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US005534645A United States Patent (19) 11 Patent Number: 5,534,645 Quotschalla et al. (45) Date of Patent: Jul. 9, 1996

54) TRIVALENT PHOSPHORUS COMPOUNDS 5,342,978 8/1994 Enlow et al...... 554/78 STABILIZED WITH AMNES FOREIGN PATENT DOCUMENTS (75) Inventors: Udo Quotschalla, Heppenheim, 0143464 6/1985 European Pat. Off.. Germany; Helmut Linhart, Reinach, 0167969 1/1986 European Pat. Off.. Switzerland 0168721 1/1986 European Pat. Off.. 0278579 8/1988 European Pat. Off.. 73) Assignee: St Geigy Corporation, Tarrytown, Primary Examiner-Johann Richter Assistant Examiner-Michael G. Ambrose 21 Appl. No.: 298,894 Attorney, Agent, or Firm-Michele A. Kovaleski pp. No.: Z95, (57) ABSTRACT (22 Filed: Aug. 31, 1994 The invention relates to a process for stabilizing a crystalline Related U.S. Application Data organic phosphite orphosphonite against hydrolysis, which comprises introducing a mixture comprising phosphite or (62) Division of Ser. No. 129,705, Sep. 30, 1993, Pat. No. phosphonite, a solvent or solvent mixture, and 0.1 to 100% 5,371,263. by weight (relative to phosphite orphosphonite) of an (30) Foreign Application Priority Data and having a temperature of 50°-100° C. as a homogeneous melt into a liquid crystallization medium whose temperature Oct. 5, 1992 (CH) Switzerland e o so w w w a as a 3104/92 during the addition is maintained 10-70° C. below the Nov. 27, 1992 CH Switzerland ...... 3647/92 temperature of the melt. (51 int. Cl...... C09K 15/32 52) Theinvention EpiO are distinguished Elsie by theirStating excellent resistance to the to 58) Field of Search ...... 558/71 hydrolysis and have a long shelf life even at high atmo 56) References Cited spheric humidity. They can be advantageously used as stabilizers for organic material against the damaging effect U.S. PATENT DOCUMENTS of heat, oxygen, and/or light. 3,553,298 1/1971 Hodan et al. . 3,787,537 1/1974 De Marcq. 11 Claims, No Drawings 5,534,645 1. 2 TRIVALENT PHOSPHORUS COMPOUNDS In principle, any organic compounds or mixtures of STABLIZED WITH AMNES compounds which are liquid in the temperature range from 10° to 60° C. under atmospheric pressure, do not cause This is a divisional of Ser. No. 08/129,705, filed Sep. 30, and are capable of dissolving a sufficient amount 1993, now U.S. Pat. No. 5,371,263. of solid phosphite or phosphonite above 50° C., in some The invention relates to a process for increasing the shelf cases up to 100° C. or are sufficiently miscible with the life of organic phosphites and phosphonites and to an melted phosphite orphosphonite, can be used as the solvent. organic phosphite orphosphonite stabilized against hydroly For example, sufficient solubility or miscibility is given if S1S. Organic phosphites and phosphonites are widely used as the homogeneous liquid mixture can contain up to 15, in heat stabilizers for synthetic polymers. However, prepara 10 particular up to 50%, by weight of phosphite or phospho tion, storage and use of phosphites and phosphonites are nite. Examples of suitable solvents are or hydro rendered difficult by the fact that these compounds hydro carbons or mixtures thereof. lyze very easily. A particular problem is storage of the Advantageously one compound or a mixture of two material at high atmospheric humidity. compounds is used as the solvent in the melt. The main Various methods have been proposed for arriving at 15 solvent is used in an amount of 20 to 500% by weight, products having improved stability to hydrolysis; these relative to the phosphite or phosphonite, and the further include, apart from preparation processes leading to purer solvent in an amount of 0-50% by weight, relative to the products and methods for purifying the ready-to-use com main solvent. The melt preferably contains an or a pounds, in particular the addition of specific stabilizers hydrocarbon as the main solvent in an amount of 20 to 500% which, on the one hand, reduce the tendency to hydrolysis by weight, relative to the phosphite or phosphonite, and a and, on the other hand, do not result in adverse effects during further solvent in an amount of 0-50, in particular 0-20, 96 the later use of the compounds. by weight, relative to the main solvent. It is also possible to EP-A-278 579 proposes to use a hydrolytically stable use a mixture of alcohols or a mixture of hydrocarbons. stabilizer mixture in which the crystalline phosphite is Examples of suitable alcohols are lower alcohols, such as embedded in an amorphous phenolic antioxidant. This sta 25 C-Calkanols, in particular C-Calkanols, such as metha bilizer mixture is obtainable by rapid cooling of a melt of nol, ethanol, propanol or isopropanol. Isopropanol and both compounds or of a suspension consisting of crystalline are particularly suitable. phosphite and liquid phenol derivatives. Examples of suitable hydrocarbons are C-Calkanes, The addition of as stabilizers against hydrolysis cycloalkanes or alkylated cycloalkanes having 6 to 12 is described, for example, in U.S. Pat. No. 3553 298. Further 30 carbon atoms, , or alkylaromatics having 6 to 10 publications regarding the stabilization of phosphites with atoms; toluene, ligroin, petroleum , xylene, and in amines are U.S. Pat. No. 3 787 537, EP-A-168 721 and particular toluene are particularly suitable. EP-A-167969. The recommended compounds are in par Frequently the further solvent used is a hydrocarbon or a ticular tertiary alkanolamines and alkylamines, mixture of hydrocarbons in the case where the main solvent and anilines; typical examples are triethylamine, diethano 35 is an alcohol, or an alcohol in the case where the main lamine, triethanolamine, di- and triisopropanolamine solvent is a hydrocarbon. Suitable alcohols and hydrocar (TIPA), tetraisopropanolethylenediamine, aniline, phe bons are the ones listed above. nylenediamine and hexamethylenetetramine. In general, the The organic phosphites orphosphonites usable according amines are used in amounts of up to about 5% by weight to the invention are solid at 20 C.; in general they are (relative to the phosphite to be stabilized); incorporation of 40 crystalline solids. the amine is effected by dry milling or by dissolution in or Phosphites are here understood to mean organic phos mixing with the phosphite melt, followed by crystallization. phites of the formula P(OR) in which the radicals R are Despite the known stabilization methods listed here, hydrocarbon radicals, which may contain hetero atoms, and there is a need for further improvement of the hydrolyric moreover a maximum of two of the three radicals R can be stability of organic phosphites and phosphonites. 45 hydrogen atoms. Hetero atoms are any atoms with the It has now been found that the stabilizing effect of amines exception of carbon and hydrogen, in particular the atoms N, can surprisingly be increased by applying the amine in a O, F, Si, P, S, Cl, Br, Sn and I. special process. Phosphonites are of phosphonous acid of the Accordingly, the invention provides a process for stabi formula P(OR)2R in which R is as defined above or can be lizing a crystalline organic phosphite orphosphonite against 50 halogen. hydrolysis, which comprises introducing a mixture compris In the process according to the invention, crude phos ing phosphite or phosphonite, a solvent or solvent mixture, phite or crude phosphonite solutions such as are obtained and 0.1 to 100% by weight (relative to the phosphite or during preparation before crystallization can be used. phosphonite ) of an amine and having a temperature of The product of the process according to the invention is 50-100° C. as a homogeneous melt into a liquid crystalli 55 a mixture of compounds comprising solid phosphite or zation medium whose temperature during the addition is phosphonite and amine. maintained 10-70° C. below the temperature of the melt. The temperature of the melt is preferably 55°-90° C., in The meltis the liquid mixture comprising amine, solvent particular 60-80° C. and the phosphite or phosphonite to be stabilized. The melt In the process according to the invention, the difference can contain a small or a large amount of solvent, for example in temperature between melt and crystallization medium is 20 or 500% by weight (relative to the phosphite or phos advantageously at least 20°C., for example 30–70° C., in phonite) and thus can also be more like a solution. The particular 40–60° C. important feature is that the melt is homogeneous, i.e. that The crystallization medium is preferably maintained at a none of the components mentioned are crystalline any more temperature being at least 10° C., for example 10°-60° C., and separation into 2 or more liquid phases does not take 65 below the resulting temperature of the liquidus. The tem place. The amine used can be an individual compound or a perature of the crystallization medium is preferably 20°-60° mixture of compounds. C. below the resulting temperature of the liquidus. 5,534,645 3 The resulting temperature of the liquidus is the tempera ture at which a homogeneous phase formed from the melt (II) and crystallization medium is in thermodynamic equilibrium with phosphite crystals; below this temperature, crystalliza tion starts, and above the mixture forms a homogeneous melt. In practice, this temperature is advantageously deter mined by mixing tests, for example by means of calorimetic (for example by DSC) and/or optical methods. Advantageously, 80-800% by weight, in particular (III) 100-500% by weight, of organic solvent, relative to the 10 phosphite or phosphonite in the melt, is used as the crys tallization medium. Advantageously, alcohols are used as the crystallization G - CH medium; thus, for example, a C-Calkanol or a mixture of 15 CH various C-Calkanols is used. C-C Alkanols, such as in which G is hydrogen or methyl, and G and G are methanol, ethanol, propanol or isopropanol, are preferably hydrogen, methyl or together are =O; preferably, the poly used as the crystallization medium. alkylpipefidine group of the formula II or III are substituted Advantageously, seed crystals are added to the crystal in the 4 position by one or two polar substituents or a polar lization medium. Accordingly, the crystallization medium 20 spiro ring system. preferably consists of a suspension of 2 to 20% by weight of X', X’ and X’ are, for example, independently of one another, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, crystalline phosphite or phosphonite, relative to the phos nonyl, decyl, hydxoxyethyl, hydroxypropyl, hydroxybutyl, phite or phosphonite in the melt. Moreover, it is advanta hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoc geous for the crystallization medium to be 50-100% satu tyl, hydroxynoyl or hydroxydecyl. rated with the amine, 100% of saturation corresponding to 25 Preferably, X, X and X are identical. an amine concentration at which dissolved and solid amine The amine of the formula I is preferably a tertiary amine, can be present side by side. particularly preferably a tri-C-Calkanolamine, in par In general, the melt contains 0.1 to 50% by weight of ticular triisopropanolamine (=amine A). amine, relative to the phosphite or phosphonite; preferably, Of importance is a process in which the amine used is a 0.2 to 25% by weight, in particular 0.5 to 20% by weight, in 30 tertiary amine of the formula I or a cyclic sterically hindered particular 1 to 10% by weight, are used (relative to the amine containing at least one group of the formulae II or III phosphite or phosphonite in the melt). in which G is hydrogen, and G' and G' are hydrogen or together are a substituent =O. During the metered addition of the melt, the crystalliza Particularly advantageously, derivatives of 2,2,6,6-tet tion medium is advantageously stirred. After both mixtures 35 ramethylpipefidine are used in the process according to the have been combined, further workup can take place in a invention. manner known perse, for example by cooling to 10°-15° C. Of importance is in particular the use of the classes of and isolation of the crystalline product. polyalkylpipefidines described below under (a) to (h), which The stabilized phosphite or phosphonite is generally carry a group of the formula II or III as mentioned above: obtained as a powder in which the amine is homogeneously distributed. Typically it contains 0.01 to 20, in particular (a) compounds of the formula IV 0.05 to 10, in particular 0.1 to 5, 96 by weight of amine GCH, CH3 G1 (IV) (relative to the phosphite or phosphonite). The amine used in the process according to the invention is preferably a sterically hindered amine or one of the 45 G11 formula I (I) GCH2 CH in which n is a number from 1 to 4, G and G', 50 independently of one another, are hydrogen or methyl, G' is hydrogen, oxyl, hydroxyl, C-Cisalkyl, in which X and X’, independently of one another, are H, C-Calkenyl, C-Calkynyl, C7-Caralkyl, C-Calkyl, C-Cowhich is interrupted by one or more C1-Cisalkoxy, C-Ccycloalkoxy, -O-and unsubstituted or substituted by one or more 55 Co-Cophenylalkoxy, C1-Csalkanoyl, C-C5alkenoyl, hydroxyl groups, or is C-Cohydroxyalkyl, and X is C1-Cisalkanoyloxy, benzyloxy, glycidyl or a group C-Coalkyl, Ca-Coalkyl which is interrupted by one or -CHCH(OH)-Z, in which Z is hydrogen, methyl or more -O-and unsubstituted or substituted by one or more phenyl, G' being preferably H, C-Calkyl, allyl, hydroxyl groups, or is -(CH2)-NX'X', or benzyl, acetyl or acryloyl and C-Cohydroxyalkyl, or in which X’ and X together are 60 G12 being, in the case where n is 1, hydrogen, -(CH2)-, -CH-O-CH- or -CH C-Calkyl which may be interrupted by one or more NX'CH-, m being an integer from the range 4 to 6 and oxygen atoms, cyanoethyl, benzyl, glycidyl, a monova X' and X’ being as defined above. lent radical of an aliphatic, cycloaliphatic, araliphatic, The sterically hindered amine is in general a cyclic unsaturated or aromatic , carbamic acid sterically hindered amine, in particular a compound from the 65 or phosphorus-containing acid or a monovalent silyl series of polyalkylpiperidine or piperazine derivatives con radical, preferably a radical of an aliphatic carboxylic taining a group of the formulae II or III acid having 2 to 18 C atoms, a cycloaliphatic carboxy 5,534,645 S 6 lic acid having 7 to 15 C atoms, an O, B-unsaturated G' as a divalent radical of a dicarbamic acid is, for carboxylic acid having 3 to 5 C atoms or an aromatic example, a hexamethylenedicarbamic acid or a 2,4- carboxylic acid having 7 to 15C atoms it being possible toluylenedicarbamic acid radical. for the carboxylic acid to be substituted in each case in the aliphatic, cycloaliphatic or aromatic portion by 1 to Preference is given to compounds of the formula IV in 3 groups -COOZ’’, in which Z' is H, C, -Coalkyl, which G is hydrogen, G' is hydrogen or methyl, n is 2, and C-Calkenyl, C-C cycloalkyl, phenyl or benzyl, G' is the diacyl radical of an aliphatic dicarboxylic acid in the case where n is 2, C-C alkylene, having 4-12 C atoms. C-Calkenylene, xylylene, a divalent radical of an Examples of polyalkylpiperidine compounds from this aliphatic, cycloaliphatic, araliphatic or aromatic dicar 10 class are the following compounds: boxylic acid, dicarbamic acid or phosphorus-contain ing acid, or a divalent silyl radical, preferably a radical 1) 4-hydroxy-2,2,6,6-tetramethylpiperidine of an aliphatic dicarboxylic acid having 2 to 36 C atoms, a cycloaliphatic or aromatic dicarboxylic acid 2) 1-allyl-4-hydroxy-2,26,6-tetramethylpiperidine having 8-14 C atoms, or an aliphatic, cycloaliphatic or 3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine aromatic dicarbamic acid having 8-14 C atoms, it 15 4) 1-(4-tert-butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetrameth being possible for the dicarboxylic acid to be substi ylpiperidine tuted in each case in the aliphatic, cycliphatic O 5) 4-stearoyloxy-2,26,6-tetramethylpiperidine aromatic portion by 1 or 2 groups -COOZ’’, 6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine in the case where n is 3, a trivalent radical of an aliphatic, 7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine cycloaliphatic or aromatic tricarboxylic acid, which 20 8) 1,2,2,6,6-pentamethylpiperidin-4-yl 3-(3,5-di-ten-butyl may be substituted in the aliphatic, cycloaliphatic or aromatic portion by -COOZ', an aromatic tricar 4-hydroxyphenyl)propionate bamic acid or a phosphorus-containing acid, or a triva 9) di(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)maleate lent silyl radical, and 10) di(2,2,6,6-tetramethylpiperidin-4-yl) succinate in the case where n is 4, a tetravalent radical of an 25 11) di(2,2,6,6-tetramethylpiperidin-4-yl)glutarate aliphatic, cycloaliphatic or aromatic tetracarboxylic 12) di(2,2,6,6-tetramethylpiperidin-4-yl) adipate acid. 13) di(2,2,6,6-tetramethylpiperidin-4-yl) sebacate The carboxylic acid radicals mentioned include in each 14) di(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate case radicals of the formula (-CO).R, the meaning of n 15) di(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) seba being given above and the meaning of R being apparent 30 from the definition given. Cate Examples of C-Calkyl substituents, if present, are 16) di(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, 17) 1-hydroxy-4-3-cyanoethyloxy-2,2,6,6-tetramethylpip n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl eridine or n-dodecyl. 35 18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate Examples of G' or G' as C-Calkyl can be the 19) trimelitic acid tri-(2,2,6,6-tetramethylpiperidin-4- abovementioned groups and in addition, for example, yl) n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. 20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine Examples of G' as C-Calkenyl can be 1-propenyol, 21) di(2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 40 4-ten-butyl-2-butenyl. 22) di-(1,2,2,6,6-pentamethylpiperidin-4-yl) dibutylma G' as C-Calkynyl is preferably propargyl. lonate G' as C-Caralkyl is in particular phenethyl and espe 23) di(1,2,2,6,6-pentamethylpiperidin-4-yl) butyl (3,5-di cially benzyl. tert-butyl-4-hydroxybenzyl)malonate Examples of G' as C-Csalkanoyl are formyl, propionyl, 45 24) di(1-octyloxy-2,26,6-tetramethylpiperidin-4-yl) seba butyryl, octanoyl, but preferably acetyl and as Cate Calkenoyl in particular acryloyl. 25) di(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) G' as a monovalent radical of a carboxylic acid is, for sebacate example, an acetic acid, caproic acid, Stearic acid, acrylic 26) hexane-1, 6 '-bis(4-carbamoyloxy-1-n-butyl-2,26,6- acid, methacrylic acid, benzoic acid or 3-(3,5-di-tert-butyl 50 tetramethyl-piperidine) 4-hydroxyphenyl)propionic acid radical. 27) toluene-2', 4'-bis(4-carbamoyloxy-1-n-propyl-2,2,6,6- G' as a monovalentsilyl radical is, for example, a radical tetramethyl-piperidine) of the formula-(CH2)-Si(Z)Z", in whichjis an integer 28) dimethylbis(2,26,6-tetramethylpiperidine-4-oxy)silane from the range 2 to 5, and Z and Z", independently of one 29) phenyltris(2.2,6,6-tetramethylpiperidin-4-oxy)silane another, are C-C or C-C alkoxy. 55 30) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phos G' as a divalent radical of a dicarboxylic acid is, for phite example, a malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, maleic acid, iraconic acid, 31) tris(1-propyl-2,26,6-tetramethylpiperidin-4-yl) phos phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, phate butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonic acid or 60 32) bis-(1,2,2,6,6-pentamethylpiperidin-4-yl) phenylphos bicycloheptenedicarboxylic acid radical. phonate G' as a trivalent radical of a tricarboxylic acid is, for 33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine example, a trimellific acid, citric acid or nitrilotriacetic acid 34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperi radical. dine G' as a tetravalent radical of a tetracarboxylic acidis, for 65 35) 4-hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpi example, the tetravalent radical of butane-1,2,3,4-tetracar peridine boxylic acid or of pyromellitic acid. 36) 1 -glycidyl-4-hydroxy-2,26,6-tetramethylpiperidine 5,534,645 7 8 (b) compounds of the formula (V) A C-C2cycloalkylene is in particular cyclohexylene. Preference is given to compounds of the formula V in GCH2 CH3 Gl (V) which n is 1 or 2, G is hydrogen, G13 G' is hydrogen or methyl, G' is hydrogen, C-Calkyl 5 or a group of the formula Gill- N G14

GCH, CH Gl GCH F. in which n is 1 or 2, G, G and G' have the meaning 10 given under (a), G' is hydrogen, C-Clalkyl, Gll-N C-Caydroxyalkyl, C-C cycloalkyl, C7-Caralkyl, C-Calkanoyl, Ca-Calkenoyl, benzoyl or a group of GCH CH the formula 2 3 15 GCH2 CH G1 G11-N and G' is hydrogen or C-C2alkyl in the case where n=1 and C-Calkylene or 1-oxo-C-Calkylene in the case 20 where n is 2. GCH, CH Examples of polyalkylpiperidine compounds of this class 2 3 are the following compounds: and 37) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethyl G' is, in the case where n is 1, hydrogen, C1-C1salkyl, 25 ene-1,6-diamine Ca-Calkenyl, C-C cycloalkyl, 38) N,N'-bis(2,2,6,6-tetramethylpipefidin4-yl)hexamethyl C-C alkyl which is substituted by a hydroxyl, cyano, ene-1,6-diacetamide alkoxycarbonyl or carbamide group, or is glycidyl, a 39) bis(2,2,66-tetramethylpiperidin-4-yl)amine formulagroup of the-CONH-Z, formula-CH, in which CHOH)-ZZ is hydrogen, or methylof the 494-benzoylanino.2266etramethylpiperidineN,N'-bis(2,26,6-tetramethylpiperidin4-yl)-N, in orthe phenyl; case where n is 2, C-Calkylene, Co-Carylene, 42clohexyl-2-hydroxypropyIEEE tS'Estelameh lpiperidin-4-yl)-N,N'-dic GN yl)-N, y xylylene, CH2CH(OH) C2 or a group 43) NN'-bis(52.66 tetramethylpiperidin-4-yl)-p-xylylene -CH-CH(OH)-CH-O-D-O-, in which Dis diamine C-Coalkylene, 35 44) N,N'-bis(2,2,6,6-tetramethylpipefidin4-yl)succinedia C-Clsarylene, C-Cacycloalkylene, or, provided G' is mide not alkanoyl, alkenoyl or benzoyl, G' can also be 45) di(2,2,6,6-tetramethylpipefidin-4-yl) N-(2,2,6,6-tetram 1-oxo-C-C-alkylene, a divalent radical of an ali- ethylpipefidin4-yl)-Baminodipropionate aminodipropi phatic, cycloaliphatic or aromatic dicarboxylic acid or Onate dicarbamic acid or else the group -CO-, or, in the 40 46) the compound of the formula case where n is 1, G' and G' together can be the divalent radical of an aliphatic, cycloaliphatic or aro matic 1,2- or 1,3-dicarboxylic acid. CH, CH3 C-C2Alkyl or C-Cisalkyl substituents, if present, have C4H9 the meaning already given under (a). 45 C-C,Cycloalkyl substitutents, if present, are in particu CH-N N-CH-CH(OH)-CH2-O lar cyclohexyl. Gas C-Caralkyl is in particular phenylethyl or espe cially benzyl. G' as C-Chydroxyalkyl is in particular CH, CH 2-hydroxyethyl or 2-hydroxypropyl. 50 Examples of G' as C-Cisalkanoyl are propionyl, CH-C-CH3 butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, butacryloyl. preferably acetyl and, as C-Calkenoyl, in particular CH, CH3 O Examples of G' as C-Csalkenyl are allyl, methallyl, 55 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl. Examples of G' as C-C alkyl which is substituted by a CH - N N -CH2-CH (OH) -CH2 - O hydroxyl, cyano, alkoxycarbonyl or carbamic group can be th. 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxy carbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonyl- 60 CH, CH propyl or 2-(dimethylaminocarbonyl)ethyl. Examples of C-Calkylene substituents, if present, are , propylene, 2,2-dimethylpropylene, tetramethyl ene, hexamethylene, octamethylene, decamethylene or 47) 4-bis(2-hydroxyethyl)amino-1,2,2,6,6-pentamethylpi dodecamethylen. 65 peridine Examples of C-Carylene substituents, if present are o-, 48) 4-(3-methyl-4-hydroxy-5-ten-butylbenzamido)-2,26,6- m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene. tetramethylpiperidine 5,534,645 9 10 49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine benzyl, glycidyl or C-Calkoxyalkyl and G' is, in the case where n is 1, hydrogen, C1-C12alkyl, C-Calkenyl, C7-Caralkyl, Cs-C,cycloalkyl, (c) compounds of the formula (VI) C-Chydroxyalkyl, C-C6alkoxyalkyl, C-Caryl, glycidyl or a group of the formula-(CH2)p-COO-Q GCH, CH3 G (VI) 5 or of the formula-(CH2)p-O-CO-Q, in which p is O 1 or 2 and Q is C-Calkyl or phenyl, and, in the case G1-N G15 where n is 2, C-Calkylene, Ca-Calkenylene, C-C arylene, a group -CH2-CH(OH)-CH2 O 10 O-D-O-CH2CH(OH)-CH-, in which D is GCH, CH C-Coalkylene, C-Carylene, C-Cacycloalkylene, Or 2 group in which n is 1 or 2, G, G and G' have the meaning -CHCH(OZ)CH-(OCH-CH(OZ)CH)-, in given under (a), and G' is C-Csalkylene or -hydroxy which Z is hydrogen, C-Calkyl, allyl, benzyl, alkylene or C-Cacyloxyalkylene, in the case where C-Calkanoyl or benzoyl, T and T2, independently n is 1, and is the group (-CH2)2C(CH2-), in the case 15 of one another, are hydrogen, C1-Calkyl or unsub where n is 2. stituted or halogen- or C-Calkyl-substituted Examples of Gas C-Calkylene or -hydroxyalkylene C-Caryl or C-Caralkyl, or T and T together with are ethylene, 1-methylethylene, propylene, 20ethylpropy the C atom linking them form a C-Cacycloalkane lene or 2-ethyl-2-hydroxymethylpropylene. ring. G' as C-Cacyloxyalkylene is, for example, 2-ethyl 20 Examples of Ci-Calkyl substituents, if present, are 2-acetoxymethylpropylene. methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, Examples of polyalkylpiperidine of this class axe the n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl following compounds: or n-dodecyl. Examples of C-Calkyl substituents, if present, can be 50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro5.5unde 25 C2C the abovementioned groups and in addition, for example, 51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro5.5 n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. undecane Examples of C-Calkoxyalkyl substituents, if present, 52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5de are methoxymethyl, ethoxymethyl, propoxymethyl, tert-bu Cai toxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert 53) 9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentam 30 butoxyethyl, isopropoxyethyl or propoxypropyl. ethyl-1,5-dioxaspiro5.5undecane - Examples of G' as C-Csalkenyl are 1-propenyl, allyl, 54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tet methallyl, 2-butenyl or 2-pentenyl. ramethyl-1,5-dioxaspiro[5.5-undecane G, T, and T, as C-Caralkyl are in particular phenethyl 55) 2,26,6-tetramethylpiperidine-4-spiro-2 '-(1, 3'-diox or especially benzyl. A cycloalkane ring formed by T and ane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4"-(2", 2", 6", 35 T together with the C atom can be, for example, a cyclo pentane, cyclohexane, cyclooctane or cyclododecane ring. 6"-tetramethylpiperidine). Examples of G' as C-Chydroxyalkyl are 2-hydroxy (d) Compounds of the formulae VIIAt, VIIB and VIIC, ethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl. preference being given to compounds of the formula G, T, and T, as Co-Coaryl are in particular phenyl, C 40 or B-naphthyl, which are unsubstituted or substituted by VIIC halogen or C-C alkyl. G16 (VIIA) Examples of Gas C-Clalkylene are ethylene, propy GCH, CH3 Gl lene, 2,2-dimethylpropylene, tetramethylene, hexamethyl N-Coco ene, octamethylene, decamethylene or dodecamethylene. 45 G' as C-Calkenylene is in particular 2-butenylene, Gill-N 2-pentenylene or 3-hexenylene. Examples of G' as Co-Carylene are o-, m- or p-phe C-N G17 nylene, 1,4-naphthylene or 4,4'-diphenylene. GCH, CH3 Examples of Z as C-Calkanoyl are propionyl, butyryl, 50 octanoyl, dodecanoyl, but preferably acetyl. GCH, CH, Gl T (VIIB) D 2S C-Coalkylene, C-Carylene O O-C-T, C-Cacycloalkylene is as defined under (b). Examples of polyalkylpiperidine compounds of this class Gil-N are the following compounds: 55 N-C= 56) 3-benzyl-1,3,8-triaza-7,799-tetramethylspiro4.5de GCH2 CH H cane-2,4-dione 57) 3-in-octyl-1,3,8-triaza-7,799-tetramethylspiro[4.5de GCH, CH3 G1 T (VIIC) cane-2,4-dione O-C-T, 58) 3-allyl-1,3,8-triaza-1,7,799-pentamethylspiro4.5de cane-2,4-dione G11-N 59) 3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5 5-N G17 decane-2,4-dione GCH CH O F. 60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro4.5decane 65 2,4-dione in which n is 1 or 2, G, G and G' have the meaning 61) 2-isopropyl-7,799-tetramethyl-1-oxa-3,8-diaza-4-ox given under (a), G' is hydrogen, C-C alkyl, allyl, ospiro-4.5 decane 5,534,645 11 12 62) 2,2-dibutyl-7,799-tetramethyl-1-oxa-3,8-diaza-4-ox -continued ospiro-4.5-decane G1 CH 63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21 -oxodispiro G2 CHG 5.1.11.2 -heneicosane 64) 2-butyl-7,799-tetramethyl-1-oxa-4,8-diaza-3-oxospiro 5 -E-(A)-N N-Gil 4.5decane 7 CHG and preferably: CH 65) 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,99-tetramethylspiro in which G and G' are as defined under (a) and G' and 4.5-decane-2,4-dione 10 G' are hydrogen, methyl or together are a substiment or the compounds of the following formulae: =O,

CH, CH3 66) C O O EC - NH CHs C- N-CHCH(OH)CH-OCH-CH(OH)CH2-N- C CH, CH3X s s CH, CH CH, CH3 CH, CH 67) NH re. CO O-C - NH CH3-N N-CH - N-(CH2)6-N- C CH, CH O CH3 CH CH3 CH CH, CH3 68) NH - C-O OcC - NH

NH NH

Cr N CH N - C CH, CH s b CH, CH3 CH, CH CH2CH2 69) (CH2) CHCH C - N -CH2CH2COOC12H25 CH,-X CH s (e) Compounds of the formula VIII, which on their part 45 E is -O- or -NG-, are preferred, A is C-Calkylene or -(CH2)-O- and X is 0 or 1, (VIII) G' is hydrogen, C-Clalkyl, C-Chydroxyalkyl or 1s 50 C6-C7cycloalkyl, G' is identical to G' or one of the groups -NG'G, -OG°, -NHCHOG' or -N(CHOG?), G' is identical to G' or G' in the case where n is 1, and is a group-E-B-E-, in which B is C-Calkylene in which n is 1 or 2 and G' is a group of one of the 55 or C-Calkylene which is interrupted by 1 or 2 formulae -N(G')- groups, in the case where n is 2, G' is C-Calkyl, cyclohexyl, benzyl, H C-Chydroxyalkyl or a group of the formula pH-k 6 CH3 G1 / O GCH -E-(A)-CH N-G 11 Gl-N CHG CH GCH r 65 CH 5,534,645 13 14 G' is C-Calkyl, cyclohexyl, benzyl, is a group fo the formula C-Chydroxyalkyl, and H3C CH3 G’ is hydrogen, C-Calkyl or phenyl, or G' and G' 5 (H. N together are C-Calkylene or -oxaalkylene, for Gll-N11 N- S example N N HC CH N -CH2CH2 CHg-N 10

-CHCH o, HC CH HC N CH or a group of the formula 15 Gil -CHCH Any C-Calkyl substituents present are, for example, N-G 11 methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl -CHCH 20 or n-dodecyl. Any C-Chydroxyalkyl substituents present are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypro pyl, 2-hydroxybutyl or 4-hydroxybutyl. Examples of A as C-Calkylene are ethylene, propylene, as 2,2-dimethylpropylene, tetramethylene or hexamethylene. Examples of G' and G' together as C-Calkylene or oxaalkylene are tetramethylene, pentamethylene or 3-oxap entamethylene. Examples of polyalkylpiperidine compounds of this class are the compounds of the following formulae: (H, 70) HC N CH HC CH

N-C4H9 N 1 S. N cars N snatch, N(C4H9)2 71) HC CH3 HC CH3 N 1 N CH5-N –ls -- N N-C2H5 N CH5 CH5 HC CH HC CH l HC CH3 72) N 1 N ls ls where R= -NH-CHCH2CH2-0 N-CH R N R HC CH

5,534,645 17 18 -continued CH R R CH 77)

HC CH C4H9 where Ris -14 N S- N-CH

N S. N s H3C CH3 CH9-N

H3C CH3 H N CH3 CH H3C CH 78) or it NH CH17 -N aS N H3C CH3 1. C8H17- N NH-(CH2)3

H3C CH H N CH H 2 fiction 79) H3C N CH H3C CH

HC CH ch HC 3 3 N nS N 3 CH3

HO-CH2CH2-N -- N els N N-CH2CH-OH C4H9 C4H9 H3C CH H3C CH3 (H-CH=CH, 80) HC N CH H3C CH3

N-CHg

H3C CH N 1s N HC CH3

HCEHC-HC-N s N els N N-CH-CH=CH C4H9 C4Hg H3C CH3 H3C CH3 (f) oligomers or polymer compounds whose recurring polyureas, polyaminotriazines, poly(meth)acrylates, structural unit contains a 2,26,6-tetraalkylpiperidine radical of the formula III, in particular polyesters, 65 poly(meth)acrylamides and copolymers thereof con polyethers, polyamides, polyamines, polyurethanes, taining such radicals.

5,534,645 23 24 -continued R 95) N-(CH2)2-N-(CH2)2 it'

R being HC CH H3C CH3 N CH O N-H, - ? S-N N-H N N HC CH s HC CH CH-N 15 and m is a number from the range 2 to 200; or copolymers whose recurring unit is composed of 2 units HC CH CH 3. H3C CH3 20 CECH or a branching of the chain and 1 unit of each R 25 -(CH2)2-N m" - - - - - N N m' and m" are each an integer from the range 0-200 on condition that m'+m" is m. 30 CH CH Further examples of polymer light stabilizers are reaction products of compounds of the formula CH CH3 CH3 CH chi-ch) (g) Compounds of the formula DX O-C-CH 35 CH (IX) HN GCH2 Gl

Gil-N EO CH3 CH (-NH 40 with epichlorohydrin; GCH2 CH polyesters obtained by reaction of butane-1,2,3,4-tetra in which G, G and G' are as defined under (a). carboxylic acid with a alcohol of the 45 Preference is given to compounds of the formula IX in formula which G is hydrogen or methyl and G' is hydrogen or methyl. CH O-CH CH-O CH Examples of such compounds are: HO / \ / V OH CH-C-CH C CH-C-CH | \ / \ / 50 96) 2,26,6-tetramethyl-4-piperidone (triacetoneamine) CH3 O-CH CH-O CH 97) 1,2,2,6,6-pentamethyl-4-piperidone 98) 2,2,6,6-tetramethyl-4-piperidone 1-oxide the carboxyl side chains of which originating from the 99) 2,3,6-trimethyl-2,6-diethyl-4-piperidone tetracarboxylic acid have been esterified with 2,2,6,6- tetramethyl-4-hydroxypiperidine; 55 (h) compounds of the formula X compounds of the formula CHH (X) GCH O C / CH-i-CH-H 60 O = O = Gl-N N--G14 OCH OR r GCH, X CH,/ 65 in which about one third of the radicals R are -CH in which n is 1 or 2 and in which G and G' are as and the others are, defined under (a) and G' is as defined under (b), the 5,534,645 25 26 meanings -CONH-Z and -CH-CH(OH)- Compounds of the formula IV in which n is an integer CH-O-D-O-being excluded for G'. from the range 1 to 4, G and G' are hydrogen, and Examples of such compounds are: G' is hydrogen or C-Cisalkyl, and CH CH, CH3 100) 5 G', in the case where n is 1, is a radical of the formula CH , -(CH2)-Si(Z)Z", in which j is an integer from the SH-N NT' (amine M) range 2 to 5 and Z and Z", independently of one H-N N-CH y 7. another, are C-C alkyl or C-Calkoxy, and X / ch, CH3 10. G', in the case where n is 2, is a radical of an aliphatic CH3 CH dicarboxylic acid having 2 to 12C atoms which may be CH3 CH, CH, 101) substituted by -COOZ', Z being C-Coalkyl, CH3 O 15 G', in the case where n is 3, is a radical of an aromatic W CH-N N-CH tricarboxylic acid having 9 to 15 C atoms, CH3-N n-cil G', in the case where n is 4, is a radical of an aliphatic O CH3 tetracarboxylic acid having 8 to 12 C atoms; amines CH3 CH CH3 20 from this class which are of particular technical interest CH3 102) are those of the formulae

CH3 O W 25 CH3-N N-CH

CH, X CH3/ The following amines are particularly preferred for use in 30 the process according to the invention:

CH3 CH3 th HN O -(CH-i- OC2H5 (amine B), OC2H5 CH CH CH3 CH3 CH CH3 O O HN O-C-(CH2)3-C-O NH (amine C),

CH CH, CH3. CH3 CH CH3 CH CH O O | CH-N O-C-(CH2)-C-O N-CH (amine D),

CH CH 3 CH3 3 5,534,645 27 28 -continued CH CH CH CH H H CH, -N -CH O O CH O O CH CH CH-CH-CH-CH CH CH 3 CH (amine E), CH O O CH O O CH-N N-CH H

CH CH 3 CH3 3 CH

and esters of butane-1,2,3,4-tetracarboxylic acid with 2 A is C-Calkylene and units each of 1,2,2,6,6-penta-methyl-4-hydroxy-piperi 20 dine and CH-OH (amine F); X is 0 or 1, compounds of the formula Vin which n is 2, G and G' are G' is hydrogen, C-Clalkyl or cyclohexyl, hydrogen, G', in the case where n is 1, is identical to G' and, in G' is hydrogen or methyl and 25 G' is hydrogen or C-Csalkyl, and the case where n is 2, is a group -E-B-E-, in G' is C-Csalkylene or 1-oxo-C-Calkylene; an which B is C-Calkylene or C-Calkylene which is amine from this class which is of particular technical interrupted by 1 or 2 groups -N(G')-, interest is the compound of the formula G' is C-C2alkyl, cyclohexyl, benzyl or 30 C-Chydroxyalkyl or a group of the formula CH3 CH CH CH c HN HN--c-NH NH (amine G); CH 35 CH3 CH CH G1 CH3 CH GCH

compounds of the formula VIIC in which n is 1, G, G and Gll-N G' are hydrogen, 40 G' is hydrogen or methyl and GCH2 CH T and T together with the C atom linking them form a Cs-Cacycloalkane ring; an amine from this class or G' is a group of the formula which is of particular technical interest is the com 45 pound of the formula CH3 O CH3 NH (amine H); 50 HC CH HN l CH2 C4H9 CH O )(CH.) N CH, CH G1-N N- as N N compounds of the formula VIII in which n is 1 or 2 G 55 HC CH N and G' are a group of one of the formulae C4H9-N CH G1 CH CH, G2 CH, HC CH 60 HC N CH3; -E-CH N-G11 or -E-(A)-N N-G11 h

CHCH CH, CH 65 amines from this class which are of particular technical interest are the compound 76) =amine J) described G' is hydrogen or methyl, above and the compounds of the formulae G' and G' are hydrogen or together are a substituent=O, E is -O- or -NG-, 5,534,645 29 30 CH3 CH3 CH3 CH3 HN 29 CH N ><- H 1N- N N CH 1N- N n C dH, ;I, dH, CH CH, CH, N 1s N and N 1s N

N N as N as CH2 CH2 CH2 CH2 ch, 1 n (H, CH-1 n (H, Os- N N O OS N N O aCH listsCH, CH, 1 YN 1) CH, CH3-li N CH3 CH,al N CH3 (amines K and L); CH CH3

compounds of the formula X in which n is 2, G' is (l) of HN-A-NH-A-NH with hydrogen or methyl and G' is C-Clalkylene; 25 an amine from this class which is of particular technical CH3 CH3 l CH3 CH interest is the compound 100) =amine M) described HN N n N NH above; and CH oligomer compounds having 2 to 10 recurring units, such CH s 2N CH as are obtainable by reaction of 30 3 N CH3 CHg C4H9 CH3 CH3 and Br-A-Br, in which A is C-Calkylene; G24-N O-H, 35 (m) of compounds of the formula CH3 CH CH2-(CH2)9 CH3 CH O-C-CH in which G' is C.-Chydroxyalkyl with an aliphatic HN C-Cadicarboxylic acid or a suitable reactive deriva- C-NH tive, such as the diester, dichloride or anhydride; CH, CH (j) of a linear oligomer polyester obtained by reaction of 3 3 O a dialcobol with butane-1,2,3,4-temacarboxylic acid with 2,2,6,6-tetramethyl-4-hydroxypiperidine; with epichlorohydrin;

CH CH3 CH CH C N C1 CH3 NH CH, CH3 NH ch, with 1 i? N s N , N HN A NH / N T3

55

60 (n) of shCCH with 4 - -o- in which A is C-Calkylene, T is C-Cisalkylene or 6 cyclohexyl, T is hydrogen or C-Cisalkyl, or T and 5 T together are Ca-Calkylene or C-Coxaalkyylene; 5,534,645 31 32 -continued - HC CH3 FO , N N-H CH 5 CH CH HC CH3 CH3 NH 10 and m is a number from the range 2 to 10; and those of the formula oligomer amines of particular technical interest include (o) those of the formulae (m again is a number from the CH range 2 to 10) 15 CH-5-ch-h s O = O = OCH OR t 20 in which about one third of the radicals R are -CH and the other are

CH CH3

H--O N-CH2-CH2-O-C-CH2-CH2-C-HO-CH3(amine N); CH C 72

CH3 NH CH, CH3 HN CH3 CH NH CH, CH3 NH CH3 CH3 CH, CH3 CH CH3 CH, CH3 CH

N HN (CH2)6-N 2 S-N (CH2)6 N H N s N (H, CH HN--CH-i-CH, CH CH

(amine P);

CH3 NH CH, CH3 HN CH3 CH3 NH CH3 CH3 NH CH CH3 CH, CH3 CH3 CH3 CH3 CH CH3

N HN (CH2)6-N 2 -N (CH2)6-N H N s N N D (amine Q) 5,534,645 33 34

-continued ch CH-C-CH-CH (anine R) O = O = OCH OR

in which about one third of the radicals R are -CH and the others are 15 CH, CH C-(c.) O-C-CH HC CH3 HN

N-H; C-NH 20 CH, CH s HC CH with epichlorohydrin (amine W). a linear polyester having 2 to 10 recurring units obtained The oligomer amines are often mixtures of compounds 25 which differ from one another with respect to their chain by reaction of butane-1,2,3,4-tetracarboxylic acid with length. a dialcohol of the formula Of particular importance is the use of the amines A, B, C, HO CH O-CH, CH-O CH3 OH D, E, F, G, H, J, K, L, M, N, O, P, Q, R, S, T, U, V and W N | / \ / \ | / 30 specified above. CH-C-CH / C\ CH-C-CH/ s In the process according to the invention, preference is CH O-CH CH-O CH given in particular to the addition of those amines whose molecular weight or average molecular weight M is in the in which the end groups and side chains are formed by range 300 to 10,000, in particular in the range 1000 to esterificadon of the free carboxyl groups with 2,2,6,6- 35 10,000. Of these, those amines whose molecular weight or tetramethyl-4-hydroxypiperidine (amine S); a copoly average molecular weight M is in the range 1500 to 10,000, mer whose recurring units are composed of 2 units for example in the range 2000 to 7500 should again be mentioned in particular. The amines of higher molecular weight are in particular sterically hindered amines. (H, 40 CECH The amines mentioned are known compounds; many of them are commercially available. In the process according to the invention preference is given to stabilization of phosphites or phosphonites having and 1 unit each of 45 one of the formulae (1) to (7), OR (1) / - - and ( )- Ri'-Y'-P N N N OR' OR." (2) CH CH3 / CH NH CH A' X-P N OR' f the reaction product of HN-(CH2)-NH-(CH2)- 55 NH, with (3) Cl CH CH3 1s CH CH nS HN N N NH 60 CH 3 s els CH O (4) CH N CH D' '-o-R, CHg CHg / 65 CH O and Br-(CH2)-Br (amine U); and the reaction prod p uct of the compound of the formula 5,534,645 35 36 -continued E, in the case where y is 3, is a radical of the formula o (5) RC(CHO), R-o-' P-O-R', Q is the radical of an at least z-valent alcohol or phenol, \ / this radical being attached to the O 5 Patom(s) via the alcoholic or phenolic O atom(s); (6) R, R and R', independently of one another, are alkyl having 1 to 30 carbon atoms; alkyl which is substituted by halogen-COOR,-CN or -CONR'R'' and has 1 to 18 carbon atoms; alkyl which is interrupted by -S-, -O- or -NR, and has 2 to 18 carbon / atoms; phenyl-C-Calkyl; cycloalkyl having 5 to 12 R15 carbon atoms; phenyl or naphthyl, phenyl or naphthyl R15 each of which is substituted by halogen, 1 to 3 alkyl radicals or alkoxy radicals having a total of 1 to 18 \ 15 carbon atoms or by phenyl-C-Calkyl, or is a radical O R14' of the formula

20 O 7 Yo (7) -(CH2) OH,

o P--Q R / 25 CH O in which m is an integer from the range 3 to 6 ( 2. R or the radicals R' independently of one another, are R16' / y-1 hydrogen; alkyl having 1 to 18 carbon atoms; in which the indices are integers and cycloalkyl having 5 to 12 carbon atoms; or phenylalkyl n' is 2, 3 or 4; p is 1 or 2; q is 2 or 3; ris 4 to 12; y is 1, 30 having 1 to 4 carbon atoms in the alkyl moiety; 2 or 3; and Z is 1 to 6; R's and R, independently of one another, are hydrogen; A, in the case where n' is 2, is alkylene having 2 to 18 alkyl having 1 to 8 carbon atoms or cycloalkyl having carbon atoms; alkylene which is interrupted by-S-, 5 or 6 carbon atoms; -O- or -NR- and has 2 to 12 carbon atoms; a R, and R, in the case where q is 2, are, independently radical of one of the formulae 35 of one another, C-C alkyl or together are a 2,3- dehydropentamethylene radical; and R5' R5' R', and R's, in the case where q is 3, are methyl; the B substituents R', independently of one another, are 40 hydrogen; alkyl having 1 to 9 carbon atoms or cyclo hexyl, the substituents R's, independently of one another, are R6 R6 hydrogen or methyl; and R16 is hydrogen or C-C alkyl and, in the case where B' 45 several radicals R's are present, the radicals R are identical or different; X and Y are each a direct bond or -O-; and Z is a direct bond; -CH-, -COR")- or -S-. or phenylene; Particular preference is given to a process in which the A, in the case where n is 3, is a radical of the formula 50 phosphite or phosphonite is one of the formulae (1), (2), (5) -CH2--1-, or (6), in which A, in the case where n' is 4, is a radical of the formula n' is 2 and y is 1 or 2; CCH.); A' is alkylene having 2 to 18 carbon atoms; p-phenylene A", in the case where n' is 2, has the meaning of A'; 55 or p-biphenylene; B' is a radical of the formula -CH2-, -CHR-; E, in the case where y is 1, is C-C alkyl, -OR or -CRR-., -S- or a direct bond; or is fluorine; and, in the case where y is 2, is p-biphenylene; C-C cycloalkylidene, or is cyclohexylidene which is substituted in the 3, 4 and/or 5 position by 1 to 4 R, R2 and R, independently of one another, are alkyl C-C alkyl radicals; 60 having 1 to 18 carbon atoms; phenyl-C-Calkyl; D', in the case where p is 1, is methyl and, in the case where cyclohexyl, phenyl; phenyl which is substituted by 1 to p is 2, is -CHOCH-; 3 alkyl radicals having a total of 1 to 18 carbon atoms; E", in the case where y is 1, is alkyl having 1 to 18 carbon the substituents R', independently of one another, are atoms, phenyl, a radical of the formula -OR' or halo- hydrogen or alkyl having 1 to 9 carbon atoms; gen, is R's is hydrogen or methyl; E, in the case where y is 2, is a radical of the formula X is a direct bond; -O-A"-O-; Y" is -O-, and 5,534,645 37 38 Z is a direct bond or -CH(R)-. R's is hydrogen, Of particular technical interest is a process for stabilizing X" is a direct bond; a phosphite or phosphonite of one of the formulae (1), (2), (5) or (6), in which Y" is -O-, and n' is 2 and y is 1; Z is a direct bond, -CH,- or -CH(CH4)- A' is p-biphenylene; Particular preference is given to phosphites, in particular E is C-Calkoxy; those of the formulae (1) and (5). R, R and R', independently of one another, are phenyl which is substituted by 2 or 3 alkyl radicals having a 10 The following compounds are examples of phosphites and total of 2 to 12 carbon atoms, phosphonites whose stability to hydrolysis can be improved the substituents R14, independently of one another, are particularly advantageously by the process according to the methyl or tert-butyl;

CH CH (Ph-1) N \ CH3 H: Jc.1 CH, O CH3 CH 3 N CH P-O C-CH3; / CH- O CH CH CH CH3 C1 CH, 1 \ CH (Ph-2) CH CH Sc (H, CH CH-C O CH ch P-O C-CH ch / CH CH - O CH NC CH /YCH, CH CH C CH, 1 \ CH CH CH (Ph-3) CH ne' \ NCH CH -C (H, 3 3 CH- O O CH3 N / CH P P ch / N CH - O O C-CH

CH CH CH CH -C / 3 3 NC CH, 1 \ /YoH, CH CH CH (Ph-4) CH (H, CH Y e." CH O N (H, CH P-O C-CH3; / CH- O CH CH CH C1 CH CH, 1 \ 5.534,645 39 40 -continued C(CH3)3 C(CH3)3 (Ph-5) O O / \ (CH3)3C O-P f -O C(CH3)3; Yo O C(CH3)3 C(CH3)3 (Ph-6) O O / \ CH3 O-P P-O CH3; \ / O O C(CH3)3 C(CH3)3 CH3 (Ph-7) \ C / CH3 1. CH (H, O (-CH / CH CHO-P\ CH-CH) vs. O -CH CH CH NC /YoH, CH CH (Ph-8) \ C 1. CH3 1. CH3 (H, ngHg O f -CH H5C2-CH / CH CH-O-P CH2 \ ch O (-CH CH CH NC/ NYoH, CH3

The phosphites and phosphonites mentioned are known 50 atmospheric humidity. An organic phosphite or phosphonite compounds; some of them are commercially available. stabilized against hydrolysis, such as obtainable by the Some commercial phosphites and phosphonites are process described above, is therefore also provided by this present as mixtures of compounds or in prestabilized form. invention. In most cases, an mine, for example a lower alkylamine or The examples which follow illustrate the process accord triisopropanolamine, has been admixed to these compounds 55 ing to the invention further. All parts or percentages given in a conventional manner in a concentration of about 1% as prestabilization. The hydrolytic stability of such products are, just as in the remaining description and in the claims, by can also be significantly improved by the process according weight, unless stated otherwise. As far as percentages are to the invention. The products of the process according to the based on phosphite or phosphonite, they refer to phosphite invention can advantageously be used as stabilizers for or phosphonite in the melt unless a different reference organic material, in particular organic polymers, for 60 amount is expressly stated. The structural formulae of the example synthetic polymers, against the damaging effect of phosphites, phosphonites and amines used in the examples heat, oxygen and/or light. Examples of such polymers can be are, if not stated directly, listed above in the text. seen, for example, from U.S. Pat. No. 4855 345, column 4, EXAMPLE 1. line 63, up to column 7, line 54. The phosphites and phosphonites stabilized according to 65 300 g of phosphite Ph-1 are brought to 70-75° C. the invention are distinguished by their excellent resistance together with 225 g of isopropanol, 2.25g of toluene and 30 to hydrolysis and have a long shelf life even at high g of amine A (striisopropanolamine) with stirring. The 5,534,645 41 42 resulting homogeneous melt is added over a period of about In Table 1 and the following tables, the column headings 1 hour with stirring to a suspension of 20 g of Ph-1 in 450 have the following meaning: g of isopropanol and 20 g of amine A whose temperature during this process is maintained at 20-30°C. by cooling. The mixture is then cooled to 10°-15° C. and stirredo in this % intr; phosphiteamount of or amine phosphonite in the melt, in the % melt;given is based on temperature range for another 3 hours. The crystalline % cont.: tional in the phosphite or phosphonite after O crystallization; product is then filterat off and dried at 60° C. under reduced Solvl, 9%: in solvent for the melt, % given is based on pressure. phosphite or phosphonite in the melt; Elemental analysis gives an amine A content of 1.2% by 10 Solv2, 96: phosphitefurther solvent orphosphonite for the melt, in %the given melt; is based on weight (relative to phosphite) for the dry product. TfoC.: temperature range of the melt or crystallization A sample serving as comparison is crystallized without medium, o w Solvent, %: solvent for crystallization medium, % given is adding3. an amine based on phosphite or phosphonite in the melt; Equal mounts of the product are then subjected to the 15 Fo isopropanol; followingo tests of resistance to hydrolysis:re MeOH: methanol,toluene; a) During storage, the time is measured in which upon % seed cr: initial charge of phosphite as seed crystals, % visual inspection the initial powder starts to deliquesce EY is based on phosphite or phosphonite in the (transition p-c) and the time which expires until the % amine: initial charge of amine in the crystallization material is liquid (transition c-1). At the last-mentioned 20 medium, % given is based on phosphite or point in time, the weightincrease during the duration of phosphonite in the melt; t ticed; th ight i indi % dec. (8 h): decomposition of the sample after 8 h in % S orage is noticed; the weig 1ICeaS gives a 11- (100% = phosphite content at the beginning of the cation of the water absorption of the material. The test test) test b)); conditions (temperature and atmospheric humidity dur- E. % W) time in St. WG deiti E. G R ingo storage) are given in the particular examples. 25 C- O solution).title in hours Numbers utti samplegiven in has brackets: become weight uquld clear b) After 8 hours of storage at 70° C. and 100% atmo- increase of the sample compared with the spheric humidity, the phosphite Ph-1 content is deter- beginning of the test (% by weight is based on the mined by liquid chromatography. beginning of storage = water content) test a)). The results can be seen from Table 1.

TABLE 1. Stabilization of bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite (Ph-1) MELT CRYST. MEDUM TEST RESULTS Ex. % % Solvent, % % % dec. c-h No. Amine intr. cont. Solv1, 26 Solv2, 9% TroC. % seed cr. amine TfoC. (8 h) p-ch (% W) Compari- none 0 - 0 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 85 (n.2 h) 005 37 (2.5) SO 1. A. O 1.2 IPA, 75 TOL, 0.75 70-75 IPA, 150 6.7 6.7 20-30 5 056 126 (2.2) 2 A 20 2.7 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 3.2 110 171 (2.0) 3 Q 20 3.5 IPA, 75 TOL, 0.75 70-75 IPA, 150 0 0. 20-30 5 025 >120 4 P 5 1.0 IPA, 75 TOL, 0.75 70-75 IPA. 150 O 0 20-30 3.4 056 144 (1.5) 5 P 10 2.7 IPA. 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 3. 160 220 6 P 20 3.8 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 1.0 200 312 (1.1) 7 C 20 2.9 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 15.2 040 72 (2,7) 8 J 10 1.5 IPA, 75 TOL, 0.75 70-75 IPA, 150 0 O 20-30 9.5 040 72 (1.0) 9 J 20 3. IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 2.0 135 171 (1.3) 10 H 10 6.5 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 12.4 056 120 (1.5) 11 K O 1.4 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 19.4 032 48 (1.0) 12 U 10 0.9 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 4.5 056 120 (1.6) 13 E 10 0.9 IPA, 75 TOL, 0.75 70-75 IPA, 150 0. 0. 20-30 8.6 032 48 (0.8)

EXAMPLE 2-13 55 Compound Ph-1 is stabilized with amines A, C, E, H, J, K, P, Q and U by the method described in Example 1; however, in contrast to Example 1, no phosphite and no 60 amine are introduced into the crystallization medium at the beginning. The product obtained is tested for resistance to EXAMPLES 14-17 hydrolysis as described in Example 1. The test conditions in A commercial phosphonite mixture containing Ph-3 as the test a storage at 50° C. and 75% atmospheric humidity. 65 Further conditions and test results are summarized in Table main component is stabilized by the method described in 1. Examples 2-13; composition of the batch:

5,534,645 45 46 -continued CH 'c CH, CH, 1 CH3 / CH3 () to (Ph-3d): 13% P N ch O (-CH CH3 CH NC YcH, CH Further compounds: 09%.

The stabilized mixture is tested for resistance to hydroly 20 Examples 14-17): sis by means of testa); test conditions: storage at 50° C. and 75% atmospheric humidity. Process conditions and test Ph-3: 35% results are summarized in Table 2. Ph-2: 09% Ph-3b: 20% EXAMPLES 18-23 25 Ph-3c: 04% Ph-3d: 15% Compounds Ph-5 and Ph-6 are stabilized by the method further compounds: 17%. described in Examples 2-13 and tested for resistance to hydrolysis by means of test a). Test conditions: storage at 50° C. and 75% atmospheric humidity. Test conditions and 30 The stabilized mixture is tested for resistance to hydroly test results are summarized in Tables 3 and 4. sis by means of testa); test conditions: storage at 50° C. and 75% atmospheric humidity. EXAMPLES 24-29 Process conditions and test results are summarized in Compound Ph-2 is stabilized by the method described in Examples 2-13 and tested for resistance to hydrolysis by 35 Table 6. means of testa); test conditions: storage at 70° C. and 100% atmospheric humidity. Process conditions and test results are summarized in Table 5. EXAMPLES 30-33 A commercial phosphonite mixture containing Ph-3 as the main component is stabilized by the method described in Examples 2-13; composition of the batch (for formulae, see 5,534,645 47 48

TABLE 2 Stabilizing of a phosphonite mixture containing the main component of the formula CH CH CH / NC -C\-CH3 N CH CH (H, CH CH- f O O CH CH \ / CH (Ph-3) P P CH / \ ch CH- O O (-CH, CH CH CH CH 1. C1 Sc CH, 1 \ / YCH, CH CH MELT CRYST MEDUM Ex. Solv 2, % TEST RESULTS No. Amine % intr. 96 cont. Solv 1, 9% % TfoC. Solvent, % seed cr. 9 amine T.C. p-clh c-1/h (% W) Comp arison none O O IPA, 300 60-65 MeOH, 400 O O 15-20 110 150 (15) 14 J 20 3.4 IPA, 300 ma 60-65 MeOH, 400 O O 5-2O >360 15 N 5 5 IPA, 300 w 60-65 MeOH, 400 O O 5.20 260 16 N 10 10 IPA, 300 --- 60-65 MeOH, 400 O O 15-2O >360 17 C 20 2.8 IPA, 300 w 60-65 MeOH, 400 O O 15-2O >360 30

TABLE 3 Stabilization of the compound of the formula C(CH3)3 C(CH3)3 (Ph-5) O O / \ (CH3)3C O-P P-O CCH3)3 \ / O O MET CRYSTMEDIUM Ex. Solv 2, % TEST RESULTS No. Amine intr. 96 cont. Solv 1, 96 % TfoC. Solvent, % seed cr. 9 amine T.C. p-clh c-l/h (% W) Comp. none O O TOL, 250 75-80 MeOH,500 O O 20-25 5 17 (30) 8 A 20 0.5 TOL, 250 w 75-80 MeOH,500 O O 2025 8 24 (33) 19 P 20 20 TOL, 250 --- 75-80 MeOH, 500 O O 20-25 8 24 (24) 20 N 10 4.8 TOL, 250 w 75-80 MeOH, 500 O O 20-25 15 48 (37) 2. N 20 10.5 TOL 250 w 75-80 MeOH, 500 O O 20-25 15 48 (28) 5,534,645 49 50 TABLE 4 Stabilization of the compound of the formula C(CH3)3 C(CH3)3 (Ph-6) O O / V CH3 O-P p-o CH \ O O C(CH3)3 C(CH3)3 MELT CRYST. MEDIUM Ex. Solv 2, % % TEST RESULTS No, Amine intr. 96 cont. Solv 1, 96 % TroC. Solvent, % seed cr. amine TIC. p-clh c-1/h (% W) Comp. none O O TOL,500 IPA, 500 75-80 IPA, 500 O O 15-20 96 168 (30) 22 A 20 1.1 TOL,500 IPA, 500 75-80 IPA, 500 0 O 15-20 400 23 N 20 2.0 TOL, 500 IPA, 500 75-80 IPA, 500 O 0 15-20 210 240

TABLE 5 Stabilization of tris(2,4,-di-tert-butylphenyl) phosphite (Ph-2) MELT CRYST MEDIUM % % Solv2, Solvent, % % TEST RESULTS Ex. No. Amine intr. cont. Solvl, 76 % TroC. % seed cr. amine TIC. p-ch c-1/h (% W) Comparison One O 0 TOL, 200 - 75 IPA, 600 0 O 20-30 026 47 (27) 24 N 2 0.7 TOL, 200 --- 75 IPA, 600 O O 20-30 216 240 (11) 25 N 5 1.8 TOL, 200 -- 75 IPA, 600 O O 20-30 216 240 (11) 26 N 10 5.1 TOL, 200 - 75 IPA, 600 O O 20-30 240 312 (16) 27 N 25 16.1 TOL, 200 - 75 EPA, 600 O O 20-30 >32 >312 (0) 28 P 2 0.1 TOL, 200 - 75 IPA, 600 0 O 20-30 192 216 29 P 5 3.8 TOL, 200 - 75 IPA, 600 0 O 20-30 216 240

40

TABLE 6 Stabilization of a phosphonite mixture containing the main component of the formula CH3 CH3 CH ne \ C CH, n 1. th CH3 CH ch CH3 - O O -CH3 CH3 \ / CH3 (Ph-3) P P ch / \ ch CH3 - O O (-CH, CH3 CH3 CH3 CH3 CH, 1 \ / YOH CH3 CH MELT CRYST. MEDUM TEST RESULTS Ex. No. Amine 96 intr. 96 cont. Solvent, % T.C. Solvent, % % seed cr. 9 amine TIC. p-clh c-l/h (% W) Comparison One O O IPA, 400 75 MeOH, 400 O O 20-30 24 48 (3.4) 30 N 5 7.5 IPA, 400 75 MeOH, 400 O 0 20-30 348 360 (0.2) 5,534,645 51 52 TABLE 6-continued Stabilization of a phosphonite mixture containing the main component of the formula CH CH3 \ CH NC C1 CH3 YoH, CH, 1 (H, ch CH- O O g-ch, CH3 \ CH (Ph-3) cy / V / P P\ / Vict CH- O O (-CH, CH CH CH3 CH3 CH, 11. C1\ Sc/ YoH, CH3 CH3 MELT CRYST MEDIUM TEST RESULTS Ex. No. Amine % intr. 96 cont. Solvent, % T/°C. Solvent, % % seed cr. % amine T/°C. p-ch c-1/h (% W) 31 N 10 8.2 IPA, 400 75 MeOH, 400 O O 20-30 504 816 (2.2) 32 N 25 32.3 IPA, 400 75 MeOH, 400 0 O 20-30 648 840 (0.9) 33 P 2 2.1 IPA, 400 75 MeOH, 400 O O 20-30 240 312 (2.6)

EXAMPLE 34-35 liquid crystallization medium whose temperature during the addition is maintained 10-70° C. below the temperature of Compound Ph-5 is stabilized by the method described in the melh wherein the phosphite is of the formula P(OR) Examples 2-13. The crystallization medium used is isopro- 30 wherein each radical R' is independently of the other panol without any further addition. The unstabilized and hydrogen or a hydrocarbon radical which optionally con stabilized compound are tested for resistance to hydrolysis tains a hetero atom selected from the group consisting of N, by means of test a). Test conditions: storage at 50° C. and O, F, Si, P, S, Cl, Br, Snor I with the proviso that a maximum 75% atmospheric humidity. of two of the three radicals R are hydrogen and wherein the Further process conditions and test result (c-l/h =time in 35 phosphonite is of the formula P(OR)2R wherein each hours until sample becomes deliquescent) are summarized in radical R and R is each independently of the other as Table 7. defined for R' or halogen and wherein the amine is of the

TABLE 7 Stabilization of the compound of the formula

(Ph-5) O O / \ (CH3)3C O-P P-O C(CH3)3 \ / O O MELT CRYSTMEDIUM RESULTS Ex. No. Amine % intr. 96 cont. Solv., 96 T/oC. Solv., 7% T.C. c-1/h Comp. Ole O 0 TOL, 250 75 IPA, 600 20-308 34 N 5 1.3 TOL, 250 75 IPA, 600 20-30 24 35 P 5 0.15 TOL, 200 75 IPA, 600 20-30 24

The examples show that the phosphites prepared and formula I stabilized according to the invention exhibit much better resistance to hydrolysis in moist air than unstabilized phos k (I) phites. 60 What is claimed is: 1. A crystalline organic phosphite or phosphonite, stabi in which X and X, independently of one another, are H, lized against hydrolysis, prepared by introducing a mixture, C-Coalkyl, C-Coalkyl which is interrupted by one or comprising a phosphite or phosphonite, a solvent or a more -O- and unsubstituted or substituted by one or more solvent mixture, and 0.1 to 100% by weight (relative to 65 hydroxyl groups, or is C-Cohydroxyalkyl, and X is phosphite or phosphonite) of an amine and having a tem C-Coalkyl, C-Coalkyl which is interrupted by one or perature of 50-100° C., as a homogeneous melt into a more -O- and unsubstituted or substituted by one or more 5,534,645 53 54 hydroxyl groups, or is -(CH2)-NX'X', or 4. A phosphite or phosphorlite according to claim 1 C-Cohydroxyalkyl, in which X and X together are wherein tile difference in temperature between melt and crystallization medium is 30–70° C. -(CH2)-, -CH-O-CH- or -CH-NX'- 5. A phosphite or phosphonite according to claim 1, CH-, m being an integer from the range 4 to 6 and X’ and wherein the crystallization medium is maintained at a tem X” being as defined above; or a cyclic sterically hindered 5 perature which is at least 10° C. below the resulting tem amine containing at least one group of the formulae II or III perature of the liquid. CH3 G I 6. A phosphite or phosphonite according to claim 1 G-CH G2 (II) wherein 80-800% by weight (relative to the phosphite or phosphonite) of a solvent is used as the crystallization 10 medium. -N 7. A phosphite or phosphonite according to claim 6 wherein a C-Csalkanol or a mixture of various C-Calkanols is used as the crystallization medium. 8. A phosphite or phosphonite according to claim 6 (III) 15 wherein the crystallization medium consists of a suspension of 2 to 20% by weight of crystalline phosphite or phospho nite, relative to the phosphite or phosphonite in the melt. 9. A phosphite or phosphonite according to claim 1 wherein the crystallization medium is saturated with G-CH2 20 50-100% by weight of amine. CH3 10. A phosphite or phosphonite according to claim 1 in which G is hydrogen or methyl, and G and G are wherein the melt contains 0.1 to 50% by weight of amine hydrogen, methyl or together are =O. (relative to the phosphite or phosphonite). 2. A phosphite or phosphonite according to claim 1 11. A phosphite or phosphonite according to claim 1 wherein the melt comprises an alcohol or a hydrocarbon in 25 wherein the amine is a tertiary amine of the formula I or a an amount of 20 to 500% by weight, relative to the phosphite cyclic sterically hindered amine containing at least one orphosphonite, as the main solvent or a further solventin an group of the formulae II or III, in which G is hydrogen and amount of 0-50% by weight, relative to the main solvent. G and G2 are hydrogen or together are a substituent =O. 3. A phosphite or phosphorlite according to claim 1 wherein the temperature of the melt is 55°-90° C. ck k k :k k