Silica gel incorporating polyazacycloalkane structural units

Details Silica gel incorporating polyazacycloalkane structural units Silica gel incorporating polyazacycloalkane structural units

2000-07-25

2003-02-25

Lovering, Richard D. (Department: 1712)

Gas separation: processes

Solid sorption

Inorganic gas or liquid particle sorbed

C210S687000, C423S219000, C423S239100, C423S584000, C502S405000, C502S407000, C516S101000, C540S474000

Reexamination Certificate

active

06524372

ABSTRACT:

This application is a 371 of PCT/FR 99/00142 filed Jan. 25, 1999.
A novel material which can be used in the field of the separation and purification of gases is disclosed. Current separation techniques, whether cryogenic distillation or adsorption on zeolites, and techniques for the purification of industrial gases by cryogenic or catalytic distillation are not always capable of being optimized, either in economic terms or in terms of purity. Many studies have furthermore shown that gases such as oxygen, hydrogen or carbon monoxide react selectively and reversibly with transition metal complexes.
BACKGROUND OF THE INVENTION
Thus, cobalt(II) complexes of cyclam or of cyclene easily fix atmospheric oxygen (Machida R., Kimura E., Kodama M.,
Inorg. Chem
., 1983, 22, 2055-2061) and result in &mgr;-peroxide species in aqueous media. However, the lifetime of the oxygen-comprising complexes in solution is limited as the latter can undergo irreversible decomposition reactions (Martell A. E., Basak A. K., Raleigh. C. J.,
Pure Appl. Chem
., 1988, 60, 1325-1329). Furthermore, these species cannot be deoxygenated simply by decreasing the dioxygen partial pressure. An improvement in the reversibility, necessary in a separation process, requires stabilization of the intermediate superoxide species. Grafting the ligand to a solid matrix should, at the same time, slow down the change from the superoxide species to the &mgr;-peroxide species, restrict hydrolysis reactions and facilitate the handling of the active complex (Tsuchida E., Nishide, H.
Top. Curr. Chem
., 1986, 32, 63-99). The incorporation of cobalt complexes with porphyrins, phthalocyanines or cyclidenes in organic or inorganic polymers, such as silica gels, and the study of the interaction of these materials with oxygen have already formed the subject of numerous studies. Generally, the complex is synthesized in a first stage and then immobilized on the polymer via a dative bond between a nitrogen atom of a pyridine or imidazole unit and the metal (Nishide H., Suzuki T., Kawakami H., Tsuchida E., J.
Phys. Chem
., 1994, 98, 5084-5088; Cameron J. H., Graham S.,
J. Chem. Soc. Dalton Trans
., 1992, 385-391; Bowman R. G., Basolo F., Burwell Jr. R. L.,
J. Am. Chem. Soc
., 1975, 97, 5125-5129). Another approach consists in attaching, in a first step, the ligand to the polymer via a covalent bond and in subsequently metallating (Wöhrle D., Gitzel J., Krawczyk G., Tsuchida E., Ohno H., Okura I., Nishisaka T.,
J. Macromol. Sci. Chem
., 1988, A25, 1227-1254; Barnes M. J., Drago R. S., Balkus Jr. K. J.,
J. Am. Chem. Soc
., 1988, 110, 6780-6785). Thus, the grafting to silica gel of tetraazamacrocyclic ligands and the study of the metallation of these materials have been carried out (Gros C., Rabiet F., Denat F., Brandes S., Chollet H., Guilard R.,
J. Chem. Soc. Dalton Trans
., 1996, 1209-1214). The sol-gel process has been studied in detail (Hench L. L., West J. K.,
Chem. Rev
., 1990, 90, 33-72) and is of major importance in the chemistry of the materials. One of the main advantages of this process is a high homogeneity of the materials obtained, thus conferring specific properties on them. Precursors of alkoxide type are among the most widely used. Thus, the hydrolysis of tetraethoxysilane in solution in an organic solvent, for example an alcohol, results in a colloidal dispersion of particles, which particles result from the polymerization of the precursor and which dispersion is referred to as a sol. This sol changes in the direction of the formation of a gel. The drying of this gel by evaporation results in a xerogel, which can itself be converted into glass or ceramic. More recently, this technique has made possible the preparation of novel organic-inorganic hybrid materials (Corriu R. J. P., Leclercq D.,
Angew. Chem. Int. Ed
., 1996, 35, 1420-1436; Schubert U., Hüsing N., Lorenz A.,
Chem. Mater
., 1995, 7, 2010-2027). The precursor is then an organic compound carrying one or more endings of trialkoxysilyl [Si(OR
3
)] or silyl [SiH
3
] type. Various organic species have been used, such as aromatic compounds, acetylenic units or linear and cyclic amines (Corriu R. J. P., Leclercq D.,
Angew. Chem. Int. Ed
., 1996, 35, 1420-1436; Khatib I. S., Parish R. V.,
J. Organomet. Chem
., 1989, 369, 9-16; Tsuda T., Fujiwara T.,
J. Chem. Soc. Chem. Commun
., 1992, 1659-1661). Battioni et al. have used this route to incorporate manganese and iron porphyrins in a silica gel and have tested the catalytic properties of these novel materials (Battioni P., Cardin E., Louloudi M., Schöllhorn B., Spyroulias G. A., Mansuy D., Traylor T. G.,
Chem. Commun
., 1996, 2037-2038).
SUMMARY OF THE INVENTION
The anchoring of a complex to a polymer via a dative bond between a base and the metal exhibits the advantage of activating the complex and of stabilizing the superoxide species by hindering one of the faces of the complex. However, the bond thus formed is weak. The grafting of the ligand via a covalent bond results, for its part, in a stronger material. Generally, the methods for the incorporation of the transition metal complexes in organic or inorganic matrices have to date been unable to result in materials which are compatible with the requirements of process engineering and can thus be used in industrial processes. In particular, the characteristics of such a material must be able to be adjusted in terms of specific surface, of porosity, whether this be the radius, the shape or the size distribution of the pores, and of particle size. The Applicant Company has found that the material which is a subject-matter of the present invention makes it possible to solve the problems set out hereinabove. A subject-matter of the invention is a compound of formula (I):
in which:
W
1
, W
2
and W
3
, which are identical or different, each represent, independently of one another, a divalent radical chosen from those represented by the general formula (A):
—[(CT
1
T
2
)
n
—[N(R
4
)]
p
—(CT
3
T
4
)
m
]
l
—  (A)
 in which:
p represents an integer equal to 0 or to 1,
l represents an integer equal to 1 or to 2,
n and m, which are identical or different, each represent, independently of one another, an integer less than or equal to 3 and greater than or equal to 1, T
1
, T
2
, T
3
and T
4
, which are identical or different, either each represent, independently of one another, a hydrogen atom, a linear or branched alkyl radical comprising from 1 to 15 carbon atoms or a [(hetero)aryl]alkyl radical comprising from 7 to 12 carbon atoms or else CT
1
T
2
and/or CT
3
T
4
represent a divalent group —(C═O)—,
R
4
represents a hydrogen atom, a linear or branched alkyl radical comprising from 1 to 15 carbon atoms which is unsubstituted or substituted by one or more functional groups, a [(hetero)aryl]alkyl radical comprising from 7 to 12 carbon atoms or a radical represented by the general formula (B):
R
5
—Si(X
1
)(X
2
)(X
3
)  (B)
 in which:
X
1
, X
2
and X
3
, which are identical or different, each represent, independently of one another, a hydrogen atom, a halogen atom or an OR
6
radical, in which R
6
represents a hydrogen atom or an alkyl radical comprising from 1 to 4 carbon atoms,
R
5
represents a divalent radical derived from a saturated or unsaturated aliphatic hydrocarbonaceous chain comprising from 1 to 10 carbon atoms, in which chain are optionally inserted one or more structural links chosen from the arylene group or the —O—, —S—, —O—C(═O)—, —N(R
7
)—C(═O)— or —N(R
7
)— fragments, in which fragments R
7
represents a hydrogen atom, an aliphatic hydrocarbonaceous radical comprising from 1 to 6 carbon atoms, a benzyl radical or a phenethyl radical, said chain being unsubstituted or substituted by one or more radicals chosen from halogen atoms, the hydroxyl group, alkyl radicals comprising from 1 to 4 carbon atoms or benzyl or phenethyl radicals,
R
1
, R
2
and R
3
, which are identical or different, each represent, independently of one another and of R
4
,

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