Note: Descriptions are shown in the official language in which they were submitted.
~1038134
The present invention relates to methods of forming
aluminum halohydrates and to the aluminum halohydrates
formed there~y.
; m e present invention reIates more particularly to
the methods of forming aluminum iodohydrate, aluminum
chlorohydrate, aluminum bromohydrate, and aluminum fluoro-
hydrate.
Generally, aluminum halohydrates have found sub-
stantial commercial usages in a wide varity of fields in-
cluding use as an active ingredient in body deodorants,
thawing salts, and for the impregnation of textiles to
- impart water repelling properties. In addition, aluminum
halohydratcs are also used for the preparation of absor- ,
ption agents or catalytically active substances. Many -
other commercial uses for thè chemicals are well known.
Prior art methods for preparing aluminum halo-
hydrates often include the step of reacting an aluminum
halide salt, such as aluminum fluoride or aluminum
chloride or aluminum bromide or aluminum iodide with
water and metallic aluminum. The process described in
the U. S. Patent No. 3,476,509 includes the use of a
water soluble thallium compound with a pH of between
2.5 and 4.4 at an elevated temperature in the order
of 70C to 105C. An aluminum hydrate formed
from an aluminum halide usually shows traces of the
j.
.' , ~ .
'
~, ''
,
'~
- ~ , . , , : ',
~ Polyliydr~t(1);il7Ei.~llldy7~p ~-
. ~
)38134
aluminum halide. This has been recognizea to be a very
serious problem especially for aluminum chlorohydrate when
used as an antiperspirant because the aluminum chloride
hydrolyzes to hydrochloric acid and results in ,evere skin
irritation1 The presence of the aluminum halide also tends
to make the aluminum halohydrates hygroscopic. ¦ ~ -
~ ' .
i The article entitled, "Basic Aluminum Compounds"
¦ by Hideo Tanabe in The ~merican Perfumer and Cosmetics,
Vol. 77, August 1962 pages 2S-30 provides a review of
~known methods for preparing aluminum halohydrates. On page
26, Tanabe presents four methods by way of equations (5),
¦ (6), (7), and (8). The four methods are briefly given
!herein for reference: !
- I! , ................................. . .
(1) More than an equivalent amount of metallic
aluminum is reacted with an acid, or metallic aluminum is
reacted with an aluminum salt with a catalyst of mercury,
iron, or copper;
(2) More than an equivalent amount of aluminum
hydroxide is reacted with an acid; -I
(3) An alkali is added to an aluminum salt solu-
tion; and
(4) An aqueous solution of an aluminum halide is
passed th~ough an anion exchange resin.
.. . . . . .
~95Pol~,~iJydrat(1)I~17~ 11dy7~p 4~
_ ; ~
~,
1038~34
i On page 26, Tanabe presents the general formula
I~ A12+n OH3n X6 and indicates that when the "n" iæ large,
'I the solution is a little turhid but can be made clear by
¦I filtration with carbon powder. Tanabe continues with an
II analysis of the aluminum chlorohydr~te and states that
j each of the four reactions results in a basic aluminum ion
j which condenses gradually into a polynuclear ion and this
condensation is influenced by various conditions such as
I temperature and time the larger the value of "n". Thus,
!~ the aluminum chlorohydrate reported by Tanabe appears to
jI show instability with both temperature and time. An
ill earlier Tanabe article in Pharm. Soc. Japan, 75, page 868
¦¦ (1955) is directed to the study of these instabilities.
I i
¦l Another earlier article by Tanabe, in Pharm. Soc.
I, ~apan, 74, page 868 ~1954) states explicitly t.hat the pro-
il perties of aluminum chlorohydrate varies with the method
of preparation.
One of the principal objects of the invention is
to provide a method for preparing aluminum iodohydrate,
aluminum chlorohydrate, aluminum bromohydrate, and aluminum
fluorohydrate by the steps of first permeating with mercury
in the presence of a hydrogen ion source such as an acid
and then contalcting the permeated aluminum with an appro-
priate halogen ion source in the presence of an excess of
i water compared to the halogen based on the formula
A1~(0~)5X wher ~X" corre6ponds to the seIected haIog _ .
' I '
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~ ~195Pl~l~yclrat~ 171~-1lldy7~p 9-
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1(~38134
i ~nother object of the present invention is to
l obtain novel aluminum iodohydrate, al~minum chlorohydrate,
! aluminum bromohydrate and aluminum fluorohydrate compounds
exhibiting novel properties.
l, '
A further object of the present invention is a
! method of preparing aluminum halohydrates having a desired
i ratio between the aluminum and halogen atoms.
Yet another object of the present invention is to
; provide a method for preparing aluminum iodohydrate, alum-
in~m chlorohydrate and aluminum bromohydrate by the use of
the corresponding halogen gas in the presence of water.
Yet another ob~ect of the present invention is a
¦ method for preparing aluminum iodohydrate from iodine
; crystals in water.
~1 ,
Further objects and advantages of the invention
will be set forth in part in the following specification and
in part will be obvious therefrom without being specifically
referred to, the same being realized and attained as pointed
out in the claims hereof.
The present invention accordingly comprises the
several steps and the relation of one or more of such steps
with respect to each of the others, all as exemplified in
following detailed disclosure, and the scope of the appli-
cation of which will be indicated in the claims. Furthermore
. .
,-.
!1 8495PolyHydrate(1)~17t~;-1lldy74p 4-
1038134
the products obtained are novel and exhibit properties which
are superior to known corresponding products. For example,
the products obtained are water-clear when dried to a
solid, are soluble in water, and are not hygroscopic. In
additiOn~ the aluminum iodohydrate, aluminum chlorohydrate,
and aluminum bromohydrate exhibit superior bactericidal
properties.
For a fuller understanding of the nature and object
of the invention, reference should be had to the following
detailed description, taken in connection with the accom-
panyi4g dra~ ngs, in which: ¦
Fig. 1 is a infrared spectra response for alu~inumiodohydrate prepared according to the present invention;
Fig. 2 is an infrared spectra response for aluminum
chlorohydrate prepared according to the present invention;
Fig. 3 is an infrared spectra response for an
aluminum bromohydrate prepared according to the present
invention; and
Fig. 4 is an infrared spectra response for an
alumin~um fluorohydrate prepared according to the present
invention.
!! 3~5~oly~iydrat(1);il71i~11ldy74p 5- j
1038134
The present invention is focused on the utilization
of the remarkable properties of a novel reactive aluminum
which is the subject of other patent applications.
Generally, the reactive aluminum is prepared by
permeating highly pure aluminum in the presence of a hydro-
gen ion source with mercury. The hydrogen ion source can
be an inorganic acid, such as hydrochloric acid or hydro-
bromic acid or the like, or an organic acid, such 2S citric
acid or acetic acid, or the like.-- The reactive aluminum in
an alkali solution such as water and sodium hydroxide will
serve as a hydrogen ion source for the formation of another
reactive aluminum~
In general, aluminum-to be permeated of at 1east
about 99% purity is suitable, purities-of at least about
99.8% are preferred, and purities of at least about 99.9~ ¦
are most preferred. ~owever, it will be recognized that in
certain instances departures from the foregoing limitation
may be permitted without departing from the true scope of
the invention. Thus, the term "high purity", "impurities"
and related terms as used in the present invention is in-
tended in a generic sense to exclude materials which exhibit 1
a pronounced t~ndency to diminish the extent of hydrogen ¦ ;
ion absorption into the aluminum. The presence of certain
metals is beneficial and their use is not excluded by the
present invention. However, beyond certain concentration
linits, even "beneficial" materials may cause deleterious
8495Polytlydra'e(1)!~17~:111dy7~p 5- 1
1038134
effects. Accordingly, the term "high purity" aluminum should
! be interpreted as excluding materials which significantly ~;
diminish hydrogen ion absorption whether the exclusion be on
a materials or concentration basis. Thus, it has been found
that certain impurities will adversely affect the interaction
between mercury and the source of hydrogen ions so as to
impair the generation of ultraviolet radiation at the proper
energy level. These impurities diminish the extent of hy-
drogen ion absorption into the aluminum and-the generation -
of ultraviolet radiation depends on this factor. These im-
purities are generally elements which form amalgams with
mercury or which compete with mercury regarding interaction
with hydrogen ions. Thus, since these impurities substan- I -
i tially diminish the rate and extent of absorption or diffu-
sion of hydrogen ions into the-mass of aluminum, they there- !
by decrease the yield of the structure since its growth
depends on the availability of large quantities of hydrogen
ions. The impurities will cause scattering which produces
high temperatures and leads to hydrogen ion starvation. Some¦
of these impurities are lead, zinc, chrominum, copper, iron,
silver, molybdemum, nic~el, tungsten, cobalt and elements
of Group I of the Periodic Table.
ll ,:
But, celrtain metals will enhance diffusion of
hydrogen ions (protons) into the mass of aluminum. These
metals include, without necessary limitation, cesium,
vanadium, zirconium, barium, lanthanum, hafnium, titanium,
thallium, palladium, and niobium. However, while these
. . .:
.
~ 1 8~95Polyliydrate~l)N~17H;Illdy74p 5-
1038134
metals enhance the diffusion of hydrogen ions, they also
may have some deleterious side effects when present in
larger amounts, e.g., they scatter hydrogen ons somewhat
inside the aluminum and can cause local reactions leading
to exothermic hot spots which can cause the reaction to
overheat and thus should only be used in limited quantities,
e.g. up to about .05% by weight of the aluminum. Above this
value, the product obtained is relatively less stable due _
to hot spot formation which impairs hydrogen ion diffusion. -1-
Another metal that may be present in the aluminum
I is magnesium. The process is operable with up to 5% by
weight and even larger proportions of magnesium but the
efficiency becomes far less thanoptimum.
. . j: .'-.~
There are other metals which tend to inhibit the , ;
diffusion of the hydrogen ions (protons). The metals may be
deliberately employed to reduce the rate of reaction so
long as the entire reaction is still sustained. Still other j
metals, one being copper, tend to destroy the reaction
entirely.
Thus, the term ~high purity aluminum" as used
herein should be accorded a significance consistent with the
limitations explained in the preceding discussion. In any
event, desired or optimum concentrations of a particular
¦~etal can be adily deten~ined in a apecific cLrc = stance.
I
~ -8-
.~
~ 8495PolyHydrate(1)~201I;Slldy74p
'~_-``
1038134
Generally, the aluminum can have any shape, but
the size of the aluminum should not fall below about l/32
inch for the longest dimension and l/64 inch for the small-
est dimension. The reaction for very small particles, par-
ticularly powder, takes place very ra~idly and is highly ;~
exothermic and the elevated temperatures produced prevent
the formation of a reactive metal. For small particles such
as powder, even cooling to a very low temperature will not
form the~reactive metal, but,~instead-forms an ordinary
amalgam.
It is convenient to use aluminum in the form
of a rod because highly pure metals are commercially avail-
able as rods. Rods having a diameter of about l/2 inch are
preferable.
The choic~ of the hydrogen ion source such as an
acid will depend upon the product to be formed and the con-
cern over impurities.
It i8 preferable to prepare a highly pure aluminum
rod for the reaction by at least partially stripping the ! `
aluminum oxide coating which usually has formed on the
surface due to exposure to air and moisture. Of course,
other than a rod s!hape can be used. If the aluminum rod has
been stripped, then hot water will be able to serve as a
hydrogen ion source although the reaction time is long.
Otherwise, it may be desirable to start out with an acid to
strip off the oxide coating on the aluminum rod in order to
initiate the reaction as quickly as possible. Of course,
the aluminum rod may be stripped mechanically with sand- -
paper or a file or the like.
... . ..
~ 8495PolyHy~rate(1)~120~ 111dy74p
~038134
The inter-reaction which occurs between the alumi-
i num, the mercury and the acid, gives rise, at the start, to
the formation of large bubbles which rise up to the surface
through the acid. After a while, i' will be observed that
instead of large ~ubbles forming at the top of the aluminum
l rod and then breaking free and rising to the surface of the
i acid, tiny bubbles will be emanating from many parts of the
upper surface of the rod. The occurrence of the multitude
of tiny bubbles indicates that the rod is becoming-converted
to a reactive aluminum-as herein used. -~
. . ' ....... '
i Generally, the rod will taXe up or absorb from
l 0.1% to 5% by weight, based on the weight of the rod, of the
I mercury depending upon the length of ,ime the reaction is
permitted to continue. ~ range of 2% to 3% by weight of the
mercury is satisfactory for many applications. The maximum
mercury content is about 5% by weight.
The reaction can be stopped on the one hand when
¦ there has taken place a desired increase in weight of the
rod due to the absorption of the metal or on the other hand
when a multitude of tiny bubbles has been produced for a
period of ten to fifteen minutes. Another basis is to test
the rod by immersing it in water; if the rod hydrolyzes the
water, it is reactive according to the requirements of this
¦¦lnvention.
. -10~
8495~oly~1ydrate(1)N1711i111dy74p 6-
'~;` . ,.
1038134
A reactive aluminum as described, displays surpris-
ingly active catalytic properties not at all suggested by
the prior art. The reactive aluminum possesses an altered
physical structure and may be used as an activator or
initiator. After grain alignment, the reactive aluminum ',
becomes an open matrix where the boundaries have expanded.
The amount of the mercury in the aluminum can be
varied in accordance with applications. In general, if a
high percent of the mercury by weight is desired, quick
cooling of the reactive aluminum after formation will preuent
the squeezing out of 'he mercury due to an exothermic re-
action and lattice expansion. Water or alcohol is con-
venient for this purpose. In cases where it is desired to
reduce the amount of mercury from, for example, several
percent by weight to, for example, 0.1% by weight, the
reactive aluminum can be heated to squeeze out the mercury. ' ~ :
1, . i .
From the above, it is clear herein, including the
! claims, what is meant by a "reactive aluminum."
,, 'I
, The reactive aluminum can replace the well ~nown
; Ziegler catalyst in many reactions to produce the same or
~ comparable results without the dangers associated with the
i Ziegler catalyst and with great economical advantage.
' ~. ,, ,
! The reactive aluminum exhibits an aligned matrix
and, it is believed, is capable of converting at least
partially to a hydride at one or more valences and produces
ions of the reactive metal along with e , Hl, OH , HO2 and
I -11- - I
, ~495~oly~Iyarate(1);~17~1:11k1~71p ~
l l
1038134
O radicals depending upon the fluid contacting the reactive
aluminum. In addition, other radicals which are highly activ
may be produced.
.
In the present invention, generally, the reactive
aluminum is reacted with water and a source of chlorine
or bromine or iodine or fluorine. In many cases, it is
convenient to use an acid form of the halogen. Sometimes,
it is convenient to use a gaseous form of the halogen,
such as chlorine gas, or bromine gas or iodine vapors.
Fluorine gas is known to be highly dangerous and so may
not be desirable for use in the method. A further
possibility is the us~ of ground iodine crystals in water.
. I
Basically, the amount of water as compared to
the available halogen atoms can be reckoned from the
formula: A12(OH)5Q; Q corresponds to the halogen, namely,
chlorine or bromine or iodine or fluorine. It is pre-
ferable to use more water than the stoichiometric equi-
valent of the formula in order to be assured of having
available hydroxyl groups for the product to be obtained.
The ratio of the aluminum atoms to the halogen
atoms varies froml the ratio of 2:1. It is highly sig-
nificant that the ratio of 2.2:1 for aluminum chlorohydrate
and 2.4:1 for aluminum bromohydrate can be obtained by
the present invention. Also, a ratio of 2.7:1 for aluminum
; 1 8~95PolyHydrate(l)Nl7l~1lldy74p 6- ,
I 1038134
! iodohydrate has been obtained by the present methods.
Surprisingly, the product obtained by the present methods
even for high ratios of aluminum to halogen is water
clear.
.
In addition, the products obtained by the present
met,hods show a stable pH of about 4.2 to about 4.3 in
contrast to products ob~ained by prior art methoQs which
have a pH of approximately 3.9. ¦-
. .:.'.' :'
In carrying out the present methods, it is
desirable to cool the reaction to below 100F in order to
avoid the incidental formation of an aluminum halide. The
presence of an aluminum halide in prior art products is
considered highly undesirable and usua ly results in the
prior art products being hygroscopic. In contrast
thereto, products obtained by the present methods are
non-hygroscopic and are therefore far more suitable for I ' ,
many applicationswhere prior art products were unsuitable.
For example, the present aluminum chlorohydrate is well
suited for use as an underarm deodorant even in high
concentrations because the absence of aluminum chloride
avoids the formation of hydrochloric acid and irritation to ,,
human skin. Testslwith even relatively concentrated solu- , ...
tions have verified this for human use.
Another significant advantage of the p-esent in-
vention is that the present product can be micronized by
spray drying and at least 99% will pass a 325 mesh. Prior
:................. -.. ,~ -~ . , .
- ~ . -
.. ..
Il 8495Po1~ydrate(1)N17~;111dy74p 7-
.~ I
',~
1038134
art products require additional treatment in order to become
micronized after spray drying. This may be related 'o the
fact that prior art products exhibit at least a 14% mois-
ture content after spray drying in contrast to the present
products which exhibit only about an 8~ moisture content
after spray drying. -
It is preferable to prepare the reactive aluminumwith the halogen acid corresponding to the aluminum halo-
hydrate to be formed in order to maintain a high purity.
Repeated washing of a reactive aluminum in hot and cold
can be used for cleansing the reactive aluminum of potential
impurities. Usually, it is highly desirable to form the
aluminum halohydrate with-a high degree of assurance that
~o mercury will appear in the product. This can be achieved
by using reac~ive aluminum with a low mercury content,
for example, no greater than on the order of about 500 to
2000 p.p.m. On the other hand, mercury can be removed
from the halohydrate product by contacting i' with ordinary
ingot aluminum of, for example, 99.5% puri'y or higher
purity aluminum of, for example, 99.99% purity or with
reactive aluminum, any of which will take up the mercury
from the product.
The aluminum iodohydrate, al~minum bromohydrate and
aluminum chlorohydrate prepared by the present me'hods
exhibit surprisingly good anti-microbial properites.
14-
.:
`.,
¦ 8495Polyll~drate(l):~171L1lldy74p 7-
(~ l I
'_,'
103~3134
Standard tests were performed to determine the anti-microbial
number, namely the concentration to completely destroy
pseudomonas and aeruginosia in l0 minutes but not 5 minutes.
The aluminum iodohydrate was effective for dilution in the
order of 1000:1 to 600:l and the aluminum chlorohydrate was
effective for a dilution in the order of 1000:1. The
aluminum bromohydrate was effective for a dilution of I --
approximately 100:1. The aluminum iodohydrate showed
surprisingly superior anti-microbial activity even compared
to IOPREP(trademark) a well known pre-curgical antiseptic.
The antimicrobial dilution of the aluminum iodohydrate
against staphylococcus and pseudomonas was 400:l in each
case as compared to the IOPREP which was 100:1 in each
case. Furthermore, one part of a 25% concentration alumi-
num iodohydrate was combined with 4 parts of Ivory (trade-
mark) soap and was found effective against staphylococcus
even after being diluted 80 times. The solution was
also effective against pseudomonas but only for a dilution
of 40 times.
. 1 `'.
Therefore, a further step in the p~sent invention ,
includes using at least the aluminum iodohydrate for
its anti-microbial proper~ies. I
With regard to unusual properties, it is noted
that the aluminum bromohydrate is suprisingly well suited
.
84~95Polyllydratc(1)l1 ~ llldy7~p
~-'' ~ I .
,~_ I
1038~34
for rireproofing such things as wood, clothes and paper.
The fireproofing properties can be imparted either by
spraying a solution of the aluminum bromohydrate on the
object or soaking the object therein. Naturally, other
methods may be used.
After preparing n aluminum halohydrate according
to the present methods, it may be desirable to enrich the
hydroxyl content of the aluminum halohydrate. The en-
richment of the hydroxyl content may be carried out by
utilizing the product obtained as described in Canadian
Patent Number 939,il6 (January 1, 1974). Briefly, the
product of Canadian Patent Number 939,116 is ~~~~ ~ ~~~ ~~~
. . . . ~
obtained by placing highly pure aluminum in contact with
mercury and an acid with a part of the aluminum exposed to
air. The aluminum can be in the form of a rod with the
mercury covering about half of the rod lying therein. A
~ovel product forms on the aluminum exposed to the air.
The temperature of the rod should be preferably maintained
below 105F. Cooling can be accomplished many different
ways but oneconvenient way is to contact the aluminum with
a large pool of mercury and use only a small amount of acid
to just barely cover the mercury. The mercury helps to
conduct heat awaylfrom the rod and therefore cools the rod. .
An operating temperature of about 90F is preferable. The
novel product obtained is extremely rich in hydroxyl groups
and can be added to the-aluminum halohydrate and mixed with
or without heating to obtain a hydroxyl enriched aluminum
ha hydrate. ¦
. , , ,. I
;~ - -16- '
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. . . ~
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- 8~95Polyllydrate(l)N17~1Lldy74p 8-
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.........
1038~34
Sometimes it is desirable to obtain an aluminum
halohydrate involving at least two different halogen atoms.
This can be easily accomplished by the present methods
of using, for example, two different acids such as
hydrochloric acid and hydrobromic acid. Other variations
include, for example, hydrofluoric acid with chlorine gas
pumped therethrough in the presence of an immersed reactive
aluminum.
The products obtained by the present method are
polymeric in nature and the above noted formula should not
be considered restrictive because the number of aluminum
atoms in a unit may exceed the number two and can easily -
be 4 or 6 with a corresponding but n~ necessarily propor- -
tional increase in the number of hydroxyl and halogen atoms
included. Furthermore, with regard to the formula, the
hydroxyl content could be less than 5 depending upon the
available quantity of hydroxyl groups.
Sometimes an alcohol soluble product is desired.
Such a product can be obtained by the use of water and
àlcohol but some instabilities over extended periods of
time have been noted for aluminum chlorohydrate.
EX~lPLES
Illustrative non-limiting examples of the practice
of the invention are set forth below. Numerous other
examples can readily be evolved in the light of the guid-
ing principles and teachings contained herein. The-examples
' . . . .
.
~ , 8~95PolyHydrate(1)1~17~111dy7~p 8-
1038134
are intended merely to illustrate the invention and not
in any sense to limit the manner in which the invention
can be practiced. The parts and percentages recited herein
and all through this specification, unless specifically
provided otherwise, refer to parts by weight and percen-
tages by weight.
E ~ ~LE 1
.
¦ The procedure for preparing an aluminum chloro-
¦ hydrate illustrates some general rules. Typically, it is
convenient to use a mass of aluminum equal to that needed
! to obtain a desired ratio. The aluminum chlorohydrate
¦ is prepared by first forming a mercury treated reactive
! aluminum rod and then reacting the reactive aluminum with
j hydrochloric acid. A rod of 54 grams of aluminum having
a purity of 99.98% by weight is permeated in the presence
of hydrochloric acid with mercury so that the permeated
mercury is between 1% to 3% by weight of the rod. Then,
i the reactive aluminum is immersed in 87 grams of 1.5 N
! hydrochloric acid. Generally, the acid can range between
0.5 N and 2 N or higher. It is preferable to maintain
theb~perature of the reaction below about 100F in order
to avoid the poss~bility of forming aluminum chloride
or a product which does exhibit a stable chemical property.
Generally, a temperature of 200E or higher should be
avoided so that halides are not formed.
. .
tJ -18- -
. -..,~, ..,,, . .- '.
` I 8495PolyHydrate(1).~1171illdy71p 3-
- 1038134
EX~rPLE 2
A reactive aluminum rod prepared according to the
; procedure of Example 1 is immersed in a solution of 126
t' grams of approximately 38% concentration hydrochloric acid
and 300 grams of water. Again, the reaction temperature is
maintained below lOO9F. After approximately 72 hours, the
. liquor contains about 50% by weight solid aluminum chloro~
: . I hydrate with the balance beiny water. The aluminum to
¦ chlorine ratio is approximately 2.04:1.
. '~ ' :
EX~`~LE 3
A eactLve aluminum rod prepared according to
¦ the procedure of Example 1 is immersed in 250 grams of 50%
by weight methanol with the balance being water; then,
36 grams of chlorine gas is bubbled therethrough over a
period of approximately 24 hours. The product obtained
had an aluminum to chlorine ratio of approximately 1.86
.
. . , ,
EX~YPLE 4
:' .
A reactive aluminum prepared according to the
procedure of Example 1 is immersed in 87 grams of 38~ by
weight concentration of hydrochloric acid mixed with 150
grams of methanol and 300 grams of water. Thç temperature
~ ~495PolyHydrate(l)N19~111dy74p
1038134
is maintained below 100F by cooling. After 72 hours, the
liquor contained approximately 50% by weight aluminum chloro-
hydrate with the balance being mainly methanol. ~he alum-
inum to chlorine ratio was approximately 1.92:1. When the
liquor wa~ permitted to dry~, alcohol soluble crystals
were obtained.
'~ .
.',
EXAMPLE 5
. I .
~n aluminum chlorohyd_ate is prepared with a
_ reactive aluminum prepared according to the procedure of
Example 1. Specifically, a reactive aluminum prepared
according to the procedure of Example 1 is Lmmersed in 250
grams of water which has bee~ twice distilled and then
chlorine gas is bubbled through the water preferably so
that the bubbles collide with the reactive aluminum. It
may be desirable to recirculate the gas which has not
been reacted. 36 grams of chlorine reacted over a period
i of approximately 72 hours produced a liquor having 46~
i by weight of aluminum chlorohydrate. 59 grams of reactive
aluminum reagent gives an aluminum to chlorine ratio of
.~1 ' . ' :.
- -20-
, " - . . . 1,
- ~ ,
~ 3495Polyl!ydrat~ Oll.lll~y7!~p
Il lW8~34
EY~PLE 6
An aluminum iodohydrate is prepared by using
59 grams of reactive aluminum prepared according to the
¦procedure of Example 1 and 127 grams of powdered iodine in
¦435 grams of water. The water and iodine is agitated so
; that the iodine contacts the reactive aluminum. An aluminum
to iodine ratio of 2.7:1 is obtained.
EXIU~LE 7
An aluminum bromohydrate is prepared by immersing
~164 grams of reactive aluminum in 600 grams of water and
I! introducing 80 grams of bromine gas into the water so that
¦Ithe bubbles contact the reactive aluminum. The gas flow
should be regulatea to occur over a period of several days.
~An aluminum to omine ratio of 2.4:1 is obt~ined.
EXAMPLE 8
An aluminum bromohydrate is prepared by immersing
59 grams of reactive aluminum in 307 grams of water contain-
ing 162 grams df hydrobromic acid and continuing the reaction
until an aluminum to bromine ratio of 2.0:1 is obtained.
It is preferable to provide cooling.
. ~ '
.
.
- -21- 1
.. .
1038134
EXA~IPLE 9
An aluminum fluorohydrate is prepared by im~mcr-
sing a reactive aluminum of 54 grams in 307 grams of
water and 40 grams of hydrofluoric acid and providing cool-
ing. A Teflon lined reactor is preferable.
EXA~LE 10
A stable hydroxyl augmented aluminum chloro-
hydrate is formed by taking 150 grams of the aluminum
chlorohydrate of Example 1 and combining it with 40 grams
of the oxygen-bearing aluminum complex of Canadian
Patent Number 939,116, and 40 grams of methanol. After
the mixture is heated to approximately 200F a stable
- product is obtained. This product is soluble in
alcohol.
EXAMPLE 11
~ A hydroxyl augmented aluminum chlorohydrate
; is obtained by adding to 150 grams of the aluminum
chlorohydrate of Example 1 40 grams of the afore-
; mentioned oxygen-bearing aluminum complex, which is
an aluminum complex including hYdroPeroxy groups.
2Q After mixing, the combination is left for 24 hours. Then,
10 grams of ethanol are added to the liquid and a re-
active aluminum i,s immersed therein for between 12 to
, 24 hours. me resulting product is an aluminum
i oxychlorohydrate which is soluble in alcohol and is
believed to be novel.
., ' . ".':
, , .
- 22 _
. - ,, , . -~, , - . . ..
~ 11 8495Polyl~drate (1) Nl~Hi~lldy74a 10-
~~ .
.'
1038~34
EXAMPLE 12
'. ''.'
- Example 11 is repeated except that no reactive
aluminum is used after the ethanol has been added.
.,
.
! EXAMPLE 13
Any of the Examples 1 to 12 is repeated with an
aluminum having a purity of at least 99.99% to obtain a
purer product of superior quality and preferable for phar-
mecutical and the like applications.
EXA.~PLE 14 . .
.
Examples 1 to 13 will result in elemental mercury
at the bottom of the reactor. This mercury can be easily
avoided by standard techniques for recovery of the
desired product. But, some mercury may be held in the liquor
obtained and may be highly undesirable. A further step
can be used to purge the mercury from the liquor. The
purging can be accomplished by using a reactive aluminum
containing no morel than about 500 to 2000 parts per million
of mercury. Such a reactive aluminum accumulates and holds
mercury so that the liquor purity is remarkably improved.
