HYDROCARBYL(POLYPHENOL)-POLY(2,2,6,6-TETRAMETHYL PIPERIDYL-1,3,5-TRIAZINES) AS STABILIZERS FOR SYNTHETIC POLYMER COMPOSITIONS

Abstract: Stabilizers for synthetic polymer compositions are pro­ vided which are hydrocarbyl(polyphenol)-poly (2,2,6,6-te­ tramethyl-piperidyl- 1,3,5-triazines) having the formula: in which: R is a hydrocarbyl group having the valence n; R₁ is selected from the group consisting of hydrogen; alkyl alkenyl, cycloalkyl, hydroxyalkyl and alkoxy having from one to about twelve carbon atoms; acyl having from about one to about twelve carbon atoms; and oxyl; Y is selected from the group consisting of wherein R₄ is lower alkyl having from one to about six car­ bon atoms; R₅ is selected from the group consisting of hy­ drogen; alkyl, hydroxy alkyl and alkoxy having from one to about twelve carbon atoms; and cycloalkyl having from three to about twelve carbon atoms; and X is selected from the group consisting of wherein: R₆ is selected from the group consisting of alkyl, hy­ droxyalkyl and alkylenealkoxy having from one to about twelve carbon atoms; cycloalkyl having from three to about twelve carbon atoms; and aryl having from six to about eighteen carbon atoms; R₇ and R₈ are selected from the group consisting of hy­ drogen; alkyl having from one to about twelve carbon atoms; cycloalkyl having from three to about twelve carbon atoms; and aryl having from six to about eighteen carbon atoms; and R₇ and R₈ taken together as a five to six member ring including the nitrogen in the ring; R₂ and R₃ are selected from the group consisting of hy­ drogen and lower alkyl having from one to about six carbon atoms; and n is a number from 2 to 4.

Description: Synthetic polymers such as polyethylene, polypropylene and polyvinyl chloride undergo degradation upon exposure to ultraviolet light, resulting in discoloration, deterioration in mechanical strength and embrittlement. Consequently, various types of stabilizers have been incorporated with these polymers to inhibit such deterioration. However, many of the available stabilizers are unsatisfactory in stabilizing effect, are unstable to heat and subject to oxidation, and are easily extracted from the synthetic polymer composition by water and organic solvents. Some of the available stabilizers impart color to the polymer compositions. Murayama et al U.S. patent No. 3,640,928, patented February 8, 1972, discloses the stabilization of synthetic polymers against photo- and thermo-deterioration thereof by incorporating therein a piperidine derivative having the general formula The 2,2,6,6-tetramethylpiperidyl compounds are particularly desirable because they do not impart color, and therefore are widely used. However, these compounds are easily volatilized from the polymer composition at elevated temperature, such as during processing, and are also extracted by water. In addition, many are unsatisfactory in their stabilizing effectiveness. Triazines containing 2,2,6,6-tetramethyl piperidyl groups have a considerably improved heat stability and therefore are preferred for many uses. Chalmers, Jack and Cook, U.S. patent No. 3,925,376 patented December 9, 1975 provide piperidinyl 1,3,5-triazine compounds having the formula: and salts thereof, wherein U is ―CH― or ―N― and Z' is a residue having the formula wherein R₁ and R₂ are the same or different and each is a straight- or branched alkyl residue having from 1 to 12 carbon atoms, or R₁ and R₂ form, together with the ring carbon atom to which they are each bound, a cycloalkyl residue having from 5 to 12 carbon atoms; X is an ―O―, ―S― or residue, wherein R is hydrogen, a straight or branched alkyl residue having from 1 to 20 carbon atoms or an aralkyl residue having from 7 to 12 carbon atoms; Y is O · , hydrogen, a straight or branched alkyl residue having from 1 to 20 carbon atoms, an alkenyl or alkynyl residue having from 3 to 12 carbon atoms, an aralkyl residue having from 7 to 12 carbon atoms or the group wherein R₈ is hydrogen, or a methyl or phenyl residue; n is 0 or 1; and A is ―CH₂―, or the group wherein R₉ is hydrogen or an alkyl residue having from 1 to 20 carbon atoms; Z'' and Z''' are the same or different and each is a piperidine residue of formula II as hereinbefore defined, a halogen atom, a substituted amino group having the formula: wherein R₃ and R₄ are the same or different and each is hydrogen, a straight- or branched alkyl residue having from 1 to 20 carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms, an aryl residue which is unsubstituted or substituted by one or more alkyl groups and having a total of from 6 to 18 carbon atoms or an aralkyl residue having from 7 to 12 carbon atoms; or R₃ and R₄, together with the nitrogen atom to which they are bound form a heterocyclic residue having 5 to 7 ring atoms; or Z'' and Z''' are an hydroxy or ether group having the formula: ―OR₅ IV wherein R₅ is hydrogen, a straight-or branched-chain alkyl residue having from 1 to 20 carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms, an aryl residue which may be unsubstituted or substituted by one or more alkyl groups, having a total of 6 to 18 carbon atoms or an aralkyl residue having from 7 to 12 carbon atoms; or Z'' and Z''' are a thiol or thio ether group having the formula: ―SR₆ V wherein R₆ is hydrogen, a straight- or branched alkyl residue having from 1 to 20 carbon atoms, a cycloalkyl, having from 5 to 12 carbon atoms or a phenyl or benzyl residue. Cassandrini and Tozzi, U.S. patent No. 4,086,204 patented April 25, 1978 provide piperidinyl triazine polymers having the general formula: in which: X, Y, Z the same or different, represent ―O―, ―S―, with R₃ being hydrogen, a straight or branched chain alkyl having 1 to 18 C atoms, a cycloalkyl having 5 to 18 C atoms, a substituted or non-substituted aryl having 6 to 18 C atoms, an aralkyl having 7 to 18 C atoms, or R₃ represents a piperidine radical of the formula: wherein each of R₄, R₅, R₇ and R₈ the same or different, are a C₁ to C₆ alkyl, and R₆ is hydrogen, O, a C₁ to C₁₈ straight or branched chain alkyl, a C₂ to C₁₈ alkenyl or alkynyl, or a C₇ to C₁₈ aralkyl; R₁ is a C₂ to C₁₈ straight or branched chain alkylene, a C₅ to C₁₈ cycloalkylene, a C₆ to C₁₈ arylene, and a C₇ to C₁₈ aralkylene. Furthermore, ―X―R₁―Y― can be a bivalent radical of a heterocycle compound with 6 to 8 members having 2 nitrogen atoms; in such case X and Y are a disubstituted nitrogen atom respectively; ―X―R₁―Y― can be also replaced by the radical in which R₉, R₁₀ the same or different, are H, a C₁ to C₁₂ alkyl, a C₅ to C₁₂ cycloalkyl, a C₆ to C₁₂ aryl, a C₇ to C₁₂ aralkyl; m is either 0 to 1; R₂ represents ―H, ―Cl, ―Br, ―OH, a straight or branched chain C₁ to C₁₈ alkyl, a C₅ to C₁₈ cycloalkyl, a substituted or not substituted C₆ to C₁₈ aryl, a C₇ to C₁₈ aralkyl, a piperidine radical of formula (II), or R₂ represents the radical in which R₁₁, R₁₂ are hydrogen, C₁ to C₁₂ alkyl, C₅ to C₁₂ cycloalkyl, C₆ to C₁₂ aryl, or C₇ to C₁₂ aralkyl; when m is 1, the radical R₂―Z― can be the same as ―X―R₁―YH, where X, Y, R₁ have the meaning above indicated. n is an integer from 2 to 200; A and B represent the terminal groups. By the term "terminal groups" it is meant the terminal groups of a molecule of formula (I) resulting from the polymerization reaction, which generally are a residue of functional groups. The nature of said residue depends on the reaction conditions, the nature and amount of the reactants used in the reaction, for example, as it is known to one skilled in the art. Said residue is preferably H for A and ―X―R₁―YH for B, in that it is preferred using an excess of bifunctional compound in the reaction for controlling the molecular weight. In formula (I) there is the condition that either radical ―X―R₁―Y― or ―(Z) m ―R₂, or both contain at least one piperidine radical of formula (II). Cassandrini and Tozzi, U.S. Patent No. 4,108,829 patented August 22, 1978, provide piperidinyl 1,3,5-triazine compounds having the general formula (I): wherein R₁, R₂ same or different are hydrogen, hydroxyl, a straight or branched chain C₁ to C₁₈ alkyl, a C₅ to C₁₈ cycloalkyl, a substituted or not substituted C₆ to C₁₈ aryl, a C₇ to C₁₈ aralkyl, or a piperidine radical of formula (II) in which R₄, R₅, R₇, R₈ same or different, are each a C₁ to C₆ alkyl and R₆ is H, O, a C₁ to C₁₂ alkyl, a C₂ to C₁₂ alkenyl or alkinyl; R₁, R₂ can also represent a group in which R₉, R₁₀ same or different, are each hydrogen, C₁ to C₈ alkyl, C₅ to C₈ cycloalkyl or C₆ to C₈ aryl; X, Y same or different represent ―O―, ―S―, R₁₁ being H, a straight or branched chain C₁ to C₁₈ alkyl, C₅ to C₁₈ cycloalkyl, C₆ to C₁₈ aryl; C₇ to C₁₈ aralkyl, or a piperidine radical of formula (II). The radicals R₁―X―, R₂―Y―, taken as a single substituent group, can also be radicals from nitrogenous heterocyclic compounds having 5 to 8 members, linked to the triazine ring by a bisubstituted nitrogen atom of said radical. They can also represent Cl― or Br―; n is an integer from 2 to 6; R₃ is a n-valent residue deriving from a polyalcohol, a polymercaptan or a polyamine by reaction of the active H atoms thereof with a halogen atom of a monohalogen triazine; R₃ can be a radical of type R₁₂―(Z) n ―, wherein R₁₂ is a n-valent, C₁ to C₁₈ aliphatic, C₅ to C₁₈ cycloaliphatic or C₆ to C₁₈ aromatic radical, and Z is ―O―; ―S―, wherein R₁₁ has the same meaning as previously indicated. When n = 2, the radical R₃ can also be the bivalent radical of a nitrogenous heterocyclic compound having 6 to 8 members, the bisubstituted nitrogen atoms of which are linked to a triazine ring; when n = 2, R₃ can also be a radical of type in which R₁₃, R₁₄ same or different, are each hydrogen, C₁ to C₁₂ alkyl, C₅ to C₁₂ cycloalkyl, C₆ to C₁₂ aryl, C₇ to C₁₂ aralkyl or a piperidine radical of formula (II). When n = 3, 4, 5, 6, R₃ can also be a radical of type in which R₁₁ has the same meaning as previously indicated; r, s, same or different, are an integer from 2 to 6 and t is an integer from 0 to 3. In formula (I) there is the condition that at least in one of the radicals R₁―X―, R₂―Y― and R₃, at least one piperidine radical of formula (II) be present. Evans and Rasberger, U.S. patent No. 4,161,592 patented July 17, 1979, provide piperidine derivatives of 1,3-pyrimidine and 1,3,5-triazine which combine a light stabilizing effect and surprisingly good antioxidative properties in one and the same molecule. Moreover, the new compounds are distinguished by good color properties. The compounds correspond to the general formula I or to addition salts thereof, in which one of the radicals R', R'' and R''' denotes a group of the formula II: wherein one of R₁ and R₃ is ―OH and the other is hydrogen, R₂ denotes C₁-C₁₂ alkyl, C₅-C₇ cycloalkyl, C₆-C₁₀ aryl or C₇-C₉ aralkyl, R₄ and R₅ are hydrogen, C₁-C₁₂ alkyl, C₅-C₇ cycloalkyl, C₆-C₁₀ aryl or C₇-C₉ aralkyl, n denotes 0 to 12 and X denotes ―O―, ―S― or ―NR₆― wherein R₆ is hydrogen or C₁-C₁₂ alkyl, and one of the radicals R', R'' and R''' denotes one of the groups in which Y is ―O― or ―NR₆― wherein R₆ has the meaning defined above, Z denotes ―O― or ―S―, m is 1 to 6, R₇ is hydrogen or C₁-C₈ alkyl and R₈ is hydrogen, oxy, C₁-C₁₂ alkyl, C₃-C₆ alkenyl, C₃-C₄ alkinyl, C₂-C₂₁ alkoxyalkyl, C₇-C₉ aralkyl, 2,3-opoxypropyl, an aliphatic acyl group with 1-4 C atoms or one of the groups ―CH₂COOR₉, ―CH₂―CH(R₁₀)―OR₁₁, ―COOR₁₂ or ―CONHR₁₂, wherein R₉ is C₁-C₁₂ alkyl, C₃-C₆ alkenyl, phenyl, C₇-C₈ aralkyl or cyclohexyl, R₁₀ is hydrogen, methyl or phenyl, R₁₁ denotes hydrogen, an aliphatic, aromatic, araliphatic or alicyclic acyl group with 1-18 C atoms, wherein the aromatic part, if appropriate, can be substituted by chlorine, C₁-C₄ alkyl, C₁-C₈ alkoxy and/or by hydroxyl, and R₁₂ denotes C₁-C₁₂ alkyl, cyclohexyl, phenyl or benzyl, and R₁₃ denotes hydrogen, ―OH or one of the groups ―O―CO―R₁₄ or ―NR₁₂―CO―R₁₄, wherein R₁₄ denotes C₁-C₁₂ alkyl or phenyl, and one of the radicals R', R'' and R''' independently of the others denotes an identical or different group of the formula II, or denotes an identical or different group III; IV or V, or denotes ―N₃ or one of the groups ―S―R₁₅, ―OR₁₇, ―P(O)―(OR₁₇)₂ or ―NR₁₈R₁₉, wherein R₁₅ denotes hydrogen C₁-C₁₈ alkyl, C₅-C₇ cycloalkyl, C₆-C₁₀ aryl, C₇-C₉ aralkyl or the group ―(C p H 2p )―CO―OR₁₆ wherein R₁₆ is C₁-C₁₈ alkyl and p denotes 1 to 6, R₁₇ denotes C₁-C₁₈ alkyl, C₆-C₁₀ aryl or C₇-C₉ aralkyl and R₁₈ and R₁₉ independently of one another denote hydrogen, C₁-C₁₃ alkyl, C₅-C₇ cycloalkyl, C₆-C₁₀ aryl, C₇-C₉ aralkyl or the group in which R₇ and R₈ have the meaning defined above. Rody and Berner, U.S. patent No. 4,234,728 patented November 18, 1980, provide s-triazine derivatives which contain, as substituents in the 2-, 4- and 6-position, at least one polyalkylpiperidine radical and at least one N-methylolamino group, or the ethers thereof. These compounds can be mono- or polytriazines, and have the formula I or II in which m is an integer from 1 to 4 and n is a value from 2 to 50, X and X' are ―O―; ―S― or ―NR⁶―, in which R⁶ is hydrogen, C₁-C₁₈ alkyl, C₃-C₈ alkenyl, C₂-C₄ hydroxyalkyl, C₂-C₁₃ alkoxyalkyl, C₅-C₁₂ cycloalkyl, C₆-C₁₀ aryl, C₇-C₉ phenylalkyl or a polyalkyl piperidine group of the formula III in which R is hydrogen or methyl, p is 0 or 1, A is C₁-C₄ alkylene, ―NR⁶―C₂―C₁₂ alkylene or ―OCH₂CH₂CH₂― and R is H, O, C₁-C₁₂ alkyl, allyl, benzyl or a ―CH₂CH(R⁸)―OH group, in which R⁸ is H, CH₃, C₂H₅ or phenyl, and R¹ and R³ are hydrogen, C₁-C₁₈ alkyl, C₃-C₈ alkenyl, C₁-C₄ hydroxyalkyl, C₂-C₁₃ alkoxyalkyl, C₅-C₁₂ cycloalkyl, C₆-C₁₀ aryl, C₇-C₉ phenylalkyl, phenyl or phenylalkyl which is substituted by 1 or 2 C₁-C₈ alkyl groups and/or OH and/or C₁-C₄ alkoxy, or a polyalkylpiperidine group of the formula III, R² is hydrogen, C₁-C₁₈ alkyl, C₃-C₈ alkenyl, C₂-C₆ hydroxyalkyl or C₃-C₆ alkoxyalkyl, R⁴, if m is 1, is hydrogen, C₁-C₁₈ alkyl, C₃-C₈ alkenyl, C₂-C₄ hydroxyalkyl, C₃-C₆ alkoxyalkyl, C₅-C₁₀ aryl, C₇-C₉ phenylalkyl, phenyl or phenylalkyl which is substituted by 1 or 2 C₁-C₈ alkyl groups and/or OH and/or C₁-C₄ alkoxy, or a polyalkylpiperidine group of the formula III, and if m is 2 is C₂-C₁₂ alkylene or oxaalkylene, C₄-C₁₂ alkenylene, C₆-C₁₀ arylene, a phenylene-Z-phenylene-radical, in which Z is ―O―, ―S―, ―SO₂―, ―CH₂― or ―C(CH₃)₂― or a radical of the formula wherein r is 2 or 3 and q is 0 or 1 and Y is a triazinyl group of the formula IV, and if m is 3 is a R³―C(CH₂―)₃ radical, in which R³ is C₁-C₄ alkyl, and if m is 4 is a C(CH₂―)₄ radical, R⁵ is C₂-C₁₂ alkylene and E and E' are corresponding end groups and at least one of the radicals R¹, R³, R⁴ or R⁵ is a piperidine radical of the formula III. Cassandrini and Tozzi, U.S. patent No. 4,263,434 patented April 21, 1981, provides piperidyltriazine derivatives which are useful for improving the stability to light, heat and oxidation of polymeric substances, and which have the general formula (I): wherein R₁, R₂ same or different are hydrogen, hydroxyl, a straight or branched chain C₁ to C₁₈ alkyl, a C₅ to C₁₈ cycloalkyl, a substituted or not substituted C₆ to C₁₈ aryl, a C₇ to C₁₈ aralkyl, or a piperidine radical of formula (II) in which R₄, R₅, R₇, R₈ same or different, are each a C₁ to C₆ alkyl and R₆ is H, O, a C₁ to C₁₂ alkyl, a C₂ to C₁₂ alkenyl or alkinyl; R₁, R₂ can also represent a group in which R₉, R₁₀ same or different, are each hydrogen, C₁ to C₈ alkyl, C₅ to C₈ cycloalkyl or C₆ to C₈ aryl; X, Y same or different represent ―O―; ―S―, R₁₁ being H, a straight or branched chain, C₁ to C₁₈ alkyl, C₅ to C₁₈ cycloalkyl, C₆ to C₁₈ aryl, C₇ to C₁₈ aralkyl, or a piperidine radical of formula (II). The radicals R₁―X―, ―R₂―Y―, taken as a single substituent group, can also be radicals from nitrogenous heterocyclic compounds having 5 to 8 members, linked to the triazine ring by a bisubstituted nitrogen atom of said radical They can also represent Cl― or Br―; n is an integer from 2 to 6; R₃ is a n-valent residue deriving from a polyalcohol, a polymercaptan or a polyamine by reaction of the active H atoms thereof with a halogen atom of a monohalogen triazine; R₃ can be a radical of type R₁₂ ―(Z) n ―, wherein R₁₂ is a n-valent, C₁ to C₁₈ aliphatic, C₅ to C₁₈ cycloaliphatic or C₆ to C₁₈ aromatic radical, and Z is ―O―, ―S―; wherein R₁₁ has the same meaning as previously indicated. When n = 2, the radical R₃ can also be the bivalent radical of a nitrogenous heterocyclic compound having 6 to 8 members, the bisubstituted nitrogen atoms of which are linked to a triazine ring; when n = 2, R₃ can also be a radical of type in which R₁₃, R₁₄, same or different, are each hydrogen, C₁ to C₁₂ alkyl, C₅ to C₁₂ cycloalkyl, C₆ to C₁₂ aryl, C₇ to C₁₂ aralkyl or a piperidine radical of formula (II). When n = 3, 4, 5, 6, R₃ can also be a radical of type in which R₁₁ has the same meaning as previously indicated; r, s, same or different, are an integer from 2 to 6 and t is an integer from 0 to 3. In formula (I) there is the condition that at least in one of the radicals R₁―X―, R₂―Y― and R₃, at least one piperidine radical of formula (II) be present. Rody, U.S. patent No. 4,288,593, patented September 8, 1981, provides polyalkylpiperidine derivatives of s-triazines of the formula in which X and X' are a divalent organic radical, X'', X₁ AND X₂ are a direct bond or a divalent organic radical, Y, Y', Y'', Y₁, Y₂, Z and Z' are ―O―, ―S―, ―NH― or ―NR³―, R is H or CH₃ and R¹, R² and R³ are a monovalent organic radical or a polyalkylpiperidine group, or the group R¹―X''―Y''― is chlorine, and R⁴ is H, O, alkyl, allyl or benzyl. These are stabilizers for polymeric materials, in particular to protect them against photochemical degradation. Nikles, U.S. patent No. 4,315,859 patented February 16, 1982, provides polymeric polyamine-1,3,5-triazines which have an excellent stabilizing action, of the general formula I wherein the symbols which may or may not recur in the compound, and which on each possible recurrence can be the same or different, are defined as follows: X is C₂-C₆ alkylene, A is ―O―, ―S― or ―NR―, wherein R, which is also recurring or non-recurring and on each possible recurrence can be the same or different, is hydrogen, C₃-C₁₂ cycloalkyl, C₇-C₁₈ aralkyl, C₆-C₁₀ aryl or the radical of the formula II wherein R³ is hydrogen, C₁-C₁₈ alkyl, C₃-C₁₂ alkenyl, C₃-C₅ alkynyl, C₃-C₁₈ alkoxyalkyl, C₂-C₄ hydroxyalkyl which is unsubstituted or substituted by phenyl or phenoxy, or C₇-C₁₈ aralkyl, and R⁴ is hydrogen or methyl, or R is also one or more of the structural units contained with the brackets of formula I, said structural unit or units being terminally saturated by U and being bound through a triazine C atom, and wherein R and R¹ as end groups, each independently of the other, can be hydrogen, C₁-C₂₃ alkyl which can be interrupted by oxygen, C₃-C₁₂ cycloalkyl, C₇-C₁₈ aralkyl, C₆-C₁₀ aryl or the radical of the formula II, and R¹ as end group can also in addition be a group of the formula III wherein R⁵ and R⁶, each independently of the other, are U, C₁-C₂₃ alkyl which can be interrupted by oxygen, C₃-C₁₂ cycloalkyl, C₇-C₁₈ aralkyl, C₆-C₁₀ aryl, the radical of the formula II or a group of the formula IV R² is halogen cyano, azido, hydrazido, phenyl, ―OR⁷, ―SR⁷ or ―NR⁸R⁸', wherein R⁷ is hydrogen, C₁-C₁₈ alkyl, C₃-C₁₂ alkenyl, C₃-C₁₈ alkoxyalkyl, C₃-C₁₂ cycloalkyl, C₇-C₁₈ aralkyl, C₆-C₁₀ aryl, or the radical of the formula II, and R⁸ and R⁸', each independently of the other, are hydrogen, C₁-C₂₃ alkyl which can be interrupted by oxygen, C₃-C₁₈ alkenyl, C₃-C₅ alkynyl, C₂-C₁₀ hydroxyalkyl, C₂-C₅ cyanoalkyl, C₃-C₁₂ cycloalkyl, C₇-C₁₈ aralkyl, C₆-C₁₀ aryl or the radical of the formula II, or R⁸ and R⁸' together with the nitrogen atom to which they are attached form a pyrrolidine ring or a piperidine, morpholine or hexamethyleneimine ring which is unsubstituted or substituted by C₁-C₄ alkyl, or R² on each of its possible recurrences can also be a radical of the formula V wherein a can be 0, 1, 2, 3 or 4, or a radical of the formula VI wherein q can be 0, 1 or 2 and r can be 0, 1, 2 or 3, whilst the sum of r + q may not be more than 3, or R² can also be one or more of the structural units contained with the brackets of formula I, said structural unit or units being terminally saturated by Q and being bound through the amine nitrogen atom, and wherein R² as end group is halogen, phenyl, ―OR⁷, ―SR⁷, ―NR⁸R⁸', a group of the formula VII, or of the formula VIII wherein A¹ is ―O―, ―S― or ―NR⁵, whilst Q is halogen, ―NR⁸R⁸', ―OH, ―OMe/b, wherein Me/b represents an alkali metal or alkaline earth metal of the valency b, and b is 1 or 2, or Q is a radical of the formula VII or VIII, U is hydrogen, a group of the formula or C₁-C₂₄ acyl, and n can be an integer from 1 to 100, with the priviso that at least one R, one R¹ or one R² is or contains a group of the formula II and, if m is 0, at least one R¹ must be a group of the formula III or IV. Rody, U.S. patent No. 4,294,963, patented October 13, 1981, provides polyalkylpiperidine derivatives of s-triazines as stabilizers for polymers. The compounds have the formula I or II wherein m is 2, 3 or 4, n is 2 to 50, p is 0 or 1, X, X' and X'' represent a direct bond, C₁-C₄ alkylene or ―OCH₂CH₂CH₂―, the O of which is not bonded to Y, Y' or Y''; Y, Y', Y'' and Y''' represent ―O―, ―S―, ―NH― or ―NR³―, Z represents C₂-C₁₂ alkylene, C₄-C₂₀ alkylene interrupted by ―O―, ―S―, ―NH― or ―NR³―, xylylene, C₆-C₁₂ arylene or phenylene Q' phenylene, wherein Q' is ―CH₂―, >C(CH₃)₂, ―SO₂― or ―O―, R represents hydrogen or C₁-C₄ alkyl, R¹, R² and R³ represent C₁-C₁₂ alkyl, C₂-C₈ alkoxyalkyl, C₂-C₄ hydroxyalkyl, C₅-C₁₂ cycloalkyl, C₇-C₁₂ aralkyl, C₃-C₁₈ alkenyl, C₆-C₁₀ aryl, phenyl which is substituted by one or two C₁-C₈ alkyl groups and/or by OH and/or by C₁-C₄ alkoxy, or represent a polyalkylpiperidinyl group of the formula III or, if Y' or Y'' is ―NR³― and X' or X'' is a direct bond, R¹ and R² together with the nitrogen atom form a pyrrolidone, piperidine or morpholine ring, R⁴ represents hydrogen, O·, C₁-C₁₂ alkyl, allyl or benzyl, A if m is 2, represents C₂-C₁₂ alkylene, C₄-C₈ alkylene, xylylene or a radical of the formula ―CH₂―C≡C―CH₂―, ―CH₂―COO―R⁵―OOC―CH₂, ―CH₂―CH(OH)―CH₂―or ―CH₂CH(OH)CH₂―D―CH₂CH(OH)CH₂―, or if m is 3, represents a group of the formula and, if m is 4, represents a group of the formula B represents C₂-C₁₂ alkylene, C₄-C₈ alkenylene, xylylene or a radical of the formula ―CH₂―COO―R⁵―OOC―CH₂, ―CH₂―CH(OH)―CH₂ or ―CH₂CH(OH)CH₂―D―CH₂CH(OH)CH₂, R⁵ represents C₂-C₈ alkylene, C₄-C₈ oxaalkylene or cyclohexylene, D represents a divalent radical of the formula ―O―R⁶―O―, ―O―C(O)―R⁷―C(O)―O―, ―OCH(R⁸)CH₂O―R⁶―OCH₂CH(R⁸)O― or R⁶ represents C₂-C₁₂ alkylene, C₆-₁₂ cycloalkylene, C₆-C₁₂ arylene or phenylene Z₁ phenylene, wherein Z₁ represents ―CH₂―, >C(CH₃)₂, ―SO₂― or ―O―, R⁷ represents a direct bond, C₁-C₁₂ alkylene, C₂-C₆ alkenylene, C₆-C₁₂ cycloalkylene or cycloalkenylene or C₆-C₁₂ arylene, R⁸ and R⁹ are hydrogen or C₁-C₄ alkyl, T represents a trivalent radical of the formulae R¹⁰ represents a trivalent aliphatic hydrocarbon radical of 3 to 10 carbon atoms, Q represents a quadrivalent radical of the formula R¹¹ represents a quadrivalent aliphatic hydrocarbon radical of 4 to 10 carbon atoms, and E and E' represent end groups. Sankyo and Ciba-Geigy British patent No. 1,496,454 discloses 3- or 5-substituted 2,2,6,6-tetra-4-piperidinol derivatives of the general formula: In this formula, R a and R b may be hydrogen, but one must be lower alkyl, alkenyl or alkynyl, so that a 3- or 5-substituent is necessary. Y is a mono to tetravalent organic group, and X can be hydrogen. Various types of Y groups are illustrated at page 6, column 1, including a group of formula which is 1,3,5-triazine. The Sankyo British patent also indicates in the summary of prior art at page 2, column 1, that German Offenlegungsschrift No. 2,319,816 discloses 2,4,6-tri(piperidyl-4-oxy-1,3,5-triazine derivatives. Rasberger and Karrer, U.S. patent No. 4,317,911, patented March 2, 1982, discloses piperidinyl isocyanurates having the general formula: These compounds have the piperidinyl group attached to the isocyanurate nucleus by way of a linking group, where X can be oxygen. Morimura, Toda and Kurumada, U.S. patent No. 4,321,374 patented March 23, 1982, provides s-triazine derivatives having the formula wherein R₁ represents hydrogen atom or methyl group, R₂ represents hydrogen atom, an alkanoyl group having from 2 to 18 carbon atoms or 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl group, n is 1 or 2, when n is 1, X represents an alkyl group having from 1 to 18 carbon atoms, benzyl group or a group of the formula ―CH₂CH₂OR₂ (wherein R₂ is as defined above) and Y represents hydrogen atom, a group of the formula or a group of the formula (wherein R₁ and R₂ are as defined above), when n is 2, X represents an alkylene group having from 2 to 6 carbon atoms, xylylene group or a group of the formula (wherein m is an integer from 1 to 4 and Z represents a group of the above formula (III)) and Y represents hydrogen atom or a group of the above formula (II). In the formula (I), R₂ as an alkanoyl group having from 2 to 18 carbon atoms can be, for example, acetyl, propionyl, butyryl, hexanoyl, octanoyl, lauroyl, palmitoyl or stearoyl, in particular, it is desirably an alkanoyl group having from 2 to 4 carbon atoms. X as an alkyl group having from 1 to 18 carbon atoms can be a straight or branched chain alkyl, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, 2-ethylhexyl, tert-octyl, decyl, dodecyl, tetradecyl or octadecyl, in particular, it is desirably an alkyl group having from 8 to 18 carbon atoms. X as an alkylene group having from 2 to 6 carbon atoms can be, for example, 1,2-ethylene, 1,2-propylene, 1,4-butylene or 1,6-hexylene, desirably 1,6-hexylene. Preferred compounds of the formula (I) are those in which R, is hydrogen atom or is R₂ is hydrogen atom. More preferred compounds of the formula (I) are those in which (1) R₁ and R₂ are hydrogen atom, n is 1, X is an alkyl group having from 8 to 10 carbon atoms and Y is hydrogen atom or 2,4-bis[2-hydroxy-N-(2,2,6,6-tetramethyl-4-piperidyl) ethylamino]-1,3,5-triazine-6-yl group; (2) R₁ and R₂ are hydrogen atom, n is 1, X is 2-hydroxyethyl group and Y is 2,2,6,6-tetramethyl-4-piperidyl group, (3) R₁ and R₂ are hydrogen atom, n is 2, X is 1,6-hexylene group or a group of the formula (wherein m is an integer from 1 to 4 and Z is 2,4-bis[2-hydroxy-N-(2,2,6,6-tetramethyl-4-piperidyl)e-thylamino]-1,3,5-triazine-6-yl group) and Y is hydrogen atom. U.K. Patent Application No. 2,117,377 published October 12, 1983 discloses piperidine derivatives that have the general formula where R denotes hydrogen, alkyl, cycloalkyl, alkenyl, aralkyl or aryl; R₁ and R'₁ denote hydrogen, alkyl, alkenyl or aralkyl; R₂ and R'₂ devote hydrogen or methyl; X and X' denote oxygen or NR₃; R₃ denotes hydrogen, alkyl, cycloalkyl or aralkyl; A and A' denote (CH₂) m X''; m equals 2 or 3; X'' has the same meaning as X and X', and n can be 0 or 1. These are used as stabilizers for polymers. U.S. patent No. 4,500,663 patented February 19, 1985, provides N,N,N-tris(2,2,6,6-tetramethyl-4-piperidone ketal)-1,3,5-triazines having the formula: wherein: R₁ is selected from the group consisting of hydrogen and alkyl having from one to about four carbon atoms; and R₂ is selected from the group consisting of hydrogen; oxyl O · ; alkyl, hydroxy alkyl and epoxyalkyl having from one to about eighteen carbon atoms; acyl having from one to about eighteen carbon atoms; cycloalkyl having from three to about eighteen carbon atoms; phenyl; phenalkyl and alkylphenyl having from seven to about twenty-four carbon atoms; as well as synthetic resin compositions having an improved resistance to deterioration and containing such compounds. U.S. patent No. 4,540,728, patented September 10, 1985, provides polymers of diallyl-1,3,5-triazino-4-(2,2,6,6-tetramethyl piperidyl) amines having a molecular weight within the range from about 800 to about 20,000, and derived from the monomer: wherein: R₁ is selected from the group consisting of hydrogen; oxyl; alkyl and hydroxyalkyl having from one to about eighteen carbon atoms; alkylaryl having from seven to about eighteen carbon atoms; epoxy alkyl having from three to about eighteen carbon atoms; and acyl having from two to about eighteen carbon atoms; Y is selected from the group consisting of where R₂ and R₃ are hydrogen or alkyl having from one to about eight carbon atoms and n is 0 or 1; Z is selected from the group consisting of in which R₄, R₅ and R₆ are selected from the group consisting of hydrogen; alkyl having from one to about eighteen carbon atoms; cycloalkyl having from three to about twelve carbon atoms; and aryl having from six to about thirty carbon atoms; as well as stabilized synthetic resin compositions having an improved resistance to deterioration by light and containing such a polymer. U.S. patent No. 4,491,643, patented January 1, 1985, provides bis(2,2,6,6-tetramethylpiperidyl-1,3,5-triazinyl)-spirodiamines and spiroglycol ethers having the formula: wherein: R₁ is selected from the group consisting of hydrogen, alkyl having from one to about eighteen carbon atoms, hydroxyalkyl having from two to about six carbon atoms; epoxyalkyl having from three to about eight carbon atoms; alkylaryl having from seven to about eighteen carbon atoms; acyl having from two to about eight carbon atoms;and oxyl; R₂ is alkylene having from one to about six carbon atoms; Z is selected from the group consisting of in which R₃ is alkyl having from one to about six carbon atoms; and R₄ is selected from the group consisting of hydrogen; alkyl having from one to about eighteen carbon atoms; cycloalkyl having from about four to about eight carbon atoms; hydroxy alkyl and alkoxyalkyl having from two to about twelve carbon atoms and dialkylamino having from two to about ten carbon atoms; X is selected from the group consisting of ―O― and in which R₅ is selected from the group consisting of hydrogen, alkyl having from one to about eighteen carbon atoms; cycloalkyl having from about four to about eight carbon atoms; hydroxy alkyl and alkoxyalkyl having from two to about twelve carbon atoms, and dialkylamino having from two to about ten carbon atoms; and Y is selected from the group consisting of: and Cl; in which R₆ is selected from the group consisting of alkyl having from one to about eighteen carbon atoms; cycloalkyl having from about four to about eight carbon atoms; hydroxy alkyl and alkoxyalkyl having from two to about twelve carbon atoms and dialkylamino having from two to about ten carbon atoms and aryl and alkaryl having from six to about twenty-four carbon atoms; R₇ and R₈ are selected from the group consisting of hydrogen, alkyl having from one to about eighteen carbon atoms; and alkylene forming a heterocyclic ring including the nitrogen atom in the ring and having from four to seven carbon atoms and no or one oxygen atom; and n is a number from 1 to about 50 representing the average number of units enclosed by the brackets; and synthetic resin compositions containing the same as light stabilizers. Additional patents disclosing such compounds include Rody U.S. patent No. 4,288,593, Morimura et al U.S. patent No. 4,322,527 and Japan Kokai No. 67749/78 and 102637/80. The Cassandrini et al compounds having more than 2 triazine rings derived from polyamines or polyols have an exceptionally good heat stability and low extractability, but the stabilizing effect of these compounds is not fully satisfactory. In accordance with the present invention, hydrocarbyl (polyphenol)-poly(2,2,6,6-tetramethyl-piperidyl-1,3,5-triazines) are provided having the formula: in which: R is a n-valent alkylene or alkylidene group; R₁ is selected from the group consisting of hydrogen; alkyl, alkenyl, hydroxyalkyl and alkoxy, all groups having from one to about twelve carbon atoms; cycloalkyl having from three to twelve carbon atoms; acyl having from about one to about twelve carbon atoms; and oxyl (O · ); Y is selected from the group consisting of wherein R₄ is lower alkyl having from one to about six carbon atoms; R₅ is selected from the group consisting of hydrogen; alkyl, hydroxy alkyl and alkoxy having from one to about twelve carbon atoms; and cycloalkyl having from three to about twelve carbon atoms; and X is selected from the group consisting of wherein: R₆ is selected from the group consisting of alkyl, hydroxyalkyl and alkylenealkoxy having from one to about twelve carbon atoms; cycloalkyl having from three to about twelve carbon atoms; and aryl having from six to about eighteen carbon atoms; R₇ and R₈ are selected from the group consisting of hydrogen; alkyl having from one to about twelve carbon atoms; cycloalkyl having from three to about twelve carbon atoms; and aryl having from six to about eighteen carbon atoms; and R₇ and R₈ taken together as a five to six member ring including the nitrogen atom in the ring; R₂ and R₃ are selected from the group consisting of hydrogen and lower alkyl having from one to about six carbon atoms; all groups being optionally substituted by one or more alkyl groups with one to twelve carbon atoms; and n is a number from 2 to 4. These compounds have an improved stabilizing effectiveness, as compared to previous compounds of this type, and impart to synthetic polymer compositions a considerably improved resistance to deterioration upon exposure to ultraviolet light. The alkylene or alkylidene group R is selected from alkylenes or alkylidenes having from one to eighteen carbon atoms. Exemplary R alkylene groups include methylene; ethylene; 1,2-propylene and 1,3-propylene; butylene, including 1,2-butylene, 2,3-butylene, 2,4-butylene and 1,4-butylene; pentylene, including 1,5-pentylene, 1,3-pentylene, 1,4-pentylene, 1,2-pentylene and 2,4-pentylene; hexylene, including 1,6-hexylene, 1,2-hexylene, 1,3-hexylene, 1,4-hexylene, 1,5-hexylene, 2,3-hexylene, 2,4-hexylene and 2,5-hexylene; heptylene, including 1,7-heptylene, 1,2-heptylene, 1,3-heptylene, 1,4-heptylene, 1,5-heptylene, 2,6-heptylene, 2,3-heptylene, 2,4-heptylene, 3,5-heptylene, and 3,4-heptylene; octylene, including 1,8-octylene, 1,2-octylene, 1,3-octylene, 1,4-octylene, 1,5-octylene, 2,7-octylene and 2,4-octylene; nonylene, including 1,9-nonylene, 2,7-nonylene, and 2,5-nonylene; decylene, including 1,10-decylene, 2,4-decylene, 2,5-decylene and 2,8-decylene; undecylene, including 1,11-undecylene, 2,10-undecylene, 3,5-undecylene and 4,8-undecylene; and dodecylene, including 1,12-dodecylene, 2,11-dodecylene, 2,4-dodecylene, and 3,6-dodecylene. Exemplary R alkylidene include methylidene, ethylidene, isopropylidene, butylidene, isobutylidene, pentylidene, isopentylidene, hexylidene, isohexylidene, heptylidene, octylidene, nonylidene, decylidene, undecylidene and dodecylidene. Exemplary R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary-butyl, secondary-butyl, amyl, isoamyl, secondary-amyl, tertiary-amyl, hexyl, isohexyl, tertiary-hexyl, heptyl, isoheptyl, secondary-heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, dodecyl, isododecyl, hexadecyl and octadecyl. Exemplary R₁, R₅, R₆, R₇ and R₈ hydroxyalkyl include 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 2,3-dihydroxy butyl, 6-hydroxy hexyl, 12-hydroxy dodecyl. Exemplary R₁, R₅, R₆, R₇ and R₈ alkoxy include methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy, heptoxyl, decoxy, dodecoxy, methoxyethyl, butoxyethyl, 2,3-epoxypropyl, ethoxydecyl, and propoxypropyl. Exemplary R₁ alkenyl include allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, and dodecenyl. Exemplary R₁ acyl include acetyl, propionyl, butyroyl, acryloyl, methacryloyl, octanoyl and benzoyl. Exemplary R₁, R₅, R₆, R₇ and R₈ cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. Exemplary R₆, R₇ and R₈ aryl include phenyl, naphthyl, tolyl, xylyl, mesityl, tertiary-butylphenyl, octylphenyl, 2,4-di-tertiary-butylphenyl, nonylphenyl and dinonylphenyl. Exemplary five- and six-member rings formed with R₇, R₈ and the nitrogen atom include pyrollidino, piperidino, morpholino and methylpiperidino. Exemplary X alkylamino include dimethyl amino, diethylamino, methyl cyclohexylamino, dipropylamino, and dicyclohexyl amino. The following compounds are exemplary: These compounds are easily prepared by known procedures, reacting cyanuric chloride with the corresponding 2,2,6,6-tetramethyl piperidine compound, followed by reaction with the corresponding hydrocarbyl polyphenol. Polyphenols useful as raw materials for preparing these compounds include 4,4'-isopropylidenediphenol, 4,4'-methylenediphenol, 4,4'-methylenebis(2,6-dimethylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)-3-phenylpropane, and 1,1,5,5-tetra(4-hydroxyphenyl)pentane and 1,1,5,5-tetra(2-methyl-4-hydroxyphenyl)pentane. The following Examples illustrate the procedure. 4,4'-Isopropylidenebisphenol, 1.71 g, 28% sodium methoxide solution in methanol, 2.90 g, sodium iodide, 0.48 g, and diethyleneglycol diethyl ether, 30 ml, were mixed and stirred for 30 minutes at 80°C. Then 2-chloro-4,6-bis(N-2,2,6,6-tetramethyl-4-piperidyl)butylamino)-1,3,5-triazine, 8.03 g, was added, and the mixture stirred for 20 hours under reflux. Then the reaction was stopped by distilling off the solvent. 50 ml of benzene was added, the solution washed with water, and then dried. The solvent was distilled off, and the product purified by passage through a silica gel column using methanol/acetone as the solvent. The product was a glassy solid melting at 108-112°C. 1,1,3-Tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1.82 g, sodium methoxide 28% solution in methanol, 1.93 g, sodium iodide, 0.36 g, and diethyleneglycol diethyl ether, 20 ml, were mixed and stirred for 30 minutes at 80°C. Then 2-chloro-4,6-bis((N-2,2,6,6-tetramethyl-4-piperidyl)butylamino)1,3 5-triazine, 5.36 g, was added, and the mixture stirred for 20 hours under reflux. The product was isolated by distilling off the solvent. 50 ml of benzene was added, and the solution washed with water and dried. The solvent was then distilled off, and the product purified by passage through a silica gel column, using methanol/acetone as the solvent. The product obtained was a glassy solid, melting at 143-147°C. The hydrocarbyl(polyphenol) poly(piperidyl triazines) of this invention are effective light stabilizers for polymeric materials that are subject to deterioration when exposed to light. Small amounts are effective. An amount within the range from about 0.001 to about 5 parts, preferably from 0.01 to 3 parts, by weight per 100 parts by weight of polymer is usually sufficient. Larger amounts can be used, if desired. Synthetic resins that can have their resistance to deterioration enhanced with the hydrocarbyl(polyphenol)poly (piperidyl triazines) according to this invention include α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-3-methylbutene, or mixtures thereof, and copolymers with other monomers such as ethylene-vinyl acetate copolymer; ethylene-propylene copolymer; polystyrene; polyvinyl acetate; polyacrylic esters; copolymers from styrene and another monomer (for example, maleic anhydride, butadiene, and acrylonitrile); acrylonitrile-butadiene-styrene copolymer, acrylic acid ester-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, polymethacrylate esters such as polymethacrylate; polyvinyl alcohol; polyvinyl formal; polyvinyl butyral; linear polyesters, polyamides; polycarbonates; polyacetals; polyurethanes; cellulosic resins; phenol-formaldehyde resins; urea-formaldehyde resins; melamine-formaldehyde resins; epoxy resins; unsaturated polyester resins; silicone resins; halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and copolymers thereof, and rubbers such as isoprene rubber, butadiene rubber, epichlorohydrin rubber, chloroprene rubber, and blends of any of the above. The hydrocarbyl(polyphenol)poly(piperidyl triazines) of the invention can be combined with conventional heat stabilizers such as phenolic antioxidants, polyvalent metal salts of organic acids, organic phosphites, thioethers, and other known heat stabilizers, thereby constituting light and heat stabilizer compositions of the invention. The phenolic antioxidant contains one or more phenolic hydroxyl groups, and one or more phenolic nuclei, and can contain from about eight to about three hundred carbon atoms. In addition, the phenolic nucleus can contain an oxy or thio ether group The alkyl-substituted phenols and polynuclear phenols, because of their molecular weight, have a higher boiling point, and therefore are preferred because of their lower volatility. There can be one or a plurality of alkyl groups of one or more carbon atoms. The alkyl group or groups including any alkylene groups between phenol nuclei preferably aggregate at least four carbon atoms. The longer the alkyl or alkylene chain, the better the compatibility with polypropylene, inasmuch as the phenolic compound then acquires more of an aliphatic hydrocarbon character, and therefore there is no upper limit on the number of alkyl carbon atoms. Usually, from the standpoint of availability, the compound will not have more than about eighteen carbon atoms in an alkyl, alicyclidene and alkylene group, and a total of not over about fifty carbon atoms. The compounds may have from one to four alkyl radicals per phenol nucleus. The phenol contains at least one and preferably at least two phenolic hydroxyls, the two or more hydroxyls being in the same ring, if there is only one. In the case of bicyclic phenols, the rings can be linked by thio or oxyether groups, or by alkylene, alicyclidene or arylidene groups. The monocyclic phenols which can be employed have the structure: R is selected from the group consisting of hydrogen; halogen; and organic radicals containing from one to about thirty carbon atoms, such as alkyl, aryl, alkenyl, alkaryl, aralkyl, cycloalkenyl, cycloalkyl, alkoxy, and acyl where R' is aryl, alkyl or cycloalkyl. x₁ and x₂ are integers from one to four, and the sum of x₁ and x₂ does not exceed six. The polycyclic phenol phenol is one having at least two aromatic nuclei linked by a polyvalent linking radical, as defined by the formula: wherein Y is a polyvalent linking group selected from the group consisting of oxygen; carbonyl; sulfur; sulfinyl; aromatic, aliphatic and cycloaliphatic hydrocarbon groups; and oxyhydrocarbon, thiohydrocarbon and heterocyclic groups. The linking group can have from one up to twenty carbon atoms. Ar is a phenolic nucleus which can be a phenyl or a polycarbocyclic group having condensed or separate phenyl rings; each Ar group contains at least one free phenolic hydroxyl group up to a total of five. The Ar rings can also include additional rings connected by additional linking nuclei of the type Y, for example, Ar-Y-Ar-Y-Ar. m₁ and m₂ are numbers from one to five, and n₁ and n₂ are numbers of one or greater, and preferably from one to four. The aromatic nucleus Ar can, in addition to phenolic hydroxyl groups, include one or more inert substituents. Examples of such inert substituents include hydrogen, halogen atoms, e.g., chlorine, bromine and fluorine; organic radicals containing from one to about thirty carbon atoms, such as alkyl, aryl, alkaryl, aralkyl, cycloalkenyl, cycloalkyl, alkoxy, aryloxy and acyloxy where R' is aryl, alkyl or cycloalkyl, or thiohydrocarbon groups having from one to about thirty carbon atoms, and carboxyl groups. Usually, however, each aromatic nucleus will not have more than about eighteen carbon atoms in any hydrocarbon substituent group. The Ar group can have from one to four substituent groups per nucleus. Typical aromatic nuclei include phenyl, naphthyl, phenanthryl, triphenylenyl,anthracenyl, pyrenyl, chrysenyl, and fluoroenyl groups. When Ar is a benzene nucleus, the polyhydric polycyclic phenol has the structure: wherein R₁, R₂ and R₃ are inert substituent groups as described in the previous paragraph; m₁ and m₃ are integers from one to a maximum of five; m₂ is an integer from one to a maximum of four; x₁ and x₃ are integers from zero to four, and x₂ is an integer from zero to three; y₁ is an integer from zero to about six and y₂ is an integer from one to five, preferably one or two. Preferably, the hydroxyl groups are located ortho and/or para to Y. Exemplary Y groups are alkylene, alkylidene, and alkenylene; arylene, alkyl arylene, arylalkylene; cycloalkylene, cycloalkylidene; and oxa- and thia-substituted such groups; tetrahydrofuranes, esters and triazino groups. The Y groups are usually bi, tri, or tetravalent, connecting two, three or four Ar groups. However, higher valency Y groups connecting more than four Ar groups, can also be used. According to their constitution, the Y groups can be assigned to subgenera as follows: 1) Y groups where at least one carbon in a chain or cyclic arrangement connect the aromatic groups, such as: 2) Y groups where only atoms other than carbon link the aromatic rings, such as -O-, -S-, and -(S) x - where x is a number from one to ten; 3) Y groups made up of more than a single atom including both carbon and other atoms linking the aromatic nuclei, such as: Although the relation of effectiveness to chemical structure is insufficiently understood, many of the most effective phenols have Y groups of subgenus 1), and accordingly this is preferred. Some of these phenols can be prepared by the alkylation of phenols or alkyl phenols with polyunsaturated hydrocarbons such as dicyclopentadiene or butadiene. Representative phenols include guaiacol, resorcinol monoacetate, vanillin, butyl salicylate, 2,6-di-tert-butyl-4-methyl phenol, 2-tert-butyl-4-methoxy phenol, 2,4-dinonyl phenol, 2,3,4,5-tetradecyl phenol, tetrahydro-α-naphthol, o-, m- and p-cresol, o-, m- and p-phenylphenol, o-, m- and p-xylenols, the carvenols, symmetrical xylenol, thymol, o-, m- and p-nonylphenol, o-, m- and p-dodecyl-phenol, and o-, m- and p-octyl-phenol, o-, and m-tert-butyl-p-hydroxy-anisole, p-n-decyloxy-phenol, p-n-decyloxy-cresol, nonyl-n-decyloxy-cresol; eugenol, isoeugenol, glyceryl monosalicylate, methyl-p-hydroxy-cinnamate, 4-benzyloxy-phenol, p-acetylaminophenol, p-stearyl-aminophenol, methyl-p-hydroxybenzoate, p-di-chlorobenzoyl-aminophenol, p-hydroxysalicyl anilide, stearyl-(3,5-di-methyl-4-hydroxy-benzyl)thioglycolate, stearyl-β-(4-hydroxy-3,5-di-t-butylphenyl)propionate, distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, and distearyl (4-hydroxy-3-methyl-5-t-butyl)benzylmalonate. Exemplary polyhydric phenols are orcinol, propyl gallate, catechol, resorcinol, 4-octyl-resorcinol, 4-dodecyl-resorcinol, 4-octadecyl-catechol, 4-isooctyl-phloroglucinol, pyrogallol, hexahydroxybenzene, 4-isohexylcatechol, 2,6-di-tertiary-butyl-resorcinol, 2,6-di-isopropyl-phloroglucinol. Exemplary polyhydric polycyclic phenols are methylene bis-(2,6-di-tertiary-butyl-phenol), 2,2-bis-(4-hydroxy phenyl)propane, methylene-bis-(p-cresol), 4,4'-benzylidene bis (2-tertiary-butyl-5-methyl-phenol), 4,4'-cyclo-hexylidene bis-(2-tertiary-butylphenol), 2,2'-methylene-bis-(4-methyl-6-(1'-methyl-cyclohexyl)-phenol), 2,6-bis-(2'-hydroxy-3'-tertiary-butyl-5'-methylbenzyl)-4-methylphenol, 4,4'-bis-(2-tertiary-butyl-5-methyl-phenol), 2,2'-bis-(4-hydroxy-phenyl)butane, ethylene bis-(p-cresol), 4,4'-oxobis-phenol, 4,4'-oxobis-(3-methyl-5-isopropyl-phenol), 4,4'-oxobis-(3-methyl-phenol), 2,2'-oxobis-(4-dodecyl-phenol), 2,2'-oxobis-(4-methyl-5-tertiary-butyl-phenol), 4,4'-thio-bis-phenol; 4,4'-thio-bis-(3-methyl-6-tertiary-butyl-phenol), 2,2'-thio-bis-(4-methyl-6-tertiary-butyl-phenol), 4,4'-n-butylidene-(2-t-butyl-5-methylphenol), 2,2'-methylene-bis-(4-methyl-6-(1'-methyl-cyclohexyl)phenol), 4,4'-cyclohexylene bis-(2-tertiary-butyl-phenol), 2,6-bis-(2'-hydroxy-3'-t-butyl-5'-methyl-benzyl)-4-methyl-phenol, 4,4'-oxobis(naphthalene-1,5-diol), 1,3'-bis-(naphthalene-2,5-diol) propane, and 2,2'-butylene bis-(naphthalene-2,7-diol), (3-methyl-5-tert-butyl-4-hydroxyphenyl)-4'-hydroxy-phenyl) propane, 2,2'-methylene-bis-(4-methyl-5-isopropylphenol), 2,2'-methylene-bis-(4-methyl-5-isopropylphenol), 2,2'-methylene-bis-(5-tert-butyl-4-chlorophenol), (3,5-di-tert-butyl-4-hydroxyphenyl-(4'-hydroxyphenyl)ethane, (2-hydroxy-phenyl)-(3',5'-di-tert-butyl-4',4-hydroxyphenyl)ethane, 2,2'-methylene-bis-(4-octylphenol), 4,4'-propylene-bis-(2-tert-butyl-phenol), 2,2'-isobutylene-bis-(4-nonylphenol), 2,4-bis-(4-hydroxy-3-t-butyl-phenoxy)-6-(n-octylthio)-1,3,5-triazine, 2,4,6-tris-(4-hydroxy-3-t-butyl-phenoxy)-1,3,5-triazine, 2,2'-bis-(3-t-butyl-4-hydroxyphenyl)thiazolo-(5,4-d)thiazole, 2,2'-bis-(3-methyl-5-t-butyl-4-hydroxyphenyl)thiazolo-(5,4-d)-thiazole, 4,4'-bis-(4-hydroxyphenyl)pentanoic acid octadecyl ester, cyclopentylene-4,4'-bis-phenol, 2-ethylbutylene-4,4'-bisphenol, 4,4'-cyclooctylene-bis-(2-cyclohexylphenol), β,β-thiodiethanol-bis-(3-tert-butyl-4-hydroxyphenoxy acetate), 1,4-butanedio-bis-(3-tert-butyl-4-hydroxyphenoxy acetate), pentaerythritol tetra-(4-hydroxyphenol propionate), 2,4,4'-tri-hydroxy benzophenone, bis-(2-tert-butyl-3-hydroxy-5-methylphenyl) sulfide, bis-(2-tert-butyl-4-hydroxy-5-methylphenyl)sulfide, bis-(2-tert-butyl-4-hydroxy-5-methylphenyl)sulfoxide, bis-(3-ethyl-5-tert-butyl-4-hydroxybenzyl)sulfide, bis-(2-hydroxy-4-methyl-6-tert-butyl-phenyl)sulfide, 4,4'-bis-(4-hydroxyphenol)pentanoic acid octadecyl thiopropionate ester, 1,1,3-tris-(2'-methyl-4-hydroxy-5'-tert-butylphenyl)butane, 1,1,3-tris-(1-methyl-3-hydroxy-4-tert-butylphenyl)butane, 1,8-bis-(2-hydroxy-5-methylbenzoyl-n-octane, 2,2'-ethylene-bis-[4'-(3-tert-butyl-4-hydroxyphenyl)-thiazole], 1-methyl-3-(3-methyl-5-tert-butyl-4-hydroxybenzyl)-naphthalene, 2,2'-(2-butene)-bis-(4-methoxy-6-tert-butylphenol)-bis-[3,3-bis- (4-hydroxy-3-t-butylphenyl)butyric acid] glycol ester, 4,4'-butylidene-bis-(6-t-butyl-m-cresol), 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, tetrakis[methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxyethyl isocyanurate, 2-octylthio-4,6-di-(4-hydroxy-3,5-di-t-butyl)phenoxy-1,3,5-triazine, 4,4'-thiobis-(6-t-butyl-m-cresol) and pentaerythritol hydroxyphenyl propionate. A particularly desirable class of polyhydric polycyclic phenols are the dicyclopentadiene polyphenols, which are of the type: in which R₁ and R₂ are lower alkyl, and can be the same or different, and n is the number of the groups enclosed by the brackets, and is usually from 1 to about 5. These are described in U.S. patent No. 3,567,683, dated March 2, 1971 to Spacht. A commercially available member of this class is Wingstay L, exemplified by dicyclopentadiene tri-(2-tert-butyl-4-methyl-phenol) of the formula: The polyhydric polycyclic phenols used in the invention can also be condensation products of phenols or alkylphenols with hydrocarbons having a bicyclic ring structure and a double bond or two or more double bonds, such as α-pinene, β-pinene, dipentene, limonene, vinylcyclohexene, dicyclopentadiene, allo-ocimene, isoprene and butadiene. These condensation products are usually obtained under acidic conditions in the form of more or less complex mixtures of monomeric and polymeric compounds. However, it is usually not necessary to isolate the individual constituents. The entire reaction product, merely freed from the acidic condensation catalyst and unchanged starting material, can be used with excellent results. While the exact structure of these phenolic condensation products is uncertain, the Y groups linking the phenolic nuclei all fall into the preferred subgenus 1. For method of preparation, see e.g., U.S. patent No. 3,124,555, U.S. patent No. 3,242,135, and British patent No. 961,504. When the stabilizer composition is used in conjunction with a polyvalent metal salt of an organic acid, the organic acid will ordinarily have from about six to about twenty-four carbon atoms. The polyvalent metal can be any metal of Group II of the Periodic Table, such as zinc, calcium, cadmium, barium, magnesium and strontium. The alkali metal salts and heavy metal salts such as lead salts are unsatisfactory. The acid can be any organic non-nitrogenous monocarboxylic acid having from six to twenty-four carbon atoms. The aliphatic, aromatic, alicyclic and oxygen-containing heterocyclic organic acids are operable as a class. By the term "aliphatic acid" is meant any open chain carboxylic acid, substituted, if desired, with nonreactive groups, such as halogen, sulfur and hydroxyl. By the term "alicyclic" it will be understood that there is intended any cyclic acid in which the ring is nonaromatic and composed solely of carbon atoms, and such acids may if desired have inert, nonreactive substituents such as halogen, hydroxyl, alkyl radicals, alkenyl radicals and other carbocyclic ring structures condensed therewith. The oxygen-containing heterocyclic compounds can be aromatic or nonaromatic and can include oxygen and carbon in the ring structure, such as alkyl-substituted furoic acid The aromatic acids likewise can have nonreactive ring substituents such as halogen, alkyl and alkenyl groups, and other saturated or aromatic rings condensed therewith. As exemplary of the acids which can be used in the form of their metal salts there can be mentioned the following: hexoic acid, 2-ethylhexoic acid, n-octoic acid, isooctoic acid, capric acid, undecylic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, ricinoleic acid, behenic acid, chlorocaproic acid, hydroxy capric acid, benzoic acid, phenylacetic acid, butyl benzoic acid, ethyl benzoic acid, propyl benzoic acid, hexyl benzoic acid, salicylic acid, naphthoic acid, 1-naphthalene acetic acid, orthobenzoyl benzoic acid, naphthenic acids derived from petroleum, abietic acid, dihydroabietic acid, hexahydrobenzoic acid, and methyl furoic acid. The water-insoluble salts are preferred, because they are not leached out when the plastic is in contact with water. Where these salts are not known, they are made by the usual types of reactions, such as by mixing the acid, or anhydride with the corresponding oxide or hydroxide of the metal in a liquid solvent, and heating, if necessary, until salt formation is complete. A variety of organic triphosphites and acid phosphites can be employed, of which the following are exemplary. The organic triphosphite can be any organic phosphite having three or more organic radicals attached to phosphorus through oxygen. The acid phosphite can be any organic phosphite having one or two organic radicals attached to phosphorus through oxygen. These radicals can be monovalent radicals, in the case of the triphosphites, diphosphites and monophisphites. The organic triphosphites in which the radicals are monovalent radicals can be defined by the formula: in which R₁, R₂ and R₃ are selected from the group consisting of alkyl, alkenyl, aryl, alkaryl, aralkyl, and cycloalkyl groups having from one to about thirty carbon atoms. The acid phosphites are defined by the same formula, but one or two of R₁, R₂ and R₃ is hydrogen or a cation of a metal or ammonium. Also included are the organic triphosphites having a bivalent organic radical forming a heterocyclic ring with the phosphorus of the type: in which R₄ is a bivalent organic radical selected from the group consisting of alkylene, arylene, aralkylene, alkarylene and cycloalkylene radicals having from two to about thirty carbon atoms, and R₅ is a monovalent organic radical as defined above in the case of R₁, R₂ and R₃; R₅ is hydrogen or a cation, in the case of the acid phosphites. Also useful organic triphosphites are mixed heterocyclic-open chain phosphites of the type: More complex triphosphites are formed from trivalent organic radicals, of the type: in which R₆ is a trivalent organic radical of any of the types of R₁ to R₅, inclusive, as defined above. A particularly useful class of complex triphosphites are the tetraoxadiphosphaspiro undecanes of the formula: where R₁ and R₂ are selected from the group consisting of aryl, alkyl, aryloxyethyl, alkyloxyethyl, aryloxyethoxyethyl, alkyloxyethoxyethyl and alkyloxypolyethoxyethyl having from about 1 to about 30 carbon atoms. In the case of the acid phosphites, one or both of R₁ and R₂ is also hydrogen or a cation. An especially preferred class of organic triphosphites and acid phosphites have a bicyclic aromatic group attached to phosphorus through oxygen, with no or one or more phenolic hydroxyl groups on either or both of the aromatic rings. These phosphites are characterized by the formula; in which Ar is a mono or bicyclic aromatic nucleus and m is an integer of from 0 to about 5. is one or a plurality of organic radicals as defined above for R₁ to R₆, taken singly or together in sufficient number to satisfy the valences of the two phosphite oxygen atoms. One or both radicals is also hydrogen, in the case of the acid phosphites, and can include additional bicyclic aromatic groups of the type (HO) m -Ar. The cation in the case of acid phosphites can be a metal, such as an alkali metal, for instance, sodium, potassium or lithium; an alkaline earth metal, for instance, barium, calcium, or a nontoxic polyvalent metal, such as magnesium, tin and zinc. Usually, the triphosphites and acid phosphites will not have more than about sixty carbon atoms. Exemplary triphosphites are monophenyl di-2-ethylhexyl phosphite, diphenyl mono-2-ethylhexyl phosphite, di-isooctyl monotolyl phosphite, tri-2-ethythexyl phosphite, phenyl dicyclohexyl phosphite, phenyl diethyl phosphite, triphenyl phosphite, tricresyl phosphite, tri(dimethylphenyl)phosphite, trioctadecyl phosphite, triisooctyl phosphite, tridodecyl phosphite, isooctyl diphenyl phosphite, diisooctyl phenyl phosphite, tri(t-octylphenyl) phosphite, tri-(t-nonylphenyl)phosphite, benzyl methyl isopropyl phosphite, butyl dicresyl phosphite, isooctyl di(octylphenyl) phosphite, di(2-ethylhexyl)(isooctylphenyl)phosphite, tri (2-cyclohexylphenyl)phosphite), tri-α-naphthyl phosphite, tri (phenylphenyl)phosphite, tri(2-phenylethyl)phosphite, ethylene phenyl phosphite, ethylene t-butyl phosphite, ethylene isohexyl phosphite, ethylene isooctyl phosphite, ethylene cyclohexyl phosphite, 2-phenoxy-1,3,2-dioxaphosphorinane, 2-butoxy-1,3,2-dioxyphosphorinane, 2-octoxy-5,5-dimethyl-dioxaphosphorinane, and 2-cyclohexloxy-5,5-diethyl dioxaphosphorinane. Exemplary pentaerythritol triphosphites are 3,9-diphenoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,6)-undecane (diphenyl-pentaerythritol diphosphite), 3,9-di(decyloxy)-2,4,8, 10-tetraoxa-3,9-diphosphaspiro (5,5)-undecane, 3,9-di (isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3-phenoxy-9-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di (methoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di(lauryloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di-p-tolyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di(methoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3-methoxyethyloxy-9-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)- undecane, 3,9-di(ethoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di(butoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3-methoxyethyloxy-9-butoxy-ethyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di(methoxyethoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di(butoxyethoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di(methoxyethoxyethoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di(methoxy (polyethoxy)ethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane where the (polyethoxy)ethyloxy group has an average molecular weight of 350),3,9-di(methoxy(polyethoxy) ethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane (where the (polyethoxy)ethyloxy group has an average molecular weight of 550). Exemplary of the bis aryl triphosphites are: bis(4,4'-thio-bis(2-tertiary-butyl-5-methyl-phenol))isooctyl phosphite, mono(4,4'-thio-bis(2-tertiary-butyl-5-methyl-phenol))di-phenyl phosphite, tri-(4,4'-n-butylidene-bis(2-tertiary-butyl-5-methyl-phenol))phosphite, (4,4'-benzylidene-bis(2-tertiary-butyl-5-methyl-phenol))diphenyl phosphite, isooctyl 2,2'-bis(-para-hydroxyphenyl)propane phosphite, decyl 4,4'-n-butylidene-bis (2-tertiary-butyl-5-methylphenol)phosphite, tri-4,4'-thio-bis (2-tertiary-butyl-5-methylphenol)phosphite, 2-ethylhexyl-2,2'-methylene-bis(4-methyl-6,1'-methylcyclohexyl)phenol phosphite, tri(2,2'-bis-(para-hydroxyphenyl)propane)phosphite, tri(4,4'-thio-bis(2-tertiary-butyl-5-methyl-phenol)phosphite, isooctyl-(2,6-bis(2'-hydroxy-3,5-dinonylbenzyl)-4-nonyl phenyl)) phosphite, tetra-tridecyl-4,4'-n-butylidene-bis(2-tertiary-butyl-5-methylphenyl)diphosphite, tetra-isooctyl-4,4'-thio-bis (2-tertiary-butyl-5-methylphenyl)diphosphite, 2,2'-methylene-bis(4-methyl-6,1'-methyl cyclohexyl phenyl) polyphosphite, isooctyl-4,4'-isopropylidene-bis-phenyl polyphosphite, 2-ethylhexyl-2,2'-methylene-bis(4-methyl-6,1'-methyl-cyclohexyl)phenyl triphosphite, tetra-tridecyl-4,4'-oxydiphenyl diphosphite, tetra-n-dodecyl-4,4'-n-butylidene bis (2-tertiary-butyl-5-methylphenyl)diphosphite, tetra-tridecyl-4,4'-isopropylidene bisphenyl diphosphite, hexa-tridecyl butane-1,1,3-tris(2'-methyl-5'-tertiary-butylphenyl-4')triphosphite. Exemplary acid phosphites are di(phenyl)phosphite, monophenyl phosphite, mono(diphenyl)phosphite, dicresyl phosphite, di-(o-isooctylphenyl)phosphite, di(p-ethylhexylphenyl) phosphite, di(p-t-octylphenyl)phosphite, di(dimethylphenyl) phosphite, di-n-butyl phosphite, di-2-ethylhexyl phosphite, mono-2-ethylhexylphosphite, diisooctyl phosphite, monoisooctyl phosphite, monododecyl phosphite, 2-ethylhexyl phenyl phosphite, 2-ethylhexyl-(n-octylphenyl)phosphite, monocyclohexyl phosphite, dicyclohexyl phosphite, di(2-cyclohexyl phenyl)phosphite, di-α-naphthyl phosphite, diphenyl phenyl phosphite, di(diphenyl) phosphite, di-(2-phenyl ethyl)phosphite, dibenzyl phosphite, monobenzyl phosphite, n-butyl cresyl phosphite and didodecyl phosphite, cresyl phosphite, t-octylphenyl phosphite, ethylene phosphite, butyl cresyl phosphite, isooctyl monotolyl phosphite and phenyl cyclohexyl phosphite. Exemplary of the bis aryl acid phosphites are: bis(4,4'-thio-bis(2-tertiary-butyl-5-methylphenol))phosphite, (4,4'-thio-bis(2-tertiary-butyl-5-methylphenol))phenyl phosphite, bis(4,4'-n-butylidene-bis(2-tertiary-butyl-5-methylphenol))phosphite, mono(4,4'-benzylidene-bis(2-tertiary-butyl-5-methylphenol))phosphite, mono(2,2'-bis-(parahydroxyphenyl) propane)phosphite, mono(4,4'-butylidene-bis(2-tertiary-butyl-5-methylphenol)phosphite, bis(4,4'-thio-bis(2-tertiary-butyl-5-methylphenol))phosphite, mono-2-ethylhexyl-mono-2,2'-methylene-bis(4-methyl-6,1'-methylcyclohexyl)phenol phosphite, bis (2,2'-bis(para-hydroxyphenyl)propane)phosphite, monoisooctyl-mono(4,4'-thio-bis(2-tertiary-butyl-5-methylphenol))phosphite, isoctyl-(2,6-bis(2'-hydroxy-3,5-dinonylbenzyl)-4-nonylphenyl)) phoshite, tri-tridecyl-4,4'-n-butylidene-bis(2-tertiary-butyl-5-methylphenyl)diphosphite, triisooctyl-4,4'-thio-bis(2-tertiary-butyl-5-methylphenyl)diphosphite, bis(2,2'-methylene-bis(4-methyl-6,1'-methyl cyclohexyl phenyl))phosphite, isooctyl-4,4'-isopropylidene-bis-phenyl phosphite, monophenyl mono(2,2'-methylene-bis(4-methyl-6,1'-methyl-cyclohexyl)) triphosphite, di-tridecyl-4,4'-oxydiphenyl diphosphite, di-n-dodecyl-4,4'-n-butylidene-bis(2-tertiary-butyl-5-methylphenyl) diphosphite, di-tridecyl-4,4'-isopropylidene bisphenyl diphosphite, tetra-tridecyl butane-1,1,3-tris(2'-methyl-5-tertiary-butylphenyl-4)-triphosphite. The thiodipropionic acid ester has the following formula: R₁OOCCH₂CH₂―S―CH₂CH₂COOY in which R₁ is an organic radical selected from the group consisting of hydrocarbon radicals such as alkyl, alkenyl, aryl, cycloalkyl and mixed alkyl aryl and mixed alkyl cycloalkyl radicals; hydroxyalkyl and hydroxyalkyloxyalkylene radicals; and esters thereof with aliphatic carboxylic acids; and Y is selected from the group consisting of (a) hydrogen, (b) a second R radical R₂, which can be the same as or different from the R₁ radical, (c) a polymeric chain of n thiodipropionic acid ester units: ―XO[OCCH₂CH₂SCH₂CH₂COOXO] n OCCH₂CH₂―S―CH₂CH₂COOZ where Z is hydrogen, R₂ or M, n is the number of thiodipropionic acid ester units in the chain, and X is a bivalent hydrocarbon group of the type of R₁,that is, alkylene, alkenylene, cycloalkylene, mixed alkylene-arylene and mixed alkylene-cycloalkylene radicals; hydroxyalkylene and hydroxyalkyloxyalkylene radicals; and esters thereof with aliphatic carboxylic acids; the value of n can range upwards from 0, but there is no upper limit on n except as is governed by the ratio of carbon atoms to sulfur atoms as stated below; and (d) a polyvalent metal M of Group II of the periodic table such as zinc, calcium, cadmium, barium, magnesium and strontium. The molecular weights of the R and Y radicals are taken such that with the remainder of the molecule the thiodipropionic ester has a total of from about ten to about sixty carbon atoms per sulfur atom. Accordingly, the various thiodipropionic acid ester species coming within the above-designated categories within the general formula can be defined as follows: (a) R₁OOCCH₂CH₂SCH₂CH₂COOH (b) R₁OOCCH₂CH₂SCH₂CH₂COOR₂ (c) R₁O[OCCH₂CH₂SCH₂CH₂COOX―O] n OCCH₂CH₂SCH₂CH₂COOZ (d) R₁OOCCH₂CH₂SCH₂CH₂COOM In the above formulae R₁ and R₂, M, X and Z are the same as before and the value of n, can range upwards from 1, but there is no upper limit on n₁ except as is imposed by the ratio of carbon atoms, as stated below. In the polymer (c), as in the other forms of thiodipropionic acid esters, the total number of carbon atoms per sulfur atom is within the range from about ten to about sixty. The R radical of these esters is important in furnishing compatibility with the polymer. The Y radical is desirably a different radical, R₂ or M or a polymer, where R is rather low in molecular weight, so as to compensate for this in obtaining the optimum compatibility and nonvolatility. Where Y is a metal, the thiodipropionic acid ester furnishes the beneficial properties of the polyvalent metal salt which is described above. The aryl, alkyl, alkenyl, and cycloalkyl groups may, if desired, contain inert, nonreactive substituents such as halogen and other carbocyclic and heterocyclic ring structures condensed therewith. Typical R radicals are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, n-octyl, isooctyl, 2-ethyl hexyl, t-octyl, decyl, dodecyl, octadecyl, allyl, hexenyl, linoleyl, ricinoleyl, oleyl, phenyl, xylyl, tolyl, ethylphenyl, naphthyl, cyclohexyl, benzyl, cyclopentyl, methylcyclohexyl, ethylcyclohexyl, and naphthenyl, hydroxyethyl, hydroxypropyl, glyceryl, sorbityl, pentaerythrityl, and polyoxyalkylene radicals such as those derived from diethylene glycol, triethylene glycol, polyoxypropylene glycol, polyoxyethylene glycol, and polyoxypropyleneoethylene glycol, and esters thereof with any of the organic acids named below in the discussion of the polyvalent metal salts; including in addition those organic acids having from two to five carbon atoms, such as acetic, propionic, butyric and valeric acids. Typical X radicals are alkylene radicals such as ethylene, tetramethylene, hexamethylene, decamethylene, alkyl-substituted alkylene radicals such as 1,2-propylene, arylene radicals such as phenylene methylenephenylene dimethylene phenylene and alicyclylene such as cyclohexylene and cyclopentylene As exemplary of the thiodipropionic acid esters which can be used, there can be mentioned the following: monolauryl thiodipropionic acid, dilauryl thiodipropionate, butyl stearyl thiodipropionate, 2-ethylhexyl lauryl thiodipropionate, di-2-ethylhexyl-thiodipropionate, diisodecyl thiodipropionate, isodecyl phenyl thiodipropionate, benzyl lauryl thiodipropionate, benzyl phenyl thiodipropionate, the diester of mixed coconut fatty alcohols and thiodipropionic acid, the diester of mixed tallow fatty alcohols and thiodipropionic acid, the acid ester of mixed cottonseed oil fatty alcohols and thiodipropionic acid, the acid ester of mixed soyabean oil fatty alcohols and thiodipropionic acid, cyclohexyl nonyl thiodipropionate, monooleyl thiodipropionic acid, hydroxyethyl lauryl thiodipropionate, monoglyceryl thiodipropionic acid, glyceryl monostearate monothiodipropionate, sorbityl isodecyl thiodipropionate, the polyester of diethylene glycol and thiodipropionic acid, the polyester of triethylene glycol and thiodipropionic acid, the polyester of hexamethylene glycol and thiodipropionic the polyester of pentaerythritol and thiodipropionic acid, the polyester of octamethylene glycol and thiodipropionic acid, the polyester of p-dibenzyl alcohol and thiodipropionic acid ethylbenzyl lauryl thiodipropionate, strontium stearyl thiodipropionate, magnesium oleyl thiodipropionate, calcium dodecylbenzyl thiodipropionate, and mono(dodecylbenzyl)thiodipropionic acid. These esters are for the most part known compounds, but where they are not available, they are readily prepared by esterification of thiodipropionic acid and the corresponding alcohol. Also useful are: (1) Thioalkanoic acid amides of Tokuno et al Japanese patent No. 16,286/68 having the formula: R is alkyl of one to eight carbon atoms, R₁ is alkyl of six to twenty-four carbon atoms, and R₂ is alkylene of one to six carbon atoms. (2) Thioalkanoic acid amides of 1,3,5-triazines of Ozeki et al Japanese patent No. 20,366/68 having the formula: R is alkyl of eight to eighteen carbon atoms. (3) Bis-thioalkanoic acid amides of Yamamoto et al Japanese patent No. 23,765/68 having the formula: R is alkyl of more than six carbon atoms, aryl or aralkyl. (4) Bis-thioalkylanoic acid amides of Ozeki et al Japanese patent No. 26,184/69 having the formula: R is alkyl of twelve to eighteen carbon atoms, and R₁ is alkylene of one to ten carbon atoms, cycloalkylene, or arylene. (5) Bis-alkylene thioalkanoic acid amides of Ozeki Japanese patent No. 31,464/69 having the formula: R is alkyl of more than six carbon atoms, aryl, or aralkyl. (6) Thioalkanoic acid amide derivatives of Minagawa etal, published Japanese application No. 106,484/74 having the formula: R is hydrocarbyl of one to twenty carbon atoms. (7) Alkylene bis-thioalkanoic acid amides of U.S. patent No. 4,279,805 to Ohzeki et al, patented July 21, 1981, having the general formula: wherein: R₁ is alkyl having from one to about fifty carbon atoms; R₂ is alkylene having from one to about three carbon atoms; and R₃ is alkylene having from about two to about twelve carbon atoms. β-Alkylthiopropionic acid esters having the general formula: wherein: R is alkyl of four to twenty carbon atoms; n is a number from 1 to 6; and R' is the residue of an alcohol having from one to six hydroxyl groups. Pentaerythritol tetra dodecyl thio propionate is an example of this group. Other conventional light stabilizers can be employed, such as hydroxybenzophenones such as 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy benzophenone, 2,4-dihydroxybenzophenone, benzotriazoles, such as 2(2-hydroxy-5-methylphenyl)benzotriazoles, 2(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2(2-hydroxy-3-5-di-t-butylphenyl) 5-chlorobenzotriazole, 2(2-hydroxy-3,5-di-t-amylphenyl)benzotriazole, benzoates such as phenylsalicylate, 2,4-di-t-butylphenyl -3,5-di-t-butyl-4-hydroxy phenylbenzoate, nickel compounds such as nickel-2,2'-thiobis(4-t-octyl-phenolate), nickel-mono-ethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, substituted acrylonitriles such as methyl-α-cyano-β-methyl-β-(p-methoxyphenyl)acrylate and oxalic anilides such as N-2-ethyl phenyl-N'-2-ethoxy-5-t-butyl phenyl oxalic diamide, N-2-ethyl phenyl-N'-2-ethoxy phenyl oxalic diamide. A sufficient amount of the stabilizer or combination is used to improve the resistance of the synthetic polymer to deterioration in physical properties when exposed to heat and light, including, for example, discoloration, reduction in melt viscosity and embrittlement. Very small amounts are usually adequate. Amounts within the range from about 0.001 to about 5% total stabilizers including the hydrocarbyl(polyphenol) poly(piperidyl triazines) of the invention by weight of the polymer are satisfactory. Preferably, from 0.01 to 3% is employed for optimum stabilization. The stabilizer systems of the invention are readily rendered in solid particulate form, comprising a blend of: (a) hydrocarbyl(polyphenol)poly(piperidyl triazines) light stabilizer in an amount of from about 10 to about 35 parts by weight; and optionally: (b) a phenolic antioxidant in an amount from about 10 to about 35 parts by weight; and/or (c) other heat or light stabilizers in an amount of from about 10 to about 35 parts by weight. The hydrocarbyl(polyphenol)poly(piperidyl triazines) light stabilizer of the invention can be employed in combination with phenolic antioxidant and/or other conventional heat and light stabilizers for the particular synthetic polymer. Thus, for example, in the case of polyvinyl chloride resins, other polyvinyl chloride resin heat stabilizers can be included, including polyvalent metal fatty acid salts such as barium and cadmium salts, of the higher fatty acids; organotin compounds; and epoxy compounds; and organic phosphites. With polyolefin resins there can be employed fatty aid salts of polyvalent metals, and the higher fatty acid esters of thiodipropionic acids, such as, for example dilauryl thiodipropionate. With polyamide resin compositions, polyamide stabilizers such as copper salts in combination with iodides and/or other phosphorus compounds and salts of divalent manganese can be used. With synthetic rubbers and acrylonitrile-butadiene-styrene terpolymers, other antioxidants and polyvalent metal salts of the higher fatty acids can be used. In addition, other conventional additives for synthetic polymers, such as plasticizers, lubricants, emulsifiers, anti-static agents, flame-proofing agents, pigments and fillers, can be employed. The stabilizer or combination is incorporated in the polymer in suitable mixing equipment, such as a mill or a Banbury mixer. If the polymer has a melt viscosity which is too high for the desired use, the polymer can be worked until its melt viscosity has been reduced to the desired range before addition of the stabilizer. Mixing is continued until the mixture is substantially uniform. The resulting composition is then removed from the mixing equipment and brought to the size and shape desired for marketing or use. The stabilized polymer can be worked into the desired shape, such as by milling, calendering, extruding or injection molding or fiber-forming. In such operations, it will be found to have a considerably improved resistance to reduction in melt viscosity during the heating, as well as a better resistance to discoloration and embrittlement on ageing and heating. The following Examples represent preferred embodiments of synthetic polymer compositions containing the stabilizers in accordance with the invention. Examples 1 to 6 Polypropylene compositions were prepared using stabilizers of the invention and two stabilizers of the prior art, having the following formulation: Ingredient Parts by Weight Polypropylene 100 Stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate 0.2 Stabilizer as shown in Table I 0.3 The compositions were thoroughly blended in a Brabender Plastograph, and then compression-molded to sheets 0.3 mm thick. Pieces 2.5 cm² were cut off from the sheets, and exposed to a high pressure mercury lamp, with and without immersion in hot water at 80°C for 15 hours. The time in hours when degradation set in, as determined by a significant discoloration and/or embrittlement, was noted as hours to failure, and the results are set forth in Table I. The stabilizers control 1 and control 2 are prior art compounds according to US-patent No. 4,108,829. The improved stabilizing effectiveness of the compounds of the invention as compared to the compounds of the prior art is apparent from the above data. Examples 7 to 12 Conventional stabilizers for polymeric materials may lose their effectiveness because of volatilization or decomposition at the high polymer processing temperatures. This is not true of the stabilizers of the invention, as shown by observing the effect of heat in repeated extrusions of ethylene-propylene copolymer compositions. The compositions were prepared using stabilizers of the invention and two stabilizers of the prior art, having the following formulation: Ingredient Parts by Weight Ethylene-propylene copolymer 100 Ca stearate 0.2 Stearyl-β-(3,5-di-t-butyl 4-hydroxyphenyl) propionate 0.1 Dilaurylthiodipropionate 0.2 Stabilizer as shown in Table II 0.2 The compositions were mixed and then extruded 5 times at a cylinder temperature of 230°C and 240°C, a head die temperature of 250°C, and a velocity of 20 rpm. The test pieces were then molded by injection molding at 250°C. The test pieces were exposed to a high pressure mercury lamp. The time in hours when degradation set in, as determined by a significant discoloration and/or embrittlement, was noted as hours to failure, and the results are set forth in Table II. The improved stabilizing effectiveness of the compounds of the invention as compared to the compounds of the prior art is apparent from the above data. Examples 13 to 18 High density polyethylene compositions were prepared using the stabilizers of the invention and two of the prior art, having the following formulation: Ingredient Parts by Weight High density polyethylene 100 Ca stearate 1 Tetrakis-(methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane 0.1 Distearyl thiodipropionate 0.3 Stabilizer as shown in Table III 0.2 The stabilizers were blended with the polymer on a two-roll mill and sheets 0.5 mm thick were prepared by compression molding of the blend. Pieces 2.5 cm² were cut off from the sheets, and exposed in a Weather-O-Meter to ultraviolet light. The time in hours when degradation set in, as determined by a significant discoloration and/or embrittlement, was noted as hours to failure, and the results are set forth in Table III. The improved stabilizing effectiveness of the compounds of the invention as compared to the compounds of the prior art is apparent from the above data. Examples 19 to 23 Ethylene vinyl actate copolymer compositions were prepared using stabilizers of the invention and two stabilizers of the prior art, having the following formulation: Ingredient Parts by Weight Ethylene-vinyl acetate copolymer 100 2,6-Di-t-butyl-p-cresol 0.1 Ca stearate 0.1 Zn stearate 0.1 Diisodecylphenyl phosphite 0.2 Stabilizer as shown in Table IV 0.2 The stabilizers were blended with the polymer on a two-roll mill at 130°C. Sheets 0.4 mm thick were then compression-molded at 140°C from the resulting blend. Pieces 2.5 cm² were cut off from the sheets, and exposed to ultraviolet light in a Weather-O-Meter for 500 hours. Tensile strength of the sheet samples was determined before and at the conclusion of the test. The results are shown in Table IV as percent retention of the initially-determined tensile strength. The improved stabilizing effectiveness of the compounds of the invention as compared to the compounds of the prior art is apparent from the above data. Examples 24 to 30 Polyvinyl chloride resin compositions were prepared having the following formulation, utilizing stabilizers in accordance with the invention and stabilizers of the prior art: Ingredient Parts by Weight Polyvinyl chloride 100 Dioctyl phthalate 48 Epoxidized soybean oil 2 Tris(nonyl phenyl) phosphite 0.2 Ca stearate 1.0 Zn stearate 0.1 Stabilizer as shown in Table V 0.3 The stabilizers were mixed with the polyvinyl chloride on a two-roll mill and then sheeted off to form sheets 1 mm thick. The light resistance of the sheets was determined by placing strips 1 cm wide in a Weather-O-Meter, and exposing them to ultraviolet light. The time required for the sheets to develop a noticeable discoloration and/or embrittlement, indicating deterioration due to oxidation in the presence of ultraviolet light, was then noted in hours as the hours to failure. The following results were obtained. The improved stabilizing effectiveness of the compounds of the invention as compared to the compounds of the prior art is apparent from the above data. Examples 31 to 35 Acrylonitrile-butadiene-styrene terpolymer resin compositions were prepared, using stabilizers of the invention and of the prior art, with the following formulation: Ingredient Parts by Weight Acrylonitrile-butadiene-styrene terpolymer 100 4,4-Butylidene-bis(2-t-butyl-m-cresol) 0.1 Stabilizer as shown in Table VI 0.3 The stabilizers were blended with the resin on a two-roll mill, and sheets 3 mm thick were prepared by compression molding of the resulting blend. Pieces 2.5 cm² were cut off from the sheets and subjected to ultraviolet light in a Weather-O-Meter for 800 hours. The tensile strength of the strips was determined before and after the test exposure, and the results are reported in Table VI as the percent of tensile strength retained at the end of the test. The improved stabilizing effectiveness of the compounds of the invention as compared to the compounds of the prior art is apparent from the above data. Examples 36 to 41 Polyurethane resin compositions were prepared using stabilizers of the invention and of the prior art, having the following formulation: Ingredient Parts by Weight Polyurethane resin (Asahi Denka U-100) 100 Ba stearate 0.7 Zn stearate 0.3 2,6-di-t-butyl-p-cresol 0.1 Stabilizer as shown in Table VII 0.3 The stabilizers were blended with the finely powdered polyurethane resin on a two-roll mill for five minutes at 70°C, and then sheeted off. The sheet was compression molded at 120°C for 5 minutes to form sheets 0.5 mm thick. Pieces 2.5 cm² were cut out from the sheets and exposed to ultraviolet light in a Weather-O-Meter for fifty hours. Elongation before and after exposure was determined, and the percent elongation retained after the exposure is given in Table VII. The improved stabilizing effectiveness of the compounds of the invention as compared to the compounds of the prior art is apparent from the above data. Examples 42 to 48 The stabilizers of this invention are effective light stabilizers for synthetic polymer coating compositions, particularly acrylic lacquers. This is demonstrated by the following experiments. The effect of the stabilizer in a two coat metallic effect finish comprising metallic effect priming lacquer and unpigmented finishing lacquer was determined. a) Metallic effect priming lacquer Methyl methacrylate, 100 g, n butyl acrylate, 66 g, 2-hydroxyethyl-methacrylate, 30 g, methacrylic acid, 4 g, xylene, 80 g, and n-butanol, 20 g, were heated with stirring at 110°C while adding a solution of azo-bis-isobutyronitrile, 2 g, dodecylmercaptan, 0.5 g, xylene, 80 g, and n-butanol, 20 g, added dropwise over 3 hours. The solution was then stirred an additional two hours at 110°C. The resulting acrylic resin solution, 12 parts, was then made into a metallic effect priming lacquer by mixing it with butoxylated methylol melamine (Mitsui Toatsu Co., Yuban 20SE60; solids content 60%) 2.5 parts, cellulose acetobutyrate (20% butylacetate solution) 50 parts, aluminum pigment (Toyo Aluminum Co., Alpaste 1123N) 5.5 parts, xylene 10 parts, butyl acetate, 20 parts, and copper phthalocyanine blue, 0.2 part. b) Unpigmented finishing lacquer An unpigmented finishing lacquer was then prepared by mixing 48 parts of the acrylic resin solution with butoxylated methylol melamine, 10 parts, xylene, 10 parts, butoxyethyl-acetate, 1 part, and the stabilizer shown in Table VIII, 0.15 part. Pieces of steel sheeting which were coated with a primer were first coated with the priming lacquer and then with the finishing lacquer. The priming lacquer was sprayed on to a thickness of about 20 µ and aired for 10 minutes. Then the clear lacquer was sprayed on to a thickness of about 30 µ. After airing for 15 minutes the samples were stoved for 30 minutes at 140°C. The coated sheets were exposed to ultraviolet light in a Weather-O-Meter. The time in hours when degradation set in, determined by cracking on the surface of the sheet, was noted as hours to failure. The results are shown in Table VIII. The improved stabilizing effectiveness of the compounds of the invention as compared to the compounds of the prior art is apparent from the above data.

Claims: Hydrocarbyl(polyphenol)-poly(2,2,6,6-tetramethyl piperidyl-1,3,5-triazines) having the formula: in which: R is a n-valent alkylene or alkylidene group having from one to eighteen carbon atoms; R₁ is selected from the group consisting of hydrogen: alkyl, alkenyl, hydroxyalkyl and alkoxy, all groups having from one to twelve carbon atoms; cycloalkyl having from three to twelve carbon atoms; acyl having from one to twelve carbon atoms; and oxyl (O . ); Y is selected from the group consisting of wherein R₄ is lower alkyl having from one to six carbon atoms; R₅ is selected from the group consisting of hydrogen; alkyl, hydroxy alkyl and alkoxy having from one to twelve carbon atoms; and cycloalkyl having from three to twelve carbon atoms; and X is selected from the group consisting of wherein: R₆ is selected from the group consisting of alkyl, hydroxyalkyl and alkylenealkoxy having from one to twelve carbon atoms; cycloalkyl having from three to twelve carbon atoms; and aryl having from six to eighteen carbon atoms; R₇ and R₈ are selected from the group consisting of hydrogen; alkyl, hydroxyalkyl, alkoxy, all groups having from one to twelve carbon atoms; cycloalkyl having from three to twelve carbon atoms; and aryl having from six to eighteen carbon atoms; and R₇ and R₈ taken together as a five to six member ring including the nitrogen atom in the ring; R₂ and R₃ are selected from the group consisting of hydrogen and lower alkyl having from one to six carbon atoms; all groups being optionally substituted by one or more alkyl groups with one to twelve carbon atoms; and n is a number from 2 to 4. A compound according to claim 1 in which Y is A compound according to claim 1 in which Y is A polyvinyl chloride resin composition having improved resistance to deterioration upon exposure to light comprising a polyvinyl chloride resin formed at least in part of the recurring group: and having a chlorine content in excess of 40%, where X is either hydrogen or chlorine; and a compound in accordance with one or more of the claims 1-3. An olefin polymer composition having improved resistance to deterioration upon exposure to light comprising an olefin polymer selected from the group consisting of polymers of alpha-olefins having from two to six carbon atoms and polystyrene, and a compound in accordance with one or more of the claims 1-3. An acrylonitrile-butadiene-styrene polymer having improved resistance to deterioration upon exposure to light comprising an acrylonitrile-butadiene-styrene polymer and a compound in accordance with one or more of the claims 1-3. An ethylene-vinyl acetate copolymer having improved resistance to deterioration upon exposure to light comprising an ethylene-vinyl acetate copolymer and a compound in accordance with one or more of the claims 1-3. A polyurethane having improved resistance to deterioration upon exposure to light comprising a polyurethane and a compound in accordance with one or more of the claims 1-3. A stabilizer composition for enhancing the resistance of synthetic polymers to deterioration upon exposure to light and heat comprising a compound in accordance with one or more of the claims 1-3 and at least one synthetic polymer heat stabilizer selected from the group consisting of phenolic antioxidants, organic phosphites, polyvalent metal salts and thiodipropionic acid esters.

Inventors: NAKAHARA, YUTAKA, TOBITA, ETSUO
Applicants: ADEKA ARGUS CHEMICAL CO., LTD.
Application year: 1986
Main classification: C07D401
IPC codes: C08K5, C07D401, C08L101