USRE31343E - Piperidine derivatives - Google Patents

Piperidine derivatives Download PDF

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USRE31343E
USRE31343E US05/938,849 US93884978A USRE31343E US RE31343 E USRE31343 E US RE31343E US 93884978 A US93884978 A US 93884978A US RE31343 E USRE31343 E US RE31343E
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iadd
iaddend
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Brian Holt
Donald R. Randell
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Novartis Corp
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Ciba Geigy Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • 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
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids
    • 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 new piperidine derivatives, and in particular to new piperidine derivatives substituted at the 1- and 4- positions and having value as stabilisers for polymeric materials.
  • acyl group derived from an aliphatic, alicyclic or heterocyclic mono-carboxylic acid an N-substituted carbamoyl group derived from an N-substituted carbamic acid, an N-substituted thiocarbamoyl group derived from an N-substituted thiocarbamic acid, a monovalent group obtained by removing an hydroxyl group from an oxo-acid, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a group having the formula: ##STR3## wherein R 1 ' and R 2 ' have their previous significance; when n' is 2, R 2 is a diacyl group derived from an aliphatic, alicyclic, aromatic or heterocyclic dicarboxylic acid, a dicarbamoyl group derived from a dicarbamic acid, a bis-thiocarbamoyl group
  • .Iadd.R 3 '.Iaddend. is a triacyl group, derived from an aliphatic, alicyclic, aromatic or heterocyclic tricarboxylic acid, a tricarbamoyl group derived from tricarbamic acid, a tris-thiocarbamoyl group derived from a tris-thiocarbamic acid, a trivalent group obtained by removing three hydroxyl groups from an oxo-acid, an alkanetriyl group, arenetriyl group or an arenetriyl trialkylene group.
  • n 1, 2, 3 or 4
  • R 1 is a monovalent residue and is an alkyl residue having from 1 to 20, preferably 1 to 12 carbon atoms, an alkenyl or alkynyl residue having from 3 to 20, preferably 3 to 12 carbon atoms, an aralkyl residue having from 7 to 12 carbon atoms, or a residue having the formula: ##STR5## wherein m is 1, 2 or 3; R 4 is hydrogen, methyl or phenyl residue, X 2 is halogen, cyano, ##STR6## --COR 5 , --CO.OR 5 , --CO.SR 5 , or --CONR 5 R 6 and X 1 is hydroxyl, halogen, cyano, --OR 5 , ##STR7## wherein R 5 is an alkyl residue having from 1 to 20 carbon atoms, an alkenyl residue having from 2 to 20 carbon atoms, a residue having the formula: ##STR5## wherein m is 1, 2 or 3; R 4 is hydrogen,
  • R 3 is a divalent residue and is an alkylene residue having from 1 to 20 carbon atoms, an alkenylene residue having from 2 to 20, preferably 3 to 20, carbon atoms, an alkynylene residue having from 2 to 20, preferably 3 to 20, carbon atoms, cycloalkylidene residue having from 5 to 12 carbon atoms, an arylene residue having 6 to 14 carbon atoms, an aralkylene residue having from 8 to 14 carbon atoms or an aliphatic, aromatic or heterocyclic diacyl residue, ##STR11## an aliphatic or aromatic dicarbamoyl or dithiocarbamoyl residue, sulphinyl or sulphonyl residue or a divalent residue obtained by removing two hydroxyl groups from a disulphonic acid, a phosphorus containing acid or a boric acid.
  • R 3 is a trivalent residue and is an .[.arenetriyl.]. .Iadd.alkanetriyl .Iaddend.or an arenetriyl-trialkylene residue, an aliphatic or aromatic triacyl residue or a triacyl residue derived from o-phosphoric, o-phosphorous or o-boric acid; and
  • R 3 is a tetravalent residue and is an alkane tetrayl residue, or a tetraacyl residue derived from an aliphatic or aromatic tetracarboxylic acid or from o-silicic acid;
  • R 1 and/or R 3 may be an alkyl residue having from 1 to 20 carbon atoms, preferred 1 to 18, examples of this substituent are methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl residue and eicosyl.
  • alkyl substitutents R 1 and/or R 3 having from 5 to 20, especially 5 to 12 carbon atoms are preferred.
  • a sub-group of alkyl residues R 1 is that containing from 1 to 4 carbon atoms, preferably methyl.
  • R 1 and/or R 3 is an alkenyl residue having from 3 to 20 carbon atoms
  • substituents are allyl, methallyl, 3-hexenyl, 4-octenyl, 6-decenyl, 10-undecenyl, and8-octadecenyl residues, however the preferred substituents in this group are allyl and methallyl residues.
  • R 1 and/or R 3 are alkynyl they may be for example propargyl, but-1- and -2-ynyl, pent-1-ynyl, hex-1-ynyl, oct-1-ynyl, dec-1-ynyl, dodec-1-ynyl, tetradec-1-ynyl and octadec-1-ynyl.
  • the preferred alkynyl substituents however are propargyl and methylpropargyl.
  • R 1 and/or R 3 is an aralkyl residue
  • suitable examples are benzyl, ⁇ -phenethyl, ⁇ -methylbenzyl, ⁇ -dimethylbenzyl, ⁇ -naphthylmethyl and p-methyl- ⁇ -methylbenzyl residues.
  • Benzyl is preferred.
  • R 1 and/or R 3 substituents is substituted alkyl derivatives having the formula: ##STR12## wherein m, R 4 , X 1 and X 2 have their previous significance, but wherein, however, R 4 is preferably hydrogen and m is preferably 1.
  • examples of this substituents R 1 and/or R 3 are 2-hydroxyethyl, 2- and 3-hydroxypropyl, 3- and 4-hydroxybutyl, 4-hydroxypentyl and 2-hydroxy-2-phenyl ethyl, preferably 2-hydroxyethyl, 2-hydroxypropyl and 2-hydroxy-2-phenylethyl.
  • R 1 and/or R 3 include 2-chloro- and 2-bromo ethyl, 2- and 3-chloro- and 2- and 3-bromopropyl, 3- and [4-chorobutyl and 2-chloro-2-phenyl ethyl, preferably 2-choroethyl, 2-chloropropyl and 2-chloro-2-phenylethyl.
  • R 1 and/or R 3 include cyanomethyl, 1- and 2- cyanobutyl, 4-cyanopentyl, 2-cyano-2-phenylethyl groups, preferably a 2-cyanoethyl group.
  • R 1 and/or R 3 may be 2,3-epoxy-n-propyl, 2,3 -epoxy-methylpropyl, but the preferred epoxyalkyl substituent is 2,3 -epoxy-n-propyl.
  • X 1 is --OR 5 , --OCOR 5 , --OCSR 5 , --OCONR 6 R 5 , --CSNR 6 R 5 , or when X 1 and/or X 2 are --COR 5 , --COOR 5 , --COSR 5 , --CONR 6 R 5 and the group R 5 is alkyl, then the alkyl group preferably has from 1 to 12, most preferred 1 to 2, carbon atoms; when R 5 is an alkenyl residue, then it preferably contains 2 to 4 carbons; when R 5 is a cycloalkyl group it preferably contains 6 carbon atoms; when R 5 is an aryl residue it preferably contains 6 or 7 carbons; and when R 5 is an aralykyl residue, it preferably has 7 or 8 carbon atoms.
  • R 5 and R 6 together with the nitrogen atom to which they are bound can form a 5- or 6-membered ring such as the pyrrolidinyl-, imidazolidinyl-, pyrazolidinyl-, piperidinyl-, piperazinyl- or morpholinyl ring.
  • R 1 and/or R 3 within this sub-group ae 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-n-butoxypropyl, 3- and 4-methoxybutyl, 3- and 4-ethoxybutyl, 3- and 4-butoxybutyl, 4-methoxypentyl, 4-ethoxypentyl, 4-n-butoxypentyl, 2-methoxy-2-phenyl ethyl, 2-ethoxy-2-phenyl ethyl; 2-acetoxyethyl, 2-n-propionoxyethyl, 2-benzoyloxy ethyl, 2-acetoxypropyl, 2-n-propionoxypropyl, 4-acetoxybutyl, 4-n-propionoxybutyl, 4-acetoxypentyl, 4-n-propionoxypentyl, 4-
  • R 7 is an unsubstituted aliphatic or substituted aliphatic residue having from 1 to 20, preferably 1 to 19, carbon atoms
  • R 7 may be a methyl, ethyl, propyl, butyl, hexyl, n-octyl, 2-ethylhexyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-heptadecyl and eicosyl, chloroethyl, chlorohexyl, methylthioethyl, ethylthioethyl, octylthioethyl, or dodecylthioethyl residue; alkenyl residues R 7 have from 2 to 20, preferably 2 to 17, most
  • acyl groups R 1 and/or R 3 are formyl, acetyl, propionyl, n-butyryl, hexanoyl, heptanoyl, octanoyl, 2-ethylhexanoyl, 2,2,4-trimethylpentanoyl, n-decanoyl, n-dodecanoyl, n-tetradecanoyl, n-hexadecanoyl, n-octadecanoyl, n-eicosoyl, acryloyl, ⁇ -methacrylol, crotonoyl, undec-10-enoyl, octadec-9-enoyl, ⁇ -methylthiopropionyl, methylthioacetyl, ⁇ -octylthiopropionyl, ⁇ -dodecylthiopropionyl, cyclopentano
  • R 1 and/or R 3 may also be a carbamoyl or thiocarbamoyl residue having the formula: ##STR13## wherein X 3 is --O-- or --S--, R 8 is hydrogen or an alkyl residue having from 1 to 4 carbon atoms and R 9 is hydrogen, an alkyl residue having from 1 to 20, preferably 1 to 8, carbon atoms, an alkenyl residue having from 3 to 20 carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms or an unsubstituted .[.alkyl.].
  • aryl for instance, alkyl or halogen-substituted aryl residue having from 6 to 12, preferably 6 to 10, carbon atoms.
  • suitable residues within this group are carbamoyl, N-methylcarbamoyl, N-ethyl-carbamoyl, N-n-propylcarbamoyl, N-isopropylcarbamoyl, N-n-butylcarbamoyl, N-n-pentylcarbamoyl, N-n-octylcarbamoyl, N-n-decylcarbamoyl, N-n-dodecylcarbamoyl, N-n-octadecyl, N-n-eisocylcarbamoyl, N-allylcarbamoyl, N-methallylcarbamoyl, N-
  • R 2 is an alkyl residue it is for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, preferably methyl, as alkenyl residue
  • R 2 is for example allyl, methallyl, 3-hexenyl, 4-octenyl, 6-decenyl, 10-undecenyl or 8-octadecenyl, peferably allyl or methallyl and as alkynyl residue for example propargyl, but-1- and -2-ynyl, penta-1-ynyl, hex-1-ynyl, oct-1-ynyl, dec-1-ynyl, dodec-1-ynyl, tetradec-1-ynyl and octadec-1-ynyl, preferably propargyl
  • R 2 as cycloalkyl is
  • R 3 may be the same as R 1 . If R 3 is alkyl it is preferably an alkyl group having from 3 to 18 carbon atoms.
  • R 3 represents an aryl residue it is for example an aromatic residue having 6 to 20 carbon atoms, preferably an aryl residue having 6 to 12 carbon atoms, most preferred phenyl.
  • R 3 is, for example an alkylene residue having from 1 to 20, preferably 2 to 6, carbon atoms such as methylene, ethylene, trimethylene, tetramethylene or hexamethylene residue.
  • Alkenylene residues R 3 preferably contain 3 to 20, most preferred 3 or 4 carbons, and may be, for instance a 1,3-propen-ene or 1,4-buten-2-ene residue.
  • Alkynylene residues R 3 preferably contain 3 to 20, most preferred 4 carbon atoms and may be, for instance a 1:4 but-2-ynylene residue.
  • R 3 is a cycloalkylidene residue, it preferably contains 7 or 8 carbon atoms, for instance a cyclohexyldimethylene residue.
  • R 3 is arylene it has preferably 6 to 12 carbon atoms and it may be for example 1,3-phenylene, or 4,4'-diphenylene.
  • R 3 is aralkylene it may be for example ⁇ , ⁇ -p-xylylene.
  • Diacyl residues R 3 include those derived from an aliphatic, aromatic or heterocyclic dicarboxylic acid.
  • aliphatic dicarboxylic acids are those having from 2 to 20, preferably alkan dicarboxylic acids having 6 to 10 carbon atoms such as malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, 1,12-dodecanedioic, 1,18 -octadecanedioic, 1,20-docosanedioic acid and N-methyliminodiacetic acid.
  • aromatic diacyl residues are those derived from phthalic, isophthalic and terephthalic acids, each optionally ring-substituted, for instance by halogen, an alkyl or alkoxy group each having from 1 to 20 carbon atoms, a hydroxy or tertiary amino group.
  • heterocyclic dicarboxylic acids examples include 2,5-thiophene dicarboxylic acid or 2,5-furandicarboxylic acid.
  • R 3 is for example an aliphatic or aromatic dicarbamoyl residue such as a divalent .[.alkyl.]. .Iadd.alkylene .Iaddend.dicarbamoyl residue for example the divalent residue of butan-1,4-dicarbamoyl or hexan-1,6-dicarbamoyl or such as a divalent .[.aryl.]. .Iadd.arylene .Iaddend.dicarbamoyl residue such as the divalent residue of .[.phenyl.]. .Iadd.phenylene.Iaddend.-1,4-dicarbamoyl.
  • R 3 is for example an aliphatic or aromatic dithicarbamoyl residue such as a divalent .[.alkyl.]. .Iadd.alkylene .Iaddend.dithicarbamoyl residue for example the divalent residue of butan-1,4-dithiocarbamoyl or hexan-1,6-dithiocarbamoyl or such as an divalent .[.aryl.]. .Iadd.arylene .Iaddend.dithiocarbamoyl residue sue as the divalent residue of .[.phenyl.]. .Iadd.phenylene.Iaddend.-1,4-dithiocarbamoyl.
  • R 3 is, for instance, a triacyl group derived from an aliphatic tricarboxylic acid such as nitrilotriacetic acid, tricarballylic acid, from an aromatic tricarboxylic acid such as benzene tricarboxylic acid or from an inorganic acid such as o-phosphorous, o-phosphoric or o-boric acid, or oxyacids, for example, benzene-1,3,5-trisulphonic acid.
  • an aliphatic tricarboxylic acid such as nitrilotriacetic acid, tricarballylic acid
  • an aromatic tricarboxylic acid such as benzene tricarboxylic acid
  • an inorganic acid such as o-phosphorous, o-phosphoric or o-boric acid, or oxyacids, for example, benzene-1,3,5-trisulphonic acid.
  • R 3 is, for instance, a tetracyl group derived from a tetracarboxylic acid, such as ethylene diamine, tetracarboxylic acid, from the tetracarboxylic acids described in British Patent Specification No. 1080335, 1,2,4,5,-benzene tetracarboxylic acid or from o-silicic acid.
  • a tetracyl group derived from a tetracarboxylic acid such as ethylene diamine, tetracarboxylic acid, from the tetracarboxylic acids described in British Patent Specification No. 1080335, 1,2,4,5,-benzene tetracarboxylic acid or from o-silicic acid.
  • R 3 preferably represents an acyl or an N- substituted carbamoyl, an alkylene group, a substituted alkylene or an aralkyl group.
  • R 1 preferably represents an alkyl, alkenyl, or substituted alkyl group such as hydroxyalkyl, alkylcarbonyloxy or aralkyl group.
  • Examples of compounds of the present invention are:
  • Toluene-2 4 ⁇ -bis[4-carbamoyloxy-1-(2'-hydrocyethyl)-2,2,6,6-tetramethylpiperidine].[.Diphenylmethane.].-4',4"-bis.Iadd.Diphenylmethane-[4-carbamoyloxy-1-(2'-cyanoethyl)-2,2,6,6-tetramethylpiperidine]
  • the invention also includes salts of the compounds of Formula I, for instance salts of inorganic acids such as phosphates, carbonates, sulphates and chlorides and salts of organic acids such as acetates, stearates, maleates, citrates, tartrates, oxalates, benzoates and substituted carbamic acids.
  • inorganic acids such as phosphates, carbonates, sulphates and chlorides
  • organic acids such as acetates, stearates, maleates, citrates, tartrates, oxalates, benzoates and substituted carbamic acids.
  • R 1 or R 3 can be represented by a monovalent, divalent or trivalent group obtained by removing 1 to 3 hydroxyl groups from a sulphonic acid, a sulphinic acid, a disulphonic acid, a phosphorus containing acid, such as o-phosphoric or o-phosphorous acid or a boric acid.
  • the following list shows compounds with acid radicals for R 3 .
  • the same radicals are also examples for R 1 .
  • a preferred sub-group of compounds of formula 1 are those compounds having the formula: ##STR14## and their salts, wherein Y is an alkyl group having from 1 to 20, preferably 1 to 4, carbon atoms, alkenyl having from 3 to 20 carbon atoms or an aralkyl residue, preferably having from 7 to 9 carbon atoms, and n 1 is 1 or 2; when n 1 is 1, R is hydrogen or a monovalent aliphatic residue having from 1 to 20, preferably 6 to 20 carbon atoms, a monovalent alicyclic residue having from 5 to 12 carbon atoms, or a monovalent aromatic residue having from 6 to 20 carbon atoms; or ##STR15## and when n 1 is 2, R is a divalent aliphatic residue having from 1 to 20, preferably 4 to 20 carbon atoms, a divalent alicyclic residue having from 5 to 12 carbon atoms or a divalent aromatic residue having from 6 to 14 carbon atoms.
  • Two sub-groups of the compounds of the formula Ia
  • substituents Y are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.butyl, n-hexyl, n-octyl, n-dodecyl, n-octadecyl, eicosyl, allyl, methallyl, oleyl, benzyl, ⁇ -methylbenzyl, p-methylbenzyl and p-methyl- ⁇ -methylbenzyl, However, it is particularly preferred that Y is methyl.
  • R can be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.butyl, t-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, n-hexyl, 2-methylpentyl, n-heptyl, 2-ethylpentyl, n-octyl, 2,2,4-trimethylpentyl, n-decl, n-undecyl, n-tridecyl, n-pentadecyl, n-heptadecyl, eicosyl, vinyl ⁇ - or ⁇ -methylvinyl, dec-9-enyl, heptadec-8-enyl, ⁇ -methythioethyl, ⁇ -octylthioethyl, ⁇ -dodecylthioe
  • R are those listed above containing from 6 to 20 carbon atoms, as well as the group having the formula: ##STR17## wherein R 10 and R 11 are the same or different and each is an alkyl group having from 1 to 6, preferably 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, sec.butyl, t-butyl, t-pentyl, (1,1,-dimethylpropyl), t-hexyl (1,1,-dimethylbutyl), but preferably methyl, isopropyl or t-butyl groups: A is -CH 2- , ##STR18## and p is 0 or 1.
  • R can be methylene, 1,2,-ethylene, 1,4-n-butylene, 1,8-n-octylene, 2,2,4-trimethyl-1, 4-butylene, 1,10-n-decylene, 1,2-eicosylene, vinylene, propenylene, 1,2-, 1,3- and 1,4-cyclohexylene, cyclohexyl-3-ene, 11,2-, 1,3- and 1,4-phenylene, p-xylylene, 1,4-, and 1,5-naphthylene, diphenylene or diphenylmethylene.
  • a further preferred sub-group of compounds of formula I are those having the formula: ##STR19## and is salts wherein Y 1 is an alkyl residue having from 1 to 12 carbon atoms, an alkenyl residue having from 3 to 12 carbon atoms or an aralkyl residue having from 7 to 9 carbon atoms and R 12 is hydrogen or an alkyl or alkylen containing up to 20 carbon atoms, and substituted alkyl having the formula ##STR20## wherein m is 1, 2 or 3, R 4 is hydrogen or methyl, .[.S 1 .].
  • X 1 is halogen or methoxy and X 2 is halogen or R 12 is an alkenyl or alkenylen having up to .Badd.20 carbon atoms, a cycloalkyl or cycloalkyliden having 5 to 12 carbon atoms, an aryl or arylen having 6 to 12 carbon atoms and q is 1 or 2.
  • Two sub-groups of compounds of the formula Ib are those having as Y 1 alkyl from 1 to 4 and alkyl having 5 to 12 carbom atoms.
  • R 12 can be for example hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl, t-butyl, n-pentyl, 2-ethylpropyl, 2-methylbutyl, n-hexyl, 2-methylpentyl, n-heptyl, 2-ethylpentyl, n-octyl, 2-ethylhexyl, 2,2,4-trimethylpentyl, n-decyl, n-dodecyl, n-tetradecyl, n-octadecyl, eicosyl, mesityl, allyl, oleyl, cyclopentyl, cyclohexyl, methylcyclohexyl, t-butylcyclohexyl, t-octylcylohexyl, eicosyl
  • Preferred monovalent groups R 12 are hydrocarbyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, 2-ethylhexyl, dodecyl, octadecyl, allyl, oleyl, cyclohexyl, benzyl, phenyl, o-, m- and p-tolyl, 2,4- and 2,6-xylyl and naphthyl.
  • R 12 can be for example methylene, 1,2-ethylene, 1,4-n-butylene, 1,6-n-hexylene, 1,8-n-octylene, 2,4,4-trimethyl-1,6-hexylene, 1,10-n-decylene, 1,2-eicosylene, 1,2-eicosenylene, 1,3- and 1,4-cyclohexylene, 1,3- and 1,4-phenylene, 2,4-tolylene, 1,5-naphthylene, 4,4'-diphenylene, 4'-diphenylemethylene, 3,3'-dimethyl-4,4'-diphenylene, 3,3'-dimethyl-4,4'-diphenylmethylene.
  • Preferred divalent groups R 12 are 1,2-ethylene, 1,6-hexylene, 2,4,4-trimethyl-1,6-hexylene, 1,3- and 1,4-phenylene, 2,4-tolylene, 1,5-naphthylene, 4,4'-diphenylmethylene.
  • examples of the group Y 1 are methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl, n-hexyl, n-octyl, n-dodecyl, allyl, ⁇ -methallyl, 10-undecenyl, benzyl, ⁇ -methylbenzyl, p-methylbenzyl, p-methyl- ⁇ -methylbenzyl, ⁇ -naphthylmethyl.
  • Particularly preferred are straight or branched alkyl having 1 to 4 carbon atoms and for reasons of ease of preparation the most preferred meaning for Y 1 is methyl.
  • R 3 is a monovalent residue and is an alkyl residue having from 1 to 20 carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms, an alkenyl or alkynyl residue having from 3 to 20 carbom atoms, an aralkyl residue having from 7 to 12 carbon atoms, or a residue having the formula: ##STR21## wherein m is 1, 2 or 3, R 4 is a hydrogen, methyl or phenyl residue, X 2 is halogen, cyano, ##STR22## --COR 5 , --CO.OR 5 , --CO.SR 5 or --CONR 5 R 6 and X 1 is hydroxyl, halogen, cyano, -OR 5 , ##STR23## wherein R 5 is an alkyl residue having from 1 to 20 carbon atoms, an alkenyl residue having from 2 to 20 carbon atoms, a cycloalkyl residue having 5
  • R 3 is an acyl group ##STR25## wherein R 7 is hydrogen, an unsubstituted aliphatic or substituted aliphatic residue having from 1 to 20 carbon atoms, an alkenyl or alkynyl residue having from 2 to 20 carbon atoms, a cycloaliphatic residue having from 5 to 12 carbon atoms, an araliphatic residue having from 7 to 14 carbon atoms, an aromatic residue having from 6 to 20 carbon atoms, or an heterocyclic residue, or R 3 represents a monovalent group obtained by removing a hydroxyl group from a sulphinic acid, a sulphonic acid, a phosphorus containing acid or a boric acid, when n is 2,R 3 is an divalent residue of an aliphatic, aromatic or heterocyclic diacyl, the group --CO-- or --CO.CO--, a sulphinyl or sulphonyl residue or
  • R 3 is a carbamoyl residue having the formula: ##STR26## wherein R 8 is hydrogen or an alkyl residue having from 1 to 4 carbon atoms, and R 9 is hydrogen, an alkyl residue having from 1 to 20 carbon atoms, an alkenyl residue having from 3 to 20 carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms or an unsubstituted aryl or substituted aryl residue having from 6 to 12 carbon atoms; and when n is 2 R 3 is a divalent aliphatic or aromatic dicarbamoyl residue.
  • R 3 is a thiocarbamoyl residue having the formula: ##STR27## wherein R 8 is hydrogen or an alkyl residue having from 1 to 4 carbon atoms, and R 9 is hydrogen, an alkyl residue having from 1 to 20 carbon atoms, an alkenyl residue having from 3 to 20 carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms or an unsubstituted aryl or substituted aryl residue having from 6 to 12 carbon atoms; and when n is 2,R 3 is a divalent aliphatic or aromatic dithiocarbamoyl.
  • R 3 is a monovalent residue and is an alkyl residue having from 1 to 20 carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms, an alkenyl or alkynyl residue having from 3 to 20 carbon atoms, an aralkyl residue having from 7 to 9 carbon atoms, or a residue having the formula: ##STR28## wherein m is 1, 2 or 3, R 4 is a hydrogen, methyl or phenyl residue, X 2 is halogen, cyano, ##STR29## --COR 5 , --CO.OR 5 , --CO.SR 5 or --CONR 5 R 6 and X 1 is hydroxyl, halogen, cyano, --OR 5 , --O--CO.R 5 , --OCSR 5 , --O.CO.NR 5 R 6 ,--CO.R 5 , --CO.OR 5 , --CO.SR 5 , --CO.NR 5
  • R 3 is an acyl group ##STR31## wherein R 7 is an aliphatic or substituted aliphatic residue having from 1 to 20 carbon atoms, an alkenyl or alkynyl residue having from 2 to 20 carbon atoms, a cycloaliphatic residue having from 5 to 12 carbon atoms, an araliphatic residue having from 7 to 14 carbon atoms, an aromatic residue having from 6 to 12 carbon atoms or an heterocyclic residue, with the proviso that only one of R 1 and R 3 can represent an unsaturated acyl group or R 3 represents a monovalent group obtained by removing a hydroxyl group from a sulphinic acid, a sulphonic acid, a phosphorus containing acid or a boric acid, when n is 2, R 3 is a divalent residue of an aliphatic, aromatic or heterocyclic diacyl residue, a carbonyl, sulphinyl or s
  • R 8 is hydrogen or an alkyl residue having from 1 to 4 carbon atoms
  • R 9 is hydrogen, an alkyl residue having from 1 to 20 carbon atoms, an alkenyl residue having from 3 to 20 carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms or an aryl or substituted aryl residue having from 6 to 12 carbon atoms
  • R 3 is a divalent residue of an aliphatic or aromatic dicarbamoyl residue..
  • R 8 is hydrogen or an alkyl residue having from 1 to 4 carbon atoms
  • R 9 is hydrogen, an alkyl residue having from 1 to 20 carbon atoms, an alkenyl residue having from 3 to 20 carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms or an aryl or substituted aryl residue having from 6 to 12 carbon atoms
  • R 3 is a divalent residue of an aliphatic or aromatic dithiocarbamoyl residue..
  • R 5 is alkyl having .Badd.1 or 2carbon atoms or phenyl or R 1 is a group of the formula and R 2 is hydrogen and R 3 when n is 1 is alkyl having 3 to 18 carbon atoms, alkenyl having 3 carbon atoms, propargyl, benzyl, .[.--CH 2 CH 2 CH.]. .Iadd.CH 2 CH 2 CN .Iaddend.or a group of the formula
  • X 2 is ##STR37## .[.of.]. .Iadd.or is a group .Iaddend.of the formula ##STR38## wherein R 7 is alkyl having 1 to 19 carbon atoms, CH 3 (CH 2 ) 11 --S--CH 2 --, cycloalkyl having 6 to 10 carbon atoms, alkenyl having 2 to 17 carbon atoms, unsubstituted aralkyl having 7 to 13 carbon atoms, C 6 H 5 -CH ⁇ CH--, aralkyl substituted by hydroxy or butyl, unsubstituted aryl having 6 to 10 carbon atoms, aryl substituted by alkyl having 1 to 4 carbon atoms, CH 3 O--, Cl, OH or ##STR39## or of the formula ##STR40## wherein R 9 is alkyl having 1 to 8carbon atoms, alkenyl having 3 carbon atoms, cyclohexyl, unsubstituted ary
  • R 3 is an acyl group ##STR44## wherein R 7 is hydrogen, an substituted aliphatic residue having from 1 to 20 carbon atoms, a alkenyl or alkynyl residue having from 2 to 20 carbon atoms, a cycloaliphatic residue having from 5 to 12 carbon atoms, an araliphatic residue having from 7 to 14 carbon atoms, or an heterocyclic residue, or R 3 represents a monovalent group obtained by removing a hydroxyl group from a sulphinic acid, a sulphonic acid, a phosphorus containing acid or a boric acid, or when n is 2, R 3 is an divalent residue of heterocyclic diacyl residue or a sulphinyl or sulphonyl residue or a divalent residue obtained by removing two hydroxyl groups from a
  • R 3 is an acyl group ##STR45## wherein R 7 is hydrogen, a cycloliphatic residue having from 5 to 12 carbon atoms or a heterocyclic residue or R 3 represents a monovalent group obtained by removing a hydroxyl group from a sulphinic acid, a sulphonic acid, a phosphorus containing acid or a boric acid or when n is 2, R 3 is a divalent residue of a heterocyclic diacyl or a sulphinyl or sulphonyl residue or a divalent residue obtained by removing two hydroxyl groups from a disulphonic acid, a phosphorus containing acid or when n is 4, R 3 is a tetraacyl residue derived from an aliphatic tetracarboxylic acid.
  • R 7 is hydrogen, substituted aliphatic residue having from 1 to 20 carbon atoms, an alkenyl or alkylnyl residue having from 2 to 20 carbon atoms, a cycloaliphatic residue having from 5 to 12 carbon atoms, an araliphatic residue having from 7 to 14 carbon atoms, or an heterocyclic residue
  • R 3 represents a monovalent group obtained by removing a hydroxyl group from a sulphinic acid, a sulphonic acid, a phosphorus containing acid or a boric acid or when n is 2
  • R 3 is a divalent residue of heterocyclic diacyl residue or a sulphinyl or sulphonyl residue or a divalent residue obtained by removing two hydroxyl groups from a disulphonic acid, a phospho
  • R 7 is hydrogen, a cycloaliphatic residue having from 5 to 12 carbon atoms or a heterocyclic residue or R 3 represents a monovalent group obtained by removing a hydroxyl group from a sulphinic acid, a sulphonic acid, a phosphorus containing acid or a boric acid or when n is 2, R 3 is a divalent residue of a heterocyclic diacyl or a sulphinyl or sulphonyl residue or a divalent residue obtained by removing two hydroxyl groups from a disulphonic acid, a phosphorus containing acid or when n is 4, R 3 is a tetraacyl residue derived from an aliphatic tetracarboxylic acid..].
  • R 3 is an acyl group ##STR48## wherein R 7 is an unsubstituted aliphatic residue having from 1 to 20 carbon atoms or an aromatic residue having from 6 to 20 carbon atoms and when n is 2, R 3 is an divalent aliphatic or aromatic diacyl residue or the groups --CO-- or --COCO-- and when n is 3, R 3 is a trivalent residue and is an aliphatic or aromatic triacyl residue or a triacyl residue derived from o-phosphoric, o-phosphorous or o-boric acid and when n is 4, R 3 is a tetravalent residue of a tetraacyl residue derived from an aromatic tetracarboxylic acid or from o-silicic acid.
  • R 7 is an unsbustituted aliphatic residue having from 1 to 20 carbon atoms or an aromatic residue having from 6 to 12 carbon atoms and when n is 2, R 3 is an divalent aliphatic or aromatic diacyl residue or the carbonyl group and when n is 3, R 3 is a trivalent residue and is an aliphatic or aromatic triacyl residue or a triacyl residue derived from o-phosphoric o-phosphorous or o-boric acid and when n is 4, R 3 is a tetravalent residue of a tetraacyl residue derived from an aromatic tetracarboxylic acid or from o-silicic acid..].
  • R is a monovalent aliphatic residue having from 1 to 20 carbon atoms or a monovalent aromatic residue having from 6 to 20 carbon atoms and when n is 2, R is a divalent aliphatic residue having from 1 to 20 carbon atoms or a divalent aromatic residue having from 6 to 20 carbon atoms.
  • n 1, 2, 3 or 4
  • R 1 is a monovalent residue and is an alkyl residue having from 1 to 20 carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms, an alkenyl or alkynyl residue having from 3 to 20 carbon atoms, an aralkyl residue having from 7 to 9 carbon atoms, or a residue having the formula: ##STR51## wherein m is 1, 2 or 3, R 4 is a hydrogen, methyl or phenyl residue, X 2 is halogen, cyano, ##STR52## --COR 5 , --CO.OR 5 , --CO.SR 5 , --CONR 5 R 6 or CS.NR 5 R 6 and X 1 is hydroxyl, halogen, cyano, ##STR53## --OR 5 , --O--CO.R 5 , OCSR 5 , --O.CO.
  • R 2 is an alkyl residue having from 1 to 4 carbon atoms, an alkenyl or alkynyl residue having 3 to 20, carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms, an aryl residue having from 6 to 11 carbon atoms or an aralkyl residue having from 7 to 9 carbon atoms or also hydrogen; and when n is 1, R 2 is a monovalent radical having the same significance as R 1 , with the proviso that only one of R 1 and R 3 can represent a unsaturated acyl group or R 3 represents a monovalent group obtained by removing a hydroxyl group from a sulphinic acid, a sulphonic acid, a phosphorus containing acid or a boric acid, or R 3 is an aryl residue or a residue having the formula: ##STR54## wherein R 1 ' is hydrogen or R 1 ' has the same significance as R 1 .
  • R 3 is a divalent residue and is an alkylene residue having from 1 to 20 carbon atoms, an alkenylene residue having from 3 to 20 carbon atoms, an alkynylene residue having from 3 to 20 carbon atoms, an arylene residue having 6 to 14 carbon atoms, an aralkylene residue having from 8 to 14 carbon atoms or an aliphatic, aromatic or heterocyclic diacyl residue, an aliphatic or aromatic dicarbamoyl or dithiocarbamoyl, a carbonyl, sulphinyl or sulphonyl residue or a divalent residue obtained by removing two hydroxyl groups from a disulphonic acid, a phosphorus containing acid or a boric acid; when n is 3, R 3 is a trivalent residue or an aliphatic or aromatic triacyl residue or a triacyl residue derived from o-phosphoric, o-phosphorous or o-boric acid or an alkanetriyl,
  • R' and R" are the same or different and each is a straight or branched alkyl group, having from 1 to 4 carbon atoms, or R' and R" together with the carbon atom to which they are attached form a cycloalkyl residue having from 5 to 12 carbon atoms;
  • Y is an alkyl group having from 1 to 20 carbon atoms, preferably 1 to 4, carbon atoms, alkenyl having from 2 to 20 carbon atoms or an aralkyl residue having from 7 to 9 carbon atoms and n 1 is 1 or 2; when n is 1, R is hydrogen or a monovalent aliphatic residue having from 1 to 20, preferably 6 to 20 carbon atoms, a monovalent alicyclic residue having from 5 to 12 carbon atoms, or a monovalent aromatic residue having from 6 to 20 carbon atoms; and when
  • n 1 and R is a monvalent aliphatic, alicyclic or aromatic residue having from 6 to 20 carbon atoms and this group has the formula: ##STR56## wherein R 10 and R 11 are the same or different and each is an alkyl group having from 1 to 6 carbon atoms, A is ##STR57## or --CH 2 CH 2 -- and p is 0 1, or
  • n 2 and R is a methylene, 1,2-ethylene, 1,4-butylene, 1,8-n-octylene, 2,2,4-trimethyl-1, 4-butylene, 1,10-n-decylene, 1,2-eicosylene, vinylene, propenylene, 1,2-, 1,3- or 1,4-cyclohexylene, cyclohexyl-3-ene, 1,2-, 1,3- or 1,4-phenylene, p-xylylene, 1,4- or 1,5-naphthylene, diphenylene or diphenylmethylene residue or the group --CH 2 CH 2 S CH 2 CH 2 -- or R is absent.
  • the following compounds of the formula IV are also compounds of the present invention: ##STR58## and its salts wherein R III and R IV are the same or different and each is a straight- or branched alkyl residue having from 1 to 12 carbon atoms or R III and R IV together with the carbon atom to which they are each attached form a cycloalkyl group having from 5 to 12 carbon atoms, Y is a straight- or branched alkyl residue having from 1 to 12 carbon atoms, an alkenyl residue having from 3 to 12 carbon atoms or an aralkyl residue having from 7 to 12 carbon atoms and R 12 is hydrogen or a saturated or unsaturated hydrocarbyl residue containing up to 20 carbon atoms optionally substituted, .[.Y.]. .Iadd.by .Iaddend.halogen or alkoxy having from 1 to 4 carbon atoms and q is 1 or 2.
  • Sub-groups of the compounds of formula IV are:
  • R 12 is a methyl, ethyl, propyl, isopropyl, n-butyl, 2-ethylhexyl, dodecyl, octadecyl, allyl, oleyl cyclohexyl, benzyl, phenyl o-, m- or p-tolyl, 2,4- or 2,6-xylyl or a naphthyl residue.
  • R 12 is a 1,2-ethylene, 1,6-hexylene, 2,4,4-trimethyl-1,6-hexylene, 1,3- or 1,4-phenylene, 2,4-tolylene, 1,5-naphthylene or 4,4'-diphenylmethylene residue.
  • a first process in which a compound of formula I is produced comprising reacting, in the presence of an acidbinding agent, a piperidinol having the formula: ##STR59## wherein R 1 and R 2 have their previous significance, with an acid halide having the formula:
  • R 3 and n have their previous significance and hal represents a halogen atom, preferably a chlorine atom.
  • Suitable acid binding agents are organic bases such as triethylamine; alternatively, an excess amount of the amine V can serve as the acid binding agent.
  • reaction is conveniently carried out by heating the reactants together in a solvent such as cyclohexane, benzene or toluene which is inert under the reaction conditions.
  • a solvent such as cyclohexane, benzene or toluene which is inert under the reaction conditions.
  • the present invention also provides a second process in which a compound of formula I is produced, comprising reacting, in the presence of a transesterification catalyst, a piperidinol compound of formula V, as hereinbefore defined, with an ester having the formula:
  • R 3 and n have their previous significance and R 13 is an alkyl residue having from 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms.
  • transesterification catalysts examples include alkali metal amides such as lithium amide.
  • a third process according to this invention in which a compound of formula I is produced comprises reacting, in the presence of an esterification catalyst, a pieridinol compound of formula V, as hereinbefore defined, with an acid having the formula:
  • esterification catalysts are neutral catalysts such as tetraalkyl titanates such as tetrabutyl titanate.
  • the second and third processes of the invention are conveniently effected by mixing the reactants together in the presence or absence of an inert solvent (for instance, benzene, toluene, xylene etc.) and agitating the reaction mixture until reaction is complete, as determined, for instance, by collecting the alcohol or water produced in the reaction, and stopping the reaction when the theoretical amount of alcohol or water, respectively, has been removed.
  • an inert solvent for instance, benzene, toluene, xylene etc.
  • a fourth process in which a compound of formula I is produced comprises reacting a compound having the formula: ##STR60## wherein R 2 , R 3 and n have their previous significance, with a compound X capable of reaction with the compound IX and of introducing into it the group R 1 as hereinbefore defined.
  • compound X may be an alkylating, alkenylating or aralkylating agent such as the halides of these groups.
  • Compound X may also be the aldehyde or ketone corresponding to the substituent R 1 , so that, when reacted with a compound of formula IX under Leuckart, Wallach or Eschweilar-Charles reaction conditions, compounds of formula I in which R 1 is methyl may be produced by reacting a compound of formula IX with formic acid and formaldehyde.
  • R 1 may be introduced before or after R 3 or in the case where R 1 and R 3 are identical may be introduced together by reacting a compound of the formula: ##STR62## with an alkylating, alkenylating, alkynylating, aralkylating, acylating agent or carbamoyloxyating agent, with an alkylating alkenylating, alkynylating, aralkylating or acylating agent.
  • Compounds of formula I wherein m is 1 and X 1 is --OH may be prepared by reacting a compound of formula XII with ethylene oxide, propylene oxide or styrene oxide.
  • R 1 represents an acyl group
  • R 2 and R 3 are as defined above
  • R 1 represents a carbamoyl or thiocarbamoyl group
  • R 2 and R 3 being as defined above with an isocyanate or thioisocyanate of the formula R 15 NCX 1 in which X 1 is ⁇ O or ⁇ S, and R 15 is the remainder of the isocyanate or thioisocyanate group.
  • R 2 in the general formula I is other than hydrogen it is preferred to introduce the appropriate group before or after the group R 1 is introduced, but before R 3 is introduced.
  • the group R 2 may be introduced by reacting a ketone of the formula ##STR76## wherein R 1 1 is hydrogen R 1 , with a Grignard reagent R 2 MgX followed by hydrolysis to produce a compound of the formula: ##STR77##
  • the acid binding agent can be an organic .Iadd.base .Iaddend.of an excess amount of the amine reactant XIV and the reactants are for example heated together in a solvent inert under the reaction conditions.
  • the process can be performed in the presence of a transesterification catalyst, such as an alkali metal, a piperidinol compound having the formula XIV, with an ester having the formula:
  • a transesterification catalyst such as an alkali metal, a piperidinol compound having the formula XIV, with an ester having the formula:
  • R and n are as defined above and R 16 is an alkyl group having from 1 to 4 carbon atoms, or with an acid having the formula:
  • R and n are as defined above.
  • the catalyst of producing compounds of the formula II can be a neutral catalyst such as tetraalkyl titanate.
  • the reactants can also be fused, the mass is agitated until reaction is complete and the reaction is stopped when the reaction is complete.
  • the completion of the reaction is determined for example by collecting, respectively, the alcohol or water produced in the reaction, and stopping the reaction when the theoretical amount of water or alcohol has been removed.
  • reaction can be effected in a solvent inert under the reaction conditions and in the presence of a strong base.
  • the present invention still further provides a composition comprising an organic material and a stabilising amount of a compound having the formula I, II or IV as hereinbefore defined.
  • the stabilisers of the invention provide effective light and/or heat stabilisation, especially for low- and high-density polyethylene and polypropylene and polystyrene as well as polymers of butene-1, pentene-1, 3-methyl-butene-1, hexane-1, 4-methylpentene-1, 4-methylhexene-1 and 4,4-dimethylpentene-1, and also co- and ter-polymers of olefines, particularly of ethylene or propylene.
  • organic materials susceptible to degradiation by the effects of light and the properties of which are improved by the incorporation therein of a compound of formula I, II or IV include natural and synthetic polymeric materials, for instance natural and synthetic rubbers, the latter including, for example, homo-, co- and ter-polymers of acrylonitrile, butadiene and styrene.
  • Specific synthetic polymers include polyvinyl chloride, polyvinylidene chloride and vinyl chloride co-polymers polyvinyl acetate as well as condensation polymers derived from ether, ester (derived from carboxylic sulphonic or carbonic acids), amide or urethane groupings. These polymers can, for instance, form the basis of surface coating media such as paints and lacquers having an oil or resin, for instance an alkyd or polyamide resin base.
  • the amount of the compound of formula I, II or IV, which is incorporated into the organic material in order to achieve maximal protection against degradation by light varies according to the properties of the organic material treated and according to the severity of the light radiation and to the length of exposure. However, for most purposes it is sufficient to use an amount of the compound of formula I, II or IV, within the range of from 0.01% to 5% by weight, more preferably within the range of from 0.1% to 2% by weight based on the weight of untreated organic material.
  • the compounds may be incorporated into the polymeric material by any of the known techniques for compounding additives with a polymer.
  • the compound and the polymer may be compounded in an internal mixer.
  • the compound may be added as a solution or slurry in a suitable solvent or dispersant, for instance an inert organic solvent such as methanol, ethanol or acetone to powdered polymer and the whole mixed intimately in a mixer, and the solvent subsequently removed.
  • the compound may be added to the polymer during the preparation of the latter, for instance at the latex stage of polymer production, to provide pre-stabilised polymer material.
  • the composition of the invention may contain one or more further additives, especially those used in polymer formulations, such as antioxidants of the phenol or amine type, U.V. absorbers and light protectants, phosphite stabilisers, peroxide decomposers, polyamide stabilisers, basic co-stabilisers, polyvinyl chloride stabilisers, nucleation agents, plasticizers, lubricants, emulsifiers, anti-static agents, flame-protectants, pigments, carbon black, asbestos, glass fibres, kaolin and talc.
  • further additives especially those used in polymer formulations, such as antioxidants of the phenol or amine type, U.V. absorbers and light protectants, phosphite stabilisers, peroxide decomposers, polyamide stabilisers, basic co-stabilisers, polyvinyl chloride stabilisers, nucleation agents, plasticizers, lubricants, emulsifiers, anti-static agents, flame-protectants, pigments, carbon black
  • the present invention therefore includes binary, tertiary and multi-component compositions containing the stabiliser of formula I, II or IV, together with one or more functional additives for polymers.
  • Suitable antioxidants are those of the hindered phenol type such as those selected from the following groups:
  • a 1 is --CR(COOR") 2 ##STR82##
  • R is hydrogen or lower alkyl, R' is lower alkyl,
  • R" is alkyl group having from 6-24 carbon atoms, w is an integer from 0 to 4.
  • Phenolic compounds having the formula: ##STR85## wherein B 1 , B 2 and B 3 are hydrogen, methyl or Q, provided that when B 1 and B 3 are Q then B 2 is hydrogen or methyl and when B 2 is Q then B 1 and B 3 are hydrogen or methyl.
  • R"' is a tetravalent radical selected from aliphatic hydrocarbons having from 1 to 30 carbon atoms, aliphatic mono- and di-thioethers having from 1 to 30 carbon atoms, aliphatic mono- and diethers having from 1 to 30 carbon atoms and z is an integer from 0 to 6.
  • Phenolic compounds having the formula ##STR88## where x is an integer of 1 or 2.
  • the preferred antioxidants consist of the hindered phenols in groups 1, 8, 9, 10, 11, 12 and 13 as mentioned above.
  • the most preferred hindered phenols are those of groups 1, 9, 11, 12 and 13.
  • antioxidants are those of the aminoaryl series for instance aniline and naphthylamine derivatives as well as their heterocyclic derivatives such as:
  • Ultraviolet absorbers and light protectants include
  • 2-(2'-hydroxyphenyl)benzotriazoles for instance 5'-methyl; 3',5'-di-t-butyl; 5'-t-butyl; 5-chloro-3', 5'-di-t-butyl; 5-chloro-3'-t-butyl-5'-methyl; 3'-sec.
  • 2-hydroxybenzophenones for instance the 4-hydroxy, 4-methoxy, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4,2', 4'-trihydroxy or 2'-hydroxy-4,4'-dimethoxy derivatives.
  • 1,3-bis(2'-hydroxybenzoyl)-benzenes for instance, 1,3-bis-(2'-hydroxy-4'-hexyloxybenzoyl)benzene 1,3-bis-(2'-hydroxy-4'-octoxybenzoyl)benzene 1,3-bis-(2'-hydroxy-4'-dodecyloxybenzoyl)benzene
  • Aryl esters from optionally substituted benzoic acids such s phenylsalicylate, octylphenylsalicylate, dibenzoyl resorcino, bis-(4-tert.butylbenzoyl) resorcinol, benzoylresorcinol and 3,5-di-tert.butyl-4-hydroxybenzoic acid-2,4-di-tert.butyl phenyl ester and -octadecyl ester and -2-methyl-4,6-di-tert.butyl phenyl ester.
  • Nickel compounds such as nickel complexes of 2,2'-thio-bis-(4-tert.octylphenol), for instance the 1:1 and 1:2 complexes, optionally having other ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine; nickel complexes of bis-(4-tert.octylphenyl) sulphone such as the 2:1 complex, optionally having other ligands such as 2-ethylcaproic acid; nickel dibutyl di-thiocarbamates; nickel salts of 4-hydroxy-3,5-di-tert.
  • Nickel compounds such as nickel complexes of 2,2'-thio-bis-(4-tert.octylphenol), for instance the 1:1 and 1:2 complexes, optionally having other ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine; nickel complexes of bis-(4-tert.octy
  • butylbenzyl-phosphonic acid mono-alkyl esters such as the methyl-, ethyl- or butyl esters; the nickel complex of 2-hydroxy-4-methyl-phenyl-undecylketonoxime; and nickel-3,5-di-tert.butyl-4-hydroxy benzoate, and
  • Phosphite stabilisers include triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphites, trinonylphenyl phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9-di-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane and tri-(4-hydroxy-3,5-di-tert.butylphenyl)phosphite.
  • Peroxide-decomposing compounds for polyolefins include esters of ⁇ -thiodipropionic acids, for instance the lauryl-, stearyl-, myristyl- or tridecyl esters, salts of mercaptobenzimidazoles such as the zinc salt and diphenylthiourea.
  • Suitable polyamide stabilisers include copper salts in combination with iodides and/or further phosphorus compounds and salts of bivalent manganese.
  • Basic co-stabilisers are, for example, polyvinylpyrrolidone, melamine, benzoguanamine, triallyl cyanurate, dicyandiamide, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth salts of higher saturated or unsaturated fatty acids such as calcium stearate.
  • Polyvinyl chloride stabilisers include organotin compounds, organo lead compounds and Ba/Cd salts of fatty acids.
  • nucleation agents examples include 4-tert.butyl benzoic acid, adipic acid and diphenylacetic acid.
  • any further additive is advantageously employed in a proportion within the range of from 0.01% to 5% by weight, based on the weight of untreated polymeric material.
  • the compounds of formula I, II or IV provide very effective stabiliser packages in polyolefine formulations.
  • Table 2 gives a list of esters prepared using the procedure of Example 34.
  • Table 3 gives a list of carbamoyloxy esters prepared using the procedure of Example 45.
  • Table 5 gives a list of ethers prepared using the procedure of Example 70.
  • Table 6 gives a list of compounds prepared using the procedure of Example 77.
  • This composition was compression moulded into films of 0.1 mm thickness at 260° C. for 6 minutes and the films so obtained were then quenched in cold water.
  • a section measuring 44 ⁇ 100 mm was separated from the 0.1 mm annealed polypropylene foil and exposed to light irradiation in a fademeter device consisting of a circular bank of 28 alternate sunlight and blacklight lamps.
  • the sunlight lamps were 2 feet long, 20-watt fluorescent lamps characterised by a peak emission of 3,100 Angstrom units; the blacklight lamps were 2 feet long, 20-watt ultraviolet lamps characterised by a peak emission of 3,500 Angstrom units.
  • the sample was rotated concentrically about the bank of lamps so that the radiation therefrom was uniformly distributed over the section under test.
  • the exposed sample was examined periodically and portions of it tested for the percent/elongation at break, the time at which the sample reached 50% of the initial elongation at break was noted.
  • the pressing was conducted at 180° C. and the pressings were compression-moulded into 1 mm. thick plaques at 150° C.
  • the plaques were stored at 20° C. and were periodically examined visually for the first sign of exudation.
  • the T.sub.(560) represents the transmission value of an unexpected sample at a wavelength of 560 .[.m.]..Iadd.n.Iaddend.m.
  • 25 parts by weight of a polyester-based film-forming polyurethane were dissolved in 75 parts by weight of a 1:1 mixture (by volume) of dimethylformamide and acetone, and 1% by weight of 4(2'-cyanoethoxy)-1,2,2,6,6-pentamethylpiperidine was added.
  • the final thickness of the film was 80-100 ⁇ .
  • the dried film samples were removed from the glass plate, mounted on white cardboard and exposed in a "Xenotest 450" exposure unit, one half of the exposed sample being covered to facilitate subsequent visual estimation of yellowing due to exposure.
  • the sample was controlled and rated visually at intervals of 100 hours.
  • the multifilament obtained was mounted on a sample holder of Xenotest 150 apparatus (Quarzlampen GmbH) using white cardboard as backing. In intervals of 200 hours of exposure time, 5 fiber samples are measured for their retained tensile strength. The data obtained are plotted against exposure time and the exposure time (T) to give 50% loss or original tensile strength is derived from graph. This value is taken as the failure time.

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US05/938,849 1971-11-30 1978-09-01 Piperidine derivatives Expired - Lifetime USRE31343E (en)

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US20160176855A1 (en) * 2013-07-30 2016-06-23 Clariant International Ltd. Novel Sterically Hindered Cyclic Amines
US10487193B2 (en) * 2015-01-07 2019-11-26 Clariant Plastics & Coatings Ltd Stabilization of polyamides

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DE3724222A1 (de) * 1987-07-22 1989-02-02 Huels Chemische Werke Ag Lichtstabilisatoren
IT1222647B (it) * 1987-09-11 1990-09-05 Eniricerche Spa Composti amminici stericamente impediti e procedimento per la loro preparazione
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EP0352221B1 (de) * 1988-06-14 1994-03-09 Ciba-Geigy Ag Verfahren zum fotochemischen Stabilisieren von ungefärbten und gefärbten Polypropylenfasern
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DE3844356A1 (de) * 1988-12-30 1990-07-05 Basf Ag 4-(2'-ethylhexanoyloxy) -2,2,6,6-tetramethyl-piperidin
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NL9101619A (nl) * 1991-09-25 1993-04-16 Harcros Chemicals Bv Stabilisatoren voor organische materialen.
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WO1997013752A1 (en) * 1995-10-12 1997-04-17 Ciba Specialty Chemicals Holding Inc. Thermally stable hindered amines as stabilizers
EP1184442A1 (en) * 2000-08-30 2002-03-06 Clariant International Ltd. Liquid crystal mixture
US6414155B1 (en) 2000-11-03 2002-07-02 Cytec Technology Corp. Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
US6727300B2 (en) 2000-11-03 2004-04-27 Cytec Technology Corp. Polymeric articles containing hindered amine light stabilizers based on multi-functional carbonyl compounds
US6545156B1 (en) * 2000-11-03 2003-04-08 Cytec Technology Corp. Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
US6492521B2 (en) 2000-11-03 2002-12-10 Cytec Technology Corp. Hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
US6525131B1 (en) 2001-09-18 2003-02-25 Crompton Corporation Aromatic diamine polyurethane curatives with improved stability
EP1444222A1 (en) * 2001-10-23 2004-08-11 Council Of Scientific And Industrial Research Tinuvin p-hindred amine light stabilizer and derivatives thereof, and a process for the preparation thereof
US6492518B1 (en) 2001-10-30 2002-12-10 Council Of Scientific And Industrial Research Tinuvin P-hindred amine light stabilizer and derivatives thereof
JP5283153B2 (ja) 2007-10-25 2013-09-04 株式会社Ａｄｅｋａ 合成樹脂組成物及び自動車内外装材
EP2270101B1 (en) 2008-03-10 2016-01-13 Adeka Corporation Synthetic resin composition, and automotive interior/exterior material comprising the same
JP5656213B2 (ja) * 2010-01-19 2015-01-21 日本化薬株式会社 カルボン酸組成物、及び該カルボン酸組成物を含有する硬化性樹脂組成物
RU2686327C2 (ru) * 2013-07-08 2019-04-25 Басф Се Новые светостабилизаторы
JP6667458B2 (ja) * 2014-05-21 2020-03-18 ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー 安定剤化合物

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US3120540A (en) * 1961-09-25 1964-02-04 Warner Lambert Pharmaccutical Bis (polymethyl)-4-piperidinol alkanoates
US3640928A (en) * 1968-06-12 1972-02-08 Sankyo Co Stabilization of synthetic polymers
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US4021432A (en) * 1971-11-30 1977-05-03 Ciba-Geigy Corporation Piperidine derivatives

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Publication number Priority date Publication date Assignee Title
US4925888A (en) 1987-10-21 1990-05-15 Basf Aktiengesellschaft Mixture for stabilizing polyurethanes
US20160176855A1 (en) * 2013-07-30 2016-06-23 Clariant International Ltd. Novel Sterically Hindered Cyclic Amines
US10487193B2 (en) * 2015-01-07 2019-11-26 Clariant Plastics & Coatings Ltd Stabilization of polyamides

Also Published As

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FR2183294A1 (ru) 1973-12-14
HU167244B (ru) 1975-09-27
NL174942B (nl) 1984-04-02
DE2258752A1 (de) 1973-06-07
FR2182789A1 (ru) 1973-12-14
FR2182789B1 (ru) 1976-01-30
CA997767A (en) 1976-09-28
GB1399239A (en) 1975-06-25
CH586252A5 (ru) 1977-03-31
FR2183293B1 (ru) 1977-07-29
RO64573A (fr) 1979-08-15
AT324009B (de) 1975-08-11
CS190377B2 (en) 1979-05-31
JPS5920709B2 (ja) 1984-05-15
IL40888A (en) 1976-10-31
NL7216278A (ru) 1973-06-04
DE2258752C2 (ru) 1989-10-26
MY7800025A (en) 1978-12-31
USRE31342E (en) 1983-08-09
SE454277B (sv) 1988-04-18
RO71050A (ro) 1981-09-24
HK47877A (en) 1977-09-23
DD106190A5 (ru) 1974-06-05
ES409079A1 (es) 1976-04-16
JPS4865180A (ru) 1973-09-08
NL174942C (nl) 1984-09-03
CH585714A5 (ru) 1977-03-15
FR2183293A1 (ru) 1973-12-14
SU584795A3 (ru) 1977-12-15
IL40888A0 (en) 1973-01-30
BE792043A (fr) 1973-05-29
FR2183294B1 (ru) 1978-05-26
IT971346B (it) 1974-04-30

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