Note: Descriptions are shown in the official language in which they were submitted.
Case 3-13154/CGC 934/~
POLYOI. ESTEP~S OE' .~LKYLIDE~IE-2, ~ '-
Bis-PHENYL CYCLIC 2HOSP~ITES
Organic polymeric materials such as pLastics and
resins, lubricating and mineral oils are subiect to thermal,
oxidative and photodegradation. A great variety of stabil-
izers are Xnown in the art for stabilizing various substrates.
Their effectiveness varies depending on the causes of degra-
dation and the substrate stabilized. During the co~rse of
this work, it was discovered that stabilizers that are very
effective long term antioxidants are relatively poor process
stabilizers and do not protect the substrate against thermal
degradation for a short time at relatively high process tem-
peratures. Many stabilizers are relatively incom~atible with
organic substrates creating problems during the life of a
product and lessening the stabilizer's effectiveness. Some
stabilizers are either too volatile or thermally or hydroly-
tically unstable to be practical as commercial stabilizers.
,
The phosphites of this invention possess an unusual
combination of desirable properties as compared to the prior
art phosphites which makes these compounds particularly ef-
fective and usefuL as stabilizers.
Phosphites are disclosed in a number of publica-
tions. U.S. 4,196,117 discloses biphenyl-cyclic phosphites
wherein the phosphorus atom is substituted by 0- or S-hydro-
carbyl or a second hydrocarbyl biphenyl cyclic phosphite group.
Soviet Union patents 378,389, 429,070 and 4aO~390 disclose
the stabilization of various polymers with organic phosphites
-- 3 --
~59~it4~ii
or mixtures including said phosphites wherein the phosphites
are methylene-bisphenyl cyclic phosphites. Additional 2,2'-
biphenyl phosphites are disclosed in Chemical Abstracts, 68,
12597s (1968), 73, 15657c (1970) and 75, 130242g (1971-).
These various compounds are indicated to be stabilizers of
various polymers. ~owever, the instant polyol esters ase
significantly more effec'ive as process stabiiizers, as
color stabilizers and in resistance to hydrolysis.
Accordingly, it is the primary object of this in-
vention to provide biphenyl cyclic phosphite compounds which
exhibit improved process stabilization perfcrmance as con-
trasted with previously known phosphite compounds.
Various other objects and advantages of this in-
vention will become evident from the following description
thereof.
The compounds of this invention correspond to the
formula:
- 4- ~ 34S
/ R R
~2 > ~L R3
\\ 1/~
R R n
wherein R is an alkyl group of 1 to 18 carbon atoms;
R is hydrogen or an alXyl gro~p of 1 to 18 carbon
atoms;
-- 5 --
~I~L59~S
R2 is alkylene or arylene of 1 to 12 carbon atoms,
R3 is an n-valent radical selected from the group
consisting of a straight- or branched-chain alkylene of 2 to
12 atoms: a straight- or branched-chain alXane-triyl, -tetrayl,
-pentayl or -hexayl of ~ to 6 carbon atoms; alkenylene of 4
to 6 carbon atoms: cycloalkylene of 6 to 12 carbon atoms:
1,4-cyclohexanedimethylene: arylene or arenetriyl of 6 to
10 carbon atoms: p-xylylene, phenylene-E-phenylene where E
is a direct bond, -O-, -S-, -NR4-, where R4 is alkyl of 1 to
18 carbon atoms; a straight- or branched-chain alkylene or
alkylidene of 1 to 12 carbon atoms or cycloalkylidene af 5 to
6 carbon atoms: said arylene or said phenylene-E-phenylene sub-
stituted by 1 to 4 alkyl groups each having 1 to 8 carbon atoms,
-(CH2) X(CH2)p where p is 2 to 6, dipentaerythrityl, and
-(CH2CIHO)z(CH2lH-) where Y is hydrogen, methyl or ethyl and z
' .
i5 1 to 10:
X is oxygen or suifur: and
.
- 6~ 984~
n is an integer of 2 to 6.
A preferred subclass of compounds fallin~ under
formula I is that in which ~ is located in ~he ortho position
to the phosphite oxygen in each phenyl ring.
The R and Rl groups are preferably straight-chain or
branched alkyl with 4-8 carbon atoms, such as n-butyl, sec.-
butyl, tert~-butyl, tert.-pentyl, 2~ethylhexyl, n-octyl
and tert-octyl* The groups tert-butyl, tert-pentyl and tert-
octyl~'are especially preferred. ~lso especially preferred
is for the Rl group to be in the para position to oxygen,
particularly if R is.tert~-alkyl.
Although R can be hydrogen or alXyl of l to 18 car-
bons, preferably it is an alXyl group of l to 8 carbon atoms,
either straight-chain or branched-chain. Especially preferred
is tert.-alXyl of 4 to 8 carbon atoms.
R is preferably alkylene or arylene of the formula
R5
C
R6/
* 1,1,3,3-tetra~ethylbutyl
1~59~
wherein R5 and R are independently hydrogen, alkyl of 1 to
11 carbon atoms or aryl, provided that the total number of car-
bon atoms does not exceed 11. Typical aryl groups for purposes
of these various substituents include phenyl, tolyl, mesityl,
xylyl and 1- and 2-naphthyl. Especial1y preferred is R2
methylene or ethylidene.
R3 is preferably ethylene, hexamethylene, 3-thia-pentamethylene
or a group of formuIae
CH3 -CH2\ 2\ / 2
CH3 -C~ -C-CH -CH or -CH2 C~2-
The alkylated al~ylidene -2,2'-bis-phenyl cyclic phos-
phites of this invention can be prepared by reacting an alkylat-
ed 2,2'-alXylidene-bisphenol with phosphorus trichloride in a
solvent to give the corresponding phosphorochlorodite which, in
turn, is reacted with a polyol in the presence of a proton accep-
tor, such as a tertiary amine, to yield the desired product.
The solvent is preferably aromatic, such as benzene,
toluene, xylene and the like. The reaction temperature is
from about room temperature to the reflux temperature of the
reaction medium. The tertîary amine may be a trial~yl amine
such as triethyl amine or other hydrocarbyl tertiary amines
such as pyridine or substituted pyridines. The synthesis o~
- 8- 1159B'~S .
the compounds of-this invention is represented by the follow-
ing sequence of equations (depicted in terms of the preferred
compounds).
Rl Rl
R ~ ~ R
R . + PC13 ~ 12 P-Cl
'.' I ,' I ./
OH ~ /
R3(XH)n
R
1 n
~598~;
where B is a cyclic or acyclic tertiary amine useful as a
proton acceptor and the other symbals are as previously
defined.
An analogous synthetic method involves substituting
alXali metal hydroxides or alkali metal car~onates ~or ter-
tia~y amines in the synthetic scheme shown above. The abovereaction seq~ences can be conducted to yield the compounds
of this invention without isolation of the intermediate
chlordite II.
The compounds of this invention are effective light
stabilizers and/or antioxidants in a wide range of crganic
polymers. Polymers which can be stabilized include:
1. Polymers of monoolsfins and diolefins, or example
polyethylene ~which optionally can be crosslinked), polypro-
pylene, polyisobutylene, polybutene-l, polymethlypentene-l,
polyisoprene or polybutadiene, as well as polymers of cyclo-
olefins, for instancP of cyclopentene or norborner.e.
2. Mixtures of the polymers mentioned under 1), for
example mi.Ytures oE polypropylene with polyethylene or with
polyisobutylene.
- 10 -
~9~
~. Copolymers of monoole~ins and diolefins with eaah
other or with other vinyl monomers, such as, for examp1e, eth-
ylene/propylene, propylene/butene-l, propylene/isobutylene,
ethylene/butene-'l, propylene/butadiene, isobutylene/isoprene,
ethylene/ethyl acrylate, ethylene/alkyl methacrylates, eth-
ylene/vinyl acetate or ethylene/acrylic acid'copolymers and
their salts (ionomers) and terpoly~ers of ethylene with pro-
pylene and a diene, such as hexadiene, dicyclopentadiene or
ethylidene-norbornene.
4. Polystyrene.
5. ' Random copolymers of styrene or ct-methylstyrene with
d'ienes or acrylic derivatives, such as, for example, styrene/
butadiene, 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 polyacrylate, a diene polymer or an eth-
ylene/propylene/diene terpolymer. and block cop'olymers of sty-
rene, such as, for example, styrene/butadiene~styrene, styrene/
isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/
ethylene/propylene/styrene.
8~S
6. Graft copolymers of styrene, such as, for example,
styrene on polybutadiene, styrene and acrylonitrile on polybu-
tadiene, styrene and alkyl acrylates or methacrylates on poly-.
butadiene, styrene and acrylonltrile on ethylene/propylene/
diene terpolymers, styrene and acrylonitrile on polyacrylates
or polymethacrylates, styrene and acrylonitrile on acrylatet
butadiene copolymers, as well as mixtures thereof with the
copolymers listed under 5), for instance the copolymer mix-
tures known as ABS-, MBS-, ASA- or AES-polymers.
7. Halogen-containing polymers, such as polychloro-
prene, chlorinated rubbers, chlorinated or sulfochlorinated
polyethylene, DoLymers from halogen-containing vinyl compounds,
as for example, polyvinyl chloride, polyvinylidene chloride,
polyvinyl fluoride, polyvinylidene fluoride, as well as co-
polymers thereof, as for example, vinyl chloride/vinylidene
chloride, vinyl chloride/vinyl acetate or vinylidene chloride/
vinyl acetate copolymers.
,
8. Polymers which are derived from ~,s-unsaturated
acids and derivatives thereof, such as polyacrylates and
polymethacrylates, polyacrylamides and polyacrylonitrile.
- 12 -
~5~ 5
9. Copolymers from the monomers mentioned under ~)
with each other or with other unsaturated monomers, such
as, for instance, acrylonitrile~butadiene, acrylonitrile/
alkyl acrylate or acrylonitriLe/vinyl chloride copolymers
or acrylonitrile/alkyl methacrylate/butadi~ne terpolymers.
10. Polymers which are derived from unsaturated al-
cohols and amines, or acyl derivatives thereof or acetals
thereof, such as polyvinyl alcohol, polyvinyl acetate,
polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,
polyvinyl~utyral, polyallyl phthalate or polyallyl-melamine.
11. Homopolymers and copolymers of cyclic ethers, such
as polyal~ylene glycols, polyethylene o~ide, polypropylene
oxide or copolymers thereof with bis-glycidyl ethers.
.
12. Polyacetals, such as polyoxymethylene and those
polyoxymethylenes which contain ethylene oxide as a comonomer.
13. Polyphenylene oxides and sulfides.
s
14. Polyurethanes which are derived from polyethers,
~olyesters 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
di-amines and dicarboxylic acids and~or from aminocarboxylic
acids or the corresponding lactams, such as polyamide 4, poly-
amide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide
12, poly-2,4,4-trimethylhexamethylene terephthalamide or poly-
m-phenylene isophthalamide, as well as copolymers thereoS with
polyethers, such as, for instance, with polyethylene glycol,
polypropylene glycol or polytetra-methylene glycols.
.
16. Poly~reas, polyimides and polyamide-imides.
17. Polyesters ~hich are derived from dicarboxylic
acids and glycols and/or from hydroxycarboxylic acids or the
corresponding lactones, such as polyethylene terephthalate,
- 14 -
115~34S
polybutylene terephthalate, poly-1,4-dimethylol-cyclohex,ane
terephthalate and polyhydroxybenzoates as well as block-co-
polyether esters derived from polyethers having hydroxyl end
qroups.
,
18. Polycarb'onates. ,
19. Polysulfones and polyethersulfones.
20. ' Crosslinked polymers which are derived frcm alde- '
hydes on the one hand and phenols, ureas and melamines on
the other hand, such as ohenol/formaldehyde resins, urea/
formaldehyde resins and melamine/formaldehyde resins.
.
21. Dryinq and non-drying alkyd resins.
22. Unsaturated polyester resins which are derived from
copolyesters of saturated and unsaturated dicarboxylic acids
with polyhydric,alcohols and vinyl compounds as crosslinkinq
agents, and also halogen-containing modifications thereof o
low flammability.
- 15 -
34~5
23. Thermosettïng acrylic resins, derived from sub-
stituted 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, polyisocyanates
or epoxide resins as crosslinklng agents.
25. Crosslinked epoxide resins which are derived from
polyepoxides, for example ~rom bis-glycidyl ethers or from
cycloaliphatic diepoxides.
26. Natural polymers, such as cellulose, rubber, gela-
tin and derivatives thereof which are chemically modified
in a polymer-homologous manner, such as cellulose acetates,
cellulose propionates and cellulose butyrates, or the cellu-
lose ethers, such as methylcellulose.
27. Naturally occurring and synthetic organic materi-
als which are pure monomeric compounds or mixtures of such
compounds, for example mineral oils, animal and vegetable
- 16- ~ 8~5
fats, oils and waxes, or oils, fats and waxes based on syn-
thetic esters ~e.g. phthalates, adipates, phosphates or
trimellitates) and also mixtures of synthetic 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 e~ulsions of such materials.
28. Aqueous emulsions of natural or synthetic rubber,
e.g. natural latex or latices of carboxylated styrene/buta-
diene copolymers.
Compounds of this invention are also particularly
e~fective in stabilizing mineral and synthe~ic fluids such
as lubricating oils, circulating oils, etc.
The compounds of this invention are particularly use-
ful as stabilizers, especially for the protection of polyole-
fins, for instance, polyethylene, polypropylene; polyisobutylene,
- 17 ~
poly(butene-l), poly(pentene-l), poly(3-methylbutene-1), poly
t4-methylpentene-1), various ethylene-propylene copolymers and
the li~e.
Other substrates in which the compounds of this inven-
tion are particularly useful-are polystyrene, including impact
polystyrene, ABS resin, S3R, isoprene, as well aq natural rub-
ber, polyesters including polyethylene terephthalate and poly-
butylene terephthalate, including copolymers. Also stabilized
are polyurethanes, polycarbonates, polyamides such as nylon 6,
6/6 and the like as well as copolyamides and polysulfones.
The compounds of this invention may be use~ alone as
the sole stabilizer having either mainly an antioxidant function
or a light stabilizing function or the stabilizer may combine
utility as an antioxidant and light stabilizer. The stabilizers
may be used with phenolic antioxidants, lubricants such as cal-
cium stearate, pigments, colorants or dyes, UV absor~ers, light
stabilizers such as hindered amines, metal deactivators, talc
and other fillers, etc.
- 18 ~ 9~45
In general, the stabilizers of ~his invention are
employed from about 0.01 to about 5% by weight of the stabil-
ized composition; although this will vary with the particular
substrate and application. An advantageous-range is from about
O.OS to about 2~, and especially 0.1 to ahout 1%.
Compounds of this invention stabilize polymers espe-
cially during high temperature processing with relatively little
change in color, even though the polymer may undergo a number
of extrusions. Among the polymers in which this property is
especially apparent are polypropylene, polyethylene, styren~cs
such as ABS, polyethylene- and polyb~tylene-terephthalates,
polycarbonates, natural rubber, synthetic rubber such as 58R.
While many compo~nds which have been used as process stabilizers
are sufficiently effective as process stabilizers for polyolefins
only in the presence of costabilizers such as phenolic antioxi-
dants, compounds of this invention are effective also in the
absence of phenolic antioxidants. Many of the compounds of
this invention combine process stabilizing pro~erties with
the ability to confer light stability on the polymer. This
is particularly important for polymer fibers where processing
temperatures are among the highest and where stahility to ac-
tinic light is a prime re~uirement.
- lg- ~L~S~i~4~
A particularly important property for stabilizers which
are trivalent phosphorus e5ters is their non-hygroscopicity and
resistance to hydrolysis in the presence of moisture in the atmos-
phere during ambient storage, especially at temperatures during
summer sub-tropical as well as tropical conditions. Hygroscopi-
city frequently results in difficulty in incorporating the pro-
cess stabilizer uniformly into the po!.ymer causing stic~iness
and blockage during compounding, while hydrolysis of the phos-
phorus ester stabilizers during storage frequently results in
compounds which are less effective.
~ he stabilizers of this invention may readily be in-
corporated into the organic polymers by conventional techniques,
at any convenient stage prior to the manufacture of shaped arti-
cles 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 emul-
sion of the polymer. The stabilized polymer compositions o~f
the invention may optionally also contain various conventional
additives, such as the following:
1. Antioxidants
- 20 -
~lS~78~S
1.1 Simple 2,6-dialXylphenols, such as, for example,
2,6-di-tert.-butyl-4-methylphenol, 2-tert.-butyl-4, 6 dimethyl-
phenol, 2,6-di-tert.-butyl-4-methoxymethylphenol and 2,6-di-
octadecy1-4-methylphenol.
1.2 Derivatives o~ al~ylated hydroquinones, such as,
for example, 2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amyl-
hydroquinone, 2,6-di-tert.-butyl-hydroquinone, 2,5-di-tert.-
butyl-4-hydroxy-~nisole, 3,5-di-tert.-hutyl-4-hydroxy-anisole,
t~is-(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.-buty~-4-methylphenol), 2,2'-thio-
bis-(4-octylphenol), 4,4'-thio-~is-(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-hydroxyphenyl)
disulphide.
1.4 Alkylidene-~isphenols, such as, for example, 2,2'-
~ethylene-bis ~6-tert.-butyl-4-methylphenol), 2,2'-methylene-bis-
- 21 -
~3l59~34S
(6-tert.-butyl-4-ethylphenol), 4~4'-methylene-bis-t6-tert~-but
2-methylphenol), 4,4'-methylene-bis-~2,6-di-tert.-butyl-phenol),
2,6-di-~3-tert.-butyl-5-methyl-2-hydroxybenzyl)-4-~ethylphenol,
2,2'-methylene-bis-C4-methyl-6-(-methylcyclohexyl)-phenol],
l,l-bis-(3,5-dimethyl-2-hydroxyphenyl)-butane, l,l-bis-(5-tert.-
butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(3,5-di-tert.-
butyl-4-hydroxyphenyl)-propane, 1,1,3-tris-(5-tert.-bu~yl-4-
hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.-butyl-4-hy-
droxy-2-methylphenyl)-4-n-dodecylmercapto-butane, 1,1,;,5-
tetra-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-pentane and
ethylene glycol bis-C3,3-bis-(3'-tert.-butyl-4'-hydroxyphenyl)-
butyrate3.
1.5 0-, N- and S-benzyl com~ounds, such as, ~or
example, 3,3',5,5'-tetra-tert.-butyl-4,4'-dihydroxydibenzyl
ether, octadecyl 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate,
tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-amine and bis-(4-
tert.-butyi-3-hydroxy-2,6-dimethyl~enzyl) dithioterephthalate.
1.6 Hydroxybenzylated malonates, such as, for
example, dioctadecyl 2, 2-bis- ~ 3,6-di-tert.-butyl-2-hydroxy-
benzyl)-malonate, dioctadecyl 2-(3-tert.-hutyl-4-hydroxy-5-
methylbenzyl)-malonate, di dodecylmercapto-ethyl 2,2-bis-(3,
- 22 -
98~s
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 Hydroxybenzyl-aromatic compou_ds, such as, for
example, 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-
trimethyl-benzene, 1,4-di-(3,5-di-tert.-butyl-4-hydroxybenzyl)-
2,3,5,6-tetramethylbenzene and 2,4,6-tris-(3,5-dl-tert.-butyl-4-
hydroxy-benzyl)-phenol.
1.8 s-Triazine comDounds, such as, for example, 2,
4-bis-octylmercapto-6-(3,5-di-tert.-butyl-4-hydroxy-anilino)-s-
triazine, 2-octylmercapto-4,6-bis-(3,;-di-tert.-butyl-4-hydroxy-
anilino)-s-triazine, 2-octylmercapto-4,6-bis(3,;-di-tert.-butyl-
4-hydroxyphenoxy~-s-triazine,2,4,6-tris-(3,5-di-tert.-butyl-4-
hydroxyphenoxy)-s-triazine, 2,4,6-tris(3,5-di-tert.-butyl-4-
hydroxyphenylethyl)-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)
propionlc acid, such as, for example, 1,3,5-tris((3,5-di-tert.-
butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazine, N,N'-
23 - ~ 5~4S
di-((3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexamethylene-
diamine and N,U'-bis-B-(~3,5-di-t-butyl-4-hydroxyphenyl~-propionyl-
hydrazine.
1.10 ~ster ~ tyl-4-hydroxyphenyl)-
propionic acid with monohydric or polyhydric alcohols, such as,
for example, with methanol, ethanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2-propanediol,diethylene glycol,
thiodiethyleneglycol, neopentylglycol, pentaerythritol, 3-thia-
undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethyl-
olethane, trimethylolpropane, tris-hydroxyethyl iso-cyanurate
and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-~2,2,2]octane.
1.11 Esters of B-(5-tert.-butyl-4-hydroxy~methyl-
phenyl?-propionic acid with monohydric or polyhydric alcohols,
such as, for example, with methanol, ethanol, octadecanol, 1,6-
hexanediol, l,9-nonanediol, ethylene glycol, 1,2-propanediol,
diethylene glycol, thiodiethyleneglycol, neopentylglycol,
pentaerythritol, ~-thia-undecanol, 3-thia-pentadecanol, tri-
methyl-hexanediol, trimethyloLethane, trimethylolpropane, tris-
hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phosDha-2,6,
7-trioxa~icyclo~2,2,2]octane.
~ 24 _ ~ ~ 5 ~ ~ ~ 5
1.12 Esters of 3,5~ tert.-butyl-4-hydroxvphenyl-
acetic acid with monohydric or polyhydric alcohols, such as,
for example, with methanol, ethanol, ocatdecanol, 1,6-hexanediol,
l,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene
glycol, thiodiglycol, neopentylglycol, penta-erythritol, 3~thia-
undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethyl-
olethane, trimethylolpropane, tris-hydroxyethyl isocyanurate
and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo~2,2,2]-octane,
especially the tetra-bis ester of pentaerythritol.
1.13 Benzylphos~honates, such as, for example, di-
methyl 3,5-di-tert.-butyl-4-hydroxybenæyl-phosphonate, diethyl
3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonate, dioctadecyl
3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonate and dicctadecyl
5-di-tert.-butyl-4-hydroxy-3-methylbenzyl-phosphonate.
The following may be mentioned as examples of fur-
ther additives that can be used together with the stabilizer
of this inventlon and the antioxldant:
1. Aminoaryl derivatives, e.g. phenyl-1-naphthyl-
amine, phenyl-2-naphthylamine, ~,N'-di-phenyl-p-phenylenedi-
25 - ~15g~5
amine, N,N'-di-2-naphthyl-p-phenylene-diamine, N-N'-di-2-
naphthyl-P-phenylenediamine~ N,N'-di-sec.-butyl-p-phenylene-
diamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-
dodecyl-2,2,4-trimethyl-1,2-dihydro-quinoline, mono- and
dioctyliminodibenzyl, polymerized 2,2,4-trimethyl-1,2-dihy-
droquinoline. Octylated diphenylamine, nonylated diphenyl-
amine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-pehnyl-
N'-isopropy]-p-phenylenediamine, N,Nr-di-sec.octyl-p-phenyl-
enediamine, N,N'-di-(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-dimethyl-N,N'-di-(sec.-octyl)-p-phenylenediamine, 2,6-
dimethyl-4-methoxyaniline, 4-ethoxy-N-sec.-butylaniline, di-
phenylamine-acetone condensation product, aldol-l-naphthyl-
amine and phenothiazine.
Discoloration effects have to be taken into account
when using the above antioxidants.
.
2. ~V-Absorbers and lisht-stabilising aqents
.
2.1 2-(2'-Hydroxyphenyl)-henzotriazoles, 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-S'-methyl-, 3'-sec.-butyl-5'-tert.-butyl,
- 2 6 - ~ 5
3'-~~methylbenzyl-5'-methyl-, 3'-~-methylbenzyl-5'-methyl-5-
chloro-, 4'-hydroxy-, 4'-methoxy-, 4'-octoxy-, 3',5'-di-tert.-
amyl-, 3'-methyl-5'-carbomethoxyethyl- and S-chloro-3',5'-di-
tert.-amyl-derivative.
2.2 2,4-bis-(2'-Hydrox ohenYl)-6-alk~l-s-triazines
-- Y _ . ~
e.g. the 6-ethyl-,. 6-heptadecyl- or 6-undecyl-derivative.
2.3 2-Hydroxybenzophenones, e.g. the 4-hydroxy-,
4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-,
4,2',4'-trihydroxy- or 2'-hydroxy-1,4'- dimethoxy-derivative.
2.4 1,3-bis-(?'-Hydroxybenzoyl)-benzenes, e.g.
1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1,3-bis(2'-
hydroxy-4'-octyloxy-benzoyl)-benzene or 1,3-bis-(2'-hydroxy-
4'-dodecyloxy-benzoyl)-benzene.
2.5 ~sters of optionaily s~hstituted benzoic acids,
e.g. phenylsalicylate, octylphenylsalicylate, dibenzoylresorcin,
bis-(4-tert.-butylbenzoyl~-resorcin, benzoylresorcin, 3,5-di-
tert.-butyl-4-hydroxybenzoic acid-2,4-di-tert.-butylphenyl es-
ter or -octadecyl ester or -2-methyl-4,6-di-tert.-butyl ester.
- 27- ~L598~
2.6 Acrylates, e.g. ~-cyano-~,B-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-(B-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~tetramethylpiperidyl)-sebacate or 3-
n-octyl-7,7,9,9-tetramethyl-1,3,~-triaza-spiro[4,5~decane-2,4-
dione.
2.8 Oxalic acid diamides, e.g. 4,4'-di-octyioxy-
oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.-butyl-oxanilide,
2,2'-di-dodecyloxy-5,5'-di-tert.-butyl-oxanilide, 2-ethoxy-2'-
ethyl-oxanilide, N,N'-bis-(3-dimethyl-aminopropyl)-oxalamide,
2-ethoxy-5-tert.-butyl-2'-ethyl-oxanilide and the mixture
thereof with 2-ethoxy-2'-ethyl-4,5'-di-tert.-butyl-oxanilide,
or mixtures of ortho- and para-methoxy- as'well as o~ o- and
p-ethoxy-disubstituted oxanilides.
- 28 - ~ 8~5
3. Metal deactivators, e.q. oxanilide, isophthalic
acid dihydrazide, sebacic acid-bis-phenylnydrazide, bis-ben-
zylidene-oxalic acid dihydrazide, ~,~'-diacetal-adipic acid
dihydrazide, N,N'-diacetal-adIpic acid dihydrazide, N,N'-
bis-salicyloyl-oxalic acid dihydrazide, N,N'-bis-salicylol-
hydrazine, M,N'-bis-(3,5-di-tert.-butyl-4-hydroxyphenylpro-
pionyl)-hydrazine, N-salicyloyl-N'-salicylalhydrazine, 3-
salicyloyl-amino-1,2,4-triazole or N,~'-bis-salicyloyl-thio-
propionic acid dihydrazide.
4. Basic co-stabilisers, e.g. alkali metal s~lts
and alkaline-earth metal salts of higher fatty acids, for
example Ca-stearate, Zn-stearate, Mg-behenate, Na-ricinoleate
or ~-palmitate.
.
5. Nucleation agents, e.g. 4-tert.-butylbenzoic
acid, adipic acid or diphenylacetic acid.
6. Phosphites, such as, for examDle~ triphenyl
phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites,
tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl
phosphite, 3,9-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphospha~
~5,5]-undecane and tri-(4-hydroxy 3,5-di-tert.butylphenyl)
phosphite.
Other additives that can be incorporated in the
stabilized compositions are thiosynergists such as dilauryl-
thiodiproprionate or distearylthiodipropionate, lubricants
sùch as stearyl alcohol, fillers, carhon black, asbestos,
kaolin, talc, glass fibers, pigments, optical brighteners,
flameprooing agents and antistatic agents.
While the instant phosphites can be beneficially
used as stabilizers for a variety of substrates, particular-
ly the polyolefins, both alone and in conjunction with other
coadditives, the combination of the instant phosphites with
selected hindered phenolic antioxidants exhibits enhanced
and particularly salubrious protection to such substrates.
The phenolic antioxidants found to be particularly useful
are selected from the group consisting of 2,6-di-tert-butyl-
4-methylphe'nol, 4,4'-thio-bis~6-tert-butyl-3-methylphen~L),
2,2'-methylene-bis(6-tert-butyl-4-methylphenoL), 4,4'-meth-
ylene-bis-(2,6-di-tert-butylphenol), 1,1,3-tris(5-tert-butyl-
- ~ 34S
.
4-hydroxy-2-methylphenyl)butane, 1,3,5-tris(3,5,di-tert-butyl-
4-hydroxybenzyL)-2,4,6-trimethylbenzene, 2- octylthio-4,6-
bis(~,5-di-tert-butyl-4-hydroxyanilino)-s-triazine, n-octa-
decyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentane-
tetrayl tetrakis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate),
1,3,5-tris(3,;-di-tert-butyl-~-hydroxybenzyl) isocyanurate
thiodiethylene bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)
and tris (2-hydroxyethyl) isocyanate ester of 3-3,5-di-tert-
butyl-4-hydroxyphenyl)propionic acid.
The compositions comprise (1) a substrate, preferably
a polyolefin such as polypropylene, (b) about 0.01 to about S~
by weight of the composition, preferably about 0.025 to about
2% and most preferably 0.025 to l~ of an instant phosphite com-
pound mixture thereof, and optionally, (c) a phenolic antioxi-
dant or mixture of said antioxidants selected from the ~roup.
cited directly above and also in a range of 0.01 to 5~, pref-
erably 0.05 to 1%, by weight of the composltion.
LiXewise, the following light stabilizers are prefer-
red for use, either alone or in conjunction with the listed
phenolic antioxidants, as additives for incorporation with the
instant stabilizers into the listed substrates: 2-(2'-hydroxy-
5'-methylphenyl)benzotriazole: 2-~3`5'-di-tert-butyl-2'-hydroxy-
3~ j984S
phenyl)benzotriazole; 2-(2'-hydroxy-3'5'-di-tert-amylphenyl)
benzotriazole; nickel bis[O-ethyl-(3,5-di-tert-butyl-4-hydroxy-
benzyl)~phosphonate; bis ~1,2,2,6,6-phentamethyl-4-piperidyl)-
2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate; bis(2,
2,6,6-tetramethyl-4-piperidyl)sebacate; dimethylsuccinate poly-
mer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol; and
polymer of 2,4-dichloro-6-octyiamino-s-triazine with N'-(2,2,6,
6-tetramethyl-4-piperidyl) hexamethylene diamine.
The following examples illustrate the preferred
embodiments of the invention. In these examples, all parts
are given by weight unless ~therwise specified.
- 32 -
~15~4~
EXAMPLE A
ol; 02-~2,2'-methylene-bis(4,6-di-tert-butYlPhenyl)~phosphoro-
chlorodite
A 500 ml flame-dried flask under nitrogen was charged
with 6.87 grams phosphorus trichloride and 100 mls of ~oluene.
Maintaining the temperature at 10-15C, a solution of 21.27
grams 2,2'-methylenebis(4,6-di-tert-butylphenol) and 10.1
grams triethylamine was added over 15 minutes. The reaction
was stirred at ambient temperature until disappearance of
starting bisphenol as shown by IR and TLC. The reaction
was filtered, rotary evaporated, and recrystallized from
heptane ~ielding 11.0 grams white cryst21s M.P. 207-217C.
Analysis calculated: C,71.22; H, 8.66. Found. C, 71.44;
H, ~.62.
In a similar manner the following phosphorochloro-
dites were made:
* 01,02-~2,2'-ethylidene-bis(4,6-di-tert-butylphenyl)~phosphoro-
chlorodite
* 01,02-~2,2'-methylene-bis~4,6-di-tert-amylphenyl)~phosphoro-
chlorodite
* Characteri7ed by I~ Spectra
- 33 ~L159~3~S
* 0l,02-~2,2'-methylene-bis(4-methyi-6-tert-butylphenyl)]
phosphorchlorodite
* 01,02-~2,2'-butylidene-bis(4,6-di-tert-butylphenyl)]
phosphorochlorodite
0l,02-[2,2'-(2-héxylidene)-bis(4,6-di-tert butylphenyl)]
phosphorochlorodite
0l,02-~2,2'dodecylidene bis(4,6-di-tert-butyLphenyl)~
phosphorochlorodite
.0 ,0 -C2,2'-methYlene-bis(4,6-di-tert-octYlphenyl)]phos-
phosphorochlorodite
0l,02-~2,2'-methylene-bis(4-tert-butyl-6-n-octadecylphenyl)]
phosphorochlorodite
* 01,02-~2,2'-ethylidene-bis(4,6-di-tert-amylphenyl)]phosphoro-
chlorodite
* characteriz~d by I~ spectra
EXAMPLE I
0,0'-Hexamethylene-bis~0 !0 -2,2'-methylene-bis(~,fi-di-tert-
buty lph enyl)phosphite]
.
A one-liter flame-dried flasX under nitrogen was
charged with 18.75 grams phosphorus trichloride and 200 ml
toluene. Maintaining the temperature between lO to 15C,
- 34 _ ~ ~
a solution of 58 grams 2,2'-methylene-~is(4,6-di-tert-butyl-
phenol) and 27.64 grams triethylamine in 250 mls toluene
was added. The reaction was stirred at ambient temperature
until disappearance of starting bisphenol by IR and TLC.
A solution of 8.07 grams 1,6- hexanediol in 13.82 grams
triethylamine was added at 10C. The reaction was stirred
at ambient temperature until complete by IR and TLC. The
reaction was filtered, rotary evaporated, and recrystal-
lized from toluene:acetone yielding 46.1 grams white
powder M.P. 259-267C. Analysis Calculated: C, 75.11;
H, 9.46. Found: C, 75.23; H, 9.06.
Employing the procedure of EX~MPLE I, other com-
pounds of the invention were prepared as shown in TA3LE I.
TAE3LE I
EXAMPLES 2 to 17
~ Rl
2~0
2 >PX ~ R
Rl
\ / n
~59
- 35 -
1.
.. ' L ~ ~, ' , u
U U ~ U .,
k. ~ U r " U U
s~
r.~ ~ r.~1 r l '~ ~ ~O r ~ J r~
~ a ~--J--a ^,~- \J~ rl rl--' a
y ' / \~ ' ~ S
Xl o o o o o o
c
_~a~ .
, ~
:!J~ _~ J
,~ a
\
U r U V U r
U
U U ~ U . U U
.
~1
- 36~ 8~5
c
, ~ C ~ .,,
o , o C , C .
U ., ~ ~ , o o , ~
'A C ~ ¢ C C :1~ ~ C
O
0 E~ ¢
A 'A A
U
:~. 'A 'A 'A 'A
,0 ~ C,~
U IJ ~.1
3 3
~ ~ t~ ' U~
O c~ ~:r ~ ~ '~
. e~
3~
~1 O o o o ~ o
.
.
~1 a~ , a--, 3--~,, a~
a ~ 5 ~ ,
U ~ .U U ~ ~ U U U
, , , , I , ,
,~ I U ~ U U ., U U
- ! ! ! ' ! ! ! ! ! !
~1~I-- _ ____ __
- 37 -
EXAMPLE 18
Processing Stability of Polypropylene
Base Formulation:
Polypropylene* lO0 . parts
Calcium stearate 0.10 parts
Pentaerythrityl tetrakis~
-[3-(3,5-di-tert.-butyl-4-
hydroxyphenyl)-propionate 0,10 parts
*Profax 6801 from Hercules Chemical
Stabili~ers ~ere solvent blended into polypropy-
lene as solutions in methylene chloride and, after removal
o~ the solvent by evaporation at reduced pressure, the
resin was extruded usin~ the following extruder conditions:
Temperature
( C)
Cylinder ~l - 232
Cylinder ~2 - 246
Cylinder ~3 - 26d
Die ~l - 260
Die ~2 - 260
Die ~3 - 260
RPM - lO0
~5~5
During extrusion (after each of the first, third and
fifth extrusions) the internal extruder pressurs was
dstermined using a pressure transducer.
Table II
Extrusion Temp-260C
Phosphite Transducer Pressure
After Extrusion (psi)
1 3 5
None 1450 1350 1150
0.05 ~ EX.l 1600 1500 1500
0.05 % EX.6 1600 1600 1450
0.05 % EX.9 1800 1800 1700
