Basic Aluminium Halogenide Complexes

Abstract

Basic aluminum halide complexes obtained by reaction of aluminum metal with hydrohalic acid and an organic acid, where either the aluminum metal is dissolved in a mixture of hydrohalic acid and organic acid, or the aluminum metal is firstly dissolved in the hydrohalic acid and then the organic acid is added.

Description

EXAMPLES

Example 1

In a column-like vessel of length 60 cm and diameter 9 cm with jacket heating and attached condenser, about 2.5 kg of pieces of aluminum in the form of small bars having in each case a weight of about 11 g were initially introduced and pickled with dilute hydrochloric acid. A 1:1 mixture of hydrochloric acid and glycolic acid was then poured in. After charging the solution and heating to about 100° C., the aluminum metal was attacked with the evolution of hydrogen. The progress of the reaction was observed by determining the aluminum and chloride content of the solution. At an aluminum:chlorine atomic ratio of 3.3:1, the reaction was terminated by discharging the solution. The resulting aluminum complex was used for active ingredients described in Examples 3 and 6.

Example 2

In a column-like vessel of length 60 cm and diameter 9 cm with jacket heating and attached condenser, about 2.5 kg of pieces of aluminum in the form of small bars having in each case a weight of about 11 g were initially introduced and pickled with dilute hydrochloric acid. A 1:1 mixture of hydrochloric acid and lactic acid was then poured in. After charging the solution and heating to about 100° C., the aluminum metal was attacked with the evolution of hydrogen. The progress of the reaction was observed by determining the aluminum and chloride content of the solution. At an aluminum:chlorine atomic ratio of 3.3:1, the reaction was terminated by discharging the solution. The resulting aluminum complex was used for active ingredients described in Examples 4, 5 and 7.

Example 3

The aluminum complex prepared in Example 1 was mixed with hydrochloric acid, water and glycine in order to obtain the composition given in Table 1.

TABLE 1
Fraction          Active ingredient 1
Aluminum % (w/w)  8.00
Chlorine % (w/w)  3.27
Glycolate % (w/w) 6.94
Glycine           7.02

Example 4

The aluminum complex prepared in Example 2 was mixed with hydrochloric acid and water in order to obtain the composition given in Table 2.

TABLE 2
Fraction         Active ingredient 2
Aluminum % (w/w) 8.00
Chlorine % (w/w) 3.33
Lactate % (w/w)  8.37
Glycine          —

Example 5

The aluminum complex prepared in Example 2 was mixed with hydrochloric acid, water and lactate in order to obtain the composition given in Table 3.

TABLE 3
Fraction         Active ingredient 3
Aluminum % (w/w) 8.00
Chlorine % (w/w) 3.27
Lactate % (w/w)  8.21
Glycine          7.00

The three complexes described in the examples were analyzed with regard to their molecular weight distribution using GPC measurements. The separating column used was an RP1 system. The eluent used was HNO₃/water, the change in the refractive index being detected.

The reference substance is standard commercial basic aluminum chloride and aluminum chloride hexahydrate.

Basic aluminum chloride shows four marked peaks at a maximum at:

TABLE 4
Peak Retention time
1    5.3 min
2    6.1 min
3    6.7 min
4    7.6 min

The monomeric aluminum chloride hexahydrate shows only one peak at 8.1 min in the chromatogram. Polymeric aluminum species thus move within the exclusion volume of the separating column and are therefore eluted and detected first. To characterize the novel active ingredients, the areas of peaks 1-4 were then compared. The results are shown in Table 5:

	TABLE 5
			Active	Active	Active
	Basic	Aluminum	ingredient 1	ingredient 2	ingredient 3
	aluminum	chloride	according to	according to	according to
	chloride	hexahydrate	the invention	the invention	the invention
Peak 1	36.9%	0	4.7%	2.2%	2.2%	Al
0-5.7 min						polymer
						high MW
Peak 2	40.7%	0	30.6%	32.7%	31.5%	Al
5.7-6.5 min						polymer
						moderate
						MW
Peak 3	10.5%	0	30.3	32.3%	32.5%	Al
6.5-7.2 min						oligomer
Peak 4	8.1%	35%	31.7%	30.8%	31.7%	Al
7.2-8.1 min						monomer

The table clearly shows that with the novel active ingredient the fractions of Al polymer with high and moderate molecular weight are significantly reduced and at the same time the fractions of Al monomer and Al oligomer greatly increase. In parallel to this, the peak maxima show a shift to lower molecular weights.

TABLE 6
	Basic	Aluminum	Active	Active	Active
Peak	aluminum	chloride	ingredient	ingredient	ingredient
maximum	chloride	hexahydrate	1	2	3
Maximum	5.27 min	0		6.53 min	6.35 min	6.35 min
1
Maximum	6.11 min	0		6.95 min	6.88 min	6.88 min
2
Maximum	6.68 min	0		7.20 min	7.05 min	7.05 min
3
Maximum	7.57 min	8.17	min	7.73 min	7.73 min	7.73 min
4

Example 6

The novel aluminum complex described in Example 1 was further processed together with zirconium salt to give an antiperspirant mixture.

TABLE 7
Zirconium-Al complex
Fraction                        Amount
Novel Al complex from Example 1 14.6 g
Basic zirconium carbonate       4.3 g
Hydrochloric acid               1.6 g
Glycine                         1.1 g

Firstly, the basic zirconium carbonate was dissolved in hydrochloric acid, glycine was added and the resulting mixture was added, with stirring, to the novel antiperspirant Al complex from Example 1.

The resulting active ingredient combination was analyzed with regard to its molecular weight distribution using GPC. The separating column used was an RP1 system. The eluent used was HNO₃/water, with the change in the refractive index being detected. The reference used was standard commercial zirconium aluminium glycine tetrachlorohydrate.

TABLE 8
Active ingredient 1 combined with zirconium
		Zr—Al complex
	ZAG	from Ex. 6
	Peak 1	19.5%	12.0%	Al polymer
	0-5.7 min			high MW
	Peak 2	40.5%	52.0%	Al polymer
	5.7-6.5 min			moderate MW
	Peak 3	2.9%	12.4	Al oligomer
	6.5-7.2 min
	Peak 4	10.5%	19.3%	Al monomer
	7.2-8.1 min

Table 8 shows that the novel active ingredient complex with the complex ligands according to the invention shows reduced fractions of high polymer, while Al oligomer and monomer species increase considerably.

Example 7

The novel aluminum complex described in Example 2 was further processed together with zirconium salt to give an antiperspirant mixture.

TABLE 9
Zirconium-Al complex
Fraction                        Amount
Novel Al complex from Example 2 13.6 g
Basic zirconium carbonate       4.3 g
Hydrochloric acid               1.8 g
Glycine                         1.1 g

Firstly, the basic zirconium carbonate was dissolved in hydrochloric acid, glycine was added and the resulting mixture was added, with stirring, to the novel antiperspirant Al complex from Example 1.

The resulting active ingredient combination was analyzed with regard to its molecular weight distribution using GPC. The separating column used was an RP1 system. The eluent used was HNO₃/water, with the change in the refractive index being detected. The reference used was standard commercial zirconium aluminium glycine tetrachlorohydrate.

TABLE 10
Active ingredient 2 combined with zirconium
		Zr—Al complex
	ZAG	from Ex. 7
	Peak 1	19.5%	4.4%	Al polymer
	0-5.7 min			high MW
	Peak 2	40.5%	43.6%	Al polymer
	5.7-6.5 min			moderate MW
	Peak 3	2.9%	21.7	Al oligomer
	6.5-7.2 min
	Peak 4	10.5%	24.6%	Al monomer
	7.2-8.1 min

Table 10 shows that the novel active ingredient complex with the complex ligands according to the invention shows reduced fractions of high polymer, while Al oligomer and monomer species increase considerably.

Claims

1. A process for producing a basic aluminum halide complex comprising the step of dissolving an aluminum metal with hydrohalic acid and an organic acid.

2. A process according to claim 1, wherein the hydrohalic acid is hydrochloric acid.

3. A process according to claim 1, wherein the organic acid is a hydroxycarboxylic acid.

4. A process according to claim 1, wherein the organic acid is glycolic acid or lactic acid.

5. A process according to claim 1, wherein the process is carried out at a temperature of from 20 to 100° C.

6. A process for producing an basic aluminum halide complex comprising the steps of dissolving an aluminum metal with a mixture of a hydrohalic acid and an organic acid and subsequently adding a hydrohalic acid, an organic acid or both.

7. A mixture of at least one basic aluminum halide complex produced by the process according to claim 1 and at least one antiperspirant active ingredient.

8. A process for producing a basic aluminum halide complex comprising the steps of dissolving an aluminum metal with hydrohalic acid and subsequently adding an organic acid.

9. A process according to claim 8, wherein the hydrohalic acid is hydrochloric acid.

10. A process according to claim 8, wherein the organic acid is a hydroxycarboxylic acid.

11. A process according to claim 8, wherein the organic acid is glycolic acid or lactic acid.

12. A process according to claim 8, wherein the process is carried out at a temperature of from 20 to 100° C.

13. A basic aluminum halide complex produced by the process according to claim 1.

14. A basic aluminum halide complex produced by the process according to claim 6.

15. A basic aluminum halide complex produced by the process according to claim 8.

16. An antiperspirant comprising a basic aluminum halide complex produced by the process according to claim 1.

17. An antiperspirant comprising a basic aluminum halide complex produced by the process according to claim 6.

18. An antiperspirant comprising a basic aluminum halide complex produced by the process according to claim 8.

19. A mixture of at least one basic aluminum halide complex produced by the process according to claim 6 and at least one antiperspirant active ingredient.

20. A mixture of at least one basic aluminum halide complex produced by the process according to claim 8 and at least one antiperspirant active ingredient.