380

Ind. Eng. Chem. Prod. Res. Dev. 1983,22,380-381

COMMUNICATIONS
Improved Synthesis of Basic Zinc Acetate, Hexakis(p-acetate)-p-oxatetrazinc
Basic zinc acetate is prepared virtually quantitatively in less than 1 h by digesting zinc oxide with glacial acetic
acid or with a mixture of acetic acid and its anhydride.
Introduction
In the course of investigating either the catalytic or
inhibitory effects of various substances on the pneumatogenesis of azoformamide, a widely used blowing agent
or pneumatogen, in aphrogenic compositions (e.g., in
foamable PVC plastics), I had occasion to prepare several
zinc carboxylates and to study their thermolytic behavior
thermogravimetrically. An attempt to prepare anhydrous
zinc acetate by the reaction of zinc oxide with glacial acetic
acid or its mixture with acetic anhydride gave not the
expected normal salt but rather the basic zinc acetate in
virtually quantitative yield. This note concerns the facile
expeditious synthesis of this basic salt, hexakis(pacetate)-p-oxatetrazinc, under mild conditions.
The basic zinc acetate was first described by Auger and
Robin (1924),who obtained the product as a sublimate by
heating zinc acetate in a vacuum at about 250 "C. They
assigned to the product the formula Zn4O(CH3COJG
without presenting supporting analytical data and pointed
out its analogy to the well-known basic beryllium acetate.
Since then it has been prepared similarly by several investigators and its composition (Wyart, 1926; Barratt et
al., 1971), molecular mass (Mead et al., 1968; Barratt et
al., 1971; Charalambous et al., 1975), and structure (Wyart,
1926; Koyama and Saito, 1954; Mead et al., 1968) have
been amply confirmed. The analogy between the normal
and the basic acetates of beryllium and zinc, prepared
conventionally, was studied by Semenenko (1958).
Early work (Auger and Robin, 1924) had shown that
basic zinc acetate is not obtainable by thermolysis of zinc
acetate a t atmospheric pressure. Nevertheless, the formation of basic zinc acetate during the thermal decomposition of zinc acetate at normal pressure has been considered with some evidence to support the claims (McAdie,
1966; Golgotiu and Rosca, 1969). Thermogravimetric
analysis itself, however, does not provide sufficient clues
to affirm the basic acetate as a thermolytic intermediate
and usually no comments are made involving the possible
presence of the basic salt in the process leading to zinc
oxide (Balarew and Stoilova, 1975). That basic zinc acetate
is indeed formed at atmospheric pressure was demonstrated quite convincingly by Djega-Mariadassou et al.
(1970) in their critical and thorough study on the thermolysis of zinc acetate. Despite this definitive study no
effort was made to use this information for the synthesis
of basic zinc acetate in preparatively significant amounts.
No yields are reported in any of these papers involving the
formation or tedious preparation of basic zinc acetate
either by the vacuum sublimation process or by thermolysis at atmospheric pressure using milligram quantities
of zinc acetate.
To circumvent the low yields and inconvenience of the
sublimative process, Hardt and Stavenow (1959) prepared
the basic salt from slurries of zinc oxide in concentrated
aqueous zinc acetate in yields up to 18%. The process is
a tedious sequence of operations that entails digestion,
evaporation, drying, baking at 150 "C, and extraction. The

baking itself requires 12 h. Higher basic zinc carboxylates

have been made by an azeotropic process involving stoichiometric quantities of zinc oxide and carboxylic acids
or zinc carboxylates (Silver and Dennison, 1966, 1968;
Mead et al., 1968). Apparently, basic zinc acetate could
not be prepared by this azeotropic procedure since it was
made in the conventional manner by vacuum sublimation
(Mead et al., 1968).
Basic zinc acetate, along with its higher homologues, was
recommended as an additive for lubricating oils (Silver and
Dennison, 1966, 1968). It has been considered as a prospective catalyst to enhance the rate of decomposition or
to reduce decomposition temperature of azoformamide in
the production of foamed plastics.
Experimental Section
All chemicals used were of reagent-grade quality, commercially available.
(a) Basic Zinc Acetate. Acetic acid (120 mL) was
added rapidly, with stirring, to 81.4 g of zinc oxide powder.
Much heat evolved and the initial thin paste soon converted into a firm coherent cake. When more acetic acid
(100 mL) was added and the mixture was boiled briefly,
the loosened cake crushed readily to give a smooth slurry;
the slurry was boiled for an additional 30 min. The
product was filtered after 30 min at ambient temperature,
washed with acetic acid, and finally rinsed with ether to
obtain 158.4 g of a white, finely granulated powder. Weight
loss at 100 "C and 2.5 torr, after preliminary drying in air,
was 3.05% (acetic acid); mp 248-250 "C (turbid melt). The
yield was 97%. Anal. Calcd for ClzHl8Ol3Zn4:C, 22.81;
H, 2.87; Zn, 41.39. Found: C, 22.60; H, 2.90, Zn, 41.4.
A sample of the compound (0.7768 g) was heated at 100
"C and 2.5 torr. After the rapid initial weight loss of sorbed
acetic acid, a linear volatilization rate of 0.17% h-' was
found (0.7552 g, 2 h; 0.7522 g, 4 h; 0.7497 g, 6 h).
Thermogravimetry (heating rate 5 "C min-') showed a
weight loss of 3% at 55 to 65 "C in either air or nitrogen.
Decomposition in air gave a 67% weight loss in the interval
of 155 to 280 "C, leaving 28% residue (zinc oxide). In
nitrogen the weight loss was 76% at 165 to 305 OC, leaving
20% of residue.
(b) In another run using a mixture of acetic acid (120
mL) and its anhydride (100 mL), a granular slurry resulted
without caking; the product settled rapidly from suspension. The dilatant product filtered easily as in the earlier
experiment. The yield of the air-dried small glassy grains
was 157.3 g (97%); mp 248-250 "C (turbid melt). Weight
loss at 100 OC and 2.5 torr was 3.06% (acetic acid). Anal.
Found: C, 22.76; H, 3.21; Zn, 41.0. The compound volatilized a t a linear rate of 0.19% h-' at 100 "C, 2.5 torr.
A 3% desorption occurred a t 55-65 "C in either air or
nitrogen. The weight loss in air was 56% in the interval
145-280 "C, leaving 40% zinc oxide as a residue. In nitrogen 74% of the weight was lost at 160 to 290 "C, leaving
22% residue. The heating rate was 5 "C min-' as before.
Zinc Acetate. Concentration of the combined filtrates
and washings from the above experiments gave the normal

0 196-432118311222-0380$01.50/0 0 1983 American Chemical Society

38 1

Ind. Eng. Chem. Prod. Res. Dev. 1983, 22, 301-302

anhydrous acetate, C4H604Zn.Anal. Calcd for Zn: 35.4.

Found Zn, 35.0. Thermogravimetric analysis at a heating
rate of 6 C min- showed a weight loss in air of 76% in
the range of 225 to 350 C, leaving 20% residue; in nitrogen
the weight loss was 80% in the range of 225 to 355 C, with
a residue of 20%.
Discussion
There was no opportunity to explore the possibility of
making other basic zinc carboxylates by the procedures
described here for basic zinc acetate. However, reaction
of zinc oxide with an excess of formic (go%), propionic,
or isobutyric acids gave only the normal salts in yields
better than 95%. Semenenko (1957) also prepared the
corresponding normal zinc carboxylates from zinc oxide
or carbonate and formic, acetic, propionic, and butyric
acids. Since the details of conditions he used were unavailable to me the apparent inconsistencies between his
results and mine, relevant to acetic acid, could not be
resolved. An azeotropic procedure with isobutyric acid also
gave only the normal salt in 97% yield in contrast to the
results reported by Silver and Dennison (1966,1968) and
Mead et al. (1968), who obtained the corresponding basic
salts from zinc oxide and certain carboxylic acids. I attribute this inconsistency to the greater proportion of acid
I used. Thus, at least with the other carboxylic acids, the
stoichiometry found with acetic acid may be inapplicable.
It seems reasonable to believe that the insolubility of the
basic salt relative to that of the normal carboxylate may
be an important factor as to which salt is produced.
4Zn0 + 6CH3C02H Zn40(CH3C02)6+ 3H2O

The use of acid anhydrides or mixtures of acid anhydride

in their respective acids would provide an access to the
basic salts. Except for acetic anhydride in acetic acid, the
possible application of acid anhydrides to make other basic
zinc carboxylates was not explored. However, physical
factors such as solubility and reaction conditions may be
more critical than we realize.
4Zn0 + 3(CH3C0)20 Zn40(CH3C02)6
Thus Hardt and Stavenow (1957) reported that basic zinc
acetate is converted into the normal salt when heated with
acetic anhydride or anhydrous acetic acid. Yet, contrary
to expectations based on these observations, basic zinc
acetate was obtained under conditions expected to give the
normal salt.

Regardless of problems associated with the general

synthesis of basic zinc carboxylates, the facility with which
such salts can form suggests that they may play an important role in the stabilization of polymers by zinc carboxylates. The formation of p-oxatetrazinc clusters in
resinous compositions should alter the rheological properties of such systems. The effects can be more pronounced with dicarboxylic acids and in ionomeric polymers
bearing carboxylic acid groups. The present simplified
synthesis of basic zinc acetate should encourage greater
attention to hexakis (p-carboxy1ato)-p-oxatetrazinccomplexes.
Acknowledgment
The author appreciates the capable assistance of J. L.
Edwards with the experimental work. The contributions
of M. D. Krol for the zinc analyses and of K. A. Gollatz
for the thermogravimetric analyses are acknowledged.
Carbon and hydrogen analyses were carried out by Galbraith Laboratories.
Registry No. Zn40(CH3C02)6,32334-63-7;CH3C02H,64-19-7;
ZnO, 1314-13-2; (CH3C0)20,108-24-7.

Literature Cited
Auger, M. V.; Robin, I. C . R . Aced. Scl. 1924, 178, 1546.
Balarew, C.; Stoilova, D. J. Therm. Anal. 1975, 7 , 561.
Barratt, R. S.; Beicher, R.; Stephen, W. I.; Uden, P. C. Anal. Chim. Acta
1971, 5 7 , 447.
Charalambous, J.; Copperthwaite, R. G.; Jeffs, S. W.; Shaw, D. E. Inorg.
Chlm. Acta 1975, 74, 53.
Djega-Mariadassou, G.; Kerboub, E.; Pannetier, G. Bull. SOC. Chlm. Fr.
1970, 1353.
Golgotiu, T.; Rosca, I. Bul. Inst. Polltch. Iasl 1969, 15, 1.
Chem. Absh. 1971, 7 4 , 150456.
Hardt, H. D.: Stavenow, F. 2. Anorg. Allg. Chem. 1959, 301, 267.
Koyama, H.; Salto, Y. Bull. Chem. SOC.Jpn. 1954, 27, 112, Chem. Abstr.
1955, 4 9 , 12909.
Mead, W. L.; Reid, W. K.; Silver, H. B. Chem. Commun. 1966, 573.
McAdie, H. G. J. Inorg. Nucl. Chem. 1966, 28, 2801.
Semenenko, K. N. Zh. Neorg. Khlm. 1957, 2 , 21 15.
Chem. Abstr. 1958, 52, 14528.
Semenenko, K. N. Zh. Neorg. Khlm. 1958, 3 , 1467.
Chem. Absh. 1959, 5 3 , 18711.
Silver, H. B.; Dennison, A. C. U.S. Patent 3367869, 1968.
Silver, H. B., Dennison, A. C. Neth. Appl. 6 608 326, 1966.
Chem. Abstr. 1967, 66, 87364.
Wyatt, M. J. Bull. SOC.Fr. Mineral. 1926, 4 9 , 148.

Research and Development

Armstrong World Industries, Znc.
Lancaster, Pennsylvania 17604

Algirdas C. Poshkus

Received for review June 14, 1982

Accepted November 9, 1982

Chemical Mixed Catalysts

A chemical mixing technique, which involves the use of distillable organometallic intermediates, has been
developed for the preparation of catalysts. To illustrate the technique, V,05-Ti0, catalysts have been prepared
with hydrolysates from titanium tetra-tert-amyl oxide and vanadium tetra-tertamyl oxide solutions. Catalysts with
V,O5 content ranging from 89 ppm to 10% have been examined for activlty in the NO-NH,-0, reaction. The
technique has the potential for providing catalysts with intimately mixed components of highly reproducible purity
and with minute and controlled amounts of dopants such as promoters and poisons.

This paper reports some preliminary results obtained

with catalysts prepared by an interesting chemical
mixing procedure. As an example of this method a V2O,-TiO2 catalyst was prepared from calcined hydrolysates
precipitated from a solution mixture of titanium tetratert-amyl oxide and vanadium tetra-tert-amyl oxide.
The procedure for the preparation of the catalyst is as
follows. (1) Titanium tetra-tert-amyl oxide is made by the
0196-4321 103/1222-0381$0 1.5010

method described previously (Bradley et al., 1952, 1955;

Mazdiyasni et al., 1969). ( 2 ) Vanadium tetra-tert-amyl
oxide is formed by first preparing tetrakis(diethy1aminolvanadium (Thomas, 1961)
VCll + 4LiNEt2 = V(NEt2)4+ 4LiC1
(1)
VC14 in benzene is added to lithium diethyl amide in ether
with the temperature maintained at <10 C. The dark
0 1983 American Chemical Society