Note: Descriptions are shown in the official language in which they were submitted.
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,
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.
- 4 -
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
R2 R3
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.
L9584
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.
-- 10 --
~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.
- 12 -
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.
- 13 -
~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:
- 14 -
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-
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.
- 16 -
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-
-17-
,~ ,,
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.
- 18 -
, ~ ,
~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~
- 19 -
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]-
-- 21 --
~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.
- 22 -
~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.
- 23 -
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.
EXAMPLE 1
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.
-24
~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
- 25 -
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.
- 26 -
~9S~
EXAMPLE 6
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.
;
EXAMPLE 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
- 27 -
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
- 28 -
.
~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.
- 30 -
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
- 31 -
. .,
:~2~58~L
EXAMPLE 9
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.
- 32 -
;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
- 33 -
~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.
EXAMPLE 12
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.
- 34 -
