Method for producing a phosphorus-containing polymer, phosphorus-containing polymer, plastic composition, molded part, and uses of the phosphorus-containing polymer

Abstract

Polyamides are known for their very good mechanical properties, thermal stability and media resistance and are therefore used as an important technical plastic in many fields. The processing thereof to fibers via the melt spinning process or to filaments by extrusion constitutes an essential processing step in the textile industry and 3D printing. Like most plastics, polyamides are also readily combustible materials, and therefore their applicability in fire-sensitive areas is limited. It is therefore necessary for technical textiles to be rendered flame-retardant. A proven strategy for this purpose is the aftertreatment of the textiles in a coating or impregnation step in which the flame retardant is applied.

Description

[0001] A process for producing a phosphorus-containing polymer, a phosphorus-containing polymer, a plastic composition, a molded part, and uses of the phosphorus-containing polymer. Polyamides are known for their excellent mechanical properties, thermal stability, and media resistance, making them an important engineering plastic in many areas. Their processing into fibers via melt spinning or into filaments via extrusion represents an essential processing step in the textile industry and 3D printing. Like most plastics, polyamides are highly flammable materials, which limits their use in fire-sensitive areas. Therefore, technical textiles require flame-retardant treatment. A proven strategy for this is the post-treatment of the textiles in a coating or impregnation step, in which the flame retardant is applied.

[0002] The disadvantage here is that the long-term effectiveness of the FR is reduced due to leaching and abrasion. Such behavior is described, for example, by AR Horrocks in Polymer Degradation and Stability, 1996, 54. Furthermore, the additional processing step increases the product's cost. Furthermore, the sealing of the textile surface limits breathability.

[0003] To overcome these disadvantages, the incorporation of a flame retardant in the form of an additive into the polymer is more advantageous because this allows intrinsically flame-retardant fibers and filaments to be obtained that do not require any further post-treatment step.

[0004] However, this approach presents its own challenges. Since the flame retardant is melt-processed together with the polyamide, it must withstand high processing temperatures, which can be around 300°C and above. Melt spinning and filament extrusion are also processes that are very sensitive to changes in melt viscosity, and the presence of the additive in particulate form in the melt can significantly disrupt the process.

[0005] These challenges of the melt spinning process are described in publications and books, such as AR Horrocks in "Flame retardant challenges for textiles and fibers: new chemistry versus innovatory solutions." Polymer Degradation and Stability 2011, 96, and H.-G. Elias "Makromoleküle" (Macromolecules), Wiley-VCH: Weinheim, 1999.

[0006] Most flame retardants suitable for polyamides are inmeltable and insoluble solids in the polyamide, present as particles. During melt spinning, these particles can lead to filament breakage and create a rough fiber surface. Polymeric flame retardants, which can be melted and processed together with the polyamide, avoid these disadvantages. For this to happen, the melting or softening temperature of the polymeric flame retardant must be below the processing temperature of the polyamide.

[0007] However, the addition of such polymeric flame retardants can affect the melt viscosity of the polymer, resulting in the inability to spin filaments, and the inability to achieve the necessary textile mechanical properties or the required fire properties. A polymeric flame retardant suitable for the melt spinning process would therefore need to be individually adapted to the respective melt spinning process with regard to its properties, such as melt viscosity, melting or softening temperature, or thermal stability. These adaptations could be achieved, for example, by deliberately varying the average molecular weight or by using different monomers.

[0008] Detailed requirements for flame retardant additives for use in polyamide can be found in numerous review articles and book chapters, such as Weil, ED; Levchik, S. Current Practice and Recent Commercial Developments in Flame Retardancy of Polyamides. Journal of Fire Sciences 2004, 22, 251-264 and Babu, K.; Das, O.; Shanmugam, V.; Mensah, RA; Försth, M.; Sas, G.; Restäs, Ä.; Berto, F. Fire Behavior of 3D-Printed Polymer Composites. J. of Mate ri Eng and Perform 2021, 30, 4745.

[0009] A polymeric flame retardant for polyamides is described, for example, in EP 2 144 950 B1. This patent claims the synthesis of a phosphorus-containing polyester that can be used as a flame retardant for polyamides.

[0010] EP 2 597 179 B1 describes the use of such a phosphorus-containing polyester as a flame retardant for polyamide fibers. The addition of this flame retardant to pure polyamide 6,6 leads to reduced textile mechanical properties. If this flame retardant is added to pure polyamide 6, the flame tests are not passed. The problem was solved in EP 2 259 7179 B1 by using a blend of polyamide 6 and polyamide 6,6 as the polymer matrix. In this way, satisfactory textile mechanical properties were achieved while simultaneously providing sufficient flame protection.

[0011] Copolymers of (10-oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl) methyl methacrylate (R1=methyl, R2=CH2, R3=R4=aryl, m=0, DOPO-MMA) and (10-oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl) methyl methacrylate (R1=H, R2=CH2, R3=R4=aryl, m=0, DOPO-MA) are described, for example, in JP2011237643A, US20140187688A1 and US201500054410A1 as well as by L. Yan, YB Zheng, X. Liang, and Q. Ma in J. Appl. Polym. Sci. 2010, 115, 1032-1038, or by S. Jiang, Y. Zhu, Y. Hu, G. Chen, X. Shi and X. Qian, in Polym. Adv. Technol. 2016, 27, 266-272.

[0012] The described processes for producing the copolymers involve exclusively free radical polymerizations. The monomers are heated together with a radical initiator or irradiated in the presence of a photoinitiator.

[0013] Of the monomers DOPO-MMA and DOPO-MA, only copolymers are described. US20140187688A1 describes the synthesis of copolymers by free radical polymerization using a chain transfer agent, which is intended to reduce the molecular weight of the product and increase temperature resistance. The application of these polymers and monomers is mainly limited to use as flame-retardant starting materials for optical lenses, flame-retardant resin formulations, flame-retardant coating materials for films, or UV-curable coating materials where meltability of the flame retardant is not required.

[0014] Homopolymers of monomers of the general structural formula 1 tend to gel during polymerization and thus become insoluble and infusible and are therefore not suitable for use as flame retardants for polyamide fibers.

[0015] The formation of insoluble polymers during the free radical polymerization of acrylates containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is described in Bier, F.; Six, J.-L.; Durand, A. DOPO-Based Phosphorus-Containing Methacrylic (Co)Polymers: Glass Transition Temperature Investigation. Macromol. Mater. Eng. 2019, 304. No information is provided regarding thermal stability.

[0016] The object of the present invention is therefore to provide a polymeric flame retardant additive that is equally suitable for various plastics, such as polyamides, in particular for pure polyamide 6 and pure polyamide 6,6. The polymeric flame retardant should be characterized by good processability, in particular good solubility, as well as good thermoplastic processability. Furthermore, the object of the invention is to provide a production process for polymers with which structural parameters, such as molecular weight and composition, can be varied within wider ranges than in a polycondensation process, which was used to produce the above-mentioned phosphorus-containing polyesters.In particular, it was an object of the present invention to provide the homopolymer and a process for the preparation of homopolymers of the monomers having the general structural formula 1 with a monomodal molecular weight distribution, which is largely free from crosslinking reactions or does not exhibit gelling during polymerisation, has the highest possible phosphorus content and is thermally stable as the end product, but at the same time has good solubility and thermoplastic properties, i.e. does not gel during polymerisation.

[0017] This object is achieved with regard to a method for producing a phosphorus-containing polymer having the features of patent claim 1, with regard to a phosphorus-containing polymer having the features of patent claim 14, with regard to a plastic composition having the features of patent claim 20, with a molded part according to patent claim 23, and with possible uses of the phosphorus-containing polymer according to patent claim 24. The respective dependent patent claims represent advantageous developments.

[0018] The present invention thus relates, in a first aspect, to a process for producing a phosphorus-containing polymer by means of a RAFT (Reversible Addition-Fragmentation Chain Transfer) polymerization reaction comprising the following steps: a) Providing at least one monomer A of the general formula I capable of radical polymerization

[0019] Formula I where

[0020] Ri is selected from the group consisting of hydrogen, methyl, ethyl or a linear or branched C3 or C4 alkyl group,

[0021] R2 is selected from the group consisting of linear or branched substituted or unsubstituted hydrocarbon groups comprising 1-20 carbon atoms,

[0022] R3 and R4 are the same or different at each occurrence and are selected from the group consisting of substituted or unsubstituted cyclic hydrocarbon groups having 6-20 carbon atoms, m is an integer selected from the group consisting of 0, 1, 2, or 3, or a mixture containing at least two different monomers A of the general formula I capable of radical polymerization or at least one monomer A of the general formula I capable of radical polymerization and at least one further monomer different from the monomer A capable of radical polymerization, b) adding at least one initiator B which starts the polymerization by releasing at least one radical, c) adding at least one agent C which is capable of reversibly transferring an organic radical to an adduct radical formed from the monomers A during the polymerization reaction,d) initiating the polymerization reaction, wherein step c) occurs before, simultaneously or after step b) or simultaneously or after step d).

[0023] Surprisingly, it was found that the method of producing the phosphorus-containing polymer has a significant influence on its solubility and thermoplastic processability. While the prior art homopolymers produced by free radical polymerization are insoluble in common organic solvents, exhibit low thermal stability, and are not thermoplastically processable, it was surprisingly found that the phosphorus-containing polymers produced by RAFT polymerization do not exhibit these disadvantages.

[0024] The polymers produced by the process according to the invention can generally be used in polymer compounds where a high phosphorus content is required. Suitable polymer matrices include thermoplastics such as polyamide 6.6, polyamide 6, polyamide 11, polyacrylate, polymethacrylate, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polycarbonate.

[0025] The polymer offers the greatest advantage in applications involving polyamide compounds, where the processing process is very sensitive to melt viscosity, making this an exclusion criterion for the corresponding additive. Furthermore, the polymer offers advantages as an additive for all polyamide applications where agglomeration within the melt can be avoided. This is particularly true for processing methods that require long service life with minimal downtime.

[0026] Important technical polyamide applications with high sensitivity to melt viscosity and requiring long equipment service life include melt spinning and 3D printing. Preferred end uses include airbag fabrics, protective clothing, upholstery covers, curtains, and carpets.

[0027] RAFT polymerization is sufficiently described in the prior art and known to those skilled in the art. RAFT polymerization is particularly suitable for the preparation of polymers based on methacrylates and acrylates with a defined, adjustable molar mass and a narrow molar mass distribution. Controlled radical polymerizations, which include RAFT polymerization, are described in publications and books, such as AHE Müller, K. Matyjaszewski, "Controlled and Living Polymerizations," Wiley VCH, 2009. Other polymerization techniques for producing polymers with a defined, adjustable molar mass and a narrow molar mass distribution include anionic and cationic-initiated polymerization and controlled radical polymerization using ATRP (Atom Transfer Radical Polymerization) or NMP (Nitroxide-Mediated Polymerization).The listed methods for the preparation of polymers with defined molecular weight distributions by controlled radical polymerization have not yet been described for the polymerization of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) based polymeric FRs.

[0028] Reversible addition-fragmentation chain-transfer polymerization (RAFT) is a suitable method for preparing polymers with a monomodal molecular weight distribution and, above all, a significantly more defined average molecular weight than that obtainable with free radical polymerization. In particular, a thiol compound of the general structural formula 2 is used as a component of the initiator system, where Z is a radical R, OR1, N(R2)2, SR3, or P(O)(OR4)2. R is a substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, or substituted or unsubstituted aryl radical. RI, R2, R3 and R4 are substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C6-C10 aryl, 3-8 membered cyclic or heterocyclic rings or N(R2)2 is a 3-8 membered heterocyclic ring.Y is a leaving group that forms a free radical and can add monomers via a radical mechanism. Y can be a substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted alkyl acid ester. The compound with the general structural formula 2 is also called a RAFT reagent and is used in combination with a radical generator. The radical generator decomposes, for example, upon increasing temperature or irradiation, and initiates polymerization. The RAFT reagent adds to the radical end of a growing polymer chain, thereby cleaving off the leaving group Y as a radical. The RAFT reagent, which has been added to the growing polymer chain, forms a dithioester or trithiocarbonate group at the chain end.This temporarily inactivates the polymer chain and prevents it from growing further until it encounters another radical, which allows the growing polymer chain to be released again and attach further monomers to its radical end. Alternatively, the dithioester or trithiocarbonate group can also be homolytically cleaved at elevated temperatures. The application of RAFT polymerization in connection with monomers of general structural formula 1 has not been described in the literature.

[0029] According to a preferred embodiment, the monomer A is selected from the group consisting of

[0030] 10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)methyl methacrylate

[0031] (Ri=methyl, R2=CH2, R3=R4=aryl, m=0, DOPO-MMA)

[0032] (10-oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)methyl acrylate (Ri=H, R2=CH2, R3=R4=aryl, m=0, DOPO-MA)

[0033] 10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)ethylmethacrylat (Ri=Methyl, R2=(CH2)2, R3=R4=Aryl, m=0, DOPO-EMA)

[0034] (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)ethylacrylat (Ri=H, R2=(CH2)2, R3=R4=Aryl, m=0, DOPO-EA)

[0035] 10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)propylmethacrylat

[0036] (Ri=Methyl, R2=(CH2)3, R3=R4=Aryl, m=0, DOPO-PMA)

[0037] (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)propylacrylat (R1=H, R2=(CH2)3, R3=R4=Aryl, m=0, DOPO-PA)

[0038] 10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)butylmethacrylat (Ri=Methyl, R2=(CH2)4, R3=R4=Aryl, m=0, DOPO-BMA) und

[0039] (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)butylacrylat (Ri=H, R2=(CH2)4, R3=R4=Aryl, m=0, DOPO-BA). Insbesondere sind die Monomere DOPO-MMA und DOPO-MA bevorzugt.

[0040] A further preferred embodiment provides that the agent C has the following general formula II

[0041] Formula II where

[0042] Y is a radical selected from the group consisting of cyano-i-propyl, l-phenylethyl, t-butyl, 4-cyanopentyl-5-carboxylic acid, phenyl, cyanoalkyl, benzyl, butyl-2-methylpropanoate, methyl-2-propanoate,

[0043] Z is a radical R selected from the group consisting of linear or branched and substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl or substituted or unsubstituted aryl radicals, OR5, N(R6)2, SR7 and P(O)(OR8)2, where each of R5, R6, R7 and R8 independently of one another are linear or branched substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C6-C10 aryl, 3-8 membered cyclic or heterocyclic rings, or N(R6)2 is a 3-8 membered heterocyclic ring; in particular methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, neopentyl, dodecyl, methylsulfanyl, ethylsulfanyl, n-propylsulfanyl, i-propylsulfanyl, n-butylsulfanyl, i-butylsulfanyl, t-butylsulfanyl, Neopentylsulfanyl, dodecylsulfanyl, particularly preferably dodecylsulfanyl.

[0044] Agent C can also be referred to as the "RAFT reagent."

[0045] The RAFT reagent with the general structural formula 2 differs from the chain transfer agent described in US20140187688A1 in that it adds to the radical chain end of a growing polymer chain, thus forming a "dormant" species that can continue to grow through reactivation, while the second polymer chain now represents a dormant species. The RAFT reagent is thus transferred from one polymer chain to another. After the transfer reaction, the polymer chain is able to continue to grow.

[0046] The chain transfer agent described in US20140187688A1, on the other hand, does not undergo the transfer itself, but rather transfers a hydrogen radical to a radical end of a growing polymer chain. After the transfer reaction, the polymer chain is no longer able to grow further, while the resulting thiol radical can initiate a new chain.

[0047] RAFT polymerization is typically terminated by lowering the temperature to room temperature. When agent C is used, a dithioester or trithiocarbonate end group remains, formed by recombination or transfer of the radical chain end with the RAFT reagent. The dithioester or trithiocarbonate end group can be cleaved by increasing the temperature, again forming a free radical at the chain end. Therefore, during subsequent processing steps in the melt or during high-temperature applications, undesirable side reactions of the resulting radical chain ends can occur, such as recombination, transfer reactions, addition of other monomers that may be present, or depolymerization. Substitution of the dithioester group or trithiocarbonate group with an unreactive group can circumvent these side reactions.

[0048] Various methods for end group substitution of polymers with dithioester or trithiocarbonate end groups have been described in publications, for example in Jesson, CP; Pearce, CM; Simon, H.; Werner, A.; Cunningham, VJ; Lovett, JR; Smallridge, MJ; Warren, NJ; Armes, SP H2O2 Enables Convenient Removal of RAFT End-Groups from Block Copolymer Nano-Objects Prepared via Polymerization-Induced Self-Assembly in Water. Macromolecules 2017, 50, 182-191 and Willcock, H.; O'Reilly, RK End group removal and modification of RAFT polymers. Polym. Chem. 2010, 1, 149-157, where the polymers are present in solution or emulsion, and the dithioester or trithiocarbonate end group is removed, for example, by adding amines or peroxides and substituted by other groups. The method of heat treatment of the solid or the addition of an excess of radical generators, such as azo compounds, for example,Azobis(isobutyronitrile) (AIBN) for cleavage of the end group is described.

[0049] A preferred RAFT reagent C for this task is 2-cyanopropan-2-yl dodecyl carbonotrithioate.

[0050] It is particularly preferred if, after step d), in particular after a conversion of at least 10 mol%, preferably at least 25 to 100 mol%, more preferably 50 to 90 mol%, or after completion of the polymerization reaction, the polymer obtained is reacted with at least one agent D which is capable of converting the organic radical bonded to the adduct radical into groups which allow neither further polymerization nor depolymerization, in particular in the case that an agent according to the general formula II is used, to convert dithioester groups and / or trithiocarbonate groups bonded to the adduct radical into groups which allow neither further polymerization nor depolymerization from the chain end.

[0051] It is preferred that the agent D is selected from the group consisting of peroxides and sterically hindered phenols, for example hydrogen peroxide, which is particularly preferred.

[0052] Agent D can be added directly to the reaction mixture in a one-pot reaction or can be carried out on the previously isolated and subsequently redissolved, suspended or emulsified polymer.

[0053] It is further preferred if, after completion of the polymerization reaction, in particular after end group substitution in step d), the phosphorus-containing polymer is heated above its glass transition temperature under vacuum for a period of 1 minute to 48 hours.

[0054] The polymerization reaction can be initiated and carried out by heating the polymerizable mixture to a temperature above standard temperature (SATP). It is also advantageous if the polymerization reaction is carried out over a period of time that allows polymerization to a conversion of 10-100% and / or at temperatures between 60°C and 100°C, preferably between 65°C and 90°C, particularly preferably between 70°C and 80°C.

[0055] The initiator B is advantageously selected from the group consisting of azo compounds, preferably azo-bis-i-butyronitrile.

[0056] In the event that a copolymerization is carried out and a further monomer capable of radical polymerization, different from monomer A, is used in a monomer mixture, this is preferably selected from the group consisting of styrene, isoprene, butadiene and acrylates with the general structural formula III

[0057] Formel III wobei

[0058] R9 Wasserstoff oder eine Methylgruppe ist und

[0059] Rio ausgewählt ist aus der Gruppe bestehend aus Methyl-, Ethyl-, n-Pro- pyl-, i-Propyl-, n-Butyl-, i-Butyl-, t-Butyl-, t-Amyl-, Benzyl-, Cyclohexyl-, 9-Anthracenyl-, 2-Hydroxyethyl-, 3-Phenyl-2-propenyl, Adamantyl-, Methyladamantyl-, Ethyladamantyl-, Isobornyl-, 2-Ethoxyethyl-, n- Heptyl-, n-Hexyl-, 2- Hydroxy propyl-, 2-Ethylbutyl-, 2-Methoxypropyl-, 2-(2-methoxyethoxyl), 2-Naphthyl-, 2-Phenylethyl-, Phenyl-, Lauryl-, Myristyl-, Cetyl-, Stearyl-, Ceryl-, i-Decyl-, 2-Ethylhexyl-, Ethyltriglycol- , Tetrahydrofurfuryl-, Butyldiglycol-, 2-Dimethylaminoethyl-, Polyethy- lenglycol-, Methylpolyethylenglycol- oder einer Glycidylgruppe.

[0060] In this case, the molar fraction of the total of monomers A in the monomer mixture is preferably between 0.1 and 99.9 mol%, preferably between 50 and 99.9 mol%, particularly preferably between 80 and 99.9 mol%. The polymerization reaction can be carried out, for example, in a solvent preferably selected from the group consisting of dimethyl sulfoxide, dimethylacetamide, dimethylformamide, PGMEA, ethyl acetate, toluene, xylene, ethylbenzene, anisole, acetone, 2-butanone, acetonitrile, tetrahydrofuran, dioxane, diethyl ether, tert.-Butyl methyl ether, pentane, hexane, heptane, cyclopentane, cyclohexane, dichloromethane, chloroform, methanol, ethanol, n-propanol, i-propanol, n-butanol, t-butanol, ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, water and mixtures and combinations thereof, wherein the amount of solvent is preferably selected such that the concentration of all monomers capable of radical polymerization is preferably a maximum of 1.5 mol / L.

[0061] In addition, the present invention relates to a phosphorus-containing polymer containing at least one repeating unit according to general formula IV

[0062] Formula IV where the radicals Ri, R2, R3, R4 and m are as defined above.

[0063] The phosphorus-containing polymer is characterized by a solubility of at least 2.0 g / l in dimethylformamide at 23 °C. The polymers of the invention thus exhibit increased solubility compared to polymers known from the prior art. The phosphorus-containing polymer of the invention can be produced by the process of the invention.

[0064] In particular, the phosphorus-containing polymers according to the invention can be prepared or can be prepared by the process according to the invention. In particular, the repeating units according to general formula IV are derived from the following radically polymerized monomers:

[0065] 10-oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)methyl methacrylate (Ri=methyl, R2=CH2, R3=R4=aryl, m=0, DOPO-MMA)

[0066] (10-oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)methyl acrylate (Ri=H, R2=CH2, R3=R4=aryl, m=0, DOPO-MA)

[0067] 10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)ethylmethacrylat (Ri=Methyl, R2=(CH2)2, R3=R4=Aryl, m=0, DOPO-EMA)

[0068] (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)ethylacrylat (Ri=H, R2=(CH2)2, R3=R4=Aryl, m=0, DOPO-EA)

[0069] 10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)propylmethacrylat (Ri=Methyl, R2=(CH2)3, R3=R4=Aryl, m=0, DOPO-PMA)

[0070] (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)propylacrylat (R1=H, R2=(CH2)3, R3=R4=Aryl, m=0, DOPO-PA)

[0071] 10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)butylmethacrylat (Ri=Methyl, R2=(CH2)4, R3=R4=Aryl, m=0, DOPO-BMA) und

[0072] (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)butylacrylat (Ri=H, R2=(CH2)4, R3=R4=Aryl, m=0, DOPO-BA).

[0073] The phosphorus-containing polymer comprises homopolymers, in this case the polymer is formed from repeating units according to general formula IV, where R 1 , R 2 , R 3 , R 4 and m can be the same or different in each repeating unit, or copolymers in which, in addition to the repeating unit according to general formula IV, further repeating units derived from other radically polymerizable monomers are present. These further repeating units are preferably selected from the group consisting of repeating units resulting from the radical polymerization of styrene, isoprene, butadiene and acrylates with the general structural formula III

[0074] Rio

[0075] Formula III where

[0076] R9is hydrogen or a methyl group and

[0077] Rio is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, t-amyl, benzyl, cyclohexyl, 9-anthracenyl, 2-hydroxyethyl, 3-phenyl-2-propenyl, adamantyl, Methyladamantyl, ethyladamantyl, isobornyl, 2-ethoxyethyl, n-heptyl, n-hexyl, 2-hydroxypropyl, 2-ethyl butyl, 2-methoxypropyl, 2-(2-methoxyethoxyl), 2-naphthyl, 2-phenylethyl, phenyl, lauryl, myristyl, cetyl, stearyl, ceryl, i-decyl, 2-ethylhexyl, ethyltriglycol, tetrahydrofurfuryl, butyldiglycol, 2-dimethylaminoethyl, polyethylene glycol, methylpolyethylene glycol or a glycidyl group.

[0078] The homopolymers from the repeating units of formula IV mentioned above have an even higher phosphorus content compared to the copolymers and thus have an improved flame retardancy.

[0079] Furthermore, the invention encompasses the use of the polymers produced as flame retardants.

[0080] In this case, it is preferred that in the case of the presence of at least one repeating unit different from the repeating unit according to general formula IV, the molar proportion of the totality of repeating units according to general formula IV, based on the totality of all repeating units, is between 0.1 and 99.9 mol%, preferably between 50 and 99.9 mol%, particularly preferably between 80 and 99.9 mol%.

[0081] The phosphorus-containing polymer has in particular a number-average molecular weight of 10,000 to 1,000,000 g / mol, preferably 15,000 to 500,000 g / mol, particularly preferably 20,000 to 100,000 g / mol and / or a polydispersity D, determined as the quotient of the weight-average molecular weight and the number-average molecular weight, of 1.1 to 5.0, preferably 1.3 to 4.5.

[0082] Furthermore, the present invention relates to a plastic composition which comprises or consists of at least one plastic and at least one phosphorus-containing polymer as described above.

[0083] The plastic composition is particularly preferably a thermoplastic plastic composition; the plastic contained therein thus represents a thermoplastic.

[0084] It is preferred that the at least one phosphorus-containing polymer is present in an amount of 0.1 to 25.0 wt.%, preferably 1.0 to 20.0 wt.%, particularly preferably 5.0 to 20.0 wt.%, based on the total plastic composition.

[0085] The thermoplastic polymer is particularly preferably selected from the group of the following polymers: a) polymers made of olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene-PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene, such as natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers, as well as copolymers in the form of statistical or block structures such as polypropylene-polyethylene (EP), EPM or EPDM with e.g. 5-ethylidene-2-norbornene as comonomer, ethylene-vinyl acetate (EVA), ethylene acrylic esters such as ethylene-butyl acrylate, ethylene-acrylic acid and their salts (ionomers), as well as terpolymers such as ethylene-acrylic acid-glycidyl (meth)acrylate, Graft polymers such as polypropylene-graft-maleic anhydride, polypropylene-graft-acrylic acid, polyethylene-graft-acrylic acid, polyethylene-polybutylacrylate-graft-maleic anhydride and blends such asLDPE / LLDPE or long-chain branched polypropylene copolymers produced with alpha-olefins as comonomers such as 1-butene, 1-hexene, 1-octene or 1-octadecene, b) polystyrene, polymethylstyrene, poly-alpha-methylstyrene, polyvinylnaphthalene, polyvinylbiphenyl, polyvinyltoluene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile (SAN), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, Styrene-maleic anhydride polymers including corresponding graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, as well as graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), as well as hydrogenated polystyrene derivatives such as polyvinylcyclohexane, c) halogen-containing polymers such asPolyvinyl chloride (PVC), polychloroprene and polyvinylidene chloride (PVDC), copolymers of vinyl chloride and vinylidene chloride or of vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo and copolymers, in particular with ethylene oxide (ECO), d) polymers of unsaturated esters such as polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate; polystearyl acrylate; Polyglycidyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, polyacrylamides, copolymers such as polyacrylonitrile-polyalkyl acrylate, e) polymers of unsaturated alcohols and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, f) polyacetals, such as polyoxymethylene (POM) or copolymers with e.g. butanal, polyphenylene oxides and blends with polystyrene or polyamides, g) polymers of cyclic ethers such asPolyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, h) polyphenylene oxides and their blends with polystyrene and / or polyimides, i) polyurethanes, from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates such as 2,4- or 2,6-toluene diisocyanate or methylene diphenyl diisocyanate, in particular also linear polyurethanes (TPU), polyureas, j) polyamides such as polyamide 6, 6.6, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as polyphthalamides, e.g. made from terephthalic acid and / or isophthalic acid and aliphatic diamines such as hexamethylenediamine or m-xylylenediamine or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, blends of different polyamides such as PA-6 and PA 6.6 or blends of polyamides and polyolefins such asPA / PP, k) polyimides, polyamideimides, polyetherimides, polyesterimides, poly(ether)ketones, polysulfones, polyethersulfones, polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins, l) polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTI), polyethylene naphthylate (PEN), poly-l,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyethylene succinate, polytetramethylene succinate, polycaprolactone, m) polycarbonates, polyester carbonates, as well as blends such as PC / ABS, PC / PBT, PC / PET / PBT, PC / PA, n) cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, o) unsaturated polyester resins made from unsaturated dicarboxylic acids and diols with vinyl compounds, e.g.Styrene, alkyd resins, p) silicones, e.g. based on dimethylsiloxanes, methylphenylsiloxanes or diphenylsiloxanes, e.g. terminated with vinyl groups, q) as well as mixtures, combinations or blends of two or more of the aforementioned polymers.

[0086] The present inventive polymers are particularly suitable as flame retardants for polyamides. If the polymers listed under a) to p) are copolymers, they can be in the form of random, block, or tapered structures. Furthermore, the polymers mentioned can be in the form of linear, branched, star-shaped, or hyperbranched structures.

[0087] If the polymers listed under a) to p) are stereoregular polymers, they can be present in the form of isotactic, syndiotactic, but also atactic forms or as stereoblock copolymers.

[0088] Furthermore, the polymers listed under a) to p) can have both amorphous and (partially) crystalline morphologies.

[0089] If necessary, the polyolefins mentioned under a) can also be cross-linked, e.g. cross-linked polyethylene, which is then referred to as X-PE.

[0090] Furthermore, the present compounds can preferably be used as flame retardants for rubbers and elastomers. These can be natural rubber (NR) or synthetic rubber materials. Suitable synthetic rubber materials consist in particular of butadiene (BR), styrene-butadiene (SBR), chloroprene (CR), isoprene (IR), isobutylene-isoprene, and acrylonitrile-butadiene (NBR or, in hydrogenated form, HNBR). Other suitable rubbers and elastomers are ethylene-propylene-diene terpolymers (EPDM) and ethylene-propylene copolymers (EPM), polyester-urethanes (AU), polyether-urethanes (EU), and silicones (MQ).

[0091] In addition to new materials, the plastics can also be recycled plastics, e.g. from industrial collections such as production waste, or plastics from household or recyclables collections.

[0092] It is also advantageous if the plastic contains at least one further additive selected from the group consisting of primary antioxidants, secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact strength improvers, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, optical brighteners, antimicrobial agents (e.g.Biocides), antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, branching agents, anticrosslinking agents, hydrophilizing agents, hydrophobizing agents, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoamers, odor scavengers, marking agents, antifogging agents, additives to increase electrical conductivity and / or thermal conductivity, infrared absorbers or infrared reflectors, gloss improvers, matting agents, repellents, fillers, reinforcing agents and mixtures thereof.

[0093] Suitable primary antioxidants (A) are phenolic antioxidants, amines and lactones:

[0094] Suitable synthetic phenolic antioxidants are, for example: Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols, such as 2,6-dinonyl-4-methylphenol, 2,4-Dimethyl-6-(l'-methylundec-l'-yl)phenol, 2,4-dimethyl-6-(l'-methylheptadec-l'-yl)phenol, 2,4-dimethyl-6-(l'-methyltridec-l'-yl)phenol and mixtures thereof;

[0095] Alkylthiomethylphenols, such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol,

[0096] 2,6-didodecylthiomethyl-4-nonylphenol;

[0097] Hydroquinones and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methyloxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,

[0098] 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate;

[0099] Tocopherols, such as α-, β-, γ-, δ-tocopherol and mixtures of these (vitamin E);

[0100] Hydroxylated thiodiphenyl ethers, such as 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-secamylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide;

[0101] Alkylidenbisphenole, wie z.B. 2,2'Methylenbis(6-tert-butyl-4-methylphenol), 2,2'-Methylenbis(6-tert-butyl-4-ethylphenol), 2,2'-Methylenbis[4-methyl-6- (a-methylcyclohexyl)phenol], 2,2'-Methylenbis(4-methyl-6-cyclhexylphenol), 2,2'-Methylenbis(6-nonyl-4-methylphenol), 2,2'-Methylenbis(4,6-di-tert- butylphenol), 2,2'-Ethylidenbis(4,6-di-tert-butylphenol), 2,2'-Ethylidenbis(6- tert-butyl-4-isobutylphenol), 2,2'-Methylenbis[6-(a-methylbenzyl)-4-nonyl- phenol], 2,2'-Methylenbis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-Me- thylenbis(2,6-di-tert-butylphenol, 4,4'-Methylenbis(6-tert-butyl-2-methyl- phenol), l,l-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan, 2,6-Bis(3-tert- butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, l,l,3-Tris(5-tert-butyl-4- hydroxy-2-methylphenyl)butan, l,l-bis(5-tert-butyl-4-hydroxy-2-methylphe- nyl)-3-n-dodecylmercaptobutan, Ethylenglycol-bis[3,3-bis(3'-tert-butyl-4'- hydroxyphenyl)butyrat], Bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclo- pentadien,Bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4- methylphenyl]terephthalat, l,l-Bis-(3,5-dimethyl-2-hydroxyphenyl)butan, 2,2-Bis(3,5-di-tert-butyl-4-hydroxyphenyl)propan, 2,2-Bis-(5-tert-butyl-4- hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutan, l,l,5,5-Tetra(5-tert- butyl-4-hydroxy-2-methylphenyl)pentan;,

[0102] O-, N- und S-Benzyl-Verbindungen, wie z.B. 3,5,3',5'-Tetra-tert-butyl-4,4'- dihydroxydibenzylether, Octadecyl-4-hydroxy-3,5-dimethylbenzylmercapto- acetat, Tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetat, Tris(3,5-di- tert-butyl-4-hydroxybenzyl)amin, Bis(4-tert-butyl-3-hydroxy-2,6-dimethyl- benzyl)dithioterephthalat, Bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfid, Iso- octyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetat; Hydroxybenzylierte Malonate, wie z.B. Dioctadecyl-2, 2-bis(3, 5-di-tert-butyl- 2-hydroxybenzyl)malonat, Dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methyl- benzyl)malonat, Didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxy- benzyl)malonat, Bis[4-(l,l,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert- butyl-4-hydroxybenzyl)malonat;

[0103] Aromatische Hydroxybenzylverbindungen, wie z.B. l,3,5-Tris(3,5-di-tert- butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzol, l,4-Bis(3,5-di-tert-butyl-4- hydroxybenzyl)-2,3,5,6-tetramethylbenzol, 2,4,6-Tris(3,5-di-tert-butyl-4-hyd- roxybenzyl)phenol;

[0104] Triazinverbindungen, wie z.B. 2,4-Bis(octylmercapto)-6-(3,5-di-tert-butyl-4- hydroxyanilino)-l,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyanilino)-l,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyphenoxy)-l,3,5-triazin, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphen- oxy)-l,2,3-triazin, l,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurat, l,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurat, 2,4,6- Tris(3,5-di-tert-butyl-4-hydroxphenylethyl)-l,3,5-triazin, l,3,5-Tris(3,5-di- tert-butyl-4-hydroyphenylpropionyl)hexahydro-l,3,5-triazin, 1,3,5-Tris(3,5- dicyclohexyl-4-hydroxybenzyl)isocyanurat;

[0105] Benzylphosphonate, wie z.B. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylp- hosphonat, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Dioctade- cyl-3, 5-di-tert-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-5-tert-butyl-4- hydroxy-3-methylbenzylphosphonat, das Calciumsalz des Monoethylesters der 3,5-Di-tert-butyl-4-hydroxybenzylphosphonsäure;

[0106] Acylaminophenole, wie z.B. 4-Hydroxylauranilid, 4-Hydroxystearanilid, Octyl- N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamat;

[0107] Ester der ß-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, n-Octanol, i-Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pen- taerythritol, Tris(hydroxyethyl)isocyanurat, N,N'-Bis(hydroxyethyl)oxamid, 3- Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octan;

[0108] Ester der ß-(5-tert-Butyl-4-hydroxy-3-methylphenyl)propionsäure mit ein- cider mehrwertigen Alkoholen, z.B. Methanol, Ethanol, n-Octanol, i-Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pen- taerythritol, Tris(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3- Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octan, 3,9-Bis[2-{3-(3- tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-l,l-dimethylethyl]- 2,4,8,10-tetraoxaspiro[5.5]undecan;

[0109] Ester der ß-(3,5-Dicyclohexyl-4-hydroxyphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6- Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris- (hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxyme- thyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octan;

[0110] Ester der (3,5-Di-tert-butyl-4-hydroxyphenyl)essigsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxy- ethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thia- pentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-l- phospha-2,6,7-trioxabicyclo[2.2.2]octan;

[0111] Amides of ß-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard®XL-1, distributed by Uniroyal); ascorbic acid (vitamin C).

[0112] Particularly preferred phenolic antioxidants are the following structures:

[0113]

[0114] Particularly preferred phenolic antioxidants are octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).

[0115] Other particularly preferred phenolic antioxidants are based on renewable raw materials such as tocopherols (vitamin E), tocotrienols, tocopherols, carotenoids, hydroxytyrosol, flavonols such as chrysin, quercetin, hesperidin, neohesperidin, naringin, morin, kaempferol, fisetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosmarinic acid, and resveratrol. Suitable amine antioxidants include:

[0116] N,N'-Di-isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(l,4-dimethylpentyl)-p-phenylendiamin, N,N'-Bis(l-ethyl-3-methyl- pentyl)-p-phenylendiamin, N,N'-Bis(l-methylheptyl)-p-phenylendiamin, N,N'- Dicyclohexyl-p-phenylendiamin, N,N'-Diphenyl-p-phenylendiamin, N,N'- Bis(2-naphthyl)-p-phenylendiamin, N-lsopropyl-N'-phenyl-p-phenylendiamin, N-(l,3-Dimethylbutyl)-N'-phenyl-p-phenylen-diamin, N-(1-Methylheptyl)-N'- phenyl-p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin, 4-(p- Toluolsulfamoyl)diphenylamin, N,N'-Dimethyl-N,N'-di-sec-butyl-p-phenylen- diamin, Diphenylamin, N-Allyldiphenylamin, 4-lsopropoxydiphenylamin, N- Phenyl-l-naphthylamin, N-(4-tert-Octylphenyl)-l-naphthylamin, N-Phenyl-2- naphthylamin, octyliertes Diphenylamin, z.B. p,p'-Di-tert-octyldiphenylamin, 4-n-Butylaminophenol, 4-Butyrylaminophenol, 4-Nonanoylaminophenol, 4- Dodecanoylaminophenol, 4-Octadecanoylamino-phenol, Bis(4-methoxyphe- nyl)amin, 2,6-Di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetra-methyl-4,4'-diaminodiphenylmethane, l,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(l',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-l-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-l,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-l,4-diaminobut-2-ene and mixtures or combinations thereof.

[0117] Preferred aminic antioxidants are: N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(l,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(l-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(l-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(l,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(l-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine

[0118] Particularly preferred amine antioxidants are the structures:

[0119] Further preferred amine antioxidants are hydroxylamines or N-oxides (nitrones), such as N,N-dialkylhydroxylamines, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-α-phenylnitrone, N-octadecyl-α-hexadecylnitrone, and Genox EP (SI Group according to the formula:

[0120] Suitable lactones are benzofuranones and indolinones such as 3-(4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-(2-hydroxyethoxy]phenyl)benzofuran-2-one), 5,7-di-tert-butyl-3-(4-ethoxy-phenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl- benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl- benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one and lactones that additionally contain phosphite groups such as

[0121] Another Antioxidants are isoindolo[2,lA]quinazolines such as Secondary antioxidants are especially phosphites or phosphonites such as

[0122] Triphenylphosphit, Diphenylalkylphosphite, Phenyldialkylphosphite, Tri(nonylphenyl)phosphit, Trilaurylphosphite, Trioctadecylphosphit, Distea- rylpentaerythritoldiphosphit, Tris-(2,4-di-tert-butylphenyl)phosphit, Diisode- cylpentaerythritoldiphosphit, Bis(2,4-di-tert-butylphenyl)pentaerythritol- diphosphit, Bis(2,4-di-cumylphenyl)pentaerythritoldiphosphit, Bis(2,6-di-tert- butyl-4-methylphenyl)pentaerythritoldiphosphit, Diisodecyloxypentaerythri- toldiphosphit, Bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritoldiphos- phit, Bis(2,4,6-tris(tert-butylphenyl)pentaerythritoldiphosphit, Tristearylsor- bitoltriphosphit, Tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylendiphospho- nit, 6-lsooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-l,3,2-dioxaphos- phocin, Bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphit, Bis(2,4-di-tert- butyl-6-methylphenyl)ethylphosphit, 6-Fluoro-2,4,8,10-tetra-tert-butyl-12- methyl-dibenz[d,g]-l,3,2-dioxaphosphocin, 2,2'2"-Nitrilo[triethyl- tris(3,3",5,5'-tetra-tert-butyl-l,l'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-l,l'-biphenyl-2,2'-diyl))phosphite, 5-butyl-5- ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphiran.,

[0123] Particularly preferred phosphites are: with n= 3-100

[0124] A preferred phosphonite is: The phosphite tris-(2,4-di-tert-butylphenyl)phosphite is particularly preferably used as a secondary antioxidant. Other secondary antioxidants include organosulfur compounds such as sulfides and disulfides, e.g., distearyl thiodipropionate, dilauryl thiodipropionate; ditridecyl dithiopropionate, ditetradecyl thiodipropionate; 3-(dodecylthio), l,l'-[2,2-bis[[3-(dodecylthio)l-oxopropoxy]methyl]l,3-propanediyl]propanoic acid esters. The following structures are preferred:

[0125] Suitable acid scavengers ("antacids") are salts of one, two, three or four-valent metals, preferably alkali, alkaline earth metals, aluminum or zinc, in particular formed with fatty acids, such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium laurate, calcium behenate, calcium lactate, calcium stearoyl-2-lactate. Other classes of suitable acid scavengers are hydrotalcites, in particular synthetic hydrotalcites based on aluminum, magnesium and zinc, hydrocalumites, zeolites, alkaline earth oxides, in particular calcium oxide and magnesium oxide as well as zinc oxide, alkaline earth carbonates, in particular calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite (magnesium hydroxide).

[0126] Suitable costabilizers are also polyols, especially alditols or cyclitols. Polyols include pentaerythritol, dipentaerythritol, tripentaerythritol, short-chain polyether polyols or polyester polyols, as well as hyperbranched polymers / oligomers or dendrimers with alcohol groups, e.g.

[0127] Preferably, the at least one alditol is selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, altritol, iditol, maltotritol, and hydrogenated oligo- and polysaccharides with polyol end groups, and mixtures thereof. Particularly preferably, the at least one preferred alditol is selected from the group consisting of erythritol, mannitol, isomalt, maltitol, and mixtures thereof.

[0128] Examples of further related sugar alcohols are Heptitol and Octitol: meso-glycero-allo-Heptitol, D-glycero-D-altro-Heptitol, D-glycero-D-manno-Heptitol, meso-glycero-yellow-Heptitol, D-glycero-D-galacto-Heptitol (Per- seitol), D-glycero-D-gluco-Heptitol, L-glycero-D-gluco Heptitol, D-erythro-L-galacto-Octitol, D-threo-L-galacto-Octitol.

[0129] In particular, the at least one cyclitol can be selected from the group consisting of inositol (myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-inositol), 1,2,3,4-tetrahydroxycyclohexane, 1, 2,3,4, 5-pentahydroxycyclohexane, quercitol, viscumitol, bornesitol, conduritol, ononitol, pinitol, pinpollitol, quebrachitol, ciceritol, quinic acid, shikimic acid and valienol, preference being given to myo-inositol (myo-inositol). Suitable light stabilizers are, for example, compounds based on 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2-(2-hydroxyphenyl)-1,3,5-triazines.

[0130] Geeignete 2-(2'-Hydroxyphenyl)benzotriazole sind beispielsweise 2-(2'-Hyd- roxy-5'methylphenyl)benzotriazol, 2-(3',5'-Di-tert-butyl-2'-hydroxyphenyl)- benzotriazol, 2-(5'-tert-Butyl-2'-hydroxy-phenyl)benzotriazol, 2-(2'-Hydroxy- 5'-(l,l,3,3-tetramethylbutyl)phenyl)benzotriazol, 2-(3',5'-Di-tert-butyl-2'- hydroxyphenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-methyl- phenyl-5-chlorobenzotriazol, 2-(3'-sec-Butyl-5'-tert-butyl-2'-hydroxy-phe- nyl)benzotriazol, 2-(2'-Hydroxy-4'-octyloxyphenyl)benzotriazol, 2-(3',5'-Di- tert-amyl-2'-hydroxyphenyl)benzotriazol, 2-(3',5'-Bis(a,a-dimethylbenzyl)-2'- hydroxyphenyl)benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-octyloxycar- bonylethyl)phenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-5'-[2-(2-ethylhexy- loxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl- 2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazol, 2-(3'- tert-Butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazol,2-(3'- tert-Butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazol, 2-(3'- tert-Butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotria- zol, 2-(3'-Dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazol, 2-(3'-tert-Butyl- 2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazol, 2,2'-Methyl- enbis[4-(l,l,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; das Produkt der Umesterung von 2-[3'-tert-Butyl-5'-(2-methoxycarbonylethyl)-2'-hydro- xyphenyl]-2H-benzotriazol mit Polyethylenglycol 300; [R— CH2CH2— COO— CH2CH2-]-2, wobei R = 3'-tert-Butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphe- nyl, 2-[2'-Hydroxy-3'-(a,a-dimethylbenzyl)-5'-(l,l,3,3-tetramethylbutyl)phe- nyl]benzotriazol, 2-[2'-hydroxy-3'-(l, 1,3, 3-tetramethylbutyl)-5'-(a, «-dimethyl benzyl)phenyl]benzotriazol.,

[0131] Geeignete 2-Hydroxybenzophenone sind beispielsweise 4-Hydroxy-, 4-Me- thoxy-, 4-Octyloxy-, 4-Decyloxy- 4-Dodecyloxy, 4-Benzyloxy, 4, 2', 4'-Tri hydroxy- und 2'-Hydroxy-4,4'-dimethyoxy-Derivate der 2-Hydroxybenzo- phenone.

[0132] Geeignete Acrylate sind beispielsweise Ethyl-a-cyano-ß,ß-diphenylacrylat, lsooctyl-a-cyano-ß,ß-diphenylacrylat, Methyl-a-carbomethoxycinnamat, Me- thyl-a-cyano-ß-methyl-p-methoxycinnamat, Butyl-a-cyano-ß-methyl-p-me- thoxycinnamat, Methyl-a-carbomethoxy-p-methoxycinnamat und N-(ß-car- bomethoxy-ß-cyanovinyl)-2-methylindolin.

[0133] Suitable esters of benzoic acids are, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0134] Suitable oxamides are, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixtures with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

[0135] Geeignete 2-(2-Hydroxyphenyl)-l,3,5-Triazine sind beispielsweise 2,4,6- Tris(2-hydroxy-4-octyloxyphenyl)-l,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphe- nyl)-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazin, 2-(2,4-Dihydroxyphenyl)-4,6- bis(2,4-dimethylphenyl)-l,3,5-triazin, 2,4-Bis(2-hydroxy-4-propyloxyphenyl)- 6-(2,4-dimethylphenyl)-l,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6- bis(4-methylphenyl-l,3,5-triazin, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6- bis(2,4-dimethylphenyl)-l,3,5-triazin, 2-(2-Hydroxy-4-tridecyloxyphenyl)-4,6- bis(2,4-dimethylphenyl)-l,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-buty- loxypropoxy)-phenyl]-4,6-bis(2,4-dimethyl)-l,3,5-triazin, 2-[2-Hydroxy-4-(2- hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-l,3,5-triazin, 2- [4-(Dodecyloxy / Tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6- bis(2,4-dimethylphenyl)-l,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-dodecy- loxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl-l,3,5-triazin, 2-(2-Hydroxy- 4-hexyloxy)phenyl-4,6-diphenyl-l,3,5-triazin, 2-(2-Hydroxy-4-methoxyphe- nyl)-4,6-diphenyl-l,3,5-triazin, 2,4,6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxyp- ropoxy)phenyl]-l,3,5-triazin, 2-(2-Hydroxyphenyl)-4-(4-methoxyphenyl)-6- phenyl-l,3,5-triazin, 2-{2-Hydroxy-4-[3-(2-ethylhexyl-l-oxy)-2-hydroxypropy- loxy]phenyl}-4,6-bis(2,4-dimethylphenyl-l,3,5-triazin.,

[0136] Geeignete Metalldeaktivatoren sind beispielsweise N,N'-Diphenyloxamid, N- Salicylal-N'-salicyloylhydrazin, N,N'-Bis(salicyloyl)hydrazin, N,N'-Bis(3,5-di- tert-butyl-4-hydroxyphenylpropionyl)hydrazin, 3-Salicyloylamino-l,2,4-tria- zol, Bis(benzyliden)oxalyldihydrazid, Oxanilid, Isophthaloyldihydrazid, Seba- coylbisphenylhydrazid, N,N'-Diacetyladipoyldihydrazid, N,N'-Bis(salicyl- oyl)oxylyldihydrazid, N,N'-Bis(salicyloyl)thiopropionyldihydrazid.

[0137] Besonders bevorzugt als Metalldeaktivatoren sind:

[0138] Suitable hindered amines are, for example, l,l-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebazate, bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebazate, bis(l,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octyl- N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-l,2,3,4-butanetetracarboxylate, l,l'-(l,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-l,3,5-triazine is the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-l-oxa-3,8-di- aza-4-oxospiro-[4,5]decane and epichlorohydrin.

[0139] The structures given above also include the sterically hindered NH, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N-cyclohexyloxy, and the N-(2-hydroxy-2-methylpropoxy) analogues. 39

[0140] Preferred hindered amines also have the following structures:

[0141] Preferred oligomeric and polymeric hindered amines have the following

[0142] Structures on:

[0143] For the compounds mentioned above, n is 3 to 100. Another suitable light stabilizer is Hostanox NOW (manufacturer: Clariant SE) with the following general structure: where R is -OC(O)-CisH3i or -OC(O)-CI?H35.

[0144] Suitable dispersants include:

[0145] Polyacrylates, e.g. copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: e.g. N,N'-1,2-ethanediylbisoctadecanamide sorbitan esters, e.g. monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups, e.g. polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride polysiloxanes: e.g. dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: e.g. polyethylene-block-polyethylene oxide, dendrimers, e.g. hydroxyl-containing dendrimers.

[0146] Suitable antinucleating agents are azine dyes such as nigrosine.

[0147] Suitable flame retardants are in particular

[0148] Inorganic flame retardants such as Al(OH)3, Mg(OH)2, AlO(OH), IVIgCO3, layered silicates such as montmorillonite or sepiolite, unmodified or organically modified, double salts such as Mg-Al-silicates, POSS (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnesite or halloysite as well as Sb2O3, Sb2Os, MOO3, zinc stannate, zinc hydroxystannate, nitrogen-containing flame retardants such as melamine, melamine, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine metal phosphates such as melamine aluminum phosphate, Melamine zinc phosphate, melamine magnesium phosphate, as well as the corresponding pyrophosphates and polyphosphates, poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine], ammonium polyphosphate, melamine borate, melamine hydrobromide,

[0149] Radical formers such as alkoxyamines, hydroxylamine esters, azo compounds, sulfenamides, sulfenimides, dicumyl or polycumyl, hydroxyimides and their derivatives such as hydroxyimide esters or hydroxyimide ethers

[0150] Phosphorus-containing flame retardants such as red phosphorus, phosphates such as resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate, ethylenediamine diphosphate, phosphinates such as salts of hypophosphorous acid and their derivatives such as alkyl phosphinate salts such as diethyl phosphinate aluminum or diethyl phosphinate zinc or aluminum phosphinate, aluminum phosphite, aluminum phosphonate, phosphonate esters, oligomers and polymeric derivatives of methanephosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their substituted compounds,

[0151] Halogen-containing flame retardants based on chlorine and bromine, such as polybrominated diphenyl oxides, such as decabromodiphenyl oxide, tris(3-bromo-2, 2-bis(bromomethyl)propyl phosphate, tris(tribromoneopentyl)phosphate, tetrabromophthalic acid, 1,2-bis(tribromophenoxy)ethane, hexabromocyclododecane, brominated diphenylethane, tris(2,3-dibromopropyl)isocyanurate, ethylene-bis(tetrabromophthalimide), tetrabromobisphenol A, brominated polystyrene, brominated polybutadiene or polystyrene-brominated polybutadiene copolymers, brominated polyphenylene ether, brominated epoxy resin, polypentabromobenzyl acrylate, optionally in combination with Sb2O3 and / or Sb2O5,

[0152] Borates such as zinc borate or calcium borate, optionally on carrier material such as silica Sulphur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzthiazole and sulfenamides,

[0153] Anti-drip agents such as polytetrafluoroethylene,

[0154] Silicon-containing compounds such as polyphenylsiloxanes,

[0155] Carbon modifications such as carbon nanotubes (CNT), expandable graphite or graphene as well as combinations or mixtures thereof.

[0156] Suitable plasticizers are, for example, phthalic acid esters, adipic acid esters, esters of citric acid, esters of 1,2-cyclohexanedicarboxylic acid, trimellitic acid esters, isosorbide esters, phosphate esters, epoxides such as epoxidized soybean oil or aliphatic polyesters.

[0157] Suitable lubricants and processing aids are, for example, polyethylene waxes, polypropylene waxes, salts of fatty acids such as calcium stearate, zinc stearate or salts of montan waxes, amide waxes such as erucic acid amide or oleic acid amides, fluoropolymers, silicones or neoalkoxy titanates and zirconates.

[0158] Suitable pigments can be inorganic or organic. Examples of inorganic pigments include titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, and carbon black. Organic pigments include anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines, and pyranthrones. Other suitable pigments include metal-based effect pigments or metal oxide-based pearlescent pigments.

[0159] Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis(styryl)biphenyls and in particular optical brighteners of the formulas:

[0160] Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid polyalkylene oxide or polyglycidyl (meth)acrylates and their copolymers, e.g. with styrene, as well as epoxides, e.g. of the following structures:

[0161] Suitable antistatic agents include ethoxylated alkylamines, fatty acid esters, alkylsulfonates and polymers such as polyetheramides.

[0162] Suitable antiozonants are the above-mentioned amines such as N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(l,4-dimethylpentyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(l-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine

[0163] Suitable rheology modifiers, e.g. for the production of controlled rheology polypropylene (CR-PP), are peroxides, alkoxyamine esters or oxyimide sulfonic acid esters.

[0164] Suitable additives for increasing the molecular weight of polycondensation polymers (chain extenders) are diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides, and polycarbodiimides. Other suitable chain extenders are polymeric compounds such as polystyrene-polyacrylate-polyglycidyl (meth)acrylate copolymers, polystyrene-maleic anhydride copolymers, and polyethylene-maleic anhydride copolymers.

[0165] Suitable hydrolysis stabilizers for polycondensation polymers such as polyesters or polyamides include epoxides, carbodiimides, polycarbodiimides, or aziridines. Suitable additives for increasing electrical conductivity include the aforementioned antistatic agents, carbon black and carbon compounds such as carbon nanotubes and graphene, metal powders such as copper powder, and conductive polymers such as polypyrroles, polyanilines, and polythiophenes.

[0166] Suitable infrared-active additives include aluminum silicates, hydrotalcites or dyes such as phthalocyanines or anthraquinones.

[0167] Suitable crosslinking agents are, for example, peroxides such as dialkyl peroxides, alkyl aryl peroxides, peroxy esters, peroxycarbonates, diacyl peroxides, peroxy ketals, silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, vinyldimethoxymethylsilane or ethylene-vinylsilane copolymers.

[0168] Suitable additives for increasing the thermal conductivity of plastic recyclates include inorganic fillers such as boron nitride, aluminum nitride, aluminum oxide, aluminum silicate, silicon carbide and also carbon nanotubes (CNT).

[0169] Suitable impact strength modifiers are usually selected for the respective polymer and are, for example, from the group of functionalized or non-functionalized polyolefins, such as ethylene copolymers such as EPDM or maleic anhydride or styrene-acrylonitrile-modified EPDM, glycidyl methacrylate-modified ethylene-acrylate copolymers or ionomers, core-shell polymers, e.g. based on MBS (methacrylate-butadiene-styrene copolymer) or acrylic ester-polymethyl methacrylate, thermoplastic elastomers (TPE), e.g. based on styrene block copolymers (styrene-butadiene (SB), styrene-butadiene-styrene (SBS) optionally hydrogenated (SEBS) or modified by maleic anhydride (SEBS-g-MAH), thermoplastic polyurethanes, copolyesters or copolyamides.

[0170] Suitable slip agents include amide waxes such as erucamide or oleamide. Suitable antiblocking agents include silica, talc, or zeolites.

[0171] Suitable demoulding aids include silicones, soaps and waxes such as montan waxes.

[0172] The present invention also relates to a molded part produced from a plastic composition described above. In particular, the molded part is in the form of plastic fibers.

[0173] Furthermore, the present invention relates to the use of the phosphorus-containing polymer according to the invention as described above as a stabilizer for thermoplastics, in particular against thermal, oxidative and / or actinic degradation, in particular as a flame retardant.

[0174] The present invention will be described in more detail below, without limiting the invention to the specific embodiments.

[0175] The monomers of the general structural formula can be prepared in various ways. A preferred synthesis route follows general reaction scheme 1, in which the alcohol of general structural formula 3 is reacted with a carboxylic acid or a carboxylic acid derivative of general structural formula 4, thereby forming the monomer of general structural formula 1.

[0176] General reaction scheme 1:

[0177] General General General

[0178] Structural Formula 3 Structural Formula 4 Structural Formula 1 The radical R1 can be hydrogen or an alkyl group. R2 is a linear or branched, substituted or unsubstituted hydrocarbon group containing 1-20 carbon atoms. R3 and R4 are the same or different groups, which are substituted or unsubstituted cyclic hydrocarbon groups containing 6-20 carbon atoms. Likewise, the number of methylene units between R3 and R4 can be 0, 1, 2, or 3.

[0179] R5 can be -OH (carboxylic acid), -CI (carboxylic acid chloride), -O-alkyl (carboxylic acid ester), or -O-(C=O)-C(=C)(R1) (carboxylic acid anhydride). Carboxylic acid anhydride is particularly preferably used for the synthesis of monomer A.

[0180] The following comparative examples and six examples according to the invention are described in the following working examples:

[0181] • Comparative example 1: Free radical polymerization: leads to insoluble products

[0182] • Inventive Example 2: RAFT polymerization at high concentration without end group cleavage leads to a soluble product with a narrow molecular weight distribution, but with lower temperature stability than in Inventive Example 2.

[0183] • Inventive Example 3: Cleavage of the end groups of the polymer from inventive Example 2 with H2O2 leads to an increase in temperature stability

[0184] • Inventive Example 4: Tempering the polymer from inventive Example 3 leads to a further increase in temperature stability

[0185] • Inventive Example 5: Demonstration of the flame retardant effect of the polymers according to the invention in polyamide.

[0186] In the examples shown, (10-oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)methyl methacrylate (general structural formula 1 with R1=methyl, R2=CH2, R3=R4=aryl, m=0, DOPO-MMA) is used as the monomer for polymerization. Both RAFT polymerization and free radical polymerization are used as polymerization processes. In all cases, initiation occurs with an azo compound as initiator B, which in the examples shown here is azo-bis-i-butyronitrile (AIBN).

[0187] Once the desired conversion has been achieved, the polymerization is terminated by cooling the reaction solution. The polymer is obtained by precipitation.

[0188] Inventive Example 3 also demonstrates the advantage of end group removal for the production of poly(10-oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)methyl methacrylate homopolymers and copolymers using RAFT polymerization. For this purpose, (10-oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)methyl methacrylate (DOPO-MMA) was polymerized, and the reaction was terminated by lowering the temperature to room temperature. The resulting polymer from Inventive Example 3 was isolated, and in Inventive Example 4, the trithiocarbonate end group was substituted in a two-stage workup.

[0189] For further characterization, the inventive polymer from Inventive Example 4 was melt-compounded into polyamide 6.6. The compounds were formed into test specimens, which were tested for fire properties.

[0190] Surprisingly, it was found that the flame retardant additive according to the invention shows reduced dripping behavior. of (10-oxo-10-

[0191] In a 25 mL two-neck flask, 5.00 g (15.7 mmol) of DOPO-MMA in 7.9 mL of DMSO are placed. The flask is purged with nitrogen for 5 minutes, and then the monomer solution is degassed for 10 minutes by passing nitrogen. 3 mg (0.02 mmol) of AIBN are added in a nitrogen countercurrent. The reaction is stirred for 15 hours at 70°C in an oil bath. This results in the formation of a gel that is no longer soluble. 2: Controlled radical -lO-i essence of a RAFT-I

[0192] In a 1 L three-necked flask, 117.14 g (0.36 mol) of DOPO-MMA in 180 mL of DMSO are placed. 0.19 mL (0.054 mmol) of 2-cyanopropan-2-yl dodecylcarbonotrithioate is added to the solution. The flask is purged with nitrogen for 5 minutes, and then the monomer solution is degassed for 10 minutes by passing nitrogen. 59 mg (0.036 mmol) of AIBN is added in a nitrogen countercurrent. The reaction is stirred for 24 hours at 70°C in an oil bath. After the reaction is complete, the reaction solution is cooled to room temperature, diluted with 300 mL of dichloromethane, and precipitated in 4 L of methanol. The product is filtered off and dried overnight at 50°C under vacuum. (Yield: 113.59 g). The polymer is again soluble in organic solvents after drying.

[0193] By means of GPC measurement with DMF / LiBr as eluent against a polystyrene calibration, the number-average molecular weight of the obtained polymer was determined to be M n= 54842 g / mol, the weight-average molar mass with M w = 88693 g / mol and the polydispersity D = 1.62. The shape of the obtained curve was monomodal. Due to its insolubility, no molecular weight could be determined for Comparative Example 1.

[0194] 3: Demonstration of the improved

[0195] The polymer from Example 2 according to the invention is suspended in a mixture of 500 mL of 30% hydrogen peroxide solution and 500 mL of water and stirred for 24 h at 80 °C. The polymer is separated by filtration, washed with methanol, and dried under vacuum at 80 °C.

[0196] The cleavage of the end groups was determined by NMR spectroscopy. nstration of the improved followed by the polymer from inventive example 4 being transferred into a one-necked flask and heated to 200 °C under vacuum and annealed for 8 h.

[0197] Testing temperature stability

[0198] For comparison, this test subjected polymer samples from inventive examples 2 to 4 to a dynamic TGA analysis. The samples were heated at a heating rate of 10 kJ / min. T5% and T10% are the temperatures at which a weight loss of 5% and 10% was observed, respectively. (Tables 2 and 3)

[0199] Table 2: Results of the dynamic TGA measurement of the inventive examples 1-5.

[0200] Table 3: Comparison of results before and after tempering based on inventive example 2 and inventive examples 3 and 4

[0201] Tables 2 and 3 show that the polymer from inventive example 2 is soluble, but still exhibits the lowest temperature stability of all samples. This is presumably due to the fact that this polymer contains trithiocarbonate end groups that are cleaved from the polymer ends upon increasing temperature, creating a radical at the chain end from which depolymerization is initiated, leading to degradation of the polymer. The treatment steps in inventive examples 3 and 4 continuously improve thermal stability. For example, after the hydrogen peroxide treatment, the temperature of the 5% and 10% mass loss in the TGA measurement is increased. This means that the end groups and thermally labile functionalities in the polymer have been removed, resulting in a polymer with a more thermally stable structure.The improvements achieved by the subsequent annealing step surprisingly show a further strong improvement in temperature stability.

[0202] To produce the PA 66 compounds in the compositions shown in Table 5, PA 66 of the type Ultramid® A3K BASF was used, into which the polymer from inventive example 4 was blended using a Process 11 twin-screw laboratory extruder (Thermo Fisher) under the extrusion conditions typical for PA 66. The extrusion process was carried out at a throughput of approximately 480 g per hour and a temperature of 260-280 °C. UL94 test specimens with a thickness of 1.6 mm were obtained from the resulting granules by injection molding. The samples were tested according to IEC / DIN EN 60695-11. For this purpose, a Bunsen burner with a defined flame was brought close to the samples. The samples were exposed to flames twice for 10 seconds, and their fire behavior was observed. The test results are listed in Table 4. Table 4:

[0203] Compared to sample 1 (without flame retardant), all samples (2-4) with the example according to the invention show reduced dripping behavior.

[0204] The samples with the addition of the polymer according to inventive example 4 exhibit charring, which protects against further ignition. This is due to a significantly changed dripping behavior of the samples with the inventive example. The pure PA 6.6 drips continuously during the test while burning. Samples 2-4 tend to

[0205] The polymer is significantly less prone to dripping. The flaming dripping observed with the pure polymer is present in the inventive example after the first flame exposure, but to a significantly reduced extent, and at the same time, the polymer surface chars. This leads to the formation of a carbon layer that protects the test specimen from further ignition during the second flame exposure. In the case of sample 1, the fire behavior remains unchanged compared to the first flame exposure. With increasing concentration of the inventive example in the compound, a continuous decrease in the dripping behavior of the sample after the first flame exposure was observed.

Claims

Patent claims 1. A process for producing a phosphorus-containing polymer by means of a RAFT (Reversible Addition-Fragmentation Chain Transfer) polymerization reaction comprising the following steps: a) Providing at least one monomer A of the general formula I capable of radical polymerization Formula I where Ri is selected from the group consisting of hydrogen, methyl, ethyl or a linear or branched C3 or C4 alkyl group, R2 is selected from the group consisting of linear or branched substituted or unsubstituted hydrocarbon groups containing 1-20 carbon atoms, R3 and R are identical or different at each occurrence and are selected from the group consisting of substituted or unsubstituted cyclic hydrocarbon groups having 6-20 carbon atoms, m is an integer selected from the group consisting of 0, 1, 2, or 3, or a mixture containing at least two different monomers A capable of radical polymerization of the general my formula I or at least one monomer A of the general formula I which is capable of radical polymerization and at least one further monomer different from the monomer A which is capable of radical polymerization, b) adding at least one initiator B which starts the polymerization by releasing at least one radical, c) adding at least one agent C which is capable of reversibly transferring an organic radical to an adduct radical formed from the monomers A during the polymerization reaction, d) initiating the polymerization reaction, wherein step c) takes place before, simultaneously or after step b) or simultaneously or after step d).

2. Process according to claim 1, characterized in that the monomer A is selected from the group consisting of 10-oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)methyl methacrylate (Ri=methyl, R2=CH2, R3=R4=aryl, m=0, DOPO-MMA) (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)methylac- rylat (Ri=H, R2=CH2, R3=R4=Aryl, m=0, DOPO-MA) 10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)ethylmethac- rylat (Ri=Methyl, R2=(CH2)2, R3=R4=Aryl, m=0, DOPO-EMA) (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)ethylacrylat (Ri=H, R2=(CH2)2, R3=R4=Aryl, m=0, DOPO-EA) 10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)propylme- thacrylat (Ri=Methyl, R2=(CH2)3, R3=R4=Aryl, m=0, DOPO-PMA) (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)propylacrylat (R1=H, R2=(CH2)3, R3=R4=Aryl, m=0, DOPO-PA) 10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)butylmethac- rylat (Ri=Methyl, R2=(CH2)4, R3=R4=Aryl, m=0, DOPO-BMA) und (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)butylacrylat (Ri=H, R2=(CH2)4, R3=R4=Aryl, m=0, DOPO-BA).

3. Process according to one of the preceding claims, characterized in that the agent C has the following general formula II Formula II where Y is a radical selected from the group consisting of cyano-i-propyl, 1-phenylethyl, t-butyl, 4-cyanopentyl-5-carboxylic acid, phenyl, cyanoalkyl, benzyl, butyl-2-methylpropanoate, methyl-2-propanoate, Z is a radical R selected from the group consisting of linear or branched and substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl or substituted or unsubstituted aryl radicals, OR5, NfReh, SR? and P(O)(ORs)2, where each of R5, Re, R? and Rs independently of one another are linear or branched substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C1-C10 aryl, 3-8 membered cyclic or heterocyclic rings, or NfReh is a 3-8 membered heterocyclic ring; in particular methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, neopentyl, dodecyl, methylsulfanyl, ethylsulfanyl, n-propylsulfanyl, i-propylsulfanyl, n-butylsulfanyl, i-butylsulfanyl, t-butylsulfanyl, Neopentylsulfanyl, dodecylsulfanyl, particularly preferably dodecylsulfanyl, in particular the agent is C 2-cyanopropan-2-yl-dodecylcarbonotrithioate.

4. Process according to one of the preceding claims, characterized in that after step d), in particular after a conversion of at least 10 mol%, preferably at least 25 to 100 mol-%, more preferably 50 to 90 mol-%, or after completion of the polymerization reaction, the resulting polymer with at least one agent D which is capable of converting the organic radical bound to the adduct radical into groups which allow neither further polymerization nor depolymerization, in particular in the case that an agent according to the preceding claim is used, of converting dithioester groups and / or trithiocarbonate groups bound to the adduct radical into groups which allow neither further polymerization nor depolymerization from the chain end.

5. Process according to the preceding claim, characterized in that the at least one agent D is selected from the group consisting of peroxides and sterically hindered phenols, for example hydrogen peroxide.

6. Process according to the preceding claim, characterized in that the agent D is added directly to the reaction mixture in a one-pot reaction or is carried out on the previously isolated and subsequently redissolved, suspended or emulsified polymer.

7. Process according to one of the preceding claims, characterized in that after completion of the polymerization reaction, in particular after end group substitution in step d), the phosphorus-containing polymer is heated above its glass transition temperature under vacuum for a period of 1 minute to 48 hours.

8. Process according to one of the preceding claims, characterized in that the polymerization reaction is initiated and carried out by heating the polymerizable mixture to a temperature above standard temperature (SATP).

9. Process according to one of the preceding claims, characterized in that the polymerization reaction is carried out over a period of time which allows the polymerization to a conversion of 10-100%, and / or at temperatures between 60°C and 100°C, preferably between 65°C and 90°C, particularly preferably between 70°C and 80°C.

10. Process according to one of the preceding claims, characterized in that the at least one initiator B is selected from the group consisting of azo compounds, preferably azo-bis-i-butyronitrile.

11. Process according to one of the preceding claims, characterized in that the at least one further monomer of the monomer mixture which is different from monomer A and capable of radical polymerization is selected from the group consisting of styrene, isoprene, butadiene and acrylates having the general structural formula III Rio Formula III where Rg is hydrogen or a methyl group and Rio is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, t-amyl, benzyl, cyclohexyl, 9-anthracenyl, 2-hydroxyethyl, 3-phenyl-2-propenyl, adamantyl, Methyladamantyl, ethyladamantyl, isobornyl, 2-ethoxyethyl, n-heptyl, n-hexyl, 2-hydroxypropyl, 2-ethylbutyl, 2-methoxypropyl, 2-(2-methoxyethoxyl), 2-naphthyl, 2-phenylethyl, phenyl, lauryl, myristyl, cetyl, stearyl, ceryl, i-decyl, 2-ethylhexyl, ethyl triglycol, tetrahydrofurfuryl, butyl diglycol, 2-dimethylaminoethyl, polyethylene glycol, methylpolyethylene glycol or a glycidyl group.

12. Process according to the preceding claim, characterized in that the molar proportion of the total of the monomers A in the monomer mixture is between 0.1 and 99.9 mol%, preferably between 50 and 99.9 mol%, particularly preferably between 80 and 99.9 mol%.

13. The process according to any one of the preceding claims, characterized in that the polymerization reaction is carried out in a solvent or a solvent mixture, the solvent being in particular selected from the group consisting of dimethyl sulfoxide, dimethylacetamide, dimethylformamide, PGMEA, ethyl acetate, toluene, xylene, ethylbenzene, anisole, acetone, 2-butanone, acetonitrile, tetrahydrofuran, dioxane, diethyl ether, tert.-Butyl methyl ether, pentane, hexane, heptane, cyclopentane, cyclohexane, dichloromethane, chloroform, methanol, ethanol, n-propanol, i-propanol, n-butanol, t-butanol, ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, water and mixtures and combinations thereof, wherein the amount of solvent is preferably chosen such that the concentration of all monomers capable of radical polymerization is preferably a maximum of 1.5 mol / L.

14. Phosphorus-containing polymer containing at least one monomer unit according to general formula IV wherein the radicals Ri, R2, R3, R4 and m are as defined in claim 1, characterized by a solubility at 23 °C in dimethylformamide of at least 2.0 g / l, wherein the total of all monomer units according to general formula IV, based on the total of all monomer units, is at least 90 mol%, preferably at least 95 mol%, more preferably at least 97.5 mol%, in particular at least 99 mol%, preparable or prepared by a process according to any one of claims 1 to 13.

15. Phosphorus-containing polymer according to the preceding claim, characterized in that the repeating unit is selected according to general formula IV from radicals derived from the following radically polymerized monomers: 10-oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)methyl methacrylate (Ri=methyl, R2=CH2, R3=R4=aryl, m=0, DOPO-MMA) (10-oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)methyl acrylate (Ri=H, R2=CH2, R3=R4=aryl, m=0, DOPO-MA) 10-oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)ethyl methacrylate (Ri=methyl, R2=(CH2)2, R3=R4=aryl, m=0, DOPO-EMA) (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)ethylacrylat (Ri=H, R2=(CH2)2, R3=R4=Aryl, m=0, DOPO-EA) 10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)propylme- thacrylat (Ri=Methyl, R2=(CH2)3, R3=R4=Aryl, m=0, DOPO-PMA) (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)propylacrylat (R1=H, R2=(CH2)3, R3=R4=Aryl, m=0, DOPO-PA) 10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)butylmethac- rylat (Ri=Methyl, R2=(CH2)4, R3=R4=Aryl, m=0, DOPO-BMA) und (10-Oxo-10-hydro-9-oxa-10-phosphaphenanthrene-10-yl)butylacrylat (Ri=H, R2=(CH2)4, R3=R4=Aryl, m=0, DOPO-BA).

16. Phosphorus-containing polymer according to one of claims 14 to 15, characterized in that it is a homopolymer and is formed from identical repeating units according to general formula IV, or is a copolymer and is formed from different repeating units according to general formula IV or from at least one repeating unit according to general formula IV and at least one further repeating unit different from the repeating unit according to general formula IV, wherein the at least one further repeating unit different from the repeating unit according to general formula IV is preferably selected from repeating units resulting from the radical polymerization of styrene, isoprene, butadiene and acrylates with the general structural formula III Rio Formula III where R9is hydrogen or a methyl group and Rio ausgewählt ist aus der Gruppe bestehend aus Methyl-, Ethyl-, n- Propyl-, i-Propyl-, n-Butyl-, i-Butyl-, t-Butyl-, t-Amyl-, Benzyl-, Cyclohexyl-, 9-Anthracenyl-, 2-Hydroxyethyl-, 3-Phenyl-2-prope- nyl, Adamantyl-, Methyladamantyl-, Ethyladamantyl-, Isobornyl- , 2-Ethoxyethyl-, n-Heptyl-, n-Hexyl-, 2- Hydroxypropyl-, 2-Ethyl- butyl-, 2-Methoxypropyl-, 2-(2-methoxyethoxyl), 2-Naphthyl-, 2- Phenylethyl-, Phenyl-, Lauryl-, Myristyl-, Cetyl-, Stearyl-, Ceryl-, i- Decyl-, 2-Ethylhexyl-, Ethyltriglycol-, Tetrahydrofurfuryl-, Butyl- diglycol-, 2-Dimethylaminoethyl-, Polyethylenglycol-, Methylpo- lyethylenglycol- oder einer Glycidylgruppe, hervorgehen.

17. Phosphorus-containing polymer according to one of claims 14 to 16, characterized by a number-average molecular weight of 10,000 to 1,000,000 g / mol, preferably 15,000 to 500,000 g / mol, particularly preferably 20,000 to 100,000 g / mol and / or a polydispersity D, determined as the quotient of the weight-average molecular weight and the number-average molecular weight, of 1.1 to 5.0, preferably 1.3 to 4.

5.

18. A plastic composition comprising at least one plastic and at least one phosphorus-containing polymer according to any one of claims 14 to 17.

19. Plastic composition according to the preceding claim, characterized in that the at least one phosphorus-containing polymer is present in an amount of 0.1 to 25.0 wt.%, preferably 1.0 to 20.0 wt.%, particularly preferably 5.0 to 20.0 wt.%, based on the total plastic composition.

20. Plastic composition according to one of claims 18 to 19, characterized in that the at least one plastic is selected from the group of thermoplastics, preferably from the group of polyamides, in particular polyamide 6.6, polyamide 6, polyamide 11; poly(meth)acrylates; polyesters, in particular polyethylene terephthalate, polybutylene terephthalate or polytrimethylene terephthalate and polycarbonates.

21. A molded part made from a thermoplastic composition according to any one of claims 18 to 20, in particular plastic fibers, woven fabrics, scrims, knits, nonwovens, protective clothing, upholstery covers, curtains, carpets, airbag fabrics, reinforcement for plastics.

22. Use of a phosphorus-containing polymer according to any one of claims 14 to 17 as a flame retardant.

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