CA1068277A - Hindered piperidine carboxylic acids, metal salts thereof and stabilized compositions - Google Patents

Abstract

Abstract of the Disclosure A compound of the formula I
wherein R1 are same and stand for hydrogen or alkyl having from 1 to 6 carbon atoms, R2 is hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 4 carbon atoms, propargyl, benzyl, alkyl substituted benzyl, aliphatic acyl having 1-4 carbon atoms, C2-C21 alkoxyalkyl or oxyl, R3 is straight-chain alkenylene of 2 to 4 carbon atoms, 1,2-cycloalkylene or 1,2-cycloalkenylene having 4 to 6 carbon atoms, 2,3-bicycloalkylene or 2,3-bicycloal-kenylene having 7 or 8 carbon atoms or 1,2-, 1,3-, or 1,4-phenylene or straight-chain alkylene of 1 to 4 carbon atoms substituted by alkyl or alkenyl of 1 to 18 carbon atoms, provided that said straight-chain alkylene substituted by alkyl has in total more than 10 carbon atoms, M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese, calcium, copper, zinc, magnesium, sodium, potassium, cobalt, tin, and dialkyl tin z has a valve of from 1 to 4, the value of z be-ing the same as the available valence of M.

The compounds I are useful as light stabilizers for synthetic polymers.

- 1a -

Description

10~8277 This invelltion relates to the stabilization of organic material normally tending to deteriorate. In particular, the invention relates to the protection of synthetic polymers against the harmful degradative effects, such as discoloration and embrittlement, caused by exposure to light, especially ultraviolet light.
It is known that actinic radiation, particularly in the near ultra-violet region, has a deleterious effect on both the appearance and properties of organic polymers. For example, normally colorless or light colored poly-esters yellow on exposure to sunlight as do such cellulosics 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.
The rate of air oxidation of polyolefins, such as polyethylene and polypropy-lene, is materially accelerated by ultraviolet light.
,~
? In United States Patent 3 120 540 there is discussed the reaction of substituted 4-piperidinol compounds with acid anhydrides having formula i ~t CH2)~
O_ C-O
'~ O
where n is 1 to 4, to yield bis(polymethyl)-4-piperidyl alkanoates. In the example of this patent the salt of 1,2,2,6~6-pentamethyl-4-piperidinol with the acid of formula ' ~ ~ O O
iC ~ _ ~ 2)2 OH

'li H3 ~ 2 -- r ,~

10~8277 is a plausible intermediate in the synthesis of the bis-(hydrogen sulfate) salt of bis(l,2,2,6,6-pentamethyl-4-piperidyl)succinate. ~he compounds of United States 3,120,540 are taughtto possess significant pharmacological acti-vity in lowering blood pressure. We have now found that acid half esters of hindered piperidines stabilize organic substrates against the degradative effect of ultraviolet light.
The present invention is accordingly directed to a new class of ultraviolet light stabilizers which consists of a compound of the formula ( R~-~ O-C-R3-C-O~_ I

CH3 CH2Rl ,., . / z wherein Rl are same and stand for hydrogen or alkyl having from 1 to 6 carbon atomsJ

` R2 is hydrogen, alkyl having 1 to 12 carbon atomsJ alkenyl having ,, .
3 to 4 carbon atoms, propargyl, benzyl, alkyl substituted benzylJ aliphatic acyl having 1-4 carbon atomsJ C2-C21 alkoxyalkyl or oxylJ
R3 is straight-chain alkenylene of 2 to 4 carbon atomsJ lJ2-cycloal-kylene or 1J2-cycloalkenylene having 4 to 6 carbon atomsJ 2J3-bicycloalkylene or 2,3-bicycloalkenylene having 7 or 8 carbon atoms or 1,2~ 3-J or 1J4-phenylene or straight-chain alkylene of l to 4 carbon atoms substituted by alkyl or alkenyl of 1 to 18 carbon atomsJ provided that said straight-chain `i alkylene substituted by alkyl has in total more than lO carbon atomsJ

M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese, calciumJ copper, zincJ magnesiumJ sodium~ potassiumJ
! cobaltJ tinJ and dialkyl tin ,.;

,, ~ - 3 -:

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

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 are methyl, ethyl, n-propyl, n-butyl and n-hexyl.
Preferably, Rl are each lower alkyl such as a methyl group, or above all hydrogen.
Substituent R2 can be hydrogen, alkyl having 1 to 12 carbon atoms, preferably alkyl having 1 to 4 carbon atoms, hydrogen and methyl being part-icularly preferred, ~-methoxy-ethyl, alkenyl having 3 to 4 carbon atoms, preferably allyl, propargyl, benzyl or alkyl substituted benzyl. Acyl R2 is especially alkanoyl with 1 to 4, especially 2 to 4 carbon atoms, e.g., acetyl, or alkenoyl with 2 to 4 carbon atoms, e.g., acryloyl or crotonyl.
Examples of R2 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-octyl, n-dodecyl, allyl, -methallyl, propargyl, . benzyl, -methyl-benzyl and ,p-dimethylbenzyl.
Examples of cyclic groups represented by R3 are 1,2-cyclobutylene, 1,2-cyclohexylene, 4-cyclohexene-1,2-ylene, bicyclo[2,2,1]hept-2,3-ylene and bicyclo[2,2,2]oct2,3-ylene, and especially bicyclo[2,2,1]hept-5-en-2,3-ylene and 1,2-phenylene.

'2''~ Examples of acyclic groups represented by R3 are octadecylethylene, dodecylethylene, 2-do-decenylethylene, 2-octenylethylene, 2-butenylene, vinylene, methyl-vinylene, octyl-vinylene and octadecyl-vinylene.
;~ Among the substituents represented by M, hydrogen and nickel are preferred.
~; A preferred group of compounds of formula I are therefore those ., wherein Rl are hydrogen or methyl, R2 is hydrogen, methyl, allyl, benzyl, acetyl, acryloyl or crotonyl, and R3, M and z have the above preferred meanings.
`~Z This invention also relates to compositions of matter which are ", , stabilized against ultraviolet light deterioration which comprise a synthetic . ~. .
; - 4 ., ';' ;

... .

106827'7 organic polymer normally subject to ultraviolet deterioration containing from about 0.005% to 5% by weight of the polymer of the compounds of formula I and preferably from 0.01 to 2% by weight.
The compounds as represented by formula I, can be used in combina-tion with other light stabilizers such as 2(2-hydroxyphenyl)benzotriazoles,

2-hydroxybenzophenones, nickel complexes and benzoates.
The compounds of this invention are stabilizers for organic material normally subject to thermal, oxidative or actinic light deterioration.
Materials which are thus stabilized include synthetic organic polymeric substances including homopolymers, copolymers, and mixtures thereof, such as vinyl resins formed from the polymerization of vinyl halides or from the copolymerization of vinyl halides with unsaturated polymerizable compounds, : e.g., vinyl esters, ~ unsaturated acids, ,~-unsaturated esters, a,~-unsaturated ketones, aj~-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)-1-i,; pentene and the like, including copolymers of ~-olefins; such as ethylene-~; propylene copolymers, and the like; polydienes such as polybutadiene, ' polyisoprene, and the like, including copolymers with other monomers;
polyurethanes such as are prepared from polyols and organic polyisocyanates, and polyamides such as polyhexamethylene adipamide and polycarbonates such as ~ those prepared from bisphenol-A and phosgene; polyacetals such as polyethylene ^;; terephthalate polyacetal; polystyrene, polyethyleneoxide; polyacrylics such .:!, as polyacrylonitrile; polyphenyleneoxides such as those prepared from 2,6-dimethylphenol and the like; and copolymers such as those of polystyrene containing copolymers of butadiene and styrene and those formed by the copolymerization of acrylonitrile, butadiene and/or styrene.
Other materials which can be stabilized by the compounds of the , - 5 -,.
:~, : . . : ~ . . .
.. . . .. .,., , . ~........... .. .

:: ~. : .
.

~068277 present invention include lubricating oil of the aliphatic ester type, i.e., ethylene diazelate, pentaerythritol tetracaproate, and the like; animal and vegetable derived oils, e.g., linseed oil, fat, tallow, lard, peanut oil, cold 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., 2-methoxyethanol, 2-(2-methoxyethoxy)-ethanol, triethylene glycol, octaethylene glycol, dibutylene glycol, dipropylene glycol and the like.
The compounds of this invention are particularly useful as UV light stabilizers, especially for the protection of polyolefins, for instance, polyethylene, polypropylene, poly-l-butene, poly-l-pentene, poly-3-methyl-1-butene, poly-4-methyl-1-pentene, 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, blow molded or the like into films, fibers, filaments, hollow spheres and the like. The heat stabilizing properties of these compounds may ~i 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 sprayed 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 . - 6 -'. -~,s : ' ' , ' , ' ' . ' '``! `

.' . ~ - i'.. '~` ' :
. ~ , .

1C~6827'7 may be dispersed or dissolved in the monomer prior to polymerization or curing.
These compounds can also be used in combination with other additives suc;h as antioxidants, sulfur-containing esters such as distearyl-~-thiodipro-pionate (DSTDP), dilauryl-~-thiodipropionate (DLTDP) in an amount of from 0.01 to 2% by weight of the organic material, and the like, pourpoint depressants, corrosion and rust inhibitors, dispersing agents, demulsifiers, antifoaming agents, fillers such as glass or other fibers, carbon black, accelerators and other chemicals used in rubber compounding, plasticizers, color stabilizers,di- and tri-alkyl- and -alkyl-phenyl-phospites, as well as other phosphites, - e.g., distearyl pentaerythritol diphosphite, heat stabilizers, ultraviolet light stabilizers, antiozonants, dyes, pigments, metal chelating agents, dyesites and the like. Often combinations with other additives such as those mentioned above, particularly the sulfur containing esters, the phosphites and/or the ultraviolet light stabilizers, will produce superior results in certain applications compared with those expected by the properties of the individual components.
The following formula represents co-stabilizers which are in certain instances very useful in combination with the stabilizers of this invention:
' 20 0 , R-O-C-f H

.~. I
i R-O-~-C H2 `~ O
, wherein R is an alkyl group having from 6 to 24 carbon atoms; and n is an integer from 1 to 6. Especially useful compounds of these are dilauryl-~-. .~ .
thiodipropionate and distearyl-~-thiodipropionate. The above co-stabilizers are used in the amount of from 0.01 to 2% by weight of the organic material, .
~ - 7 -106827'7 and preferably from 0.1 to 1%.
Although the compounds of this invention may to some degree also be effective as thermal stabilizers, if the processing of the polymer is carried out at high temperatures it is advantageous to incorporate additional antioxidants.
In most applications, it is desirable to incorporate into the resin compositionJ sufficient thermal antioxidants to protect the plastic against thermal and oxidative degradation. The amount of antioxidant required will be comparable to that of the actinic stabilizer. Namely, from about 0.005%
to 5% and preferably from 0.01% to 2% by weight. Representative of such antioxidants are phosphite esters, such as triphenylphosphite and dibutylphos-phite and alkyl arylphosphites such as dibutylphenylphosphite, and the like.
The best results have been obtained with the preferred class of thermal antioxidants, the hindered phenols. These compounds have been found ` to provide the best thermal stabilization with the least discoloration in the compositions of the invention. Among these phenolic antioxidants are included the following:
di-n-octadecyl(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate 2,6-di-tert-butylphenol 2,2'-methylene-bis(6,tert-butyl-4-methylphenol) 2,6-di-tert-butylhydroquinone ~i octadecyl-(3,5-di-tert-butyl-4-hydroxybenzyl-thio)acetate ., 1,1,3-tris~3-tert-butyl-6-methyl-4-hydroxyphenyl)-butane1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)2,3~5,6-tetramethylbenzene 2,4-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-6-(n-octylthio)-1,3,5-triazine 2,4-bis-(4-hydroxy-3,5-di-tert-butylphenoxy)-6-(n-octylthioethylthio) -1,3,5-triazine :~

~' .

~ ,. : :: .
.

~068Z7~

2,4-bis-(n-octylthio)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine 2,4,6-tris-(4-hydroxy-3,5-di-tert-butylphenoxy)-1,3,5-triazine n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate 2-(n-octylthio)ethyl-3,5-di-tert-butyl-4-hydroxybenzoate n-octadecanoyl-di-2-[3-(3,5-di-tert-butyl-4-hydroxy-phenyl) propionyloxy]ethylamine 1,2-propylene di-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]
pentaerythrityl tetra[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
di-octadecyl-(3,5-di-tert-butyl-4-hydroxy-benzyl)-phosphonate di-octadecyl-1-(3,5-di-tert-butyl-4-hydroxyphenyl)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 . I
employed with similar improved results. The above exemplified antioxidants , and other related antioxidants which are incorporated herein by reference, are disclosed in greater detail in the following patents:
Netherlands Patent Specification 67/1119, issued February 19, 1968; Nether-lands Patent Specification 68/03498 issued September 18, 1968; United States ~` Patents, 3,255,191; 3,330,859; 3,644,482; 3,281,505; 3,531,483; 3,285,855;

3,364,250; 3,368,997; 3,356,944 and 3,758,549.
~, The compounds of this invention may be prepared by reacting a piperidinol of the formula . i:
g : jl ,', .~, ,, ,, , ,,, ... ., . -, -, -. - .. - - - - .. , - : .

106827!7 ~Rl R2 - N ~ OH II

~ 2 1 wherein Rl and R2 are as defined above in formula I, with an acid anhydride of the formula '' O
" .
wherein R3 is as defined above. In the case of 1, 3 and 1,4-phenylene, the 'J~ compounds may be prepared by reacting the piperidinol II with isophthalic or ' terephthalic acid via usual esterification procedures.
An alternative procedure in the preparation of the compounds of this invention is the reaction of the piperidinol II with a diacid of the formula R3~COOH)2 IV
wherein R3 is as defined above.
The acids and acid anhydrides which are reacted with the compounds of formula II may be prepared by methods well known in the art.
~ The metal salts of the present invention can be prepared by treating `,;'t the hindered piperidine carboxylic acids of formula I with a reactive form r4 of the metal or metal complex, e.g., sodium hydroxide or the like. Al-~ ternatively, and preferably in the case of metal complexes and metals other ;~
;~ than the alkali metals, a double decomposition is employed. Thus for example, ?l -- 10 ~

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

101i8~77 a sodium salt of the present invention is treated with nickel chloride. In a similar fashion use of other halides such as manganese dichloride, barium ch]oride and the like results in formation of the corresponding metal derivative.
The compounds of formula II may be prepared similarly to procedures presented in the published German Patent Application DT-OS 2,352,658, especi-ally by reducing a corresponding 4-piperidone by catalytic hydrogenation or, e.g., with lithium aluminum hydride. The corresponding 4-ketone can be prepared by reacting an aliphatic ketone, this being e.g. a higher homologue of acetone, with ammonia, e.g., 2,3,6-trimethyl-2,6-diethyl-4-oxopipe~ridine is obtained from methylethylketone and ammonia, similar to W. Traube in Chem.
Ber. 41 (1908), 777. The corresponding 4-ketone can also be obtained by hydrolysis of an alkyl-substituted tetrahydropyridine in the presence of an acidic catalyst, similar to United States Patent 3,513,170, or to published German Patent Applications 2,429,745; 2,429,746; 2,429,935; 2,429,936 and 2,429,937.
Compounds of formula I with R2 being acyl may be prepared by acylation of the corresponding N-H compounds with the corresponding carboxylic acid, anhydride, ester or halide as known per se.
The following examples, presented for illustration and not limit-ation, will further serve to typify the nature of the present invention.
,~
ExamPle 1 . .
2,6-Diethyl-2,3,6-trimethyl piperidin-4-ol In a 2-liter, 3-necked flask equipped with a stirrer, condenser, thermometer and nitrogen inlet were placed 197.3 g ~1.0 moles) of 2,6-diethyl-2,3,6-trimethyl piperidin-4-one, 500 ml of 2N sodium hydroxide and ' 500 ml of absolute ethanol. To the stirred reaction mixture, maintained :1 under nitrogen, was added portionwise 18.92 m ~0.5 moles) of sodium boro-. ' i - 11 -,; .
, .~ - . . . ~ - .. . - - : ,., ......... :. : .

-hydride over a 1-1/2 hour period. The reaction mi.xture was then stirred overnight at room temperature. The reaction mixture was decanted into a 4-liter separatory funnel and 2 liters of water were added. The aqueous layer was separated and the organic layer diluted with 500 ml of ether. The ether solution was washed with 2 x 1 1 water. The first aqueous layer was extracted with 2 x 50 ml of ether, then the combined ether extracts were washed with 500 ml of water. The ether layers were combined, dried over 4A molecular sieves and evaporated under reduced pressure, giving 187.4 g of the desired 2,6-diethyl-2,3,6-trimethyl piperidin-4-ol which was purified further by vacuum distillation, b.p. 111-115/6mm.
Example 2 0-mono-(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4')2-n-octylsuccinate In a l-liter, 3-necked flask equipped with a stirrer, thermometer, condenser and nitrogen inlet were placed 63.69 g (0.3 moles) of 2-n-octyl-succinic anhydride, 300 ml of VM~P Naphtha (an aliphatic hydrocarbon solvent, b.p. 120-140) and 59.79 g (0.3 moles) of 2,6-diethyl-2,3,6-trimethyl piperidin-4-ol. The reaction mixture was heated to reflux for 3 hours, then cooled to room temperature, at which time a gel formed in the reaction flask.
.` The reaction mixture was transferred to a l-necked resin flask and evaporated under vacuum at 100C to constant weight, giving, after cooling, 126.8 g of the desired half ester as a dark brown glass, which was characterized by the following analyses:
, Elemental Analysis:
Calculated for C24H45N4 F-W- 411-61 '~ Calculated: C, 70.03; H, 11.02; N, 3.40 Found: C, 69.93; H, 10.90; N, 3.67 . ~
* trademark ;~
~, , :: : '; . , :, .- , , ~ , . -,, - , . . . . . .
.. . . - . , ~
-, , , ~ : : : ' 1()6827~7 Example 3 Ni(II) Bis[O-I~no~2',6'-diethyl-2',3',6' trimethyl piperidyl-4')2-n-octyl succinate]
In a 300 ml, 3-necked flask equipped with a stirrer, nitrogen in:Let, air condenser and dropping funnel were placed 20.58 g ~0.05 moles) of O-mono-2',6'-diethyl-2',3',6'-trimethyl piperidyl-4')2-n-octyl succinate, 100 ml of water, and 25 ml of 2N NaOH ~0.05 moles). The reaction mixture was stirred until solution was complete ~1-1/2 hours), then a solution of 5.94 g ~0.05 moles) of NiC12 6H20 in 25 ml of water was added dropwise over a 10-minute period to the stirred solution. A copious green precipitate formed immediately. The reaction mixture was allowed to stir for 1 hour.
Then 150 ml of ether was added with vigorous stirring. The reaction mixture - was transferred to a separatory funnel, and the aqueous layer separated. The organic layer was washed with 200 ml of water and dried over 4A molecular sieves. The ether solution was filtered and evaporated to dryness, giving 19.8 g of the desired Ni salt as a green glass.
Example 4 Zn(II~_Bis[O-mono~2',6'-diethyl-2',3',6'-trimethyl piperidyl-4')2-n-octyl succinate]
~ 20 In a 300 ml, 3-necked flask equipped with a stirrer, nitrogen inlet, ~ air condenser and dropping funnel were placed 20.58 g (0.05 moles) of O-mono-~; 2',6'-diethyl-2',3',6'-trimethyl piperidyl-4')2-n-octyl succinate, 100 ml of water, and 25 ml of 2N NaOH ~0.05 moles). The reaction mixture was stirred ' until solution was complete ~1-1/2 hours), and then 12.17 ml of a 2.055 N
solution of ZnC12 in H20 was added dropwise over a 10-minute period to the stirred solution. A copious gummy precipitate formed immediately. The ' reaction mixture was stirred vigorously for 1-1/2 hours, then the aqueous layer was decanted from the gummy precipitate. The precipitate was dissolved 1068Z7~

in 500 ml of chloroform and the chloroform solution washed with 2 x 250 ml of water, and dried over 4A molecular sieves. The chlorofor~ solution was evaporated to dryness, giving 19.2 g of the desired Zn salt as a tacky brown glass.
Example 5 By following the procedure of Example 3 and substituting for the NiC12 6H20 an equivalent amount of the following metal chlorides:

a) MgC12-6H20 b) CoC12 6H20 c) CaC12 there was produced the following metal salts:
a) ~g(II) Bis[0-mono(2',6'-diethyl-2',3',6'-trimethylpiperidyl-4') 2-n-octyl succinate], a tan, gummy solid.
b) Co(II) Bis[0-mono(2',6'-diethyl-2',3',6'-trimethylpiperidyl-4') 2-n-octyl succinate], a purple glass.
c) Ca(II) Bis[0-mono(2',6'-diethyl-2',3',6'-trimethylpiperidyl-4') 2-n-octyl succinate], a tan, tacky glass.
Example 6 0-mono~2',6'-d ethyl-2',31,6'-trimethyl piperidyl-4')2-n-octadecen-2"-yl-succinate ., By following the procedure of Example 2 and substituting for the 2-n-octyl succinic anhydride an equivalent amount of 2-n-octadecen-2'-yl succinic anhydride is produced the above-named half ester.
i:
Example 7 By following the procedure of Example 2 and substituting for the : ~
2-n-octyl succinic anhydride an equivalent amount of the following anhydrides:

a) cyclohexane 1,2-dicarboxylic anhydride b) bicyclol2.2.1]hept-5-ene-1,2-dicarboxylic anhydride ,~ - 1~ -:`' ,;

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

1~)68277 there are produced the following half esters:
a) 0-mono(2',6'-diethyl-2',3',6'-trimethyl-piperidyl-4')cyclohexane-1,2-dicarboxylate b) 0-mono~2',6'-diethyl-2',3',6'-trimethyl-piperidyl-4')bicyclo[2.2.
l]hept-5-ene-2,3-dicarboxylate.
Example 8 By following the procedure of Example 3 and substituting for the 0-mono(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4')2-n-octyl succinate and the NiC12 6H20 equivalent a unts of:
a) 0-mono(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4')2-n-octade-cen-2"-yl succinate + CoC12 6H20 b) 0-mono(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4')cyclohexane 1,2-dicarboxylate + MgC12 6H20 c) 0-mono(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4')bicyclo [2.2.1]hept-5-ene-1,2-dicarboxylate + NiC12 6H20 there are produced the following metal salts:
a) Co(II) Bis[0- no(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4') 2-n-octadecen-2"-yl succinate]
b) Mg(II) Bis[0- no(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4') cyclohexane-1,2-dicarboxylate]
c) Ni(II) Bis [0-mono(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4') bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate.
Example 9 Artiicial Light Exposure Test : .
` Deterioration of most polymers caused by ultraviolet light is so q slow at ambient temperatures, even in the absence of stabilizers, that testing .:j of the effects of stabilizers generally must be conducted either at higher temperatures or in an accelerated artificial light exposure device in order ~; , - 1 5 ~! _ , ,,, .. ;. . ' -.. ,. : .`

to yield results in a convenient period of time. The tests conducted on polymers using an artificial light exposure device is described below:
a) Sample Preparation 5 mil Film - Unstabilized polypropylene powder ~Hercules Profax 6501) is thoroughly blended with 0.5% by weight of 0-mono(2',6'-diethyl-2', 3',6'-trimethyl piperidyl-4)-2-n-octyl succinate and 0.2% by weight of dioctadecyl 3,5-di-t-butyl-4-hydroxy-benzylphosphonate. The blended material is then milled on a two roll mill for 5 minutes at 182C. The milled sheet is then compression molded at 220C into 5 mil thick film under a pressure of 175 psi and water cooled in the press.
b) Testing Method This test is conducted in a FS/BL unit, basically of the American Cyanamid design, which consists of 40 tubes of alternating fluorescent sun-lamps and black lights ~20 of each). The 5 mil sample film which are mounted on 3" x 2" IR card holders with 1/4" x 1" windows are placed on a rotating drum 2 inches from the bulbs in the FS/BL unit. The time in hours is noted for the development of 0.5 carbonyl absorbance units as determined on an Infrared Spectophotometer. The development of carbonyl functional groups in the polymer is proportional to the amount of degradation caused by the ultraviolet light exposure.
Polypropylene stabilized with the above hindered piperidine compound is found to be much more stable than the unstabilized polypropylene.
Polypropylene is likewise stabilized when the following stabilizers are sub-stituted for 0-mono(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4')2-n-octyl succinate in the procedures described abovet a) Ni(II) Bis ~0-mono(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4') 2-n-octyl succinate]
b) Zn(II) Bis [0-mono(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4') ~3 . . .
- :: , . , . , -: :.
,: - ~ . " . : :

2-n-octyl succinate]
c) Mg(II) Bis [O-mono~2',6'-diethyl-2',3',6'-trimethyl piperidyl-4') 2-n-octyl succinate]
: d) Co(II) Bis [O- no~2',6'-diethyl-2',3',6'-trimethyl piperidyl-4') 2-n-octyl succinate]
e) Ca(II) Bis [O-monol2',6'-diethyl-2',3',6'-trimethyl piperidyl-4') 2-n-octyl succinate]
f) O-mono(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4')cyclohexane-1,2-dicarboxylate 10 g) Ni(II) Bis [O-mono(2',6'-diethyl-1',2',3',6'-tetramethyl piperidyl-4')2-n-octyl succinate]
. h) Ni(II) Bis [O-mono(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4') ` bicyclo[2.Z.l]hept-5-ene-2,3-dicarboxylate]
i) Co(II) Bis [O-mono(2',6'-diethyl-2',3',6'-trimethyl piperidyl-4') : 2-n-octadecen-2"-yl succinate]
j) Ni(II) Bis [O-mono(2',6'-di-n-butyl-2',6'-dimethyl-3'-n-propyl piperidyl-4')2-n-octadecen-2"-yl succinate]
,~
Other hindered phenolic antioxidants may be used in place of di--^ octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate in the above mentioned compositions, for example, di-n-octadecyl ~-(3-t-butyl-4-hydroxy-4-methyl-.J benzyl)malonate, 2,4-bis-(n-octylthio)-6-(3,4-di-t-butyl-4-hydroxyaniline)-1, , 3 3,5-triazine, octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl) propionate, , pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)]propionate, tris-., .
;' (3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-4-methyl-~ phenol, N,N,N-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, and :, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-trimethylbenzyl.
`il j The above compositions are also stabilized when the following W
absorbers are included in the formation at 0.01 to 2%:

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

~068277 a) 2(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole b) 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate c) 2-hydroxy-4-n-octoxybenzophenone d) [2,2'-thiobis(4-t-octylphenolate)]-n-butylamine nickel II
e) p-octylphenyl salicylate f) 2,2'-dihydroxy-4-4'-dimethoxybenzophenone g) 2(2'-hydroxy-5'-methylphenyl)-benzotriazole.
Example 10 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 0.2% by weight of O-mono(2',6'-diethyl -2',3',6'-trimethyl piperidyl-4')2-n-octyl succinate.
The unstabilized resin is dissolved in chloroform 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 sheet of uniform thickness (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 ;~ 20 Tensile Testing Apparatus (Instron Engineering Corporation, Quincy, Massachu-setts). The remaining portions of the strips are placed in an FS/BL chamber according to Example 6(B) except that the sample are mounted and white ` cardboard stock and the time to 50% reduction in elongation is measured. The g~ stabilized polystyrene resin retains its elongation property longer than the unstabilized resin.
Exa~
~`~ Unstabilized linear polyethylene is solvent blended in methylene chloride with 0.5% by weight of the substrate of the nickel complex of 0-mono (2',6'-diethyl-2',3',6'-trimethyl piperidyl-4')2-n-octyl succinate and then -, :
:: . . - .

-~06827~7 vacuum dried. The resin is then extrusion compounded on a 1 înch 24/1=L/D
extruder, melt temperature 450F ~232C) and pressed for 7 minutes at a te~nperature of 163C and a pressure of 2,000 psi into a sheet of unlform thickness of 100 mil. The sheets are then cut into plaques of 2 inch x 2 inch. The plaques are then exposed in an 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 12 A quantity of SBR emulsion containing 100 g of rubber ~500 ml of 20% SBR obtained from Texas United States, 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.
To the emulsion is added 50 ml of 25% NAC} solution. A 6% NaCl solution adjusted with hydrochloric 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 J coagulate and the addition is slowed down in order to maintain uniform 1 agitation. The addition of the acidic 6% NaCl solution is terminated when a - 20 pH 3.5 is reached. The coagulated crumb-rubber slurry at pH 3.5 is stirred `~ for 1/2 hour.
The coagula~ed rubber is isolated by filtration through cheese cloth, and rinsed with distilled water. After three subsequent washings with q fresh distilled water, the coagulated rubber is dried, first at 25 mm Hg and finally to constant weight under high vacuum (>lmm) at 40-45C.
.,~ The dried rubber (25 g~ is heated under nitrogen at 125C in a

4 Brabender mixer and to this is added with mixing 0.25 g (0.5%) of Co(II) bis[O-mono(2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')2-n-octyl succinate].

. ' The COmpOSitiQn iS mixed or 5 minu~es after which it is cooled i~nd compres-sion molded at 125C into 5" x 0.025" plaques.
The plaques are exposed to an Xenon Arc weatherometer 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 13 The 50 g of polyacetal resin containing 0.1% of an acid scavenger, dicyandiamide, is added 0.2% by weight of Ca(II) bis[0-mono(2',6'-diethyl-2', 3',6'-trimethylpiperidyl-4')-2-n-octyl succinate 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 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 2-1/2 inch x 125 mil. Thereafter, the testing procedure of Example 10 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 14 i 20 Unstabilized thoroughly dried polyethylene terphthalate chips are '~'d, dry blended with 1.0% of ZN(II) bis [0-mono(2',6'-diethyl-2',3',6'-trimethyl-piperidyl-4')2-n-octyl succinate]. 60/10 denier multifilament is melt spun at a melt temperature of 290C. The oriented fiber is wound on white cards and exposed in an Xenon Arc Fadeometer. Color measurements are made periodically with a Hunter Color Difference Meter Model D25. The stabilized samples are found to be much more light stable than the unstabilized samples.
-~i Example 15 ~J~ a) A composition comprising acrylonitrile-butadiene-styrene ~i i ~ - 20 --'~

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

10~8277 terpolymer and 1% by weight of 0-mono-~2',6'-diethyl-2',3',6'-trimethyl-piperidyl-4')2-n-octadecènyl succinate resists embrittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer.
b) A composition comprising polyurethane prepared from toluene diisocyanate and alkylene polyols and 1.0% by weight of Ni~II) bis[0-mono-2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')cyclohexane-1,2-dicarboxylate is more stable to sunlight, fluorescent sunlamps, black lights and fluores-cent lights than the unformulated polyurethane.
c) A composition comprising a polycarbonate prepared from bisphenol-, 10 A and phosgene and 1% by weight of Ni(II) bis [0-mono~2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')2-n-octadecen-2"-yl succinate] resists discoloration ?' due to exposure to ultraviolet light longer than one which does not contain the stabilizer.
- d) A composition comprising polymethylmethacrylate and 0.25% by weight of 0-mono~2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')2-n-octadecen- -`~ 2"-yl succinate resists discoloration due to exposure to ultraviolet light longer than one which does not contain the stabilizer.
Example 16 ....
a) A stabilized polyamide ~nylon 6,6) is prepared by incorporating therein 0.1% of Ni~II) bis [0-mono-~2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')-phthalate]. The light stability of the stabilized composition is super-ior to that of an unstabilized polyamide.
b) A stabilized polyphenylene oxide polymer (prepared by polymeriz-ing 2,6-dimethylphenol is prepared by incorporating therein 0.5% by weight of Ni(II)bis[0-mono(2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')cyclohex-4-ene-1,2-dicarboxylate]. The stabilized compositions resist embrittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

. -!

106827'7 c) A stabilized crystalline polystyrene is prepared by incorporatingtherein 0.1% weight of Ni(II)bis[0-mono(2',6'-di-n-butyl-2',6-dimethyl-3'-n-propyl-piperidyl-4')2-n-octadecen-2"-yl succinate]. The stabilized composi-tion resists embrittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer.
Antioxidants may also be incorporated into each of the above mention-ed compositions, for example, di-n-octadecyl-~,~'-bis(3-butyl-4-hydroxy-5-methylbenzyl) malonate 2,4-bis(4-hydroxy-3,5-di-t-butylphenoxy)-6-(n-octylthi-oethylthio)-1,3,5-triazine, 2,4-bis(3,5-di-t-butyl-hydroxyphenoxy)-6-(n-octylthio-1,3,5-tria~ine di-n-octadecyl 3~3',5'-di-t-butyl-4-hydroxyphenyl) ^;l propionate, respectively.
The invention encompasses compounds having the formula I, in which M is M'(R)n where R represents water, alcohols, glycols, diols, triols, tetraols, pentols, hexitols as well as ammonia, amines, and amino alcohols.
M' is a metal, like the above M. In the case of M', z represents the primary value and n represents the coordination number of the metals.
The compounds wherein M is M'(R)n may be prepared by mixing equimolar ratios of the compounds containing M and the co-ligand R in an appropriate solvent, refluxing, and subsequently evaporating to dryness. More specifically, when M is Nickel or R is n-butylamine the compound may be suspended in isopropanol, the n-butylamine added, and the mixture refluxed until solution is achieved, then evaporated to dryness.
Example 17 0-mono(2,2,6,6-tetramethyl~ip-e-ridin-4-ol) cyclohexane-1,2-dicarboxylate A. In a 500 ml 3-necked flask equipped with a stirrer, thermometer, nitrogen inlet and Dean-Stark trap with condenser were placed 15.73 g (0.1 , ., moles) of 2,2,6,6-tetramethylpiperidin-4-ol and 300 ml of xylene. The reaction mix*ure was heated briefly to reflux to remove w~ter in the solvent, then . , , :..
. .. ... ...... .. . . . ... . .... . . .

- .: . . . .

1068Z7'7 cooled to 100 and 15.42 g ~0.1 moles) of cyclohexane-1,2-dicarboxylic anhydride was added in one portion. The reaction mixture was then heated under reflux with stirring for 5 hours, then cooled to room temperature and filtered with suction. The collected solids were washed twice with hot isopropanol and dried, yielding 29.25 g of the desired product as a white powder, m.p. 231-235.
B. By essentially following the above procedure (A), and substitut-.,.
ing for the cyclohexane-1,2-dicarboxylic anhydride an equivalent amount of a) cyclohex-4-ene-1,2-dicarboxylic anhydride b) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride c) phthalic anhydride there were respectively obtained the following compounds:

, a) 0-mono(2,2,6,6-tetramethylpiperidin-4-ol) cyclohex-4-ene-1,2-dicarboxylate, m.p. 245-247 b) 0-mono(2,2,6,6-tetramethylpiperidin-4-ol) bicyclo[2.2.1]hept-

5-ene-2,3-dicarboxylate, m.p. 225-229 c) 0-mono(2,2,6,6-tetramethylpiperidin-4-ol) phthalate, m.p. 310-''':'1 '!'I C. By essentially following the above procedure (A), and substitut-,;
ing for the reactants appropriate quantities of the following reagents:
a) l-n-dodecyl-2,2,6,6-tetramethylpiperidin-4-ol and cyclohex-4-~;~ ene-1,2-dicarboxylic anhydride .;
b) l-benzyl-2,2,6,6-tetramethyl piperidin-4-ol and bicyclo[2.2.1]
hept-5-ene-2,3-dicarboxylic anhydride .~ there are respectively obtained the following compounds:
a) 0-mono(l-n-dodecyl-2,2,6,6-tetramethylpiperidin-4-ol)cyclohex-1 4-ene-1,2-dicarboxylate b) 0-mono(l-benzyl-2,2,6,6-tetramethylpiperidin-4-ol)bicyclo[2.2.1]
hept-5-ene-2,3-dicarboxylate :, ; ~ , . . . . . .

~06827'7 Example 18 0-mono(2,2,6,6-tetramethylpiperidin-4-ol-maleate A. In a 300 ml 3-necked flask equipped with a stirrer, condenser with Dean-Stark trap, N2 inlet, drying tube and thermometer were placed 31.~2 g (0.20 moles) of 2,2,6,6-tetramethylpiperidin-4-ol and 200 ml of xylene.
The reaction mixture was heated briefly to reflux, then cooled to 80C and 19.83 g (0.20 moles) of maleic anhydride was added. The reaction mixture was heated under reflux for 2-1/2 hours and allowed to cool to room temperature.
The precipitate was collected by suction filtration and triturated with 400 ml of hot isopropanol. The collected solids were dried under vacuum, giving the desired material as a tan solid, m.p. 251-253C.
- B. By essentially following the above procedure (A), and substitut-ing for the maleic anhydride an equivalent amount of 2-dodecen-1-yl succinic anhydride there was respectively obtained 0-mono(2,2,6,6-tetramethylpiperidin-4-ol)2-dodecene-1-yl succinate, m.p. 171-174C.
~; C. By essentially following the above procedure (A), and substitut-ing for the reactants appropriate quantities of the following reagents:

- a) 1,2,2,6,6-pentamethyl piperidin-4-ol and dodecyl-succinic `2 anhydride b) 1-propargyl-2,2,6,6-tetramethylpiperidin-4-ol and citraconic , anhydride there are respectively obtained the following compounds:
a) 0-mono(1,2,2,6,6-pentamethyl piperidin-4-ol) dodecyl succinate b) 0-mono(l-propargyl-2,2,6,6-tetramethylpiperidin-4-ol)methyl-maleate.
~,~ Example 19 .~ ~
Ni(II)bislO-mono(2,2,6,6-tetramethylpiperidin-4-ol) cyclohexane-1,2-dicarboxylate]

i ~,1 '", . . ' , , ` ;. ` ' ~ ' . ~ "

A. In a 500 ml l-necked flask were placed 12.46 g ~0.04 moles) of O-mono(2,2,6,6-tetramethylpiperidin-4-ol)cyclohexane-1,2-dicarboxylate and 40 ml of methanol. To the suspension was added 40.0 ml of l.ON methanolic KOH
solution and the reaction mixture was swirled until solution was obtained.
The reaction mixture was then concentrated to dryness under reduced pressure and dried further under vacuum at 80/0.1 mm for one hour. To the thus formed potassium salt was then added 100 ml of anhydrous methanol and a solution of 4.75 g ~0.02 moles) of NiC12 6 H20 in 50 ml of methanol was added with stirring over a 10-minute period. The reaction mixture was then filtered with suction and the filtrate reduced to one-half volume under reduced pressure.To the methanolic solution was added 75 ml of ethanol, the mixture filtered , with suction, and the filtrate reduced to one-half volume. The above pro-;~ cedure was repeated once more with ethanol, and twice more using isopropanol.
After the final addition of isopropanol, the reaction mixture was filtered by suction and the filtrate concentrated under reduced pressure. The residue ;~ was dried further under vacuum at 80C (0.1 mm) for one hour, yielding the S desired nickel salt as a green powder after grinding.
$i B. By following the above procedure (A) and substituting for the O-mono(2,2,6,6-tetramethylpiperidin-4-ol~cyclohexane-1,2-dicarboxylate an q 20 equivalent amount of a) O-mono(2,2,6,6-tetramethylpiperidin-4-ol cyclohex~4-ene-1,2-dicarboxylate ~; ~ b) O-mono(2,2,6,6-tetramethylpiperidin-4-ol)bicyclo[2.2.1]hept-5-~3 ~ ene-2,3,dicarboxylate there was respectively obtained the following materials ~ ~ a) Ni(II) bis[O-mono(2,2,6,6-tetramethylpiperidin-4-ol)-cyclohex-4-`~ ene-1,2-dicarboxylate], a green powder ~ b) Ni(II)bis[O-mono(2,2,6,6-tetramethylpiperidin-4-ol)-bicyclo[2.2.1]
`~ hept-5-ene-2,3,dicarboxylate], a yellow green powder.

~ - 25 -::: : , :. , . ." , , -Z7`'7 Example 20 A. By essentially following the procedure of Example l9(A) and substituting the following metal complexes for nickel chloride a) Cupric Chloride b) Manganese Chloride c) Cobalt(ous) Chloride d) Zinc Chloride e) Calcium Chloride f) Magnesium Chloride There are respectively obtained:
a) Copper(II)bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol)cyclohexa-ne-1,2-dicarboxylate]
b) Manganese~II)bis~0-mono(2,2,6,6-tetramethylpiperidin-4-ol) . cyclohexane-1,2-dicarbvxylate]
` c) Cobaltous bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol)cyclo-hexane-1,2-dicarboxylate]
d) Zinc bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol)cyclohexane-l, 2-dicarboxylate]
2i e) Calcium(II)bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol)cyclo-hexane-1,2-dicarboxylate]
B. By essentially following the procedure of Example 3(A) and `~ substituting for the reactants appropriate quantities of the following ~ reagents:
;~ a) 0-mono(2,2,6,6-tetramethylpiperidin-4-ol)bicyclo[2.2.1]hept-5-: .c ene-2,3-dicarboxylate and manganese chloride b) 0-mono(2,2,6,6-tetramethylpiperidin-4-ol) maleate and zinc ~ chloride ;q~ c) 0-mono(2,2,6,6-tetramethylpiperidin-4-ol) 2-dodecene-l-yl-~:
t - 26 -~:~t . .~

succinate and magnesium chloride there are respectively obtained:
a) Manganese(II)bis~O- no(2,2,6,6-tetramethylpiperidin-4-ol) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate]
b) Zinc bis [O-mono(2,2,6,6-tetramethylpiperidin-4-ol)maleate]
c) Magnesium(II)bis~O-mono(2,2,6,6-tetramethylpiperidin-4-ol)2-dodecene-l-yl succinate]
. Example 21 Ni(II)bis[O-mono(2,2,6,6-tetramethylpiperidin-4-ol)phthalate]
A. In a 500 ml 3-necked flask equipped with a stirrer, thermometer . and dropping funnel were placed 15.27 g (0.05 moles) of O-mono(2,2,6,6-tetra-methylpiperidin-4-ol)phthalate and 20 ml of anhydrous methanol. To the stirred suspension was added 50 ml of lN methanolic KOH and 70 ml of methanol and the reaction mixture was stirred and heated briefly to 45 to aid solution.
t The reaction mixture was then cooled to room temperature and a solution of ~, 5.94 g (0.025 moles) of NiC12.6 H20 in 20 ml of methanol was added over a 5-`~ minute period, and 10 ml of methanol were used to wash the dropping funnel.
The reaction mixture was allowed to stir for 10 minutes and 170 ml of isopro-panol were added. After a further 45 minutes, the reaction mixture was filtered with suction and the filtrate was concentrated to dryness under ~.,, reduced pressure. The residue was further dried under vacuum at 65/0.1 mm for one hour, yielding the desired nickel salt as a green glassy powder.
~, B. By essentially following the above procedure (A), and substitut-inB the following metal complexes for nickel chloride a) Manganese Chloride b) Magnesium Chloride c) Zinc Chloride there are respectiveIy obtained:

, ;~
~3 - . ,. 1. .. ,, . . . ~ . ` - ' . . ; ~ . ': , :

106~Z77 a) Manganese(II)bis[0-mono(2,2,6~6-tetramethylpiperidin-4-ol) phthalate]
b) Magnesium~II)bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol) phthalate]
c) Zinc bis10-mono(2,2,6,6-tetramethylpiperidin-4-ol)phthalate]
Example 22 Barium bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol cyclohexane-1,2-dicarboxylate In a liter l-necked flask equipped with a magnetic stirrer were placed15.57 g (0.05 les) of 0-mono(2,2,6,6-tetramethylpiperidin-4-ol) carboxylate and 200 ml of methanol. To the stirred suspension was added 25 ml of an IN solution of Ba(OH)2 in methanol. The reaction mixture was stirred at room temperature for 15 minutes and the slurry changed character to a milky solution. The reaction mixture was evaporated to dTyness under reduced pres-sure and the desired barium salt obtained as a colorless resin after drying under vacuum at 65%/0.1 mm.
Exa~ple :Z3 Artific al Light Exposure Test (same as example 9) TABLE I
`,Light Stabilization Data in Polypropylene ~ Additive*Time in Hours to 0.5 Carbonyl -x~ Absorbance Units ~,Ji O-monot2,2,6,6-tetramethyl-piperidin-4-ol)cyclohexane-, 1,2-dicarboxylate 1310 - 0-mons)(2,2,6,6-tetramethyl-~! piperidin-4-ol)cyclohex-4--.~ ene-1,2-dicarboxylate 570 :.1 :
0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)bicyclo[2.2.1]
hept-5-ene-2,3-dicarboxylate 1240 , ~

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

~068277 TABLE I
Light Stabilization Data in Polypropylene Additive~~ Time in Hours to 0.5 Carbonyl Absorbance Units 0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)phthalate 220 Ni(II)bis[0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)cyclohexane-1,2-dicarboxylate] ~3010 Ni(II)bis[0-monot2,2,6,6-tetramethyl-piperidin-4-ol)cyclohex-4-ene-1,2-dicarboxylate] 2060 - Ni(II)bis[0- not2,2~6,6-tetramethyl-piperidin-4-ol)maleate] 990 Ni(II)bis[0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)phthalate] 1210 Base resin only 200 , TABLE II
s Light Stabilization Data in PolyproPylene :~ Additive Time in Hours to 0.5 Carbonyl Absorbance Units*
0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)2-dodecene-1-yl succinate 1970 0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)maleate 2510 Ni(II)bis[0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)-2-dodecene-1-yl succinate] 3420 Ni(II)bis[0-mono(2,2,6,6-tetramethyl-ji piperidin-4-ol)-bicyclo[2.2.1]hept i~ 5-ene-2,3-dicarboxylate] >1520 Base resin only 420 The formulation contains 0.5% additive and base resin containing 0.2%
antioxidant dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate.
, ~
~ - 29 -;~
:-~

,! ' . , , , ' , : . ' ' ' , "' ~ , : , '" " " ' . ' . ' ' . ' ~ ' . ., ,' ,,, , ' . ' Other hindered phenolic antioxidants may be used in place of di-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl) phosphonate in the above mentioned compositions, for example, di-n-octadecyl ~-(3-t-butyl-4-hydToxy-4-methyl-benzyl)malonate, 2,4-bis(n-octylthio)-6-(3,4-di-t-butyl-4-hydroxyaniline)-lJ3,5-triazine, octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl) propionate, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)]propionate, tris-(3,5,di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-4-methyl-phenol, N,N,N-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-trimethylbenzyl.
The following W absorbers are included in the formulation at 0.01 to 2%:
a) 2(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole b) 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate c) 2-hydroxy-4-n-octoxybenzophenone d) [2,2'-thiobis(4-t-octylphenolate)]-n-butylamine nickel II
e) p-octylphenyl salicylate f) 2,2'-dihydroxy-4,4'-dimethoxybenzophenone g) 2(2'-hydroxy-5'-methylphenyl)-benzotriazole.
~5 ExamDle 24 High impact polystyrene resin containing elastomer ti.e., butadiene-styrene) is stabilized against loss of elongation properties due to exposure to ultraviolet light by incorporation of 0.2% by weight of 0-mono(2,2,6,6-:
tetramethylpiperidin-4-ol)cyclohexane-1,2-dicarboxylate.
- The unstabilized resin is dissolved in chloroform and the stabilizer . then added, after which the mixture is cast on a glass plate and the solvent i 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 sheet of uniform thickness (25 mil). The . ~ , ~;, - 30 -, , ~

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

10t;8277 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 6(B) except that the sample 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 0.5% by weight of the substrate of the nickel complex of O-mono (2,2,6,6-tetramethylpiperidin-4-ol)maleate 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 2,000 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 an FS/BL exposure device and color measurements made periodically using a Hunter Color Difference Meter Model D25. Polyethylene stabilized y 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 obtained from Texas United States, Synpol 1500) previously stored under nitrogenj is placed in a beaker and stirred vigorously. The pH of the emulsion is adjusted to 10.5 with a 0.5N NaOH solution.
i To the emulsion is added 50 ml of 25% NACl solution. A 6% NaCl , solution adjusted with hydrochloric 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 ~.

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

. . .
.. . . . . . .

106~277 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 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-tetramethylpiperidin-4-ol)cyclohex-4-ene-1,2-dicarboxylate, is mixed for 5 minutes after which it is cooled and compression molded at 125C into . 5" x 0.025" plaques.
,~
The plaques are exposed to an Xenon Arc weatherometer 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 'il unstabilized samples.
s Example 27 The 50 g of polyacetal resin containing 0.1% of an acid scavenger, dicyandiamide, is added 0.2% by weight of Ni(II)bis[0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)-2-dodecen-1-yl succinate] 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 then cooled .' .;1 ~
"~ 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 2-1/2 inch x 125 mil. Thereafter, the testing procedure of Example 8 is followed to determine the light stability of the anples. The stabilized samples are found to be much re stable than the i ~, - 32 -1~ti8277 unstabilized samples.
Example 28 Unstabilized thoroughly dried polyethylene terphthalate chips are dry blended with 1.0% of O-mono 2(2,2,6,6-tetramethylpiperidin-4-ol)2-dodecene-l-yl succinate. 60/10 denier multifilament is melt spun at a melt temperature of 290C. The oriented fiber is wound on white cards and exposed in an Xenon Arc Fadeometer. Color measurements are made periodically with a Hunter Color Difference Meter Model D25. The stabilized samples are found to be much more light stable than the unstabilized samples.
Example 29 a) A composition comprising acrylonitrile-butadiene-styrene terpolymer and 1% by weight of Ni(II)bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol) maleate] resists embrittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer.
-~ b) A composition comprising polyurethane prepared from toluene diisocyanate and alkylene polyols and 1.0% by weight of 0-mono(2,2,6,6-tetramethylpiperidin-4-ol)cyclohexane-1,2-dicarboxylate is more stable to sun-light, fluorescent sunlamps, black lights and fluorescent lights than the unformulated polyurethane.
`;! 20 c) A composition comprising a polycarbonate prepared from bisphenol-A
.
and phosgene and 1% by weight of O-mono(2,2,6,6-tetramethylpiperidin-4-ol) bicyclo[2.2.1] hept-5-ene-2,3-dicarboxylate resists discoloration due to exposure to ultraviolet light longer than one which does not contain the stabilizer.
d) A composition comprising polymethylmethacrylate and 0.25% by weight of Ni(II~bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol)cyclohexane-1,2-dicarboxylate] resists discoloration due to exposure to ultraviolet light longer than one which does not contain the stabilizer.

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10~82'77 Example 30 a) A stabilized polyamide (nylon 6,6) is prepared by incorporating therein 0.1% of Ni(II)bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol)bicyclo [2.2.1]hept-5-ene-2,3-dicarboxylate]. The light stability of the stabilized composition is superior to that of an unstabilized polyamide.
b) A stabilized polyphenylene oxide polymer (prepared by polymerizing 2,6-dimethylphenol is prepared by incorporating therein 0.5% by weight of Ni(II)bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol)cyclohex-4-ene-1,2-dicarboxylate]. The stabilized compositions resists embrittlement due to ` 10 exposure to ultraviolet light longer than one which does not con*ain the stabilizer.
i c) A stabilized crystalline polystyrene is prepared by incorporating therein 0.1% weight of Ni(II)bis[O-mono(2,2,6,6-tetramethylpiperidin-4-ol) cyclohex-4-ene-1,2-dicarboxylate]. The stabilized composition resists embrittlement due to exposure to ultraviolet light longer than one which does not contain the stabilizer.
Antioxidants may also be incorporated into each of the above mentioned compositions, for example, di-n-octadecyl-a,a'-bis(3-butyl-4-hydroxy-5-methyl-benzyl) malonate 2,4-bis(4-hydroxy-3,5-di-t-butylphenoxy)-6-(n-octylthio-ethylthio)-1,3,5-triazine, 2,4-bis(3,5-di-t-butyl-hydroxyphenoxy)-6-(n-octylthio-1,3,5-triazine di-n-octadecyl 3(3',5'-di-t-butyl-4-hydroxyphenyl) ~;` propionate, respectively.
:, ~ - 34 -.,.,,,. ~. " ,: . : . ~ . ...... .

. . -- .

Claims (47)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula I

wherein each R1 is the same and stands for hydrogen or methyl, R2 is hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 4 carbon atoms, propargyl or benzyl, R3 is straight-chain alkenylene of 2 to 4 carbon atoms, 1,2-cyclo-alkylene or 1,2-cycloalkenylene having 4 to 6 carbon atoms, 2,3-bicycloalkyl-ene or 2,3-bicycloalkenylene having 7 or 8 carbon atoms or 1,2- 1,3-, or 1,4-phenylene, or straight-chain alkylene of 1 to 4 carbon atoms substituted by alkyl or alkenyl of up to 18 carbon atoms, provided that said straight-chain alkylene substituted by alkyl has in total more than 10 carbon atoms, M is hydrogen or a metal selected from the group consisting of barium nickel, manganese, calcium, copper, zinc, magnesium, sodium, potassium, cobalt, tin, and dialkyl tin z has a value of from 1 to 4, the value of z being the same as the available valence of M.

2. A compound as claimed is claim 1, wherein R2 is hydrogen, methyl, allyl or benzyl.

3. A compound as claimed in claim 1, wherein each R1 is methyl.

4. A compound according to Claim 3 wherein R3 is 1,2-cycloalkylene or 1,2-cycloalkenylene having 4 to 6 carbon atoms.

5. A compound according to Claim 3 wherein R3 is 2,3-bicycloalkylene or 2,3-bicycloalkenylene having 7 to 8 carbon atoms.

6. A compound according to Claim 3 wherein R3 is 1,2-, 1,3- or 1,4-phenylene.

7. A compound according to Claim 3 wherein R3 is straight-chain alkenylene of 2 to 4 carbon atoms.

8. A compound according to Claim 3 wherein R3 is straight-chain alkylene of 1 to 4 carbon atoms substituted by alkyl or alkenyl of 1 to 18 carbon atoms.

9. A compound according to Claim 3 wherein M is selected from hydrogen or nickel.

10. A compound according to Claim 3 which is 0-mono(2',6'-diethyl-2', 3',6'-trimethylpiperidyl-4')2-n-octyl succinate.

11. A compound according to Claim 3 which is Ni(II) Bis[O-mono(2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')2-n-octyl succinate].

12. A compound according to Claim 3 which is Co(II) Bis[O-mono(2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')2-n-octyl succinate].

13. A compound according to Claim 3 which is Ca(II) Bis[O-mono(2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')2-n-octyl succinate].

14. A compound according to Claim 3 which is Mg(lI) Bis[O-mono(2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')2-n-octyl succinate].

15. A compound according to Claim 3 which is Zn(II) Bis[0-mono(2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')2-n-octyl succinate].

16. A compound according to Claim 3 which is Ni(II) Bis[0-mono(2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')2-n-octadecen-2"-yl succinate].

17. A compound according to Claim 3 which is 0-mono(2',6'-diethyl-2',3', 6'-trimethylpiperidyl-4')2-n-octadecen-2"-yl succinate.

18. A compound according to Claim 3 which is 0-mono(2',6'-diethyl-2',3', 6'-trimethylpiperidyl-4')cyclohexane-1,2-dicarboxylate.

19. A compound according to Claim 3 which is Ni(II) Bis [0-mono(2',6'-diethyl-2',3',6'-trimethylpiperidyl-4')cyclohexane-1,2-dicarboxylate.

20. A compound as claimed in Claim 1, wherein each R1 is hydrogen.

21. A compound according to Claim 20 wherein R3 is 1,2-disubstituted cycloalkylene or cycloalkenylene having 4 to 6 carbon atoms.

22. A compound according to Claim 20 wherein R3 is 2,3-disubstituted bicycloalkylene or bicycloalkenylene having 7 to 8 carbon atoms.

23. A compound according to Claim 20 wherein R3 is 1,2-, 1,3- or 1,4-disubstituted phenylene.

24. A compound according to Claim 20 wherein R3 is straight-chain alkenylene of 2 to 4 carbon atoms.

25. A compound according to Claim 20 wherein R3 is straight-chain alkylene of 1 to 4 carbon atoms substituted by alkyl or alkenyl of 1 to 18 carbon atoms.

26. A compound according to Claim 20 wherein M is selected from hydrogen or nickel.

27. A compound according to Claim 20 which is 0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)cyclohexane-1,2-dicarboxylate.

28. A compound according to Claim 20 which is 0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate.

29. A compound according to Claim 20 which is Ni (II)bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol)cyclohexane-1,2-dicarboxylate].

30. A compound according to Claim 20 which is Ni (II)bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol)cyclohex-4-ene-1,2-dicarboxylate].

31. A compound according to Claim 20 which is 0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)2-dodecene-1-yl succinate.

32. A compound according to Claim 20 which is 0-mono(2,2,6,6-tetramethyl-piperidin-4-ol)maleate.

33. A compound according to Claim 20 which is Ni(II)bis[0-mono]2,2,6,6-tetramethylpiperidin-4-ol)-2-dodecene-1-yl-succinate].

34. A compound according to Claim 20 which is 0-mono-(2,2,6,6-tetramethyl-piperdin-4-ol)cyclohex-4-ene-1,2-dicarboxylate.

35. A compound according to Claim 20 which is 0-mono-(2,2,6,6-tetramethyl-piperidin-4-ol)phthalate.

36. A compound according to Claim 20 which is Ni(II)bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate].

37. A compound according to Claim 20 which is Ni(II) bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol)phthalate].

38. A compound according to Claim 20 which is Ni(II)bis[0-mono(2,2,6,6-tetramethylpiperidin-4-ol)maleate].

39. A composition of matter stabilized against ultraviolet deterioration which comprises a synthetic organic polymer normally subject to ultraviolet deterioration containing from a) 0.005% to 5% of a stabilizing compound according to Claim 1, b) 0 to 5% of a phenolic antioxidant, c) 0 to 5% of a thio co-stabilizer, and d) 0 to 5% of a U.V. absorber.

40. A composition of matter stabilized against ultraviolet deterioration which comprises a synthetic organic polymer normally subject to ultraviolet deterioration containing from a) 0.005% to 5% of a stabilizing compound according to Claim 1, b) 0 to 5% of a phenolic antioxidant, c) 0 to 5% of a phosphite co-stabilizer and d) 0 to 5% of a U.V. absorber.

41. A composition of Claim 39 wherein the organic material is a polyolefin.

42. A composition of Claim 41 wherein the polyolefin is polypropylene.

43. A composition according to claims 39-40, containing a compound according to Claim 3 as item a).

44. A composition according to Claims 39-40, containing a compound according to Claim 20 as item a).

45. A process for preparing a compound according to Claim 1 by reacting a piperidinol of the formula II

wherein R1 and R2 are as defined above in formula I, with an acid anhydride of the formula III

wherein R3 is as defined above or with a diacid of the formula R3-(COOH)2 IV
wherein R3 is as defined above.

46. A process for preparing a compound according to Claim 3 by reacting a piperidinol of the formula II
wherein R1 and R2 are as defined above in formula I, with an acid anhydride of the formula III

wherein R3 is as defined above or with a diacid of the formula R3-(COOH)2 IV
wherein R3 is as defined above.

47. A process for preparing a compound according to Claim 20 by reacting a piperidinol of the formula II

wherein R1 and R2 are as defined above in formula I, with an acid anhydride of the formula III

wherein R3 is as defined above or with a diacid of the formula R3-(COOH)2 wherein R3 is as defined above.