Vinyl chloride polymer stabilizer comprising a metal organophosphonate

A stabilizer composition is disclosed that enhances the resistance to deterioration upon heating of vinyl chloride polymers. The stabilizer composition comprises (A) a metal salt of a sulfur--and nitrogen--free monocarboxylic acid or a phenol and (B) a metal P-hydrocarbonphosphonate having at least one to thirty carbon atoms in the hydrocarbon group. Vinyl chloride polymer compositions stabilized with the above disclosed stabilizer composition are also disclosed.

BACKGROUND OF THE INVENTION 
This invention relates to a new stabilizer composition for enhancing the 
resistance to deterioration upon heating of vinyl chloride polymers, and 
to vinyl chloride polymers having enhanced resistance to deterioration in 
initial color, heat stability and clarity as a result of incorporating 
therein a stabilizer composition according to this invention. 
There is a voluminous literature on the stabilization of vinyl chloride 
polymers. Patent disclosures of materials stated to be useful in 
minimizing deterioration of vinyl chloride polymers on heating number well 
over one thousand. Among the more important heat stabilizers in commercial 
use are mild alkalis such as sodium carbonate, disodium phosphate, and 
sodium and potassium salts of partially esterified phosphoric acids; 
carboxylates and phenolates of zinc, cadmium, and the alkaline earth 
metals; inorganic and organic lead salts; organotin carboxylates, as 
disclosed by Quattlebaum in U.S. Pat. No. 2,307,157; organotin mercaptides 
as disclosed by Leistner in U.S. Pat. Nos. 2,641,588 and 2,641,598; 
various metal-free organic compounds such as the polyols, e.g. mannitol, 
sorbitol, glycerol, pentaerythritol, organic phosphites, 1,2-epoxides, 
e.g., soybean oil epoxide, isooctyl epoxy-stearate, and the diglycidyl 
ether of 2,2-bis(p-hydroxyphenyl) propane, and nitrogen compounds, e.g., 
phenylurea, N,N'-diphenylthiourea, and 2-phenylindole. For detailed 
discussion of heat stabilizers for vinyl halide resins, reference may be 
made to the articles, L. I. Nass, in "Encyclopedia of Polymer Science and 
Technology" (N. Bikales, ed.) Vol. 12 pages 737 to 768 (1970); N. L. Perry 
"Barium-Cadmium Stabilization of Polyvinyl Chloride," Rubber Age 85 
449-452 (June, 1959), and by H. Verity-Smith, British Plastics 27 176-179, 
213-217, 307-311 (1954); the brochure by the same author The Development 
of the Organotin Stabilizer (Tin Research Institute, 1959) and the book La 
Stabilisation des Chlorures de Polyvinyle by F. Chevassus (Amphora, Paris, 
1957). 
There have also been disclosures of the effectiveness of certain phosphorus 
compounds having organic groups directly linked to phosphorus in 
stabilizing organic materials subject to various deteriorating influences. 
E. K. Bolton in U.S. Pat. No. 2,230,371 of Feb. 4, 1941 disclosed the 
incorporation in organic substances subject to oxidative decomposition 
catalyzed by copper and its compounds of small amounts of a phosphorus 
compound of the class of organic monophosphonic acids and organic 
dihydroxyphosphines, that is compounds having the organic radical directly 
attached to phosphorus and having two hydrogens replaceable by metal. In a 
direct comparison of an organic monophosphonic acid and its dodecyl ester 
(having only one replaceable hydrogen) in a gasoline oxidation induction 
period test, only the former compound was effective, thus demonstrating 
the critical requirement of two replaceable acidic hydrogen atoms in the 
molecule. 
G. Denison Jr., in U.S. Pat. No. 2,346,155 of Apr. 11, 1944 disclosed a 
hydrocarbon oil containing a combination of stabilizing agents, comprising 
a thioether or seleno ether and an oxide, sulfide, or selenide having 
directly connected to an oxygen, sulfur or selenium atom both a metal in a 
basic form and an acid-forming element such as those of Periodic groups 
IIIA, IV, VB, and VIB. Denison's disclosure encompasses untold thousands 
of compounds in over 150 classe, of which 28 are classes of phoshorus 
compounds among which phosphonic acids and phosphonic acid monoesters are 
mentioned in the form of metal salts. 
C. B. Havens in U.S. Pat. No. 2,959,568 of Nov. 8, 1960 disclosed 
haloethylen polymers stabilized with an inorganic salt of 
phenyl-phosphonic acid. In an example, an 85-15 copolymer of vinylidene 
chloride and vinyl chloride was heated at 178.degree. C. until the 
pressure of evolved hydrohalide gas evidenced thermal degradation. Nothing 
is disclosed about the effect if any on initial color or eventual color 
changes of any of Havens' phenylphosphonates. W. Leistner in U.S. Pat. No. 
2,997,454 of Aug. 22, 1961 disclosed polyvinyl chloride compositions of 
excellent initial color stabilized with a combination of an organic 
triphosphite with a heavy metal fatty acid salt to which there is added a 
phosphorus compound having at least one hydrogen atom of acidic character. 
The phosphorus acids in Leistner's compositions are defined by the formula 
##STR1## 
In this formula, phosphorus has a valence of three or five, the additional 
two valences being indicated by dotted line bonds. Typical phosphorus 
acids coming within this general formula are the following: 
##STR2## 
In the above formulae R.sub.1 and R.sub.2 represent an organic aliphatic, 
aromatic or nonaromatic alicyclic hydrocarbonor heterocyclic radical 
having from one to about thirty carbon atoms. R.sub.1 and R.sub.2 in I, 
II, III(a) and IV may be the same or different. 
R. Harrington, Jr. in U.S. Pat. No. 3,274,014 of Sept. 20, 1966 disclosed 
yarn compositions of synthetic fibers having incorporated a small amount 
of a metal monoalkyl or monoaryl phosphate, metal dialkyl phosphate, metal 
alkyl phosphonate, metal alkyl (alkyl phosphonate) or metal dialkyl 
phosphite that are resistant to ultraviolet light. Examples show among 
others yarns spun from dopes of modified vinylidene chloride-acrylonitrile 
copolymer containing either zinc (ethyl phosphonate) or zinc 
bis(ethyl(ethyl phosphonate)). 
J. Spivack in U.S. Pat. No. 3,310,575 of Mar. 21, 1967 disclosed metal 
derivatives of monobasic and dibasic hindered phenol substituted 
phosphonic acids that have thermal stabilizing properties for polymeric 
substances as well as rendering the polymeric substance more amenable to 
dyeing and reducing the tendency of the polymeric substance to discolor 
upon exposure to light, whether dyed or not. Spivack's phosphonate 
derivatives are characterized by the formula: 
EQU [P].sub.m M.sub.x [G].sub.p 
wherein 
M is a metal having an available valence of from 1 to 4; 
G is an anion having an available valence of from 1 to 3; and 
P is of the formula: 
##STR3## 
and wherein z has a value of from 0 to 6, 
y has a value of from 1 to 4, 
n has a value of from 0 to 1. 
m has a value of from 1 to 3, 
x has a value of from 1 to 2, and 
p has a value of from 0 to 3, 
n,m,p and x being so selected as to satisfy the expression 
##EQU1## 
wherein r is the valence of anion G and has a value of from 1 to 3. 
The group M consists either of a metal in full free valence state such as 
sodium, cadmium, zinc, barium, nickel, aluminum, tin, chromium, cobalt, 
iron, copper, titanium, vanadium, and the like, or of a metal derivative 
in which part but not all of its full free valence state is satisfied by 
alkyl substitution, e.g. dialkltin. Preferably M is a metal in its full 
free valence state, particularly those having a valence of 2 to 4 such as 
cadmium, zinc, barium, nickel, iron, copper, aluminum, tin, chromium, 
titanium, vanadium, and cobalt. Of these, aluminum and the transitional 
metals, particularly nickel, are especially useful. 
The available valence bonds of the metal will be satisfied by one or more 
phosphonate or O-alkyl phosphonate groups and, if needed, by anions, 
organic or inorganic. Thus when n=0, there may be one (m=1) or more (m=2 
or 3) phosphonate groups. Likewise there may be one or more O-alkyl 
phosphonate groups (n=1). In some instances, as in the case of aluminum or 
chrominum, three phosphonate groups combined with two metal atoms (x=2) to 
satisfy the valence requirements. In the case of mixed salts, one, two or 
three monovalent anions will make up the valence requirements. In all 
instances, the compounds will contain at least one phosphonate group or at 
least one O-alkyl phosphonate group and the values of n,m,p and x is such 
that the following expression is satisfied: 
##EQU2## 
wherein r is the valence of anion G and has a value of from 1 to 3. 
The anion G may be organic or inorganic. Illustrative of such organic 
anions are carboxylate, such as those derived from carboxylic acids 
containing from 1 to 30 carbon atoms, preferably 2 to 18 carbon atoms, 
e.g. acetate, laurate, stearate, benzoate, malonate, maleate, succinate, 
and the like; phenates and alkyl substituted phenates; alkyl- and 
aryl-sulfates and -sulfonates; alkyl- and arylphosphates and 
-phosphonates; and inorganic anions such as chloride, bromide, iodide, 
fluoride, nitrate, cyanide, cyanate, thiocyanate, sulfate, and the like. 
A. DiBattista in U.S. Pat. No. 3,824,192 disclosed as part of a 
multicomponent stabilizer system containing a phenolic antioxidant, a 
sulfur compound synergist, an ultraviolet light absorber, and a benzoate 
type co-light stabilizer, an organophosphorometal compound that is either 
Spivack's above hindered phenol substituted metal phosphonate derivative 
or a metal and metal complex salt of a hindered phenolic alkylphosphinic 
acid represented by the formula 
##STR4## 
wherein M is a metal or metal complex cation, this cation having an 
available valence of from 1 to 4; 
z has a value of from 0 to 6; 
v has a value of from 1 to 4; and 
y has a value of from 1 to 4, the value of v being the same as the 
available valence of M. 
Disclosures are also acknowledged of stabilizer compositions including 
metal derivatives of organic phosphorus compounds having no direct carbon 
to phosphorus linkage. P. Klemchuk in U.S. Pat. No. 3,219,605 of Nov. 23, 
1965 disclosed that cadmium, barium, calcium, or zinc salts of monoalkyl 
phosphites are remarkably effective light stabilizers for polyvinyl 
chloride compositions, alone or in combination with other light and/or 
thermal stabilizers. The metal salts are defined by the formula 
##STR5## 
wherein R is an alkyl radical, e.g. alkyl having from 1 to 30 carbon 
atoms, preferably having from 1 to 12 carbon atoms, and 
M is a divalent metal which may be cadmium, barium, calcium or zinc. 
Farbwerke Hoeschst in French Pat. No. 1,412,321 of Aug. 16, 1965 disclosed 
the stabilization against light of polyvinyl chloride with 0.1 to 5% by 
weight of nickel organic phosphites containing only nickel, phosphorus, 
carbon, hydrogen and oxygen, along with barium-cadmium soaps, organic 
phosphite, epoxy compounds, and optionally ultraviolet absorbers. 
T. Kamijo in U.S. Pat. No. 3,312,658 of Apr. 4, 1967 disclosed a stabilizer 
combination of alkyl-substituted phenolic antioxidant with a synergistic 
agent which is a nickel salt of a monoester or diester of phosphoric acid, 
represented by one or both of the formulas: 
##STR6## 
where the R radicals are selected from the group consisting of alkyl, 
aryl, alkaryl and cycloalkyl radicals. 
SUMMARY OF THE INVENTION 
In accordance with this invention, a stabilizer composition capable of 
enhancing the resistance to deterioration of a vinyl chloride polymer in 
initial color, clarity, and heat stability upon heating at 175.degree. C. 
comprises (A) at least one metal salt of a nitrogen- and sulfur-free 
monocarboxylic acid having 6 to 24 carbon atoms or a phenol having 6 to 30 
carbon atoms, and (B) at least one metal P-hydrocarbonphosphonate having 
directly linked to phosphorus one aromatic, aliphatic, or cycloaliphatic 
hydrocarbon group having 1 to 30 carbon atoms, and three oxygen atoms of 
which at least one and not more than two are linked to metal. For each 100 
parts of vinyl chloride polymer being stabilized, the quantity of 
stabilizer composition used suitably provides 0.01 to 5 parts by weight of 
the metal carboxylic acid salt and 0.01 to 5 parts of the metal 
P-hydrocarbonphosphonate. The ratio of metal carboxylic acid salt to metal 
P-hydrocarbonphosphonate in the stabilizer composition is preferably 
within the range from 5:1 to 1:5. 
The metal P-hydrocarbonphosphonate can be represented by the formula: 
##STR7## 
in which R is an aromatic group having 6 to 30 carbon atoms, an aliphatic 
group having 1 to 30 carbon atoms, or a cycloaliphatic group having 5 to 
30 carbon atoms, M is a metal having a valence of m, R' is a group R or a 
metal equivalent unit M.sub.1/m and m is an integer from 1 to 4. M can be 
a metal of Group I of the Periodic Table having a atomic weight less than 
50, such as potassium, sodium, lithium; a metal of Group II having an 
atomic weight between 20 and 150, such as barium, cadmium, strontium, 
zinc, calcium, and magnesium; a metal of Group IV having an atomic weight 
between 90 and 220, such as zirconium, tin, and lead; and antimony, and 
tin substituted with two alkyl groups having from 1 to 12 carbon atoms, 
and nickel. 
The metal in the metal salt of a carboxylic acid is selected from among the 
metals M and can be the same or different from the metal in the metal 
P-hydrocarbonphosphonate. 
DESCRIPTION OF PREFERRED EMBODIMENTS 
The metal salt component of the stabilizer component is preferably a salt 
of a bivalent metal, such as barium, cadmium, nickel, lead, calcium, 
magnesium, strontium, stannous tin, and zinc. Four-valent tin with two of 
the four valences linked through carbon to alkyl groups, i.e. dialkyltin 
salts such as dimethyltin, di-n-butyltin, di-isobutyltin, 
di-2-ethylhexyltin and di-n-octyltin carboxylates and substituted 
phenolates, are also among the preferred metal salts in the stabilizer 
composition according to this invention. In the salt, the acid may be any 
mono-carboxylic acid free of nitrogen and sulfur having from six to 
twenty-four carbon atoms. The aliphatic, aromatic, alicyclic and 
oxygen-containing heterocyclic organic acids are operable as a class. By 
the term "aliphatic acid" is meant any open chain carboxylic acid, 
substituted, if desired, with non-reactive groups, such as halogen, and 
hydroxyl. By the term "alicyclic" it will be understood that there is 
intended any cyclic acid in which the ring is non-aromatic and composed 
solely of carbon atoms, and such acids may if desired have inert, 
non-reactive substituents such as halogen, hydroxyl, alkyl radicals, 
alkenyl radicals and other carbocyclic ring structures condensed 
therewith. The oxygen containing heterocyclic compounds can be aromatic or 
non aromatic and can include oxygen and carbon in the ring structure, such 
as alkyl substituted furoic acid. The aromatic acids likewise can have 
non-reactive ring substituents such as halogen, alkyl and alkenyl groups, 
and other saturated or aromatic rings condensed therewith. 
As exemplary of the acids which can be used in the form of their metal 
salts there can be mentioned the following: hexoic acid, 2-ethylhexoic 
acid, sorbic acid, n-octoic acid, isooctoic acid, 3,5,5-trimethyl hexoic 
acid, pelargonic acid, capric acid, neodecanoic acid, undecylenic acid, 
lauric acid, myristic acid, isodecanoic acid, palmitic acid, isostearic 
acid, stearic acid, oleic acid, ricinoleic acid, erucic acid, behenic 
acid, chlorocaproic acid, 12-hydroxy stearic acid, 12-ketostearic acid, 
phenyl stearic acid, benzoic acid, phenylacetic acid, p-t-butylbenzoic 
acid, ethylbenzoic acid, isopropylbenzoic acid, bromobenzoic acid, 
salicylic acid, naphthoic acid, 1-naphthaleneacetic acid, orthobenzoyl 
benzoic acid, 5-t-octylsalicyclic acid, naphthenic acids derived from 
petroleum, abietic acid, dihydroabietic acid, hexahydrobenzoic acid, and 
methyl furoic acid, as well as partially esterified dibasic acids such as 
monobutyl phthalate, isooctyl maleate, ethylene glycol maleate, and 
2-ethoxy ethylmaleate. 
The water-insoluble salts are preferred, because they are not leached out 
when the plastic is in contact with water. Where these salts are not 
known, they are made by the usual types of reaction, such as by mixing the 
acid, acid chloride or anhydride with the corresponding oxide or hydroxide 
of the metal in a liquid solvent, and heating, if necessary, until salt 
formation is complete. 
In combination with the above metal salts of organic acids, or in lieu 
thereof, a metal salt of an optionally hydrocarbonsubstituted phenol can 
be used. The hydrocarbon substituents contain from one to twenty-four 
carbon atoms each. The metal can be an alkali metal or alkaline earth 
metal such as sodium, potassium, lithium, calcium, strontium, magnesium, 
and barium. Among such polyvalent metal phenolates there can be mentioned 
the magnesium, barium, calcium, strontium, tin and zinc salts of phenol, 
ethylphenol, cresol, xylenol, butyl phenol, isoamyl phenol, isooctyl 
phenol, 2-ethylhexyl phenol, t-nonylphenol, n-decyl phenol, t-dodecyl 
phenol, t-octyl phenol, isohexyl phenol, octadecyl phenol, diisobutyl 
phenol, methyl propyl phenol, diamyl phenol, methyl isohexyl phenol, 
methyl t-octyl phenol, di-t-nonyl phenol, ortho or para phenyl phenol. The 
metal phenolate should be compatible with the halogen-containing resin. 
Mixtures of salts of various metals can be used, and many such mixtures are 
known to give enhanced effects, such as mixed zinc and tin salts with the 
alkaline earth metal salts, e.g., barium and zinc stearates, as in U.S. 
Pat. No. 2,446,976. 
In the metal P-hydrocarbon phosphonate according to this invention, 
aromatic R groups include phenyl and preferably groups having 7 or more 
carbon atoms such as 1-naphthyl, 2-naphthyl, tolyl, xylyl, ethylphenyl, 
butylphenyl, t-butylphenyl, octylphenyl, isooctylphenyl, nonylphenyl, 
2,4-di-t-butylphenyl, p-dodecylphenyl, didodecylphenyl, cyclohexylphenyl, 
dicyclohexylphenyl, benzyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 
7-phenylheptyl, p-ethoxybenzyl, 2,4-dichlorobenzyl, p-pentadecylbenzyl, 
and trimethylbenzyl. 
Aliphatic R groups include methyl, ethyl, propyl, isopropyl, butyl, 
isobutyl, t-butyl, s-butyl, amyl, neopentyl, isoamyl, hexyl, decyl, 
isodecyl, lauryl, tridecyl, C.sub.12 -.sub.15 mixed alkyl, stearyl, 
eicosyl, docosyl, triacontanyl, allyl, methallyl, oleyl, 2-hydroxyethyl, 
12-hydroxyoctadecyl, and ether substituted groups such as 2-methoxyethyl, 
2-ethoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2-isobutoxyethyl, 
2-hexyloxyethyl, 2-cyclohexyloxyethyl, 2-phenoxyethyl, 
2(2'-methoxyethoxy)ethyl, 2(2'-ethoxyethoxy)ethyl, 
2(2'-isopropoxyethoxy)ethyl, 2(2'-butoxyethoxy)ethyl, 
2(2'-butoxyethoxy)ethyl, 2(2'-isobutoxyethoxy)ethyl, and residue of 
triethylene glycol monoethylether, -monobutylether, or residue of 
glycerin-1,2-dimethyl ether, -1,3-dimethylether, -1,3-diethylether, 
-1-ethyl-2-propylether, or nonylphenoxypolyethoxyethyl, and 
lauroxypolyethoxyethyl. 
Cycloaliphatic groups include cyclopentyl, cyclohexyl, methylcyclopentyl, 
dimethylcycobutyl, 4-methylcyclohexyl, 4-t-butyl-cyclohexyl, cyclooctyl, 
cyclododecyl, 1,2,3,4-tetrahydro-2-naphthyl, decahydro-1-naphthyl, 
hydrodicyclopentadienyl, cholesteryl, and dehydroabietyl. 
When the metal P-hydrocarbonphosphonate is of a one-valent metal, such as 
potassium, and R' is an R group, such as butyl, the phosphonate is an 
ester-salt having one metal atom per P-hydrocarbonphosphonate group. Such 
a compound, for which m=1, can be represented by the formula 
##STR8## 
and exemplified by potassium butyl P-butanephosphonate in which R and R' 
are butyl and M is potassium. When R' is also a one-valent metal, the 
phosphonate is a salt having two metal atoms per P-hydrocarbonphosphonate 
group, exemplified by dipotassium butanephosphonate in which R is butyl 
and both R' and M are potassium. 
When the metal P-hydrocarbonphosphonate is of a two-valent metal, such as 
magnesium, and R' is an R group, such as butyl, the phosphonate is an 
ester salt having usually two P-hydrocarbonphosphonate groups per metal 
atom. Such a compound, for which m=2, can be represented by the formula 
##STR9## 
or more fully 
##STR10## 
and exemplified by magnesium di(butyl P-butanephosphonate). Two-valent 
metals having a strong tendency to form basic salts, such as lead and 
dialkyltin, also furnish ester salts having two P-hydrocarbonphosphonate 
groups for two or more metal atoms. 
To include such basic salts, the preceding formula can be written as 
##STR11## 
in which a is zero or an integer from 1 to about 4 for metals such as lead 
and dialkyltin. 
When the metal P-hydrocarbonphosphonate is of a two-valent metal and R' is 
a metal equivalent, the phosphonate is a salt having a 1:1 ratio of 
P-hydrocarbonphosphonate groups to metal atoms. Such a compound, for which 
m=2, can be represented by the formula 
##STR12## 
as an algebraic equivalent of 
##STR13## 
as well as by an 8-membered "cyclic dimer" or a 12-membered "cyclic 
trimer" or a "linear polymer" formula, and exemplified by magnesium 
butanephosphonate (1:1), in which R is butyl and M is magnesium. 
When the metal P-hydrocarbonphosphonate is of a three-valent metal, such as 
antimony, and R' is an R group, such as butyl, the phosphonate is an 
ester-salt having three P-hydrocarbonphosphonate groups per metal atom. 
Such a compound, for which m=3, can be represented by the formula 
##STR14## 
or more fully 
##STR15## 
and exemplified by antimony tri(butyl P-butanephosphonate). When the metal 
P-hydrocarbonphosphonate is of a three-valent metal and R' is a metal 
equivalent, the phosphonate is a salt having a 3:2 ratio of 
P-hydrocarbonphosphonate groups to metal atoms. Such a compound, for which 
m=3, can be represented by the formula 
##STR16## 
or more fully 
##STR17## 
both algebraic equivalents of 
##STR18## 
and exemplified by antimony butanephosphonate (2:3). 
When the metal P-hydrocarbonphosphonate is of a four-valent metal, such as 
zirconium, and R' is an R group, such as butyl, the phosphonate is an 
ester salt having four P-hydrocarbonphosphonate groups per metal atom or, 
in the case of basic zirconium salts, four P-hydrocarbonphosphonate groups 
for two or more zirconium atoms. Such a compound, for which m=4, can be 
represented by the formula 
##STR19## 
or more fully 
##STR20## 
in which b is zero or an integer from 1 to about 4 in the case of basic 
zirconium salts, and exemplified by zirconium tetra(butyl 
P-butanephosphonate) in which R and R' are butyl, M is zirconium and b is 
zero, and zirconyl di(butyl P-butanephosphonate) in which R and R' are 
butyl, M is zirconium, and b is one. 
When the metal P-hydrocarbonphosphonate is of a four-valent metal, such as 
zirconium, and R' is a metal equivalent, the phosphonate is a salt having 
two P-hydrocarbonphosphonate groups per metal atom or, in the case of 
basic zirconium salts, two P-hydrocarbonphosphonate groups for two or more 
zirconium atoms. Such a compound can be represented by the formula 
##STR21## 
or more fully by 
##STR22## 
in which b is zero or an integer from 1 to about 4 in the case of basic 
zirconium salts, and exemplified by zirconium butanephosphonate (1:2) in 
which b is zero and by zirconyl butanephosphonate (1:1) in which b is one. 
Several methods are available for preparing the metal 
P-hydrocarbonphosphonates according to this invention, for example the 
reaction of a hydrocarbonphosphonic acid or hydrocarbonphosphonic acid 
monoester with a metal oxide or hydroxide (reactions 1a and 1b below), or 
the reaction of alkyl metal hydrocarbonphosphonate with a metal halide or 
metal carboxylate (reactions 2a and 2b below), or by heating a 
hydrocarbonphosphonic acid diester with a metal carboxylate (reaction 3 
below). The latter reaction produces as a by-product a carboxylic acid 
ester that need not be removed and can be left to remain as a solvent for 
the desired product to assist in its use according to this invention. (In 
the reaction equations below R and R' indicate hydrocarbon groups). 
##STR23## 
Metal P-hydrocarbonphosphonates used according to this invention can also 
be prepared by a reaction introducing the P-hydrocarbon group into an 
organic phosphorous acid ester starting material, such as by reacting a 
phosphorous acid monoester dialkali metal salt with a metal halide 
(reaction 4 below).

The following Synthesis Examples describe the preparation of metal 
P-hydrocarbonphosphonate salts according to this invention. 
SYNTHESIS EXAMPLE--1 
Barium Tridecanephosphonate (1:1) 
##STR25## 
Tridecylphosphonic acid disodium salt 123 g (0.4 mole), distilled water 500 
ml and ethanol 30 ml were charged into a reaction flask and dissolved by 
stirring at room temperature. To this solution, 20% barium chloride aq. 
solution 416 g (0.4 mole) was added and allowed to react for one hour at 
room temperature. The compound precipitated was filtered off, repeatedly 
washed with water until free of sodium chloride and dried to obtain 154 g 
of white powder. 
Yield: 96% of theoretical. Ba%: 34.21 (Calculated 34.34); P%: 7.68 
(calculated 7.77) 
SYNTHESIS EXAMPLE--2 
Zinc octadecanephosphonate (1:1) 
##STR26## 
Stearylphosphonic acid disodium salt 189 g (0.5 mole), distilled water 500 
ml and ethanol 30 ml were charged to a reaction flask and dissolved by 
stirring at room temperature. To this was added 50% zinc chloride aq. 
solution 136 g (0.5 mole), and allowed to react for one hour at room 
temperature. The compound precipitated was filtered off, repeatedly washed 
with water until free of sodium chloride and, dried to obtain 193 g of a 
white powder. 
Yield: 97% of theoretical. Zn%: 16.25 (calculated 16.37); P%: 7.73 
(calculated 7.81) 
SYNTHESIS EXAMPLE--3 
Barium di(tridecyl P-tridecanephosphonate) 
##STR27## 
Tridecylphosphonic acid monotridecyl ester, 178 g (0.4 mole), barium 
hydroxide octahydrate 63 g (0.2 mole), distilled water 500 ml and ethanol 
30 ml were charged into a reaction flask and reacted for two hours, at 
50.degree. C. while stirring. The compound precipitated was filtered off, 
and dried to obtain 199 g of white powder. 
Yield: 97% of theoretical. Ba%: 13.15 (calculated 13.33); P%: 5.98 
(calculated 6.04) 
SYNTHESIS EXAMPLE--4 
Strontium (di(butyl P-phenylmethanephosphonate) 
##STR28## 
Benzylphosphonic acid dibutyl ester 227 g (0.8 mole) and 2-ethylhexoic acid 
strontium salt 150 g (0.4 mole) are charged in a reaction flask, and 
reacted for 5 hours at 150.degree. C. while stirring, to obtain a light 
yellow clear liquid. 
Addition of a large volume of acetone into the solution, gives a 
precipitate which is collected, washed with acetone, and dried to obtain 
the product as a white powder weighing 213 g. 
Yield: 98% of theoretical. Sr%: 16.16 (calculated 16.24); P%: 11.35 
(calculated 11.44) 
The stabilizer composition of this invention is applicable to any vinyl 
chloride polymer. The term "vinyl chloride polymer" as used herein is 
inclusive of any polymer formed at least in part of the recurring group, 
##STR29## 
and having a chlorine content in 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, such 
as copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl 
chloride with maleic or fumaric acids or esters, and copolymers of vinyl 
chloride with acrylonitrile, 1-butene, propylene, ethylene, 1-hexene, or 
vinyl n-dodecyl ether. 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 invention is of application to the stabilization of rigid polyvinyl 
chloride resin compositions, that is, resin compositions which are 
formulated to withstand high processing temperatures, of the order of 
190.degree. C. and higher, and of plasticized polyvinyl chloride resin 
compositions of conventional formulation where resistance to heat 
distortion is not a requisite. The respective definitions of rigid and 
plasticized resins are as follows. The rigid resins are those resins to 
which plasticizers are not added, and which are generally worked at about 
190.degree. C. The ASTM definition (1961 D-883, Part 9, page 804) is as 
follows: 
"a plastic which has a stiffness or apparent modulus of elasticity greater 
than 7000 grams per square centimeter (100,000 psi) at 23.degree. C." 
The plasticized resin would therefore have a modulus of elasticity of less 
than 7000 grams per square centimeter, and would have added to it the 
plasticizer compound. Conventional plasticizers well known to those 
skilled in the art can be employed such as, for example, dioctyl 
phthalate, octyl diphenyl phosphate and epoxidized soybean oil. 
The stabilizer combinations of this invention are effective in improving 
initial color and heat stability of polyvinyl chloride resins in the 
absence of any other additives. However, it has long been recognized that 
polyvinyl chloride resins containing several types of heat stabilizers are 
better protected than those containing only one heat stabilizer. It is 
therefore an important aspect of this invention that these stabilizer 
combinations when used with additional heat stabilizers, provide greatly 
improved resistance to heat degradation not obtainable with the other heat 
stabilizers alone. 
The stabilizer composition of this invention shows synergistic interaction 
and provides improved effectiveness when used together with certain known 
useful additives, including 1,2-epoxides, hindered phenols, organic 
phosphites, the esters, amides, and hydrazides of 
thiodialkylenedicarboxylic acids, 3-aminocrotonic acid, and 
nitrilotrialkylenetricarboxylic acids, ketoacetic acid compounds, 
aliphatic polyhydric alcohols having 3 to 8 alcoholic hydroxyl groups, 
aliphatic and aromatic betadiketones, and certain polyether alcohol esters 
of phosphoric acid. 
Phenol stabilizers can be included with the stabilizer composition of this 
invention in amounts corresponding to 0.01 to about 0.2 parts per parts of 
polymer being stabilized. Typical phenol stabilizers are butylated 
hydroxy-toluene (BHT), 4,4'-isopropylidenebisphenol, and 
1,1,3-tris(2'-methyl-4'-hydroxy-5'-t-butylphenyl)butane. A comprehensive 
disclosure of phenol stabilizers at column 16 line 49 to column 21 line 8 
of M. Minagawa U.S. Pat. No. 3,849,370 issued Nov. 19, 1974 is here 
incorporated by reference. 
Aliphatic polyhydroxy compounds can be included with the stabilizer 
composition of this invention in amounts corresponding to 0.1 to about 1 
part per 100 parts of polymer being stabilized. Typical aliphatic 
polyhydroxy compounds are glycerol, polyglycerol, mono-, di-, and 
tripentaerythritol, mannitol, sorbitol, and partial esters of these with 
saturated and unsaturated fatty acids having 6 to 22 carbon atoms. 
Organic phosphite stabilizers can be included with the stabilizer 
composition of this invention in amounts corresponding to 0.05 to about 2 
parts by weight per 100 parts by weight of polymer being stabilized. 
Typical phosphite stabilizers are triphenyl phosphite, diphenyl phosphite, 
tris(nonylphenyl) phosphite, 2-ethylhexyl diphenyl phosphite, diisodecyl 
phenyl phosphite, trinonyl phosphite, and pentaerythritol bis(n-octadecyl 
phosphite). The phosphite stabilizer can have one or a plurality of 
phosphite ester groups and from 10 to about 75 carbon atoms. A 
comprehensive disclosure of organic phosphite stabilizers at column 13 
line 63 to column 15 line 48 of M. Minagawa U.S. Pat. No. 3,849,370 is 
here incorporated by reference. 
Oxirane or 1,2-epoxide stabilizers can be included with the stabilizer 
composition of this invention in amounts corresponding to 0.2 to about 20 
parts by weight per 100 parts by weight of polymer being stabilized. 
Typical 1,2-epoxide stabilizers are epoxidized polybutadiene, epoxysoybean 
oil, epoxylinseed oil, and 2-ethylhexyl epoxystearate. The epoxide 
stabilizer can have one or a plurality of oxirane or 1,2-epoxide groups 
and from 15 to 150 carbon atoms. A comprehensive disclosure of epoxide 
stabilizers at column 26 lines 12 to 40 and column 27 lines 17 to 51 of M. 
Minagawa U.S. Pat. No. 3,869,423 is here incorporated by reference. 
The esters, amides, and hydrazides of thiodialkylene dicarboxylic acids and 
nitrilotri-alkylenetricarboxylic acids can be included with the stabilizer 
composition of this invention in amounts corresponding to 0.1 to about 1 
part per 100 parts of polymer. Typical of these are dimethyl 
thiodipropionate, dilauryl and distearyl thiodipropionates, 
2,2'-thiobis(acetyl ethanolamine), 
3,3'-thiobis(propionyldiisopropanolamine, nitrilotriacetic acid (NTA) 
propylene glycol ester, NTA tris (ethylamide), NTA bis(hydroxyethyl) 
N-butylamide, 3,3'-thiodipropionyldihydrazide and 
6,6'-thiodihexanoyldihydrazide. A comprehensive disclosure of 
thiodipropionate compounds that can be used from column 21 line 9 to 
column 22 line 65 of M. Minagawa U.S. Pat. No. 3,849,370 is here 
incorporated by reference. 
Ketoacetic acid compounds that can be used with the stabilizer compositions 
of this invention in amounts of about 0.05 to about 0.5 parts per 100 
parts of polymer being stabilized include 2-ethylhexyl acetoacetate, 
glyceryl tris(acetoacetate) and dehydroacetic acid. A comprehensive 
disclosure of ketoacetic acid compounds that can be used from column 2 
line 32 to column 5 line 10 of U.S. Pat. No. 3,346,536 issued Oct. 10, 
1967 is here incorporated by reference. 
Organic nitrogen compounds that can be used with the stabilizer 
compositions of this invention in amounts of about 0.05 to about 0.5 parts 
per 100 parts of polymer being stabilized include 2-ethylhexyl 
3-aminocrotonate, 1,4-butanediol bis(3-aminocrotonate) and 2,2'thiodiethyl 
3-aminocrotonate; thiocarbanilide and 2-phenylindole, 1,3-dibutylthiourea, 
phenylurea, and p-ethoxyphenylurea. 
Betadiketones also called 1,3-diketones, or diacylmethanes have two to 
three acyl groups linked to a single carbon atom. The acyl groups can be 
aromatic, cycloaliphatic, or aliphatic, and preferably have from 2 to 30 
carbon atoms. Using the diacylmethane system of nomenclature, illustrative 
1,3-diketone compounds that can be used in the stabilized vinyl chloride 
compositions of this invention include acetylhexanoyl-methane, 
acetyl-heptanoyl-methane, hexanol-propanoyl methane, 
acetyl-octadecanoyl-methane, acetyl-tetradecanoyl-methane, 
acetyl-dodecanoyl-methane, di-octadecanoyl-methane, 
butanoyl-octanoyl-methane, 1-acetyl-1-octanoyl-ethane, triacetylmethane, 
trihexanoylmethane, acetyl-benzoyl-methane, hexanoyl-benzoyl-methane, 
Octadecanoyl-benzoyl-methane, tetradecanoyl-benzoyl-methane, 
Dodecanoyl-benzoyl-methane, formyl-benzoyl-methane, 
heptanoyl-benzoyl-methane, acetyl-hexahydrobenzoylmethane, 
dibenzoylmethane, phenylacetyl-benzoyl-methane, 
benzoyl-nonylbenzoyl-methane, benzoylidacetyl-methane, 
di(hexahydrobenzoyl)methane, tribenzoylmethane, 
benzoyl-p-methoxybenzoyl-methane, di(p-methoxybenzoyl)methane, 
di(p-chlorobenzoyl)methane, di(3,4-methylenedioxbenzoyl)methane, 
1-acetyl-1-benzoylnonane, alpha-acetyl-alpha-benzoyl-toluene, 
di(p-t-butylbenzoyl)methane, benzoyl-trifluoroacetyl-methane, 
diacetylmethane, acetyl-octanoyl-methane, and dipivaloylmethane. 
Alkyl acid phosphates have 1 to 2 alkyl groups of 8 to 20 carbon atoms per 
phosphate ester group. Stearyl acid phosphate, di(2-ethylhexyl)acid 
phosphate, and dilauryl acid phosphate are representative. 
Ether alcohol acid phosphate esters have 1 to 2 ether alcohol groups per 
phosphate ester group, and can be presented by a formula 
##STR30## 
where the number of ether groups in the ether alcohol represented by a is 
from 1 to about 22 and the number of ether alcohol groups represented by b 
is from 1 to 2, and X is a hydrocarbon group having 1 to about 20 carbom 
atoms. Commercial mixtures of homologous products, usually characterized 
by an average value of a, such as ethoxylated nonylphenol phosphate with 
average of 6 oxyethylene units or ethoxylated C.sub.12 -C.sub.15 alkyl 
phosphate with average of 12 oxyethylene units are satisfactory. 
Stabilizer compositions in accordance with this invention can be in solid, 
liquid or paste form. Liquid compositions can be prepared by blending the 
ingredients and heating at 40.degree. to 200.degree. C. for up to 6 hours 
to achieve visual homogeneity and storage stability. Inert ingredients 
that can be added to the stabilizer compositions to improve their handling 
convenience include solvents such as hydrocarbons, 2-ethylhexanol, 
isodecyl alcohol, 2-ethoxyethanol, and 2(2-butoxyethoxy)ethanol; paste 
consistency modifiers such as finely divided silica, polyethylene glycols 
and polypropylene glycols and their monoalkyl and monaryl ethers, and 
water; anticaking agents such as talc, magnesium trisilicate, sodium 
silicoaluminate, and aluminum calcium silicate. 
Following are the methods used in testing vinyl chloride polymer 
compositions containing stabilizer compositions according to this 
invention or control compositions used for comparison purposes. 
Oven heat stability: 
Samples of each indicated formulation proportioned to 200 grams of vinyl 
chloride polymer are compounded on a two-roll mill until well mixed and 
removed in the form of sheets 1 mm in thickness. Strips cut from each 
sheet are exposed in an air circulating oven at the indicated temperature, 
and one strip of each formulation removed every five minutes and attached 
to a record card. Heat stability was recorded as the time in minutes to 
the first failure point represented by a deep orange, red, brown or black 
color. 
Clarity and Initial Color: 
These properties are rated visually by comparing samples of each indicated 
formulation to a standard, to which is assigned the rating "medium". 
Unless otherwise indicated, the standard used is a sample of Control 1-1, 
e.g. the base formulation of Example 1 with 0.7 part barium stearate and 
0.3 part zinc stearate as stabilizers. Clarity is rated by viewing samples 
against a black background and initial color by viewing samples against a 
white background. 
Plate-out: 
Calender or roll plate-out is caused by an incompatibility of vinyl 
chloride polymer compound constituents under processing conditions with 
subsequent deposit on the rolls of the equipment. As the deposit builds up 
in thickness, it will affect the surface appearance of the vinyl sheeting 
being produced and it may interfere with heat sealability and printability 
of the material. 
Plate-out is measured through incorporation in the test compound of a red 
pigment which tends to disperse within the plate-out layer. The red 
plate-out layer on the mill rolls is then picked up by a clean-up batch. 
The extent of discoloration of the clean-up batch is a measure of the test 
compound's tendency to plate-out. 
The test procedure is as follows: 
There is added to the test compound 2 phr of a 50% pigment dispersion in 
DOP of Permanent Red 2B pigment. The test compound is charged to the 
laboratory mill and allowed to run on the mill without disturbing it 3 
minutes after the compound is fused and well mixed. The mill temperature 
is 172.degree.-177.degree. C. After 3 minutes, the red pigmented compound 
is removed from the mill and discarded. The following clean-up compound is 
then charged to the mill and run for 3 minutes. 
______________________________________ 
Resin 100 parts by weight 
DOP 30 
TiO.sub.2 2 
Precipitated silica 
2 
Liquid cadmium-barium 
stabilizer 2 
Stearic acid 0.5 
______________________________________ 
The quantity of clean-up compound is proportioned to 200 parts of resin. 
The clean-up compound removes from the mill the plate-out and red pigment 
left from the test compound. The extent of color development of the 
clean-up compound is a measure of the test compound's plate-out 
characteristics. A numerical measure of plate-out is provided by comparing 
the colored clean-up compound with a series of standard compounds to which 
known amounts of the red pigment are added. The numerical "plate-out 
value", then, is the concentration of pigment, in mg/kg of resin, that 
most nearly matches the color of the clean-up compound at the end of the 
test. 
Weatherability: Samples are exposed in a carbon arc accelerated weathering 
unit (Atlas Electric Devices Co. "Weatherometer") operated without water 
spray at 52.degree. C. black panel temperature and 41.degree.-44.degree. 
C. air temperature. Samples are examined once daily for failure signs 
including spotting, uniform darkening, stiffening, and/or embrittlement, 
any one of which marks the failure of the sample. Weatherability is 
expressed in hours to such failure. 
The metal P-hydrocarbonphosphonates contained in stabilizer compositions 
examined in vinyl chloride polymers stabilized according to this invention 
are included in the listing of compounds by name and abbreviated formula 
in Table 1. 
TABLE 1 
______________________________________ 
Metal P-hydrocarbonphosphonates 
No. 1 Barium tridecanephosphonate (1:1) 
##STR31## 
No. 2 Calcium tridecanephosphonate (1:1) 
##STR32## 
No. 3 Magnesium tridecanephosphonate (1:1) 
##STR33## 
No. 4 Zinc octadecanephosphonate (1:1) 
##STR34## 
No. 5 Barium di(ethyl P-octanephosphonate) 
##STR35## 
No. 6 Barium di(phenyl P-octanephosphonate) 
##STR36## 
No. 7 Calcium di(p-t-butylphenyl P-dodecanephosphonate) 
##STR37## 
No. 8 Barium di(nonylphenyl P-dodecanephosphonate) 
##STR38## 
No. 9 Barium phenylmethanephosphonate (1:1) 
##STR39## 
No. 10 
Magnesium phenylmethanephosphonate (1:1) 
##STR40## 
No. 11 
Calcium di(dodecyl P-phenylmethanephosphonate) 
##STR41## 
No. 12 
Barium di(toly P-phenylmethanephosphonate) 
##STR42## 
No. 13 
Strontium di(butyl P-phenylmethanephosphonate) 
##STR43## 
No. 14 
Calcium C.sub.20-28 alkanephosphonate (1:1) 
##STR44## 
No. 15 
Barium di(cyclohexyl P-octanephosphonate) 
##STR45## 
No. 16 
Zinc di(benzyl P-tridecanephosphonate) 
##STR46## 
No. 17 
Strontium di(2,4-di-t-butylphenyl P-tridecanephosphonate) 
##STR47## 
No. 18 
Barium di(xylyl P-octanephosphonate) 
##STR48## 
No. 19 
Barium o-tolylmethanephosphonate (1:1) 
##STR49## 
No. 20 
Calcium p-tolylmethanephosphonate (1:1) 
##STR50## 
No. 21 
Barium di(p-methylbenzyl P-dodecanephosphonate) 
##STR51## 
No. 22 
Barium octanephosphonate (1:1) 
##STR52## 
No. 23 
Barium butanephosphonate (1:1) 
##STR53## 
No.24 Barium dodecanephosphonate (1:1) 
##STR54## 
No.25 Barium di(tridecyl P-tridecanephosphonate) 
##STR55## 
No. 26 
Zinc octanephosphonate (1:1) 
##STR56## 
No. 27 
Cadmium di(ethyl P-octanephosphonate) 
##STR57## 
No. 28 
Lead di(octyl P-butanephosphonate) 
##STR58## 
No. 29 
Cadmium di(phenyl P-octanephosphonate) 
##STR59## 
No. 30 
Sodium ethyl P-octanephosphonate 
##STR60## 
No. 31 
Nickel di(p-t-butylphenyl P-dodecanephosphonate) 
##STR61## 
No. 32 
Potassium p-t-butylphenyl P-dodecanephosphonate 
##STR62## 
No. 33 
Stannous di(p-nonylphenyl P-alkane (C.sub.12-15) 
phosphonate 
##STR63## 
No. 34 
Antimony tri(dodecyl P-phenylmethanephosphonate) 
##STR64## 
No. 35 
Dibutyltindi(benzyl P-tridecanephosphonate) 
##STR65## 
No. 36 
Cadmium di(p-tolyl P=phenylmethanephosphonate) 
##STR66## 
No. 37 
Lithium octyl P-phenylmethanephosphonate 
##STR67## 
No. 38 
Zirconium tetra(butyl P-phenylmethanephosphonate) 
##STR68## 
No. 39 
Cadmium di(2,4-di-t-butylphenyl P-tridecanephosphonate) 
##STR69## 
No. 40 
Nickel di(cyclohexyl P-octanephosphonate) 
##STR70## 
No. 41 
Lead di(xylyl P-octanephosphonate) 
##STR71## 
No. 42 
Sodium cyclohexylphenyl P-dodecanephosphonate 
##STR72## 
No. 43 
Antimony tri(P-methylbenzyl P-dodecanephosphonate) 
##STR73## 
No. 44 
Dioctyltin di(octyl P-octanephosphonate) 
##STR74## 
No. 45 
Lead di(tridecyl P-tridecanephosphonate) 
##STR75## 
No. 46 
Cadmium di(2-ethoxyethyl P-octanephosphonate) 
##STR76## 
No. 47 
Cadmium tridecanephosphonate (1:1) 
##STR77## 
No. 48 
Sodium dodecanephosphonate (2:1) 
##STR78## 
No. 49 
Lead tridecanephosphonate (1:1) 
##STR79## 
No. 50 
Nickel tridecanephosphonate (1:1) 
##STR80## 
No. 51 
Dibutyltin octadecanephosphonate (1:1) 
##STR81## 
No. 52 
Potassium octanephosphonate (2:1) 
##STR82## 
No. 53 
Cadmium phenylmethanephosphonate (1:1) 
##STR83## 
No. 54 
Lead phenylmethanephosphonate (1:1) 
##STR84## 
No. 55 
Antimony o-tolylmethanephosphonate (2:3) 
##STR85## 
No. 56 
Lithium phenylmethanephosphonate (2:1) 
##STR86## 
No. 57 
Zirconium p-tolylmethanephosphonate (1:2) 
##STR87## 
No. 58 
Cadmium C.sub.20-28 alkanephosphonate (1:1) 
##STR88## 
No. 59 
Stannous octanephosphonate (1:1) 
##STR89## 
No. 60 
Lead octanephosphonate (1:1) 
##STR90## 
______________________________________ 
EXAMPLES 1-1 TO 1-5 
A sheet of 1 mm in thickness was prepared by mixing on a two roll mill the 
following formulation, and submitted to the performance tests shown. 
The stabilizer compositions used and the test results are shown in Table-2. 
______________________________________ 
(Formulation) 
______________________________________ 
PVC (Geon 103EP) 100 parts by weight 
DOP 48 
Epoxidized soybean oil 
2.0 
Stearic acid 0.2 
Stabilizers as shown in Table-2 
______________________________________ 
Table - 2 
______________________________________ 
No. Control Examples 
Stabilizers 1-1 1-1 1-2 1-3 1-4 1-5 
______________________________________ 
Ba stearate 0.7 0.3 
Zn stearate 0.3 0.3 0.3 0.3 0.3 0.3 
Ba tridecanephosphonate 
0.4 
(1:1) 
Ba di (ethyl P- 0.4 
octanephosphonate) 
Ca tridecanephosphonate 0.4 0.2 
(1:1) 
Ba phenylmethanephosphonate 0.4 
(1:1) 
Heat Stability 
45 70 70 60 60 60 
(190.degree. C.)min. 
very very very very 
Initial Color 
medium good good good good good 
Clarity " very very very very very 
good good good good good 
Plate Out (mg/kg) 
150 5 5 5 5 15 
______________________________________ 
The stabilizer compositions of this invention are shown to be superior to 
Control 1-1 in every property examined. 
EXAMPLES 2-1 TO 2-4 
Milled sheets of PVC with various barium-zinc combinations were submitted 
to performance tests carried out in the same way as in Examples 1-1 to 
1-5. 
The stabilizers used and the test results are shown in Table-3. 
______________________________________ 
(Formulation) 
______________________________________ 
PVC (Geon 103 EP) 100 parts by weight 
DOP 50 
Stearic acid 0.3 
Epoxidized soybean oil 
2.0 
Zn toluate 0.7 
Ba salts (Table-3) Variable weights* 
______________________________________ 
*adjusted to same Ba level as 1.1 part by weight of Ba nonylphenolate 
Table-3 
__________________________________________________________________________ 
Heat Plate 
Stability 
Out Weather- 
Initial Heat (175.degree. C.) 
Value 
ability 
No. Basalts (phr) 
Color 
Clarity 
Coloring 
min mg/kg 
hours 
__________________________________________________________________________ 
Control Inferior 
Inferior 
2-1 Ba nonylphenolate (1:1) 
to to very 90 350 950 
Control 
Control 
inferior 
1-1 1-1 
Example 
2-1 Ba tridecanephos- 
phonate (1:1) (0.8) 
good good very good 
105 10 1800 
2-2 Ba di(phenyl P-octane- 
phosphonate) (1.3) 
" " " 105 5 1700 
2-3 Ba di(poly P-phenyl- 
methanephosphonate (1.3) 
" " " 120 10 1750 
2-4 Ba di(cyclohexyl P- 
octanephosphonate) (1.3) 
" " " 120 10 2000 
__________________________________________________________________________ 
The results show the superiority of the stabilizer composition of this 
invention in each property examined. 
EXAMPLES 3-1 TO 3-15 
The performance tests shown were carried out on samples milled up according 
to the following formulation for agricultural film. 
The metal P-hydrocarbonphosphonate added to each formulation and the test 
results are shown in Table-4. 
______________________________________ 
(Formulation) 
______________________________________ 
PVC (Geon 103EP) 100 parts by weight 
DOP 45 
Trixylylphosphate 5 
Epoxidized soybean oil 
3 
Bisphenol A diglycidyl 
ether (Epikote 828) 2 
Ba stearate 0.4 
Zn stearate 0.8 
Diphenylisooctylphosphite 
0.5 
Sorbitan monopalmitate 
1.5 
(anti-fog additive and lubricant) 
Samples (Table-4). 0.8 
______________________________________ 
Table 4 
______________________________________ 
Heat 
Stability 
(190.degree. C.) 
Weatherability 
No. Samples min hours 
______________________________________ 
Control 
3-1 none 60 600 
3-2 Ba bis(monoisooctyl 
acidphosphate) 105 1300 
3-3 Ca bis(monotridecyl 
acidphosphate) 90 1200 
3-4 Ni bis(monotridecyl 
acidphosphate) 90 1200 
Example 
3-1 Mg tridecanephos- 
phonate (1:1) 120 2000 
3-2 Ca di(p-t-butylphenyl 
P-dodecanephosphonate 
110 1800 
3-3 Ba di(nonylphenyl P- 
dodecanephosphonate) 
120 2000 
3-4 Ca di(dodecyl P-phenyl- 
methanephosphonate) 
115 1900 
3-5 Sr di(butyl P-phenyl- 
methanephosphonate) 
130 2000 
3-6 Ba di(cyclohexyl P- 
octanephosphonate) 
130 2100 
3-7 Ba di(xylyl P-octane- 
phosphonate) 125 2100 
3-8 Ba O-tolymethane- 
phosphonate (1:1) 
130 2200 
3-9 Ba di(p-methylbenzyl P- 
dodecanephosphonate) 
130 2000 
3-10 Ba dodecanephosphonate 
(1:1) 125 1900 
3-11 Li octyl P-phenyl- 
methanephosphonate 
120 2100 
3-12 Ni di(cyclohexyl P- 
octanephosphonate) 
&gt;120 2600 
3-13 Na cyclohexylphenyl P- 
dodecanephosphonate 
120 2000 
3-14 Li phenylmethane- 
phosphonate (2:1) 
120 2100 
3-15 Zr p-tolylmethane- 
phosphonate (1:2) 
120 2700 
______________________________________ 
As shown by the above results, agricultural film formulations containing 
the stabilizer compositions of this invention were dramatically improved 
over prior art formulations. 
EXAMPLES 4-1 to 4-11 
The same tests as in Examples 1-1 to 1-4 were carried with a composition of 
this invention to which varying organic phosphites were added. 
The organic phosphites used and the test results are shown in the following 
Table-5. 
______________________________________ 
(Formulation) 
______________________________________ 
PVC 100 parts by weight 
DOP 50 
Stearic acid 0.3 
Zn toluate 0.7 
Ba tridecanephosphonate 
0.7 
(1:1) 
Epoxidized linseed oil 
1.0 
Organic phosphite (Table-5) 
0.5 
______________________________________ 
Table 5 
______________________________________ 
Heat 
Stability 
Initial 
No. Organic Phosphites 
(175.degree. C.) 
Color* 
Clarity* 
______________________________________ 
Example min 
4-1 none 60 good good 
mono- 
4-2 (2-ethylhexyl)diphenyl- very very 
phosphite 80 good good 
4-3 ditridecylmonophenyl- very very 
phosphite 85 good good 
4-4 diisodecylmonophenyl- very very 
phosphite 80 good good 
4-5 monotridecyldiphenyl- very very 
phosphite 80 good good 
4-6 tris(nonylphenyl)- very very 
phosphite 75 good good 
tris 
4-7 (2,4-di-t-butylphenyl)- very very 
phosphite 75 good good 
4-8 triphenylphosphite 
70 very very 
good good 
4-9 diphenylacid- 90 very very 
phosphite good good 
4-10 diisodecylacid- 90 very very 
phosphite good good 
4-11 monoisodecylacid- 
90 very very 
phosphite good good 
______________________________________ 
*by comparison to Control 11 above. 
The test results show the beneficial interaction of organic phosphites with 
the stabilizer composition of this invention. 
EXAMPLES 5-1 to 5-15 
To observe the synergistic effect when there are incorporated in PVC other 
additives together with the stabilizer composition of this invention, the 
same tests as in Examples 1-1 to 1-5 were carried out with samples of the 
following formulation. 
The additives used and the test results are shown in Table-6. 
______________________________________ 
(Formulation) Parts by weight 
______________________________________ 
PVC (Geon 103EP) 100 
DOP 48 
Epoxidized soybean oil 
2.0 
Zn octoate 0.2 
Ca tridecanephosphonate 
0.7 
(1:1) 
Stearic acid 0.3 
Additives (Table 6) 
______________________________________ 
Table 6 
______________________________________ 
Heat 
Stability 
Example Amount (175.degree. C.) 
No. Additives (phr) mins 
______________________________________ 
5-1 none -- 70 
5-2 BHT antioxidant 0.2 95 
5-3 dilaurylthiodipropionate 
0.2 95 
5-4 diphenylthiourea 0.2 95 
5-5 thiodiglycol bis 0.3 110 
(aminocrotonate) 
5-6 stearyl acid phosphate 
0.3 110 
5-7 pentaerythritol 0.3 100 
5-8 tris(hydroxyethyl) 
0.3 100 
isocyanurate 
5-9 dehydroacetic acid 
0.05 95 
5-10 Zn dehydroacetate 0.3 95 
5-11 benzoylacetone 0.05 100 
5-12 dibenzoylmethane 0.05 100 
5-13 sorbitol 0.3 115 
5-14 nonylphenoxypolyethoxy 
phosphoric acid 0.2 105 
5-15 tridecyloxypolyethoxy 
phosphoric acid 0.2 105 
______________________________________ 
These results show the helpful interaction of the above additives with the 
stabilizer composition of this invention. 
EXAMPLES 6-1 to 6-7 
To examine the effect in a polymer blend of PVC and ABS, a sheet was 
prepared according to the following formulation, and used to measure heat 
stability at 190.degree. C., plate-out value and clarity. 
The stabilizers used and the test results are shown in Table-7. 
______________________________________ 
(Formulation) Parts by weight 
______________________________________ 
PVC (Geon 103EP-8) 100 
ABS (Blendex 111) 10 
Epoxidized soybean oil 
3 
cq stearate 0.2 
Tetra(C.sub.12-15 alkyl)bis 
phenol diphosphite 1.5 
Samples (Table 7) 1.2 total, as shown 
______________________________________ 
Table 7 
__________________________________________________________________________ 
Heat Plate 
Stability 
Out 
No. Sample (190.degree. C.) 
Value 
Clarity 
__________________________________________________________________________ 
Control min mg/kg 
6-1 Ca ricinoleate 
0.7 
75 250 Inferior to 
Zn octoate 0.5 Control 1-1 
Example 
6-1 Ca p-tolylmethane- 
phosphonate (1:1) 
0.7 
Zn octoate 0.5 
90 25 Superior 
6-2 Zn octadecane- 
phosphonate (1:1) 
0.5 
Ca di(p-t-butylphenyl P- 
105 10 " 
dodecanephosphonate) 
0.7 
6-3 Mg tridecane- 
phosphonate (1:1) 
0.7 
Zn octanephosphonate (1:1) 
0.5 
95 25 " 
6-4 Mg phenylmethane- 
phosphonate (1:1) 
0.7 
Zn di(benzyl P-tridecane- 
100 15 " 
phosphonate) 0.5 
6-5 Ca C.sub. 20-28 alkane- 
phosphonate (1:1) 
0.7 
Zn di(benzyl P-tridecane- 
105 10 " 
phosphonate) 0.5 
6-6 Sr di(2,4-di-t-butylphenyl 
P-tridecanephosphonate) 
0.3 
Ba octanephosphonate (1:1) 
0.4 
100 20 " 
Zn octanephosphonate (1:1) 
0.5 
6-7 Ba butanephosphonate (1:1) 
0.7 
Zn laurate 0.5 
105 10 " 
__________________________________________________________________________ 
These results show that PVC-ABS polymer blends are improved in each 
property tested by the stabilizer compositions of this invention. 
EXAMPLES 7-1 to 7-12 
A sheet of 1 mm in thickness was prepared by milling each of the following 
formulations and submitted to heat-ageing at 190.degree. C., initial 
color, plate-out, and weatherability measurements. 
The results are shown in the following Table-8. 
______________________________________ 
(Formulation) Parts by weight 
______________________________________ 
PVC (Geon 103EP) 100 
DOP 20 
Epoxidized soybean oil 
2 
Stearic acid 0.2 
Monooctyldiphenyl phosphite 
0.5 
Stabilizer as shown in Table 8 
______________________________________ 
Table 8 
__________________________________________________________________________ 
Amount 
Heat 
(Parts 
Stability Plate 
Weather- 
by (190.degree. C.) 
Initial Out ability 
No. Stabilizers Weight) 
min Color* 
Clarity* 
Value 
hrs 
__________________________________________________________________________ 
Control 
7-1 Ba stearate 0.6 90 medium 
medium 
120 800 
Cd stearate 0.4 
7-2 
##STR91## 0.3 75 Inferior 
good 100 600 
Ba stearate 0.7 
Example 
7-1 Zn stearate 0.3 
Ni di(p-t-butylphenyl 
105 good good 5 2500 
P-dodecanephosphonate) 
0.7 
7-2 Zn octoate 0.2 very 
Ba octanephos- 
0.8 105 good good 10 1800 
phonate (1:1) 
7-3 Ba-12-OH-stearate 
0.7 
Cd di(phenyl P-octane- 
120 very very 5 2000 
phosphonate) good good 
7-4 Zn laurate 0.5 
Cd di(phenyl P- 
0.5 105 very good 10 1700 
octanephosphonate) good 
7-5 Zn myristate 0.2 
Ni tridecane- 105 good " 10 2300 
phosphonate (1:1) 
0.6 
7-6 Zn octoate 0.3 
Ba octanephos- 
0.7 105 " " 15 1800 
phonate (1:1) 
7-7 Na octoate 0.6 
Pb di(octyl P-butane- 
105 " " 10 1700 
phosphonate) 0.2 
7-8 Cd stearate 0.2 
K octanephosphonate (2:1) 
0.8 120 very good 
good 5 2000 
7-9 Ni stearate 0.6 
Sb tri(dodecyl P-phenyl 
105 good " 5 1800 
methanephosphonate) 
0.4 
7-10 Ba octoate 0.7 
Ba di(p-methylbenzyl 
0.3 105 very good 
very good 
5 2000 
P-dodecanephosphonate) 
7-11 Cd laurate 0.4 
Na cyclohexylphenyl P- 
120 " good 5 1700 
dodecanephosphonate 
0.6 
7-12 Ba ricinolate 
0.7 
Ba a-tolymethane- 
0.2 105 " " 5 2200 
phosphonate (1:1) 
__________________________________________________________________________ 
*Compared to Control 71 
The results show that the stabilizer compositions of this invention are 
dramatically superior to prior art compositions in every property tested. 
EXAMPLES 8-1 to 8-7 
Performance tests were carried out as shown in Table-9 with PVC samples of 
the following formulation. 
The stabilizers used and the test results are shown in Table-9. 
______________________________________ 
(Formulation) Parts by weight 
______________________________________ 
PVC (Geon 103EP) 100 
DOP 50 
Stearic acid 0.3 
Epoxidized soybean oil 
2.0 
Zinc toluate 0.7 
Stabilizer Table 9) Variable weight* 
______________________________________ 
*equivalent in moles of metal to 1.1 part by weight of Banonyl phenolate. 
Table 9 
______________________________________ 
Heat 
Stability 
Plate Weather- 
Stabilizers (175.degree. C.) 
Out ability 
No. phr min Value hrs 
______________________________________ 
Control 
8-1 Ba nonylphenolate 
85 350 800 
(1.1 part by weight) 
8-2 Ba tetraphenyldi- 
20 20 900 
phosphite (1.2) 
8-3 Ba tetratridecyldi- 
30 10 900 
phosphite (2.0) 
Example 
8-1 Na ethyl P-octane- 
phosphonate (0.5) 
105 5 1500 
8-2 K p-t-butylphenyl- 
P-dodecane- 
phosphonate (0.8) 
90 5 1400 
8-3 Ni di(cyclohexyl- 
P-octane- 
phosphonate) (1.2) 
105 10 1800 
8-4 Ni 
tridecanephosphonite 
105 8 2000 
(1:1) (.6) 
8-5 K octanephosphonate 
120 5 1600 
(2:1) (0.5) 
8-6 Li phenylmethane- 
phosphonate (2:1) (0.4) 
105 10 1500 
8-7 Na dodecane- 90 5 1400 
phosphonate (2:1) (0.6) 
______________________________________ 
The results show the much improved heat stability and excellent plate-out 
and weathering properties of the compositions stabilized according to this 
invention. 
EXAMPLES 9-1 to 9-11 
The performance tests shown in Table-10 were carried out in the same way as 
in Examples 4-1 to 4-11 with the following formulation containing organic 
phosphites together with a stabilizer composition of this invention. The 
phosphites used and the results are shown in Table-10. 
______________________________________ 
(Formulation) Parts by weight 
______________________________________ 
PVC (Geon 103EP) 100 
DOP 50 
Stearic acid 0.3 
Zn-stearate 0.5 
Ni tridecanephosphonate 
0.7 
(1:1) 
Epoxidized linseed oil 
1.0 
Organic phosphites (Table 10) 
______________________________________ 
Table 10 
__________________________________________________________________________ 
Heat 
Stability 
Example 
Organic (180.degree. C.) 
Initial* 
No. Phosphite Compounds 
Amount 
min Color Clarity* 
__________________________________________________________________________ 
9-1 none -- 80 good good 
9-2 monoisodecyl acid phosphite 
0.1 95 very good 
very good 
9-3 diisodecyl acid phosphite 
0.1 100 " " 
9-4 diphenyl acid phosphite 
0.2 105 " " 
9-5 mono-2-ethylhexyldiphenyl 
phosphite 0.5 110 " " 
9-6 ditridecyl phenyl phosphite 
0.5 120 " " 
9-7 diisodecyl phenyl phosphite 
0.3 110 " " 
9-8 tris(nonylphenyl) phosphite 
0.3 115 " " 
9-9 tris(2,4-di-t-butylphenyl) 
phosphite 0.3 120 " " 
9-10 
triphenyl phosphite 
0.5 105 " " 
9-11 
tridecyl diphenyl phosphite 
0.3 115 " " 
__________________________________________________________________________ 
*compared to Control 71. 
These results demonstrate the helpful synergism of stabilizer compositions 
of this invention with organic phosphites. 
EXAMPLES 10-1 to 10-4 
To observe the effects of stabilizer combinations of this invention on 
PVC-ABS polymer blend, a sheet was prepared and used to measure heat 
stability at 190.degree. C., plate-out value and weatherability according 
to the following formulation. 
The stabilizers used and the test results are shown in Table-11. 
______________________________________ 
(Formulation) Parts by weight 
______________________________________ 
PVC (Geon 103EP-8) 100 
ABS (Blendex 111) 10 
Epoxidized soybean oil 
3 
Ba-stearate 0.8 
Tetra (C.sub.12-15 alkyl) 
bisphenol A . diphosphite 
1.5 
Stabilizers 0.6 total 
______________________________________ 
Table 11 
__________________________________________________________________________ 
Heat 
Stability 
Plate 
Weather- 
(190.degree. C.) 
Out ability 
No. Stabilizers Amount 
min Value 
hrs 
__________________________________________________________________________ 
Control 
10-1 Cd-stearate 0.3 
90 50 700 
##STR92## 0.3 
Example 
10-1 Cd di(ethyl P-octane- 
phosphonate) 0.2 90 10 1500 
Cd-stearate 0.4 
10-2 Sn di(P-nonylphenyl 
P alkane(C.sub.12-15)phos- 
90 5 1500 
phonate) 0.3 
Pb-octoate 0.3 
10-3 Bu.sub.2 Sn octadecanephos- 
phonate (1:1) 0.3 90 6 1700 
Zn-stearate 0.3 
10-4 Bu.sub.2 Sn di(benzyl P-tri- 
decanephosphonate) 
0.4 
Zr P-tolylmethane- 105 5 1800 
phosphonate (1:2) 
0.2 
__________________________________________________________________________ 
These results show that PVC-ABS polymer blends are greatly improved by 
stabilizer compositions of this invention.