Basic metal salts having improved color and stability and vinyl halide polymers containing same

In accordance with the present invention, it has been found that the color and stability of basic alkali and alkaline earth metal salts prepared from mixtures containing a phenol can be improved by conducting the reaction in the absence of free oxygen and thereafter post-treating the reaction product with at least one compound capable of displacing the hydrogen of the phenolic hydroxyl groups present in the mixture while maintaining oxygen free atmosphere. Generally, the metal salts will be alkaline earth metal salts of phenols such as calcium and barium salts. A preferred example of the compound capable of displacing the hydrogen of the phenolic hydroxyl group is an epoxide such as ethylene oxide and propylene oxide.

BACKGROUND OF THE INVENTION 
This invention relates to a novel method for the preparation of basic metal 
salt 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 lighter colored hydrocarbon-soluble basic alkali and alkaline 
earth metal salts of alkyl phenols and/or monocarboxylic acids where 
phenols are used as promoters. 
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 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 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 neutral and basic 
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. 
A variety of oil-soluble salts of monovalent and polyvalent metals have 
been utilized as stabilizers for vinyl halide polymers. The metals include 
the alkaline earth 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 basic metal 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. 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 cadium-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. 
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, 12 to 30% 
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 dark in color and 
cannot be utilized when light colored vinyl halide polymers are desired. 
When dark colored stabilizers are added to vinyl halide polymer 
formulations, the color is carried over into the finished polymer 
rendering the polymer unsatisfactory when and clear polymers are desired. 
SUMMARY OF THE INVENTION 
In accordance with the present invention, it has been found that the color 
and stability of basic alkali and alkaline earth metal salts prepared from 
mixtures containing a phenol can be improved by conducting the reaction in 
the absence of free oxygen and thereafter post-treating the reaction 
product with at least one compound capable of displacing the hydrogen of 
the phenolic hydroxyl groups present in the mixture while maintaining 
oxygen free atmosphere. Generally, the metal salts will be alkaline earth 
metal salts of phenols such as calcium and barium salts. A preferred 
example of the compound capable of displacing the hydrogen of the phenolic 
hydroxyl group is an epoxide such as ethylene oxide and propylene oxide. 
The invention of this application also relates to the improved metal salts 
prepared in accordance with the process of the invention. Vinyl halide 
polymer compositions comprising a vinyl halide polymer and a stabilizing 
amount of the metal salts of the invention also are described and claimed. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The process of the first present invention for improving the color and 
stability of basic alkali and alkaline earth metal salts prepared from 
mixtures containing a phenol comprises the steps of 
(A) preparing, in the absence of free oxygen, a mixture (A-1) comprising 
(A-1-1) at least one alkali or alkaline earth metal base, and 
(A-1-2) at least one alkyl phenol, the ratio of the equivalents of said 
alkali or alkaline earth metal base to the alkyl phenol being greater than 
1:1, or 
a mixture (A-2) comprising 
(A-2-1) at least one alkali or alkaline earth metal base, 
(A-2-2) at least one phenol, 
(A-2-3) at least one monocarboxylic acid, and 
(A-2-4) optionally at least one aliphatic alcohol, the ratio of equivalents 
of monocarboxylic acid to phenol being at least about 1.1:1, and the ratio 
of equivalents of the metal base to the combination of the other 
components being greater than 1:1, 
(B) treating said mixture with an acidic gas in the absence of free oxygen 
until the titratable basicity (phenolphthalein indicator) of the mixture 
has been substantially reduced, and 
(C) treating the mixture with at least one compound capable of displacing 
the hydrogen of the phenolic hydroxyl groups present in the mixture in the 
absence of free oxygen. 
It is preferred that the entire process involving steps (A), (B) and (C) be 
conducted in the absence of free oxygen since the presence of oxygen or 
oxidizing agents results in more highly colored product. Generally, the 
process is conducted in an atmosphere of nitrogen. 
A second critical feature of the method of the present invention is step 
(C) wherein the basic metal salt which is produced as an intermediate at 
the conclusion of step (B) is treated with a compound capable of 
displacing the hydrogen of any phenolic hydroxyl groups present in the 
mixture. If the phenolic hydroxyl groups are not displaced in accordance 
with the method of the present invention, the product obtained by the 
process is darker in color and, on standing, continues to darken in color. 
When the process of the present invention is followed, the initial product 
is light in color and does not appreciably darken on standing. 
Throughout this specification and claims, the term "basic" as applied to 
the alkali or alkaline earth metal salts is used to refer to metal 
compositions wherein the ratio of total metal contained therein to the 
organic moieties is greater than the 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. In some instances, the degree 
to which excess metal is found in the basic metal salt is described in 
terms of a "metal ratio". Metal ratio as used herein indicates the ratio 
of total of alkali or alkaline earth metal in the oil-soluble composition 
to the number of equivalents of the organic moiety. The basic metal salts 
often have been referred to in the art as "overbased" or "superbased" to 
indicate at the presence of an excess of the basic component. 
The process of the present invention may be used to prepare lighter colored 
basic salts of phenates and carboxylates. When basic alkali or alkaline 
earth metal salts of alkyl phenols are desired, the mixture utilized in 
step (A) comprises 
(A-1-1) at least one alkali or alkaline earth metal base, and 
(A-1-2) at least one alkyl phenol, the ratio of the equivalents of said 
alkali or alkaline earth metal base to the alkyl phenol being greater than 
1:1. 
When the desired basic metal salt is a salt of a monocarboxylic acid, the 
mixture utilized in step (A) of the process comprises 
(A-2-1) at least one alkali or alkaline earth metal base, 
(A-2-2) at least one phenol, 
(A-2-3) at least one monocarboxylic acid, and 
(A-2-4) optionally at least one aliphatic alcohol, the ratio of equivalents 
of monocarboxylic acid to phenol being at least about 1.1:1, and the ratio 
of equivalents of the metal base to the combination of the other 
components being greater than 1:1. 
The mixtures utilized in step (A) of the process of the present invention 
are prepared and maintained in the absence of free oxygen. An atmosphere 
of nitrogen is preferred. 
The alkali or alkaline earth metal bases utilized as component (A-1-1) and 
(A-2-1) may be derived from any of the alkali or alkaline earth metals. 
Metal bases derived from alkaline earth metals are preferred, and of 
these, the calcium and barium bases are particularly preferred. The metal 
bases include the metal oxides and hydroxides, and in some instances, the 
sulfides, hydrosulfides, etc. 
The mixtures which are prepared in step (A) also contain at least one alkyl 
phenol (A-1-2) or phenol (A-2-2). 
The alkyl phenol reactant (A-1-2) 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 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 phenols (A-2-1) which are present in the mixture (A-2) 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; polyisobutene-substituted 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, nonylphenol and diisobutylphenol (i.e., 
tertiary octylphenol) are preferred. 
In addition to the alkali or alkaline earth metal base and the phenol, the 
mixture (A-2) also contains (A-2-3) at least one monocarboxylic acid. 
The monocarboxylic acids may be aliphatic or aromatic monocarboxylic acids 
of 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, 
alpha-nitrolauric 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 mixture (A-2) useful in step (A) in the process of the present 
invention optionally may contain (A-2-4) at least one aliphatic alcohol 
which serves as a promoter in the overall process. 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 amount of the phenol (A-2-2) and optionally the alcohol (A-2-4) 
included in the mixture (A-2) 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. Generally, at 
least about 0.1 equivalent and preferably from about 0.05 to about 10 
equivalents of the phenol (and the alcohol if present) per equivalent of a 
monocarboxylic is employed. Larger amounts, for example, up to about 20 to 
about 25 equivalents of alcohol and/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. 
The amount of basic alkali or alkaline earth metal base utilized in step 
(A-1) for the preparation of basic phenates is an amount which is more 
than one equivalent of the base per equivalent of 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. 
When preparing the mixture (A-2), the amount of phenol (A-2-2) and the 
optional alcohol (A-2-4) included in the mixture is not critical except 
that the ratio of equivalents of monocarboxylic acid to phenol should be 
at least about 1.1:1; that is, the monocarboxylic acid is present in 
excess with respect to the phenol. The ratio of equivalents of the metal 
base of the combination of the other components in mixture (A-2) should be 
greater than 1:1 in order to provide a basic product. More generally, the 
ratio of equivalents will be at least 3:1. 
The second step of the process of the present invention (B) involves 
treating the mixtures (A-1) or (A-2) described above with an acidic gas in 
the absence of free oxygen until the titratable basicity of the mixture 
has been substantially reduced. The titratable basicity is determined 
using a phenolphthalein. Generally, the titratable basicity is reduced to 
a base number below about 10. 
The first two steps of the process of the present invention require no 
unusual operating conditions other the exclusion of free oxygen. The 
ingredients in step (A) are mixed, generally heated and then treated with 
the acidic gas, and the mixture may be heated to a temperature which is 
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 used 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. 
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. 
Procedures for preparing basic alkali and alkaline earth metal salts of 
alkyl phenols involving steps (A) and (B) of the present invention are 
well known in the art, and it is not believed necessary to unduly lengthen 
the specification with additional description of the procedures. The 
procedures known in the art can be utilized so long as the steps are 
conducted in the absence of free oxygen. Examples of patents which 
describe the preparation of 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 preparation of the basic salts of monocarboxylic acids utilizing (A-2) 
and (B) also 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 third step in the process of the present invention involves (C) 
treating the mixture with at least one compound capable of displacing the 
hydrogen of the phenolic hydroxyl groups present in the mixture in the 
absence of free oxygen. Examples of compounds which are capable of 
displacing the hydrogen of the phenolic hydroxyl groups present (as well 
as any alcoholic hydroxyl groups present) include, for example, epoxy 
compounds, phosgene, diazomethane, alkali metal alkoxides, metal 
sulfoxides, carbonates and isocyanates. It has been observed that when the 
phenol-containing products are treated in this manner, improved color and 
color stability is obtained. The amount of such compounds which are 
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 in the mixture, and an excess is 
generally utilized since the compounds can also react with the hydrogen of 
the alcoholic hydroxyl groups present. 
Preferably, the basic compositions obtained in step (B) of the present 
invention are post-treated with at least one epoxide. Although any epoxide 
compound which is capable of reacting with the hydrogen atom of the 
phenolic hydroxyl group can be utilized beneficially, it is generally 
preferred that the epoxide be a low molecular weight epoxide such as 
ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, butyl 
eopxy 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 hydrogens of the 
phenolic hydroxyl group such as the epoxides, and the basic compositions 
containing phenol generally is 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 while excluding free oxygen. 
The following examples illustrate the preparation of the basic alkaline 
earth metal salts in accordance with the method of the present invention. 
Unless otherwise indicated in the following examples and elsewhere in the 
specification and claims, all parts and percentages are by weight, and all 
temperatures are in degrees centigrade.

EXAMPLE 1 
A mixture of 165 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 are 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 to reduce the 
titratable basicity of the mixture is about 8. 
The carbon dioxide feed is then stopped while maintaining the nitrogen 
purge for an additional 30 minutes to dry the mixture. Propylene oxide (73 
parts) is then passed into the mixture over a period of about 30-40 
minutes while maintaining the temperature of the reaction mixture at about 
150.degree. C. The mixture then is filtered hot (about 125.degree. C.) 
with a filter aid, and the filtrate is the desired product characterized 
by a base number of 10 and a barium content of 35%. The ASTM color 
(DD1500) is found to be less than 1.5. 
EXAMPLE 2 
The general procedure of Example 1 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 carbonation, 
the filtrate is adjusted with mineral oil to provide an intermediate 
product containing 20.6% barium and a sulfate ash of 35.0%. This 
intermediate product is then treated with propylene oxide as in Example 1. 
EXAMPLE 3 
In this example, samples are taken of the reaction mixture after increasing 
amounts of propylene oxide have been introduced, and the various samples 
are observed for absorbance and ASTM color on oxidation. 
A mixture of 2112 parts of mineral oil and 580 parts of a commercially 
available mixture of aliphatic alcohols containing an average of from 12 
to 18 carbon atoms is prepared and purged with nitrogen for 30 minutes 
with stirring, and a nitrogen purge is maintained until carbonation 
begins. The mixture is heated to about 95.degree. C. whereupon 4220 parts 
of barium hydroxide monohydrate are added slowly over a period of 5 to 10 
minutes. The mixture then is heated to about 150.degree. C. whereupon 496 
parts of nonylphenol and 908 parts of oleic acid are added slowly over a 
period of 45 minutes. The mixture then is treated with carbon dioxide at a 
rate of about 10 SCFH for 3.5 hours through a titratable basicity of 8. 
The carbon dioxide feed is stopped, the nitrogen purge is resumed, and 
propylene oxide is added in amounts specified in the following table via 
nitrogen sweep with sub-surface feed while maintaining a temperature of 
about 150.degree. C. Samples of the mixture are withdrawn after each 
propylene oxide addition for oxidation testing. At the end of the 
reaction, the mixture is filtered while hot. The final filtered product 
contains 34% barium and has an ASTM color of less than 1.5. 
The observations on the samples taken during the propylene oxide addition 
for oxidation testing are summarized in the following Table I. 
TABLE I 
______________________________________ 
Wt. 
of 
PrO 
Ad- 
ded Absorbance.sup.1 /ASTM Color on Oxidation.sup.2 /min 
(g) 0 10' 20' 30' 60' 90' 120' 
______________________________________ 
0 0.035 0.261 0.464 0.659 1.619 2.186 0.S..sup.3 
&lt;0.5 &lt;1.5 &lt;2.5 &lt;3.0 &lt;4.5 5.0 6.0 
192 0.031 0.139 0.218 0.298 0.578 0.819 0.878 
&lt;0.5 &lt;0.5 &lt;1.5 &lt;2.0 &lt;3.0 3.0 3.0 
57 0.029 0.079 0.117 0.140 0.291 0.434 0.436 
&lt;0.5 &lt;0.5 0.5 4.0 &lt;2.0 &lt;2.0 &lt;2.0 
49 0.034 0.063 0.078 0.085 0.183 0.227 0.259 
&lt;0.5 &lt;0.5 &lt;0.5 &lt;0.5 &lt;1.5 &lt;2.0 &lt;2.0 
32 0.040 0.081 0.086 0.087 0.138 0.175 0.185 
&lt;0.5 &lt;0.5 &lt;0.5 &lt;0.5 &lt;1.0 1.0 &lt;1.5 
______________________________________ 
.sup.1 Measured using spectrometer. Lower numbers mean clearer product, 
light transmitted. 
.sup.2 Heated 400 g. sample to 150.degree. C. (300.degree. F.) and bubble 
oxygen through sample for stated time at 2.0 SCFH. ASTM Test DD1500 on 
scale of 0.5 to 8, 0.5 being lightest color. 
.sup.3 Off scale. 
The basic alkali and alkaline earth metal salts prepared in accordance with 
the process of the present invention are readily adaptable for use as 
stabilizers in plastic formulations, especially vinyl halide polymers and 
copolymers. Because the basic alkali and alkaline earth metal compositions 
of the present invention are clear and generally light in color, they are 
particularly useful for preparing clear 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, etc. 
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, polyvinylbormide, 
polyvinylfluoride, polyvinylidenechloride, chlorinated polyethylene, 
chlorinated polypropylene, brominated polyethylene, rubber hydrochloride, 
vinylchloridevinyl-acetate copolymer, vinylchloride-ethylene copolymer, 
vinylchhloride 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, 
##STR1## 
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. 
The stabilizing action of these compositions is enhanced by the use of 
additional polyvalent metal salts of carboxylic acids. The polyvalent 
metal salts which may optionally be used in addition to the 
above-described basic alkali or alkaline earth metal salts 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, palmitic 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 stabilizing action of the basic metal salts prepared in accordance with 
this invention also can be enhanced by the use of one or more organic 
phosphite. The organic phosphites can be any organic phosphite having one 
or more organic groups attached to phosphorus through oxygen. More 
generally, the organic phosphite 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 pentaerythritol and other neopentyl alcohols. 
The basic alkali and alkaline earth metal salts prepared in accordance with 
the procedure of the present invention may be included in vinyl halide 
polymer compositions in an amount sufficient to provide the desired 
heat-stabilizing properties to the vinyl halide polymer 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. Generally, the basic salts are added in amounts 
to provide from about 0.1 to about 5% and more generally from about 0.1 to 
about 2% of the metal salt based on the weight of the vinyl halide 
polymer. The conventional additional additives may be included in amounts 
normally used in the art. For example, the neutral metal salts such as the 
cadmium carboxylate salts are included in an amount of from about 0.1 to 
about 3% by weight, and the other ingredients mentioned above may be each 
included in amounts of from zero to about 1% or more. 
The utility of the metal salts prepared in accordance with the procedure of 
the present invention is demonstrated by the following example wherein the 
product of Example 1 is utilized as a stabilizer in the following vinyl 
halide formulations. In these examples, all of the ingredients are 
premixed except the resin, and the mixture then is mixed with the GEON 30 
until uniform. The formulation is processed 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. 
______________________________________ 
Ex. A Ex. B 
______________________________________ 
Ingredients (g) 
GEON 30 200 200 
Dioctyl Phthalate 100 100 
Stearic Acid 0.5 0.5 
Prod. of Ex. 1 1.17 1.17 
Cd. octoate 0.84 0.84 
Heat Stability* at 
356.degree. F. (180.degree. C.) 
Initial clear clear 
15 min. clear clear 
30 min. v. sl. v. sl. 
yel. yel. 
60 min. sl. yel. 
v. sl. 
yel. 
______________________________________ 
*Heat stability is run on 0.060" milled sheets of polymer in oven test.