Adducts of tetrasubstituted pyrophosphato titanates and/or amines, having the formula EQU X.sub.c Ti[OP(O)(OR.sup.1)OP(O)(OR.sup.2)OR.sup.3)].sub.4-c (NR.sup.4 R.sup.5 R.sup.6)d[P(OR.sup.7)(OR.sup.8)(OR.sup.9)]e, are useful in improving the physical and chemical properties of many filled resins.

BACKGROUND OF THE INVENTION 
The present invention relates to adducts of tetrasubstituted pyrophosphato 
titanates with phosphites and/or amines. The pyrophosphato titanate 
adducts of the present invention are useful in controlling the viscosity, 
flow and the conductivity of many filled resins. They improve the physical 
and chemical properties of many filled resins thereby permitting more 
valuable and more stringent usage with maintained ease of processing. They 
also serve as acid catalysts in various applications and inhibit 
water/salt caused corrosion in treated substrates. 
The titanates of the present invention differ from the pyrophosphato 
titanates disclosed in U.S. Pat. Nos. 4,122,062 and 4,087,402 primarily by 
the controlled reactivity of the titanates presently mentioned which 
permits long term storage of said titanates and of the treated 
filler/pigment resin at ambient to moderately elevated temperatures, and a 
very specific initiation of functional rates of activity to occur at 
controlled temperatures depending upon the specific adduct ligand 
employed. Other advantages conferred upon pyrophosphato titanates by 
adduction as taught in the present invention include a substantially 
reduced tendency for such adducts to crystallize as compared to their 
non-adducted analogs thereby permitting greater ease of dispersion in more 
vehicles and decreased acidity. In addition, many of the nitrogeneous 
adducts are water soluble, thereby permitting use of aqueous vehicles in 
conjunction with fillers and pigments which were heretofore incompatible 
in water as well as the incorporation of water as a diluent in organic 
systems which were previously incapable of accepting significant water 
dilution. 
SUMMARY OF THE INVENTION 
The pyrophosphato titanate adducts of the present invention may be 
represented by the following formula: 
EQU X.sub.c Ti[OP(O)(OR.sup.1)OP(O)(OR.sup.2)(OR.sup.3)].sub.4-c (NR.sup.4 
R.sup.5 R.sup.6).sub.d [P(OR.sup.7)(OR.sup.8)(OR.sup.9)].sub.e I 
In Formula I, c is 1 or 2; d is 0, 1 or 2; and e is 0, 1 or 2, with the 
proviso that d plus e must be 1 or 2. When c is 2, X is either RO- or a 
group which taken together with the Ti to which it is attached forms a 
ring having the following Formula (VI): 
##STR1## 
when c is 1, however, X must be RO--. In Formula VI, each of f, g, h and i 
is O or 1, with the proviso that at least one of g, h and i is 1 and that 
the sum of f, g, h and i is 2 or 3. Each R is independently chosen from 
among 1 to 10 carbon alkyl groups, 3 to 10 carbon alkenyl groups, 7 to 10 
carbon aralkyl groups, 2 to 10 carbon oxyalkylene groups and 3 to 10 
carbon dioxyalkylene groups. R.sup.1, R.sup.2, R.sup.4, R.sup.7, each 
R.sup.10 and R.sup.11 are independently chosen from among hydrogen, 6 to 
10 carbon aryl groups, 7 to 20 carbon aralkyl groups, 1 to 20 carbon alkyl 
groups, 3 to 20 carbon alkenyl groups, 2 to 20 carbon oxyalkylene groups 
and 3 to 20 carbon oligooxyalkylene groups, except that one and only one 
of R.sup.1 and R.sup.2 must be hydrogen. R.sup.5, R.sup.6, R.sup.8 and 
R.sup.9 are independently chosen from the same groups as R.sup.1, R.sup.2, 
R.sup.4, R.sup.7, R.sup.10 and R.sup.11 except that R.sup.5, R.sup.6, 
R.sup.8 and R.sup.9 may not be hydrogen. R.sup.5 and R.sup.6 may also be 
independently chosen from among 1 to 10 carbon alkyl, 3 to 10 carbon 
alkenyl, 6 to 10 carbon aryl and 7 to 10 carbon aralkyl groups. These last 
four groups optionally have from 1 to 3 carboxylate groups or from 1 to 3 
carboxamide groups as substituents. Each such substituent may be saturated 
or unsaturated and have from 1 to 5 carbon atoms. R.sup.5 and R.sup.6 may 
also be independently chosen from among 1 to 10 carbon alkanols, 2 to 6 
carbon alkadiols or 7 to 10 carbon aralkanols. When aromatic carbons are 
present in R, R.sup.2, R.sup.4, R.sup.7, R.sup.10 and R.sup.11 groups, 
each of said carbons is optionally substituted by 1 or 2 independently 
selected halogen atoms (for example, fluorine, chlorine, bromine or 
iodine). 
The present invention also relates to the use of such adducts for treating 
particulate fillers, including pigments, the compositions of fillers and 
the aforesaid adducts with thermoplastics, thermosets and coating or 
casting resins, and the use of such adducts in conjunction with coating 
and casting resin compositions in the absence of particulates. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The aforementioned alkyl and alkenyl groups, and alkyl and alkylene 
portions of the other aforementioned groups may be straight chain, 
branched chain or cyclic. Examples of alkyl groups are methyl, hexyl and 
decyl. Examples of cyclic alkyl groups are cyclohexyl and cyclooctyl. 
Allyl and crotyl are examples of alkenyl groups. Oxyalkylene groups are 
exemplified by methoxymethyl and methoxyethyl. Aralkyl groups are 
exemplified by benzyl and beta naphthyl methyl. Examples of R.sup.1, 
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, 
R.sup.10 and R.sup.11 are likewise numerous. In addition to the above 
mentioned groups cited as examples of R, these groups are also exemplified 
by higher carbon analogs of the above such as octadecatrienyl and 
2,4,6-trimethyl-1-cyclohexyl as well as by naphthyl and biphenyl aralkyl 
groups such as 2-phenethyl, 2-chloro, 4-bromophenyl or naphthyl. In 
addition to the above, R.sup.5 and R.sup.6 are exemplified by such groups 
as 3-methacrylpropyl, and 2-acrylamidoethyl hydroxy methyl and dihydroxy 
octyl. 
The inorganic materials that may be treated with the titanate adducts of 
the present invention 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 
absorbed water, or both. Examples of such reactive inorganic materials are 
the metal oxides of zinc, magnesium, lead, and calcium and aluminum, iron 
filings and turnings, and sulfur. Examples of inorganic materials that are 
reinforcing materials are metals, clay, carbon black, calcium carbonate, 
barium sulfate, silica, mica, glass and asbestos. Examples of such 
inorganic materials that are pigments are titanium dioxide, iron oxides, 
zinc chromate and ultramarine blue. As a practical matter, it is 
preferable that the particle size of the inorganic material should not be 
greater than 1 mm, preferably from 1 micron to 500 microns. 
It is imperative that the titanate adduct 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 and 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, 
for example, whether it is thermoplastic or thermosetting, and its 
chemical structure, as will be readily understood by those skilled in the 
art. 
Where the inorganic material is pretreated with the titanate adduct, it may 
be admixed in any convenient type of intensive mixer, such as a Henschel 
(trademark of Prodex) or Hobart (trademark of Hobart Corporation) mixer or 
a Waring (trademark of Dynamics Corporation of America) 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, preferably 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 177.degree. to 232.degree. C.; high density 
polyethylene from 204.degree. to 246.degree. C.; and polystyrene from 
232.degree. to 260.degree. C. 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 (trademark of Farrel Corporation) mixers, double 
concentric screws, counter or corotating twin screws and ZSK type of 
Werner and Pfleiderer (trademark of Werner & Pfleiderer) and Bussex 
(trademark of Bussex Corp.) mixers. 
When the titanate adduct 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 titanate adduct may also react with the 
polymeric material if one or more of the groups on the titanate adduct is 
reactive with the polymer. 
The ratio of pyrophosphato titanate to adducting agents is preferably 1:1 
or 1:2, with the latter ratio most preferred. Each adducting ligand may be 
the same or different. In those formulations in which either the 
phosphorus based or the nitrogen based adducting agents are different, the 
product obtained is usually a mix of possible adducts including mixed as 
well as identical ligands. In those adducts wherein combinations of 
nitrogen and phosphorus are employed, it is often possible by control of 
stoichiometry and mode of addition to maintain an almost complete 
dispersity of product, if so desired. 
When used in conjunction with particulates, the adducts of the present 
invention are employed at levels of at least 0.01 parts by weight, 
preferably from 0.1 to 5 parts by weight, and most preferably from 0.2 to 
2 parts by weight, per 100 parts by weight of inorganic solid. The portion 
of adduct actually chosen by one skilled in the art is a function of the 
inorganic solid, its surface area and the particular titanium adduct 
selected. Upon reaction between the titanate and the surface of the 
inorganic solid, the titanate becomes chemically bonded to at least a 
portion of the inorganic solid, thereby modifying the surface 
considerably. The modified inorganic solid is generally far more easily 
dispersed in organic media than is the untreated solid. For treatment 
purposes, the titanate may be added to a suitable vehicle, such as water 
or a resin to be filled depending upon the investigator's desire and/or 
the nature of the titanate being employed. This addition is followed by 
appropriate shear to create an adequate level of dispersion. The treated 
particulate, in addition to being more effectively coated, will almost 
certainly have substantially valuable additional properties, such as the 
ability to act as a catalyst, improved adhesion to substrate, and/or the 
ability to activate a cross-linking agent in appropriate vehicle systems, 
primarily due to the availability or organo-functionality added by 
attached titanate molecules. 
The amount of treated filler added to a resin generally ranges from about 
1% to about 15% for a pigment and from about 1% to about 500% for an 
extender (all percentages are % by weight based on the weight of the 
resin). A wide variety of resins may be filled with fillers that are 
treated with the titanate adducts of the present invention. Examples of 
such resins are coating resins, casting resins, thermoplastic resins and 
thermosetting resins. Examples of all of the foregoing may be found in the 
reference Modern Plastics Encyclopedia. 
In many instances, it is advantageous to dilute the titanate with an 
appropriately compatible fluid before the titanate is introduced into 
resin vehicles or before it is mixed with an inorganic particulate. 
Examples of appropriate inert fluids are aromatic hydrocarbons, ethers and 
glycol ethers. In many applications involving the use of nitrogeneous 
adducts of pyrophosphato titanates, water may also be utilized as a 
solubilizing inert vehicle, particularly in applications involving 
subsequent use in aqueous systems, such as latex products. 
The compounds of the present invention may be prepared by numerous routes. 
Among the synthetic routes which have proven successful are the addition 
of appropriate phosphites (Formula II) and/or amines (Formula III) to the 
corresponding pyrophosphato titanates (Formula IV) described in U.S. Pat. 
No. 4,122,062 and U.S. Pat. No. 4,087,402. The reaction of tetraalkyl 
titanate phosphite adducts (Formula V), preparation of which is described 
in U.S. Pat. No. 4,080,353 with addition of an appropriate pyrophosphate, 
an amine and/or a phosphite and/or a chelating agent may also be utilized, 
as may processes employing titanium tetrachloride in place of tetraalkyl 
titanates. The aforementioned formulae are shown below: 
Formula II 
EQU P(OR.sup.7)(OR.sup.8)(OR.sup.9) 
Formula III 
EQU NR.sup.4 R.sup.5 R.sup.6 
Formula IV 
EQU X.sub.c Ti[OP(O)(OR.sup.1)OP(O)(OR.sup.2)(OR.sup.3)].sub.4-c 
Formula V 
EQU (RO).sub.4 Ti(P)(OR.sup.7)(OR.sup.8)(OR.sup.9).sub.d 
In Formulae II, III, IV and V, the various notations and functional groups 
have the definitions given above for Formula I. 
Another synthetic route found useful for the preparation of the phosphite 
adducts of the present invention wherein the adduct ligands are 
homogeneous is the reaction of tetraalkyl titanate with an admixture of 
disubstituted pyrophosphoric acid and the phosphite ligand(s). This last 
technique is the preferred one for the preparation of mono and di- 
phosphite adducts of such pyrophosphato titanates. Variations of the 
aforementioned synthetic routes will be apparent to those skilled in the 
art. 
The preparation of phosphite adducts of corresponding pyrophosphato 
titanates may be accomplished under adiabatic conditions (since minimal 
heat evolution occurs) at any convenient temperature between approximately 
-20.degree. C. and approximately 150.degree. C. The addition of the 
phosphite to the pyrophosphato titanate in either direct or reverse order 
of addition will, in general produce minimal visual or thermal indication 
of reaction. However, typically, a bathochromic shift of the absorption 
maximum toward, and, occasionally even into the visual absorption range, 
will generally be observed. Additionally, the melting point will be 
depressed below that of the corresponding unadducted precursor. Solubility 
of the resulting titanate in hydrocarbon media will generally be increased 
at the expense of the dispersibility in water. By contrast, those adducts 
produced by the addition of appropriately substituted amines to 
pyrophosphato titanates or their phosphite adducts will generally provide 
substantial exotherms of formation together with displacement of 
stoichiometric proportions of phosphite, if present, and will produce 
products of considerably enhanced water solubility as compared to the 
parent pyrophosphato titanate. Techniques employing the addition of 
dibasic pyrophosphates to tetrasubstituted titanate adducts of phosphite 
and/or amines will also generate substantial exotherms of formation and in 
both of these latter two synthetic approaches, temperatures should be kept 
within the range of approximately 0.degree. C. to approximately 
150.degree. C. by external cooling in order to minmize product degradation 
and/or by-product formation. Examples 1 through 4 below, are illustrative 
of the above mentioned techniques in the order indicated above for the 
preparation of pyrophosphato organo titanate adducts of the present 
invention. Subsequent examples 5 through 17 are illustrative of the 
utility of the materials of the present invention for a variety of 
applications, such as corrosion control, pigment/filler dispersion, 
catalyst activity control and impact improvement. Preferred methods of 
incorporation of the titanate adducts of the present invention into filled 
resin systems and their uses both in the presence and in the absence of 
fillers, for purposes other that those listed above are also illustrated.

EXAMPLE 1 
Preparation of Di(butyl,methyl) pyrophosphato ethylene titanate di(dioctyl 
phosphite) 
This example illustrates the sequential addition mode of phosphite adduct 
formation. 
206 g of dimethyl acid pyrophosphate (1 mole) and 296 g of dibutyl acid 
pyrophosphate (1 mole) were charged into a 2 liter stainless steel and 
glass assembly comprising a mechanically stirred 2 liter glass vessel 
equipped with a thermometer, addition funnel, and a water cooled jacket. 
285 g of tetraisopropyl titanate (1 mole) was added via the addition 
funnel over a period of 1 hour. Cooling sufficient to prevent the reaction 
mass temperature from exceeding 150.degree. C. was maintained throughout 
the addition period. After 20 minutes of further mixing, 62 g of ethylene 
glycol (1 mole) were added over a period of about 20 minutes, at an 
addition rate and at a cooling rate such that the temperature of the 
reaction mass was kept between 42.degree. and 46.degree. C. 612 g dioctyl 
phosphite (2 moles) were then added, all at once. The resulting mass was 
transferred to a 2 liter flask equipped for vacuum distillation and was 
distilled from a water bath to give a pot residue having a boiling point 
of 80.degree. C. 231 g of isopropyl alcohol (3.85 moles, GLC assay greater 
than 98%) were recovered as a distillate via liquid nitrogen cooling of 
volatiles. Product recovery was 1246 g (100% yield). The product was a 
pale yellow low viscosity liquid which crystallized slowly from a 40% 
solution in n-hexane at -20.degree. C. to give light amber platelike 
crystals having a melting point of 48.degree..+-.3.degree. C. Recovery was 
1014 g (81%). The omission of byproduct isopropanol removal lowered product 
recovery on crystallization to 63%, but otherwise gave unchanged results. 
EXAMPLE 2 
Preparation of Di(butyl, methyl) pyrophosphato ethylene titanate di(dioctyl 
phosphite) 
This example illustrates the preparation of the example adduct in situ. 
The procedures, reaction conditions and materials examplified in Example 1 
were employed except that the dioctylphosphite was introduced with the 
pyrophosphates prior to titanate addition. The nature of the crude product 
produced and its yield (1248 g, 100%) were essentially unchanged, but this 
order of addition was found to provide several operating advantages. Among 
the advantages were lower and more uniform exotherms of tetraisopropyl 
titanate addition (possibly due to the larger mass in the pot "heat sink", 
and/or to the more efficient cooling made possible by the reaction mass' 
considerably lower viscosity) and virtual freedom from the formation of 
crystalline intermediates of undetermined nature which formed copiously 
during the procedure given in Example 1, unless the dispersion of 
tetraisopropyl titanate added was extremely efficient. 
It should be noted that other tetraalkyl titanates, e.g., methyl, n-butyl, 
t-butyl, or sec-octyl may be substituted for the tetraisopropyl titanate 
used in the illustration. However, the use of n-alkyl titanates frequently 
results in ligand exchange with the pyrophosphate moiety and may therefore 
result in complex product mixtures, especially via the procedure outlined 
in Example 1. Furthermore, the removal of higher boiling by-product 
alkanols, if desired, usually proved more difficult than the removal of 
the more volatile lower alkanols. The removal of by-product alcohol is 
optional and is not required for the preparation of the products of the 
present invention. Said removal merely facilitates product purification 
and/or may eliminate side reactions in alcohol sensitive substrates such 
as polyesters and urethanes and/or may provide decreased product 
flammability. 
EXAMPLE 3 
Preparation of Di(butyl,methyl) pyrophosphato, ethylene titanate di(dioctyl 
phosphite) 
Tetraisopropyl titanate di(dioctylphosphite), 901 g (1 mole), was charged 
to a 2 liter stainless steel vessel equipped with an efficient agitator 
and external cooling. Temperature was maintained at or below 45.degree. C. 
during the sequential addition of 206 g (1 mole) of dimethyl acid 
pyrophosphate followed by 296 g (1 mole) of dibutyl acid pryophosphate 
over a period of approximately one hour each. Ethylene glycol 62 g (1 
mole) was then added. The reaction mixture was then transferred to a Pyrex 
(trademark of Corning Glass for heat resistant borosilicate glass) glass 
system equipped for simple vacuum distillation and was distilled to give 
1238 g (99% yield) of pale yellow oil having a boiling point of greater 
than 90.degree. C. which slowly crystallized to produce a white waxy 
crystalline mass having a melting point of 49.degree..+-.4.degree. C. 
This procedure was not as satisfactory as that of Example 1, because it 
suffered from the formation of localized gels during pyrophosphate 
addition. These gels made mixing difficult. 
EXAMPLE 4 
Numerous examples of chelated pyrophosphato titanate adducts prepared via 
the procedure given in Examples 1 to 3 are given in Table 1. Each titanate 
adduct is identified by a symbol in the extreme left hand column that 
similarly identifies the adduct in the Examples that follow. 
TABLE 1 
__________________________________________________________________________ 
Method of 
Melting 
Calculated 
Pyrophosphato Titanate Adduct 
Preparation 
Point .degree.C. 
% P/Found % P 
__________________________________________________________________________ 
(A) ethylene di(butyl, octyl)pyro- 
1,2,3 &lt;0 16.4/16.1 
phosphato titanate di(tris- 
ethylphosphite) 
(B) 1-oxo-1,3-propylene di(bis- 
2,3 42 .+-. 5 
15.0/14.8 
phenyl)pyrophosphato titanate 
dilaurylphosphite 
(C) 1-oxo-2-phenylethylene, di(2- 
1,2,3 54 .+-. 3 
11.3/11.2 
chloro-p-cresyl, methyl)pyro- 
phosphato titanate, triphenyl 
phosphite 
(D) neopentenyl, di(bisoctadecyl) 
1,3 27 .+-. 6 
9.74/9.5 
pyrophosphato titanate di(butyl, 
propyl phosphite) 
(E) 1,3 propylene, di(bisoctadecyl) 
1 &lt;0 9.26/9.3 
pyrophosphato titanate di(di- 
benzyl phosphite) 
(F) oxoethylene di(butyl, methoxy- 
1,2 &lt;0 9.46/9.3 
ethoxyethyl) pyrophosphato 
titanate dimethoxethylphosphite 
(G) ethylene di(methyl, 11, 14-hexa- 
1,2,3 34 .+-. 6 
16.2/16.1 
decadienyl) pyrophosphato 
titanate di(bismethyl phosphite) 
(H) 1,2-propenyl, di bis(2-bromo-3- 
1,3 64 .+-. 2 
12.5/12.6 
chloro-4-t-butylphenyl) pyro- 
phosphato titanate di(bishexa- 
decyl phosphite) 
(I) ethylene di(butyl,methyl) pyro- 
1,2,3 73 .+-. 4 
16.9/16.8 
phosphato titanate di(tris- 
ethylamine) 
(J) oxoethylene di(butyl, octyl) 
1 42 .+-. 5 
13.3/12.9 
pyrophosphato titanate 2-di- 
methylaminoisobutanol 
(K) ethylene di(bisoctyl)pyrophos- 
1,3 82 .+-. 4 
9.65/9.9 
phato titanate di(3-dimethyl- 
aminopropylmethacrylamide 
(L) benzylethylene di(phenyl, lauryl) 
1 76 .+-. 4 
9.57/9.7 
pyrophosphato titanate di(ethyl- 
aminoethyl acrylate 
(M) ethylene, di(butyl, methyl) pyro- 
1 not isolated* 
phosphato titanate di(bisoctyl) 
phosphite 
(N) oxoethylene di(butyl, octyl)pyro- 
1 not isolated* 
phosphato titanate diphenyl phos- 
phite 
(O) 2-methyl-2,4-butenyl di(di-p- 
1 not isolated* 
chlorobenzyl)pyrophosphato 
titanate di(butoxyethyl, methyl 
phosphite 
(P) oxoethylene, di(benzyl, 2- 
1,2 not isolated* 
pentenyl)pyrophosphato titanate 
di(2-dimethylamino) isobutanol 
(Q) 2,3-butenyl di(bis-4-methoxy- 
1 not isolated* 
phenyl)pyrophosphato titanate 
diethylamine 
(R) 2,3-dimethyl-2,3-butenyl di(bis- 
1 not isolated* 
methyl)pyrophosphato titanate 
triethylamine, dibutyl phosphite 
(S) oxoethylene di(p-bromobenzyl) 
1 not isolated* 
pyrophosphato titanate methyl- 
aminoethanol 
(T) 1-oxoprop-1,3-enyl di(butoxy- 
1 not isolated* 
methoxyethyl, isobutyl)pyro- 
phosphato titanate di(bistridecyl) 
phosphite 
(U) methoxyethylene di(bispropyl) 
1 not isolated* 
pyrophosphato titanate di 
propylamino ethyl methacrylate 
(V) isopropyl, tri(butyl,methyl) 
1,2,3 &lt;0 17.0/16.8 
pyrophosphato titanate di(bis- 
octyl phosphite) 
(W) isopropyl, tri(bisoctyl)pyro- 
1,2, 16 .+-. 5 
12.9/12.8 
phosphato titanate triethanol- 
amine 
(X) isooctyl, tri(bismethyl)pyro- 
1,2,3 not isolated* 
phosphato titanate tripropyl 
phosphite 
(Y) ethoxytriglycolyl, tri(4-bromo- 
1 14 .+-. 6 
15.3/15.1 
phenyl,methyl)pyrophosphato 
titanate di(methoxyethyl) 
phosphite 
(Z) 4-ethoxybenzyl tri(di-alphanaph- 
1 64 .+-. 5 
10.4/10.1 
thyl) pyrophosphato titanate di 
(di-ethylaminoethyl(methacrylate) 
(AA) 
t-butyl, tri(bisbutyl) pyro- 
1 12 .+-. 4 
17.2/17.0 
phosphato titanate tri-methyl 
phosphite, dimethylaminoethanol 
(AB) 
methyl,tri(bis-4-chlorophenyl) 
1 48 .+-. 3 
15.8/15.5 
pyrophosphato titanate dioctyl 
phosphite, dimethylaminoethyl 
formamide 
(AC) 
allyl, tri(allyl,methyl)pyro- 
1,3 23 .+-. 3 
20.2/19.9 
phosphato titanate trimethyl 
phosphite, dioctyl phosphite 
(AD) 
(2,2-diallyloxymethyl)ethyl 
1,2 38 .+-. 4 
11.9/11.7 
tri(bisbutyl)pyrophosphato 
titanate di(trisphenyl phosphite) 
(AE) 
1-(2-butenyl)tri(methyl, octyl) 
1 31 .+-. 3 
13.1/12.9 
pyrophosphato titanate, tri- 
ethylamine, dioctyl phospite 
__________________________________________________________________________ 
*by-product alcohol not removed, reaction mixture used as such. 
EXAMPLE 5 
This example illustrates the utility of various titanate adducts of the 
present invention as corrosion retardants. 
Xylene degreased 20 mil panels of cold rolled steel were dip coated with a 
1 weight percent solution of additive in toluene followed by a toluene 
wash and were then oven dried at 150.degree. C. in a nitrogen atmosphere. 
The dried panels were cooled, weighed, subjected to 100 hours of 100% 
humidity at 40.degree. C. exposure in an environmental cabinet, re-dried, 
cooled, and re-weighed. The corrosion rate in mils per year was calculated 
from the following equation: 
______________________________________ 
Corrosion rate = 
(weight loss/panel weight) (20 mils) (8670 hours/year/100 
______________________________________ 
hours) 
The results of a study of selected examples of the titanates of the present 
invention are given in Table 2. 
TABLE 2 
______________________________________ 
Indicated % 
Adduct Corrosion Rate (mils/yr) 
of Control 
______________________________________ 
None (control) 
172 100 
A 38 22 
B 26 15 
C 69 40 
D 81 47 
E 24 14 
F 13 8 
G 32 19 
H 19 11 
I 20 12 
J 31 18 
K 38 22 
L 35 20 
X 17 10 
Y 20 12 
AB 26 15 
AC 18 10 
AD 41 24 
AE 38 22 
______________________________________ 
In each instance, the materials of the present invention improved humidity 
resistance of cold rolled steel by at least two-fold and in the case of 
the F material, the improvement was twelve-fold. 
EXAMPLE 6 
Titanate adducts M through U, identified above, were compounded into an 
alkyl-melamine baking enamel having a brown color as indicated below. The 
resultant formulations were each oven baked at 100.degree. C. for a period 
adequate to provide a film pencil hardness (Society of Coatings Technology 
Test) of F-H at 1.3.+-.0.2 mils dry film thickness. The results of this 
study are given in Table 3. 
The following materials were premixed, on a high shear disperser, at 
ambient temperature for fifteen minutes: 
______________________________________ 
Material Kilograms Liters 
______________________________________ 
soya alkyd short oil, 
172 174 
Cook #S-157-A-2 (trademark of 
Cook Paint and Varnish Co.) 
pyrophosphato titanate adduct 
0.397 0.33 
titanium dioxide, DuPont #R-960 
21 5.08 
(trademark of E.I. DuPont 
de Nemours, Co.) 
magnesium silicate 32 12.0 
lamp black 0.9 0.512 
red iron oxide 3.2 0.648 
yellow iron oxide 15 3.72 
bentonite clay 1.1 0.633 
fumed silica 1.1 0.523 
soya lecithin 1.4 1.42 
______________________________________ 
Tetraoctyltitanate di(dioctyl)phosphite (0.188 kilograms, 0.20 liters) was 
added to the above mixture and the mixture was further mixed on a sand 
mill until the particle size was Hegman 6.5 grind guage. The resulting 
blend was added to the following Material Letdown Solution and was mixed 
at ambient temperature. 
______________________________________ 
Material Letdown Solution 
Kilograms Liters 
______________________________________ 
xylene 41.8 48.5 
Butyl Cellosolve (trademark of Union 
10.2 11 
Carbide Corporation) 
triethylamine 2.0 2.73 
n-butanol 0.90 1.12 
50% melamine formaldehyde resin, 
74.5 76 
Cargil #2218 (trademark of 
Cargill Inc.) 
6% Cobalt naphthenate 0.90 0.95 
______________________________________ 
The resulting paint composition had the following properties: 
______________________________________ 
weight per liter 1.05 
viscosity (#2 Zahn .+-. 6 sec.) 
28.0 
volume solids (%) 32.0 
weight solids (%) 49.0 
thickness dry film 1.0-1.75 
pencil hardness F-H 
gloss (.+-.5.degree.) 55.0 
letdown solution to grind ratio 
5:1 
______________________________________ 
The bake time at 93.degree. C. required to achieve specification hardness 
was determined for several titanate adducts of the present invention. The 
results are shown in Table 3. 
TABLE 3 
______________________________________ 
Bake Time at 93.degree. C. 
Time required to 
Pyrophosphato Titanate 
achieve specification 
Adduct Employed hardness (+ 2 minutes) 
______________________________________ 
None (control) 117 
M 43 
N 41 
O 57 
P 84 
F 21 
Q 39 
R 48 
S 83 
T 42 
U 38 
______________________________________ 
The reduction in bake time required in order to achieve specification 
properties is clearly shown to be substantial for all members of the class 
tested. A considerable reduction in cost results from the savings in both 
time and energy expended during backing. 
EXAMPLE 7 
This example illustrates the utility of certain pyrophosphato titanate 
adducts in the simultaneous control of viscosity and pot life of polyester 
casting resins. 
Polyester resin composites were prepared by thoroughly admixing in the 
following order, 100 g of polyester resin (#30001, trademark of Reichold 
Chemical Co.), 0.5 g of pyrophosphato titanate adduct, 100 g of talc (#42, 
trademark of Englehard Mineral & Chemical Co.), and 1 g of 6% cobalt 
naphthenate. The resultant dispersions were deaerated by mixing in vacuo 
to eliminate variable air entrainment. The viscosities of the dispersions 
were then measured employing a Brookfield RVF viscosimeter (trademark of 
Brookfield Corp., Stoughton, Mass.). Thereafter, 0.5 g of methyl ethyl 
ketone peroxide was added to 100 g aliquots of deaerated dispersion and 
pot life was measured (time to achieve 2 million cps viscosity) at 
21.degree. C. The results are given in Table 4. 
TABLE 4 
______________________________________ 
Viscosity of Composite 
Adduct Employed 
(thousands of poise) 
Minutes 
______________________________________ 
None 2.7 33 
N 1.6 109 
O 1.3 127 
F 0.8 18 
T 1.4 142 
U 0.6 14 
V 3.7 37 
W 5.2 35 
______________________________________ 
The data show that the phosphite adducts N, O and T retard the increase of 
viscosity due to premature gellation, thereby providing substantially 
increased useful working pot life, whereas the unsaturated nitrogen based 
adducts F and U act as accelerators, useful where rapid cure is desired. 
Furthermore, all of the adducts tested, other than V and W, provided the 
bonus of lower composite viscosities useful in many low energy application 
situations. Adducts V and W acted as thixotropes without material effect on 
pot life, a characteristic not shared by conventional thixotropes such as 
fumed silica and asbestos which, normally, markedly slow peroxide cures. 
EXAMPLE 8 
This example illustrates the use of various pyrophosphato titanate adducts 
to improve the scrubbability of a latex coating. 
Test batches of latex paint were prepared by mixing 25 g of titanium 
dioxide (DuPont #R931, trademark of E. I. DuPont de Nemours) in 20 g of 
ethylene glycol monobutyl ether containing 0.25 g of pyrophosphato 
titanate adduct on a high shear disperser (at constant torque) to a Hegman 
grind gauge of minus 6. This was followed by letdown (dilution) with 100 g 
of acrylic latex (Ucar 4550, trademark of Union Carbide Corp.). Test 
panels were then prepared as 3 mil wet (about 2 mil dry) drawdowns on 
toluene degreased mild steel and the resultant films were dried at 
25.degree. C. for 48 hours prior to scrub testing. The scrub tester 
employed was a 1/8" wide, 10 micron silica impregnated phenolic grinding 
wheel rotated at 10 RPM. Grinding was continued in each case until 
magnetic dust was detected. Results are given in Table 5. 
TABLE 5 
______________________________________ 
Grind Time (minutes) 
Adduct Required for -6(Hegman) 
Scrub Cycles 
______________________________________ 
Control 22 38 
B 14 57 
C 12 83 
D 13 71 
E 9 46 
Q 14 143 
G 15 71 
H 12 62 
I 14 49 
J 13 53 
K 15 168 
______________________________________ 
These data show that the use of the adducts of the present invention 
markedly improved both the grinding efficacy and the scrub resistance in 
those formulations in which they were employed and that in several cases 
(C, F and K) the improvements in scrub resistance were twofold or higher. 
EXAMPLE 9 
This example illustrates the utility of pyrophosphato titanium adducts of 
the present invention for the improvement of epoxy polyamide coatings. 
The coating components A and B were prepared separately by mixing the 
ingredients listed in Tables 6A and 6B, respectively, in the order 
indicated at 33.degree. C. to 45.degree. C., using a Cowles dissolver 
(trademark of Moorhouse Cowles Co.). Components A and B were admixed at 
ambient temperature using the same equipment. Q-panels (trademark of 
Q-Panel Corp.) of cold rolled steel were coated with portions of the test 
coating to provide a film one mil dry thickness. The coatings were aged 
for one week at ambient temperature before testing. Test results are given 
in Table 6C. 
TABLE 6A 
______________________________________ 
Component A 
BLSC Control 
Silica System 
Ingredient Parts by weight 
Parts by weight 
______________________________________ 
epoxy resin (Araldite 
210 210 
571CX80, trademark 
of Ciba-Geigy Corp.) 
basic lead silicochromate 
480 None 
(BLSC) 
titanium dioxide 30 30 
red iron oxide 15 15 
fumed silica 6.4 6.4 
talc 235 235 
amorphous silica None 400 
xylene 193 193 
diacetone alcohol 
96 96 
urea formaldehyde resin 
10.5 10.5 
(Beetle 216-8, trademark 
of America Cyanamid Corp.) 
chelated pyrophosphato 
None 3.3 
titanate adduct 
parts by weight 1276 1199 
______________________________________ 
TABLE 6B 
______________________________________ 
Component B 
BLSC Control Silica System 
Ingredient Parts by weight 
Parts by weight 
______________________________________ 
polyamide curative 
105 105 
(Araldite 820, trademark 
of Ciba-Geigy Corp.) 
xylene 24 24 
butanol 12 12 
parts by weight 
141 141 
______________________________________ 
The cost per gallon of the Component A BLSC Control was $1.35; the cost per 
gallon of the Component A titanate adduct formulation was about $0.66. 
TABLE 6C 
______________________________________ 
Rusting Stripped 
after 1000 
panel rust- 
hour salt 
ing after 
Initial Four Month fog expo- 
500 hours, 
viscosity 
viscosity sure at 100% humid- 
Adduct KU* KU 27.degree. C. 
ity at 27.degree. C. 
______________________________________ 
BLSC 
(Control) 
192 216 M (moderate) 
S (severe) 
B 112 126 Sl (slight) 
Sl 
C 103 104 Sl M 
D 106 118 Sl Sl 
E 102 104 Sl Sl 
Q 116 109 Sl M 
G 109 111 M M 
H 113 115 Sl Sl 
I 96 100 M Sl 
J 101 107 Sl Sl 
______________________________________ 
*Krebs units 
Note that as compared with the BLSC Control, each of the pyrophosphato 
titanate adducts of the present invention provided improved protection 
against corrosion at a cost considerably lower than that of the BLSC 
Control without the employment of environmentally damaging heavy metals as 
required by the best previously available technology. Also demonstrated are 
the massive viscosity reduction achieved via the use of the products of the 
present invention as a major contributing capability to the functional 
utility of the silica system since control viscosity would otherwise 
prevent effective application coverage. 
EXAMPLE 10 
This example illustrates the utility of pyrophosphato titanium adducts of 
the present invention as adhesion promoters for polymer laminates. 
The titanate adducts listed in Table 7 below were compounded into virgin 
low density polyethylene (LDPE). Thirty mil sheets of the LDPE were 
extrusion laminated onto preformed 50 mil Surlin (trademark of DuPont de 
Nemours for metalated polyolefin) ionomer sheets at 107.degree. C., 
employing a 24:1 vented National Plastics Machinery (trademark) extruder. 
The peel strength of each laminate was measured with a constant speed 
motor and a strain gauge at 27.degree. C. after 24 hours at ambient 
temperature and pressure. The results are given below in Table 7. The 
formuations contained 0.2 weight percent of the indicated chelated 
pyrophosphato titanium adduct on LDPE. 
TABLE 7 
______________________________________ 
Adduct Peel Strength, kg/cm.sup.2 
______________________________________ 
Control 4.8 
A 9.0 
B 19 
C 20 
D 17 
E 20 
G 17 
H 16 
I 24 
Z 13 
______________________________________ 
Note that in each instance, the use of the adducts improved peel strength 
(bonding) between the dissimilar polymer layers. 
EXAMPLE 11 
This example illustrates the utility of pyrophosphato titanium adducts of 
the present invention in enhancing the tensile and elongation properties 
of cellulosics (cross-linked low density polyethylene filled with cotton 
linters). 
One hundred parts by weight of low density cross-linkable polyethylene, 20 
parts cotton linters (chopped to 20-45 micron length, 0.5 parts dicumyl 
peroxide and 0.2 parts of pyrophosphato titanate adduct were compounded on 
a two roll mill at 93.degree..+-.6.degree. C. (all parts given are parts by 
weight). Samples were then press cured at 149.degree. C. for 20 minutes. 
The samples were equilibrated at 21.degree. C. for 24 hours prior to 
testing on an Instron (trademark of Instron Corporation) tensile tester at 
an extention rate of 0.2 inches/min. The results are given below in Table 
8. 
TABLE 8 
______________________________________ 
Adduct Tensile Strength, kg/cm.sup.2 
Elongation at Break, % 
______________________________________ 
Control 
6.11 .times. 10.sup.3 
80 
A 6.53 .times. 10.sup.3 
90 
D 7.95 .times. 10.sup.3 
170 
Q 10.9 .times. 10.sup.3 
230 
K 8.80 .times. 10.sup.3 
210 
______________________________________ 
EXAMPLE 12 
This example illustrates the use of pyrophosphato titanate adducts as 
viscosity control agents and/or dispersants in dissimilar media (for 
example, water and mineral oil). 
In each instance, the indicated titanate was precoated at 0.5 weight 
percent on HiSil 223 (trademark of PPG Industries) in a household type 
blender prior to dispersion in the liquid vehicle (water or mineral oil) 
at 70 weight percent HiSil using a Hochmeyer disperser (trademark of 
Hochmeyer Corp.). The resulting dispersions were evaluated at 27.degree. 
C. using a Brookfield RVF viscometer (trademark). The results are given in 
Table 9. 
TABLE 9 
______________________________________ 
Aqueous dispersion visco- 
Mineral Oil dispersion 
Additive 
sity MCPS (10.sup.3 centipoise) 
viscosity MCPS 
______________________________________ 
Control 152 23 
A 130 28 
B 37 56 
C 52 72 
D 168 22 
E 182 18 
Q 154 21 
G 172 19 
H 41 62 
I 227 separates rapidly 
J 47 62 
K 164 18 
Z 194 17 
Y 184 18 
AD 171 
______________________________________ 
This example demonstrates the wide range of viscosity control available in 
vehicles as diverse as water and mineral oil via the employment of small 
proportions of pyrophosphato titanium adducts in conjunction with a single 
(silica) particulate. 
EXAMPLE 13 
This example illustrates the utility of pyrophosphato titanium adducts as 
promoters of conductivity in metal filled polymer composites. In each 
instance, the metal indicated was precoated with the specified adduct by 
admixture in a household type blender prior to incorporation into the 
polymer base on a laboratory two roll mill. The formulations were press 
cured and formed as 6 inch.times.6 inch.times.100 mil sheets for 20 
minutes at 170.degree. C. and stress relieved at 27.degree. C. for 24 
hours, prior to evaluation. Resistivities were measured using a field 
effect transistor type ohmeter equipped with a decade runup box of 
10.sup.1 to 10.sup.9 ohms range on a through the sample basis. The results 
are given in Table 10 (Tables 10a, 10b and 10c). 
TABLE 10 
______________________________________ 
TABLE 10a 
Formulation (in parts by weight): nickel (1 micron nomimal pow- 
der, manufactured by Potter Industries), 87.5; Geon 103EP 
(trademark of B.F. Goodrich Co. for PVC resin), 7; dioctyl 
phthalate, 4.5; mixed barium, cadmium and zinc oxalate stabilizer, 
0.05, epoxidized soybean oil, 0.5; pyrophosphato titanate 
adduct, 0.25. 
Resistance Resistance 
Adduct ohm/cm Nickel ohm/cm Tin 
______________________________________ 
Control 1.3 .times. 10.sup.6 
3.9 .times. 10.sup.6 
B 16 6.2 .times. 10.sup.2 
C 28 4.8 .times. 10.sup.2 
Q 45 87 
E 63 1.1 .times. 10.sup.2 
K 1.1 .times. 10.sup.2 
96 
______________________________________ 
TABLE 10b 
______________________________________ 
Formulation (in parts by weight): nickel (1 micron nominal pow- 
der), 75; SWS (trademark of Stauffer Chemichal Co. for silicone 
resin), 24; dicumyl peroxide, 1.0; pyrophosphato titanium adduct, 
0.25. 
Adducts Resistance ohm/cm 
______________________________________ 
Control 1.6 .times. 10.sup.8 
B 2.0 .times. 10.sup.4 
C 1.4 .times. 10.sup.4 
E 4.7 .times. 10.sup.2 
Q 6 .times. 10.sup.2 
K 1.7 .times. 10.sup.2 
Y 5.7 .times. 10.sup.5 
Z 6.2 .times. 10.sup.3 
AA 4.1 .times. 10.sup.3 
AB 8.1 .times. 10.sup.1 
AD 6.2 .times. 10.sup.2 
AE 3.8 .times. 10.sup.2 
______________________________________ 
TABLE 10c 
______________________________________ 
Formulation (in parts by weight): Viton E430 (trademark of E.I. 
duPont de Nemours for fluoroelastomer), 24; calcium hydroxide 
powder, regent grade (manufactured by J.T. Baker Chemical 
Company), 1.28; nickel (1 micron nominal powder), 75; 
pyrophosphato titanium adduct, 0.25. 
Adduct Resistance ohm/cm 
______________________________________ 
Control 9 .times. 10.sup.8 
B 5 .times. 10.sup.5 
C 7 .times. 10.sup.4 
E 1.8 .times. 10.sup.2 
Q 38 
K 61 
F 6.1 .times. 10.sup.6 
M 5 .times. 10.sup.3 
P 8 .times. 10.sup.3 
AB 3.4 .times. 10.sup.2 
______________________________________ 
In each and every instance the use of pyrophosphato titanate adduct 
provided for substantial conductivity enhancement versus the control, 
despite the gross variation in polymer binders employed; (i.e. the 
silicone and Viton (trademark) are grossly differing thermosets, and the 
PVC is a thermoplastic). 
EXAMPLE 14 
This example illustrates the use of selected pyrophosphato titanium adducts 
as insulation value enhancers in hard clay filled flexible polyvinyl 
chloride. 
SP-33 Clay (trademark of Burgess Pigment Co.), 20 parts by weight; dioctyl 
phthalate, 50; and pyrophosphato titanium adduct, 0.01; were admixed in a 
household type blender. The resulting mixture was added to polyvinyl 
chloride resin (Geon 103EP, trademark of B. F. Goodrich Co.), 100; 
epoxidized soybean oil, 3; powdered lead diphthalate, 3; and stearic acid, 
0.3, all quantities are in parts by weight. The mix was compounded on a 
laboratory two-roll mill at 135.degree. C. and press-formed for 10 minutes 
at 160.degree. C. prior to evaluation of resistance of a sheet having a 
cross-section of about 100 mils by employing a mehohm Bridge coupled to a 
10.sup.4 -10.sup.5 ohm decade box assembly. The results are shown in Table 
TABLE 11 
______________________________________ 
Adduct Resistance ohms/cm 
______________________________________ 
Control 5 .times. 10.sup.12 
B 2 .times. 10.sup.13 
C 3 .times. 10.sup.13 
D 8 .times. 10.sup.12 
Q 7 .times. 10.sup.12 
J 1 .times. 10.sup.13 
______________________________________ 
These data show that significant resistivity increases result from the 
employment of pyrophosphato titanate adducts in vinyl based insulation. 
EXAMPLE 15 
This example illustrates the advantages in terms of shelf stability 
resulting from the adduction of pyrophosphato titanates with certain types 
of amines and/or phosphites. 
Test formulations containing 40 weight percent Bakelite CK-1634 phenolic 
resin (trademark of Union Carbide Corp.) and 10 weight percent of powdered 
coal (Carbofil #1--Shamokin Filler Co.), together with 0.2 weight percent 
of pyrophosphato titanate (as shown) in xylene were coated on aluminum 
Q-pannels (trademark of Q-Pannel Corp.) to a wet film thickness of 5 mils 
and placed in a 150.degree. C. forced draft oven until the resultant film 
showed a pencil hardness of 3 H. A second sample of each formulation was 
shelf aged in a closed container, at 25.degree..+-.3.degree. C. to 
determine package stability. The test results are shown in Table 12. 
TABLE 12 
______________________________________ 
Pryophosphato Titanate 
Shelf Life (days).sup.(1) 
Cure Time Min. 
______________________________________ 
Control (none) 
60 .+-. 3 25 .+-. 3 
A 55 .+-. 5 16 .+-. 2 
non-adducted A.sup.(2) 
22 .+-. 2 15 .+-. 2 
B &gt;120 14 .+-. 2 
non-adducted B 
20 .+-. 3 15 .+-. 2 
J &gt;120 17 .+-. 2 
non-adducted J 
20 .+-. 3 16 .+-. 2 
(same as A) 
K &gt;120 20 .+-. 2 
non-adducted K 
28 .+-. 3 19 .+-. 2 
Q &gt;120 16 .+-. 2 
non-adducted Q 
22 .+-. 3 15 .+-. 2 
(same as A) 
AA 74 .+-. 5 11 .+-. 2 
non-adducted AA 
18 .+-. 3 10 .+-. 2 
AE 82 .+-. 5 12 .+-. 2 
non-adducted AE 
16 .+-. 4 12 .+-. 2 
______________________________________ 
.sup.(1) Time to 100% Brookfield (trademark) viscosity increase 
.sup.(2) Prepared as disclosed in U.S. Pat. No. 4,122,062 or 4,087,402 
This example shows that while both adducted and non-adducted pyrophosphato 
titanates decrease cure time with consequent reduction in energy 
requirements when employed in conjunction with phenolic resins, the 
non-adducted analogs negatively effect formulation shelf life whereas 
their adducted analogs either effect shelf life positively or negligibly 
compared to the control. This example also shows that the choice of 
adducting agent also has a substantial effect on the properties of the 
resulting adduct. 
EXAMPLE 16 
This example shows the advantages of appropriate adduction of pyrophosphato 
titanates for purposes of melting point depression and ease of dispersion. 
One gram of the specified adducts of the present invention and, 
separately, their non-adducted analogs were added to separate 200 mil 
portions of water. 100 grams of Optiwhite Calcined Clay (trademark of 
Burgess Corp.) was then dispersed at 30.degree..+-.5.degree. C. using a 
Hochmeyer disperser and the viscosity of each dispersion measured 
immediately and after boiling for two hours at 30.degree..+-.1.degree. C. 
using a Brookfield RVF viscometer (trademark of Brookfield Corp.). The 
results are shown in Table 13. 
TABLE 13 
______________________________________ 
Pyrophosphato 
Initial 30.degree. C. 
Boiled dispersion 
Titanate Employed 
viscosity (cps) 
30.degree. C. viscosity (cps) 
______________________________________ 
Control 4.3 .times. 10.sup.5 
&gt;10.sup. 7 
I 6.7 .times. 10.sup.3 
&gt;10.sup.7 
non-adducted I 
4.1 .times. 10.sup.5 
&gt;10.sup.7 
J 3.9 .times. 10.sup.3 
5.2 .times. 10.sup.4 
non-adducted J 
4.5 .times. 10.sup.5 
&gt;10.sup.7 
K 6.3 .times. 10.sup.4 
4.7 .times. 10.sup.4 
non-adducted K 
5.0 .times. 10.sup.5 
&gt;10.sup.7 
L 3.9 .times. 10.sup.3 
8.4 .times. 10.sup.3 
non-adducted L 
4.0 .times. 10.sup.5 
&gt;10.sup.7 
W 6.1 .times. 10.sup.3 
&gt;10.sup.7 
non-adducted W 
4.2 .times. 10.sup.5 
`10.sup.7 
Z 4.8 .times. 10.sup.5 
5.2 .times. 10.sup.5 
non-adducted Z 
4.5 .times. 10.sup.5 
&gt;10.sup.7 
AB 2.9 .times. 10.sup.2 
&gt;10.sup.7 
non-adducted AB 
4.5 .times. 10.sup.5 
&gt;10.sup.7 
AE 8.2 .times. 10.sup.4 
9.5 .times. 10.sup.5 
non-adducted AE 
4.1 .times. 10.sup.5 
&gt;10.sup.7 
______________________________________ 
This example shows that pyrophosphato titanate adducts of the present 
invention may be utilized to achieve controlled viscosity reduction of 
aqueous clay dispersions at ambient temperature with or without controlled 
viscosity lowering after boiling whereas their non-adducted analogs give 
essentially negligible response in comparable formulations. 
EXAMPLE 17 
This example shows the utility of adduction of pyrophosphato titanates with 
amines of Formula III and/or phosphites of Formula II with respect to 
melting point reduction and with respect to solubility enhancement in 
selected media. 
The indicated phosphato titanates, prepared according to the procedures 
described in U.S. Pat. Nos. 4,122,062 or 4,087,402, were converted to the 
indicated adducts via the procedure outlined in Example 1 and solubility 
(as weight percent) at 25.degree..+-.3.degree. C. was measured in n-hexane 
(Hexane sol.). Melting points of the phosphato titanate were determined 
before and after adduction. The results are given in Table 14. 
TABLE 14 
______________________________________ 
Pyrosphos- Pyrophos- 
Melt- 
phato non- Hexane phato ing Hexane 
adducted 
Melting sol. wt. Titanate 
Point sol. wt. 
Titanate 
Point .degree.C. 
% adduct .degree.C. 
% 
______________________________________ 
I dec 182 &lt;0.5 I 73 .+-. 4 
7 
V 171-174 &lt;0.5 V &lt;0 &gt;25 
AA 158-161 1 AA 12 .+-. 4 
&gt;25 
AC 179-184 &lt;0.5 AC 23 .+-. 3 
&gt;25 
AE 129-134 3 AE 31 .+-. 3 
12 
______________________________________ 
This example shows the improvement in hexane solubility and melting point 
lowering effected upon prior art phosphato titanates via the practice of 
adduction as described in the present invention. 
EXAMPLE 18 
This example shows the utility of pyrophosphato titanate adducts as 
thermally activated catalysts in the controlled interconversion of esters, 
i.e., the transesterification of ethyl propionate with methyl butyrate in 
solutions containing ethyl acetate. 
In a 2 liter pyrex flask equipped with facilities for mechanical agitation, 
pot and head thermometers, innert gas inlet, fractionating column (30 
theoretical plates), automatic reflux-takeoff assembly, vacuum receivers, 
external heat and vacuum sources was placed 3 M each of ethyl (acetate, 
ethyl propionate and methyl butyrate, together with 1.0 g of the indicated 
catalyst. Vacuum and reflux ratios were adjusted to 25 mm and 25:1, 
respectively, and the pot contents distilled to recover 97.+-.1% of the 
feed overhead. Analysis of the distillate(s) was performed by gas liquid 
chromatography results are given in Table 15. 
TABLE 15 
__________________________________________________________________________ 
Catalyst % Yield Byproduct 
% Recovery 
% Yield % Recovery 
% Recovery 
Employed Methyl Acetate 
Ethyl Acetate 
Methyl Propionate 
Ethyl Propionate 
Methyl Butyrate 
__________________________________________________________________________ 
Sulfuric 
Acid 97 2 &lt;1 95 &lt;1 
Aluminum 
Chloride 94 5 4 97 &lt;1 
B 13 85 84 13 3 
Non adducted B 
89 9 8 90 3 
H 7 91 90 8 1 
Non adducted H 
91 8 5 92 2 
I &lt;1 99+ 94 5 3 
Non adducted I 
87 11 10 88 2 
J 2 96 93 5 2 
Non adducted J 
94 4 5 95 1 
__________________________________________________________________________ 
.sup.a All numerical data in mole %.? 
Note that both conventional acid catalysts and nonadducted pyrophosphato 
titanates, when employed in the above system, produce substantial 
proportions of byproduct methyl acetate due to preferential volatilization 
of same once formed, whereas the adducts of the instant invention, having 
little catalytic activity until temperatures in excess of 50.degree. C., 
permitted recovery by vacuum distillation of the bulk of the ethyl acetate 
prior to onset of catalytic transesterification.