Inorganic-organic composites and methods of reacting the same with organo-titanium compounds

Novel organo-titanates, mixtures thereof, and products thereof and inorganic particulate surfaces and methods of making such reaction products. The reaction, which preferably occurs in an organic medium, modifies the inorganic surface by forming a monomolecular organic complex layer. The modified surface causes complete dispersion and improved compatibility of the inorganic particles or fibers in organic media and results in lower viscosity, high inorganic-to-organic ratios than heretofore obtainable, and improved physical properties in polymer systems, and more complete chemical utilization of reactive inorganic compounds.

BACKGROUND OF THE INVENTION 
Inorganic materials have long been used as fillers, pigments, 
reinforcements and chemical reactants in polymers. They are essentially 
hydrophilic, i.e., easily wetted by water or able to adsorb water. 
However, their compatibility with polymers is limited. Therefore, poor 
utilization is obtained of the potential reinforcement, of color or 
opacity, or chemical reactivity of inorganic materials. 
For example, zinc oxide is a commonly used component in rubber compounds. 
When comminuted zinc oxide is added to a rubber compound as a dry powder, 
it is difficult to disperse it completely in the rubber. On the other 
hand, predispersion of the zinc oxide in an organic medium which is a 
plasticizer for the rubber forms a stiff paste which is not dusty, is easy 
to weigh, and aids in the dispersion in the rubber. 
Likewise, other comminuted inorganic solids such as magnesium oxide, 
calcium oxide, other metal oxides, and fillers such as clay, calcium 
carbonate, colloidal silica and carbon black may be predispersed in an 
organic plasticizer or polymer prior to addition to a rubber or plastic 
compound. 
Organo-titanium compounds are well known. A wide variety may be prepared 
from tetraalkyl ortho titanates by reaction with organic acids. 
Organo-titanates having di- or tri- alkyl hydrolyzable groups and with, 
therefore, only one or two organic groups which are non-hydrolyzable have 
been used to treat the surfaces of inorganic materials in order to render 
them hydrophobic, as for example in U.S. Pat. No. 3,660,134. Such di- or 
tri- alkyl hydrolyzable titanates form a multi-molecular layer or envelope 
around the inorganic particles, resulting in less efficient use of the 
organo-titanate, as well as a weaker bond between the inorganic particle 
surface and the organic continuous phase. 
The reaction is accomplished by adding the organo-titanate to a suspension 
of the inorganic material in an inert solvent such as naphtha, 
trichloroethylene, toluene or hexane. After the reaction is completed, the 
solvent is removed and the treated, dried inorganic material is 
subsequently incorporated in an organic polymer system. U.S. Pat. No. 
3,697,475, for example, incorporates such treated inorganic fillers in 
thermoplastic polymer films. 
SUMMARY OF THE INVENTION 
The novel organo-titanates of the invention may be represented by the 
formula: 
EQU Ti(OR).sub.4-n (OCOR').sub.n 
where OR is a hydrolyzable group; R' is a non-hydrolyzable group; and n is 
between about 3.0 and 3.50, preferably from 3.1 to 3.25. The aforesaid 
compounds are preferred for treating the inorganic solids for reasons 
hereinafter set forth. 
Another composition of matter of the invention is the reaction products of 
organo-titanates having the above general formula, wherein n is between 3 
and 3.5, preferably above 3, and most desirably between 3.1 and 3.25 and 
inorganic solids. The amount of the organo-titanate compound required is 
at least 0.1 part, preferably 0.5 to 10 parts, per 100 of the inorganic 
solid. The reaction takes place on the surface of the inorganic solid, 
whereby the hydrolyzable group is removed and a bond is established, thus 
forming an organic, hydrophobic surface layer on the inorganic solid. The 
inorganic solid, prior to surface modification, is difficult to disperse 
in an organic medium because of its hydrophilic surface. However, when the 
organo-titanium compound is incorporated into an organic medium (low 
molecular weight liquids or higher molecular weight polymeric solids), the 
surface of the inorganic solid is wet-out, agglomerates are readily broken 
into individual particles, and a dispersion having improved properties is 
formed. Alternatively, the organo-titanate may be first reacted with the 
inorganic solid in the absence of an organic medium and thereafter admixed 
with the latter. 
The method of the present invention converts the surfaces of inorganic 
materials from a hydrophilic to a hydrophobic state preferably by reaction 
in an organic medium. This preferred procedure eliminates the prior art 
intermediate steps of dispersing the inorganic material in a solvent, 
reacting, filtering and drying the inorganic solid before dispersing it in 
a polymer. 
By means of the present invention, the dispersion of inorganic materials in 
organic polymer media is improved in order to obtain: (1) lower viscosity 
or higher loading of the dispersate in the organic medium; (2) higher 
degrees of reinforcement by the use of fillers, thereby resulting in 
improved physical properties in the filled polymer; (3) more complete 
utilization of chemical reactivity, thereby reducing the quantity of 
inorganic reactive solids required; (4) more efficient use of pigments and 
opacifiers; (5) higher inorganic-to-organic ratios in a dispersion, and 
(6) shorter mixing times to achieve dispersion. 
Also, according to the invention herein, the reaction with the single 
hydrolyzabel group of the organo-titanate may be carried out neat or in an 
organic medium to form a liquid, solid, or paste-like solid dispersion 
which can be used in the compounding of the final polymeric system. Such 
dispersions are very stable, i.e., having no tendency to settle, separate, 
or harden on storage to a non-dispersible state. 
Moreover, the invention simplifies the making of inorganic dispersions in 
organic media by providing a means to eliminate the solvent, to reduce the 
cost of processing equipment, and to reduce the time and energy required 
to disperse an inorganic solid material in a liquid or polymeric organic 
solid. 
The objectives of the invention are achieved by the production of a novel 
liquid ester that simplifies the making of a dispersion in situ. 
The present invention results in the formation of a reinforced polymer 
which has a lower melt viscosity, improved physical properties, and better 
pigmenting characteristics than are displayed in prior art materials. 
The practice of the present invention achieves a product comprising natural 
or synthetic polymers which contain particulate or fibrous inorganic 
materials which reinforce, pigment, or chemically react with the polymer 
to produce a product having superior physical properties, better 
processing characteristics, and more efficient utilization of pigments. 
Amongst the advantages gained by the practice of this embodiment of the 
present invention is the dispensing with the use of volatile and flammable 
solvents as required in the prior art. Thus, it is not necessary to dry 
the filler or to recover solvents. Furthermore, there is no possibility of 
a multi-molecular layer formation since there is only one hydrolyzable 
group in the organo-titanate reactant. Also, the practice of the present 
invention results in a non-oxidizing dispersion. 
While many of the compounds of the basic starting material Ti(OR).sub.4 may 
be used in preparing the polyesters, from the viewpoint of reactivity and 
economy, tetraisopropyl titanate is preferred. Referring to the above 
formula, R, which forms part of the hydrolyzable group, may be a straight 
chain, branched or cyclic alkyl group having from 1 to 5 carbon atoms per 
molecule. The groups include methyl, ethyl, n- and isopropyl, n-, sec-, 
and t-butyl, pentyl and cyclopentyl. By "hydrolyzable" is meant a group 
which will cleave in an aqueous solution having a pH of about 7 at a 
temperature of less than 100.degree. C. Hydrolysis may be determined by 
analyzing for liberated acids and alcohols. Conversely, "non-hydrolyzable" 
means a group that will not hydrolyze under the aforesaid conditions. 
With regard to the non-hydrolyzable groups (OCOR'), these are preferably 
formed from organic acids having 6 to 24 carbon atoms, such as stearic, 
isostearic, oleic, linoleic, palmitic, lauric and tall oil acids. 
Isostearic acid is particularly advantageous because it forms a triester 
that is a liquid at room temperature, which is more readily soluble in 
organic media. However, the R' group may have from 1 to up to 50 carbon 
atoms. A major consideration is the total number of carbon atoms in the 
non-hydrolyzable groups. The sum of the carbon atoms in the three R' 
groups must be at least 15. Furthermore, at least one R' group must have a 
long chain, as defined below, in order to give the necessary viscosity 
reduction to the reaction product of the organic titanate and the 
inorganic material. As an example, two R' groups may be isopropyl and the 
long chain R', lauryl. Materials which can be readily liquefied or 
dissolved at conventional mixing temperatures are most desirable. 
Equivalent polytitanates may also be used. 
Generally, the R' groups have up to 50 carbon atoms, preferably being an 
alkyl group having up to 24 carbon atoms; an alkenyl group having up to 18 
carbon atoms; or an aryl, alkaryl, or aralkyl group having up to 24 carbon 
atoms. Where the R' group is the long chain group, it must have at least 5 
carbon atoms. Additionally, the aforesaid groups may be substituted with 
halo, nitro, amino, carboxyl, epoxy, or hydroxyl ether or ester groups. 
Generally from 1 to 6 of such substitutions may occur. Still further, the 
R' group may contain intermediate hetero-atoms such as oxygen, sulfur or 
nitrogen in the chain. 
All of the R' groups in the organo-titanate compound need not be the same. 
They may be mixtures of two or more groups, the preparation of which shall 
be readily understood by those skilled in the art. For example, the 
Ti(OR).sub.4 starting material may be reacted with two or more organic 
acids. 
The selection of the R' groups for the organo-titanate depends on the 
particular application. The optimum groups depend on the filler and the 
monomeric or polymeric organic material, and the desired properties of the 
filled material. One skilled in the art may determine suitable 
organo-titanates for specific applications by limited experimental work in 
light of the teachings herein. 
Examples of the R' groups are numerous. These include straight chain, 
branched chain and cyclic alkyl groups such as hexyl, heptyl, octyl, 
decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl, 
eicosyl, docosyl, tetracosyl, cyclohexyl, cycloheptyl and cyclooctyl. 
Alkenyl groups include hexenyl, octenyl and dodecenyl. 
Groups derived from saturated and unsaturated fatty acids are also useful. 
In these cases the OCOR' group may be caproyl, caprylyl, capryl, lauryl, 
myristyl, palmityl, stearyl, arachidyl, behenyl, lignoceryl, dodecylenyl, 
palmitoleyl, oleyl, ricinoleyl, linoleyl, linolenyl, and gadoleyl. 
Halo-substituted groups include bromohexyl, chlorooctadecyl, iodotetradecyl 
and chlorooctahexenyl. One or more halogen atoms may be present, as for 
example in difluorohexyl or tetrabromooctyl. Ester-substituted aryl and 
alkyl groups include 4-carboxyethylcapryl and 3-carboxymethyltoluyl. 
Amino-substituted groups include aminocaproyl, aminostearyl, aminohexyl, 
aminolauryl and diaminooctyl. 
In addition to the foregoing aliphatic groups, groups containing 
hetero-atoms, such as oxygen, sulfur or nitrogen, in the chain may also be 
used. Examples of these radicals are ethers of the alkoxyalkyl type, 
including methoxyhexyl and ethoxydecyl. Alkylthioalkyl groups include 
methylthiododecyl groups. Primary, secondary and tertiary amines may also 
serve as the terminal portion of the hydrophobic group. These include 
diisopropylamino, methylaminohexyl, and aminodecyl. 
The aryl groups include the phenyl and naphthyl groups and substituted 
derivatives. Substituted alkyl derivatives include toluyl, xylyl, 
pseudocumyl, mesityl, isodurenyl, durenyl, pentamethylphenyl, ethylphenyl, 
n-propylphenyl, cumyl, 1,3,5-triethylphenyl, styryl, allylphenyl, 
diphenylmethyl, triphenylmethyl, tetraphenylmethyl, 1,3,5-triphenylphenyl. 
Nitro- and halo-substituted may be exemplified by chloronitrophenyl, 
chlorodinitrophenyl, dinitrotoluol, and trinitroxylyl. 
Amine-substituted components include methylaminotoluyl, 
trimethylaminophenyl, diethylaminophenyl, aminomethylphenyl, 
diaminophenyl, ethoxyaminophenyl, chloroaminophenyl, bromoaminophenyl and 
phenylaminophenyl. Halo-substituted aryl groups include fluoro-, chloro-, 
bromo-, iodophenyl, chlorotoluyl, bromotoluyl, methoxybromophenyl, 
dimethylaminobromophenyl, trichlorophenyl, bromochlorophenyl, and 
bromoiodophenyl. 
Groups derived from aromatic carboxylic acids are also useful. These 
include methylcarboxylphenyl, dimethylaminocarboxyltoluyl, 
laurylcarboxyltoluyl, nitrocarboxyltoluyl, and aminocarboxylphenyl. Groups 
derived from substituted alkyl esters and amides of benzoic acid may also 
be used. These include aminocarboxylphenyl and methoxycarboxyphenyl. 
Titanates wherein R' is an epoxy groups include tall oil epoxides (a 
mixture of 6 to 22 carbon alkyl groups) containing an average of one epoxy 
group per molecule and glycidol ethers of lauryl or stearyl alcohol. 
Substituted naphthyl groups include nitronaphthyl, chloronaphthyl, 
aminonaphthyl and carboxylnaphthyl groups. 
Specific compounds which have been prepared and found operative in the 
practice of the instant invention include: (CH.sub.3).sub.2 
CHOTi[OCO(CH.sub.2).sub.14 CH(CH.sub.3).sub.2 ].sub.2 
OCOC(CH.sub.3).dbd.CH.sub.2 ; (CH.sub.3).sub.2 CHOTi [OCO(CH.sub.2).sub.14 
CH(CH.sub.3).sub.2 ][OCOC(CH.sub.3).dbd.CH.sub.2 ].sub.2 ; 
##STR1## 
where n is greater than 8 and less than 15; 
[(CH.sub.3).sub.2 CHOTi[OCO(CH.sub.2).sub.14 CH(CH.sub.3).sub.2 ].sub.2 
OCO].sub.2 C.sub.34 H.sub.78 ; (CH.sub.3).sub.2 CHOTi[OCO(CH.sub.2).sub.16 
CH.sub.3 ].sub.3 ; 
##STR2## 
(CH.sub.3).sub.2 CHOTi[OCO(CH.sub.2).sub.5 NH.sub.2 ].sub.3 ; 
(CH.sub.3).sub.2 CHOTi[OCOCH.sub.2 CH.sub.2 NH.sub.2 ].sub.3 ; and 
##STR3## 
where the sum of p + q is more than 6 and less than 18. 
The inorganic materials may be particulate or fibrous and of any shape or 
particle size, the surfaces of which are reactive with the hydrolyzable 
group of the organo-titanium compound by means of hydroxyl groups, or 
adsorbed water, or both. Examples of inorganic reinforcing materials 
include metals, clay, carbon black, calcium carbonate, barium, sulfate, 
silica, mica, glass and asbestos. Reactive inorganic material examples 
include the metal oxides of zinc, magnesium, lead, and calcium and 
aluminum, iron fillings and turnings, and sulfur. Examples of inorganic 
pigments include titanium dioxide, iron oxides, zinc chromate, ultramarine 
blue. As a practical matter, the particle size of the inorganic material 
should not be greater than 1 mm, preferably from 1 micron to 500 micron. 
It is imperative that the organic titanate be properly admixed with the 
inorganic material so as to permit the surface of the latter to react 
sufficiently. The optimum amount of the titanate to be used is dependent 
on the effect to be achieved, the available surface area of and the bonded 
water in the inorganic material. 
Reaction is facilitated by admixing under the proper conditions. Optimum 
results depend on the properties of the titanate, namely, whether it is a 
liquid or solid, and its decomposition and flash point. The particle size, 
the geometry of the particles, the specific gravity, the chemical 
composition, among other things, must be considered. Additionally, the 
treated inorganic material must be thoroughly admixed with the polymeric 
medium. The appropriate mixing conditions depend on the type of polymer, 
whether it is thermoplastic or thermosetting, its chemical structure, 
etc., as will be readily understood by those skilled in the art. 
Where the inorganic material is pretreated with the organic titanate, it 
may be admixed in any convenient type of intensive mixer, such as a 
Henschel or Hobart mixer or a Waring blender. Even hand mixing may be 
employed. The optimum time and temperature is determined so as to obtain 
substantial reaction between the inorganic material and the organic 
titanate. Mixing is performed under conditions at which the organic 
titanate is in the liquid phase, at temperatures below the decomposition 
temperature. While it is desirable that the bulk of the hydrolyzable 
groups be reacted in this step, this is not essential where the materials 
are later admixed with a polymer, since substantial completion of the 
reaction may take place in this latter mixing step. 
Polymer processing, e.g., high shear mixing, is generally performed at a 
temperature well above the second order transition temperature of the 
polymer, desirably at a temperature where the polymer will have a low melt 
viscosity. For example, low density polyethylene is best processed at a 
temperature range of 350.degree. to 450.degree. F.; high density 
polyethylene from 400.degree. to 475.degree. F.; polystyrene from 
450.degree. to 500.degree. F.; and polypropylene from 450.degree. to 
550.degree. F. Temperatures for mixing other polymers are known to those 
skilled in the art and may be determined by reference to existing 
literature. A variety of mixing equipment may be used, e.g., two-roll 
mills, Banbury mixers, double concentric screws, counter or corotating 
twin screws and ZSK type of Werner and Pfaudler and Busse mixers. 
When the organic titanate and the inorganic materials are dry-blended, 
thorough mixing and/or reaction is not readily achieved and the reaction 
may be substantially completed when the treated filler is admixed with the 
polymer. In this latter step, the organic titanate may also react with the 
polymeric material if one or more of the R' groups is reactive with the 
polymer. 
To illustrate further the invention, attention is directed to the following 
examples: 
EXAMPLE A: PREATION OF ORGANO-TITANATE ESTERS 
One mole of tetraisopropyl titanate is admitted to a vessel equipped with 
an agitator, an internal heating and cooling means, a vapor condenser, a 
distillate trap and liquid-solid feed input means. Agitation is commenced 
with the tetraisopropyl titanate at room temperature. Liquid isostearic 
acid is metered into the vessel at a controlled rate so that the 
exothermic reaction is maintained below about 350.degree. F. until 3.19 
moles of the acid are added. The isopropanol is removed from the reaction 
product by distillation at 150.degree. C. at 50 mm Hg to remove 
potentially objectionable volatiles. 
The organic titanate thus produced has an average of 3.19 moles of 
isostearate per molecule. This material is hereinafter referred to as the 
"isostearate 3.19 ester." The ester structure is determined by 
ascertaining the isopropanol liberated from the reaction and the residual 
isostearic acid. It is found that about from 3.1 to 3.3 moles of 
isopropanol are recovered in the typical run. Substantially no unreacted 
isostearic acid is detected. The physical properties of the ester are: 
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Specific Gravity at 74.degree. F. 
0.944 
Flash Point (COC), .degree. F. 
315 
Viscosity, LV, at 74.degree. F., cps. 
120 
Pour Point, .degree. F. Below -5 
Decomposition Point, .degree. F. 
Above 400 
Gardner Color 15 Max 
Appearance Reddish 
Oily Liquid 
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The above run is repeated, except that instead of adding 3.19 moles of the 
isostearic acid, 1.0, 2.0 and 3.0 moles are added. This results in the 
formation of mixtures of isopropyl isostearate titanates having an average 
number of isostearate groups per molecule of 1, 2 and 3 moles, 
respectively. 
EXAMPLE B 
This example demonstrates the effect of admixing the isostearate 3.19 ester 
with various fillers dispersed in naphthenic oil. The fillers employed 
include calcium carbonate, calcined clay, high surface area silica, carbon 
black, and chemically oxidized carbon black. The effect of varying 
percentages of the titanate ester on the viscosity of the end product is 
also shown in the data below; 
__________________________________________________________________________ 
Fillers Dispersed in Mineral Oil (Naphthenic Oil) 
1 2 3 4 5 6 7 8 
__________________________________________________________________________ 
CaCO.sub.3, parts by wt. 
15 35 50 50 70 75 
Mineral Oil, " 85 65 50 50 30 25 
Titanate Ester, % on Filler 
-- -- -- 0.5 0.5 0.5 
Brookfield Viscosity 
at 25.degree. C., cps. 
82 1,600 
32,500 
280 2,320 
12,600 
Calcined Clay, parts by wt. 
30 30 50 65 
Mineral Oil, " 70 70 50 35 
Titanate Ester, % on Filler 
-- 3 3 3 
Brookfield Viscosity 
at 25.degree. C., cps. 
30,000 
215 1,280 
22,000 
Hi Surface area silica, 
5 10 15 20 5 10 15 20 
parts by weight 
Mineral Oil, " 95 90 85 80 95 90 85 80 
Titanate Ester, % on Filler 
-- -- -- -- 1 1 1 1 
Brookfield Viscosity 
at 25.degree. C., cps. 
120 615 5,750 
7,000 
114 520 4,700 
4,100 
Hi Surface area silica, 
5 10 15 20 5 10 15 20 
parts by weight 
Mineral Oil, " 95 90 85 80 95 90 85 80 
Titanate Ester, % on Filler 
2 2 2 2 3 3 3 3 
Brookfield Viscosity 
at 25.degree. C., cps. 
92 465 4,200 
3,800 
86 345 3,000 
3,500 
Commercially Oxidized 
Carbon Black, pts. by wt. 
10 15 20 25 10 15 20 25 
Mineral Oil, " 90 85 80 75 90 85 80 75 
Titanate Ester, % on Filler 
-- -- -- -- 3 3 3 3 
Brookfield Viscosity 
at 25.degree. C., cps. 
462 1,612 
5,000 
16,800 
350 1,125 
3,300 
7,700 
__________________________________________________________________________ 
A regular grade of carbon black was chemically oxidized in situ to 
convert carboxyl 
groups to hydroxyl groups. The results are shown below: 
Type of Treatment Brookfield Viscosity at 77.degree. F., cps. of 
Dispersion 
__________________________________________________________________________ 
Carbon Black (untreated) 
9,200 
Carbon Black (5% chemically 
oxidized) 15,800 
Carbon Black (5% chemically 
oxidized and treated with 
2,700 
3% titanate ester) 
__________________________________________________________________________ 
The aforesaid data clearly show that materials reacted in situ with the 
titanate ester make dispersions having substantially reduced Brookfield 
viscosities. Marked reductions in viscosity are shown particularly with 
the calcium carbonate, calcined clay, and carbon black. This reduced 
viscosity greatly enhances the ease of mixing these fillers with 
organic-type materials and results in improved dispersion at lower energy 
requirements for mixing. 
The effect of isostearic isopropyl titanates on the dispersion and chemical 
reactivity of zinc oxide is shown in the following examples:

EXAMPLE 1: EFFECT OF ISOSTEARATE ESTERS ON THE DISPERSION OF ZINC OXIDE IN 
AN ORGANIC MEDIUM 
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Formulation Parts by Weight 
______________________________________ 
Zinc oxide (-325 mesh, 
90 
S.A. 5.3 m.sup.2 /gm.) 
Hydrocarbon oil 7 
(Naphthenic process oil) 
Ester as shown below 3 
______________________________________ 
PENETRATION (ASTM TEST NO. D1231) AT 74.degree. F. 
______________________________________ 
Isostearate Esters 
Days 
after 1.0 2.0 3.0 3.19 3.70 
Mixing mol. mols. mols. mols.* mols. 
______________________________________ 
0 (Could 160 170 165 615 
not 
2 make 125 140 150 -- 
disper- 
4 sion) 89 105 118 -- 
6 " 85 105 115 -- 
7 " 80 90 112 -- 
______________________________________ 
*The "isostearate 3.19 ester 
The greater the degree of penetration, the more fluid is the mix. After 
aging, the isostearate 3.19 ester gives the most desirable penetration 
characteristics. It can be seen by the data that, desirably, the most 
stable fluid mix is obtained with three or slightly more mols of 
isostearate in the titanate ester. 
The dispersion made with the isostearate 3.19 ester was compared with the 
same zinc oxide in the untreated powder form in a natural rubber compound 
except that 10% less zinc oxide was used when making the rubber compound 
with the treated zinc oxide dispersion described in Example 1. The 
formulation and test results are shown in Example 2, as follows: 
EXAMPLE 2: EFFECT OF TREATED ZINC OXIDE 
DISPERSION IN A NATURAL RUBBER COMPOUND 
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FORMULATION 
Zinc Oxide 90% Zinc Oxide 
Powder (pts. 
Dispersion 
by weight) (Example 1) 
______________________________________ 
Natural Rubber 100 100 
Peptizer--REOGEN 
2 2 
Stearic Acid 2.5 2.5 
Zinc Oxide Powder 
3.5 -- 
90% Zinc Oxide -- 3.5 
Dispersion (iso- 
stearate 3.19 ester) 
HAF Black (N330) 
45 45 
Sulfur 2.5 2.5 
Ultra-Accelerator 
.5 .5 
(AMAX No. 1) 
______________________________________ 
PHYSICAL PROPERTIES 
Stress PSI at 300% Elongation (S), Tensile Strength PSI (T), % Elongation 
(E), Hardness, Shore A (H). 
______________________________________ 
Press Cures 
at 290.degree. F. 
S T E H S T E H 
______________________________________ 
15 min. 1120 2850 500 55 1380 3810 550 57 
45 min. 1380 2890 460 59 1640 3780 520 59 
60 min. 1460 2900 460 59 1520 3610 500 60 
______________________________________ 
RATE AND STATE OF CURE 
Rheometer at 290.degree. F., 60 Sec. Preheat, 
60 Min. Motor, 100 Range, 3.degree. Arc 
______________________________________ 
Zinc Oxide 90% Zinc Oxide 
Powder (pts. 
Dispersion 
by weight) (Example 1) 
______________________________________ 
Max. Torque 56.2 in./lbs. 77 in./lbs. 
Min. Torque 15 " 22.5 " 
T90 (% degree 19.5 minutes 17.5 minutes 
of cure) 
T95 " 24 " 22 " 
T2 " 2.2 " 2.7 " 
______________________________________ 
______________________________________ 
PROCESS TIME 
Mooney Scorch at 250.degree. F. 
Time Scorch Minutes 5 Minutes 5 
Begins 
Time to 5 3 3 
Point Rise 
Total Time 8 8 
Rise Last 3 3.5 
Minute 
Plasticity 16 35 
______________________________________ 
The table in Example 2 shows the great improvement in physical properties 
of a natural rubber compound achieved by the use of the isostearate 3.19 
treatment of the zinc oxide surface even when 10% less zinc oxide is used. 
Tensile strength is increased by 30%, elongation by 10%, stress at 300% 
elongation by 10%. It is significant that hardness is not affected. The 
Mooney plasticity is more than doubled at 250.degree. F., while the 
rheometer data at 290.degree. F. shows that the treated zinc oxide 
provides a tighter cure. 
The following Example 3 shows the improvement in properties obtained when 
using the zinc oxide dispersion made with the isostearate 3.19 ester of 
Example 1 in an oil-black extended SBR (styrene-butadiene rubber) 
compound: 
EXAMPLE 3: EFFECT OF TREATED ZINC OXIDE DISPERSION IN A STYRENE-BUTADIENE 
RUBBER COMPOUND 
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FORMULATION 
Compound Zinc Oxide 90% Zinc Oxide 
SBR, Oil-Black Powder (pts. Dispersion 
Extended by weight) (Example 1) 
______________________________________ 
PP 1849 245 245 
(Phillips 
Petroleum SBR) 
Zinc Oxide 3 -- 
90% Zinc Oxide -- 3 
Dispersion (iso- 
stearate 3.19 ester) 
Anti-Oxidant 1 1 
(Flexzone 3C) 
Accelerator-CBTS 
1.3 1.3 
Sulfur 2.1 2.1 
Accelerator-TMTM 
0.55 0.55 
Ultra-Accelerator 
1.2 1.2 
(Vultac #5) 
Resin Modifier 10 10 
Nebony 100 
Stearic Acid 1 1 
______________________________________ 
PHYSICAL PROPERTIES 
Stress PSI at 300% Elongation (S), Tensile Strength PSI (T), % Elongation 
(E), Hardness, Shore A (H). 
______________________________________ 
Zinc Oxide 90% Zinc Oxide 
Powder (pts. Dispersion 
Press Cures 
by weight) (Example 1) 
at 307.degree. F. 
S T E H S T E H 
______________________________________ 
30 min. 1175 2775 600 59 1325 2929 580 59 
Press Cures 
at 280.degree. F. 
40 min. 1240 2800 580 60 1350 2700 530 61 
______________________________________ 
RATE AND STATE OF CURE 
Rheometer at 280.degree. F., 60 Sec. Preheat, 60 Min. Motor, 50 Range, 
1.degree. Arc 
______________________________________ 
Max. Torque 25.75 in./lbs. 25.75 in./lbs. 
Min. Torque 5.75 " 5.65 " 
TS-2 9.5 minutes 8.25 minutes 
TC-90 22.5 " 21.75 " 
______________________________________ 
Rheometer at 340.degree. F., 60 Sec. Preheat, 12 Min. Motor, 50 Range, 
1.degree. Arc 
______________________________________ 
Max. Torque 21.1 in./lbs. 22.8 in./lbs. 
Min. Torque 5.4 " 5.1 " 
TS-2 2.15 minutes 1.9 minutes 
TS-90 3.9 " 3.7 " 
______________________________________ 
______________________________________ 
PROCESS TIME 
Mooney Data at 212.degree. F. 
Initial 50.5 51.5 
1.5 minutes 40.5 41.5 
4.0 minutes 36.5 37.5 
______________________________________ 
The data in Example 3 show an equal or improved condition of physical 
properties with the use of 10% less of zinc oxide. In actual processing, 
it has been observed that the isostearate 3.19 ester treated zinc oxide 
dispersion of Example 1 is incorporated into the rubber compound in about 
one-fourth to one-fifth of the time otherwise required for untreated zinc 
oxide powder. Additionally, the treated zinc oxide powder was non-dusty. 
The above data also show that the compound which contains the treated zinc 
oxide dispersion has a higher degree of reactivity as well as a tighter 
final cure, as evidenced by the increase in torque, as compared to the 
untreated zinc oxide. 
The following Examples 4, 5 and 6 illustrate the effectiveness of 
isostearate 3.19 ester in reducing the viscosity of dispersions of various 
inorganic solids in a hydrocarbon oil. 
The dispersion of zinc oxide in a hydrocarbon oil results in a greatly 
reduced viscosity when it is reacted with isostearate 3.19 ester, as can 
be seen in the following Example 4: 
EXAMPLE 4 
______________________________________ 
Parts by Weight 
______________________________________ 
Zinc Oxide 50 50 
Naphthenic Process Oil 
50 47.5 
Isostearate 3.19 ester 
0 2.5 
Brookfield Viscosity at 
460,000 80,000 
74.degree. F. cps (centipoises) 
______________________________________ 
The reduction in viscosity of the zinc oxide dispersion in a hydrocarbon 
oil by the in situ reaction with the isostearate 3.19 ester was 83%. 
The viscosity of a dispersion of titanium oxide is similarly reduced by the 
isostearate 3.19 ester, as shown in the following Example 5: 
EXAMPLE 5 
______________________________________ 
Parts by Weight 
______________________________________ 
Titanium Dioxide 50 50 
Naphthenic Process Oil 
50 47.5 
Isostearate 3.19 Ester 
0 2.5 
Brookfield Viscosity at 
110,000 900 
74.degree. F. cps. 
______________________________________ 
The reduction in viscosity of the titanium dioxide dispersion in 
hydrocarbon oil by the in situ reaction with the isostearate 3.19 ester 
was 99%. 
The viscosity of a dispersion of carbon black in a hydrocarbon oil is 
similarly reduced by the same ester, as shown in the following Example 6: 
EXAMPLE 6 
______________________________________ 
Parts by Weight 
______________________________________ 
Carbon Black FEF N550 30 30 
Naphthenic Process Oil 
70 65 
Isostearate 3.19 Ester 
0 3 
Brookfield Viscosity at 
104,000 46,000 
79.degree. F., cps. 
______________________________________ 
The reduction in viscosity of the carbon black dispersion in a hydrocarbon 
oil by the in situ reaction with the isostearate 3.19 ester was 56%. 
The viscosity of a dispersion of calcium carbonate in a liquid epoxy resin 
is reduced when the isostearate 3.19 ester is added, as shown in the 
following Example 7: 
EXAMPLE 7 
______________________________________ 
Parts by Weight 
______________________________________ 
Calcium carbonate (low 
50 50 
oil absorption type) 
Liquid epoxy resin 50 45 
(epoxide equivalent -185) 
Isostearate 3.19 ester 
0 5 
Brookfield Viscosity at 
550,000 110,000 
74.degree. F., cps. 
______________________________________ 
The reduction in viscosity of the calcium carbonate dispersion in liquid 
epoxy resin by the in situ reaction with the isostearate 3.19 ester was 
80%. 
The viscosity of a dispersion of colloidal silica in a liquid polysulfide 
rubber is reduced when the isostearate 3.19 ester is added, as shown in 
the following Example 8: 
EXAMPLE 8 
______________________________________ 
Parts by Weight 
______________________________________ 
Colloidal silica (Neosil A) 
50 50 
Liquid polysulfide rubber 
50 45 
(Thiokol TP-90B) 
Isostearate 3.19 ester 
0 5 
Brookfield Viscosity at 
8,000 2,250 
74.degree. F., cps. 
______________________________________ 
The penetration of a paste dispersion of calcium carbonate in a liquid 
(thiokol) polysulfide rubber was increased when the isostearate 3.19 ester 
was added. Alternatively, when the amount of calcium carbonate in the 
dispersion was increased 50%, the penetration remained the same, through 
the addition of an increased amount of the isostearate 3.19 ester. These 
effects are shown in the following Example 9: 
EXAMPLE 9 
______________________________________ 
Parts by Weight 
______________________________________ 
Calcium carbonate (Purecal 
200 200 300 
SC) 
Polysulfide liquid rubber 
100 100 100 
(Thiokol LP-32) 
Isostearate 3.19 ester 
0 4 15 
Penetration (ASTM Test 
45 82 46 
No. D-1321) 
______________________________________ 
The dispersions of Examples 4 through 9 were initially prepared without the 
isostearate 3.19 ester by preblending the pigment or filler with the 
organic liquid medium using a Pony mixer. This preblend was then ground on 
a three-roll mill to make the final dispersion. Viscosity or penetration 
measurements were made for a control comparison. 
The effect of the titanate ester was then evaluated by a second set of 
tests in which the titanate ester was added to the organic liquid medium 
and the dispersion made as described before. Viscosity measurements made 
on the new batches disclosed very considerable and significant reduction 
in viscosity demonstrating that the isostearate esters of the invention 
are effective with a variety of inorganic materials and in different 
liquid organic media. This reduction in viscosity indicates that inorganic 
materials treated by the processes disclosed herein can (1) be used in 
higher loadings, (2) become more completely dispersed in the organic 
medium and in the end product, and (3) create viscosity levels which lend 
themselves to improved manufacturing processes such as reduced energy 
levels for mixing or for pumping of such dispersions. 
These examples demonstrate that the inorganic materials do not have to be 
pretreated and the surface modification can be accomplished in situ by the 
use of the isostearate titanate ester. Also, the ester is effective in 
reducing viscosity of a wide variety of inorganic materials in a wide 
variety of organic media. 
The following Example 10 shows the effectiveness of isostearate 3.19 ester 
in producing a shorter mixing time and lower viscosity in a dispersion of 
magnesium oxide in hydrocarbon oil. In actual mixing, it is necessary to 
add the magnesium oxide to the hydrocarbon oil in increments in order to 
obtain the maximum degree of inorganic to organic loading in the shortest 
possible tiem. The table below outlines this procedure and the results 
obtained: 
EXAMPLE 10 
______________________________________ 
Parts by Weight 
______________________________________ 
Magnesium Oxide 55 55 
Naphthenic Process Oil 
45 42 
Isostearate 3.19 ester 
0 3 
______________________________________ 
______________________________________ 
Increment 
Addition No. Weight Time in Minutes 
______________________________________ 
1 16.67 0 0 
2 8.33 0.5 0.5 
3 8.33 1.0 1.0 
4 8.33 2.0 2.0 
5 5.00 4.0 2.5 
6 4.17 4.5 3.0 
7 4.17 5.0 3.5 
55.00 
Time to Complete Dispersion 
6.5 4.5 
Penetration (ASTM Test 
160 230 
No. D-1321) 
______________________________________ 
The resultant dispersion was therefore made 30% softer while requiring 31% 
less mixing time. 
EXAMPLE 11 
The effect of reacting the isostearate 3.19 ester with calcium carbonate (a 
precipitated small particle grade) in situ in low density polyethylene 
(LDPE, sp.g. 0.918) is shown in the table below. This table compares the 
metl viscosity vs. time in making a dispersion of calcium carbonate in low 
density polyethylene having a melt index of 7, when 70 parts of calcium 
carbonate are blended with 28 parts of LDPE. 
In these experiments, 2.85% of the isostearate 3.19 ester (based on the 
calcium carbonate) was added before starting the mixing in a Brabender 
high intensity mixer. The mixing was carried out at a maximum temperature 
of 200.degree. F., and at 8 RPM, using a 5 Kg weight on the ram, while the 
melt viscosity was observed by measuring the torque applied to the mixer 
in gram meters. 
Similar experiments were made when the isostearate ester was omitted, and 
when two other dispersion aids, namely, aluminum tristearate and 
polyglycerol 400 mono-oleate, were used at the same concentration, namely, 
2.85% (based on CaCO.sub.3). The results are also shown in the following 
table: 
______________________________________ 
Torque Readings (gms.-meter.sup.2) 
Time (seconds) 
Additives 30 60 90 120 150 190 
______________________________________ 
Isostearate 1250 900 900 900 750 750 
3.19 Ester 
No Additive 2000 2000 1900 1750 1750 1750 
Aluminum 1900 1400 1300 1250 1250 1250 
Tristearate 
Polyglycerol 2150 1400 1150 1000 1000 1000 
400 Mono-Oleate 
______________________________________ 
When no additive was employed, the torque after 30 seconds of mixing was 
2,000 gm.-sq. meter, and after 190 seconds was 1750. 
When the isostearate 3.19 ester was used, the torque had dropped to 1250 
gm.-sq. meter in 30 seconds, and was 750 at 190 seconds, showing the great 
reduction in melt viscosity in a very short time. 
When the aluminum tristearate was used, the torque had dropped to 1,900 
gm-sq. meter after 30 seconds, and to 1,250 after 190 seconds, appreciably 
higher than the titanate ester. The polyglycerol 400 mono-oleate additive 
produced a torque of 2,150 gm.-sq. meter after 30 seconds of mixing, and a 
torque of 1,000 after 190 seconds of mixing. 
The effectiveness of the isostearate 3.19 ester as a dispersion agent was 
also demonstrated by an additional test in which the 70% CaCO.sub.3 
dispersion was mixed with additional LDPE polymer in the ratio of 1 to 9, 
and then made into film by blown-film extrusion. The resulting film was 
then examined visually to measure the number of remaining agglomerated 
particles per square foot. When no dispersion additive was employed, there 
were 312 agglomerates per square foot. When the titanate ester was 
employed, the number of agglomerates dropped to 16 per square foot. 
EXAMPLE 12 
This example is similar in procedure to that described in Example 11. 
Titanium dioxide (rutile) was used as the inorganic dispersed phase in the 
same LDPE as used in Example 11. The dispersion was made at 75 parts 
TiO.sub.2 using 2.67% dispersion additive (based on the TiO.sub.2), and 23 
parts of LDPE. 
The following table shows that with no dispersion additive the torque on 
the Brabender mixer after 30 seconds was 2,250 gm.-sq. meter, and after 
180 seconds had dropped to 1,100. When the isostearate 3.19 ester was 
added, the torque after 30 seconds was reduced to 1,250 gm.-sq. meter, and 
after 180 seconds was 750. 
______________________________________ 
Torque Readings (gms.-meter.sup.2) 
Time (seconds) 
Additive 30 60 90 120 150 180 
______________________________________ 
Control 2250 1750 1250 1250 1150 1100 
No Additive 
Isostearate 1250 900 900 900 750 750 
3.19 ester 
Polyglycerol 2000 1500 1250 1000 1000 1000 
400 Mono-Oleate 
Aluminum 1000 750 750 600 500 500 
Tristearate 
______________________________________ 
When the TiO.sub.2 dispersion was reduced in concentration to 7.5% and blow 
film made, the number of agglomerates per square foot without additive was 
600, and with the isostearate ester the agglomerate count was reduced to 
150 per square foot. There was also a very noticeable increase in opacity 
and whiteness. 
It can also be seen from the table that in the case of TiO.sub.2 dispersion 
the polyglycerol 400 mono-oleate was inferior, while the aluminum stearate 
was superior to the titanate ester as a dispersion aid. 
EXAMPLE 13 
This example is similar in procedure to Examples 11 and 12. The inorganic 
dispersed phase was yellow iron oxide and 50 parts were used with 4% 
dispersion additive (based on the iron oxide), and 48 parts of LDPE. The 
following table shows the results. 
______________________________________ 
Torque Readings (gms.-meter.sup.2) 
Time (seconds) 
Additive 30 60 90 120 150 180 
______________________________________ 
Control 2500 1750 1000 1000 1000 1000 
No Additive 
Isostearate 2500 1400 850 750 750 750 
3.19 ester 
Aluminum 2000 1250 850 800 800 800 
Tristearate 
Polyglycerol 2000 1100 1000 900 800 800 
400 Mono-Oleate 
______________________________________ 
When no dispersion additive was employed, the torque on the Brabender was 
2,500 gm.-sq. meter after 30 seconds, and 1,000 after 180 seconds. When 
the isostearate 3.19 ester was added, the torque after 30 seconds was also 
2,500 gm.-sq. meter, but after 180 seconds the torque had dropped to 750. 
When the yellow oxide dispersion was reduced to a concentration of 5% and 
converted into blown film, the agglomerate count was 685 per square foot 
when no dispersion additive was employed. When the isostearate 3.19 ester 
was added, the agglomerate count dropped to 113 per square foot. 
The above table also shows that the titanate ester was superior to aluminum 
stearate or polyglycerol 400 mono-oleate in reducing the melt viscosity. 
EXAMPLE 14 
The isostearate 3.19 titanate ester was used to study the effect of impact, 
tensile and melt index properties of injection-grade, high density 
polyethylene (HDPE) with mineral fillers at a loading range of 30-60%. 
A laboratory Banbury was used to masterbatch the organic titanate with the 
HDPE at a concentration of 5%. The resultant compound was ground in a 
Cumberland grinder employing a 14 mesh screen, and thereafter dry-blended 
in a Henschel-type mixer with the filler to give the desired 
filler-to-organic titanate ratio. The dry blend was mixed with more HDPE 
to give the desired percent filler, using the Banbury in 3 minutes cycle 
times, 60 psi ram pressure, and a drop temperature of 200.degree. F. The 
finished compounds were ground and injection-molded into plaques having 
dimensions of 0.105 .times. 0.500 .times. 2.375 inches for testing. The 
molding took place at 400.degree. F.; at an injection pressure of 1,000 
psi; ram forward, 10 seconds; and mold close time of 15 seconds. 
The results obtained are shown in the following table: 
__________________________________________________________________________ 
Impact 
Titanate Ester, Tensile 
Tensile 
Strength 
Filler, 
percent, EVA, Melt index, 
Strength, 
Modulus 
ft.-lb./in. 
Formulation percent 
based on filler 
percent 
g./10 min. 
p.s.i. 
10.sup.3 p.s.i. 
of notch 
__________________________________________________________________________ 
Control (HDPE only) 
0 0 19.7 2,050 98.0 0.93 
BaSO.sub.4 30 0 20.8 2,430 81.7 0.58 
30 3 22.0 2,460 49.0 0.60 
40 3 22.3 2,220 59.4 0.64 
50 3 22.3 2,060 63.3 0.76 
60 3 22.0 1,770 70.0 0.91 
Aluminum Silicate 
30 0 14.0 2,510 99.8 0.40 
30 3 12.9 3,020 133.2 0.60 
40 3 8.4 2,790 140.1 0.53 
50 3 1.5 2,490 145.3 0.45 
60 3 0 2,350 150.9 0.37 
Calcium Metasilicate, 
30 0 16.5 2,330 72.2 0.56 
CaSiO.sub.3 30 3 16.5 2,230 87.2 0.77 
40 3 16.5 2,020 106.0 0.81 
50 3 14.9 1,800 121.3 0.88 
60 3 12.0 1,610 130.8 0.93 
CaCO.sub.3 30 0 16.3 1,960 217.9 0.53 
30 3 18.8 2,330 180.6 0.57 
40 3 18.4 1,730 163.4 0.78 
50 3 17.7 1,770 150.9 0.97 
60 3 17.8 1,800 130.8 1.01 
Ethylene-Vinyl 
40 3 5.8 2.7 2,900 112.1 0.82 
Acetate Polymer 
40 3 10.8 2.9 2,710 109.3 1.52 
with Calcined 
40 3 15.8 5.7 2,470 106.0 2.39 
Clay Filler 40 3 20.8 7.5 2,180 102.2 4.54 
__________________________________________________________________________ 
The aforesaid table shows that the isostearate 3.19 ester works most 
effectively with calcium carbonate and barium sulfate. The 30% filler/HDPE 
system with the organic titanate has better impact strength than the 
equivalent filled system without the titanate ester. In the case of the 
40% filler/HDPE system containing calcium carbonate, calcium metasilicate, 
and barium sulfate, the impact strength was equal to or better than the 
high density polyethylene. Additionally, the stiffness or tensile modulus 
of the calcium carbonate filled HDPE is significantly reduced by 3% of the 
organic titanate. Surprisingly, it decreases with increased loading. Even 
though the modulus is reduced significantly, the tensile strength is 
maintained relatively constant with loadings as high as 60%. 
Finally, the melt index of the barium sulfate-or calcium carbonate-filled 
HDPE remains reasonably constant. At 60% loading, they have flow 
characteristics similar to the 100% HDPE with no filler. 
EXAMPLE 15 
In this example the application of the invention to filled low density 
polyethylene is described. The unfilled polyethylene admixed with 40% 
calcium carbonate is tested for volume resistivity (V.R.), tensile 
strength, modulus, elongation and tear strength, as compared to the 
polyethylene filled with calcium carbonate after having been dry-blended 
with 1%, 2% and 3% of the isostearate 3.19 ester of the invention as a 
coupling agent. The results are shown in the following table: 
______________________________________ 
Unfilled 
Properties Polyethylene 
40% Calcium Carbonate 
______________________________________ 
Percent -- 0% 1% 2% 3% 
Isostearate 
3.19 Ester 
V.R., 50.degree. C. 
60+ 60+ 60+ 60+ 60+ 
ohm-cm .times. 10.sup.14 
Tensile 1638 1464 1245 1222 1124 
Strength, psi 
300% 1204 -- -- -- 964 
Modulus, psi 
Elongation 530 40 80 150 420 
Tear Strength, 
500 228 262 276 284 
Die C: 
Pounds per inch 
Relative energy 
1100 100 230 280 450 
to tear 
______________________________________ 
It will be noted that the treatment with the organo-titanate improves the 
elongation and the tear strength as compared to the untreated filled 
material. However, it should be noted that these properties are not 
restored to the level of the unfilled polyethylene. 
EXAMPLE 16 
This example shows the effect of the isostearate 3.19 ester dry-blended 
with calcium carbonate on the impact strength of filled polypropylene. In 
these experiments, the heat-aged and unaged impact strengths are compared 
for unfilled polypropylene, polypropylene filled with 40 weight percent 
calcium carbonate, and polypropylene filled with 40 weight percent calcium 
carbonate which had been previously dry-blended with the amounts of the 
isostearate 3.19 ester (based on CaCO.sub.3) as shown in the table below. 
Heat aging at 150.degree. C. is an accelerated test of the long term aging 
effects at ambient temperatures. The dry blending was done with a high 
intensity Henschel type mixer at ambient temperature for a period of at 
least 30 sec. at 3600 rpm. 
The following table shows the impact strength of the unaged and heat-aged 
samples: 
______________________________________ 
Unnotched Izod 
Impact Strength 
ft. lb./in. width 
Heat Aged at 150.degree. C. 
Composition Unaged for 48 hours. 
______________________________________ 
Unfilled Polypropylene 
8.3 Not tested 
Polypropylene containing 
6.3 0.57 
40% calcium carbonate 
Polypropylene containing 
5.9 6.0 
40% calcium carbonate 
dry-blended with 0.5% 
isostearate 3.19 ester 
Polypropylene containing 7.0 
6.2 
40% calcium carbonate 
dry-blended with 0.75% 
isostearate 3.19 ester 
Polypropylene containing 
8.5 7.2 
40% calcium carbonate 
dry-blended with 1% 
isostearate 3.19 ester 
Polypropylene containing 
12.2 Not tested 
40% calcium carbonate 
and 3% isostearate 3.19 
ester 
______________________________________ 
The above data clearly show that the addition of the isostearate 3.19 ester 
of the invention substantially maintains the impact strength of the filled 
polypropylene in spite of the heat aging, whereas without the isostearate 
3.19 ester, the filled polypropylene loses its impact strength (becomes 
brittle) to a marked degree. The data also show that the impact strength 
of filled polypropylene is greatly improved by the use of 3% of the 
isostearate 3.19 ester. 
EXAMPLE 17 
In this example, the effect of the isostearate 3.19 ester on calcium 
carbonate-filled polypropylene is evaluated. Two methods are employed to 
ascertain the effect of the mixing procedures on the physical properties 
of the end product. In the first method, the calcium carbonate and the 
organic titanate compound are dry-blended in a Henschel mixer at 3600 rpm 
for one minute. The mixing takes place initially at room temperature, but 
the admixture increases in temperature during the mixing operation. 
Thereafter, test samples are formed by dry-blending with polypropylene, 
followed by screw injection molding at 450.degree. F. In the second 
method, the material from the Henschel mixer is compounded in a high shear 
double concentric screw mixer at 450.degree. F. Thereafter, samples are 
injection molded at this same temperature. The following table shows the 
results obtained. 
__________________________________________________________________________ 
Flexural 
Falling 
Notched 
Unnotched 
Tensile Modulus, 
Dart Impact, 
Izod Izod 
Strength, psi 
10.sup.3, psi 
ft.-lbs./in. 
ft.-lbs./in. 
ft.-lbs./in. 
__________________________________________________________________________ 
Method 1 
No Filler 5,000 240 1.0 0.7 Not tested 
40% CaCO.sub.3 
6,460 950 0.6 0.4 2.6 
No titanate ester 
40% CaCO.sub.3 
5,715 635 1.0 0.6 3.3 
0.3% titanate ester* 
40% CaCO.sub.3 
5,125 590 1.4 1.1 6.0 
0.6% titanate ester* 
Method 2 
40% CaCO.sub.3 
4,740 460 2.5 2.0 7.4 
0.6% titanate ester* 
Extruded (high shear 
mixing) 
__________________________________________________________________________ 
*based on CaCO.sub.3 
The above table clearly shows that the polypropylene containing the treated 
calcium carbonate has substantially improved properties, as compared to 
the untreated filled material. Where 0.6% of the organic titanate is used, 
the impact strength is markedly improved. Similarly, the use of the double 
concentric screw used in Method 2 results in a further improvement of 
properties. It is hypothesized that this additional high shear mixing 
provides a more thorough reaction between the organic titanate and the 
inorganic material. 
EXAMPLE 18 
The application of the invention to polystyrene is shown in this example. 
The table below shows a comparison of the specific gravity and melt index 
of polystyrene, polystyrene admixed 50/50 with calcium carbonate, and 
polystyrene admixed 50/50 with calcium carbonate which has been pretreated 
with 0.5 part of the isostearate 3.19 ester. The titanate ester and the 
calcium carbonate were dry-blended in a high shear dry blender initially 
at ambient conditions. The filler was admixed with the polystyrene in a 
two-roll mixer at a temperature of 307.degree. F. until mixing was 
complete. The sheets were comminuted and the specific gravity and melt 
index determined: 
______________________________________ 
Melt Index at 190.degree. C., 
Method E (ASTM) 
Material Specific By Weight By Relative 
Formulation Gravity in gms. Vol. in mls. 
______________________________________ 
Unfilled 1.04 0.90 0.86 
Polystyrene 
Polystyrene 1.50 0.36 0.24 
50% CaCO.sub.3 
Polystyrene 1.49 1.17 0.79 
50% pretreated CaCO.sub.3 
.5% isostearate 3.19 
ester 
______________________________________ 
The aforesaid table shows that the treated filled polystyrene is more 
readily moldable. The untreated filled polystyrene has a melt index which 
indicates that it cannot be as readily molded on conventional equipment.