EP1401941A1 - Stabilised metallocene polyolefins - Google Patents

Abstract

Stabilised thermoplastic moulded masses, comprising (A) at least one polyolefin A), produced by application of at least one metallocene catalyst and (B) at least one stabiliser B), selected from the following groups b1) bis b4): (b1) sterically hindered amines based on glycolurils, (b2) sterically hindered amines based on 4-formylaminopiperidines, (b3) sterically hindered amines based on maleic acid imide/ alpha -olefin copolymers and (b4) sterically hindered amines selected from particular individual compounds.

Description

Stabilized metallocene polyolefins

description

The invention relates to stabilized thermoplastic molding compositions containing

A) at least one polyolefin A), produced using at least one metallocene catalyst, and

B) at least one stabilizer B) selected from the following groups bl) to b4) bl) sterically hindered amines based on glycolurils, b2) sterically hindered amines based on 4-formylamino-piperidines, b3) sterically hindered amines Based on maleic acid-imide-α-olefin copolymers, b4) sterically hindered amines selected from

Bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6, 6-tetramethylpiperidin-4-yl) succinate,

Bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) sebacate, bis (l-octyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate. Bis (1,2,2,6,6-pentamethylpiperidin-4-yl) -n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1- (2-hydroxyethyl) ) -2,2, 6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N, N'-bis (2, 2, 6, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino- 2, 6-dichloro-1, 3, 5-triazine, tris (2,2,6, 6-etra ethyl-piperidine-4-yl) nitrilotriacetate, tetrakis (2,2, 6, 6-tetramethyl-piperidine -4-yl) -1,2,3, 4-butane-tetracarboxyla, 1, 1 '- (1, 2-ethylene) -bis (3,3,5, 5-tetramethyl-piperazinone), 4-benzoyl- 2, 2,6, 6-tetramethylpiperidine, 4-stearyloxy-2, 2,6, 6-tetramethylpiperidine, bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) -2-n -butyl-2- (2-hydroxy-3,5-di-tert-butylbenzydmalonate, 3-n-octyl-7, 7, 9,9-tetramethyl-l, 3, 8-triazaspiro [4.5] decan-2, 4-dione, bis {l-octyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-octyl-oxy-2,2,6,6-etramethyl-piperidin-4-yl) succinate, the condensation prod product from N, N '- bis (2,2, 6, 6-tetramethylpiperidin-4-yl) hexamethylene diamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine, the Condensation product from 2-chloro-4, 6-bis (4-n-butylamino-2, 2,6, 6-tetramethylpiperidin-4-yl) -l, 3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, the condensation product

2-chloro-4, 6-di- (4-n-butylamino-l, 2,2,6, 6-pentamethyl-piperidin-4-yl) -l, 3,5-triazine and 1,2- Bis- (3-amino-propyla- mino) ethane, 8-acetyl-3-dodecyl-7, 7, 9, 9-tetra-methyl-1,3,8-triaza-spiro [4.5] -decane-2,4-dione, 3-dodecyl-l - (2,2,6, 6-tetramethylpiperidin-4-yl) - pyrrolidin-2, 5-dione, 3-dodecyl-l ~ (1,2,2,6, 6-penta-methyl-piperidin-4- yl) pyrroli-din-2,5-dione, a mixture of 4-hexadecyloxy and 4-stearyloxy-2, 2,6, 6-tetramethyl-piperidine, the condensation product of N, N'-bis- (2.2 , 6,6-tetramethylpiperidin-4-yl) hexamethylene diamine and 4-cyclohexylamino-2, 6-dichloro-l, 3, 5-triazine, the condensation product of 1, 2-bis (3-aminopropylamino) - ethane and 2,4,6-trichloro-l, 3,5-triazine, 4-butylamino-2,2,6,6-tetramethylpiperidine, N- (2,2,6,6-tetramethylpiperidine -4-yl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethylpiperidin-4-yl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1- oxa-3, 8-diaza-4-oxo-spiro [4.5] -decane, the condensation product from 7,7,9, 9-tetramethyl-2-cycloundecyl-l-oxa-3, 8-diaza-4-oxospiro- [4.5] decane and epichlorohydrin, the condensation product from 4-amino-2, 2,6, 6-tetramethyl-piperidine with tetramethylolacetylene diureas and poly (methoxypropyl-3-oxy) - [4- (2,2,6, 6-tetramethyl) piperidinyl] siloxane.

In addition, the invention relates to the use of the molding compositions for the production of moldings, films and fibers and moldings, films and fibers from the molding compositions mentioned. Finally, the invention relates to a method for producing the molding compositions.

The use of sterically hindered amines as light and antiaging agents in polymers is known. They act due to light-related aging and destruction of the polymer, which can e.g. as yellowing, discoloration, cracking or embrittlement.

For the stabilization of polyolefins which are produced by means of metallocene catalysts (so-called metallocene polyolefins), DE-A 100 03 866 proposes a stabilizer mixture which contains certain substituted piperidines and certain substituted triazines as sterically hindered amines. The property profile of these stabilized metallocene polyolefins is not entirely satisfactory.

The object was to remedy this disadvantage and to provide stabilized metallocene polyolefins with an optimized property profile. Accordingly, the stabilized thermoplastic molding compositions defined at the outset were found. In addition, the use of the molding compositions for the production of molded articles, films and fibers and also molded articles, films and fibers from the molding compounds mentioned has been found, as well as a process for the production of the molding compounds.

The components of the molding composition are described in more detail below.

Component A)

The molding compositions contain, as component A), at least one polyolefin which has been prepared using at least one metallocene catalyst. Such polyolefins are also referred to as metallocene polyolefins. All polyolefins are suitable as component A), in the production of which metallocene catalysts are also used. The metal locen complexes described below are examples, but are not an exhaustive list.

The olefins which can be polymerized by means of a metallocene catalyst are in particular ethylene and α-olefins, for example propylene, 1-butene, 4-methyl-1-pentene, 5-methyl-1-hexene; Isohexene, isooctene; Cycloolefins (eg cyclopentadiene (monomer or dimer) or norbornene) or styrene and mixtures of olefins, for example ethylene-propylene or propylene mixed with small amounts of higher α-olefins. In this case preference is given to the C ₂ - or C-01efins and their copolymers.

Polymers are understood to mean both homopolymers and copolymers of one of the monomers mentioned as the main monomer and other monomers as comonomers.

Preferred polyolefins are the homopolymers and copolymers of ethylene and the homopolymers and copolymers of propylene. They are described in more detail below.

Ethylene polymers:

Polyethylene produced using metallocene catalysts, for example, is available as Luflexen ^® (Fa. Basell) commercially. The metallocene catalyst system is described in more detail below. The following compounds of the general formula are suitable as metallocene complexes:

in which the substituents have the following meaning:

M titanium, zirconium, hafnium, vanadium, niobium or tantalum,

X fluorine, chlorine, bromine, iodine, hydrogen or C ~ to Cio-alkyl,

R ⁸ to R ^{12 are} hydrogen, Ci- to Cio-alkyl, 5- to 7-membered

Cycloalkyl, which in turn can carry a C 1 -C 10 -alkyl group as a substituent, Cg- to C 5 ~ aryl or arylalkyl, where optionally two adjacent radicals together can represent cyclic groups having 4 to 15 C atoms or Si (R ¹³ ) ₃ with

R "CI- to Cio-alkyl, C ₃ - to Cι ₀ cycloalkyl or C ₆ ~ to Cι ₅ aryl,

represents X or

being the leftovers

R ¹⁴ to R ¹⁸ hydrogen, Cι ~ to Cio-alkyl, 5- to 7-membered cycloalkyl, which in turn is a Cι ~ to Cio-alkyl

To C ₅ aryl or aryl alkyl, and wherein optionally also be ^¬ two neighboring radicals can together be 4 to 15 C-atoms form a cyclic group, or Si (R ¹⁹⁾ ₃ with - may bear a substituent, C ₆ R ¹⁹ Ci to Cio alkyl, Cg to C ₅ aryl or C ₃ to

Cιo ^_ cycloalkyl,

or wherein the radicals R ¹¹ and Z together form a group -R ²⁰ -A- in which 22 22 _R 22 22

- M ³ - _ M ³ M ³ M ³ CR ²³

R20 j | | |

R21 R21 R21 21

R22 R22 22 22

M ^{3 '}

_R 21

R 1 _R 21 _R 21

= BR ²² , = AIR ²² , -Ge-, -Sn-, -0-, -S-, = SO, = S0 ₂ , NR ²² , = CO, = PR ²² or = P (0) R ²² ,

where R ²¹ , R2 _unc j 23 are the same or different and a hydrogen atom, a halogen atom, a Cι-Cιo ~ alkyl group, a

Cι-Cιo-fluoroalkyl group, a Cg-Cio-fluoroaryl group, a Cg-Cio-aryl group, a Ci-Cio-alkoxy group, a C ₂ -Cιo-alkenyl group, a C -C ₄ o-arylalkyl group, a C ₈ -C ₄ mean o-arylalkenyl group or a C -C ₄ o-alkylaryl group or where two adjacent radicals each form a ring with the atoms connecting them, and

M ^{3 is} silicon, germanium or tin,

NR ²⁴ p _R 24

A O, S or ^ mean with

R 4 C 1 to C 10 alkyl, C ₆ to C ₅ aryl, C ₃ to C ₀ cycloalkyl, alkylaryl or Si (R ²⁵ ) ₃ ,

R ^{25 is} hydrogen, -C ~ to Cio-alkyl, Cg- to cis-aryl, which in turn can be substituted with Cι ~ to C ₄ alkyl groups or C ₃ - to Cio-cycloalkyl or wherein the radicals R ¹¹ and R ¹⁷ together form a group -R2 ⁰ _.

Particularly suitable metallocene complexes are described, for example, in DE-A 198 06 435, page 3, line 68 to page 5, line 67. It is expressly referred to the passage mentioned.

Such complex compounds can be synthesized by methods known per se, the reaction of the appropriately substituted cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum being preferred. Examples of corresponding manufacturing processes include in the Journal of Organometallic Chemistry, 369 (1989), 359-370.

Mixtures of different metallocene complexes can also be used.

The metallocene complexes are usually activated by an activator connection. Suitable activators are, in particular, compounds which form metallocenium ions. Suitable metal ocenium ion-forming compounds are, in particular, complex compounds selected from the group consisting of strong, neutral Lewis acids, the ionic compounds with Lewis acid cations and the ionic compounds with Bronsted acids as the cation.

Compounds of the general formula are strong, neutral Lewis acids

M ⁴ X ¹ X ² X ³

preferred in the

M ⁴ _e j_ _n element of III. Main group of the periodic table means, in particular B, Al or Ga,

l, X ² and X ³ for hydrogen, Ci- to Cio-alkyl, C _ß - to Cis-aryl, alkyl-aryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C- Atoms in the aryl radical or fluorine, chlorine, bromine or iodine are, in particular for haloaryls, preferably for pentafluorophenyl.

Compounds of the general formula are ionic compounds with Lewis acid cations [(Y ^{a +} ) QιQ ₂ -. , Q _z ] ^{d +}

suitable in which

an element of the I. to VI. Main group or the I. to VIII. Subgroup of the periodic table means

Qi to Q _z for single negatively charged residues such as Ci to C28 ~ alkyl, Cg to Cis aryl, alkylaryl, arylalkyl,

Haloalkyl, haloaryl each having 6 to 20 carbon atoms in the aryl and 1 to 28 carbon atoms in the alkyl radical, C 1 -C to cycloalkyl, which can optionally be substituted by C 1 -C 1 -alkyl groups, halogen, C 1 -C 4 ₂₈ alkoxy, Cg to cis aryloxy, silyl or

mercaptyl

a stands for integers from 1 to 6, z stands for integers from 0 to 5 d corresponds to the difference a-z, whereby d is greater than or equal to 1.

Carbonium cations, oxonium cations and sulfonium cations as well as cationic transition metal complexes are particularly suitable. In particular, the triphenylmethyl cation, the silver cation and the 1,1'-dimethylferrocenyl cation should be mentioned. They preferably have non-coordinating counterions, in particular boron compounds, as also mentioned in WO-A 91/09882, preferably tetrakis (pentafluorophenyl) borate.

Ionic compounds with Bronsted acids as cations and preferably also non-coordinating counterions are mentioned in WO-A 91/09882; the preferred cation is N, N-dimethylanilinium.

All commercially available ethylene copolymers are suitable as ethylene copolymers, for example Luflexen® types (from Basell), Norde® (DuPont), Engage®, Affinity®, Elite® (all Dow) and Finacene® (Atofina). All α-olefins with 3 to 10 C atoms are suitable as comonomers, in particular propylene, but-1-ene, hex-1-ene and oct-1-ene, and also alkyl acrylates and methacrylates with 1 to 20 C atoms in Alkyl radical, especially butyl acrylate. Other suitable comonomers are dienes such as butadiene, isoprene and ocadiene and dicyclopentadiene. They are usually statistical copolymers or block or impact copolymers.

Block or impact copolymers of ethylene and comonomers are polymers in which a homopolymer of the comonomer or a random copolymer of the comonomer is prepared with up to 15% by weight, preferably up to 6% by weight, of ethylene and then in the second stage, a comonomer-ethylene copolymer with ethylene contents of 15 to 80 wt .-% polymerized. As a rule, so much of the comonomer-ethylene copolymer is polymerized in that the copolymer produced in the second stage has a proportion of 3 to 60% by weight in the end product.

The polymerization for the production of the ethylene-comonomer copolymers takes place by means of a metallocene catalyst system as previously described.

In addition to polyethylene, which is produced using metallocene catalysts, the molding compositions according to the invention can also contain polyethylene, which is produced in the conventional way or by means of catalyst systems based on polymerization-active metal complexes.

Suitable classic polyethylene (PE) homopolymers include:

PE-LD (LD = low density), obtainable by the high pressure process (ICI) at 1000 to 3000 bar and 150 to 300 ° C with oxygen or peroxides as catalysts in autoclaves or tubular reactors. Heavily branched with branches of different lengths, crystallinity 40 to 50%, density 0.915 to 0.935 g / cm ³ , average molecular weight up to 600,000 g / mol.

PE-LLD (LLD = linear low density), available with metal complex catalysts in the low pressure process from the gas phase, from a solution (e.g. petrol), in a suspension or with a modified high pressure process. Weakly branched with unbranched side chains, molecular weights higher than with PE-LD.

- PE-HD (HD = high density), available according to the medium pressure (Phillips) and low pressure (Ziegler) process. According to Phillips at 30 to 40 bar, 85 to 180 ° C, chromium oxide as a catalyst, molar masses about 50,000 g / mol. According to Ziegler at 1 to 50 bar, 20 to 150 ° C, titanium halides, titanium esters or aluminum aluminum alkyls as catalysts, molar mass about 200,000 to 400,000 g / mol. Carried out in suspension, solution, gas phase or Dimensions. Very weakly branched, crystallinity 60 to 80%, density 0.942 to 0.965 g / cm ³ .

PE-HD-HMW (HMW = high olecular weight), available according to the Ziegler, Phillips or gas phase method. High density and high molecular weight.

PE-HD-UHMW (UHMW = ultra high molecular weight) available with modified Ziegler catalyst, molecular weight 3,000,000 to 6,000,000 g / mol.

Polyethylene, which is produced in a gas phase fluidized bed process using (usually supported) catalysts, e.g. Lupolen® (from Basell).

Propylene polymers:

The term polypropylene is to be understood below to mean both homopolymers and copolymers of propylene. Copolymers of propylene contain minor amounts of monomers copolymerizable with propylene, for example C ₂ -C ₈ alkene, such as, inter alia, ethylene, but-1-ene, pent-1-ene or hex-1-ene. Two or more different comonomers can also be used.

Suitable polypropylenes include Homopolymers of propylene or copolymers of propylene with up to 50% by weight of other alk-1-enes polymerized in with up to 8 carbon atoms. The copolymers of propylene are statistical copolymers or block or impact copolymers. If the copolymers of propylene have a statistical structure, they generally contain up to 15% by weight, preferably up to 6% by weight, of other alk-1-enes with up to 8 C atoms, in particular ethylene, but-1 -en or a mixture of ethylene and but-l-ene.

Block or impact copolymers of propylene are polymers in which, in the first stage a propylene homopolymer or a random copolymer of propylene with up to 15 wt .-% before Trains t ^¬ up to 6 wt .-%, of other alk-1-ene with up to 8 carbon atoms and then in the second stage a propylene-ethylene copolymer with ethylene contents of 15 to 80% by weight, the propylene-ethylene copolymer additionally containing further C ₄ -Cs May contain alk-l-ene, copolymerized. As a rule, so much of the propylene-ethylene copolymer is polymerized in that the copolymer produced in the second stage has a proportion of 3 to 60% by weight in the end product. The polypropylenes are manufactured using metallocene catalysts.

Metallocenes are to be understood here as meaning complex compounds of metals from subgroups of the periodic table with organic ligands, which together with compounds forming metallocenium ions result in effective catalyst systems. The metallocene complexes are generally supported in the catalyst system for use in the production of polypropylene. Inorganic oxides are frequently used as carriers, but organic carriers in the form of polymers, for example polyolefins, can also be used. Preference is given to the inorganic oxides described above, which are also used to prepare the titanium-containing solid component a).

Typically used metallocenes contain titanium, zirconium or hafnium as central atoms, zirconium being preferred. In general, the central atom is bonded via a π bond to at least one, usually substituted, cyclopentadienyl group and to further substituents. The further substituents can be halogens, hydrogen or organic radicals, with fluorine, chlorine, bromine or iodine or a C 1 -C 8 -alkyl group being preferred.

The cyclopentadienyl group can also be part of a corresponding heteroaromatic system.

Preferred metallocenes contain central atoms which are bonded to two substituted cyclopentadienyl groups via two identical or different π bonds, those which are particularly preferred in which substituents of the cyclopentadienyl groups are bonded to both cyclopentadienyl groups. In particular, complexes are preferred whose substituted or unsubstituted cyclopentadienyl groups are additionally substituted by cyclic groups on two adjacent carbon atoms, it being possible for the cyclic groups to also be integrated in a heteroaromatic system.

Preferred metallocenes are also those which contain only one substituted or unsubstituted cyclopentadienyl group, but which is substituted by at least one radical which is also bonded to the central atom.

Suitable metallocene compounds are, for example, ethylene bis (indenyl) zirconium dichloride, ethylene bis (tetrahydroindenyl) zirconium dichloride,

Diphenylmethylene-9-fluorenylcyclopentadienylzirconium dichloride, dimethylsilanediylbis (-3-tert. Butyl-5-methylcyclopentadienyl) - zirconium,

Dirnethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4 (4'-methylphenyl) -indenyl) zirconium dichloride,

Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-ethyl-4 (4'-tert.butylphenyl) -indenyl) zirconium dichloride,

Ethanediyl (2-ethyl-4-azapentalene) (2-ethyl- (4'-tert. Butylphenyl) -indenyl) zirconium dichloride,

Dirnet ylsilanediylbis (2-methyl-4-azapentalen) zirconium dichloride, dimethylsilanediylbis (2-methyl-4-thiapentalen) zirconium dichloride dimethylsilanediylbis (-2-methylindenyl) zirconium dichloride,

Dimethylsilanediylbis (-2-methylbenzindenyl) zirconium dichloride dimethylsilanediylbis (-2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilanediylbis (-2-methyl-4-naphthylindenyl) zirconium dichloride,

Dimethylsilanediylbis (-2-methyl-4-isopropylindenyl) zirconium dichloride or

Dimethylsilanediylbis (-2-methyl-4, 6-diisopropylindenyl) zirconium dichloride and the corresponding dimethylzirconium compounds.

The metallocene compounds are either known or can be obtained by methods known per se. Mixtures of such metallocene compounds can also be used for catalysis, furthermore the metallocene complexes described in EP-A 416 815.

The metallocene catalyst systems also contain compounds which form metal ocenium ions. Strong, neutral Lewis acids, ionic compounds with Lewis acid cations or ionic compounds with Bronsted acids as the cation are suitable. Examples of these are tris (pentafluorophenyDboran, tetrakis (pentafluorophenyDborat or salts of N, N-dimethylanilinium. Also suitable as metallocenium ion-forming compounds are open-chain or cyclic alumoxane compounds. These are usually prepared by reacting trialkylaluminum with water and are generally found as Mixtures of different lengths, both linear and cyclic chain molecules.

In addition, the metallocene catalyst systems metal-organic compounds of the metals of I., II. Or III. Main groups of the periodic table contain such as n-butyl lithium, n-butyl-n-octyl magnesium or tri-iso-butyl aluminum, triethyl aluminum or trimethyl aluminum.

In addition to polypropylene made using metallocene catalysts, those of the invention

Molding compounds also contain polypropylene, which is produced in the classic way, or by means of catalyst systems based on polymerization-active metal complexes.

The polymerization for the classic production of polypropylene can be carried out using a Ziegler-Natta catalyst system. In particular, catalyst systems are used which, in addition to a titanium-containing solid component a), also have cocatalysts in the form of organic aluminum compounds b) and electron donor compounds c).

In particular, conventional Ziegler-Natta catalyst systems contain a titanium-containing solid component a), i.a. Halides or alcohols of trivalent or tetravalent titanium, also a halogen-containing magnesium compound, inorganic oxides such as silica gel as a carrier and electron donor compounds c). In particular, carboxylic acid derivatives and ketones, ethers, alcohols or organosilicon compounds are suitable as such.

The titanium-containing solid component can be prepared by methods known per se. Examples include: in EP-A 45 975, EP-A 45 977, EP-A 86 473, EP-A 171 200, GB-A 2 111 066, US-A 4 857 613 and US-A 5 288,824. The method known from DE-A 195 29 240 is preferably used.

In addition to trialkyl aluminum, suitable aluminum compounds b) are also those compounds in which an alkyl group has been replaced by an alkoxy group or by a halogen atom, for example by chlorine or bromine. The alkyl groups can be the same or different. Linear or branched alkyl groups are possible. Trialkylaluminum compounds are preferably used, the alkyl groups of which each have 1 to 8 carbon atoms, for example trimethylaluminum, triethylaluminium, tri-isobutylaluminum, trioctylaluminum or methyldiethylaluminum or mixtures thereof.

In addition to the aluminum compound b), electron donor compounds c) such as monofunctional or polyfunctional carboxylic acids, carboxylic acid anhydrides or carboxylic acid esters, furthermore ketones, ethers, alcohols, lactones, and organophosphorus and organosilicon compounds are generally used as further cocatalyst, the electron donor compounds c) being identical or can be different from the electron donor compounds used to produce the titanium-containing solid component a). The production of the polypropylenes is carried out by polymerization in at least one, often also in two or more reaction zones connected in series (reactor cascade), in the gas phase, in a suspension or in a liquid phase (bulk phase). The usual reactors used for the polymerization of C ₂ -C ₈ -alk-1-enes can be used. Suitable reactors include continuously operated stirred tanks, loop reactors or fluidized bed reactors. The size of the reactors is not essential. It depends on the output that is to be achieved in or in the individual reaction zones.

In particular, fluidized bed reactors and horizontally or vertically stirred powder bed reactors are used as reactors. The reaction bed generally consists of the polymer of C ₂ -C ₈ -alk-1-enes, which is polymerized in the respective reactor.

The polymerization for producing the polypropylenes used is carried out under customary reaction conditions at temperatures from 40 to 120 ° C., in particular from 50 to 100 ° C. and pressures from 10 to 100 bar, in particular from 20 to 50 bar.

Suitable polypropylenes generally have a melt flow rate (MFR), according to ISO 1133, of 0.1 to 200 g / 10 min., In particular 0.2 to 100 g / 10 min., At 230 ° C. and under a weight of 2.16 kg.

Component B)

The molding compositions contain at least one stabilizer as component B), selected from the following groups b1 to b4):

bl) sterically hindered amines based on glycolurils, b2) sterically hindered amines based on 4-formylaminopiperidines, b3) sterically hindered amines based on maleic acid imide-α-olefin copolymers, b4) sterically hindered amines selected from

Bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1,2,2,6,6-penta- methylpiperidin-4-yl) sebacate, bis (l-octyloxy-2, 2, 6, 6-tetra-methylpiperidin-4-yl) sebacate, bis (1,2,2,6, 6-pentamethyl-piperidin-4- yl) -n-butyl-3, 5-di-tert-butyl-4-hydroxybenzylma- lonat, the condensation product from 1- (2-hydroxyethyl) - 2,2,6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N, N 'bis (2, 2, 6, 6-tetramethyl-piperidin-4-yl) hexamethylenediamine and 4-tert-octyl- amino-2, 6-dichloro-l, 3,5-triazine, tris (2,2,6,6-tetramethyl-piperidin-4-yl) nitrilotriacetate, tetrakis (2,2,6,6-tetra-methylpiperidine- 4-yl) -1,2,3, 4-butane tetracarboxylate, 1, 1'- (1,2-ethylene) -bis (3, 3, 5, 5-tetramethylpiperazinone), 4-benzoyl-2,2 , 6, 6-tetramethylpiperidine, 4-stearyloxy

2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) -2-n-butyl-2- (2-hydroxy-3,5-di- tert-butylbenzyl) malonate, 3-n-octyl-7, 7, 9,9-tetramethyl-l, 3, 8-triazaspiro- [4.5] -decane-2,4-dione, bis (l-octyloxy- 2,2, 6, 6-tetramethyl-piperidin-4-yl) sebacate, bis (l-octyloxy-2, 2, 6, 6-tetramethyl-piperidin-4-yl) succinate, the condensation product from N, N'- Bis- (2,2,6, 6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino-2, 6-dichloro-l, 3, 5-triazine, the condensation product of 2-chloro-4, 6- bis (4-n-butylamino-2, 2, 6, 6-tetra-methylpiperidin-4-yl) -1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, the condensation product 2-chloro-4, 6-di- (4-n-butylamino-l, 2,2,6, 6-pentamethy-piperidin-4-yl) -1, 3, 5-triazine and 1,2-bis- (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7, 7,9, 9-tetramethyl-l, 3, 8-triazaspiro [4.5] - decane-2,4-dione, 3-dodecyl-l- (2,2,6,6-tetramethylpiperidine

4-yl) pyrrolidin-2, 5-dione, 3-dodecyl-l- (1,2,2,6, 6-pentamethyl-piperidin-4-yl) pyrrolidin-2, 5-dione, a mixture of 4- Hexadecyloxy- and 4-stearyloxy-2,2, 6, 6-tetramethylpiperidine, the condensation product of N, N'-bis (2, 2, 6, 6-tetramethyl-piperidin-4-yl) -hexamethylene diamine and 4 -Cyclohexylamino-2, 6-dichloro-l, 3, 5-triazine, the condensation product of 1,2-bis (3-aminopropylamino) -ethane and 2,4,6-trichloro-1,3,5-triazine , 4-butylamino-2, 2,6, 6-tetramethylpiperidine, N- (2, 2, 6, 6-tetramethylpiperidin-4-yl) -n-dodecylsuccinimide, N- (1,2,2,6, 6- Pentamethylpiperidin-4-yl) -n-dodecylsuccinimide, 2-undecyl-7, 7,9, 9-tetramethyl-l-oxa-3, 8-diaza-4-oxo-spiro [4.5] -decane, the condensation product from 7 , 7, 9, 9-tetramethyl-2-σycloundecyl-l-oxa-3, 8-diaza-4-oxospiro- [4.5] decane and epichlorohydrin, the condensation products from 4-amino-2,2,6,6 -tetramethylpiperidine with tetramethylolacetylene diureas and poly (methoxypropyl-3-oxy) - [4- (2,2,6,6-tetramethyl ) piperidinyl] siloxane.

The amines b4) are individual compounds, so that further information is unnecessary. These individual compounds are known and commercially available.

The following can be said about the amines of groups bl) to b3). bl) Amines based on glycolurils (group bl))

The amines based on glycolurils are preferably the compounds of the general formula (I)

wherein:

n stands for a number from 1 to 70,

R ¹ and R independently of one another represent hydrogen, Ci-Cg-alkyl, C ₇ -Ci ₂ ~ aralkyl, aryl, or a carboxylic ester group or R ¹ and R ² together represent a tetra, penta- or hexamethylene group or an optionally substituted radical of the formula

mean,

R ³ , R ⁴ , R ⁵ and R ^{6 are} independently alkyl,

R ⁷ and R ⁸ independently of one another represent hydrogen or alkyl or one with the associated carbon atom

group

form,

X and Y independently of one another have the meanings oxygen, sulfur or NR ¹⁰ , where R ^{10 is} hydrogen, Ci-Ce-alkyl or C-Cι ₂ aralkyl,

R ⁹ for hydrogen, -CC ₂₂ - alkyl, which can be substituted by hydroxyl, carbonyl, carboxylic esters, carboxyl, carbamoyl, sulfonyl, sulfinyl or thiol groups, C ₃ -C ₂₂ alkenyl, C ₃ -C ₂₂ ~ Alkynyl, C ₇ -Ci ₂ aralkyl, C 1 -C ₂₂ ^_ alkyl, C ₄ -C ₂₂ cycloalkylalkyl, an optionally substituted heterocycle, chlorine, bromine, iodine, hydroxy, alkoxy, carboxyl, carboxylic ester, sulfonamido, optionally substituted carbamoyl, a urea group, a urethane group, or for - (-CH ₂ -) -D

is in which k is a number from 1 to 10 and D is -CN, -NH ₂ , -NHR ¹¹ or -NR ¹¹ R ¹² , wherein R ¹¹ and R ^{12 are the} same or different and for -C-C ₂₂ alkyl, C Acyl, carbamoyl, sulfonyl, sulfinyl, C2-C22-alkenyl, C ₃ -C ₂₂ -alkynyl, C ₃ -Ci ₂ -cycloalkyl, aralkyl, oligomeric or polymeric polyamine, it being possible for these radicals to be further substituted, or in which R ¹¹ and R ¹² together with the nitrogen atom to which they are attached form a 3 to 20-membered ring system,

A is the same or different and represents a direct bond or a bridge member with the proviso that at least one of the radicals A is a bridge member if R ⁹ does not have the meaning - (- CH2-) ~ ^D , and

B represents a further bridge member or a direct bond, and - the acid addition salts and hydrates of the compounds of general formula I.

In addition to hydrogen, individual radicals R ¹ and R ² are, for example: methyl, ethyl, propyl, butyl, penyl, hexyl, benzyl, phenylethyl, phenylpropyl, phenylbutyl, methylbenzyl, phenyl, tolyl, carbomethoxy, carboethoxy, carbopropoxy or carbobutoxy.

R ¹ and R ² are preferably ethyl, benzyl, carbomethoxy or carboethoxy and in particular hydrogen, methyl or phenyl.

R ⁹ preferably represents hydrogen, -CC ₂₂ alkyl, in particular -C ₄ alkyl, preferably methyl, which can be substituted by a hydroxyl or carboxyl group, C ₃ -Cs alkenyl, especially allyl, C ₇ -Ci _2- aralkyl, especially benzyl, -CH ₂ -CN, - (CH ₂ ) 2-CN; further possible meanings for R ⁹ are, for example, the following:

-CH2CH2-OH, -CH ₂ CH2CH ₂ -0H, -CH ₂ -CH-CH3.

0H, H0- (CH ₂ ) -, H0- {CH ₂ ) 2-0- (CHz) 2-, -CNH- (CH ₂ ) -, rr

-CH-COOH -CH-COOH -CH-COOH -CH-COOH -CH-COOH i ^ CH ₃ 1 CH-CH ₂ CH3. CH ₂ -Cl C 6HH ₂₂ CCHH ₂₂ SSCCHH33. CCHH ₂₂ --CCeßHH! S. CH ₂ 0H

CH ₃ CH3

i OOH

-CH ₂ - ^" -C00H, H00C-CCH ₂ J-, (~. - ^ - COOH, and

, CH ₃

CH ^

CH ₂ -CN

where o = 1 to 21 and r = 1 to 20.

n is preferably 1 to 40, particularly preferably 1.

The radicals R ³ , R ⁴ , R ⁵ and R ⁶ are preferably C 1 -C 6 -alkyl radicals, in particular C 1 -C ₄ -alkyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl. Methyl and ethyl are particularly preferred.

The term aryl stands in particular for phenyl, its C 1 -C ₄ -alkyl or C 1 -C ₄ alkoxy substitution products, for example tolyl or xylyl, and for halophenyl or optionally substituted naphthyl.

The term C ₃ -Ci ₂ cycloalkyl preferably stands for

H ₃ C0 CK ₃ CH ₃

H3C0 -

0QCH ₃ - • O tCH3 < ^»~ <-Ö- • C 0H3 -

C, H ₃

<

H3C 0 '-' Q C- ₂ Hs • C ₂ H _S - • ^H3Cz -0- • nC- ₃ H7 •

with n = 1 to 20

The radicals R ⁷ and R ⁸ are preferably hydrogen or C ₁ -C alkyl, for example methyl. The term used here includes-t- ^• straight-line-branched and branched - residues -, - in particular Ci-Cg-alkyl, for example methyl, ethyl, n-prop _Υ __, .. propyl, butyl, pentyl and hexyl. Examples of other branched alkyl radicals are the following:

(CH _Z I H3,

-CH ₂ -CH-CH ₃ , -CH ₂ -CH ₂ -CH-CH ₃ or -CH ₂ -CH- (CH ₂ ) ₃ -CH ₃ , where n = 0-21. CH ₃ CH3 CH ₂ -CH ₃

The term C ₇ -C ₂ aralkyl preferably comprises C ₇ -Cι ₂ phenylalkyl such as benzyl or phenylethyl, and their C1-C4-alkyl or Cι-C ₄ alkoxy-substitution products, PH ₃

-I ^C H ₂ ⁾ - ^ * ^"H"" ^ - '- ^CH2 - ( ^""0CH3'" ^CHzCH2 ~ {

H ₃ C0

■ where n> l Ut 6,. CH ₂ - H ₃ CH ₂ - CH ₂ CH ₂ -

ÖO. O ^Q. 06. θ6.

The term carboxylic ester group stands in particular for a group o

8th

-C — 0-C i-Cv alkyl.

The term includes C ₃ -C ₂₂ alkenyl, linear and branched so as ^¬ polyunsaturated radicals. C ₃ -Ci ₂ alkenyl, for example allyl, butenyl, pentenyl, hexenyl or heptenyl, is preferred. The term C ₃ -C 22 ~ alkynyl stands for straight-chain or branched, mono- or polyunsaturated residues. Preferred is C ₃ -C ₁₂ alkynyl, for example propargyl, butynyl, pentynyl, hexynyl or octynyl.

The term "oligomeric or polymeric polyamine" means, for example, the groupings

H ₂ N CH ₂ -CH ₂ -MH - (x - 1 to 30).

The term optionally substituted carbamoyl is, for example, (R ¹³ ) ₂ NCO-, where R ^{13 is} hydrogen or C 1 -C ₄ -alkyl.

Bridge members A and B are divalent aliphatic, araliphatic or aromatic groups, which can optionally contain oxygen, nitrogen or sulfur as heteroatoms. They can, in particular at the ends, have the groupings - CO-O-, -CO-NR ¹⁴ , -S0 ₂ -0-, -S0 ₂ -NR ¹⁴ -, where R ^{14 is} hydrogen, C 1 -C ₈ -alkyl, C ₂ to C ₂ aralkyl, C ₂ to C ₄ hydroxyalkyl, C ₅ to C ₇ cycloalkyl, C ₇ to C ₂ cycloalkylalkyl or C ₂ to Cg alkyl containing ether oxygen.

R ¹⁴ can in particular be hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methylpropyl, benzyl, phenylethyl, methoxyphenylethyl, 2-hydroxyethyl, 2-hydroxypropyl, cyclopentyl, cyclohexyl, cycloheptyl or methylcyclohexyl , ^~

Alkyl groups R ¹⁴ containing ether oxygen are, for example:

(CH ₂ ) ₃ 0CH ₃ , (CH ₂ ) ₃ OC ₂ H ₅ , (CH ₂ ) ₃ OC ₃ H ₇ , (CH ₂ ) ₃ 0C ₄ H ₉ , (CH ₂ ) ₂ 0 (CH ₂ ) ₂ OCH ₃ , (CH ₂ ) ₂ θ (CH ₂ ) ₂ OCH ₂ H ₅ , (CH ₂ ) ₂ 0 (CH ₂ ) ₂ OC ₃ H ₇ , (CH ₂ ) ₃ 0 (CH ₂ ) OC ₄ H ₉ , ( C ₂ H ₄ 0) ₃ C ₂ H ₅ , (C ₂ H ₄ θ) ₃ C ₄ H ₉ ,

(CH ₂ CHO) CH _{3 /} (CH ₂ CHO) C ₂ H ₅ , (CH ₂ CHO) ₂ CH ₂ or (CH ₂ CHO) C ₄ H ₉ .

CH ₃ CH ₃ CH ₃ CH ₃

In particular, A and B are alkyl, cycloalkyl, aralkylene, alkylene or aralkylene radicals substituted by CO or SO ₂ .

Individual pontics are, for example: HCH ₂ ) -, -CCH ₂ ) CH - CH-, - (CH ₂ ) -CSC-, - (CH ₂ ) - -, -ICH ₂ ) P p P> = 'q, -.

<CH ₂ ) -

- (CH ₂ 1

(Tl ^ M-, - (CH ₂ ) - ^ JP ^P '-tCH _a ) ₂ 0, - (CH ₂ J ₂ 0tCH ₂ ) r-,

- (CH ₂ ) 3θ "CH ₂ ) ₂ -, -CH-CH ₂ -0 (CH ₂ ) ₂ -, - (CH ₂ > ₂ 0CH-CH ₂ -, -CH-CH ₂ 0CH-CHr-, CH ₃ CH ₃ CH ₃ CH ₃

-C- (CHa) -, -C- (CH ₂ ) -0- (CH ₂ J -C-,

S ^q S ^qq l

SH CH ₃ C0NH -CH ₂ -SCH ₃ ,

-CH- -CH- -C 5HH-

CHs-CβHs. CHjOH CH (CH ₃ ) ₂ ,

where p = 1 to 20 and q = 0 to 4.

Further examples of bridge links -B- are as follows:

^ - .. - - "" l ¹ - -CW- (CHa) - HC-,

P H

(CH ₂ ) (CH ₂ ) H "H ^q

⁴ ιrOvl ^■ -4 -θτ * -

-'- i * ^H2 - <-> i- ^c - • - H. • - ^c -C _o ^c -

-30-

35

40

45

-, CH _{2) Γ} Q- ₍ CH ₂₎ -, - _(C H _{2> r} ζ. _(CH2) _ ₍ HCH, H _Γ -CCH „ _; ,

P

.

above

_B evorzugte bridge members are (CH _{2) n,} where n is preferably 1 to 5, especially 1, 2, 5.

If heterocylene, in particular non-aromatic heterocycles, are present in the compounds b1), these can be, for example, the following:

r, Qr HN ^< -0 - '* ^! * 0 s * -o

(CH ₂ ) C = 0) H ^P ICH ₂ )

I P

CH ₃

O ^, 0-f ~ O s - ^

, where Z «is hydrogen, alkyl, C-acyl or H0- and p * mean 1 to 20.

Exemplary urea groups are the following:

Exemplary urethane groupings are the following: -0-C-NH- (CH ₂ I-CH ₃

Y and Z are, independently of one another, in particular oxygen, and also sulfur or -NR ¹⁰ .

R ¹⁰ is hydrogen, -C ~ to Cs-alkyl or C ₇ -Cι ₂ aralkyl.

R ¹¹ and R ¹² are, independently of one another, in particular hydrogen, in addition also

- <CH ₈ »-CH ₃ , -C- (CH) -CH ₃ .

in which

1 = 0 to 22.

Insofar as R ¹¹ and R ¹² form a ring system together with the nitrogen atom to which they are attached, this can be, for example:

and R ¹⁵ can assume all of the above meanings of R ⁹ .

Compounds of the general formula (I) with n = 1, in which the bridge member A has the groupings -CO-O, -CO-NR ⁹ -, -S0-NR ⁹ -, can be obtained by reaction of compounds of the general formula II

analogous to the process of FR-A-2 291 203 with aminocarboxylic acid star H ₂ NB-COOR or ammosulfonic acids H ₂ -B-S0 ₃ or the corresponding alkyl esters, for example the ethyl esters, followed by catalyzed transesterification or esterification with substituted piperidine 4-amines or piperidin-4-ols can be prepared. The following scheme shows the reaction sequence for an exemplary compound III.

catalyst

The catalyst of the second reaction step can be an alkali alcoholate such as sodium methylate, an alkali hydroxide such as sodium hydroxide, an acid or preferably a tetraalkyl orthotitanate such as tetrabutyl orthotitanate.

Compounds of the general formula I can also be prepared by reacting compounds of the general formula II with compounds of the general formula IV.

The compound of formula II can in situ by reaction of compounds of general formula V

be produced with formaldehyde or a formaldehyde source.

The compounds of the formula I (with BR ⁹ = H) can be converted into the compounds with, for example, BR ⁹ = CH ₃ by processes known from the literature, for example by reductive amination.

Compounds of the general formula I in which R ^{9 is} - (CH ₂ ) -CN can advantageously also by reaction of compounds of the general formula VI

be prepared with glycolic acid nitrile or a glycolic acid nitrile source. The reaction of glycolonitrile with sterically hindered amines is described in DE-A-3 208 570.

The compounds bl) can be in the form of the free bases as hydrates or as salts. Suitable anions are e.g. of inorganic acids and in particular organic carboxylic acids and organic sulfonic acids.

Inorganic anions are e.g. Chloride, bromide, sulfate, methosulfate, tetrafluoroborate, phosphate or rhodanide.

Examples of carboxylic acid anions are: formate, acetate, propionate, hexanoate, cyclohexanoate, lactate, stearate, dodecyl benzoate, benzoate, acrylate, methacrylate, citrate, malonate or succinate, and anions of polycarboxylic acids with up to 3000 COOH groups.

Sulfonic acid anions are, for example, benzenesulfonate or tosylate.

Further details on the amines b1) can be found in EP-A 272 590.

The amine bl) based on glycolurils is particularly preferably the compound of the formula (bl)

where R is hydrogen or methyl. It is commercially available with R = H as üvinul® 4049 H from BASF.

b2) Amines based on 4-formylaminopiperidines (group b2))

The amines based on 4-formylaminopiperidines are preferably the compounds of the general formula (I)

in the

n 1 or 2,

R ¹ , R ² , R ³ and R ⁴ independently of one another are C 1 -C ₄ -alkyl or

R ¹ and R ² or R ³ and R ⁴ together form a tetramethylene or penta - e thy 1 en group,

R ^{5 is} hydrogen or C 1 -C ₄ -alkyl,

R ⁶ are hydrogen, ~ to C ₂₂ ^_ alkyl, C ₃ - to C ₂₂ -alkenyl, optionally substituted by Cι ~ C ₄ alkyl, fluorine, chlorine, Cι ~ to C ₄ -alkoxy, methylenedioxy, ethylenedioxy, and / or di- C 1 -C ₄ -alkylamino substituted C - to Ci ₂ -phenylalkyl, Cι ~ to C ₂₂ ~ alkanoyl, C ₂ - to C ₃ -cyanalkyl, Cι ~ to C ₂₂ -hydroxyalkyl or C ₂ - to C ₂₂ -aminoalkyl and

- if n = 1 -

Y is hydrogen, C ~ to C ₂₂ alkyl, C ₃ -C to C ₂ alkenyl, C ₃ - to Ci ₂ cycloalkyl or bicycloalkyl, C to C substituted by cyano, hydroxy or carbo-C 1 -C ₄ alkoxy ₂ 2-alkyl, interrupted by ether oxygen, nitrogen or sulfur C ₄ -C ₂₂ ~ alkyl, optionally by C ₁ -C ₄ alkyl, fluorine, chlorine, -CC ₄ alkoxy, methylenedioxy, ethylenedioxy or di-Cι-C ₄ ~ alkyl-amino-substituted C- to C ₂₂ ~ phenyl- or diphenylalkyl, optionally substituted by -C ~ C ₄ -alkyl or carbo-Cι-C ₄ -alkoxy-substituted phenyl, heterocyclic radicals containing ^C ι ~ C ₂₂ ~ alkyl or a radical of the formula

- if n = 2 - YC ₂ to C ₂₂ alkylene, C ₃ to C ₂₂ cycloalkylene, C ₈ to Ci ₄ phenylalkylene, phenylene or C ₄ to bis interrupted by ether oxygen, nitrogen, sulfur or 5- or 6-membered heterocycles Is C ₃₀ alkylene,

as well as the acid addition salts of these compounds.

The compounds b2) have extremely good stabilizing properties, have no intrinsic color, are well compatible with organic polymers, show a low vapor pressure and are stable against thermal decomposition.

R ¹ to R ⁴ are preferably methyl. Hydrogen is preferred for R ⁵ .

For R ⁶ , apart from hydrogen, the following are suitable, for example: methyl, ethyl, propyl, butyl, pentyl, hexyl; Benzyl, phenylethyl, phenylpropyl, methylbenzyl; allyl; Acetyl, propionyl, butanoyl, pentanoyl, benzoyl; Cyanomethyl, hydroxyethyl and aminoethyl.

For R ⁶ , methyl, acetyl, cyanomethyl, aminoethyl and especially hydrogen are preferred.

For Y, in addition to hydrogen, e.g. to call:

a) -C ₂₂ -C alkyl, such as methyl, ethyl, n- and i-propyl, n- and i-butyl, n- and i-pentyl, hexyl, octyl, decyl, dodecyl, octa-decyl, pivalyl , 3, 3-dimethylbutyl-2, neopentyl, 4-methyl-pentyl-2 and 2-ethylhexyl;

b) C ₃ -C ₂₂ alkenyl such as allyl, butenyl, pentenyl and oleyl;

c) C ₃ -C ₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl and bicycloheptyl, of which cyclopentyl and cyclohexyl are preferred;

d) C ₂ -C ₂₂ alkyl substituted by cyan, hydroxy or carboalkoxy, such as cyanomethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, carbomethoxyethyl and carboethoxyethyl;

e) C ₄ -C ₂₂ -Al yl interrupted by ether oxygen or nitrogen and optionally substituted by hydroxy, such as - (CH ₂ ) ₃ N (CH ₃ ) ₂ , - (CH ₂ ) ₃ N (C ₂ H ₅ ) ₂ , - (CH ₂ ) ₃ -OCH ₃ , - (CH ₂ ) ₃ -0-CH (CH ₃ ) ₂ , - (CH ₂ ) ₂ 0- (CH ₂ ) ₂ -0H, -CH ₂ - (CH ₂ ) ₂ -CH ₂ -N (CH ₂ ) 3, - (CH ₂ ) ₂ -N [CH (CH ₃ ) ₂ ] ₂ , - (CH ₂ ) ₂ -N (C ₂ H ₅ ) ₂ , - (CH ₂ ) ₂ N (CH ₃ ) ₂ , - (CH ₂ ) ₂ OCH ₃ and - (CH ₂ ) OCH ₂ CH ₃ ;

f) optionally substituted C -C ₂₂ -phenyl- and diphenylalkyl such as benzyl, methoxybenzyl, methylbenzyl, ethylbenzyl, isopropylbenzyl, trimethylbenzyl, fluorobenzyl, chlorobenzyl, methylenedioxybenzyl, phenylethyl, phenylpropyl and phenylbutyl, diphenyl, dimethylaminobenzyl diphenylpropyl-2;

g) optionally substituted phenyl such as phenyl, tolyl and phenyl substituted by carbo-C ₄ -alkoxy;

h) heterocyclic radicals of the formula

wherein R ¹ to R ^{6 have} the meaning given above;

i) Heterocycles containing -CC ₂₂ alkyl such as

-CH_ J, - _CH _ _^ , ^ _HJ Ü3, ^ ^{r <} ? ^■ - '

- (CHJ) -N '^","<"* -CH ₂ CH_V)

k) C ₂ -C ₂₂ alkylene and C ₅ -C ₂₂ cycloalkylene such as - (CH ₂ ) ₀ -CH (with o = 1 to 21),

-CH ₂ -CH-, -ξ-f,, -OrO, - -cHr-Q-

-CH

1) Cs-Ci ₄ -phenylalkylene and phenylene such as

) Alkylene interrupted by ether oxygen, nitrogen or heterocycles such as - (CH ₂ ) ₃ 0 (CH ₂ U0 (CH ₂ ) r, - (CH ₂ ) ₃ 0 (CH ₂ ) ₂ 0 (CH ₂ ) ₂ 0 (CH ₂ ) 3-

- (CH ₂ ) ₂ N- (CH ₂ ) r-, - (C3H ₆ 0) _r -C ₃ H ₆ - with r = 1 to 33, CH3

- (CH ₂ ) 3 → HCH) 3-, - (CH ₂ ) ₂ -N _ _J , CH ₂ ) ₂ -, - (CH ₂ ) ₃ -N _ _j , N- (CH ₂ ) 3-, CH3

- {CH ₂ ) ₃ 0 (CH ₂ ) ₂ 0 (CH ₂ ) 3-,,

with s = 0 to 7.

Compounds of the general formula (I) can be prepared by reacting compounds of the following general formula (II) with formic acid or formic acid esters. For this, the methyl and the ethyl ester are preferred. You can work with or without a catalyst. Catalysts can be Lewis acids, of which especially titanium orthoesters and specifically titanium orthobutylate should be mentioned here.

Compounds of the general formula (I) with R ⁶ = H can be converted into compounds of the general formula (I) with R ⁶ H by methods known per se, such as alkylation, reductive amination, reaction with glycolonitrile and others.

The compounds b2) can be present in the form of the free bases or as salts. Suitable anions are e.g. of inorganic acids and in particular of organic carboxylic acids and organic sulfonic acids.

As inorganic anions e.g. To name chloride, bromide, sulfate, methosulfate, tetrafluoroborate, phosphate and rhodanide.

As carboxylic acid anions, e.g. Formate, acetate, propionate, hexanoate, cyclohexanoate, lactate, stearate, dodecyl benzoate,

Benzoate, acrylate, methacrylate, citrate, malonate or succinate so- such as anions of polycarboxylic acids with up to 3000 COOH groups.

Sulfonic acid anions are, for example, benzenesulfonate or tosylate.

Further details on the amines b2) can be found in EP-A 316 582.

The compound of the formula (b2) based on 4-formylaminopiperidines is particularly preferably used as the amine b2)

where R is hydrogen or methyl. It is commercially available with R = H as Uvinul® 4050 H from BASF.

b3) amines based on maleimide-α-olefin copolymers (group b3))

Preferred amines based on maleimide-α-olefin copolymers are those compounds which are composed of structural units of the general formula (I)

in the R ¹ for a tetramethylpiperidinyl radical of the formula II

R ₃ wherein R ^{3 is} hydrogen, C ₁ -C ₆ -alkyl, for yl, C ₂ - to C6-alkanoyl, C 1 ~ to C ₂ alkoxy, C ₅ - to C ₆ -cycloalkoxy, cyano-methyl, 2-hydroxyethyl, Benzyl or a radical of the formula -CR ⁴ = CH-CO-OR ⁵ referred to, wherein R ^{4 is} hydrogen, Cι ~ to C ₆ alkyl or a radical of the formula - CO-OR ⁵ and

R5 is Ci to Cis alkyl, C ₅ to C ₈ cycloalkyl, C ₇ to C ₈ aralkyl, phenyl or tolyl,

stands, where

R ¹ in an amount of up to 8 mol%, based on II, can also denote hydrogen, Ci to C ₂₂ alkyl or C ₅ to C ₈ cycloalkyl, and

R ^{2 represents} a mixture of C ₁₄ to C ₂₈ alkyl groups, two of these alkyl groups, which must not differ by more than two C atoms, each make up at least 30% of this mixture,

with an average molecular weight of 1000 to 50,000.

Maleimide-α-olefin copolymers with an average molecular weight of 1500 to 10,000, in particular from 2000 to 5000, are preferred. The molecular weight data are number-average molecular weights.

The radical R ² is a mixture of C ₁₄ - to C ₂₈ -alkyl groups, preferably C ₁₅ - to C ₂₄ -alkyl groups, in particular C ₈ - to C ₂₂ -alkyl groups, so the copolymer is Cι ₆ - to C ₃ o ~ α-olefins, preferably Cι ₈ - to C ₂₆ ^_ a-01efine, in particular C ₂₀ - to C ₂₄ -α-01efine as building blocks. R ² is preferably linear alkyl groups.

The presence of a mixture of alkyl groups for R ² is to be understood as meaning that, on a statistical average over the total number of all copolymer molecules present, two specific alkyl groups, which must not differ by more than two C atoms, in each case at least 30%, preferably in each case at least 40% constitute the ^¬ ser mixture. In particular, the blends of 3 specific alkyl groups such as octadecyl, Eisocyl and docosyl where ^¬ make two of these groups, which differ by 2 carbon atoms more than 40% and the third group of 3 to 18% of the mixture of ^¬; Here, further alkyl groups with slightly less than 18 or slightly more than 22 carbon atoms can be present in the mixture in small amounts, usually less than 2%.

Suitable alkyl radicals, which in the form of C to C ₆ - to (for R ³ and R ^4), Ci to Cie (for R ⁵⁾ and Cι to C ~ ₂ alkyl radicals (for R ¹⁾ angespro ^¬ Chen, coming branched and especially straight chain Treads into consideration, especially methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert. -Butyl, n-amyl, iso-amyl, sec.-amyl, tert.-amyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl , n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and n-docosyl.

Suitable straight-chain or branched C ₂ - to C ₆ -alkanoyl for R ^{3 are} acetyl in particular, but also propionyl, butyryl, isobutyryl, pentanoyl and hexanoyl.

Suitable straight-chain or branched C 1 to C ₂ alkoxy groups for R ³ are, in particular, C 1 -C ₈ -alkoxy groups such as n-hexoxy, iso-hexoxy, n-octoxy, 2-ethylhexoxy and iso-octoxy, but also methoxy , Ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, n-nonoxy, n-decoxy, n-undecoxy and n-dodecoxy ,

C ₅ - to C _δ- cycloalkoxy groups for R ³ are especially cyclopentoxy and cyclohexoxy.

As C ₅ - to C ₈ -cycloalkyl radicals for R ¹ and R ⁵ , especially cyclopentyl and cyclohexyl, also cycloheptyl, cyclooctyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl and dimethylcyclohexyl come into consideration.

Suitable C ₇ - to Ci _δ aralkyl radicals for R ⁵ are, for example, naphthylmethyl, diphenylmethyl or methylbenzyl, but especially C ₇ - to Cig-phenylalkyl such as 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl , 2-phenyl-prop-2-yl, 4-phenylbutyl, 2,2-dimethyl-2-phenylethyl, 5-phenylamyl, 10-phenyldecyl, 12-phenyldodecyl or especially benzyl.

Suitable tolyl ortho, eta come and especially p-tolyl costume in Be ^¬.

The radical R ¹ preferably represents a tetramethylpiperidinyl radical II, in which R ³ denotes hydrogen, C ₁ -C ₆ -alkyl, in particular methyl, or a radical of the formula -CH = CH-CO-OR ⁶ , where R ⁶ denotes Ci to Ce alkyl, especially methyl or ethyl.

The presence of up to 8 mol%, in particular up to 5 mol%, based on II, hydrogen, C 1 -C ₂₂ -alkyl or C ₅ - to C ₈ -cycloalkyl as substituents R ¹ on maleimide nitrogen is so to understand that the statistical average of the total number of all copolymer molecules with structural units I this mixture of tetramethylpiperidinyl residues II and other substituents R ¹ can occur. The incorporation of small amounts of radicals R ¹ other than tetramethylpiperidinyl substituents causes a slight modification in the properties of the maleimide-a-olefin copolymers b2).

For the preparation of the maleimide-α-olefin copolymers one can e.g. Maleic anhydride-α-olefin copolymers, built up from structural units of the formula III

with 4-amino-tetramethylpiperidines of the general formula IV

and if desired up to 8 mol%, in particular up to 5 mol%, based on IV, ammonia, -C ~ to C ₂ alkylamine or C ₅ - to C ₈ cycloalkylamine, in an organic solvent at 100 to 220 ° C. implement. The molar ratio of anhydride groups in ^¬ is primary amine III to IV expediently 1: 1 or approximately 1: 1.

Aromatic hydrocarbons such as toluene, xylenes or mesitylene and halogen ^¬ or nitrocarbons such as chlorobenzene, dichlorobenzenes or nitrobenzene are particularly suitable as organic solvents. Technical mixtures of such aromatics are particularly important. In addition, aromatic-free hydrocarbon mixtures can also be used if they have a correspondingly high boiling range.

The range from 120 to 200 ° C., in particular from 140 to 175 ° C., should preferably be selected as the reaction temperature. The water formed in the reaction is expediently distilled off azeotropically. The reaction is usually carried out at normal pressure carried out and is usually complete after 1 to 5 hours.

The maleic anhydride-α-olefin copolymers with structural units III used as starting material can be obtained by known production processes by polymerizing maleic anhydride with the corresponding α-olefin mixtures, for example based on Houben-Weyl, Methods of Organic Chemistry, Volume E20 / 2, pp. 1237-1248 (1987).

Both the maleimide-α-olefin copolymers b3) with structural units I and the maleic anhydride-α-olefin copolymers with structural units III used as the starting material are generally 1: 1 copolymers composed alternately of maleic acid derivative and olefin.

Further details on the amines b3) can be found in WO-A 94/12544.

Compounds of the formula (b3]

in which R denotes a C 1 -C 6 -alkyl can not only by reacting the copolymers of the formula III with the corresponding 1-alkyl-substituted 4-amino-tetramethylpiperidines of the formula IV (ie R ³ corresponds to a C 1 -C ₆ -Alkyl) her ^¬ , but also, for example, by polymer-analogous alkylation with common alkylating agents, starting from those compounds of the formula (b3) in which R is hydrogen.

The polymer-analogous introduction of a methyl group in the 1-position of the piperidine ring (ie R in the formula (b3) denotes methyl) suc- ceeds in an elegant manner by means of Leuckart reaction just ^¬ appropriate starting dung from the corresponding unsubstituted Verbin ^¬. The unsubstituted copolymer is in this case usually described in an inert organic solvent such as already for the reaction of maleic anhydride-α-olefin copolymers of the formula III with 4-amino-tetramethylpiperidines of formula IV above, dissolved and nacheinan at elevated temperature ^¬ the reacted with formaldehyde and formic acid. More details on the Implementation conditions can be found analogously to the publication WO 01/74777 on pages 8 and 9.

Particular preference is given to using amine b3) maleimide-α-olefin copolymers of the formula (b3) in which R is hydrogen or methyl, and where n is chosen such that the molecular weight is about 3500. The compound is commercially available with R = H as Uvulin® 5050 H from BASF.

proportions

The stabilizers are contained in the molding compositions according to the invention in customary amounts. The total amount of stabilizers (sum of all amines b1 to b4)) is preferably 0.001 to 10, particularly preferably 0.1 to 5 and in particular 0.2 to 1% by weight, based on the stabilized thermoplastic molding composition.

The preferred proportions of the individual amines b1), b2), b3) and b4) depend in a known manner on the desired property profile of the stabilized thermoplastic molding compositions according to the invention, depending on the properties of the (non-stabilized) polyolefin A. In particularly preferred embodiments, the proportion of the individual compound with the above formula bl) (for example Uvinul® 4049 H) is 0.1-0.3% by weight, of the individual compound with the above formula b2) (for example Uvinul® 4050 H) 0, 1 - 0.5 wt .-%, or the individual compound with the above formula b3) (eg Uvinul® 5050 H) 0.2 - 0.8 wt .-%, each based on the stabilized thermoplastic molding composition.

Optional component C)

The molding compositions according to the invention can, if desired, contain a further component C) or a plurality of further components C), C ') etc.

Suitable components C) are selected from polymers which are different from the polyolefins A) and further additives which are different from the stabilizers B). Examples of polymers C) are:

Polyolefins that were not produced using metallocene catalysts,

Vinyl polymers, in particular homopolymers and copolymers of styrene and vinyl chloride, fluoropolymers and copolymers, Polyacrylic and polymethacrylic polymers, poly (meth) acrylic acid esters,

polyoxymethylenes

Polyamides, - aromatic polyesters, especially polycarbonates and polyesters of terephthalic acid, aromatic polysulfides and sulfones, aromatic polyethers, aliphatic polyesters (polyglycols), - polyaryletherke one,

Polyimides, liquid crystalline polymers,

Polyurethanes, thermoplastic elastomers, - naturally occurring polymers e.g. on cellulose or

Starch-based, photodegradable and water-soluble polymers, electrically conductive polymers.

These polymers are known and e.g. in Saechtling (ed.), Kunststoff-Taschenbuch, 27th edition, Hanser-Verlag München 1998, pp. 371-595. They are commercially available, so there is no need for further details.

Other additives are particularly suitable as component C). It goes without saying that these additives C) are different from the stabilizers B). Examples of such further additives C) are mentioned below under Nos. 1 to 14.

1. Antioxidants

1.1. Alkylated monophenols, for example 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-Diocta-decyl-4-methylphenol, 2,4, 6-tricyclohexylphenol, 2, 6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example , 2, 6-Dinonyl-4-methylphenol, 2, 4-dimethyl-6- (1 '-methylundec-1' -yDphenol, 2, 4-dimethyl-6- (1 '-methylheptadec-1' -yl ) phenol, 2,4-dimethyl-6- (l'-methyltridec-l'-yl) phenol and mixtures thereof. 1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example

2, 6-di-tert-butyl-4-methoxyphenol, 2, 5-di-tert-butylhydroquinone, 2, 5-di-tert-amylhydroquinone, 2, 6-diphenyl-4-octadecyloxyphenol, 2, 6-di- tert-butyl hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxy-phenyl stearate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thio-bis (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.

1.6. Alkylidene bisphenols, for example 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2, 2-methylenebis [4- methyl-6- (a-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2, 2 '- Methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidibis (6-tert-butyl-4-) isobutylphenol), 2, 2 'methylenebis [a-methylbenzyl) -4-nonylphenol], 2, 2' methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4 '- Methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2- methylphenyl) butane, 2, 6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 1, 3-tris (5-tert-butyl-4-hydroxy-2 -methylphenyl) butane, 1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethyl - glycolbis [3, 3-bis (3 '-tertbutyl-4 '-hydroxypheny1) butyrate], B is (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) 6-tert-butyl-4- methylphenyl] terephthalate, 1, 1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5, di-tert-butyl-4-hydroxyphenyl) propane, 2, 2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmer-captobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2 -methyl-phenyl) entane.

1.7. 0-, N- and S-benzyl compounds, for example 3,5,3 ', 5' tetra-tert-butyl-4, 4 '-dihydroxydibenzylether, octadecyl-4-hydroxy-3, 5-dimethylbenzylmercaptoacetate, tridecyl -4-hydroxy 3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) a in, bis- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3, 5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for example diocta-decyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, diocta-decyl-2- (3-tert-butyl-4-hydroxy-5 -methylbenzyl) -malonate, didode-cylmercaptoethyl-2,2-bis- (3, 5-di-tert-butyl-4-hydroxy-benzyl) malonate, bis (4- (1, 1, 3, 3-tetramethylbu- tyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di tert-butyl-4-hydroxybenzyl) -2,3,5, 6-tetra-methylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

1.10. Triazine compounds, for example 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3, 5-di-tert-butyl-4-hydroxyanilino) -1, 3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4- hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5 -Tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-tris (4-tert-buty1-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl- 4-hydroxyphenylpropionyl) hexahydro-l, 3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

11.1. Benzylphosphonates, for example dimethyl-2, 5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3, 5-di-tert- butyl 4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl 4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.13. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1 , 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N 'bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol propane, 4-hydroxymethyl-l-phospha-2 , 6, 7-trio-xabicyclo [2.2.2] octane.

1.14. Esters of ß- (5-tert-butyl-4 ~ hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexane - diol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N 'bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3- Thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6, 7-trio-xabicyclo [2.2.2] octane.

1.15. Esters of ß- (3, 5-dicyclohexyl-4-hydroxyphenyl) ropionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2 Propanediol, neopentyl glycol, miodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N 'bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylymethyl-l, 4-methylethyl propane phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

16.1. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2- Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol-propan, 4-hydroxymethyl-4-hydroxymethyl , 6, 7-trioxabicyclo [2.2.2] octane.

1.17. A ide of ß- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis- (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyD ydrazide, N, N '-Bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide.

1.18. Ascorbic acid (vitamin C) 19.1. Amine-like antioxidants, for example N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine , N, N'-bis (l-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-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- (1, 3- Dimethylbutyl) -N-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N '-phenyl-p-phenlenediamine, 4- (p-toluenesulfamoyl ) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenyiamine, 4-isopropoxydipheny-laminate, N-phenyl-1-naphthylamine, N- ( 4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p '-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol , 4-dodecanoyl aminophenol, 4-octadecanoylamine ophenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butyt-4-dimethylaminomethylphenol, 2,4'-diaminodi - phenylmethane 4,4'-diaminodiphenylmethane, N, N, N ', N-tetramethyl- 4,4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) a ino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3' -dimethylbutylphenylamine, tert-octylated N-phenyl-1-naphthyl-a in, a mixture of mono- and dialkylated tert-butyl-tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenyl amines, a mixture of mono - and dialkylated dodecyldiphenyl amines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3, 3-dimethyl-4-Hl, 4- benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl-tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphe-nothiazine, N, N, N, N '-tetraphenyl-1, 4 -diaminobut-2 -en, N, N- bis (2,2,6,6-tetramethylpiperid-4-yl) hexamethylene diamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2, 2, 6, 6-tetramethyl-piperidin-4-one, 2,2,6, 6-tetramethyl-piperidin-4-ol.

2. UV absorbers and light stabilizers

2.1. 2- (2'-Hydroxyphenyl) benzotriazoles, for example

2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl- 2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'- (1, 1,3, 3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5' -di-tert-butyl- 2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert- butyl-2'-hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-4' -octyloxy-phenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2' - hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2 '-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3 '-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonyl ethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy- 5 '- (2-methoxycarbonyl ethyl) phenyl) -5-chlorobenzotriazole , 2- (3'-tert-Butyl-2 '-hydroxy-5' - (2-methoxycarbonyl-ethyl) phenyl) benzotriazole, 2- (3'-tert-Butyl-2'-hydroxy-5 '- (2nd -oc- tyloxycarbonylethyl) phenyl) benzotriazole, 2- (3 'tert-butyl-5' - [2- (2-ethylhexyloxy) carbonyl ethyl] -2 '-hydroxyphenyl) benzotriazole, 2- (3' -dodecyl-2 '-hydroxy-5'-methylphenyl) benzotriazole,

2- (3'-tert-Butyl-2 '-hydroxy-5' - (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2 '-methylbis [4- (1, 1, 3, 3-tetramethylbutyl) - 6- benzotriazol-2-ylphenol]; the transesterification product of 2- [3 'tert-butyl-5' - (2-methoxycarbonyl ethyl) -2 '-hydroxyphenyl] -2H-bcnzotriazole with polyethylene glycol 300;

[R-CH ₂ CH ₂ -COO-CH ₂ CH ₂ ] ₂ - wherein R = 3'-tert-butyl-4'-hydroxy-5 '-2H-benzotriazol-2-ylphenyl, 2- [2' -hydroxy -3 '- (α, α - dimethylbenzyl) -5' - (1, 1, 3, 3-tetramethylbutyl) phenyl] benzotriazole; 2- [2 '-Hydroxy-3' - (1,1,3, 3-tetramethylbutyl) -5 '- (α, α-dimethylbenzyl) phenyl] benzotriazole.

2.2. 2-hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodeσyloxy, 4-benzyloxy, 4, 2 ', 4' trihydroxy and 2 '- Hydroxy-4, 4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, such as, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyDresorcin benzoylresorcinol, 2,4-di-tert-butylphenyl-3, 5-di -butyl-4-hydroxybenzoate, hexadecyl-3, 5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3, 5-di-tert-butyl-4-hydroxy-benzoate, 2-methyl-4, 6 -di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl-α-cyano-ß, ß-diphenyl acrylate, isooctyl-α-cyano-ß, ß-diphenyl acrylate, methyl-α-carbomethoxycinnate, methyl-α-cyano-ß-methyl-p-methoxycinnamate, Butyl-α-cyano-ß-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N- (ß-carbomethoxy-ß-cyanovinyl) -2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of 2, 2'-thiobis [4- (1,1, 3, 3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, with or without additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel di-butyldithiocarbamate, nickel salts of the monoalkyl esters, for example the methyl or ethyl ester, of 4-hydroxy-3, 5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, for example of 2-hydroxy-4-methylphenylundecyl ketoxime, Nikkei complexes of l-phenyl-4-lauroyi-5-hydroxypyrazole, with or without additional ligands.

2.6. Oxamides, 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 mixture with 2-ethoxy-2'-ethyl-5, 4'-di-tert-butoxanilide, mixtures of o- and p-methoxydisubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.7. 2- (2-hydroxyphenyl) -1.3.5-triazines, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine,

2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -

1.3, 5-triazine, 2- (2,4-dihydroxyphenyl) -4, 6-bis (2,4-dimethylphenyl) -1,3, 5-triazine, 2,4-bis (2-hydroxy-4 -propyloxyphenyl) - 6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3 , 5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4, 6-bis (2,4-dimethylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) - 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) henyl] -4, 6- bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -

4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2nd , 4-dimethylphenyl) -1,3, 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4, 6-bis (2,4-dimethylphenyl ) -1, 3, 5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4, 6-diphenyl-l, 3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4 , 6-diphenyl-l, 3, 5-triazine,

2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6- phenyl-l, 3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-l-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl ) - 1,3,5-triazine.

3. Metal deactivators, for example N, N'-diphenyloxamide, N-salicylal-N-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N '~ bis (3, 5-di-tert-butyl -4-hydroxyphenylpropionyl) hydrazine, 3-salicylicoylamino-l, 2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N'-diacetyladipoyldihydrazide (N, N '-Bl ) oxalyl dihydrazide, N, N 'bis (salicyloyl) thiopropionyl dihydrazide. 4. phosphites and phosphonites, for example triphenylphosphite, diphenylalkylphosphites, phenyldialkylphosphites, tris (nonylphenyldphosphite, trilaurylphosph.it, trioctadecylphosphite, distearylpentaerythritol diphosphite, tris (2, 4-di-tert-butylphitophosphite di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl- methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis- (2,4-di-tert-butyl-6-) methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6 -Isooctyloxy-2,4,8,10-tetra-tert-butyl-12-H-diben [d, g] -1,3,2-dioxaphosphocin, bis (2,4-di-tert-butyl-6- methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite, 6-fluoro-2,4, 8,10-tetra-tert-butyl-12-methyldibenz [d, g] -1 , 3.2-dioxaphosphocin,

2, 2 ', 2 "-Nitrilo [triethyltris (3, 3', 5, 5 '-tetra-tert-butyl-1, 1' - biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3rd , 3 ', 5, 5' -tetra-tert-butyl-1, 1 '-biphenyl-2, 2'-diyl) phosphite, 5-butyl-5-ethyl-2- (2,4,6-tri- tert-butylphenoxy) -1,3, 2-dioxaphosphirane.

5. Hydroxylamines, for example N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, -dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine , N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-oceadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6.Nitrones, for example N-benzyl-a-phenyl-nitron, N-ethyl-α-methy1-nitron, N-Octy1-α-heptyl-nitron, N-Laury1a-undecy1-nitron, N-tetradecyl-α- tridecyl-nitron, N-hexadecyl-α-pentadecyl-nitron, N-Ocadecyl-α-heptadecyl-nitrone, N-Hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecyl-nitron, N-Hepladecyl-α-heptadecyl -nitrone, N-octadecyl-α-hexadecyl-nitron, nitrone, derived from N, N-dialkylhydroxylamine, derived from hydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate or distearyl thiodipropionate.

8. Peroxide scavengers, for example esters of (3-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters,

Mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (ß-dodecylmercapto) propionate. 9. Polyamide stabilizers, for example copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

10. Basic costabilisers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, sodium styrenate, magnesium stolate antimate, magnesium stolomate, magnesium stolate antimate, magnesium stolate antimate, magnesium stolate antioxidant - cholate or zinc pyrocatecholate.

11. Nucleating agents, for example inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). 1, 3; 2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1,3; 2,4-di (paramethyldibenzylidene) sorbitol and 1, 3; 2,4-di (benzylidene) sorbitol.

12. Fillers and reinforcing agents, for example calcium. carbonate, silicates, glass fibers, hollow glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers from other natural products, synthetic fibers.

13. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, radiation-reflecting agents, radiation diffusers, rheology additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those described in US 4,325,863; U.S. 4,338,244; US 5,175,312; US 5,216,052; U.S. 5,252,643; DE-A-43 16 611; DE-A-43 16 622; DE-A-43 16 876; EP-A-0 589 839 or EP-A-0 591 102 or 3- [4- (2-aceto-xyethoxy) phenyl] -5, 7-di-tert-butyl-benzof uran-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- [2nd -hydroxyethoxy] phenyl) benzofuran-2on], 5, 7-di-tert-butyl-3- (4-ethoxyphenyl) 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.

The weight ratio of the further additives C) to the stabilizers B) can be, for example, 100: 1 to 1: 100.

The further additives C) mentioned are used in customary amounts, in particular in amounts of 0.001 to 50% by weight, based on the stabilized thermoplastic molding composition.

In the process according to the invention, the stabilizers B) and, if present, the further components C) are added to the polyolefin. The addition takes place in the usual way. So you can add the stabilizers B) and possibly the other additives C) to the starting monomer (olefin monomers) and polymerize the mixture of monomers and stabilizers. The stabilizers can also be added during the polymerization of the olefin monomers. A prerequisite for addition before or during the polymerization is that the stabilizers are stable under the polymerization conditions, that is to say they do not decompose or decompose only slightly.

Stabilizers B) and, if present, further components C) are preferably added to the finished polyolefin A). This is done in the usual way according to mixing processes known per se, for example by melting in a mixing device at temperatures of 150 to 300 ° C.

However, the components can also be mixed "cold" without melting and the powdery or granular mixture is only melted and homogenized during processing.

It goes without saying that the stabilizer (s) B) and the components C) can be added together or separately from one another, all at once, in portions or continuously, over time, constantly or along a gradient. For example, one can add some of the stabilizers already during the polymerization of the olefin monomers and the rest Add only the finished poly ^¬ olefin.

As a mixing apparatus for carrying out the method according to the invention are, for example, discontinuously operating heated internal mixers ^¬ be with or without stamp, continuously operating kneaders, such as continuous internal mixers, screw kneader having axially oscillating screws, Banbury mixers, soft extruders as well as roller mills, mixing mills with heated rollers and calenders.

Mixing is preferably carried out in a conventional extruder, in which the components can be mixed or introduced individually, for example completely into the extruder via a funnel, or else introduced at a later point in the extruder to form the melted or solid product in the extruder. One or two-shaft extruders, for example, are particularly suitable for melt extrusion. A twin screw extruder is preferred.

The mixtures obtained can, for example, be pelletized or granulated, or can be processed by generally known processes, for example by extrusion, injection molding, foaming with blowing agents, deep-drawing, blow molding or calendaring.

Moldings (including semi-finished products, foils, fibers, films and foams) of all kinds can be produced from the molding compounds, e.g. items of daily use, packaging and foils, moldings in the entire outdoor area, e.g. Garden furniture, windows and fittings, lamp housings, automotive exterior parts. The moldings, films and fibers are the subject of the invention.

The molding compositions according to the invention are distinguished by an optimized, balanced profile of properties. This also applies to the molded parts, fibers and foils made from it.

An interesting point from the point of view of plastics processing should be mentioned finally.

It is known that polyolefins which have been prepared using metallocene catalysis are usually distinguished by a narrow molecular weight distribution - the proportion of short-chain polymers is markedly reduced compared to those of polyolefins which have been prepared by means of Ziegler-Natta catalysts. Traditionally used process aids, such as waxes, metal stearates and fatty acid derivatives, which have been or will be added during processing of plastics to prevent melt breakage (visible as rough or scaly surfaces), therefore reach their performance limits and are increasingly being replaced by more effective auxiliaries, especially fluoroelastomers and silicones. The mode of action of fluoroelastomers, for example, is based on the assumption that, if at all, they can only be mixed to a small extent with the polyolefins and therefore still migrate to the surface of the polymer melt in the processing device, for example an extruder, where they melt between the melt and the surface of the processing device Form a sliding layer. Attachments, which can then lead to melt breakage, are prevented.

In extrusion experiments by the applicant with polyolefins which had been mixed with various commercially available light stabilizers, it was found that, in most cases, compared to the unstabilized polyolefin, significantly higher amounts of fluoroelastomer had to be added in order to prevent melt breakage or to break the melt came when the elastomers were used in the usual proportions of about 0.1 wt .-% based on the polymer. This negative influence was comparatively small when using the Tinuvin 622 product (Ciba), but could be significantly reduced again in the case of the Uvinul® 5050H. This made it possible to reduce the amount of fluoroelastomer significantly below the usual concentration without the melt breakage of the polyolefin additive with Uvinul® 5050H occurring.

Claims

claims

1. Stabilized thermoplastic molding compositions containing

A) at least one polyolefin A), produced using at least one metallocene catalyst, and

B) at least one stabilizer B) selected from the following groups bl) to b4) bl) hindered amines based on glycolurils, b2) hindered amines based on 4-formylaminopiperidines, b3) hindered amines based on Maleimide-α-olefin copolymers, b4) sterically hindered amines selected from

Bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6, 6-tetramethylpiperidin-4-yl) succinate, bis (1, 2, 2, 6, 6-pentamethylpiperidine 4-yl) sebacate, bis (l-octyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate, bis (1,2, 2, 6, 6-pentamethylpiperidin-4-yl) -n- butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product from 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product from N, N'-bis (2,2, 6, 6-tetra-methylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-l, 3,5-triazine, tris (2,2 , 6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, tetrakis (2,2,6, 6-tetramethylpiperidin-4-yl) -1,2,3,4-butane-tetracarboxylate, 1, 1 '- ( 1, 2-ethylene) - bis (3, 3, 5, 5-tetramethylpiperazinone), 4-benzoyl-

2,2,6,6-tetramethylpiperidine, 4-stearyl-oxy-2, 2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) -2-n -butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7, 7, 9, 9-tetra-methyl-1, 3, 8-triazaspiro [4.5] decan-2, 4-dione,

Bis (l-octyloxy-2, 2,6, 6-tetramethylpiperidin 4-yl) sebacate, bis (l-octyloxy-2, 2,6, 6-tetramethyl-piperi-din-4-yl) succinate, the condensation product N, N'- bis (2,2,6, 6-tetramethylpiperidin-4-yl) hexamethylene diamine and 4-morpholino-2, 6-dichloro-l, 3,5-triazine, the condensation product of 2- Chloro-4, 6-bis (4-n-butylamino-2, 2, 6, 6-tetramethyl-piperidin-4-yl) - 1, 3, 5-triazine and 1,2-bis (3-amino -propylamino) ethane, the condensation product of 2-chloro-4, 6-di- (4-n-butylamino-1, 2,2,6, 6-pentamethyl-piperidin-4-yl) - 1, 3, 5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7, 7,9, 9-tetra-methyl-l, 3, 8-triazaspiro [4.5] decan-2,4-dione, 3-dodecyl-l- (2,2,6,6-tetramethylpiperidin-4-yl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1 , 2,2, 6, 6-penta-methylpiperid-4-yl) pyrrolidin-2,5-dione, a mixture of 4-hexadecyloxy and 4-stearyloxy-2, 2, 6, 6-tetramethyl - piperidine, the condensation product of N, N'-bis (2,2,6, 6-tetramethylpiperidin-4-yl) hexamethylene diamine and 4-cyclohexylamino-2, 6-dichloro-l, 3, 5 - triazine, the condensation product of 1,2-bis (3-aminopropylamino) -ethane and 2,4,6-tri-chloro-l, 3,5-triazine, 4-butylamino-2,2,6,6 -tetramethylpiperidine, N- (2, 2, 6, 6-tetramethyl-piperidin-4-yl) -n-dodecyl-succinimide, N- (1,2,2, 6, 6-pentamethylpiperidin-4-yl) - n -dodecylsuccinimide, 2-undecyl-7, 7.9, 9-tetra-methyl-l-oxa-3, 8-diaza-4-oxo-spiro [4.5] -decane, the condensation product from 7, 7,9,9 -Tetramethyl-2-cycloundecyl-l-oxa-3, 8-diaza-4-oxospir o- [4.5] decane and epichlorohydrin, the condensation products

4-Amino-2, 2, 6, 6-tetramethyl-piperidine with tetramethylolacetylene diureas and poly (methoxypropyl-3-oxy) - [4- (2,2,6, 6-tetramethyl) - piperidinyl] siloxane.

2. Molding compositions according to claim 1, in which the total amount of stabilizers is 0.001 to 10% by weight, based on the stabilized thermoplastic molding composition.

3. Molding compositions according to claims 1 to 2, in which an amine of the formula as amine bl) based on glycolurils

where R is hydrogen or methyl is used.

Molding compositions according to Claims 1 to 3, in which an amine of the formula as amine b2) based on 4-formylaminoρiperidines

where R is hydrogen or methyl is used.

5. Molding compositions according to claims 1 to 4, in which an amine of the formula as amine b3) based on maleimide-α-olefin copolymers

where R is hydrogen or methyl is used, n being chosen so that the molecular weight is about 3500.

6. Molding compositions according to claims 1 to 5, in which a compo ^¬ component C) is selected from polymers, which are different from the polyolefins A), and other additives which are different from the stabilizers B).

7. Use of the molding compositions according to claims 1 to 6 for the production of moldings, films and fibers.

Moldings, films and fibers from the molding compositions according to ^¬ challenging 1 to 6.

Process for the preparation of the molding compositions according to claims 1 to 6, characterized in that components A), B) and optionally C) are mixed at 150 to 300 ° C with melting in a mixing device.