USRE30385E - Light and heat stabilizers for polyolefins - Google Patents

Light and heat stabilizers for polyolefins Download PDF

Info

Publication number
USRE30385E
USRE30385E US06/057,786 US5778679A USRE30385E US RE30385 E USRE30385 E US RE30385E US 5778679 A US5778679 A US 5778679A US RE30385 E USRE30385 E US RE30385E
Authority
US
United States
Prior art keywords
hydrogen
tetramethylpiperidine
carboxylate
compound
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/057,786
Inventor
Ray L. Hillard
William B. Hardy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wyeth Holdings LLC
Original Assignee
American Cyanamid Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by American Cyanamid Co filed Critical American Cyanamid Co
Priority to US06/057,786 priority Critical patent/USRE30385E/en
Application granted granted Critical
Publication of USRE30385E publication Critical patent/USRE30385E/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/60—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D211/62—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines

Definitions

  • This invention relates to esters of 2,2,6,6-tetramethylpiperidine-4-carboxylic acid, and more particularly to esters represented by formula (I): ##STR2## where R is hydrogen or alkyl (C 1 -C 8 ); R' is hydrogen, hydroxyl or alkoxy (C 1 -C 8 ); R" is alkyl (C 1 -C 20 ), alkylene (C 2 -C 12 ), cycloalkyl, wherein the cycloaliphatic ring contains 5- or 6-carbon atoms, cycloalkylene, wherein the cycloaliphatic ring may contain lower alkyl substituents, arylene, aralkylene and alkenyl (C 3 -C 20 ); n is an integer from 1 to 4.
  • the invention also relates to the use of these esters as stabilizers against photo- and thermal degradation, particularly against degradation induced by UV light, of synthetic polymers, especially polyolefins.
  • the invention further relates to polymer compositions stabilized by the incorporation therein of said esters.
  • Stabilizers for synthetic and naturally occurring polymers including UV stabilizers
  • UV stabilizers have been the subject of continuing investigation for many years, and numerous compounds have been suggested for such purpose.
  • Recent patent literature has described a considerable number of stabilizer compounds which are derivatives of hindered amines of the type: ##STR3## wherein R 1 and R 2 may be the same or different and represent an alkyl of 1 to 4 carbon atoms. Of particular interest is 2,2,6,6-tetramethylpiperidine and its derivatives.
  • esters of formula (I) provide superior stabilizing properties against photodegradation of synthetic polymers, particularly polypropylene, as compared with the esters of formula (II).
  • esters of 2,2,6,6-tetramethylpiperidine-4-carboxylic acid are superior to esters of 2,2,6,6-tetramethyl-4-hydroxypiperidine, as represented by (II).
  • R" is a monovalent aliphatic or cycloaliphatic radical derived from an aliphatic or cycloaliphatic alcohol.
  • Representative alcohols include methanol, ethanol, n-propanol, ispropanol, n-butanol, sec. butanol, tert.
  • butanol amyl alcohol, isoamyl alcohol, neopentyl alcohol, n-hexanol, n-octanol, 2-ethylhexyl alcohol, n-decyl alcohol, n-dodecyl alcohol, stearyl alcohol, eicosanol, and the like; cyclopentanol, cyclohexanol, methyl cyclohexanol, and the like.
  • R" is a divalent alkylene, cycloalkylene, arylene or aralkylene radical derived from an alkanediol, cycloalkanediol, dihydric phenol or aralkylene diol.
  • diols ethylene glycol, 1,2- and 1,3-propane diol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, cyclopentanediol, 1,4-cyclohexanediol, 1,4-cyclohexane dimethanol, 1,4-cyclohexanediethanol, and the like; hydroquinone, ⁇ , ⁇ -xylylene glycol, and the like.
  • R radicals derived from diols containing a heteroatom in the chain, such as thiodiethanol, diethanolamine, and diethylene glycol.
  • R" is a trivalent or tetravalent aliphatic radial derived from an aliphatic polyol.
  • polyols are glycerol, trimethylolpropane, pentaerythritol, and the like,
  • synthetic polymer is intended to include polyolefins, and particularly poly- ⁇ -olefins, such as polyethylene, polypropylene, polybutylene and copolymers thereof, for example, ethylenepropylene copolymer. Also intended are polyolefins such as polystyrene, polybutadiene, polyisoprene, and the like, and copolymers, such as ethylene-vinylacetate copolymers, styrene-butadiene copolymers, acrylonitrile-butadienestyrene polymers (ABS plastics), and the like. The invention is particularly directed to the stabilization of polypropylene.
  • polyolefins such as polystyrene, polybutadiene, polyisoprene, and the like
  • copolymers such as ethylene-vinylacetate copolymers, styrene-butadiene copolymers, acrylonitrile-butadienestyren
  • the compounds of formula (I) may be prepared readily by conventional esterification of the carboxylic acid (III): ##STR5##
  • the carboxylic acid (III) may be obtained in accordance with procedures similar to those described by Sadyky-Zade et al, Zh, Organ. Khim. 9, 1841-44 (1973), U.S. Pat. No. 3,274,227, or Weizmann et al, J. Am. Chem. Soc. 70, 1153-58 (1948), whereby 2,2,6,6-tetramethylpiperidin-4-one (IV) is reacted with chloroform in the presence of a base to form the corresponding 4-trichloromethyl-4-hydroxy derivative (V) followed by hydrolysis of (V) in the presence of water or an alcohol, such as methanol, to give the carboxylic acid (III), where R' is hydroxyl or alkoxy. ##STR6##
  • the intermediate carboxylic acid (III), wherein R' is hydrogen may be prepared in accordance with procedures similar to those described by Simchen et al in Synthesis, 1975, No. 9, pages 605-607, whereby the 4-bromo compound (VI) is reacted with a tetraalkylammonium cyanide, such as tetraethylammonium cyanide, in a suitable solvent, such as dichloromethane, acetonitrile or dimethyl sulfoxide, followed by hydrolysis of the nitrile (VII).
  • a suitable solvent such as dichloromethane, acetonitrile or dimethyl sulfoxide
  • the 4-bromo compound (VI) is readily obtained by reaction of 2,2,6,6-tetramethylpiperidin-4-ol (VIII) with conc. hydrobromic acid to form the 4-bromo hydrobromide salt (IX), which is then neutralized with a base, e.g. sodium carbonate.
  • a base e.g. sodium carbonate.
  • Compound (III) wherein R' is hydroxyl may also be prepared in accordance with procedures similar to those described by Nazarov et al, J. Gen. Chem. U.S.S.R. (English) 26, 3877-3889 (1956) whereby the ketone (IV) is reacted with potassium cyanide in the presence of an acid to produce the corresponding cyanohydrin (X) which may then be hydrolyzed to the hydroxy acid.
  • ester derivatives of this invention are listed below. It is, however, to be understood that the invention is not limited thereto.
  • the compounds of the invention may be incorporated into the polymer substrate by any of the various standard procedures used in the art, at any stage prior to the manufacture of shaped articles therefrom, including filaments, fibre, yarn, film, sheet, other molded articles, and the like.
  • the mixing, extrusion, etc. or a suspension or emulsion of the stabilizer may be mixed with a suspension or emulsion of the polymer, and the like.
  • esters of formula (I) which may be incorporated into the polymer may vary widely depending on the type, properties and particular uses of the polymer to be stabilized. In general, they may be added in amounts ranging from about 0.01 to 5% by weight based on the polymer, preferably about 0.01 to 2% by weight, and preferably 0.01 to 1% by weight in polyolefins.
  • the compounds may be used alone or in combination with other known stabilizers, fillers, or other compounding ingredients commonly used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Compounds of the formula: ##STR1## wherein R is hydrogen or alkyl (C1 -C8), R' is hydrogen, hydroxyl or lower alkoxy (C1 -C8); R" is alkyl (C1 -C20), alkylene (C2 -C12), cycloalkyl, wherein the alicyclic ring contains 5- or 6-carbon atoms, cycloalkylene, wherein the alicyclic ring may contain lower alkyl substituents, alkenyl (C3 -C20), arylene or aralkylene; n is an integer from 1 to 4, are useful for stabilizing polyolefin polymer against photo and thermal degradation.

Description

This is a reissue of U.S. Pat. No. 4,064,102, dated Dec. 20, 1977. .Iaddend.
This invention relates to esters of 2,2,6,6-tetramethylpiperidine-4-carboxylic acid, and more particularly to esters represented by formula (I): ##STR2## where R is hydrogen or alkyl (C1 -C8); R' is hydrogen, hydroxyl or alkoxy (C1 -C8); R" is alkyl (C1 -C20), alkylene (C2 -C12), cycloalkyl, wherein the cycloaliphatic ring contains 5- or 6-carbon atoms, cycloalkylene, wherein the cycloaliphatic ring may contain lower alkyl substituents, arylene, aralkylene and alkenyl (C3 -C20); n is an integer from 1 to 4.
The invention also relates to the use of these esters as stabilizers against photo- and thermal degradation, particularly against degradation induced by UV light, of synthetic polymers, especially polyolefins. The invention further relates to polymer compositions stabilized by the incorporation therein of said esters.
Stabilizers for synthetic and naturally occurring polymers, including UV stabilizers, have been the subject of continuing investigation for many years, and numerous compounds have been suggested for such purpose. Recent patent literature has described a considerable number of stabilizer compounds which are derivatives of hindered amines of the type: ##STR3## wherein R1 and R2 may be the same or different and represent an alkyl of 1 to 4 carbon atoms. Of particular interest is 2,2,6,6-tetramethylpiperidine and its derivatives.
U.S. Pat. No. 3,640,928 (Murayama to Sankyo Company, Ltd.) particularly describe esters, and their use in stabilizing polymers, of the type represented by formula (II): ##STR4## wherein R1 and R2 are as defined above; R3 is an acyl, diacyl or triacyl group derived from aliphatic, alicyclic or heterocyclic mono-, di- or tricarboxylic acids; n is 1 to 3.
We have now discovered, quite unexpectedly, that esters of formula (I) provide superior stabilizing properties against photodegradation of synthetic polymers, particularly polypropylene, as compared with the esters of formula (II).
It is surprising and unexpected that esters of 2,2,6,6-tetramethylpiperidine-4-carboxylic acid, as represented by (I), are superior to esters of 2,2,6,6-tetramethyl-4-hydroxypiperidine, as represented by (II).
In the above formula (I), when n is 1, R" is a monovalent aliphatic or cycloaliphatic radical derived from an aliphatic or cycloaliphatic alcohol. Representative alcohols include methanol, ethanol, n-propanol, ispropanol, n-butanol, sec. butanol, tert. butanol, amyl alcohol, isoamyl alcohol, neopentyl alcohol, n-hexanol, n-octanol, 2-ethylhexyl alcohol, n-decyl alcohol, n-dodecyl alcohol, stearyl alcohol, eicosanol, and the like; cyclopentanol, cyclohexanol, methyl cyclohexanol, and the like.
When n is 2, R" is a divalent alkylene, cycloalkylene, arylene or aralkylene radical derived from an alkanediol, cycloalkanediol, dihydric phenol or aralkylene diol. Representative of such diols are ethylene glycol, 1,2- and 1,3-propane diol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, cyclopentanediol, 1,4-cyclohexanediol, 1,4-cyclohexane dimethanol, 1,4-cyclohexanediethanol, and the like; hydroquinone, α,α-xylylene glycol, and the like. Also included within the definition of R" are radicals derived from diols containing a heteroatom in the chain, such as thiodiethanol, diethanolamine, and diethylene glycol.
When n is 3 or 4, R" is a trivalent or tetravalent aliphatic radial derived from an aliphatic polyol. Representative of such polyols are glycerol, trimethylolpropane, pentaerythritol, and the like,
The term "synthetic polymer", as used herein is intended to include polyolefins, and particularly poly-α-olefins, such as polyethylene, polypropylene, polybutylene and copolymers thereof, for example, ethylenepropylene copolymer. Also intended are polyolefins such as polystyrene, polybutadiene, polyisoprene, and the like, and copolymers, such as ethylene-vinylacetate copolymers, styrene-butadiene copolymers, acrylonitrile-butadienestyrene polymers (ABS plastics), and the like. The invention is particularly directed to the stabilization of polypropylene.
The compounds of formula (I) may be prepared readily by conventional esterification of the carboxylic acid (III): ##STR5##
The carboxylic acid (III) may be obtained in accordance with procedures similar to those described by Sadyky-Zade et al, Zh, Organ. Khim. 9, 1841-44 (1973), U.S. Pat. No. 3,274,227, or Weizmann et al, J. Am. Chem. Soc. 70, 1153-58 (1948), whereby 2,2,6,6-tetramethylpiperidin-4-one (IV) is reacted with chloroform in the presence of a base to form the corresponding 4-trichloromethyl-4-hydroxy derivative (V) followed by hydrolysis of (V) in the presence of water or an alcohol, such as methanol, to give the carboxylic acid (III), where R' is hydroxyl or alkoxy. ##STR6##
The intermediate carboxylic acid (III), wherein R' is hydrogen, may be prepared in accordance with procedures similar to those described by Simchen et al in Synthesis, 1975, No. 9, pages 605-607, whereby the 4-bromo compound (VI) is reacted with a tetraalkylammonium cyanide, such as tetraethylammonium cyanide, in a suitable solvent, such as dichloromethane, acetonitrile or dimethyl sulfoxide, followed by hydrolysis of the nitrile (VII). ##STR7##
The 4-bromo compound (VI) is readily obtained by reaction of 2,2,6,6-tetramethylpiperidin-4-ol (VIII) with conc. hydrobromic acid to form the 4-bromo hydrobromide salt (IX), which is then neutralized with a base, e.g. sodium carbonate. ##STR8##
Compound (III) wherein R' is hydroxyl may also be prepared in accordance with procedures similar to those described by Nazarov et al, J. Gen. Chem. U.S.S.R. (English) 26, 3877-3889 (1956) whereby the ketone (IV) is reacted with potassium cyanide in the presence of an acid to produce the corresponding cyanohydrin (X) which may then be hydrolyzed to the hydroxy acid.
Representative examples of the ester derivatives of this invention are listed below. It is, however, to be understood that the invention is not limited thereto.
1. methyl 2,2,6,6-tetramethylpiperidine-4-carboxylate
2. n-butyl 2,2,6,6-tetramethylpiperidine-4-carboxylate
3. n-octyl 2,2,6,6-tetramethylpiperidine-4-carboxylate
4. stearyl 2,2,6,6-tetramethylpiperidine-4-carboxylate
5. cyclopentyl 2,2,6,6-tetramethylpiperidine-4-carboxylate
6. cyclohexyl 2,2,6,6-tetramethylpiperidine-4-carboxylate
7. 4-methylcyclohexyl 2,2,6,6-tetramethylpiperidine-4-carboxylate
8. allyl 2,2,6,6-tetramethylpiperidine-4-carboxylate
9. ethyl 2,2,6,6-tetramethylpiperidine-4-hydroxy-4-carboxylate
10. n-hexyl 2,2,6,6-tetramethylpiperidine-4-hydroxy-4-carboxylate
11. cyclohexyl 2,2,6,6-tetramethylpiperidine-4-hydroxy-4-carboxylate
12. allyl 2,2,6,6-tetramethylpiperidine-4-hydroxy-4-carboxylate
13. isopropyl 2,2,6,6-tetramethylpiperidine-4-methoxy-4-carboxylate
14. 2-ethylhexyl 2,2,6,6-tetramethylpiperidine-4-ethoxy-4-carboxylate
15. stearyl 2,2,6,6-tetramethylpiperidine-4-butoxy-4-carboxylate
16. cyclohexyl 2,2,6,6-tetramethylpiperidine-4-octyloxy-4-carboxylate
17. 1,2-ethylene 2,2,6,6-tetramethylpiperidine-4-carboxylate
18. 1,4-butylene 2,2,6,6-tetramethylpiperidine-4-carboxylate
19. 1,6-hexamethylene 2,2,6,6-tetramethylpiperidine-4-carboxylate
20. 2-butylene 2,2,6,6-tetramethylpiperidine-4-carboxylate
21. thiodiethylene 2,2,6,6-tetramethylpiperidine-4-carboxylate
22. 1,4-cyclohexylene 2,2,6,6-tetramethylpiperidine-4-hydroxy-4-carboxylate
23. 2-butylene 2,2,6,6-tetramethylpiperidine-4-hydroxy-4-carboxylate
24. iminodiethylene 2,2,6,6-tetramethylpiperidine-4-ethoxy-4-carboxylate
25. oxydiethylene 2,2,6,6-tetramethylpiperidine-4-octyloxy-4-carboxylate
26. 2-ethyl-1,2,3-propanetriyl 2,2,6,6-tetramethylpiperidine-4-carboxylate
27. neopentanetetrayl 2,2,6,6-tetramethylpiperidine-4-hydroxy-4-carboxylate
28. 2-ethyl-1,2,3-propanetriyl 2,2,6,6-tetramethylpiperidine-4-ethoxy-4-carboxylate
29. p-phenylene 2,2,6,6-tetramethylpiperidine-4-carboxylate
30. p-xylylene 2,2,6,6-tetramethylpiperidine-4-carboxylate
31. methyl 1-methyl-2,2,6,6-tetramethylpiperidine-4-carboxylate
32. n-butyl 1-ethyl-2,2,6,6-tetramethylpiperidine-4-hydroxy-4-carboxylate
33. ethyl-1-methyl-2,2,6,6-tetramethylpiperidine-4-methoxy-4-carboxylate
34. p-phenylene 1-methyl-2,2,6,6-tetramethylpiperidine-4-hydroxy-4-carboxylate
35. p-xylylene 1-butyl-2,2,6,6-tetramethylpiperidine-4-methoxy-4-carboxylate, and the like.
The compounds of the invention may be incorporated into the polymer substrate by any of the various standard procedures used in the art, at any stage prior to the manufacture of shaped articles therefrom, including filaments, fibre, yarn, film, sheet, other molded articles, and the like. Thus, the mixing, extrusion, etc. or a suspension or emulsion of the stabilizer may be mixed with a suspension or emulsion of the polymer, and the like.
The amount of the esters of formula (I) which may be incorporated into the polymer may vary widely depending on the type, properties and particular uses of the polymer to be stabilized. In general, they may be added in amounts ranging from about 0.01 to 5% by weight based on the polymer, preferably about 0.01 to 2% by weight, and preferably 0.01 to 1% by weight in polyolefins.
The compounds may be used alone or in combination with other known stabilizers, fillers, or other compounding ingredients commonly used.

Claims (10)

We claim:
1. A compound represented by the formula: ##STR10## wherein R is hydrogen or alkyl (C1 -C8), R' is hydrogen, or lower alkoxy (C1 -C8); R" is alkylene (C2 -C12), cycloalkylene, wherein the alicyclic ring may contain lower alkyl substituents, arylene or aralkylene, n is 2.
2. A compound as defined in claim 1 wherein R' is hydrogen.
3. A compound as defined in claim 1 wherein R' is lower (C1 -C8) alkoxy.
4. A synthetic polyolefin polymer composition stabilized against photo- and thermal degradation comprising an effective stabilizing amount of a compound of claim 1.
5. A composition as defined in claim 4 wherein said polyolefin is polypropylene.
6. A composition as defined in claim 4 wherein said compound is incorporated in an amount of about 0.01 to 5% by weight.
7. A composition as defined in claim 5 wherein said compound is incorporated in an amount of about 0.01 to 2% by weight.
8. A compound as defined in claim 1 wherein R is hydrogen.
9. A compound as defined in claim 1 wherein R" is alkylene (C2 -C12). .Iadd.10. A compound represented by the formula ##STR11##.Iaddend. wherein R is hydrogen or alkyl (C1 -C8), R' is hydrogen or lower alkoxy (C1 -C8); R" is ##STR12##
and n is 2. .Iadd.11. A compound represented by the formula ##STR13## wherein R is hydrogen or alkyl (C1 -C8) R' is hydrogen or lower alkoxy (C1 -C8); R" is ##STR14## and n is 2. .Iaddend.
US06/057,786 1979-07-16 1979-07-16 Light and heat stabilizers for polyolefins Expired - Lifetime USRE30385E (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US06/057,786 USRE30385E (en) 1979-07-16 1979-07-16 Light and heat stabilizers for polyolefins

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US06/057,786 USRE30385E (en) 1979-07-16 1979-07-16 Light and heat stabilizers for polyolefins

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US05/668,156 Reissue US4064102A (en) 1976-03-18 1976-03-18 Light and heat stabilizers for polyolefins

Publications (1)

Publication Number Publication Date
USRE30385E true USRE30385E (en) 1980-08-26

Family

ID=22012759

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/057,786 Expired - Lifetime USRE30385E (en) 1979-07-16 1979-07-16 Light and heat stabilizers for polyolefins

Country Status (1)

Country Link
US (1) USRE30385E (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4369274A (en) 1981-07-20 1983-01-18 American Cyanamid Company Hindered amine light stabilizers for polymers
US6414155B1 (en) 2000-11-03 2002-07-02 Cytec Technology Corp. Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
US6492521B2 (en) 2000-11-03 2002-12-10 Cytec Technology Corp. Hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
US6545156B1 (en) 2000-11-03 2003-04-08 Cytec Technology Corp. Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
US6727300B2 (en) 2000-11-03 2004-04-27 Cytec Technology Corp. Polymeric articles containing hindered amine light stabilizers based on multi-functional carbonyl compounds
US20050004518A1 (en) * 2003-05-05 2005-01-06 Call Evan W. Infusion syringe
US7691922B2 (en) 2004-07-03 2010-04-06 U.S. Borax Inc. Performance enhancement in the stabilization of organic materials
US10184106B2 (en) 2012-06-20 2019-01-22 Genentech, Inc. Methods for viral inactivation and other adventitious agents

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US591483A (en) * 1897-10-12 Coora
US2759942A (en) * 1952-03-05 1956-08-21 Olin Mathieson Substituted piperidinecarboxylates and methods of preparing same
US3534048A (en) * 1966-06-15 1970-10-13 Sankyo Co 2,2-dimethyl-4,4,6,6-tetrasubstituted-piperidine-1-oxide derivatives
US3684803A (en) * 1967-08-11 1972-08-15 Ciba Geigy Corp 1,4,4-substituted piperidine derivatives
US3850877A (en) * 1972-07-28 1974-11-26 Ciba Geigy Corp Piperidine stabilizers for polymers
US3887517A (en) * 1972-10-25 1975-06-03 Sankyo Co Piperidine derivatives and their use as stabilizers
US3929804A (en) * 1972-07-28 1975-12-30 Ciba Geigy Corp 4-Piperidine acetamide compounds
US3959291A (en) * 1973-02-03 1976-05-25 Ciba-Geigy Corporation Piperidine derivatives

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US591483A (en) * 1897-10-12 Coora
US2759942A (en) * 1952-03-05 1956-08-21 Olin Mathieson Substituted piperidinecarboxylates and methods of preparing same
US3534048A (en) * 1966-06-15 1970-10-13 Sankyo Co 2,2-dimethyl-4,4,6,6-tetrasubstituted-piperidine-1-oxide derivatives
US3684803A (en) * 1967-08-11 1972-08-15 Ciba Geigy Corp 1,4,4-substituted piperidine derivatives
US3850877A (en) * 1972-07-28 1974-11-26 Ciba Geigy Corp Piperidine stabilizers for polymers
US3929804A (en) * 1972-07-28 1975-12-30 Ciba Geigy Corp 4-Piperidine acetamide compounds
US3887517A (en) * 1972-10-25 1975-06-03 Sankyo Co Piperidine derivatives and their use as stabilizers
US3959291A (en) * 1973-02-03 1976-05-25 Ciba-Geigy Corporation Piperidine derivatives

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Noller, Chemistry of Organic Compounds, 2nd Edition, 1957, p. 254. *
Sperber et al., J.A.C.S., vol. 81, 1959, pp. 704-709. *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4369274A (en) 1981-07-20 1983-01-18 American Cyanamid Company Hindered amine light stabilizers for polymers
EP0070388A1 (en) * 1981-07-20 1983-01-26 American Cyanamid Company Novel light stabilizers for polymers
US6414155B1 (en) 2000-11-03 2002-07-02 Cytec Technology Corp. Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
US6492521B2 (en) 2000-11-03 2002-12-10 Cytec Technology Corp. Hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
US6545156B1 (en) 2000-11-03 2003-04-08 Cytec Technology Corp. Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
US6696570B2 (en) 2000-11-03 2004-02-24 Cytec Technology Corp. Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
US6727300B2 (en) 2000-11-03 2004-04-27 Cytec Technology Corp. Polymeric articles containing hindered amine light stabilizers based on multi-functional carbonyl compounds
US20050004518A1 (en) * 2003-05-05 2005-01-06 Call Evan W. Infusion syringe
US7691922B2 (en) 2004-07-03 2010-04-06 U.S. Borax Inc. Performance enhancement in the stabilization of organic materials
US10184106B2 (en) 2012-06-20 2019-01-22 Genentech, Inc. Methods for viral inactivation and other adventitious agents

Similar Documents

Publication Publication Date Title
US4064102A (en) Light and heat stabilizers for polyolefins
DE19741777B4 (en) Monomeric bisphosphites as stabilizers for halogen-containing polymers and for lubricants
US4481315A (en) Polyalkylpiperidine light stabilizers
EP0014683B1 (en) Polyalkylpiperidine derivatives of s-triazines, their use as stabilizers for polymers and polymer compositions stabilized with these compounds
JPS6335658B2 (en)
JP2002524646A (en) Weatherproof blend of arylate polymer and polycarbonate
US4255301A (en) Glycol carbonate ester stabilizers for synthetic resins
USRE30385E (en) Light and heat stabilizers for polyolefins
EP0057885B1 (en) Substituted diazaspirodecanes, their preparation and their use for the stabilisation of organic polymers and these stabilised polymers
EP0107805A2 (en) Mixed 2,2,6,6-tetramethyl piperidinyl carboxylic acid ester and amide light stabilizers and stabilized synthetic polymers
EP0070388A1 (en) Novel light stabilizers for polymers
CA1165764A (en) Polymeric light stabilizers containing tetraalkyl piperidine moieties
EP0176604B1 (en) High-molecular piperidine groups contained in esters, process for their preparation, their use as stabilisers for polymers and polymers containing them
AU624456B2 (en) Triazine-based light stabilizers for plastics
US4771091A (en) Substituted diazaoxaspirodecanes, preparation thereof and use thereof as stabilizers for polymers
CA2005233C (en) Melamine-based light stabilizers for plastics
JPS6345417B2 (en)
US4986932A (en) Stabilizer system for polyolefins comprised of monocarboxylic acid esters of a piperidinol and a benzophenone or benzotriazole
US4412020A (en) Novel light stabilizers for polymers
EP0291238A2 (en) Monomeric and oligomeric glutarate-based light stabilisers for plastics
US4757104A (en) Gamma radiation resistant carbonate polymer compositions containing linolenic compounds
CA1287053C (en) Polyalkyl piperidin-4-yl substituted tartrate-derived acetal ester and amide light stabilizers for plastics
JPS62135480A (en) Light stabilizer for plastic based on olygomeric malonate
US4293467A (en) Isopropylidenedicyclohexylene esters and their use as light stabilizers
DE3788958T2 (en) Bis- (2,2,6,6-tetramethyl-piperidyl) diimides and their use as light stabilizers for synthetic polymers.