Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3472—Five-membered rings
  • C08K5/3475—Five-membered rings condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
  • C07D249/18—Benzotriazoles
  • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2

Definitions

• This invention pertains to new benzotriazole UV absorbers having an ultra long ester or amide moiety attached to the molecule are very efficacious as UV absorbers while not blooming when incorporated into polyolefin films and for candle wax.
• the original stabilizers are often simple, relatively inexpensive molecules involving some warhead moiety.
• molecular adjustments to these original stabilizers are made to meet the new requirements.
• European Patent Application 315,155 A2 describes some negative type silver halide photographic material which contain development accelerators which are inter alia benzotriazoles substituted on the benzo ring by d i alky lam inoalkyl amide groups. None of these materials are UV absorbers and are clearly structurally different from the instant compounds. Likewise, United States Patent No. 4,778,728 describes some benzotriazole corrosion inhibitors which are structurally very different from the instant compounds.
• WO 97/42261 describes amide functional UV absorbers which resist blooming and migration which are inter alia benzotriazole UV absorbers substituted on the phenyl ring by - CONH-alkyl amide moieties having up to 18 carbon atoms in the alkyl chain.
• the instant long chain alkyl ester or amide compounds do not overlap with these amide compounds. Indeed, the instant compounds have 25-100 carbon atoms for each alkyl group.
• United States Patent Nos. 5,280,124 and 5,977,219 and copending application Serial No. 09/234,880 describe benzotriazole UV absorbers substituted on the phenyl ring by long chain alkyl ester groups of up to 24 carbon atoms and on the benzo ring with electron withdrawing groups in the 5-position.
• the phenyl ring can be substituted by long chain alkyl ester groups of 20 to 100 carbon atoms.
• the instant compounds are useful in protecting candles from discoloration.
• candles have been known for many centuries going back to the eighth century B.C. The nature of candles is described in Ullmann's Encyclopedia of Industrial Chemistry, Volume A5 at pages 29-30 where it is seen that candles are made from paraffin, beeswax and stearin as basic materials, and where a host of additives may also be present.
• EP 359,488 A3 and EP 133,964 B1 describe stabilized waxes used in cosmetics where the waxes are the same or similar to those used in candles.
• EP 5,922 A1 describes lip cosmetics where the waxes are useful in lipsticks and are related to those useful in candles.
• the light absorbers compared are 4-octyloxy-2-hydroxy- benzophenone UV-531 ; 4-methoxy-2-hydroxybenzophenone UV-9; 2-(2-hydroxy-5-methyl- phenyl)-2H-benzotriazole UV-5365; 2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole UV- 5411 and 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole UV-2337).
• United States Patent No. 5,964,905 teaches dyed and scented candle gels containing triblock copolymers and a hydrocarbon oil of high flash point.
• a light (UV) absorber may be used to improve the shelf stability of the candle color when exposed to visible or ultraviolet light.
• Two preferred absorbers are ethylhexyl p- methoxycinnamate (PARSOL® MCX, Roche) and 2-(2-hydroxy-5-tert-octylphenyl)-2H- benzotriazole (CYASORB® 5411 , Cytec).
• Japanese Hei 5-93164 discloses the use of benzotriazole UV absorbers and hindered amines in stabilizing pigmented wax crayons.
• WO 00/22037 describes the stabilization of solid, shaped and colored wax articles using a malonate UV absorber which may be substituted by a hindered amine group.
• the instant invention pertains to new benzotriazole UV absorbers which are not only effective UV absorbers, but also very resistant to blooming when incorporated into polyolefin films, particularly polyethylene films.
• the instant benzotriazoles are of formula I, II or III
• Gi and G ⁇ are independently hydrogen or halogen
• G 2 and G 2 ' are independently hydrogen, halogen, nitro, cyano, E 3 SO-, E 3 SO 2 -, - COOG 3l perfluoroalkyl of 1 to 12 carbon atoms, -P(O)(C 6 H 5 ) 2 , -CO-G 3 , -CO-NH-G 3 , -CO- N(G 3 ) 2 , -N(G 3 )-CO-G 3 ,
• G 3 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight of branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms; or G 3 is Ti or T 2 ,
• Ei is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms; or E-i is alkyl of 1 to 24 carbon atoms substituted by one or two hydroxy groups; or Ei is the group -(CH 2 ) m -CO-X-T ⁇ where m is 0, 1 or 2; or E ! is the group -(CH 2 ) p -X-CO-T 2 where p is 1 , 2 or 3,
• E 2 and E 2 ' are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by one to three alkyl of 1 to 4 carbon atoms; or E 2 and E 2 ' are independently said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more -OH, -OCOEn, -OE 4 , -NH 2 , -NHCOE 11 ( -NHE 4 or -N(E 4 ) 2) or mixtures thereof, Where E 4 is straight or branched chain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interrupted by one or more -
• X is -O- or -N(E 16 )-
• E 16 is hydrogen, CrC 12 -alkyl, C 3 -C 12 -alkyl interrupted by 1 to 3 oxygen atoms, or is cyclohexyl or C 7 -C 15 aralkyl,
• En is a straight or branched chain Crdsalkyl, C 5 -C 12 cycloalkyl, straight or branched chain C 2 -C 18 alkenyl, C 6 -C 1 aryl or C 7 -C 15 aralkyl; or En is ⁇ or T 2 ,
• E 3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or 1 ,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6 to 16 carbon atoms,
• L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene, , , ', ⁇ '-tetramethyl-m-xylylene or cycloalkylidene
• T is -SO-, -SO 2 -, -SO-E-SO-, -SO 2 -E-SO 2 -, -CO-, -CO-CH 2 -CO-, -CO-E-CO-, -COO-E- OCO- or -CO-NGs-E-NGs-CO-,
• E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or alkylene interrupted or terminated by cyclohexylene of 8 to 12 carbon atoms;
• G 5 is G 3 or hydrogen
• Ti is straight or branched chain alkyl of 25 to 100 carbon atoms, or said alkyl substituted by one hydroxyl group and interrupted by one oxa moiety, or a mixture of such alkyl moieties; or
• Tj is -(R-O) n -R-OG 3 where R is ethylene, propylene, trimethylene, 1 ,2-butylene or tetramethylene, and n is 6 to 49 so that the total number of carbon atoms in Ti is at least 25, and
• T 2 is straight or branched alkyl of 23 to 100 carbon atoms
• E ⁇ and E 2 is a group -(CH 2 ) r ⁇ -CO-X-T 1 or a group - (CH 2 )p-X-CO-T 2 , or G 3 is T or T 2 .
• alkyl radicals in the various substituents may be linear or branched.
• alkyl containing 1 to 20 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t- butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethyIhexyI, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
• alkenyl radicals in the various substituents may be linear or branched.
• Examples of C 2 - C ⁇ 8 alkenyl are vinyl, allyl, 2-methylallyl, butenyl, hexenyl, undecenyl and octadecenyl.
• Cr-Cgphenylalkyl is for example benzyl, phenylpropyl, ⁇ , ⁇ -dimethylbenzyl or ⁇ -methylbenzyl.
• Cg-Cnphenylalkyl is for example ⁇ , ⁇ -dimethylbenzyl, ⁇ . ⁇ -metylethylbenzyl or ⁇ , ⁇ - diethylbenzyl.
• C 5 -C 12 cycloalkyl is typically cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl.
• Alkyl substituted by-OH is typically 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl.
• C ⁇ -C 24 alkyl substituted by C C 8 alkoxy, preferably by C r C alkoxy, in particular by methoxy or ethoxy is typically 2-m ethoxy ethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3- butoxypropyl, 3-octoxypropyl and 4-methoxybutyl.
• C ⁇ -C 8 Alkoxy and, preferably C C 4 alkoxy, are typically methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy or octoxy.
• C 2 -C 18 alkylene bridges interrupted by at least one N or O atom are, for example, -CH 2 -O-CH 2 -CH 2 , -CH 2 -O-CH 2 -CH 2 -CH 2 , -CH 2 -O-CH 2 -CH2-CH2-CH2-, -CH 2 -O-CH 2 -CH 2 -O-CH2-, -CH 2 -NH-CH 2 -CH 2 , -CH 2 -NH-CH2-CH2-CH 2) -CH 2 -NH-CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -NH-CH 2 -CH 2 -NH-CH2- or -CH 2 -NH-CH 2 -CH 2 -O-CH2-.
• Aryl is preferably phenyl or naphthyl.
• T, or T 2 is an alkyl group or a -(R-O) n -R-OG 3 group that such moieties are usually a mixture of molecular weights falling within the scope of the total number of atoms indicated.
• R is ethylene
• the group Ti is -(CH 2 CH 2 O) n -CH 2 CH 2 OG 3 where n is 12 to 49.
• R is propylene
• the group ⁇ is -(CH(CH 3 )CH 2 O) n -CH(CH 3 )CH 2 OG 3 where n is 8 to 32.
• R is trimethylene
• the group Ti is -(CH 2 CH 2 CH 2 O) n -CH 2 CH 2 CH 2 OG 3 where n is 8 to 32.
• R is tetramethylene
• the group Ti is -(CH 2 CH 2 CH 2 CH 2 O) n -CH 2 CH 2 CH 2 CH 2 OG3 where n is 6 to 24.
• R is also 1 ,2-butylene so that T ⁇ is -(CH(CH 2 CH 3 )CH 2 O) n - CH(CH 2 CH 3 )CH 2 OG 3 where n is 6 to 24.
• G 2 is hydrogen, chloro, fluoro, cyano, E 3 SO-, E 3 SO 2 -, -COOG 3 , CF 3 , -CO-G 3 , -CO-NH- G 3 or -CO-N(G 3 ) 2 ,
• G 3 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight of branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or phenyl; or G 3 is T-i or T 2 ,
• E 1 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or phenyl; or E ⁇ is the group -(CH 2 ) m -CO-X-T 1 where m is 0, 1 or 2; or E- ⁇ is the group -(CH 2 ) p -X-CO-T 2 where p is 1 , 2 or 3,
• E 2 is straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or phenyl; or E 2 is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more -OH, -OCOEn, -OE 4> -NHCOEn, -NHE 4 or - N(E ) 2) or mixtures thereof, where E 4 is straight or branched chain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interrupted by one or more -O-, -NH- or -NE 4 - groups or mixtures thereof and which can be unsubstituted or substituted by one or more -OH, -OE 4 or -NH 2 groups or mixtures thereof; or E 4 is T t
• X is -O- or -N(E 1 ⁇ )- E 16 is hydrogen
• En is a straight or branched chain C C 18 alkyl, C 5 -C ⁇ 2 cycloalkyl, C 6 -C 14 aryl or C 7 - C ⁇ 5 aralkyl; or En is T or T 2 ,
• E 3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or aryl of 6 to 10 carbon atoms,
• Ti is straight or branched chain alkyl of 25 to 70 carbon atoms, or said alkyl substituted by one hydroxyl group and interrupted by one oxa moiety, or a mixture of such alkyl moieties; or
• Ti is -(R-O)n-R-OH where R is ethylene, propylene, trimethylene or tetramethylene, and n is 6 to 49 so that the total number of carbon atoms in Ti is at least 25, and
• T 2 is straight or branched alkyl of 23 to 70 carbon atoms
• E- and E 2 is a group -(CH 2 ) m -CO-X-T 1 or a group - (CH 2 )p-X-CO-T 2 , or G 3 is T ⁇ or T 2 .
• G 2 and G 2 ' are independently hydrogen, chloro, fluoro, cyano, E 3 SO-, E 3 SO 2 -, COOG 3l CF 3 , -CO-G 3 , -CO-NH-G 3 or -CO-N(G 3 ) 2
• G 3 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight of branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or phenyl; or G 3 is Ti or T 2 ,
• E 2 and E 2 ' are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or phenyl; or E 2 and E 2 ' are independently said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more -OH, -OCOEn, -OE 4> -NHCOEn, -NHE 4 or -N(E 4 ) 2 , or mixtures thereof, where E 4 is straight or branched chain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interrupted by one or more -O-, -NH- or -NE - groups or mixtures thereof and which can be unsubstituted or substituted by one or more -OH, -OE 4 or -NH
• En is a straight or branched chain C C 18 alkyl, C 5 -C 12 cycloalkyl, C 6 -C ⁇ aryl or C 7 - C 5 aralkyl; or En is Ti or T 2 ,
• E 3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or aryl of 6 to 10 carbon atoms,
• L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene, cc ( ⁇ , ⁇ , -tetramethyl-m-xylylene or cycloalkylidene,
• Ti is straight or branched chain alkyi of 25 to 70 carbon atoms, or said alkyl substituted by one hydroxyl group and interrupted by one oxa moiety, or a mixture of such alkyl moieties; or
• Ti is -(R-O)n-R-OH where R is ethylene, propylene, trimethylene or tetramethylene, and n is 6 to 49 so that the total number of carbon atoms in Ti is at least 25, and
• T 2 is straight or branched alkyl of 23 to 70 carbon atoms; and with the proviso that at least one of E 2 and E 2 'is a group a group - (CH 2 )p-X-CO-T 2 , or at least one of G 6 and G 7 is T- ⁇ or T 2 .
• Specifically preferred compounds are:
• compositions stabilized against thermal, oxidative or light-induced degradation which comprise
• the organic material is a natural, semi- synthetic or synthetic polymer.
• polymers which can be stabilized include 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1 -ene, poly-4-methylpent-1 -ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbomene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
• HDPE high density polyethylene
• LDPE low density polyethylene
• LLDPE linear low density polyethylene
• BLDPE branched low density polyethylene
• Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
• a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table.
• These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
• These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide.
• These catalysts may be soluble or insoluble in the polymerisation medium.
• the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, lla 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).
• 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, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (iono
• Hydrocarbon resins for example C 5 -C 9
• hydrogenated modifications thereof e.g. tackifiers
• mixtures of polyalkylenes and starch
• Polystyrene poly(p-methylstyrene), poly( ⁇ -methylstyrene).
• Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/- 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 styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/
• Graft copolymers of 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; styrene and acrylon
• Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichloro- hydrin 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 acetals 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. 14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
• Polyamides and copolyamides derived from diamines and dicarboxyiic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexa- methylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m- phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytet
• Polyesters derived from dicarboxyiic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene tereph- thalate, poly-1 ,4-dimethyloIcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
• Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxyiic 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 acrylates, urethane acrylates or polyester acrylates.
• Crosslinked epoxy resins derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic diepoxides.
• 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, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.
• polyblends for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA
• 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
• synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
• synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
• synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
• synthetic esters e.g. phthalates, adipates, phosphates or trimell
• Polysiloxanes such as the soft, hydrophilic polysiloxanes described, for example, in U.S. Patent No. 4,259,467; and the hard polyorganosiloxanes described, for example, in U.S. Patent No. 4,355,147.
• Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins include the urethane acrylates, polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups and the acrylated melamines.
• the polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst.
• Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsatu rated aliphatic oligomer.
• Epoxymelamine resins such as light-stable epoxy resins crosslinked by an epoxy functional coetherified high solids melamine resin such as LSE-4103 (Monsanto).
• the compounds of the present invention are employed in from about 0.01 to about 5% by weight of the stabilized composition, although this will vary with the particular substrate and application.
• An advantageous range is from about 0.05 to about 3%, and especially 0.05 to about 2%.
• some high performance films or in UV absorbing layers of laminates such as those produced by coextrusion may contain from 5-15% by weight of the instant compounds. Concentrations of 5-10% by weight are typical in certain coextrusion applications.
• the polymer is a thermoplastic polymer.
• the instant compounds are effective stabilizers for a polymer which is a polyolefin, polycarbonate, a styrenic, ABS, a nylon (polyamide), a polyester, a polyurethane, a polyacrylate, a rubber modified styrenic, poly(vinyl chloride), poly(vinyl butyral), polyacetal (polyoxymethylene), or other blends or copolymers such as poly(ethylene/1 ,4-cyclohexylene- dimethylene terephthalate) PETG or an ethylene/acrylic acid copolymer or salts thereof (an ionomer).
• a polymer which is a polyolefin, polycarbonate, a styrenic, ABS, a nylon (polyamide), a polyester, a polyurethane, a polyacrylate, a rubber modified styrenic, poly(vinyl chloride), poly(vinyl butyral), polyacetal (polyoxymethylene
• One particularly preferred class of polymers is a polyester; such as poly(ethylene terephthalate), poly utylene terephthalate) or polyethylene naphthalenedicarboxylate), or copolymer poly(ethylene/1,4-cyclohexylenedimethylene terephthalate) PETG.
• thermoplastic polymers such as the polyolefins and polycarbonates.
• polyethylene or polypropylene are especially preferred.
• the polyolefin is low density polyethylene (LDPE).
• the stabilizers of the instant invention may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom.
• the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer.
• the resulting stabilized polymer compositions of the invention may optionally also contain from about 0.01 to about 10%, preferably from about 0.025 to about 2%, and especially from about 0.1 to about 2% by weight of various conventional additives, such as the materials listed below, or mixtures thereof.
• Alkylated monophenols for example,
• esters of ⁇ -(3.5-di-tert-butyl-4-hvdro ⁇ yphenyl)-propionic acid with monohydric or polyhydric alcohols for example,
• Diarylamines for example, diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, 4,4'-di- tert-octyl-diphenylamine, reaction product of N-phenylbenzylamine and 2,4,4- trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, reaction product of N-phenyl-1 -naphthylamine and 2,4,4-trimethylpentene.
• Esters of optionally substituted benzoic acids for example, phenyl salicylate, 4-tert- butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)- resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.
• benzoylresorcinol 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.
• Acrylates for example, ⁇ -cyano- ⁇ , ⁇ -diphenylacrylic acid ethyl ester or isooctyl ester, ⁇ - carbomethoxy-cinnamic acid methyl ester, ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, ⁇ -carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-( ⁇ - carbomethoxy- ⁇ -cyanovinyl)-2-methyl-indoline.
• Nickel compounds for example, nickel complexes of 2,2'-thio-bis-[4-(1, 1,3,3- tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, optionally with additional Hgands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexes of 1-phenyl-4- lauroyl-5-hydroxy-pyrazole, optionally with additional Hgands.
• Hgands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarba
• Sterically hindered amines for example bis-(2,2,6,6-tetramethylpiperidyl) sebacate, bis- (1 ,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acid bis-(1 ,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of 1-hydroxyethyl- 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'- (2,2,6 ) 6-tetramethylpiperidyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-s- triazine, tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4- piperidyl) 1
• Oxalic acid diamides for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert- butyl-oxanilide, 2,2'-di-dodecyIoxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis (3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and para- methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.
• Hvdroxyphenyl-s-triazines for example 2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4- octyloxyphenyl)-s-t ⁇ azine; 2,6-bis-(2,4-dimethyIphenyI)-4-(2,4-dihydroxyphenyl)-s-triazine;
• Metal deactivators for example, N,N'-diphenyloxalic acid diamide, N-salicylal-N'- salicyloylhydrazine, N,N'-bis-salicyloylhydrazine, N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenyl- propionyl)-hydrazine, 3-saIicyloylamino-1 ,2,4-triazole, bis-benzylidene-oxalic acid dihydrazide.
• Phosphites and phosphonites for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, di- isodecylpentaerythritol diphosphite, di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite, di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite, di-(2,4-di-tert-butyl-6-
• esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis-( ⁇ -dodecylmercapto)-propionate.
• esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis-( ⁇ -dodecylmercapto)-propionat
• Hvdroxylamines for example, N,N-dibenzylhydroxyIamine, N,N- iethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecyl- hydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N.N- ialkylhydroxylamine derived from hydrogenated tallow amine. 7. Nitrones.
• N-benzyl-alpha-phenyl nitrone N-ethyl-alpha-methyl nitrone, N- octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl- alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha- heptadecyl nitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrone
• 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 Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K 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 Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K
• Nucleating agents for example, 4-tert-butyl-benzoic acid, adipic acid, diphenylacetic acid.
• Fillers and reinforcing agents for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
• additives for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, anti-static agents, blowing agents and thiosynergists such as dilauryl thiodipropionate or distearyl thiodipropionate.
• Benzofuranones and indolinones for example those disclosed in US-A-4325863, US-A- 4338244 or US-A-5175312, or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2- one, 5,7-di-tert-butyi-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert- butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)- benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloy
• Amine Oxides for example amine oxide derivatives as disclosed in U.S. Patent Nos. 5,844,029 and 5,880,191 , e.g. didecyl methyl amine oxide, tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amine oxide.
• the co-stabilizers with the exception of the benzofuranones listed under 13, are added for example in concentrations of 0.01 to 10%, relative to the total weight of the material to be stabilized.
• compositions comprise, in addition to components (a) and (b) further additives, in particular phenolic antioxidants, light stabilizers or processing stabilizers.
• Particularly preferred additives are phenolic antioxidants (item 1 of the list), sterically hindered amines (item 2.6 of the list), phosphites and phosphonites (item 4 of the list), UV absorbers (item 2 of the list) and peroxide-destroying compounds (item 5 of the list).
• additives which are also particularly preferred are benzofuran-2- ones, such as described, for example, in US-A-4325 863, US-A-4,338 244 or US-A- 5175312.
• the phenolic antioxidant of particular interest is selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
• a most preferred phenolic antioxidant is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4- hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-tri- methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1 ,3,5-tris(3,5-di-tert-butyl-4- hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis(4,6-di-tert- butylphenol).
• the hindered amine compound of particular interest is selected from the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1 ,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1 ,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl- 7,7,9,9-tetramethyl-1 ,3,8-triaza-spiro[4.5]decane-2,4-dio ne, tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,
• a most preferred hindered amine compound is bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1, 2,2,6,6- pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,N',N",N"'-tetrakis[(4,6- bis(butyl-(1 ,2,2,6,6-pentamethylpiperidin-4-yl)a
• the instant composition can additionally contain another UV absorber selected from the group consisting of the benzotriazoles, the s-triazines, the oxanilides, the hydroxybenzophenones, the malonates, the salicylates, the benzoates and the ⁇ - cyanoacrylates.
• another UV absorber selected from the group consisting of the benzotriazoles, the s-triazines, the oxanilides, the hydroxybenzophenones, the malonates, the salicylates, the benzoates and the ⁇ - cyanoacrylates.
• the instant composition may additionally contain an effective stabilizing amount of at least one other 2-hydroxyphenyl-2H-benzotriazoIe; another tris-aryl-s-triazine; or hindered amine or mixtures thereof.
• the 2-hydroxyphenyl-2H-benzotriazole is selected from the group consisting of
• the other tris-aryl-s-triazine is selected from the group consisting of 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine; 2,4-bis(2,4-dimethylphenyl)- 6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)phenyl]-s-triazine; and 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-5- ⁇ - cumylphenyl]-s-triazine .
• One objective of this invention is to provide new benzotriazole UV absorbers which are non-blooming at high concentrations in polyolefins, absorb more than 90% of UV light, especially in the near visible range just below 400 nm.
• the areas where the instant benzotriazoles will find great utility include packaging films, solar control films, optical films, food wrap, medical packaging and the like. Non-blooming, non-migrating UV absorbers are particularly needed for the food packaging applications.
• Such bottles are used for various items such as foods, food oils, vitamins, milk, beverages and beer which materials may have light sensitivity where the presence of the UV absorber in the bottle itself can provide desirable protection not only to the bottle itself, but also to its contents. In such situations, the resistance of the instant compounds to blooming or to migration is highly desirable.
• the instant compounds having a long chain hydrocarbyl moiety present which exhibit excellent compatibility with hydrocarbon waxes such as those used for candles, provide excellent light stability protection to white, dipped, dyed, unscented and/or scented candles.
• a further subject of the invention is a composition which comprises
• the stabilized compositions may additionally contain an effective stabilizing amount of at least one other UV absorber selected from the group consisting the benzotriazoles, the s- triazines, the hydroxy-benzophenones, the ⁇ -cyanoacrylates, the oxanilides, the malonates, the salicylates and the benzoates.
• at least one other UV absorber selected from the group consisting the benzotriazoles, the s- triazines, the hydroxy-benzophenones, the ⁇ -cyanoacrylates, the oxanilides, the malonates, the salicylates and the benzoates.
• compositions preferably contain an additional 2-hydroxyphenyl-2H-benzotriazole which is selected from the group consisting of
• compositions may also contain an effective amount of a hindered amine.
• the instant invention also pertains to candle wax compositions which comprises
• An effective amount of benzotriazole alone or plus the hindered amine in the candle wax is 0.01 to 10% by weight, preferably 0.1 to 2 % by weight; and most preferably 0.1 to 0.5% by weight based on the wax.
• the weight ratio of benzotriazole to hindered amine is 10:1 to 1:10; preferably 4:1 to 1 :4; most preferably 2:1 to 1 :2 based on the candle wax.
• benzotriazole of formula I, II or III is
• a hindered amine When a hindered amine is added it is preferably selected from the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1 ,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)- butylmalonate, the polycondensation product of 1 -(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy- piperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexa- methylenebis(amino-2,2,6,6-tetramethylpiperidine),
• the composition may additionally comprise a phenolic antioxidant, phosphite, long chain N,N-dialkylhydroxylamine, nitrone or amine oxide.
• the phenolic antioxidant is selected from the group consisting of n-octadecyI 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),
• candles contain a host of various components.
• the base materials may be made up of the following:
• paraffin wax paraffin wax, natural oils, polyamide plus fatty acid/ester, fatty acids such as stearin, opacifiers, beeswax, glycerides plus oxidized wax, alcohols, and ethylene oligomers.
• Candles also contain a number of additives such as the following:
• mold release agents fragrances, insect repellants or insecticides, hardeners, crystal modifiers, clarifiers, guttering reducers, colorants, f.p. control agents, stretchability improvers, gelling agents, extrusion aids, and vortex reducers.
• Each of the various components are meant to control or modify the properties of the candle to insure proper burning, reduce channelling, aid in uniform melting, and the like.
• the colorants and fragrances obviously are there to provide the proper color, scent or other aesthetic appeal.
• these gel candles usually contain a copolymer selected from the group consisting of a triblock, radial block, diblock or multiblock copolymer classically made up of at least two thermodynamically incompatible segments containing both hard and soft segments.
• Typical of such block copolymers is KRATON® (Shell Chemical Co.) which consists of block segments of styrene monomer units and rubber monomer or comonomer units.
• KRATON® D series is a linear ABA block with styrene-butadiene-styrene (SBS) or styrene-isoprene-styrene (SIS).
• Candles may also contain other stabilizers such as phenolic antioxidants, phosphites, long chain N,N-dialkylhydroxylamines, nitrones, amine oxides and the like, particularly phenolic antioxidants such as are described above.
• stabilizers such as phenolic antioxidants, phosphites, long chain N,N-dialkylhydroxylamines, nitrones, amine oxides and the like, particularly phenolic antioxidants such as are described above.
• Yet another subject of the invention is an article of manufacture, which is a flexible or rigid mono- or multi-layered construction suitable for packaging films, food wrap, medical packaging or beverage container, which is prepared from a composition comprising a compound of formula I, II or III and a polymer which is selected from the group consisting of a polyolefin, polycarbonate, a styrenic, ABS, a nylon (polyamide), a polyester, a poly- urethane, a polyacrylate, a rubber modified styrenic, poly(vinyl chloride), poly(vinyl butyral), polyacetal (polyoxymethylene), or other blends or copolymers such as poly(ethylene/1 ,4- cyclohexylenedimethylene terephthalate) PETG or an ethylene/acrylic acid copolymer or salts thereof (an ionomer).
• a polyolefin polycarbonate
• a styrenic ABS
• a further subject of the invention is the use of a compound of formula I, II, or III for the stabilization of an organic material subject to thermal, oxidative or light-induced degradation.
• Example 6 is a comparative example
• Example 7 denotes the preparation of a low density polyethylene (LDPE) film in which are incorporated commercial and experimental UV absorbers.
• Examples 8-19 provides the results of UV absorber migration from the films prepared in Example 7. Migration is a measure of whether the UV absorber will bloom from the polyolefin composition.
• LDPE low density polyethylene
• Polyethylene monoalcohol(s), both average molecular weights of 460 and of 700, are obtained from the Aldrich Chemical Company.
• Polyethylene powder (640 I) is obtained from the Dow Chemical Company. All other reagents and solvents are obtained from commercial sources.
• the commercial UV absorbers used for comparisons are all provided by the Ciba Specialty Chemicals Company as:
• TINUVIN® 326 5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole; designated in the Examples as Example A;
• TINUVIN® 327 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphe ⁇ yl)-2H-benzotriazole; designated in the Examples as Example B;
• TINUVIN® 360 2,2'-methylene-bis[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]; designated in the Examples as Example C;
• TINUVIN® 1577 - 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyI)-s-triazine designated in the Examples as Example D;
• Fully refined wax with a melting point of 137-141 °C and ⁇ 0.5% oil content is obtained from the Astor Wax Company.
• Dyes are supplied by French Color and Chemical Corporation. Additional wax samples are supplied by the Candle Corporation of America. These samples contained red, green or yellow dyes and fragrances. Still other wax samples are supplied by the Candle-Lite Corporation which contain gray, green or blue dyes and fragrances.
• UV absorbers and hindered amine stabilizers are obtained from the Ciba Speciality Chemicals Corporation.
• the wax plaques described above are cut into eight equal pieces (3.5" x 2.125"; 8.89 cm x 5.40 cm).
• Triplicate samples of each are exposed under a bank of six (6) cool-white fluorescent lamps (40 watts) or under a bank of six (6) UV lamps having a wavelength of 368 nm with the test samples being twelve (12) inches (30.48 cm) below the lamps.
• Dye color fade (or color change) is measured by a Macbeth ColorEye Spectrophotometer with a 6 inch integrating sphere. The conditions are: 10 degree observer; D65 illu inant and 8 degree viewing angle.
• the carbon is removed by filtration and the toluene solution is passed through a bed of silica gel.
• the toluene is removed by distillation to yield 135 g of a light yellow oil which solidified on cooling.
• the desired product is obtained in two forms, one melting at 35-51 °C and the second melting at 58-63°C.
• the polyethylene monoalcohol with an average molecular weight of 460 has a nominal formula which may be written as CH 3 (CH 2 CH 2 ) n CH 2 OH where n is 9 to 19.
• the alkyl group in the title compound is a mixture of alkyl moieties ranging from eicosyl (C 2 o) to tetracontanyl (C 0 ) groups.
• the title compound is a mixture of alkyl moieties as described in Example 1.
• the title compound is a mixture of alkyl moieties as described in Example 1.
• the polyethylene monoalcohol with an average molecular weight of 700 has a nominal formula which may be written as CH 3 (CH 2 CH 2 ) n CH 2 OH where n is 19 to 29.
• the alkyl group in the title compound is a mixture of alkyl moieties ranging from tetracontanyl (C 0 ) to hexacontanyl (C 60 ) groups. Analysis of the product;
• Ground low density polyethylene powder (Dow 640 I) is tumble blended with the desired quantity of test UV absorber and 0.30% by weight of Superfloss antiblock agent.
• the blended resin is twin-screw compounded at 450°F (232°C).
• the resulting pellets are blown at 400°F (204°C) into a monolayer film of approximately 3 mil thickness.
• Blown films are used to study the migration of the test UV absorber from the interior of the film to the film surface. Additives that migrate tend to produce a white deposit on the film surface which can be easily scraped off. This is the phenomenon called blooming. It is clear that, if the additive blooms on to the surface of the film and is easily removed therefrom, it cannot serve to protect the film itself which is its purpose.
• Visual assessment of the film surface is performed at approximately 30 day intervals up to 375 days.
• the films are stored at room temperature.
• Example 8 The test UV absorbers are present at a 0.2 % by weight concentration in the 3 mil LDPE films prepared in Example 7 and held at room temperature for 122 days. The films are observed after 0, 10, 30, 60 and 122 days.
• UV absorber of 0 10 30 60 122
• test UV absorbers are present at a 0.2 % by weight concentration in the 3 mil LDPE films prepared in Example 7 and held at room temperature for 375 days. The films are observed after 152, 182, 211, 255 and 375 days.
• test UV absorbers are present at a 0.4 % by weight concentration in the 3 mil LDPE films prepared in Example 7 and held at room temperature for 122 days. The films are observed after 0, 10, 30, 60 and 122 days. blooming after days*
• UV absorber of 0 10 30 60 122
• test UV absorbers are present at a 0.4 % by weight concentration in the 3 mil LDPE films prepared in Example 7 and held at room temperature for 375 days. The films are observed after 152, 182, 211, 255 and 375 days.
• test UV absorbers are present at a 0.8 % by weight concentration in the 3 mil LDPE films prepared in Example 7 and held at room temperature for 122 days. The films are observed after 0, 10. 30. 60 and 122 days. blooming after days*
• UV absorber of 0 10 30 60 122
• test UV absorbers are present at a 0.8 % by weight concentration in the 3 mil LDPE films prepared in Example 7 and held at room temperature for 375 days. The films are observed after 152, 182, 211 , 255 and 375 days.
• test UV absorbers are present at a 1.2 % by weight concentration in the 3 mil LDPE films prepared in Example 7 and held at room temperature for 122 days. The films are observed after 0, 10, 30, 60 and 122 days.
• UV absorber of 0 10 30 60 122
• test UV absorbers are present at a 1.2 % by weight concentration in the 3 mil LDPE films prepared in Example 7 and held at room temperature for 375 days. The films are observed after 152, 182, 211, 255 and 375 days.
• Example 5 no no no no no no * "yes” means a white deposit is clearly observed on the film surface indicating that migration or blooming has occurred.
• test UV absorbers are present at a 1.6 % by weight concentration in the 3 mil LDPE films prepared in Example 7 and held at room temperature for 122 days. The films are observed after 0, 10, 30, 60 and 122 days.
• UV absorber of 0 10 30 60 122
• test UV absorbers are present at a 1.6 % by weight concentration in the 3 mil LDPE films prepared in Example 7 and held at room temperature for 375 days. The films are observed after 152, 182, 211 , 255 and 375 days. blooming after days*
• test UV absorbers are present at a 2.0 % by weight concentration in the 3 mil LDPE films prepared in Example 7 and held at room temperature for 122 days. The films are observed after 0, 10, 30, 60 and 122 days. blooming after days *
• UV absorber of 0 10 30 60 122
• test UV absorbers are present at a 2.0 % by weight concentration in the 3 mil LDPE films prepared in Example 7 and held at room temperature for 375 days. The films are observed after 152, 182, 211 , 255 and 375 days.
• AI is allyl; tBu is tert-butyl; Cu is ⁇ -cumyl; Do is dodecyl; Me is methyl; tOc is tert-octyl; and Ph is phenyl.
• Examples 36-50 Following the general procedure of Example 35, the following compounds, of instant formula I are prepared where E 2 is the group -CH 2 CH 2 CH 2 -X-CO-T 1 ; Gi is H except for Example 39 where it is Cl; G 3 is absent except for Examples 46 where it is methyl and Example 47 where it is octadecyl; Example * J ⁇ L_ JJ ⁇ X 3— Ti 36 H H C 19 -C 39 alkyl
• T 2 is a straight chain alkyl of 30 to 50 carbon atoms.
• This allyl intermediate is prepared as follows:
• the O-allyl compound (14.2 g) as prepared above is charged to a reactor and heated to 190-195°C and held at that temperature for five hours. Flash column chromatography with silica gel and ethyl acetate/heptane solvent as eluent to give the title compound in 12.2 g yield as a yellow oil.
• nBu is n-butyl; tBu is tert-butyl; Cu is ⁇ -cumyl; Do is dodecyl; Me is methyl; Ocd is octadecyl; tOc is tert-octyl; and Ph is phenyl.
• * * is C 3 o-C 50 alkyl. '* is C 20 -C 40 alkyl.
• Examples 83-100 Using the synthetic procedure similar to that of Example 82, the instant compounds of formula III where in Examples 83-84 and 95, G 3 is C 3 o-C 5 oalkyl; and where in Examples 88- 90, E 3 is respectively phenyl, butyl and dodecyl.
• the stabilizers include a compound of Example 2 alone or with a hindered amine bis(1 ,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA or bis(1 -octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN® 123, CIBA.
• the ⁇ E values represent the change in color after exposure. A low ⁇ E value indicates less change in color and is highly desired.
• Example 105 The instant compound alone or with the hindered amine provides excellent protection to the white unscented candle wax from discoloration.
• the stabilizers include a compound of Example 1 alone or with a hindered amine bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA or bis(1 -octyloxy- 2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN® 123, CIBA.
• the ⁇ E values represent the change in color after exposure. A low ⁇ E value indicates less change in color and is highly desired.
• the instant compound alone or with the hindered amine provides excellent protection to the green scented candle wax from dye fade.
• the stabilizers include a compound of Example 3 alone or with a hindered amine bis(1 ,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA or bis(1 -octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN® 123, CIBA.
• the ⁇ E values represent the change in color after exposure. A low ⁇ E value indicates less change in color and is highly desired.
• B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole
• C is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB® 81 , CIBA.
• D is bis(1 ,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA.
• E is C 20 -C 40 alkyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyI-4-hydroxyhydro- cinnamate, compound of Example 3.
• ⁇ E values represent the change in color after the indicated days of exposure. A low ⁇ E value indicates less change in color and is highly desired.
• *A is octyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN® 384, CIBA.
• B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole
• C is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB® 81 , CIBA.
• D is bis(1 ,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA.
• E is C 20 -C 40 alkyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydro- cinnamate, compound of Example 3.
• F is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN® 123, CIBA).
• G is C 20 -C 40 alkyl 3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, compound of Example 1.
• ⁇ E values represent the change in color after the indicated days of exposure. A low ⁇ E value indicates less change in color and is highly desired.
• *A is octyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN® 384, CIBA.
• B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole
• C is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB® 81, CIBA.
• D is bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA.
• E is C 20 -C 40 alkyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydro- cinnamate, compound of Example 3.
• F is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN® 123, CIBA).
• ⁇ E values represent the change in color after the indicated days of exposure. A low ⁇ E value indicates less change in color and is highly desired.
• *A is octyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN® 384, CIBA.
• B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole
• C is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB® 81, CIBA.
• D is bis(1 ,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA.
• E is C 20 -C 40 alkyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydro- cinnamate, compound of Example 3.
• F is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN® 123, CIBA).
• G is C 20 -C 40 alkyl 3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, compound of Example 1.
• H is C 20 -C 40 alkyl 3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyI-4-hydroxyhydrocinnamate, compound of Example 2.
• I is 1 -(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-octadecanoyloxypiperidine.
• ⁇ E values represent the change in color after the indicated days of exposure. A low ⁇ E value indicates less change in color and is highly desired. ⁇ E after
• *A is octyl 3-(benzotriazoI-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN® 384, CIBA.
• C is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB® 81 , CIBA.
• D is bis(1 ,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA.
• F is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN® 123, CIBA).
• G is C 20 -C 40 alkyl 3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, compound of Example 1.
• H is C 20 -C 40 alkyl 3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, compound of Example 2.
• J is 2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1 -cyclohexyloxy-2,2,6,6-tetramethylpiperidin- 4-yl)amino-s-triazine.
• ⁇ E values represent the change in color after the indicated days of exposure. A low ⁇ E value indicates less change in color and is highly desired.
• *A is octyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN® 384, CIBA.
• B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole
• C is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB® 81 , CIBA.
• D is bis(1 ,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA.
• F is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN® 123, CIBA).
• G is C 2 o-C 40 alkyl 3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, compound of Example 1.
• H is C 20 -C 40 alkyl 3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, compound of Example 2.
• J is 2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1 -cyclohexyloxy-2,2,6,6-tetramethylpiperidin-

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