Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2001-08-03
2004-01-06
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
Reexamination Certificate
active
06673737
ABSTRACT:
FIELD OF THE INVENTION
The invention includes a compositions of matter comprising a composition of the formula A
+
B
−
covalently bonded to a support, a composition comprising supported A
+
B
−
and an ionic liquid immobilized in said supported A
+
B
−
as well as a composition comprising supported A
+
B
−
having an ionic liquid immobilized in said supported A
+
B
−
and further having catalyst immobilized in the ionic liquid. Methods for making the compositions are also taught.
BACKGROUND OF THE PRIOR ART
The art proposes AlCl
x
based ionic liquids deposited or impregnated onto a solid. For example, EP 553,009 B1 proposes a “catalyst comprising an organic or mineral porous support and at least one mixture constituted by at least one halide of a compound chosen from Aluminum and Boron and at least one compound chosen from ammonium halides and amine hydrohalides.
U.S. Pat. No. 5,693,585 proposes a catalyst composition containing a porous organic or mineral support, preferably silica, and at least one active phase containing at least one aluminum halide, at least one quaternary ammonium halide and/or at least one amine hydrohalide, and at least one cuprous compound.
WO 99/03163 proposes the alkylation of aromatic compounds using as a catalyst a supported ionic liquid composition. The catalyst comprises an ionic liquid, which consists essentially of an organic base and a metal halide, and a support that may be a macroporous polymer or metal oxide, such as silica.
WO 00/15594 proposes a process for the carbonylation of alkyl aromatic compounds using acidic ionic liquids.
Immobilized Ionic Liquids as Lewis Acid Catalysts for the Alkylation of Aromatic Compounds with Dodecene by DeCastro et al.,
J. Catalysis
196, 86-94 (2000) teaches immobilized ionic liquids as Lewis Acid catalysts for the alkylation of aromatic compounds with dodecene. The ionic liquid used throughout the experiments consisted of 1-butyl-3-methylimidazolium chloride and AlCl
3
. The support materials that were used included SiO
2
, Al
2
O
3
, TiO
2
, ZrO
2
and some mixtures of thereof.
SUMMARY OF THE INVENTION
The invention includes a composition comprising a support selected from the group consisting of organic and inorganic supports and a composition of the formula
A┐
⊕
B
⊖
wherein A is selected from the group consisting of compounds of the general formulae:
and wherein each occurrence of Z is independently selected from the formula
(Y)
n
X
m
where
Y is OR or R
and wherein X is halide and wherein p is an integer from 1 to 4, r is an integer from 0 to 10, 1, 1′ and 1″ are integers from 0 to 4 wherein 1+1′+1″+p≦4
n+m=3 and wherein n ranges from 0 to 3 and m ranges from 0 to 3 and wherein said cyclic systems (depicted by circles) contain 4 to 10 atom in addition to one or more nitrogen atoms, and may also contain sulfur or oxygen atoms singly or double bonded to said ring and wherein said cyclic system may be a single, double or triple ring system and wherein B
−
is selected from the group consisting of salts, anions, alkylates and halogenated salts of the Group Ib, IIIb, IVb, Vb, VIb, VIIb, IIIa, IVa, Va, VIa, VIIa, and VIIIa elements of the periodic table (see
Basic Inorganic Chemistry
, by Cotton and Wilkinson, 1976, Wiley, inside cover) and wherein g is an integer from 1 to 4, x is 1 or 2 and y is 1 or 2, wherein each R in the above formulae is independently selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, halogenated aralkyl, oxygen, nitrogen, or sulfur substituted alkyl, oxygen, nitrogen or sulfur substituted aryl, oxygen, nitrogen or sulfur substituted aralkyl, oxygen, nitrogen or sulfur substituted cycloalkyl groups having from 1 to 12 carbon atoms and mixtures thereof, and wherein each R′ in the above formulae is independently selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, halogenated aralkyl, oxygen, nitrogen, or sulfur substituted alkyl, oxygen, nitrogen or sulfur substituted aryl, oxygen, nitrogen or sulfur substituted aralkyl, oxygen, nitrogen or sulfur substituted cycloalkyl groups having from 1 to 12 carbon atoms and mixtures thereof, and wherein said compound having the formulae A
+
B
−
is covalently bonded to said support through said A
+
group.
The invention further includes a composition comprising a support selected from organic and inorganic supports having covalently bonded thereon said composition A
+
B
−
described above, wherein said composition is covalently bonded to said support through A
+
and an ionic liquid coulombically attached to said support.
The invention further includes a composition comprising a support selected from organic and inorganic supports having covalently bonded thereon said composition A
+
B
−
described above, wherein said composition is covalently bonded to said support through B
−
and an ionic liquid coulombically attached to said support and an effective amount of a catalyst immobilized within said ionic liquid.
One skilled in the art can readily determine if the composition A
+
B
−
has been covalently bonded to the support by utilizing solid state NMR and solid state FTIR techniques to monitor the bonding.
A method of preparing a supported composition comprising;
covalently bonding a compound having the formula A
+
B
−
to a support selected from organic and inorganic supports, wherein said composition A
+
B
−
is covalently bonded to said support through A
+
and wherein said composition A
+
B
−
has the formulae shown above and wherein said covalent bond is established through a chemical reaction between said support and said compound said chemical reaction being selected from the group consisting of condensation reactions, ring opening reactions, and hydrosilylation reactions which take place between said composition A
+
B
−
and said support.
The method may further comprise depositing an ionic liquid dissolved in a solvent onto said support and thereafter evaporating said solvent.
The method may still further comprise adding a catalytically active material to the composition by adding the catalytic material to said solvent along with said ionic liquid or adding a catalytic material to the composition by dissolving the catalyst in a solvent, mixing with the composition and thereafter evaporating off the solvent. The catalyst can be added prior to, following, or in conjunction with the ionic liquid.
DETAILED DESCRIPTION OF THE INVENTION
The composition A
+
B
−
may be referred to herein as an ionic liquid moiety or a modified ionic liquid. The composition is prepared by mixing and refluxing precursors compounds which when reacted will yield the composition A
+
B
−
. For example an alkylating electrophile may be refluxed with a neutral nitrogen containing compound having at least one silicon based anchor group. Such silicon based anchor groups are Si-halogen or Si-alkoxy groups or mixture thereof. Alternatively, one could reflux a neutral nitrogen containing compound having a lone electron pair on the nitrogen atom with an electrophile having a silicon based anchor group. Such reactions and precursors are easily selected by the skilled artisan with the teaching herein.
Alkylating electrophiles include, for example, butyl chloride, ethyl chloride, hexyl chloride, and methyl triflate.
Neutral nitrogen containing compounds which have silicon based anchor groups include, for example, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.
Neutral nitrogen containing compounds having a lone electron pair on the nitrogen include, for example, imidazoles, pyrazoles, thiazoles, isothiazoles, azathiozoles, oxothiazoles, oxazines, oxazolines, oxazoboroles, dithiozoles, triazoles, selenozoles, oxaphospholes, pyrroles, boroles,
Cook Raymond Arnold
Mehnert Christian Peter
Bakun Estelle C.
Bell Mark L.
Brown Jennine
ExxonMobil Research and Engineering Company
Wang Joseph C.
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