HK1068905B - Melt polycarbonate exhibiting an improved resistance to hydrolysis - Google Patents

Description

Melt polycarbonate with improved hydrolysis resistance

The invention relates to melt polycarbonates having improved hydrolysis resistance, to compositions containing them and to moldings having improved hydrolysis resistance.

Polycarbonates are produced industrially by the interfacial process or by transesterification in the melt (melt polymerization). The melt polymerization process is favored because it can be carried out without the use of phosgene or chlorinated solvents. The interfacial process produces polycarbonates having unusual color but resistance to hydrolysis. It is known to add phosphorus-based additives to such polycarbonates in order to further improve the color. However, the addition of these phosphorus compounds decreases the hydrolysis resistance of the polycarbonate produced by the interfacial process. To recover some of the loss of hydrolysis resistance, epoxy compounds are usually added. However, the combination of the epoxy compound and the phosphorus compound does not give the polycarbonate any superior resistance to hydrolysis than that obtained without the addition of these two types of materials. The epoxide is preferably added to compensate for the loss of hydrolysis resistance caused by the phosphorus compound.

Surprisingly, it has been found that the resistance to hydrolysis of polycarbonates produced by melt polymerization is improved by the addition of phosphides. This effect occurs even without the addition of hydrolysis stabilizers based on epoxides.

The present invention accordingly provides polycarbonates, copolycarbonates and/or polyester carbonates obtained by melt polymerization and containing organophosphorus compounds. The present invention also provides compositions comprising one or more of the foregoing polymers. Finally, the present invention provides the use of an organophosphorus compound to improve the hydrolysis resistance of polycarbonates and polyester carbonates produced by the melt polymerization process.

Suitable organophosphorus compounds according to the invention are, for example, phosphines, phosphine oxides, phosphinous esters, (phosphinites) phosphonites, phosphites, diphosphines, ditriphosphinates, diphosphonites, diphosphites, phosphinites, phosphonates, phosphates, diphosphonates and diphosphate compounds and also oligomeric derivatives of the abovementioned phosphorus compounds.

Phosphine (PR) suitable according to the invention₃) And phosphine Oxide (OPR)₃) The compound is, for example, wherein R is hydrogen, C₁-C₁₀₀Alkyl radicals or unsubstituted or substituted C₆-C₁₄Aryl group. The radicals R may be identical or different. The most preferred radicals R are phenyl, 2-tert-butylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-di-tert-butylphenyl, 2, 4, 6-tri-tert-butylphenyl, p-nonylphenyl and naphthylene. A particularly preferred phosphine is triphenylphosphine.

Suitable phosphinites (P (OR) R according to the invention₂) Phosphonite (P (OR)₂R) and phosphites (P (OR)₃) The compound is, for example, wherein R is hydrogen or C₁-C₁₀₀Alkyl radicals, or unsubstituted or substituted C₆-C₁₄Aryl group. The radicals R may be identical or different. The most preferred radicals R are phenyl, 2-tert-butylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-di-tert-butylphenyl, 2, 4, 6-tri-tert-butylphenyl, p-nonylphenyl and CH₃To C₁₈H₃₇。

Suitable phosphinites (PO (OR) R according to the invention₂) Phosphonate ester (PO (OR)₂R) and phosphate (PO (OR)₃) The compound is, for example, wherein R is hydrogen or C₁-C₁₀₀Alkyl radical, or unsubstituted or substituted C₆-C₁₄Aryl group. The radicals R may be identical or different. The most preferred radicals R are phenyl, 2-tert-butylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-di-tert-butylphenyl, 2, 4, 6-tri-tert-butylphenyl, p-nonylphenyl and CH₃To C₁₈H₃₇。

Diphosphine compounds R suitable according to the invention₂P-X-PR₂Is, for example, wherein R is hydrogen or C₁-C₁₀₀Alkyl radicals, or unsubstituted or substituted C₆-C₁₄Aryl radicals are those corresponding to formula (2) below. The radicals R may be identical or different. Other suitable compounds are those in which X is divalent C₁-C₁₀₀Alkyl radicals or unsubstituted or substituted C₆-C₁₄Aryl group. Preferred divalent radicals are phenylene, biphenylene, 2-diphenylpropane and naphthylene.

Suitable bis-phosphinites ((RO) RP-X-PR (OR)) and diphosphonites ((RO) according to the invention₂P-X-P(OR)₂) And diphosphite ((RO)₂P-OXO-P(OR)₂) The compound is, for example, wherein R is C₁-C₁₀₀Alkyl radicals or unsubstituted or substituted C₆-C₁₄Aryl group. The radicals R may be identical or different. Suitable compounds are those in which X is divalent C₁-C₁₀₀Alkyl radicalRadicals or unsubstituted or substituted C₆-C₁₄Aryl group. Particularly preferred divalent radicals are phenylene, biphenylene and naphthylene.

In particular, X may be a radical of formula (2)

Or a group of the formula (3)

Wherein the content of the first and second substances,

r represents a substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl group, Cl or Br, and n is 0, 1 or 2, and

z represents C₁-C₈Alkylene or C₅-C₁₂Cycloalkylene radical, S, SO₂Or a single bond.

Diphosphites suitable according to the invention are those of the formula

Wherein R is C₁-C₁₀₀Alkyl radicals, or unsubstituted or substituted C₆-C₁₄An aryl group. Y is tetravalent C₁-C₁₀₀An alkoxy group. The most preferred tetravalent compound is pentaerythritol.

The most preferred phosphites are triphenyl phosphite, tris (2-tert-butylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (2, 6-di-tert-butylphenyl) phosphite (Irganox 168)^®：

Tris (2, 4, 6-tri-tert-butylphenyl) phosphite, (2, 4, 6-tri-tert-butylphenyl) - (2-butyl-2-ethyl-propane-1, 3-diyl) phosphite (Ultranox 641)^®：

Bis (2, 4-dicumyl-phenyl) pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite, tris (p-nonylphenyl) phosphite, diphenyl-isodecyl phosphite, diisodecyl-phenyl phosphite, triisodecyl phosphite, trilauryl phosphite and [ tris (3-ethoxybutyl) -3-yl) -methyl ] phosphite. The most preferred phosphine is triphenylphosphine. The most preferred phosphonite is tetrakis (2, 4-di-tert-butylphenyl) [1, 1-biphenyl ] -4, 4' -diyl diphosphonite.

The most preferred phosphates are tris (2-ethylhexyl) phosphate, triphenyl phosphate, tris (2-tert-butylphenyl) phosphate, tris (2, 4-di-tert-butylphenyl) phosphate, tris (2, 6-di-tert-butylphenyl) phosphate and tris (2, 4, 6-tri-tert-butylphenyl) phosphate.

These phosphorus compounds are commercially available and may contain varying amounts of impurities. It is preferred to use the appropriate compounds in high purity and with only insignificant amounts of acid groups. Amine compounds and residual salts such as alkali metal salts and alkaline earth metal salts.

The phosphorus compound may also be used in the form of a mixture of more than one phosphorus compound in order to optimize the properties of the polycarbonate composition. These phosphorus compounds are also commercially available in mixtures with further stabilizers and additives, such as UV absorbers, mold release agents, glasses, other polymers, sterically hindered phenols and lactones, etc.

The phosphorus compounds used according to the invention are assumed to be present in the form of a physical mixture with the polycarbonate/polyestercarbonate. The amount of phosphorus compound according to the invention which shows an effect is from 10ppm to 30% relative to the amount of melt polycarbonate. The phosphorus compounds are preferably used in amounts of from 10ppm to about 1% by weight, relative to the weight of the polycarbonate, in order to produce the desired effect according to the invention.

The phosphorus compound added according to the invention can be added to the precursor or to the catalyst solution before the melt polymerization. The phosphorus compound can also be added during the melt polymerization or directly into the melt stream at the end of the melt polymerization. Finally, the phosphorus compound can be mixed with the polycarbonate/polyestercarbonate in a further step, for example during compounding.

The action of the phosphorus compounds used according to the invention is shown in the melt polycarbonate of the general formula (1)

Wherein the method numbers represent repeating structural units,

m may be Ar or a polyfunctional group A, B, C or a group D, wherein Ar may be a group represented by the formula (2)

Or particularly preferably a group represented by the formula (3)

Wherein

Z represents C₁-C₈Alkylene or C₅-C₁₂Cycloalkylene radicals X, SO₂Or a single bond, or a mixture of single bonds,

r represents a substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl group, Cl or Br, and n is 0, 1 or 2,

wherein the polyfunctional group A is a group of the formula

Wherein the polyfunctional group B is a group of the formula

Wherein the multifunctional group C is a group of the formula

Wherein the group D is a group of the formula

And the sum of the polyfunctional groups A, B, C and D is > 5ppm,

wherein Y is H or a group of formula (4)

Wherein:

r, identical or different, represents H, C₁-C₂₀Alkyl radical, C₆H₅Or C (CH)₃)₂C₆H₅And

n may be 0, 1, 2, or 3,

wherein X is Y or- (MOCOO) Y,

wherein

M and Y are defined in the same manner as described above.

Particularly preferred are polycarbonates having pseudoplastic properties (Y), which are defined by the limits of the following equation

(Q)c+ax^b＞y＞-c+ax^b

Although y.gtoreq.1

Wherein a, b and c are constants, and

-c is 0.3-0.1, preferably 0.2-0.1 and most preferably about 0.1,

-b-14.831 ± 0.005 to 0.002, preferably ± 0.004 to 0.002 and most preferably ± about 0.002 and

-a ═ 0.1262 ± 0.005 to 0.003, preferably ± 0.004 to 0.003 and most preferably ± about 0.003 and

-x is the relative viscosity of the polycarbonate. These particularly preferred polycarbonates and their preparation are described in the application filed concurrently with the present application with the internal filing number Le A34498.

The polycarbonates according to the invention can have weight average molecular weights of 5,000-80,000, preferably 10,000-60,000, most preferably 15,000-40,000, determined by gel permeation chromatography.

Ar is preferably defined as follows:

the polyfunctional group a is preferably a group a 1:

the group B is preferably a group B1:

the polyfunctional group C is preferably a group C1:

in the groups (B1) and (C1), X is defined in the same manner as above. The group D is preferably a group D1:

the foregoing melt polycarbonates are described by way of example only. The proportions of components A to D may also be present in the melt polycarbonate in greater or lesser proportions.

The preparation of aromatic polycarbonates by the melt transesterification process is now known and described, for example, in Schnell, Chemistry and Physics of polycarbonates (polycarbonate Chemistry and Physics), Polymer Reviews volume 9, Interscience Publishers, New York, London, Sydney 1964; see: D.C. Prevorsek, B.T. Debona and Y.Kesten, corporation Research Center, Allied chemical corporation, Moristown, New Jersey 07960, "Synthesis of Poly (ester) carbonate Copolymers" (Synthesis of Poly (ester) carbonate Copolymers), Journal of Polymer Science, Polymer Chemistry edition, Vol.19, 75-90 (1980); freetag, U.G. Grigo, P.R.Muller, N.Nouvertne, Bayer AG, "Polycarbonates", Encyclopedia of Polymer science and Engineering, Vol.11, second edition, 1988, P648-718; and Des.U.Grigo, K.Kirchner and P.R.Muller "Polycarbonate" (Polycarbonate), Becker/Braun, Kunststoff-Handbuch, Vol.31, Polycarbonate, Polyacetole, Polyester, Cellulosester, CarlHanser Verlag, Munich, Vienna 1992, P117-299.

The polycarbonate/polyester carbonates for use with phosphorus compounds according to the invention are prepared by the melt transesterification of a suitable diphenol and a diaryl carbonate in the presence of a suitable catalyst. The polycarbonates may also be prepared by condensation of carbonate oligomers having hydroxyl or carbonate end groups with suitable diphenols and also diaryl carbonates.

A suitable diaryl carbonate within the scope of the present invention is diaryl carbonate which is di-C₆-C₁₄Aryl esters, preferably diesters of phenol or alkyl-substituted phenols, i.e., diphenyl carbonate, di (toluene) carbonate and di (4-tert-butyl) phenyl carbonate. Diphenyl carbonate is most preferred.

Suitable carbonate oligomers are described by the general formula (1) above, and have a molecular weight of 153-15,000.

In the appropriate di-C₆-C₁₄Also included among the aryl esters are asymmetric diaryl esters, which contain a mixture of aryl substituents. Phenyl-tolyl carbonate and 4-tert-butylphenyl-phenyl carbonate are most preferred.

Also included in suitable diaryl esters are more than one di-C₆-C₁₄A mixture of aryl esters. The most preferred mixture is a mixture of diphenyl carbonate, ditolyl carbonate and bis (4-tert-butylphenyl) carbonate.

The diaryl carbonate may be used in an amount of 1.00 to 1.30mol, particularly preferably 1.02 to 1.20mol, and most preferably 1.05 to 1.15mol, based on 1mol of the diphenol.

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

wherein:

r represents substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br and

n is 0, 1 or 2.

The 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 those corresponding to the general formula (6):

wherein:

z is C₁-C₈Alkylene or C₅-C₁₂Cycloalkylene radical, S, SO₂Or a single bond, or a mixture of single bonds,

r is a substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl group, Cl or Br and

n is 0, 1 or 2.

Preferred diphenols are 4, 4 '-dihydroxydiphenyl, 4' -dihydroxydiphenyl sulfide, 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-bis (4-hydroxyphenyl) propane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 2-bis (3-methyl-4-hydroxyphenyl) propane, 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-bis (4-hydroxyphenyl) -1-phenylethane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 1-bis (4-hydroxy-group) -3, 3, 5-trimethylcyclohexane.

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

Mixtures of more than one diphenol are also included in the suitable diphenols, which lead to copolycarbonates. The most preferred mixed components are 1, 3-bis [2- (4-hydroxyphenyl) isopropyl ] benzene, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane, 2-bis (4-hydroxyphenyl) propane, 4' -dihydroxybiphenyl and 2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane.

In addition, branching agents, such as compounds containing trifunctional phenolic hydroxyl groups, may be added. It is clear that these compounds produce branching in the polymer and increase the non-Newtonian flow behaviour. Among suitable branching agents are phloroglucinol, 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-bis [4, 4-bis (4-hydroxyphenyl) cyclohexyl ] propane, 2, 4-bis (4-hydroxyphenyl isopropyl) phenol, 2, 6-bis (2-hydroxy-5' -methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2, 4-dihydroxyphenyl) propane, hexa (4- (4-hydroxyphenylisopropyl) phenyl) orthoterephthalate, tetrakis (4-hydroxyphenyl) methane, tetrakis (4- (4-hydroxyphenyl-isopropyl) -phenoxy) methane, 1, 4-bis ((4', 4 "-dihydroxy-triphenyl) methyl) benzene, and isatin biscresol, pentaerythritol, 2, 4-dihydroxybenzoic acid, 1, 3, 5-trimellitic acid, cyanuric acid.

Suitable catalysts for preparing the polycarbonates according to the invention are, for example, those of the formula (7)

Wherein the content of the first and second substances,

R¹、R²、R³and R⁴Independently of one another, may represent identical or different C₁-C₁₈Alkylene radical, C₆-C₁₀Aryl or C₅-C₆Cycloalkyl radicals and

X^-may represent an anion, its corresponding acid-base pairHaving a pK_b＜11。

Preferred catalysts are fluorinated tetraphenyl *, tetraphenyl * tetraphenylborate and tetraphenyl * phenoxide. Most preferred is tetraphenyl * phenolate. * preferred amounts of salt catalyst are, for example, 10 per mole of diphenol^-2-10^-8The most preferred amount of catalyst is 10 moles per mole of diphenol^-4-10^-6And (3) mol. In addition to the * salt, other co-catalysts may optionally be used in order to increase the rate of polymerization. Promoters include alkali and alkaline earth metal salts, for example, hydroxides, alkoxides or phenoxides of lithium, sodium and potassium, preferably hydroxides, alkoxides or phenoxides of sodium. Sodium hydroxide and sodium phenolate are most preferred. The amount of cocatalyst may be, for example, from 1 to 200ppb, preferably from 5 to 150ppb, most preferably from 10 to 125ppb, in each case calculated as sodium.

The polycarbonates may be prepared by carrying out the reaction in stages at temperatures of 150 ℃ and 400 ℃ and residence times of 15min to 5hr per stage at pressures of 1000-0.01 mbar.

The compositions according to the invention may contain, in addition to the polycarbonates or polyester carbonates, other polymer components and customary additives. Possible polymer components are, for example, styrene/acrylonitrile copolymers (SAN), acrylonitrile/butadiene/styrene terpolymers (ABS), polymethyl methacrylate (PMMA), fluorinated Polyolefins (PTFE), polyphenylene sulfides (PPS), polyolefins such as polyethylene, polypropylene and ethylene-propylene rubbers, epoxy resins, polyesters such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), Polycyclohexanedimethanol (PCT), copolyesters of ethylene glycol and cyclohexenedimethanol terephthalic acid in a ratio of 1: 4 of the two components (PCGT), copolymers of ethylene glycol and cyclohexenedimethanol terephthalic acid in a ratio of 4: 1 of the two components (PETG), and other polycarbonates prepared by the interfacial process and mixtures of the aforementioned components. Further additives are mould release agents, stabilizers, antioxidants, flame retardants, colorants and pigments, antistatic agents, nucleating agents, anti-drip agents, organic and further inorganic fillers, and reinforcing agents.

The polycarbonates according to the invention may be present in the compositions according to the invention in amounts of preferably from 5 to 95% by weight, particularly preferably from 10 to 90% by weight, most preferably from 20 to 80% by weight, relative to the weight of the composition. The further polymer components may be present in the compositions according to the invention in an amount of preferably from 1 to 60% by weight, particularly preferably from 1 to 40% by weight, most preferably from 2 to 30% by weight, relative to the weight of the composition.

The compositions may contain up to 60% by weight, preferably from 10 to 40% by weight, of inorganic materials such as fillers and/or reinforcing agents, relative to the filled or reinforced molding composition. The flame retardant may be present in the composition according to the invention in an amount of up to 35% by weight, preferably from 10 to 25% by weight, relative to the weight of the composition.

These and other components or additives which may be present in the compositions according to the invention are exemplified below, in addition to the polycarbonate/polyestercarbonate.

These substances are found in numerous publications, for example, Additives for plastics handbook, John Murphy, 1999, and are commercially available.

1. Suitable antioxidants are, for example

Alkylated monophenols, for example 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4, 6-dimethylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2, 6-di-tert-butyl-4-isobutylphenol, 2, 6-dicyclopentyl-4-methylphenol, 2- (. alpha. -methylcyclohexyl) -4, 6-dimethylphenol, 2, 6-dioctadecyl-4-methylphenol, 2, 4, 6-tricyclohexylphenol, 2, 6-di-tert-butyl-4-methoxymethylphenol, nonylphenols, the side chains of which are linear or branched, for example 2, 6-dinonyl-4-methylphenol, 2, 4-dimethyl-6- (1 ' -methylundec-1 ' -yl) phenol, 2, 4-dimethyl-6- (1 ' -methylheptadec-1 ' -yl) phenol, 2, 4-dimethyl-6 ' - (1 ' -methyltridec-1 ' -yl) phenol.

Alkylthiomethylphenols, for example 2, 4-dioctylthiomethyl-6-tert-butylphenol, 2, 4-dioctylthiomethyl-6-methylphenol, 2, 4-dioctylthiomethyl-6-ethylphenol, 2, 6-di-dodecylthiomethyl-4-nonylphenol.

Hydroquinones and alkylated hydroquinones, for example 2, 6-di-tert-butyl-4-methoxyphenol, 2, 5-di-tert-butylhydroquinone, 2, 5-di-tert-amylhydroquinone, 2, 6-diphenyl-4-octadecyloxyphenol, 2, 6-di-tert-butylhydroquinone, 2, 5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) adipate.

Tocopherols, such as alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol and mixtures thereof (vitamin E).

Hydroxylated thiodiphenyl ethers, for example 2, 2 '-thiobis (6-tert-butyl-4-methylphenol), 2' -thiobis (4-octylphenol), 4 '-thiobis (6-tert-butyl-3-methylphenol), 4' -thiobis (6-tert-butyl-2-methylphenol), 4 '-thiobis (3, 6-di-sec-amylphenol), 4' -bis (2, 6-dimethyl-4-hydroxyphenyl) disulfide.

Alkylidenebisphenols, for example 2, 2 ' -methylenebis (6-tert-butyl-4-methylphenol), 2 ' -methylenebis (6-tert-butyl-4-ethylphenol), 2 ' -methylenebis [ 4-methyl-6- (. alpha. -methylcyclohexyl) phenol ], 2 ' -methylenebis [ 4-methyl-6-cyclohexylphenol ], 2 ' -methylenebis (6-nonyl-4-methylphenol), 2 ' -methylenebis (4, 6-di-tert-butylphenol), 2 ' -ethylenebis (6-tert-butyl-4-isobutyl-phenol), 2, 2 '-methylenebis [6- (. alpha. -methylbenzyl) -4-nonylphenol ], 2' -methylenebis [6- (. alpha.,. alpha. -dimethylbenzyl) -4-nonylphenol ], 4 '-methylenebis (2, 6-di-tert-butylphenol), 4' -methylenebis (6-tert-butyl-2-methylphenol), 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2, 6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 3-tris (5-tert-butyl-4-, 1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethyleneglycol bis [3, 3-bis (3 ' -tert-butyl-4 ' -hydroxyphenyl) butyrate ], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3 ' -tert-butyl-2 ' -hydroxy-5 ' -methylbenzyl) -6-tert-butyl-4-methylphenyl ] terephthalate, 1-bis (3, 5-dimethyl-2-hydroxyphenyl) butane, 2-bis (3, 5-di-tert-butyl-4-hydroxyphenyl) propane, and mixtures thereof, 2, 2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1, 5, 5-tetrakis (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

O-, N-and S-benzyl compounds, for example 3, 5,3 ', 5 ' -tetra-tert-butyl-4, 4 ' -dihydroxydibenzyl ether, octadecyl-4-hydroxy-3, 5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3, 5-di-tert-butylbenzylmercaptoacetate, tris (3, 5-di-tert-butyl-4-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-hydroxybenzylmercaptoacetate.

Hydroxybenzylated malonates, for example 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.

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

Triazine Compounds, for example 2, 4-bis (octylmercapto) -6- (3, 5-di-tert-butyl-4-hydroxyanilino) -1, 3, 5-triazine, 2-octylmercapto-4, 6-bis (3, 5-di-tert-butyl-4-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-hydroxyphenylethyl) -1, 3, 5-triazine, 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1, 3, 5-triazine, 1, 3, 5-tris (3, 5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

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

Esters of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono-or polyhydric alcohols, e.g.with methanol, ethanol, N-octanol, isooctanol, 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' -bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

Esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono-or polyhydric alcohols, for example with methanol, ethanol, N-octanol, isooctanol, 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' -bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2, 2, 2] octane.

Esters of beta- (3, 5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono-or polyhydric alcohols, e.g.with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N' -bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

Esters of 153, 5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N' -bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

Amides of beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N '-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N '-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, N' -bis [2- (3- [3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine]Propionyloxy) ethyl]Oxamide (Naugard)^®XL-1 from Uniroyal).

1.17 ascorbic acid (vitamin C)

Amino antioxidants, for example N, N ' -diisopropyl-p-phenylenediamine, N ' -di-sec-butyl-p-phenylenediamine, N ' -bis (1, 4-dimethylpentyl) -p-phenylenediamine, N ' -bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N ' -bis (1-methyl-heptyl) -p-phenylenediamine, N ' -dicyclohexyl-p-phenylenediamine, N ' -diphenyl-p-phenylenediamine, N ' -bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N ' -phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine, N- (1-methyl-heptyl) -N ' -phenyl-p-phenylenediamine, N ' -di-sec-butyl-p-phenylenediamine, N ' -di-butyl-p-phenylenediamine, N, N-cyclohexyl-N '-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamide) diphenylamine, N' -dimethyl-N, N '-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p, p' -di-tert-octyldiphenylamine, 4-N-butyl-aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, p- (4-methoxyphenyl) amine, p-toluenesulfonamide, N-tert-octyldiphenylamine, N-octyldiphenylamine, 4-butylaminophenol, 4-butyrylaminophenol, 4-nonan, 2, 6-di-tert-butyl-4-dimethylaminomethylphenol, 2, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylmethane, N, N, N ', N ' -tetramethyl-4, 4 ' -diaminodiphenylmethane, 1, 2-bis [ (2-methylphenyl) amino ] ethane, 1, 2-bis (phenyl-amino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3 ' -dimethylbutyl) phenyl ] amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono-and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-and dialkylated nonyldiphenylamines, a mixture of mono-and dialkylated dodecyldiphenylamines, a mixture of mono-and dialkylated isopropyl/isohexyldiphenylamines, A mixture of mono-and dialkylated tert-butyldiphenylamines, 2, 3-dihydro-3, 3-dimethyl-4H-1, 4-benzothiazine, phenothiazine, a mixture of mono-and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono-and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N, n, N ', N' -tetraphenyl-1, 4-diaminobut-2-ene, N, n-bis (2, 2,6, 6-tetramethylpiperidin-4-yl) hexamethylenediamine, bis (2, 2,6, 6-tetrapiperidin-4-yl) sebacate, 2,6, 6-tetramethylpiperidin-4-one, 2,6, 6-tetramethylpiperidin-4-ol. These compounds may be used alone or in the form of a mixture.

1.19. Suitable thiosynergistic compounds are, for example, lauryl thiodipropionate and/or distearyl thiodipropionate.

2. UV absorbers and light stabilizers may be used in the compositions according to the invention in amounts of from 0.1 to 15% by weight, preferably from 3 to 8% by weight, relative to the weight of the composition. Suitable UV absorbers and light stabilizers are, for example:

2.12- (2' -hydroxyphenyl) benzotriazoles, for example: 2- (2' -hydroxy)Phenyl-5 ' -methylphenyl) benzotriazole, 2- (3 ', 5 ' -di-tert-butyl-2 ' -hydroxyphenyl) benzotriazole, 2- (5 ' -tert-butyl-2 ' -hydroxyphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' - (1, 1, 3, 3-tetramethyl-butyl) phenyl) benzotriazole, 2- (3 ', 5 ' -di-tert-butyl-2 ' -hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 ' -tert-butyl-2 ' -hydroxy-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (3 ' -sec-butyl-5 ' -tert-butyl-2 ' -hydroxyphenyl) benzotriazole, and mixtures thereof, 2- (2 ' -hydroxy-4 ' -octyloxy-phenyl) benzotriazole, 2- (3 ', 5 ' -di-tert-amyl-2 ' -hydroxyphenyl) benzotriazole, 2- (3 ', 5 ' -bis (. alpha.,. alpha. -dimethylbenzyl) -2 ' -hydroxyphenyl) benzotriazole, 2- (3 ' -tert-butyl-2 ' -hydroxy-5 ' - (2-octyloxycarbonyl-ethyl) phenyl) -5-chlorobenzotriazole, 2- (3 ' - (tert-butyl) -5 ' - [2- (2-ethyl-hexyloxy) carbonylethyl]-2 ' -hydroxyphenyl) -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) phenylbenzotriazole, 2' -methylenebis [4- (1, 1, 3, 3-tetramethylbutyl) -6-benzotriazol-2-ylphenol](ii) a 2- [3 ' -tert-butyl-5 ' - (2-methoxycarbonylethyl) -2 ' -hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300, [ R-CH₂CH₂-COO-CH₂CH₂]₂Wherein R is 3 ' -tert-butyl-4 ' -hydroxy-5 ' -2H-benzotriazol-2-ylphenyl, 2- [2 ' -hydroxy-3 ' - [ α, α -dimethylbenzyl)]-5' - (1, 1, 3, 3-tetramethylbutyl) phenyl]Benzotriazole, 2- [2 ' -hydroxy-3 ' - (1, 1, 3, 3-tetramethylbutyl) -5 ' - (alpha, alpha-dimethylbenzyl) phenyl]Benzotriazole.

2.22-hydroxybenzophenones, for example the 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4, 2 ', 4' -trihydroxy-and 2 '-hydroxy-4, 4' -dimethoxy derivatives.

Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) is benzenediol, 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.

Acrylates, for example ethyl- α -cyano- β, β -diphenylacrylate, isooctyl- α -cyano- β, β -diphenylacrylate, methyl- α -methoxycarbonylcinnamate, methyl- α -cyano- β -methyl-p-methoxycinnamate, butyl- α -cyano- β -methyl-p-methoxycinnamate, methyl- α -methoxycarbonyl-p-methoxycinnamate and N (β -methoxycarbonyl- β -cyanovinyl) -2-methyldihydroindole.

Nickel compounds, for example nickel complexes of 2, 2' -thiobis [4- (1, 1, 3, 3-tetramethylbutyl) phenol ], such as the 1: 1 or 1: 2 complex, with or without additional ligands, for example N-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, e.g.the methyl or ethyl ester of 4-hydroxy-3, 5-di-tert-butylbenzylphosphoric acid, nickel complexes of ketoximes, e.g.of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

Sterically hindered amines, for example bis (2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (2, 2,6, 6-tetramethyl-4-piperidyl) succinate, bis (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-hydroxy-benzylmalonate, condensate of 1- (2-hydroxyethyl) -2, 2,6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, Linear or cyclic condensates of N, N '-bis (2, 2,6, 6-tetramethyl-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, 2-ethylene) bis (3, 3, 5, 5-tetramethylpiperazinone), 4-benzoyl-2, 2,6, 6-tetramethylpiperidine, 4-octadecyloxy-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-tetramethyl-piperidyl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethyl-piperidyl) succinate, N' -bis (2, 2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholinyl-2, 6-dichloro-1, 3, linear or cyclic condensates of 5-triazine, condensates of 2-chloro-4, 6-bis (4-n-butylamino-2, 2,6, 6-tetramethylpiperidinyl) -1, 3, 5-triazine and 1, 2-bis (3-aminopropyl-amino) ethane, condensates of 2-chloro-4, 6-bis (4-n-butylamino-1, 2, 2,6, 6-pentamethylpiperidinyl) -1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7, 7, 9, 9-tetramethyl-1, 3, 8-triazaspiro [4, 5] decane-2, 4-dione, 3-dodecyl-1- (2, 2,6, 6-tetramethyl-4-piperidyl) pyrrolidine-2, 5-dione, 3-dodecyl-1- (1, 2, 2,6, 6-pentamethyl-4-piperidyl) pyrrolidine-2, 5-dione, a mixture of 4-hexadecyloxy-and 4-octadecyloxy-2, 2,6, 6-tetramethylpiperidine, a condensation product of N, N' -bis- (2, 2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine, 1, 2-bis (3-aminopropylamino) ethane and 2, 4, 6-trichloro-1, the condensation product of 3, 5-triazine and 4-butylamino-2, 2,6, 6-tetramethylpiperidine (CAS reg.no. [136504-96-6 ]); n- (2, 2,6, 6-tetramethyl-4-piperidyl) -7-dodecyl-succinimide, N- (1, 2, 2,6, 6-pentamethyl-4-piperidyl) -N-dodecyl-succinimide, 2-undecyl-7, 7, 9, 9-tetramethyl-1-oxa-3, 8-diaza-4-oxospiro [4, 5] -decane, a reaction product of 7, 7, 9, 9-tetramethyl-2-cycloundecyl-1-oxa-3, 8-diaza-4-oxospiro [4, 5] decane and epichlorohydrin, 1-bis (1, 2, 2,6, 6-pentamethyl-4-piperidinyloxycarbonyl) -2- (4-methoxyphenyl-oxycarbonyl) ) Reaction products of ethylene, N '-bis (formyl) -N, N' -bis (2, 2,6, 6-tetramethyl-4-piperidyl) -hexamethylenediamine, diesters of 4-methoxymethylenemalonic acid with 1, 2, 2,6, 6-pentamethyl-4-hydroxypiperidine, poly [ methylpropyl-3-oxo-4- (2, 2,6, 6-tetramethyl-4-piperidyl) ] siloxane, malonic anhydride- α -olefin copolymers with 2, 2,6, 6-tetramethyl-4-aminopiperidine or 1, 2, 2,6, 6-pentamethyl-4-aminopiperidine.

Oxamides, for example 4, 4 ' -dioctyloxyoxanilide, 2 ' -diethoxyoxanilide, 2 ' -dioctyloxy-5, 5 ' -di-tert-butyloxanilide, 2 ' -didodecyloxy-5, 5 ' -di-tert-butyloxanilide, 2-ethoxy-2 ' -ethyloxanilide, N ' -bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2 ' -ethyloxanilide and its reaction with 2-ethoxy-2 ' -ethyl-5, 4 ' -di-tert-N, mixtures of oxanilides, mixtures of o-and p-methoxy-disubstituted oxanilides and mixtures of o-and p-ethoxy-disubstituted oxanilides.

82- (2-hydroxyphenyl) -1, 3, 5-triazines, for example 2, 4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1, 3, 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl-4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2, 4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (4-methylphenyl) -1, 3, 5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- [ 2-hydroxy-4- (2-hydroxy-3-butoxypropoxy) phenyl ] -4, 6-bis (2, 4-dimethyl) -1, 3, 5-triazine, 2- [ 2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl ] -4, 6-bis (2, 4-dimethyl) -1, 3, 5-triazine, 2- [4- (dodecyloxy/tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- [ 2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4, 6-diphenyl) -1, 3, 5-triazine, 2- (2-hydroxy-4-methoxy-phenyl) phenyl-4, 6-diphenyl) -1, 3, 5-triazine, 2, 4, 6-tris [ 2-hydroxy-4- (3-butoxy-2-hydroxy-propoxy) 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-oxo) -2-hydroxypropoxy ] phenyl } -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine.

These compounds may be used alone or in the form of a mixture.

3. Suitable metal deactivators are, for example, N, N ' -diphenyloxamide, N-salicylal-N ' -salicyloyl hydrazine, N, N ' -bis (salicyloyl) hydrazine, N, N ' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2, 4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N ' -diacetyladipoyl dihydrazide, N, N ' -bis (salicyloyl) oxalyl dihydrazide, N, N ' -bis (salicyloyl) thiomalonyl dihydrazide. Single compounds or mixtures thereof may be used.

5. Suitable peroxide trapping agents are, for example: esters of beta-thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl esters, zinc mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetradodecylmercapto propionate. Single compounds or mixtures thereof may be used.

6. Suitable basic costabilizers are, for example: melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts, alkaline earth metal salts of higher fatty acids, such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. Single compounds thereof or mixtures thereof may be used.

7. Suitable nucleating agents are, for example, inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably alkaline earth metal salts thereof; organic compounds such as monocarboxylic or polycarboxylic acids and their salts, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymers such as ionic copolymers (ionomers). 1,3: 2, 4-bis (3 ', 4' -dimethylbenzylidene) sorbitol, 1, 3: 2, 4-bis (p-methyldibenzylidene) sorbitol and 1, 3: 2, 4-bis (benzylidene) sorbitol is particularly preferred. A single compound thereof or a mixture thereof may be used.

8. Suitable fillers and reinforcing agents are, for example, calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wollastonite, and wood flour or fibers of other natural products, synthetic fibers. These compounds may be used alone or in the form of a mixture.

9. Suitable further additives are, for example, plasticizers, lubricants, emulsifiers, pigments, viscosity improvers, catalysts, flow-control agents, optical brighteners, flame retardants, antistatics, and blowing agents.

10. Suitable benzofuranones and indolinones are, for example, those described in U.S.4,325,863; U.S.4,338,244; U.S.5,175,312; U.S.5,216,052; U.S.5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102, or 3- [4- (2-acetoxyethoxy) phenyl ] -5, 7-di-tert-butyl-benzofuran-2-one, 5, 7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl ] benzofuran-2-one, 3' -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-ethoxy-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, lactone antioxidants such as

These compounds act as antioxidants, for example. These compounds may be used alone or in the form of a mixture.

11. Suitable fluorescent plasticizers are "Plastics Additives Handbook", edited by R.G pochter and H.M muller, Hanser Verlag, third edition, 1990, P775 to 789, to name a few.

12. Suitable mold release agents are esters of aliphatic acids and alcohols, for example pentaerythritol tetrastearate and glycerol monostearate. They are used alone or in a mixture, preferably in an amount of 0.02 to 1% by weight, relative to the weight of the composition.

13. Suitable flame-retardant additives are phosphates, i.e.triphenyl phosphate, resorcinol diphosphate, bromine-containing compounds such as brominated phosphates, brominated oligocarbonates and polycarbonates, and salts such as C₄F₉SO₃ ^-Na⁺。

14. Suitable impact modifiers are butadiene rubbers with grafted styrene/acrylonitrile or methyl methacrylate, ethylene/propylene rubbers with grafted maleic anhydride, ethyl acrylate and butyl acrylate rubbers with grafted methyl methacrylate or styrene/acrylonitrile, interpenetrating networks of siloxanes and acrylates with grafted methyl methacrylate or styrene/acrylonitrile.

15. Suitable polymers are SAN, ABS, PMMA, PTFE, PSU, PPS, polyolefins such as polyethylene, polypropylene and ethylene/propylene rubbers, epoxy resins, polyesters such as PBT, PET, PCT, PCTG and PETG and other polycarbonates produced by the interfacial process.

16. Suitable antistatics are sulfonates, e.g. C₁₂H₂₅SO^3-Or C₈F₁₇SO^3-Tetraethylammonium salt of (a).

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

18. Epoxy group-containing compounds, for example, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylcarboxylate, copolymers of glycidyl methacrylate and epoxysilanes.

19. Compounds containing anhydride groups, for example, maleic anhydride, succinic anhydride, benzoic anhydride and phthalic anhydride.

The compounds in classes 18 and 19 act as melt stabilizers. They may be used alone or in admixture.

The compositions (molding compounds) according to the invention are prepared by blending the relevant components in a known manner and melt compounding and melt extrusion at about 300 ℃ such as at 200 and 400 ℃ using conventional equipment such as closed compounders, extruders and twin-screw screws. The blending of the individual components can be carried out sequentially or simultaneously, and can in fact be carried out at about 20 ℃ (room temperature) or at elevated temperature.

The moulding compositions according to the invention can be used for producing moulded parts of any type. These mouldings can be produced by injection moulding, extrusion and blow moulding processes. Another shaping method of processing is the production of moldings by thermoforming using previously prepared sheets or films.

Examples of moldings according to the invention are profiles, films, shell parts of various types, for example for domestic applications such as juicers, coffee machines and mixers, for office equipment such as monitors, printing machines and copiers, for sheets, pipes, electrical installation ducts, windows, doors and profiles for the building sector, for interior decoration and for outdoor applications and in the electrical engineering sector, for example for switches and sockets. Furthermore, the mouldings according to the invention can be used for interior components and structural parts of tracked vehicles, boats, aircraft, automobiles and other vehicles, and also for body-building components of automobiles.

The mouldings according to the invention may be transparent or opaque. Further mouldings are, in particular, optical and magneto-optical memories such as microdisk, Compact Disc (CD) or Digital Versatile Disc (DVD), packaging for food and beverages, optical lenses and prisms, lighting panes, automotive light panes, glazing for buildings and automobiles, glazing of various types such as for greenhouses and the like, so-called double-wall sheets or hollow sheets.

The following examples serve to explain the invention in more detail.

Examples

Polycarbonate compositions based on two melt polycarbonates and a linear polycarbonate obtained by the interfacial process were prepared. The seven phosphorus compounds used according to the invention were extrusion compounded with polycarbonate using a ZSK33 twin-screw extruder. This means that the effect of adding phosphorus compounds to different polycarbonates can be directly compared.

The resistance to hydrolysis is determined by placing the polycarbonate composition in a Zwick MeltIndexer (Texvzval melt index determinator) at 300 ℃ according to ASTM method D1238. The extruded granular composition was first conditioned in air to give a moisture content of 0.12% and then subjected to the melt flow index test. The molecular weight of the extruded composition and the molecular weight of the composition after the stability test were determined by correlating the results of the relative viscosity measurements. The molecular weight drop is calculated by difference. The relative viscosity was determined using a 0.5% solution in dichloromethane at 20 ℃.

The yellowness index is determined using the CIELAB method on injection-molded specimens having a thickness of 4 mm.

The water content in the polycarbonate was determined by Karl Fischer titration.

TABLE 1

Examples		1	2	3	4	5	6	7	8
										PC1	％	100.00	99.97	99.99	99.9
PC2	％					100.00	99.97	99.99	99.9
										Phosphorus compound 1	％		0.03				0.03
Phosphorus compound 2	％			0.01				0.01
										Phosphorus compound 3	％				0.1				0.1
Mw		28,949	28,561	28,432	28,561	28,820	28,561	28,561	28,561
										MwAfter hydrolysis resistance test, the water content was 0.12%		25,584	25,713	27,525	26,619	28,043	26,360	26,888	26,360
MwReduce		3,366	2,848	906	1,942	777	2,201	1,673	2,201
										YI		3.5	2.7	2.6	3.5	3.5	2.6	1.7	3.5

Note:

PC1 is a bisphenol-A polycarbonate prepared by melt polymerization using 256ppm of Compound A, 21ppm of Compound B, 59ppm of Compound C, and 175ppm of Compound D.

PC2 is a bisphenol-A polycarbonate prepared by the interfacial process using < 5ppm of compound A, B, C and D.

The phosphorus compound 1 is tris [ (3-ethoxybutylcyclyl-3) methyl ] phosphite.

Phosphorus compound 2 is tris [ (2-ethylhexyl) phosphate.

The phosphorus compound 3 is triphenylphosphine.

Table 2 gives further examples of various phosphorus compounds having different oxidation states of phosphorus.

TABLE 2

Examples		9	10	11	14	15	16	17
									PC3	％	100.00	99.95	99.95	99.95	99.95	99.95	99.95
Phosphorus compound 4	％		0.05
									Phosphorus compound 1	％			0.05
Phosphorus compound 5	％				0.05
									Phosphorus compound 6	％					0.05
Phosphorus compound 7	％						0.05
									Phosphorus compound mixture 8	％							0.05
Mw		27,266	27,914	27,266	28,043	27,914	28,043	28,043
									MwAfter the hydrolysis resistance test, the test piece was,the water content is 0.12 percent		25,066	27,266	25,584	27,137	25,842	26,878	26,490
MwReduce		2,201	647	1,683	906	2,071	1,165	1,554
									YI		4.3	4.2	3.6	3.3	3.2	3.3	3.0

Note:

PC3 is a bisphenol-A polycarbonate prepared by melt polymerization using 231ppm of Compound A, 10ppm of Compound B, 53ppm of Compound C, and 144ppm of Compound D. Phosphorus compound 4 is tris (2, 4-di-tert-butylphenyl) phosphite. Phosphorus compound 5 is 2, 4, 6-three tert butyl phenyl-3-butyl-2-ethyl-1, 3-propylene glycol phosphite.

Phosphorus compound 6 is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite

The phosphorus compound 7 being tetrakis (2, 4-di-tert-butylphenyl) [1, 1-biphenyl ]4, 4' -diyl diphosphonite

The phosphorus compound mixture 8 was 57% of tris (2, 4-di-tert-butylphenyl) phosphite, 28% of octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 15% of a compound represented by the general formula (8)

The results obtained show that the loss of molecular weight is reduced due to the addition of the phosphorus compound to the melt compounded polymer. This effect is contrary to the effect typically observed with polycarbonates prepared by the interfacial process. It is therefore considered that the hydrolysis resistance of the melt-polymerized polycarbonate is improved by adding the phosphorus compound, while the hydrolysis resistance of the polycarbonate prepared by the interfacial method is lowered.

Claims (12)

1. A composition comprising a melt polycarbonate of the general formula (1) and a phosphorus-containing organic compound;

wherein the general formula (1) is:

wherein, the brackets represent repeating structural units,

m may be Ar or a multifunctional group A, B, C and a group D,

wherein Ar is represented by the following structural formula:

the polyfunctional group A is a group of the following structural formula

The polyfunctional group B is a group of the following structural formula

The multifunctional group C is a group of the following structural formula

The polyfunctional group D is a group of the following structural formula

And the sum of the polyfunctional groups A, B, C and D is > 5ppm,

wherein Y is H or a group of formula (4)

Wherein:

r, identical or different, represents H, C₁-C₂₀Alkyl radical, C₆H₅Or C (CH)₃)₂C₆H₅And

n may be 0, 1, 2, or 3,

wherein X is Y, and X is Y,

wherein

Y is as defined above;

the phosphorus-containing organic compound is selected from:

phosphine (PR)₃) Phosphine Oxide (OPR)₃) A phosphinic acid ester (P (OR) R₂) Phosphonite (P (OR)₂R), phosphite (P (OR)₃) Phosphinic acid ester (PO (OR) R₂) Phosphonate ester (PO (OR)₂R) and/or phosphate (PO (OR)₃) And R may be hydrogen, C₁-C₁₀₀Alkyl radicals or unsubstituted or substituted C₆-C₁₄Aryl groups, the groups R may be the same or different;

and

diphosphine (R)₂P-X-PR₂) Bis-phosphinite ((RO) RP-X-PR (OR)), diphosphonite ((RO)₂P-X-P(OR)₂) Diphosphite ((RO)₂-P-OXO-P(OR)₂) Diphosphonates, diphosphate compounds and compounds of the general formula (RO)_mR_2-mP-XP(OR)_mR_2-mAnd R is C₁-C₁₀₀Alkyl radicals or unsubstituted or substituted C₆-C₁₄An aryl group, n is 0, 1, 2 or 3, m is 0, 1 or 2, and X is a group of the formula (2) or of the formula (3)

Wherein R represents a substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl group, Cl or Br, and n is 0, 1 or 2,

and Z is C₁-C₈Alkylene or C₅-C₁₂Cycloalkylene radical, S, SO₂Or a single bond; for the diphosphines described above, R may also be hydrogen;

the polycarbonate has a weight average molecular weight of 5,000-80,000 as determined by gel permeation chromatography.

2. A composition according to claim 1, wherein

Phosphine (PR)₃) And phosphine Oxide (OPR)₃) The compound is selected from: wherein R is hydrogen, C₁-C₁₀₀Alkyl radicals or unsubstituted or substituted C₆-C₁₄Aryl radicals, the radicals R may be identical or different;

phosphinic acid esters (P (OR) R₂) Phosphonite (P (OR)₂R) and phosphites (P (OR)₃) The compound is selected from: wherein R is hydrogen or C₁-C₁₀₀Alkyl radicals, or unsubstituted or substituted C₆-C₁₄Aryl radicals, the radicals R may be identical or different;

phosphinate esters (PO (OR) R₂) Phosphonate ester (PO (OR)₂R) and phosphate (PO (OR)₃) The compound is selected from: wherein R is hydrogen or C₁-C₁₀₀Alkyl radical, or unsubstituted or substituted C₆-C₁₄Aryl radicals, the radicals R may be identical or different;

diphosphine compound R₂P-X-PR₂Selected from: wherein R is hydrogen or C₁-C₁₀₀Alkyl radicals, or unsubstituted or substituted C₆-C₁₄Aryl radicals, the radicals R being identical or different, and wherein X is a divalent C₁-C₁₀₀Alkyl radicals or unsubstituted or substituted C₆-C₁₄An aryl group; and

bis-phosphinite ((RO) RP-X-PR (OR)), diphosphonite ((RO)₂P-X-P(OR)₂) And diphosphite ((RO)₂P-OXO-P(OR)₂) The compound is selected from: wherein R is C₁-C₁₀₀Alkyl radicals or unsubstituted or substituted C₆-C₁₄Aryl radicals, the radicals R being identical or different, and wherein X is a divalent C₁-C₁₀₀Alkyl radicals or unsubstituted or substituted C₆-C₁₄Aryl group.

3. A composition according to claim 1, wherein

The phosphite is selected from: triphenyl phosphite, tris (2-tert-butylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (2, 6-di-tert-butylphenyl) phosphite; tris (2, 4, 6-tri-tert-butylphenyl) phosphite, (2, 4, 6-tri-tert-butylphenyl) - (2-butyl-2-ethyl-propane-1, 3-diyl) phosphite, bis (2, 4-dicumyl-phenyl) pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite, tris (p-nonylphenyl) phosphite, diphenyl-isodecyl phosphite, diisodecyl-phenyl phosphite, triisodecyl phosphite, trilauryl phosphite and tris [ (3-ethoxybutyl) -3-yl) -methyl ] phosphite;

the phosphate ester is selected from: tris (2-ethylhexyl) phosphate, triphenyl phosphate, tris (2-tert-butylphenyl) phosphate, tris (2, 4-di-tert-butylphenyl) phosphate, tris (2, 6-di-tert-butylphenyl) phosphate and tris (2, 4, 6-tri-tert-butylphenyl) phosphate.

4. A composition according to claim 1, wherein the phosphorus-containing organic compound is a compound of the formula

Wherein R is C₁-C₁₀₀Alkyl radicals, or unsubstituted or substituted C₆-C₁₄An aryl group; and Y represents tetravalent C₁-C₁₀₀An alkoxy group.

5. The composition according to any of claims 1 to 4, wherein the phosphorus-containing organic compound is present in an amount of from 10ppm to 30 wt.%, relative to the weight of the melt polycarbonate.

6. A composition according to any one of claims 1 to 4, wherein the phosphorus-containing organic compound is of the formula

7. A composition according to any one of claims 1 to 4, wherein the phosphorus-containing organic compound is of the formula

8. A composition according to any one of claims 1 to 4, wherein the phosphorus-containing organic compound is triphenyl phosphate.

9. A molded article comprising the composition according to any one of claims 1 to 5.

10. Use of the phosphorus-containing organic compounds as claimed in any of claims 1 to 8 for increasing the hydrolysis resistance of melt polycarbonates and moldings containing them.

11. Use according to claim 10, wherein the amount of phosphorus-containing organic compound is from 10ppm to 2 wt.%, relative to the weight of the melt polycarbonate.

12. Use according to claim 11, wherein the amount of phosphorus-containing organic compound is from 10ppm to 1 wt.%, relative to the weight of the melt polycarbonate.