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
  • C07D211/40—Oxygen atoms
  • C07D211/44—Oxygen atoms attached in position 4
  • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
• • 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
  • C07D211/56—Nitrogen atoms
  • C07D211/58—Nitrogen atoms 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
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
  • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
  • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member

Definitions

• the present invention relates to compounds belonging to the group of enamines. More specifically, the present invention relates to compounds belonging to the group of enamines consisting of derivatives of .-keto-esters, or /3-keto- a ides or 1, 3-diketones with primary or secondary aliphatic or aromatic amines carrying at least one sterically hindered amine group in the molecule, a process for their preparation and their use as a ⁇ tioxi- dants for organic polymers.
• the present invention also relates to the polymeric compositions stabilized with the above compounds and the end-articles obtained from these compositions.
• organic polymers undergo degradation over a period of time as a result of exposure to atmospheric agents and light and they also easily undergo thermoxidative degradation during processing and transformation processes.
• stabilizing compounds are usually introduced into the organic polymers.
• the Applicant has now found that compounds belonging to the group of enamines consisting of derivatives of 3-keto-esters, or 3-keto-amides or 1, 3-diketones with primary or secondary, aliphatic or aromatic amines carrying at least one sterically hindered amine group in the molecule, are capable of stabilizing organic polymers to which they are added improving their resistance to thermo-oxidation.
• the present invention therefore relates to compounds belonging to the group of enamines consisting of derivatives of 3-keto-esters, or 3-keto-amides or 1, 3-diketones with primary or secondary, aliphatic or aromatic amines carrying in the molecule at least one sterically hindered amine group having general formula
• - m represents an integer from 1 to 3 , extremes included;
• - n represents an integer from 1 to 4 , extremes included;
• R 1 represents a triazine having one of the following general formula (II) , (III) or (IV) :
• R j represents a hydrogen atom; a linear or branched ⁇ -C ⁇ alkyl group; a -NHR 6 amine group or a -SR 6 group wherein R 6 represents a hydrogen atom or a linear or branched C.,-C 18 alkyl group; R, and R 2 , the same or different, represent a hydrogen atom; a linear or branched C ⁇ C ⁇ alkyl group; a linear or branched C 2 -C 8 alkoxyalkyl group; a C 5 -C 8 cycloalkyl group optionally containing a heteroatom selected from oxygen, nitrogen and sulfur; a C & -C ⁇ a aryl group; a C 7 -C 20 arylalkyl or alkylaryl group; a group having general formula (V):
• R 7 represents a hydrogen atom; a linear or branched ⁇ -C ⁇ alkyl group, said alkyl group optionally substituted with a -NHR 8 group or an -OR g group wherein R 8 represents a hydrogen atom, a linear or branched C_,-C 18 alkyl group, or a 6 -C a aryl group; an -01 ⁇ group wherein R-, represents a hydrogen atom, or a linear or branched C ⁇ -C ⁇ alkyl group ; or, R 1 and R 2 considered jointly with the nitrogen atom, represent a C 5 -C 8 heterocyclic group optionally containing a second heteratom selected from oxygen, nitrogen and sulfur;
• R 3 and R 4 represent a linear or branched alkyl group; a C 6 -C 18 aryl group; a C 7 -C 20 alkylaryl or arylalkyl group; a linear or branched C ⁇ -C 8 alkoxyl group; or, R 4 represents a group having general formula (VI):
• R 7 has the same meanings defined above; or, R 4 represents an NR 10 R 11 group wherein R 10 and R , the same or different, represent a hydrogen atom; a linear or branched ⁇ -C ⁇ alkyl group; a linear or branched C 2 -C 8 alkoxyalkyl group; a C 5 -C 8 cycloalkyl group optionally containing a heteroatom selected from oxygen, nitrogen and sulfur; a C 6 -C 18 aryl group; a C 7 -C 20 arylalkyl or alkylaryl group; a triazine having one of the following general formulae (II), (III) or (IV):
• R 7 has the same meanings defined above; or, R 10 and R considered jointly with the nitrogen atom, represent a C 5 -C 8 heterocyclic group option- ally containing a second heteroatom selected from oxygen, nitrogen and sulfur; or R 4 represents a group having one of the following general formulae (VII) , (VIII) or (IX) :
• R 12 represents a hydrogen atom; or a linear or branched C ⁇ -C ⁇ alkyl group; - R 13 represents a linear or branched C,-C 18 alkyl group; a -COCH 2 COCH 3 group; or a direct bond ; provided that, when R 1 and R 2 are different from the group having general formula (V) , R 4 represents a group having general formula (VI) .
• the compounds having general formula (I) can be used as antioxidants for organic polymers.
• R 1 , R 2 , R 10 and R groups, as well as a hydrogen atom are: methyl, ethyl, propyl, isopropyl, butyl, octyl, cyclohexyl, benzyl, phenyl, ethylphenyl, methoxyethyl , 4- (2 , 2 , 6 , 6-tetramethyl) piperidinyl , 4- (2 , 2 , 6 , 6-tetramethyl) -1-butoxyethylpiperidinyl , 4- ( 2 , 2 , 6 , 6-tetramethyl ) -1-butoxypiperidinyl , 4- (2 , 2 , 6, 6-tetramethyl) -1-methylpiperidinyl , 3 , 5-dioctylaminotriazine, 3 , 5-dibutylaminotriazine, etc.
• Examples of C 5 -C 8 heterocyclic groups, when R 1 and R 2 or R 10 and R n are considered jointly with the nitrogen atom, are: morpholine, pyrrolidine, piperidine, piperazine, thiomorpholine, thiazolidine, benzothiazol- idine, etc.
• R 3 and R groups are: methyl, ethyl, propyl, isopropyl, phenyl, oxymethyl , oxyethyl , oxybu- tyl, etc.
• R 4 groups when R 4 represents a group ⁇
• R 4 groups when R represents a group having general formula (VII) , (VIII) or (IX) and n is 2 , are :
• R 4 groups when R 4 represents a group having general formula (VII) , (VIII) or (IX) and n is
• R 4 groups when R 4 represents a group having general formula (VII) , (VIII) or (IX) and n is
• R 7 groups are: methyl, ethyl, propyl, butyl, ethoxy, butoxy, ⁇ -hydroxyethyl, 3-methoxyethyl , 3-butoxyethyl, methylaminoethyl , etc.
• R,, R 6 , R 8 , R,, R 12 and R 13 groups when said groups represent a linear or branched C j -C ⁇ alkyl group, are: methyl, ethyl, propyl, isopropyl, butyl, octyl, etc.
• a further object of the present invention relates to a synthesis process of compounds having general formula (I) .
• a process for the synthesis of the compounds having general formula (I) of the present invention comprises the reaction of 1-4 moles of a primary or secondary, aliphatic or aromatic amine, having general formula (X) :
• the above reaction takes place in the presence of an inert organic solvent, preferably a hydrocarbon, in particular toluene, at a temperature ranging from 60 °C to 16Q°C, preferably from 115°C to 150°C, at atmospheric pressure, and for a time ranging from 0.5 to 24 hours, preferably from 3 to 10 hours.
• an inert organic solvent preferably a hydrocarbon, in particular toluene
• Acetic acid can optionally be added as catalyst to this reaction.
• reaction water is released which is separated by azeotropic distillation "t using an apparatus for the azeotropic distillation, whereas the organic solvent is recycled.
• the solvent and possible acetic acid present are removed by distilla- tion thus obtaining a raw product.
• the desired compound having general formula (I) is purified from the raw product thus obtained by fractionated distillation, operating under vacuum, at a pressure ranging from 0.1 mm/Hg to 50 mm/Hg and a temperature ranging from 40 °C to 200 °C. Or, said compound having general formula (I) is separated by crystallization using techniques known in the art.
• Examples of primary or secondary, aliphatic or aromatic amines, having general formula (X) which can be used for the purposes of the present invention are: cyclohexylamine, n-butylamine, tert-butylamine, n-octy- lamine, tert-octylamine, n-octadecylamine, n-dodecylam- ine, benzyla ine, 2-methoxyethylamine, 2-furfurylamine, pyrrolidine, piperidine, morpholine, dibenzylamine, aniline, diphenylamine, melamine, 4-amino-2 , 2 , 6 , 6-te- tramethylpiperidine, 4-amino-2, 2,6, 6-tetramethyl-1-me- thylpiperidine, 4-amino-2 ,2,6, 6-tetramethyl-l-butoxyet- hylpiperidine, l-amino-3
• Examples of /3-keto-esters or -keto-amides , or 1, 3-diketones having general formula (XI) are: ethyl aceto-acetate, t-butyl aceto-acetate, octadecyl aceto- acetate, ethyl benzoylacetate, acetyl-acetone, benzoyl- acetone, dibenzoyl methane, p-toluylacetone, 4- (2, 2, 6, 6-tetramethyl) piperidinyl aceto-acetate, N-methyl-4- (2, 2, 6, 6-tetramethyl)piperidinyl aceto- acetate, aceto-acetamide, acetoacetanilide, aceto-acet- 4- (2 , 2 , 6, 6,-tetramethylpiperidine) amide, aceto-acet- (3 , 5-dibutyltriazine) -1-amide, etc.
• polymers of mono-olefins and diolefins such as, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-l-ene, polyiso- prene . or polybutadiene ; as well as polymers of cyclo-olefins such as, for example, cyclopentene or norbornene; polyethylene (which can be optionally cross-linked) such as, for example, high density polyethylene (HDPE) , low density poly- ethylene (LDPE) , linear low density polyethylene (LLDPE) , branched low density polyethylene (BLDPE) .
• HDPE high density polyethylene
• LDPE low density poly- ethylene
• LLDPE linear low density polyethylene
• BLDPE branched low density polyethylene
• polyethylene and polypropylene can be prepared with various methods known in literature, preferably using the following methods:
• radicalic polymerization generally carried out at a high pressure and high temperature ;
• catalytic polymerization using a catalyst which normally contains one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table.
• metals generally have one or more ligands such as, for example, oxides, halides, alcoholates, ethers, amines, alkyls, alkenyls and/or aryls which can be it- or ⁇ -co-ordinated.
• ligands such as, for example, oxides, halides, alcoholates, ethers, amines, alkyls, alkenyls and/or aryls which can be it- or ⁇ -co-ordinated.
• These metal complexes can be in free form or supported in substrates such as, for example activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide.
• These catalysts can be soluble or insoluble in the 7 reaction medium.
• the catalysts can be used alone or in the presence of other activators such as, for example, metal alkyls, metal hydrides, halides of metal alkyls, oxides of metal alkyls or metal alkyloxanes, these metals being elements belonging to groups la, Ila and/or Ilia of the Periodic Table.
• the activators can be conveniently modified with other ester, ether, amine or silyl-ether groups. These catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta) , TNZ (DuPont) , metallocene or "single site catalyst" (SSC) .
• copolymers ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethyl- ene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with polypropylene and a diene such as, for example, hexadiene, dicyclopentadiene or ethylidene-norbor- nene; and mixtures of these copolymers with each other or with the polymers cited in paragraph (1) such as, for example, polypropylene/ethylene- propylene copolymers,
• Hydrocarbon resins for example, C 3 -C 9
• Hydrocarbon resins comprising their hydrogenated modifications (for example, adhesive agents) and mixtures with polyalkylene and starch.
• Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/ alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylo- nitrile/methylacrylate; mixtures, having a high impact strength, between copolymers of styrene and another polymer such as, for example, a polyacry- late, a polymer of a diene or an ethy- lene/propylene/diene terpolymer, block polymers of styrene such as, for example, styrene/butadiene/ styrene,
• Grafted copolymers of styrene or ⁇ -methylstyrene such as, for example, styrene in polybutadiene, styrene in polybutadiene or polybutadiene-acrylo- nitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) in polybutadiene; styrene, acrylonitrile and methylmethacrylate in polybutadiene; styrene and maleic anhydride in polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide in polybutadiene; styrene and male- imide in polybutadiene; styrene and alkylacrylates or methacrylates in polybutadiene; styrene and acrylonitrile in ethylene/propylene/diene terpoly- mers, styrene
• Polymers containing halogens such as, for example, polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, ethylene and chlorinated ethylene copolymers, homopoly ers and copolymers of epichlorohydrin, in particular polymers of vinyl compounds containing halogens such as, for example, polyvinyl chloride, poly- vinylidenechloride, polyvinyl fluoride or polyvin- ylidenefluoride; and also their copolymers such as, for example, vinyl chloride/vinylidenechlo- ride, vinyl chloride/vinyl acetate or vinylidene- chloride/vinyl acetate.
• halogens such as, for example, polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, ethylene and chlorinated ethylene copolymers, homopoly ers and copolymers of epichlorohydrin,
• Polymers deriving from ⁇ ,3-unsaturated acids and their derivatives such as, for example, polyacry- lates and polymethacrylates, polymethyl methacry- lates, polyacrylamides and polyacrylonitriles, modified with butyl acrylate.
• Polyacetals such as, for example, polyoxymethylene and polyoxymethylenes which contain ethylene oxide as comonomer; polyacetals modified with thermo- X Z. plastic polyurethanes, acrylates or MBS.
• Polyamides and copolyamides deriving from dia ines and dicarboxylic acids and/or aminocarboxylic acids or from the corresponding lactams such as, for example, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12 , aromatic polyamides obtained starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid and with or without an elastomer as modifier, for example, poly-2, 4, 4-trimethylhexamethylene terephthala ide or poly-m-phenylene isophthala ide; and also block copolymers of the above polyamides with poly- olefins, olefinic copolymers, ionomers or elastomers chemically bound or grafted; or with polye- thers such as, for example, polyethylene glycol,
• polypropylene glycol or polytetramethylene glycol as well as polyamides or copolyamides modified with EPDM or ABS ; and polyamides condensed during processing (“RIM polyamide system”) .
• RIM polyamide system polyamides condensed during processing
• Polyesters deriving from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or from the corresponding lactones such as, for example, polyethylene terephthalate, polybutylene tereph- thalate, poly-1, 4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters deriving from polyethers with hydroxyl-terminated groups; and also polyesters modified with polycarbonates or MBS.
• Cross-linkable acrylic resins deriving from substituted acrylates such as, for example, epoxy acrylates, urethane acrylates or polyester acrylates.
• Alkyd resins resins based on polyesters or acrylated resins cross-linked with melamine resins, urea resins, resins based on polyisocyana- tes or epoxy resins.
• cross-linked epoxy resins deriving from polyepoxi- des such as, for example, bis-glycidyl ethers or cycloaliphatic diepoxides.
• Natural polymers such as, for example, cellulose, rubber, gelatine, and their derivatives chemically modified to give homologous polymers such as, for example, cellulose acetates, propionates and butyrates, or cellulose ethers such as, for example, methyl-cellulose; as well as hydrocarbon resins ("rosins") or their derivatives.
• polyblends such as, for example, PP/EPDM, polyamides/EPDM or ABS , zs
• PVC/EVA PVC/ABS, PVC/MBS , PC/ABS , PBTP/ABS , PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/ther- moplastics PUR, PC/thermoplastics PUR, POM/acryla- tes, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.
• the compounds having general formula (I) can be used in the stabilization of poly- ols.
• (I) can be added to the organic polymers, optionally in the presence of other additives, in the step following their preparation, or immediately before the transformation process.
• the compounds having general formula (I) of the present invention are incorporated into the polymer to be stabilized in a quantity ranging from 0.02% to 3% by weight, preferably between 0.05% and 1%.
• a further object of the present invention relates to polymeric compositions containing an organic polymer and an effective quantity of one or more compounds having general formula (I) .
• the compounds having general formula (I) of the present invention can be combined with other conventional additives or their mixtures. These additives are added in a quantity ranging from about 0.1% to about 5% by weight of the weight of the polymeric compositions to be stabilized, preferably from about 0.5% to about 3% by weight. Some of the additives used are listed below as an example. 1.
• Alkylthiomethylphenols such as, for example: 2 , 4-dioctylthiomethyl-6-t-butylphenol ;
• Hydroquinones and alkylated hydroquinones such as, for example:
• Tocopherols such as, for example: ⁇ -tocopherol, .-tocophercl, ⁇ -tocopherol, ⁇ S-tocopherol and their mixtures (Vitamin E) .
• Hydroxylated thiodiphenyl ethers such as, for example:
• Alkylidene-bisphenols such as, for example:
• Triazine compounds such as, for example:
• Benzylphosphonates such as, for example: dimethyl-2 , 5-di-t-butyl-4-hydroxybenzylphosphona- te; diethyl-3 , 5-di-t-butyl-4-hydroxybenzylphosphcnate; dioctadecyl-3 , 5-di-t-butyl-4-hydroxybenzylphospho- nate ; dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylpho- sphonate ; calcium salts of monoethyl ester of 3,5-di-t- butyl-4-hydroxybenzylphosphonic acid.
• Acylaminophenols such as, for example: 4-hydroxylauranilide; 4-hydroxystearanilide; octyl-N- ( 3 , 5-di-t-butyi-4-hydroxyphenyl) carbamate .
• esters of ⁇ - (3 , 5-di-t-butyl-4-hydroxyphenyl) pro- pionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6- hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol , tris (hydroxyethyl) isocyanurate, N,N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3- thiopentadecanol, trimethylhexandiol , trimethyl- olpropane, 4-hydroxymethyl-l-phospho-2 , 6, 7-trioxa- bicyclo[2.2. 2] octane.
• esters of ⁇ - (5-t-butyl-4-hydroxy-3-methylphe- nyl)propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6- hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N' -bis (hydroxyethyl) oxamide, 3-thioundecanol,
• monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6- hexandiol, 1, 9-nonandiol, ethylene glyco
• 3-thiopentadecanol trimethylhexandiol, trimethy- lolpropane, 4-hydroxymethyl-l-phospho-2 , 6,7-trio- xabicyclo [2.2.2] octane .
• esters of ⁇ - (3 , 5-dicyclohexyl-4-hydroxyphenyl) pro- pionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6-he- xandiol, 1, 9-nonandiol, ethylene glycol, 1,2-pro- panediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thio- pentadecanol , trimethylhexandiol, trimethylol- propane, 4-hydroxymethyl-l-phospho-2 , 6, 7-trioxabi- cyclo[2.2.2]octane.
• esters of (3 , 5-di-t-butyl-4-hydroxyphenyl) acetic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6- hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N' -bis (hydroxyethyl) oxamide , 3-thioundecanol , 3-thiopentadecanol, trimethylhexandiol, trimethy- lolpropane, 4-hydroxymethyl-l-phospho-2 , 6,7-trio- xabicyclo [2.2.2] octane .
• 2-hydroxybenzophenones such as, for example: 4-hydroxy-; 4-methoxy-; 4-octyloxy-; 4- decyloxy-; 4-dodecyloxy- ; 4-benzyloxy- ; 4, 2 ',4'- trihydroxy- ; 2 ' -hydroxy-4 , 4 ' -dimethoxy .
• Esters of benzoic acids optionally substituted, such as, for example: phenyl salicylate, 4-t- butylphenyl salicylate, octylphenyl salicylate, benzoyl-resorcinol , bis (4-t-butylbenzoyl) -resor- cinol, dibenzoyl-resorcinol, 2 , 4-di-t-butylphenyl- 3 , 5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3 , 5- di-t-butyl-4-hydroxybenzoate, octadecyl-3 , 5-di-t- butyl-4-hydroxybenzoate, 2-methyl-4, 6-di-t-butyl- phenyl-3 , 5-di-t-butyl-4-hydroxybenzoate.
• benzoyl-resorcinol bis (4-t-butylbenzoyl) -res
• Acrylates such as, for example, ethyl or isoctyl ⁇ -cyano-3 ,/3-diphenylacrylate ; methyl ⁇ -carbometho- xycinnamate, methyl or butyl ⁇ -cyano-3-methyl-p- methoxycinnamate, methyl ⁇ -carbomethoxy-p-methoxy- cinnamate, N- (/3-carbomethoxy-_-cyanovinyl) -2- methylindoline.
• Nickel compounds such as, for example, complexes of 2,2'-thio-bis-[4-(l,l,3,3-tetramethylbutyl)phe- nol], for example 1:1 or 1:2 complexes, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3 , 5-di-t-butyl- benzyl-phosphonic acid, such as methyl or ethyl esters, nickel complexes with ketoximes such as 2- hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of l-phenyl-4-lauroyl-5-hydroxypyrazol with or without additional ligands. 7
• Oxamides such as, for example: 4,4' -dioctyloxyoxanilide ; 2,2' -diethoxyoxanilide ;
• Metal-deactivators such as, for example: N,N- diphenyloxamide, N-salicylal-N' -salicyloyl-hydra- zine, N,N'-bis(salicyloyl)hydrazine; N,N'-bis (3 , 5- di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3- salicyloylamino-1, 2 , 4-triazole, bis (benzylidene) o- xalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diace- tyladipoyl dihydrazide, N,N'-bis (salicyloyl) oxal- lyl dihydrazide, N,N'-bis (salicyloyl) thiopropionyl di
• Phosphites and phosphonites such as, for example: triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phos- phite, distearyl pentaerythritol diphosphite, tris (2 , 4-di-t-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2 , 4-di-t-butyl- phenyl) pentaerythritol diphosphite, bis (2 , 5-di-t- butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphit
• Agents which are capable of destroying peroxides such as, for example, esters of -thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2- mercaptobenzimidazole, zinc dibutyldithiocarbama- te, dioctadecyldisulfide pentaerythritol tetrakis (/3-dodecylmercapto)propionate.
• esters of -thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters
• mercaptobenzimidazole or zinc salt of 2- mercaptobenzimidazole zinc dibutyldithiocarbama- te
• dioctadecyldisulfide pentaerythritol tetra
• Stabilizers of polyamides such as, for example, copper salts combined with compounds of iodine and/or phosphorous, divalent manganese salts.
• Basic co-stabilizers such as, for example: mela- mine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, derivatives of hydrazine, amines, polyamides, polyure- thanes, salts of alkaline metals and salts of earth-alkaline metals of fatty acids such as, for example, Ca-stearate, Zn-stearate, Mg-stearate, Mg-behenate, Na-ricinoleate, K-palmitate, antimo- nium-pyrocatecholate , tin-pyrocatecholate .
• Nucleating agents such as, for example: 4-t-butyl- benzoic acid, adipic acid, diphenylacetic acid.
• Fillers and reinforcing agents such as, for example: calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
• additives such as, for example: plastici- zers, lubricants, emulsifying agents, pigments, optical brighteners, flame-retardants (for exam- pie, bromides, chlorurates, phosphorates and phosphorous/halogen mixtures) , antistatic agents, blowing agents, thiosynergizing agents such as, for example, dilauryl thiodipropionate or diste- aryl thiodipropionate.
• Benzofuranones and indolinones such as, for ex.: 3- [ 4- ( 2-acetoxyethoxy) phenyl ] -5 , 7-di-t-butylben- zofuran-2-one ;
• a non-stabilized polyol was used, of the type Glendion FG 3501 sold by EniChem S.p.A., and the stabilizer was added at levels of 0.15%.
• the oxygen absorption induction time measurement was carried out on the polyol at a temperature of 130 °C and 140 °C under a stream of oxygen. The greater the oxygen absorption induction time, the better is the stabilizing system used.
• the solvent and acetic acid are removed by distillation and the raw residue thus obtained is subjected to fractionated distillation.
• This distillation is carried out in a distiller consisting of a 100 ml boiler equipped with a thermome- ter, stirrer, column, condenser and device for the collection of fractions.
• Compound Nr. 1 thus obtained, analyzed by gas- chromatography (GC) proves to be 97.5% pure, with a yield of about 89.2%.
• Amine 4-amino-2, 2 , 6, 6-tetramethylpiperidine; 31.25 g (0.2 moles) .
• Carbonyl compound ethyl aceto-acetate; 26.03 g (0.2 moles) .
• - Solvent toluene; 50 g.
• Amine 4-amino-2 , 2 , 6, 6-tetramethylpiperidine;
• the raw residue obtained is not subjected to fractionated distillation as the end- product crystallizes in the reaction medium at room temperature.
• the product obtained is filtered, washed with toluene and dried.
• Amine 4-amino-2 , 2 , 6, 6-tetramethylpiperidine; 62.5 g (0.4 moles) .
• Carbonyl compound acetylacetone; 40.05 g (0.4 moles) .
• the raw residue obtained is not subjected to fractionated distillation as the end- product crystallizes in the reaction medium at room 4 ⁇ > temperature.
• the product obtained is filtered, washed with toluene and dried.
• Amine octadecylamine; 53.9 g (0.2 moles).
• Carbonyl compound ethyl acetoacetate; 26.03 g (0.2 moles) .
• Reaction time and temperature 1 h 45' at 118 °C- 130°C.
• the product is isolated as boiler residue after distillation under vacuum of the solvent and acetic acid.
• Amine 4-amino-2 , 2 , 6, 6-tetramethylpiperidine;
• Reaction water separated 3.2 g - Reaction time and temperature: 5 hours at 122 °C-
• Amine 4-amino-2 , 2 , 6 , 6-tetramethylpiperidine ;
• Carbonyl compound octadecyl aceto-acetate; 30 g (0.085 moles) .
• Reaction time and temperature 3 h 45' at 132 °C- 138 0 C.
• the raw reaction mass is not subjected to fractionated distillation as the end-product crystallizes in the reaction medium at room temperature.
• the product obtained is filtered, washed with toluene and dried.
• Amine 4-amino-2 , 2 , 6 , 6-tetramethylpiperidine ; 38.57 g (0.247 moles).
• Carbonyl compound dibenzoyl methane; 44.85 g (0.2 moles) .
• the raw reaction mass is not subjected to fractionated distillation as the end-product crystallizes in the reaction medium at room temperature.
• the product obtained is filtered, washed with toluene and dried.
• Amine 4-amino-2 , 2 , 6 , 6-tetramethylpiperidine ;
• Carbonyl compound aceto-acetanilide; 35.44 g (0.2 moles) .
• - Solvent methanol; 100 g.
• Reaction water separated in this case the reaction water is not separated.
• Reaction time and temperature 13 h at 20°C-26 ⁇ , C.
• the raw reaction mass is not subjected to fractionated distillation as the end-product crystallizes in the reaction medium at room temperature.
• the product obtained is filtered, washed with n-pentane and dried.
• - Product obtained 54.34 g.
• GC Purity > 97%.
• Amine 4-amino-2 , 2 , 6 , 6-tetramethylpiperidine; 31.25 g (0.2 moles).
• Carbonyl compound benzoyiacetone; 32.44 g (0.2 moles) .
• the systems analyzed are brought in 5 minutes to the test tempera- ture under nitrogen. Oxygen is then passed (7 ml/h) and the oxidation kinetics are observed in relation to the heat developed during the process.
• the induction time is calculated in the intersection point with the time axis of the tangent at the oxidation curve at 1 W as illustrated in Figure 1: the abscissa indicates the time in minutes, the ordinate the trend of the heat developed in mW.
• the addition of the polyol is obtained by mixing the polyol with the products to be analyzed, Compounds 1-11 and 2 , 6-di-t-butyl-4-methylphenol (BHT), in a quantity equal to 0.15%, the mixture being stirred until complete dissolution of the products used is obtained.
• BHT 6-di-t-butyl-4-methylphenol
• Table 1 indicates the induction times in minutes of the oxygen absorption during the thermo-oxidation of the polyol at 130 °C and at 140 °C.

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