CH691181A5 - Stabilizer composition for polymer materials. - Google Patents

Description

       

  
 



  This invention relates to a stabilizer composition for polymeric materials according to claim 1. The invention also relates to a solid masterbatch composition or a liquid concentrate containing the stabilizer composition mentioned above. The invention further relates to a method for stabilizing organic, polymeric material selected from the group consisting of special polyolefins, a stabilizing amount of the stabilizer composition according to the invention being added to the polymeric material. The invention also relates to a stabilized, polymeric material which contains the stabilizer composition according to the invention and the above-mentioned polymeric material.



  The rapid progress in the development of polymerization catalysts, especially supported catalysts and metallocenes, for the production of polyolefins provides a variety of polymers which differ significantly in their properties from the earlier plastics. The problem of maintaining these better properties during the processing of the plastics and in the use of the articles produced therefrom has arisen, in particular in the case of polyolefins, using catalyst systems of the 2nd to 5th generation, which are no longer removed from the polymers after the polymerization , tightened. Although such catalysts can be deactivated with catalyst poisons such as steam, aliphatic alcohols, ethers or ketones, their residual activity can still remain to a certain extent.

   Such catalyst residues can damage the polymer, causing premature failure in end use; In addition, such catalyst residues can reduce the effectiveness of additives that are supposed to prevent damage to the plastics.



  It is known that various cations with a positive charge> / = 2, especially transition metal ions from the 3d, 4d and 5d series, which are typical catalysts for olefin polymerization, can catalyze the decomposition of phosphites and phosphonites, especially hydrolysis of these typical processing stabilizers. This ultimately leads to products with acidic properties and to the undesired release of phenol. These decomposition products as such can additionally trigger many disadvantageous secondary effects, such as, for example, negative interactions with other additives, in particular sterically hindered amine UV stabilizers or phenolic antioxidants, which may then disrupt the overall balance of the additive system.

   As a result, problems can arise during the processing of the polymer, e.g. in the form of gel particles, various types of specks and precipitates, as well as during use, e.g. in the form of reduced mechanical properties, surface cracks or premature embrittlement when the polymer is exposed to daylight and climatic influences. Many of these undesirable processes taking place in the polymer are caused by a certain acidity that is either present since the beginning or is formed during the life of the polymer. To solve this problem, appropriate amounts of acid scavengers, such as metal stearates or oxides, are added to the polymer. One of the most commonly used acid scavengers is calcium stearate, which is commonly used in concentrations of 0.03-0.15%.



  Nevertheless, various other undesirable processes are observed in polymers which cannot be directly linked to the formation of acid because of acid scavengers. Although details of such reactions or mechanisms are not yet fully known, the consequences are clearly visible. For example, combinations of certain additives have negative interactions, which often manifest themselves as reduced overall effectiveness compared to the individual effectiveness of the individual additives, which they show when used individually with the same polymer.



  An example of such a negative interaction is the simultaneous use of certain processing stabilizers, e.g. Sandostab <TM> P-EPQ or Irgafos <TM> 12, together with sterically hindered amines (HALS) in UV-stabilized polyolefins. Both types of additives are commercially important products and are essential for the production of high-performance plastics. These phosphorus compounds are known for their exceptional stabilizing properties during the processing of the polymer in the melt; HALS compounds are the stabilizers of the prior art for protecting polyolefins against the harmful influence of UV light. These two types of additives - HALS and phosphorus stabilizers - have an antagonistic effect. It is therefore strongly recommended not to use these together (see the publication by Dr.

   WHERE. Drake from Ciba-Geigy, Basel in "Plastic News", April 1989, pages 36-45). It is particularly mentioned that in these cases the effectiveness of HALS compounds as UV stabilizers is drastically reduced, which significantly limits the industrial use of such additive combinations.



  The invention is therefore based on the object of avoiding the disadvantages mentioned above and a highly effective stabilizer composition for stabilizing polyolefins, produced with catalyst systems of the II. To V. [and higher] generation, which are no longer removed from the polymer after the polymerization, to provide.



  According to the invention, this object is achieved by a stabilizer composition which



  a) at least one processing stabilizer which is selected from the group consisting of phosphites, mono- and diphosphonite compounds of the formulas I or II
EMI3.1
 
 
EMI4.1
 
 
 



  wherein
 m is either 0 or 1;
 n is either 0 or 1;
 each R10 and each R11, independently of one another, is an aliphatic, alicyclic or aromatic group with 1-24 carbon atoms which is optionally further substituted (for example by linear or branched aliphatic groups or alkaryl substituents) [hereinafter the monovalent values of R10 or R11, called];
 or
 wherein both groups R10 and / or R11 form a cyclic group with a single phosphorus atom [hereinafter referred to as the divalent values of R10 and R11, respectively];
 Y is -O-, -S-, -CH (R15) - or -C6H4-, wherein
 R15 is hydrogen or C1-8alkyl or COOR6 and R6 C1-8alkyl,



  b) at least one acid scavenger, selected from the group consisting of sodium stearate, magnesium stearate, zinc stearate, magnesium or magnesium / zinc hydrotalcites, optionally coated with 5 to 50% metal stearate, zinc oxide, zinc hydroxide, calcium oxide, calcium hydroxide, magnesium oxide and magnesium hydroxide,



  c) at least one UV stabilizer selected from compounds which have at least one 2,2,6,6-tetraalkylpiperidinyl group
 and if necessary



  d) at least one sterically hindered phenolic antioxidant, selected from the group consisting of octadecyl 3- (3 min, 5 min -di.-tert.-butyl-4 min -hydroxyphenyl) propionate, tetrakis [methylene-3- (3 min , 5 min -di-tert-butyl-4 min -hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxylphenyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxylphenyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) trione and tris [3,5-di-tert-butyl-4-hydroxybenzyl] isocyanurate,
 includes.



  According to the invention, a synergistic additive package is made available, i.e. a stabilizer composition for polyolefins, in which highly effective processing stabilizers and sterically hindered UV stabilizers are combined without sacrificing the individual effectiveness of the additives contained therein. The selected acid scavengers are able to compensate for the negative interactions between processing stabilizers and HALS compounds. In some cases, superior efficacy of the HALS compounds is even observed compared to analog formulations containing processing stabilizers without negative interactions.



  In component a), the monovalent values of R10 and R11 are preferably, independently of one another, linear, branched or cyclic aliphatic groups with 1-24 carbon atoms; or aromatic groups, e.g. Phenyl, preferably 1 to 5 times substituted with C1-12alkyl or aralkyl groups, such as. B. with R10 = R11 = 2,4-di-tert-butyl phenyl.



  The weight ratio of component a) to b) in the stabilizer composition according to the invention is preferably 3: 1 to 1: 7, particularly preferably 2: 1 to 1: 2.



  A typical weight ratio of component a) to d) is 1: 5 to 5: 1, preferably 1: 3 to 3: 1. The amount of component c), relative to the sum of components a) plus b) plus d), can vary from 1: 100 to 100: 1, preferably from 1:20 to 20: 1. The synergistic additive package, which contains the components a), b), c) and d), is used in particular in amounts of 0.05 to 2% by weight, preferably 0.1 to 1% by weight.



  Component a) is preferably a mixture of



  i) 50-90% of a diphosphonite of the formula (a)
EMI6.1
 
 



  ii) 5-25% of a monophosphonite of the formula (b)
EMI6.2
 
 



  iii) 5-25% of a phosphite of formula (c)
EMI6.3
 
 



  wherein each R10 is a 2,4-di-tertiary-butylphenyl radical; all percentages are percentages by weight, the sum of components (a), (b) and (e) giving 100%.



  Component a) is particularly preferably a process product consisting of:



  i) 60-65 parts of the diphosphonite of formula 1a
EMI7.1
 
 



  (Tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite)



  ii) 10-15 parts of the monophosphonite of formula 1b
EMI7.2
 
 



  (Bis (2,4-di-tert-butylphenyl) biphenylene monophosphonite)



  iii) 10-15 parts of the phosphite of formula 1c
EMI8.1
 
 



  (Tris (2,4-di-tert-butylphenyl) phosphite)



  iv) up to 3.5 parts of 2,4-di-tert-butyl phenol;



  v) up to 1% inorganic chloride;



  vi) up to 0.5% volatiles;



  vii) up to 5% of a compound of the formula
EMI8.2
 
 



  This process product is commercially available as a Sandostab <TM> P-EPQ available from CLARIANT International LTD, Switzerland.



  As component a), the compound of formula II, chemically characterized as 2.2 min, 2 min -nitrilo [triethyl-tris (3.3 min, 5.5 min -tetra-tert-butyl-1.1 min -biphenyl-2,2 min -diyl) phosphite], can be used, as obtained by the process described in Example 4 of US Pat. No. 4,318,845 or in Example 4 of US Pat. No. 4,374,219, with a melting range of 121 -134 ° C, or in its amorphous, solid form with a melting range of 105-110 ° C according to US Patent 5 276 076 or in its triclinic beta modification with a melting range of 200-207 ° C according to US Patent 5 326 802 or in their gamma modification with a melting range of 178-185 ° C according to US Patent 5,331,031 or in their monoclinic alpha modification with a melting range of 145-165 ° C according to US Patent 5,334,739, or in the form of mixtures,

   Melting or solutions thereof.



  The divalent values of R10 and R11 are preferably e.g.
EMI9.1
 
 
 



  where each R14 can independently be a C1-22alkyl or a C7-22aralkyl group and p = 0 to 4, preferably 1 to 3.



  The 2,2,6,6-tetraalkylpiperidinyl residue of component c) corresponds to the formula alpha)
EMI9.2
 
 
 



  in which
 R is hydrogen, oxygen; -OH; C1-24 alkyl; -O-C1-24 alkyl; -O-CO-C1-24 alkyl; Is -O-CO-phenyl or -COR5; and R5 is -C (R3) = CH2, C1-6 alkyl, phenyl, CO-C1-24 alkyl, -CO-phenyl, -NR7R8, -CH2-C6H5, -CO-OC1-12 alkyl or -COOH; R3 is hydrogen or C1-4 alkyl; R7 is hydrogen, C1-12alkyl, C5-6cycloalkyl, phenyl, phenyl-C1-4alkyl or C1-12alkylphenyl and R8 is C1-12alkyl or hydrogen,
 each R1, independently of one another, is -CH3 or -CH2 (C1-4alkyl) or both radicals R form a - (CH2) 5 group; and
 each R2, independently of one another, is -CH3 or -CH2 (C1-4alkyl) or both radicals R2 form a - (CH2) 5 group.



  The radical corresponding to the formula alpha) is known as the active group in many hindered amine light stabilizers (HALS).



  A component which contains a radical of the formula alpha min is particularly preferred for component c)
EMI10.1
 
 
 



  where R min is hydrogen, oxygen, OH, C1-12 alkyl, O-C1-12 alkyl or -CO-C1-8 alkyl.



  Component c) is preferably selected from the compounds from HALS 1 to HALS 18


 NECK 1
 
EMI11.1
 
 


 NECK 2
 
EMI11.2
 
 


 NECK 3
 
EMI11.3
 
 


 NECK 4
 
EMI12.1
 
 
 



  where R20 is
EMI12.2
 
 


 NECK 5
 
EMI12.3
 
 


 NECK 6
 
EMI13.1
 
 


 NECK 7
 
EMI13.2
 
 


 NECK 8
 
EMI13.3
 
 


 NECK 9
 
EMI14.1
 
 


 NECK 10
 
EMI14.2
 
 


 NECK 11
 
EMI14.3
 
 


 NECK 12
 
EMI15.1
 
 
 



  wherein R21 is C12-14alkyl (e.g. a mixture of C12H25 and C14H29);


 NECK 13
 
EMI15.2
 
 


 NECK 14
 
EMI 15.3
 
 


 NECK 15
 
EMI16.1
 
 
 



  where R21 is as defined above


 NECK 16
 
EMI16.2
 
 


 NECK 17
 
EMI 16.3
 
 


 NECK 18
 
EMI17.1
 
 
 



  where in HALS 1 to HALS 18
 R R is min and R min is hydrogen, oxygen, OH, C1-12 alkyl, O-C1-12 alkyl or -CO-C1-8 alkyl
 and
 n min is a number between 3 and 20.



  Component c) is even more preferably selected from:
 Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate;
 Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) (3,5-ditert. Butyl-4-hydroxybenzyl) butylmalonate;
 Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate;
 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro (4,5) decane -2,4-dione;
 Succinic acid bis (2,2,6,6-tetramethyl-4-piperidinyl) ester;
 Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate;
 (2,2,6,6-tetramethyl-4-piperidyl) / beta, beta, beta min, beta min -tetramethyl-3.9- (2,4,8,10-tetraoxaspiro (5 min, 5) undecane) diethyl) -1,2,3,4-butane tetra carboxylate;
 7-oxa-3,20-diazadispiro (5.1.11.2) heneicosan-20-malonic acid, 2,2,4,4-tetra-methyl-21-oxo, dodecyl ester ("Hostavin" N 24);
 Octadecene (N- (2,2,6,6-tetramethylpiperidinyl-4-N-maleimido-oxalic acid diamide) copolymer;

  
 N- (2,2,6,6-tetramethyl-4-piperidinyl) -Nmin amino oxamide;
 OO-t-amyl-O- (1,2,2,6,6-pentamethyl-4-piperidinyl) monoperoxy carbonate;
  beta-alanine-N- (2,2,6,6-tetramethyl-4-piperidinyl) dodecyl ester;
 Ethanediamide-N- (1-acetyl-2,2,6,6-tetramethylpiperidinyl) -N min -dodecyl;
 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione;
 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidinyl) pyrrolidine-2,5-dione;
 3-dodecyl-1- (1-acetyl, 2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione;

   ("Sanduvor" <TM> 3058)
 4-benzoyloxy-2,2,6,6-tetramethylpiperidine;
 1- [2- (3,5-di-tert-butyl-4-hydroxyphenylpropionyloxy) ethyl] -4- (3,5-di-tert-butyl-4-hydroxyphenyl-propionyloxy) -2,2,6,6- tetramethyl piperidine;
 2-Methyl-2- (2 min min, 2 min min, 6 min min, 6 min min -tetramethyl-4 min min -piperidinylamino) -N- (2 min, 2 min, 6 min, 6 min -tetra-methyl -4 min -piperidinyl) propionylamide;
 1,2-bis (3,3,5,5-tetramethyl-2-oxopiperazinyl) ethane-l-isopropyl-3,3,5,5-tetramethyl-2-piperazinone
 Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate;
 4-oleoyloxy-2,2,6,6-tetramethylpiperidine;
 Poly - [(6-morpholino-s-triazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidinyl) imino] hexamethylene-2,2,6,6-tetramethyl-4- piperidinyl) imi no)];

  
 Poly- [6- [1,1,3,3-tetramethyl-butyl) imino] -s-triazine-2,4-diyl) [2- (2,2,6,6-tetramethyl-4-piperidinyl) imino ] hexamethylene- [4- (2,2,6,6-tramethyl-4-piperidinyl) imino)];
 1,3,5-triazine-2,4,6-triamine-N min, N min min - [ethanediyl-bis [[[4,6-bis [butyl (1,2,2,6,6-pentamethyl- 4-piperidinyl) amine] -1,3,5-triazi n-2-yl] imino] propane-diyl]] to [N min, N min min -dibutyl-N min, N min min -bis (1.2 , 2,6,6-pentamethyl-4-piperidinyl)];
 Succinic acid, polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol;
 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro [5.1.11.2] heneicosan-21-one;
 Bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate;
 Poly (methylpropyl-3-oxy- [2,2,6,6-tetramethyl-4-piperidinyl] siloxane);
 1,3,5,7,9,11-Hexaaza-4,10-dione-tricyclo [12.1.1.013,14] tetradecane-1,7-bis (2,2,6,6-tetramethyl-4-piperidinyl ).



  Are particularly suitable as component c)
 Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate;
 Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate;
 Succinic acid bis (2,2,6,6-tetramethyl-4-piperidinyl) ester;
 Poly - [(6-morpholino-s-triazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidinyl) imino] hexamethylene - [(2,2,6,6-tetramethyl- 4-piperidiny l) in ino)];
 Poly- [6- [1,1,3,3-tetramethyl-butyl) imino] -s-triazine-2,4-diyl) [2- (2,2,6,6-tetramethyl-4-piperidinyl) imino ] hexamethylene- [4- (2,2,6,6-tramethyl-4-piperidinyl) imino)];
 1,3,5-triazine-2,4,6-triamine-N min, N min min - [ethanediyl-bis [[[4,6-bis [butyl (1,2,2,6,6-pentamethyl- 4-piperidinyl) amine] -1,3,5-tria zin-2-yl] imino] propane-diyl]] to [N min, N min min -dibutyl-N min, N min min -bis (1.2 , 2,6,6-pentamethyl-4-piperidinyl)];
 Succinic acid, polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol;

  
 Bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate;
 Poly (methylpropyl-3-oxy- [2,2,6,6-tetramethyl-4-piperidinyl] siloxane)



  In addition, component c) can optionally be combined with known UV absorbers.



  Components a) to c) and optionally d) of the stabilizer composition according to the invention can be added individually or together as an additive package to the polymeric materials to be stabilized. This additive package can be prepared by mixing components a) to c) and optionally d) in a suitable mixer. The powder mixture obtained is preferably compressed into non-dusting granules in accordance with a known method.



  Another possibility for producing an additive package consists in melt mixing components a) to c) and optionally d), a homogeneous melt mass being obtained which is cooled and granulated by known processes.



  Further additives which can be added to a composition according to the invention are both antioxidants and UV absorbers (for example 2- (2 min-hydroxyphenyl) -benztriazoles, 2-hydroxybenzophenones, 1,3-bis (2 min -hydroxybenzoyl) benzene, salicylates, cinnamic acid esters and oxalic acid diamides; UV quenchers such as benzoates and substituted benzoates, antistatic agents, flame retardants, lubricants, plasticizers, nucleating agents, metal deactivators, biocides, impact modifiers, fillers, pigments and fungicides.



  The invention also relates to solid masterbatch compositions or liquid concentrates which are used as stabilizers in organic, polymeric materials. A masterbatch composition contains 10 to 80% by weight, preferably 15 to 40% by weight, of a stabilizer composition according to the invention and 90 to 20% by weight, preferably 85 to 60% by weight, of an organic polymeric material which are identical or is compatible with the polymeric material to be stabilized.



  The liquid concentrate contains 10 to 80% by weight of a stabilizer composition according to the invention and 90 to 20% by weight of a solvent.



  Another object of the invention is a method for stabilizing organic, polymeric materials by adding a stabilizing amount of the stabilizer composition according to the invention or the solid masterbatch or the liquid concentrate to the polymeric material. As already mentioned, this stabilizing amount depends on the polymeric material to be stabilized, but is independent of the metering method used.



  The stabilizer composition or the masterbatch composition according to the invention can be incorporated into the polymeric material to be stabilized according to known methods. Of particular importance is the production of a free-flowing dry mixture from the polymeric material and the stabilizer composition or the coating of shaped polymer particles with the stabilizer composition according to the invention in the form of a liquid, a solution or a suspension / dispersion.



  Of particular importance is the mixing of the stabilizer composition or masterbatch composition according to the invention with the polymeric material to be stabilized in the melt, e.g. in a melt mixer or during the molding process, which comprises the production of films / foils, tubes, fibers and foams by extrusion, injection molding, blow molding, spinning or cable covering.



  The polymeric material to be stabilized according to the invention is selected from a group consisting of homopolyolefins and copolyolefins which have been prepared in the presence of a so-called II or higher generation catalyst system (the catalyst system no longer being removed from the polymer after the polymerization), and also mixtures and blends with each other or with other polymers.



  Preferred polyolefins are selected from the group consisting of homopolypropylene, copolypropylene, homopolyethylene, copolyethylene as well as mixtures and blends with one another or with other polymers.



  The poly- and copolyolefins mentioned are produced according to newer methods with catalysts of the II. To V. [and higher] generation which have not been subjected to a catalyst removal step after the polymerization. By "catalyst removal" is meant a process that completely removes the catalyst residues in polyolefins, or treating the polyolefins with compounds that can react with the catalyst residues and thereby inactivate or dissolve these residues, e.g. Alcohols or water. These inactivated or dissolved catalyst residues are then removed by physical methods such as filtration, washing and centrifuging.

   On the other hand, the process step necessary for suspension polymerization to separate the polymer obtained from the dispersion medium, e.g. a solvent or the liquid monomer, not under the above-mentioned definition of a catalyst removal step, although the catalyst dissolved in the dispersion medium could be removed by a separation step.



  Neither does the addition of small amounts of catalyst poisons such as ethers, alcohols, ketones, esters and water to the resulting polymer, with the aim of inactivating the catalyst remaining after completion of the polymerization, or treating the resulting polymer suspension with gas, e.g. Air or nitrogen, with the aim of removing the dispersion medium, under the definition of a catalyst removal step mentioned above.



  Generation I catalysts mean titanium halide catalysts and an organic aluminum compound or an organic aluminum halide.



  Generation II catalysts mean generation I catalysts which are applied to a carrier made of an organic magnesium compound or which are based on an organic chromium compound which is supported by an SiO2 carrier.



  Generation III catalysts refer to complex catalysts of the Ziegler type which are supported by an organic halogen-containing magnesium compound.



  Generation IV catalysts mean generation III catalysts with a silane donor.



  A generation V catalyst means an organic bis-indenyl titanium compound which is activated with an aluminum alkyl compound and is supported by alumoxane or bis-cyclopentadienyl titanium halide.



  Further generations of highly specific catalysts currently under development, which are particularly advantageous for the production of highly tactical poly-alpha-olefins, also fall under the above-mentioned generations of supported catalyst systems. Examples of the microstructure of such highly tactical polyolefins are syndiotactic polypropylene, isotactic stereoblock polymer, isotactic polypropylene which contains steric defects (so-called anisotactic polypropylene) which are statistically distributed over the polymer chain or stereo-irregular (non-tactical) stereoblock polymers. An overview of the latest developments in the field of metallocene-based catalyst systems is given by: W.N. Riss and H. Ledwinka: Kunststoffe 83 (1993) 8, pages 577-583; R. Mülhaupt: Nachr. Chem. Tech. Labs 41 (1993) 12, pages 1341-1351; R.

   Leaversuch: Modem Plastics, October 1991, pages 46-49, and W. Spaleck: Hoechst High Chem Magazine 14 (1993), pages 44-48. Due to the rapid progress in the development of catalyst systems of newer generations, the commercial importance of these polymers with new, very interesting properties is increasing.



  These generations of catalysts are described in the publication of the "Twelfth Annual International Conference on Advances in Stabilization and Controlled Degradation of Polymers", which took place on May 21-23. May 1990 in Lucerne, Switzerland, on pages 181 to 196 in an article by Rolf Mülhaupt with the title "New Trends in Polyolefin Catalysts and Influence on Polymer Stability". The content of this article is hereby incorporated by reference, in particular Table 1 on page 184, which describes the different generations of catalysts:
 <tb> <TABLE> Columns = 6 Table I: Development of the polyolefin catalysts
 <tb> Head Col 1: generation
 <tb> Head Col 2: example
 <tb> Head Col 3: Cat.

   Activity (gPP / gTi H atm)
 <tb> Head Col 4:% Akt.Ti
 <tb> Head Col 5: tacticity
 (% insoluble.
 in heptane)
 <tb> Head Col 6: process technology
 <tb> <SEP> I. <SEP> TiCl4 / AlR3 <SEP> 40 <SEP> 0.01 <SEP> 45% <CEL AL = L> removal of catalyst residues and atactic PP
 <tb> <SEP> TiCl3 / AlEt2Cl <SEP> 30 <SEP> 0.1 <SEP> 92% <SEP> removal of catalyst residues
 <tb> <SEP> II. <SEP> Mg (OEt2) / TiCl4 / AlR3 <SEP> 40,000 <SEP> 50% <SEP> No removal of the catalyst residues
 <tb> <SEP> SiO2 / Cp2Cr <SEP> 40,000 <SEP> HDPE <SEP> (mainly HDPE / LLDPE)
 <tb> <SEP> IlI. <SEP> Mod.TiCl3Kat. <SEP> 5000 <SEP> 1 <SEP> 95% <SEP> No cleaning
 <tb> <CEL CB = 2 AL = L> MgCl2 / TiCl4 / AlR3 + ester donor <SEP> 20,000 <SEP> 10 <SEP> 92%
 <tb> <SEP> IV. <SEP> MgCl2 / TiCl4 / AlR3 + silane donor <SEP> 40,000 <SEP> 18 <SEP> 99% <SEP> No cleaning <SEP> No extrusion
 <tb> <SEP> V. <CEL AL = L> bis-indenyl-TiR2
 on (AlCH3O) x <SEP> 40,000 <SEP> 100 <SEP> 99% <SEP> new PP,

   tight MWD
 <tb>
 R = organic residue; HDPE = high density polyethylene, LLDPE = linear low density polyethylene, Cp = cyclopentadienyl, Et = ethyl, PP = polypropylene, MWD = molecular weight distribution and x = an integer greater than 2 (preferably 2-100).
  
 <tb> </TABLE>



  The invention also relates to a stabilized polymeric material which



  a) a stabilizer composition according to the invention,
 and



  b) a polymeric material selected from the group of homopolyolefins and copolyolefins, preferably homopolypropylene, copolypropylene, homopolyethylene, copolyethylene, which were produced in the presence of a catalyst system of the so-called II. or higher generation, and mixtures and blends with one another or with other polymers,
 includes.



  Furthermore, in this specification, where a range is given, the numbers that define that range are also included. Any group that can be either linear or branched is linear or branched unless the opposite is stated.



  For the avoidance of doubt, t.butyl in this description means tertiary butyl, (-C (CH3) 3).



  The following examples illustrate the invention, all parts and percentages being parts by weight and percentages by weight, unless the opposite is stated.


 Examples
 



  All examples are made with polymeric materials made with second or higher generation catalysts without removal of catalyst residues. The preparation of the samples was carried out as follows:



  According to the recipe, a free-flowing dry mixture is produced from the powdered polymer and all additives, which is melt-mixed in a single-screw extruder at 210-220 ° C and processed into polymer granulate with homogeneously distributed additives. This granulate is used for the production of pressed or blown films or for the production of fibers. The UV stability of the end products is measured with an Atlas Weatherometer WOM 65 WRC (artificial weathering at 63 ° C "black panel temperature"), either using the method according to CAM 7, i.e. 102 minutes dry / 18 minutes wet cycle or only dry without artificial rain during the entire radiation period with a xenon lamp. A UVCon device is used for the UVA tests.

   Depending on the application, the assessment was based on the deterioration of the mechanical properties, e.g. Tensile strength or elongation at break, and / or the increase in the carbonyl index to a value of 0.3 compared to the unweathered reference sample.



  The following brand names are used in the examples:
 <tb> <TABLE> Columns = 2
 <tb> <SEP> Irganox <TM> 1010: <SEP> this is an antioxidant based on a sterically hindered phenol, available from Ciba-Geigy, Switzerland
 <tb> <SEP> Sanduvor <TM> 3944: <SEP> this is a high molecular weight oligomeric HALS available from
 CLARIANT International, Switzerland
 <tb> <SEP> Sandostab <TM> P-EPQ: <SEP> a mixture consisting of components (i) to (vii), as on page 6ff. described, available from CLARIANT International, Switzerland
 <tb> <SEP> Irgafos <TM> 12: <CEL AL = L> 2.2 min, 2 min min -Nitrilo [triethyl-tris (3.3 min, 5.5 min -tetra-tert-butyl-1.1 min -biphenyl-2.2 min - diyl) phosphite], available from Ciba-Geigy, Switzerland
 <tb> <SEP> Irgafos <TM> 168: <SEP> Tris (2,4-di-tert-butylphenyl) phosphite, available from Ciba-Geigy, Switzerland
 <tb> <SEP> Irganox <TM> 3114:

   <SEP> Tris [3,5-di-tert-butyl-4-hydroxybenzyl] isocyanurate, available from Ciba-Geigy, Switzerland
 <tb> <SEP> L-55 R: <SEP> Hydrotalcite, a magnesium aluminum hydroxide carbonate hydrate coated with 18% sodium stearate, available from Reheis Inc, Berkeley Heights, NJ, USA
 <tb> <SEP> Hysafe 510: <SEP> a magnesium hydrotalcite available from J.M. Huber Corp., Havre de Grace, MD, USA
 <tb> <SEP> Ultranox 626: <SEP> a commercial phosphite processing stabilizer from G.E. Specialty Chemicals
 <tb> </TABLE>



  The following abbreviations are used in the examples:
 <tb> <TABLE> Columns = 2
 <tb> <SEP> MFI: <SEP> Melt Flow Index
 <tb> <SEP> ZnSt2: <SEP> zinc stearate
 <tb> <SEP> CaSt2: <CEL AL = L> calcium stearate
 <tb> <SEP> Next: <SEP> sodium stearate
 <tb> <SEP> I-168: <SEP> Irgafos <TM> 168
 <tb> <CEL AL = L> I-12: <SEP> Irgafos <TM> 12
 <tb> <SEP> P-EPQ: <SEP> Sandostab <TM> P-EPQ
 <tb> <SEP> WOM: <CEL AL = L> Weatherometer
 <tb> <SEP> COI: <SEP> carbonyl index
 <tb> <SEP> tf: <SEP> time until sample breaks (determined using COI measurements)
 <tb> <SEP> U 626: <SEP> Ultranox 626
 <tb> <SEP> H-510: <SEP> Hysafe 510
 <tb> <SEP> ZnO: <CEL AL = L> zinc oxide
 <tb> <SEP> t50: <SEP> time until the sample fails, measured by the decrease in the original tensile strength value to 50%
 <tb> </TABLE>


 example 1
 
 <tb> <TABLE> Columns = 2
 <tb> <SEP> samples:

   <SEP> Press foils with a thickness of 100 µm made of homopolypropylene, which has an MFI value (230 ° C, 2.16 kg) of 1.8 g / 10 min
 <tb> <SEP> UV weathering: <SEP> Atlas WOM 65 WRC under CAM 7 conditions
 <tb> <SEP> test criteria: <SEP> time to failure of the samples, measured based on the increase in the COI value to 0.3, referred to as "tf"
 <tb> <SEP> formulations: <SEP> All samples are with 0.05% Irganox <TM> 1010 and 0.15% Sanduvor <TM> 3944 (HALS connection) base stabilized.

   They also contain the additives listed below
 <tb> </TABLE>
 <tb> <TABLE> Columns = 4
 <tb> Head Col 1: No.
 <tb> Head Col 2: other additives
 <tb> Head Col 3: tf
 <tb> <SEP> A) <SEP> 0.07% I-168 <SEP> 2210 h <SEP> 100%
 <tb> <SEP> 0.01% CaSt2
 <tb> <CEL AL = L> B) <SEP> 0.07% P-EPQ <SEP> 1825 h <SEP> 83%
 <tb> <SEP> 0.10% CaSt2
 <tb> <SEP> C) <SEP> 0.07% I-168 <CEL AL = L> 1920 h <SEP> 87%
 <tb> <SEP> 0.10% VAT
 <tb> <SEP> D) <SEP> 0.07% P-EPQ <SEP> 2520 h <CEL AL = L> 114%
 <tb> <CEL CB = 2 AL = L> 0.10% NaSt
 <tb> </TABLE>



  The comparison between formulations A) and B) shows the effectiveness-reducing effect of Sandostab <TM> P-EPQ versus Irgafos <TM> 168 in the UV stabilization of polypropylene, examined on the HALS compound Sanduvor <TM> 3944. This confirms analogous studies from the scientific literature cited above. However, when the acid scavenger calcium stearate used in formulations A) and B) is replaced by sodium stearate in the formulation according to the invention, the disadvantages mentioned, which occur when combining Sandostab, surprisingly occur P-EPQ with HALS compounds were not observed. In fact, a 14% higher activity of the HALS compound compared to the reference formulation A) was demonstrated.

   Comparative example C) also shows that the beneficial effect of sodium stearate only with Sandostab <TM> P-EPQ and HALS occurs and not with Irgafos <TM> 168.


 Example 2
 



  The samples, formulations and test criteria are identical to those in Example 1. The weathering tests are carried out under the even tougher conditions of a UVCon device. The aim is to show that the stabilizer effectiveness achieved is independent of the test methods used and that the test results obtained show the same order as in Example 1.
 <tb> <TABLE> Columns = 4
 <tb> Head Col 1: No.
 <tb> Head Col 2: other additives
 <tb> Head Col 3: tf
 <tb> <SEP> A) <SEP> 0.07% I-168 <SEP> 1715 h <SEP> 100%
 <tb> <SEP> 0.01% CaSt2
 <tb> <CEL AL = L> B) <SEP> 0.07% P-EPQ <SEP> 980 h <SEP> 57%
 <tb> <SEP> 0.10% CaSt2
 <tb> <SEP> C) <SEP> 0.07% I-168 <CEL AL = L> 1390 h <SEP> 81%
 <tb> <SEP> 0.10% VAT
 <tb> <SEP> D) <SEP> 0.07% P-EPQ <SEP> 1770 h <CEL AL = L> 103%
 <tb> <CEL CB = 2 AL = L> 0.10% NaSt
 <tb> </TABLE>



  These experimental results confirm the superiority of the formulation D) according to the invention over the reference formulation A) and underline the results of Example 1. The use of sodium stearate selectively neutralizes the negative interaction between Sandostab <TM> P-EPQ and HALS.


 Example 3
 
 <tb> <TABLE> Columns = 2
 <tb> <SEP> samples: <SEP> press films with a thickness of 100 μm made of a homopolypropylene (film quality) which has an MFI (230 ° C., 2.16 kg) of 1.8 g / 10 min
 <tb> <SEP> UV weathering: <SEP> Atlas WOM 65 WRC under CAM 7 conditions
 <tb> <CEL AL = L> test criteria: <SEP> time until the sample failed based on the increase in the COI value to 0.3, referred to as "tf"
 <tb> <SEP> formulations:

   <SEP> All samples contain 0.05% Irganox <TM> 1010, 0.10% Sanduvor <TM> 3944 and 0.07% Sandostab <TM> P-EPQ as basic stabilization and the other additives mentioned below
 <tb> </TABLE>
 <tb> <TABLE> Columns = 4
 <tb> Head Col 1: No.
 <tb> Head Col 2: other additives
 <tb> Head Col 3: tf
 <tb> <SEP> A) <SEP> 0.1% CaSt2 <SEP> 1233 h <SEP> 100%
 <tb> <SEP> B) <SEP> 0.1% tax <CEL AL = L> 1588 h <SEP> 126%
 <tb> <SEP> C) <SEP> 0.5% tax <SEP> 1500 h <SEP> 121%
 <tb> <SEP> D) <SEP> 0.0% tax <CEL AL = L> 1067 h <SEP> 87%
 <tb> </TABLE>



  These examples again show the advantages of sodium stearate over calcium stearate in formulations, the Sandostab <TM> contain P-EPQ and HALS compounds (the presence of the phenolic antioxidant Irganox <TM> 1010 is optional and of no importance for UV stability). If no stearate is used at all, the effectiveness of formulation D) is even worse than that of reference formulation A).

   It can be deduced from the results of Examples 1 and 3 that the preferred concentrations of sodium stearate, defined as the ratio of Sandostab <TM> P-EPQ to NaSt, between 3/1 to 1/7, preferably between 2/1 to 1/2.


 Example 4
 
 <tb> <TABLE> Columns = 2
 <tb> <SEP> samples: <SEP> 160/14 dtex multifilaments, made from a polypropylene with an MFI (230 ° C, 2.16 kg) of 12 g / 10 min
 <tb> <SEP> UV weathering: <SEP> Atlas WOM 65 WRC under DRY conditions
 <tb> <SEP> test criteria: <SEP> time to failure (4), measured by reducing the original tensile strength to 50%
 <tb> <SEP> formulations: <SEP> All samples are with 0.05% Irganox <TM> 3114 and 0.20% Sanduvor <TM> 3944 base stabilized and contain the other additives mentioned below
 <tb> </TABLE>
 <tb> <TABLE> Columns = 4
 <tb> Head Col 1:

   No.
 <tb> Head Col 2: other additives
 <tb> Head Col 3: t50
 <tb> <SEP> A) <SEP> 0.08% I-168 <SEP> 551 h <SEP> 100%
 <tb> <SEP> 0.06% CaSt2
 <tb> <CEL AL = L> B) <CEL AL = L> 0.08% P-EPQ <SEP> 493 h <SEP> 89%
 <tb> <SEP> 0.06% CaSt2
 <tb> <SEP> C) <SEP> 0.08% P-EPQ <SEP> 733 h <CEL AL = L> 133%
 <tb> <SEP> 0.06% L-55R
 <tb> <SEP> D) <SEP> 0.08% P-EPQ <SEP> 613 h <SEP> 111%
 <tb> <CEL CB = 2 AL = L> 0.06% H-510
 <tb> <SEP> E) <SEP> 0.08% P-EPQ <SEP> 585 h <SEP> 106%
 <tb> <SEP> 0.06 MgSt2
 <tb> </TABLE>



  The above examples show that the invention can also be used for additive formulations which are used for UV stabilization of PP fibers. While calcium stearate is unsuitable, the negative interaction between Sandostab <TM> P-EPQ and the HALS compound (this interaction has never been seen with similar formulations, the Irgafos Contained <TM> 168, observed, see Comparative Example 4A), some other acid scavengers were able to overcome this antagonism in this application too. According to the invention, it is now possible to add Sandostab <TM> P-EPQ and any phenolic antioxidants present to achieve higher melt and color stability of the polymer without impairing the highly effective UV stabilization achieved by the HALS compound.

   Of the above formulations, C) contains Sandostab <TM> P-EPQ and L-55R, the most preferred. Examples D) and E) also show better results than Comparative Examples A) and B). In addition, the use of the coated embodiment of the hydrotalcite (L-55R) is preferred compared to the uncoated embodiment (H-510). However, both embodiments of hydrotalcite are magnesium stearate in formulations with Sandostab <TM> P-EPQ preferable. The effectiveness of the acid scavengers decreases in the above formulations in the order E) <D) <C) and clearly exceed the comparative examples A) and B). Only the commonly used calcium stearate (formulation B) cannot be used.

   It acts as a pure acid scavenger, without neutralizing the antagonism between Sandostab To own <TM> P-EPQ and HALS.


 Example 5
 
 <tb> <TABLE> Columns = 2
 <tb> <SEP> samples: <SEP> An LLDPE (copolymer of ethylene and octets (film quality)) with a density of 0.920 g / cm <3> and an MFI (190 ° C, 2.16 kg) of 1.0 g / 10 min
 <tb> <SEP> UV weathering: <SEP> Atlas WOM 65 WRC under CAM 7 conditions
 <tb> <CEL AL = L> test criteria: <SEP> time to failure, measured by the decrease in the original elongation at break to 50% (i.e. the maximum elasticity of the films)
 <tb> <SEP> formulations: <SEP> All samples contain 0.07% Irganox for basic stabilization <TM> 1076 and 0.15% Sanduvor <TM> 3944 and the other additives mentioned below
 <tb> </TABLE>
 <tb> <TABLE> Columns = 4
 <tb> Head Col 1:

   No.
 <tb> Head Col 2: other additives
 <tb> Head Col 3: t50
 <tb> <SEP> A) <SEP> 0.10% P-EPQ <SEP> 2567 h <SEP> 100%
 <tb> <SEP> 0.10% CaSt2
 <tb> <CEL AL = L> B) <SEP> 0.10% P-EPQ <SEP> 3160 h <SEP> 123%
 <tb> <SEP> 0.05% tax
 <tb> <SEP> C) <SEP> 0.10% P-EPQ <CEL AL = L> 3135 h <SEP> 122%
 <tb> <SEP> 0.15% NaSt
 <tb> <SEP> D) <SEP> 0.10% P-EPQ <SEP> 2494 h <CEL AL = L> 97%
 <tb> <CEL CB = 2 AL = L> 0.00% NaSt
 <tb> <SEP> E) <SEP> 0.10% U-626 <SEP> 2888 h <SEP> 113%
 <tb> <SEP> 0.10% VAT
 <tb> </TABLE>



  This series of tests shows that the present selection of acid scavengers according to the invention also shows the negative interactions between Sandostab in polyethylene <TM> P-EPQ and HALS compound neutralized. The results described in Example 3, in particular also the preferred quantitative ratios of Sandostab P-EPQ to sodium stearate from 3/1 to 1/7, preferably from 2/1 to 1/2, used in additive packages for UV-stabilized plastics are confirmed. Example E), the Ultranox 626 as a comparison to Sandostab <TM> P-EPQ contains is listed for additional reference. Ultranox 626 is like the aforementioned Irgafos <TM> 168, known for not reducing the effectiveness of HALS compounds in UV stabilized plastics (see EP 0 553 498 A2 and W.O. Drake, K.D.

   Cooper "Recent Advances in Processing Stabilization of Polyolefins", especially Fig. 21). Formulations B) and C) according to the invention even outperform the good stabilization results of Ultranox 626 in their effectiveness.


 Example 6
 
 <tb> <TABLE> Columns = 2
 <tb> <SEP> samples: <SEP> Molded films of 100 µm thick, made of high molecular polypropylene with an MFI (230 ° C, 5.0 kg) of 1.3 g / 10 min or 0.4 g / 10 min
 <tb> <SEP> UV weathering: <SEP> UVCon UVA weathering apparatus
 <tb> <CEL AL = L> test criteria: <SEP> Time to failure measured by increasing the COI to 0.3
 <tb> <SEP> formulations: <SEP> All samples are with 0.05% Irganox <TM> 1010 and 0.15% Sanduvor <TM> 3944 base stabilized and contain the other additives mentioned below
 <tb> </TABLE>
 <tb> <TABLE> Columns = 4
 <tb> Head Col 1:

   No.
 <tb> Head Col 2: other additives
 <tb> Head Col 3: tf
 <tb> <SEP> A) <SEP> 0.07% P-EPQ <SEP> 805 h <SEP> 100%
 <tb> <SEP> 0.10% CaSt2
 <tb> <CEL AL = L> B) <SEP> 0.07% I-12 <SEP> 807 h <SEP> 100%
 <tb> <SEP> 0.10% CaSt2
 <tb> <SEP> C) <SEP> 0.07% I-168 <CEL AL = L> 1056 h <SEP> 130%
 <tb> <SEP> 0.10% CaSt2
 <tb> <SEP> D) <SEP> 0.07% P-EPQ <SEP> 1098 h <SEP> 136%
 <tb> <SEP> 0.10% ZnO
 <tb> <SEP> E) <SEP> 0.07% I-12 <SEP> 1061 h <SEP> 132%
 <tb> <SEP> 0.10% ZnO
 <tb> <SEP> F) <SEP> 0.07% P-EPQ <SEP> 1025 h <CEL AL = L> 127%
 <tb> <SEP> 0.05% ZnSt2
 <tb> <SEP> 0.05% ZnO
 <tb> <SEP> G) <SEP> 0.07% I-12 <SEP> 1022 h <CEL AL = L> 127%
 <tb> <SEP> 0.05% ZnSt2
 <tb> <SEP> 0.05% ZnO
 <tb> </TABLE>



  This series of tests shows that the present invention also applies to the use of Irgafos <TM> 12 can be expanded into additive formulations for UV stabilized plastics. Despite its excellent hydrolysis resistance, which is even better than that of Irgafos <TM> 168 (see lecture by WO Drake and KD Cooper, both from Ciba-Geigy: "Recent Advances in Processing Stabilization of Polyolefins" presented on February 21-24, 1993, page 419 and Fig. 23) Irgafos <TM> 12 the same negative interactions with HALS compounds as Sandostab <TM> P-EPQ. Special combinations with acid scavengers according to the invention compensate for the already mentioned antagonism and thereby allow the use of Irgafos <TM> 12 also in UV-stabilized plastics, provided that these plastic additives are formulated according to the invention.

   The formulations according to the invention, the Sandostab <TM> P-EPQ or Irgafos Containing <TM> 12 in conjunction with other additives allows the manufacturer of plastics, compound compounds or plastic end products both advantages, namely the high effectiveness of the high-performance processing stabilizers on the one hand and the unlimited effectiveness of the HALS compounds on the other, for use in a wide range to use on UV-stabilized polymers.



  Furthermore, the test series of example 6 with formulations D) and E) shows clear advantages when combining Sandostab <TM> P-EPQ or Irgafos <TM> 12 preferably with ZnO (French processing type, available from Saint Joe Company, Monica, PA, USA, Seido Chem. Ind. Co., Osaka, Japan, or others) in UV-stabilized polyethylenes. Combinations of ZnO with ZnSt2 (commercially available zinc stearate for polyolefins) and Sandostab according to the invention <TM> P-EPQ or Irgafos <TM> 12, according to formulations F) and G) in UV-stabilized polyethylenes, are also better than the corresponding reference formulations A) and B).


    

Claims (11)

    1. Containing a stabilizer composition    a) at least one processing stabilizer selected from the group consisting of phosphites, mono- and diphosphonite compounds of the formulas I or II EMI35.1     EMI35.2          wherein  m is either 0 or 1;  n is either 0 or 1;  each R10 and R11, independently of one another, is an aliphatic, alicyclic or aromatic group having 1-24 carbon atoms [hereinafter defined as the monovalent values of R10 and R11, respectively];  or  both groups R10 and / or R11 form a cyclic group with a single phosphorus atom [hereinafter defined as the divalent values of R10 and  R11];  Y is -O-, -S-, -CH (R15) - or -C6H4-, where R15 is hydrogen or C1-8alkyl or COOR6 and R6 is C1-8alkyl,    b) at least one acid scavenger selected from the group consisting of sodium stearate, magnesium stearate, zinc stearate, magnesium or magnesium / zinc hydrotalcites, optionally coated with 5 to 50% metal stearate, zinc oxide, zinc hydroxide, calcium oxide, calcium hydroxide, magnesium oxide and magnesium hydroxide,    c) at least one UV stabilizer selected from compounds containing at least one 2,2,6,6-tetraalkylpiperidinyl group    and if necessary    d) at least one sterically hindered phenolic antioxidant, selected from the group consisting of octadecyl-3- (3 min, 5 min -di.tert.-butyl-4 min -hydroxyphenyl) propionate, tetrakis [methylene-3- (3 min, 5 min -di-tert-butyl-4 min -hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4, 6-tris (3,5-di-tert-butyl-4-hydroxylphenyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxylphenyl) -1,3,5- triazine-2,4,6- (1H, 3H, 5H) trione and tris [3,5-di-tert-butyl-4-hydroxybenzyl] isocyanurate. 2. Composition according to claim 1, wherein the weight ratio of components a) to b) is 3: 1 to 1: 7, preferably 2: 1 to 1: 2. 3. The composition of claim 1 or 2, wherein component a) is a mixture of    i) 50-90% by weight of a diphosphonite of the formula (a) EMI37.1        ii) 5-25% by weight of a monophosphonite of the formula (b) EMI37.2        iii) 5-25% by weight of a phosphite of the formula (c) EMI37.3          wherein each R10 is a 2,4-di-tertiary-butylphenyl group. 4th  A solid masterbatch composition containing 10 to 80% by weight, preferably 15 to 40% by weight, of a stabilizer composition according to one of the preceding claims 1 to 3 and 90 to 20% by weight, preferably 85 to 60% by weight. %, of a polymeric material which is identical or compatible with the polymeric material to be stabilized. 5. A liquid concentrate containing 10 to 80 wt .-% of a stabilizer composition according to one of the preceding claims 1 to 3 and 90 to 20 wt .-% of a solvent. 6.  Use of a stabilizer composition according to one of the preceding claims 1 to 3 or a solid masterbatch composition according to claim 4 or a liquid concentrate according to claim 5 as a stabilizer in polymeric materials which have been prepared in the presence of catalysts which    a) are applied to a carrier made of an organic magnesium compound or are based on an organic chromium compound which is supported by an SiO2 carrier,    b) are complex catalysts of the Ziegler type which are supported by an organic, halogen-containing magnesium compound,    c) are of type b) and also contain a silane donor,    d) consist of an organic bis-indenyl titanium compound,  which is activated with an aluminum alkyl compound and is supported by alumoxane or biscyclopentadienyl titanium halide, and the catalysts have not been removed after the polymerization. 7. Use according to claim 6, wherein the polymeric materials are selected from the group consisting of homopolypropylene, propylene copolymers, homopolyethylene, ethylene copolymers and mixtures (blends) thereof or with other polymers. 8. A method for stabilizing polymeric materials, selected from the group consisting of homopolyolefins and copolyolefins, and mixtures (blends) thereof or with other polymers, by adding a stabilizing amount of a stabilizer composition according to any one of the preceding claims 1 to 3 to the polymers to be stabilized Materials. 9.  The method of claim 8, wherein the polymeric materials are selected from the group consisting of homopolypropylene, propylene copolymers, homopolyethylene, ethylene copolymers and mixtures (blends) thereof or with other polymers. 10. A stabilized polymeric material comprising    a) a stabilizer composition according to one of the preceding claims 1 to 3,  and    b) a polymeric material selected from the group consisting of homopolyolefins and copolyolefins which have been prepared in the presence of catalysts according to claim 6 and wherein the catalysts have not been removed after the polymerization, and also mixtures (blends) thereof or with other polymers. 11.  A stabilized polymeric material according to claim 10, selected from the group consisting of homopolypropylene, propylene copolymers, homopolyethylene, ethylene copolymers and mixtures (blends) thereof or with other polymers.