proportion of oligomers with k = 1 of 70 mol%, a proportion of oligomers with k = 2 of 18 mol%, and a proportion of oligomers with k > 3 of 12 mol% (Rabitle™ FP 110, Fushimi, Japan). 2024PF30096-Abroad

[0292] Bl (not according to the invention)

[0293] Polyacrylic acid with an average molecular weight of approximately 450,000 g / mol (M v ) (CAS No. 9003-01-4, Polyacrylic acid, Sigma Aldrich, Germany).

[0294] B-2 (according to the invention)

[0295] Polyacrylic acid Na salt with an average molecular weight of approximately 5,100 g / mol (Mw ) (CAS No. 9003-04-7, Poly(acrylic acid sodium salt), Sigma Aldrich, Germany).

[0296] B-3 (according to the invention)

[0297] Polyacrylic acid (partially cross-linked sodium salt)

[0298] (CAS No. 76774-25-9, Poly(acrylic acid) partial sodium salt, copolymer consisting of 2-propenoic acid sodium salt trimethylolpropane triacrylate, Sigma Aldrich, Germany).

[0299] B-4 (according to the invention)

[0300] Poly(4-styrenesulfonic acid-co-maleic acid) ratio of styrenesulfonic acid to maleic acid 1:1, partial sodium salt, with an average molecular weight of 20,000 g / mol (M w ) (CAS No. 68037-40-1, Poly(4-styrenesulfonic acid-co-maleic acid) sodium salt, Sigma Aldrich, Germany).

[0301] B-5 (according to the invention)

[0302] Masterbatch of a partially sodium-deprotonated polyacrylic acid and polyethylene in a ratio of approximately 1:1 (determined by FTIR) with a sodium content of 4.3% (determined by ICP-OES)

[0303] (Paxymer™ BGMB62, Paxymer AB, Sweden).

[0304] B-6 (according to the invention)

[0305] Polyaspartic acid sodium salt (CAS No. 181828-06-8), BLD Pharmatech GmbH, Germany). 2024PF30096-Abroad

[0306] - 33 -

[0307] B-7 (according to the invention) Carboxymethylcellulose sodium salt, (CAS No. 9004-32-4, Sodium carboxymethylcellulose sodium salt, Sigma Aldrich, Germany).

[0308] Thermoplastic polymer Cl

[0309] Linear polycarbonate based on bisphenol-A with a weight-averaged molecular weight M w of 25,000 g / mol (determined by GPC in methylene chloride as solvent against a bisphenol A polycarbonate standard at room temperature).

[0310] Thermoplastic polymer C-2

[0311] Linear polycarbonate based on bisphenol-A with a weight-averaged molecular weight M w of 31,000 g / mol (determined by GPC in methylene chloride as solvent against a bisphenol A polycarbonate standard at room temperature).

[0312] Thermoplastic polymer C-3

[0313] Linear polycarbonate based on bisphenol-A with a weight-averaged molecular weight M w of 28,000 g / mol (determined by GPC in methylene chloride as solvent against a bisphenol A polycarbonate standard at room temperature).

[0314] Thermoplastic polymer C-4

[0315] Polymethacrylmethylimide copolymer from Röhm GmbH (Pleximid® 8803) with a softening temperature (VST / B 50; ISO 306:2013) of 130°C. Acid value: 22.5 mg KOH / g, determined according to DIN 53240-1:2013-06. MMI (methyl methacrylimide) content: 36.8 wt%, MMA (methyl methacrylate) content: 51.7 wt%, MMS (methyl methacrylic acid) + MMAH (methyl methacrylic anhydride) content: 11.5 wt%, each based on the total weight of PMMI and determined by quantitative λ-NMR spectroscopy.

[0316] Thermoplastic polymer C-5

[0317] Lotryl™ 24MA02T (SK Functional Polymer, France) is an ethylene-methyl acrylate copolymer with a methyl acrylate-derived structural unit content of 24 wt% and a melt flow rate of 2 g / 10 min at 190 °C and 2.16 kg measured according to ISO 1133-1 (version 2012-03). Component B3 has a melting point of 95 °C, measured by differential scanning calorimetry (DSC). Component C-5 is produced in a tubular reactor. 2024PF30096-Abroad

[0318] - 34 -

[0319] Thermoplastic polymer C-6

[0320] Lotryl™ 24MA07T Acrylate Copolymer (SK Functional Polymer, France) is an ethylene-methyl acrylate copolymer with a methyl acrylate-derived structural unit content of 24% by weight and a melt flow rate of 7 g / 10 min at 190 °C and 2.16 kg measured according to DIN EN ISO 1133-1 (version 2022-10). Component B6 has a melting point of 97 °C, measured by differential scanning calorimetry (DSC). Component C-6 is produced in a tubular reactor.

[0321] Thermoplastic polymer C-7

[0322] Plexiglas™ 8H (Evonik Performance Materials GmbH, Darmstadt), polymethyl methacrylate

[0323] DL

[0324] Mold release agent. Pentaerythritol tetrastearate, commercially available as Loxiol VPG 861 from Emery Oleochemicals Group.

[0325] D-2

[0326] Irganox B900 Antioxidant. Irganox™ B900 from BASF (mixture of Irgafos™ 168 (tris-(2,4-di-tert-butylphenyl) phosphite) and Irganox™ 1076 (octadecyl-3-(3,5-di-tert-butyl-4-10 hydroxyphenyl) propionate) in a wt. ratio of 4:1)

[0327] Production of thermoplastic molding compounds and molded parts

[0328] The thermoplastic compositions listed in Table 1 were used to produce molding compounds on a Coperion GmbH ZSK26 MC 18 twin-shaft extruder (Stuttgart, Germany) at a melt temperature of approximately 260°C at the die exit. A vacuum of 100 mbar (absolute) was applied. The residence time of the melt mixture in the extruder was approximately 30 s.

[0329] The test specimens were produced on an Arburg 270 E injection molding machine at a melt temperature of 260°C and a tool temperature of 80°C.

[0330] Inspection of the molded parts produced from the molding compounds

[0331] To determine the content of free bisphenol A (abbreviated as [BPA]), the granules produced in the extruder were dissolved in dichloromethane and precipitated with acetone. The precipitated polymer fraction was filtered off, and the filtrate was analyzed by high-performance liquid chromatography with a UV detector (HPLC-UV) using an external standard. A C18 phase was used as the column material, and water and methanol in a gradient were used as the eluents. 2024PF30096-Abroad

[0332] - 35 -

[0333] The change in melt flow rate (MVR) after storing the granules for one day at 95°C and 100% relative humidity (or for seven days at 95°C and 100% relative humidity for examples V8 and 9) serves as a measure of hydrolysis resistance. The MVR is determined according to ISO 1133 (2012 version) at 240°C (or 260°C for examples V8 and 9) on the extruded granules using a ram load of 2.16 kg (or 5 kg for examples V8 and 9).

[0334] Flame retardancy is assessed according to UL94V on rods measuring 127 x 12.7 x 3.0 mm. The evaluation focused on whether at least one of the five rods produced per molding compound exhibited burning dripping. Only if no burning dripping was observed on any of the rods was compliance with the flame retardancy requirement ensured.

[0335] The toughness was determined at room temperature on test specimens with dimensions of 60 mm x 60 mm x 2 mm in the puncture test according to ISO 6603-2 (version of April 2002) and the puncture energy was measured in J.

[0336] 2024PF30096-Abroad

[0337] - 36 -

[0338] Table 1: Polymer compositions and their properties; all quantities are given as

[0339] Weight parts

[0340] 2024P30096

[0341] - 37 -

[0342] The data in Table 1 show that the inventive component A-2 (inventive example 3) achieves better dripping behavior in the UL94V test than the prior art component Al (examples VI and V2). Furthermore, the composition containing the inventive component A-2 in a combination of component Bl and component B-2 (example 3) achieves higher penetration energies than compositions containing component Al (examples VI and V2). However, if the Brønsted acid groups in component B are not at least partially deprotonated (component Bl), burning dripping is observed, and thus the flame retardancy requirement is not met.The data on the MVR before and after hydrolysis, as well as the free BPA content, further show that component A-2, compared to component Al, makes the composition less sensitive to hydrolytic degradation due to storage under high humidity combined with thermal exposure, as well as due to residual moisture under compounding conditions. Examples 5 and 6 of the invention show that both a fully deprotonated component B-2 and a partially deprotonated, partially crosslinked component B-3 fulfill the requirement. Example 7 of the invention shows that a copolymer consisting of styrenesulfonic acid and maleic acid (component B-4) partially deprotonated with a cation-containing base (sodium hydroxide) also fulfills the requirement.Example 9 according to the invention shows that a masterbatch of a partially deprotonated polyacrylic acid with polyethylene as component B-5 also fulfills the objective and that the molding compounds equipped with such a masterbatch to be flame-retardant exhibit small differences in the MVR measurements before and after hydrolysis even under higher thermal stress and higher stamping load, i.e., improved hydrolysis resistance.

[0343] 2024PF30096-Abroad

[0344] - 38 -

[0345] Table 2: Polymer compositions and their properties; all quantities are given as

[0346] Weight parts

[0347] The data in Table 2 show that compositions containing other thermoplastic polymers also do not exhibit burning dripping in the flame retardant test when the flame retardant preparation according to the invention is added (Examples 11, 14, 15 and 16). If component B is missing, as in V10 or VI 3, burning dripping is observed, just as with the absence of component A (VI 2). Examples 17 and 18 according to the invention show further components B.

Claims

1. 2024PF30096-Abroad Patent claims 1. Flame retardant preparation containing A) a cyclic phosphazene according to formula (1) (1) R are the same or different and each for - CI - to C8 alkyl, preferably methyl, ethyl, propyl or butyl, - CI - to C8- Alkoxy, preferably Methoxy, Ethoxy, Propoxy or Butoxy, - optionally substituted by alkyl, preferably Cl-C4-alkyl, C5- to C6-cyclo-alkyl, - optionally by alkyl, preferably Cl-C4-alkyl and / or hydroxy-substituted, C6- to C20-aryloxy, preferably phenoxy, naphthyloxy, - optionally substituted by alkyl, preferably Cl-C4-alkyl, C7- to C12- Aralkyl, preferably phenyl-Cl-C4-alkyl, or - an OH residue and k represents 0 or an integer from 1 to 15, preferably a number from 1 to 10, B) a polymer containing structural units containing Bronsted acid groups, wherein the content of structural units containing Bronsted acid groups in component B is at least 50 wt. % and wherein at least some of the Bronsted acid groups are deprotonated.

2. Flame retardant preparation according to claim 1, characterized in that all residues R in component A are phenoxy residues.

3. Flame retardant preparation according to one of the preceding claims, characterized in that component B contains carboxyl groups, wherein at least a part of the carboxyl groups are deprotonated.

4. Flame retardant preparation according to one of the preceding claims, characterized in that component B contains structural units derived from a monomer 2024PF30096-Abroad - 40 - selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, wherein at least some of the Bronsted acidic groups are deprotonated.

5. Flame retardant preparation according to one of the preceding claims, characterized in that component B is a polymer selected from the group consisting of polyacrylic acid and polymethacrylic acid, wherein at least a part of the Bronsted acidic groups are deprotonated, as well as mixtures of the two compounds.

6. Flame retardant preparation according to any one of the preceding claims comprising 60 to 99.5 parts by weight, based on a total of 100 parts by weight of components A and B, of component A and 0.5 to 40 parts by weight, based on a total of 100 parts by weight of components A and B, of component B.

7. Composition comprising a flame retardant preparation or its components, each according to at least one feature specified in claims 1 to 5, and at least one polymer according to component C.

8. Composition according to claim 9, comprising a total of 1 to 40 parts by weight of components A and B and 60 to 99 parts by weight of component C, each based on a total of 100 parts by weight of components A to C.

9. Composition according to one of claims 7 or 8, comprising components A and B in the proportions specified in claim 6.

10. Composition according to one of claims 7 to 9, characterized in that component C is a thermoplastic polymer selected from the group consisting of polycarbonates, polyester carbonates, polyesters, polyolefins, vinyl(co)polymers and polyamides as well as mixtures thereof.

11. Composition according to any one of claims 7 to 10, further comprising as component D 0.01 to 30 parts by weight, based on a total of 100 parts by weight of components A to C, at least one polymer additive different from components A to C.

12. Composition according to one of the preceding claims, characterized in that the composition is free of polyfluorinated alkyl substances. 2024PF30096-Abroad 13. Use of a flame retardant preparation containing A) a cyclic phosphazene according to formula (1) (1) R are the same or different and each for - CI - to C8 alkyl, preferably methyl, ethyl, propyl or butyl, - CI - to C8- Alkoxy, preferably Methoxy, Ethoxy, Propoxy or Butoxy, - optionally substituted by alkyl, preferably Cl-C4-alkyl, C5- to C6-cycloalkyl, - optionally by alkyl, preferably Cl-C4-alkyl and / or hydroxy-substituted, C6- to C20-aryloxy, preferably phenoxy, naphthyloxy, - optionally substituted by alkyl, preferably Cl-C4-alkyl, C7- to C12-aralkyl, preferably phenyl-Cl-C4-alkyl, or - an OH residue and k represents 0 or an integer from 1 to 15, preferably a number from 1 to 10, B) a polymer containing structural units containing Bronsted acid groups, wherein the content of structural units containing Bronsted acid groups in component B is at least 50 wt.% and wherein at least some of the Bronsted acid groups are deprotonated, for reducing the burning dripping of a polymer in a flame retardancy test.

14. Thermoplastic molding compound made from a composition according to any one of claims 7 to 12.

15. Molded body comprising a composition according to any one of claims 7 to 12 or obtained from a thermoplastic molding compound according to claim 14.

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