Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
  • C07D327/06—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B63/00—Purification; Separation; Stabilisation; Use of additives
  • C07B63/04—Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/16—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
  • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated

Definitions

• the present invention relates to compositions comprising an organic material, preferably a polymer or a lubricant, and to benzoxathiane derivatives, as well as to the use thereof for stabilizing organic materials against oxidative, thermal or light-induced degradation and/or as reducers of surface energy for organic materials.
• the known stabilizers do not satisfy in every respect the high requirements which a stabilizer is required to meet, especially with regard to shelf life, water absorption, sensitivity to hydrolysis, in-process stabilization, color properties, volatility, migration behavior, compatibility and improvement in protection against light.
• a stabilizer for organic materials that are sensitive to oxidative, thermal and/or light-induced degradation and/or meet the requirements as reducers of surface energy for organic materials, for example, for increasing the oil and water repellency of organic materials.
• benzoxathiane derivatives are particularly suitable for use as stabilizers for organic materials that are susceptible to oxidative, thermal or light-induced degradation and/or as reducers of surface energy for organic materials.
• the invention relates to a composition
• a composition comprising a) an organic material subject to oxidative, thermal or light-induced degradation, and b) at least one compound of the formula I
• Ri and R 2 independently of each other are hydrogen, Ci-C 25 alkyl, C 2 -C 25 alkenyl, un- substituted or with d-C 4 alkyl substituted phenyl; unsubstituted or with CrC 4 alkyl substituted C 7 -C 9 phenylalkyl; -CH(R 7 )-S(O) n -R 8 or -CH(R 7 )-S(O) n -CH 2 -CH(R 7 )-R 9!
• R 3 and R 4 independently of each other are hydrogen, Ci-C 25 alkyl, unsubstituted or with Ci-C 4 alkyl substituted phenyl,
• R 5 and R 6 independently of each other are hydrogen, Ci-C 25 alkyl, C 2 -C 25 alkyl interrupted by oxygen; unsubstituted or with Ci-C 4 alkyl substituted phenyl; halogen, -CN,
• R 7 is hydrogen, Ci-Ci 2 alkyl, — N N , unsubstituted or with halogen or Ci-C 4 alkyl
• R 13 substituted phenyl
• Rs is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
• R 9 is -CN, -S(O) n -RiO , -C-R 10 , -C-O-R 11 , -C-N , -N N or -NO 2 ,
• Rio is hydrogen, Ci-C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or Ci-C 4 alkyl-substituted phenyl; unsubstituted or Ci-C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
• Rn is hydrogen, alkali metal, Ci-C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or d- C 4 alkyl-substituted phenyl; unsubstituted or Ci-C 4 alkyl-substituted C 5 -C 8 cycloalkyl; or C 3 -C 25 alkyl which is interrupted by oxygen or sulfur;
• Ri 2 and Ri 3 independently of one another are hydrogen, Ci-C 25 alkyl, Ci-C 4 alkanoyl, C 7 -C 9 phenylalkyl, unsubstituted or Ci-C 4 alkyl-substituted phenyl; or Ri 2 and Ri 3 , together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic ring which is unsubstituted or is substituted by CrC 4 alkyl or is interrupted
• Ri 4 is hydrogen, d-C 8 alkyl or benzyl, and n is O 1 or 2.
• Alkyl having up to 25 carbon atoms is a branched or unbranched radical , for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trime- thylhexyl, 1 ,1 ,3,3-te
• Alkanoyl having up to 4 carbon atoms is a branched or unbranched radical, for example for- myl, acetyl, propionyl, butanoyl or pivaloyl.
• Alkenyl having 2 to 25 carbon atoms is a branched or unbranched radical such as, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2- butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadece- nyl.
• Alkyl-substituted phenyl which preferably contains 1 to 3, especially 1 or 2 alkyl groups, is, for example, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl- 6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.
• Cr-CgPhenylalkyl is, for example, benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl or 2-phenyl- ethyl.
• Ci-C 4 alkyl substituted Cr-Cgphenylalkyl is, for example 4-methylbenzyl, 4-methyl- ⁇ - methylbenzyl, 4-methyl- ⁇ , ⁇ -dimethylbenzyl or 4-methylphenyl-2-ethyl.
• C3-C 2 5Alkyl interrupted by oxygen or sulfur is, for example, CH 3 -O-CH 2 CH 2 -, CH 3 -S-CH 2 CH 2 - , CH 3 -O-CH 2 CH 2 -O-CH 2 CH 2 -, CH 3 -(O-CH 2 CH 2 -) 2 O-CH 2 CH 2 -, CH 3 -(O-CH 2 CH 2 -) 3 O-CH 2 CH 2 - or CH 3 -(O-CH 2 CH 2 -) 4 O-CH 2 CH 2 -.
• Halogen is for example fluoro, chloro, bromo or iodo. - A -
• a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms is for example -(CF 2 ) m CF 3 or -CI-I 2 CI-I 2 (CF 2 VCF 3 wherein m is 3 to 19, preferably 3 to 12.
• the prefluoroalkyl moieties represent also mixtures of perfluoroalkyl moieties which means that R 8 usually concomitantly contains a small fraction of perfluoroalkyl groups with a lower number of carbon atoms and small fraction of perfluoroalkyl groups with a higher number of carbon atoms.
• Unsubstituted or d-C 4 alkyl-substituted C 5 -C 8 cycloalkyl is, for example, cyclopentyl, methyl- cyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cycloheptyl or cyclooctyl. Preference is given to cyclohexyl and tert-butylcyclohexyl.
• Ri 2 and R 1 3 preferably form with the nitrogen atom to which they are attached, a 6-membered heterocyclic ring interrupted by oxygen, such as, for example,
• compositions which are of interest include those comprising as component (b) a compound of the formula I, wherein
• Ri and R 2 independently of each other are hydrogen, Ci-Ci 8 alkyl, C 2 -Ci 8 alkenyl, unsubstitu- ted or with Ci-C 4 alkyl substituted phenyl; unsubstituted or with Ci-C 4 alkyl substituted C 7 -C 9 - phenylalkyl; -CH(R 7 )-S(O) n -R 8 or -CH(R 7 )-S(O) n -CH 2 -CH(R 7 )-R 9!
• R 3 and R 4 independently of each other are hydrogen, Ci-Cisalkyl, unsubstituted or with Ci-C 4 alkyl substituted phenyl,
• R 5 and R 6 independently of each other are hydrogen, CrCi 8 alkyl, C 2 -Ci 8 alkyl interrupted by
• R 7 is hydrogen, Ci-Ci 2 alkyl or phenyl
• R 8 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
• R 9 is -CN, -S(O) n -RiO , - ftC-R 10 , - ftC-O-R 11 , - ftC-N / R 12 , -N N or -NO 2 ,
• R 1 0 is hydrogen, Ci-Ci 8 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or d-C 4 alkyl-substituted phenyl; unsubstituted or d-C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
• R 11 is hydrogen, Ci-Ci 8 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or d-C 4 alkyl-substituted phenyl; unsubstituted or d-C 4 alkyl-substituted C 5 -C 8 cycloalkyl; or C 3 -Ci 8 alkyl which is interrupted by oxygen or sulfur;
• Ri 2 and Ri 3 independently of one another are hydrogen, Ci-Ci 8 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or Crdalkyl-substituted phenyl; or Ri 2 and R 1 3, together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic ring which is unsubsti-
• Ri4 is hydrogen, Ci-C 8 alkyl or benzyl, and n is O 1 or 2.
• Compositions that are of interest include those comprising as component (b) at least one compound of the formula I wherein R 3 and R 5 are hydrogen.
• compositions comprising as component (b) at least one compound of the formula I wherein
• Ri and R 2 independently of each other are CrC 4 alkyl, -CH(R 7 )-S(O) n -R 8 or
• R 7 is hydrogen or CrC 4 alkyl
• Rs is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
• Rn is hydrogen or d-C ⁇ alkyl, and n is O, 1 or 2.
• compositions comprising as component (b) at least one compound of the formula I wherein
• Ri and R 2 independently of each other are Ci-C 4 alkyl, -CH(R 7 )-S(O) n -R 8 or -CH(R 7a )-S(O) n -CH 2 -CH(R 7b )-R 9 ,
• R 7, R 7a and R 7b independently of each other are hydrogen or Ci-C 4 alkyl
• R 8 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms, O
• R 9 is — C-O-R 11 .
• Rn is hydrogen or Ci-Ci 2 alkyl, and n is O, 1 or 2.
• compositions comprising as component (b) at least one compound of the formula I wherein R 8 is -(CF 2 ) m CF 3 or -CH 2 -CH 2 -(CF 2 ) m CF 3 , and m is 3 to 12.
• Preference is likewise given to compositions comprising as component (b) at least one compound of the formula I wherein
• Ri and R 2 independently of each other are hydrogen, d-C ⁇ alkyl, phenyl, benzyl, -CH(R 7 )-S(O) n -R 8 or -CH(R 7 )-S(O) n -CH 2 -CH(R 7 )-R 9 ,
• R 3 and R 4 independently of each other are hydrogen, d-C ⁇ alkyl or phenyl
• R 5 and R 6 independently of each other are hydrogen, d-C ⁇ alkyl, phenyl, halogen, -CN
• R 7 is hydrogen or d-C ⁇ alkyl
• R 8 is -(CF 2 ) m CF 3 or -CH 2 -CH 2 -(CF 2 ) m CF 3 ,
• R 9 is -CN, -C-R 10 , -C-O-R 11 or — C-N /
• Rio Ci-Ci 2 alkyl, C 7 -C 9 phenylalkyl, phenyl or C 5 -C 8 cycloalkyl,
• Rn is hydrogen, Ci-Ci 2 alkyl, benzyl, phenyl or C 5 -C 8 cycloalkyl or C 3 -Ci 8 alkyl,
• Ri 2 and Ri 3 independently of one another are hydrogen, Ci-Ci 2 alkyl, benzyl, phenyl; or Ri 2 and Ri 3 , together with the nitrogen atom to which they are attached, form a 6-membered heterocyclic ring, m is 3 to 12, and n is O 1 or 2.
• compositions comprising as component (b) at least one compound of the formula I wherein
• Ri is d-dalkyl, -CH(R 7 )-S(O) n -R 8 or -CH(R 7 )-S(O) n -CH 2 -CH(R 7 )-R 9 ,
• R 2 is d-dalkyl, -CH(R 7 )-S(O) n -R 8 or -CH(R 7 )-S(O) n -CH 2 -CH(R 7 )-R 9 ,
• R 3 is hydrogen
• R 4 is hydrogen or phenyl
• R 5 is hydrogen
• R 6 is hydrogen or phenyl
• R 7 is hydrogen
• R 8 is -CH 2 -CH 2 -(CF 2 ) 3 CF 3 or -CH 2 -CH 2 -(CF 2 ) 7 CF 3 ,
• R 9 is — C-O-R 11 , Rii is hydrogen or CrC 8 alkyl, and n is 0 1 or 2.
• compositions comprising as component (b) at least one compound of the formula I wherein
• compositions comprising as component (b) at least one compound of the formula I wherein
• R 9 is -CN, -S(O) n -RiO , -C-R 10 , -C-N N , or -NO 2 .
• compositions comprising as component (b) at least one compound of the formula I wherein R 11 is CrC 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or CrC 4 alkyl-substituted phenyl; unsubstituted or CrC 4 alkyl-substituted C 5 -C 8 cycloalkyl; or C 3 -C 25 alkyl which is interrupted by oxygen or sulfur.
• R 11 is CrC 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or CrC 4 alkyl-substituted phenyl; unsubstituted or CrC 4 alkyl-substituted C 5 -C 8 cycloalkyl; or C 3 -C 25 alkyl which is interrupted by oxygen or sulfur.
• compositions comprising as component (b) at least one compound of the formula I wherein R 12 and R 13 independently of one another are CrC 25 alkyl, CrC 4 alkanoyl, C 7 -C 9 phenylalkyl, unsubstituted or CrC 4 alkyl-substituted phenyl; or R 12 and R 13 , together with the nitrogen atom to which they are attached, form a 5-, 6- or 7- membered heterocyclic ring which is unsubstituted or is substituted by C- ⁇ -C 4 alkyl or is
• Component (b) is suitable for stabilizing organic materials against oxidative, thermal or light- induced degradation. Examples of such materials are:
• Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
• 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,
• a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb 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.
• 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 Ia, Na 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), metallocene or single site catalysts (SSC).
• Mixtures of the polymers mentioned under 1 for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
• 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 copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g.
• ethylene/norbornene like COC ethylene/1 -olefins copolymers, where the 1 -olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene- norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl a
• Hydrocarbon resins for example C 5 -Cg
• hydrogenated modifications thereof e.g. tackifiers
• mixtures of polyalkylenes and starch
• Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
• Polystyrene poly(p-methylstyrene), poly( ⁇ -methylstyrene).
• Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
• Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/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 terpolymer; and block copolymers of sty
• Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6. especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
• PCHE polycyclohexylethylene
• PVCH polyvinylcyclohexane
• Homopolymers and copolymers may have any stereostructure including syndiotactic, isotac- tic, hemi-isotactic or atactic; where atactic polymers are preferred.
• Stereoblock polymers are also included.
• Graft copolymers of vinyl aromatic monomers such as styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene- acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile 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; s
• 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, poly- amide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 1 1 , 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 elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or po- ly-m-phenylene isophthalamide; and also block copolymers of the aforementioned poly- amides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glyco
• Polyureas Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydan- toins and polybenzimidazoles.
• Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones or lactides for example polyethylene terephthalate, polybutylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate and polyhydroxybenzoates as well as copolyether esters derived from hydroxyl- terminated polyethers, and also polyesters modified with polycarbonates or MBS.
• Copolyesters may comprise, for example - but are not limited to polybutylenesuccinate/terephtalate, polybutyleneadipate/terephthalate, polytetramethyleneadipate/terephthalate, polybutylensuccinate/adipate, polybutylensuccinate/carbonate, poly-3-hydroxybutyrate/octanoate copolymer, poly-3- hydroxybutyrate/hexanoate/decanoate terpolymer.
• aliphatic polyesters may comprise, for example - but are not limited to - the class of poly(hydroxyalkanoates), in particular, poly(propiolactone), poly(butyrolactone), poly(pivalolactone), poly(valerolactone) and poly(caprolactone), polyethylenesuccinate, polypropylenesuccinate, polybutylenesuccinate, polyhexamethylenesuccinate, polyethyleneadipate, polypropyleneadipate, polybutyleneadi- pate, polyhexamethyleneadipate, polyethyleneoxalate, polypropyleneoxalate, polybutylene- oxalate, polyhexamethyleneoxalate, polyethylenesebacate, polypropylenesebacate, polybu- tylenesebacate and polylactic acid (PLA) as well as corresponding polyesters modified with polycarbonates or MBS.
• poly(hydroxyalkanoates) in particular, poly(propiolactone), poly(butyrolactone
• polylactic acid designates a homo-polymer of preferably poly-L-lactide and any of its blends or alloys with other polymers; a co-polymer of lactic acid or lactide with other monomers, such as hydroxy-carboxylic acids, like for example glycolic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid, 4-hydroxy-valeric acid, 5-hydroxy-valeric acid, 6-hydroxy-caproic acid and cyclic forms thereof; the terms "lactic acid” or "lactide” include L-lactic acid, D-lactic acid, mixtures and dimers thereof, i.e. L- lactide, D-lactide, meso-lacide and any mixtures thereof. 19. Polycarbonates and polyester carbonates.
• 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.
• Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
• Blends of the aforementioned polymers for example PP/EPDM, PoIy- 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, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
• polyblends for example PP/EPDM, PoIy- 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/
• Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
• synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
• Aqueous emulsions of natural or synthetic rubber e.g. natural latex or latices of carbo- xylated styrene/butadiene copolymers.
• Preferred organic materials are natural, semi-synthetic or, preferably, synthetic polymers.
• Particularly preferred organic materials are synthetic polymers, most preferably thermoplastic polymers.
• Especially preferred organic materials are polyacetals, polyolefins such as polypropylene or polyethylene, polyether/polyurethanes, polyesters such as polybutylene terephthalate, polycarbonates or vulcanisates.
• Particular preferred organic materials are also polyurethanes, especially those derived from hydroxyl-terminated polyethers, as well as mixtures of polyurethanes and hydroxyl-terminated polyethers. Mixtures of polyurethanes and hydroxyl-terminated polyethers occur, for example, during the preparation of polyurethanes from hydroxyl-terminated polyethers.
• Component (b) will preferably be added to the organic material to be stabilized in concentrations of from 0.0005 to 10 %, preferably 0.001 to 2 %, typically 0.01 to 2 %, based on the weight of said material [component (a)].
• Component (b) is likewise used for polyurethane production, especially for preparing flexible polyurethane foams. In this context the novel compositions and the products produced therefrom are effectively protected against degradation. In particular, scorching during foam production is avoided.
• the polyurethanes are obtained, for example, by reacting polyethers, polyesters and polybutadienes which contain terminal hydroxyl groups with aliphatic or aromatic polyisocyanates.
• Polyethers having terminal hydroxyl groups are known and are prepared, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydro- furan, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 , or by addition reaction of these epoxides, alone or as a mixture or in succession, with starting components containing reactive hydrogen atoms, such as water, alcohols, ammonia or amines, for example ethylene glycol, propylene 1 ,3- and 1 ,2-glycol, trimethylolpropane, 4,4'- dihydroxydiphenylpropane, aniline, ethanolamine or ethylenediamine.
• epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydro- furan, styrene oxide or epichlorohydrin
• starting components containing reactive hydrogen atoms such as water, alcohol
• Sucrose polyethers are also suitable in accordance with the invention. In many cases preference is given to those polyethers which predominantly (up to 90% by weight, based on all the OH groups present in the polyether) contain primary OH groups. Furthermore, polyethers modified by vinyl polymers, as are formed, for example, by polymerizing styrene and acrylonitrile in the presence of polyethers, are suitable, as are polybutadienes containing OH groups.
• These compounds generally have molecular weights of 400-10000 and are polyhydroxy compounds, especially compounds containing from two to eight hydroxyl groups, especially those of molecular weight from 800 to 10 000, preferably from 1000 to 6000, for example polyethers containing at least 2, generally 2 to 8, but preferably 2 to 4, hydroxyl groups, as are known per se for the preparation of homogeneous polyurethanes and cellular polyurethanes.
• Suitable polyisocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, for example ethylene diisocyanate, 1 ,4-tetramethylene diisocyanate, 1 ,6- hexamethylene diisocyanate, 1 ,12-dodecane diisocyanate, cyclobutane 1 ,3-diisocyanate, cyclohexane 1 ,3- and -1 ,4-diisocyanate and also any desired mixtures of these isomers, 1- isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydrotolylene diisocyanate and also any desired mixtures of these isomers
• isocyanate group-containing distillation residues as they are or dissolved in one or more of the abovementioned polyisocyanates, which are obtained in the course of the industrial preparation of isocyanates. It is additionally possible to use any desired mixtures of the abovementioned polyisocyanates.
• polyisocyanates which are readily obtainable industrially, for example 2,4- and 2,6-tolylene diisocyanate and any desired mixtures of these isomers (“TDI”), polyphenyl-polymethylene-polyisocyanates as prepared by aniline- formaldehyde condensation followed by phosgenization (“crude MDI”), and polyisocyanates containing carbodiimide, urethane, allophanate, isocyanurate, urea or biuret groups (“modified polyisocyanates”).
• TDI 2,4- and 2,6-tolylene diisocyanate and any desired mixtures of these isomers
• CAMDI polyphenyl-polymethylene-polyisocyanates as prepared by aniline- formaldehyde condensation followed by phosgenization
• polyisocyanates containing carbodiimide, urethane, allophanate, isocyanurate, urea or biuret groups modified polyisocyanates
• Component (b) is also suitable for stabilizing polyolefins which are in long-term contact with extracting media.
• the novel compositions may comprise further costabi- lizers (additives), typically the following:
• Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 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-meth- oxymethylphenol, 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- dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di- dodecylthiomethyl-4-nonylphenol.
• Hydroquinones 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-hy- droxyphenyl) 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).
• Hydroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4 ,4'-th iobis (6-tert-buty I- 2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.
• 2,2'-thiobis(6-tert-butyl-4-methylphenol 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol
• 4 ,4'-th iobis (6-tert-buty I- 2-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-meth- ylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphe- nol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methylbenzyl)- 4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethyl
• 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- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
• dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate di-octadecyl-2-(3-tert-butyl-4-
• Aromatic hydroxybenzyl compounds for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrameth- ylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
• Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 2-octylmercapto-4,6-bis(3,5-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-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
• 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- ⁇ -tert-butyl ⁇ -hydroxy-S-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, trimethylol- propane, 4-hydroxy
• esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl)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, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-
• esters of ⁇ -(3,5-dicvclohexyl-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-i-phospha ⁇ j-trioxabi
• esters of 3,5-di-tert-butyl-4-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- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[
• 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,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2- naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3- dimethylbutyl)-N'-phenyl-
• 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 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-sec-
• 2-Hydroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy benzophenone derivatives.
• Esters of substituted and unsubstituted benzoic acids for example 4-tert-butylphenyl 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 3,5-di-tert-butyl-4- hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
• Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphe- nylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinna- mate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, methyl ⁇ -carbomethoxy-p-methoxycin- namate and N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline.
• Nickel compounds for example nickel complexes of 2,2'-thiobis[4-(1 ,1 ,3,3-tetramethyl- butyl)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 ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
• additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanol
• Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1 , 2,2,6, 6-pentamethyl-4- piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, 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-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4- tert-octyla
• N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide N-(1 ,2,2,6,6- pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-di- aza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9, 9-tetramethyl-2-cycloundecyl-1 -oxa- 3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1 ,1-bis(1 , 2,2,6, 6-pentamethyl-4- piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,2,
• Oxamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxani- lide, N,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.
• N-alkyl-N,N'-diarylformamidines for example, benzoic acid, 4-[[(methylphenyl- amino)methylene]amino] ethyl ester [for example: Tinuvin® 101 supplied by Ciba Specialty Chemicals Inc.]; benzoic acid, 4-[[(ethylphenylamino)methylene]amino] ethyl ester; 2- propenoic acid, 3-(4-methoxyphenyl)-, 2-ethylhexyl ester [for example: Uvinul® 3088 supplied by BASF]; 2-propenoic acid, 2-cyano-3,3-diphenyl-, ethyl ester [for example: Uvinul® 3035 supplied by BASF]; or 2-propenoic acid, 2-cyano-3,3-diphenyl-, 2-ethylhexyl ester [for example: Uvinul® 3039 suppied by BASF].
• benzoic acid
• Metal deactivators for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
• Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphos
• Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N, N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
• Nitrones for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N
• Thiosynergists for example dilauryl thiodipropionate or distearyl thiodipropionate.
• Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ - dodecylmercapto)propionate.
• esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
• mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole zinc dibutyldithiocarbamate
• dioctadecyl disulfide pentaerythritol tetrakis( ⁇ - dodecyl
• Polyamide stabilizers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
• Basic co-stabilizers 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 zinc pyrocatecholate.
• Basic co-stabilizers 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 ric
• 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 copolymers (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 copolymers (
• Fillers and reinforcing agents for example calcium carbonate, 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 costabilizers are added, for example, in concentrations of from 0.01 to 10%, based on the overall weight of the organic material to be stabilized.
• the compounds of the formula I can be used in particular together with phenolic antioxidants, light stabilizers and/or processing stabilizers.
• compositions comprise, in addition to compounds of the formula I, a compound of the organic phosphite or phosphonite type.
• the fillers and reinforcing agents are added to the polyolefin in concentrations, for example, of from 0.01 to 40%, based on the organic material to be stabilized.
• compositions comprise in addition to components (a) and (b) further additives as well, especially alkaline earth metal salts of higher fatty acids, for example calcium stearate, calcium lactate and/or calcium stearoyl-2-lactylate.
• alkaline earth metal salts of higher fatty acids for example calcium stearate, calcium lactate and/or calcium stearoyl-2-lactylate.
• a conventional stabilizer combination for the processing of polymeric organic materials such as, for example, polyolefins
• the combination of a phenolic antioxidant with a secondary antioxidant based on an organic phosphite or phosphonite is recommended.
• many polyolefin processors are obliged to operate processes in the high-temperature range above approx. 280 0 C.
• the inclusion of a processing stabilizer of the formula I is particularly suitable for high-temperature applications, especially in the temperature range above 300 0 C.
• Technical materials and moulded articles for instance based on HD polyethylene such as, for example, pipes and their technical variants (fittings), can be manufactured with a higher output and fewer rejects.
• a further advantage of the compounds of the formula I is also that they can be used in a very small amount, which results in a reduction in the overall antioxidant concentration compared with conventional stabilizer mixtures.
• the use of a low concentration of a compound of the formula I allows the overall stabilizer concentration to be reduced by approximately a third in, for example, polyolefins, which at the same time represents an economic advantage.
• the compounds of the formula I and other optional additives are incorporated into the organic polymeric material according to known methods, for example before or during shaping to moulded articles or alternatively by coating the organic polymeric material with a solution or dispersion of the compounds and subsequently evaporating the solvent.
• the compounds of the formual I can also be added to the materials to be stabilized in the form of a master batch which contains these compounds, typically in a concentration of, for example, from 2.5 to 25 % by weight.
• the compounds of the formula I may also be added before or during polymerization or before crosslinking.
• the compounds of the formula I, and where applicable further additives, may be incorporated into the material to be stabilized in pure form or encapsulated in waxes, oils or polymers.
• the compounds of the formula I, and where applicable further additives may also be sprayed onto the polymer to be stabilized. They are able to be used to dilute other additives (e.g. the above-mentioned conventional additives) or melts thereof, so that they can also be sprayed together with these additives onto the polymer to be stabilized.
• Application by spraying during the deactivation of the polymerization catalysts is especially advantageous, in which case spraying is conveniently effected with the vapour used for deactivation.
• the materials stabilized in this way can be employed in a wide variety of forms, for example as films, fibres, tapes, moulding compositions, profiles or as binders for coating materials, especially powder coatings, adhesives or putties.
• polyolefins stabilized in this way can likewise be employed in a wide variety of forms, especially as thick-layer polyolefin mouldings which are in long-term contact with extractive media, such as, for example pipes for liquids or gases, films, geomembranes, tapes, strips, profiles or tanks.
• extractive media such as, for example pipes for liquids or gases, films, geomembranes, tapes, strips, profiles or tanks.
• the preferred thick-layer polyolefin mouldings have a layer thickness of from 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10 mm.
• Also of particular interest is a process for stabilizing thick-layer polyolefin mouldings that are in long-term contact with extractive media, wherein the thick-layer polyolefin mouldings are pipes or geomembranes, which comprises incorporating in or applying to said mouldings at least a compound of the formula I.
• geomembranes refers to films which are employed, for example, in landfill sites and are required to have a service life of up to 300 years.
• Extractive media are, for example, liquid or gaseous inorganic or organic materials.
• gaseous inorganic materials are oxygen; nitrogen; oxides of nitrogen; for example NO, laughing gas or NO 2 ; oxides of sulfur, for example sulfur dioxide; halogens, for example fluorine or chlorine; Bronstedt acids, for example hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid or hydrocyanic acid; or bases, for example ammonia.
• gaseous organic materials are CrC 4 alkanes, for example methane, ethane, propane or butane; carbon monoxide; carbon dioxide; or phosgene.
• liquid inorganic materials are water, chlorinated drinking water or aqueous salt solutions, for example sodium chloride solution (brine) or sodium sulfate solution; bromine; acid halides, e.g. titanium tetrachloride, thionyl chloride, nitrosyl chloride or trimethylsilyl chloride; alkalis, for example aqueous sodium hydroxide (NaOH), aqueous potassium hydroxide (KOH), aqueous ammonia solution, aqueous sodium bicarbonate solution or aqueous sodium carbonate solution.
• aqueous salt solutions for example sodium chloride solution (brine) or sodium sulfate solution
• bromine acid halides, e.g. titanium tetrachloride, thionyl chloride, nitrosyl chloride or trimethylsilyl chloride
• alkalis for example aqueous sodium hydroxide (NaOH), aqueous potassium hydroxide (KOH), aqueous am
• liquid organic materials are organic solvents or liquid organic reagents.
• organic solvents are aliphatic hydrocarbons, for example pentane, hexane, heptane, octane, petroleum spirit, nonane or decane; alcohols, for example methanol, ethanol, isopropanol, butanol, pentanol, amyl alcohol, cyclohexanol, pentaerythritol, ethylene glycol, ethylene diglycol, methylcellosolve, polyethylene glycol or glycerol; ketones, for example acetone, diethyl ketone, methyl ethyl ketone, diphenyl ketone or cyclohexanone; ethers, for example diethyl ether, dibutyl ether, tetrahydrofuran or dioxane; aromatic hydrocarbons, for example benzene, toluene or xylene; heterocyclic solvents, for example furan, pyridine, 2,6-luti
• extractive media are also mixtures and solutions, especially aqueous mixtures, emulsions or solutions, of liquid or gaseous inorganic and organic materials as listed above.
• the present invention relates also to new compounds of the formula I
• Ri and R 2 independently of each other are hydrogen, Ci-C 25 alkyl, C 2 -C 25 alkenyl, unsubsti- tuted or with d-C 4 alkyl substituted phenyl; unsubstituted or with CrC 4 alkyl substituted
• R 3 and R 4 independently of each other are hydrogen, Ci-C 25 alkyl, unsubstituted or with
• Ci-C 4 alkyl substituted phenyl Ci-C 4 alkyl substituted phenyl
• R 5 and R 6 independently of each other are hydrogen, Ci-C 25 alkyl, C 2 -C 25 alkyl interrupted by oxygen; unsubstituted or with Ci-C 4 alkyl substituted phenyl; halogen, -CN, -NO 2 ,
• R 7 is hydrogen, Ci-Ci 2 alkyl, — N N , unsubstituted or with halogen or Ci-C 4 alkyl substitu-
• Rs is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
• R 9 is -CN, -S(O) n -RiO , -C-R 10 , -C-O-R 11 , -C-N , -N N or -NO 2 ,
• Rio is hydrogen, Ci-C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or Ci-C 4 alkyl-substituted phenyl; unsubstituted or Ci-C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
• Rn is hydrogen, alkali metal, Ci-C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or Ci-C 4 alkyl-sub- stituted phenyl; unsubstituted or Ci-C 4 alkyl-substituted C 5 -C 8 cycloalkyl; or C 3 -C 25 alkyl which is interrupted by oxygen or sulfur;
• Ri 2 and Ri 3 independently of one another are hydrogen, Ci-C 25 alkyl, Ci-C 4 alkanoyl, C 7 -C 9 - phenylalkyl, unsubstituted or Ci-C 4 alkyl-substituted phenyl; or Ri 2 and Ri 3 , together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic ring which is unsubstituted or is substituted by CrC 4 alkyl or is interrupted by oxygen, sulfur or
• Ri 4 is hydrogen, d-C 8 alkyl or benzyl, and n is O, 1 or 2.
• the preferred general symbols are identical to those of the compounds of the formula I disclosed in the composition with an organic material.
• Ri is Ci-C 4 alkyl, -CH(R 7 )-S(O) n -R 8 or -CH(R 7 )-S(O) n -CH 2 -CH(R 7 )-R 9!
• R 2 is Ci-C 4 alkyl, -CH(R 7 )-S(O) n -R 8 or -CH(R 7 )-S(O) n -CH 2 -CH(R 7 )-R 9!
• R 3 is hydrogen
• R 4 is hydrogen or phenyl
• R 5 is hydrogen
• R 6 is hydrogen or phenyl
• R 7 is hydrogen
• R 8 is -CH 2 -CH 2 -(CF 2 ) 3 CF 3 or -CH 2 -CH 2 -(CF 2 ) 7 CF 3 ,
• Rn is hydrogen or Ci-C 8 alkyl, and n is O, 1 or 2.
• the compounds of the formula I are prepared from the corresponding phenols (see Table 2).
• Ri and R 2 independently of each other are hydrogen, Ci-C 25 alkyl, C 2 -C 25 alkenyl, unsubsti- tuted or with Ci-C 4 alkyl substituted phenyl; unsubstituted or with Ci-C 4 alkyl substituted
• R 3 is H
• R 4 is hydrogen, d-C ⁇ alkyl, unsubstituted or with d-C 4 alkyl substituted phenyl,
• R 5 and R 6 independently of each other are hydrogen, CrC 25 alkyl, C 2 -C 25 alkyl interrupted by oxygen; unsubstituted or with Ci-C 4 alkyl substituted phenyl; halogen, -CN, -NO 2 ,
• R 7 , R 7a and R 7b independently of each other are hydrogen, Ci-Ci 2 alkyl, unsubstituted or with Ci-C 4 alkyl substituted phenyl;
• R 8 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
• R 9 is -CN, -S(O) n -Ri 0 , -C-R 10 , -C-O-R 11 , -C-N , -N N or -NO 2 ,
• Rio is hydrogen, Ci-C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or Ci-C 4 alkyl-substituted phenyl; unsubstituted or Ci-C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
• Rn is hydrogen, alkali metal, Ci-C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or Ci-C 4 alkyl-sub- stituted phenyl; unsubstituted or Ci-C 4 alkyl-substituted C 5 -C 8 cycloalkyl; or C 3 -C 25 alkyl which is interrupted by oxygen or sulfur;
• Ri 2 and Ri 3 independently of one another are hydrogen, Ci-C 25 alkyl, Ci-C 4 alkanoyl, C 7 -C 9 - phenylalkyl, unsubstituted or Ci-C 4 alkyl-substituted phenyl; or Ri 2 and Ri 3 , together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic ring which is unsubstituted or is substituted by Ci-C 4 alkyl or is interrupted by oxygen, sulfur or
• Ri 4 is hydrogen, Ci-C 8 alkyl or benzyl, and n is O,
• R 15 is -CH(R 7a )-S(O) n -CH 2 -CH(R 7b )-R 9 ,
• R 7 , R 7a and R 7b and R 9 have the meaning as indicated for the compound of formula Ia
• R 5 and R 6 have the meaning as indicated for the compound of formula Ia, and X and Y independently of each other are halogen.
• Halogen can be fluorine, chlorine, bromine or iodine. Chlorine and iodine are the preferred halogens. Examples of compounds of formula III are diiodomethane and benzal chloride.
• the molar ratio of the compound of formula Ill/compound of formula Il is 1/1 to 10/1 , more preferably 3/1 to 7/1 and most preferably 4.5/1 to 5.5/1.
• the reaction of the compound of formula Il with the compound of formula III takes place in the presence of a base.
• bases are alkali metal hydroxide such as sodium hydroxide, alkali metal and earth alkaline metal carbonates such as calcium carbonate and ammonia.
• alkali metal hydroxide such as sodium hydroxide
• alkali metal and earth alkaline metal carbonates such as calcium carbonate and ammonia.
• sodium hydroxide is used.
• the molar ratio of the compound of the base/compound of formula Il is 1/1 to 10/1 , more preferably 3/1 to 7/1 and most preferably 4.5/1 to 5.5/1.
• the reaction is usually carried out in a solvent.
• the solvent is preferably in polar and aprotic organic solvent such as sulfolane, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, paraformamide and N,N-dimethylformamide. Sulfolane is the preferred solvent.
• the reaction is usually performed at a temperature of 10 to 40 0 C, preferably from 15 to 30 0 C, more preferably from 20 to 25 0 C.
• the compound of formula Ia can be isolated from the reaction mixture, for example by chromatography or crystallization.
• Ri and R 2 independently of each other are hydrogen, CrC 25 alkyl, C 2 -C 25 alkenyl, unsubsti- tuted or with d-C 4 alkyl substituted phenyl; unsubstituted or with CrC 4 alkyl substituted
• R 3 and R 4 independently of each other are hydrogen, Ci-C 25 alkyl, unsubstituted or with
• Ci-C 4 alkyl substituted phenyl Ci-C 4 alkyl substituted phenyl
• R 5 and R 6 independently of each other are hydrogen, Ci-C 25 alkyl, C 2 -C 25 alkyl interrupted by oxygen; unsubstituted or with Ci-C 4 alkyl substituted phenyl; halogen, -CN, -NO 2 ,
• R 7 , R 73 and R 7 b idependently of each other are hydrogen, d-C ⁇ alkyl, — N N
• R 13 unsubstituted or with halogen or Ci-C 4 alkyl substituted phenyl
• R 8 is a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
• R 9 is -CN, -S(O) n -Ri 0 , -C-R X 1 1 0 O , -C-O-R 1 X 1 1 1 1 , -C-N , -N N or -NO 2 ,
• Rio is hydrogen, CrC 2 5alkyl, C 7 -C 9 phenylalkyl, unsubstituted or d-C 4 alkyl-substituted phenyl; unsubstituted or d-C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
• Rn is hydrogen, alkali metal, CrC 2 5alkyl, C 7 -C 9 phenylalkyl, unsubstituted or d-C 4 alkyl-sub- stituted phenyl; unsubstituted or d-C 4 alkyl-substituted C 5 -C 8 cycloalkyl; or C 3 -C 25 alkyl which is interrupted by oxygen or sulfur;
• Ri 2 and Ri 3 independently of one another are hydrogen, d-C 25 alkyl, d-C 4 alkanoyl, C 7 -C 9 - phenylalkyl, unsubstituted or d-C 4 alkyl-substituted phenyl; or Ri 2 and Ri 3 , together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic ring which is unsubstituted or is substituted by d-C 4 alkyl or is interrupted by oxygen, sulfur or
• Ru is hydrogen, Ci-C 8 alkyl or benzyl, and n is 1 or 2
• the compounds of formula Ib, wherein n is 1 can be prepared by oxidation of the compound of formula Ia with sodium periodate.
• the compounds of formula Ib, wherein n is 2 can be prepared by oxidation of the compound of formula Ia with 3-chloro- peroxybenzoic acid (m-CPBA).
• m-CPBA 3-chloro- peroxybenzoic acid
• Ri and R 2 independently of each other are hydrogen, Ci-C 25 alkyl, C 2 -C 25 alkenyl, unsubsti- tuted or with Ci-C 4 alkyl substituted phenyl; unsubstituted or with Ci-C 4 alkyl substituted
• R 7 is hydrogen, Ci-Ci 2 alkyl, — N N , unsubstituted or with halogen or Ci-C 4 alkyl substitu-
• R 9 is -CN, -S(O) n -Ri 0 , -C-R 10 , -C-O-R 11 , -C-N , -N N or -NO 2 ,
• Rio is hydrogen, Ci-C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or d-C 4 alkyl-substituted phenyl; unsubstituted or d-C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
• Rn is hydrogen, alkali metal, Ci-C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or d-C 4 alkyl-sub- stituted phenyl; unsubstituted or d-C 4 alkyl-substituted C 5 -C 8 cycloalkyl; or C 3 -C 25 alkyl which is interrupted by oxygen or sulfur;
• Ri 2 and Ri 3 independently of one another are hydrogen, d-C 25 alkyl, d-C 4 alkanoyl, C 7 -C 9 - phenylalkyl, unsubstituted or d-C 4 alkyl-substituted phenyl; or Ri 2 and Ri 3 , together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic ring which is unsubstituted or is substituted by d-C 4 alkyl or is interrupted by oxygen, sulfur or
• Ru is hydrogen, d-C 8 alkyl or benzyl
• Ri 5 is -CH(R 7 )-S(O) n -CH 2 -CH(R 7 )-R 9
• n is O 1 or 2.
• the preferred general symbols are identical to those of the compounds of the formula I disclosed in the composition with an organic material.
• n is preferably 0.
• phenols of the formula Il are prepared according to conventional synthetic methods, for example compounds of formula Il wherein n is 0 and R 7a is H can be prepared by reacting the compound of formula IV
• R 1 and R 2 have the meaning as indicated for the compounds of formula II, with H-S(O ) n -CH 2 -CH(R7b)-R9, wherein n is 0 and R 7b and R 9 have the meaning as indicated for the compound of formula II, and paraformaldehyde.
• a preferred embodiment of the present invention is also a process for stabilizing an organic material against oxidative, thermal or light-induced degradation and/or for reducing the surface energy of organic materials, which comprises incorporating therein or applying thereto at least a compound of the formula I.
• a preferred embodiment of the present invention is the use of the compounds of the formula I as stabilizers against oxidative, thermal or light-induced degradation and/or as reducers of surface energy for organic materials.
• compositions according to the invention can be advantageously used for the preparation of various shaped articles.
• Examples are: 1-1 ) Floating devices, marine applications, pontoons, buoys, plastic lumber for decks, piers, boats, kayaks, oars, and beach reinforcements.
• I-2) Automotive applications in particular bumpers, dashboards, battery, rear and front linings, moldings parts under the hood, hat shelf, trunk linings, interior linings, air bag covers, electronic moldings for fittings (lights), panes for dashboards, headlamp glass, instrument panel, exterior linings, upholstery, automotive lights, head lights, parking lights, rear lights, stop lights, interior and exterior trims; door panels; gas tank; glazing front side; rear windows; seat backing, exterior panels, wire insulation, profile extrusion for sealing, cladding, pillar covers, chassis parts, exhaust systems, fuel filter / filler, fuel pumps, fuel tank, body side mouldings, convertible tops, exterior mirrors, exterior trim, fasteners / fixings, front end module, glass, hinges, lock systems, luggage / roof racks, pressed/stamped parts, seals, side impact protection, sound deadener / insulator and sunroof.
• Road traffic devices in particular sign postings, posts for road marking, car accessories, warning triangles, medical cases, helmets, tires.
• I-5) Devices for space applications in particular rockets and satellites, e.g. reentry shields.
• I-6) Devices for architecture and design, mining applications, acoustic quietized systems, street refuges, and shelters.
• Appliances, cases and coverings in general and electric/electronic devices personal computer, telephone, portable phone, printer, television-sets, audio and video devices), flower pots, satellite TV bowl, and panel devices.
• 11— 3 Devices for the electronic industry, in particular insulation for plugs, especially computer plugs, cases for electric and electronic parts, printed boards, and materials for electronic data storage such as chips, check cards or credit cards. 11-4) Electric appliances, in particular washing machines, tumblers, ovens (microwave oven), dish-washers, mixers, and irons.
• Covers for lights e.g. street-lights, lamp-shades.
• shutters e.g. roller shutters
• Hygienic articles in particular diapers (babies, adult incontinence), feminine hygiene articles, shower curtains, brushes, mats, tubs, mobile toilets, tooth brushes, and bed pans.
• Glass substitutes in particular extruded or co-extruded plates, glazing for buildings (monolithic, twin or multiwall), aircraft, schools, extruded sheets, window film for architectural glazing, train, transportation, sanitary articles, and greenhouse.
• Plates walls, cutting board), extrusion-coating (photographic paper, tetrapack and pipe coating), silos, wood substitute, plastic lumber, wood composites, walls, surfaces, furniture, decorative foil, floor coverings (interior and exterior applications), flooring, duck boards, and tiles.
• IV-1 Plates (walls and cutting board), trays, artificial grass, astroturf, artificial covering for stadium rings (athletics), artificial floor for stadium rings (athletics), and tapes.
• Woven fabrics continuous and staple, fibers (carpets / hygienic articles / geotextiles / monofilaments; filters; wipes / curtains (shades) / medical applications), bulk fibers (applications such as gown / protection clothes), nets, ropes, cables, strings, cords, threads, safety seat-belts, clothes, underwear, gloves; boots; rubber boots, intimate apparel, garments, swimwear, sportswear, umbrellas (parasol, sunshade), parachutes, paraglides, sails, "balloon-silk", camping articles, tents, airbeds, sun beds, bulk bags, and bags.
• Non-woven fabrics such as medical fabrics and related apparel, industrial apparel, outdoor fabrics, in- home furnishing and construction fabrics.
• V Films (packaging, dump, laminating, agriculture and horticulture, greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, waste bags, wallpaper, stretch film, raffia, desalination film, batteries, and connectors.
• VI-1 Food packing and wrapping (flexible and solid), bottles.
• VI-2) Storage systems such as boxes (crates), luggage, chest, household boxes, pallets, shelves, tracks, screw boxes, packs, and cans.
• Vl 1-1 Extrusion coating (photo paper, tetrapack, pipe coating), household articles of any kind (e.g. appliances, thermos bottle / clothes hanger), fastening systems such as plugs, wire and cable clamps, zippers, closures, locks, and snap-closures.
• Support devices articles for the leisure time such as sports and fitness devices, gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops, tops and stoppers for bottles, and cans.
• sports and fitness devices gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops, tops and stoppers for bottles, and cans.
• Footwear (shoes / shoe-soles), insoles, spats, adhesives, structural adhesives, food boxes (fruit, vegetables, meat, fish), synthetic paper, labels for bottles, couches, artificial joints (human), printing plates (flexographic), printed circuit boards, and display technologies.
• a further embodiment of the present invention relates to a shaped article, in particular a film, pipe, profile, bottle, tank or container, fiber containing a composition as described above.
• a further embodiment of the present invention relates to a molded article containing a composition as described above.
• the molding is in particular effected by injection, blow, compression, roto-molding or slush-molding or extrusion.
• the organic materials to be protected are preferably organic, especially synthetic, polymers.
• thermoplastic materials are protected with particular advantage. Attention should be drawn above all in this context to the outstanding activity of the stabilizers of the formula I as processing stabilizers (heat stabilizers). For this purpose they are advantageously added to the polymer prior to or during its processing.
• processing stabilizers heat stabilizers
• other polymers too for example elastomers
• lubricants or hydraulic fluids can be stabilized against degradation, for example light-induced or thermooxidative degradation.
• Elastomers can be taken from the above listing of possible organic materials.
• the invention relates also to compositions comprising a functional fluid, preferably from the series of lubricants, hydraulic fluids and metal-working fluids and also fuels for powering engines of the 4-stroke, Otto, 2-stroke, diesel, Wankel and orbital types, and at least one compound of the formula I.
• the compounds of the formula I may preferably be used in lubricants and fuels as multifunctional stabilizers, that is to say they combine in themselves antioxidative, friction-reducing, extreme-pressure-protection and wear-protection action and also anti-corrosion properties.
• Preferred lubricants and fuels and related products are engine oils, turbine oils, gear oils, hydraulic fluids, diesel or Otto fuels, metal-working fluids and lubricating greases.
• Especially preferred lubricants are mineral oils, synthetic oils or mixtures thereof.
• Products known per se are used as functional fluids from the series of lubricants, hydraulic fluids and metal-working fluids.
• the lubricants are especially oils and greases, for example based on a mineral oil. Oils are preferred.
• a further group of lubricants that may be used are vegetable or animal oils, greases, tallows and waxes or mixtures thereof with one another or mixtures with the mentioned mineral or synthetic oils.
• Vegetable and animal oils, greases, tallows and waxes are, for example, palm-kernel oil, palm oil, olive oil, rapeseed oil, rape oil, linseed oil, groundnut oil, soybean oil, cottonseed oil, sunflower oil, pumpkin seed oil, coconut oil, maize oil, castor oil, tree nut oil and mixtures thereof, fish oils, tallows obtained from slaughtered animals, such as beef tallow, neatsfoot oil and bone oil, and modified, epoxidised and sulfoxidised forms thereof, for example epoxidised soybean oil.
• the mineral oils are based especially on hydrocarbon compounds.
• Examples of synthetic lubricants include lubricants based on aliphatic or aromatic carboxy esters, polymeric esters, polyalkylene oxides, phosphoric acid esters, poly-alpha-olefins or silicones, a diester of a divalent acid with a monohydric alcohol, such as, for example, di- octyl sebacate or dinonyl adipate, a triester of trimethylolpropane with a monovalent acid or with a mixture of such acids, such as, for example, trimethylolpropane tripelargonate, trimethylolpropane tricaprylate or mixtures thereof, a tetraester of pentaerythritol with a monovalent acid or with a mixture of such acids, such as, for example, pentaerythritol tetracapry- late, or a complex ester of monovalent and divalent acids with polyhydric alcohols, for example a complex ester of tri
• Metal-working fluids and hydraulic fluids may be prepared on the basis of the same substances as those described above for the lubricants, such fluids frequently being emulsions of such substances in water or other liquids.
• Lubricant and fuel compositions according to the invention are used, for example, in internal combustion engines, e.g. in motorised vehicles equipped with, for example, engines of the Otto, diesel, two-stroke, Wankel or orbital type.
• the compounds of the formula I are readily soluble in lubricants and fuels, metal-working fluids and hydraulic fluids and are therefore especially suitable as additives for lubricants and fuels, metal-working fluids and hydraulic fluids.
• the compounds of the formula I are effective even in very small amounts. They are mixed in with the lubricants advantageously in an amount of from 0.01 to 5 % by weight, preferably in an amount of from 0.05 to 3 % by weight and very especially in an amount of from 0.1 to 2 % by weight, in each case based on the lubricant.
• the compounds of the formula I may be mixed in with the lubricants and fuels in a manner known per se.
• the compounds of the formula I are readily soluble, for example, in oils. It is also possible to prepare a so-called master batch, which may be diluted, as a function of use, with the appropriate lubricant or fuel to the concentrations suitable for use. In such cases concentrations above 1 % by weight are possible.
• the lubricants and fuels, metal-working fluids and hydraulic fluids may additionally comprise other additives that are added in order to improve their basic properties still further; such additives include: further antioxidants, metal passivators, rust inhibitors, viscosity index improvers, pour-point depressants, dispersants, detergents, coefficient of friction reducers, further extreme-pressure additives and anti-wear additives.
• Such further additives are added advantageously in an amount of from 0.01 to 5 % by weight.
• metal deactivators e.g. for copper
• metal deactivators are: a) Benzotriazoles and derivatives thereof, e.g. 2-mercaptobenzotriazole, 2,5-dimercapto- benzotriazole, 4- or 5-alkylbenzotriazoles (e.g.
• tolutriazole and derivatives thereof, 4,5,6,7-tetrahydrobenzotriazole, 5,5'-methylenebis-benzotriazole; Mannich bases of benzotriazole or tolutriazole, such as 1-[di(2-ethylhexyl)aminomethyl]tolutriazole and 1- [di(2-ethylhexyl)aminomethyl]benzotriazole; alkoxyalkylbenzotriazoles, such as 1 -(no- nyloxymethyl)benzotriazole, 1-(1-butoxyethyl)benzotriazole and 1-(1-cyclohexyloxybu- tyl)tolutriazole.
• Mannich bases of benzotriazole or tolutriazole such as 1-[di(2-ethylhexyl)aminomethyl]tolutriazole and 1- [di(2-ethylhexyl)amin
• 1 ,2,4-Triazoles and derivatives thereof e.g. 3-alkyl- (or -aryl-)1 ,2,4-triazoles, Mannich bases of 1 ,2,4-triazoles, such as 1-[di(2-ethylhexyl)aminomethyl]-1 ,2,4-triazole; alkoxy- alkyl-1 ,2,4-triazoles, such as 1-(1-butoxyethyl)-1 ,2,4-triazole; acylated 3-amino-1 ,2,4-tri- azoles.
• 3-alkyl- (or -aryl-)1 ,2,4-triazoles Mannich bases of 1 ,2,4-triazoles, such as 1-[di(2-ethylhexyl)aminomethyl]-1 ,2,4-triazole; alkoxy- alkyl-1 ,2,4-triazoles, such as 1-(1-butoxyethyl)-1 ,2,4-tri
• Imidazole derivatives e.g. 4,4'-methylenebis(2-undecyl-5-methyl)imidazole and bis[(N- methyl)imidazol-2-yl]carbinol-octyl ether.
• Sulfur-containing heterocyclic compounds e.g. 2-mercaptobenzothiazole, 2,5-dimer- capto-1 ,3,4-thiadiazole, 2,5-dimercaptobenzothiadiazole and derivatives thereof; 3,5- bis[di(2-ethylhexyl)aminomethyl]-1 ,3,4-thiadiazolin-2-one.
• Amino compounds e.g. salicylidene-propylenediamine, salicylaminoguanidine and salts thereof.
• rust inhibitors are:
• Organic acids, their esters, metal salts, amine salts and anhydrides e.g. alkyl- and alkenyl-succinic acids and their partial esters with alcohols, diols or hydroxycarboxylic acids, partial amides of alkyl- and alkenyl-succinic acids, 4-nonylphenoxyacetic acid, alkoxy- and alkoxyethoxy-carboxylic acids, such as dodecyloxyacetic acid, dodecyloxy- (ethoxy)acetic acid and amine salts thereof, and also N-oleoyl-sarcosine, sorbitan mo- nooleate, lead naphthenate, alkenylsuccinic acid anhydrides, e.g. dodecenylsuccinic acid anhydride, 2-(2-carboxyethyl)-1-dodecyl-3-methylglycerol and salts thereof, especially sodium and triethanolamine salts
• Nitrogen-containing compounds e.g.: i. Primary, secondary or tertiary, aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, e.g. oil-soluble alkylammonium carboxylates, and 1-[N, N- bis(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol.
• Heterocyclic compounds e.g.: substituted imidazolines and oxazolines, e.g. 2-hepta- decenyl-1-(2-hydroxyethyl)-imidazoline.
• Phosphorus-containing compounds e.g.:
• Glycerol derivatives e.g.:
• Glycerol monooleate 1-(alkylphenoxy)-3-(2-hydroxyethyl)glycerols, 1-(alkylphenoxy)-3- (2,3-dihydroxypropyl)glycerols, 2-carboxyalkyl-1 ,3-dialkylglycerols.
• viscosity index improvers examples are:
• Polyacrylates polymethacrylates, vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene/acrylate copolymers, polyethers.
• pour-point depressants are:
• Poly(meth)acrylates ethylene/vinyl acetate copolymer, alkylpolystyrenes, fumarate copolymers, alkylated naphthalene derivatives.
• dispersants/surfactants examples are:
• Sulfur- and/or phosphorus- and/or halogen-containing compounds such as, for example, chlorinated paraffins, sulfurated olefins or vegetable oils (soybean/rape oil), alkyl- or aryl-di- or -tri-sulfides, zinc dialkyldithiophosphat.es, zinc dithiocarbamates such as zinc diamyldi- thiocarbamate, molybdenum dithioates such as molybdenum dithiocarbamates, triaryl phosphates such as tritolyl phosphate, tricresyl phosphate, phenyl phosphate isopropyl ester, amine salts of mono- or di-alkylphosphoric acids such as the amine salts of mono-/di-hexyl phosphate, amine salts of alkylphosphonic acids such as the amine salt of methylphospho- nic acid, triaryl phosphites such as tri
• coefficient of friction reducers are:
• Emulsifiers petroleum sulfonates, amines, such as polyoxyethylated fatty amines, non-ionic surface-active substances;
• Buffers alkanolamines
• Biocides triazines, thiazolinones, tris-nitromethane, morpholine, sodium pyridenethol;
• Petrol dyes, especially azo dyes
• Antioxidants aminic, especially para-phenylenediamines, or phenolic, e.g. 2,6-di-tert-butyl- phenol, as described above;
• Metal deactivators especially N,N'-disalicylidene-1 ,2-propane, benzotriazole, EDTA;
• Rust inhibitors for example carboxylic acids, sulfonates, amines or amine salts;
• Dispersants e.g. esters, high-molecular-weight amines, Mannich bases, succinimides, borated succinimides;
• Detergents for example fatty acid amides, nonpolymeric amines, polybutene succinimides, polyether amines, low-molecular-weight amines, sulfonates, salicylic acid derivatives; Demulsifiers: for example long-chain alcohols or phenols containing poly-ethylene or
• Antiknock agents tetralkyl lead, manganese methylcyclopentadienyltricarbonyl;
• Oxygen compounds esters of vegetable oils, ethers, alcohols for improving burn behaviour
• Diesel ignition improvers (cetane improvers), e.g. alkyl nitrates, ether nitrates, alkyl diglycol nitrates, organic peroxides;
• cetane improvers e.g. alkyl nitrates, ether nitrates, alkyl diglycol nitrates, organic peroxides;
• Especially preferred further additives in lubricants are aminic antioxidants, especially mixtures of mono- and di-alkylated tert-butyl-/tert-octyl-diphenylamines.
• the present invention relates also to the use of the components of the formula I for stabilizing organic materials against oxidative, thermal or light-induced degradation, especially as additives in lubricants and fuels, hydraulic fluids or metal-working fluids, preferably in hydraulic oils and gear oils.
• the use according to the invention includes protection of the metal components to be lubricated against mechanical attrition (wear protection) and corrosion protection activity and also antioxidation activity - with respect both to the lubricant and to the metal components.
• Example 1 Preparation of the compound 101 (Table 1 ).
• Example 2 In analogy to Example 1 starting from the compounds 202, 203, 204, 205, 206 and 207 (see Table 2) the compounds 102, 103, 104, 105, 106 and 107 are prepared. In analogy to Example 1 starting from compound 210 (see Table 2) the compound 102 is prepared. In analogy to Example 1 starting from compound 211 (see Table 2) the compound 101 is prepared. In analogy to Example 1 starting from compound 212 (see Table 2) the compound 104 is prepared.
• Example 2 Preparation of the compound 108 (Table 1 ).
• Example 3 Preparation of the compound 1 10 (Table 1 ).
• the organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 9.80 g of an orange liquid.
• the volatiles are distilled in a Kugelrohr (0.08 mbar; temperature: 120 0 C) and then the residue is crystallized in acetonitrile to give 1.30 g of the compounds 1 10a and 110b as a mixture of diastereoisomers, pale yellow solid. Both diastereoisomers are subsequently separated via multiple crystallization to give the major diastereoisomer 1 10a as a pale yellow solid, m.p. 161-164°C and the minor diastereoisomer 1 10b as a pale yellow solid, m.p. 120-125 0 C.
• Example 5 Preparation of the compound 1 13 (Table 1 ).
• Example 6 Preparation of the compound 1 14 (Table 1 ).
• Example 7 Preparation of the compound 1 16 (Table 1 ).
• Example 8 Preparation of the compound 1 17 (Table 1 ).
• Example 9 Preparation of the compound 1 18 (Table 1 ).
• Example 10 Preparation of the compound 1 19 (Table 1 ).
• Example 1 1 Preparation of the compound 120 (Table 1 ).
• the organic phase is dried over sodium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 24.5 g of a yellow liquid.
• the crude product is purified by flash chromatography (hexane/ethyl acetate: 19 : 1 ) to give 23.3 g of the compound 210 as colourless liquid.
• Example 13 Preparation of the compound 212 (Table 2).
• Example 14 Preparation of the compound 202 (Table 2).
• Example 15 Stabilization of multiple-extruded polypropylene.
• This blend is then extruded in an extruder having a cylinder diameter of 20 mm and a length of 400 mm at 100 rpm, the 3 heating zones being adjusted to the following temperatures: 260, 270, 28O 0 C.
• the extrudate is cooled by drawing it through a water bath and is then granulated. This granulate is repeatedly extruded. After 3 extrusions, the melt index is measured (at 230°C/2.16 kg). A substantial decrease in the melt index denotes good stabilization, for example limited polymeric chain degradation.
• Table 3 The results are summarized in Table 3.
• Example 16 Water and oil repellency in polypropylene.
• the sample preparation is a combination of polypropylene nonwovens and the additive and a thermal treatment (e.g. 130 0 C for 10 minutes), which enables the migration of the additive to the surface and a proper surface rearrangement of the chemical groups.
• This extra heat cycle is needed to melt the compounds of the formula I in order to obtain a homogeneous redistribution over the surface of the substrate.
• An industrial sample of polypropylene nonwoven, fabric weight: 40 g/m 2 is dipped into a 1 % isopropanol solution of the test compound, simultaneously applying ultrasonic energy for one minute. After that, the sample is dried overnight at room temperature and then two hours at 90 0 C in an oven. A part of the sample is afterwards annealed for 10 minutes at 130 0 C.
• the treated nonwoven samples are evaluated in the water repellency test similar to INDA test method 80.8 (99).
• the wetting behavior of the nonwovens is tested with a series of water/ isopropanol mixtures. The observation of the wetting behavior is rated from 0 (water wetting, no repellency) to 10 (optimum water repellency). The results are summarized in Table 4.
• the treated nonwoven samples are evaluated in the oil repellency test similar to AATCC test method 1 18-1997 / ISO 14419. This test follows the same concepts of the already described for water repellency test method, but using, as test solvents, a series of hydrocarbons. The observation of the wetting behavior is rated from 0 (no repellency) to 8 (optimum repellency).
• a stabilizer composition based on the compound 101 according to the invention 0.71 g (0.45 %, based on the polyol) of a stabilizer composition based on the compound 101 according to the invention is dissolved in 157.1 g of Lupranol 2084® [trifunctional polyether polyol containing predominantly secondary hydroxyl groups; hydroxyl number 48 mg KOH/g, water content less than 0.1 %, acid number less than 0.06 mg KOH/g)] supplied by Elastogran BASF.
• Lupranol 2084® trifunctional polyether polyol containing predominantly secondary hydroxyl groups; hydroxyl number 48 mg KOH/g, water content less than 0.1 %, acid number less than 0.06 mg KOH/g
• Dynamic heat ageing of foam samples is used as a measure of scorch resistance (Dynamic AIu Block Test).
• the foam samples are typically heated in an oven or an aluminum block and scorch resistance is assessed by measuring the color change.
• the temperature is increased at a constant rate and the color change determined as a function of the temperature (30 minutes at temperatures between 170 and 230 0 C).
• the foam color quality is reported in terms of Yellowness Index (Yl) determined on the foam samples in accordance with the ASTM 1926-70 Yellowness Test. Low Yl values denote little discoloration, high Yl values severe discoloration of the samples. The whiter the foam the better is the foam stabilized.
• Table 5 The results are summarized in Table 5.

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