Homogeneous stabilizer compositions for vinyl halide polymers

In accordance with the present invention, it has been found that liquid stabilizer compositions for vinyl halide polymers that are compatible with and form stable mixtures with epoxidized glycerides can be prepared by a process which comprises heating a non-homogeneous mixture comprising (A) at least one epoxidized glyceride, (B) at least one hydrocarbon-soluble, (B-1) basic alkali or alkaline earth metal salt of an alkyl phenol, or (B-2) basic alkali or alkaline earth metal salt of a monocarboxylic acid, and (C) a hydrocarbon diluent, at an elevated temperature until the mixture is homogeneous. Generally, the metal salts are alkaline earth metal salts such as calcium and barium, and the basic alkaline earth metal salt utilized in this system is a salt of an aliphatic monocarboxylic acid prepared in the presence of a phenol promoter. The invention also relates to stabilizer compositions thus prepared and to stabilizer compositions optionally containing (D) substantially neutral polyvalent metal salts of carboxylic acids and/or (E) organic phosphites. Vinyl halide polymer compositions comprising a vinyl halide polymer and a stabilizing amount of the homogeneous stabilizer compositions of the invention also are described and claimed.

BACKGROUND OF THE INVENTION 
This invention relates to a novel method for the preparation of homogeneous 
stabilizer compositions for vinyl halide polymers, the stabilizer 
compositions so prepared, and to vinyl halide polymers stabilized 
therewith. More particularly, the invention relates to a process for 
preparing homogeneous compositions comprising epoxidized glycerides such 
as vegetable oils, and hydrocarbon-soluble basic alkali and alkaline earth 
metal salts of alkyl phenols and/or monocarboxylic acids. 
Many organic polymers, more particularly halogen containing organic 
polymers are conveniently and economically processed into useful articles 
of commerce by methods employing heat to melt or soften the polymer. The 
use of such heat can be and often is detrimental to the polymer, 
especially where the polymer is exposed to high (100.degree. C. to 
200.degree. C.) processing temperatures for any extended period of time. 
It is well known that many organic polymers, including halogen containing 
organic polymers, will undergo color changes and various other physical 
changes upon exposure to high temperatures over a period of time unless 
properly protected. The color change is gradual but visually perceptable 
during short-term exposure to high processing temperatures, but on 
exposure to high processing temperatures the change in color accelerates 
and becomes greater in intensity. Color changes occuring during the first 
several minutes of exposure to high processing temperatures are commonly 
referred to as early color or early discoloration. Avoidance of such early 
color or early discoloration is particularly important where white or 
light colored products are to be produced. It is of course also important 
to prevent or reduce discoloration and deterioration of the organic 
polymer during extended exposure to high processing temperatures as may be 
encountered in some processes or fabricating methods. 
A variety of stabilizer systems have been suggested and used to inhibit or 
prevent this deterioration. These stabilizer systems are for the most part 
presumed to act in such a manner as to neutralize hydrogen halide that is 
generated to prevent further dehydrohalogenation which could result 
because of the presence of free hydrogen halide. Among the stabilizer 
systems that have been suggested and used in the prior art are oil-soluble 
salts of such metals as barium, cadmium, zinc, zirconium, tin, calcium. 
Generally, the above metal salt stabilizers are used in combination with 
one or more organic phosphites. 
In many applications, the stabilizer systems incorporated into vinyl halide 
polymers will contain an auxiliary stabilizer which is an epoxidized 
vegetable oil, an epoxidized fatty acid, or an ester of an epoxidized 
fatty acid such as epoxidized soybean oil, epoxidized tall oil, and butyl 
epoxy stearate. 
In the commercial use of stabilizer systems for vinyl halide polymers, has 
become common practice to prepare mixtures of the various stabilizers 
which facilitate the handling and storage of the stabilizers. For example, 
useful stabilizer systems comprising blends of oil-soluble salts of 
polyvalent metals, organic phosphites, and auxiliary stabilizers such as 
epoxidized soybean oils are often prepared for use as needed. 
A variety of oil-soluble salts of monovalent and polyvalent metals have 
been utilized as stabilizers for vinyl halide polymers. The metals include 
the alkali metals, zinc, calcium, tin, barium, aluminum, strontium, 
zirconium and magnesium. The metal salts may be neutral salts although 
basic or "overbased" metal salts are preferred since these contain larger 
amounts of the metal. In some applications, mixtures of neutral and metal 
basic salts are utilized such as mixtures of neutral cadmium carboxylates 
with overbased barium phenates, carboxylates and/or sulfonates. 
U.S. Pat. No. 4,159,973 describes stabilizer systems for vinyl halide resin 
compositions which comprise mixtures of (a) specified overbased barium 
salt complexes that are compatible with epoxidized vegetable oil, (b) a 
polyvalent metal salt component, (c) at least one organic phosphite, and 
(d) an aromatic or aliphatic hydrocarbon solvent. Examples of the 
polyvalent metal salts include cadmium, zinc, zirconium, tin and calcium 
salts of aromatic as well as aliphatic carboxylic acids. The organic 
phosphites may be secondary or tertiary aryl, alkyl or alkaryl phosphites. 
It is reported that vinyl halide resin compositions containing such 
stabilizer systems are characterized by excellent heat and light 
stability, color and clarity. 
An anti-yellowing additive for stabilizing vinyl chloride polymers is 
described in U.S. Pat. No. 4,252,698. The additive comprises the mixture 
of at least one overbased sulfonate or phenolate compound of lithium, 
sodium, potassium, magnesium, calcium, strontium, barium, zinc, titanium, 
aluminum, zirconium or tin, and a 1,3-di-ketone compound having about 5 to 
about 30 carbon atoms or a metal salt thereof wherein the metal may be any 
one of the metals described above for the overbased sulfonate or phenolate 
compound. 
U.S. Pat. No. 3,194,823 describes barium- and cadmium-containing organic 
complexes useful in stabilizing halogen-bearing polymeric compositions. In 
general, the complexes are prepared from a mixture comprising (a) an 
alcohol, (b) an aliphatic monocarboxylic acid compound, and (c) a mixture 
of barium and cadmium bases optionally in the presence of a phenol. Such 
cadmium- and barium-containing basic complexes can be utilized in vinyl 
halide polymers in combination with other stabilizing agents such as 
epoxidized soybean oil and organic phosphites. 
The polyvalent metal components of the stabilizers which have been utilized 
for vinyl halide polymers usually contain a barium compound which may be a 
salt of a monocarboxylic acid such as octanoic acid, neodecanoic acid, or 
naphthenic acid; a salt of an alkyl phenol such as octyl phenol, nonyl 
phenol, etc.; or an overbased barium salt complex. The use of overbased 
barium salt complexes has increased in recent years because the overbased 
salts contain high amounts of barium such as, for example, 21 to 35% 
barium or higher. 
Overbased barium salt complexes are well known, and various procedures for 
preparing such overbased barium salt complexes from carboxylic acids, 
sulfonic acids and alkyl phenols using an acidic gas such as carbon 
dioxide or sulfur dioxide to reduce the basicity are disclosed in, for 
example, the following U.S. Pat. Nos.: 2,616,904; 2,760,970; 2,767,164; 
2,798,852; 2,802,816; 3,027,325; 3,031,284; 3,342,733; 3,533,975; 
3,773,664; and 3,779,922. 
While many overbased barium salts such as the overbased barium alkyl 
phenate complexes described in some of the above patents are effective 
stabilizers for vinyl halide polymers, they often are incompatible with 
epoxidized soybean oil and other epoxidized vegetable oils. When the 
overbased barium compounds are combined, for example, with conventional 
oil-soluble cadmium and/or zinc carboxylic acid salts and organic 
phosphites, and the resulting stabilizer system is blended with an 
epoxidized vegetable oil, the resulting blend generally becomes cloudy as 
the incompatible components precipitate. Because such blends are not 
homogeneous, they present handling and storage problems. 
U.S. Pat. No. 4,159,973 describes overbased barium salt complexes that are 
compatible with epoxidized vegetable oils. The barium salts are obtained 
by forming a reaction mixture that consists essentially of a basic barium 
compound, an alkyl phenol and an inert organic diluent wherein the mixture 
contains at least 0.75 mole of alkyl phenol per mole of the barium 
compound, and the reaction mixture is maintained at a temperature of at 
least 180.degree. C. while treating it with an acidic gas such as carbon 
dioxide until the product is substantially neutral. If less than 0.75 mole 
of alkyl phenol is included in the mixture, and the mixture is treated 
with carbon dioxide at a temperature below 180.degree. C., the barium 
compound obtained is reported to be incompatible with epoxidized vegetable 
oils. 
U.S. Pat. No. 4,401,779 issued Aug. 30, 1983 to Bae et al describes 
homogeneous liquid stabilizer systems which impart heat and light 
stability to polyvinyl chloride resins. The systems contain as the 
essential and only stabilizers, a liquid barium carbonate-barium alkyl 
phenate and a cadmium salt of a branch chain aliphatic carboxylic acid 
having from about 8 to about 10 carbon atoms, or mixtures thereof in an 
amount of at least which 85% with up to about 15% of one or more cadmium 
salts of aromatic carboxylic acids having from about 7 to about 11 carbon 
atoms and saturated and unsaturated straight chain aliphatic carboxylic 
acids having from about 12 to about 22 carbon atoms. The barium and 
cadmium salts are present in amounts sufficient to form a homogeneous 
liquid. 
SUMMARY OF THE INVENTION 
In accordance with the present invention, it has been found that liquid 
stabilizer compositions for vinyl halide polymers that are compatible with 
and form stable mixtures with epoxidized glycerides can be prepared by a 
process which comprises heating a non-homogeneous mixture comprising (A) 
at least one epoxidized glyceride, (B) at least one hydrocarbon-soluble, 
(B-1) basic alkali or alkaline earth metal salt of an alkyl phenol, or 
(B-2) basic alkali or alkaline earth metal salt of a monocarboxylic acid, 
and (C) a hydrocarbon diluent, at an elevated temperature until the 
mixture is homogeneous. Generally, the metal salts are alkaline earth 
metal salts such as calcium and barium, and the basic alkaline earth metal 
salt utilized in this system is a salt of an aliphatic monocarboxylic acid 
prepared in the presence of a phenol promoter. The invention also relates 
to stabilizer compositions thus prepared and to stabilizer compositions 
optionally containing (D) substantially neutral polyvalent metal salts of 
carboxylic acids and/or (E) organic phosphites. Vinyl halide polymer 
compositions comprising a vinyl halide polymer and a stabilizing amount of 
the homogeneous stabilizer compositions of the invention also are 
described and claimed. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The liquid homogeneous stabilizer compositions of the present invention are 
prepared by heating a non-homogeneous mixture which comprises (A) at least 
one epoxidized glyceride, (B) at least one hydrocarbon-soluble basic 
alkali or alkaline earth metal salt, and (C) a hydrocarbon diluent at an 
elevated temperature until the mixture is homogeneous. Non-homogeneous 
mixtures of such compositions can be rendered homogeneous generally by 
heating the mixture at temperatures within the range of from above ambient 
temperature to about 150.degree. C. or higher for periods of from a few 
minutes to about one or two hours or more. The homogeneous mixture remains 
homogeneous when cooled to ambient temperature, and remains homogeneous 
over an extended period of time. 
It also has been observed that once the above mixtures are rendered 
homogeneous, other standard stabilizers for vinyl halide resins can be 
blended into the homogeneous mixture without destroying the homogenity of 
the mixture. Examples of standard stabilizer compositions which can be 
blended into such mixtures and which will be described in more detail 
hereinafter include (D) substantially neutral metal salts of carboxylic 
acids and (E) organic phosphites. 
The epoxidized glycerides used as component (A) in the mixtures of the 
invention are derived from glycerides having the general formula 
##STR1## 
wherein R.sub.1, R.sub.2 and R.sub.3 are each independently hydroxyl or 
fatty acid groups with the proviso that at least one of R.sub.1, R.sub.2 
and R.sub.3 is a fatty acid group. The fatty acids may contain from about 
12 to about 30 carbon atoms in the chain, and the acids may be unsaturated 
acids containing from zero to 3 double bonds. 
Preferably the epoxidized glycerides are epoxidized triglycerides where 
R.sub.1, R.sub.2 and R.sub.3 are the same or different fatty acid groups. 
The epoxidized triglycerides may be and preferably are epoxidized natural 
oils such as vegetable, animal and marine oils. Specific examples of 
epoxidized oils (triglycerides) which are useful as component (A) include 
epoxidized vegetable oils such as castor oil, coconut oil, corn oil, 
cottonseed oil, linseed oil, olive oil, palm oil, peanut oil, rapeseed 
oil, sesame oil, soybean oil, sunflower oil and tung oil; animal oils such 
as beef tallow and pig fat; and marine oils such as fish oil. Epoxidized 
vegetable oils, especially epoxidized soybean oil, are particularly 
preferred. Epoxidized soybean oil is generally used as a stabilizer for 
vinyl halide polymers. 
The second component (B) of the homogeneous mixtures of the present 
invention may be at least one hydrocarbon-soluble (B-1) basic alkali or 
alkaline earth metal salt of an alkyl phenol. Throughout the 
specification, the term "basic" as applied to the alkali or alkaline earth 
metal salts useful in the mixtures of the present invention is used to 
refer to metal salt compositions wherein the ratio of total metal 
contained therein to the organic moieties is greater than a stoichiometric 
ratio of the neutral metal salt. That is, the number of metal equivalents 
is greater than the number of equivalents of the organic moiety. Such 
compositions often have been referred to in the art as "overbased" or 
"superbased" to indicate an excess of the basic component. 
The basic alkali or alkaline earth metal salts of alkyl phenols useful as 
component (B-1) are known and described in the prior art. Generally, the 
basic metal salts of alkyl phenols can be prepared by the process 
comprising preparing a mixture comprising 
(a) at least one alkyl phenol, and 
(b) more than one equivalent of at least one alkali or alkaline earth metal 
base, per equivalent of said phenol (a), and thereafter treating said 
mixture with an acidic gas until the titratable basicity has been 
substantially reduced. The titratable basicity of such compositions is 
determined utilizing a phenolphthalein indicator. Generally, the mixtures 
are treated with the acidic gas until the titratable basicity is reduced 
to a base number of below about 10. 
The above process for preparing overbased phenates requires no unusual 
operating conditions. The ingredients are mixed, heated and then treated 
with the acidic gas. In some instances, the product mixture obtained from 
this process may contain a small amount of undissolved material which can 
be removed conveniently, for example, by filtration. Generally, the 
reactants are heated prior to treatment with the acidic gas, and the 
mixture may be heated to a temperature sufficient to drive off some of the 
water contained in the mixture. The treatment of the mixture with the 
acidic gas preferably is conducted at elevated temperatures, and the range 
of temperatures required for this step may be any temperature above 
ambient temperature up to about 200.degree. C., and more preferably from a 
temperature of about 75.degree. C. to about 200.degree. C. Higher 
temperatures may be used such as 250.degree. C., but there is no apparent 
advantage in the use of such higher temperatures. Ordinarily, a 
temperature of about 150.degree. C. is satisfactory. 
The alkyl phenol reactant may be derived from phenol itself or from 
naphthol, or from other polynuclear phenolic compounds. It may also be a 
bisphenol such as is obtained from the condensation of an aldehyde with a 
phenol. The alkyl phenols may contain one or more alkyl groups on the 
aromatic nucleus, and it is necessary that the number of carbon atoms in 
the alkyl groups be sufficient to yield oil-soluble overbased metal 
phenates. Thus, the alkyl groups on the alkyl phenol will contain a total 
of at least 6 carbon atoms, and generally will contain up to about 150 
carbon atoms. If there is only one alkyl group on the alkyl phenol, the 
alkyl group will contain at least about 6 carbon atoms, but if there are 
two alkyl groups, the sum of the carbon atoms in the two alkyl groups will 
equal at least about 6. For example, one alkyl group may contain 2 carbon 
atoms and the other alkyl group 4 carbon atoms. Specific examples of alkyl 
groups containing at least 6 carbon atoms include hexyl, isoheptyl, 
diisobutyl, n-decyl, tetrapropyl, octadecyl, polyisobutyl (derived from 
polyisobutene fractions of various molecular weights) dedecyl, etc. 
Specific examples of alkyl phenols which are contemplated for use in the 
preparation of overbased phenates useful in the process of the present 
invention include hexylphenol, heptylphenol, octylphenol, dodecylphenol, 
octadecylphenol, nonylphenol, and higher alkylated phenols; octylnaphthol, 
dodecylnaphthol, and higher alkylated naphthols; a condensation product of 
formaldehyde and two moles of octylphenol, or a condensation product of 
acetone and two moles of heptylphenol, etc. 
The alkylphenol compound useful in the preparation of the overbased 
phenates may contain other groups in addition to the alkyl groups. Thus, 
halogen, nitro, alkoxy, etc. groups may be present. 
The metal bases which are reacted with the alkyl phenols may be alkali or 
alkaline earth metal bases, although alkaline earth metal bases are 
preferred. The basic metal compounds include the metal oxides and 
hydroxides, and in some instances, the sulfides, hydrosulfides, etc. of 
the alkaline earth metal, calcium and barium are preferred, and the most 
preferred is barium. 
By the term "acidic gas" as used in this specification and in the claims is 
meant a gas which upon reaction with water will produce an acid. Thus, 
such gases as sulfur dioxide, sulfur trioxide, carbon dioxide, carbon 
disulfide, hydrogen sulfide, etc. are exemplary of the acidic gases which 
are useful in the process of this invention. Of these acids, sulfur 
dioxide and carbon dioxide are preferred, and the most preferred is carbon 
dioxide. 
As indicated above, the amount of the basic alkali or alkaline earth metal 
base utilized in the preparation of the overbased phenates is an amount 
which is more than one equivalent of the base per equivalent of the 
phenol, and more generally will be an amount sufficient to provide at 
least three equivalents of the metal base per equivalent of alkyl phenol. 
Larger amounts can be utilized to form more basic compounds, and the 
amount of metal base included may be any amount up to that amount which is 
no longer effective to increase the proportion of metal in the product. 
Procedures for preparing basic alkali and alkaline earth metal salts of 
alkyl phenols are well known in the art and is not believed necessary to 
unduly lengthen the specification with additional description of the 
procedures. Examples of patents which describe the preparation of such 
basic metal phenates include, for example, U.S. Pat. Nos. 2,989,463; 
2,968,642; and 2,971,014, the specifications of which are hereby 
incorporated by reference for the disclosures of the preparation of 
overbased metal phenates. 
The hydrocarbon-soluble basic metal salt useful in the process of the 
present invention may be (B-2) a basic alkali or alkaline earth metal salt 
of a monocarboxylic acid. The preparation of such basic salts is known in 
the art and any of the basic alkali or alkaline earth metal salts of 
monocarboxylic acids are useful in the process and product of the present 
invention. Generally, such basic metal salts are obtained by preparing a 
mixture comprising 
(a) at least one monocarboxylic acid, 
(b) more than one equivalent of at least one alkali metal or alkaline earth 
metal base per equivalent of said acid, and 
(c) optionally and preferably, at least one promoter selected from the 
group of aliphatic alcohols, phenols, or mixtures thereof, and thereafter 
treating said mixture with an acidic gas until the titratable basicity of 
the mixture has been substantially reduced. The alkali metal and alkaline 
earth metal bases and the acidic gases described above, also are useful in 
the preparation of the basic monocarboxylic acids of this invention. As 
stated previously, the preferred metal bases are the alkaline earth metal 
bases, and more preferably the calcium and barium metal bases. The 
preferred acidic gases are sulfur dioxide and carbon dioxide with carbon 
dioxide being preferred. 
The general procedure of preparing and basic metal salts of monocarboxylic 
acids is similar to the procedure utilized for preparing the basic 
phenates described above. The reactants are mixed with stirring and 
generally with heating to insure thorough mixing, and where it is 
desirable to remove water, the temperature of the mixture is raised to a 
temperature sufficient to drive off the water such as at a temperature of 
above 100.degree. C. The step of treating the mixture with an acidic gas 
also is as described above and is preferably conducted at elevated 
temperatures such as above 100.degree. C. A particularly convenient method 
for carrying out the process involves the stirring and heating of the 
mixture to insure an intimate mixture of reactants, heating this mixture 
to a temperature above 100.degree. C. to remove some water, and then 
bubbling an acidic gas through this heated mixture until the titratable 
basicity of the mixture has been substantially reduced. 
The monocarboxylic acids which can be converted to basic metal salts which 
are useful in the present invention may be aliphatic or aromatic 
monocarboxylic acids or mixtures thereof. Among the aliphatic 
monocarboxylic acids which can be utilized in the present invention are 
the aliphatic monocarboxylic acids containing an average of at least about 
6 carbon atoms and more generally an average of from about 6 to about 30 
carbon atoms. In most instances the monocarboxylic acid of the aliphatic 
monocarboxylic acid will be at least one substituted or unsubstituted 
aliphatic monocarboxylic acid such as n-hexanoic acid, capric acid, 
caprylic acid, 2-ethylhexanoic acid, undecanoic acid, lauric acid, 
myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, 
linolenic acid, tung oil acids, tall oil acids, ricinoleic acid, 
3,5,5-trimethyl-hexanoic acid, alpha-chlorostearic acid, alphanitrolauric 
acid, omega-amino-pentadecanoic acid, lauroxy-acetic acid, eicosanoic 
acid, mono-lauryl adipate, phenyloleic acid, phenylstearic acid, 
chlorophenylstearic acid, xylylstearic acid, alpha-pyridyloleic acid, 
tetracosanoic acid, behenic acid, stearolic acid, etc. A preference is 
expressed for the higher fatty acids such as lauric, palmitic, oleic, 
linoleic, linolenic, stearic, myristic, palmitic, etc., acids and mixtures 
of fatty acids containing an average of at least about 12 carbon atoms. 
The monocarboxylic acid also may be an aromatic monocarboxylic acid such as 
alkyl aromatic carboxylic acids and hydroxy-substituted aromatic 
carboxylic acids. The alkyl aromatic carboxylic acids may contain one or 
more alkyl groups such as butyl, hexyl, heptyl, octyl, dodecyl, octadecyl, 
etc. Generally, the total number of carbon atoms in the alkyl group(s) is 
at least 6 and will generally range from about 6 to about 150 carbon atoms 
in the alkyl groups. The aromatic carboxylic acids also may contain one or 
more hydroxyl groups attached to the aromatic moiety. Specific examples of 
such aromatic carboxylic acids include benzoic acid, salicyclic acid, 
4-hexylbenzoic acid, etc. 
The preparation of the basic salts of monocarboxylic acids optionally may 
be conducted in the presence of (c) at least one promoter selected from 
the group consisting of aliphatic alcohols, phenols, or mixtures thereof. 
The alcohols which are useful as promoters include any one of the various 
available substituted or unsubstituted aliphatic or cycloaliphatic 
alcohols containing from 1 to about 20 or more carbon atoms. In most 
cases, the alcohol will be unsubstituted, i.e., it will conform to the 
formula ROH, where R is an aliphatic hydrocarbon radical or cycloaliphatic 
hydrocarbon radical containing from 1 to 20 carbon atoms. However, in some 
instances, the alcohol may contain organic and/or inorganic substituents 
such as aromatic groups, homocyclic groups, heterocyclic groups, and 
nitro, ether, ester, sulfide, keto, amino, nitroso, etc., groups. 
Examples of alcohols useful as promoters include methanol, ethanol, 
n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol-1, 
n-pentanol-2, isoamyl alcohol, n-hexanol-1, n-hexanol-2, 
4-methylpentanol-2, n-heptanol, primary isooctanol (prepared for example, 
by the well known Oxo process), 2-ethylhexanol, n-octanol, 
3,5,5-trimethyl-hexanol, cyclohexanol, methyl-cyclohexanol, 
ethylcyclohexanol, benzyl alcohol, beta-phenethyl alcohol, 
2-alpha-pyridyl-ethanol-1, tetrahydrofurfuryl alcohol, 
2-cyclohexyl-ethanol-1, n-decanol, lauryl alcohol, isododecanol (prepared 
for example, by the hydration of triisobutylene), myristyl alcohol, oleyl 
alcohol, n-eicosanl, n-tricosanol, n-triacontanol, 2-phenoxy-ethanol-1, 
2-phenoxyethoxyethanol-1, 6-chloro-n-hexanol-1, 8-nitro-n-octanol-1, 
4-amino-cyclohexanol, ethylene glycol mono-oleate, glyceryl dipalmitate, 
2-n-butoxy-ethanol-1, diethylene glycol mono-ethyl ether, 
2-thiobutoxy-ethanol-1, etc. Of the various available alcohols, a 
preference is expressed for the aliphatic monohydric alcohols. 
Particularly preferred are the alkanols containing from about 12 to about 
18 carbon atoms. In lieu of a single alcohol, mixtures of two or more 
different alcohols may also be used. 
The phenols which are optionally present in the herein-described process as 
promoters include principally substituted and unsubstituted monohydric or 
polyhydric phenols. The substituents may be organic and/or inorganic. 
Examples of such phenols include phenol itself and alkylated and 
cycloalkylated mononuclear or polynuclear phenols containing from one to 
150 or more carbon atoms in the substituent group or groups such as, for 
example, ortho-, meta-, and para-cresols; xylenols; para-ethylphenol; 
ortho, para-diethylphenol; n-propylphenol; para-isopropylphenol; tertiary 
butylphenol; n-amylphenol; para-tertiary amylphenol; 
para-cyclopentylphenol; cyclohexylphenol; methylcyclohexylphenol; 
secondary-hexylphenol; heptylphenol; diisobutylphenol; 
3,5,5-trimethyl-n-hexylphenol; n-decylphenol; cetylphenol; oleylphenol; 
wax-alkylated phenol; polyisobutenesubstituted phenol in which the 
polyisobutene substituent contains from about 20 to about 150 carbon 
atoms, etc; aryl-substituted phenols such as phenylphenol, diphenylphenol, 
and naphthylphenol; polyhydroxy aromatic compounds such as alizarin, 
quinizarin, hydroquinone, catechol, pyrogallol, etc.; monohydroxy 
naphthalenes such as alpha-naphthol and beta-naphthol; polyhydroxy 
naphthalenes such as naphthohydroquinone and naphthoresorcinol; alkylated 
polyhydroxy aromatic compounds such as octylcatechol and 
mono-(triisobutyl) pyrogallol; and substituted phenols such as 
para-nitrophenol, picric acid, ortho-chlorophenol, tertiarybutyl 
chlorophenols, para-nitro ortho-chlorophenol, para-aminophenol, etc. In 
most instances the phenol, if used, will be a mono-alkyl phenol containing 
from about 4 to about 12 carbon atoms in the alkyl group. Thus, 
commercially available mono-alkyl phenols such as para-tertiary 
butylphenol, heptylphenol, and diisobutylphenol (i.e., tertiary 
octylphenol) are preferred. 
The amount of the alcohol or phenol which is included in the mixture as a 
promoter is not critical. The promoters are included in the mixture to 
contribute to the utilization of the acidic gas during treatment of the 
mixture with the acidic gas. The amount of alcohol present in the mixture 
prior to treatment with the acidic gas is not critical. However, at least 
about 0.1 equivalent and preferably from about 0.05 to about 10 
equivalents of an alcohol or phenol per equivalent of a monocarboxylic 
generally is employed. Larger amounts, for example, up to about 20 to 
about 25 equivalents of alcohol or phenol may be used, especially in the 
case of lower molecular weight alcohols and phenols. Water, which may 
optionally also be present in the mixture, may be present as water added 
as such to the mixture, or the water may be present as "wet alcohol", 
"wet" phenol, hydrates of the alkali or alkaline earth metal salts, or 
other type of chemically combined water with the metal salts. 
In addition to the components described above, the reaction mixtures used 
to prepare the basic metal salts ordinarily will contain a diluent. 
Generally, any hydrocarbon diluent can be employed, and the choice of 
diluent is dependent in part on the intended use of the mixture. Most 
generally, the hydrocarbon diluent will be a non-volatile diluent such as 
the various natural and synthetic oils of lubricating viscosity. The 
natural oils include animal oils and vegetable oils (e.g., castor oil, 
lard oil) as well as solvent-refined or acid-refined mineral lubricating 
oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. 
Kerosene can be used. Synthetic oils include hydrocarbon oils and 
halo-substituted hydrocarbon oils such as polymerized and interpolymerized 
olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene 
copolymers, chlorinated polybutylenes, etc.). Other classes of synthetic 
oils include alkylene oxide polymers and interpolymers and derivatives 
thereof; esters of dicarboxylic acids; silicon-based oils; etc. 
It is important that an excess of the alkali metal or alkaline earth metal 
compound be utilized with respect to the amount of alcohol, alkyl phenol 
and/or monocar- boxylic acid included in the reaction mixture. Thus, if 
one mole of a carboxylic acid is used, then more than one mole of an 
alkali metal and more than 0.5 mole of the basic alkaline earth metal 
compound must be utilized. Preferably, a stoichiometric excess of the 
alkali or alkaline earth metal compound should be used. As is known in 
this art, the basicity of the product which results depends upon the 
amount of such excess alkali or alkaline earth metal compound included in 
the mixture, and the degree to which excess metal is found in the product 
may be described in terms of a "metal ratio". Metal ratio as used herein 
indicates the ratio of total alkali or alkaline earth metal in the 
oil-soluble composition to the amount of monocarboxylic acid and phenol 
and/or alcohol used in the process, on an equivalent basis. A composition, 
for example, having 4 equivalents of barium and 1 equivalent of oleic acid 
as a metal ratio of 4. An oil-soluble composition having 3.8 equivalents 
of calcium and 1.9 equivalents of palmitic acid has a metal ratio of 2. As 
much as 15 or more equivalents of the basic alkali or alkaline earth metal 
compound, per equivalent of acid or phenol may be employed with success in 
this process. The preparation of the basic salts of monocarboxylic acids 
is well known and different procedures have been described in the prior 
art such as in U.S. Pat. Nos. 3,194,823 and 3,147,232, the disclosures of 
which are hereby incorporated by reference for their description of such 
procedures. 
The following examples illustrate the preparation of the basic metal salts 
useful in the invention. Unless otherwise indicated in the following 
examples and elsewhere in the specification and claims, all parts and 
percentages are by weight, and temperatures are in degrees centigrade.

EXAMPLE 1 
A mixture of 300 grams of mineral oil, 99 grams (0.76 equivalent) of octyl 
alcohol, 257 grams (3.36 equivalents) of barium oxide, 234 grams (0.81 
equivalent) of oleic acid, and 45 grams (5 equivalents) of water is heated 
with stirring to reflux temperature in about 1 hour. The mixture then is 
heated to a temperature of 135.degree.-145.degree. C., and maintained at 
this temperature for a period of about 0.5 hour. This mixture is treated 
with CO.sub.2 (2 cubic ft. per hour) at 145.degree. C. for a period of 
about 2 hours. The resulting mixture is heated to 190.degree. C. and 
filtered. The filtrate has the following analysis: 
______________________________________ 
Sulfate ash 34.5% 
Metal ratio 2.9 
Neut. No. 0.4 (acidic). 
______________________________________ 
EXAMPLE 2 
A mixture of 897 grams of mineral oil, 190 grams (1.15 equivalents) of 
octyl alcohol, 386 grams (4.88 equivalents) of barium oxide, 347 grams 
(1.22 equivalents) of stearic acid, and 67 grams (7.4 equivalents) of 
water is heated with stirring to reflux temperature in about 1 hour. The 
mixture then is heated to a temperature of 145.degree. C., and maintained 
at this temperature for a period of about 0.5 hour. This mixture is 
treated with CO.sub.2 (2.5 cubic ft. per hour) at 145.degree. C. for a 
period of about 1.5 hours and then heated to 190.degree. C. and filtered. 
The filtrate has the following analysis: 
______________________________________ 
Sulfate ash 25.87% 
Metal ratio 3.1 
Neut. No. 0.3 (acidic). 
______________________________________ 
EXAMPLE 3 
A mixture of 2576 grams of mineral oil, 240 grams (1.85 equivalents) of 
octyl alcohol, 740 grams (20.0 equivalents) of calcium hydroxide, 2304 
grams (8 equivalents) of oleic acid, and 392 grams (12.3 equivalents) of 
methyl alcohol is heated with stirring to a temperature of about 
50.degree. C. in about 0.5 hour. This mixture then is treated with 
CO.sub.2 (3 cubic ft. per hour) at 50.degree.-60.degree. C. for a period 
of about 3.5 hours. The resulting mixture is heated to 150.degree. C. and 
filtered. The filtrate has the following analysis: 
______________________________________ 
Sulfate ash 24.1% 
Metal ratio 2.5 
Neut. No. 2.0 (acidic). 
______________________________________ 
EXAMPLE 4 
A mixture of 932 grams of mineral oil, 100 grams (0.77 equivalent) of octyl 
alcohol, 370 grams (10.0 equivalents) of calcium hydroxide, 287 grams (1.0 
equivalent) of oleic acid, and 150 grams (4.6 equivalents) of methyl 
alcohol is heated with stirring to a temperature of about 55.degree. C. in 
about 0.5 hour. This mixture then is treated with CO.sub.2 (2 cubic ft. 
per hour) at 55.degree. C. for a period of about 6 hours. The resulting 
mixture is heated to 150.degree. C. and filtered. The filtrate has the 
following analysis: 
______________________________________ 
Sulfate ash 30.6% 
Metal ratio 7.5 
Neut. No. 3.0 (basic). 
______________________________________ 
EXAMPLE 5 
A mixture of 1800 grams of mineral oil, 598 grams (4.6 equivalents) of 
octyl alcohol, 952 grams (18.3 equivalents) of strontium oxide, 1376 grams 
(4.88 equivalents) of oleic acid, and 249 grams (27.7 equivalents) of 
water is heated with stirring to the reflux temperature in about 1.5 
hours. The mixture is then heated to a temperature of 145.degree. C., and 
maintained at this temperature for a period of aobut 0.5 hour. This 
mixture is treated with CO.sub.2 (4 cubic ft. per hour) at 145.degree. C. 
for a period of about 1 hour. 
EXAMPLE 6 
A mixture of 2926 parts of mineral oil, 300 parts (1.56 equivalents) of 
heptylphenol and 347 parts (1.64 equivalents) of a mixture of normal 
C.sub.12-18 primary alcohols in heated to 132.degree. C. under nitrogen, 
with stirring. Barium hydroxide monohydrate, 248 parts, is added with 
stirring over one-half hour while water is collected by distillation. When 
water evolution has ceased, the mixture is dried for 15 minutes at 
137.degree. C. There is then added 713 parts (2.6 equivalents) of a 
eutectic mixture of palmitic and stearic acids, followed by 1702 parts 
(total 20.6 equivalents) of barium hydroxide monohydrate, the latter being 
added portionwise over 31/2 hours while water is again removed by 
distillation. The temperature is increased to 150.degree. C. during the 
final portion of barium hydroxide addition. The mixture is then blown with 
carbon dioxide at 150.degree. C. for 21/4 hours and purged with nitrogen 
at 150.degree. C. Finally, a filter aid material is added and the mixture 
is filtered, yielding a 53% solution in mineral oil of the desired basic 
barium salt which contains 37.06% barium sulfate ash. 
EXAMPLE 7 
To a mixture of 142 parts (0.5 equivalent) of stearic acid, 134 parts (0.5 
equivalent) of oleyl alcohol, 115 parts (0.6 equivalent) of heptylphenol 
and 1100 parts of mineral oil is added slowly, at room temperature, 674 
parts (8 equivalents) of barium oxide. An exothermic reaction takes place 
which causes the temperature to rise to 70.degree. C. Water, 101 parts, is 
added gradually, whereupon the temperature rises to 120.degree. C. The 
mixture is held for 4 hours at 130.degree.-140.degree. C. and then heated 
to 160.degree. for one-half hour to remove volatile materials. It is then 
blown with carbon dioxide at 145.degree.-150.degree. C. until it is 
neutral to phenolphthalein. Finally, it is filtered using a filter aid 
material. The filtrate is a 50% solution in mineral oil of the desired 
basic barium salt containing 34.99% barium sulfate ash. 
EXAMPLE 8 
A mixture of 368 parts (1.3 equivalents) of oleic acid, 150 parts (0.8 
equivalent) of heptylphenol, 260 parts (1.3 equivalents) of tridecyl 
alcohol, 1515 parts of mineral oil and 32 parts of water is heated to 
76.degree. C., and 184 parts of barium hydroxide monohydrate is added over 
7 minutes at 76.degree.-92.degree. C. Additional barium hydroxide 
monohydrate, to a total of 982 parts (10.4 equivalents), is added over 
about 2 hours. The mixture is then heated at 145.degree.-157.degree. C. 
and blown with carbon dioxide for 2 hours. After all water has been 
removed, the product is filtered, yielding a 54% solution in mineral oil 
of the desired basic barium salt which has a barium sulfate ash content of 
36.2%. 
EXAMPLE 9 
Following the procedure of Example 8, a basic barium salt is obtained from 
150 parts (0.8 equivalent) of heptylphenol, 368 parts (1.3 equivalents) of 
oleic acid, 982 parts (10.4 equivalents) of barium hydroxide monohydrate, 
370 parts (1.75 equivalents) of a mixture of normal C.sub.12-14 primary 
alcohols, 1405 parts of mineral oil and 32 parts of water. The product 
contains 36.07% barium sulfate ash. 
EXAMPLE 10 
Following the procedure of Example 8, a basic barium salt is prepared from 
150 parts (0.8 equivalent) of heptylphenol, 368 parts (1.3 equivalent) of 
oleic acid, 982 parts (10.4 equivalents) of barium hydroxide monohydrate, 
324 parts (1.3 equivalents) of oleyl alcohol, 1451 parts of mineral oil 
and 32 parts of water. The product, a 56% solution in mineral oil, 
contains 35.65% barium sulfate ash. 
EXAMPLE 11 
Following the procedure of Example 8, a basic barium salt is prepared from 
720 parts (2.6 equivalents) of tall oil acid, 300 parts (1.56 equivalents) 
of heptylphenol, 1900 parts (20.1 equivalents) of barium hydroxide 
monohydrate, 374 parts (1.64 equivalents) of a mixture of normal 
C.sub.12-18 primary alcohols and 65 parts of water. The product, a 53% 
solution in mineral oil of the desired basic salt, contains 37.79% barium 
sulfate ash. 
EXAMPLE 12 
A mixture of 300 parts (1.56 equivalents) of heptylphenol, 347 parts (1.64 
equivalents) of a mixture of normal C.sub.12-18 primary alcohols and 2000 
parts of mineral oil is heated to 100.degree.-105.degree. C., and 1960 
parts (20.7 equivalents) of barium hydroxide monohydrate is added over 18 
minutes. The mixture is heated to 150.degree. C. and water is collected by 
distillation. After 98 parts of water have been collected, 360 parts of 
tall oil acid is added over 20 minutes. Water distillation is continued 
for 21/2 hours, and then an additional 360 parts (total 2.6 equivalents) 
of tall oil acid is added. After an additional one-half hour of heating, 
the mixture is blown with carbon dioxide at 145.degree.-150.degree. C. for 
3 hours. The mixture is purged with nitrogen until substantially all 
volatile matter has been removed and then 1098 parts of mineral oil is 
added and the mixture is filtered, using a filter aid material. The 
filtrate is the desired 51% solution of a basic barium salt containing 
36.6% barium sulfate ash. 
EXAMPLE 13 
A mixture of 225 parts of mineral oil and 100 parts of dodecylphenol is 
prepared, purged with nitrogen and heated to about 90.degree. C. whereupon 
214.6 parts of barium hydroxide monohydrate are added over a period of 
about 1 hour. The mixture then is heated to about 150.degree. C. and 
treated with carbon dioxide while maintaining the temperature at about 
150.degree.-155.degree. C. for about 2 hours while removing water. After 
all of the water has been removed, the material is filtered yielding the 
desired product which is adjusted with additional mineral oil to form an 
oil solution containing 28.5% barium and about 43% mineral oil. 
EXAMPLE 14 
A mixture of 65 parts of commercially available mixture of aliphatic 
alcohols containing 12 to 18 carbon atoms, 141 parts of nonylphenol and 
600 parts of mineral oil is prepared and purged with nitrogen to remove 
any oxygen present in the system. The nitrogen purge is maintained 
throughout the entire process. After a period of about 20 minutes, the 
mixture is heated while stirring to a temperature of from about 90.degree. 
C. to about 98.degree. C. At this temperature, 1200 parts of barium 
hydroxide monohydrate is added incrementally over a 30-minute period and 
the temperature of the mixture is then increased to about 
150.degree.-155.degree. C. while removing any water which is driven off 
during the heating. Oleic acid (258 parts) is then added over a 30-40 
minute period while again removing the water of reaction which comes over. 
After all of the oleic acid is added, the mixture is treated with carbon 
dioxide at a rate of about 2 SCFH for approximately 4 hours while 
monitoring the titratable basicity of the mixture. The base number of the 
final product is about 8. 
EXAMPLE 15 
The general procedure of Example 14 is repeated utilizing 325 parts of the 
alcohol mixture containing from 12 to 18 carbon atoms, 675 parts of a tall 
oil fatty acid, 1870 parts of mineral oil, 1840 parts of barium hydroxide 
monohydrate, and 281 parts of nonylphenol. At the end of the reaction, the 
filtrate is adjusted with mineral oil to provide a product containing 
20.6% barium and a sulfate ash of 35.0%. 
In some instances, it is desirable to post-treat the basic metal salts of 
alkyl phenols (B-1) and the basic metal salts of monocarboxylic acids 
(B-2) prepared utilizing phenols are promoters with at least one compound 
capable of displacing the hydrogen of any phenolic hydroxyl groups 
remaining in the product mixture. It has been observed that when the 
phenol-containing products are treated in this manner, improved color and 
color stability is obtained. A variety of compounds are capable of 
displacing the hydrogen of the phenolic hydroxyl group, and these include 
epoxy compounds, phosgene, diazomethane, metal alkoxides, metal 
sulfoxides, carbonates, isocyanates, etc. The amount of such compounds 
which is reacted with the phenol-containing basic products preferably is 
an amount which is sufficient to react and displace all of the hydrogens 
on the phenolic hydroxyl groups present. 
Preferably, the above-described basic compositions are post-treated with at 
least one epoxide. Although any epoxy compound which is capable of 
reacting with the hydrogen atom of the phenolic hydroxyl group can be 
utilized beneficially, it generally is preferred that the epoxide be a low 
molecular weight epoxide such as ethylene oxide, propylene oxide, butylene 
oxide, epichlorohydrin, butyl epoxy stearate, glycidyl methacrylate, etc. 
Particularly preferred are the lower alkyl epoxides containing 7 carbons 
or less, and especially ethylene and propylene oxides. 
The reaction between the compound capable of displacing hydrogen in the 
phenolic hydroxyl group such as the epoxides, and the basic compositions 
containing phenol is generally carried out at about from ambient 
temperature to about 200.degree. C. The most convenient method is to 
introduce the epoxide gradually into the basic composition which is 
usually dissolved in a suitable non-polar solvent such as mineral oil, 
kerosene, or the like. 
The following example illustrate the post-treatment of the basic 
compositions containing or derived from phenol with a reactive compound 
such as an epoxide. 
EXAMPLE 16 
The basic barium salt obtained in Example 14 is maintained in a nitrogen 
atmosphere and propylene oxide is fed into the composition (about 73 
parts) over a period of about 30-40 minutes while maintaining the 
temperature of the reaction mixture at about 150.degree. C. The mixture is 
then filtered while hot, and the filtrate is the desired product 
characterized by a base number of 10 and a barium content of 35%. 
In addition to the epoxidized glycerides (A) and the hydrocarbon-soluble 
basic metal salts (B), the mixtures which are treated in accordance with 
the process of the present invention also contain (C) a hydrocarbon 
diluent. Such mixtures, even though including a hydrocarbon diluent are 
non-homogeneous mixtures but can be rendered homogeneous by heating at an 
elevated temperature until the mixture becomes homogeneous. 
Generally, any hydrocarbon diluent can be employed, and the choice of 
diluent is dependent in part on the intended use of the mixture. Most 
generally, the hydrocarbon diluent will be a non-volatile diluent such as 
the various natural and synthetic oils of lubricating viscosity. The 
natural oils include animal oils and vegetable oils (e.g., castor oil, 
lard oil) as well as solvent-refined or acid-refined mineral lubricating 
oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. 
Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon 
oils such as polymerized and interpolymerized olefins (e.g., 
polybutylenes, polypropylenes, propylene-isobutylene copolymers, 
chlorinated polybutylenes, etc.). Other classes of synthetic oils include 
alkylene oxide polymers and interpolymers and derivatives thereof; esters 
of dicarboxylic acids; silicon-based oils; etc. In most instances, the 
basic metal salts (B-1) and (B-2) are prepared from mixtures containing 
non-volatile hydrocarbon diluents such as mineral oil, and thus, the 
hydrocarbon diluent (C) in some instances, may be derived exclusively from 
the diluent present in said basic metal salts. In other words, the 
non-homogeneous mixture which is treated in accordance with the present 
invention is prepared by mixing (A) at least one epoxidized triglyceride 
with at least one oil solution of a hydrocarbon-soluble basic metal salt 
(B-1) and/or (B-2). Additional solvent can be added as desired. When the 
basic metal salt (B-1) and/or (B-2) and (C) comprise a hydrocarbon 
solution of the salt, such solutions may contain the metal in various 
concentrations. For example, hydrocarbon solutions of the metal salts 
(B-1) and/or (B-2) can be prepared containing from about 15 to about 45% 
barium. Other solutions can be prepared containing from about 5 to about 
20% of calcium. 
As mentioned previously the process of the present invention comprises 
heating a non-homogeneous mixture of the type described above to an 
elevated temperature until the mixture is homogeneous. Temperatures above 
about ambient temperature and more generally above 40.degree. C. to as 
high as 150.degree. C. or higher, although higher temperatures do not 
appear to be necessary or desirable. Generally, the mixture of components 
(A), (B) and (C) is heated to a temperature of about 80.degree. C. for a 
period of about 0.5 hour. The temperature and time of heating can be 
readily determined by one skilled in the art and for each individual 
mixture. Once the mixture has been rendered homogeneous by heating, the 
mixture may be cooled to ambient temperature and retains the homogeneous 
nature. Moreover, the homogeneity of the mixture is maintained for 
extended periods of time. 
The relative amounts of components (A), (B) and (C) incorporated into the 
mixture can be varied over a wide range and will be dependent upon the 
desired end use for the mixture once it has been rendered homogeneous. 
Generally, the weight ratio of component (A) to component (B) will vary 
from about 1:10 to about 10:1. The amount of hydrocarbon diluent 
(component (C)) present in the mixture will be a minor amount (e.g., up to 
about 20% by weight), and is an amount which results in a non-homogeneous 
mixture. 
The following examples (except those identified as Control examples) 
illustrate the process of the present invention for preparing homogeneous 
mixtures. 
CONTROL-1 
A mixture of 12.3 parts of the product of Example 16 and 8 parts of 
epoxidized soybean oil (Drapex 6.8) is prepared at room temperature with 
stirring. The mixture remains non-homogeneous despite extended stirring, 
and does not become homogeneous when stirring is terminated and the 
mixture is allowed to stand at ambient temperature for an extended period 
of time. 
CONTROL-2 
A mixture of 47.6 parts of the oil solution prepared in Example 16 and 32 
parts of epoxidized soybean oil is prepared at ambient temperature. This 
mixture remains non-homogeneous at ambient temperature even when stirred 
for an extended period of time. 
EXAMPLE A 
A sample of a non-homogeneous mixture obtained in Control-2 in a 4-ounce 
bottle is placed in an oven at a temperature of about 162.degree. C. for 
about 30 minutes. The mixture becomes homogeneous. 
EXAMPLES B-J 
The procedure of Example A is repeated with the following mixtures which 
are initially non-homogeneous but become homogeneous on heating. 
TABLE I 
______________________________________ 
Ex- 
am- Basic Barium Salt 
Epoxidized Oil % Ba in 
ple Source Amount(g) Type Amount(g) 
Product 
______________________________________ 
B Example 13 
30 Soybean 
20 17.07 
C Example 13 
40 Soybean 
10 22.76 
D Example 13 
45 Soybean 
5 25.60 
E Example 13 
47.5 Soybean 
2.5 27.03 
F Example 16 
30 Soybean 
20 20.64 
G Example 16 
40 Soybean 
10 27.52 
H Example 16 
45 Soybean 
5 30.96 
I Example 16 
47.5 Soybean 
2.5 32.68 
J Example 13 
14.4 Soybean 
40 7.53 
______________________________________ 
The liquid homogeneous stabilizer compositions prepared in accordance with 
the process of the present invention may contain in addition to the 
epoxidized glyceride (A) and the hydrocarbon-soluble basic alkali or 
alkaline earth metal salts (B-1) or (B-2) and (C) hydrocarbon diluent, (D) 
at least one neutral polyvalent metal salt of a carboxylic acid. In 
accordance with the procedure of the present invention, after the 
non-homogeneous stabilizer compositions have been rendered homogeneous in 
accordance with the present invention, one or more polyvalent metal salts 
of carboxylic acids can be blended into the homogeneous composition and 
the composition retains its homogeneity. The polyvalent metal salts which 
may optionally be used in addition to the above-described basic alkali or 
alkaline earth metal salts (B-1) and (B-2) are most often neutral metal 
salts of cadmium, zinc, zirconium, tin, calcium, strontium, or mixtures 
thereof, the preferred salts being cadmium salts and mixtures of cadmium 
and zinc salts. 
The optional polyvalent metal salts generally will be salts of aliphatic or 
benzenoid monocarboxylic acids. The useful aliphatic acids are 
straight-chain and branched-chain alkanoic acids having from 2 to about 22 
carbon atoms and preferably from about 6 to about 12 carbon atoms. 
Examples of the preferred aliphatic acids are caproic acid, 
2-ethylhexanoic acid, caprylic, neooctanoic acid, neodecanoic acid, 
pelargonic acid, lauric acid, malmitic acid, myristic acid, stearic acid, 
behenic acid, oleic acid, linoleic acid, etc. Examples of aromatic 
carboxylic acids that can be utilized in the formation of the polyvalent 
metal salts include benzoic acid, ortho-, meta-, and para-toluic acid, 
ortho-, meta-, and para-ethylbenzoic acid, ortho-, meta-, and para-, 
butylbenzoic acid, chlorobenzoic acid, bromobenzoic acid and hydroxy 
benzoic acid. When included in the stabilizer systems of this invention, 
the neutral polyvalent metal salts generally will be present in amounts 
from about 1 to about 20% by weight. 
The homogeneous stabilizer compositions of the present invention also may 
include (E) one or more organic phosphite. The organic phosphite useful in 
the stabilizer compositions of the present invention can be any organic 
phosphite having one or more organic groups attached to phosphorus through 
oxygen. More generally, the organic phosphite component of the stabilizer 
systems of the present invention generally will be secondary or tertiary 
phosphites having 2 or 3 organic groups attached to the phosphorus through 
oxygen, and most often, these groups are monovalent groups. Thus, the 
phosphites may be secondary phosphites such as diaryl phosphites, aryl 
alkyl phosphites and dialkyl phosphites, or tertiary phosphites, such as 
trialkyl phosphites, triaryl phosphites, dialkyl monoaryl phosphites and 
monoalkyl diaryl phosphites. Also useful are cyclic phosphites derived 
from pentaerithitol and other neopentyl polyhydric alcohols. A preferred 
group of phosphites are the trialkyl, triaryl, dialkyl monoaryl, and 
monoalkyl diaryl phosphites in which the alkyl groups are straight-chain 
or branched-chain groups having from about 3 to about 18 carbon atoms and 
preferably from about 4 to about 10 carbon atoms, and the aryl groups are 
phenyl groups or substituted phenyl groups in which the substituents are 
halogen, hydroxyl groups or alkyl groups having from 1 to about 12 carbon 
atoms. Specific examples of useful organic phosphites include: triphenyl 
phosphite, tri-(p-tert butylphenyl) phosphite, tri-(hydroxyphenyl) 
phosphite, diphenyl phosphite, diphenyl dodecyl phosphite, phenyl 
di-2-ethylhexyl phosphite, phenyl didecyl phosphite, di-(nonylphenyl) 
2-chloroethyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, and 
the like. Another preferred group of phosphites are the secondary 
phosphites that contain the aforementioned aryl and/or alkyl groups. These 
include, for example, diphenyl hydrogen phosphite, di(chlorophenyl) 
hydrogen phosphite, octaphenyl octyl hydrogen phosphite, phenyl decyl 
hydrogen phosphite, phenyl octadecyl hydrogen phosphite, di-2-ethylhexyl 
phosphite, and hexyl decyl phosphite. A single phosphite or a mixture of 
two or more of these compounds may be used. 
When the non-homogeneous stabilizer compositions have been rendered 
homogeneous in accordance with the process of the present invention, it is 
also sometimes desirable to add volatile solvents to the stabilizer 
compositions of the present invention as a diluent prior to use as a 
stabilizer in vinyl halide polymers. Examples of solvents which can be 
utilized include the aliphatic, cycloaliphatic and aromatic hydrocarbons, 
the aliphatic, cycloaliphatic and aromatic alcohols, ether alcohols, and 
ether alcohol esters. Kerosene is an often used diluent in polymer 
stabilizer systems. 
It also is desirable in some instances to add additional epoxidized soybean 
oil to the homogeneous compositions once they have been rendered 
homogeneous in accordance with the present invention. It has been observed 
in some instances that attempts to convert non-homogeneous liquids to 
homogeneous liquids containing large amounts of epoxidized triglycerides 
are not successful whereas a preliminary conversion of a mixture 
containing lesser amounts of epoxidized triglyceride and the basic metal 
salts to a homogeneous solution followed by the addition of the remaining 
epoxidized triglyceride results in a mixture containing the desirable 
amount of epoxidized triglyceride, and the mixture retains its 
homogeneity. 
In addition to the afore-mentioned components, the stabilizer compositions 
of the present invention may contain other heat and light stabilizers such 
as organo tin compounds antioxidants, lubricants, peptizing agents and 
other additives that are ordinarily employed in the production of 
stabilizers for vinyl halide polymers. 
The following examples illustrate the stabilizer compositions of the 
present invention containing components in addition to the epoxidized 
triglyceride and the basic alkali or alkaline earth metal salt. The 
following Examples K-M of homogeneous stabilizing compositions are 
obtained by first preparing a homogeneous clear solution of the indicated 
epoxidized triglyceride and basic alkali or alkaline earth metal salt in 
accordance with the method of the invention and thereafter blending the 
other components into the homogeneous mixture. In Examples K, L and M, 
described in Table II, the components are added in the order given in 
Table II at room temperature. 
TABLE II 
______________________________________ 
Example 
Components K.sup.1 L M 
______________________________________ 
Product of Example A 
19.9 19.9 19.9 
Cadmium Octoate.sup.2 
8.4 8.4 8.4 
Triphenyl phosphite (TPP) 
8.0 8.0 8.0 
Kerosene 3.7 3.7 3.7 
Epoxidized Soybean Oil 
-- 8.0 40.0 
Condition of Blend 
initial clear clear clear 
after 2.5 clear clear clear 
months 
______________________________________ 
.sup.1 Numbers are weight in grams. 
.sup.2 Available from Synthetic Products, Inc. under general trade 
designation "SYNPRON 1202". 
Stabilizer compositions containing additional components such as phosphites 
and neutral metal salts can also be prepared from the homogeneous products 
of Examples B-I. The preparation of such stabilizer compositions is 
illustrated in Table III. In Examples N-U, the components are added in the 
order given in Table III at room temperature with stirring. 
TABLE III 
______________________________________ 
Components 
Product of 
Examples 
Example N O P Q R S T U 
______________________________________ 
B 23.98 
C 17.99 
D 15.99 
E 15.14 
F 19.83 
G 14.88 
H 13.22 
I 12.53 
Kerosene -- 5.61 7.61 8.46 3.77 8.72 10.38 
11.07 
Cadmium 8.4 8.4 8.4 8.4 8.4 8.4 8.4 8.4 
octoate 
Triphenyl 
8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 
phosphite 
(TPP) 
Results 
Initial cond. 
clear .fwdarw. 
.fwdarw. 
.fwdarw. 
.fwdarw. 
.fwdarw. 
.fwdarw. 
clear 
overnight 
clear .fwdarw. 
.fwdarw. 
.fwdarw. 
.fwdarw. 
.fwdarw. 
cldy. 
cldy. 
one week clear .fwdarw. 
.fwdarw. 
.fwdarw. 
.fwdarw. 
.fwdarw. 
cldy. 
cldy. 
two months 
clear .fwdarw. 
.fwdarw. 
.fwdarw. 
sl. sl. cldy. 
cldy. 
cldy. 
cldy. 
______________________________________ 
EXAMPLE V 
A homogeneous stabilizer composition is prepared from the composition of 
Example J by adding to the stirred product of Example J, 9.21 grams of 
kerosene, 8.4 grams of cadmium octoate and 8.0 grams of triphenyl 
phosphite in that order. This composition contains a large amount of the 
epoxidized soybean oil which is desired in vinyl halide stabilization, and 
the composition is homogeneous. 
The homogeneous stabilizer compositions of the invention are readily 
adaptable for use as stabilizers in plastic formulations such as vinyl 
halide polymers and copolymers as well as other polymers such as 
polyethylene, polyisobutylene, polystyrene, copolymers of isobutylene with 
isoprene, butadiene, styrene and the like. 
Vinyl halide polymers and other halogen containing resins that can be 
stabilized with the basic alkali and alkaline earth metal salt composition 
of this invention include polyvinylchloride, polyvinylbromide, 
polyvinylfluoride, polyvinylidenechloride, chlorinated polyethylene, 
chlorinated polypropylene, brominated polyethylene, rubber hydrochloride, 
vinylchloride-vinyl-acetate copolymer, vinylchloride-ethylene copolymer, 
vinylchloride propylene copolymer, vinylchloridestyrene copolymer, 
vinylchloride-isobutylene copolymer, vinylchloride-vinylidenechloride 
copolymer, vinylchloride-styrene-acrylonitrile-terpolymer, 
vinylchloride-butadiene copolymer, vinylchloride-isoprene copolymer, 
vinylchloride-chlorinated propylene copolymer, 
vinylchloride-vinylidenechloride-vinylacetate terpolymer, 
vinylchloride-ethyl-acrylate copolymer, vinylchloride-maleate-copolymer, 
vinylchloride-methylmethacrylate copolymer, vinylchloride-acrylonitrile 
copolymer, internally plasticized polyvinylchloride, and blends of the 
above halogen-containing resin and alpha-olefin polymers. The terms 
"polyvinylchloride" and "vinyl chloride polymer" as used herein include 
any polymer formed at least in part of the recurring group, 
##STR2## 
and having a chlorine content of excess of 40%. In this group, the X 
groups can each be either hydrogen or chlorine. In polyvinyl chloride 
homopolymers, each of the X groups is hydrogen. Thus, the term includes 
not only polyvinyl chloride homopolymers but also after-chlorinated 
polyvinyl chlorides as a class, for example, those disclosed in British 
Pat. No. 893,288 and also copolymers of vinyl chloride in a major 
proportion and other copolymerizable monomers in a minor proportion, as 
already mentioned. 
The invention also is applicable to mixtures of polyvinyl chloride in a 
major proportion with a minor proportion of other synthetic resins such as 
chlorinated polyethylene or copolymers of acrylonitrile with butadiene and 
styrene. 
In addition to the homogeneous stabilizer compositions of this invention 
described above, the stabilized vinyl halide polymer compositions may 
contain other additives such as pigments, dies, processing aids, impact 
modifiers, extenders, and lubricants, the amount is ordinarily employed 
for the purposes indicated. 
The vinyl halide polymers stabilized with the compositions of the present 
invention may be prepared by any suitable and convenient procedure. Such 
procedures include dry blending with a conventional mix such as a Henschel 
blender, mixing on a two or three roll heat mill, and tumbling. 
The amount of the stabilizer compositions of the present invention utilized 
in stabilizing polymer compositions, especially vinyl halide polymer 
compositions, is an amount which is sufficient to provide the desired 
stabilizing properties. The amount of the homogeneous compositions of the 
present invention added to vinyl halide polymers also will be dependent 
upon the relative amounts of the various components contained in the 
homogeneous composition, and such amounts can be readily determined by one 
skilled in the art of vinyl halide formulations. In general, vinyl halide 
polymers may be formulated to contain from about 0.1 to about 10 parts by 
weight per 100 parts of vinyl halide polymer, of the stabilizer 
compositions of the present invention, and the stabilizer compositions 
generally will comprise from about 1% to about 20% by weight of the 
neutral polyvalent metal and 1% to about 20% by weight of phosphorus per 
part by weight of the basic metal salt. 
The utility of the homogeneous stabilizer compositions of the present 
invention is demonstrated by the following examples wherein the 
compositions of the invention are utilized as stabilizers in the vinyl 
halide formulation comprising 200 grams of GEON 30, 100 grams of 
dioctylphthalate and 0.5 gram of stearic acid. The stabilizers in Examples 
II-V are premixed and thereafter blended with the GEON 30 mixture until 
uniform. The formulation is process on a two roll mill for 10 minutes; the 
front roll is maintained at about 160.degree. C. and the back roll at 
about 150.degree. C. The vinyl halide formulations prepared in this manner 
are identified in the following Table IV. The initial color of the vinyl 
halide polymers formed in this manner is observed and recorded in Table 
IV. The heat stability of the vinyl halide polymers obtained in Examples 
I-V is observed and is summarized also in Table IV. 
TABLE IV 
______________________________________ 
Comparison of Vinyl Halide Systems 
______________________________________ 
Stabilizer 
Example Source Amount(g) Initial Color 
______________________________________ 
I Prod. of Ex. J 
810 clear 
II Prod. of Ex. 13 
1.44 
Cd Octoate 0.84 
T.P.P. 0.80 
Epox. Soybean 
4.00 clear 
III Prod. of Ex. R 
4.00 
Epox. Soybean 
4.00 clear 
IV Prod. of Ex. 16 
1.20 
Cd Octoate 0.84 
T.P.P. 0.80 
Epox. Soybean 
4.00 clear 
V Barium Octoate 
2.56 
Cd Octoate 0.84 
T.P.P. 0.80 
Epox. Soybean 
4.00 clear 
______________________________________ 
Heat Stability (180.degree. C.)* 
Example 15 min. 30 min. 60 min. 
120 min. 
______________________________________ 
I clear v.sl.yel. sl.yel. 
yel. 
II clear v.sl.yel. sl.yel. 
yel. 
III clear v.sl.yel. sl.yel. 
yel. 
IV clear v.sl.yel. sl.yel. 
yel. 
V clear clear sl.yel. 
yel. 
______________________________________ 
*Heat stability is run on 0.060" milled sheets of polymer in oven test.