EP1401941A1 - Polyolefines a metallocenes stabilisees - Google Patents

Polyolefines a metallocenes stabilisees

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Publication number
EP1401941A1
EP1401941A1 EP02724310A EP02724310A EP1401941A1 EP 1401941 A1 EP1401941 A1 EP 1401941A1 EP 02724310 A EP02724310 A EP 02724310A EP 02724310 A EP02724310 A EP 02724310A EP 1401941 A1 EP1401941 A1 EP 1401941A1
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Prior art keywords
bis
tert
butyl
methyl
tetramethyl
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EP02724310A
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German (de)
English (en)
Inventor
Sylke Haremza
Manfred Appel
Hubert Trauth
Erik Hofmann
Alban Glaser
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment

Definitions

  • the invention relates to stabilized thermoplastic molding compositions containing
  • At least one polyolefin A produced using at least one metallocene catalyst
  • 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.
  • the invention relates to a method for producing the molding compositions.
  • sterically hindered amines as light and antiaging agents in polymers. They act due to light-related aging and destruction of the polymer, which can e.g. as yellowing, discoloration, cracking or embrittlement.
  • 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.
  • the molding compositions contain, as component A), at least one polyolefin which has been prepared using at least one metallocene catalyst.
  • 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 ⁇ -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 ⁇ -olefins. In this case preference is given to the C 2 - or C-01efins and their copolymers.
  • ethylene and ⁇ -olefins for example propylene, 1-butene, 4-methyl-1-pentene, 5-methyl-1-hexene; Isohexene, isooctene; Cycloolefins (eg cyclopenta
  • 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.
  • 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:
  • 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 14 to R 18 hydrogen, C ⁇ ⁇ to Cio-alkyl, 5- to 7-membered cycloalkyl, which in turn is a C ⁇ ⁇ to Cio-alkyl
  • 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
  • R 21 , R2 unc j 23 are the same or different and a hydrogen atom, a halogen atom, a C ⁇ -C ⁇ o ⁇ alkyl group, a
  • C ⁇ -C ⁇ o-fluoroalkyl group a Cg-Cio-fluoroaryl group, a Cg-Cio-aryl group, a Ci-Cio-alkoxy group, a C 2 -C ⁇ o-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
  • 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 C ⁇ ⁇ 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 _.
  • 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.
  • 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.
  • Main group of the periodic table means, in particular B, Al or Ga,
  • Ci- to Cio-alkyl 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.
  • Qi to Q z for single negatively charged residues such as Ci to C28 ⁇ alkyl, Cg to Cis aryl, alkylaryl, arylalkyl,
  • 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.
  • 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.
  • ethylene copolymers are suitable as ethylene copolymers, for example Luflexen® types (from Basell), Norde® (DuPont), Engage®, Affinity®, Elite® (all Dow) and Finacene® (Atofina).
  • All ⁇ -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.
  • a comonomer-ethylene copolymer with ethylene contents of 15 to 80 wt .-% polymerized.
  • the polymerization for the production of the ethylene-comonomer copolymers takes place by means of a metallocene catalyst system as previously described.
  • 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 low density
  • LD low density
  • ICI high pressure process
  • PE-LLD linear low density
  • 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.
  • a solution e.g. petrol
  • HD high density
  • Phillips medium pressure
  • Ziegler low pressure
  • Phillips 85 to 180 ° C
  • chromium oxide as a catalyst
  • molar masses about 50,000 g / mol.
  • 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.
  • PE-HD-HMW high olecular weight
  • HMW high olecular weight
  • available according to the Ziegler, Phillips or gas phase method High density and high molecular weight.
  • PE-HD-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).
  • catalysts e.g. Lupolen® (from Basell).
  • 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.
  • 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).
  • metallocenes typically contain titanium, zirconium or hafnium as central atoms, zirconium being preferred.
  • the central atom is bonded via a ⁇ 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 ⁇ bonds, those which are particularly preferred in which substituents of the cyclopentadienyl groups are bonded to both cyclopentadienyl groups.
  • 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,
  • 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.
  • 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.
  • 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.
  • 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).
  • 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).
  • 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).
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • MFR melt flow rate
  • 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- ⁇ -olefin copolymers, b4) sterically hindered amines selected from
  • the amines b4) are individual compounds, so that further information is unnecessary. These individual compounds are known and commercially available.
  • the amines based on glycolurils are preferably the compounds of the general formula (I)
  • 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
  • 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
  • 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-C ⁇ 2 aralkyl,
  • 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
  • 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:
  • 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.
  • 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.
  • C 3 -Ci 2 cycloalkyl preferably stands for
  • 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 ⁇ __, .. propyl, butyl, pentyl and hexyl. Examples of other branched alkyl radicals are the following:
  • C 7 -C 2 aralkyl preferably comprises C 7 -C ⁇ 2 phenylalkyl such as benzyl or phenylethyl, and their C1-C4-alkyl or C ⁇ -C 4 alkoxy-substitution products, PH 3
  • carboxylic ester group stands in particular for a group o
  • 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.
  • 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.
  • oligomeric or polymeric polyamine means, for example, the groupings
  • 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:
  • a and B are alkyl, cycloalkyl, aralkylene, alkylene or aralkylene radicals substituted by CO or SO 2 .
  • bridge links -B- are as follows:
  • B evorzugte bridge members are (CH 2) n, where n is preferably 1 to 5, especially 1, 2, 5.
  • heterocylene in particular non-aromatic heterocycles, are present in the compounds b1), these can be, for example, the following:
  • Z « is hydrogen, alkyl, C-acyl or H0- and p * mean 1 to 20.
  • Exemplary urea groups are the following:
  • 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 -C ⁇ 2 aralkyl.
  • R 11 and R 12 are, independently of one another, in particular hydrogen, in addition also
  • R 11 and R 12 form a ring system together with the nitrogen atom to which they are attached, this can be, for example:
  • R 15 can assume all of the above meanings of R 9 .
  • 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
  • glycolonitrile 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.
  • 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.
  • the amine bl) based on glycolurils is particularly preferably the compound of the formula (bl)
  • the amines based on 4-formylaminopiperidines are preferably the compounds of the general formula (I)
  • 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 C ⁇ ⁇ C 4 alkyl, fluorine, chlorine, C ⁇ ⁇ to C 4 -alkoxy, methylenedioxy, ethylenedioxy, and / or di- C 1 -C 4 -alkylamino substituted C - to Ci 2 -phenylalkyl, C ⁇ ⁇ to C 22 ⁇ alkanoyl, C 2 - to C 3 -cyanalkyl, C ⁇ ⁇ to C 22 -hydroxyalkyl or C 2 - to C 22 -aminoalkyl and
  • 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-C ⁇ -C 4 ⁇ alkyl-amino-substituted C- to C 22 ⁇ phenyl- or diphenylalkyl, optionally substituted by -C ⁇ C 4 -alkyl or carbo-C ⁇ -C 4 -alkoxy-substituted phenyl, heterocyclic radicals containing C ⁇ ⁇ C 22 ⁇ alkyl or a radical of the formula
  • 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,
  • 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 .
  • 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.
  • R 6 methyl, acetyl, cyanomethyl, aminoethyl and especially hydrogen are preferred.
  • -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;
  • C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl and bicycloheptyl, of which cyclopentyl and cyclohexyl are preferred;
  • 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;
  • phenyl such as phenyl, tolyl and phenyl substituted by carbo-C 4 -alkoxy;
  • R 1 to R 6 have the meaning given above;
  • 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-
  • 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.
  • 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.
  • 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.
  • inorganic anions e.g. To name chloride, bromide, sulfate, methosulfate, tetrafluoroborate, phosphate and rhodanide.
  • 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.
  • the compound of the formula (b2) based on 4-formylaminopiperidines is particularly preferably used as the amine b2)
  • Preferred amines based on maleimide- ⁇ -olefin copolymers are those compounds which are composed of structural units of the general formula (I)
  • R5 is Ci to Cis alkyl, C 5 to C 8 cycloalkyl, C 7 to C 8 aralkyl, phenyl or tolyl,
  • 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,
  • Maleimide- ⁇ -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 C ⁇ 6 - to C 3 o ⁇ ⁇ -olefins, preferably C ⁇ 8 - to C 26 _ a-01efine, in particular C 20 - to C 24 - ⁇ -01efine as building blocks.
  • R 2 is preferably linear alkyl groups.
  • 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.
  • 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 ⁇ ;
  • 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 C ⁇ 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.
  • 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 ⁇ - cycloalkoxy groups for R 3 are especially cyclopentoxy and cyclohexoxy.
  • 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 ⁇ 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.
  • C 7 - to Ci 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-
  • Suitable tolyl ortho, eta come and especially p-tolyl costume in Be ⁇ .
  • maleimide- ⁇ -olefin copolymers For the preparation of the maleimide- ⁇ -olefin copolymers one can e.g. Maleic anhydride- ⁇ -olefin copolymers, built up from structural units of the formula III
  • 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 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- ⁇ -olefin copolymers with structural units III used as starting material can be obtained by known production processes by polymerizing maleic anhydride with the corresponding ⁇ -olefin mixtures, for example based on Houben-Weyl, Methods of Organic Chemistry, Volume E20 / 2, pp. 1237-1248 (1987).
  • Both the maleimide- ⁇ -olefin copolymers b3) with structural units I and the maleic anhydride- ⁇ -olefin copolymers with structural units III used as the starting material are generally 1: 1 copolymers composed alternately of maleic acid derivative and olefin.
  • 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.
  • R H as Uvulin® 5050 H from BASF.
  • 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.
  • 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.
  • 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:
  • Vinyl polymers in particular homopolymers and copolymers of styrene and vinyl chloride, fluoropolymers and copolymers, Polyacrylic and polymethacrylic polymers, poly (meth) acrylic acid esters,
  • Polyamides especially polycarbonates and polyesters of terephthalic acid, aromatic polysulfides and sulfones, aromatic polyethers, aliphatic polyesters (polyglycols), - polyaryletherke one,
  • thermoplastic elastomers thermoplastic elastomers, - naturally occurring polymers e.g. on cellulose or
  • Starch-based, photodegradable and water-soluble polymers, electrically conductive polymers are examples of Starch-based, photodegradable and water-soluble polymers, electrically conductive polymers.
  • 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.
  • 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-
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.
  • 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.
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • 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.
  • 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,
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
  • esters of ⁇ - (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 [
  • 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
  • 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.
  • 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.
  • 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.
  • 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,
  • R 3'-tert-butyl-4'-hydroxy-5 '-2H-benzotriazol-2-ylphenyl, 2- [2' -hydroxy -3 '- ( ⁇ , ⁇ - dimethylbenzyl) -5' - (1, 1, 3, 3-tetramethylbutyl) phenyl] benzotriazole; 2- [2 '-Hydroxy-3' - (1,1,3, 3-tetramethylbutyl) -5 '- ( ⁇ , ⁇ -dimethylbenzyl) phenyl] benzotriazole.
  • 2-hydroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dode ⁇ yloxy, 4-benzyloxy, 4, 2 ', 4' trihydroxy and 2 '- Hydroxy-4, 4'-dimethoxy derivatives.
  • 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.
  • 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.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel di-butyldithi
  • 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.
  • 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.
  • 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,
  • 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.
  • N-benzyl-a-phenyl-nitron for example N-benzyl-a-phenyl-nitron, N-ethyl- ⁇ -methy1-nitron, N-Octy1- ⁇ -heptyl-nitron, N-Laury1a-undecy1-nitron, N-tetradecyl- ⁇ - tridecyl-nitron, N-hexadecyl- ⁇ -pentadecyl-nitron, N-Ocadecyl- ⁇ -heptadecyl-nitrone, N-Hexadecyl- ⁇ -heptadecylnitrone, N-octadecyl- ⁇ -pentadecyl-nitron, N-Hepladecyl- ⁇ -heptadecyl -nitrone, N-octadecyl- ⁇ -hexadecyl-nitron, nitrone, derived from N, N
  • Thiosynergists for example dilauryl thiodipropionate or distearyl thiodipropionate.
  • Peroxide scavengers for example esters of (3-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters,
  • Polyamide stabilizers for example copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.
  • 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.
  • 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 ste
  • 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).
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • the components can also be mixed "cold" without melting and the powdery or granular mixture is only melted and homogenized during processing.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne des matières à mouler thermoplastiques stabilisées contenant (A) au moins une polyoléfine A) produite par utilisation d'au moins un catalyseur métallocène, et (B) au moins un stabilisant B) choisi parmi le groupe b1) à b4) avec: (b1) amines à encombrement stérique à base de glycoluriles; (b2) amines à encombrement stérique à base de 4-formyl aminopipéridines, (b3) amines à encombrement stérique à base de copolymères imide d'acide maléique- alpha -oléfine; (b4) amines à encombrement stérique choisies parmi des composés individuels donnés.
EP02724310A 2001-05-15 2002-05-10 Polyolefines a metallocenes stabilisees Withdrawn EP1401941A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10123732A DE10123732A1 (de) 2001-05-15 2001-05-15 Stabilisierte Metallocen-Polyolefine
DE10123732 2001-05-15
PCT/EP2002/005150 WO2002092684A1 (fr) 2001-05-15 2002-05-10 Polyolefines a metallocenes stabilisees

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EP1401941A1 true EP1401941A1 (fr) 2004-03-31

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US (1) US20040138350A1 (fr)
EP (1) EP1401941A1 (fr)
JP (1) JP2004525251A (fr)
CN (1) CN1541246A (fr)
DE (1) DE10123732A1 (fr)
WO (1) WO2002092684A1 (fr)

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DE102005061954A1 (de) * 2005-12-23 2007-07-05 Basf Ag Verfahren zur Wiedergewinnung von Ruthenium aus gebrauchten Rutheniumoxid-haltigen Katalysatoren
CN101370865B (zh) * 2006-01-13 2011-09-28 巴斯夫欧洲公司 稳定剂混合物
US20090170984A1 (en) * 2006-03-31 2009-07-02 Basf Se Composition containing polymers, colouring agents and stabilisers
DE502008002175D1 (de) * 2007-08-28 2011-02-10 Basf Se Stabilisatormischung
JP5602352B2 (ja) 2007-09-21 2014-10-08 住友化学株式会社 光安定化ポリプロピレン
JP5487611B2 (ja) * 2007-12-21 2014-05-07 住友化学株式会社 ポリプロピレン系樹脂組成物及びそれからなる成形体
WO2012052376A1 (fr) * 2010-10-20 2012-04-26 Basf Se Stabilisants lumière oligomères à fonctionnalisation spécifique
CN102101897B (zh) * 2010-12-24 2013-02-06 上海化工研究院 侧链含杂环的茂金属催化剂及其在烯烃聚合中的应用
CN106118012A (zh) * 2016-08-18 2016-11-16 东莞市宇豪塑胶科技有限公司 电脑外壳专用pc/abs合金改性工程塑料及其制备方法

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JP2004525251A (ja) 2004-08-19
US20040138350A1 (en) 2004-07-15
DE10123732A1 (de) 2002-11-21
WO2002092684A1 (fr) 2002-11-21
CN1541246A (zh) 2004-10-27

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