KR20030094299A - Polycarbonate having pronounced shear thinning behaviour - Google Patents

Abstract

The present invention relates to novel branched melt-polymerized polycarbonates having significant non-Newtonian flow behavior, compositions containing them, and shaped bodies produced therefrom.

Description

POLYCARBONATE HAVING PRONOUNCED SHEAR THINNING BEHAVIOUR}

Polycarbonates are industrially produced using an interface process or by transesterification in a melt (melt polymerization method). The importance of the melt polymerization process is increasing because it can be carried out without using phosgene or chlorinated solvent. Polycarbonates produced by the interfacial methods currently used are linear and these polymers do not contain any polyfunctional structural units. This type of linear polycarbonate lacking multifunctional structural units that can cause branching has only a weak non-Newtonian flow behavior. In order to obtain branching during the interfacial method, a branching agent must be added. The resulting branching with multifunctional structural units increases the fluidity of the polymer at low shear rates and decreases at high shear rates.

Polycarbonates produced using melt polymerization methods contain essentially multifunctional structural units. The creation of inevitable multifunctional branched structural units during polymerization is known and described, for example, in Angelwandte Chemie 20, pp. 633-660, 1956.

US 5 932 683 describes a melting process in which molten polycarbonates having three specific structural units are formed. A special relationship between reaction time and reaction temperature is mentioned as a parameter for the preparation of the corresponding polycarbonates. The polycarbonates described have a flow behavior specially prepared at high shear rates. However, flow behavior is typically associated with inferior fluidity at low shear rates.

The present invention relates to novel branched melt-polymerized polycarbonates having significant non-Newtonian flow behavior, compositions containing them, and shaped bodies produced therefrom. The invention also relates to a process for producing such polycarbonates.

Accordingly, it is an object of the present invention to develop molten polycarbonates which are not less fluid than polycarbonates which are not branched at shear rates in addition to having good fluidity at high shear rates.

This object has been achieved by a melting process which produces a molten polycarbonate containing new tetrafunctional structural units and which does not correspond to the parameters mentioned in US Pat. No. 5,932,683. However, such specific branched polycarbonates nevertheless have improved flow behavior at high shear rates while exhibiting flow behavior equivalent to that from the interface of unbranched polycarbonates at low shear rates. Thus, the polycarbonates according to the invention can be used particularly successfully in injection molding, which is also equivalent to unbranched polycarbonates when extruded.

Polycarbonates according to the invention have the general formula

Here, square brackets include repeating structural units of polycarbonate,

M can be Ar, or multifunctional compound A, wherein

Ar may be a compound represented by the formula (2), or particularly preferably a compound represented by the formula (3),

Wherein Z is C ₁ -C ₈ -alkylidene or C ₅ -C ₁₂ -cycloalkylidene, S, SO ₂ or a single bond, R is substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br, n represents 0, 1 or 2,

Y is H or a compound of formula 4,

Wherein R ′ may be H, C ₁ -C ₂₀ -alkyl, C ₆ H ₅ or C (CH ₃ ) ₂ C ₆ H ₅ , which may be the same or different and n represents 0, 1 or 2 Indicate,

Multifunctional compound A is a compound of formula A and may be present in the polycarbonate in an amount of 201 to 5000 ppm, preferably 350 to 2000 ppm, most preferably 300 to 1000 ppm:

Here, X is Y or-(MOCOO) Y as in the following compounds B, C and D, where M and Y are as defined above.

Compound A is particularly preferably a compound of formula A1:

The polycarbonates according to the invention may further contain compounds B, C and D.

Compound B may be a multifunctional compound of formula B and may be present in the polycarbonate in an amount of 1501 to 10,000 ppm, preferably 1550 to 3000 ppm, most preferably 1600 to 2000 ppm:

Compound B is particularly preferably a compound of formula B1:

Compound C may be a multifunctional compound of formula C and may be present in the polycarbonate in an amount of 351 to 5000 ppm, preferably 400 to 2000 ppm, most preferably 450 to 1000 ppm:

Compound C is particularly preferably a compound of formula C1:

X in compounds A1, B, B1, C and C1 is as defined for compound A.

Compound D may be a compound of Formula D and may be present in the polycarbonate in an amount of 751 to 5000 ppm, preferably 800 to 2000 ppm, most preferably 850 to 1500 ppm:

Compound D is particularly preferably a compound of formula D1:

The polycarbonate according to the present invention is measured by gel permeation chromatography and may have a weight average molecular weight of 5,000 to 80,000, preferably 10,000 to 60,000, most preferably 15,000 to 40,000.

The polycarbonate according to the invention may also be defined by the shear dilution ratio y according to the following equation:

Where x is the relative viscosity of the polycarbonate. Shear dilution ratio serves to quantify the flow behavior. Shear dilution ratio is the ratio of the viscosity at low shear rate to the viscosity at high shear rate. According to the invention, the shear dilution ratio is the ratio of the viscosity at a shear rate of 50 s ⁻¹ to the viscosity at a shear rate of 5000 s ⁻¹ measured at 280 ° C.

Despite the large number of branching and associated non-Newtonian flow behaviors, the polycarbonates according to the invention have excellent color and color stability during injection molding. This exhibits significantly smaller yellowing than known molten polycarbonates.

The preparation of aromatic polycarbonates by melt transesterification methods is known and described, for example, in "Schnell", Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York, London, Sydney 1964. DC Prevorsek, BT Debona and Y. Kesten, Corporate Research Center, Allied Chemical Corporation, Moristown, New Jersey 07960, "Synthesis of Poly (ester) carbonate Copolymers" in Journal of Polymer Science, Polymer Chemistry Edition , Vol. 19, 75-90 (1980); D. Freitag, U. Grigo, PR Muller, N. Nouvertne, Bayer AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Vol. 11, Second Edition, 1988, pp. 648-718; finally Des. U. Grigo, K. Kircher and PR Muller "Polycarbonate" in Becker / Braun, Kunststoff-Handbuch, Vol. 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich , Vienna, 1992, pp. 117-299).

The polycarbonates according to the invention, which may be polyester carbonates, are produced by melt transesterification of suitable diphenols and carboxylic acid diaryl esters in the presence of a suitable catalyst. Polycarbonates may also be prepared by condensation of carbonate oligomers containing hydroxy or carbonate endgroups with suitable diphenols and carboxylic acid diaryl esters.

Suitable carboxylic acid diaryl esters in the context of the present invention are diesters of di-C ₆ -to C ₁₄ -arylesters, preferably phenols or alkyl-substituted phenols, ie diphenyl carbonate, dicresyl carbonate and di- 4-tert-butylphenyl carbonate. Most preferred is diphenyl carbonate.

Suitable carbonate oligomers are those described in Formula 1 above having a molecular weight of 220 to 15,000.

Suitable di-C ₆ -C ₁₄ -aryl esters also include asymmetric diaryl esters containing a mixture of aryl substituents. Most preferred are phenylcresyl carbonate and 4-tert-butylphenyl carbonate.

Suitable diaryl esters also include mixtures of one or more di-C ₆ -C ₁₄ -aryl esters. Most preferred mixtures are mixtures of diphenyl carbonate, dicresyl carbonate and di-4-tert-butylphenyl carbonate.

With respect to 1 mole of diphenol, the carboxylic acid diaryl ester can be used in an amount of 1.00 to 1.30 moles, particularly preferably in an amount of 1.02 to 1.20 moles, most preferably in an amount of 1.05 to 1.15 moles.

Suitable dihydroxybenzene compounds in the context of the present invention are compounds corresponding to formula (5):

Where

R is substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br,

n represents 0, 1 or 2.

Most preferred dihydroxybenzene compounds are 1,3-dihydroxybenzene, 1,4-dihydroxybenzene and 1,2-dihydroxybenzene.

Suitable diphenols in the context of the present invention are compounds corresponding to formula (6)

Where

Z is C ₁ -C ₈ -alkylidene or C ₅ -C ₁₂ -cycloalkylidene, S, SO ₂ or a single bond,

R is substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br,

n represents 0, 1 or 2.

Preferred diphenols are 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl sulfide, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,2-bis (4- Hydroxyphenyl) benzene, 1,3-bis (4-hydroxyphenyl) benzene, 1,4-bis (4-hydroxyphenyl) benzene, bis (4-hydroxyphenyl) methane, 2,2-bis ( 4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis ( 3-chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis ( 3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, 1,2-bis [2- (4-hydroxyphenyl) isopropyl] benzene, 1,3-bis [ 2- (4-hydroxyphenyl) isopropyl] benzene, 1,4-bis [2- (4-hydroxyphenyl) isopropyl] benzene, 1,1-bis (4-hydroxyphenyl) -1-phenyl Ethane, 2,4-bis (4-lower Idoxyphenyl) -2-methylbutane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) Propane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Most preferred diphenols are 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl, 1, 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and 1,3-bis [2 -(4-hydroxyphenyl) isopropyl] benzene.

Suitable diphenols also include mixtures of one or more diphenols, in which case copolycarbonates may be formed. Most preferred mixtures are 1,3-bis [2- (4-hydroxyphenyl) isopropyl] benzene, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2 -Bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

In addition, branching agents such as compounds containing three functional phenol OH groups can be added. This can obviously branch polymers and increase non-Newtonian polymers. Suitable branching agents include phloroglucinol, 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole, 4,6-dimethyl-2,4,6- Tris (4-hydroxyphenyl) hept-2-ene, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) Benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] Propane, 2,4-bis (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) 2- (2,4-dihydroxyphenyl) propane, hexakis (4- (4-hydroxyphenylisopropyl) phenyl) ortho terephthalate, tetrakis (4-hydroxyphenyl) methane, tetrakis (4 -(4-hydroxyphenylisopropyl) phenoxy) methane and 1,4-bis (4 ', 4 "-dihydroxytriphenyl) methyl) benzene, isatin biscresol, pentaerytri Acid, 2,4-dihydroxy benzoic acid, trimesic acid and cyanuric are included.

Suitable catalysts for the preparation of the polycarbonates according to the invention are, for example, catalysts of the formula:

Where

R ¹ , R ² , R ³ and R ⁴ may represent the same or different C ₁ -C ₈ -alkylene, C ₆ -C ₁₀ -aryl or C ₅ -C ₆ -cycloalkyl,

X ⁻ can represent a cocatalyst as well as an anion (where the corresponding acid-base pair H ⁺ + X ↔ HX ⁻ has a pK _b of <11).

Preferred catalysts are tetraphenylphosphonium fluoride, tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium phenolate. Tetraphenylphosphonium phenolate is most preferred. The preferred amount of phosphonium salt catalyst is 10 ^-2 to 10 ^-8 moles, per mole of diphenol, and the most preferred amount of catalyst is 10 ^-4 to 10 ^-6 moles, per mole of diphenol. Additional cocatalysts are used in addition to the phosphonium salts to increase the rate of polymerization. Such cocatalysts include salts of alkali and alkaline earth metals, for example hydroxides, alkoxides and aryl oxides of lithium, sodium and potassium, preferably hydroxides, alkoxides or aryl oxides of sodium. Most preferred are sodium hydroxide and sodium phenolate. The amount of cocatalyst is in each case in the range of 201 to 10,000 ppb, preferably 220 to 1500 ppb, most preferably 240 to 500 ppb, calculated as sodium.

The polycarbonate may be prepared under reaction conditions carried out stepwise at a temperature of 150 ° C. to 400 ° C., the residence time in each step may be 15 minutes to 5 hours, and the pressure is 1000 to 0.01 mbar.

The present invention also provides a polycarbonate composition containing the polycarbonate according to the present invention, as well as a molded article containing such a composition.

The composition according to the invention may contain further polymer components and customary additives in addition to polycarbonate or polyester carbonate. Polymer components that can be used are, for example, styrene / acryl / nitrile terpolymer (SAN), acrylic / butadiene / styrene terpolymer (ABS), polymethyl methacrylate (PMMA), fluorinated polyolefin (PTFE), polyphenyl Polyolefins such as styrene (PPS), polyethylene, polypropylene and ethylene / propylene rubber, epoxy resins, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polycyclohexene dimethanol (PCT), Copolyester (PCTG) of ethylene glycol and cyclohexene dimethanol terephthalic acid in a 1: 4 ratio, and copolyester (PETG) of ethylene glycol and cyclohexene dimethanol terephthalic acid in a two-component ratio of 4: 1 Esters, and other polycarbonates produced by interfacial processes, and also mixtures of the aforementioned components. Additional additives include release agents, stabilizers, antioxidants, flame-proofing agents, colorants and pigments, antistatic agents, nucleating agents, anti-dripping agents, and organic and additional inorganic fillers and Adjuvants.

The polycarbonates according to the invention are preferably 5 to 95 wt.%, Particularly preferably 10 to 90 wt.%, Most particularly preferably 20 to 80 wt, based on the weight of the composition in the composition according to the invention. It may be present in an amount of.%. The further polymer component of the composition according to the invention is preferably 1 to 60 wt.%, Particularly preferably 1 to 40 wt.%, Most preferably 2 to 30 wt.%, Based on the weight of the composition. It may be present in an amount of.

The composition may contain up to 60 wt.%, Preferably 10 to 40 wt.%, Inorganic materials, such as fillers and / or reinforcements, based on the filled or reinforced molding composition. The refractory agent may be present in the composition according to the invention in an amount of up to 35 wt.%, Preferably from 10 to 25 wt.%, Based on the weight of the composition.

In addition to polycarbonate / polyester carbonates, these and further components or additives which may possibly be included in the compositions according to the invention are described by way of example below.

These materials can be found in many documents, such as, for example, Additives for Plastics Handbook, John Murphy, 1999, and are available commercially.

1. Suitable antioxidants are for example:

1.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-3-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4 -Ethyl, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol , 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tertiary -Butyl-4-methoxymethylphenol, nonylphenol which may be linear or branched in the side chain, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylun Deck-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1 ' -Yl) phenol.

1.2. Alkylthio methyl phenols, such as 2,4-di-octyl thiomethyl -6-3-tert-butylphenol, 2,4-di-octyl-thio-6-methylphenol, 2,4-octylthio-6- Ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones such as 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-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3 , 5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis (3,5-di-tert-butyl-4 Hydroxyphenyl) adipate.

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

1.5. Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4 ' -Thiobis (6-tert-butyl-3-methyl-phenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6 Di-tert-amyl-phenol), 4,4'-bis (2,6-dimethyl-4-hydroxy-phenol) disulfide.

1.6. Alkylidenebisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2 , 2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexyl-phenol), 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'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4 ' Methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-3) Tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1- Bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercapto Ethane, ethylene glycol-bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (tert-butyl-4-hydroxy-5-methylphenyl) di Cyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] -terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tertiary -Butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane .

1.7. O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy -3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydrate Hydroxybenzyl) amine, 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-hydroxybenzyl mercaptoacetate.

1.8. Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3- Tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, Bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds such as 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-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) phenol.

1.10. Triazine compounds such as 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-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy Phenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) -hexahydro-1,3,5 Triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11. Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.12. Monohydric or polyhydric alcohols such as 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-thia Undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and β- (3 Ester with, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid .

1.13. Monohydric or polyhydric alcohols such as 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-thia Undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and β- (5 Ester with tert-butyl-4-hydroxy-3-methylphenyl) propionic acid .

1.14. Monohydric or polyhydric alcohols such as 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-thiaoundanol, 3-thiapenta Decanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and β- (3,5-dicyclohexyl- Ester with 4-hydroxyphenyl) propionic acid .

1.15. Monohydric or polyhydric alcohols such as 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-thiaoundanol, 3-thiapenta Decanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and 3,5-di-tert-butyl- Esters with 4-hydroxyphenylacetic acid .

1.16. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid , for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenyl Propionyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamide, N, N'-bis (3,5- Di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propy Onyloxy) ethyl] oxamide (Naugard ™ XL-1 from Uniroyal).

1.17. Ascorbic acid (vitamin C)

1.18. Amine-type antioxidants such as N, N'-diisopropyl-p-phenylenediamine, N, N'-di-tert-butyl-p-phenylenediamine, N, N'-bis (1 , 4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-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-phenyl Rendiamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl)- N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N '-Di-tert-butyl-p-phenylenediamine, diphenylamine, N-allyl-diphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4 -Tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine, 4 -n-butylaminophenol, 4-n-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenol) amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diamino-diphenylmethane, N, N, N ', N'-Tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, Bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, monoalkylated and dialkylated tert-butyl tert-octyldi Mixtures of phenylamines, mixtures of monoalkylated and dialkylated nonyldiphenylamines, mixtures of monoalkylated and dialkylated dodecyldiphenylamines, mixtures of monoalkylated and dialkylated isopropyl / isohexyldiphenylamines, monoalkylated And mixtures of dialkylated tert-butyldiphenylamine, 2,3-dihydro Rho-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, monoalkylated and dialkylated mixtures of tert-butyl / 3-octyl phenothiazine, monoalkylated and dialkylated 3 Mixtures of rapid-octyl phenothiazine, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2 , 6,6-tetramethylpiperid-4-yl) -hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetra Methylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol. Individual compounds or mixtures thereof may be used.

1.19. Suitable thiosynergists are, for example, dilauryl thiodipropionate and / or distearyl thiodipropionate.

2. UV-absorbers and light stabilizers can be used in the compositions according to the invention in amounts of 0.1 to 15 wt.%, Preferably 3 to 8 wt.%, Based on the weight of the composition. Suitable UV-absorbers and light stabilizers are for example:

2.1. 2- (2'-hydroxyphenyl) benzotriazole , for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tertiary-2 '-Hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-(1,1,3 , 3-tetramethyl-butylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'- Tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5'-tert-butyl-2'-hydroxyphenyl) Benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole , 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' -(2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl]- 2'-hydroxyphenyl) -5-chloro Benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) -phenyl) -5-chlorobenzotriazole, 2- (3'- Tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-( 2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl ) Benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-( 2-isooctyloxycarbonylethyl) phenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol] Transesterification products of 2- [3'-tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; -CH ₂ CH ₂ -COO-CH ₂ CH ₂ ] ₂ , wherein R is 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl , 2- [2 '-Hydroxy-3'-(α, α-dimethylbenzyl) -5 '-(1,1,3,3-tetramethylbutyl) phenyl] benzotriazole, 2- [2'-hydroxy-3' -(1,1,3,3-tetramethylbutyl) -5 '-(α, α-dimethylbenzyl) phenyl] benzotriazole.

2.2. 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'- Trihydroxy and 2'-hydroxy-4,4 '-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids , for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) Resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert -Butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3,5 Di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates such as ethyl-α-cyan-β, β-diphenyl acrylate, isooctyl-α-cyan-β, β-diphenyl acrylate, methyl-α-carbomethoxy cinnamate, methyl-α -Cyan-β-methyl-p-methoxy cinnamate, butyl-α-cyan-β-methyl-p-methoxy cinnamate, methyl-α-carbomethoxy-p-methoxy cinnamate and N- (β Carbomethoxy-β-cyanvinyl) -2-methylindolin.

2.5. 2,2'-thiobis [4- (1,1,3,3-tetra) with or without further ligands such as nickel compounds such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine Methylbutyl) phenol] nickel complex such as 1: 1 complex or 1: 2 complex, nickel dibutyl dithiocarbamate, monoalkyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid For example nickel salts of methyl or ethyl esters, ketoximes, for example nickel complexes of 2-hydroxy-4-methylphenylundecyl ketoxime, 1-phenyl-4-lauroyl- with or without further ligands Nickel complex of 5-hydroxypyrazole.

2.6. Stericly hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) Succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl ) Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl), n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, 1 Condensate of-(2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, N, N'-bis (2,2,6,6-tetra Linear or cyclic condensates of methyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6, 6-tetramethyl-4-piperidyl) -nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tet Lamethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl 2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6- Tetramethylpiperidyl) succinate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1 Linear or cyclic condensates of, 3,5-triazine, 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3 Condensate of, 5-triazine with 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-bis (4-n-butylamino-1,2,2,6,6-penta Condensate of methyl piperidyl) -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl -1,3,8-tria Spiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dode Sil-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 4-hexadecyloxy- and 4-stearyloxy-2, Mixtures of 2,6,6-tetramethylpiperidine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2, Condensation products of 6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine and 4- Condensation product of butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl ) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane, 7,7, Reaction product of 9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-thiaza-4-oxospyro [4.5] decane with epichlorohydrin, 1,1-bis (1,2 , 2,6,6-pentamethyl-4-piperidyloxocarbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis (formyl) -N, N'-bis (2 , 2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, dimethoxy 4-methylmethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine 2,2,6 ester, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, maleic anhydride / α-olefin copolymer Reaction product of, 6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides , for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanyl Reed, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethoxyanilide, N, N'-bis (3-dimethylaminopropyl ) Oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxyanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,5'-di-tert-butoxanilide , a mixture of o- and p-methoxy-disubstituted oxanilides, and a mixture of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2- (2-hydroxyphenyl) -1,3,5-triazine , for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine , 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4- Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxy Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl ] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl]- 4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4-dodecyloxy / tridecyloxy-2-ha Hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy Oxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) Phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2 , 4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4 -(4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxy Propyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

These compounds can be used individually or in the form of mixtures.

3. Suitable metal derivatives are, for example, N, N'-diphenyloxamide, N-salicyl-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'- Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide , Oxanilide, isophthaloyl dihydrazide, sebacoylbisphenyl hydrazide, N, N'-diacetyladipoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihay Drazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide. These compounds can be used individually or in the form of mixtures.

4. Suitable phosphites and phosphonites that can be used as heat stabilizers include, for example, triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tri (nonylphenyl) phosphite, trilauryl phosphite, Trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-3 Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4- Di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis ( 2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphona , 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphosine, 6-fluoro- 2,4,8,10-tetra-tert-butyl-12-methyldibenz [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-tert-butyl) 6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12 -Methyldibenz [d, g] -1,3,2-dioxaphosphosine, 2,2 ', 2 "-nitrilo [triethyltris (3,3', 5,5'-tetra-3) Tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3 ', 5,5'-tetra-tert-butyl-1,1'- Biphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl-2- (2,4,6-tri-tert-butylphenoxy) -1,3,2-dioxaphosphore Phosphorus is included Such compounds may be used individually or in the form of mixtures.

Especially preferred are tris (2,4-di-tert-butylphenyl) phosphite (Irgafos ™ 168; Ciba-Geigy), triphenylphosphine, or (2,4,6-tri-3 Tert-butylphenyl)-(2-butyl-2-ethylpropane-1,3-diyl) phosphite (Ultranox ™ 641; GESpecialty Chemicals).

Examples of suitable phosphites and phosphonites are also compounds of the formulas 8-14:

5. Suitable peroxide catchers are for example esters of β-thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole or 2-mercaptobenzimidazole Zinc salt, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (dodecyl mercapto) propionate. These compounds can be used individually or in the form of mixtures.

6. Suitable basic co-stabilizing agents are for example alkali metal salts of melamine, poly (vinylpyrrolidone), dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, higher fatty acids. And alkaline earth metal salts, such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. These compounds can be used individually or in the form of mixtures.

7. Suitable nucleating agents include, for example, inorganic materials such as talc, metal oxides such as titanium dioxide or magnesium oxide, preferably phosphates, carbonates or sulfates of alkaline earth metals; Organic compounds such as monocarboxylic acids or polycarboxylic acids and salts thereof, such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; Polymeric compounds such as ionic copolymers (ionomers). Especially preferred are 1,3: 2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyl-dibenzylidene) sorbitol and 1,3: 2, 4-di (benzylidene) sorbitol. These compounds can be used individually or in the form of mixtures.

8. Suitable fillers and reinforcing agents are, for example, calcium carbonate, silicates, glass fibers, glass balls, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wollastonite, sawdust and other Powders or fibers of other natural products, synthetic fibers. These compounds can be used individually or in the form of mixtures.

9. Other suitable additives are, for example, plasticizers, lubricants, emulsifiers, pigments, viscosity modifiers, catalysts, flow-controlling agents, optical brighteners, flame retardants, antistatic agents and blowing agents.

10. Suitable benzofuranones and indolinones are described, for example, in US 4,325,863; US 4,338,244; US 5,175,312; US 5,216,052; US 5,252,643; DE-A-43 16 611; DE-A-43 16 622; DE-A-43 16 876; Those described in EP-A-0 589 839 or EP-A-0 591 102, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran- 2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis- [5,7 -Di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl ) Benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl- 4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butylbenzofuran- 2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, a lactone antioxidant such as Formula 15:

These compounds, for example, act as antioxidants. These compounds can be used individually or in the form of mixtures.

11. Suitable fluorescent plasticizers (fluorescing plasticisers) is described in the literature ( "Plastics Additives Handbook", Eds . R. Gachter and H. Muller, Hanser Verlag, 3 rd Edition, 1990, pp. 775-789).

12. Suitable release agents are esters of aliphatic acids with alcohols, for example pentaerythritol tetrastearate and glycerol monostearate, which are alone or as a mixture, preferably 0.02 to 1 wt.%, Based on the weight of the composition. It is used in the amount of.

13. Suitable flame retardant additives are phosphate esters, i.e. triphenyl phosphate, resorcinol di-phosphoric acid esters, brominated phosphate esters, bromine, such as brominated oligonucleotide carbonate and polycarbonate-containing compound, and ^{_{C 4 F 9 SO 3 - Na}} + And salts.

14. Suitable components for imparting impact resistance are butadiene rubbers grafted with styrene-acrylonitrile or methyl methacrylate, ethylene-propylene rubbers grafted with maleic anhydride, methyl methacrylate or styrene-acrylonitrile grafted Acrylate networks grafted with ethyl acrylate and butyl acrylate rubbers, interpenetrating siloxanes and methyl methacrylate or styrene-acrylonitrile.

15. Suitable polymers include SAN, ABS, PMMA, PTFE, polyolefins such as PSU, PPS, polyethylene, polypropylene and ethylene-propylene rubber, epoxy resins, polyesters such as PBT, PET, PCT, PCTG and PETG, and interfacial methods. Other polycarbonates produced in.

16. Suitable antistatic agents are sulfonate salts, for example tetraethylammonium salts of C ₁₂ H ₂₅ SO ^3- or C ₈ F ₁₇ SO ^3- .

17. Suitable colorants are pigments and organic and inorganic dyes.

18. Compounds containing epoxy groups , such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, copolymers of glycidyl methacrylate and epoxysilane.

19. Compounds containing anhydride groups such as maleic anhydride, succinic anhydride, benzoacetic anhydride and phthalic anhydride.

Compounds of groups 18 and 19 act as melt stabilizers. These can be used individually or in mixtures.

The composition according to the invention (molding composition) mixes the respective components in a known manner and the resulting mixture is mixed in conventional devices such as internal kneaders, extruders and double-shaft screws. It is produced by melt compounding and melt extrusion at a temperature of about 200 ° C., for example between 200 ° C. and 300 ° C. Individual components may be mixed continuously or simultaneously, at about 20 ° C. (room temperature) or higher.

The molding compositions according to the invention can be used to produce shaped articles of all forms. These molded bodies can be produced by injection molding, extrusion and blow molding methods. A further form of processing is the production of shaped bodies by deep-drawing from previously prepared sheets or films.

Examples of the molded article according to the present invention include, for example, for home appliances such as juicers, coffee makers, mixers; For office equipment such as monitors, printers, copiers; For sheets, tubes, electrical installation conduits, windows, doors and profile sections for construction areas, interior and exterior materials; Profile sections, films and all forms of casing parts are included in the electrotechnical field such as switches and plugs. In addition, the molded articles according to the invention can be used for internal installations and structural parts for rail vehicles, ships, aircraft, buses and other motor vehicles, and motor vehicle fuselage parts.

Molded articles according to the invention may be transparent or opaque. Additional molded articles include optical and magneto-optical data storage media such as mini disks, compact disks (CDs) or digital versatile discs (DVDs), food and beverage packaging, optical lenses And prisms, lenses for illumination purposes, motor vehicle headlamp lenses, panes for buildings and motor vehicles, other forms of panes such as greenhouses, so-called web treated double sheets or hollow sheets.

The following examples are provided to further illustrate the present invention.

Example

The polymers of Examples 1-3 were prepared by melt polymerizing diphenylcarbonate and bisphenol A in the melt using tetraphenylphosphonium phenolate as the catalyst and 250 ppb sodium phenolate as calculated by sodium. The amounts of monomers and catalysts are shown in Table 1. Reaction conditions are shown in Table 2. The measured relative viscosity, yellowing index (YI), melt viscosity, shear dilution ratio and amount of multifunctional compound of the solution are shown in Table 3.

Comparative Examples 1, 2 and 3 are linear polycarbonates and were prepared by conventional interfacial polymerization. These are sold under the trade names Makrolon ™ 2808, 2408 and 3108 (Bayer AG). Comparative Examples 4 and 5 are branched polycarbonates prepared by the interfacial polymerization method. Corresponding products are sold under the trade names Makrolon ™ 1243 and 1239 (Bayer AG). Comparative Examples 7, 8 and 9 were prepared by the reaction of diphenyl carbonate and bisphenol A in the melt using tetraphenylphosphonium phenolate as catalyst. The polycarbonate of Example 6 was prepared by reacting diphenylcarbonate and bisphenol A in the melt using tetraphenylphosphonium phenolate as the catalyst and 100 ppb sodium phenolate calculated as sodium.

For the polymerization, conventional transesterification vessels suitable for heating and evacuating the material and capable of sufficiently long mixing and residence times can be used.

Relative viscosity was measured at 0.5 ° C. in 0.5% solution of methylene chloride.

The yellowing index (YI) was measured on 4 mm thick injection molded samples according to the CIELAB method. Injection molding was performed at 270 ° C, 300 ° C and 330 ° C.

Melt viscosity was measured at 280 ° C. using the test method according to ISO 11443. Non-Newtonian flow behavior was quantified by calculating the shear dilution ratio. The shear dilution ratio was calculated as the melt viscosity at a shear rate of 50 s ⁻¹ divided by the melt viscosity at a shear rate of 5,000 s ⁻¹ .

The amount of multifunctional compound was measured by separating the monomer compound using HPLC (high pressure liquid chromatography) after complete hydrolysis of the polycarbonate. These compounds have been characterized by magnetic resonance spectroscopy.

Example C6 C7 C8 C9 One 2 3 DPC, Mall 1.18 1.173 1.187 1.168 1.178 1.214 1.209 BPA, Mall 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Sodium phenolate (ppb), calculated as sodium 100 0.0 0.0 0.0 250 250 250 Tetraphenylphosphonium phenolate, mole 0.00004 0.00004 0.00004 0.00004 0.00004 0.00004 0.00004 DPC: diphenyl carbonate; BPA: Bisphenol A

Reaction Conditions for Comparative Examples 6-9 and Examples 1-3 Minutes Temperature (℃) Pressure (mbar) Pre-condensation reaction 45 190 1000 Reactor I 20 190 200 Reactor II 20 230 80 Reactor III 10 250 50 Reactor IV 10 270 25 Reaction Conditions for Comparative Example 6 Evaporator I 45 275 7.4 Evaporator II 130 310 1.40 Reaction Conditions for Comparative Example 7 Evaporator I 45 275 7.3 Evaporator II 130 312 1.00 Reaction Conditions for Comparative Example 8 Evaporator I 45 275 5.5 Evaporator II 130 312 0.5 Reaction Conditions for Comparative Example 9 Evaporator I 45 275 7.3 Evaporator II 130 312 0.98 Reaction Conditions for Example 1 Evaporator I 45 275 8.5 Evaporator II 120 310 2.25 Reaction Conditions for Example 2 Evaporator I 45 275 6.5 Evaporator II 120 310 0.90 Reaction Conditions for Example 3 Evaporator I 45 275 6.5 Evaporator II 120 310 1.26

These new melt-polymerized polycarbonates contain multifunctional structural units, have a high degree of branching and have significant non-Newtonian flow properties, but polycarbonates exhibit surprisingly good flow behavior. The polycarbonates of the examples where 250 ppb of sodium phenolate were used have a high degree of branching, expressed in shear dilution ratio. The comparative example with only 100 ppb sodium phenolate has a shear dilution ratio equivalent to the shear dilution ratio of linear polycarbonate with the same viscosity. Thus, significant non-Newtonian flow characteristics were obtained only in the presence of relatively large amounts of branched compounds. High branching was obtained without the conventional formation of compounds with high yellowness.

Claims (10)

Melt-Polymerized Polycarbonate of Formula 1: <Formula 1> Where Square brackets indicate repeating structural units, M can be Ar, or multifunctional compound A, wherein Ar may be a compound represented by Formula 2, or a compound represented by Formula 3, <Formula 2> <Formula 3> Wherein Z is C ₁ -C ₈ -alkylidene or C ₅ -C ₁₂ -cycloalkylidene, S, SO ₂ or a single bond, R is substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br, n represents 0, 1 or 2, Multifunctional compound A is a compound of formula A, which may be present in the polycarbonate in an amount of 200 to 5000 ppm, <Formula A> Y is H or a compound of formula 4, <Formula 4> From here, R may be H, C ₁ -C ₂₀ -alkyl, C ₆ H ₅ or C (CH ₃ ) ₂ C ₆ H ₅ , may be the same or different, n represents 0, 1, 2 or 3, X is Y or-(MOCOO) Y, where M and Y are as defined above. The melt-polymerized polycarbonate according to claim 1, wherein compound B of formula B is present: <Formula B> Wherein Ar and X are as defined above. The melt-polymerized polycarbonate according to claim 1 or 2, wherein compound C of formula C is present: <Formula C> Wherein Ar and X are as defined above. The melt-polymerized polycarbonate according to any one of claims 1 to 3, wherein compound D of formula D is present: <Formula D> Wherein Ar is as defined above. The polycarbonate according to any one of claims 1 to 4, having a shear dilution ratio y according to the following formula: <Equation 1> Where x is the relative viscosity of the polycarbonate. A composition containing a melt-polymerized polycarbonate according to any one of claims 1 to 5. A molded article containing the composition according to claim 6. Diphenols and / or carbonate oligomers having hydroxy or carbonate end groups are prepared at temperatures from 150 ° C. to 400 ° C. and pressures from 1,000 mbar to 0.01 mbar in the presence of a catalyst, wherein the catalyst is quaternary Compounds are used and polycatalysts are used as cocatalysts, salts of alkali and alkaline earth metals such as hydroxides, alkoxides and aryloxides of silicon, sodium and potassium in amounts of 201 to 10,000 ppb calculated as amine salts, sodium Melt polymerization method for the preparation of carbonate: <Formula 7> Where R ¹ , R ² , R ³ and R ⁴ may represent the same or different C ₁ -to C ₁₈ -alkylene, C ₆ -to C ₁₀ -aryl or C ₅ -to C ₆ -cycloalkyl, X ⁻ may represent an anion, where the corresponding acid-base pair H ⁺ + X ⁻ ↔ HX has a pK _b of <11. The melt polymerization method according to claim 8, wherein the catalyst is a mixture of tetraphenylphosphonium phenolate and sodium phenolate. 10. The melt polymerization process according to claim 9, wherein the catalyst is a mixture of tetraphenylphosphonium phenolate and sodium phenolate, and 210 to 500 ppb sodium is present.