Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
  • C07C239/08—Hydroxylamino compounds or their ethers or esters
  • C07C239/20—Hydroxylamino compounds or their ethers or esters having oxygen atoms of hydroxylamino groups etherified
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
  • C07D211/94—Oxygen atom, e.g. piperidine N-oxide

Definitions

• the instant invention pertains to a process for preparing sterically hindered amine ethers, e.g. N-hydrocarbyloxy substituted sterically hindered amine compounds and mixtures thereof, by the reaction of the corresponding N-oxyl intermediate with a 1-alkene in the presence of an organic hydroperoxide, optionally together with a further catalyst, and some novel compound mixtures obtainable by this process.
• the instant invention also pertains to a process of hydrogenating unsaturated amine ethers, and some novel compound mixtures obtainable by this process.
• the compounds made by the processes are particularly effective in the stabilization of polymer compositions against harmful effects of light, oxygen and/or heat and as flame-retardants for polymers.
• WO 01/92228 describes a process for the preparation of amine ethers, e.g. N-hydrocarbyk oxy substituted hindered amine compounds, by the reaction of the corresponding N-oxyl intermediate with a hydrocarbon in the presence of an organic hydroperoxide and a copper catalyst.
• amine ethers e.g. N-hydrocarbyk oxy substituted hindered amine compounds
• WO 03/045919 describes a process for the preparation of amine ethers, e.g. N-hydrocarbyloxy substituted hindered amine compounds, by the reaction of the corresponding N-oxyl intermediate with a hydrocarbon in the presence of an organic hydroperoxide and an iodide catalyst.
• amine ethers e.g. N-hydrocarbyloxy substituted hindered amine compounds
• N-alk-2-enyloxy substituted sterically hindered amine ethers and mixtures thereof can most suitably be prepared from N-oxyl intermediate and a 1-alkene in the presence of an organic hydroperoxide and optionally a further catalyst.
• the process of the invention does not require high reaction temperature.
• the corresponding N-alkoxy substituted sterically hindered amines can be prepared from said N-alk-2-enyloxy substituted sterically hindered amines by hydrogenation. With the procedure according to this invention purer products may be obtained. The obtained product mixtures may contain less isomers.
• present invention pertains to a process for the preparation of a sterically hindered amine ether which comprises reacting a corresponding sterically hindered aminoxide with a C 5 -C ⁇ 8 alk-1-ene in the presence of an organic hydroperoxide.
• the present invention further pertains to a process, wherein the sterically hindered amine ether obtained by reacting a corresponding sterically hindered aminoxide with a C 5 -C ⁇ 8 alk-1- ene in the presence of an organic hydroperoxide is subsequently hydrogenated.
• the sterically hindered amine oxide preferably used in the process of the present invention contains at least one group of formula (II)
• Gi, G 2 , G 3 and G are independently alkyl of 1 to 4 carbon atoms or G and G 2 and/or G 3 and G are together tetramethylene or pentamethylene.
• the sterically hindered amine oxide used in the process of the present invention is a compound of formula (Ha)
• G ⁇ G 2 , G 3 and G 4 are as defined for formula (II);
• the sterically hindered amine ether obtained according to the present invention contains at least one group of formula (III)
• G ⁇ G 2 , G 3 and G are as defined for formula (II) and
• E is C 5 -C 18 alkyl or C 5 -C 18 alk-2-enyl.
• C 5 -C ⁇ 8 alkyl as substituent E is preferably a mixture of the radicals
• C 5 -C ⁇ 8 alk-2-enyl as substituent E is preferably a mixture of the radicals
• C 5 -C ⁇ 8 alkyl comprises the branched and unbranched isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl and the term C 2 -C ⁇ 5 alkyl comprises ethyl and the branched and unbranched isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl.
• the obtained sterically hindered amine ether is preferably a compound of formula (Ilia) wherein Gi, G 2j G 3 and G are as defined for formula (II);
• E 10 is as defined for formula (Ha).
• d and G 3 are methyl and G 2 and G 4 are independently methyl or ethyl.
• the obtained sterically hindered amine ether is preferably one of formulae (A) to (O)
• n 0 or 1 ;
• Ri is hydrogen, hydroxyl or hydroxymethyl
• R 2 is hydrogen, alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12 carbon atoms;
• n is 1 to 4; when n is 1 , R 3 is hydrogen, alkyl of 1 to 18 carbon atoms, alkoxycarbonylalkylenecarbonyl of 4 to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2- (hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkyl is interrupted by oxygen, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, or acyl radical of an aromatic acid containing 7 to 15 carbon atoms;
• R3 is alkylene of 2 to 18 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;
• R 3 is a trivalent acyl radical of an aliphatic or unsaturated aliphatic tricarboxylic acid containing 6 to 18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic acid containing 9 to 15 carbon atoms;
• R 3 is a tetravalent acyl radical of an aliphatic or unsaturated aliphatic tetracarboxylic acid, especially 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-but-2-enetetracarboxylic acid, 1,2,3,5- pentanetetracarboxylic acid and 1 ,2,4,5-pentanetetracarboxylic acid, or R 3 is a tetravalent acyl radical of an aromatic tetracarboxylic acid containing 10 to 18 carbon atoms;
• p 1 to 3
• Rt is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbon atoms or phenyl;
• R 5 is hydrogen, phenyl, alkyl of 1 to 18 carbon atoms, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7 to 12 carbon atoms, an acyl radical of an aromatic carboxylic acid containing 7 to 15 carbon atoms, or R . and R5 together are -(CH 2 ) 5 CO-, phthaloyl or a divalent acyl radical of maleic acid;
• R 5 is alkylene of 2 to 12 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl radical of a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbon atoms, or a divalent acyl radical of an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;
• R 5 is a trivalent acyl radical of an aliphatic or unsaturated aliphatic tricarboxylic acid containing 6 to 18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic acid containing 9 to 15 carbon atoms;
• r is 1 to 4, when r is 1,
• R 6 is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbon atoms, -NHalkyl of 1 to 18 carbon atoms or -N(alkyl) 2 of 2 to 36 carbon atoms,
• Re is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of 2 to 18 carbon atoms, -NH- alkylene-NH- of 2 to 18 carbon atoms or -N(alkyl)-alkylene-N(alkyl)- of 2 to 18 carbon atoms, or R 6 is 4-methyl-1,3-phenylenediamino,
• R 6 is a trivalent alkoxy radical of a saturated or unsaturated aliphatic triol containing 3 to 18 carbon atoms
• Re is a tetravalent alkoxy radical of a saturated or unsaturated aliphatic tetraol containing 4 to 18 carbon atoms
• R 7 and R 8 are independently chlorine, alkoxy of 1 to 18 carbon atoms, -O-Ti, amino substituted by 2-hydroxyethyl, -NH(alkyl) of 1 to 18 carbon atoms, -N(alkyl)T 1 with alkyl of 1 to 18 carbon atoms, or -N(alkyl) 2 of 2 to 36 carbon atoms,
• R 9 is oxygen, or R 9 is nitrogen substituted by either hydrogen, alkyl of 1 to 12 carbon atoms
• R 10 is hydrogen or methyl
• R11 and R 12 are independently hydrogen or the group T 2 , T 2 is
• R13 is hydrogen, phenyl, straight or branched alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, straight or branched alkyl of 1 to 4 carbon atoms substituted by phenyl, cycloalkyl of 5 to 8 carbon atoms, cycloalkenyl of 5 to 8 carbon atoms, alkenyl of 2 to 12 carbon atoms, glycidyl, allyloxy, straight or branched hydroxyalkyl of 1 to 4 carbon atoms, or silyl or silyloxy substituted three times independently by hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms;
• R ⁇ 4 is hydrogen or silyl substituted three times independently by hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms;
• d is 0 or 1 ;
• h 0 to 4.
• k 0 to 5;
• x is 3 to 6;
• y is 1 to 10;
• z is an integer such that the compound has a molecular weight of 1000 to 4000 amu, e.g. z may be from the range 3-10;
• R1 5 is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to 8 carbon atoms, especially branched alkylamino of 3 to 8 carbon atoms such as tert-octylamino, -N(alkyl)T 1 with alkyl of 1 to 8 carbon atoms, or -N(alkyl) 2 of 2 to 16 carbon atoms,
• Ri 6 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted once by chlorine and once by R ⁇ 5 , or s-triazinyl substituted twice by R1 5 with the condition that the two R 15 substituents may be different;
• R ⁇ 7 is chlorine, amino substituted by alkyl of 1 to 8 carbon atoms or by T ⁇ -N(alkyl)T 1 with alkyl of 1 to 8 carbon atoms, -N(alkyl) of 2 to 16 carbon atoms, or the group T 3 ,
• R 18 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substituted twice by -N(alkyl) 2 of 2 to 16 carbon atoms or s-triazinyl substituted twice by -N(alkyl)T 1 with alkyl of 1 to 8 carbon atoms;
• F- 30 is hydrogen, alkyl of 1 to 18 carbon atoms, alkoxycarbonylalkylenecarbonyl of 4 to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2- (hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkyl is interrupted by oxygen, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic
• alkyl comprises, for example, methyl, ethyl and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.
• alkoxy are methoxy, ethoxy, propoxy, butoxy, octyloxy etc..
• alkenyl are vinyl and especially silyl.
• cycloalkyl examples include cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, dimethyicyclopentyl and methylcyclohexyl.
• an aliphatic carboxylic acid is acetic, propionic, butyric, stearic acid.
• An example of a cycloaliphatic carboxylic acid is cyclohexanoic acid.
• An example of an aromatic carboxylic acid is benzoic acid.
• An example of an aliphatic dicarboxylic acid is malonyl, maleoyl or succinyl, or sebacic acid.
• An example of a residue of an aromatic dicarboxylic acid is phthaloyl.
• An example of a monovalent silyl radical is trimethylsilyl.
• aryl examples are phenyl and naphthyl.
• substituted aryl examples are methyl-, dimethyl-, trimethyl-, methoxy- or phenyl-substituted phenyl.
• Acyl radicals of monocarboxylic acids are, within the definitions, a residue of the formula -CO-R", wherein R" may stand inter alia for an alkyl, alkenyl, cycloalkyl or aryl radical as defined.
• Preferred acyl radicals include acetyl, benzoyl, acryloyl, methacryloyl, propionyl, butyryl, valeroyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, pentadecanoyl, stearoyl.
• Polyacyl radicals of polyvalent acids are of the formula (-CO)n-R" . wherein n is the valency, e.g.2, 3, 4, 5 or 6.
• the C 5 -C ⁇ 8 alk-1-ene is an unbranched alkene.
• the C 5 -C ⁇ 8 alk-1-ene is preferably C 6 -C 12 alk-1-ene, in particular C 6 -C 8 alk-1-ene, for example 1-octene.
• the alkylation process of the present invention is preferably carried out in the presence of a further catalyst.
• the further catalyst is preferably selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, lanthanum, cerium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth; the compounds thereof; substituted and unsubstituted ammonium iodides and phosphonium iodides.
• the further catalyst may also be quaternary ammonium or phosphonium halogenides such as chlorides or bromides.
• the structure of the ammonium or phosphonium cation is less important; usually, quaternary ammonium or phosphonium cations contain 4 hydrocarbon residues bonded to the central nitrogen or phosphorus atom, which may be, for example, alkyl, phenylalkyl or phenyl groups. Some readily available materials are tetra-d- C 12 alkylated.
• the further catalyst may also be any other iodide compound, including organic and inorganic iodide compounds.
• examples are alkaline or alkaline earth metal iodides, or onium iodides such as sulfonium iodides, especially quartemary sulfonium iodides.
• Suitable metal iodides are, inter alia, those of lithium, sodium, potassium, magnesium or calcium.
• the further catalyst is more preferably selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, cerium; the halides and oxides thereof; substituted and unsubstituted ammonium iodides and phosphonium iodides.
• the further catalyst is most preferably selected from the group consisting of manganese, iron, cobalt, nickel, copper; the halides thereof; substituted and unsubstituted ammonium iodides and phosphonium iodides, for example substituted and unsubstituted quaternary ammonium or phosphonium iodides, especially tetraalkyl ammonium iodides or tetraphenylphosphonium iodide and triphenylalkylphosphonium iodides.
• the further catalyst can be bound to an organic or inorganic polymer backbone, rendering a homogenous or heterogeneous catalytic system.
• the further catalysts mentioned above may contain anionic ligands commonly known in complex chemistry of transition metals, such hydride ions (H ⁇ ) or anions derived from inorganic or organic acids, examples being halides, e.g. F ⁇ , Cl ⁇ Br " ⁇ or l ⁇ fluoro complexes of the type BF 4 ⁇ PF 6 -, SbF 6 ⁇ or AsF 6 — . anions of oxygen acids, alcoholates or acetylides or anions of cyclopentadiene or oxides.
• H ⁇ hydride ions
• anions derived from inorganic or organic acids examples being halides, e.g. F ⁇ , Cl ⁇ Br " ⁇ or l ⁇ fluoro complexes of the type BF 4 ⁇ PF 6 -, SbF 6 ⁇ or AsF 6 — .
• Anions of oxygen acids are, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C ⁇ -C 8 carboxylic acid, such as formate, acetate, propionate, butyrate, benzoate, phenylacetate. mono-, di- or trichloro- or -fluoroacetate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate) .
• Anionic ligands and neutral may also be present up to the preferred coordination number of the complex cation of the further catalyst, especially four, five or six. Additional negative charges are counterbalanced by cations, especially monovalent cations such as Na + , K + , NH 4 + or (C r C 4 alkyl) 4 N + .
• the further catalysts mentioned above may also contain neutral ligands such as inorganic or organic neutral ligands commonly known in complex chemistry of transition metals.
• neutral ligands such as inorganic or organic neutral ligands commonly known in complex chemistry of transition metals.
• Suitable inorganic ligands are selected from the group consisting of aquo (H 2 O), amino, nitrogen, carbon monoxide and nitrosyl.
• Suitable organic ligands are selected from the group consisting of phosphines, e.g.
• the further catalst can further contain heterocyclic e ⁇ " donor ligands which are derived, for example, from unsubstituted or substituted heteroarenes from the group consisting of furan, thiophene .
• the sterically hindered aminoxides also referred to as N-oxyl educts for the instant process which include compounds with at least one group of formula (II) or compounds of formula (lla) are largely known in the art; they may be prepared by oxidation of the corresponding N- H hindered amine with a suitable oxygen donor, e.g. by the reaction of the corresponding N- H hindered amine with hydrogen peroxide and sodium tungstate as described by E. G. Rozantsev et al., in Synthesis, 1971, 192; or with tert-butyl hydroperoxide and molybdenum (VI) as taught in United States Patent No. 4,691 ,015, or obtained in analogous manner.
• a suitable oxygen donor e.g. by the reaction of the corresponding N- H hindered amine with hydrogen peroxide and sodium tungstate as described by E. G. Rozantsev et al., in Synthesis, 1971, 192; or with tert
• the preferred amount of C 5 -C ⁇ 8 alk-1-ene for the instant process depends, of course, on the relative number of reactive hindered amine nitroxyl moieties in the starting amine oxide.
• the reaction is typically carried out with a ratio of 1 to 100 moles of C 5 -C ⁇ 8 alk-1-ene per mole of nitroxyl moiety with the preferred ratio being 1 to 50 moles per mole of nitroxyl moiety, and the most preferred ratio being 1 to 30 moles of C 5 -C ⁇ 8 alk-1-ene per mole of nitroxyl moiety.
• the preferred amount of organic hydroperoxide is 0.5 to 20 moles per mole of nitroxyl moiety, with the more preferred amount being 0.5 to 5 moles of peroxide per mole of nitroxyl moiety and the most preferred amount being 0.5 to 3 moles of peroxide per mole of nitroxyl moiety.
• the organic hydroperoxide used in the process of present invention can be of the formula R- OOH, wherein R usually is a hydrocarbon containing 1 - 8, preferably 3-18 carbon atoms. R is advantageously aliphatic, for example an alkyl group, preferably C C 12 alkyl. Most preferably, the organic hydroperoxide is tert-butyl-hydroperoxide or cumyl hydroperoxide.
• the preferred amount of further catalyst is from about O.0001 to 0.5, especially 0.0005 to 0.1 molar equivalent per mole of nitroxyl moiety, with a ratio of 0.001 to 0.05 moles of further catalyst per mole of nitroxyl moiety being the most preferred.
• the reaction is preferably run at 0° to 100°C; more preferably at 20° to 100°C, especially in the range from 20 to 80°C.
• the C 5 -C 18 alk-1-ene may serve two functions both as reactant and as solvent for the reaction.
• the reaction can also be carried out using an inert organic or inorganic solvent.
• Such solvent may be used, especially if the further catalyst is not very soluble in the C 5 - C ⁇ 8 alk-1-ene.
• Typical inert solvents are acetonitrile, aromatic hydrocarbons like benzene, chlorobenzene, CCI 4 , alcohols (e.g. methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether), or alkanes like hexane, decane etc., or mixtures thereof.
• Inorganic solvents such as water are possible as well.
• the instant process can be run in air or in an inert atmosphere such as nitrogen or argon.
• the instant process can be run under atmospheric pressure as well as under reduced or elevated pressure.
• One variation involves the addition of a solution of organic hydroperoxide to a mixture of the N-oxyl hindered amine, the C 5 -C ⁇ 8 alk-1- ene and solvent (if used), and optionally further catalyst which has been brought to the desired temperature for reaction.
• the proper temperature may be maintained by controlling the rate of peroxide addition and/or by using a heating or cooling bath.
• the reaction mixture is conveniently stirred till the starting amineoxide has disappeared or is no longer being converted to the desired product, e.g. compound of formulae (A) to (O).
• the reaction can be monitored by methods known in the art such as UV-VIS spectroscopy, thin layer chromatography, gas chromatography or liquid chromatography. Additional portions of catalyst can be added while the reaction is in progress. After the initial hydroperoxide charge has been added to the reaction mixture, more hydroperoxide can be added dropwise to bring the reaction to completion.
• a second variation of the instant process is to simultaneously add separate solutions of the hydroperoxide and the nitroxyl compound to a mixture of the C 5 -C 18 alk-1-ene. solvent (if used) and optionally further catalyst.
• the nitroxyl compound may be dissolved in water or the solvent used in the reaction, for example an alcohol. Some of the nitroxyl compound may be introduced into the reaction mixture prior to starting the peroxide addition, and all of the nitroxyl compound should be added prior to completing the peroxide addition.
• Another variation of the instant process involves the simultaneous addition of separate solutions of the hydroperoxide and of the aqueous or solvent solution of the further catalyst to a mixture of the nitroxyl compound, C 5 -C ⁇ 8 alk-1-ene, and solvent (if used). Some of the further catalyst may be introduced into the reaction mixture prior to starting the peroxide addition.
• Still another variation of the instant process is the simultaneous addition of separate solutions of the hydroperoxide, of the aqueous or solvent solution of the nitroxyl compound, and of an aqueous or solvent solution of the further catalyst to the Cs-C 18 alk-1-ene and solvent (if used).
• a portion of the nitroxyl compound and/or catalyst may be introduced into the reaction mixture prior to starting the hydroperoxide addition. All of the nitroxyl compound should be added prior to completing the hydroperoxide addition.
• the present invention also pertains to a process, wherein the sterically hindered amine ether obtained by reacting a corresponding sterically hindered aminoxide with a C 5 -C ⁇ 8 alk-1-ene in the presence of an organic hydroperoxide is subsequently hydrogenated. Hydrogenation may take place without premature isolation of the intermediate, without washings to destroy (excess) peroxide and without solvent change, excess olefin thereby being co-hydrogenated.
• the hydrogenation is carried out in the presence of a hydrogenation catalyst.
• the hydrogenation catalyst is preferably selected from the group consisting of platinum, palladium, ruthenium, rhodium, Lindlar catalyst, platinum compounds, palladium compounds, ruthenium compounds, rhodium compounds, iridium compounds, nickel compounds, zinc compounds and cobalt compounds.
• the hydrogenation catalyst can be bound to an organic or inorganic polymer backbone, rendering a homogenous or heterogeneous catalytic system. Hydrogenation can also be carried out as transfer hydrogenation such as described in S. Murashi et al., Chem. Rev. (1998), 98, 2599-2660 or with further hydrogenation methods such as described in Larock, comprehensive organic transformations.
• the hydrogenation catalyst is selected from the group consisting of platinum, palladium, ruthenium, platinum compounds, palladium compounds and ruthenium compounds.
• the hydrogenation catalyst is selected from the group consisting of platinum, palladium and ruthenium; platinum, palladium and ruthenium immobilized on carbon; PtO 2 , Pd-CaCO 3 -PbO, RuCIH[PPh 3 ] 3l RhCI[PPh 3 ] 3 and RuH 2 [P(Ph) 3 ] 4 .
• the preferred amount of hydrogenation catalyst is 0.0001-0.2 mol per mol of unsaturated amine ether moiety.
• the hydrogenation reaction is preferably run at 0 ° to 80 C; especially in the range 20-60°C.
• the hydrogen pressure is preferably 1-20 atm.
• the process for the preparation of a sterically hindered amine ether which comprises reacting a corresponding sterically hindered aminoxide with a C 5 -C 18 alk-1-ene in the presence of an organic hydroperoxide and optionally hydrogenating the reaction product results in a mixture of sterically hindered amine ethers.
• the instant invention relates also to mixtures of sterically hindered amine ethers defined below.
• the first mixture according to the instant invention is of formula (Za)
• Q 1 is C 2 -C 15 alkyl
• Qi is C 3 -C 15 alkyl.
• such mixture is represented by formulae (A) -to (O), wherein each E is replaced
• such mixture is represented by formula (C), wherein each E is replaced by E-,.
• the second mixture according to the instant invention contains at least one group of formula (Y)
• such mixture is of formula (Ya)
• E 10 is as defined for formula (lla) and E 2 is as defined for formula (Y).
• E 10 is as defined for formula (lla) and E 2 is as defined for formula (Y).
• such mixture is represented by formulae (A) to (O), wherein each E is replaced by E 2 .
• the second mixture according to the present invention that consists of compounds containing groups of formula (Y).
• a mixture of sterically hindered amine ethers is preferred, wherein the ratio E 1a :E 1 and E 2a :E 2b respectively is independently from 1 :9 to 7:3, in particular from 1 :4 to 3:2, for example 3:7 to 1 :1 , most preferred from 7:13 to 9:11.
• the groups E ⁇ a and E 1 and independently E 2a and E 2b are distributed statistically in the molecule.
• the ratio E 1a :E 1b and E 2a :E 2 respectively in mixtures of the present invention is independent of the number of amine ether groups per molecule.
• Any mixture resulting from the processes of this invention may be separated to reveal the single amine ether components which can be afforded by conventional methods such as for example chromatography, distillation, precipitation or fractioned crystallization. However, for practical purposes it is not necessary to do so or it is even advantageous to use the mixtures unseparated.
• another aspect of the instant invention is the use of the mixtures according to this invention as stabilizers for organic material against degradation by light, oxygen and/or heat or as flame retardant for organic material, as well as a process for flame retarding or stabilizing an organic material against degradation by light, oxygen and/or heat, which process comprises applying to or incorporating into said material a mixture of sterically hindered amine ethers containing at least one group of formula (Y) or a mixture of sterically hindered amine ethers of formula (Za).
• composition comprising
• Organic materials to be protected against the damaging effect of light, oxygen and/or heat, or against fire are in particular organic polymers, preferably synthetic organic polymers.
• the sterically hindered amine ether mixtures of this invention exhibit high thermal stability, compatibility and good persistence in the materials they are incorporated in or applied to.
• Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbomene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), higti density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahig__h molecular weight polyethylene (HDPE-UHM ), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
• HDPE high density polyethylene
• HDPE-HMW higti density and high molecular weight polyethylene
• HDPE-UHM high density and ultrahig__h molecular weight polyethylene
• MDPE medium density poly
• Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: a) radical polymerisation (normally under high pressure and at elevated temperature). b) catalytic polymerisation using a catalyst that normally conta ⁇ ns one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
• ligand typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
• These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium.
• the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, I la and/or Ilia of the Periodic Table.
• the activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metalloc-ene or single site catalysts (SSC).
• Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copo- lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethy- lene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and
• Hydrocarbon resins for example C 5 -C 9 ) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
• Hydrocarbon resins for example C 5 -C 9
• hydrogenated modifications thereof e.g. tackifiers
• Polystyrene poly(p-methylstyrene), poly( -methylstyrene).
• Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acryloni- trile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpo- lymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/iso- prene/styrene, s
• Graft copolymers of styrene or ⁇ -methylstyrene for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacryl ⁇ nitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylo- nitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene
• Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
• Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.
• Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
• Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
• Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
• Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams 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 starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an ela- stomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly- m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polyte
• Polyureas Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
• Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
• Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
• Crosslinkable acrylic resins derived from substituted acrylates for example epoxy acry- lates, urethane acrylates or polyester acrylates.
• Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
• Blends of the aforementioned polymers for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE.
• mixtures of sterically hindered amine ethers of this invention preferably sterically hindered amine ethers of formulae (A) to (O), wherein E is replaced by E ⁇ as defined for formula (Za) or by E 2 as defined for formula (Y), as stabilizers in synthetic organic polymers, for example a coating or a bulk polymer or article formed therefrom, especially in thermoplastic polymers and corresponding compositions as well as in coating compositions, for example in acid or metal catalyzed coating compositions.
• Thermoplastic polymers of most importance in present compositions are polyolefines (TPO) and their copolymers, such as listed above under items 1-3, thermoplastic polyurethan (TPU), thermoplastic rubber (TPR), polycarbonate, such as in item 19 above, and blends, such as in item 27 above.
• TPO polyolefines
• TPU thermoplastic polyurethan
• TPR thermoplastic rubber
• polycarbonate such as in item 19 above
• blends such as in item 27 above.
• PE polyethylene
• PP polypropylene
• PC polycarbonate
• PC/ABS blends polycarbonate blends
• the mixtures of sterically hindered amine ethers of present invention are added to the material to be stabilized in amounts of from 0.01 to 10 %, preferably from 0.01 to 5 %, in particular from 0.01 to 2 % (based on the material to be stabilized). Particular preference is given to the use of the novel mixtures of sterically hindered amine ethers in amounts of from 0.05 to 1.5 %, especially from 0.1 to 0.5 %. Where mixtures of sterically hindered amine ethers of present invention are used as flame retardants, dosages are usually higher, e.g. 0.1 to 25 % by weight, mainly 0.1 to 10 % by weight of the organic material to be stabilized and protected against inflammation.
• incorporation into the materials can be effected, for example, by mixing in or applying the mixtures of sterically hindered amine ethers and, if desired, further additives by the methods which are customary in the art.
• incorporation can take place prior to or during the shaping operation, or by applying the dissolved or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices.
• a further possibility for incorporating the mixtures of sterically hindered amine ethers into polymers is to add them before, during or directly after the polymerization of the corresponding monomers or prior to crosslinking. In this context the mixtures of sterically hindered amine ethers can be added as it is or else in encapsulated form (for example in waxes, oils or polymers).
• the mixtures of sterically hindered amine ethers can also be added in the form of a masterbatch containing said compound in a concentration, for example, of from 2.5 to 25 % by weight to the polymers that are to be stabilized.
• the mixtures of sterically hindered amine ethers can judiciously be incorporated by the following methods: - as emulsion or dispersion (e.g. to latices or emulsion polymers), as a dry mixture during the mixing in of additional components or polymer mixtures, by direct introduction into the processing apparatus (e.g. extruders, internal mixers, etc), as solution or melt.
• emulsion or dispersion e.g. to latices or emulsion polymers
• the processing apparatus e.g. extruders, internal mixers, etc
• Novel polymer compositions can be employed in various forms and/or processed to give various products, for example as (to give) films, fibres, tapes, moulding compositions, profiles, or as binders for coating materials, adhesives or putties.
• the present compositions comprise as component C further additives.
• the further additives are antioxidants, UV-absorbers, light stabilizers, metal deactivators, phosphites, phosphonites, hydroxylamines, nitrones, thiosynergists, peroxide scavengers, basic co-stabilizers, nucleating agents, fillers, reinforcing agents, benzofuranones, indolinones and/or flameproofing agents.
• the novel compositions may as additional component C comprise one or more conventional additives such as, for example, those indicated below. 1.
• Antioxidants such as, for example, those indicated below.
• Al ylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethyl phenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4- methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec
• Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioc- tylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl- ⁇ -ethylphenol, 2,6-di-dodecylthiomethyl- 4-nonyl phenol.
• Hvdroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert- butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4- hydroxyphenyl) adipate.
• 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquino
• Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (Vitamin E).
• Hvdroxylated thiodiphenyl ethers for example 2,2'-thiobis(6 ⁇ tert ⁇ butyl-4-methylphenol).
• Alkylidenebisphenols for example 2,2 , -methylenebis(6-tert-butyl-4-methylphenol) .
• 2,2'- methylenebis(6-tert-butyl-4-ethylphenol) 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol) ) 2,2'-methylenebis(6-nonyl-4-me- thylphenol
• tridecyl-4-hydroxy- 3,5-di-tert-butylbenzylmercaptoacetate tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine J bis(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy- benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
• Hydroxybenzylated malonates for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hy- droxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di- dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 , 1 ,3,3-te- trarhethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
• Aromatic hvdroxybenzyl compounds for example 1 ,3,5-tris-(3_5-di-tert-butyl-4-hydroxy- 1 ,4-bis(3 J 5-di-tert-butyl-4-hydroxybenzyl)-2 ) 3,5,6-tetrame- thylbenzene, 2,4,6-tris(3 J 5-di-tert-butyl-4-hydroxybenzyl)phenol.
• Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3 . 5-di-tert-butyl-4-hy- droxyanilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5- triazine, 2-octylmercapto-4,6-bis(3 J 5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6- tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris-(3,5-di-tert-butyl-4-hydroxy- benzyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-di
• Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
• Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
• esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9- nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymet yl-1
• esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or poly- hydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'- bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trio
• esters of ⁇ -(3,5-dicyclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2
• esters of 3,5-di-tert-butv -hvdroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- arnide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]oct
• Aminic antioxidants for example N.N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec- butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1- ethyl-3-methylpentyl)-p-phenylenediamine, N l N'-bis(1-methylheptyl)-p-phenylenediamine, N.N'-dicyclohexyl-p-phenylenediamine, N.N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naph- thyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)- N'-
• p'-di-tert-octyldiphenylamine 4- n-butylaminophenol. 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylamino- phenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dime- thylaminomethylphenol, 2,4'-diaminodiphenylmethane.
• phenothiazine a mixture of mono- und dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylated tert-octyl-phe- nothiazines, N-allylphenothiazin, N.N.N'jN'-tetraphenyl-l ⁇ -diaminobut ⁇ -ene, N,N-bis- (2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine 1 bis(2,2,6,6-tetramethylpiperid-4-yl)- sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2 J 6,6-tetramethylpiperidin-4-ol.
• 2-(2'-Hvdroxyphenyl)benzotriazoles for example 2-(2'-hydroxy-5'-methylphenyl)-benzo- triazole, 2-(3 , ,5 , -di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5 ,1 .
• Esters of substituted and unsubstituted benzoic acids as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl benzoate, 2-methyl-4,6-di-tert-butylphenyl 3 J 5-di-tert-butyl-4-hydroxybenzoate.
• Nickel compounds for example nickel complexes of 2,2 , -thio-bis-[4-(1,1 ) 3,3-tetrame- thylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of kefoxirnes, e.g. of 2-hydroxy-4-methylphe- nyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
• additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldi
• sterically hindered amines for example bis(2,2,6,6-tetramethyl-4- piperidyl)sebacate, bis(2,2,6 J 6-tetramethyl-4-piperidyl)succinate, bis(1 ,2,2,6,6-pentamethyl-4- piperidyl)sebacate, bis(1-octyloxy-2,2 J 6,6-tetramethyl-4-piperidyl)sebacate J bis(1 ,2,2,6,6- pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6 .
• 6-tetramethyl-4-hydroxypiper ⁇ dine and succinic acid linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4- tert-octylamino ⁇ -dichloro-I.S.S-triazine, tris(2 J 2,6 I 6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1 ,2,3,4-butane-tetracarboxylate, 1 , 1 '-(1 ,2-ethanediyl)- bis(3 l 3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6 1 6-tetramethylp ⁇ peridine, 4-stearyloxy- 2,2,6,6-tetramethylpiperidine, bis(1 ) 2 > 2,6,6-pentamethylpipe
• Oxamides for example 4,4'-dioctyloxyoxanilide, 2,2-diethoxyoxanilide, 2,2'-dioctyloxy- S. ⁇ '-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide 1 2-ethoxy-2'-ethyloxanilide, N J N , -bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2 , -ethyl-5 ) 4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
• Metal deactivators for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl) hydrazine, IM,N , -bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, S-salicyloylamino-l. ⁇ -triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydraz.de, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyl dihydrazide, N,N'-bis ⁇ salicyloyl)thiopropionyl dihydrazide.
• Phosphites and phosphonites for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di- tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, di
• phosphites Especially preferred are the following phosphites:
• Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos ® 168, Ciba-Geigy), tris(nonylphenyl) phosphite,
• Nitrones for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-oc- tyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone, N- hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl- alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadiecyl-nitrone, N-heptadecyl-alpha-hep- tadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitro
• Thiosvner ⁇ ists for example, dilauryl thiodipropionat-e or distearyl thiodipropionate.
• Peroxide scavengers for example esters of ⁇ -thioclipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimicfazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ - dodecylmercapto)propionate.
• esters of ⁇ -thioclipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimicfazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ - dodecyl
• Polyamide stabilisers for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
• Basic co-stabilisers for example, melamine, polyvinylpyrrolidone, dicyandiamide. triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zink pyrocatecholate.
• Basic co-stabilisers for example, melamine, polyvinylpyrrolidone, dicyandiamide. triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium
• Nucleating agents for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolym-ers (ionomers).
• inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
• organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
• polymeric compounds such as ionic copolym-ers (
• Fillers and reinforcing agents for example, calcium carbon-ate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
• additives for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
• the conventional additives are judiciously employed in amounts of 0.1-10 % by weight, for example 0.2-5 % by weight, based on the material to be stabilized.
• Example 1 Preparation of an O-octenyl sterically hindered amine ether from the corresponding nitroxide and 1-n-octene with a tert-BuOOH/CuBr 2 catalyst system.
• Example 2 Preparation of an O-octenyl sterically hindered amine ether (same compound as in example 1) from the corresponding nitroxide and 1-n-octene with a tert-BuOOH/Bu 4 NI catalyst system.
• the aqueous phase is then separated and washed with cyclohexane.
• the combined organic phases are passed through a plug of silica gel and washed with brine, dried over MgSO , filtered and the solvent is distilled off on a rotary- evaporator, yielding 11 g (82.3% of theory) of product exhibiting the same 1 H-NMR spectrum as above.
• Example 3 Preparation of an O-octyl sterically hindered amine ether by hydrogenation of O- octenyl sterically hindered amine ether (product of example 1 or 2). 2,2,6,6-Tetramethyl-1- 2,2,6,6-Tetramet y[-1- n-octyloxy-piperidine (1-ethyl-n-hexyloxy)-piperidine
• a mixture of 10 g (37.4 mmol) of the crude product of example 1 or 2 and 1.9 g Pd on charcoal (10%) in 100 ml methanol is hydrogenated at 25°C and 4 bar hydrogen pressure. Filtration and evaporation of the solvent yields 7 g (69.5% of theory) of a slightly orange oil, a mixture of 2,2,6,6-tetramethyl-l-n-octyloxy-piperidine (ca 40 mol% by 1 H-NMR) and 1-(1- ethyl-n-hexyloxy)-2,2,6,6-tetramethyl-piperidine (ca 60 mol% by 1 H-NMR).
• Example 4 (comparison): Preparation of an O-octyl sterically hindered amine ether by direct coupling of the corresponding nitroxide and n-octane with a tert-BuOOH/CuBr 2 catalyst system.
• the greenish emulsion is cooled down to 25°C and stirred with 75 g of an aqueous 20% Na 2 SO 3 solution until the disappearance of excess tert-butylhydroperoxide.
• the aqueous phase is then separated and washed with octane.
• the combined organic phases are washed with brine, dried over MgSO , filtered and the solvent is distilled off on a rotary- evaporator.
• Example 5 Preparation of an O-octenyl sterically hindered amine ether from the corresponding nitroxide and 1-n-octene with a tert-BuOOH/CuBr 2 catalyst system.
• the green emulsion is cooled down to 25°C and stirred with 85 g of an aqueous 20% Na 2 SO 3 solution until the disappearance of excess tert-butylhydroperoxide.
• the aqueous phase is then separated and washed with cyclohexane.
• the combined organic phases are washed with brine, dried over MgSO , filtered and the solvent is distilled off on a rotary-evaporator.
• Example ⁇ Preparation of an O-octyl sterically hindered amine ether by hydrogenation of an O-octenyl sterically hindered amine ether (product of example 5).
• Example 7 (comparison): Preparation of an O-octyl sterically hindered amine ether by direct coupling of the corresponding nitroxide and n-octane with a tert-BuOOH/CuBr 2 catalyst system.
• Example 8 Preparation of an O-octenyl sterically hindered amine ether by coupling of the corresponding nitroxide and 1-n-octene with a tert-BuOOH/CuBr 2 catalyst system.
• R, R' mixture of n-oct-2-ene-1-yl and 1-vinyl-n-hexyl
• Example 9 Preparation of an O-octenyl sterically hindered amine ether (same compound as in example 8) by coupling of the corresponding nitroxide and 1-n-octene with a tert- BuOOH/Bu 4 NI catalyst system.
• the yellow emulsion is cooled down to 25°C and stirred with 47 g of an aqueous 20% Na 2 SO 3 solution until the disappearance of excess tert- butylhydro peroxide.
• the aqueous phase is then separated and washed with pentane.
• the combined organic phases are washed with brine, dried over MgSO 4 , filtered and the solvent is distilled off on a rotary-evaporator to give 14.49 g (79% of theory) of a yellowish oil exhibiting the same 1 H-NMR spectrum as the mixture of example 8.
• Example 10 Preparation of an O-octyl sterically hindered amine ether by hydrogenation of an O-octenyl sterically hindered amine ether (product of example 8)
• R, R' mixture of 1-n-octyl and 1-ethyl-n- exyl
• Example 11 Preparation of an O-octyl sterically hindered amine ether by coupling of the corresponding nitroxide and 1-n-octene with a tert-BuOOH/CuCI 2 catalyst system followed by hydrogenation (same product as in example 10)
• the green emulsion is cooled down to 25°C and stirred with 22 g of an aqueous 20% Na 2 SO 3 solution until the disappearance of excess tert- butylhydroperoxide.
• the organic phase is separated, washed with brine, dried over MgSO 4 , filtered and the solvent distilled off on a rotary-evaporator yielding a yellow oil.
• Example 12 Preparation of an O-octyl sterically hindered amine ether (same product as in examples 10 and 11) by coupling of the corresponding nitroxide and 1-n-octene with a tert- BuOOH/Bu 4 NI catalyst system followed by hydrogenation.
• Example 12a Preparation of an O-octyl sterically hindered amine ether (same product as in examples 10 -12) without isolation of the intermediate, i.e. without solvent change.
• t-Butylhydroperoxide (70% in water; 2.1g, 16.3mmol) is added at 60°C within 15 minutes to a stirred mixture of bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate (Prostab® 5415, Ciba Specialty Chemicals Inc.; 4.6g, 9.0mmol), 1-octene (97%; 20.8g, 179.8mmol) and Bu NI (0.067g, 0.18mmol). The temperature of the reaction mixture is held at 60°C for a total of 4.5 hours. The yellow emulsion is cooled down to 25°C and the water-phase split off.
• Example 13 Preparation of an O-hexenyl sterically hindered amine ether from the corresponding the corresponding nitroxide and 1-n-hexene with a tert-BuOOH/CuBr 2 catalyst system.
• aqueous phase is then separated and washed with pentane.
• the combined organic phases are washed with water, dried over MgSO 4 , filtered and the solvent distilled off on a rotary-evaporator to give 17.75 g (88% of theory) of a yellow liquid.
• Example 14 Preparation of an O-hexyl sterically hindered amine ether by hydrogenation of the O-hexenyl sterically hindered amine ether (product of example 13).
• R, R' mixture of n-oct-2-ene-1-yl and 1-vinyl-n-hexyl
• R, R' mixture of 1-n-octyl and 1-ethyl-n-hexyl
• the amino ethers of the present invention are incorporated into a thermosetting acryl / melamine clear coat (based on Viacryl® SC 303 / Viacryl® SC 370 / Maprenal® MF 650) in a concentration of 1% based on the solids content of the formulation (solids content: 50.4%).
• the clear coat is sprayed onto silver metallic base coat resulting after cure (130°C / 30') in a dry film t ickness of the clear coat of 40 ⁇ m.
• electro coated aluminium panels (10x30cm) as commercially available from ACT Laboratories (ACT Laboratories, Inc., Southfield, Michigan 48075, USA) are being used. The panels are subsequently exposed in a Xenon - WOM wetherometer (Atlas Corp.) according to SAE J 1960. The 20° gloss is recorded in regular intervals.
• Table 1 Table 1 l:
• Viacryl SC 303 acrylic resin (Solutia, formerly Vianova Resins) 27.51 g (65% solution in xylene/butanol, 26:9 wt./wt.)
• Viacryl SC 370 acrylic resin (Solutia, formerly Vianova Resins) 23.34g (75% in Solvesso 100: aromatic hydrocarbon, bp.

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• 2005
  • 2005-03-07 WO PCT/EP2005/050995 patent/WO2005090307A1/en not_active Ceased
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  • 2005-03-07 JP JP2007503327A patent/JP2007529467A/ja active Pending
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