United States Patent 19 11 Patent Number: 5,371,263 Quotschalla Et Al

USOO537263A United States Patent 19 11 Patent Number: 5,371,263 Quotschalla et al. 45. Date of Patent: Dec. 6, 1994

54 PROCESS FOR STABILIZING TRIVALENT O167969 1/1986 European Pat. Off. . PHOSPHORUS COMPOUNDS WITH O168721 1/1986 European Pat. Off. . AMNES 0278579 8/1988 European Pat. Off. . 75) Inventors: Udo Quotschalla, Heppenheim, Primary Examiner-Patricia L. Morris Germany; Helmut Linhart, Reinach, Assistant Examiner-Michael G. Ambrose Switzerland Attorney, Agent, or Firm-Luther A. R. Hall 73 Assignee: Ciba-Geigy Corporation, Ardsley, 57 ABSTRACT N.Y. The invention relates to a process for stabilizing a crys 21 Appl. No.: 129,705 talline organic phosphite or phosphonite against hydro lysis, which comprises introducing a mixture compris 22 Filed: Sep. 30, 1993 ing phosphite or phosphonite, a solvent or solvent mix 30 Foreign Application Priority Data ture, and 0.1 to 100% by weight (relative to phosphite or phosphonite) of an amine and having a temperature Oct. 5, 1992 CH Switzerland ...... 3104/92 of 50-100° C. as a homogeneous melt into a liquid Nov. 27, 1992 CH Switzerland ...... 3647/92 crystallization medium whose temperature during the 51 Int. Cl...... C07F 9/48; CO7F 9/141 addition is maintained 10-70° C. below the tempera 52 U.S. Cl...... 558/71 ture of the melt. 58) Field of Search ...... 558/71 The phosphites or phosphonites stabilized according to 56 References Cited the invention are distinguished by their excellent resis U.S. PATENT DOCUMENTS tance to hydrolysis and have a long shelf life even at high atmospheric humidity. They can be advanta 3,553,298 1/1971 Hodan et al...... 260/967 geously used as stabilizers for organic material against 3,787,537 1/1974 De Marcq ...... 260/954 the damaging effect of heat, oxygen, and/or light. FOREIGN PATENT DOCUMENTS O143464 6/1985 European Pat. Off. . 12 Claims, No Drawings 5,371,263 1. 2 can be an individual compound or a mixture of com PROCESS FOR STABLIZNG TRIVALENT pounds. PHOSPHORUS COMPOUNDS WITH AMNES In principle, any organic compounds or mixtures of compounds which are liquid in the temperature range The invention relates to a process for increasing the from 10 to 60° C. under atmospheric pressure, do not shelf life of organic phosphites and phosphonites and to cause solvolysis and are capable of dissolving a suffi an organic phosphite or phosphonite stabilized against cient amount of solid phosphite or phosphonite above hydrolysis. 50 C., in some cases up to 100 C., or are sufficiently Organic phosphites and phosphonites are widely used miscible with the melted phosphite or phosphonite, can as heat stabilizers for synthetic polymers. However, O be used as the solvent. For example, sufficient solubility preparation, storage and use of phosphites and phospho or miscibility is given if the homogeneous liquid mixture nites are rendered difficult by the fact that these com can contain up to 15, in particular up to 50, 26 by weight pounds hydrolyze very easily. A particular problem is of phosphite or phosphonite. Examples of suitable sol storage of the material at high atmospheric humidity. vents are alcohols or hydrocarbons or mixtures thereof. Various methods have been proposed for arriving at 5 products having improved stability to hydrolysis; these Advantageously one compound or a mixture of two include, apart from preparation processes leading to compounds is used as the solvent in the melt. The main purer products and methods for purifying the ready-to solvent is used in an amount of 20 to 500% by weight, use compounds, in particular the addition of specific relative to the phosphite orphosphonite, and the further stabilizers which, on the one hand, reduce the tendency solvent in an amount of 0-50% by weight, relative to to hydrolysis and, on the other hand, do not result in the main solvent. The melt preferably contains an alco adverse effects during the later use of the compounds. hol or a hydrocarbon as the main solvent in an amount EP-A-278 579 proposes to use a hydrolytically stable of 20 to 500% by weight, relative to the phosphite or stabilizer mixture in which the crystalline phosphite is phosphonite, and a further solvent in an amount of 0-50, embedded in an amorphous phenolic antioxidant. This 25 in particular 0-20, 26 by weight, relative to the main stabilizer mixture is obtainable by rapid cooling of a Solvent. It is also possible to use a mixture of alcohols or melt of both compounds or of a suspension consisting of a mixture of hydrocarbons. crystalline phosphite and liquid phenol derivatives. Examples of suitable alcohols are lower alcohols, The addition of amines as stabilizers against hydroly such as C1-C5alkanols, in particular C1-C3alkanols, sis is described, for example, in U.S. Pat. No. 3,553,298. 30 such as methanol, ethanol, propanol or isopropanol. Further publications regarding the stabilizing of phos Isopropanol and methanol are particularly suitable. phites with amines are U.S. Pat. No. 3,787,537, EP-A- Examples of suitable hydrocarbons are C6-C13al 168 721 and EP-A-167969. The recommended com kanes, cycloalkanes or alkylated cycloalkanes having 6 pounds are in particular tertiary alkanolamines and to 12 carbon atoms, benzene, or alkylaromatics having 6 alkylamines, pyridines and anilines; typical examples are 35 to 10 atoms; toluene, ligroin, petroleum ether, xylene, triethylamine, diethanolamine, triethanolamine, di- and and in particular toluene are particularly suitable. triisopropanolamine (TIPA), tetraisopropanole Frequently the further solvent used is a hydrocarbon thylenediamine, aniline, phenylenediamine and hexa or a mixture of hydrocarbons in the case where the main methylenetetramine. In general, the amines are used in solvent is an alcohol, or an alcohol in the case where the amounts of up to about 5% by weight (relative to the main solvent is a hydrocarbon. Suitable alcohols and phosphite to be stabilized); incorporation of the amine is hydrocarbons are the ones listed above. effected by dry milling or by dissolution in or mixing The organic phosphites or phosphonites usable ac with the phosphite melt, followed by crystallization. cording to the invention are solid at 20 C.; in general Despite the known stabilization methods listed here, they are crystalline solids. there is a need for further improvement of the hydro 45 Phosphites are here understood to mean organic lytic stability of organic phosphites and phosphonites. phosphites of the formula P(OR)3 in which the radicals It has now been found that the stabilizing effect of Rare hydrocarbon radicals, which may contain hetero amines can surprisingly be increased by applying the atoms, and moreover a maximum of two of the three amine in a special process. radicals R can be hydrogen atoms. Hetero atoms are Accordingly, the invention provides a process for 50 any atoms with the exception of carbon and hydrogen, stabilizing a crystalline organic phosphite or phospho in particular the atoms N, O, F, Si, P, S, Cl, Br, Sn and nite against hydrolysis, which comprises introducing a I. mixture comprising phosphite or phosphonite, a solvent Phosphonites are esters of phosphonous acid of the or solvent mixture, and 0.1 to 100% by weight (relative formula P(OR)2R in which R is as defined above or can to the phosphite or phosphonite) of an amine and hav 55 be halogen. ing a temperature of 50-100 C. as a homogeneous melt In the process according to the invention, crude into a liquid crystallization medium whose temperature phosphite or crude phosphonite solutions such as are during the addition is maintained 10-70° C. below the obtained during preparation before crystallization can temperature of the melt. be used. The melt is the liquid mixture comprising amine, 60 The product of the process according to the inven solvent and the phosphite or phosphonite to be stabi tion is a mixture of compounds comprising solid phos lized. The melt can contain a small or a large amount of phite or phosphonite and amine. solvent, for example 20 or 500% by weight (relative to The temperature of the melt is preferably 55°-90° C., the phosphite orphosphonite) and thus can also be more in particular 60-80 C. like a solution. The important feature is that the melt is 65 In the process according to the invention, the differ homogeneous, i.e. that none of the components men ence in temperature between melt and crystallization tioned are crystalline any more and separation into 2 or medium is advantageously at least 20 C., for example more liquid phases does not take place. The amine used 30-70° C., in particular 40-60 C. 5,371,263 3 4. The crystallization medium is preferably maintained or -C2H4-NX-C2H4-, m being an integer from at a temperature being at least 10 C., for example the range 4 to 6 and X1 and X2 being as defined above. 10-60C., below the resulting temperature of the liqui The sterically hindered amine is in general a cyclic dus. The temperature of the crystallization medium is sterically hindered amine, in particular a compound preferably 20-60 C. below the resulting temperature 5 from the series of polyalkylpiperidine or -piperazine of the liquidus. derivatives containing a group of the formulae II or III The resulting temperature of the liquidus is the tem perature at which a homogeneous phase formed from the melt and crystallization medium is in thermody CH3 (II) namic equilibrium with phosphite crystals; below this O temperature, crystallization starts, and above the mix ture forms a homogeneous melt. In practice, this tem perature is advantageously determined by mixing tests, for example by means of calorimetric (for example by G-CH2 DSC) and/or optical methods. 15 CH3 Advantageously, 80-800% by weight, in particular 10-500% by weight, of organic solvent, relative to the phosphite or phosphonite in the melt, is used as the CH3 G1 (III) crystallization medium. G-CH G2 Advantageously, alcohols are used as the crystalliza 20 tion medium; thus, for example, a C1-C5alkanol or a mixture of various C1-C5alkanols is used. C1-C3Ak anols, such as methanol, ethanol, propanol or isopropa G-CH nol, are preferably used as the crystallization medium. CH3 Advantageously, seed crystals are added to the crys 25 tallization medium. Accordingly, the crystallization in which G is hydrogen or methyl, and G1 and G2 are medium preferably consists of a suspension of 2 to 20% hydrogen, methyl or together are =O; preferably, the by weight of crystalline phosphite or phosphonite, rela polyalkylpiperidine group of the formula II or III are tive to the phosphite or phosphonite in the melt. More substituted in the 4 position by one or two polar substit over, it is advantageous for the crystallization medium 30 uents or a polar spiro ring system. to be 50-100% saturated with the amine, 100% of satu X1, X2 and Xare, for example, independently of one ration corresponding to an amine concentration at another, ethyl, propyl, butyl, pentyl, hexyl, heptyl, oc which dissolved and solid amine can be present side by tyl, nonyl, decyl, hydroxyethyl, hydroxypropyl, hy side. droxybutyl, hydroxypentyl, hydroxyhexyl, hydrox In general, the melt contains 0.1 to 50% by weight of 35 yhepty, hydroxyoctyl, hydroxynonyl or hydroxyde anine, relative to the phosphite or phosphonite; prefer cyl. ably 0.2 to 25% by weight, in particular 0.5 to 20% by Preferably, X1, X2 and X3 are identical. weight, in particular 1 to 10% by weight, are used (rela The amine of the formula I is preferably a tertiary tive to the phosphite or phosphonite in the melt). amine, particularly preferably a tri-C2-C4alkanolamine, 40 in particular triisopropanolamine (=amine A). During the metered addition of the melt, the crystalli Of importance is a process in which the amine used is zation medium is advantageously stirred. After both a tertiary amine of the formula I or a cyclic sterically mixtures have been combined, further workup can take hindered amine containing at least one group of the place in a manner known perse, for example by cooling formulae II or III in which G is hydrogen, and G1 and to 10-15 C. and isolation of the crystalline product. 45 G2 are hydrogen or together are a substituent =O. The stabilized phosphite or phosphonite is generally Particularly advantageously, derivatives of 2,2,6,6- obtained as a powder in which the amine is homoge tetramethylpiperidine are used in the process according neously distributed. Typically it contains 0.01 to 20, in to the invention. particular 0.05 to 10, in particular 0.1 to 5, 9% by weight Of importance is in particular the use of the classes of of amine (relative to the phosphite or phosphonite). 50 polyalkylpiperidines described below under (a) to (h), The amine used in the process according to the inven which carry a group of the formula II or III as men tion is preferably a sterically hindered amine or one of tioned above: the formula I (a) compounds of the formula IV

X1 (I) 55 (IV) GCH2 CH3 G1 x^ Ya in which XI and X2, independently of one another, are 60 H, C1-C2alkyl, C4-Coalkyl which is interrupted by one or more -O- and unsubstituted or substituted by one GCH2 CH3 or more hydroxyl groups, or is C2-C20hydroxyalkyl, and Xis C2-C20alkyl, C-C20alkyl which is interrupted in which n is a number from 1 to 4, G and G, indepen by one or more -O- and unsubstituted or substituted 65 dently of one another, are hydrogen or methyl, by one or more hydroxyl groups, or is -(CH2 G is hydrogen, oxyl, hydroxyl, C1-C18alkyl, C3-C- On-NXX, or C2-C20hydroxyalkyl, or in which X2 8alkenyl, C3-C8alkynyl, C7-C12aralkyl, C1-C18alkoxy, and X together are -(CH2)n-, -C2H4-O-C2H C5-C8cycloalkoxy, C7-C9phenylalkoxy, C1-C8alkan 5,371,263 5 6 oy, C3-C5alkenoyl, C1-C18alkanoyloxy, benzyloxy, pendently of one another, are C1-C4alkyl or C1-C4alk glycidyl or a group -CH2CHOH)-Z, in which Z is OXy. hydrogen, methyl or phenyl, Gill being preferably H, G12 as a divalent radical of a dicarboxylic acid is, for C1-C4alkyl, allyl, benzyl, acetyl or acryloyl and example, a malonic acid, succinic acid, glutaric acid, G12 being, in the case where n is 1, hydrogen, C1-C1 adipic acid, suberic acid, sebacic acid, maleic acid, ita 8alkyl which may be interrupted by one or more oxygen conic acid, phthalic acid, dibutylmalonic acid, dibenzyl atoms, cyanoethyl, benzyl, glycidyl, a monovalent radi malonic acid, butyl(3,5-di-tert-butyl-4-hydroxybenzyl)- cal of an aliphatic, cycloaliphatic, araliphatic, unsatu malonic acid or bicycloheptenedicarboxylic acid radi rated or aromatic carboxylic acid, carbamic acid or cal. phosphorus-containing acid or a monovalent silyl radi O G12 as a trivalent radical of a tricarboxylic acid is, for cal, preferably a radical of an aliphatic carboxylic acid example, a trimellitic acid, citric acid or nitrilotriacetic having 2 to 18 C atoms, a cycloaliphatic carboxylic acid acid radical. having 7 to 15 C atoms, an afé-unsaturated carboxylic G12 as a tetravalent radical of a tetracarboxylic acid acid having 3 to 5 C atoms or an aromatic carboxylic is, for example, the tetravalent radical of butane-1,2,3,4- acid having 7 to 15 C atoms it being possible for the 15 tetracarboxylic acid or of pyromellitic acid. carboxylic acid to be substituted in each case in the G12 as a divalent radical of a dicarbamic acid is, for aliphatic, cycloaliphatic or aromatic portion by 1 to 3 example, a hexamethylenedicarbamic acid or a 2,4- groups -COOZ12, in which Z12 is H, C1-C20alkyl, toluylenedicarbamic acid radical. C3-C12alkenyl, C5-C7cycloalkyl, phenyl or benzyl, Preference is given to compounds of the formula IV 20 in which G is hydrogen, Gli is hydrogen or methyl, n is in the case where n is 2, C2-C12alkylene, C4-C12alke 2, and G12 is the diacyl radical of an aliphatic dicarbox nylene, xylylene, a divalent radical of an aliphatic, cy ylic acid having 4-12 C atoms. cloaliphatic, araliphatic or aromatic dicarboxylic acid, Examples of polyalkylpiperidine compounds from dicarbamic acid or phosphorus-containing acid, or a this class are the following compounds: divalentsilyl radical, preferably a radical of an aliphatic 25 1) 4-hydroxy-2,2,6,6-tetramethylpiperidine dicarboxylic acid having 2 to 36 C atoms, a cycloali 2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine phatic or aromatic dicarboxylic acid having 8-14 C 3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine atoms, or an aliphatic, cycloaliphatic or aromatic dicar 4) 1-(4-tert-butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetrame bamic acid having 8-14 C atoms, it being possible for thylpiperidine the dicarboxylic acid to be substituted in each case in 5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine the aliphatic, cycloaliphatic or aromatic portion by 1 or 6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine 2 groups -COOZ12, 7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine in the case where n is 3, a trivalent radical of an ali 8) 1,2,2,6,6-pentamethylpiperidin-4-yl g-(3,6-di-tert phatic, cycloaliphatic or aromatic tricarboxylic acid, butyl-4-hydroxyphenyl)propionate which may be substituted in the aliphatic, cycloaliphatic 35 9) di(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)maleate or aromatic portion by -COOZ12, an aromatic tricar 10) di(2,2,6,6-tetramethylpiperidin-4-yl) succinate bamic acid or a phosphorus-containing acid, or a triva 11) di(2,2,6,6-tetramethylpiperidin-4-yl)glutarate lent silyl radical, and 12) di(2,2,6,6-tetramethylpiperidin-4-yl) adipate in the case where n is 4, a tetravalent radical of an 13) di(2,2,6,6-tetramethylpiperidin-4-yl) sebacate aliphatic, cycloaliphatic or aromatic tetracarboxylic 14) di(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate acid. 15) di(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) The carboxylic acid radicals mentioned include in sebacate each case radicals of the formula (-COR, the mean 16) di(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthal ing of n being given above and the meaning of R being ate apparent from the definition given. 45 17) 1-hydroxy-4-3-cyanoethyloxy-2,2,6,6-tetramethyl Examples of C1-C12alkyl substituents, if present, are piperidine methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, 18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-unde 19) trimellitic acid tri-(2,2,6,6-tetramethylpiperidin cyl or n-dodecyl. 4-yl) ester Examples of G11 or G12 as C1-C18alkyl can be the 50 20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperi abovementioned groups and in addition, for example, dine n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. 21) di(2,2,6,6-tetramethylpiperidin-4-yl) diethylmalon Examples of Gllas C3-C8alkenyl can be 1-propenyol, ate allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2 22) di-(1,2,2,6,6-pentamethylpiperidin-4-yl) dibutylma octenyl, 4-tert-butyl-2-butenyl. 55 lonate Gill as C3-C8alkynyl is preferably propargyl. 23) di(1,2,2,6,6-pentamethylpiperidin-4-yl) butyl (3,5-di G11 as C7-C12aralkyl is in particular phenethyl and tert-butyl-4-hydroxybenzyl)malonate especially benzyl. 24) di(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) seb Examples of G 11 as C1-C8alkanoyl are formyl, propi aCate onyl, butyryl, octanoyl, but preferably acetyl and as 25) di(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin C3-C5alkenoyl in particular acryloyl. 4-yl) sebacate G12 as a monovalent radical of a carboxylic acid is, 26) hexane-1,6'-bis(4-carbamoyloxy-1-n-butyl-2,2,6,6- for example, an acetic acid, caproic acid, stearic acid, tetramethyl-piperidine) acrylic acid, methacrylic acid, benzoic acid or f3-(3,5-di 27) toluene-2',4'-bis(4-carbamoyloxy-1-n-propyl-2,2,6,6- tert-butyl-4-hydroxyphenyl)propionic acid radical. 65 tetramethyl-piperidine) G12 as a monovalent silyl radical is, for example, a 28) dimethylbis(2,2,6,6-tetramethylpiperidine-4-oxy)si radical of the formula -(CH2)-Si(Z)22", in which j lane is an integer from the range 2 to 5, and Z' and Z', inde 29) phenyltris(2,2,6,6-tetramethylpiperidin-4-oxy)silane 5,371,263 7 8 30) tris(1-propyl-2,26,6-tetramethylpiperidin-4-yl) phosphite Examples of G1 as C1-C4alkyl which is substituted 31) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) by a hydroxyl, cyano, alkoxycarbonyl or carbamic phosphite group can be 2-hydroxyethyl, 2-hydroxypropyl, 2 32) bis-(1,2,2,6,6-pentamethylpiperidin-4-yl) phenyl 5 phosphonate cyanoethyl, methoxycarbonylmethyl, 2-ethoxycar 33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine bonylethyl, 2-aminocarbonylpropyl or 2-(dime 34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethyl piperidine thylaminocarbonyl)ethyl. 35) 4-hydroxy-N-(2-hydroxypropyl)-2,26,6-tetrame O Examples of C2-C2alkylene substituents, if present, thylpiperidine 36) 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine are ethylene, propylene, 2,2-dimethylpropylene, tetra (b) compounds of the formula (V) methylene, hexamethylene, octamethylene, decameth ylene or dodecamethylen. (V) 15 GCH2 CH3 Gl Examples of C6-C1sarylene substituents, if present Gl3 are o-, m- or p-phenylene, 1,4-naphthylene or 4,4'- G11-N G14 diphenylene. 20 A C6-C12cycloalkylene is in particular cyclohexyl GCH, CH3 ele. Preference is given to compounds of the formula Vin in which n is 1 or 2, G, G1 and G11 have the meaning which n is 1 or 2, G is hydrogen. Gli1 is hydrogen or given under (a), G3 is hydrogen, C1-C12alkyl, C2-C- 25 saydroxyalkyl, Cs-C7cycloalkyl, C7-C8aralkyl, C2-C1 methyl, G3 is hydrogen, C1-C12alkyl or a group of the 8alkanoyl, C3-C5alkenoyl, benzoyl or a group of the formula formula

GCH2. CH3G 30 GCH2 CH3 G1

Gill-N Gill-N

35 GCH, CH3 GCH2 CH3

and Gis, in the case where n is 1, hydrogen, C1-C1sal and G is hydrogen or C1-C12alkyl in the case where kyl, C3-C8alkenyl, C5-C7cycloalkyl, C1-C4alkyl which 40 n=1 and C2-C8alkylene or 1-oxo-C2-C8alkylene in the is substituted by a hydroxyl, cyano, alkoxycarbonyl or case where n is 2. carbamide group, or is glycidyl, a group of the formula -CH2-CH(OH)-Z or of the formula -CONH-Z, Examples of polyalkylpiperidine compounds of this in which Z is hydrogen, methyl or phenyl; class are the following compounds: in the case where n is 2, C2-C12alkylene, C6-C12ary 45 lene, xylylene, a -CH2-CHOH)-CH2-group or a 37) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hex group -CH2-CHOH)-CH2-O-D-O-, in amethylene-1,6-diamine which D is C2-C10alkylene, C6-C15arylene, C6-C12cy 38) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hex cloalkylene, or, provided G13 is not alkanoyl, alkenoyl or benzoyl, G1 can also be 1-oxo-C2C12alkylene, a 50 amethylene-1,6-diacetamide divalent radical of an aliphatic, cycloaliphatic or aro 39) bis(2,2,6,6-tetramethylpiperidin-4-yl)amine matic dicarboxylic acid or dicarbamic acid or else the group -CO-, or, in the case where n is 1, G13 and G1 40) 4-benzoylamino-2,2,6,6-tetramethylpiperidine together can be the divalent radical of an aliphatic, 41) N,N'-bis(2,26,6-tetramethylpiperidin-4-yl)-N,N'- cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid. 55 dibutyladipamide C1-C12Alkyl or C1-C18alkyl substituents, if present, have the meaning already given under (a). 42) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'- Cs-C7Cycloalkyl substituents, if present, are in par dicyclohexyl-2-hydroxypropylene-1,3-diamine ticular cyclohexyl. G13 as C7-C8aralkyl is in particular phenylethyl or 60 43) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-p-xyly especially benzyl. G13 as C-Cshydroxyalkyl is in par lene diamine ticular 2-hydroxyethyl or 2-hydroxypropyl. Examples of G13 as C2-C1salkanoyl are propionyl, 44) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)suc butyryl, octanoyl, dodecanoyl, hexadecanoyl, octade cinedianide canoyl, but preferably acetyl and, as C3-C5alkenoyl, in 65 45) di(2,2,6,6-tetramethylpiperidin-4-yl) N-(2,2,6,6-tet particular acryloyl. Examples of Gas C2-C8alkenyl are ally, methallyl, ramethylpiperidin-4-yl)-3-aminodipropionate 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl. 46) the compound of the formula

5,371,263 11 12 Examples of G17 as C2-Cahydroxyalkyl are 2-hydrox 64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxos yethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydrox piro4.5decane ybutyl. and preferably: G7, T1 and T2 as C6-C10aryl are in particular phenyl, 65) 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethyl a- or f-naphthyl, which are unsubstituted or substituted spiro4.5-decane-2,4-dione by halogen or C1-C4alkyl. or the compounds of the following formulae:

CH3 CH3 CH3 CH3 66) NH-CEO OEC-NH CH3-N N-CH3 CHCH, C-N-CH2CHOH)CH2-(OCH-CHOH)CH-N-C CHCH, CH3 CH3 CH3 CH3 67) NH- CEO OcC-NH CH3-N N-CH C-N-(CH2)6-N-C CH3 CH3 9. CH3 CH3 CH3 CH3 CH3 CH3 68) NH-CEO OC-NH NH NH C-N CH2 N-C CH3 CH3 CH3 CH3 CH3 CH3 chic 69) O ?ch), HN CH2CH2 C-N-CH2CH2COOC2H25 CH3 CH3 , Examples of G7 as C2-C12alkylene are ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, 40 hexamethylene, octamethylene, decamethylene or dodecamethylene. Gas C4-C12alkenylene is in particular 2-butenylene, 2-pentenylene or 3-hexenylene. Examples of G7 as C6-C12arylene are o-, m- or p 45 phenylene, 1,4-naphthylene or 4,4'-diphenylene. Examples of Z as C2-C12alkanoyl are propionyl, (e) Compounds of the formula VIII, which on their butyryl, octanoyl, dodecanoyl, but preferably acetyl. part are preferred, D as C2-Coalkylene, C6-C15arylene or C6-C12cy cloalkylene is as defined under (b). 50 (VIII) Examples of polyalkylpiperidine compounds of this class are the following compounds: 56) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro4.5- decane-2,4-dione 57) 3-in-octyl-1,3,8-triaza-7,7,99-tetramethylspiro[4,5- 55 G19 decane-2,4-dione 58) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro4.5- decane-2,4-dione in which n is 1 or 2 and G18 is a group of one of the 59) 3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethyl formulae spiro4.5decane-2,4-dione 60 60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro[4.5dec CH3 ane-2,4-dione G CHG 61) 2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4- CH oxospiro-4.5decane W -E-(A)-CH N-G 11 o 62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4- 65 oxospiro-4.5-decane 63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodis piro5.1.11.2-heneicosane CH3 CHG 5,371,263 13 14 -continued G CH3 -CH2CH2 G2 CHG N O, } 5 -CH2CH2 / -E-(A)-N N-G 11 \ ( or a group of the formula CH3 CH2G O -CH2CH2 in which G and G11 are as defined under (a) and Gland Y-Gil G2 are hydrogen, methyl or together are a substituent / -O, -CH2CH2 E is -O- or -NG13-, A is C2-C6alkylene or -(CH2)3-O- and 15 or G2 is a group of the formula x is 0 or 1, G3 is hydrogen, C1-C12alkyl, C2-Cshydroxyalkyl or H3C CH3 Cs-C7cycloalkyl, CH G19 is identical to G18 or one of the groups 19 -NG21G22, -OG23, -NHCH2OG23 or -N(C- 20 Gll-N N- s H2OG23)2, N N G20 is identical to G18 or G19 in the case where n is 1, N and is a group -E-B-E-, in which B is C2-C8alky- Hic CH, 4H9-N lene or C2-C8alkylene which is interrupted by 1 or 2 9 -N(G2)- groups in the case where n is 2, 25 G2 is C1-C12alkyl, cyclohexyl, benzyl, C1-C4hy- HC CH droxyalkyl or a group of the formula 3 3 H3C N CH3 GCH2 CH3 Gl G11 30 Any C1-C12alkyl substituents present are, for exam Gil-N ple, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl. GCH2 CH3 35 Any C1-C4hydroxyalkyl substituents present are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxy G' is C1-C12alkyl, cyclohexyl, benzyl, C1-C4hy- propyl, 2-hydroxybutyl or 4-hydroxybutyl. droxyalkyl, and Examples of A as C2-C6alkylene are ethylene, propy G' is hydrogen, C1-C12alkyl or phenyl, or G' and lene, 2,2-dimethylpropylene, tetramethylene or hexa G?’ together are C4-Csalkylene or -oxaalkylene, for 40 methylene. example Examples of G2 and G22 together as C4-C5alkylene or oxaalkylene are tetramethylene, pentamethylene or 3-oxapentamethylene. Examples of polyalkylpiperidine compounds of this 45 class are the compounds of the following formulae:

fH, 70) CH3 N CH3 CH3 CH3 ss - els

5,371,263 23 24 -continued 94) -HN (CH2)6 N-C-CH2-c.

CH3 CH3 CH3 CH3 CH3 N CH3 CH3 N CH3 H H

95) N-(CH2)2-N-(CH2)2

R being H3C CH3 Hs H. 20 CH2-C-CH2-CH - 11 S-N Ne-H o= o OCH3 OR N S. N N H3C CH3 CH9-N 25 in which about one third of the radicals R are -C2H5 and the others are

H3C CH3 H3C CH3 H3C N CH3 30 H N-H, or a branching of the chain H3C CH3 R 35 and m is a number from the range 2 to 200; or -(CH2)2-N--, copolymers whose recurring unit is composed of 2 g units m" and m' are each an integer from the range 0-200 on condition that m' --In' is m. 40 CH3 Further examples of polymer light stabilizers are l=CH, reaction products of compounds of the formula

CH3, CH3 (H-H). 45 and 1 unit each of O-C-CH2

HN area

C NH O EO and O EO CH3 CH3 y 50 N N C13H27 with epichlorohydrin; CH3 CH3 polyesters obtained by reaction of butane-1,2,3,4-tet- CH3 NH CH3 racarboxylic acid with a bifunctional alcohol of the 55 formula (g) Compounds of the formula IX

HOV CHins fOscarCH *V /CHO 2 V CHins MOH GCH2, CH3 Gl (IX) CH-C-CHV WC V WCH--CH2 CH3 O-CH2 CH-O CH3 Gila-N cO the carboxyl side chains of which originating from the tetracarboxylic acid have been esterified with GCH2 CH3 2,2,6,6-tetramethyl-4-hydroxypiperidine; 65 compounds of the formula in which G, G and G11 are as defined under (a). 5,371,263 25 26 Preference is given to compounds of the formula IX amines from this class which are of particular technical in which G is hydrogen or methyl and G11 is hydrogen interest are those of the formulae or methyl. Examples of such compounds are: 96) 2,2,6,6-tetramethyl-4-piperidone (triacetoneamine) CH3 CH3 (amine B) 97) 1,2,2,6,6-pentamethyl-4-piperidone 98) 2,2,6,6-tetramethyl-4-piperidone 1-oxide fH, 99) 2,3,6-trimethyl-2,6-diethyl-4-piperidone HN o-Cho-i-ochs. OC2H5 (h) compounds of the formula X CH3 10 CH3 GCH2 CH3 CH3 CH3. CH3 (amine C) y O O Gl-N G14 15 HN O-C-(CH2)s-C-O NH,

) / CH3 CH3 GCH2 CH3 CH3 CH3

CH CH, C ine O in which n is 1 or 2 and in which G and G 11 are as CH3 3 3. CEgmine D) defined under (a) and G is as defined under (b), the O O meanings -CONH-Z and -CH2-CHOH)-CH CH3- O-C-(CH2)8-C-O N-CH3, 2-O-D-O-being excluded for G1. Examples of such compounds are: CH3 CH3 25 CH3 CH3 CH3 CH3 100) CH3 CH 3 CH 3 (amineine E)E CH3. CH3 eO H H CH3 CH-N N-H (amine M) 30 CH3-N N-CH3 H-N N-CH2 2 ( CH3 O O CH X-/ CH3 CH3 cH OF Oc bH CH3 CH3 CH2-CH-CH-CH2 CH 35 CH' O= o- CH3 CH3 CH3 101) O O CH3 CH3, CH3 CH3- N-CH3 2Oa y- CH-N N-CH3 w H H CH3-N N-CH2 2-7( CH CHs H'CH X / o?CH3 CH3 and esters of butane-1,2,3,4-tetracarboxylic acid with 2 CH3 CH3 units each of 1,2,2,6,6-pentamethyl-4-hydroxy-piperi CH3. CH3 102) dine and C13H27-OH (amine F); y 2O 45 compounds of the formula V in which n is 2, G and Glare hydrogen, CH3-N N-CH G11 is hydrogen or methyl and G3 is hydrogen or C1-C3alkyl, and CH3 CH3 G1 is C2-C8alkylene or 1-oxo-C2-C8alkylene; an 50 amine from this class which is of particular technical The following amines are particularly preferred for interest is the compound of the formula use in the process according to the invention: Compounds of the formula IV in which n is an inte CH3 CH3 ger from the range 1 to 4, G and G are hydrogen, and CH3 CH3 G1 is hydrogen or C1-C18alkyl, and 55 Cls G12, in the case where n is 1, is a radical of the for HN HN--c-Nh NH (amine G); mula-(CH2)-Si(Z)22", in which jis an integer from CH3 the range 2 to 5 and Z' and Z', independently of one CH3 CH3 another, are C1-C4alkyl or C1-C4alkoxy, and CH3 CH3 G12, in the case where n is 2, is a radical of an ali phatic dicarboxylic acid having 2 to 12 C atoms which compounds of the formula VIIC in which n is 1, G, may be substituted by -COOZ12, Z12 being C1-C20al G1 and G17 are hydrogen, kyl, Gil is hydrogen or methyl and G12, in the case where n is 3, is a radical of an aro 65 T1 and T2 together with the C atom linking them matic tricarboxylic acid having 9 to 15 C atoms, form a C5-C14cycloalkanering; an amine from this class G12, in the case where n is 4, is a radical of an ali which is of particular technical interest is the compound phatic tetracarboxylic acid having 8 to 12 C atoms; of the formula 5,371,263 27 28

CH3 O CH3 NH 5 HN s O ls (CH2)9 (amine HD CH3 CH 1. CH3 2 compounds of the formula VIII in which n is 1 or 2 O G18 and G19 are a group of one of the formulae

CH CHs GNG1 CH CH3 15 a-E-a-CH N-G 11 or -E-(A)-N N-G 11 7 CH3 7 CH3 CH3 CH3 G11 is hydrogen or methyl, G1 and G2 are hydrogen or together are a substituent 25 -O, CH3 E is -O- or -NG 13-, CH2 A is C2-C6alkylene and NN 1. x is 0 or 1, N N G13 is hydrogen, C1-C12alkyl or cyclohexyl, 30 G20, in the case where n is 1, is identical to G18 and, 1. in the case where n is 2, is a group -E-B-E-, in N which B is C2-C8alkylene or C2-C8alkylene which is CH1 CH2 CH2 NCH, interrupted by 1 or 2 groups -NCG2)-, 35 os-Nn eo G2 is C1-C12alkyl, cyclohexyl, benzyl or C1-C4hy CH3 droxyalkyl or a group of the formula CH3 CH CH3 CH3 CH3 CH, N CH3 CH3 CH3 (amines K and L): compounds of the formula X in which n is 2, G11 is hydrogen or methyl and G1 is C2-C12alkylene; 45 an amine from this class which is of particular techni GCH, CH3 cal interest is the compound (100) =amine M) de scribed above; and or G21 is a group of the formula oligomer compounds having 2 to 10 recurring units, 50 such as are obtainable by reaction of H3C CH3 (i) of

in which G2 is C2-C5hydroxyalkyl with an aliphatic C2-C12dicarboxylic acid or a suitable reactive deriva tive, such as the diester, dichloride or anhydride; 65 (j) of a linear oligomer polyester obtained by reaction amines from this class which are of particular techni of a dialcohol with butane-1,2,3,4-tetracarboxylic acid cal interest are the compound 76)=amine J described with 2,26,6-tetramethyl-4-hydroxypiperidine; above and the compounds of the formulae (k) of 5,371,263 29 30

CH3 NH CH3 CH3 NH CH3 CH3 - CH3 CH3 CH3 CH3 with CeCH2 with O A y FO and 5 C3H27 HN-m-m-mA NH

C N C N2 - O N N N T31 Nr. CH3 15 CH3 in which A is C2-C6alkylene, T is C1-C18alkylene or cyclohexyl, T is hydrogen or C1-C18alkyl, or T3 and and those of the formula T together are C4-C6alkylene or C3-C5oxaalkylene; (o) (1) of H2N-A-NH-A-NH2 with

C CH3 CH3 CH3 1s CH3 CH3 HN N 1 N NH CH,-- CH-CH CH o=t o=t 3 -- 2N. CH3 25 bch, br CH3 N CH3 C4H9 in which about one third of the radicals R are -C2H5 and Br-A-Br, in which A is C2-C6alkylene; and the others are (m) of compounds of the formula 30

CH3. CH3 C-C) O-C-CH2 35 HN

C-NH CH3 CH3 y and n is a number from the range 2 to 10; 40 oligomer amines of particular technical interest in with epichlorohydrin; clude those of the formulae (m again is a number from (n) of the range 2 to 10)

CH3 CH3 O O-CH3 (amine N);

CH3 CH3

CH3 NH CH3 CH3 HN CH3 CH3 NH CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3

- N HN-a- (CH2)6 -N e S-N- (CH2)6-N H (amine P); N y N H. H. HN-C-CH-C-CH3 CH3 CH3 5,371,263 31 32 -continued CH3 NH CH3 CH3 HN CH3 CH3 NH CH3 CH3 NH CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3

N HN (CH2)6 N 2 -N (CH2)6 N H (amine Q) N N Sa C O

CH3 ch,--CH-ch (amine R) o=l o= bch, br in which about one third of the radicals R are -C2H5 and the others are 25 Cl CH3 CH3 1. CH3 CH3 HN N N NH 30 CHR 1N 2- CH3 CH3 N CH3 C4H9 C4H9 a linear polyester having 2 to 10 recurring units ob 35 and Br-(CH2)2-Br (amine U); and the reaction prod tained by reaction of butane-1,2,3,4-tetracarboxylic acid uct of the compound of the formula with a dialcohol of the formula CH3 CH3 H-phy HO CH3 O-CH2 CH-O CH3 OH O-C-CH2 M / N / N / CH-C-CH C CH-C-CH2 , N / N. / HN CH3 O-CH2 CH-O CH3 C-NH CH3 CH3 in which the end groups and side chains are formed by 45 esterification of the free carboxylic groups with 2,2,6,6- tetramethyl-4-hydroxypiperidine (amine S); a copoly with epichlorohydrin (amine W). mer whose recurring units are composed of 2 units The oligomer amines are often mixtures of com pounds which differ from one another with respect to their chain length. CH3 50 Of particular importance is the use of the amines A, B, C, D, E, F, G, H, J, K, L, M, N, O, P, Q, R, S, T, U, V and W specified above. In the process according to the invention, preference is given in particular to the addition of those amines and 1 unit each of 55 whose molecular weight or average molecular weight Mn is in the range 300 to 10,000, in particular in the range 1000 to 10,000. Of these, those amines whose molecular weight or average molecular weight Mis in o4 -o and o\)- (amine T); 60 the range 1500 to 10,000, for example in the range 2000 N to 7500 should again be mentioned in particular. The amines of higher molecular weight are in particular sterically hindered amines. CH3 CH3 The amines mentioned are known compounds; many CH3 NH CH3 of them are commercially available. 65 In the process according to the invention preference the reaction product of H2N-(CH2)2-NH-(CH2 is given to stabilization of phosphites or phosphonites )2-NH2 with having one of the formulae (1) to (7), 5,371,263 33 34

R's R's OR'2 (1) / R'1-Y-P s N 5 OR's T B (2) R6 R6 OR'2 / A X-P s 10 N OR's ( ) B ( )

O (3) or phenylene; R", V 15 A, in the case where n is 3, is a radical of the formula P-O-H-A. -CH2-1-; R'sA. ? A", in the case where n is 4, is a radical of the formula O g C(CH2)4, 2O A', in the case where n' is 2, has the meaning of A'; (4) O B' is a radical of the formula -CH2-; -CHR'4-; V -CR'1R4-; -S- or a direct bond; or is C5-C7cy D P-O-R' , cloalkylidene; or is cyclohexylidene which is substi M tuted in the 3, 4 and/or 5 position by 1 to 4 C1-C4alkyl CH3 O 25 radicals; p D'in the case where p is 1, is methyl and, in the case where p is 2, is -CH2OCH2-; O O (5) E", in the case where y is 1, is alkyl having 1 to 18 / V carbon atoms, phenyl, a radical of the formula -OR1 R1-O-P P-O-R', V / 30 or halogen; O O E", in the case where y is 2, is a radical of the formula -O-A'-O-; (6) E", in the case where y is 3, is a radical of the formula R4 R4'C(CH2O3: 35 Q' is the radical of an at least z-valent alcohol or phenol, this radical being attached to the Patom(s) via O R4 the alcoholic or phenolic O atom(s); R1, R'2 and R3, independently of one another, are alkyl having 1 to 30 carbon atoms; alkyl which is substi / R's 40 tuted by halogen, -COOR4, -CN or -CONR4R4' E. P Z" y and has 1 to 18 carbon atoms; alkyl which is interrupted by -S-, -O- or -NR'4, and has 2 to 18 carbon \ R15 atoms; phenyl-C1-C4alkyl; cycloalkyl having 5 to 12 carbon atoms; phenyl or naphthyl; phenyl or naphthyl O R4 45 each of which is substituted by halogen, 1 to 3 alkyl radicals or alkoxy radicals having a total of 1 to 18 R4 carbon atoms or by phenyl-C1-C4alkyl; or is a radical of y the formula o17P No (T) 50 R's O O V -(CH2) OH, P Q' A 55 gh O in which m is an integer from the range 3 to 6; R16 J, R4 or the radicals R4' independently of one another, 60 are hydrogen; alkyl having 1 to 18 carbon atoms; cyclo in which the indices are integers and alkyl having 5 to 12 carbon atoms; or phenylalkyl hav n' is 2, 3 or 4; p is 1 or 2; q is 2 or 3; r is 4 to 12; y is ing 1 to 4 carbon atoms in the alkyl moiety; 1, 2 or 3; and z is 1 to 6; R's and R'6, independently of one another, are hydro A, in the case where n' is 2, is alkylene having 2 to 18 gen; alkyl having 1 to 8 carbon atoms or cycloalkyl having 5 or 6 carbon atoms; carbon atoms; alkylene which is interrupted by -S-, 65 R'7 and R's, in the case where q is 2, are, indepen -O- or -NR'4- and has 2 to 12 carbon atoms; a dently of one another, C1-C4alkyl or together are a radical of one of the formulae 2,3-dehydropentamethylene radical; and 5,371,263 35 36 R'7 and R's, in the case where q is 3, are methyl; the substituents R14, independently of one another, are the substituents R14, independently of one another, hydrogen or alkyl having 1 to 9 carbon atoms; are hydrogen; alkyl having 1 to 9 carbon atoms or cy R'15 is hydrogen or methyl; clohexyl; X is a direct bond; the substituents R15, independently of one another, Y' is -O-; and are hydrogen or methyl; and Z' is a direct bond or -CH(R16)-. R16is hydrogen or C1-C4alkyl and, in the case where Of particular technical interest is a process for stabi several radicals R16 are present, the radicals R16 are lizing a phosphite orphosphonite of one of the formulae identical or different; (1), (2), (5) or (6), in which X and Y are each a direct bond or -O-; and 10 n' is 2 and y is l; Z is a direct bond; -CH2-; -COR16)2- or -S-. A is p-biphenylene; Particular preference is given to a process in which E is C1-C18alkoxy; the phosphite or phosphonite is one of the formulae (1), R1, R'2 and R3, independently of one another, are (2), (5) or (6), in which phenyl which is substituted by 2 or 3 alkyl radicals n' is 2 and y is 1 or 2; 15 having a total of 2 to 12 carbon atoms; A is alkylene having 2 to 18 carbon atoms; p-phenylene the substituents R'14, independently of one another, are or p-biphenylene; methyl or tert-butyl; E", in the case where y is 1, is C1-C18alkyl, -OR1 or R15 is hydrogen; fluorine; and, in the case where y is 2, is p-bipheny X is a direct bond; lene; 20 Y' is -O-; and R1,R2 and R3, independently of one another, are alkyl Z' is a direct bond, -CH2- or -CH(CH3)-. having 1 to 18 carbon atoms; Particular preference is given to phosphites, in partic phenyl-C1-C4alkyl; cyclohexyl; phenyl; phenyl which ular those of the formulae (1) and (5). is substituted by 1 to 3 alkyl radicals having a total of The following compounds are examples of phos 1 to 18 carbon atoms; 25 phites and phosphonites whose stability to hydrolysis can be improved particularly advantageously by the process according to the invention;

CH3 CH3 (Ph-1) N \-CH3 CH CH3 -C CH3 o, (H, Hs p-o (-CH: CH- O CH3 CH3 CH3 CH3 CH3 -CV CH3

CH3 (Ph-2) CH3N/ C CH H. 3 CH3-C O th3 N H. P-O C-CH3; (Hs / h3 CH- O Chas CH3 /NoH, CH3 cH3 CH31-C V

5,371,263 39 -continued CH3

1YeCH3 CH3 (H, nihs O -CH, H5C-CH N / CH3 CH2O-P\ CH2} V . -CH, Ph.) CH3 CH3 n /C CH CH3 The phosphites and phosphonites mentioned are known compounds; some of them are commercially 20 available. A sample serving as comparison is crystallized with Some commercial phosphites and phosphonites are out adding an amine. present as mixtures of compounds or in prestabilised Equal amounts of the product are then subjected to form. In most cases, an amine, for example a lower the following tests of resistance to hydrolysis: alkylamine or triisopropanolamine, has been admixed to 25 a) During storage, the time is measured in which these compounds in a conventional manner in a concen upon visual inspection the initial powder starts to deli tration of about 1% as prestabilization. The hydrolytic quesce (transition p-c) and the time which expires until stability of such products can also be significantly im the material is liquid (transition c-f). At the last-men proved by the process according to the invention. tioned point in time, the weight increase during the The products of the process according to the inven duration of storage is noticed; the weight increase gives tion can advantageously be used as stabilizers of organic an indication of the water absorption of the material. material, in particular organic polymers, for example The test conditions (temperature and atmospheric hu synthetic polymers, against the damaging effect of heat, midity during storage) are given in the particular exam oxygen and/or light. Examples of such polymers can be ples. seen, for example, from U.S. Pat. No. 4,855,345, column 35 b) After 8 hours of storage at 70° C. and 100% atmo 4, line 63, up to column 7, line 54. spheric humidity, the phosphite Ph-1 content is deter The phosphites and phosphonites stabilized accord mined by liquid chromatography. ing to the invention are distinguished by their excellent The results can be seen from Table 1. resistance to hydrolysis and have a long shelf life even EXAMPLE 2-13 at high atmospheric humidity. An organic phosphite or 40 phosphonite stabilized against hydrolysis, such as ob Compound Ph-1 is stabilized with amines A, C, E, H, tainable by the process described above, is therefore J, K, P, Q and Uby the method described in Example 1; also provided by this invention. however, in contrast to Example 1, no phosphite and no The examples which follow illustrate the process amine are introduced into the crystallization medium at according to the invention further. All parts or percent 45 the beginning. The product obtained is tested for resis ages given are, just as in the remaining description and tance to hydrolysis as described in Example 1. The test in the claims, by weight, unless stated otherwise. As far conditions in test a: storage at 50 C. and 75% atmo as percentages are based on phosphite or phosphonite, spheric humidity. they refer to phosphite or phosphonite in the melt un Further conditions and test results are summarized in less a different reference amount is expressly stated. The 50 Table 1. structural formulae of the phosphites, phosphonites and In Table 1 and the following tables, the column head amines used in the examples are, if not stated directly, ings have the following meaning: listed above in the text. % intr.: amount of amine in the melt, % given is based EXAMPLE 1. on phosphite or phosphonite in the melt; 55 % cont.: amine content in the phosphite orphosphonite 300 g of phosphite Ph-1 are brought to 70-75 C. after crystallization; together with 225 g of isopropanol, 2.25 g of toluene Solv1, 26: main solvent for the melt, % given is based and 30 g of amine A (=triisopropanolamine) with stir on phosphite or phosphonite in the melt; ring. The resulting homogeneous melt is added over a Solv2, 2%: further solvent for the melt, % given is based period of about 1 hour with stirring to a suspension of 60 on phosphite or phosphonite in the melt; 20 g of Ph-1 in 450 g of isopropanol and 20 g of amine T/C.: temperature range of the melt or crystallization A whose temperature during this process is maintained medium; at 20-30 C. by cooling. The mixture is then cooled to Solvent, %: solvent for crystallization medium, 76 10-15 C. and stirred in this temperature range for given is based on phosphite or phosphonite in the another 3 hours. The crystalline product is then filtered 65 melt; off and dried at 60' C. under reduced pressure. IPA: isopropanol; Elemental analysis gives an amine A content of 1.2% TOL: toluene; by weight (relative to phosphite) for the dry product. MeOH: methanol; 5,371,263 41 42 % seed cr.: initial charge of phosphite as seed crystals, c-l/h (% W): time in hours until sample has become % given is based on phosphite or phosphonite in the liquid (clear solution). Numbers given in brackets: melt; weight increase of the sample compared with the % amine: initial charge of amine in the crystallization beginning of the test (% by weight is based on the medium, % given is based on phosphite or phospho- 5 beginning of storage= water content) test a).

TABLE 1. Stabilization of bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite (Ph-1) MELT CRYST. MEDUM TEST RESULTS % % Solvent, % seed % % dec. Ex. No. Amine intr. cont. Solv1, 2, Solv2, 2 TMC. % C. amine T/C. (8 h) p-c/h c-I/h (7% W) Compari- none O O IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 85(n.2 h) 005 37 (2.5) SO A. 10 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 O O 20-30 5 O25 > 120 4. P 5 1.0 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 3.4 056 144 (1.5) 5 P O 2.7 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 3.1 160 220 6 P 20 3.8 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 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 O O 20-30 9.5 040 72 (1.0) 9 J 20 3.1 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 2.0 35 171 (1.3) O H 10 6.5 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 12.4 056 120 (1.5) 1 K O 1.4 IPA, 75 TOL, O.75 70-75 IPA, 150 O O 20-30, 19.4 O32 48 (1.0) 2 U 10 09 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 4.5 O56 120 (1.6) 3 E 10 0.9 IPA, 75 TOL, 0.75 70-75 IPA, 150 O O 20-30 8.6 032 48 (0.8)

nite in the melt; % dec. (8h): decomposition of the sample after 8 h in % EXAMPLES 14-17 (100% = phosphite content at the beginning of the A commercial phosphonite mixture containing Ph-3 test) test b); as the main component is stabilized by the method de p-c/h: time in hours until deliquescence begins testa); scribed in Examples 2-13; composition of the batch:

CH3 CH3 (Ph-3): 43% CH3/ \CH3 C -C CH3 CH3 (H, CH3 CH- O O CH3 CH3 \ / CH3 P P fH, / \ (Hs CH- O O i-CH, CH3 CH CH3 3 CH3 -C CN CH3 CH3 'ch3. CH3

CH3 (Ph-2): 17% CH3N/ CN SH: CH3 CH- O CH3 \ CH3 P-O C-CH3 H. / CH3 CH3-C o CH3N H C 3 Y CH3 CH3 CH51 -C \ 5,371,263 43 44 -continued CH3 CH3 (Ph-3b): 17% CH3No / Vc1 CH3 ? V CH3 CH3 CH3 \l-CH3 CH3 O -C CH3/ CH3 S P CH3 CH3 / O CH3 O / CH3 P CH-i-CH, \ phs CH3 O (-CH, CH3 CH3 CN CH3 CH3

CH3 CH3 CH3 (Ph-3c): 01% CH3. A V CH3 CH3 M CH3 n C c1 na C CH3 / V W CH3 CH3 CH3 CH3 CH ?h; O O CH CH 3 No c1 3 / P P CH3 / N CH3 O O ch,--CH, CH-i-CH, CH3 CH3 CH3 (Ph-3d): 13% \-CH3 -C CH3 CH3 O CH3 / CH3 P \ Hs O -ch, CH3 CH3 C CH3 CH3 Further compounds: O9%. 100% atmospheric humidity. Process conditions and The stabilized mixture is tested for resistance to hy test results are summarized in Table 5. drolysis by means of test a); test conditions: storage at 50 C. and 75% atmospheric humidity. Process condi EXAMPLES 30-33 tions and test results are summarized in Table 2. A commercial phosphonite mixture containing Ph-3 as the main component is stabilized by the method de EXAMPLES 18-23 scribed in Examples 2-13; composition of the batch (for Compounds Ph-5 and Ph-6 are stabilized by the formulae, see Examples 14-17): method described in Examples 2-13 and tested for resis Ph-3: 35% tance to hydrolysis by means of testa). Test conditions: Ph-2: 09% storage at 50 C. and 75% atmospheric humidity. Test Ph-3b; 20% conditions and test results are summarized in Tables 3 Ph-3c: 04% and 4. Ph3d: 15% further compounds: 17%. EXAMPLES 24-29 The stabilized mixture is tested for resistance to hy Compound Ph-2 is stabilized by the method described 65 drolysis by means of testa); test conditions: storage at in Examples 2-13 and tested for resistance to hydrolysis 50° C. and 75% atmospheric humidity. Process condi by means of testa); test conditions: storage at 70° C. and tions and test results are summarized in Table 6. 5,371,263 45 46 TABLE 2 Stabilizing of a phosphonite mixture containing the main component of the formula (Ph-3) CH3 CH3 VCH3 CH3/ CS C CH3 CH3 fH, CH3 CH- O O CH3 CH3 \ / CH3 P P Hs / \ CH3 CH- O o CH3 CH3 CH3 CH3 CH3 A CN CH3 CH1 CV CH3 CH3

MELT % 2. CRYST. MEDIUM. TEST RESULTS Ex. No. Amine intr. cont. Soivl, 7% Solv2, 2 TAC. Solvent, % 2 seed cr. % amine T/C. p-c/h c-l/h (% W) Comparison none O O IPA, 300 60-65 MeOH, 400 O O 15-20 O 150 (15) i4 20 3.4 IPA, 300 60-65 MeOH, 400 O O 15-2O >360 15 N 5 5 IPA, 300 60-65 MeOH, 400 O 0 5-20 260 16 N 10 O IPA, 300 60-65 MeOH, 400 O O 15-20 360 17 C 20 2.8 IPA, 300 w 60-65 MeOH, 400 O 0 15-20 -360

TABLE 3 Stabilization of the compound of the formula C(CH3)3 C(CH3)3 (Ph-5) O O A. V (CH3)3C O-P P-O C(CH3)3 V W O O

MELT % % CRYST. MEDIUM TEST RESULTS Ex. No. Amine intr. cont. Solv1, 2, Solv2, 2 TAC. Solvent, % 2 seed cr. 2% amine T/C. p-c/h c-l/h (7% W) Comparison none O O TOL, 250 W 75-80 MeOH, 500 O O 20-25 5 17 (30) 18 A. 20 0.5 TOL, 250 ma 75-80 MeOH, 500 O O 20-25 8 24 (33) 19 P 20 2.0 TOL, 250 W 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) 21 N 20 10.5 TOL, 250 o 75-80 MeOH, 500 O O 20-25 15 48 (28)

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 C(CH3)3 V A. O O C(CH3)3 C(CH3)3

MELT % 9% CRYST. MEDIUM TEST RESULTS Ex. No. Amine intr. cont. Solv1, 2, Solv2, 26 T/C. Solvent, % % seed cr. 9% amine T/C. p-c/h c-l/h (7% W) Comp. ce 0 0 TOL,500 IPA, 50 75-80 IPA, 500 O O 5-20 96 168 (30) 22 A 20 1.1 TOL, 500 IPA, 50 75-80 IPA, 500 O 0 15-20 400 23 N 20 2.0 TOL,500 IPA, 50 75-80 IPA, 500 O O 15-20 210 240 5,371,263 47 48 TABLE 5 Stabilization of tris(2,4-di-tert-butylphenyl) phosphite (Ph-2) MELT CRYST. MEDIUM % % % TEST RESULTS Ex. No. Amine intr. cont. Solvl, 9% Solv2, 26 T/C. Solvent, % 9% seed cr. amine T/C. p-c/h c-l/h (% W) Comparison e O O TOL, 200 AO 75 IPA, 600 O 0 20-30 026 47 (27) 24 N 2 0.7 TOL, 200 75 IPA, 600 O 20-30 216 240 (11) 25 N s 1.8 TOL, 200 am 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 PA, 600 O O 20-30 >32 >312 (O) 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 O O 20-30 216 240

TABLE 6 Stabilization of a phosphonite mixture containing the main component of the formula h-3 CH CH (Ph-3) CH3 CH3/ 3 C C n CH3 CH3 Y Hs CH3 CH- O O CH3 CH3 \ / CH3 P P sh; / \ CH3 CH- O O CH3 CH3 CH3 CCH3 CHs. /CH CH1 \ CH3 CH3 MELT CRYST. MEDUM TEST RESULTS Ex, No. Amine % intr. % cont. Solvent, % T/C. Solvent, % 9% seed cr. 9% amine T/C. p-c/h c-l/h (% W) Comparison none O O IPA, 400 75 MeOH, 400 O O 20-30 24 48 (34) 30 N s 7.5 IPA, 400 75 MeOH, 400 O O 20-30 348 360 (0,2) 31 N O 18.2 IPA, 400 75 MeOH, 400 O O 20-30 SO4 816 (2.2) 32 N 25 32.3 IPA, 400 75 MeOH, 400 O O 20-30 648 840 (0.9) 33 P 2 2. IPA, 400 75 MeOH, 400 O O 20-30 240 312 (2.6)

ter resistance to hydrolysis in moist air than unstabilized EXAMPLE 34-35 40 phosphites. ydroly Compound Ph-5 is stabilized by the method described What is claimed is: in Examples 2-13. The crystallization medium used is 1. A process for stabilizing a crystalline organic phos isopropanol without any further addition. The unstabil phonite or phoshonite against hydrolysis, which com ized and stabilized compound are tested for resistance to prises introducing a mixture comprising phosphite or hydrolysis by means of testa). Test conditions: storage phosphonite, a solvent or a solvent mixture, and 0.1 to at 50 C. and 75% atmospheric humidity. Further pro 100% by weight (relative to phosphite or phosphonite) cess conditions and test result (c-l/h=time in hours of an amine and having a temperature of 50-100° C. as until sample becomes deliquescent) are summarized in a homogeneous melt into a liquid crystallization me Table 7. dium whose temperature during the addition is main TABLE 7 Stabilization of the compound of the formula CCH3)3 CCH3)3 (Ph-5)

MELT CRYST. MEDUMRESULTS Ex. No. Amine 26 intr. 9% cont. Solv, 9% T/C. Solv, 9% T/C. c-1/h Comp. Oe O O TOL, 250 75 IPA, 600 20-30 8 34 N 5 1.3 TOL, 250 75 IPA, 600 20-30 24 35 P 5 0.15 TOL, 200 75 EPA, 600 20-30 24 tained 10-70° C. below the temperature of the melt. The examples show that the phosphites prepared and 2. Process according to claim 1, in which the melt stabilized according to the invention exhibit much bet comprises an alcohol or a hydrocarbon in an amount of 5,371,263 49 50 20 to 500% by weight, relative to the phosphite or in which X1 and X2, independently of one another, are phosphonite, as the main solvent and a further solvent in H, C1-C20alkyl, C4-C20alkyl which is interrupted by an amount of 0-50% by weight, relative to the main one or more -O- and unsubstituted or substituted by solvent. one or more hydroxyl groups, or is C2-C20hydroxyal 3. A process according to claim 1, in which the tem kyl, and X3 is C2-C20alkyl, C4-C20alkyl which is inter perature of the melt is 55°-90° C. rupted by one or more -O- and unsubstituted or 4. A process according to claim 1, in which the differ substituted by one or more hydroxyl groups, or is ence in temperature between melt and crystallization -(CH2)n-NXX2, or C2-C20hydroxyalkyl, or in medium is 30-70 C. which X2 and X3 together are -(CH2)n-, -C2 O H4-O-C2H4- or -C2H4-NX-C2H4-, m being 5. A process according to claim 1, in which the crys an integer from the range 4 to 6 and Xland X2 being as tallization medium is maintained at a temperature which defined above; or a cyclic sterically hindered amine is at least 10 C. below the resulting temperature of the containing at least one group of the formulae II or III liquid. 6. A process according to claim 1, in which 80-800% S by weight (relative to the phosphite orphosphonite) of G-CH2 G2 (II) a solvent are used as the crystallization medium. 7. A process according to claim 6, in which a C1-C- -N salkanol or a mixture of various C1-C5alkanols is used as the crystallization medium. G-CH2 8. A process according to claim 6, in which the crys CH3 tallization medium consists of a suspension of 2 to 20% (III) by weight of crystalline phosphite or phosphonite, rela tive to the phosphite or phosphonite in the melt. 9. A process according to claim 1, in which the crys 25 tallization medium is saturated with 50-100% of amine. 10. A process according to claim 1, in which the melt G-CH2 contains 0.1 to 50% by weight of amine (relative to the CH3 phosphite or phosphonite). 30 in which G is hydrogen or methyl, and G1 and G2 are 11. A process according to claim 1, in which the hydrogen, methyl or together are =O. anine used is one of the formula I 12. A process according to claim 10, in which the amine used is a tertiary amine of the formula I or a (I) cyclic sterically hindered amine containing at least one 35 group of the formulae II or III, in which G is hydrogen and G1 and G2 are hydrogen or together are a substitu ent cO.