Neoalkyl phosphite provided which exhibit improved levels of stability. The phosphites are hindered and are useful in stabilizing thermoplastic compositions.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to phosphites, and more particularly, relates 
to neo-alkyl phosphites, the preparation thereof, and polymer compositions 
stabilized therein. 
2. Description of the Related Art 
Organic phosphites are known thermal oxidative stabilizing agents for 
polymers and other organic materials. Such phosphites however typically 
suffer from one or more of the following problems resulting from 
structural deficiencies: (a) they degrade to alcohols which undergo 
H.sub.2 O (water) generation through beta-elimination of a hydrogen with 
an --OH group, and it is believed that this H.sub.2 O generation can lead 
to further degradation of the phosphite; (b) they experience hydrolytic 
instability upon exposure to moisture which attacks the bond between the 
oxygen atoms and the phosphorus atom (O--P bonds); and (c) they degrade 
into alcohol degradation products which have boiling points of less than 
250.degree. C. which volatilize out of phosphite stabilized polymeric 
compositions under normal polymer processing conditions, for example 
degradation products such as low molecular weight diols such as 1,3 
propane diol (BP 213.degree. C.), 2,2 dimethyl-1,3 propane diol (BP 
206.degree. C.), 2,2 diethyl-1,3 propane diol (BP 240.degree. C.), and 2 
methyl, 2 propyl-1,3 propane diol (BP 234.degree. C.). Finally, in 
processes for making organic phosphites it is desirable to be able to make 
the phosphite from a direct reaction between alcohols and PCl.sub.3 but if 
a beta-hydrogen is present in the alcohol, then undesirable alkylchlorides 
will most likely form. 
Neo-alkyl phosphites derived from a neoglycol with PCl.sub.3 are known, see 
Dever, et al., U.S. Pat. No. 3,714,302, which is incorporated herein by 
reference. While these neo-alkyl phosphites have no .beta.-hydrogens, they 
lack stearic bulk on the .alpha.-carbons which merely have hydrogen 
radicals thereon, thus rendering the phosphites susceptible to hydrolytic 
instability, and possibly volatile degradation products. 
Accordingly, it would be desirable to provide phosphites which have few 
beta-hydrogens (preferably no beta-hydrogens) and have stearic bulk on the 
.alpha.-carbon. 
SUMMARY OF THE INVENTION 
The present invention provides organic phosphite esters which (a) have few 
hydrogens on the beta-carbons, and preferably no hydrogens on the 
beta-carbons, and (b) have stearic bulk on at least one alpha-carbon. The 
phosphites are suitable for use as thermal oxidative stabilizers in 
polymeric compositions.

DETAILED DESCRIPTION OF THE INVENTION 
The phosphites include those of the general formula: 
##STR1## 
wherein each R.sup.2 is independently selected from hydrogen and 
hydrocarbon radicals provided however that at least one R.sup.2 is a 
hydrocarbon which provides stearic bulk to the .alpha.-carbon it is 
attached to, wherein the combined total number of beta-hydrogen on each 
R.sup.2 radical is no greater than one, and preferably zero, wherein the 
R.sup.1 and R.sup.2 radicals have a combined total of carbon atoms of at 
least five; and wherein the R.sup.3 is a hydrocarbon radical having at 
least six carbon atoms and may contain phosphite moieties. 
Preferably the phosphite is obtained by the reaction of a neoglycol with 
PCl.sub.3 in the absence of a catalyst, HCl acceptor and solvent to 
produce an intermediate product of the formula: 
##STR2## 
wherein R.sup.1 and R.sup.2 are defined above, followed by reaction with 
HO--R.sup.3 wherein R.sup.3 is defined above. Alternatively, other 
reaction processes and steps may be employed to yield the desired product. 
Transesterification processes such as those disclosed in Heckenbleikner et 
al., U.S. Pat. No. 3,056,823, which is incorporated herein by reference, 
may also be employed. The phosphites can be made, for instance, by 
reacting a diol of the formula 
##STR3## 
with triphenylphosphite by heating in the presence of an alkaline 
catalyst, e.g., an alkali metal, alkaline earth metal or metal alcoholate. 
The reaction proceeds essentially as a substitution reaction, with an 
aliphatic group replacing one or more aryl groups in the triaryl 
phosphites. The proportions of the aliphatic alcohol and triaryl phosphite 
are selected accordingly. Thus there is used 1 mole of aliphatic diol to 
replace 2 moles of aryl radicals from the original phosphite, with the 
liberation of 2 moles of phenol. Reaction temperatures may vary widely but 
in general are between about 120.degree. and 150.degree. C. 
In practice, the dihydric alcohol, triphenyl phosphite ester and catalyst 
may be mixed together in any desired order, preferably before heating is 
started. The materials are then heated together, as, for example, under a 
reflux condenser, until the substitution of aliphatic for aryl components 
has reached the desired state. This can be determined by no further change 
in observable properties such as the boiling point of the mixture. The 
period of heating required is usually 2-5 hours. Heating is then 
discontinued. The phenol or other arylhydroxy compound liberated during 
the reaction as well as any unreacted aliphatic diol are distilled off in 
vacuum, and the resultant phosphite triester is recovered from the still 
residue and purified by conventional means. 
R.sup.3 may contain phosphite moieties. 
As set out above, suitable diols are those of the formula 
##STR4## 
wherein each R.sup.1 is preferably independently selected from the group 
consisting of alkyl radicals having from 1 to 10 carbon atoms, wherein 
each R.sup.2 is independently selected from the group consisting of 
hydrogen and alkyl radicals having from 3 to 20 carbon atoms, provided 
that at least one R.sup.2 is an alkyl radical having from 3 to 20 carbon 
atoms (preferably 4 to 6 carbon atoms). As described herein, the 
.alpha.-carbons are those directly attached to the oxygen atom and the 
.beta.-carbons are those located two carbons from the oxygen atoms, thus 
the .beta.-carbons are those attached to the .alpha.-carbons and the 
.alpha.-carbons are those attached to the oxygen atoms. For illustrative 
purposes, a phosphite of the formula 
##STR5## 
has no hydrogens attached to the beta carbons, and the corresponding diol 
##STR6## 
has no hydrogens attached to the beta-carbons. Preferably the phosphites 
of the present invention have no more than one hydrogen attached to each 
beta-carbon, preferably have no more than a total of two such 
beta-hydrogens for the entire phosphite, and more preferably have no more 
than one such beta-hydrogen, and most preferably have no hydrogens 
attached to the beta carbons. Neotype glycols utilizable in the invention 
having beta, beta dialkyl substitutions and having at least one R.sup.2 
being a hydrocarbon radical to provide the .alpha.-carbon with stearic 
bulk. Specific neo-glycols include those having no hydrogens attached to 
the beta carbons: 
2,2-dimethyl-1-t-butyl-1,3 propane diol, 
2,2-dimethyl-1,3-di-t-butyl propane diol, 
2-ethyl-2-butyl-1-t-butyl-1,3 propane diol, 
2-ethyl-2-butyl-1,3-di-t-butyl-1,3 propane diol, 
2,2-dimethyl-1-t-butyl-1,3-propane diol, 
2,2-diethyl-1-t-butyl-1,3-propane diol, 
2,2-dipropyl-1-t-butyl-1,3-propane diol, 
2,2,-dibutyl-1-t-butyl-1,3 propane diol, 
2,2-diphentyl-1-t-butyl-1,3-propane diol, 
2,2-dihexyl-1-t-butyl-1,3-propane diol, 
2-methyl-2-ethyl-1-t-butyl-1,3-propane diol, 
2-methyl-2-propyl-1-t-butyl-1,3-propane diol, 
2-methyl-2-butyl-1-t-butyl-1,3-propane diol, 
2-methyl-2-pentyl-1-t-butyl-1,3-propane diol, 
2-methyl-2-hexyl-1-t-butyl-1,3-propane diol, 
2-ethyl-2-propyl-1-t-butyl-1,3-propane diol, 
2-ethyl-2-butyl-1-t-butyl-1,3-propane diol, 
2-ethyl-2-pentyl-1-t-butyl-1,3-propane diol, 
2-ethyl-2-hexyl-1-t-butyl-1,3-propane diol, 
2-propyl-2-butyl-1-t-butyl-1,3-propane diol, 
2-propyl-2-pentyl-1-t-butyl-1,3-propane diol, 
2-propyl-2-hexyl-1-t-butyl-1,3-propane diol, 
2-butyl-2-pentyl-1-t-butyl-1,3-propane diol, 
2-butyl-2-hexyl-1-t-butyl-1,3-propane diol, 
2-pentyl-2-hexyl-1-t-butyl-1,3-propane diol, 
2,2-dimethyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2,2-diethyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2,2-dipropyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2,2,-dibutyl-1-t-butyl-3-t-butyl-1,3 propane diol, 
2,2-dipentyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2,2-dihexyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2-methyl-2-ethyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2-methyl-2-propyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2-methyl-2-butyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2-methyl-2-pentyl- 1-t-butyl-3 -t-butyl-1,3 -propane diol, 
2-methyl-2-hexyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2-ethyl-2-propyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2-ethyl-2-butyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2-ethyl-2-pentyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2-ethyl-2-hexyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2-propyl-2-butyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2-propyl-2 -pentyl - 1 -t-butyl - 3 -t-butyl-1,3 -propane diol, 
2-propyl-2 -hexyl- 1-t-butyl-3 -t-butyl-1,3-propane diol, 
2-butyl-2-pentyl-1-t-butyl-3-butyl-1,3-propane diol, 
2-butyl-2-hexyl-1-t-butyl-3-t-butyl-1,3-propane diol, 
2-pentyl-2-hexyl-1-t-butyl-3-t-butyl-1,3-propane diol 
As indicated, at least one R.sup.2 is preferably a tertiary alkyl, and may 
be represented by the formula: 
##STR7## 
wherein each R.sup.4 is independently selected from the group consisting 
of an alkyl radical having from 1 to 10 carbon atoms, preferably each 
R.sup.4 is a methyl group. 
Neodiols having one beta-hydrogen include those wherein at least one 
R.sup.2 is of the formula: 
##STR8## 
where R.sup.4 is as defined above. Specific neodiols having one 
beta-hydrogen include: 
2,2-dimethyl-1-(2-propyl)-1,3-propane diol, 
2,2-diethyl-1-(2-propyl)-1,3-propane diol, 
2,2-dipropyl-1-(2-propyl)-1,3-propane diol, 
2,2,-dibutyl-1-(2-propyl)-1,3 propane diol, 
2,2-dipentyl-1-(2-propyl)-1,3-propane diol, 
2,2-dihexyl-1-(2-propyl)-1,3-propane diol, 
2-methyl-2-ethyl-1-(2-propyl)-1,3-propane diol, 
2-methyl-2-propyl-1-(2-propyl)-1,3-propane diol, 
2-methyl-2-butyl-1-(2-propyl)-1,3-propane diol, 
2-methyl-2-pentyl-1-(2-propyl)-1,3-propane diol, 
2-methyl-2-hexyl-1-(2-propyl)-1,3-propane diol, 
2-ethyl-2-propyl-1-(2-propyl)-1,3-propane diol, 
2-ethyl-2-butyl-1-(2-propyl)-1,3-propane diol, 
2-ethyl-2-pentyl-1-(2-propyl)-1,3-propane diol, 
2-ethyl-2-hexyl-1-(2-propyl)-1,3-propane diol, 
2-propyl-2-butyl-1-(2-propyl)-1,3-propane diol, 
2-propyl-2-pentyl-1-(2-propyl)-1,3-propane diol, 
2-propyl-2-hexyl-1-(2-propyl)-1,3-propane diol, 
2-butyl-2-pentyl-1-(2-propyl)-1,3-propane diol, 
2-butyl-2-hexyl-(2-propyl)-1,3-propane diol, 
2-pentyl-2-hexyl-(2-propyl)-1,3-propane diol 
The moiety of the formula 
EQU O--R.sup.3 
may be another phosphite moiety or may be derived from an alcohol of the 
formula 
EQU H--O--R.sup.3 
which includes alcohols of the formula 
##STR9## 
wherein each R.sup.5 is independently selected form the group consisting 
of hydrogen and hydrocarbon radicals, preferably at least two of the 
R.sup.5 groups are alkyl radicals having from one to ten carbon radicals, 
more preferably at least two of the R.sup.5 groups are t-butyl groups, 
preferably the sum of carbon atoms in the R.sup.5 groups is at least 6 and 
more preferably two R.sup.5 groups adjacent the oxygen are each alkyl 
groups. 
The phosphite of the present invention may be diphosphites where R.sup.3 
contains a phosphite moiety. Suitable diphosphites include those of the 
formula 
##STR10## 
wherein R.sup.1 and R.sup.2 for each phosphite moiety are defined above, 
wherein R.sup.6 is a divalent hydrocarbon radical preferably having few, 
more preferably zero hydrogens attached to the beta-carbon. The moiety 
--O--R.sup.6 --O-- may be derived from a diol of the formula 
EQU HO--R.sup.6 --OH 
Suitably R.sup.6 structures include 
##STR11## 
wherein each R.sup.7 is independently selected from alkyl radicals having 
from 1 to 6 carbon atoms, and R.sup.8 is a divalent hydrocarbon radical 
having from 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Suitable 
phosphites include those of the following structures: 
##STR12## 
Preferably each R.sup.1 is methyl. Examples of specific structures 
include: 
##STR13## 
The phosphites are useful for stabilizing polymers from thermal oxidative 
degradation. Suitable polymeric compositions include polyolefins 
(polypropylene, polyethylene, polybutene, poly (2-methyl-pentene), 
polycarbonates, polyesters (PET, PBT, PCTG), polyamides polyurethanes, 
rubber modifiers, graft copolymers (MBS, ABS, MB, ASA) and polystyrenes. 
The present invention also is a stabilized polymer composition which 
includes an effective amount of one or more of the phosphites described 
above. An amount of the phosphites of the invention is considered to be an 
"effective amount" when the polymer composition containing the phosphites 
of the invention shows improved stability in any of its physical or color 
properties in comparison to an analogous polymer composition which does 
not include a phosphite of the invention. In most polymer compositions, 
however, it will be preferred that the phosphites be present in an amount 
equal to about 0.01 to about 2 parts by weight per 100 parts by weight 
resin (phr). Amounts of about 0.01 to about 1 phr are more preferred, 
although most compositions will contain about 0.025 phr or more. The 
polymer composition may be thermoset in nature including unsatured 
polyesters, phenolics, epoxie, urethanes, coating resins and crosslinkable 
latexes. 
The polymer may also be any thermoplastic known in the art, such as 
polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, 
polyimides, polyphenylene ethers, styrenic polymers, polycarbonates, 
acrylic polymers, polyamides, polyacetals, halide containing polymers and 
polyolefin homopolymers and copolymers. Mixtures of different polymers, 
such as polyphenylene ether/styrenic resin blends, polyvinyl chloride/ABS 
or other impact modified polymers, such as methacrylonitrile and 
alphamethylstyrene containing ABS, and polyester/ABS or polycarbonate/ABS 
and polyester plus some other impact modifier may also be used. Such 
polymers are available commercially or may be made by means well known in 
the art. However, the phosphites of the invention are particularly useful 
in thermoplastic polymers, such as polyolefins, polycarbonates, 
polyesters, polyphenylene ethers and styrenic polymers, due to the extreme 
temperatures at which thermoplastic polymers are often processed and/or 
used. 
Polymers of monoolefins and diolefins, for example polypropylene, 
polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or 
polybutadiene, as well as polymers of cycloolefins, for instance of 
cyclopentene or norbornene, polyethylene (which optionally can be 
crosslinked), for example high density polyethylene (HDPE), low density 
polyethylene (LDPE) and linear low density polyethylene (LLDPE) may be 
used. Mixtures of these polymers, for example, mixtures of polypropylene 
with polyisobutylene, polypropylene with polyethylene (for example 
PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for 
example LDPE/HDPE), may also be used. Also useful are copolymers of 
monoolefins and diolefines with each other or with other vinyl monomers, 
such as, for example, ethylene/propylene, LLDPE and its mixtures with 
LDPE, propylene/butene-1, ethylene/hexene, ethylene/ethylpentene, 
ethylene/heptene, ethylene/octene, propylene/ isobutylene, 
ethylene/butane-1, propylene/butadiene, isobutylene, isoprene, 
ethylene/alkyl acrylates, ethylene/alkyl methacrylates, ethylene/vinyl 
acetate (EVA) or ethylene/acrylic acid copolymers (EAA) and their salts 
(ionomers) and terpolymers of ethylene with propylene and a diene, such as 
hexadiene, dicyclopentadiene or ethylidene-norbornene; as well as mixtures 
of such copolymers and their mixtures with polymers mentioned above, for 
example polypropylene/ethylene propylene-copolymers, LDPE/EVA, LDPE/EAA, 
LLDPE/EVA and LLDPE/EAA. 
Thermoplastic polymers may also include styrenic polymers, such as 
polystyrene, poly-(p-methylstyrene), poly-(.alpha.-methylstyrene), 
copolymers of styrene or .alpha.-methylstyrene with dienes or acrylic 
derivatives, such as, for example, styrene/butadiene, 
styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/maleic 
anhydride, styrene/butadiene/ethyl acrylate, 
styrene/acrylonitrile/methylacrylate, mixtures of high impact strength 
from styrene copolymers and another polymer, such as, for example, from a 
polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; 
and block copolymers of styrene, such as, for example, 
styrene/butadiene/styrene, styrene/isoprene/styrene, 
styrene/ethylene/butylene/styrene or styrene/ethylene/propylene styrene. 
Styrenic polymers may additionally or alternatively include graft 
copolymers of styrene or alpha-methylstyrene such as, for example, styrene 
on polybutadiene, styrene on polybutadiene-styrene or 
polybutadiene-acrylonitrile; styrene and acrylonitrile (or 
methacrylonitrile) on polybutadiene and copolymers thereof; styrene and 
maleic anhydride or maleimide on polybutadiene; sytrene, acrylonitrile and 
maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and 
methyl methacrylate on polybutadiene, styrene and alkyl acrylates or 
methacrylates on polybutadiene, styrene and acrylonitrile on 
ethylene/-propylene/diene terpolymers, styrene and acrylonitrile on 
polyacrylates or polymethacrylates, styrene and acrylonitrile on 
acrylate/butadiene copolymers, as well as mixtures of with the styrenic 
copolymers indicated above. 
Nitrile polymers are also useful in the polymer composition of the 
invention. These include homopolymers and copolymers of acrylonitrile and 
its analogs, such as polymethacrylonitrile, polyacrylonitrile, 
acrylonitrile/-butadienepolymers, acrylonitrile/alkyl acrylate polymers, 
acrylonitrile/alkyl methacrylate/butadiene polymers, and various ABS 
compositions as referred to above in regard to styrenics. 
Polymers based on acrylic acids, such as acrylic acid, methacrylic acid, 
methyl methacrylic acid and ethacrylic acid and esters thereof may also be 
used. Such polymers include polymethylmethacrylate, and ABS-type graft 
copolymers wherein all or part of the acrylonitrile-type monomer has been 
replaced by an acrylic acid ester or an acrylic acid amide. Polymers 
including other acrylic-type monomers, such as acrolein, methacrolein, 
acrylamide and methacrylamide may also be used. 
Halogen-containing polymers may also be useful. These include resins such 
as polychloroprene, epichlorohydrin homo-and copolymers, polyvinyl 
chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, 
chlorinated polyethylene, chlorinated polypropylene, florinated 
polyvinylidene, brominated polyethylene, chlorinated rubber, vinyl 
chloride-vinylacetate copolymers, vinyl chloride-ethylene copolymer, vinyl 
chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl 
chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride 
copolymer, vinyl chloride-styrene-maleic anhydride tercopolymer, vinyl 
chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene 
copolymer, vinyl chloride isoprene copolymer, vinyl chloride-chlorinated 
propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate 
tercopolymer, vinyl chloride-acrylic acid ester copolymers, vinyl 
chloride-maleic acid ester copolymers, vinyl chloride-methacrylic acid 
ester copolymers, vinyl chloride-acrylonitrile copolymer and internally 
platicized polyvinyl chloride. 
Other useful thermoplastic polymers include homopolymers and copolymers of 
cyclic ethers, such as polyalkylene glycols, polyethylene oxide, 
polypropylene oxide or copolymers thereof with bis-glycidyl ethers; 
polyacetals, such as polyoxymethylene and those polyoxymethylene which 
contain ethylene oxide as a comonomer; polyacetals modified with 
thermoplastic polyurethanes, acrylates or methacrylonitrile containing 
ABS; polyphenylene oxides and sulfides, and mixtures of polyphenylene 
oxides with polystyrene or polyamides; polycarbonates and 
polyester-carbonates; polysulfones, polyethersulfones and 
polyetherketones; and polyesters which are derived from dicarboxylic acids 
and diols and/or from hydroxycarboxylic acids or the corresponding 
lactones, such as polyethylene terephthalate, polybutylene terephthalate, 
poly-1,4-dimethylol-cyclohexaneterephthalate, 
poly-2(2,2,4(4-hydroxyphenyl)-propane) terephthalate and 
polyhydroxybenzoates as well as block-copolyetheresters derived from 
polyethers having hydroxyl end groups. 
Polyamides and copolyamides which are derived from diamines and 
dicarboxylic acids and/or from aminocarboxylic acids or the corresponding 
lactams, such as polyamide, 4,polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 
and 4/6, polyamide 11, polyamide 12, aromatic polyamides obtained by 
condensation of m-xylene, diamine and adipic acid; polyamides prepared 
from hexamethylene diamine and isophthalic or/and terephthalic acid and 
optionally an elastomer as modifier, for example 
poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene 
isophthalamide may be useful. Further copolymers of the aforementioned 
polyamides with polyolefins, olefin copolymers, ionomers or chemically 
bonded or grafted elastomers; or with polyethers, such as for instance, 
with polyethylene glycol, polypropylene glycol or polytetramethylene 
glycols and polyamides or copolyamides modified with EPDM or ABS may be 
used. 
Polyolefin, polyalkylene terephthalate, polyphenylene ether and styrenic 
resins, and mixtures thereof are more preferred, with polyethylene, 
polypropylene, polyethylene terephthalate, polyphenylene ether 
homopolymers and copolymers, polystyrene, high impact polystyrene, 
polycarbonates and ABS-type graft copolymers and mixtures thereof being 
particularly preferred. 
The resulting stabilized polymer compositions of the invention may 
optionally also contain various conventional additives, such as the 
following: 
1. Antioxidants 
1.1 Alkylated monophenols, for example: 2,6-di-tertbutyl-4-methylphenol, 
2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 
2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 
2,6-dicyclopentyl-4-methylphenol, 2-(alpha-methylcyclohexyl)-4,6 
dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6,-tricyclohexyphenol, 
2,6-di-tert-butyl-4-methoxymethylphenol. 
1.2 Alkylated hydroquinones, for example, 
2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 
2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4octadecyloxyphenol. 
1.3 Hydroxylated thiodiphenyl ethers, 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-(6-tert-butyl-2-methylphenol). 
1.4 Alkylidene-bisphenols, for example, 
2,2'-methylene-bis-(6-tert-butyl-4-methylphenol), 
2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol), 
2,2'-methylene-bis-(4-methyl-6-(alphamethylcyclohexyl)phenol), 
2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 
2,2'-methylene-bis-(6-nonyl-4-methylphenol), 
2,2'-methylene-bis-(6-nonyl-4-methylphenol), 
2,2'-methylene-bis-(6-(alpha-methylbenzyl)-4-nonylphenol), 
2,2'-methylene-bis-(6-(alpha,alpha-dimethylbenzyl)-4-nonyl-phenol). 
2,2'-methylene-bis-(4,6-di-tert-butylphenol), 
2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol), 
4,4'-methylene-bis-(2,6-di-tert-butylphenol), 
4,4'-methylene-bis-(6-tert-butyl-2-methylphenol), 
1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenol)butane. 
2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 
1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 
1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-dodecyl-mercaptobutane, 
ethyleneglycol-bis-(3,3,-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate)-di 
-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene, 
di-(2-(3'-tert-butyl-2'hydroxy-5'methyl-benzyl)-6-tert-butyl-4-methylpheny 
l)terephthalate. 
1.5 Benzyl compounds, for example, 
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6 -trimethylbenzene, 
bis-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl 
3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetate, 
bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol-terephthalate. 
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate. 
1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 
dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, calcium salt of 
monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 
1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate. 
1.6 Acylaminophenols, for example, 4-hydroxy-lauric acid anilide, 
4-hydroxy-stearic acid amilide, 
2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine, 
octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate. 
1.7 Esters of beta-(3,5-di-tert-butyl-4-hydroxyphenol)-propionic acid with 
monohydric or polyhydric alcohols, for example, methanol, 
diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol, 
penta-erythritol, neopentylglycol, tris-hydroxyethylisocyanurate, 
thiodiethyleneglycol, di-hydroxyethyl oxalic acid diamide. 
1.8 Esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid 
with monohydric or polyhydric alcohols, for example, methanol, 
diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol, 
pentaerythritol, neopentylglycol, tris-hydroxyethyl isocyanurate, 
thidiethyleneglycol, dihydroxyethyl oxalic acid diamide. 
1.9 Esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid 
with mono-or polyhydric alcohols, e.g., with methanol, diethylene glycol, 
octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, 
neopentyl glycol, tris(hydroxyethyl) isocyanurate, thiodiethylene glycol, 
N,N-bis(hydroxyethyl) oxalic acid diamide. 
1.10 Amides of beta-(3,5-di-tert-butyl-4-hydroxyphenol)-propionic acid for 
example, 
N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylen-diamine, 
N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, 
N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine. 
2. UV absorbers and light stabilizers. 
2.1 2-(2'-hydroxyphenyl)-benzotriazoles, for example, 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-,4'-octoxy,3',5'-di-tert-amyl-3',5'-bis-(alpha, 
alpha-dimethylbenzyl)-derivatives. 
2.2 2-Hydroxy-benzophenones, for example, the 
4-hydroxy-4-methoxy-,4-octoxy,4-decyloxy-,4-dodecyloxy-,4-benzyloxy,4,2',4 
'-trihydroxy- and 2'hydroxy-4,4'-dimethoxy derivative. 
2.3 Esters of substituted and unsubstituted benzoic acids for example, 
phenyl salicylate, 4-tert-butylphenyl-salicilate, octylphenyl salicylate, 
dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)resorcinol, 
benzoylresorcinol, 
2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoate and 
hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate. 
2.4 Acrylates, for example, alpha-cyano-beta, beta-diphenylacrylic 
acid-ethyl ester or isooctyl ester, alpha-carbomethoxy-cinnamic acid 
methyl ester, alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methyl ester 
or butyl ester, alpha-carbomethoxy-p-methoxy-cinnamic acid methyl ester, 
N-(beta-carbomethoxy-beta-cyano-vinyl)-2-methyl-indoline. 
2.5 Nickel compounds, for example, nickel complexes of 
2,2'-thio-bis(4-(1,1,1,3-tetramethylbutyl)-phenol), such as the 1:1 or 1:2 
complex, optionally with additional ligands such as n-butylamine, 
triethanolamine or N-cyclohexyldiethanolamine, nickel 
dibutyldithiocarbamate, nickel salts of 
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as 
of the methyl, ethyl, or butyl ester, nickel complexes of ketoximes such 
as of 2-hydroxy-4-methyl-penyl undecyl ketoxime, nickel complexes of 
1-phenyl-4-1auroyl-5-hydroxy-pyrazole, optionally with additional ligands. 
2.6 Sterically hindered amines, for example 
bis(2,2,6,6-tetramethylpiperidyl)-sebacate, 
bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacate, 
n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid 
bis(1,2,2,6,6,-pentamethylpiperidyl)ester, condensation product of 
1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid, 
condensation product of 
N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylendiamine and 
4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, 
tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, 
tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetra-carbonic 
acid, 1,1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone). Such 
amines include hydroxylamines derived from hindered amines, such as 
di(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate: 1-hydroxy 
2,2,6,6-tetramethyl-4-benzoxypiperidine; 
1-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di-tert-butyl-4-hydroxy 
hydrocinnamoyloxy)piperdine; and 
N-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-71)-epsiloncaprolactam. 
2.7 Oxalic acid diamides, for examples, 4,4'-dioctyloxy-oxanilide, 
2,2'-di-octyloxy-5',5'-di-tert-butyloxanilide, 
2,2'-di-dodecyloxy-5',5'-di-tert-butyl-oxanilide, 
2-ethoxy-2'-ethyl-oxanilide, N,N'-bis(3-dimethylaminopropyl)-oxalamide, 
2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 
2-ethoxy-2'ethyl-5,4-di-tert-butyloxanilide and mixtures of ortho-and 
para-methoxy-as well as of o- and p-ethoxy-disubstituted oxanilides. 
3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide, 
N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine, 
N,N'-bis-(3,5-di-tert-butyl-4-hydrophenylpropionyl)hydrazine, 
salicyloylamino-1,2,4-triazole, bis-benzyliden-oxalic acid dihydrazide. 
4. Phosphites and phosphonites, for example, triphenyl phosphite, 
diphenylalkyl phosphites, phenyldialkyl phosphites, 
tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, 
distearyl pentaerythritol diphosphite, 
tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol 
diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite 
tristearyl sorbitol triphosphite, and 
tetrakis(2,4-di-tertbutylphenyl)-4,4'-biphenylene diphosphonite. 
5. Peroxide scavengers, for example, esters of betathiodipropionic acid, 
for example the lauryl, stearyl, myristyl or tridecyl esters, 
mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, 
zinc-dibutyldithiocaramate, dioctadecyldisulfide, 
pentaerythritoltetrakis-(beta-dodecylmercapto)-propionate. 
6. Polyamide stabilizers, for example copper salts in combination with 
iodides and/or phosphorus compounds and salts of divalent manganese. 
7. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, 
dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine 
derivatives, amines, polyamides, polyurethanes, alkali metal salts and 
alkaline earth metal salts of higher fatty acids, for example, Ca 
stearate, calcium stearoyl lactate, calcium lactate, Zn stearate, Mg 
stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc 
pyrocatecholate. 
8. Nucleating agents, for example, 4-tert butylbenzoic acid, adipic acid, 
diphenylacetic acid. 
9. Fillers and reinforcing agents, for example, calcium carbonate, 
silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, 
metal oxides and hydroxides, carbon black and graphite. 
10. The present invention may also be used in conjunction with aminoxy 
propanoate derivatives such as methyl-3-(N,N-dibenzylaminoxy)propanoate; 
ethyl-3-(N,N-dibenzylaminoxy)propanonoate; 
1,6-hexamethylene-bis(3-N,N-dibenzylaminoxy)proponoate); 
methyl-(2-(methyl)-3(N,N-dibenzylaminoxy)propanoate); 
octadecyl-3-(N,N-dibenzylaminoxy)propanoic acid; tetrakis 
(N,N-dibenzylaminoxy)ethyl carbonyl oxymethy)methane; 
octadecyl-3-(N,N-diethylaminoxy)propanoate; 
3-(N,N-dibenzylaminoxy)propanoic acid potassium salt; and 
1,6-hexamethylene bis(3-(N-allyl-N-dodecyl aminoxy)propanoate). 
11. Other additives, for example, plasticizers, lubricants, emulsifiers, 
pigments, optical brighteners, flameproofing agents, anti-static agents, 
blowing agents and thiosynergists such as 
dilaurythiodipropionateordistearylthiodipropionate. 
Polymeric particles may be coated with the present phosphites alone or in 
combination with other stabilizers for stabilization of the polymeric 
material. Particles may be spherical in shape and may be made by processes 
such as "Reactor Granule Technology" as disclosed in P. Galli and J. C. 
Halock, The Reactor Granule--A Unique Technology for the Production of a 
New Generation of Polymer Blends, Society of Plastics Engineers, 
Polyolefin III International Conference Feb. 24-27, 1991 and as disclosed 
in Pedrazzeth et al. U.S. Pat. No. 4,708,979 entitled Process for the 
Stabilization of Spherically Polymerized Polyolefins issued Nov. 24, 1987 
both of which are disclosed herein by reference. Particle formation may be 
achieved by supported Ziegler-Natta Catalyst systems. Suitable commercial 
processes are known by the trademarks: Spheripol, Addipol and Spherilene. 
Olefin polymers may be produced by polymerization of olefins in the 
presence of Ziegler-Natta catalysts optionally on supports such as but not 
limited to Mg Cl.sub.2, chronium salts and complexes thereof, optionally 
supported on Silica or other materials. They may also be produced 
utilizing catalysts based on cyclopentadiene complexes of metals typically 
complexes of Ti or Zr. 
Consistent with the invention, the phosphites of the invention may be added 
to the polymer at any time prior to or during fabrication into articles 
and may be combined with the polymer by any of a variety of means known in 
the art, such as by preblending or by being fed directly into fabrication 
equipment. 
The polypropylene compositions may include residual catalyst such as 
Ziegler catalysts which may be carried on a support (i.e. TiCl.sub.3 on 
MgCl.sub.2). Other stabilizers may also be incorporated in the 
compositions. 
EXAMPLES 
The following examples illustrate the thermal oxidative stabilizing ability 
of the phosphites of the present invention in polypropylene. The 
formulation in examples A-B and 1,2 where polypropylene containing 600 
parts per million (ppm) of phosphite, 500 ppm phenolic antioxidant 
(Irganox 1010 available from Ciba-Giegy), 500 ppm calcium stearate. 
Example A was a commercially available phosphite. 
In Examples A and 1-2 the YI value is the yellowness index for the 
polypropylene compositions after the 5th extrusion pass, and the delta YI 
is the change in the yellowness index from the 1st extrusion pass to the 
5th extrusion pass; the MF is the melt flow index at 230.degree. F. after 
the 5th extrusion pass, and the delta MF is the change in the yellowness 
index from one 1st extrusion pass to the 5th extrusion pass. Extrusion of 
the formations is as follows: Equipment: 1" Killion extruder with two 
stage screw (3:1 compression ratio) and a Maddox mixing element at 2:1 
ratio, and Screw RPM at 100, back pressure at 1000 PSI that was 
established on Blend #1 during start-up and purge cycle. The ingredients 
were blended using Turbula Blender for 30 minutes. Liquid Additives were 
weighed into small amount of resin and then blended into approximately 1 
pint of resin using Waring Blender. This blend of additive and resin then 
added to balance of resin and placed into Turbula blender for 30 minutes. 
Temperature profile of extruder: Rear: 200.degree. C. Middle: 240.degree. 
C., Front: 258.degree. C., Die: 260.degree. C. Actual Stock 
Temperature=262.degree. C. HS is hydrolytic stability of the phosphite 
composition in polymer determined by testing at 60.degree. C./75% relative 
humidity in days to loss of 50% of the phosphite; UV is yellowing upon 
exposure to ultraviolet light with "P" indicating that it did not yellow 
and with "F" indicating that it yellowed. Hydrolytic stability requires 
bulk on the x carbon and requires a minimum of B hydrocarbons. Examples A, 
B and C are comparative examples. Examples 1-7 illustrate the present 
invention. 
______________________________________ 
YI/ MF/ 
Ex. Phosphate Delta YI Delta MF HS UV 
______________________________________ 
A I168 5.87/2.91 11.49/5.54 
-- -- 
1 P-1 4.00/2.48 6.0/1.25 64 P 
2 P-2 6.04/2.97 6.0/1.36 54 P 
3 P-3 -- -- 22 F 
4 P-4 -- -- 4 P 
5 P-5 -- -- 15 F 
6 P-3 -- -- 22 F 
7 P-6 -- -- 37 P 
B P-7 -- -- &lt;2 P 
C P-8 -- -- 12 F 
______________________________________ 
Note the improved hydrolytic stability of P-4 over P- and of P-3 over P-8. 
I168 is a phosphite of the formula tri(2,4-di-t-butyl phenyl) phosphite. 
##STR14##