Reactive hindered amine light stabilizers

Abstract: There are provided reactive hindered amine light stabilizers of the formula wherein R is e.g., hydrogen, hydroxyl or alkyl of 1 to 20 carbons; R¹ is, hydrogen or lower alkyl of 1 to 4 carbons; R² is, e.g., hydrogen or alkyl of 1 to 20 carbons; R³ is, e.g., a direct bond or an alkylene or branched alkylene diradical of 1 to 14 carbons; and R⁴ is, e.g., hydrogen or a primary or secondary alkyl group of 1 to 8 carbons, containing a light stabilizing group, a heat stabilizing group, and a reactive hydrazide functionality in the same molecule. The reactive stabilizers are prepared by reacting 4-amino-2,2,6,6-­ tetraalkylpiperidines with diesters (or mono ester acid chlorides) of dicarboxylic acids followed by hydrazinolysis of the ester group of the intermediate mono ester-amide. The compounds are useful for introducing permanent heat and light stability to coreactive polymers or copolymers.

Description: Background of the Invention This invention relates to N-(2,2,6,6-tetraalkyl-4-piperidinyl)amide-hydrazides of dicarboxylic acids which contain a hindered amine light stabilizing group (photooxidative stabilizer) and a reactive hydrazide group (heat stabilizer). Polymers such as polyolefins (e.g., polyethylene, polypropylene, etc.) styrenics (e.g., polystyrene, rubber modified polystyrene, ABS, MBS, etc.), polyvinyl chloride, polycarbonates, polyesters, polyphenylene ethers, and polyamides, for example, are subject to degradation and discoloration upon exposure to heat and/or light with consequent deterioration of their mechanical properties. Various stabilizers have been proposed to inhibit such deterioration. Hindered piperidine compounds have found extensive use in the photostabilization of polyolefins. Hydrazides have been used to prevent deterioration of polyolefins by heat, oxidation, or heavy metal contamination. Derivatives of hydrazides are also commercially available for use as polymer stabilizers. (See Encyclopedia of Polymer Science and Engineering, 2nd Ed. Vol. 2, pp 83-84). Four examples were found in the literature where the hindered amine moiety and the hydrazide moiety (-R-C(=O)-NH-NH 2 , where R is not O, N, or S) are present in the same molecule. None of these prior art hydrazides fall under general structure I of the present invention. Sterically hindered 4-aminopiperidine derivatives which can be used as light-stabilizers for organic polymers are known from U.S. Patent 4,191,683. SUMMARY OF THE INVENTION This invention is directed to reactive N-(2,2,6,6-tetraalkyl-4-piperidinyl)-amide hydrazides having the following formula: where R is selected from hydrogen, oxyl, hydroxyl, alkyl of 1 to 20 carbons, alkenyl or alkynyl of 3 to 8 carbons, aralkyl of 7 to 12 carbons, aliphatic acyl of 1 to 10 carbons, aromatic acyl of 7 to 13 carbons, alkoxycarbonyl of 2 to 9 carbons, aryloxycarbonyl of 7 to 15 carbons, alkyl, aryl, cycloalkyl or aralkyl substituted carbamoyl of 2 to 13 carbons, 2-cyanoethyl, hydroxyalkyl of 1 to 6 carbons, epoxyalkyl of 3 to 10 carbons or a polyalkylene oxide group of 4 to 30 carbons. R 1 is selected from hydrogen or lower alkyl of 1 to 4 carbons. R 2 is selected from hydrogen, alkyl of 1 to 10 carbons, cycloalkyl of 5 to 12 carbons, aralkyl of 7 to 12 carbons, aryl of 6 to 12 carbons, 2-cyanoethyl or a radical of the formula R 3 is selected from a direct bond, an alkylene or branched alkylene diradical of 1 to 14 carbons, an alkenylene diradical of 2 to 10 carbons, an oxydialkylene or thiodialkylene diradical of 4 to 10 carbons or an o-, m- or p-phenylene or substituted phenylene diradical where the substituents may be C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxy, bromine, chlorine, mercapto or C 1 -C 4 alkylmercapto. R 4 is selected from hydrogen, a primary or secondary alkyl of 1 to 8 carbons, an aralkyl of 7 to 12 carbons or a cycloalkyl of 5 to 12 carbons. Especially, R is H, C 1-4 alkyl, C 3 -alkenyl, benzyl, 2-cyanoethyl or acetyl, R 1 is H or CH 3 , R 2 is H, C 1-4 alkyl or 2,2,6,6-tetramethyl-4-piperidinyl, R 3 is a direct bond, C 1-8 alkylene or o-, m- or p-phenylene and R 4 is H, primary or secondary C 1-4 alkyl, benzyl or cyclohexyl. Preferably, R is hydrogen, acetyl or methyl, R 1 is hydrogen, R 2 is hydrogen or a 2,2,6,6-tetramethyl-4-piperidinyl radical, R 4 is H or CH 3 , and R 3 is a direct bond or a 1,2-ethylene diradical. Most preferably, R 3 is a direct bond or C 1 -C 8 alkylene, especially -CH 2 CH 2 - and R, R 1 , R 2 and R 4 are hydrogen. This invention also comprehends the preparation of the compound of Formula I. Method A The N-(2,2,6,6-tetraalkyl-4-piperidinyl)amide-hydrazides of Formula I are prepared by reacting the 4-amino-2,2,6,6-tetraalkylpiperidines of Formula II with half ester-half acid chloride of Formula III to form the intermediate half ester-half amides of Formula IV . The intermediate half ester-half amides are then reacted with a primary or secondary alkyl hydrazine, hydrazine or hydrazine hydrate to form the compounds I. Method B The N-(2,2,6,6-tetraalkyl-4-piperidinyl)amide-hydrazides of Formula VIII may also be prepared by reacting the amino compounds of Formula II with essentially equivalent amounts or an excess of a dicarboxylic acid diester of Formula VI to form the intermediate half ester-half amide of Formula VII . The intermediate VII is then reacted with a primary or secondary alkylhydrazine, hydrazine or hydrazine hydrate to form the compounds I with the limitation R 3 may not be an alkenylene or ethylene diradical. Detailed Description Of The Invention The compounds I are reactive additives that can be attached to coreactive polymers to form polymer bound additives containing photooxidative and thermal oxidative stabilizing groups. For example, the reactive N-(2,2,6,6-tetraalkyl-4-piperidinyl)amide-hydrazides can be reacted with anhydride copolymers such as styrene-maleic (SMA) copolymers, octadecene-maleic anhydride copolymer and ethylene-maleic anhydride copolymer to name just a few. Once reacted with the coreactive polymers the stabilizer groups become attached to the polymers and will not be lost via volatilization, migration or extraction. Examples of the reactive hindered amine light stabilizers of this invention include the following non limiting list of hydrazides: 1. N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-N′-aminooxamide, 2. N-(1-benzoyl-2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminooxamide, 3. N-(1-allyl-2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminooxamide, 4. N-(1-benzyl-2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminooxamide, 5. N-(1-ethoxycarbonyl-2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminooxamide, 6. N-(1-dodecyl-2,6-diethyl-2,3,6-trimethyl-4-piperidinyl)-N′-aminooxamide, 7. N-(2,2,6,6-tetramethyl-4-piperidinyl)-N-butyl-N′-aminooxamide, 8. N-(2,2,6,6-tetramethyl-4-piperidinyl)-N-phenyl-N′-aminosuccinamide, 9. N-(2,2,6,6-tetramethyl-4-piperidinyl)-N-methyl-N′-methyl-N′-aminomalonamide, 10. N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminoterephthalamide, 11. N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-butyl-N′-aminosebacamide, 12. N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminododecandiamide, 13. N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminosuberic acid diamide, 14. N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminoglutaric acid diamide, 15. N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-amino-2-methylsuccinamide, 16 N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-amino-2,3-dimethylsuccinamide, 17. N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminopimelic acid diamide, 18. N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminoundecandiamide, 19. N-(1-beta-hydroxyethyl-2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminoadipic acid diamide, 20. N(1-beta-cyanoethyl-2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminosuccinamide, 21. N-(1-phenoxycarbonyl-2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminooxamide, 22. N-(2,6-diethyl-2,3,6-trimethyl-4-piperidinyl)-N′-aminooxamide, and 23. N,N-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminooxamide. Compounds I are prepared by Methods A and B The reaction sequence of Method A is illustrated by the following equations. where R, R 1 , R 2 , R 3 , and R 4 are as previously defined and R 5 is lower alkyl of 1 to 6 carbons or phenyl and preferably is methyl or ethyl. Since HCl is liberated in the first step it is preferable to run the reaction in the presence of a hydrogen chloride acceptor such as a tertiary amine, an inorganic base or an excess of the amine II. Preferably, a 100% excess of the amine II is used as the hydrogen chloride acceptor. The amine hydrochloride formed can be separated from the reaction mixture by filtration or may be removed by washing the reaction mixture with water. (The amine can be regenerated by neutralization with a stronger base.) The reaction can be run in a variety of non-reactive solvents such as hydrocarbons, chlorinated hydrocarbons or ethers. Preferably, the reaction is run in the lower boiling solvents so the product can be isolated by stripping off the solvent. The reaction is exothermic so gentle cooling is advisable to control the temperature. The intermediate ( IV ) is isolated and dissolved in a polar solvent and converted to the desired hydrazide by stirring with an equivalent amount or slight excess of a primary or secondary-alkylhydrazine, hydrazine or hydrazine hydrate. Depending upon R 3 , the reaction may go at room temperature or may require refluxing. Preferably, the hydrazinolysis reaction is carried out in methanol or ethanol at 10-30°C but other solvents such as isopropanol or ethylene glycol are also acceptable. In most cases the I compounds can be purified by recrystallization from the lower alcohols. Examples of suitable mono ester acid chloride include: the mono esters (preferably the mono methyl or ethyl esters) of phthaloyl, isophthaloyl, terephthaloyl, adipoyl, azelayoyl, succinyl, oxalyl, malonyl, fumaroyl, sebacoyl and suberoyl chlorides. Examples of suitable amino-substituted hindered amine light stabilizers ( II ) include: 4-amino-2,2,6,6-tetramethylpiperidine, 4-amino-1,2,2,6,6-pentamethylpiperidine, 4-amino- 2,6-diethyl-2,3,6-trimethylpiperidine, 4-amino-2,6-diethyl- 1,2,3,6-tetramethylpiperidine, 4-amino-1-(2-cyanoethyl)-2,2,6,6-tetramethylpiperidine, 4-[N-(n-butyl)amino]-2,2,6,6-tetramethylpiperidine, 4-[N-(ethyl)amino]-1-ethoxycarbonyl-2,2,6,6-tetramethylpiperidine, 4-[N-(hexyl)amino]-1-benzyl-2,2,6,6-tetramethylpiperidine, 4-amino-1-allyl-2,2,6,6-tetramethylpiperidine, 4-amino-1-benzoyl-2,2,6,6-tetramethylpiperidine, 4-[N-(methyl)amino]-1-dodecyl-2,2,6,6-tetramethylpiperidine, 4-[N-(phenyl)amino]-1,2,2,6,6-pentamethylpiperidine, 4-[N-(benzyl)amino]-2,2,6,6-tetramethylpiperidine, 4-[N-(cyclohexyl)amino]-2,2,6,6-tetramethylpiperidine, 4-amino-2,6-diethyl-2,3,6-trimethylpiperidine, and bis-(2,2,6,6-tetramethyl-4-piperidinyl)amine, Examples of suitable hydrazines include hydrazine, hydrazine hydrate, 35-85% hydrazine hydrate, methyl, ethyl, propyl,, isopropyl, n-butyl, sec-butyl, n-amyl, sec-amyl, n-hexyl and n- and sec-octyl hydrazines. Preferably, the amine is 4-amino-2,2,6,6-tetramethylpiperidine or bis-(2,2,6,6-tetramethyl-4-piperidinyl)amine, the acid chloride is ethyl (or methyl)oxalyl chloride or ethyl (or methyl) succinyl chloride and the hydrazine is 85% hydrazine hydrate. The reaction sequence of Method B is illustrated by the following equations: where R 6 is the same as R 3 except R 6 may not be an alkenylene diradical or an ethylene diradical. The reactions are preferably run neat, or in alcoholic or glycol solvents and most preferably neat or in methanol if the diesters are activated. The amines ( II ) react quite readily with the oxalic acid diesters at room temperature and gentle cooling is advisable in the early stages of the reaction to minimize side reactions. In the case of the other diesters (i.e, R 6 is not a direct bond), heating or refluxing is necessary. The reactions can be monitored by gas chromatography and depending upon the starting amines and diesters, the reaction temperature can be adjusted up or down to speed up or slow down the reaction. In some cases it is preferable to distill of the alcohol as it forms. When using dialkyl oxalates in methanol or ethanol, it is preferable to cool the alcohol solution of the oxalate below room temperature (5-10°C) before adding the amine and then let the temperature rise to room temperature or above over the course of 1/2 to 1 hour. After the oxalate is converted to the half ester-half amide, an equivalent amount of a primary or secondary alkyl hydrazine, hydrazine or hydrazine hydrate is added. The (alkyl) hydrazine readily reacts with the half-ester to form the amide-hydrazide. Any unreacted dialkyl oxalate is readily converted to insoluble oxalic acid dihydrazide which is removed by filtration. Depending upon the amount of alcohol present, the reaction mixture may have to be heated to dissolve all the product before filtering off the oxalic acid dihydrazide. The product is isolated by stripping off the solvent or by cooling the filtrate and crystallizing out the product. When using dialkyl oxalates, the first step of the reaction sequence is preferably run in excess dialkyl oxalate to minimize side products. The excess oxalate is removed, preferably by vacuum stripping, and the hydrazinolysis of the intermediate half ester-half amide is preferably carried out in methanol, ethanol, propanol, or isopropanol. When using diesters of other dicarboxylic acids, more severe heating conditions are required for both steps. However, the reactions can be monitored by infrared spectroscopy, liquid or gas chromatography and the heating conditions and length of reaction adjusted accordingly. Suitable amines ( II ) are those illustrated for Method A. Likewise the same hydrazines are suitable for both Methods A and B. Suitable diesters include the methyl, ethyl, propyl, isopropyl and phenyl diesters or mixtures thereof of oxalic, malonic, substituted malonic, glutaric, adipic, 2-methylglutaric, 3-methylglutaric, 2,2-dimethylglutaric, 3,3-dimethylglutaric, pimelic, adipic, suberic, azelaic, sebacic, undecanedioic, 1,10-decanedicarboxylic, 1,12-dodecanedicarboxylic, o-, m- and p- phthalic and 3,3′-thiodipropionic acid. Diesters of fumaric acid and succinic acid were found to be unacceptable in this method. Preferably, the amine is 4-amino-2,2,6,6-tetramethylpiperidine, the diester is diethyl oxalate, and the hydrazine is 85% hydrazine hydrate; the first step is run in excess diethyl oxalate and the hydrazinolysis step is run in methanol. Most of the amines ( II ) can be prepared by reductive amination of triacetonamine (or its alkylated analogs) or by alkylation or acylation of triacetonamine followed by reductive amination (See U.S. Patent 4,191,683 or W. B. Lutz, S. Lazarus and R. I. Meltzer, J. Org. Chem 1962 , 27 , 1695). The alkylated and acylated derivatives (i.e, R is alkyl, alkenyl, aralkyl, aliphatic acyl, aromatic acyl, alkoxycarbonyl, aryloxycarbonyl, alkyl, aryl, cycloalkyl or aralkyl substituted carbamoyl, 2-cyanoethyl, or hydroxyalkyl) can be prepared by alkylating or acylating the unsubtituted (i.e, R is H) intermediate half ester-half amide by techniques well known in the art (e.g, acylation with acid chlorides, chloroformates, carbamoyl chlorides, isocyanates etc. or alkylation with alkyl halides or epoxides) (See U.S. Pats. 4,348,524 and 4,191,683) followed by hydrazinolysis in a polar solvent. The mono esters of the diacid chlorides are either commercially available or can be readily prepared by methods well-known in the art from the corresponding mono esters of the dicarboxylic acids and chlorinating agents such as thionyl chloride, phosgene, phosphorous trichloride or phosphorous pentachloride. The following examples are intended as illustrations and not limitations of the invention. Example I Preparation of N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminosuccinamide Into a 3-neck 500 ml round bottom flask were weighed 31.5 grams (0.2 mole) of 4-amino-2,2,6,6-tetramethylpiperidine and 30.3 grams (0.3 mole) of triethylamine. The amines were diluted with 200 ml methylene chloride and the flask was equipped with a magnetic stirrer, thermometer, reflux condenser, and dropping funnel containing 32.9 grams (0.2 mole) ethyl succinyl chloride. The flask and its contents were cooled in an ice bath to 5°C and the acid chloride was added dropwise to the stirring solution over 1/2 hour while holding the temperature between 5-15°C. After the addition was completed, the ice bath was removed and the solution was stirred an additional hour. The CH 2 Cl 2 solution was washed three times with 100 ml portions of water, dried over anhydrous Na 2 SO 4 , filtered and the methylene chloride stripped off on a rotating evaporator under reduced pressure. The residue was an orange-yellow viscous liquid weighing 38.2 grams. An infrared scan of the residue showed a strong NH band at 3300 cm -1 and two strong carbonyl peaks at 1730 cm -1 and 1640 cm -1 and an amide band at 1550 cm -1 . The residue was dissolved in 200 ml of ethanol and transferred to a 500 ml 3-neck flask equipped with a magnetic stirrer, thermometer and dropping funnel containing 26.4 grams of 85% hydrazine hydrate. The hydrazine hydrate was added dropwise over 5 minutes at room temperature. The reaction was stirred 1 hour at room temperature and then allowed to stand overnight. An IR scan indicated there was a small amount of ester unreacted (shoulder at 1730 cm -1 ) so the reaction mixture was refluxed for 1 hour. The ethanol, water, and residual hydrazine were stripped off on a rotating evaporator under vacuum leaving a mushy solid. The solids were slurried in methylene chloride, were filtered off, and were air dried. The dry product weighed 28.2 grams. It was purified by recrystallization from isopropanol. The purified product melted at 208-210°C. The infrared spectra of the product (nujol mull) contained a very sharp NH peak at 3300 cm -1 and a broad NH band centered at 3230 cm -1 , a strong carbonyl band with shoulders centered at 1610 cm -1 and an amide band at 1550 cm -1 . The ester band at 1730 cm -1 had completely disappeared. Example II Preparation of N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminomalonamide Into a 3-neck 250 ml round bottom flask were weighed 15.6 grams (0.1 mole) of 4-amino-2,2,6,6-tetramethylpiperidine and 10.1 grams (0.1 mole) of triethylamine. The amines were diluted with 100 ml of methylene chloride; the flask was equipped with a magnetic stirrer, thermometer, reflux condenser, and dropping funnel containing 11.8 grams (0.078 mole) of ethyl malonyl chloride. The ethyl malonyl chloride was added dropwise to the stirring solution of the amines without any cooling. The reaction was quite exothermic and the temperature rose from 22°C to 42°C where the refluxing methylene chloride controlled the temperature. The reaction was stirred for an additional hour while the temperature receded to 35°C. The clear solution was allowed to stand overnight. The next day the reaction mixture was added to a stirring solution of 10.6 grams of sodium carbonate in 200 ml of water. The methylene chloride layer was separated and stripped off on a rotating evaporator. The residue weighed 17.9 grams. An infrared scan of the residue showed a strong carbonyl at 1740 cm -1 (ester), a carbonyl at 1660-1680 cm -1 (amide), and an amide band at 1550 cm -1 . An additional 1.1 grams of intermediate was obtained by reextracting the aqueous layer with another 100 ml of methylene chloride and stripping off the solvent. The intermediate was dissolved in 100 ml of ethanol in a 250 ml 3-neck flask equipped with a reflux condenser, a thermometer, a magnetic stirrer, and a dropping funnel containing 11.8 grams (0.2 mole) of 85% hydrazine hydrate. The hydrazine hydrate was added over 5 minutes and then the reaction was stirred an additional 1-1/4 hours at room temperature, warmed to reflux, and refluxed 2 hours. (Gas chromatography indicated the hydrazinolysis was completed after the 1 hour stir at room temperature). The reaction was cooled to 60°C and filtered through a fluted filter to remove a small amount of insolubles. The filtrate was then stripped to dryness on a rotating evaporator under vacuum. The residue weighed 18.8 grams and was pink in color. The color seemed to carry over from the starting ethyl malonyl chloride. The crude product was recrystallized from isopropanol. The infrared spectra of the product (in methylene chloride) showed a broad NH band at 3300 cm -1 , a strong carbonyl band with shoulders centered at 1680 cm -1 , and an amide band at 1550 cm -1 . The ester band at 1740 cm -1 had completely disappeared. The recrystallized product had a melting range of 177-179°C. Example III Preparation of N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminooxamide Method A Into a 3-neck 500 ml round bottom flask was weighed 32.0 g (0.2 mole) of 4-amino-2,2,6,6-tetramethylpiperidine. The amine was diluted with 200 ml of methylene chloride and the flask was equipped as in Example I. The dropping funnel contained a solution of 13.7 grams (0.1 mole) of ethyl oxalyl chloride in 15 ml of methylene chloride. The acid chloride solution was added to the stirring amine solution over 1/2 hour while holding the temperature between 10-20°C. The reaction was stirred an additional 2 hours at room temperature. The reaction mixture was washed twice with 50 ml of water and twice with 50 ml of saturated sodium bicarbonate solution, was dried over anhydrous Na 2 SO 4 , and was filtered; the methylene chloride was stripped off on a rotating evaporator under reduced pressure. The residue was a light yellow viscous liquid which slowly solidified. The residue weighed 19.8 grams (77% crude yield). An infrared spectrum of the residue showed an NH band at 3300 cm -1 , strong carbonyl bands at 1730 cm -1 (ester) and 1680 cm -1 (amide), and an amide band at 1530 cm -1 . The residue was dissolved in 100 ml of ethanol in a 250 ml 3-neck flask equipped as in Example I. The dropping funnel contained 13.4 grams (0.225 mole) of 85% hydrazine hydrate which was added over 20 minutes to the stirring ethanol solution at 30°C. The reaction was stirred an additional hour. The reaction mixture was transferred to a round bottom flask and the ethanol and excess hydrazine were stripped off on a rotating evaporator leaving 21.5 grams of a light yellow viscous liquid which solidified to a white waxy solid upon standing. The crude product contained a small amount of residual solvent. The product was recrystallized from isopropanol yielding a white powder having a melting point of 153-155°C. The infrared spectra of the product showed NH bands at 3300 cm -1 , a strong carbonyl band with shoulders centered at 1640-1670 cm -1 , a weak carbonyl band at 1600 cm -1 , and an amide band at 1530 cm -1 . The ester band at 1730 cm -1 had completely disappeared (nujol mull). In chloroform solution the infrared spectrum had NH bands at 3300 and 3400 cm -1 , a very strong carbonyl band at 1680 cm -1 and another carbonyl band at 1620 cm -1 and an amide band at 1510 cm -1 . Method B Into a 3-neck 500 ml round bottom flask was weighed 43.8 grams (0.3 mole) of diethyl oxalate. The diethyl oxalate was diluted with 280 ml of methanol and cooled to 5°C in an ice water bath. The flask was equipped with a magnetic stirrer, a thermometer, a reflux condenser and an addition funnel containing 47.0 grams (0.3 mole) of 4-amino-2,2,6,6-tetramethylpiperidine. The amine was added to the stirred solution over 40 minutes at 5°C and for 1-1/4 hours at 20°C. Upon completion of the stirring periods the rection mixture was cooled to 15°C and 17-1/2 ml (0.3 mole) of 85% hydrazine hydrate were added dropwise over approximately 1 hour. The first 12 ml were added over 20 minutes at 15-22°C. The remainder was added in increments over 50 minutes while following the reaction by gas chromatography. Upon disappearance of the intermediate oxamate, the reaction mixture was heated to reflux to dissolve any insoluble product. The reaction was filtered hot to remove the insoluble oxalic acid dihydrazide (side product). The filtrate was cooled to 10°C and the white solids that formed were filtered off and vacuum dried for 2 hours at 50°C. The product weighed 48.8 grams and assayed 98.4% by gas chromatographic analysis. The infrared spectra was similar to the infrared spectra of the product obtained by Method A. The methanol filtrate was stripped to dryness leaving 16.3 grams of a mixture containing approximately 58% of the desired product and 34% N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)oxamide as analyzed by gas chromatography. Alternate Method B Step 1. Into a 3-neck 1500 ml round bottom flask was added 730.5 grams (5.0 mole) of diethyl oxalate. The flask was equipped with a magnetic stirring bar, a thermometer, and a dropping funnel containing 156.3 grams (1.0 mole) 4-amino-2,2,6,6-tetramethylpiperidine. The amine was added dropwise to the stirring diethyl oxalate over 15 minutes while controlling the temperatures between 20 and 30°C. The reaction mixture was stirred an additional 15 minutes at room temperature. The magnetic stirrer, thermometer, and addition funnel were removed and the side necks of the flask stoppered. The flask was then placed on a rotating evaporator and the ethanol generated during the reaction was stripped off under reduced pressure at 25-35°C. After the ethanol had been stripped off, the vacuum was released and the receiver drained of ethanol. The vacuum was reapplied and the excess diethyl oxalate stripped off by heating the flask in an oil bath at 140°C under full vacuum. After constant weight was reached, the residue was cooled to room temperature, dissolved in 200 ml of methanol, and transferred to a 500 ml dropping funnel. Step 2. Into a 3-neck 1 liter flask containing a magnetic stirrer, a thermometer, and the addition funnel containing the methanol solution of ethyl N-(2,2,6,6-tetramethyl-4-piperidyl)oxamate from Step 1, were added 400 ml of methanol followed by 67 grams (1.14 moles) of 85% hydrazine hydrate. The temperature of the solution was adjusted to 10°C with a water bath. The methanol solution of the intermediate was added to the stirred hydrazine solution dropwise over 15 minutes while controlling the temperature at 10-20°C. After the addition was completed, the reaction mixture was stirred an additional 20 minutes at room temperature and then warmed to 60-65°C to dissolve the product in the methanol. The warm solution was stirred 5 minutes at 60-65°C and then filtered warm to remove any insoluble oxalic acid dihydrazide. The filtrate was cooled with stirring to 0°C to crystallize the product. The crystallized product was filtered, washed with hexane, refiltered, and dried overnight in a vacuum oven at 65°C. The dry product weighed 218.5 grams and assayed 98%. Example IV Preparation of N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminoadipamide Method A Adipoyl chloride monomethyl ester was prepared from adipic acid monomethyl ester and thionyl chloride. Into a 3-neck 500 ml round bottom flask was weighed 34.4 grams (0.22 mole) of 4-amino-2,2,6,6-tetramethylpiperidine. The amine was diluted with 200 ml methylene chloride; the flask was equipped as in Example I. The dropping funnel contained 17.9 grams (0.1 mole) of adipoyl chloride monomethyl ester. The acid chloride was added to the stirring amine solution over 10 minutes while holding the temperature below 20°C with an ice-water bath. The reaction flask was stirred an additional 30 minutes at room temperature and then the contents in the flask were added to a solution of 10.6 grams (0.1 mole) of sodium carbonate in 200 ml of water. The mixture was stirred for 5 minutes and then was transferred to a separatory funnel. The methylene chloride layer was separated, washed with 200 ml of water, dried over anhydrous sodium sulfate, and filtered; the methylene chloride was stripped off on a rotating evaporator under reduced pressure. The residue was a light yellow viscous liquid weighing 25.5 grams. An infrared spectrum of the intermediate product showed an NH band at 3300 cm -1 , strong carbonyl bands at 1740 cm -1 (ester) and 1650 cm -1 (amide), and an amide band at 1560 cm -1 . The residue was dissolved in 200 ml of methanol and transferred to a 500 ml 3-neck flask equipped with a thermometer, magnetic stirrer, reflux condenser, and dropping funnel containing 15.2 grams (0.225 mole) of 85% hydrazine hydrate. The hydrazine hydrate was added dropwise over 10 minutes at 27-28°C. The reaction mixture was heated to 50°C in a water bath and stirred 1 hour at 45-50°C. It was then allowed to stand at room temperature over the weekend. A gas chromatographic scan indicated all the intermediate adipamate had reacted. The reaction mixture was transferred to a round bottom flask and the methanol, water, and excess hydrazine were stripped off on a rotating evaporator leaving a white solid. The solid was slurried in hexane, filtered, and air dried. The product weighed 23.65 grams and had a melting point of 170-173°C. The infrared spectra of the product (nujol mull) showed NH bands at 3240 cm -1 , strong carbonyls at 1600 cm -1 , and an amide band at 1550 cm -1 . The ester band at 1740 cm -1 had completely disappeared. In chloroform solution the infrared spectra showed NH bands at 3240 cm -1 , 3340 cm -1 , and 3440 cm -1 , a strong carbonyl band at 1650 cm -1 , and an amide band 1510 cm -1 . Method B Into a 50 ml 3-neck flask were weighed 17.4 grams (0.1 mole) of dimethyl adipate and 15.6 grams (0.1 mole) of 4-amino-2,2,6,6-tetramethylpiperidine. The flask was equipped with a magnetic stirring bar, thermometer, Dean-Stark trap, and reflux condenser. The flask was placed in an oil bath and heated to 166°C over 1-1/2 hours and heated an additional 4 hours with the temperature rising to 173°C; 3.0 ml of methanol formed in the Dean-Stark trap. The reaction was cooled to room temperature and analyzed by gas chromatography and liquid chromatography. The semi-solid product was a mixture of the starting dimethyl adipate, the desired methyl N-(2,2,6,6-tetramethyl-4-piperidinyl)adipamate and N,N′-di(2,2,6,6-tetramethyl-4-piperidinyl)adipamide. The 4-amino-2,2,6,6-tetramethylpiperidene had completely reacted. The semi-solid mixture was slurried in 100 ml of methyl t-butyl ether and filtered to remove the diamide impurity (8.9 g). The filtrate was stripped on a rotating evaporator to remove the methyl t-butyl ether. The residue was a yellow viscous liquid (13.6 g). Gas chromatography indicated it was a mixture of approximately 70% of the desired adipamate and 25-30% dimethyl adipate. Into a 100 ml 3-neck flask were added the crude mixture of the methyl N-(2,2,6,6-tetramethyl-4-piperidinyl)adipamate and dimethyl adipate and 50 ml of methanol. The flask was equipped with a magnetic stirrer, thermometer, reflux condenser and addition funnel containing 4.5 g (0.077 mole) of 85% hydrazine hydrate. The hydrazine hydrate was added dropwise over 5 minutes and the reaction mixture was stirred an additional 1-1/2 hours at room temperature, heated to reflux, and refluxed 11 hours at 68°C filtered hot. The filtrate was cooled to room temperature and refiltered. The combined filter cake after drying weighed 2.8 grams and was primarily adipic acid dihydrazide. The filtrate was stripped on a rotating evaporator leaving 8.5 grams of a cream colored solid. The product contained approximately 1.4% residual adipic acid dihydrazide. An infrared scan of the product (chloroform solution) showed a sharp NH band at 3440 cm -1 and a broad NH band at 3300 cm -1 , a very strong carbonyl band at 1650 cm -1 , and an amide band at 1510 cm -1 . A wet method assay indicated the product was 80% N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminooxamide. Example V Preparation of N-(2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminoazelamide Method A Azelaoyl chloride monomethyl ester was prepared from azelaic acid monomethyl ester and thionyl chloride. Methyl N-(2,2,6,6-tetramethyl-4-piperidinyl)azelamate was prepared in the same manner as the preparation of methyl N- (2,2,6,6-tetramethyl-4-piperidinyl)adipamate (Example IV) except 23.16 grams (0.1 mole) of azelaoyl chloride monomethyl ester was substituted for the adipoyl chloride monomethyl ester used in Example IV. The product was a light yellow viscous liquid weighing 32.1 grams. An infrared spectrum of the intermediate product showed an NH band at 3300 cm -1 , a strong carbonyl band at 1760 cm -1 (ester), a strong broad carbonyl band at 1640-1660 cm -1 , and an amide band at 1550 cm -1 . The intermediate product was dissolved in 200 ml methanol and treated with 15.2 grams (0.225 mole) of 85% hydrazine hydrate as in Example IV. After stirring for two days at room temperature, a gas chromatographic scan indicated that all of the azelamate had reacted. The reaction mixture was transferred to a 500 ml round bottom flask and the methanol, water, and excess hydrazine hydrate were stripped off. The residue was a pasty solid. It was slurried in methylene chloride and the solids were filtered off. The solids were transferred to a flask to strip off any residual methylene chloride. The flask was heated with a heat gun and the solids were melted and resolidified upon cooling. The product was a sticky solid which weighed 24.7 grams. The infrared spectra of the product (chloroform solution) showed an NH band at 3300 cm -1 , a strong carbonyl band centered at 1640 cm -1 , and an amide band at 1520-1540 cm -1 . The ester band at 1760 cm -1 had completely disappeared. Example VI Preparation of N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-N′-aminooxamide Methyl N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate was prepared from diethyloxalate and 4-amino-2,2,6,6-tetramethylpiperidine according to the first step in Example IIIB. The ethyl ester undergoes ester interchange in methanol to form the methyl ester. Into a 125 ml 3-neck flask was added 18.2 grams (0.075 mole) of methyl N-(2,2,6,6-tetramethyl-4-piperidinyl)oxamate, 75 ml of methylene chloride and 8.1 grams (0.08 mole) of triethylamine. The flask was equipped with a magnetic stirrer, thermometer, reflux condenser, and addition funnel containing 5.9 grams (0.075 mole) of acetyl chloride in 10 ml of methylene chloride. The solution in the flask was cooled to 7°C in an ice bath and the acetyl chloride solution was added dropwise while holding the temperature at 7-9°C. The addition was exothermic and white solids formed during the addition. The reaction mixture was stirred 1 hour at 5-15°C. Gas chromatography indicated that the starting material had disappeared and a new higher boiling material had formed. The reaction mixture was stirred into 100 ml of saturated sodium bicarbonate solution. The dark methylene chloride layer was separated and washed with an additional 50 ml of saturated sodium bicarbonate solution. The methylene chloride layer was separated, dried over anhydrous sodium sulfate, filtered, and stripped off on a rotating evaporator. The brown residue (14.5 grams) was slurried in methyl t-butyl ether and filtered. The tan filter cake was air dried and weighed 11.5 grams. The product had a melting point of 125-129°C. An infrared scan (chloroform solution) contained strong carbonyl bands at 1675 cm -1 , 1600 cm -1 , and 1495 cm -1 , a weak carbonyl band at 1715 cm -1 , and a weak shoulder at 1745 cm -1 . Into a 100 ml 3-neck flask was weighed 8.0 grams (0.028 mole) of methyl N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-oxamate (prepared above); 50 ml of methanol was added. The flask was equipped with a magnetic stirrer, thermometer, reflux condenser, and a dropping funnel containing 1.7 ml of (0.029 mole) of 85% hydrazine hydrate. The 85% hydrazine hydrate was added dropwise to the stirring slurry of the acetylated oxamate. The reaction temperature rose from 20 to 26°C during the addition. The reaction was stirred for an additional hour at room temperature. A gas chromatographic scan taken 45 minutes into the stir period indicated that all of the starting oxamate had reacted to form the hydrazide. The reaction slurry was filtered and the white filter cake was air dried. A gas chromatographic scan of a methylene chloride solution of the product indicated the complete absence of the starting oxamate and the presence of a new higher boiling peak. A liquid chromatographic scan showed the presence of a single component. An infrared scan of the product in chloroform solution had strong carbonyl bands at 1660 cm -1 , 1610 cm -1 , and 1490 cm -1 . The dried product weighed 5.0 grams (m.p. 126-129°C).

Claims: Claims for the following Contracting States : BE, CH, DE, FR, GB, IT, LI, NL, SE A compound of the formula wherein: R is selected from hydrogen, oxyl, hydroxyl, alkyl of 1 to 20 carbons, alkenyl or alkynyl of 3 to 8 carbons, aralkyl of 7 to 12 carbons, aliphatic acyl of 1 to 10 carbons, aromatic acyl of 7 to 13 carbons, alkoxycarbonyl of 2 to 9 carbons, aryloxycarbonyl of 7 to 15 carbons, alkyl, aryl, cycloalkyl or aralkyl substituted carbamoyl of 2 to 13 carbons, 2-cyanoethyl, hydroxyalkyl of 1 to 6 carbons, epoxyalkyl of 3 to 10 carbons, or a polyalkylene oxide of 4 to 30 carbons, R 1 is selected from hydrogen or lower alkyl of 1 to 4 carbons, R 2 is selected from hydrogen, alkyl of 1 to 10 carbons, cycloalkyl of 5 to 12 carbons, aralkyl of 7 to 12 carbons, aryl of 6 to 12 carbons, 2-cyanoethyl, or a radical of the formula R 3 is selected from a direct bond, alkylene or branched alkylene diradical of 1 to 14 carbons, alkenylene diradical of 2 to 10 carbons, an oxydialkylene or thiodialkylene diradical of 4 to 10 carbons or o-, m- or p-phenylene or substituted phenylene diradical where the substituent may be C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxy, bromine, chlorine, mercapto, or C 1 -C 4 alkyl mercapto, and R 4 is selected from hydrogen, a primary or secondary alkyl group of 1 to 8 carbons, an aralkyl group of 7 to 12 carbons, or a cycloalkyl group of 5 to 12 carbons. The compound of claim 1 where R is selected from hydrogen, alkyl of 1 to 4 carbons, alkenyl of 3 carbons, benzyl, 2-cyanoethyl, or acetyl, R 1 is selected from hydrogen or methyl, R 2 is selected from hydrogen, alkyl of 1 to 4 carbons, or 2,2,6,6-tetramethyl-4-piperidinyl, R 3 is selected from a direct bond, an alkylene diradical of 1 to 8 carbons, or an o-, m- or p-phenylene diradical, and R 4 is selected from hydrogen, primary or secondary alkyl of 1 to 4 carbons, benzyl, or cyclohexyl. The compound of claim 2 where R is selected from hydrogen, methyl, or acetyl, R 1 is hydrogen, R 2 is selected from hydrogen or 2,2,6,6-tetramethyl-4-piperidinyl, R 3 is selected from a direct bond or a 1,2 ethylene diradical, and R 4 is hydrogen or methyl. The compound of claim 3 where R, R 1 , R 2 and R 4 are hydrogen and R 3 is a direct bond or an alkylene diradical of 1-8 carbons, especially a 1,2-ethylene diradical. The compound of claim 3 where R 1 , R 2 and R 4 are hydrogen, R is methyl or acetyl and R 3 is a direct bond. A process for preparing the compound of claim 1 by (1) reacting an amine of the formula with a mono ester acid chloride of the formula in an inert solvent such as a hydrocarbon, chlorinated hydrocarbon or ether solvent, and then (2) reacting the intermediate half ester-half amide with a hydrazine of the formula R 4 -NH-NH 2 in a polar solvent and isolating the compound of claim 1 by crystallization from the polar solvent or by evaporation of the solvent where R, R 1 , R 2 , R 3 , and R 4 are as previously defined in claim 1 and R 5 is lower alkyl of 1 to 6 carbons or phenyl. The process of claim 6 where R, R 1 , R 2 , R 3 and R 4 are as previously defined in claim 2, R 5 is methyl or ethyl, the solvent in step (1) is a hydrocarbon or chlorinated hydrocarbon solvent and the solvent in step (2) is a low molecular weight alcohol or glycol. The process of claim 7 where R 1 , R 2 , R 3 and R 4 are as previously defined in claim 3 and R 5 is methyl or ethyl. The process of claim 7 where the amine is 4-amino-2,2, 6,6-tetramethylpiperidine, the mono ester acid chloride is ethyl oxalyl chloride or ethyl succinyl chloride, the hydrazine is 85% hydrazine hydrate, the solvent in step (1) is methylene chloride and the solvent in step (2) is methanol. A process for the preparation of the compound of claim 1 having structure where R, R 1 ,R 2 and R 4 are as previously defined in claim 1 and R 6 is a direct bond, an alkylene or branched alkylene diradical of one carbon or 3 to 14 carbons, an oxydialkylene or thiodialkylene diradical of 4 to 10 carbons or an o-, m- or p-phenylene or substituted phenylene diradical where the substituents may be C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxy, bromine, chlorine, mercapto or C 1 -C 4 alkylmercapto, by (1) reacting an amine of formula with a dialkyl or diphenyl diester of formula either neat or in the presence of a polar solvent to form an intermediate half ester-half amide of formula and then (2) reacting the intermediate with a hydrazine of formula R 4 NH-NH 2 and isolating a product of formula by crystallization from the solvent or by evaporation of the solvent where R, R 1 , R 2 , R 4 and R 6 are as previously defined and R 5 is as defined in claim 6. The process of claim 10 where the amine is reacted with a dialkyl or diphenyl oxalate where R 6 is a direct bond, neat or in a polar solvent and then reacting the intermediate half-ester half-amide where R 6 is a direct bond with a hydrazine in a polar solvent and isolating the compound of claim 1 where R 3 is a direct bond by crystallization from the solvent or by evaporation of the solvent. The process of claim 10 where the amine is 4-amino-2,2,6,6-tetramethylpiperidine, the diester is dimethyl adipate, the hydrazine is hydrazine hydrate and step (1) is run neat and the hydrazinolysis is run in methanol, ethanol, propanol or isopropanol. A process of claim 11 where the amine is 4-amino-2,2,6,6-tetramethylpiperidine or bis-(2,2,6,6-tetramethyl-4-piperidinyl)amine, the oxalate diester is dimethyl or diethyl oxalate, the hydrazine is 85% hydrazine hydrate and the solvent is methanol, ethanol, propanol or isopropanol. A process of claim 11 where the amine is 4-amino-2,2,6,6-tetramethylpiperidine, the oxalate diester is dimethyl or diethyl oxalate, the solvent is excess oxalate diester, the excess oxalate diester is removed and replaced with methanol or ethanol before reacting the intermediate with a hydrazine which is 85% hydrazine hydrate. The use of a compound of any one of claims 1 to 5 for stabilizing polymers and copolymers. Claims for the following Contracting State : ES A process for preparing a compound of the formula wherein: R is selected from hydrogen, oxyl, hydroxyl, alkyl of 1 to 20 carbons, alkenyl or alkynyl of 3 to 8 carbons, aralkyl of 7 to 12 carbons, aliphatic acyl of 1 to 10 carbons, aromatic acyl of 7 to 13 carbons, alkoxycarbonyl of 2 to 9 carbons, aryloxycarbonyl of 7 to 15 carbons, alkyl, aryl, cycloalkyl or aralkyl substituted carbamoyl of 2 to 13 carbons, 2-cyanoethyl, hydroxyalkyl of 1 to 6 carbons, epoxyalkyl of 3 to 10 carbons, or a polyalkylene oxide of 4 to 30 carbons, R 1 is selected from hydrogen or lower alkyl of 1 to 4 carbons, R 2 is selected from hydrogen, alkyl of 1 to 10 carbons, cycloalkyl of 5 to 12 carbons, aralkyl of 7 to 12 carbons, aryl of 6 to 12 carbons, 2-cyanoethyl, or a radical of the formula R 3 is selected from a direct bond, alkylene or branched alkylene diradical of 1 to 14 carbons, alkenylene diradical of 2 to 10 carbons, an oxydialkylene or thiodialkylene diradical of 4 to 10 carbons or o-, m- or p-phenylene or substituted phenylene diradical where the substituent may be C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxy, bromine, chlorine, mercapto, or C 1 -C 4 alkyl mercapto, and R 4 is selected from hydrogen, a primary or secondary alkyl group of 1 to 8 carbons, an aralkyl group of 7 to 12 carbons, or a cycloalkyl group of 5 to 12 carbons, by (1) reacting an amine of the formula with a mono ester acid chloride of the formula in an inert solvent such as a hydrocarbon, chlorinated hydrocarbon or ether solvent, and then (2) reacting the intermediate half ester-half amide with a hydrazine of the formula R 4 -NH-NH 2 in a polar solvent and isolating the compound by crystallization from the polar solvent or by evaporation of the solvent where R, R 1 , R 2 , R 3 and R 4 are as previously defined and R 5 is lower alkyl of 1 to 6 carbons or phenyl. The process of claim 1 where R is selected from hydrogen, alkyl of 1 to 4 carbons, alkenyl of 3 carbons, benzyl, 2-cyanoethyl, or acetyl, R 1 is selected from hydrogen or methyl, R 2 is selected from hydrogen, alkyl of 1 to 4 carbons, or 2,2,6,6-tetramethyl-4-piperidinyl, R 3 is selected from a direct bond, an alkylene diradical of 1 to 8 carbons, or an o-, m- or p-phenylene diradical, and R 4 is selected from hydrogen, primary or secondary alkyl of 1 to 4 carbons, benzyl, or cyclohexyl, and R 5 is methyl or ethyl, the solvent in step (1) is a hydrocarbon or chlorinated hydrocarbon solvent and the solvent in step (2) is a low molecular weight alcohol or glycol. The process of claim 2 where R is selected from hydrogen, methyl, or acetyl, R 1 is hydrogen, R 2 is selected from hydrogen or 2,2,6,6-tetramethyl-4-piperidinyl, R 3 is selected from a direct bond or a 1,2-ethylene diradical, and R 4 is hydrogen or methyl, and R 5 is methyl or ethyl. The process of claim 3 where R, R 1 , R 2 , and R 4 are hydrogen, R 3 is a direct bond or an alkylene diradical of 1 to 8 carbons, especially a 1,2-ethylene diradical, R 5 is ethyl and the hydrazine is 85% hydrazine hydrate, the solvent in step (1) is methylene chloride and the solvent in step (2) is methanol. The process of claim 3 where R 1 , R 2 and R 4 are hydrogen, R is methyl or acetyl and R 3 is a direct bond. A process of claim 1 for the preparation of a compound having structure where R, R 1 , R 2 and R 4 are as previously defined in claim 1 and R 6 is a direct bond, an alkylene or branched alkylene diradical of one carbon or 3 to 14 carbons, an oxydialkylene or thiodialkylene diradical of 4 to 10 carbons or an o-, m- or p-phenylene or substituted phenylene diradical where the substituents may be C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxy, bromine, chlorine, mercapto or C 1 -C 4 alkylmercapto, by (1) reacting an amine of formula with a dialkyl or diphenyl diester of formula either neat or in the presence of a polar solvent to form an intermediate half ester-half amide of formula and then (2) reacting the intermediate with a hydrazine of formula R 4 NH-NH 2 and isolating a product of formula by crystallization from the solvent or by evaporation of the solvent where R, R 1 , R 2 , R 4 and R 6 are as previously defined and R is as defined in claim 1. The process of claim 6 where the amine is reacted with a dialkyl or diphenyl oxalate where R 6 is a direct bond, neat or in a polar solvent and then reacting the intermediate half-ester half-amide where R 6 is a direct bond with a hydrazine in a polar solvent and isolating the compound of claim 1 where R 3 is a direct bond by crystallization from the solvent or by evaporation of the solvent. The process of claim 6 where the amine is 4-amino-2,2,6,6-tetramethylpiperidine, the diester is dimethyl adipate, the hydrazine is hydrazine hydrate and step (1) is run neat and the hydrazinolysis is run in methanol, ethanol, propanol or isopropanol. A process of claim 7 where the amine is 4-amino-2,2,6,6-tetramethylpiperidine or bis-(2,2,6,6-tetramethyl-4-piperidinyl)amine, the oxalate diester is dimethyl or diethyl oxalate, the hydrazine is 85% hydrazine hydrate and the solvent is methanol, ethanol, propanol or isopropanol. A process of claim 7 where the amine is 4-amino-2,2,6,6-tetramethylpiperidine, the oxalate diester is dimethyl or diethyl oxalate, the solvent is excess oxalate diester, the excess oxalate diester is removed and replaced with methanol or ethanol before reacting the intermediate with a hydrazine which is 85% hydrazine hydrate. The use of a compound prepared according to the processes of any one of claims 1 to 10 for stabilizing polymers and copolymers.

Inventors: KAZMIERCZAK ROBERT THADDEUS, MACLEAY RONALD EDWARD, KAZMIERCZAK, ROBERT THADDEUS, MACLEAY, RONALD EDWARD
Applicants: ATOCHEM NORTH AMERICA ELF, ELF ATOCHEM NORTH AMERICA, INC.
Application year: 1988
Main classification: C07D211
IPC codes: C07D211, C08K5