USOOS214147A United States Patent (19) 11) Patent Number: 5,214,147 Kazmierczak et al. 45) Date of Patent: May 25, 1993 54 PROCESS FOR PREPARING REACTIVE 4,993,392 3/1991 Cantatore et al. .................. 54.6/190 HINDERED AMNE LIGHT STABILIZERS 5,017,721 5/1991 Messina et al. ..................... S46/244 75 Inventors: Robert T. Kazmierczak; Ronald E. FOREIGN PATENT DOCUMENTS MacLeay, both of Williamsville, 226700 5/1986 Czechoslovakia . N.Y. 22997 1/1981 European Pat. Off. 0022997 1/1981 European Pat. Off. (73) Assignee: Elf Atochem North America, Inc., 54-95649 7/1979 Japan. Philadelphia, Pa. 54-103461 8/1979 Japan. (21) Appl. No.: 805,719 2197318 5/1988 United Kingdom ................ 54.6/190 (22 Filed: Dec. 6, 1991 OTHER PUBLICATIONS Gala et al. Can. Jour. Chem. vol. 60, pp. 710-715 (1982). Related U.S. Application Data "Anionic Polymerization to Cationic Polymerization,' 60 Division of Ser. No. 619,287, Nov. 27, 1990, Pat, No. Encyclopedia of Polymer Science and Engineering, vol. 2, 5,101,033, which is a division of Ser. No. 310,408, Feb. pp. 83, 84 (John Wiley & Sons). 13, 1989, Pat. No. 4,983,738, which is a continuation-in Wilson B. Lutz et al., "New Derivatives of 2,26,6-Tet part of Ser. No. 84,602, Aug. 12, 1987, abandoned. ramethylpiperidine,' pp. 1695-1703 (May 1962). 51) Int. C. ............................................ CO7D 211/30 Primary Examiner-Donald G. Daus 52) U.S.C. .................................... 54.6/190; 546/224; Attorney, Agent, or Firm-Panitch Schwarze Jacobs & 546/244 Nadel 58) Field of Search ................ 54.6/190, 191, 224, 244 (57) ABSTRACT (56) References Cited N-(2,26,6-tetraalkyl-4-piperidinyl)amide-hydrazides of U.S. PATENT DOCUMENTS dicarboxylic acids contain a light stabilizing group, a 3,022,345 2/1962 Szmuszkowicz ..................... 564/15 heat stabilizing group, and a reactive hydrazide func 3,706,797 12/1972 McKillip et al. ................... 54.6/15 tionality in the same molecule. The reactive stabilizers 3,870,680 3/1975 Schurdak. are prepared by reacting 4-amino-2,2,6,6-tetraalkyl 3,907,803 9/1975 Ramey et al. ......................... S46/6 piperidines with diesters (or mono ester acid chlorides) 4,038,247 7/1977 Muller et al. 4,095,028 6/1978 Hall et al. ............................. 560/44 of dicarboxylic acids or dialkyl itaconates followed by 4,153,596 5/1979 Oertel et al. ........................ 54.6/190 hydrazinolysis of the ester group of the intermediate 4,191,683 3/1980 Brunetti et al. ..................... 546/186 mono esteranide. The compounds are useful for intro 4,223,147 9/1980 Oertel et al. ...... ... S46/190 ducing permanent heat and light stability to coreactive 4,304,714 12/1981 Wheeler et al. ...................... 560/75 polymers or copolymers. They are also useful in the 4,309,546 l/1982 Karret ................................. S46/208 stabilization of inert polymeric systems against the de 4,336,183 6/1982 Nakahara et al. .................... 54.6/19 gradative effects of heat and light when merely mixed 4,348,524 9/1982 Karrer et al. ....................... 54.6/190 with, rather than reacted with, the polymers for which 4,692,486 9/1987 Gugumus ............................ 546/188 stabilization is sought. 4,730,017 3/1988 Avar .............. 524/103 4,801,749 1/1989 Kazmierczak et al. ... S64/158 4,824,884 4/1989 MacLeay et al. ................... S46/244 18 Claims, No Drawings 5,214,147 1. 2 -continued PROCESS FOR PREPARING REACTIVE Me Me N / HNDEREDAMINE LIGHT STABILIZERS C-CH2 O W V CROSS-REFERENCE TO RELATED HN CHCHyrc-NHNH, APPLICATION C-CH2 / N This application is a division of copending application Me Me Chemical Abstracts Registry Number 72436-11-4 Ser. No. 07/619,287 filed Nov. 27, 1990, now U.S. Pat. Japanese Patent 79/103461; CA92:59703 No. 5,101,033 which is a division of copending applica- 10 Japanese Patent 79/95649; CA92:42845j tion Ser. No. 07/310,408 filed Feb. 13, 1989, now U.S. Pat. No. 4,983,738, which is a continuation-in-part of Me Me c-CH O-H-C-NHNH2 copending U.S. patent application Ser. No. 84,602, filed / V / Aug. 12, 1987 now abandoned. 15 HN O V / V BACKGROUND OF THE INVENTION C-CH2 O-CH2 N This invention relates to N-(2,2,6,6-tetraalkyl-4- Me Me Chemical Abstracts Registry Number 77246-76-5 piperidinyl)amide-hydrazides of dicarboxylic acids U.S. Pat. No. 4,336,183; CA92:217369g which contain a hindered amine light stabilizing group 20 European Publ. Patent Appl. 22997; CA94:176176s (photooxidative stabilizer) and a reactive hydrazide group (heat stabilizer). In addition, this invention relates None of these prior art hydrazides fall under general to the stabilization of polymeric systems against the structure I of the present invention. degradative effects of heat and/or light. SUMMARY OF THE INVENTION Polymers such as polyolefins (e.g., polyethylene, 25 This invention is directed to reactive N-(2,26,6-tetr polypropylene, etc.) styrenics (e.g., polystyrene, rubber aalkyl-4-piperidinyl)amidehydrazides having the fol modified polystyrene, ABS, MBS, etc.), polyvinyl chlo lowing formula: ride, polycarbonates, polyesters, polyphenylene ethers, and polyamides, for example, are subject to degradation 30 and discoloration upon exposure to heat and/or light CH3 CH2R1 C-CH-Ri O O with consequent deterioration of their mechanical prop / V erties. R-N, CH-N-C-R-C-N-NH2 V W Various stabilizers have been proposed to inhibit such 35 C-CH2 R2 R4 deterioration. Hindered piperidine compounds have / N found extensive use in the photostabilization of polyole CH3 CHR fins. Hydrazides have been used to prevent deteriora where tion of polyolefins by heat, oxidation, or heavy metal R is hydrogen, oxy, hydroxy, aliphatic of to 20 car contamination. Derivatives of hydrazides are also com bons, araliphatic of 7 to 12 carbons, aliphatic acyl of 2 to mercially available for use as polymer stabilizers. (See 10 carbons, aryl acyl of 7 to 13 carbons, alkoxycarbonyl Encyclopedia of Polymer Science and Engineering, of 2 to 9 carbons, aryloxycarbonyl of 7 to 15 carbons, 2nd Ed. Vol. 2, pp. 83-84). aliphatic aryl, alicyclic or araliphatic substituted car Four examples were found in the literature where the bamoyl of 2 to 13 carbons, 2-cyanoethyl, hydroxyali hindered amine moiety and the hydrazide moiety 45 phatic of 1 to 6 carbons, epoxyaliphatic of 3 to 10 car (-R-C(=O)-NH-NH2, where R is not O, N, or S) bons, or a polyalkylene oxide group of 4 to 30 carbons; R1 is hydrogen or lower alkyl of 1 to 4 carbons; are present in the same molecule. R2 is hydrogen, aliphatic of 1 to 10 carbons, alicyclic of 5 to 12 carbons, araliphatic of 7 to 12 carbons, aryl of M e M e O N / 6 to 12 carbons, 2-cyanoethyl or a radical of the formula C-CH / V / HN C V A N Rl-CH2 CH3 R' C-CH2 OH 55 7 / N C-CH Me Me / V Chemical Abstracts Registry Number 66651-22-7 Re-N CH-; V / U.S. Pat. Nos. 4,153,596 and 4,223,147 C-CH / N Me M e Rl-CH2 CH3 N / C-CH2 R is a direct bond, an alkylene diradical of 1 to 14 HN ah-NHCHCH-C-NHNH, carbons, an alkenylene diradical of 2 to 10 carbons, an C-CH2 oxydialkylene or thiodialkylene diradical of 4 to 10 / N 65 carbons, or a substituted or unsubstituted o-, m- or p Me Me phenylene diradical where the substituents may be Chemical Abstracts Registry Number 66651-23-8 lower alkyl, lower alkoxy, hydroxy, bromo, chloro, U.S. Pat. Nos. 4,53,596 and 4,223,147 mercapto or lower alkylmercapto; 5,214,147 3 4. R2 and R may be linked together to form a 5-mem with coreactive polymers, to stabilize the polymers bered lactam ring; and against the degradative effects of light and heat. R is hydrogen, a primary or secondary aliphatic of 1 Non-limiting examples of reactive hindered amine to 8 carbons, an araliphatic of 7 to 12 carbons or alicyc light and heat stabilizers of this invention, which may lic of 5 to 12 carbons. also be used for light and heat stabilization of inert As used herein, the term "acy' refers to a radical polymers, include the following non-limiting list of generated from a carboxylic acid by removal of the OH hydrazides: group to provide a free valence on the C(=O) group, (1) N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-N'- for example DC(=O) -OH would become the aminooxamide, DC(=O)- substituent, referred to generally as a D 10 (2) N-(1-benzoyl-2,26,6-tetramethyl-4-piperidinyl)-N'- acyl group. aninooxamide, Preferably, R, when aliphatic, is alkyl of 1 to 20 car (3) N-(1-allyl-2,26,6-tetramethyl-4-piperidinyl)-N'- bons, alkenyl of 3 to 8 carbons or alkynyl of 3 to 8 aminooxamide, carbons; when araliphatic, is aralkyl of 7 to 12 carbons; (4) N-(1-benzyl-2,26,6-tetramethyl-4-piperidinyl)-N'- the aliphatic, alicyclic and araliphatic substituents for 15 aminooxamide, the carbamoyl of 2 to 13 carbons preferably are alkyl, (5) N-(1-ethoxycarbonyl-2,2,6,6-tetramethyl-4- cycloalkyl and aralkyl, respectively; the hydroxy ali piperidinyl)-N'-aminooxamide, phatic group preferably is hydroxy alkyl of 1 to 6 car (6) N-(1-dodecyl-2,6-diethyl-2,3,6-trimethyl-4- bons; and the epoxy aliphatic group preferably is epoxy piperidinyl)-N'-aminooxanide, 20 (7) N-(2,26,6-tetramethyl-4-piperidinyl)-N-butyl-N'- alkyl of 3 to 10 carbons.