New cumylphenol derivatives are described which are useful as reactive diluents, plasticizers and impact modifiers for polymeric materials. The derivatives include the higher alkanoic, alkenoic, aryl carboxylic and alkaryl carboxylic esters of monocarboxylic acids, the esters of polycarboxylic acids and inorganic acids, and glycidyl, alkenyl and aralkyl ethers. The borate esters of cumylphenol are particularly useful as impact modifiers with flame retardant properties.

BACKGROUND OF THE INVENTION 
Cumylphenol and certain of its derivatives have been described in the prior 
art. See particularly Tsivunin et al., Biol. Akliv. Soldin. 1968, 172-5 
(Russ.). Finding a use for such materials has been particularly desirable 
since they are readily available as by-products from commercial processes 
such as the making of phenol from cumene. 
Similarly, it has long been desired to improve the properties of polymeric 
material and reactive diluents, plasticizers and impact modifiers which 
serve such functions at low costs have long been sought. Though numerous 
materials are known to satisfy these needs, they are frequently deficient 
because of their costs or because of incompatibility with the particular 
polymer. 
BRIEF DESCRIPTION OF THE INVENTION 
The invention concerns derivatives of cumylphenol and their use in 
polymeric materials. More specifically, the invention describes higher 
alkyl, alkenyl, aryl and alkaryl monocarboxylic acid esters of 
cumylphenol; polycarboxylic acid esters of cumylphenol; inorganic esters 
of cumylphenol; and glycidyl, alkenyl and aralkyl ethers of cumylphenol. 
These materials are useful as reactive diluents in epoxy, phenolic, and 
urethane compounds; effective as plasticizers in polyvinyl chloride, 
polystyrene and urethane; and useful as impact modifiers in 
styrene-acrylonitrile, polystyrene, phenolic and polyvinyl chloride 
resins. Additionally, the borate ester has flame retardant properties. 
While not each and every cumylphenol derivative is effective in all of the 
aforesaid applications, these compounds all exhibit useful properties 
within certain of the aforesaid fields. 
DETAILED DESCRIPTION OF THE INVENTION 
Cumylphenol and derivatives thereof have been found useful as reactive 
diluents for a variety of resins, e.g., epoxy, furan, phenolic, urethane, 
polyester and acrylate resins. The glycidyl ether derivative serves this 
function for urethane resins. The alkenoic esters are useful in polyesters 
and acrylates. These compounds are new compositions of matter and provide 
a low cost replacement for conventionally employed co-monomeric materials. 
In certain instances, their use improves the chemical and physical 
properties of the cured resins. 
In still another embodiment of the invention, it has been found that esters 
of cumylphenol are useful as non-reactive plasticizers for polyurethanes. 
The benzoate and the higher acyl esters, which are unique compounds, may 
be used for rigid polyvinyl chloride. Here again the cost of the finished 
resin may be markedly reduced. 
In a further embodiment of the invention, the borate, benzoyl, and 
glutarate esters and the benzyl and allyl ethers of cumylphenol have been 
found to be useful impact modifiers for polystyrene, 
styrene-acrylonitrile, phenolic and vinyl chloride resins. 
The derivatives of cumylphenol which are useful in the invention may be 
represented by the following formula: 
##STR1## 
wherein R is an acyl group, 
##STR2## 
a glycidyl group having 3 to 6 carbon atoms; an alkenyl group having from 
3 to 12 carbon atoms, or an aralkyl group having from 7 to 12 carbon 
atoms; and wherein the R' above is an alkyl group having 6 to 12 carbon 
atoms, alkenyl group having 2 to 12 carbon atoms, aryl group having from 6 
to 12 carbon atoms or aralkyl group having from 7 to 12 carbon atoms. 
When R is a glycidyl group, the preferred radical is 
##STR3## 
when it is an alkenyl, the preferred radicals are allyl and methallyl; and 
when it is aralkyl, the preferred radical is benzyl. Most preferably, R' 
is a phenyl, vinyl or isopropenyl group. The acetyl derivative is 
described by Tsivunin et al., Biol. Akliv Soldin. 1968, 172-5 (Russ.). 
However, the glycidyl, alkenyl and aralkyl ethers; the aryl carboxylic, 
alkaryl carboxylic and alkenoic esters; and the higher alkyl carboxylic 
esters of cumylphenol are new compositions of matter. 
Still another group of derivatives are the cumylphenol esters of 
polyfunctional acids. The compounds may be based on both organic and 
inorganic acids. These materials may be readily prepared by reacting, for 
each mole of acid, a number of moles of cumylphenol equal to the 
functionality of the acid. In the case of the organic acids, these are 
novel compounds and may be have two or three carboxylic acid groups and 
from 2 to 8 additional carbon groups per molecule. Such compounds may be 
saturated or unsaturated, aliphatic or aromatic. Most preferred is the 
derivative of glutaric acid, i.e., dicumylphenyl glutarate. Other 
compounds include the derivatives of cinnamic acid, crotonic acid, sorbic 
acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, 
succinic acid, fumaric acid. Half esters of these acids may also be used, 
in which case only sufficient cumylphenol is reacted to combine with the 
unesterified carboxyl group. 
With respect to the esters of inorganic compounds, these include the 
borate, phosphite and phosphate esters. The borate esters are novel 
compounds. 
Where the cumylphenol derivatives are used as reactive diluents, they may 
be present in from about 10 to about 200 parts per 100 parts of the resin, 
preferably from about 20 to about 50 parts. 
In non-reactive plasticizer applications, from 15 to 60 wt. %, preferably 
from 20 to 40 wt. %, of the appropriate ester of the cumylphenol is used 
based on total weight of resin. 
As an impact modifier, from 0.5 to 30 wt. %, preferably from 1 to 10, of 
the cumylphenol derivative should be used for each part of the resin in 
question. 
In the applications of the invention where the cumylphenols are used as 
reactive diluents or non-reactive plasticizers, the cumylphenol compound 
is initially blended with the appropriate resin along with other desired 
components. The blend is fed to the polymerizing reactor and the resin 
polymerized in accordance with known techniques for the particular resin. 
The resins which are cured and formed in the practice of the invention 
include those generically referred to as "liquid thermoset resins." By 
this term is meant resins which are in the liquid state under conditions 
of application and include casting resins, i.e., liquid monomer or 
incompletely polymerized polymers, usually containing catalysts or curing 
agents, capable of becoming hard after they are cast in molds; and coating 
resins, i.e., liquid monomers or incompletely polymerized polymers, 
optionally in a solvent or non-solvent extender, which are capable of 
application by casting, potting, brushing, rolling, spraying or dipping. 
These include paints, varnishes, enamels, lacquers, and casting and 
potting resins. 
Of these resin, those of particular interest in the instant invention are 
furans, phenolics and urethanes. These may briefly be described as 
follows: 
The furan resins are thermosetting resins obtained primarily by the 
condensation polymerization of furfural alcohol in the presence of a 
strong acid, sometimes in combination with formaldehyde or furfural. The 
term also includes resins made by condensing phenol with furfuryl alcohol 
or furfural, and furfuryl-ketone polymers. 
Phenolic resins are a family of thermoset resins made by the reaction of 
phenols with aldehydes such as formaldehyde, acetaldehyde, or furfural in 
the presence of either acidic or basic catalysts. For casting, B-stage 
resins are generally used. Examples of the phenols are di- and trivalent 
phenols such as cresol, resorcinol and cardanol. In casting resin 
applications, a large excess of formaldehyde is generally used with sodium 
hydroxide as the catalyst. The reaction is usually carried out at about 
64.degree. C. 
The polyurethanes are a family of resins produced by reacting diisocyanates 
with organic compounds containing two or more active atoms to form 
polymers having free isocyanate groups. A detailed description of these 
resins is given in U.S. Pat. No. 3,060,137, issued Oct. 23, 1962. These 
groups, under the influence of heat or catalyst, will react with each 
other or with water, glycols, etc., to form thermosetting materials. 
Rigid polyvinyl chloride resins optionally contain extenders, pigments, 
stabilizers and a small proportion of plasticizers wherein the proportion 
of plasticizer is insufficient to reduce tensile modulus below about 2000 
psi. 
Polystyrene resins are thermoplastic resins prepared by the polymerization 
of high purity styrene, generally in the presence of free radical 
producing catalysts. They may be made by any of the conventional 
polymerization methods. 
Styrene-acrylonitrile polymers are readily prepared by copolymerizing 
styrene and acrylonitrile in the presence of a free radical catalyst. See 
Teach, W. C., et al., "Polystyrene," Plastics Application Series, Reinhold 
Publishing Corp., New York, 1960.

The following examples show specific embodiments of the invention: 
EXAMPLE A: Preparation of Cumylphenyl Glycidyl Ether 
The cumylphenyl glycidyl ether was prepared as follows: a 3-liter flask 
equipped with a mechanical stirrer, thermometer, addition funnel, and 
external heating and cooling devices was charged sequentially with 1 liter 
of benzene, 1 liter of 4.5 wt. % aqueous sodium hydroxide and 1 mole of 
cumylphenol. The cumylphenol salt dispersion formed after mixing was 
cooled to 10.degree.-15.degree. C., mixed and maintained at 
10.degree.-15.degree. C. during the addition of 1.1 moles of 
epichlorohydrin over a four hour period. After the addition of the 
chlorohydrin, the reaction mix was warmed to 50.degree. C. for 8 hours. 
The two phases which formed were separated and the water phase discarded. 
The organic phase was thrice washed with cold water and the residual 
organic material fractionated. One hundred ninety grams (71 mole %) of a 
pale yellow oil having a boiling point at 5 mm Hg of 
258.degree.-263.degree. C. was obtained. The oil had an Epoxide Number 
determined by MgCl.sub.2 -HCl titration of 3.72 meq/g, while the 
theoretical Epoxide Number for cumylphenol glycidyl ether is 3.73 meq/g. 
The cumylphenyl glycidyl ether has the following properties: 
______________________________________ 
Color (Gardner) Max. 2 
Specific Gravity, 77.degree. F. (25.degree. C.) 
1.10 
Wt./Gal., lbs., at 25.degree. C. (77.degree. F.) 
9.2 
Weight per Epoxide (WPE) 286 
Molecular Weight 268 
Viscosity, cps at 25.degree. C. (77.degree. F.), Max. 
120 .+-. 10 
Flash Point, COC, .degree.F. (.degree.C.) 
250 (121) 
Purity, % 96.5 
______________________________________ 
This compound is useful as a viscosity reducing co-monomer in epoxy 
formulations, as a heat stabilizer in vinyl resins, and as an impact 
modifier for phenolics. 
EXAMPLE B: Preparation of Cumylphenyl Benzyl Ether 
The apparatus and procedure of Example A was used, except that benzyl 
chloride (in place of the epichlorohydrin) was added and the temperature 
was maintained at 50.degree. C. The reaction mixture was refluxed for two 
hours and the product recovered as described in Example 1. The yield of 
the benzyl either was 74 mole% and the product had a boiling point of 
218.degree. to 221.degree. C. at 1 mm Hg. 
The cumylphenyl benzyl ether has the following properties: 
______________________________________ 
Appearance: Waxy Solid/Heavy Liquid 
Specific Gravity 1.04 
Wt./Gal., lbs. 8.66 
Viscosity at 200.degree. F. (93.degree. C.), cps 
25 .+-. 5 
Flash point (COC), Min., .degree.F. (.degree.C.) 
350 (176) 
Vapor Pressure (mm Hg.), 
Max. 200.degree. F. (93.degree. C.) 
1 
Pour Point, Max. .degree.F. (.degree.C.) 
(supercools easily) 150 (66) 
Minimum Assay by gas chromatograph 
(GC)% 85 
______________________________________ 
This compound is useful as an impact modifier for styrene resins, e.g., ABS 
and SAN, polyphenylene oxide and polyphenylene sulfide. It is also 
effective in making cellulose compatible with styrenic resins and styrenic 
resins compatible with nylon and polyester. 
EXAMPLE C: Preparation of Cumylphenyl Allyl Ether 
The apparatus and procedure of Example A was used to prepare the allyl 
ether, except that allyl chloride was used in place of the 
epichlorohydrin. A yield of 84 mole % was obtained. The allyl ether had a 
boiling point of 186.degree. to 190.degree. C. at 1 mm Hg. 
The cumylphenyl allyl ether has the following properties: 
______________________________________ 
Appearance: Moderate Viscosity Yellow Liquid 
Specific Gravity 1.03 
Wt./Gal., lbs. 8.60 
Viscosity at 75.degree. F. (24.degree. C.), cps 
130 .+-. 15 
Flash Point (COC), Min. .degree.F. (.degree.C.) 
200 (93) 
Vapor Pressure at 75.degree. F. (24.degree. C.), 
(mm Hg.) Max. 1 
Pour Point, Max. .degree.F. (.degree.C.) 
0 (-18) 
Min. Assay by GC, % 85 
______________________________________ 
This compound is useful as a reactive diluent for unsaturated polyesters 
and as a peroxide reactive plasticizer for vinyls and ink applications. 
EXAMPLE D: Preparation of Tri(cumyl phenyl) Borate 
This ester was prepared by refluxing for two hours equal molar amounts of 
cumylphenol with tri-n-butyl borate. About 93% of by-product butanol was 
then recovered by fractionation. The residue boiled at over 150.degree. C. 
at 1 mm Hg. Elemental analysis showed a boron content of 1.7%, 
substantially the same as the calculated value. 
The tri(cumyl phenyl) borate has the following properties: 
______________________________________ 
Appearance: White-tan crystalline solid 
Specific Gravity 1.10 
Wt./Gal., lbs. 9.16 
Viscosity at 300.degree. F., cps 
70 .+-. 10 
Flash Point (COC), .degree.F. (.degree. C.), Min. 
600 (316) 
Acid Number, Meg./100g. Max. 
0.5 
Melting Range, .degree.F. (.degree.C.) 
205-228 (96-109) 
______________________________________ 
This compound is useful as a flame retardant in resins and the like and as 
a plasticizer for cellulose ethers and esters. 
EXAMPLE E: Preparation of Cumylphenyl Benzoate 
Cumylphenyl benzoate is prepared in accordance with the following 
procedure: one mole of cumylphenol was dissolved in 600 ml of benzene 
containing 1.2 moles of triethylamine in a 2-liter stirred glass reactor 
equipped with external heating and cooling devices. The reaction mass was 
cooled to and maintained at 15.degree.-20.degree. C. during the addition 
of 1.1 moles of benzoyl chloride over a period of 1.5 hours. After 
completion of addition, the resulting slurry was heated to and maintained 
at 40.degree.-45.degree. C. for 1 hour, and thereafter cooled to ambient 
temperature and filtered. The filter cake was washed with 200 ml of 
toluene and the combined washings and filtrate distilled to give 214.9 g 
(68 mole %) of a pale yellow oil having a boiling point at 0.5 mm Hg of 
261.degree.-265.degree. C., a specific gravity at 55.degree. C. of 1.082, 
and a viscosity at 55.degree. C. of 215 cps. On standing, the oil 
solidified to form a white solid having a melting point of 
43.degree.-46.5.degree. C. 
The cumylphenyl benzoate has the following properties: 
______________________________________ 
Color (Gardner), Max. 4 
Specific Gravity 1.13 
Wt./Gal., lbs. 9.4 
Viscosity at 100.degree. C. (212.degree. F.), cps 
15 
Flash Point, COC, Min., .degree.F. (.degree.C.) 
450 (232) 
Hydroxyl Number, Meg./100g (Max.) 
0.2 
Acid Number, Meg./100g (Max.) 
0.2 
Saponification Value 188 
Pour Point (Supercools easily), 
.degree.F. (.degree.C.) 140 (60) 
______________________________________ 
This compound is useful as a process aid, i.e., melt index improver, for 
rigid vinyl systems and thermoplastic polyesters and for reaction 
injection molded urethanes, particularly where high mineral filler 
loadings are employed. 
EXAMPLE F: Preparation of Dicumylphenyl Glutarate 
This compound was prepared by reacting 1 mole of dimethyl glutarate with 2 
l moles of cumylphenyl acetate in the presence of 0.5 wt. % of sulfuric 
acid as catalyst. During the reaction, acetic acid was distilled overhead 
until the bottoms product boiled over 150.degree. C. at 1 mm Hg. 
Thereafter, the product was neutralized with calcium carbonate, filtered 
and recrystallized from toluene. The product obtained was a hard, white, 
waxy solid. The yield was 83% of theory. 
The dicumylphenyl glutarate has the following properties: 
______________________________________ 
Appearance: Hard White Wax 
Specific Gravity 1.13 
Wt./Gal., lbs. 9.41 
Viscosity at 350.degree. F. (176.degree. C.), cps 
140 .+-. 15 
Flash Point (COC), Min. .degree.F. (.degree.C.) 
700 (371) 
Vapor Pressure (mm Hg.), Max. 
200.degree. F. (93.degree. C.) 
1 
Melting Range, .degree.F. (.degree.C.) 
250-280 (121-138) 
Acid Number, Meq./100g Max. 
0.5 
______________________________________ 
This compound is useful as a process aid in polyacrylate and 
polyacrylonitrile extrusion and molding operations. 
EXAMPLE G: Preparation of Cumylphenyl Acrylate 
Cumylphenyl acrylate was prepared in the apparatus described in Example A. 
One mole of cumylphenol and 2 moles of calcium carbonate were slurried in 
the presence of 1 liter of toluene solvent. During a period of 2 hours, 
one mole of acryl chloride was added to the solution while the temperature 
was maintained at 40.degree. to 50.degree. C. The reaction mixture was 
filtered and the filtrate distilled at 5 mm Hg. to produce a pale yellow 
oil boiling at 198.degree. to 203.degree. C. The yield was 84%. Gas 
chromatographic assay indicated that less than 3% of unreacted cumyl 
phenol was retained in the product. 
The cumylphenyl acrylate has the following properties: 
______________________________________ 
Appearance: Pale Yellow Oil 
Specific Gravity 1.07 
Wt./Gal., lbs. 8.91 
Viscosity at 75.degree. F. (24.degree. C.), cps 
105 .+-. 10 
Flash Point (COC), min. .degree.F. (.degree.C.) 
300 (150) 
Vapor Pressure at 75.degree. F. (24.degree. C.)(mm Hg) 
1 
Acid Number, Meq. 1100g. Max. 
0.5 
Pour Point, Max. .degree.F. (.degree.C.) 
0 (-18) 
______________________________________ 
This compound is useful as a co-monomer in peroxide cured acrylates, 
polyesters and alkyl resin formulations. It also imparts greater impact 
strength and higher curing rates as compared with conventional 
co-monomers, e.g., phenyl acrylate. 
EXAMPLE H: Preparation of Cumylphenyl Methacrylate 
The methacrylate ester was prepared by the procedure described in Example 
G, except that methacryl chloride was used in place of acryl chloride. The 
yield was 84%. 
The cumylphenyl methacrylate has the following properties: 
______________________________________ 
Appearance: Pale Yellow Oil 
Specific Gravity 1.06 
Wt./Gal., lbs. 8.83 
Viscosity at 75.degree. F. (24.degree. C.), cps 
110 .+-. 15 
Flash Point (COC), Min. .degree.F. (.degree.C.) 
330 (149) 
Boiling Range, .degree.F. (.degree.C.) at 5 mm 
415-431 (213-222) 
Acid Number, Meq./100g. max. 
0.5 
Pour Point, Max .degree.F. (.degree.C.) 
18 (-8) 
______________________________________ 
This compound is useful for the same application as the cumylphenyl 
acrylate. It is often superior, however, in enhancing impact strength, but 
it does not as effectively enhance the cure rate. 
EXAMPLE I: Preparation of Cumylphenyl 2-ethylhexanoate 
Cumylphenyl 2-ethylhexanoate was prepared in accordance with the following 
procedure: a 2-liter flask equipped with a mechanical agitator, a ten 
theoretical plate fractionating column, an automatic reflux splitter pot, 
vapor thermo-controllers, a condenser, receivers, and external heating and 
cooling devices, was charged with 2 moles of cumylphenyl acetate, 5 moles 
of 2-ethylhexanoic acid and 5 grams of 98% sulfuric acid. Heat was 
supplied externally and the distillate was collected at a 20:1 reflux 
ratio at a vapor temperature below 120.degree. C. at atmospheric pressure. 
A total of 64 cc of distillate was collected in 24 hours. The residual pot 
contents were cooled to ambient temperature and extracted 5 times with 2 
l. of 8% sodium bicarbonate dried over anhydrous Na.sub.2 SO.sub.4 and 
fractionated to give 408 g. (58 mole %) of a pale yellowish oil. The oil 
had a boiling point at 0.2 mm Hg of 252.degree.-257.degree. C., a specific 
gravity 20/20 of 1.045 and a saponification value of 2.82 meq/g. The 
cumylphenyl 2-ethylhexanoate ester has a theoretical saponification value 
of 2.85 meq/g. 
EXAMPLE J: Preparation of Cumylphenyl Phosphite 
Three moles of cumyl phenol dissolved in 2 l. of toluene were treated at 
75.degree.-80.degree. C. with 1 mole of phosphorus trichloride. The 
resulting by-product HCl gas was scrubbed with standard 1 M. aqueous NaOH. 
The HCl recovery was 96% of theory. The crude reaction product was 
crystallized on cooling and, after standing overnight, was recrystallized 
from petroleum ether (b.p. 40.degree.-60.degree. C.) to yield 582 g. (87 
mole % yield) of beige leaflets m.p. 69.degree.-71.degree. C. This product 
may be used as an antioxidant or antiozonant. 
EXAMPLE K: Preparation of Cumylphenyl Phosphate 
The phosphorus trichloride utilized in the above example was replaced by 1 
mole of phosphorus oxychloride to prepare the cumylphenyl phosphate. The 
HCl by-product recovery was 93% of theory. Using dioxane as the 
recrystallization solvent, a yield of 561 g. of white plate-like crystals 
were obtained having a m.p. of 128.degree.-131.degree. C. (82 mole%). The 
product may be used as a process aid (melt index improver) and impact 
modifier for rigid vinyl in place of triphenyl phosphate which is now used 
commercially. 
EXAMPLE 1 
This example shows the effect of cumylphenol and its derivatives on the 
physical properties of epoxy resins. Formulations were prepared using Epon 
828 (average viscosity, 16,000 centipoise) epoxy resins, 100 parts; 
triethylenetetramine as a curative, 12 parts; and Berkley #1 sand in 
amounts shown in the following table; and with cumylphenol and its acetate 
and glycidyl ether derivatives. The compressive strength and the tensile 
strength of compositions, cured at ambient temperature, were measured 
after five days. The following table shows the formulations and the 
results obtained: 
Table I 
______________________________________ 
Parts Compressive 
Tensile 
by Strength, 
Strength, 
Additive Weight Epoxy Sand psi M psi M 
______________________________________ 
None -- 88 200 12.0 0.9 
None -- 88 250 10.9 0.76 
None -- 88 300 9.5 0.71 
None -- 88 350 NP NP 
Cumylphenol 
22 66 200 17.3 1.2 
Cumylphenol 
22 66 250 16.9 1.0 
Cumylphenol 
22 66 300 16.5 0.91 
Cumylphenol 
22 66 350 15.8 0.82 
Cumylphenol 
22 66 400 NP NP 
Cumylphenyl 
Acetate 22 66 200 19.4 1.65 
Cumylphenyl 
Acetate 22 66 250 18.1 1.51 
Cumylphenyl 
Acetate 22 66 300 17.3 1.38 
Cumylphenyl 
Acetate 22 66 400 14.8 1.16 
Cumylphenyl 
Acetate 22 66 450 12.1 0.94 
Cumylphenyl 
Acetate 22 66 500 NP NP 
Cumylphenyl 
Glycidyl Ether 
22 66 200 14.6 1.08 
Cumylphenyl 
Glycidyl Ether 
22 66 250 13.7 0.98 
Cumylphenyl 
Glycidyl Ether 
22 66 300 12.1 0.92 
Cumylphenyl 
Glycidyl Ether 
22 66 400 9.9 0.83 
Cumylphenyl 
Glycidyl Ether 
22 66 450 NP NP 
______________________________________ 
NP = nonpourable 
The above table clearly shows that the compressive strength and the tensile 
strength are markedly improved by substituting the cumylphenyl or its 
derivatives for a portion of the epoxy composition. The table further 
shows that 400, 500 and 450 parts of sand were added in the cases of the 
cumylphenol, the cumylphenyl acetate and the cumylphenyl glycidyl ether, 
respectively, before the non-pourable condition occurred. This shows that 
the additives of the invention all have an effect of reducing the 
viscosity of the mixture. This is of great advantage, since it permits 
higher loading the lower cost compositions. 
EXAMPLE 2 
This example shows the use of cumylphenyl glycidyl ether as a reactive 
diluent for polyurethane. 
Five polyurethane compositions containing 100 parts by weight of 
polyurethane (Adiprene CM, trademark of E. I. DuPont deNemours & Co.), a 
reaction product of diisocyanate and polyalkylene ether glycol, 30 parts 
of HAF carbon black, 1 part of mercaptobenzothiazole, 4 parts of 
2,2'-benzothiazyl disulfide, 0.5 part of zinc chloride-2,2'-benzothiazyl 
disulfide, 0.75 part of sulfur and 0.5 part of cadmium stearate were 
prepared. The first formulation contained no plasticizer or reactive 
diluent. Second, third and fourth formulations were also prepared, these 
containing dioctyl phthalate (DOP), doctyl sebecate (DOS) and a heavy 
aromatic naphtha oil diluent (Sundex 790, a trademark of Sun Oil Company), 
respectively. The first two of these materials are conventionally known 
non-reactive plasticizers, while the fourth is a reactive plasticizer. To 
a fifth formulation, 15 parts by weight of the cumylphenyl glycidyl ether 
(CGE) of the invention was added. The compositions were cured for 60 
minutes at 140.degree. C., and the physical properties tested. The results 
are shown in the following table: 
Table II 
______________________________________ 
1 2 3 4 5 
______________________________________ 
Plasticizer None DOP DOS Napththa 
CGE 
300% Modulus psi 
2850 1900 1750 1700 1810 
Tensile psi 4050 3800 3550 4550 5200 
Elongation at Break % 
420 470 460 540 530 
Hardness Durometer A 
70 62 61 62 67 
______________________________________ 
The above data clearly show that the cumylphenyl glycidyl ether of the 
invention was effective in reducing the modulus of the polyurethane 
formulation. They further show that it is substantially better than the 
other plasticizers, since the cured composition has a much better tensile 
strength and, of the compositions tested, there is the least loss of 
hardness. This combination of properties is particularly useful, as will 
be readily recognized by one skilled in the art, and most surprising and 
unexpected. Furthermore, even in the case of the naphtha oil, the other 
reactive diluent, the tensile strength was much better. This may be 
attributable to the glycidyl ether improving the cure. 
EXAMPLE 3 
This example shows the utility of p-cumylphenyl benzoate as a processing 
aid and lubricant for the extrusion of rigid PVC. 
The following formulations were premixed in a high intensity mixer (Disona) 
and ambient temperature and extruded through a standard type 4" pipe die 
at 180.degree..+-.10.degree. C., at a fixed power input. The physical 
properties of the extrudate and the rate of extrusion are also shown in 
the table below: 
Table III 
______________________________________ 
Formulations 1 2 
______________________________________ 
PVC resin* 100 100 
Triphenyl phosphite 
(stabilizer) 0.5 0.5 
Diphenyl phthalate 
(processing aid) 1.0 -- 
Calcium stearate 1.0 1.0 
Oxidized polyethylene 
(Allied Chemical Corp. AC 629A) 
0.2 -- 
Wax (Hoechst XL165) 1.0 2.2 
Cumylphenyl benzoate -- 1.0 
Extrusion Rate, inches/min. 
8" 10.4" 
Impact Strength, psi 205 210 
Flexural Strength, psi 
16.2M 19.1M 
______________________________________ 
*VC 100, Bordon Chemical trademark for a low to medium molecular weight 
resin. 
The addition of the benzoate ester resulted in a 24% extrusion rate 
improvement and an 18% flex strength improvement, without any sacrifice of 
impact strength. Other experiments show that the benzoate ester is unique 
in this regard and that similar improvements do not result from other 
cumylphenol derivatives. 
EXAMPLE 4 
To show the efficacy of the 2-ethylhexanoate ester as a plasticizer for 
flexible polyvinyl chloride, 100 parts of a medium molecular weight PVC 
resin were admixed with 40 parts by weight of 5 micron calcium carbonate, 
and 2 parts by weight of Thermogard S stabilizer (a trademark of M & T 
Chemicals, Inc.). Three formulations were prepared. The first contained 30 
parts by weight of triethylene glycol dibenzoate (TGD), the second 30 
parts by weight of dioctyl phthalate (DOP), and the third 30 parts by 
weight of the cumylphenyl 2-ethylhexanoate (CPE) of the invention. The 
following table shows the physical properties of the blend after cure: 
Table IV 
______________________________________ 
1 2 3 
______________________________________ 
Plasticizer TGD DOP CPE 
Hardness Shore A Scale 
76 75 76 
100% Modulus 1550 1320 1350 
Tensile Strength, psi 
2350 1890 2510 
% Elongation 290 310 340 
______________________________________ 
The above table clearly shows that the compound of the invention 
effectively reduces the modulus of the formulation. In comparison to the 
other plasticizers, the 2-ethylhexanoate ester-containing formulation has 
the best tensile strength and percent elongation. 
EXAMPLE 5 
In this example an acrylonitrile-styrene copolymer (Bakelite RMD 4420, a 
trademark of Union Carbide Corp.) was admixed with 3 parts per 100 parts 
by weight of the cumylphenol derivative shown in the table below. The 
elongation, tensile strength, and notched Izod impact strength obtained in 
each case was compared with the acrylonitrile composition control. 
Table V 
______________________________________ 
Notched Izod 
Tensile Impact 
Strength Strength 
Additive Elongation % 
psi ft.lb./in. 
______________________________________ 
None 2.3 10,000 0.45 
Cumylphenyl 
benzoate 5.5 11,200 0.85 
Cumylphenyl 
borate 2.8 13,500 0.60 
Cumylphenyl 
glutarate 3.2 10,500 0.60 
Cumylphenyl 
benzyl ether 
7.4 12,800 0.90 
______________________________________ 
The above table shows that each of the cumylphenol derivatives evaluated 
increased the elongation, tensile strength and impact strength of the 
acrylonitrile-styrene copolymer. The benzoate ester and the benzyl ether 
were the most effective in enhancing elongation while the borate ester 
improved the tensile strength by about 35%. Impact strength was improved 
in all cases with the greatest increase being shown with the benzoate 
ester and the benzyl ether. 
EXAMPLE 6 
In this example, 100 parts of polystyrene (Dylene, a trademark of Arco 
Chemical Company) were admixed in a drum tumbler with 2 parts of the 
cumylphenol derivative shown in the following table. Input samples were 
prepared by profile extrusion at 375.degree. F. in a non-vented Hartig 
extruder using a general purpose mixing screw, L/D ratio of 24:1. 
The following Table shows the results obtained: 
Table VI 
______________________________________ 
Notched Izod 
Tensile Impact 
Ultimate Strength Strength 
Additive Elongation, % 
psi ft.lb./in. 
______________________________________ 
None 1.8 6,700 0.35 
Cumylphenyl 
benzyl ether 
5.2 8,600 0.80 
Cumylphenyl 
allyl ether 
3.1 7,400 0.55 
______________________________________ 
The above table clearly shows that the elongation, tensile strength, and 
notched impact strength are improved by the addition of the cumylphenol 
derivatives. The benzyl ether is the most outstanding in improving the 
physical properties. 
EXAMPLE 7 
In this example, the effect of the cumylphenol derivatives on the tensile 
and impact strength of unfilled phenolic resins is shown. The resin used 
was a Bakelite Resin 2620 (trademark of Union Carbide Corp.). For each 100 
parts of resin, 3 parts of additive (shown in the table below) along with 
0.2 parts of p-toluenesulfonic acid were admixed in a high shear Cowles 
mixer at 140.degree. to 160.degree. F. The material was thereafter cast 
into test specimens, 6".times.1/4".times.1/4", in a Teflon coated steel 
mold and cured at 300.degree. F. for 2 hours. 
Table VII 
______________________________________ 
Notched Izod 
Impact Tensile 
Additive ft.lb./in. Strength, psi 
______________________________________ 
None 0.55 7,200 
Cumylphenyl borate 
0.62 8,900 
Cumylphenyl benzoate 
0.85 7,500 
Cumylphenyl benzyl ether 
1.05 7,400 
______________________________________ 
The above data clearly show that the borate ester against greatly improves 
the tensile strength of the resin. Smaller improvements are shown with the 
cumyl phenyl benzoate and the benzyl ether; however, the benzyl ether has 
a substantial effect on the impact strength, almost doubling the value 
achieved. This is particularly significant, since impact strength is 
improved without sacrificing tensile strength. 
EXAMPLE 8 
In this example, 100 parts of an unfilled polyvinyl chloride resin Bakelite 
QSAP-7 (a trademark of Union Carbide Corp.) was compounded at a 
temperature of 300.degree. F. in a twin screw Anger extruder (L/D=24:1) 
with 2 parts of microcrystalline wax, 1 part of calcium stearate, 1 part 
of lead diphthalate, and 3 parts of the cumylphenyl derivative shown in 
the following table. The extruder has a PVC screw and X-alloy coated 
barrel. Prior to extrusion the components were blended in a Wellex high 
shear mixer. Test samples were profile extruded at a temperature of 
300.degree. F. into 1/4" square rods and cut into pieces 6" long. The 
following results were obtained: 
Table VIII 
______________________________________ 
Notched Izod 
Impact Tensile 
Additive ft.lb./in. Strength, psi 
______________________________________ 
None 0.65 5,800 
Cumylphenyl benzoate 
0.90 6,300 
Cumylphenyl borate 
0.85 5,900 
Cumylphenyl benzyl ether 
1.15 7,400 
Dicumylphenyl glutarate 
1.05 7,200 
______________________________________ 
The above table shows that the cumylphenol derivatives improved the notched 
Izod impact without lessening the tensile strength of the unfilled 
polyvinyl chloride. The benzyl ether and the glutarate ester were 
particularly outstanding since not only did they result in the greatest 
improvement in impact strength, but they also gave the greatest 
improvement in tensile strength. These additives did not affect the 
clarity of the polyvinyl chloride, though the material became a light tan 
color.