CA1051903A - Piperidine carboxylic acids and their metal salts - Google Patents

Abstract

PIPERIDINE CARBOXYLIC ACIDS AND THEIR METAL SALTS
Abstract of the Disclosure A compound of the formula

Description

~oS~903 This invention relates to the stabilization of organic material normally tending to deteriorate.
In particular, the invention relates to the pro-tection of snyt~etic polymexs against the harmful degradative effects, such as discoloration and em-brittlement caused by exposuxe to light, especially ultraviolet li~ht.

It is known that actinic radiation, par'icular'y in the near ultraviolet region, has a deleterious ef~ect on both the appearance and properties of organic polymers.
~or example, normally colorless or light colored poly-esters~yellow on exposure to sunlight as do such cellu-losics as cellulose acetate. Polystyrene discolors and cracks, with accompanying loss of its desirable physical properties when exposed to actinic light, while vinyl resins, such as polyvinyl chloride and polyvinyl acetate spot and degrade. l'he rate of air oxidation of polyolefins such as polyethylene and polypropylene is materially acc`elerated by ultraviolet li~ht.

. . ', ' - .,' :
~' , ' , .

~ . .

lOS~903 It has been proposed to stabilize polymeric materials against ultraviolet light deterioration by the use of various types of ultraviolet absorbers.
Thus, U.S. 3,004,896 discloses for this purpose 2(2-hydroxyphenyl)benzotriazole derivatives, while U.S.
3,189,630 discloses certain metal salts of hydroxy-benzoic acids which are useful as actinic stabilizers in synthetic polymers.

~ dditionally, in U.S. Patent 3,120,540 there is discussed the reaction of substituted 4-piperidin~l compounds with acid anhydrides having the formula . / 2 n\
O=C \ j C=O
O

where n is 1 to 4, to yield bis(polymethyl)-4-piperidinol alkanoates. In the example of this patent the probable formation of CH ~ o-8-(CH2)2-C-H

is mentioned as an intermediate in the synthesis of the bis(hydrogen sulfate)salt of bis(1,2,2,6,6-.

105~903pent~methyl-4-piperidyl)succinate.~ The compounds of U.S. 3,120,540 are taught to possess significant pharmacological activity in lowering blood pressure.
We h~ve now found that certain acid half esters of hindered piperidines stabilize organic substrates against the degradative effect of ultraviolet light and that the degree of stabili~ation achieved is significantly greater in the case of higher acid half esters than in the case of the above-mentioned succinic acid half-ester. We have also found that certain hetero-atom containing piperidine hal~-esters and salts of piperidine half esters are use~ul as stabilizers of organic materials.

The present invention is directed to a new class of W -stabilizers, namely compound of the formula I

~C~ ~ "
R3- ~ R5- C0--R4- CO-- ~ M

~ 1 R2 wherein -Rl and R2 independently of each other are straight-or branched-chain alkyl having from 1 to 6 carbon atoms, or together with the carbon to which they are bound form a cyclo-pentyl or cyclohexyl ring, which is unsubstituted or subs~i-tuted with a methyl group, '.

, .

R3 is hydrogen, alkyl having 1 to 12 carbon atoms, ~-methoxyethyl, alkenyl having 3 or 4 carbon atoms, propargyl, benzyl, or alkyl substituted benzyl, M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese, calcium, zinc, sodium, cobalt, tin, dialkyl tin, lithium, potassium, magnesium and aluminium, and z has a value of from 1 to 4, the value of z being the same as the available valence of M, .R5 is oxy or imino, and, if M is hydrogen and R5 is oxy, R4 is straight- or branched-chain alkylene having 5 to 10 carbon atoms, or the group (CH2)mY(CH2)n wherein Y is - -:
oxygen or sulfur and m and n independently of each other are an integer of from l to 3, and, in all other cases, R4 is straight or branched-chain alkylene having 1 to 10 carbon atoms, phenylene or alkyl-phenylene, or the group (CH2)mY(CH2)n wherein Y is oxygen or sulfur and m and n inde-pendently of each other are an integer from 1 to 3.
Furthermore, the invention is directed to stabiliz d polymers containing as stabilizer a compound^of the formula I

R3--N~R5--C~R4--C~OtM

\~ R2 _~J

... .... ..
-: . ~ . . .

-,., ..... ... ~. . ~ ., . ; ..

lOS1903 wherein Rl and R2 independently of each other are straight-or branched-chain alkyl having from 1 to 6 carbon atoms, or together with the carbon to which they are bound form a cyclo-pentyl or cyclohexyl ring, which is unsubstituted or substi-tuted with a methyl group, R3 is hydrogen, alkyl having 1 to 12 carbon atoms, ~-methoxyethyl, alkenyl having 3 or 4 carbon atoms, propargyl, benzyl, or alkyl substituted ben7.yl, . M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese, calcium, zinc, sodium, cobalt, tin, dialkyl tin, lithium, potassium, magnesium and aluminium, and z has a value of from 1 to 4, the value of z being the same as the available valence of M, R5 is oxy or imino, and, R4 is straight- or branched-chain alkylene having 1 to 10 carbon atoms, phenylene or alkyl-phenylene, or the group (CH2)mY(CH2)n wherein Y is oxygen or sulfur and m and n inde- :
pendently of each other are an integer of from 1 to 3.

The present invention is preferably directed to a new class of ultraviolet light stabilizers which consist of a compound of the formula .

,:

"~ o_ll_R4 ~ ~ I

wherein Rl and R2 independently of each other are straight- or branched-chain alkyl having from 1 to 6 carbon atoms, or together with the carbon to which they are bound form a cyclopentyl or cyclohexyl ring, which is unsubstituted or sub-stituted with a methyl group, R3 is hydrogen, alkyl havin~.l to 12 carbon atoms, ~-methoxyethyl, alkenyl having 3 or 4 carbon atoms, propargyl, benzyl or alkyl substituted benzyl, R4 is straight or branched-chain alkylene having 5 tolO carbon atoms, or the group (CH2)mY(CH2)n wherein Y is oxygen or sulfur and m and n independently of each other are an integer from 1 to 3, M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese, calcium, zinc, sodium, cobalt,tin, dialkyl tin, lithium, potassium, magnesium and aluminium, and z has a value of from 1 to 4, the value of z being the same as the avail~ble valence of ~S.
Examples of Rl and R2 are methyl, ethyl, iso-propyl, n~butyl and n-hexyl. Preferably, Rl and R2 are each a methyl group. Representative of ., - 6 -~ 051903 Rl and R2 as cycloalkyl groups are cyclohexyl, cyclopentyl,

2-methyl, 3-methyl and 4-methylcyclohexyl, and 2-methyl and

3-methylcyclopentyl. The preferred cycloalkyl groups are cyclohexyl and 2-methylcyclohexyl. Most preferably, Rl and R2 are each a methyl group.
Substituent R3 can be hydrogen,alkyl having 1 to 12 carbon atoms, preferably alkyl having 1 to 4 carbon atoms, -methyl being particularly preferred, ~-me~hoxyethyl, alkenyl , ~ having 3 to 4 carbon atoms, preferably allyl, propargyl, benzyl ~ ~ b~t/
- or alkyl substituted ~cy~yl. Hydrogen and methyl are particularly preferred.
Examples of R3 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-octyl, n-dodecyl, ~ , ~-methallyl, propargyl, benzyl, a-methylbenzyl, p-methylbenzyl and a, p-dimethylbenzyl.
The preferred alkylene residue R4 is straight-chain alkylene having 5 to 10, especially 5-8 carbon atoms,or the group (CH2)mY(CH2)n wherein Y is oxygen or sulfur and m and n inde-pendently of each other are 1 or 2.
Among the substituents represented by M, hydrogen, nickel and manganese are preferred. Particularly preferred are hydrogen and nickel. Equally preferred is cobalt.
The present invention is also preferably directed to a new class of ultraviolet light stabilizers which consist of a compound of the formula 1~)51903 R ~ ~--O-~-R4-C-O~U

wherein Rl and R2 independently of each other are straight- or branched-chain alkyl having from 1 to 6 carbon atoms, or together with the carbon to which they are bound form a cyclopentyl or cyclohexyl ring, which is unsubstituted or sub-stituted with a methyl group, R3 is hydrogen, alkyl having 1 to 12 carbon atoms, ~-methoxyethyl, alkenyl having 3 or 4 carbon atoms, propar~gyl, benzyl or alkyl substituted benzyl, R4 is straight or branched-chain alkylene having 1 to 4 carbon atoms, M is a metal selected ~rom the group consisting of barium, nickel, manganese, calcium, zinc, iron, sodium, cobalt, tin, dialkyl tin, lithium, potassium, magnesium and aluminium, and z has a value of from 1 to 4, the value of z being the same as the available valence of M.
Examples of Rl and R2 are methyl, ethyl, isopropyl, n-butyl and n-hexyl. Preferably, Rl and - . . . ~

''' ~ , .', ' ~

1~51903 R2 are each a rnethyl ~roup. Representative of Rl and R2 as cycloalkyl groups are cyclohexyl, cyclopentyl, 2-methyl, 3-methyl and 4-methylcyclohexyl, and 2-methyl and 3-methylcyclopentyl. The preferred cycloalkyl groups are cyclohexyl and 2-methylcyclohexyl. Most preferably, Rl and R2 are each a methyl group.- -Substituent R3 can be hydrogen, alkyl having 1 to12 carbon atoms, preferably alkyl having 1 to 4 carbon a~oms, methyl being particularly preferred, ~-methoxyethyl, alkenyl having 3 to 4 carbon atoms, preferably allyl, propargyl, benzyl or alkyl substituted beyzyl. Hydrogen and methyl are particularly preferred.

Examples of R3 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-octyl, n-dodecyl, alkyl, a-methallyl, propargyl, benzyl, ~-methylbenzyl, p-methylbenzyl and a, p-dimethylbenzyl.
The preferred alkylene residue R4 is straight-chain alkylene having 1 to 4 carbon atoms.

Among the substitue~ts represented by M, nickel and manganese are preferred. Particularly preferred is nickel. Equally pre~erred is cobalt.
The present invention is also directed to a new class of ultraviolet light stabilizers which consist of a compound of the formula _ 9 _ . ' ' .

H o O

~ R ~ N C P~4 C ~

wherein Rl and R2 independently of each other are straight-or branched-chain lower alkyl having 1 to 6 carbon ~toms, or together with the carbon to which they are bound form a cy-clopentyl or cyclohexyl ring, which is unsubstituted or sub- .
stituted.with a methyl group, R3 is hydrogen, alkyl having 1 to 12 carbon atoms, ~-methoxyethyl al]cenyl having 3 or 4 carbon atoms, propargyl, benzyl, or alkyl substituted benzyl, ~ R4 is straight- or branched-chain alkylene having 1 to 10 carbon a.toms, phenylen~, phenylene substituted with one or more alkyl groups, or the group -(CH2)mY(CH2)n-, wherein Y is oxygen or sulfur and m and n independently of each other are an integer o~ from 1 to 3, M is hydrogen or a metal selected from the group con-sisting of barium, nickel, manganese, calcium, zinc, sodium, cobalt, tin, dialkyl tin, lithium, potassium, magnesium and aluminium, and a value of from 1 to 4, the value of z being the same as the available valence of M.

.

105~903 Examples of Rl and R2 are methyl, ethyl, isopropyl, n-butyl or n-hexyl Preferably, Rl and R2 are each a methyl - group. Examples of the cycloalkyl groups, as represented by Rl and R2, are cyclohexyl, cyclopentyl, 2-methy~, 3-methyl-and 4-methylcyclohexyl, and 2-methyl-and 3-methylcyclopentyl.
The preferred cycloalkyl groups are cyclohexyl and 2-methyl-cyclohexyl. ~lost preferably, Rl and R2 are each a methyl group.
Substituent R3 can be hydrogen, alkyl having 1 to 12 carbon atoms, preferably alkyl having 1 to 4 carbon atoms, methyl being particularly preferred, ~-methoxyethyl, alkenyl having 3 or 4 carbon atoms, preferably allyl, propargyl, benzyl or alkyl substituted benzyl. Particularly preferred are hydro-gen and methyl.
Examples of R3 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-octyl, n-dodecyl, allyl,`a-methallyl, propargyl, benzyl, a-methylbenzyl, p-methylbenzyl and a, p-dimethylbenzyl.
The preferred alkylene residue R4 is straight-chain alkylene having 1 to 10, especially 1-8 carbon atoms, or the group ~(CH2)mY(CH2)n-, wherein Y is oxygen or sulfur and m and n independently of each other are 1 or 2, or more preferably 1. Particularly pre-ferred is straight-chain alkylene of 1 to 8 carbon atoms.
Among the substituents represented by M, hydrogen, nickel and manganese are preferred. Particularly preferred are 105190;~
hydrogen and ni.ckel.
This invention also relates to compositions of matter which are stabilized against ultraviolet liyht deterioration which cor.prises a synthetic organic polymer normally subject to ultraviolet deterioration containing from about 0.005~ to 5% by weight of the polymer of the compounds as defined and preferably from 0,01 to 2~/o by weight.
This invention accordingly relates also to compositions comprising organic materials which are subject to ultraviolet light degradation stabilized wi`th compounds having the formula R ~ ~-R4-1C-~ I

wherein Rl and R2 independently of each other are straight- or branched-chain alkyl having from 1 to 6 carbon atoms, or together with the carbon to which they are bound form a cyclopentyl or cyclohexyl ring, which is unsubstituted or sub-stituted with a methyl group, R3 is hydrogen, alkyl having 1 to 12 carbon atoms, ~-methoxyethyl, alkenyl having 3 or 4 carbon atoms, pro-.. . . .

~051903 paryyl, benzyl or alkyl substi~uted benzyl, and R4 is straight- or branched-chain alkylene having 1 to 4 carbon atoms.

Examples of Rl and R2 are methyl, ethyl, isopropyl, n-butyl and n-hexyl. Preferably, Rl and R2 are each a methyl group. Representative of Rl and R2 as cycloal~yl groups are cyclohexyl, cyclopentyl, 2-methyl, 3-methyl and 4-me~ylcyclohexyl, and 2-methyl, and 3-methylcyclopentyl. The preferred cycloalkyl groups are cyclohexyl and 2-methylcyclohexyl. Most preferably Rl and R2 are each a methyl group.
Sub`stituent R3 can be hydrogen, alkyl having 1 to 12 carbon atoms, preferably alkyl having 1 to 4 carbon atoms, methyl being particularly preferred, ~-methoxyethyl, alkenyl having 3 to 4 carbon atoms, preferably allyl, propargyl, benzyl or alkyl substituted beyzyl. Hydrogen and methyl are particularly preferred.

Examples of R3 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, lsobutyl, n-hexyl, n-octyl, n~dodecyl, alkvl, ~-methallyl, propargyl, benzyl, ~-methylbenzyl, p-methylbenzyl and ~, p-dimethylbenzyl.

The preferred alkylene residue R4 is straight-chain alkylene having 1 to 4 carbon atoms.

The compounds as represented by formula I, can be used in combination with other light stabilizers such as :,.

2(2-hydroxyphenyl)ben~otriaæole~, 2-hydroxyben~ophenones, nickel complexes and benzoates.
The compounds of this invention are stabilizers o~ oryanic material normally subject to thermcll, oxidative or actinic light deterioration.
Materials which are thus stahili~ed include synthetic oryanic polymeric substances including homopolymers, copolymers, and mixtures thereof, such as vinyl resins formcd from the polymeri~ation o~ vinyl halides or from the copolymerization of vinyl halides with un-saturated polymeri~able compounds, e.g., vinyl esters, a,~-unsaturated acids, ~ unsaturated esters, ~
unsaturated ketones, a,R-unsaturated aldehydes and unsaturated hydrocarbons such as butadienes and styrene;
poly-~-olefins such as high and low density polyethylene, cross-linked polyethylene, polypropylene, poly(4-methyl-pentane-l and the like, including copolymers of a-olefins;
such as ethylene-propylene copolymeLs, and the like;
dienes such as polybutadiene, polyisoprene, and the like, including copolymers with other monomers; poly-urethanes such as are prepared ~rom polyols and organic polyisocyanates, and polyamides such as polyhexamethylene adipamide and polycaprolactam; polyesters such as poly-ethylene terephthalates; polycarbonates such as those prepared ~ron~ bisphenol-A and phosyene; polyacetals such as polyethylene terephthalate polyacetal; poly-styrene, polyethyleneoxide; polyacrylics such as poly-' ' acrylonitrile; po]yphenylencoY~ides such as those prepared from 2,6-~imethy]phcnol and the like; and copolymers such as those o~ polystyrene co~taining copolymers of butadiene and styrene and those formed by the co-polymerization of acrylonitrile, butadiene and/or styrene.

Other materials which can be stabili~ed by the compou~ds o~ the present invention include lubricating oil of the aliphatic ester type, i.e;, di(1,2-ethylene)-azelate, pentaerythritol tetra-caproate, and the like; animal and vegetable derived -oils, e.g., linseed oil, fat, tallow, lard, peanut oil, cod liver oil, castor oil, palm oil, corn oil, cottonseed oil, and the like; hydrocarbon materials, such as gasoline, mineral oil, fuel oil, drying oil, cutting fluids, waxes, resins, and the like, salts of fatty acids such as soaps and the like; and alkylene glycols, e.g., ~-methoxyethyleneglycol, methoxytri-ethyleneglycol, triethy_ene glycol, octaethylene-glycol, dibutyleneglycol, dipropyleneglycol and the like.

The compounds of this invention are particularly useful as W light stabiliæers, especially for the protection of polyolefins, for instance, polyethylene, polypropylene, poly(butene-l), poly(pentene-1), poly ., .
- , .
.. .

~ 051g~3 (3-methylbutcne-1), poly(~-rnethylpentene-1), various ethylene-propylene copolymers and the like.

In general, the stabilizers of this invention are employed from about 0.01 to about 5~ by weight of the stabilized composition, although this will vary with the particular substrate and application.
An advantageous range is from about 0.05 to about 2% and especially 0.1 to about 1%.

For addition to polymeric substrates, the stabilizers can be blended before polymerization or after polymerization, during the usual processing operations, for example, by hot-milling, the composition then being extruded, pressed, blo~
molded or the like into films, fibers, filaments, hollow spheres and the like. The heat stabilizing properties of these cornpounds may advantageously stabilize the polymer against degradation during such processing at the high temperature generally encountered. The stabilizers can also be dissolved in suitable solvents and spxayed on the surface ~`
of films, fabrics, filaments or the like to provide effective stabilization. Where the polymer is prepared from a liquid monomer as in the case of styrene, the stabilizer may be dispersed or dissolved in the monomer prior to polymerization or curing.

. ~
' . . . ' -.

: .

10519~13 Thcse compounds can also be used in combination with other additives such as antioxi.dants, sulfur-containing esters such as distearyl-~-thiodipropionate (DSTDP), dilauryl-~-thiodi.2ropionatP (DLTDP) in an amount oi rom 0.01 to 2% by weight of the organic material, and the like, pourpoint depressants, corrosion and rust inhi~itors, dispersing agents, demulsifiers, anti.~oami.ng agents, fillers such as glass or other filers, car~on black, accelerators and the other chemicals used in rubber compoundinq, plasticizers, color stabilizers, di- and tri-alkyl- and -alkylphenyl-phosphites, heat stabilizers, ultraviolet light sta-bili.zers, antiozonants, dyes, pigments, metal chelating agents, dyesites and the like. Often combinations such.as these, particularly the sul~ur containing esters, the phosphites and/or the ultraviolet light stabilizers will produce superior resu~ts in certain applications to those expected by the properties of the individual components.

.
The following for~ula represents co-stabilizers which are in ~ertain instances very useful in combination with the stabilizers of this invention:
O
In 2n R-O-C-C H
n 2n :
. . . , 10~1903 wherein X is an alkyl group having frorn 6 to 24 carbon atoms; and n is an integer frorn 1 to 6. Especially useful compounds of this typ~ are dilauryl-~-thiodi-propionate and distearyl-~-thiodipropionate. The above co-stabi.lizers are used in the amount of from 0.01 to 2% by weight of the organic material, and preferably from 0.1 to 1~.

Although the compo~nds of this invention may to some degree also be effective as thermal stabiliæers, if the processing of the polymer is carri.ed out at high temperatures it is advantageous to incorporate additional antioxidants.

In most applications, it is desirable to incorporate into the resin composition, sufficient thermal antioxidants to protect the plastic against thermal and oxidative degradation. The amount of antioxidant required will be comparable to that of the actini~ stabilt~r. Namely, from about 0.005 to 5~ and pre~erably from 0.01% to 2% by weight Representative of such antioxidants are phosphite esters, such as triphenylphosphite and dibutyl-phosphite and alkyl arylphosphites such as dibutyl-phenylphosphite, and the like.

The best results have been obtained wi.th ;'' ~

lOSl90;~
the preferred class o~ therm21 antioxidants, the hindered phenols. These compounds hav~ been found to provide the best thermal stabilizati.on with the least discolorati.on in the compositions of the invention.
~noung these phenolic antioxidants are included the following:

di-n-octadecyl(3-5-butyl-4-hydroxy-S-methylbenzyl)malonate 2,6-di-t-butylphenol 2,2'-methylene-bis(6-t-butyl-4-methylphenol) 2,6-di-t-butylhydroquinone octadecyl-(3,5-di-t-butyl-4-hydroxybenzyl-thio)acetate 1,1,3-~ris(3-t-butyl-6-methyI-4-hydroxvphenyl)-butane 1,4-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2,3-5,6-tetramethylbenzene 2,4-bis-(3,5-di-t-butyl-4-hydrox~yphenoxy)-6-(n-octylthio)-1,3,5-triazine 2,4-bis-(4-hydroxy-3,5-di-t-butylphenoxy)-6-(n-octylthioethylthio)-l,3,5-triazine 2,4-bis-(n-oct~lthio)-6-(3,5-di~t-butyl-4-hydroxyanilino)-1,3,5-triazine 2,4,6-tris-(4-hydroxy-3,5-di-t-butyl~henoxy)-:
1,3,5-triazine n-octadecyl-~-(3,5-di-t-butvl-4-hydroxyphenyl) . - . . ,: . .
.- . ';

, . , , -~ OS1903 propionate n-octadccyl-3,5-di-t-butyl-4-hydro~ybenzoate 2-(n-octyltlliG)ethyl-3,5-di-t-butyl-4-hydroxybenzoate stearamido N,N-bis-{ethylene 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}
1,2-propylene glycol bis-{3-(3,5-di-t-butyl-

4-hydroxyphenyl)propionate}
pentaerythritol tetrakis-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}
dioctadecyl-3,5-di-t-butyl-4-hydroxybenzyl--phosphonate di-n-octadecyl-l-(3,5-di-t-butyl-~-hydroxy-phenyl)-ethanephosphonate The above phenolic hydrocarbon stabilizers are known and many are commercially available.

.
The above antioxidants have been listed only for the purpose of illustration and it is important to note that any other antioxidant can be employed with similar improved results. The above exemplified anti-oxidants and other related antioxidants which are incorporated herein by reference, are disclosed in greater detail in the following patents:
~etherlands Patent Specification 67/1119, issued February 19, 1968; Netherlands Patent Specification .

10515~03 68/03498 issued September 18, 1~6~; U.S. ~atents 3,255,191; 3,330,~',9, 3,6q4,~l~2, 3,2~1,505; 3,~31,~,~3, 3,285,~55; 3,364,250; 3,368,997; 3,357,944 and 3,758,54g.

The compounds of this invention may be prepared by reacting a piperidinol of the formula . H OH

Rl ~ ~ CH3 II

wherein Rl, R2, and R3 are as defined above via a usual esterifi.cation procedure with a diacid of the f~rmula O ' , ' R4 ~ -OH) III

` wherein R4 is as d fined above, or conveniently with an acid ~nhydride thereof such as succinic anhydride and glutaric -anhydride. In the process of reacting an acid of formula III

with a compound of formula II the esterification catalyst is preferably a neutral catalyst, for instance a tetraalkyl titanate. -~.. - .

Thè acids and acid anhydrides which are reacted with the compounds for formula II may all be prepared by methods well known in the art.

: .

The compounds of forrnula II may be prepared accor~-ing to procedures presented in DT-OS 2.352.658.
The metal salts of the present invention can be prepared by treating the hindered piperidine carboxylic acids of formula I ~ith a reactive form of the metal or metal complex, e.g., sodium hy~roY.ide or the like; Alternatively, and preferably in the case of metal complexes and metals other than the alkali metals, a double decomposition is employed.
Thus, for example, a sodium salt of the present invention is treated with nickel chloride. In a similax fashion use of other halides such as manganese dichloride, barium chloride and the like results in formation of the corresponding metal derivative.
~ The compounds of formula I wherein M is hydrogen and R5 is imino may be prepared by reacting a compound of the formula 1 ~ CH3 IV
R2 1 ~H3 wherein ~ 1~ R2 and R3 are as defined above~ with (a) a cyclic anhydride or the formula ~ ' lOS1~03 (CIL~) 0~ ~_O V
O
herein p is 1, 2 or 3, or (b) a cyclic anhydride of the formula (lH2)m Y (IH2)n VI
~0~

wherein Y is as defined above, or (c) a half methyl ester of a diacid of the following formula O O
Il 11 CH3-O-C-R4-~-OH VII

wherein R4 is as defined above, or (d) a half methyl ester of a diacid of the following formula O O
Il 11 CH3--O--C(CH2)mY(CH2)nC--OH

wherein m, n, and Y are as defined above.
Examples of cyclic anhydrides as defined above are~ -~
succinic,glutaric, and glycolic anhydrides. .
Examples of half esters of aliphatic diacids are O-- ~3 -' ~

, - ' ~. : .

mono methyl adipate, O-mono me~hyl malonate, O-mono rnethyl sebacate, and O-mono methyl thio dipropionate.
- The R3 substituted compounds of formula IV may be prepared by alkylation of the compound of formula H3C ~ R
~ N ~ IX

wherein Rl and R2 are as defined above with an alkylation agent R3X according to the procedure of Lutz, Lazarus and Meltzer, J. Ory. Chem. 27 1695 ~1962~ and by subsequent treatment of the ketone group with hydrox~lamine hydrochloride to produce the oxime, which is then reduced to the corresponding ~ine witll Lithium Alwninum Hydrîde according to t~le proce~ure given in the above reference. X in R3X is e.g. halogen.
The compound of formula IV where Rl and R2 are alkyl groups and R3 is hydrogen are known compounds w~ich may be pre-pared in accordance wit~ known procedures. The compounds of formula IV where Rl and R2 form cycloalkyl sroups and R3 is hy-drogen may be prepared by known l"rocedures, such as those dis-cussed in J. Synthetic Chem. Japan 29 1971 and references con-tained therein.
The followin~ examples, presented for illustration and not limitation, wiil further serve to typify the nature of the present invention.

: ' . ': ' . ' . .. ' . ~ : ~ , ~ ' ~. '. " ' , .

10519(~3 Example 1 O-mono(1,2,2,6,6-~entamethylpiperidin 4-ol)succinate A. In a 1 liter 3-necked flask equipped with a stirrer, thermometer, condenser with a-water separator and drying tube; and nitrogen inlet were placed 18.~3 g (0.1 moles) of 1,2,2,6,6-pentamethyl-piperidin-4-ol monohydrate and 500 ml of xylene.
Thè reaction mixture was heated to reflux under nitrogen with stirring and the water of hydration was collected in the water separator. The reaction mixture was then cooled to room temperature and 10.0 g (0.1 moles) of succinic anhydride were added.
The reaction mixture was heated under reflux for 6 hours and allowed to stand overnight. To the re-action mixture was added 500 ml of hexane and the precipitate was collected by suction, washed with hexane and dried under vacuum. The solid was re-crystallized from acetonitrile, giving 21.0 g of the desired material as colorless crystals, m.p. ;
163-165C.

B. By following the above procedure (A), and suhstituting for the succinic anhydride an equivalent amount of glutaric anhydride, there is obtained o-mono ~1,2,2,6,6-pentamethyl-piperidln-4-ol)glutarate.

., . ~ .

.
: ' " ' '"- '' '' ' ' ~ , :
. : ''' C. By following the above procedure (~.) and substituting for the l,2,2,6,6-pentamethylpiperidin-4-01 an equivalen~ amount of the following reagents:

(a) l-n-dodecyl-2,2,6,6-tetrame~hylpiperidin-4-ol.

(b) l-benzyl-2,2,6,6-tetramethylpiperidin-4-ol (c) l-allyl-2,2,6,6-tetramethylpiperidin-4-ol there are re~pectively obtained:

~ a? O-mono(l-n-dodecyl-2,2,6,6-tetramethylpiperidin-4-ol)succinate (b) O-mono(l-benzyl-2,2,6,6-tetramethylpiperidin-4-ol)succinate (c) O-mono(l-allyl-2,2,6,6-tetramethylpiperidin-4-ol)succinate Example 2 O-m no(2,2,6,6-tetramethylpiperidin-4-ol)suc inate In a l-liter 3-necked flask e~uipped with a stirrer, condenser, nitrogen inlet, thermometer and drying tube were placed 47.2 g (0.3 moles) of 2,2,6,6-tetramethylpiperid;.n-4-ol, 30 g (0.3 moles) of succinic anhydride and 500 ml of benzene.
The reaction mixture was heated under reflux for 4 hours, during which time a colorless precipitate had accumulated ' ' ~ ' ~' 10~i1903 in the flask. The reaction mi~ture was cooled and the precipitated solids were collected by suction and triturlted with 2 x 1500 ml of hot ethanol. The combined solids were dried at 60 in a vacuum oven, yielding about 65 g of the desired material as a colorless powder, m.p. 263-265 C.

Example 3 O-mono(2 ! 2,6,6 tetramethylpiperidin-4-ol)adiPate In a 2-liter 3-necked flask equipped with a stirrer, thermometer, water collector (Dean-Stark trap), condenser, drying tube and nitrogen inlet were placed l-liter of dry xylene, 50.4 g (0.32 moles) of 2,2,6,6-tetramethylpiperidin-4-ol, 58.5 g (0.40 moles) of adipic acid, and 9.6 ml of titanium tetraisopropylate. The reaction mixture was heated under reflux for a total of .
28 hours, during which time the theoretical amount of water had collected in the Dean-Stark trap and a precipitate had formed. The reaction mixture was cooled to room temperature, filtered, and the collected solids washed well with xylene and isopropanol and dried. The collected solids were recrystallized in several portions from 2B Ethanol, yielding, after suction, filtration, drying and com~ination, about 75 g of white crystals, m.p. 218-221C of the desired material.

105~903 O-mono-(2,2,6,6-tetramethyl-piperidin-4-ol)sebacate A. In a 3 liter 3-necked fl~sk equipped with a stirrer, thermometer, condenser with water separator and drying tube, and nitrogen inlet tube were placed a mixture of 161.6 g (0.8 moles) of sebacic aci.d, 50.4 g (0.32 moles) of 2,2,6,6-tetramethylpiperidin-4-ol and 2000 ml of xylene.
To the mixture was added 9.6 ml (0.032 moles) of tetraisopropyl titanate. The reaction mix~ure was heated under reflux with stirring and 6.0 ml of water were collected over a 30 hour period.
The reaction mixture was cooled and the xylene was removed by decantation. The residue was re-crystallized from warm dimethylformamide, then from isopropanol, yielding 26.9 g of ~hite crystals, m.p. 174 to 178C of the desired material.

B. By following the above procedure (A), and substituting for the sebacic acid an equivalent amount of:
(a) pimelic acid (b) tetramethyl succinic acid -~
(c) azelaic acid - - ~ . .: . . .

.~ . . :. . :
'........ , . :

td) thiodipropionic acid (e) suberic acid (f) thiodiglycolic acid there is respectively obtained the following compounds:
(a) O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)pimelate (b) O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)tetramethyl succinate (c) O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)azelate (d) O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)thiodipropionate (e) O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)suberate , (f) O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)thiodiglycolate.

C. By essentially following the above procedure (A), and substituting the reactants appropriate quantities -' of the following reagents (a) l-n-dodecyl-2,2,6,6-tetramethyl piperidin-4-ol and sebacic acid -' (b) l-benzyl-2;2,6,6-tetramethyl piperidin-4-ol and azelaic acid (c) l-allyl-2,2,6,6-tetramethyl piperidin-4-ol and suberic acid ~ ,.

' ' ~

::. :

10~19(~
there are respectively obtained the following cornpounds:
(a) o-mono(l-n-dodecyl-2,2,6,~-tetr~n~thyl-piperidin-4-ol)sebacate.

(b) O-mono(l-benzyl-2,2,6,6-tetramethyl piperidin-4-ol) azelate.

(c) O-mono(l-allyl-2,2,6,6-tetramethyl piperidin-4-ol) su~erate.

Example S :

O-mono(1,2,2,6,6-pentamethyl-piperidyl-4)diglycola1e In a l liter 3-necked flask equipped with a stirrer, thèrmometer, condenser with water separator and drying tube, and nitrogen inlet, was placed 18.93 g (O.lO moles) of 1,2,2,6,6-penta-methyl-piperidine-4-ol monohydrate and 500 ml of xylene. The-reaction mixture was heated under reflux with stirring until l.8 ml of water had been collected in the water separator. The reaction mixture was cooled to 40C and ll.6 g (O.lOrmoles) of diglycolic anhydride were added. The reaction mixture was heated slowly to reflux. The anhydride appeared to go into solution; then a precipitate was noted. The reaction mixture was heated under reflux for 4 hours and allowed to cool o~ernight.

: : .. . .
: ~. .,. --:

.~, . . .

1053~903 The precipitated solids were collected by suct~on, washed with hexane and dried in air. The product was recrystallized from e~hanol-isopropanol, and dried under vacuum at 60C over P205, yielding 14.7 g of colorless crystals, m.p. 194-198C, of the desired material.

' Example 6 ~ickel bis{O-mono(2,2,6,6-tetramethyl-.
~i~eridin-4-ol)sebacate}
.

A. In a 2 liter 3-necked flask equipped with a thermometer, dropping funnel, stirrer and nitrogen inlet were placed 20.49 g (0.06 moles) of o-mono(2,2,6,6-tetramethylpiperidin-4-ol)sebacate and 1200 ml of absolute methanol. To the mixture was added via pipette 60 ml of 1 N KOH in methanol.
To the clear solution was then added a solution of 7.13 g (0.03 moles) of NiC12 6H2O in 120 ml of absolute methanol over a 10 minute period. ~The reaction mixture was stirred at room temperature for 1 hour and a'_ 50C for 1 hour. The green -~-methanolic solution was then evapoxated under reduced pressure and 1200 ml of isopropanol was added. The isopropanol solution was heated to 50C for one hour .

1051~03 and allo~ed to stand overnight. The isopropanol solution was filtered with suction and the filtr~te evaporated under reduced pressure. The re~idue was treated with 850 ml of benzene, filtered with suction, and the benzene solution evaporated under reduced pressure and dried at 70C wlder vacuum, yielding 18.5 g of a pale green glassy solid of the desired material.

B. By following the above procedure (A~
and substituting for the o-mono(2,2,6,6-tetra-methylpiperidin-4-ol)sebacate an equivalent amount o~: .
(a) O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)pimelate ~ (b) O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)tetramethyl succinate (c) O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)thiodiglycolate (d) O-mono(l-n-dodecyl-2,2,6,6-tetramethyl-piperidin-4-ol)sebacate (e) 0-mono~l-benzyl-2,2,6,6-tetramethyl piperidin-4-ol)azelate (f) Ormono(l-allyl-2~2~6~6-tetramethyl piperidin-4-~l)suberatel .
' .

: : ' 105~903 there .is respectively obtained the following compounds:

(a) nickel complex of O-mono(2,2,6,6-tetramethyl-pi.peridin-4-ol)pimelate (b) nickel complex of O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)tetramethyl succinate (c) nickel complex o~ o-mono(2,2,6,6-tetramethyl-piperidin-4-ol)thiodiglycolate.
(d) nickel complex of O-mono(l-n-dodecyl-2,2,6,6-tetramethyl piperidin-4-ol)sebacate . (e) nickel complex of O-mono-(l-benzyl-2,2,6,6-tetramethyl piperidin-4-ol)azelate (f) nickel complex of O-mono(l-allyl-2,2,6,6-tetramethyl piperidin-4-ol)suberate.

Example 7 By essentially following the procedure of Example 6(A) and substituting the foliowing metal complexes for nickel chloride:

(a) manganese chloride (b) zinc chloride (c) ferric chloride (d) cobalt(ous) chloride there is thus xespectively obtained:

' ' , ,:
':
; :' ' ~.,. ' 105~903 (a) mangc~nese compleY. of bis{0-mono (2,2,6,6~tetramethylpiperidin-4-ol)sebacate}
(b) zinc complex of bis{O-mono(2,2,6,6-tetramethylpiperidin-4-ol)sebacate}
(c) iron complex of bis{O-mono(2,2,6,6-tetramethylpiperidin-4-ol3sebacate}
(d) cobalt complec of bis{O-mono(2,2,6,6-tetramethylpiperidin-4-ol)sebacate}.

.. . .
Example 8 ' Ni(II) bis{O-mono(1,2,2,6,6-penta-methy~piperidin-4-ol)di~lycolate}

~ In a 100 ml l-necked flask equipped with a magnetic stirrer and distillation head were placed 2.87 g (0.01 moles) of O-mono-(1,2,2,6,6-tetramethylpiperidin-4 ol)diglycolate, 1.26 g (0.005 moles) of nickel acetate tetrahydrate and 50 ml of water. The reaction mixture was heated slowly to distillation temperature. The distillate collected was assayed by titration with 0.1 N ~OH with phenophthalein as indicator.
The distillatiGn was continued until 9~ o the ~'~
theoretical amount of acetic acid had been collected. ~`

'' ' The reaction mixture was then evaporated under vacuum, and the rcsidue dissolved in methanol, filtered and the filtrate evaporated under reduced pressure. The green powdery residue, m.p. 210 (d) weighed 3.28 g and proved to be the desired material. - -Example 9 Nickel bis-~O-mono-{1,2,2,6,6-~entamethyl piperidin-4-ol}succinate) A. In a l-liter 3-necked flask equipped with a stirrer, thermometer, condenser, dropping funnel and nitrogen inlet were placed 5.4 g (10.02 moles) of o-mono (1,2,2,6,6-pentamethylpiperidin-4-ol)succinate and 200 ml of absolute methanol. To the stirred mixture was added via a volumetric pipette 20.0 ml of 1.0 N KOH
in methanol. To the stirred solution was added dropwise over a 10~minute period a solution of 2.37 g (0.01 moles) of NiC12 6H2O in 50 ml of absolute methanol. The dropping funnel was rinsed with an additional 50 ml of absolute methanol and the reaction mixture was heated at 50 for a 2-hour period. The green reaction mixture was then cooled and evaporated to dryness under reduced pressure.
The residue was treated with 20 ml of isopropanol and .,.

.
.

lOS1903 the mixture he-ated 2 hours at 50C. The reaction mixture, after cooling to room temperature was filtered with suction, the solids ~ashed with isopropanol, and the filtrate evaporated to dryness under reduced pressure.
The residue was taken up in benzene, the solution filtered with suction, and the benzene filtrate evaporated under reduced pressure. The residue was dried at 70 under vacuum, and the desired material obtained as a green glass.

B. By following the above procedure (A) and substituting or the O-mono(1,2,2,6,6-pentamethyl-piperidin-4-ol)succinate an equivalent amount of:

(a) O-mono~l-n-dodecyl-2,2,6,6-tetramethyl-piperidin-4-ol)succinate (b) O-mono(l-benzyl-2,2,6,6-tetramethyl-piperidin-4-ol)succinate (c) O-mono(l-allyl-2,2,6,6-tetramethyl-piperidin-4-ol)succinate there is respectively obtained the following compounds:

(a) nickel II bis(O-mono{l-n-dodecyl-2,2,6,6 tetramethylpiperidin-4-ol}succinate) (b) nickel II bis(o-mono{l-ben~yl-2,2,6,6-tetrametllylpiperidin-4-ol}succinate) 105~903 (c) nickel II bis(O-mono{l-allyl-2,2,~,6-tetramethylpiperidin-4-ol}succinate) Example 10 Nic~el II bis(O-moilo{2,2,6,6-tetramethvl--~iperidin-4-ol}succinate) . A. In a 500 ml l-necked flask equipped with a magnetic stirrer, thermometer and dropping funnel were placed 2.85 g (0.01 moles) of o-mono(2,2,6,6-tetramethyl-piperidin-4-ol)succinate and 100 ml of absolute methanol.
To the stirred mixture was added via volumetric pipette 100 ml of 0.1N KOH in methanol. To the stirred solution was tpen added dropwise over a 10-minute period a solution of 1.188 g (0.005 moles) of NiC12 ~H2O in 20 ml of absolute methanol. An additional 20 ml of methanol was used to rinse the dropping funnel. The reaction mixture was heated at 50 for two hours, cooled to room temperature and evaporated to approximately 100 ml under reduced pxessure. To the methanolic solution was added 100 ml of absolute ethanol. The solution was allowed to stand ovexnight whereupon a white precipitate formed, the precipitate was collected by suction, rinsed with ethanol, and the filtrate reduced to one-half volume under .

1(~5~903 rcduced pressure. The above operatior,s (addition of ethanol, standing~ riltration and evaporation) were repeated once more. Then isoprop~nol wa-; substitu~cd for ethanol and the operations repeated twice more. The filtrate was evaporated to dryness and the green glassy residue was dissolved in bell~ene, the benzene solution filtered with suction and the filtrate evaporated under reduced pressure. The residue was dried under vacuum at 70 C
yielding the desired nickel salt as a green glassy solid.

B. By following the above procedure (~) and substi~uting for the O-mono[2,2,6,6-tetramethyl-piperidin-4-ol)succinate an equivalent amount of o-mono(2~2,6~6-tetramethylpiperidin--4-ol)adipate there was produced nickel II bis(O-mono{2,2,6,6-tetramethylpiperidin-4-ol}adipate).

Example l~

By essentially following the pxocedure of ,_ .
Example 9 (A) and substituting the following metal complexes for nickel chloride:

~a) manganese chloride (b) ~inc chlorlde (c) ferric chloride ~OS1903 (d) cobalt(ous) chloride there are respectively obtained:
(a) manganese complex of O-mono(1,2,2,6,6-pentamethylpip2ridin-4-ol)succinate (b) zinc complex of O-mono(1,2,2,6,6-penta-methylpiperi~in-4-ol)succinate (c) iron complex of O-mono(1,2,2,6,6-penLamethyl-piperidin-4-ol)succinate (d) cobalt complex of O-mono(1,2,2,6,6-penta-methylpipe^idin 4-ol)succinate Example 12 N-(2,2,6,6-Tetrame~lylpiperidyl~4) Succinamic Acid A. In a l-liter 3-necked flask equipped with a stirrer, thermometer, and condenser equipped with a water separator and nitrogen inlet, were placed lS.9S g. (0.1 moles) of 4-amino-2~2,6,6-tetramethylpiperidine and 500 ml of xylene. The mixture was heated to reflux and a small amount of ~ater was re~oved from the reaction with the water separator. The reaction mix'ure was cooled to 40 C and lO.O g. (0.10 moles) of succinic anhydride were added. The reaction mixture was heated to xeflux, at which point a precipitate began to appeax. The heating ur,der reflux was continued for 6 hours ~nd th~n the rcaction mixture was allowed to cool. The precip.itated solids were collected by - suction, and recrystallized from acetone-water and dried under vacuum at 100 C, of the desired material.

B. By essentially ~ollowing the above procedure (A) and subs~ltuting for the succinic anhydride an equivalent amount of (a) glut~ric anhydride (b) glycolic anhydride (c) tetramethyl succinic anhydride There is respectively produced the following compounds:
(a) N-(2,2,6,6-tetramethylpiperidyl-4) glutaramic acid (b) N-(2,2,6,6-tetramethylpiperidyl-4) glycolamic acid (c) N-(2,2,6,6-tet~ametnylpiperidyl-~) tetramethyl succinamic acid C. By essentially followin~ p~ocedure (A) and sub s~itutin~ for the 4-amino-2,2,6,6-tetr~-nethylpi.peridine an equi~-alent amount of (a) 4-amino-1,2,2,6,6-pentamethylplper.idine (b) 4-a~ino-1-n-dodecyl-2,2,6,6-t~etramethylpiperidine (c) ~-amino-l-benæyl-2,2,6,6-tetramethylpiperidine Tilere is respectively produced the following compounds (a) N~(1~2,2,6,6-pentamethylpiperldyl-~ succinamic acid (b) N-~l-n-dodecyl-2,2,6,6-tetramethyl-4) succinamic ., .......... : . .

.

1~51903 acid (c~ N-(1-benzyl-2,2~6,6-tetramethyl-4) succinamic acid Example 13 N-(2,2,6,6-~etrameth~piperidyl-4) Sebacamic ~cid A. In a 250 ml 3-necked fl~sk equipped ~ith a stirrer, thermometer, and Dean-Stark trap equipped with a dry-ice con-denser were placed 15.95 g. ~0.1 moles) of 4-amino-2,2,6,6-tetramethylpiperidine, and 21.63 g. (0 1 moles) of O-methyl sebacat~. The reaction mixture was heated, with stirring under nitrogen at 180-200 C until the methanol was obtained in the Dean-Stark trap and the dry-ice condenser. The reaction mix-ture was then heated under vacuum at this temperature tO remove the last traces of methanol. The reaction mixture was then cooled and the residue recrystallized from ethanol-water, giving the desired product ar colorless crystals.

B. In the previous experiment A, substituting for the O-methyl sebacate, aneguivalent amount of O-methyl adipic acid half ester, there is produced N~(2,2,6,6-~tetramethyl- ;
piperidyl-4) adipamic acid.

C. In the previous experiment A, substituting for ,: :
. .. ' ;'~.,, 105~903 the ~ a~ino 2,2,6,6-tetrameth~lpipcridine an ec~ivalent alQount of 4-amino-1,2,2,6,6-pcntamethylpiperidine, tnere is produced N-(1,2,2,6,6-pentamethylpiperidyl-4) sebacamic acid.

Example 14 , N.LC~e~ ~I bis [N-(2,2,6,6-r~etrameth~l-~iperid~ suclnamateJ

A. In a l-liter 3-necked flask e~uipped with a dropping funnel, magnetic stirrer and nitrogen inlet were placed 5.13 g.
(0.02 moles) of N-(2,2,6,6-t~t~amethylpiperidyl-4) succin&mic acid in 250 ml of dry methanol.To the stirred solution was added via pipette 20 ml of 1 N methanolic KOH. The solution was stirred ~u~til cleax and then a solution of 2.38 g. (0.01 moles) of NiC12-6H2O in 50 ml of methanol was added over a 10 minute`period. At the end of the addition, the reaction mix~
ture was heated slowly to 60 C and st.irred for two hours.
The reaction mixture was then cooled to room temperature and reduced to one-half the original volume under vacuum. To the methanolic so.lution was then added 150 ml of isopropanol, and the reaction mixture heated at 60 for two hours and allowed to cool to room temperature. The salts deposited on standing were filtered ~ith suction and the filtrate reduced to one-half volume under vacuum. To the reduced filtrate was again added 150 ml of isopropanol and the heating and filtration procedure repeated. The filtrate was evaporated to dryness . ~

undcr vacuum and thcn takcn up in absolute ethanol, heated to 65 for two hours, cooled and flltered, and the filtrate evaporaJLed nnder reduced prcssure, the res.idue, a green glassy powder m.p. 240-250 C (d) proved to be the desired compound by analysis or nickel content.

, B. By essentially following procedure (~) and sub-stituting fOL^ N-(2,2,6,6-tetrc).methylpiperidyl-4) succinarr,ic acid an equivalent amount of (a) N-(2,2,6,6-tetr~neth~lpiperid~1-4~ glutaramic acid (b) N-(1,2,2,6,6-pentamethylpiperidyl-4) succinamic acid (c) N-(2,2,6,6-tetramethylpiperidyl-4.) sebacamic acid There is respectivel~r produced the following Ni-compounds (a) Nickel II bis [N-(2,2,6,6-tetramethylpiperidyl-4 glutaramate~
(b) Nickel II bis ~N-(1,2,2,6,6-pentamethylpiperidyl-4) succinamate]
(c) Nickel II bis [N-(2,2,6,6-tetramethylp.:peridyl-4) sebacamate~

Exam~le 15 By essentially following the procedure of Example --14(A) and substituting the following metal complexes for nickel chloride: .

~a) manganese chlorid~
(b) æinc chloride (c) ferric chloride (d~ cobalt(ous) chloride ere is thus respectively obtained:
(a) manganese complex of N-[2~2,6,6-tetramethvl-piperidyl-4] succinamate (b) zinc complex of N-[2,2,6,6-tetram~thylpiperidyl-4] succinamate (c) ir~n complex of N-[2,2,6,6~tetrameth~1piperidyl-4] succln~nate (d) cobalt complex of N-[2,2,6,6-tetrameth~lpiperidyl-4] succinamate.

~ a~le16 . ' ' ,. .

~rtificial Light ~x~osure Test Deterioration of most polymers caused ~y ultraviolet light is so slow at &~bient tempe.ratures, even il~ the absence of stabilizexs, that testing of the e~ects of stabilizers generally must be con-ducted either at higher temp~ratures or in an accel-exated arti~icial li~ht exposure device in order to yield results in a convenient period o~ time. The tests conducted on polymexs using an axtifi.cial li~ht exposure device is described below:

..

~051903 (a) Samplc~ Pre~clxa~i~n , ,

5 ~il ~'ilm - Unstabilized poly-propylene po~der tHercules Profa~ 6501) is ~loroughly blended with the indicated amounts o~ additives. The blended matcrial is then milled on a two roll mill fox 5 minutes at 1~2C. The milled sheet is then compxession molded at 2~0C in~o 5 mil thick film u,ndex a pressure of 175 psi and water cooled iD the press.

(b) Test nq ~Set.hoa ' This test is conducted in a FS/~L unit, bas~cally of the American Cyanamid design, whic3~ consists of ~0 tu~es o~ alternating ~luore~cent ~unlamps and black lights (20 of each). Tlie 5 mil s~ple film ~hich are mounted on 3" x 2"
IR card holde~s wi~h 1/4" x 1" ~indows and are placed on a xo~ating drum 2 inches from the bulbs,in the ~SJBL ~nit. The time in hours is noted`ox the development o~ 0.5 caxbonyl absorbance u~i~s as determine~ on an Infxared Spectophotometex. The developmen~
o~ carbonyl functional groups in the polymex ' ' ' 105~903 .is proportional to t.lC alltOUJlt 0~ degradation cause(1 by'the ultra~iGlc~ li(Jht e~:posure.

The test resulcs reportcd below were obtained according to the procedures described above. The ~ounts o tl~e additi.ves are expressed in wo~ight per cent based on the weight of the polymer.

, ~ , . . . :
L....... '' .' .~ . ' '' ~
. .

~051903 TABLE I a Li~ht ~Stabilization ~ata in Poly~ropylene Time in Hours to 0.5 Carbonyl- Ab-Additive sorbance Units Formulation A* ~ormulation B~*
0-mono(1,2,2,6,6-penta-methyl-pi.peridin-4-ol) succinate . 2155 2115 0-mono(2,2,6,6-tetra-methyl-p-peridin-4-ol) succinate 485 1040 O-mono(2,2,6,6-tetra-nlethyl-piperidin-4-ol) adipate 1850 2395 Blank 215 * Formulation A contains 0.5~ additive and 0.2 antioxidant dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate.
** Formulation B contains 0.25% additive, 0.25%
W absorber 2(2'-hydroxy-3',5'-di-t-butyl-phenyl)-5-chlorohenzotriazole, and 0.2~
antioxidant dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate.

Proportionately ~ood stabilization is obtained when in the compositions of Table I the compounds of this invention are present in the concentrations of 0.1~ and 1%.

1~5~903 T~BLr~ Ib Light Stabilizatioll Data in Polyprop~ ne Time in Hours .to Additive 0.5 Carbon~l Absorbance Units . Formulation A* Foxmulation B**
0-mono(2,2,6,6-tetra-methylpiperidin-4-ol) sebacate 2330 2495 nickel bis{0-mono(2,2,

6,6-tetramethylpiperidin-4-ol)sebacate} 3635 . 2335 0-mono(1,2,2,6,6-penta-methyl piperidin-4-ol) diglycolate 1295 1~20 nickel bis{0-mono(1,2,2, 6,6-pentamethyl piperidin-4-ol)diglycolate} 565 1125 .
Blank 215 .,_ * Formulation A contains 0.5% additive and 0.2%
antioxidant dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate.
** Formulation B contains 0.25% additive, 0.25%
W absorber 2(2'-hydroxy-3',5'-di-t-butyl-phenyl)-5-chlorobenzotriazole, and 0.2~ antioxidant dioctadecyl 3,5-di-t-butyl-4-hydroxybenzyl-phosphonate.

Proportionately good stabilization is obtained when in the Compositions of Table I the compounds of this invention are present in the concentrations of 0.1% and 1~.

--.

.
. . :

.:: . . ..... ,:' ' T~BLE Ic Light Stabili.zation Data in .
Polypropylene Time in Hours to O.S Carbonyl Ab-Additive sorb~nce Uni.ts F m _ ation A* For~ulation B**
Nickel bis{O-mono tl,2~2~6~6-pentameth piperidin-4-ol)suc-cinate} 3390 2860 Nickel bis~0-mono(2,2, 6,6-tetram~thylpiperidin 4-ol)succinate} 1760 2304 Nickel bis{0-mono~2,2~ .
6,6-tetramethylpiperidin-4-ol)adipate} 4000 3130 Blank 215 * Formulation A c~ntains 0.5~ additive and 0.2%
a~ntioxidant dioctadecyl 3,S-di-t-butyl-4-hydroxybenzylphosphonate.
** Formulation B contains 0.25% additive, 0.25 W absorber 2(2'-hydroxy-3',5'-di-t-kutyl-phenyl)-5-chlorobenzotriaæole, and 0.2~.
antioxidant dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate.

Proportionately good stabilization is obtained whcn .
in the compositions of Table I the compounds o~ :-this invention are present in the concentrations of 0.1~ and 1%.

,, .

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Other hirldcred pher,olic antioxidar-ts may be used in place of di-octadecyl(3,5-di-t-butyl-4-hydroxy~etlzyl)phosphonate in the abovc mentioned compositions for example, di-n-octadecyl ~-(3~t-butyl-4-hydroxy-.~-methylbenzyl)malonate, 2,4-bis ~n-octylthio)-6-(3,4-di--t-b~tyl-~-hydroxyaniline)-1,3,5-triazine, oc.adecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, pentaerythritol-tetra-kis{3-(3,5-di-t-butyl-4-hydroxyphenyl)}propionate, tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanura'.e, 2,6-di-tert-butyl-4-methylphenol, N,N,N-tris-(3,5-di-tert-butyl-4-hydroxyhenzyl)isocyanurate, and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-trimethylbenzyl.

The compositions of Table I are also stabiliz,ed when 2(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzo-triazole is replaced with the following W absorbers:
(a) 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate (b) 2-hydroxy-4-n-octoxybenzophenone (c) {2,2'-thiobis(4-t-octylphenolate)}-n-butylamine nic]~el II
(d) p-octylphenyl salicylate (e) 2,2'-dihydroxy-4,4'-dimethoxybenzo-phenone (f) 2(2'-hydroxy-5'-methylphenyl)-benzo-triazole.

: :~
' ,:
- ' ' Example 17 High Lmpact polystyrene resin containing elastomer (i.e., butadiene-styrene) is stabilized against loss of elonga~ion properties due to exposure to ultraviolet light by incorporation of 0.3% by weight of O-mono(1,2,2,6,6-pentamethyl-piperidin-4-ol)succinate.

The unstabilized resin is dissolv~d in chloro-form and the stabilizer then added, after which the mixture is cast on a glass plate and the solvent evaporated to yield a uniform fllm which, upon drying, is removed and cut up, and then pressed for 7 minutes at a temperature of 163C and a pressure of 2,000 pounds per square inch into a sheet of uniform thick-ness (~25 mil). The sheets are then cut into strips approximately 4 x 0.5 inches. A portion of these strips is then measured for percent of elongation in the Instron Tensile Testing Apparatus (Instron Engineering Corporation, ~;
Quincy, Massachusetts). The remaining portions of the strips are placed in an FS/BL chamber according to Example 4 (b) except that the samples are mounted and white cardboard stock and the time to 50% reduction in elongation is measured. The stabilized polystyrene resin retains its elongation property longer than the unstabilized resin.

_ - 52 -,: ~

lOS191)3 Example 18 ' Unstabilized linear polyethylene is solvent blended in methylene chloride with 0.5~ by weight of the substrate of O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)succinate and then vacuum dried.
The resin is then extrusion compounded on a l inch 24/l=L/D extruder, melt temperature 450F (232C) and pressed for 7 minutes at a temperature of 163C
and a pressure of 2000 psi into a sheet of uniform thickness of 100 mil. The sheets are then cut into plaques of 2 inch x 2 inch. The plaques are then exposed in a FS/BL exposure device and color measure-ments made periodically using a Hunter Color Difference Meter Model D25. Polyethylene stabilized with the, ~-above compound is found to be much more stable than ' '-the unstabilized polyethylene or the polyethylene stabilized only with an antioxidant.

Example ~9 A quantity of SBR emulsion containing 100 g of rubber (500 ml of 20% SBR obtained from Texas U.S., Synpol 1500) previously stored under nitrogen, is placed in a beaker and stirred vigorously. The pH
of the emulsion is adjusted to 10.5 with a 0.5N

NaOH solution.

., . , , : ~
, ~ , 105~903 To the emulsion is added 50 ml of 25~6 NaCl solution. A 6% NaCl solution adjusted with hydro-chloric acid to a pH 1.5 is added in a thin stream with vigorous stirring. When pH 6.5 is reached, the rubber begins to coagulate and the addition is slowed down in order to maintain uniform agitation. ~ The addition of ~he acidic 6% NaCl solution is terminated when a pH 3.5 is reached. The coagulated crumb-rubber sl~lrry at pH 3.5 is stirred for 1/2 hour.

.

The coagulated rubber is isolated by filtration through cheese cloth, and rinsed with distilled water.
After three subsequent washings with fresh distilled water, the coagulated rubber is dried, first at 25 mm Hg and finally to constant weight under high vacuum (>1 mm) at 40-45C.

The dried rubber (25 g) is heated under nitrogen at 125C in a Brabender mixer and to this is added with mixing 0.25 g (0.5%) of 0-mono(2,2, 6,6-tetramethyl piperidin-4-ol)adipate. The composition is mixed for 5 minutes after which it is cooled and compression molded at 125~C
into 5" x 0.025" plaques.

The plaques are exposed to a xenon arc weather-ometer and the color measurement (L-b) is made after 45, 125 and 290 hours. The samples stabilized with the above compound are found to be much more light stable than the unstabilized samples.

.:: ' :, .

: ~ . . . .
: :"' lOS1903 E~ample 20 To 50 g of polyacetal r~sin containing 0.1%of an acid scavenger, dicyandiamide, is added 0.2~
by weight of ~mono(2,2,6,6-tetramethylpiperidin-4-ol) adipate and milled for 7 minutes at 200C in a Erabendex Plasti-recorder. The milled formulation is subsequéntly pressed into a 40 mil sheet at 215C at 350 psi for 90 seconds then cooled quickly in a cold press at 350 psi.
The stabilized sheets are then remolded for 2 minutes at contact pressure and foL 3 minutes at 300 psi at 215C to give plaques 1 1/2 inch x 2 1/4 inch x 125 mil. Thereafter, the testing procedure of Example 9 is followed to determine the light stability of the samples. The stabilized samples are found to be much more stable than the unstabilized samples. , -'~

Example 21 Unstabilized thoroughly dried polyethylene terephthalate chips are dry blended with 1.0% of 0-mono-(2,2,6,6-tetramethylpiperidin-4-ol)succinate.
60/10 denier multifilament is melt spun at a melt temperature of 290C. The oxiented fiber is wound on white cards and exposed in a Xenon Arc Fadeometer.
Color measurements are made periodically with a Hunter Color Di~ference Meter Model D25. The stabilized samples are found to be much more light stable than the un-stabilized samples.

': . - :: .

lOS1903 Example 2~

(a) A composition comprising acrylonitrile-butadiene-styrene terpolymer and 1% by weight of O-mono (l-n-dodecyl-2,2,6,6-tetramethylpiperidin-4-ol)succinate resists embrittlement due to exposure to ultraviolet light longer than one which does not contain the stab~lizer.
' (b) A composition comprising polyurethane prepared fxom toluene diisocyanate and alkylene polyols and 1.0% by weight of O-mono(1,2,2,6,6-pentamethyl-piperid.in-4-ol succinate is more stable to sunlight, fluorescent sunlamps, black lights and fluorescent lights than the unformulated polyurethane.

(c) A composition comprising a polycarbonate "
prepared from bisphenol--A and phosgene and 1% by weight of o-m`ono(l-benzyl-2~2~6,6-tetramethylpiperidin-4-ol) succinate resists dis-oloration due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

(d) A composition comprising polymethyl-methacrylate and 0.25% by weig~.t of O-mono(l-allyl-2,2,6,6-tetramethylpiperidin-4-ol)succinate resists discolorati.on due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

_ - 56 -: ~ , .

lOS1903 Example 2~

(a) A stabilized polyamid~ (nyl~n 6,6) is prepared by incorporating therein 0.1% of ~mono(1,2,2,6,6-pentamethylpiperidin-4-ol)succ~.nate. The light stability of the stabilized composition is superior to ~hat of an unstabilized polyamide.

(b) A.stabilized polyphenylene oxide polymer (prepared by polymerizing 2,6-dimethylphenol is pre-pared by.incorporating therein 0.5% by weigIIt of O-mono (l-n-dodecyl-2,2,6,6-tetramethylpiperidin-4-ol)succinate.
The stabilized compositions resist embrittlement due to exposure to ultrav.iolet light longer than one which does not contain the stabilizer.

, (c) A stabilized crystalline polystyrene is prepared by incorporating therein 0.1% by weight of O-mono(2,2,6,6-tetramethylpiperidin-4-ol)adipate. The stabilized composition resists embrittiement due to exposure to ultraviolet light longer than one which does not contain the stabillzer.

~ ntioxidants.may also be incorporated into each o the aI~ove mentioned compositions, for example, di-n-octadecyl-n,~'-bist3-bu~yl-4-hydxoxy-5-methylb6nzyl) malonate 2~-bi~4-hydroxy-3~5-di-t-butylph~noxy)^6-(n-octylthioe~}lylthio)-1,3,5-triazin~, 2,~-bis(3,5-di-t-,. : ', ' ,'' ,, ,:

105~903 butyl-hydroYypheno~y)-6-(n-octyl~l)io)-1,3,5~triazine di-n-octadccyl 3(3',5'-di-t-bu~yl-~-]1ydroxyphenyl)~ro-- pionatc, respectively.

Example24 High impact polystyrene resin containing elastomer (i.e., butadiene-styrene) is stabilized against loss of elongation properties due to exposure to ultraviolet light by incorporation of 0.3% by weight of O-mono(2,2;6,6-tetramethylpiperidin-4-ol) sebacate.

The unstabilized resin is dissolved in chloro-form and the stabilizer then added, after which the mixture is cast on a glass plate and the solvent evaporated to yield a uniform film which, upon drying, is removed and cut up, and then pressed for 7 minutes at a temperature of 163C and a pressure of 2,000 pounds per square inch into a sheet of uniform thick-ness (25 mil). The sheets are then cut int~o strips approximately 4 x 0.5 inches. A portion of these strips is then measured for percent of elongation in the Instron Tensile Testing Apparatus ~Instron Engineering Corporation, Quincy, Massachusetts). The remaining portions of the strips are placed in an FS/BL chamber according to . - 58 --' ', ~;

105~903 Example 6 (B) except that the s~mples are mounted and white cardboard stock and the time to 50~ reduction in elongation is measured. The stabilized polystyrene resin retains its elongation property longer than the unstabilized resin.

Example 25 Unstabilized linear polyethylene is solvent blended in methylene chloride with 0.~% by weight of the substrate of the nickel complex of O-mono(2,2-6,6-tetramethylpiperidin-4-ol)sebacate and then vacuum dried. The resin is then extrusion compounded on a 1 inch 24/1=L/D extruder, melt temperature 450F (232C) and pressed for 7 minutes at a temperature of 163C and a pressure of 2000 psi into a sheet of uni~orm thic~ness of 100 mil. The sheets are then cut into plaques of 2 inch x 2 inch. The plaques are then exposed in a FS/BL exposure device and color measurements made periodically using a Hunter Color Difference Meter Model D25. Polyethylene stabilized with the above compound is found to be much more stable than the unstabilized polyethylene or the polyethylene stabilized only with an antioxidant.

Example 26 A quantity of SBR emulsion containing 100 g of rubber (500 ml of 20% SBR obtaincd from Texas U.S., Synpol 1500) previously stored under nitrogen, is placed in a beakèr and stirred vigorously. The pH
of the emulsion is adjusted to 10.5 with a 0.5N
NaOH solution.

To the emulsion is added 50 ml of 25% NaCl solution A 6% NaCl solution adjusted with hydro-chloric acid to a pH 1.5 is added in a thin stream with vigorous stirring. When pH 6.5 is reached, the rubber begins to coagulate and th~ addition is slowed down in order to maintain uniform agitation. The -addition of the acidic 6% NaC1 solution is terminatea -'~
when a pH 3.5 is reached. The coagulated crumb-rubber slurry at pH 3.5 is stirred for 1/2 hour.

The coagulated rubber is isolated by filtration through cheese cloth, and rinsed with distilled water.
After three subsequent washings with fresh distilled `
water, the coagulated rubber is dried, first at 25 mm Hg and finally to constànt weight under high vacuum 1>1 mm) at 40-45C.

', ~ , 105~903 The dried rubher (25 y) is heated under nitrogen at 125C in a ~rabender mixer and to this is added with mixing 0.25 g (O.5%) of ~-mono(1,2,2,6,6-pentamethyl piperidin-4-ol)diglycolate. The composition is mexed for 5 minutes after whi~h it is cooled and compression molded at 125C into 5" x o.n25" plaques.

The. plaques are exposed to a xenon arc weather-ometer ~nd the color measurement (L-b) is made after 45, 125 and 290 hours. The samples stabilized with the above compound are found to be much more light stable than the unstabilized samples.

Example 27 . .

To 50 g of polyacetal resin containing ~.1%
of an acid scavenger, dicyandiamide, is added 0.2%
by weight of the nickel complex o 0-mono(2,2,6,6-tetramethylpiperidin-4-ol)thiodiglycolate and milled for 7 minutes at 200C in a Brabender Plasti-recorder.
The milled formulation is subsequently pressed into a 40 n~il sheet at 215C at 350 psi for 90 seconds then cooled quickly in a cold press at 350 psi. The stabilized sheets are then remolded for 2 minutes at contact pressure and for 3 minutes at 300 psi at 215C to give plaques 1 1/2 inch x 2 1/4 inch x 125 lO~lgO3 mil. Thereafter, the testing procedure of Example is followed to determine the light stability of the samples. The stabilized samples are found to be mu~h more stable than the unstabilized sar~lples.

Example 28 Unstabilized thoroughly dried polyethylene terephthalate chips are dry blended with 1.0~ of 0-mono(2,2,6,6-tetramethylpiperidin-4-ol)suberate. 60/10 denier multifilament is melt spun at a melt temperature of 290C. The oriented fiber is wound on white cards and exposed in a Xenon Arc Fadeometer. Color measure-ments are made periodically with a Hunter Color Difference Meter Model D25. The stabilized samples are found to be much more light stable than the un-stabilized samples.

Example 29 (a) A composition comprising acrylonitrile-butadiene-styrene terpolymer and 1% by weight of the nickel complex of 0-mono(1,2,2,6,6-pentamethyl piperidin-4-ol)diglycolate~resists embrittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

1~51903 (h) ~ composition comprising polyuxethane prepared from toluene diisocyanate and alkylene polyols and 1.0~ by weight of 0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)tetramethyl succinate is more stable to sunlight, fluorescent sunlamps, black lights and fluorescent lights than the unformulated polyurethane.

....
(c) A composition comprising a polycarbonate prepared from bisphenol-A and phosgene and 1~ by weight of O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)pimelate resists discoloration due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

(d) A composition comprising polymethyl-methacrylate and 0.25% by weight of the nickel complex of ~mono(2,2,6,6-tetramethyl-piperidin-4-ol)azelaté
resists discoloration due to exposure to ultraviolet light longer than one which does not contain the -~
stabilizer.

Example 30 (a) A stabilized polyamide (ny]on 6,6) is prepared by incorporating therein 0.1~ of 0-mono(2,2, 6,6-tetramethyl-piperidin-4-ol)sebacate. The light stability of the stabilized composition is superior to that of an unstabilized polyamide.

:
: .

,. . . .
.:;.~ .- ., ~ : . .
...,: :; .' ' '~" .', :

~051903 (b) A stabilized p~lyphenylene oxide polymer (prepared by pol~nerizing 2,6-dimethylphenol is pre-pared by incorporating therein 0.5% by weight of the manganese complex of O-mono(2,2,6,6-tetrame'~hyl-piperidin-4-ol)sebacate. The stabilized compo~itions resist embrittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer. "

(c) A stabilized crystalline polystyrene is prepared by incorporating therein 0.1% by weight of the zinc complex of O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)sebacate. The stabilized composition re.sists embrittlement due to exposure to ultraviolet light longer than one whi~h does not contain'the stabilizer.

.
Antioxidants.may also be incorporated into each of the above mentioned compositions, for example, di-n-o~tadecyl-a,a'-bis(3-butyl-4-1~ydrox,y~5-methylbenzyl) malonate 2,4-bis(4-hydroxy-3,5-di-t-butylphenoxy)~6-(n-octylthioethylthio)-1,3`,5-triazin2, 2,4-bis(3,5-di-t-b~tyl-hydroxyphenoxy)-6-(n-oct.ylthio)-1,3,5-triazine di-n-octadecyl 3(3',5'-di-t-butyl-4-hydroxyphenyl)pro-pionate, respectively.

lOS1903 Exam~) e 31 Hiyh impact polystyrene resin containing elastomer (i.e., butadiene-styrene) is stabilized against loss of elongation properties due to exposure to ultraviolet light by incorporation of 003~ by weight of the nickel complex of O-mono(1,2,2,6,6-pentamethyl piperidin-4-ol)succinate.

The unstabilized resin is dissolved in chloro-form and the stabilizer then added, after which the mixture is cast on a g]ass plate and the solvent evaporated to yield a uniform film which, upon drying, is removed and cut up, and then pressed for 7 minutes at a temperature of 163C and a pressure of 2,000 -pounds per square inch into a sheet of uniform thick-ness (25 mil). The sheets are then cut into strips approximately 4 x 0.5 inches. A por'ion of these strips is then measured for percent of el~ngation in the Instron Tensile Testing Apparatus (Instron Engineering Corporation, Q~uincy, Massachusetts). The remaining portions of the strips are placed in an FS/BL chamber according to Example 4(b)except that the samples are mounted ana white cardboard stock and the time to 50% reduction in elongat~on is measured. The stabiliæed polystyrene resin retains its elongation property longer than the unstabilized resin.

.

, ; , , ~ .

~0~903 E~am~le 32 Unstabi'ized linear polyethylene is solvent blended in methylene chloride with 0.5% by weight of the substrate of the nickel complex of O-mono- .
(2,2,6,6-tetramethyl piperidin-4-ol)succinate and then vacuum dried. The resin is then extrusion compounded on a 1 inch 24/1=L/D extruder, melt temper~ture 450F (232C) and pressed for 7 minutes at a temperature of 163C and a pressure of 2000 psi into a sheet of uniform thickness of 100 mil. The sheets are then cut into plaques of 2 inch x 2 inch. The plaques are then exposed in a FS/B~
~xposure device and color measurements made pexiodically using a Hunter Color Difference Meter ~odel D25. Poly~

, , ,_ .
ethylene stabilized with the above compound is found to be much more stable than the unstabilized poly-ethylene or the polyethylene stabilized only with an antioxidant. --Example 33 A quantity of SBR emulsion containing 100 g of rubber (500 ml of 20% SBR obtained from Texas U.S., Synpol 1500) previously stored under nitrogen, is placed in a beaker and stirred vigorously. The pH

, ,, ~

- ,, lOS19(~3 of the emulsion is adjus~ed to 10.5 with a 0.5~J
NaOH solution.

To the emulsion is added 50 ml of 25~ Na~1 -solution. A 6% NaCl solution adjusted with hyd~o-chloric acid to a pH 1.5 is added in a thin ~tream with vigoxous stirring. When pH 6.5 is reached, the rubber begins to coagulate and the addition is slowed down in oxdex to maintain uniform agitation. The addition of the acidic 6~ NaCl solution is terminated when a pl~ 3.5 is reached. The coagulated crumb-rubber slurry at p~ 3.5 is stirxed for l/2 hour.

., .
The coagulated rubber is isolated by filtration through cheese cloth, and rinsed with distilled water.
After three subsequent washinys with fresh distilled water, the coagulated rubber is dried, first at 25 mm Hg and finally to constant weight under high vacuum (>1 mm) at 40-45C.

The dried rubber (25 g) is heated under nitrogen at 125C in a Brabender mixer and to this is aaded with mixing 0.25 g (0.5%) of the nickel complex of 0-mono(2,2, 6,6-tetramethyl piperidin-4-ol)adipate. The composition - 67 - -~

. .. .: . ';., .~ . ::

is mixed for 5 minutes after ~hich it is cooled and compression molded at 125C into 5" x 0.025" plaques.

The plaques are exposed to a xenon arc weather-ometer and the color measurement (L-b) is made after 45, 125 and 290 hours. The samples stabilized with the above compound are found to be much more light stable than the unstabilized samples.

~ .

Example 34 To 50 g of polyacetal resin containing 0.1~
of an acid scavenger, dicyandiamide, is added C.2%
by weight of the nickel complex of C~mono(1,2,2,6,6' pentamethyl piperidin-4-ol)succinate and milled for

7 minu~es at 200C in a Brabender Plasti-recor~ler.
The milled formulation is subsequently pressed into a 40 mil sheet at 215C at 350 psi for 90 seconds then c~oled quic};ly in a cold press at 350 psi.
The stabilized sheets are then remolded for 2 minutes at contact pressure and for 3 minutes at 300 psi at 215C to give plaques 1 1/2 inch x 2 1/4 inch x 125 mil. Thereafter, the testing procedure of Example 9 is followed to determine the light stability of the samples. The stabilized samples are found to be much more stable than the unstabilized samples.

" ,. ..
.:
. ~ . . . -, ' , ~

Exam~Je 3j Unstabilizea thoroughly dried polyethylene terephthalate chips are dry blended with 1.0~ of the niclcel complex O-mono(2,2,6,6-tetramethyl piperidin-4-ol)adipate. 60/10 denier multifilament is melt spun at a melt temperature o 290C. The oriented fiber is wound on white cards and exposed in a Xenon Arc Fadeometer. Color measurements are made periodically with a Hunter Color Difference Metex Model D25. The stabilized sample~ are found to be much more light stable than the unstabilized samples.

Example 36 (a) A composition comprising acrylonitrile-butadiene-styrene terpolymer and 1~ by weight of the nickel complex of O-mono(1,2,2,6,6-pentamethylpiperidin-4-Ol)succinate resists er~rittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

~ b) A composition compri.sing polyurethane prepared from toluene diisocyanate and alkylene pol~rols and 1.0~ by we.ight of the nickel comple~ of O -mono (2,2,6,6-tetramethylpiperidin-4-ol)succinate is more - 69 ~

105~ 3 stable to sunlight, fluorescent sunlamps, black lights and fluorescent lights than the unformulated polyurethane.

(c) A composition comprising a polycarbonate -~-prepared from bisphenol-A and phosgene and 1~ by weight of the nickel complex of O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)adipate resists discoloration due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

, ~d) A composition comprising polymethyl-methacrylate and 0.25% by weight of the nickel complex of O-mono(1,2,2,fi,6-pentamethylpiperidin-4-ol)succinate resists discoloration due-to exposure to ultraviolet light longer than one ~hich does not contain the stabi7izer.

Example 37 (a) A stabilized polyamide (nylon 6,6) is prepared by incorporating therein 0.1% of the cobalt complex of O-mono(1,2,2,6,6-pentamethylpiperidin-4-ol) succinate. The light stability of the stabilized composition is superior to that of an ~mstabilized polyamide.

(b) A stabilized polyphenylene oxide polymer (prepared by polymerizing 2,6-dimethylphenol is pre-- , ' ',: ` . ' ~ ~ , ~0~1903 pared by incorporating therein 0.5~ by ~7eight of the manganese complex of O-mono~1,2,2,6,6-pentamethyl-piperidin-4-ol)succinate. The stabilized cc~ ositions resist embrittlement due to exposure to ultraviolet light longer ~an one which does not contain the stabilizer.

(c) A stabilized crystalline polystyrene is prepared by incorporating therein 0.1~ by weight of t~le æinc complex of o-mono(1,2,2,6,6-pentamethyl-piperidin-4-ol)succinate. The stabilized compcsition resists embrittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

~ ntioxidants may also be incorporated into eacll o~ the above r,entioncd compositions, for exam~le, di-n-o~ctadecyl-~,~'-bis~3-butyl-4-hydro~y-S-methylbenzyl) malona~e 2,4-bis~4-hydroxy-3~5-di-t-butylphenoxy)-~-(n-octylthioethylthio)-1,3;5-tria~ine, 2,4-bis(3,5-di-t-butyl-}lydrox~henoxy)-6-(n-octylthio)-1,3,5-triazine di-n-octadecyl 3(3`,5'-di-t-bu~yl-4-hydroxyphenyl~pro-piona~e, respecti~ly.

:' ' ~ ' ' '' :` ' ' lOS1903 ~,Y.~] ~ 38 High impact polystyrene resin containing elasto~er (i.e., butadiene-styxene) is stabilized agains~ loss of clongation properties due to exposure to ultxaviolet light by incorporation o~ 0.3~ by weight o ~-(2,2,6;6-tetrameth~lplperidyl-4) succinamic RCi~d, The unstabilized resin is dissolved in chloro-form and the stabilizer then added, after which the mixture is cast on a glass plate and the solvent evaporated to yield a uniform film which, upon drying, is removed and cut up, and then pressed for 7 minutes at a te~perature of 163C and a pressure of 2,000 ~, pounds per square inch into a sheet of uniform thick-ness (25 mil). The sheets are then cut into strips approximately 4 x 0.5 inches. A portion of these strips is then measured for percent of elongation in the Instron Tensile Testing Apparatus (Instron Engineering Corporation, Quincy, Massachusetts). The remaining portions of the stxips are placed in an FS~BL chamber according to Example 7(B) except that the samples are mounted and white cardboard stoc]c and the time to 50% reduction in elongation is measured. The stabili~ed polyst~rene resin retains its elongation property longer than the unstabiliæed resin.

lOS1903 Unstabilized linear polyethylene is solvent blended in methylene chloride with 0.5~ by weight o the substrate of nickel bis [N-(2,2,6,6-tetramethyl- . -piperidyl~ uccinamate~
and then vacuum dried. The resin is then extrtl~ion compounded on a 1 inch 24/1=L/D
extruder, melt temperature 450F (232C) and pressed or 7 minutes at a temperature of 163C and a pressure of 2000 psi into a sheet of un~.form thickness of 100 mil. The sheets are then cut into plaques of 2 inch x 2 inch. The plaques are then exposed in a FS/BL
exposure device and color measurements made periodically using a Hunter Color Difference Meter Model D25. Poly-ethylene stabilized with the above compound is found to be much more stable than the unstabilized poly-e~hylene or the polyethylene stabilized only with an antioxidant.

Example 40 A quantity of SBR emulsion containing 100 g :
of rubber (500 ml of 20% SBR obtained from Texas V~S., .~
Synpol 1500) previously stGred under nitro~en, i5 ~.
placed in a beakër and stirred vigoxously. The pll .. .. . . . .. . -:
.. . . . . . . .
.
- . ~ , . . . . ~
.
~ ' .

~OS1~03 of the ernulsion is adjustcd to 1~.5 with a 0.5 NaOII solution.

To the ~mulsion is added 50 ml of 25g NaCl solution. A 6% NaCl s~lution adjusted with hydro-chloric acid to a pH 1.5 is added in a thin stream with viyorous stirring. When pH 6.5 is reached, the rubber begins to coagulate and the addition is slowed down in order to maintain uniform agitation. The addition of the acidic 6~ NaCl solution is terminated when a pH 3.5 is reached. The coagulated crumb-rubber slurry at pH 3.5 is stirred for 1/2 hour.

The coagulated rubber is isolated b~ ~iltration through cheese c]oth, and rinsed with distilled water.
After three subsequent washings ~ith fresh distilled water, the coagulated rubber is dried, first at 25 mm Hg and finally to constant weight under high vacuum ( <1 mm) at 40-45C.

The dried rubber (25 g) is heated under nitrogen at 125C in a Brabender mixer and to this is added with mixing N-~1,2,2,6,6-pentar.~ethylplpexidyl-4) succinamic acid. The conp~sition is m.ixed for 5 mi1~utes after which .it is cooled and co~npression molded at 12S C into S x 0,025" plaques.

10519(~3 '~he pla~ues are cxposed to a xenon arc weathexmometer and the color measurement (L-b) is made aftcr 45, 125 and 290 hours. The samples stabili~ed with the above compound are found to be much more liyht stable than the unstabiliæed samples.

Example 41 .
To 50 g of polyacetal resin containing 0.1%
of an acid scavenger, dicyandiamide, is added 0.2%
by weight o~ nickel II bis [N-(2,2,~,6-tetramethyl-piperidyl-4) sebacamate] and -milled for 7 minutes at 200C in a Brabender Plasti-recorder. The milled formulation is subsequently pressed into a 40 mil sheet at 215C at 350 psi for 90 seconds ther. cooled quickly in a cold press at 350 psi.-The stabilized sheeis are then remolded for 2 minutes at contact pressure and for 3 minutes at 300 psi at 215C to give plaques 1 1/2 inch x 2 1/4 inch x 125 mil. Thereafter, the testing procedure of Example 9 is followed to determine the li~ht stability of the samples~ The stabilized samples are found to be much more stable than the unstabilized samples.

. .
'. -. .
.

' . : .

~051903 Ex~mple 42 Unstabilized thoroughly dried polyethylene terephthalatc chips are dry blended Wi~}l 1.0% of N-(2,2,6,6-tetramethylpiperidyl-4) tetramethyl succinamic acid. 60/10 denier multifilament is melt spun at a melt temperature of 290C. The oriented fiber is wound on white cards and exposed in a Xenon Arc Fadeometer. Color measurements are made periodically with a H~ulter Color Difference Meter Model D25. The stabili~ed samples are ~ound to be much more light stable than the unstabilized samples.

Example 43 , (a) A composition comprising acrylonitrile-butadiene-st~:cene terpolymer and 1~ by weight of N-(l-n-dodecyl-2,2,6,6-tetramethyl-piperidyl-4) succinamic acid resists embrittle-ment due to exposure to ultraviolet light longe~ than ~ne ~hich does not contain the stabili~er.

(b) A composition comprising polyurethane prepared from toluene diisocyanate and al~ylene polyols and 1.0% by weight of N-(l-benzyl-2,2,6,6-tet~ameth~l-,.

.

lOS19()3 piperidyl-4) succinamic acid is more stable to sunli(3ht, ~luorescent sunlanlps, black lights and ~luorescent lights than the urlform,ulated polyurcthane.

(c) A composition comprising a polycarbonate prepaxed from bisphenol-~ and phosgene and 1% by weight N-(2,2,6,~~tetrame~1ylpiperidyl-4) glutaramic acid resists discoloration due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

~ dj A composition comprisin~ polymethyl-methacrylate and 0.25~ by wei~ht o N-(2,2,6,6~-tetra-ethylpiperidyl-4) glycolamic acid~
resists discoloration due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

Example 44 :

(a) A stabilized polyamide (nylon 6,6) is prepared by incorporating therein 0.1~ o~ ~-(2,2,6,6-tetramethylpipe~idyl-4) succi}lamic aci~.
The light stability o~ the stabilized composition is superior to ~hat of an unstabilized polyamicie.

~ ' ~ " ' . ' ' ' ' ~: ' ..
' ':. ' ~0519()3 (b) A stabilized po]ypl-lenylene o~ide pol~ner (pxepared hy pol~nerizing ~,6-dimetllylphenol i5 pre-pared b~r incorporatiny therein 0.5~ by weight of ~ickel bis [N-(2,2,6,6~tetramethylpiperidyl-4) succinamate]. . The stabilized com~os.it.ions resist embrittlem~nt due to exposure to ultraviolet light longer than one which does not contain the s~abilizex.

(c) A stabilized crys~alline polystyrcne is prepaxed by incorporatin~ therein 0.1% by weight of N-(2,2,6,6-tetrame~hylpiperidyl--4~ tetrameth~l-succinamic acid. The s~abilized composition resists embrittlemellt due to exposure to ultraviolet light longer than one which does not con-.
tain the stabllizer.

~ ntioxidan~s may also be incorporatcd into each of the above men~ion2d compositions, lor example, di-n~octadecyl~ bis(3-butyl-~s-hy~roxy-5-methylbenz~
malon~t~ 2~ bis(~-hydroxy-3~5-di-t-bu~ pheiloxy)-6-(n oc.t~lthioQ~hylthio)-1,3,5-~riazine, 2~s~bis (3 ~ S-di-t-bu~rl-hyaro~pheno~ 6-(n-octyltllio)-1,3,5-triazine di-n-~ctadecyl 3(3',5'-di-~-butyl-4-hy~roxyphenyl)pro~
pionate, respecti~rely~

Claims (40)

WHAT WE CLAIM IS:

1. A compound of the formula wherein R1 and R2 independently of each other are straight-or branched-chain alkyl having from 1 to 6 carbon atoms, or together with the carbon to which they are bound form a cyclo-pentyl or cyclohexyl ring, which is unsubstituted or substi-tuted with a methyl group, R3 is hydrogen, alkyl having 1 to 12 carbon atoms, .beta.-methoxyethyl, alkenyl having 3 or 4 carbon atoms, propargyl, benzyl, or alkyl substituted benzyl, M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese, calcium, zinc, sodium, cobalt, tin, dialkyl tin, lithium, potassium, magnesium and aluminium, and z has a value of from 1 to 4, the value of z being the same as the available valence of M, R5 is oxy or imino, and, if M/is hydrogen and R5 is oxy, R4 is straight- or branched-chain alkylene having 5 to 10 carbon atoms, or the group (CH2)mY(CH2)n wherein Y is oxygen or sulfur and m and n independently of each other are an integer of from 1 to 3, and, in all other cases, R4 is straight or branched-chain alkylene having 1 to 10 carbon atoms, phenylene or alkyl-phenylene, or the group (CH2)mY(CH2)n wherein Y is oxygen or sulfur and m and n inde-pendently of each other are an integer from 1 to 3.

2. A compound as claimed in claim 1 wherein R1 and R2 independently of each other are straight- or branched-chain alkyl having from 1 to 6 carbon atoms, or together with the carbon to which they are bound form a cyclopentyl or cyclohexyl ring, which is unsubstituted or sub-stituted with a methyl group, R3 is hydrogen, alkyl having 1 to 12 carbon atoms, .beta.-methoxyethyl, alkenyl having 3 or 4 carbon atoms, propargyl, benzyl, or alkyl substituted benzyl, R4 is straight- or branched-chain alkylene having 5 to 10 carbon atoms, or the group (CH2)mY(CH2)n wherein Y is oxygen or sulfur and m and n independently of each other are an integer of from 1 to 3, M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese; calcium, zinc, sodium, cobalt, tin, dialkyl tin, lithium, potassium, magnesium and aluminium, and z has a value of from 1 to 4, the value of z being the same as the available valence of M.

3. A compound according to Claim 2 wherein R1 and R2 are each methyl.

4. A compound according to Claim 3 wherein R4 is straight-chain alkylene having 5 to 10 carbon atoms, or the group (CH2)mY(CH2)n wherein Y is oxygen or sulfur and m and n independently of each other are 1 or 2, M is hydrogen, nickel, cobalt or manganese, and z has a value of 1 or 2.

5. A compound according to Claim 4 wherein M is nickel or hydrogen.

6. A compound according to Claim 5 wherein R4 is straight-chain alkylene having 5 to 8 carbon atoms.

7. A compound according to Claim 5 wherein R4 is the group (CH2)mY(CH2)n and Y, m and n are as defined in Claim 3.

8. A compound according to Claim 3 which is O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)sebacate.

9. A compound according to Claim 3 which is nickel bis{O-mono(2,2,6,6-tetramethylpiperidin-4-ol)sebacate}.

10. A compound according to Claim 3 which is O-mono(1,2,2,6,6-pentamethyl piperidin-4-ol)diglycolate.

11. A compound according to Claim 3 which is nickel bis{O-mono(1,2,2,6,6-pentamethylpiperidin-4-ol)diglycolate}.

12. A compound according to claim 1 wherein R1 and R2 independently of each other are straight- or branched-chain alkyl having from 1 to 6 carbon atoms, or together with the carbon to which they are bound form a cyclopentyl or cyclohexyl ring, which is unsubstituted or sub-stituted with a methyl group, R3 is hydrogen, alkyl having 1 to 12 carbon atoms, .beta.-methoxyethyl, alkenyl having 3 or 4 carbon atoms, propargyl, benzyl or alkyl substituted benzyl, R4 is straight- or branched-chain alkylene having 1 to 4 carbon atoms, M is a-metal selected from the group consisting of barium, nickel, manganese, calcium, zinc, sodium, cobalt, tin, dialkyl tin, lithium, potassium, magnesium and aluminium, and z has a value of from 1 to 4, the value of z being the same as the available valence of M.

13. A compound according to Claim 12 wherein R1 and R2 are each methyl.

14. A compound according to Claim 13 wherein R4 is straight-chain alkylene having 1 to 4 carbon atoms, and M is nickel, cobalt or manganese.

15. A compound according to Claim 14 wherein M is nickel.

16. A compound according to Claim 15 wherein R3 is hydrogen.

17. A compound according to Claim 15 wherein R3 is methyl.

18. A compound according to Claim 15 wherein R4 is straight-chain alkylene having 4 carbon atoms.

19. A compound according to Claim 15 which is nickel bis[O-mono(1,2,2,6,6-pentamethyl piperidin-4-ol)succinate].

20. A compound according to Claim 15 which is nickel bis[O-mono(2,2,6,6-tetramethyl-piperidin-4-ol) succinate].

21. A compound according to Claim 15 which is nickel bis[O-mono(2,2,6,6-tetramethyl-piperidin-4-ol) adipate].

22. A compound according to claim 1 of the formula wherein R1 and R2 independently of each other are straight-or branched-chain lower alkyl having 1 to 6 carbon atoms, or together with the carbon to which they are bound form a cy-clopentyl or cyclohexyl ring, which is unsubstituted or sub-stituted with a methyl group, R3 is hydrogen, alkyl having 1 to 12 carbon atoms, .beta.-methoxyethyl, alkenyl having 3 or 4 carbon atoms, propargyl, benzyl, or alkyl substituted benzyl, R4 is straight- or branched-chain alkylene having 1 to 10 carbon atoms, phenylene, phenylene substituted with one or more alkyl groups, or the group -(CH2)mY(CH2)n-, wherein Y is oxygen or sulfur and m and n independently of each other are an integer of from 1 to 3, M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese, calcium, zinc, sodium, cobalt, tin, dialkyl tin, lithium, potassium, mag-nesium and aluminium, and z has a value of from 1 to 4, the value of z being the same as the available valence of M.

23. A compound according to Claim 21, wherein R1 and R2 are each methyl, R4 is straight-chain alkylene having 1 to 8 carbon atoms or the group -(CH2)mY(CH2)n , wherein Y is oxygen or sulfur and m and n independently of each other are 1 or 2, M is hydrogen, nickel, cobalt or manganese, and z has a value of 1 or 2, the value of z being the same as the available valence of M.

24. A compound according to Claim 23, wherein R4 is straight-chain alkylene having 1 to 8 carbon atoms and M is hydrogen.

25. A compound according to Claim 23, wherein R4 is the group -(CH2)mY(CH2)n- and M is hydrogen.

26. A compound according to Claim 23, wherein R4 is straight-chain alkylene having 1 to 8 carbon atoms and M is nickel or manganese.

27. A compound according to Claim 23, wherein R4 is the group -(CH2)mY(CH2)n- and M is nickel or manganese.

28. A compound according to Claim 23, wherein M is hydrogen or nickel.

29. A compound according to Claim 23, which is N-(2,2,6,6-tetramethylpiperidyl-4-)succinamic acid.

30. A compound according to Claim 23, which is nickel bis[N-[2,2,6,6-tetramethylpiperidyl-4-)succinamate].

31. A composition of matter stabilized against ultraviolet deterioration which comprises a synthetic organic polymer normally subject to ultraviolet deterior-ation containing from (a) 0,005 to 5% of a stabilizing compound of the formula wherein R1 and R2 independently of each other are straight- or branched-chain alkyl having from 1 to 6 carbon atoms, or together with the carbon to which they are bound form a cyclopentyl or cyclohexyl ring, which is unsubstituted or substituted with a methyl group, R3 is hydrogen, alkyl having 1 to 12 carbon atoms, .beta.-methoxyethyl, alkenyl having 3 or 4 carbon atoms, propargyl, benzyl, or alkyl substituted benzyl, M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese, calcium, zinc, sodium, cobalt, tin, dialkyl tin, lithium, potassium, magnesium and aluminium, and z has a value of from 1 to 4, the value of z being the same as the available valence of M, R5 is oxy or imino, and, R4 is straight- or branched-chain alkylene having 1 to 10 carbon atoms, phenylene or alkyl-phenylene, or the group (CH2)mY(CH2)n wherein Y is oxygen or sulfur and m and n independently of each other are an integer of from 1 to 3.

32. A composition of Claim 31, wherein the stabilizer is as defined in Claim 2, 3 or 4.

33. A composition of Claim 31 and including a phenolic antioxidant selected from di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphos-phonate, di-n-octadecyl-.alpha.,.alpha.'-bis(3-butyl-4-hydroxy-5-methylbenzyl) malonate and 2,4-bis(4-hydroxy-3,5-di-tert-butylphenoxy)-6-(n-octylthio-ethylthio)-1,3,5-triazine, and (c) a thio co-stabilizer selected from dilauryl-.beta.-thiodi-propionate and distearyl-.beta.-thiodipropionate.

34. A composition of Claim 33 wherein the organic material is polyolefin,

35. A composition of Claim 34 wherein the polyolefin is polypropylene.

36. A composition of Claim 31 wherein R1 and R2 are each methyl, R3 is hydrogen or methyl, and R4 is straight-chain alkylene having 1 to 4 carbon atoms, R5 is oxy and M is hydrogen.

37. The composition of Claim 31 consisting essentially of the organic material polypropylene, stabilized with the stabilizer of (a) with di-n-octadecyl(3,5-di-tert.-butyl-4-hydroxybenzyl)phos-phonate and 0 to 5% of 2(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole.

38. The composition of Claim 37 wherein the stabilizer of (a) is O-mono(1,2,2,6,6-pentamethyl-piperidin-4-ol)succinate.

39. The composition of Claim 37 wherein the stabilizer of (a) is O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)succinate.

40. The composition of Claim 37 wherein the stabilizer of (a) is O-mono(2,2,6,6-tetramethyl-piperidin-4-ol)adipate.