CA1219584A - N-substitute (4-hydroxyphenylthiomethyl) amine or ureide stabilizers - Google Patents
N-substitute (4-hydroxyphenylthiomethyl) amine or ureide stabilizersInfo
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- CA1219584A CA1219584A CA000446968A CA446968A CA1219584A CA 1219584 A CA1219584 A CA 1219584A CA 000446968 A CA000446968 A CA 000446968A CA 446968 A CA446968 A CA 446968A CA 1219584 A CA1219584 A CA 1219584A
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- 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
- C07C323/23—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 nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/39—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 nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
- C07C323/43—Y being a hetero atom
- C07C323/44—X or Y being nitrogen atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
- C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/28—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen, oxygen and sulfur
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/20—Thiols; Sulfides; Polysulfides
- C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
- C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/089—Overbased salts
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Abstract
Case 3-14317/CGC 1032/+
N-SUBSTITUTED (4-HYDROXYPHENYLTHIOMETHYL) AMINE OR UREIDE STABILIZERS
Abstract of the Disclosure N-substituted amines or ureides having a 4-hydroxyphenylthiomethyl group of the formula I or II
(I)
N-SUBSTITUTED (4-HYDROXYPHENYLTHIOMETHYL) AMINE OR UREIDE STABILIZERS
Abstract of the Disclosure N-substituted amines or ureides having a 4-hydroxyphenylthiomethyl group of the formula I or II
(I)
Description
958~L
Case 3-14317/CGC 1032/+
_ . _ N-SUBSTITUTED (4-HYDROXYPHENYLTHIOMETHYL) AMINE OR UREIDE STABILIZERS
Background of the Invention Organic polymeric materials such as plastics and resins, are subject to thermal, oxidative and photo-degradation. A
great variety of stabilizers are known in the art for stabi-lizing a diversity of substrates. Their effectiveness varies depending upon the causes of degradation and the substrate stabilized. In general, it is difficult to predict which stabilizer will be most effective and mos-t economical for any one area of application. For example, stabilizer effective-ness in reducing volatility may depend upon preventing bond scission in the su~strate molecule. Limiting embrittlement and retaining elasticity in a polymer or rubber may require prevention of excessive crosslinking and/or chain scission.
Prevention of discoloration may require inhibiting reactions which yield new chromophores or color bodies in the sub-strate or stabilizer. Problems of process stability and in-compatibility must also be considered.
It has now been determined that the (hydroxyphenylthio) amine and ureide derivatives of this invention possess an unusual combination of desirable properties which makes them particularly effective and useful as stabilizers. The compounds are particularly effective in protecting high im-pact polystyrene and ABS resins, rubbers such as polybuta-diene and styrene -butadiene rubber, and other elastomers wherein retention of elasticity and inhibition of cross~
linking, crazing, discoloration, odor formation and exuda-~J~
58~
tion are basic requirements.
Objects of the Invention It is the primary object of this invention to provide aclass of mercaptophenol derivatives which exhibit a broad range of improved stabilization performance characteristics.
Various other objects and advantages of this invention will become evident from the following description thereof.
Detailed Disclosure The N-substituted compounds of this invention which each have at least one 4-hydroxyphenylthiomethyl moiety are of formula I or II
¦ HO ~ SC~2 t N / (I~
~Z~
r~O ~ SC~2 ~ ~ ~ CH25 R2 R3 ~3 R2 _ _ P _ _ q wherein Rl and R2 are independently alkyl o~ 1 to 18 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, phenyl, phenyl substituted by alXyl of 1 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms or aralkyl substituted by alkyl of 1 to 12 carbon atoms; R2 may also represent hydrogen:
R3 is hydrogen or methyl;
G and E are independently phenyl or phenyl substituted by alkyl of 1 to lZ carbon atoms or by phenyl;
~' .
G may also be ~ydrogen or alkyl of 1 to 18 carbon atoms;
n i5 1 or 2, ~ is -N~-phenylene-~H-, ~ -phenylene-N~ , ~ phenylene-Q-phenylene-NH-, ,N-phenylene-Q-Phenylene-N~ where 2 '5 alkylene of 1 to 6 carbon atoms, alkylidene of 2 ~o 6 carbon atoms~ -S02-, -SO-, -S-, -S-S-, -O- or -CO-, or .
~;~19S89~
T is -N~CONH- or \
\L /
where L is a straight or branched chain alkylene of 2 to 3 carbon atoms, and p and q are independently 1 or 2 with the sum of p plus q equally the valence of T.
When Rl and R2 are alkyl, they may be for example methyl, ethyl, isopropyl, n-butyl, tert-butyl, tert-amyl,
Case 3-14317/CGC 1032/+
_ . _ N-SUBSTITUTED (4-HYDROXYPHENYLTHIOMETHYL) AMINE OR UREIDE STABILIZERS
Background of the Invention Organic polymeric materials such as plastics and resins, are subject to thermal, oxidative and photo-degradation. A
great variety of stabilizers are known in the art for stabi-lizing a diversity of substrates. Their effectiveness varies depending upon the causes of degradation and the substrate stabilized. In general, it is difficult to predict which stabilizer will be most effective and mos-t economical for any one area of application. For example, stabilizer effective-ness in reducing volatility may depend upon preventing bond scission in the su~strate molecule. Limiting embrittlement and retaining elasticity in a polymer or rubber may require prevention of excessive crosslinking and/or chain scission.
Prevention of discoloration may require inhibiting reactions which yield new chromophores or color bodies in the sub-strate or stabilizer. Problems of process stability and in-compatibility must also be considered.
It has now been determined that the (hydroxyphenylthio) amine and ureide derivatives of this invention possess an unusual combination of desirable properties which makes them particularly effective and useful as stabilizers. The compounds are particularly effective in protecting high im-pact polystyrene and ABS resins, rubbers such as polybuta-diene and styrene -butadiene rubber, and other elastomers wherein retention of elasticity and inhibition of cross~
linking, crazing, discoloration, odor formation and exuda-~J~
58~
tion are basic requirements.
Objects of the Invention It is the primary object of this invention to provide aclass of mercaptophenol derivatives which exhibit a broad range of improved stabilization performance characteristics.
Various other objects and advantages of this invention will become evident from the following description thereof.
Detailed Disclosure The N-substituted compounds of this invention which each have at least one 4-hydroxyphenylthiomethyl moiety are of formula I or II
¦ HO ~ SC~2 t N / (I~
~Z~
r~O ~ SC~2 ~ ~ ~ CH25 R2 R3 ~3 R2 _ _ P _ _ q wherein Rl and R2 are independently alkyl o~ 1 to 18 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, phenyl, phenyl substituted by alXyl of 1 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms or aralkyl substituted by alkyl of 1 to 12 carbon atoms; R2 may also represent hydrogen:
R3 is hydrogen or methyl;
G and E are independently phenyl or phenyl substituted by alkyl of 1 to lZ carbon atoms or by phenyl;
~' .
G may also be ~ydrogen or alkyl of 1 to 18 carbon atoms;
n i5 1 or 2, ~ is -N~-phenylene-~H-, ~ -phenylene-N~ , ~ phenylene-Q-phenylene-NH-, ,N-phenylene-Q-Phenylene-N~ where 2 '5 alkylene of 1 to 6 carbon atoms, alkylidene of 2 ~o 6 carbon atoms~ -S02-, -SO-, -S-, -S-S-, -O- or -CO-, or .
~;~19S89~
T is -N~CONH- or \
\L /
where L is a straight or branched chain alkylene of 2 to 3 carbon atoms, and p and q are independently 1 or 2 with the sum of p plus q equally the valence of T.
When Rl and R2 are alkyl, they may be for example methyl, ethyl, isopropyl, n-butyl, tert-butyl, tert-amyl,
2-ethylhexyl, isooctyl, n-octyl, tert-octyl, n-dodecyl or n-octadecyl. Preferably Rl ~nd R2 are branched alkyl of 4 to 8 carbon atoms such as tert-butyl, tert-amyl or tert-octyl.
Most preferably Rl and R2 are tert-butyl.
R3 is hydrogen or methyl, preferably hydrogen.
G and E are independently phenvl or phenyl substituted by phenyl or by alkyl of 1 to 8 carbon atoms such as methyl~
n-butyl or octyl, preferably methyl.
9~84 G may also be hydrogen or al'~yl of 1 to 18 with the alkyl radicals being for example methyl, ethyl, n~butyl, octyl, dodecyl or octadecyl.
Preferably E is phenyl when n is 1 or 2. When n is 1, preferably G is also phenyl.
.
The phenylene in the definitions of T is 1,2-phenylene, 1,3-phenylene or 1,4-phenylene, and is preferably 1,4-phenylene.
Q as alkylene may be methylene, ethylene, trimethylene, hexamethylene, preferably methylene.
Q as alkylidene is for example ethylidene, 2,2~propylidene, or l,l-butylidene.
~ is ethylene~ propylene or trimethylene, preferably ethylene.
p and q are preferably each 1 or 2, most preferably 2.
The amines of this invention may be prepared by the reaction of an aromatic amine, a mercaptophenol and a source oF
formaldehyde, optionally in the presence of an organic solvent g~84 such as methanol at ambient temperatures. The aromatic amine may be a monoamine such as aniline, diphenylamine, or a poly-amine such as p-phenylenediamine or 4,4'-methylenedianiline.
The stoichiometry employed depends on the product desired.
The source of formaldehyde i5 most conveniently formalin, a 37~ aqueous solution of formaldehyde.
Paraformaldehyde and trioxane may also be used.
- When the ureides of the instant invention are prepared, it is preferred to prepare first the appropriate N-substituted hydroxy~ethyl derivative of the ureide using for exzmple urea and formaldehyde ~ollowed by reaction of the mercaptophenol with the hydroxymethylureide in a lower alkanol, such as methanol, in the presence of an excess of anhydrous hydrogen chloride.
The starting materials needed to prepare these imides are items of commerce or can be prepared by ~nown methods. The preparation of ~ercaptophenols is described by E. B Hotelling, et al., J. ~rg. Chem 24, 1598 ~1~59).
51!3~
~he intermediate mer~aptophenols correspond to the formula Rl HO~SH
wherein R1, R2 and R3 are as previously defined. Preferred ~-mercaptophenols include 2,6-di-tert.butyl- and 2-tert.-butyl-6-methyl-4-mercaptophenol as well as 2,6-dimethyl-4-mercapto-phenol and 2-tert-butyl-5-methyl-4-mercapto-phenol.
Compounds of this invention are effective in stabilizing organic materials such as plastics, polymers and resins.
The compounds of the invention are par~icularly useful as stabilizers, especially for the protection of polyolefins, homopolymers or copolymers, for instance, polyethylene, poly-propylene, polyisobutylene, poly(butene-l), poly(pentene-l), poly(3-methylbutene-1), poly(4-methyl-pentene-1), various ethylene-propylene copolymers EPM, EPDM, and the like; poly-styrene and copolymers or terpolymers of styrene, including impact polystyrene, ABS resin~ SBR, polyisoprene, as well as natural rubber, polyesters including polyethylene tereph.halate and polybutylene terephthalate, including copolymers.
' ~lZ19SI~
Polyurethanes,polycarbonates, polyamides such as nylon 6, 6/6 and the like as well as copolyamides and poly-sulfones are also stabilized.
Compounds of this invention are also particularly use-ful as stabilizers for mineral and synthetic lubricating oils.
In general, polymers which can be stabilized include:
1. Polymers of monoolefins and diolefins, for example polyethylene (which optionally can be crosslinked), poly-propylene, polyisobutylene,polybutene-~, polymethylpentene-l, polyisoprene or polybutadiene, as well as polymers of cyclo-olefins, for instance of cyclopentene or norbornene.
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyethylene or with polyisobutylene.
Most preferably Rl and R2 are tert-butyl.
R3 is hydrogen or methyl, preferably hydrogen.
G and E are independently phenvl or phenyl substituted by phenyl or by alkyl of 1 to 8 carbon atoms such as methyl~
n-butyl or octyl, preferably methyl.
9~84 G may also be hydrogen or al'~yl of 1 to 18 with the alkyl radicals being for example methyl, ethyl, n~butyl, octyl, dodecyl or octadecyl.
Preferably E is phenyl when n is 1 or 2. When n is 1, preferably G is also phenyl.
.
The phenylene in the definitions of T is 1,2-phenylene, 1,3-phenylene or 1,4-phenylene, and is preferably 1,4-phenylene.
Q as alkylene may be methylene, ethylene, trimethylene, hexamethylene, preferably methylene.
Q as alkylidene is for example ethylidene, 2,2~propylidene, or l,l-butylidene.
~ is ethylene~ propylene or trimethylene, preferably ethylene.
p and q are preferably each 1 or 2, most preferably 2.
The amines of this invention may be prepared by the reaction of an aromatic amine, a mercaptophenol and a source oF
formaldehyde, optionally in the presence of an organic solvent g~84 such as methanol at ambient temperatures. The aromatic amine may be a monoamine such as aniline, diphenylamine, or a poly-amine such as p-phenylenediamine or 4,4'-methylenedianiline.
The stoichiometry employed depends on the product desired.
The source of formaldehyde i5 most conveniently formalin, a 37~ aqueous solution of formaldehyde.
Paraformaldehyde and trioxane may also be used.
- When the ureides of the instant invention are prepared, it is preferred to prepare first the appropriate N-substituted hydroxy~ethyl derivative of the ureide using for exzmple urea and formaldehyde ~ollowed by reaction of the mercaptophenol with the hydroxymethylureide in a lower alkanol, such as methanol, in the presence of an excess of anhydrous hydrogen chloride.
The starting materials needed to prepare these imides are items of commerce or can be prepared by ~nown methods. The preparation of ~ercaptophenols is described by E. B Hotelling, et al., J. ~rg. Chem 24, 1598 ~1~59).
51!3~
~he intermediate mer~aptophenols correspond to the formula Rl HO~SH
wherein R1, R2 and R3 are as previously defined. Preferred ~-mercaptophenols include 2,6-di-tert.butyl- and 2-tert.-butyl-6-methyl-4-mercaptophenol as well as 2,6-dimethyl-4-mercapto-phenol and 2-tert-butyl-5-methyl-4-mercapto-phenol.
Compounds of this invention are effective in stabilizing organic materials such as plastics, polymers and resins.
The compounds of the invention are par~icularly useful as stabilizers, especially for the protection of polyolefins, homopolymers or copolymers, for instance, polyethylene, poly-propylene, polyisobutylene, poly(butene-l), poly(pentene-l), poly(3-methylbutene-1), poly(4-methyl-pentene-1), various ethylene-propylene copolymers EPM, EPDM, and the like; poly-styrene and copolymers or terpolymers of styrene, including impact polystyrene, ABS resin~ SBR, polyisoprene, as well as natural rubber, polyesters including polyethylene tereph.halate and polybutylene terephthalate, including copolymers.
' ~lZ19SI~
Polyurethanes,polycarbonates, polyamides such as nylon 6, 6/6 and the like as well as copolyamides and poly-sulfones are also stabilized.
Compounds of this invention are also particularly use-ful as stabilizers for mineral and synthetic lubricating oils.
In general, polymers which can be stabilized include:
1. Polymers of monoolefins and diolefins, for example polyethylene (which optionally can be crosslinked), poly-propylene, polyisobutylene,polybutene-~, polymethylpentene-l, polyisoprene or polybutadiene, as well as polymers of cyclo-olefins, for instance of cyclopentene or norbornene.
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyethylene or with polyisobutylene.
3. Copolymer of monoolefins and diolefins with each other or with other vinyl monomers, such as, for example, ethylene/
propylene, propylene/butene-l, propylene/isobutylene, ethy-lene/butene-l, propylene/butadiene, isobutylene/isoprene, ethylene/ethyl acrylate, ethylene/alkyl methacrylates, ethy-lene/vinyl acetate or ethylene/acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene.
~. Polystyrene.
5. Random copolymers of styrene of ~-methylstyrene with dienes or acrylic derivatives, such as, for example, styrenef~utadiene, styrene/acrylonitrile, styrene/alkyl methacrylates, styrene/acrylonitrile/methyl acrylate;
mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacry-late, a diene polymer or an ethylene/propylene/diene ter-polymer; and bloc~ copolymers of styrene, such as, forexample, styrene/butadiene/styrene, styrene/isoprene/
styrene, styrene/ethylene/butylene/styrene or styrene/
ethylene/propylene/styrene.
6. Graft copolymers of styrene, such as, for example, styrene on polybutadiene, styrene and acrylonitrile on polybutadiene, styrene and alkyl acrylates or methacry-lates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylo-nitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 5), for instance the copolymer mixtures known as ABS-, MsS-, ASA- or AES-polymers.
7. Halogen-containing polymers, such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated poly-ethylene, polymers from halogen-containing vinyl-compounds, as for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, as for example, vinyl chloride/vinyli-dene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
.~ j ~. ,, ,,~ ~
~9S84 8. Polymers which are derived from ~ unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitrile.
9. Copolymers from the monomers mentioned under 8) with each other or with other unsaturaked monomers, such as, for instance, acrylonitrile/butadiene, acrylonitrile/
alkyl acrylate or acrylonitrile/vinyl chloride copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers 10. Polymers which are derived from unsaturated alcohols and amines, or acyl derivatives thereof or acetals there-of, such as polyvinyl alcohol, polyvinyl acetate, poly-vinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinylbutyral, polyallyl phthalate or polyallylme-lamine.
11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, poly-propylene oxide or copolymers thereof with bis-glycidyl ethers.
12. Polyacetals, such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer.
~9S~
13. Polyphenylene oxides and sul~ides.
14. Polyurethanes which are derived ~rom polyethers, polyesters or polybutadienes with terminal hydroxyl groups on the one side and aliphatic or aromatic polyisocyanates on the other side, as well as precursors thereof.
15. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarbo-xylic acids of the corresponding lactams, such as poly-amide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, poly-2,4,4-trimethylhexa-methylene terephthalamide or poly-m-phenylene iso-phthalamide, as well as copolymers thereof with poly-ethers, such as for instance, with polyethylene glycol polypropylene glycol or polytetxamethylene glycols.
;
16. Polyureas, polyimides and polyamide-imides.
17. Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as poly-ethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates as well as block copolyether-estersderived from polyethers having hydroxyl end groups.
58~
18. Polycarbonates.
19. Polysulfones and polyethersulfones.
20. Crosslinked polymers which are derived from aldehydes one the one hand and phenols, ureas and mela-mines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formal-dehyde resins.
21. Drying and non-drying alkyd resins.
22. Unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated di-carboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof o low flammability.
23. Thermosetting acrylic resins, derived from substi-tuted acrylic esters, such as epoxy-acrylates, urethane-acrylates or polyester-acrylates.
24. Alkyd resins, polyester resins or acrylate resins in admixture with melamine resins, urea resins, poly-isocyanates or epoxide resins as crosslinking agents.
25. Crosslinked epoxide resins which are derived from polyepoxides, for example from b.is-glycidyl ethers or from cycloaliphatic diepoxides and aromatic diepoxides.
26. Natural polymers, such as cellulose, rubber, ge-latin and derivatives thereof which are chemically modi-fied in a polymer-homologous manner, such as cellu-lose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers, such as methyl-cellulose.
27. Naturally occuring and synthetic organic materials wich are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vege-table fats, oils and waxes, or oils~ fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellithates) and also mixtures of syn-thetic esters with mineral oils in any weight ratios, which materials may be used as plasticizer for polymers or as textile spinning oils, as well as aqueous emulsions of such materials.
28. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/
butadiene copolymers.
~12~951~9, In general, the stabilizers of this 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 ad-vantageous range is from about 0,05 to about 2 %, and especially 0.1 to abou-t 1 %.
The stabilizers of the instant invention may readily be incorpoxated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, 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 stabilized polymer composition of the invention may optionally also con-tain various conventional additives, such as the following:
9s~
1. Antioxidants 1.1. Simple 2.6-dialkylphenolS, such as, for example, 2,6-di-tert.-butyl-4-methylphenol, 2-tert~-butyl-4,6-dimethylphenol, 2,6-di-tert.-butyl-4-methoxymethylphenol and 2,6-di-octadecyl-4-methylphenol.
1.2. Derivatives of alkylated hydroquinones, such as, for example, 2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amyl -hydroquinone, 2,6-di-tert.-butyl- ~ydro-quinone, 2,6-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert.-butyl-4-hydroxy-anisole, tris-(3,5-di-tert.-butyl-4-hydroxyphenyl) phosphite, 3,5-di-tert.-butyl-4-hydroxyphenyl stearate and bis-(3,5-di-tert.-butyl-4-hydroxyphenyl) adipate.
1.3. Hydroxylated thiodiphenyl ethers, such as, for example, 2,2'-thio-bis-(6-tert.-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol), 4,4'-thio-bis-(3,6-di-sec.-amylphenol), 4,4'-thio-bis-(6-tert.-butyl-2-methylphenol) and 4,4'-bis-(2,6-dimethyl-4-hydroxy-phenyl) disulphide.
1.4. Alkylidene-bis~henols, such as, for example, 2,2'-methylene-bis-(6-tert.-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tert.-;butyl-4-ethylphenol ?,
propylene, propylene/butene-l, propylene/isobutylene, ethy-lene/butene-l, propylene/butadiene, isobutylene/isoprene, ethylene/ethyl acrylate, ethylene/alkyl methacrylates, ethy-lene/vinyl acetate or ethylene/acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene.
~. Polystyrene.
5. Random copolymers of styrene of ~-methylstyrene with dienes or acrylic derivatives, such as, for example, styrenef~utadiene, styrene/acrylonitrile, styrene/alkyl methacrylates, styrene/acrylonitrile/methyl acrylate;
mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacry-late, a diene polymer or an ethylene/propylene/diene ter-polymer; and bloc~ copolymers of styrene, such as, forexample, styrene/butadiene/styrene, styrene/isoprene/
styrene, styrene/ethylene/butylene/styrene or styrene/
ethylene/propylene/styrene.
6. Graft copolymers of styrene, such as, for example, styrene on polybutadiene, styrene and acrylonitrile on polybutadiene, styrene and alkyl acrylates or methacry-lates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylo-nitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 5), for instance the copolymer mixtures known as ABS-, MsS-, ASA- or AES-polymers.
7. Halogen-containing polymers, such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated poly-ethylene, polymers from halogen-containing vinyl-compounds, as for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, as for example, vinyl chloride/vinyli-dene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
.~ j ~. ,, ,,~ ~
~9S84 8. Polymers which are derived from ~ unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitrile.
9. Copolymers from the monomers mentioned under 8) with each other or with other unsaturaked monomers, such as, for instance, acrylonitrile/butadiene, acrylonitrile/
alkyl acrylate or acrylonitrile/vinyl chloride copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers 10. Polymers which are derived from unsaturated alcohols and amines, or acyl derivatives thereof or acetals there-of, such as polyvinyl alcohol, polyvinyl acetate, poly-vinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinylbutyral, polyallyl phthalate or polyallylme-lamine.
11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, poly-propylene oxide or copolymers thereof with bis-glycidyl ethers.
12. Polyacetals, such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer.
~9S~
13. Polyphenylene oxides and sul~ides.
14. Polyurethanes which are derived ~rom polyethers, polyesters or polybutadienes with terminal hydroxyl groups on the one side and aliphatic or aromatic polyisocyanates on the other side, as well as precursors thereof.
15. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarbo-xylic acids of the corresponding lactams, such as poly-amide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, poly-2,4,4-trimethylhexa-methylene terephthalamide or poly-m-phenylene iso-phthalamide, as well as copolymers thereof with poly-ethers, such as for instance, with polyethylene glycol polypropylene glycol or polytetxamethylene glycols.
;
16. Polyureas, polyimides and polyamide-imides.
17. Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as poly-ethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates as well as block copolyether-estersderived from polyethers having hydroxyl end groups.
58~
18. Polycarbonates.
19. Polysulfones and polyethersulfones.
20. Crosslinked polymers which are derived from aldehydes one the one hand and phenols, ureas and mela-mines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formal-dehyde resins.
21. Drying and non-drying alkyd resins.
22. Unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated di-carboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof o low flammability.
23. Thermosetting acrylic resins, derived from substi-tuted acrylic esters, such as epoxy-acrylates, urethane-acrylates or polyester-acrylates.
24. Alkyd resins, polyester resins or acrylate resins in admixture with melamine resins, urea resins, poly-isocyanates or epoxide resins as crosslinking agents.
25. Crosslinked epoxide resins which are derived from polyepoxides, for example from b.is-glycidyl ethers or from cycloaliphatic diepoxides and aromatic diepoxides.
26. Natural polymers, such as cellulose, rubber, ge-latin and derivatives thereof which are chemically modi-fied in a polymer-homologous manner, such as cellu-lose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers, such as methyl-cellulose.
27. Naturally occuring and synthetic organic materials wich are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vege-table fats, oils and waxes, or oils~ fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellithates) and also mixtures of syn-thetic esters with mineral oils in any weight ratios, which materials may be used as plasticizer for polymers or as textile spinning oils, as well as aqueous emulsions of such materials.
28. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/
butadiene copolymers.
~12~951~9, In general, the stabilizers of this 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 ad-vantageous range is from about 0,05 to about 2 %, and especially 0.1 to abou-t 1 %.
The stabilizers of the instant invention may readily be incorpoxated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, 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 stabilized polymer composition of the invention may optionally also con-tain various conventional additives, such as the following:
9s~
1. Antioxidants 1.1. Simple 2.6-dialkylphenolS, such as, for example, 2,6-di-tert.-butyl-4-methylphenol, 2-tert~-butyl-4,6-dimethylphenol, 2,6-di-tert.-butyl-4-methoxymethylphenol and 2,6-di-octadecyl-4-methylphenol.
1.2. Derivatives of alkylated hydroquinones, such as, for example, 2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amyl -hydroquinone, 2,6-di-tert.-butyl- ~ydro-quinone, 2,6-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert.-butyl-4-hydroxy-anisole, tris-(3,5-di-tert.-butyl-4-hydroxyphenyl) phosphite, 3,5-di-tert.-butyl-4-hydroxyphenyl stearate and bis-(3,5-di-tert.-butyl-4-hydroxyphenyl) adipate.
1.3. Hydroxylated thiodiphenyl ethers, such as, for example, 2,2'-thio-bis-(6-tert.-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol), 4,4'-thio-bis-(3,6-di-sec.-amylphenol), 4,4'-thio-bis-(6-tert.-butyl-2-methylphenol) and 4,4'-bis-(2,6-dimethyl-4-hydroxy-phenyl) disulphide.
1.4. Alkylidene-bis~henols, such as, for example, 2,2'-methylene-bis-(6-tert.-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tert.-;butyl-4-ethylphenol ?,
4,4'-methylene-bis-(6-tert.-butyl-2-methylphenol !, 4,4'-methylene-bis-(2,~-di-tert.-butylphenol), 2,6-di-(3-tert,-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 2,2'-methylene-bis-[4-methyl-6-(~-methyl-cyclohexyl)-phenol], l,l-bis-(3,5-dimethyl-2-hydroxy-phenyl)-butane, l,l-bis(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-butanç, 2,2-bis-(3,5-di-tert.-butyl-4-hydroxy-- ~5 -513~
phenyl)propane, 1,1,3-tris (5-tert~-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis~ ~5-tert,-butyl-4-hydroxy--2-methylphenyl)-4-n-dodecylmercaptobutane, l,1,5,5-tetra-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-pentane and ethylene glycol bis-[3,3-bis-~3'-tert.-butyl-4'-hydroxyphenyl)-butyrate].
1.5. O-, N- and S-benzyl compounds, such as, for example, 3,3',5,5'-tetra-tert.-butyl-4,4'-dihydroxy-dibenzyl ether, octadecyl 4-hydroxy~3,5-dimethyl-benzyl-mercaptoacetate, tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-amine and bis -(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate.
l 6. Hydroxybenzylated malonates, such as, for example, dioctadecyl 2,2-bis-(3,5-di-tert.-butyl-2-hydroxy-benzyl)-malonate, dioctadecyl 2-(3-tert~-butyl-4-hydroxy-
phenyl)propane, 1,1,3-tris (5-tert~-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis~ ~5-tert,-butyl-4-hydroxy--2-methylphenyl)-4-n-dodecylmercaptobutane, l,1,5,5-tetra-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-pentane and ethylene glycol bis-[3,3-bis-~3'-tert.-butyl-4'-hydroxyphenyl)-butyrate].
1.5. O-, N- and S-benzyl compounds, such as, for example, 3,3',5,5'-tetra-tert.-butyl-4,4'-dihydroxy-dibenzyl ether, octadecyl 4-hydroxy~3,5-dimethyl-benzyl-mercaptoacetate, tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-amine and bis -(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate.
l 6. Hydroxybenzylated malonates, such as, for example, dioctadecyl 2,2-bis-(3,5-di-tert.-butyl-2-hydroxy-benzyl)-malonate, dioctadecyl 2-(3-tert~-butyl-4-hydroxy-
5-methvl-benzyl3-malonate, di-dodecylmercapto-ethyl 2,2-bis~(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate and di-[4-(1,1,3,3-tetramethylbutyl)-phenyl]
2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate.
1.7. ~ydroxybenzyl-aromatic compounds, such as, for example, l,3,5-tris-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-2,4,6-trimethyl-benzene, 1,4-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and 2,4,6-tri-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-phenol.
s~
.8. s-Triazine compounds, such as, for example, 2,4-bis-octylmercapto-6-(3,5-di-tert.-butyl-4-hydroxy-anillno)-s-triazine, 2-octylmercap*o-4,6-bis-(3,5-di-tert.-butyl-4-hydroxy-anilino)-s-triazine, 2 octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tri~(3,5-di-tert -butyl-4-hydroxyphenyl-ethyl)~s-triazine and 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)isocyanurate.
1.9. Amides of ~-(3,5-di-tert.-butyl-4-hydroxyphenyl) propionic acid, such as, for example, 1,3,5-tris-3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazine and N,N'-di(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexamethylene-diamine. N~N'-bis-~-(3,5-di-t-butyl-4-hydroxyphenyl-propionyl)-hydrazine.
l.10. Esters of ~-(3,5-di-tert.-butyl-4-hydroxyphenyl) ~ro~ionic_acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, l,9-nonanediol, ethylene glycol, 1,2-pro-panediol, diethyleneglycol, triethylPne glycol, thiodi-ethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexane-,~ ,, 95~
diol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2,2,2]octane.
1.11. Esters of ~(5-tert.-butyl~4-hydroxy-3-methylphenyl)-pr_pionic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, l,9-nonanediol, ethyleneglycol, 1,2-pro-panediol, diethylene glycol, triethylene glycol, thiodi-ethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol tri-methylolethane, trimethylolpropane, tris-hydroxyethyl iso-cyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabi-cyclo[2,2,2]octane.
1.12. Esters of 3~5--dI--tert.-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexane-diol,l~9-nonanediol~ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiglycol,neopentylglycol, penta-ery-thritol, 3-thia-undecanol, 3-thia-pentadecanol, tri-methylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, especially the tetra-bis ester of pentaerythritol.
, ~ , ~1~195~4 1.13. Benzylphosphonates, such a~, for example, di-methyl 3, 5-di-tert.-butyl-4-hydroxybenzyl-phosphonate, diethyl 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonate, dioctadecyl 3,5-di-tert.butyl-4-hydxoxybenzyl-phosphonate and dioctadecyl 5-tert.~utyl-4-hydroxy-3-methylbenzyl-phosphonate.
The following may be mentioned as examples of further additives that can be used together with the stabilizer of this invention and the antioxidant:
1. Aminoaryl derivat ves, e.g.
phenyl-l-naphthylamine, phenyl-2-naphthylamine, N,N'-di-phenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylene-diamine, N,N'-di naphthyl-p-phenylenediamine, N,N'-di-sec.-butyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, mono- and dioctyliminodibenzyl, poly-merized 2,2, ~trimethyl-1,2-dihydroquinoline.
Octylated diphenylamine, nonylated diphenyl-amine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-di-sec.octyl-p-phenylenediamine, N-phenyl-N~-sec.octyl-p-phenylenediamine~
lZ~3S84 N,N'-di-(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-di-methyl-N~N'-di-~sec.-octyl)-p-phenylenediamine~ 2,6-dimethyl-~-methoxyaniline, 4-ethoxy-N-sec.-butylaniline, diphenyl-amine-acetone condensation product, aldol-l-naphthylamine and phenothiazine.
Discoloration effects have to be taken into acccount when using the above antioxidants.
2. U~-Absorbers and light-stabilizing agents 2.1. 2-~2'-Hydroxyphenyl)-benzotriazoles, e.g. the 5'-methyl-, 3',5'-di-tert.-butyl-, 5'-tert.butyl-, 5'-(1,1,3, 3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert.-butyl-, 5-chloro-3'-tert.-butyl-5'-methyl-, 3'-sec.-butyl-5'-tert.-butyl-,3'-alpha-methylbenzyl-5'-methyl-, 3'-alpha-methyl-benzyl~5'-methyl-5-chloro-, 4'-hydroxy-, 4'-methoxy-, 4'-octoxy-, 3',5'-di-tert.-amyl-, 3'-methyl-5'-carbomethoxy-ethyl-, 3',5'-bis-(alpha,alpha-dimethylbenzyl),3',5'-bis-(alpha,alpha-dimethyl benzyl)-5-chloro-, 3',5'-di-tert.-octylphenyl, 3',5'-di-tert.-octylphenyl-5-chloro- and 5-chloro-3',5'-di-tert.-amyl-derivatives.
2 2. 2,4-bis-(2'-lIydroxyphenyl)-6-alkyl-s-triazines, e.g.
.
the 6-ethyl-, 6-heptadecyl- or 6-undecyl-derivative.
- 20 ~
i .~
2 . 3 . 2-Hydroxybenzophen ones, e.g. the 4-hydroxy-, 4-methoxy-, 4-octoxy , 4-decyloxy-, 4-dodecyloxy~, 4-ben-zyloxy-, 2',4,4'-trihydroxy- or 2'-hydroxy~4,4'-dimethoxy-derivative.
2.4. 1,3-bis-(2'-Hydroxybenzoyl)-benzenes~ e.g. 1,3-bls-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1,3-bis-(2'-hydroxy-4'-octyloxy-benzoyl)-benzene or 1,3-bis-(2'-hydroxy-4'dodecyloxy-ben~oyl)-benzene.
2.5. Esters of optionally substituted benzoic acids, e g phenylsalicyla~e, octylphenylsalicylate, dibenzoylresorcin, bis-(4-tert.-butylbenzoyl)-resorcin, benzoy~lresorcin, 3,5-di-tert.butyl-4-hydroxybenzoic acid-2,4-di-tert.-butyl-phenyl ester or -octadecyl ester or n-hexadecyl ester or -2-methyl-4, 6-di-tert.-butyl ester.
2.6. Acrylates, e.g. a-cyano-~,~-diphenylacrylic acid-ethyl ester or -isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, ~-cyano-~-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester or N-(~-carbomethoxyvinyl)-2-methyl-indoline.
2.7. Sterically hindered amines, e.g. 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyl-oxy-2,2,6,6-tetramethyl-piperidine, bis-(2,2,6,6-tetramethyl-piperidyl)-sebacate or 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4,5]-~f~ ii84 decane- 2,4-dione.
2.8. Oxalic acid diamides, e.g. 4,4'~di-octyloxy-oxanilide, 2,2'-di~dodecyloxy-5,5'~di~ter-t.-butyl-oxanilide, 2-ethoxy-2'-ethyl~oxanilide, N,N'~bis~(3-dimethyl-aminopropyl)-oxalamide, 2-ethoxy-5-tert.~butyl-2'-ethyl-5,4'-di-tert.-butyl-oxanilide, or mixtures of ortho-and para-methoxy-as well as of o- and p-e-thoxy-disubstituted oxanilides.
3. Metal deactivators, e.g.
oxanilide, isophthalic acid dihydrazide, sebacic acid-bis-phenylhydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetyl-adipic acid dihydrazide, N,N'-bis-salicyl-oyl-oxalic acid dihydrazide, N,N'-bis-salicyloyl-hydrazine, N,N'-bis(3,5-di-tert,-butyl-4-hydroxyphenyl-propionyl)-hydrazine, N-salicyloyl-N' -s~licylalhydrazine, 3-salicyloyl-amino-1,2,4-triazole or N,N'-bis -salicyloyl-thiopropionic acid dihydrazide.
4. Basic co-stabilizers, e.g.
alkali metal salts and alkaline-earth metal salts of higher fatty acids, for example Ca-stearate, Zn-stearate, Mg-behenate, Na-ricinoleate or K-palmitate.
5. Nucleation agents, e.g.
4-tert.-butylbenzoic acid, adipic acid or diphenylacetic acid.
~9~
2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate.
1.7. ~ydroxybenzyl-aromatic compounds, such as, for example, l,3,5-tris-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-2,4,6-trimethyl-benzene, 1,4-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and 2,4,6-tri-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-phenol.
s~
.8. s-Triazine compounds, such as, for example, 2,4-bis-octylmercapto-6-(3,5-di-tert.-butyl-4-hydroxy-anillno)-s-triazine, 2-octylmercap*o-4,6-bis-(3,5-di-tert.-butyl-4-hydroxy-anilino)-s-triazine, 2 octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tri~(3,5-di-tert -butyl-4-hydroxyphenyl-ethyl)~s-triazine and 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)isocyanurate.
1.9. Amides of ~-(3,5-di-tert.-butyl-4-hydroxyphenyl) propionic acid, such as, for example, 1,3,5-tris-3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazine and N,N'-di(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexamethylene-diamine. N~N'-bis-~-(3,5-di-t-butyl-4-hydroxyphenyl-propionyl)-hydrazine.
l.10. Esters of ~-(3,5-di-tert.-butyl-4-hydroxyphenyl) ~ro~ionic_acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, l,9-nonanediol, ethylene glycol, 1,2-pro-panediol, diethyleneglycol, triethylPne glycol, thiodi-ethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexane-,~ ,, 95~
diol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2,2,2]octane.
1.11. Esters of ~(5-tert.-butyl~4-hydroxy-3-methylphenyl)-pr_pionic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, l,9-nonanediol, ethyleneglycol, 1,2-pro-panediol, diethylene glycol, triethylene glycol, thiodi-ethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol tri-methylolethane, trimethylolpropane, tris-hydroxyethyl iso-cyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabi-cyclo[2,2,2]octane.
1.12. Esters of 3~5--dI--tert.-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexane-diol,l~9-nonanediol~ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiglycol,neopentylglycol, penta-ery-thritol, 3-thia-undecanol, 3-thia-pentadecanol, tri-methylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, especially the tetra-bis ester of pentaerythritol.
, ~ , ~1~195~4 1.13. Benzylphosphonates, such a~, for example, di-methyl 3, 5-di-tert.-butyl-4-hydroxybenzyl-phosphonate, diethyl 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonate, dioctadecyl 3,5-di-tert.butyl-4-hydxoxybenzyl-phosphonate and dioctadecyl 5-tert.~utyl-4-hydroxy-3-methylbenzyl-phosphonate.
The following may be mentioned as examples of further additives that can be used together with the stabilizer of this invention and the antioxidant:
1. Aminoaryl derivat ves, e.g.
phenyl-l-naphthylamine, phenyl-2-naphthylamine, N,N'-di-phenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylene-diamine, N,N'-di naphthyl-p-phenylenediamine, N,N'-di-sec.-butyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, mono- and dioctyliminodibenzyl, poly-merized 2,2, ~trimethyl-1,2-dihydroquinoline.
Octylated diphenylamine, nonylated diphenyl-amine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-di-sec.octyl-p-phenylenediamine, N-phenyl-N~-sec.octyl-p-phenylenediamine~
lZ~3S84 N,N'-di-(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-di-methyl-N~N'-di-~sec.-octyl)-p-phenylenediamine~ 2,6-dimethyl-~-methoxyaniline, 4-ethoxy-N-sec.-butylaniline, diphenyl-amine-acetone condensation product, aldol-l-naphthylamine and phenothiazine.
Discoloration effects have to be taken into acccount when using the above antioxidants.
2. U~-Absorbers and light-stabilizing agents 2.1. 2-~2'-Hydroxyphenyl)-benzotriazoles, e.g. the 5'-methyl-, 3',5'-di-tert.-butyl-, 5'-tert.butyl-, 5'-(1,1,3, 3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert.-butyl-, 5-chloro-3'-tert.-butyl-5'-methyl-, 3'-sec.-butyl-5'-tert.-butyl-,3'-alpha-methylbenzyl-5'-methyl-, 3'-alpha-methyl-benzyl~5'-methyl-5-chloro-, 4'-hydroxy-, 4'-methoxy-, 4'-octoxy-, 3',5'-di-tert.-amyl-, 3'-methyl-5'-carbomethoxy-ethyl-, 3',5'-bis-(alpha,alpha-dimethylbenzyl),3',5'-bis-(alpha,alpha-dimethyl benzyl)-5-chloro-, 3',5'-di-tert.-octylphenyl, 3',5'-di-tert.-octylphenyl-5-chloro- and 5-chloro-3',5'-di-tert.-amyl-derivatives.
2 2. 2,4-bis-(2'-lIydroxyphenyl)-6-alkyl-s-triazines, e.g.
.
the 6-ethyl-, 6-heptadecyl- or 6-undecyl-derivative.
- 20 ~
i .~
2 . 3 . 2-Hydroxybenzophen ones, e.g. the 4-hydroxy-, 4-methoxy-, 4-octoxy , 4-decyloxy-, 4-dodecyloxy~, 4-ben-zyloxy-, 2',4,4'-trihydroxy- or 2'-hydroxy~4,4'-dimethoxy-derivative.
2.4. 1,3-bis-(2'-Hydroxybenzoyl)-benzenes~ e.g. 1,3-bls-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1,3-bis-(2'-hydroxy-4'-octyloxy-benzoyl)-benzene or 1,3-bis-(2'-hydroxy-4'dodecyloxy-ben~oyl)-benzene.
2.5. Esters of optionally substituted benzoic acids, e g phenylsalicyla~e, octylphenylsalicylate, dibenzoylresorcin, bis-(4-tert.-butylbenzoyl)-resorcin, benzoy~lresorcin, 3,5-di-tert.butyl-4-hydroxybenzoic acid-2,4-di-tert.-butyl-phenyl ester or -octadecyl ester or n-hexadecyl ester or -2-methyl-4, 6-di-tert.-butyl ester.
2.6. Acrylates, e.g. a-cyano-~,~-diphenylacrylic acid-ethyl ester or -isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, ~-cyano-~-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester or N-(~-carbomethoxyvinyl)-2-methyl-indoline.
2.7. Sterically hindered amines, e.g. 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyl-oxy-2,2,6,6-tetramethyl-piperidine, bis-(2,2,6,6-tetramethyl-piperidyl)-sebacate or 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4,5]-~f~ ii84 decane- 2,4-dione.
2.8. Oxalic acid diamides, e.g. 4,4'~di-octyloxy-oxanilide, 2,2'-di~dodecyloxy-5,5'~di~ter-t.-butyl-oxanilide, 2-ethoxy-2'-ethyl~oxanilide, N,N'~bis~(3-dimethyl-aminopropyl)-oxalamide, 2-ethoxy-5-tert.~butyl-2'-ethyl-5,4'-di-tert.-butyl-oxanilide, or mixtures of ortho-and para-methoxy-as well as of o- and p-e-thoxy-disubstituted oxanilides.
3. Metal deactivators, e.g.
oxanilide, isophthalic acid dihydrazide, sebacic acid-bis-phenylhydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetyl-adipic acid dihydrazide, N,N'-bis-salicyl-oyl-oxalic acid dihydrazide, N,N'-bis-salicyloyl-hydrazine, N,N'-bis(3,5-di-tert,-butyl-4-hydroxyphenyl-propionyl)-hydrazine, N-salicyloyl-N' -s~licylalhydrazine, 3-salicyloyl-amino-1,2,4-triazole or N,N'-bis -salicyloyl-thiopropionic acid dihydrazide.
4. Basic co-stabilizers, e.g.
alkali metal salts and alkaline-earth metal salts of higher fatty acids, for example Ca-stearate, Zn-stearate, Mg-behenate, Na-ricinoleate or K-palmitate.
5. Nucleation agents, e.g.
4-tert.-butylbenzoic acid, adipic acid or diphenylacetic acid.
~9~
6. Phosphites, such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl) phosphite, trilauryl phosphite, triocta-decyl phosphite, 3,9-di-n-octadecyloxy- or 3,9-bis(2,4-tert.-butylphenyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]-undecane and tri-(4-hydroxy-3,5-di-tert.butylphenyl)phos-phite.
Other additives that can be incorporated in the stabi-lized compositions are thiosynergists such as dilauryl-thiodipropionate or distearylthiodipropionate, lubricants such as stearyl alcoholl fillers, carbon black, asbestos, kaolin, talc,glass fibres, pigments, optical brighteners, flameproofing agents and antistatic agents.
The compounds of this invention may be used alone as the sole stabiliæer having either mainly an antioxidant function or a light stabilizing function or the stabilizer may combine utility as an anti-oxidant and light stabilizer. The stabilizers may be used with phenolic antioxidants, lubricants such as calcium stearate, pigments, colorants or dyes, UV absorbers, light stabilizers such as hindered amines, metal deactivators, talc and other fillers, etc.
S8~
The following examples are presented for the purpose of illustration only and are not to be c4nstrued to limit the nature or scope of the instant invention in any manner whatsoever.
N-(3,5-Di-tert-butyl-4-hydroxyphenylthiomethyl)-N,N-diphenyl-amine .. . .. . _ _ _ In a 100 ml flask under nitrogen, a mixture of 8.46 grams of diphen~lamine, 11.92 grams of 2,6-di-tert-butyl-4-mercaptophenol, 4.06 grams of 37% aqueous formaldehyde, and 35 ml methyl alcohol is stirred overnight. The solvent is removed in vacuo and the residue recrystallized from petroleum ether to give 12.02 grams (57% yield) of white crystals, m.p. 71-75C.
Anal. Calcd. for C27~33NOs: C, 77.3; H, 7.9; N, 3.3.
Found: C, 77.4; H, 8.0; N, 3.3.
EXAM~LE 2 N-(3,5-Di~tert-butyl-4~hydroxyphenylthiomethyl)-N,N-bis(p-tert-octylphenyl)amine ~ hen using tne procedure o. Example 1, an eouivalent amount of bis(p-tert-octylphenyl)amine is substituted for diphenylamine, the akove named compound is obtained having a melting point of 105-108C.
~f~S~
EXAMPLE ~
N '-Bis[3,5-di-tert-butyl-4-hydroxy~henylthiomethyl]ur-ea In a 500 ml flas~ under nitrogen, 11.92 grams 2,6-di-tert-butyl-4-mercapLophenol and 3.00 grams of 1,3-bis(hydroxy-methyl)urea dissolved in 100 ml methyl alcohol are treated with an excess of anhydrous gaseous hydrogen chloride. The reaction mixture is stirred overnight, the solid iltered and washed with methyl alcohol, and dried to give 9.4 grams (67% yield) of white solid, m.p. 213-216C.
nal. Calcd~ for C31H48N2Q3S2 C~ 66-4; ~ 8 Foundu C, 66.6; H; 8.4; N, 5.1 ;
~ EXAMPLE 4 . ~._. _ 1,3-Bis(3,5-di-tert-butyl-4-hydroxyphenylthiomethyl)-2-imidazolidone _ _ _ . . . . . _ _ . . _ _ In a 300 ml flask under ni~rogen, a solution of 3~65 grams of 1,3-bis(hydroxymethyl)-2-imidazolidone and 11.92 grams of 2,~-di-tert-butyl-4-mercaptophenol in 100 ml methyl alcohol is treated with an excess of anhydrous hydrogen chloride. The reaction mixture is cooled, and the residue recrystallized from methyl alcohol to give 11.43 grams of white solid, m.p.
173-176C.
Anal. Calcd. for C33H50N203S2 C~ 67-5; H~ 8-6; N~ -~ound: C, 67.3; H, 8.7; N, 4.8 EXAMPLE S
N,N-Bis(3,5-di-tert-butyl-4-hydroxyphenylthiomethyl)-N-~hen ~
The procedure of Example 1 is repeated using 4.66 grams of aniline, 8.11 grams of 37~ agueous formaldehyde, and 23.84 grams of 2,6-di-tert-butyl-4-mercaptophenol.
T~e solid obtained is filtered off ~nd recrystallized from methanol to give 23.38 grams (83% yield) of white solid, m~p. 119-121C.
.~ l .
Anal. Calcd. for C36HslN02S2: C, 72.8; H, 8.7; N, 2.4.
~ound: C, 72.9; ~, 8.9; N, 2.5.
~9S~
N,N,N',N'-Tetrakis(3,5-di-tert-butyl-4-hydroxyphenylthio-methyl)- - hen lenediamine P ~ Y . , .~
The procedure of Example 1 is repeated using 2.70 grams of p-phenylenediamine, 8.12 grams of 37~ aqueous formaldehyde, and 23.84 grams of 2,6-di-tert-butyl-4-mercaptophenol. The solid obtained is filtered off and recrystallized from a heptane~toluene mixture to give 17.92 grams (65% yield) of a white solid, m.p. 150-160C.
nal. Calcd. for C66~g6N2O4S4: C, 71.4, H, 8,7; N, 2.5.
~ound: C, 71.5; H, 8.7; N, 2.7.
;
This example illustrates the stabilizing effectiveness ! of the instant stabilizer combination in impact polystyrene ( I PS ) .
A solution of eight weight percent polybutadiene rubber ~irestone - DIENE 55) dissolved in styrene monomer is prepared on a roller mill. The indicated amount of stabili~er is also ~ntroduced at this point. S00 ppm of zinc stearate is added to s~
~id in removing the sample from the bottle after the polymerization. The bottle ~s screwed into the polymerization apparatus which is equipped with a double helical ribbon stirrer. Since most commercial IPS bulk polymerizations are thermally initiated processes, no initiator ls used in this laboratory process. A nitrogen atmosphere is established and then the reactor is heated to 121C within 1/2 hour. Heating continues at 121C with efficient stirring until there is a 30 to 35% monomer conversion (ca. 2~1/2 hours). The stirring rate is controlled to yield a two to four micron rubber particle size. The bottles are removed from the polymerization apparatus, blanketed with nitgrogen, capped, and then placed in a fluidiæed bed sand bath to complete the pol~merization. The bottles are heated in the bath in the following fashion: one hour at 100C to equilibrate the temperature, one hour to reach 140~C and then an additional eight hours with the temperature increasing at the rate o 10C per hour to a maximum of 220C.
After the resin cools, the bottle is broken and the glass is removed. The average weight of the polymer block prepared is slightly over 600 grams. The block is then placed into a vacuum oven at 200C and a vacuum of 1 mm Hg applied as the polymer is heated for 45 minutes in order to remove all volatiles. The block is then removed from the oven, immediately placed in a heated (2~5C) hydraulic press and then pressed into a thick slab between two sheets of aluminum foil .
~l9~ii8~3L
~three minutes heating, five minutes in a cold press). The ~lab ~s split with a band saw and the pieces are granulated.
All batches are extruded at 205C and then pelletized.
The pellets are compression molded at 205 into 125 mil (3.175 mm) tensile bars. The bars are then aged at 150C on glass plates placed on rotating shelves in a forced air oven. Other tensile bars are aged at 80~C suspended from rotating shelves in a forced air oven. The specimen yellowness index is determined on the bars at various intervals accordinq to ASTM
D-1925-63T. Correspondingly, the bars are periodically measured for percent elongation in the Instron Tensiie Testing Apparatus (Instron Engineering Corporation, Massachusetts) at a pull rate of 5 mm/minute according to ASTM D638.
The test data are given below.
Oven A~ed Samples @ 80C
% Elongation by weight ~ours at B0C
Additive Conc. add. 0 300 600 9Q0 1200 ~one - 33 9 3 Compo~lnd of 0.1 40 24 17 12 9 Example l Yellowness Inde~
None - 7 l~ 45 59 Compound of 0.1 -3 1 ll 25 30 Example l _ ~9 _ Oven Aged Samples @ 150C
~ Elongation % by weight Hours at 150C
Additive Conc. add. O1/2 1 1 1/2 2 None ~ 337 7 3 3 Compound of 0.1% 3630 13 13 10 Example 1 Yellowness Index None - 7 18 30 38 43 Compound of 0,1 -3-3 3 4 7 Example 1 ExAMpLE 8 Unstabilized polypropylene powder (Hercules Profax 650~) is thoroughly blended with the indicated amount o additive.
~he blended materials are then milled on a two roll mill at 182C for 5 minutes, after which time the stabilized polypropylene is sheeted from the mill and allowed to cool.
The milled polypropylene is then cut into pieces and compression molded on a hydraulic press at 220C and 175 psi (1.2 x 106 Pa) into 25 mil (00635 mm) thick plaques. The sample is exposed in a fluorescent sunlight/black light (FS/BL3 chamber till failure. Failure is taken as the hours required to reach 0.5 carbonyl absorbance by infrared spectroscopy on the exposed plaques.
8~
Additive Conc. 9~FS/BL Te;t Results Additive by weight~Hours to Pailure) Non~ - 200-300 Compound of Ex. l 0.2 400 Compound of Ex. 3 0 . 2 320 Compound of Ex. 4 0.2 360 Compound of Ex. 5 0.2 460 . ., :~2~58~L
Inhibitlon of Oxidation of Petroleum Turbine Oil This test is performed according to ASTM procedure 943-81, 300 ml of Exxon rurbine Oil (LO 5084) containlng 0,25~
by weight of the compound of Example 1 and 60 ml of distilled water are charged into a large glass tube and heated by an oil bath maintained at ~5~. Oxygen is bubbled at a rate of 3 liters per hour through the delivery tube and through the oil mix~ure. Iron-copper catalyst coils are mounted in the oxygen delivery tube. Samples of oil a~e removed periodically and the acid number determined. The oil under test is considered to have failed ~hen an acid number of 2.0 has been attained. The oil stabilized by the compound of Example 1 is determined to have an oxidation lifetime of 3700 hours and exhibits only a slight amount of sludge. In the absence of the compound of example 1, the oil is determined to have an oxida ion lifetime of 140 hours.
;84 EXAMP~E 10 Inh~bition of Oxidation of Synthetlc Polyester Aircraft Turbine Oil 160 Grams of mixed polyester o~ oyal Lubricant Co;
Royal Mixed Polyol Ester Aircraft Base Oil) containing 1.0% by weight of the compound of Example 1 is charged into a tube.
Dry air is bubbled at a rate of 3 liters/hour through the oil mixture maintained at 202.2C.
The test is run till either one of two end-points is reached whichever is first. These are running for 48 hours or till an acid number of 4.0 is achieved.
The oil stabili~ed by the compound of Example 1 is heated for 48 hours after which time the acid number is still only 1.1. In the absence of the compound of Exa~ple 1, the oil develops an acid number of 4.~ in 1PSS than 24 hours.
EXAMP~E ll Stabi zation of Ethylene-Propylene Terpolymer A terpolymer oE ethylene, propylene and 1,4-hexadiene (or dicyclopentadiene) is aissolved in cyclohexane containing ~9S~
1~ by weight (based on the terpolymer) o a stabilizer compound of this invention. After thorough mixing, the solvent is removed by steam coagulation and the resulting polymer residue is dried at 40-50C in the presence of air. Measurement of polymer color, gel content and viscosity change indicates that samples of terpolymer containing a compound of this invention are much more stable than is the terpolymer in the absence of said compound.
Stabilization of Polybutadiene Rubber Polybutadiene rubber is dis~olved in cyclohexane containing 1~ by weight (based on polymer) of a compound of this invention. After thorough mixing, the solvent is removed by steam coagulation to isolate the polymer re~idue. The polymer i~ then mixed at 150C in a ~rabender Plasticorder Torque-Rheometer. The change in torque is monitored as a function of time. The polymer containing a compound of this invention shows minimum change in torque after 30 minutes whereas unstabilized polybutadiene fails in two (21 minutes in this test.
Other additives that can be incorporated in the stabi-lized compositions are thiosynergists such as dilauryl-thiodipropionate or distearylthiodipropionate, lubricants such as stearyl alcoholl fillers, carbon black, asbestos, kaolin, talc,glass fibres, pigments, optical brighteners, flameproofing agents and antistatic agents.
The compounds of this invention may be used alone as the sole stabiliæer having either mainly an antioxidant function or a light stabilizing function or the stabilizer may combine utility as an anti-oxidant and light stabilizer. The stabilizers may be used with phenolic antioxidants, lubricants such as calcium stearate, pigments, colorants or dyes, UV absorbers, light stabilizers such as hindered amines, metal deactivators, talc and other fillers, etc.
S8~
The following examples are presented for the purpose of illustration only and are not to be c4nstrued to limit the nature or scope of the instant invention in any manner whatsoever.
N-(3,5-Di-tert-butyl-4-hydroxyphenylthiomethyl)-N,N-diphenyl-amine .. . .. . _ _ _ In a 100 ml flask under nitrogen, a mixture of 8.46 grams of diphen~lamine, 11.92 grams of 2,6-di-tert-butyl-4-mercaptophenol, 4.06 grams of 37% aqueous formaldehyde, and 35 ml methyl alcohol is stirred overnight. The solvent is removed in vacuo and the residue recrystallized from petroleum ether to give 12.02 grams (57% yield) of white crystals, m.p. 71-75C.
Anal. Calcd. for C27~33NOs: C, 77.3; H, 7.9; N, 3.3.
Found: C, 77.4; H, 8.0; N, 3.3.
EXAM~LE 2 N-(3,5-Di~tert-butyl-4~hydroxyphenylthiomethyl)-N,N-bis(p-tert-octylphenyl)amine ~ hen using tne procedure o. Example 1, an eouivalent amount of bis(p-tert-octylphenyl)amine is substituted for diphenylamine, the akove named compound is obtained having a melting point of 105-108C.
~f~S~
EXAMPLE ~
N '-Bis[3,5-di-tert-butyl-4-hydroxy~henylthiomethyl]ur-ea In a 500 ml flas~ under nitrogen, 11.92 grams 2,6-di-tert-butyl-4-mercapLophenol and 3.00 grams of 1,3-bis(hydroxy-methyl)urea dissolved in 100 ml methyl alcohol are treated with an excess of anhydrous gaseous hydrogen chloride. The reaction mixture is stirred overnight, the solid iltered and washed with methyl alcohol, and dried to give 9.4 grams (67% yield) of white solid, m.p. 213-216C.
nal. Calcd~ for C31H48N2Q3S2 C~ 66-4; ~ 8 Foundu C, 66.6; H; 8.4; N, 5.1 ;
~ EXAMPLE 4 . ~._. _ 1,3-Bis(3,5-di-tert-butyl-4-hydroxyphenylthiomethyl)-2-imidazolidone _ _ _ . . . . . _ _ . . _ _ In a 300 ml flask under ni~rogen, a solution of 3~65 grams of 1,3-bis(hydroxymethyl)-2-imidazolidone and 11.92 grams of 2,~-di-tert-butyl-4-mercaptophenol in 100 ml methyl alcohol is treated with an excess of anhydrous hydrogen chloride. The reaction mixture is cooled, and the residue recrystallized from methyl alcohol to give 11.43 grams of white solid, m.p.
173-176C.
Anal. Calcd. for C33H50N203S2 C~ 67-5; H~ 8-6; N~ -~ound: C, 67.3; H, 8.7; N, 4.8 EXAMPLE S
N,N-Bis(3,5-di-tert-butyl-4-hydroxyphenylthiomethyl)-N-~hen ~
The procedure of Example 1 is repeated using 4.66 grams of aniline, 8.11 grams of 37~ agueous formaldehyde, and 23.84 grams of 2,6-di-tert-butyl-4-mercaptophenol.
T~e solid obtained is filtered off ~nd recrystallized from methanol to give 23.38 grams (83% yield) of white solid, m~p. 119-121C.
.~ l .
Anal. Calcd. for C36HslN02S2: C, 72.8; H, 8.7; N, 2.4.
~ound: C, 72.9; ~, 8.9; N, 2.5.
~9S~
N,N,N',N'-Tetrakis(3,5-di-tert-butyl-4-hydroxyphenylthio-methyl)- - hen lenediamine P ~ Y . , .~
The procedure of Example 1 is repeated using 2.70 grams of p-phenylenediamine, 8.12 grams of 37~ aqueous formaldehyde, and 23.84 grams of 2,6-di-tert-butyl-4-mercaptophenol. The solid obtained is filtered off and recrystallized from a heptane~toluene mixture to give 17.92 grams (65% yield) of a white solid, m.p. 150-160C.
nal. Calcd. for C66~g6N2O4S4: C, 71.4, H, 8,7; N, 2.5.
~ound: C, 71.5; H, 8.7; N, 2.7.
;
This example illustrates the stabilizing effectiveness ! of the instant stabilizer combination in impact polystyrene ( I PS ) .
A solution of eight weight percent polybutadiene rubber ~irestone - DIENE 55) dissolved in styrene monomer is prepared on a roller mill. The indicated amount of stabili~er is also ~ntroduced at this point. S00 ppm of zinc stearate is added to s~
~id in removing the sample from the bottle after the polymerization. The bottle ~s screwed into the polymerization apparatus which is equipped with a double helical ribbon stirrer. Since most commercial IPS bulk polymerizations are thermally initiated processes, no initiator ls used in this laboratory process. A nitrogen atmosphere is established and then the reactor is heated to 121C within 1/2 hour. Heating continues at 121C with efficient stirring until there is a 30 to 35% monomer conversion (ca. 2~1/2 hours). The stirring rate is controlled to yield a two to four micron rubber particle size. The bottles are removed from the polymerization apparatus, blanketed with nitgrogen, capped, and then placed in a fluidiæed bed sand bath to complete the pol~merization. The bottles are heated in the bath in the following fashion: one hour at 100C to equilibrate the temperature, one hour to reach 140~C and then an additional eight hours with the temperature increasing at the rate o 10C per hour to a maximum of 220C.
After the resin cools, the bottle is broken and the glass is removed. The average weight of the polymer block prepared is slightly over 600 grams. The block is then placed into a vacuum oven at 200C and a vacuum of 1 mm Hg applied as the polymer is heated for 45 minutes in order to remove all volatiles. The block is then removed from the oven, immediately placed in a heated (2~5C) hydraulic press and then pressed into a thick slab between two sheets of aluminum foil .
~l9~ii8~3L
~three minutes heating, five minutes in a cold press). The ~lab ~s split with a band saw and the pieces are granulated.
All batches are extruded at 205C and then pelletized.
The pellets are compression molded at 205 into 125 mil (3.175 mm) tensile bars. The bars are then aged at 150C on glass plates placed on rotating shelves in a forced air oven. Other tensile bars are aged at 80~C suspended from rotating shelves in a forced air oven. The specimen yellowness index is determined on the bars at various intervals accordinq to ASTM
D-1925-63T. Correspondingly, the bars are periodically measured for percent elongation in the Instron Tensiie Testing Apparatus (Instron Engineering Corporation, Massachusetts) at a pull rate of 5 mm/minute according to ASTM D638.
The test data are given below.
Oven A~ed Samples @ 80C
% Elongation by weight ~ours at B0C
Additive Conc. add. 0 300 600 9Q0 1200 ~one - 33 9 3 Compo~lnd of 0.1 40 24 17 12 9 Example l Yellowness Inde~
None - 7 l~ 45 59 Compound of 0.1 -3 1 ll 25 30 Example l _ ~9 _ Oven Aged Samples @ 150C
~ Elongation % by weight Hours at 150C
Additive Conc. add. O1/2 1 1 1/2 2 None ~ 337 7 3 3 Compound of 0.1% 3630 13 13 10 Example 1 Yellowness Index None - 7 18 30 38 43 Compound of 0,1 -3-3 3 4 7 Example 1 ExAMpLE 8 Unstabilized polypropylene powder (Hercules Profax 650~) is thoroughly blended with the indicated amount o additive.
~he blended materials are then milled on a two roll mill at 182C for 5 minutes, after which time the stabilized polypropylene is sheeted from the mill and allowed to cool.
The milled polypropylene is then cut into pieces and compression molded on a hydraulic press at 220C and 175 psi (1.2 x 106 Pa) into 25 mil (00635 mm) thick plaques. The sample is exposed in a fluorescent sunlight/black light (FS/BL3 chamber till failure. Failure is taken as the hours required to reach 0.5 carbonyl absorbance by infrared spectroscopy on the exposed plaques.
8~
Additive Conc. 9~FS/BL Te;t Results Additive by weight~Hours to Pailure) Non~ - 200-300 Compound of Ex. l 0.2 400 Compound of Ex. 3 0 . 2 320 Compound of Ex. 4 0.2 360 Compound of Ex. 5 0.2 460 . ., :~2~58~L
Inhibitlon of Oxidation of Petroleum Turbine Oil This test is performed according to ASTM procedure 943-81, 300 ml of Exxon rurbine Oil (LO 5084) containlng 0,25~
by weight of the compound of Example 1 and 60 ml of distilled water are charged into a large glass tube and heated by an oil bath maintained at ~5~. Oxygen is bubbled at a rate of 3 liters per hour through the delivery tube and through the oil mix~ure. Iron-copper catalyst coils are mounted in the oxygen delivery tube. Samples of oil a~e removed periodically and the acid number determined. The oil under test is considered to have failed ~hen an acid number of 2.0 has been attained. The oil stabilized by the compound of Example 1 is determined to have an oxidation lifetime of 3700 hours and exhibits only a slight amount of sludge. In the absence of the compound of example 1, the oil is determined to have an oxida ion lifetime of 140 hours.
;84 EXAMP~E 10 Inh~bition of Oxidation of Synthetlc Polyester Aircraft Turbine Oil 160 Grams of mixed polyester o~ oyal Lubricant Co;
Royal Mixed Polyol Ester Aircraft Base Oil) containing 1.0% by weight of the compound of Example 1 is charged into a tube.
Dry air is bubbled at a rate of 3 liters/hour through the oil mixture maintained at 202.2C.
The test is run till either one of two end-points is reached whichever is first. These are running for 48 hours or till an acid number of 4.0 is achieved.
The oil stabili~ed by the compound of Example 1 is heated for 48 hours after which time the acid number is still only 1.1. In the absence of the compound of Exa~ple 1, the oil develops an acid number of 4.~ in 1PSS than 24 hours.
EXAMP~E ll Stabi zation of Ethylene-Propylene Terpolymer A terpolymer oE ethylene, propylene and 1,4-hexadiene (or dicyclopentadiene) is aissolved in cyclohexane containing ~9S~
1~ by weight (based on the terpolymer) o a stabilizer compound of this invention. After thorough mixing, the solvent is removed by steam coagulation and the resulting polymer residue is dried at 40-50C in the presence of air. Measurement of polymer color, gel content and viscosity change indicates that samples of terpolymer containing a compound of this invention are much more stable than is the terpolymer in the absence of said compound.
Stabilization of Polybutadiene Rubber Polybutadiene rubber is dis~olved in cyclohexane containing 1~ by weight (based on polymer) of a compound of this invention. After thorough mixing, the solvent is removed by steam coagulation to isolate the polymer re~idue. The polymer i~ then mixed at 150C in a ~rabender Plasticorder Torque-Rheometer. The change in torque is monitored as a function of time. The polymer containing a compound of this invention shows minimum change in torque after 30 minutes whereas unstabilized polybutadiene fails in two (21 minutes in this test.
Claims (16)
1. A compound of formula I or II
(I) (II) wherein R1 and R2 are independently alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, phenyl, phenyl substituted by alkyl of 1 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms or aralkyl substituted by alkyl of 1 to 12 carbon atoms; R2 may also represent hydrogen;
R3 is hydrogen or methyl;
G and E are independently phenyl or phenyl substituted by alkyl of 1 to 12 carbon atoms or by phenyl;
G may also be hydrogen or alkyl of 1 to 18 carbon atoms;
n is 1 or 2, T is -NH-phenylene-NH-, ?-phenylene-? , -NH-phenylene-Q-phenylene-NH-,?-phenylene-Q-phenylene-? where Q is alkylene of 1 to 6 carbon atoms, alkylidene of 2 to 6 carbon atoms, -SO2-, -SO-, -S-, -S-S-, -O- or -CO-, or T is -NHCONH- or where L is a straight or branched chain alkylene of 2 to 3 carbon atoms, and p and q are independently 1 or 2 with the sum of p plus q equally the valence of T.
(I) (II) wherein R1 and R2 are independently alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, phenyl, phenyl substituted by alkyl of 1 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms or aralkyl substituted by alkyl of 1 to 12 carbon atoms; R2 may also represent hydrogen;
R3 is hydrogen or methyl;
G and E are independently phenyl or phenyl substituted by alkyl of 1 to 12 carbon atoms or by phenyl;
G may also be hydrogen or alkyl of 1 to 18 carbon atoms;
n is 1 or 2, T is -NH-phenylene-NH-, ?-phenylene-? , -NH-phenylene-Q-phenylene-NH-,?-phenylene-Q-phenylene-? where Q is alkylene of 1 to 6 carbon atoms, alkylidene of 2 to 6 carbon atoms, -SO2-, -SO-, -S-, -S-S-, -O- or -CO-, or T is -NHCONH- or where L is a straight or branched chain alkylene of 2 to 3 carbon atoms, and p and q are independently 1 or 2 with the sum of p plus q equally the valence of T.
2. A compound according to claim 1 wherein R1 and R2 are branched alkyl of 4 to 8 carbon atoms.
3. A compound according to claim 2 wherein R1 and R2 are each tert-butyl.
4. A compound according to claim 1 wherein R3 is hydrogen.
5. A compound according to claim 1 wherein E and G are each phenyl when n is 1.
6. A compound according to claim 1 wherein E is phenyl when n is 1 or 2.
7. A compound according to claim 1 where in the definitions of T,phenylene is 1,4-phenylene.
8. A compound according to claim 1 wherein Q is methylene.
9. A compound according to claim 1 wherein L is ethylene.
10. A compound according to claim 2 wherein p and q are each 1 or 2.
11. A compound according to claim 10 wherein p and q are each 2.
12. A composition of matter comprising an organic material subject to oxidative, thermal and actinic degradation stabilized with an effective stabilizing amount of a compound according to claim 1.
13. A composition according to claim 12, wherein the organic material is a synthetic polymer.
14. A composition according to claim 13, wherein said synthetic polymer is a polyolefin homopolymer or copolymer.
15. A composition according to claim 13, wherein said synthetic polymer is a styrene homopolymer, copolymer or terpolymer.
16. A composition according to claim 12, wherein the organic material is a mineral or a synthetic lubricating oil.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46540983A | 1983-02-10 | 1983-02-10 | |
| US465,409 | 1983-02-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1219584A true CA1219584A (en) | 1987-03-24 |
Family
ID=23847696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000446968A Expired CA1219584A (en) | 1983-02-10 | 1984-02-08 | N-substitute (4-hydroxyphenylthiomethyl) amine or ureide stabilizers |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0119160B1 (en) |
| JP (1) | JPS59161352A (en) |
| CA (1) | CA1219584A (en) |
| DE (1) | DE3461184D1 (en) |
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| US4560799A (en) * | 1984-02-03 | 1985-12-24 | Ciba-Geigy Corporation | Tri- and Tetra-(substituted hydroxyphenylthio) alkane and cycloalkane stabilizers and stabilized compositions |
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-
1984
- 1984-02-06 EP EP84810067A patent/EP0119160B1/en not_active Expired
- 1984-02-06 DE DE8484810067T patent/DE3461184D1/en not_active Expired
- 1984-02-08 CA CA000446968A patent/CA1219584A/en not_active Expired
- 1984-02-10 JP JP2424284A patent/JPS59161352A/en active Granted
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Also Published As
| Publication number | Publication date |
|---|---|
| DE3461184D1 (en) | 1986-12-11 |
| EP0119160B1 (en) | 1986-11-05 |
| EP0119160A1 (en) | 1984-09-19 |
| JPH0463871B2 (en) | 1992-10-13 |
| JPS59161352A (en) | 1984-09-12 |
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