Catalysts for olefin selective epoxidation with atmospheric...

Details Catalysts for olefin selective epoxidation with atmospheric... Catalysts for olefin selective epoxidation with atmospheric...

2000-01-07

2001-06-19

Nazario-Gonzalez, Porfirio (Department: 1621)

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

Organic compounds

Heavy metal containing

C502S150000, C502S162000, C546S002000, C549S003000, C549S206000

Reexamination Certificate

active

06248913

ABSTRACT:

The present invention relates to compounds which selectively catalyze the epoxidation of olefins by atmospheric oxygen, to a process for preparing them and to their use.
Epoxides (oxiranes), for example ethylene oxide, propylene oxide, 1,2-butene oxide and similar epoxides, are widely used intermediates in the production of many products. The oxirane function in such compounds is very reactive and ring-opening reactions take place in the presence of nucleophilic reactants. Thus, epoxides can, for example, be hydrolyzed to give glycols which are employed as deicing agents or as reactive monomers for preparing condensation polymers.
Polyether polyols prepared by ring-opening polymerization of epoxides are widely used as intermediates in the production of polyurethane foams, elastomers, coatings, sealing compositions or similar products.
The reaction of epoxides with alcohols leads to glycol ethers which are used, for example, as polar solvents.
For the preparation of epoxides, many different compounds which are supposed to selectively catalyze the epoxidation of alkenes have been developed.
Thus, for example, Huybrecht (J. Mol. Catal. 71, 129 (1992); EP-A-311983) describes the epoxidation of olefins using hydrogen peroxide in the presence of titanium silicate compounds as catalyst. However, the process disclosed here cannot be implemented economically, since hydrogen peroxide is firstly a relatively expensive oxidizing agent and secondly cannot be utilized completely since it partly decomposes into water and oxygen.
The epoxidation of propylene using atmospheric oxygen in the presence of tungsten- or molybdenum-containing catalysts is described in DE-C-22 35 229. The epoxidation reaction is carried out in a solvent which can be oxidized by oxygen to form hydroperoxides. However, the hydroperoxides formed undergo further reactions to give oxygen-containing by-products, generally alcohols, which are obtained as coproducts of the reaction.
Molybdenum complexes which catalyze the epoxidation of ethylene by t-butyl hydroperoxide (TBHP) have been described by Kelly et al. (Polyhedron, Vol. 5, 271-275, (1986)). As complexes having a high catalytic activity, mention is made of complexes such as MoO
2
(8-hydroxyquinoline)
2
, MoO
2
(phenylene-bissalicylimine) (=MoO
2
(salphen)), MoO
2
(5-nitroso-8-hydroxyquinoline)
2
. The actual active catalyst is a molybdenum complex which has added-on TBHP and one equivalent of epoxide.
Although the process proceeds with high selectivity, an expensive oxidizing agent is used. In addition, reproducibility problems occur, which prevents industrial use of the process.
The epoxidation of 1-octene using molybdenum catalysts has been subject matter of a study in J. Prakt. Chem. (1992, 334, 165-175). In the presence of molybdenyl acetylacetonate, a selectivity for 1,2-epoxyoctane of 34% is found; in the presence of molybdenum trioxide, the selectivity is 28%. Likewise, it is confirmed that the position of the transition metal in the Periodic Table and its oxidation state have by far the greatest influence on the catalyst activity, with the structure of the catalyst complex itself playing only a subordinate role.
In studies of epoxidation catalysts (J. Prakt. Chem. 1984, 326, 1025-26; DD-A-159 075), the complex MoCl
2
(NO)
2
(HMP) (HMP=hexa-methylphosphoramide) containing divalent molybdenum displayed the best epoxide selectivity of 43.8%, but has the disadvantage of using the carcinogenic HMP ligand.
Epoxidation catalysts based on molybdenum which allow olefins to be oxidized selectively in the presence of atmospheric oxygen are disclosed in DE-A44 47 233 and DE-A-44 47 231, but these catalysts too do not display satisfactory epoxide selectivities, particularly not in the case of octene oxide.
Heterogenized Mo complexes for epoxidizing olefins are also known from WO-A-94/04268. However, the compounds disclosed have the disadvantage of needing expensive hydroperoxides and, moreover, the ligands used are not sufficiently oxidation-stable in the presence of oxygen.
It has surprisingly been found that a series of bidentate, cyclically substituted ligands give excellent yields and selectivities in the oxidation of olefins using atmospheric oxygen.
The invention accordingly provides catalysts for the selective oxidation of olefins in the presence of air or oxygen, comprising compounds of the formula (1)
Mo
x
O
y
(L)
z
  (1)
where
x is 1, 2 or 3,
y is an integer from 0 to 2x+1, preferably y is ≧1,
z is an integer from 1 to 2x and
2y+z is preferably 5 or 6,
wherein the ligand L is a compound of the formula (2) or (3)
 where
n is0 or 1,
X is a nitrogen, oxygen or sulfur atom,
Y is hydrogen, C
1
-C
8
-alkyl, C
1
-C
8
-alkoxy, F, Cl, Br, I, COOCH
3
, C
6
-C
14
-aryl or C
3
-C
8
-cycloalkyl,
R
3
and R
4
form a ring containing from 4 to 8 carbon atoms onto which one or two aromatic rings may be fused,
R
1
and R
2
are hydrogen, branched or straight-chain C
1
-C
12
-alkyl or branched or straight-chain C
1
-C
12
-haloalkyl which substitute the ring formed by R
3
and R
4
and/or the rings fused onto this ring,
or the ligand L is a compound of the formula (4) or (5)
where R is hydrogen, C
1
-C
8
-alkyl, C
1
-C
8
-alkoxy, COOCH
3
, carbonyl oxygen, C
6
-C
14
-aryl or C
3
-C
8
-cycloalkyl and n is 1 or 2 and m is from 1 to 6.
The ligand is generally bound in a bidentate fashion to the metal center which can bind up to two such ligands. In the case of the tetradentate ligand (5), only one ligand is bound. The dioxo complexes can be in the form of cis or trans isomers
Examples of preferred ligands L are the following compounds:
Complexes of the formula (1) are prepared by reacting a suitable precursor with the appropriate ligands in an organic solvent. Suitable precursors are, for example, the commercially available oxo-acetylacetonates such as molybdenyl acetylacetonate MoO
2
(acac)
2
or oxo-dithiocarbamates, e.g. molybdenyl bis(N,N-diethyldithiocarbamate), the pyridyl and/or acetate complexes of the oxides, the higher oxides, e.g. molybdenum trioxide, or the corresponding acids and their salts.
The precursor is suspended in an organic solvent. Most suitable organic solvents are polar protic solvents such as methanol or ethanol and aprotic solvents such as acetonitrile or methyl tert-butyl ether (MTBE) or halogenated hydrocarbons such as CH
2
Cl
2
, CHCl
3
or CCl
4
.
While stirring, the appropriate ligand is subsequently added, preferably in dissolved form. The amount of ligand used is preferably twice that of the precursor used.
After the reaction is complete, the solvent is removed by filtration and the residue is washed. The filter residue obtained can be used as catalyst in this form or after drying under reduced pressure.
Supported complexes can be prepared by adding a suitable support material during and/or after the synthesis of the complex. Here, the starting complex of the formula (1) is dissolved in an organic solvent or water, the support material is added and the mixture is stirred. The ratio of complex/support material is preferably in the range from 1:1 to 1:1000, in particular in the range from 1:2 to 1:100.
Suitable support materials are inorganic and organic supports. Examples of inorganic supports are aluminum oxides, silicon dioxides, aluminosilicates, titanium dioxide, zirconium dioxide, thorium dioxide, lanthanum oxide, magnesium oxide, calcium oxide, barium oxide, tin oxide, cerium dioxide, zinc oxide, boron oxide, boron nitride, boron carbide, boron phosphate, zirconium phosphate, silicon nitride, carbon and silicon carbide.
Suitable organic supports are all polymers possessing donor centers which can undergo interactions with the Mo center, or functionalized polymers which form a chemical bond on reaction with the complexes of the formula 1 or ligands of the formulae (2)-(4). In the latter case, the heterogenized ligand obtained in this way has to be converted into the complex by reaction with a suitable precursor (e.g. MoO
2
(acac)
2
) in an organic solvent. Examples of such supports are polypyridines

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