Alkoxylation process using antimony catalyst

Details Alkoxylation process using antimony catalyst Alkoxylation process using antimony catalyst

2002-07-26

2004-05-11

Keys, Rosalynd (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S618000, C502S152000, C502S150000, C502S169000, C502S224000, C423S087000, C423S466000

Reexamination Certificate

active

06734327

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to the preparation of highly active antimony catalyst compositions and the use of such catalyst compositions in chemical reactions including the selective addition reaction of an epoxide with an active hydrogen containing organic or inorganic compound, for example in the production of alkylene glycol ethers by the alkoxylation of lower alcohols with an alkylene oxide, to produce alkoxylated products.
BACKGROUND OF THE INVENTION
A variety of compounds have been proposed as catalysts for promoting addition reactions of epoxides and organic compounds containing active hydrogen. For example, the use of compounds which are basic in nature and are soluble in the reaction medium such as soluble basic salts of the alkali metals of Group I of the Periodic Table, e.g. sodium, potassium, rubidium and cesium, and of the alkaline earth metals of Group II of the Periodic Table, e.g. calcium, strontium and barium are well documented in the literature. Alkali metal hydroxides and alkoxides have long been used in the commercial production of glycol ethers. In general, these basic catalysts provide acceptably low by-product formation but when used in amounts sufficient to provide acceptable activity, the selectivity, i.e. the amount of mono-alkoxylate produced as compared to the di-, tri- and higher alkoxylates produced, is somewhat deficient and could desirably be increased to improve process economics.
It is also well known that compounds having a strong acidic nature which are soluble in the reaction mixture can be used to catalyze the addition reaction of epoxides and hydroxylated compounds such as alcohols. For example, triflic acid and various soluble metal salts of triflic acid are described as catalysts for the alkoxylation reaction of alkanols and epoxides in U.S. Pat. No. 4,543,430 and Australian Patent No. 538,363.
Other acid compounds disclosed in the prior art as being useful to catalyze alkoxylation reactions include certain Lewis acid or Friedel-Crafts compounds. For example, in United Kingdom Patent 796,508 and in U.S. Pat. Nos. 3,359,331; 4,188,311; 4,983,778 and 5,057,628, antimony halides, in particular SbCl
5
are disclosed as being useful alkoxylation catalysts. U.S. Pat. No. 5,210,523 discloses the use of SbBr
5
and SbCl
5
complexed with certain Lewis bases as catalysts in alkoxylation reactions.
In general, the acid compounds disclosed in the prior art as useful alkoxylation catalysts are recognized as being highly active and providing excellent selectivity in producing a narrow range of alkoxylation products. However, corrosion and instability problems make many of these compounds difficult to use commercially and as a group, acid compounds, when used as alkoxylation catalysts, tend to promote side reactions leading to unacceptable levels of undesirable by-products being formed. Accordingly, industry continues to seek catalysts for the addition reaction of epoxides and organic or inorganic compounds, especially alcohols, that will provide a combination of high activity, good selectivity and minimal by-product formation.
SUMMARY OF THE INVENTION
According to the present invention, applicants have discovered that novel active catalyst compositions useful in a wide range of chemical reactions are obtained when certain fluorine containing antimony compounds (and/or their hydrogen, metal and ammonium salts) are reacted with active hydrogen-containing compounds. The resulting novel active catalyst compositions comprise a compound or mixture of compounds represented by the empirical formula
SbFX
m
Y
4−m
wherein m is 0 to 3, a complex of such a compound or mixture of such compounds being represented by the empirical formula
R.SbFX
m
Y
4−m
wherein m is 0 to 3, or a combination thereof. In each formula, X is an anionic moiety and Y is an anion or anions resulting from the deprotonation of an active hydrogen-containing compound(s). When the catalyst is a complex or mixture of complexes, R is one or more neutral active hydrogen containing compound(s) acting as molecules of solvation and may include the compound(s) capable of being deprotonated to provide the anion Y.
The novel active catalyst compositions are useful generally in promoting chemical reactions and are uniquely effective in catalyzing the addition reaction of an epoxide and an organic or inorganic compound containing an active hydrogen, in particular alkanols, over a wide range of reaction temperatures and catalyst concentrations to obtain alkoxylation products at a high rate with excellent selectivity and remarkably low unwanted by-product formation compared to previously known catalysts.
DESCRIPTION OF THE INVENTION
The novel active catalyst compositions of the present invention comprise a compound or mixture of compounds represented by the empirical formula
 SbFX
m
Y
4−m
where m is 0 to 3, a complex of such a compound or mixture of complexed compounds being represented by the empirical formula
R.SbFX
m
Y
4−m
where m is 0 to 3, or a combination of such compounds and complexes. In each formula, X is an anionic moiety and Y is an anion or anions resulting from the deprotonation of an active hydrogen-containing compound(s). When the catalyst is a complex or mixture of complexes, R is one or more neutral active hydrogen containing compound(s) acting as molecules of solvation and may include the compound(s) capable of being deprotonated to provide the anion Y. Examples of X include fluorine, chlorine, bromine, iodine, sulfonates including tosylate, nosylate, mesylate, methane sulfonate and the like, cyanides, or mixtures thereof.
The novel catalyst compositions of the present invention are prepared by contacting at least one antimony precursor compound containing at least one fluorine, represented by the formula
Sb(V)FX
4
and henceforth referred to as neutral catalyst precursors, wherein Sb(V) is antimony in a +5 oxidation state, X is an anionic moiety typically selected from the group comprising fluorine, chlorine, bromine, iodine, a sulfonate such as tosylate, nosylate, mesylate, methane sulfonate and the like, and a cyanide, or mixture thereof, or at least one salt thereof represented by the formula
M
n+
[Sb(V)FX
5
]
n
n−
and henceforth referred to as ionic catalyst precursors, where M
n+
is selected from the group of hydrogen, ammonium, alkali, alkali earth and transition metals, or mixtures of such precursor compound and salt, where n is 1-4, with at least one active hydrogen containing compound, here represented by HY, under appropriate conditions of time and temperature to cause deprotonation of the active hydrogen containing compound and replacement of at least one, and up to all, of X in the precursor compound(s), via formation of HX, with anion Y resulting from such deprotonation. Particularly useful neutral catalyst precursor compounds are antimony pentafluoride and antimony pentahalides containing a mixture of fluoride and chloride. When ionic catalyst precursors are used, appropriate conditions of time and temperature to cause the dissociation of M
n+
(X
−
)
n
may precede the deprotonation of the active hydrogen containing compound to facilitate preparation of the active catalyst composition. Particularly useful ionic catalyst precursor compounds are hydrogen hexafluoroantimonate and hydrogen hexafluoroantimonate hexahydrate.
The active hydrogen containing compounds useful in preparing the catalyst compositions of the present invention include all compounds which are capable of undergoing deprotonation by the catalyst precursors at temperatures of from about 20° C. to about 200° C. at times typically ranging from from a few seconds to several days to yield an anion capable of replacing at least one X. Additionally, the active hydrogen containing compounds useful in preparing the catalyst compositions of the present invention may also act as a molecule or molecules of solvation to 1) the catalyst precursor compound or complex, and/or 2) the active catalyst composition of the present inventio

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