CA1038134A - Aluminum halohydrates - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

The invention is concerned with a method for preparing an aluminum halohydrate in which there is first formed a reactive aluminum by permeating highly pure aluminum in the presence of a hydrogen ion source with less than about 5% by weight of mercury, and afterwards this reactive aluminum is reacted with an aqueous solution of a halogen acid of chlorine, bromine, iodine or fluorine at a temperature of less than 200°F to form a liquor of the aluminum halohydrate.
The liquor is then collected.

Description

~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.
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)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: !
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(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.

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~, 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 _ .

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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-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 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 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.
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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-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.
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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.
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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.

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8495~oly~1ydrate(1)N1711i111dy74p 6-'~;` . ,.

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. ' ~ :
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From the above, it is clear herein, including the ! claims, what is meant by a "reactive aluminum."
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, 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 , ~495~oly~Iyarate(1);~17~1:11k1~71p ~
l l 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- , ! 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 :................. -.. ,~ -~ . , .
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Il 8495Po1~ydrate(1)N17~;111dy74p 7-.~ I
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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.

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'_,' 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.
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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 .
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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. ¦
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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-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.
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` I 8495PolyHydrate(1).~1171illdy71p 3-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 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.
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~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 ' . ' :.

, " - . . . 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.

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.

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.

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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.

~ 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.
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~ 11 8495Polyl~drate (1) Nl~Hi~lldy74a 10-~~ .
.' 1038~34 '. ''.' - Example 11 is repeated except that no reactive aluminum is used after the ethanol has been added.
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! 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.

Claims (11)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-

1. A method of preparing a polymeric aluminum halohydrate having a ratio of aluminum to halogen atoms of from 2:1 to 2.7:1 and a stable pH of about 4.2 to about 4.3 which comprises:
reacting an aqueous solution of a halogen acid selected from hydrocholric acid, hydrobromic acid, hydro-iodic acid and hydrofluoric acid with mercury permeated aluminum of a purlty of at least 99.98% by weight, the mercury content of said mercury permeated aluminum ranging from about 0.1 to about 5.0 percent by weight;
and collecting the formed aluminum halohydrate.

2. The method of claim 1, wherein said mercury permeated aluminum has a mercury content ranging from about 2 percent to about 3 percent by weight.

3. The method of claim 1, wherein said aluminum has a purity of at least 99.99 percent.

4. The method of claim 1, wherein the reaction is carried out at a temperature below 100° F.

5. The method of claim 1, wherein the collected aluminum halohydrate is spray dried.

6. The method of claim 1, wherein said mercury permeated aluminlum is prepared by permeating aluminum in the presence of a hydrogen ion source with mercury.

7. A method of preparing a polymeric aluminum halohydrate having a ratio of aluminum to halogen of from 2:1 to 2.7:1 and a stable pH of from about 4.2 to about 4.3 which comprises:
reacting, in an aqueous medium, a gaseous halogen selected from chlorine, bromine and iodine with mercury permeated aluminum of a purity of at least 99.98% by weight, the mercury content of said mercury permeated aluminum ranging from about 0.1 percent to about 5 percent by weight;
and collecting the formed aluminum halohydrate.

8. The method of claim 7, wherein said mercury permeated aluminum has a mercury content ranging from about 2 percent to about 3 percent by weight.

9. The method of claim 7,wherein said aluminum has a purity of at least 99.99 percent.

10. The method of claim 7, wherein the reaction is carried out at a temperature below 100° F.

11. The method of claim 7, wherein said mercury permeated aluminum is prepared by permeating aluminum in the presence of a hydrogen ion source with mercury.