PVC Plasticized with tetracarboxylates

Anhydrides and esters of alkyl or cycloalkyl tetracarboxylic acids and polyvinyl chloride plastic compositions containing said esters as plasticizers.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to polycarboyxlic acid compositions. More 
particularly, the invention is concerned with anhydrides and esters of 
alkyl or cycloalkyl tetracarboxylic acids which esters are useful as 
plasticizers in polyvinyl chloride plastic compositions. 
2. Description of the Prior Art 
Resins such as polyvinyl chloride and its copolymers are widely employed in 
the field of plastics materials. Such resins are generally hard and 
somewhat brittle by nature, and it is customary to add plasticizing agents 
to improve their workability during forming operations. Ordinarily some of 
the plasticizer is retained in the product formed where it 
characteristically provides certain desirable properties to the product. 
Among these characteristics is the ability of the plasticizer to impart 
low-temperature flexibility. Also the plasticizer must be characterized by 
low volatility to prevent its loss by evaporation. Furthermore, the 
plasticizer should be compatible with the resin and resist extraction when 
contacted with hydrocarbons or water. Vinyl chloride polymers in 
particular have been plasticized with tetra-alkyl alkenyl 
tetracarboxylates which are addition products of dialkyl fumarates and 
dialkyl alkenyl succinates. See, for instance, U.S. Pat. No. 2,806,011. 
Esters of polycarboxylic acids have been suggested for use as synthetic 
lubricants. In general, they are characterized by higher viscosity 
indices, lower pour points and higher flash points and mineral oils of 
corresponding viscosity. Dialkyl alkenyl succinates prepared from the 
alkenyl succinic acid anhydride in particular have been suggested for this 
purpose. see, for instance, U.S. Pat. No. 2,561,232. 
SUMMARY OF THE INVENTION 
In accordance with the present invention, there are provided useful new 
alkyl or cycloalkyl tetracarboxylic acid compounds of the formula 
##STR1## 
wherein A and C are monovalent succinic acid groups having attachment to B 
at either of the two carbon atoms of A or C having unsatisfied valences 
and a hydrogen atom attached to the other unsatisfied carbon atom; and 
wherein B is a connecting alkane or cycloalkane group of 4 to 30 carbon 
atoms having 2 of the above-described monovalent groups A and C, which may 
be the same or different, attached at carbon atoms 1 and 2 or at carbon 
atoms 1 and 3; and optionally having carbon atom 1 and carbon atom 4 
connected by a 1-8 carbon methylene bridge; the remainder of the 
unsatisfied carbon valences of said bivalent hydrocarbon group being 
attached to hydrogen atoms; and wherein R.sup.1 is H and R.sup.2 and 
R.sup.3 are H or the same or different hydrocarbyl groups; X and Y 
together are --O-- or X and Y are the same or different groups having the 
structure: --OR, in which R is H or the same or different alkyl or 
cycloalkyl groups having from 1 to 8 carbon atoms each. 
The present invention also relates to polyvinyl chloride plastic 
compositions containing the above-described esters in amounts sufficient 
to impart plasticizing properties. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The tetracarboxylic acid compounds in accordance with this invention as 
described above may contain from about 4 to about 30 carbon atoms in the 
connecting alkyl or cycloalkyl group B. For present purposes, it is 
preferred to react monoolefinic straight-chain aliphatic or cycloaliphatic 
hydrocarbons with the dicarboyxlic acid compounds to give the desired 
alkenyl or cycloalkenyl bis(succinic anhydride), hereinafter termed 
"ABSA". The alkyl or cycloalkyl bis(succinic anhydride) or alkyl or 
cycloalkyl bis(succinic acid) which may be used to provide the tetra-alkyl 
or tetracycloalkyl esters of this invention is suitably obtained by the 
reduction of the alkenyl or cycloalkenyl groups by hydrogenation to the 
corresponding alkyl or cycloalkyl group. Monoolefinic aliphatic 
hydrocarbons of from about 4 to 20 carbon atoms are preferred for ease of 
purification of the tetracarboxylic acid compound product thereof. 
The olefinic hydrocarbons may be linear or cyclic in nature. The 
unsaturation may be either terminal, as in the case of alpha-olefins, or 
internal, as in the case of beta, gamma and other such olefins. It is also 
possible for the monoolefinic hydrocarbon reactants to have various 
nonreactive substituents. Such substituents include the halogens, for 
example chlorine and bromine, nitro groups, aryl groups, alkoxy groups, 
carboalkoxy groups and the like. 
Illustrative linear straight-chain and branched-chain olefins include: 
1-butene, 2-butene, 3-hexene, 2-octene, 2,2,4-trimethylpentene-3, 
diisobutylene, 4-methyloctene-1, 7-dodecene, 8-eicosene, 1-triacetene, and 
the like. Illustrative cycloaliphatic olefinic hydrocarbons include: 
cyclopentene, cyclohexene, 4-methylcyclopentene, 4-ethylcyclohexene, 
1-methyl-4-ethylcyclohexene and the like. 
The dicarboxylic acid compounds are characterized by having the carboxyl 
groups or derivatives thereof in the 1,4-position and unsaturation in the 
2,3-position. Such acid compounds are illustrated by maleic acid and 
citraconic acid as well as anhydrides thereof. Fumaric acid and mesaconic 
acid are also illustrative. 
The unsaturated dicarboxylic acid derivatives as described, for example, 
dialkyl maleate such as dimethyl maleate, may be reacted as such with the 
olefinic hydrocarbon. However, for present purposes, it is preferred to 
react the unsaturated dicarboxylic acid or its anhydride with the olefinic 
hydrocarbon and then prepare the corresponding derivative from the 
tetracarboxylic acid or dianhydride, as the case may be. 
The reaction of the monoolefinic hydrocarbon with unsaturated dicarboxylic 
acid compound is thermal and non-catalytic. The reactants are heated at a 
temperature of at least about 150.degree. C. Since thermal decomposition 
of many alkenyl bis(succinic anhydrides) to spirodilactones occurs at 
about 250.degree. C., the preferred temperature range is from about 
200.degree. to about 250.degree. C. in the case of the acid anhydrides. 
The reaction of the olefinic hydrocarbon and the unsaturated dicarboxylic 
acid compound occurs at various pressures. For example, atmospheric 
pressure is satisfactory for the higher-molecular-weight reactants which 
are in liquid state at reaction temperature. On the other hand, 
lower-molecular-weight hydrocarbons and acid compounds are reacted in 
closed vessels under autogenous pressures. Where desired, higher pressures 
may be obtained using inert gases. The process may be either batch or 
continuous. 
The proportions of olefinic hydrocarbon and unsaturated dicarboxylic acid 
compound may vary from 2 mols of dicarboxylic acid to about 1 mol of 
olefinic hydrocarbon up to about 1 mol of dicarboxylic acid compound for 
each carbon in the olefinic hydrocarbon. Preferably 2 mols of unsaturated 
dicarboxylic acid compound are reacted with 1 mol of olefinic hydrocarbon. 
The reaction time varies from a few minutes to several hours. Some 
reaction will occur in as short a time as 10 minutes. On the other hand, 
reaction times of from 50 to 60 hours may be indicated. For present 
purposes, reaction is carried out in a period of from about 2 to about 8 
hours for optimum yield and minimization of undesirable side reactions and 
by-products. 
The reaction of monoolefinic hydrocarbon and unsaturated dicarboxylic acid 
compounds may be carried out by a single-step procedure where the entire 
amounts of reactants are heated together. However, it is advantageous to 
employ a multi-step procedure in which excess olefinic hydrocarbon, up to 
a 10:1 mol ratio of olefin to dicarboxylic acid compound, is unsaturated 
dicarboxylic acid compound to give the monoalkenyl dicarboxylic acid 
compound as the monoadduct of the first step. The excess olefin is then 
distilled from the monoadduct of the first step and a second mol of 
unsaturated dicarboxylic acid compound is adducted to give hydrocarbyl 
polycarboxylic acid product having an average of at least 4 carboxyl 
groups per molecule. In like manner, additional unsaturated dicarboxylic 
acid compound or corresponding 2,3-unsaturated monocarboxylic acid 
compound of 3 to 7 carbon atoms such as acrylic acid, methacrylic acid, 
methyl methacrylate, etc. may be added. 
In carrying out the reaction of the olefinic hydrocarbon and unsaturated 
dicarboxylic compound mixing may be used to provide proper contact of the 
reactants. Polymerization inhibitors to prevent undesirable side reaction 
of the olefinic hydrocarbon and the unsaturated dicarboxylic acid 
compounds are also useful such as hydroquinone, orthocresol, or butylated 
hydroxytoluene. Also, it may be desirable to maintain low conversion rates 
of 50% or less and to recycle the unreacted materials in the reaction. 
This avoids overlong reaction periods which lead to undesirable 
by-products as evidenced by poor color. 
The hydrocarbyl tetracarboxylic acid product of the process of this 
invention may be used as it comes from the reaction. However, in most 
instances it is desirable to remove unreacted hydrocarbon and other 
materials by such means as fractional distillation, solvent extraction, 
decantation and the like. 
Certain modifications of the hydrocarbyl polycarboxylic acid product of the 
process of the present invention may also be contemplated. For example, 
the alkenyl group may be halogenated, epoxidized or hydrogenated. Also the 
carboxyls may be reduced to provide hydroxy analogs useful in the 
preparation of polysulfates and other derivatives having a variety of 
surface-active properties. 
Hydrogenation of the double bond of the alkenyl group is readily 
accomplished by any of the well-known hydrogenation processes. Catalytic 
hydrogenation is preferred. See, for instance, the "Catalytic 
Hydrogenation" section et. seq. at pages 10-25, inclusive of the text 
entitled "Organic Preparations" by Weygand, published 1945 by Interscience 
Publishers, Inc., New York. Satisfactory catalysts include those 
containing nickel, platinum or palladium in either the free or supported 
state. Raney nickel is a particularly preferred unsupported catalyst. 
Supported catalysts include platinum on kieselguhr, palladium on carbon, 
etc. 
The following examples illustrate the process according to the present 
invention and products derived therefrom. These examples are in no manner 
intended to limit the invention described. Unless otherwise indicated, 
percentages are on a weight basis.

EXAMPLE 1 
Preparation of Octenyl Succinic Anhydride 
A 1-gallon stirred autoclave was flushed with nitrogen and then charged 
with 1,800 g. (16.05 mols) of octene-1, 1,136 g. (11.6 mols) of maleic 
anhydride, and 20 g. of p-hydroquinone. The autoclave was closed and 
heated for 19 hours at 200.degree. C. At the end of this time, the 
reaction mixture was charged to a Rotovac apparatus operating at 
50.degree. C. and 20 mm. of pressure, wherein 573.3 g. (5.12 mols) of 
octene-1 were removed. The concentrated reaction mixture was next charged 
to a wiped-film evaporator operating at 150.degree. C. under 0.1 mm. of 
pressure. In this way there was obtained 736 g. (8.23 mols) of octenyl 
succinic anhydride, 23.3 g. (0.21 mol) of octene-1, and 479.6 g. of 
high-boiling bottoms. Based on 100% conversion of maleic anhydride, the 
yield of octenyl succinic anhydride was 71% (mol). The product was a pale 
yellow, viscous liquid. 
This product had an NMR spectrum consistent with the structure of octenyl 
succinic anhydride. The infrared spectrum showed strong adsorption at 
1,790 and 1,875 cm.sup.-1. Analysis calculated for C.sub.12 H.sub.18 
O.sub.3 : C, 68.54%, H, 8.62%; Found: C, 68.44%, H, 8.60%. 
EXAMPLE 2 
Preparation of Octenyl Bis(Succinic Anhydride) 
A 1-liter, 3-necked round-bottom flask, equipped with a stirrer, a 
thermometer, a gas inlet tube, and a reflux condenser was flushed with 
nitrogen. It was then charged with 383 g. (1.82 mols) of octenyl succinic 
anhydride and 100 g. (1.0 mol) of maleic anhydride. The contents of the 
flask were heated under nitrogen with stirring for 16 hours at 200.degree. 
C. At the end of this time, the resulting solution was charged to a 
wiped-film evaporator operating at 135.degree.-140.degree. C. under 0.075 
mm. of pressure. In this way there was obtained 179 g. (0.85 mol) of 
distilled overhead, identified as octenyl succinic anhydride and 293 g. 
(0.95 mol) of undistilled octenyl bis(succinic anhydride). There was no 
recovery of unconverted maleic anhydride. Therefore, the yield of octenyl 
bis(succinic anhydride) based on maleic anhydride consumed was 95%. 
This product was a low melting semisolid. It was purified by vacuum 
sublimation of 100.degree. C. and 10.sup.-5 mm. pressure. The NMR 
spectrum was consistent with octenyl bis(succinic anhydride). Infrared 
spectra showed strong adsorption at 1,710, 1775 and 1,865 cm.sup.-1. The 
sublimed material was a tacky semisolid. Analysis calculated for C.sub.16 
H.sub.21 O.sub.6 : C, 62.3%, H, 6.53%; Found: C, 62.1%, H, 6.46%. 
Table I which follows is a compilation of other alkenyl bis(succinic 
anhydrides prepared essentially as in Examples 1 and 2. 
TABLE I 
__________________________________________________________________________ 
ALKENYL BIS(SUCCINIC ANHYDRIDES) 
Alkenyl Succinic 
Maleic 
Reaction 
Anhydride Maleic 
Reaction 
Alkenyl Bis- 
Anhy- 
Condi- Charged 
Anhy- 
Condi- (Succinic 
Ex. 
Olefin dride 
tions Recovered 
Step 2 
dride 
tions Anhydride) 
No. 
Name Grams 
Grams 
T.degree. C 
Hr Grams Grams Grams 
T.degree. C 
Hr Grams 
__________________________________________________________________________ 
3 Cyclohexene 500 294 200 19 378 218 67 200 17 81 
4 C.sub.15 -C.sub.20 Isomerized 
Olefin Commercial Sample 450 
66 220 8 389 
5 Octene-2 550 250 200 22 138 201 50 250 18 63 
6 Penetene-1 256 179 200 19 112 111 32 200 4 59 
7 2-Methylpentene-2 
420 245 200 19 337 300 85 200 7 124 
8 Octenes.sup.1 
220 98 200 16 149 140 34 205 8 84 
9 Diisobutylene 
224 98 200 19 187 118 45 200 24 87 
10 Dodecene-1 336 98 200 19 200 532 98 230 22 119 
11 C.sub.7 -C.sub.9 Alpha-Olefin 
500 142 200 19 272 300 98 210 7 184 
__________________________________________________________________________ 
.sup.1 Equilibrium mixture of n-octenes 
EXAMPLE 12 
Preparation of Tetramethyl Octenyl Bis(Succinate) 
Octenyl bis(succinic anhydride), 50 g. (0.163 mol), was heated at reflux in 
200 ml. of methanol for 18 hours, then 2 ml. of conc. H.sub.2 SO.sub.4 was 
added to the solution which was heated at reflux for 6 hours. The cooled 
mixture was poured into 1 liter of water. The organic layer was separated, 
dried and then distilled at 190.degree.-210.degree. C. at 0.6 mm. of 
pressure to afford 58.5 g. (0.145 mol) of product. 
The tetramethyl ester was obtained as an oil. The NMR spectrum was 
consistent with the assigned structure. Infrared analysis showed strong 
adsorptions at 1,740, 1,440 and 1,165 cm.sup.-1. Analysis calculated for 
C.sub.20 H.sub.32 O.sub.8 : C, 59.98%, H, 8.05%; Found: C, 60.04%, H, 
7.89%. 
EXAMPLE 13 
Preparation of Tetrabutyl Octenyl Bis(Succinate) 
50 g. (0.163 mol) of octenyl bis(succinic anhydride) was heated at reflux 
for 18 hours in a solution of 3 g. of p-toluene sulfonic acid and 150 ml. 
of 1-butanol in 150 ml. dry toluene. Water from the esterification 
reaction was collected in a Dean-Stark moisture receiver. When the 
theoretical amount of water was collected, heating was stopped and the 
solution cooled, washed with three 50 ml. portions of 10% NaOH solution, 
then two ml. portions of water. The organic layer was dried over 
MgSO.sub.4, filtered, toluene and unreacted butanol were removed from the 
solution by means of a rotary evaporator at 70.degree. C. and 20 mm. 
pressure. The residual oil was purified by passing it through a wiped-film 
evaporator operating at 240.degree.-250.degree. C. and 0.1 mm. of 
pressure. The ester, 68 g. (0.119 mol), was taken overhead as a very pale 
yellow viscous oil. Analysis was consistent with the tetrabutyl structure. 
The following Table II is a compilation of esters prepared from the alkenyl 
bis(succinic anhydrides) of this invention by procedures essentially the 
same as Examples 12 and 13. 
TABLE II 
__________________________________________________________________________ 
ESTERS OF ALKENYL BIS(SUCCINIC ANHYDRIDES) 
Alkenyl Bis- 
(Succinic Anhydride) 
Ex. No. 
Alkenyl Group 
Tetraesters 
__________________________________________________________________________ 
14 Pentenyl n-Butyl 
15 Cyclohexenyl n-Butyl 
16 Octenyl Methyl 
n-Butyl 
n-Octyl 
17 C.sub.15 -C.sub.20 Alkenyl 
Methyl 
18 C.sub.7 -C.sub.9 Alkenyl 
Methyl 
n-Butyl 
n-Octyl 
Isobutyl 
19 Dodecenyl n-Butyl 
20 Octadecenyl n-Butyl 
__________________________________________________________________________ 
The vinyl chloride polymer compositions of the invention contain the esters 
of hydrocarbyl tetracarboxylic acid in amounts sufficient to impart 
plasticizing properties. The quantity of plasticizer depends upon the 
particular polymer to be plasticized and upon its molecular weight. 
However, it is generally found that from about 5 to about 50 percent by 
weight of plasticizer based on the total polymer composition will be 
satisfactory from the standpoint of overall utility. 
The vinyl chloride polymers of the composition are a well known class of 
materials. Such materials include polyvinyl chloride and the copolymers of 
at least 70 percent by weight of vinyl chloride with other unsaturated 
monomers including vinyl acetate, vinylidene chloride, etc. 
In further illustration of the vinyl chloride polymer compositions 
according to the present invention, several compositions were prepared and 
subjected to typical tests for evaluation of their properties. These 
compositions and the test results are given in the following Table III. 
In the test mixtures, 40 g. of polyvinyl chloride were combined in molten 
form with 20 g. of the plasticizer to be tested and 0.8 g. of a 
conventional barium-cadmium stabilizer (Thermolite 116). 
The compositions were tested for weight loss under heat conditions by aging 
in an oven at 88.degree. C. The aging process was carried out in 
circulating air and lasted for 64 hours. Tests were also carried out on 
the vinyl chloride polymer compositions to demonstrate resistance to 
extraction by hydrocarbons and water. In these tests, specimens of the 
vinyl chloride polymer compositions were placed in kerosene or in water in 
closed jars. The kerosene jars were maintained at 50.degree. C. for 24 
hours and the water jars were maintained at 50.degree. to 55.degree. C. 
for 24 hours. The percent weight loss of plasticizer was determined by the 
initial and final weights of the specimens. 
The flexibility characteristics were determined by observing the lower 
temperature limit of usefulness in accordance with the standard method 
outlined in ASTM D 1043-61T. In this test, the torsional flexibility of 
the plastic is determined at various temperatures and the temperature at 
which the vinyl composition exhibits an arbitrarily established minimum 
flexibility is noted as the low temperature flexibility of the 
composition. 
The Shore hardness of the vinyl chloride composition is determined in 
accordance with the standard method using the Shore instrument (ASTM D 
676-49T). In this test, the hardness is determined in units of from 1 to 
100, according to its resistance to penetration by a standard needle which 
is applied to the composition under a stadard load for a standard length 
of time. The lower numbers indicate the harder compositions having greater 
resistance to penetration. 
TABLE III 
__________________________________________________________________________ 
TETRAESTERS OF ALKENYL BIS(SUCCINIC ANHYDRIDE) AS PLASTICIZERS 
Oven Aging 
Extraction Flexibility 
Ex. Tetra- 
Wt. Loss 
By Kerosene 
By H.sub.2 O 
Temperature 
Shore 
No. 
Alkenyl Group ester 
% % % .degree. C. 
Hardness 
__________________________________________________________________________ 
21 Dioctyl phthalate 
-- 1.0 8.0 0.2 -27 83 
22 Tri(octyl/decyl) mellitate.sup.1 
-- 0.8 13.1 0.2 -26 91 
23 Pentenyl n-butyl 
1.6 3.1 0.3 -19 82 
24 Octenyl n-butyl 
0.7 4.8 0.3 -22 85 
25 Octenyl methyl 
1.4 2.3 1.4 -12 86 
26 C.sub.7 -C.sub.9 alkenyl 
i-butyl 
7.5 9.0 0.3 -28 82 
27 C.sub.7 -C.sub.9 alkenyl 
n-butyl 
0.9 6.5 0.3 -24 84 
28 C.sub.7 -C.sub.9 alkenyl 
methyl 
4.1 5.5 5.9 -15 87 
29 Hydrogenated octenyl 
n-butyl 
3.0 5.4 0.3 -25 83 
30 Dodecyl methyl 
1.6 4.3 0.7 -17 87 
31 C.sub.15 -C.sub.20 alkenyl 
methyl 
0.8 1.9 0.3 -13 89 
__________________________________________________________________________ 
.sup.1 Prepared from a commercial mixture of octanol and decanol 
In the above table, Examples 1 and 2 were dioctyl phthalate and octyl/decyl 
trimellitate, respectively. These are widely accepted commercial 
plasticizers and were included in the evaluations for the purpose of 
comparison. 
Hydrogenation of alkenyl or cycloalkenyl bis anhydride, acid or ester to 
the corresponding alkyl or cycloalkyl connecting group is illustrated by 
the following examples. 
EXAMPLE 32 
Hydrogenation of Octenyl bis-(Succinic Acid) 
A 10-g sample of octenyl bis(succinic acid) was hydrogenated in 120 ml of 
water over approximately 4 g of W-2 Raney nickel catalyst at an initial 
H.sub.2 pressure of 50 psi for 14 hours. Slightly more (110%) of the 
theoretical pressure drop was realized at the end of this time. The 
catalyst was removed by filtration and water under reduced pressure by 
means of a rotary evaporator. The residue was dried in a vacuum desiccator 
over P.sub.2 O.sub.5 for several days to afford a white deliquescent 
powder which was not further characterized. 
EXAMPLE 33 
Hydrogenation of Octenyl bis(Succinic Anhydride) 
Octenyl bis(succinic anhydride) (31 g [1 mol]) in 150 ml anhydrous dioxane 
was hydrogenated over 3 g of 5% palladium-on-carbon catalyst at an initial 
hydrogen pressure of 50 psi. At the end of 42 hours, 80% of the 
theoretical pressure drop was realized, and no more hydrogen was taken up 
even after the addition of fresh catalyst. The catalyst was then removed 
by filtration and dioxane removed under reduced pressure by means of a 
rotary evaporator to leave 31.6 g of brown, tacky residue. A small portion 
of this material was purified by high vacuum sublimation (130.degree. C at 
5 .times. 10.sup.-3 mm Hg) and obtained as a colorless semisolid. 
Analysis calculated for C.sub.16 H.sub.22 O.sub.6 : C, 62.32%; H, 6.53%. 
Found: C, 66.46%, H, 7.79%. 
In addition to providing flexibility to the final plastic object, a 
satisfactory plasticizer must not change the color of the plastic; and it 
must not be easily removed by either volatilization or extraction. Tests 
have been devised to measure all of the above properties. Surprisingly, 
extractability by soapy water or kerosene is less for the hydrogenated 
ABSA as compared to ABSA. The following runs illustrate this effect. 
PVC test blanks were prepared by mixing 40 parts of PVC, 20 parts of the 
test plasticizer, and 0.8 part of a stabilizer (tin stearate) in a 
Brabender mixer until homogeneity was obtained. The resulting mixture was 
extruded into sheets, which were cut into appropriate-size test swatches. 
Different swatches, from the same blended mixture, were tested for: (1) 
color, (2) flex temperature, (3) tensile properties, (4) hardness, (5) 
volatility, and (6) extractability. The results are shown in Table V 
Long-term soapy water extraction tests were carried out at 70.degree. C. on 
swatches of PVC containing the tetra-n-butyl ester of octenyl-bis(succinic 
acid) and the corresponding hydrogenated compound. The results were as 
follows in Table IV: 
TABLE IV 
______________________________________ 
Weight Loss, % 
Unsaturated 
Saturated Commercial 
Time, hrs 
Compound Compound Dioctyl Phthalate 
______________________________________ 
50 6 3 8 
120 12 6 17 
190 16 10 20 
______________________________________ 
The above results, and particularly those of the long-term soapy water 
extraction tests, show that the hydrogenated ABSA compounds have a 
surprisingly low solubility as compared to the unsaturated ABSA compounds. 
This improvement in resistance to extraction by soapy water due to two 
additional hydrogens in the molecule is wholly unpredictable and, 
therefore, unexpected. 
TABLE V 
__________________________________________________________________________ 
Plasticized PVC Sheet 
Tensile Properties.sup.3 
100% Break Vola- 
Extraction Loss 
Identity Flex Modu- 
Break Elon- 
Hardness 
tility 
Kero- 
Water 
Run 
Tetra-n-butyl Temp.,.sup.2 
lus, 
Strength, 
gation, 
Shore A,.sup.4 
Loss,.sup.5 
sene,.sup.6 
Distilled, 
Soapy, 
No. 
Ester of Color.sup.1 
.degree. C 
psi psi % 10 Sec. 
% % %.sup.7 
%.sup.8 
1 Octene-1 ABSA.sup.9 
&lt;1 -22 1940 
2880 240 85 1.7 4.8 0.3 6.1 
2 Hydrogenated 1.sup.10 
2 -25 1810 
2990 260 83 3.0 5.4 0.3 ---.sup.14 
3 C.sub.7 -C.sub.9 Alkenyl ABSA.sup.11 
3 -24 1900 
2920 240 84 0.9 6.5 0.3 -- 
4 Hydrogenated 3 
&lt;1 -24 1890 
2750 220 85 1.7 7.6 0.3 7.5 
5 Pentene-1 ABSA.sup.12 
3 -19 1990 
2840 220 82 1.6 3.1 0.3 -- 
6 Hydrogenated 5 
&lt;1 -19 2110 
3000 220 85 1.3 2.5 0.4 12.6 
7 Dodecene-1 ABSA.sup.13 
9 -20 2000 
2660 210 89 1.3 5.0 0.3 3.1 
8 Hydrogenated 7 
3 -20 1920 
2510 200 89 1.2 4.5 0.2 2.4 
9 Isobutylene ABSA.sup.13 
7 -24 1850 
3010 235 80 6.8 8.6 1.6 -- 
10 Hydrogenated 9 
4 -20 1800 
2920 240 83 3.3 4.2 1.5 13.7 
11 Propylene ABSA 
4 -26 2000 
3170 250 80 2.2 10.2 
0.5 -- 
12 Hydrogenated 11 
4 -24 1710 
2820 240 82 1.2 4.7 0.6 15.1 
13 Cyclohexene ABSA 
3 -12 2010 
2630 200 87 1.8 1.4 0.7 9.8 
14 Hydrogenated 13 
4 - 3 2370 
2770 180 89 1.1 0.2 0.5 8.4 
__________________________________________________________________________ 
.sup.1 Color by Gardner scale 
.sup.2 ASTM D 1043-61T 
.sup.3 ASTM D 412-64T 
.sup.4 ASTM D 1706-61 
.sup.5 After 64 hours in 83.degree. C circulating air 
.sup.6 After 24 hours at 50.degree. C 
.sup.7 After 24 hours at 58.degree. C 
.sup.8 After 48 hours at 80.degree. C 
.sup.9 Example 24 
.sup.10 Example 29 
.sup.11 Example 27 
.sup.12 Example 23 
.sup.13 Average of two runs 
.sup.14 See long-term soapy water extraction results of Table IV 
It will be seen from the evaluation that the vinyl chloride polymer 
compositions of the invention containing esters of alkyl or cycloalkyl 
tetracarboxylic acid have desirable chemical and physical properties when 
compared to the presently accepted plastics compositions of the art. 
The vinyl chloride compositions of the invention, as illustrated by the 
above examples, may also contain other materials commonly used with such 
compositions along with the plasticizer. For example, stabilizer such as 
the salts and soaps of lead, tin, calcium, barium, zinc, lithium, as well 
as organo phosphites and epoxidized oils and esters and the like may be 
used. Also dyes, pigments, opacifiers, fillers and the like may be used. 
While the character of this invention has been described in detail with 
numerous examples, this has been done by way of illustration only and 
without limitation of the invention. It will be apparent to those skilled 
in the art that modifications and variations of the illustrative examples 
may be made in the practice of the invention within the scope of the 
following claims.