Patent US5166372A successfully refreshed from Google Patents.
US5166372A
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Epoxidation process
Assignee: Lyondell Chemical Technology LP
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Filing: 1992-02-07
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Granted: 1992-11-24
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Expires: 2012-02-07
Abstract
Abstract Olefins are epoxidized by hydrogen peroxide in the presence of an organorhenium oxide catalyst and an alkyl aryl secondary alcohol solvent. High yields of epoxides with minimal non-selective loss of either hydrogen peroxide or olefin are realized. The epoxidation may comprise one step of an integrated process wherein an oxidant mixture is generated by molecular oxygen oxidation of the alkyl aryl secondary alcohol and used directly in the epoxidation without further purification or extraction.
Inventors
- 👤 Guy L. Crocco
- 👤 Wilfred F. Shum
- 👤 John G. Zajacek
- 👤 Haven S. Kesling, Jr.
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 04:23
CPC Classifications
C; C07; C07D; C07D301/00; C07D301/02; C07D301/03; C07D301/12; Y; Y02; Y02P; Y02P20/00; Y02P20/10
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
44 words
A method of epoxidizing an olefin which comprises contacting the olefin with an oxidant mixture comprised of hydrogen peroxide and an alkyl aryl secondary alcohol in the presence of an organorhenium oxide catalyst under conditions effective to epoxidize the olefin to form an epoxide.
Claim 2
Independent Claim
44 words
A method of epoxidizing an olefin which comprises contacting the olefin with an oxidant mixture comprised of hydrogen peroxide and an alkyl aryl secondary alcohol in the presence of an organorhenium oxide catalyst under conditions effective to epoxidize the olefin to form an epoxide.
Claim 3
Dependent Claim
15 words
The method of claim 1 wherein the alkyl aryl secondary alcohol is α-methyl benzyl alcohol.
Claim 4
Dependent Claim
21 words
The method of claim 1 wherein said oxidant mixture is produced by contacting the alkyl aryl secondary alcohol with molecular oxygen.
Claim 5
Dependent Claim
15 words
The method of claim 1 wherein said olefin is a C 2 -C 30 olefin.
Claim 6
Dependent Claim
228 words
The method of claim 1 wherein the organorhenium oxide catalyst is selected from the group consisting of: (a) compounds having the general formula R.sup.1.sub.a Re.sub.b O.sub.c wherein a is 1-6, b is 1-4, c is 1-14, Re has a valance of from 5-7, and R 1 is alkyl or aralkyl; (b) compounds having the general formula (R.sup.2 Re).sub.d O.sub.e R.sup.3.sub.f ·L.sub.g wherein d is 1 or 2, e is an integer of from 1 to 3·d, f is 0 or an integer of from 1 to 2·d, g is an integer of from 1 to 3·d, Re has a valance of 5 to 7, R 2 is alkyl or aralkyl, R 3 is alkyl, aralkyl, or aryl, and L is an ligand containging 1 to 3 heteroatoms selected from O and N and coordinated to Re; (c) substances having the general formula (polymer).sub.h ·(R.sup.4.sub.i Re.sub.j O.sub.k).sub.l wherein the polymer has ligand sites containing 1 to 3 heteroatoms selected from O and N and coordinated to Re, the ratio ##EQU3## represents the molar ratio of ##EQU4## and is from 0.01 to 10, i is an integer of from 1 to 6, j is an integer of from 1 to 4, k is an integer of from 1 to 14, Re has a valence of from 5 to 7, and R 4 is alkyl or aralkyl; and (d) mixtures thereof.
Claim 7
Dependent Claim
15 words
The method of claim 1 wherein the oxidant mixture additionally comprises an alkyl aryl ketone.
Claim 8
Dependent Claim
12 words
The method of claim 1 wherein the oxidant mixture additionally comprises water.
Claim 9
Dependent Claim
25 words
The method of claim 1 wherein said contacting is carried out at a temperature in the range of from about -30° C. to 100° C.
Claim 10
Dependent Claim
23 words
The method of claim 1 wherein the concentration of hydrogen peroxide in said oxidant mixture is from about 1 to 10 weight percent.
Claim 11
Dependent Claim
24 words
The method of claim 1 wherein the concentration of alkyl aryl secondary alcohol in said oxidant mixture is at least about 30 weight percent.
Claim 12
Dependent Claim
20 words
The method of claim 1 wherein the molar ratio of hydrogen peroxide to olefin is from about 1:10 to 10:1.
Claim 13
Dependent Claim
25 words
The method of claim 1 wherein the molar ratio of Re in the organorhenium oxide catalyst to hydrogen peroxide is from about 0.01:100 to 1:100.
Claim 14
Independent Claim
204 words
A method of epoxidizing a C 2 -C 30 olefin which comprises contacting the olefin with an oxidant mixture comprised of hydrogen peroxide, methyl benzyl alcohol, acetophenone, and water in the presence of an organorhenium oxide catalyst having the general formula (R.sup.2 Re).sub.d O.sub.e R.sup.3.sub.f ·L.sub.g wherein d is 1 or 2, e is an integer of from 1 to 3 d, f is 0 or an integer of from 1 to 2·d, g is an integer of from 1 to 3·d, Re has a valence of 5 to 7, R 2 is alkyl or aralkyl, R 3 is alkyl, aralkyl, or aryl, and L is a ligand containing 1 to 3 heteroatoms selected from O and N and coordinated to Re at a temperature of from about 31 30° C. to 100° C. to form an epoxide, the concentration of hydrogen peroxide in said oxidant mixture being from about 1 to 10 weight percent, the concentration of methyl benzyl alcohol in said oxidant mixture being at least about 30 weight percent, the molar ratio of hydrogen peroxide:olefin is from about 1:10 to 10:1, and the molar ratio of Re in the organorhenium oxide catalyst to hydrogen peroxide is from about 0.01:100 to 1:100.
Claim 15
Independent Claim
204 words
A method of epoxidizing a C 2 -C 30 olefin which comprises contacting the olefin with an oxidant mixture comprised of hydrogen peroxide, methyl benzyl alcohol, acetophenone, and water in the presence of an organorhenium oxide catalyst having the general formula (R.sup.2 Re).sub.d O.sub.e R.sup.3.sub.f ·L.sub.g wherein d is 1 or 2, e is an integer of from 1 to 3 d, f is 0 or an integer of from 1 to 2·d, g is an integer of from 1 to 3·d, Re has a valence of 5 to 7, R 2 is alkyl or aralkyl, R 3 is alkyl, aralkyl, or aryl, and L is a ligand containing 1 to 3 heteroatoms selected from O and N and coordinated to Re at a temperature of from about 31 30° C. to 100° C. to form an epoxide, the concentration of hydrogen peroxide in said oxidant mixture being from about 1 to 10 weight percent, the concentration of methyl benzyl alcohol in said oxidant mixture being at least about 30 weight percent, the molar ratio of hydrogen peroxide:olefin is from about 1:10 to 10:1, and the molar ratio of Re in the organorhenium oxide catalyst to hydrogen peroxide is from about 0.01:100 to 1:100.
Claim 16
Dependent Claim
60 words
The method of claim 13 wherein the C 2 -C 30 olefin has the general structure ##STR5## wherein R 5 , R 6 , R 7 , and R 8 are the same or different and are selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 6 -C 15 aryl, and C 7 -C 20 aralkyl.
Claim 17
Dependent Claim
54 words
The method of claim 13 wherein the C 2 -C 30 olefin is selected from the group consisting of ethylene, propylene, isobutylene, 2-butene, 1-butene, allyl alcohol, cyclohexene, allyl chloride, styrene, 1-octene, butadiene, 1-pentene, 2-pentene, 2,3-dimethyl-2-butene, 2-methyl-2-butene, cyclooctene, stilbene, phenyl allyl ether, α-methyl sytrene, methallyl alcohol, 1-decene, 1-dodecene, 1-hexadecene, 1-hexene, methyl allyl ether, and norbornene.
Claim 18
Dependent Claim
20 words
The method of claim 13 wherein R 2 is methyl, d is 1, e is 3, and f is 0.
Claim 19
Dependent Claim
26 words
The method of claim 13 wherein the ligand is selected from the group consisting of tertiary amines, tertiary amine oxides, aromatic azacycles, and aromatic azacycle oxides.
Claim 20
Dependent Claim
19 words
The method of claim 13 wherein the ligand is selected from the group consisting of pyridine and pyridine N-oxide.
Claim 21
Dependent Claim
70 words
An integrated process for the production of an epoxide comprising the steps of (a) contacting an alkyl aryl secondary alcohol with molecular oxygen under conditions effective to form an oxidant mixture comprised of the alkyl aryl secondary alcohol, an alkyl aryl ketone, and hydrogen peroxide; and (b) contacting the oxidant mixture with an olefin and an organorhenium oxide catalyst under conditions effective to epoxidize the olefin to form an epoxide.
Claim 22
Dependent Claim
70 words
An integrated process for the production of an epoxide comprising the steps of (a) contacting an alkyl aryl secondary alcohol with molecular oxygen under conditions effective to form an oxidant mixture comprised of the alkyl aryl secondary alcohol, an alkyl aryl ketone, and hydrogen peroxide; and (b) contacting the oxidant mixture with an olefin and an organorhenium oxide catalyst under conditions effective to epoxidize the olefin to form an epoxide.
Claim 23
Dependent Claim
24 words
The method of claim 19 comprising the additional step of separating the epoxide from the alkyl aryl secondary alcohol and the alkyl aryl ketone.
Claim 24
Dependent Claim
41 words
The method of claim 20 comprising the additional step of reacting the alkyl aryl ketone with hydrogen in the presence of a transition metal hydrogenation catalyst under conditions effective to convert the alkyl aryl ketone to the alkyl aryl secondary alcohol.
Claim 25
Dependent Claim
15 words
The method of claim 19 wherein the alkyl aryl secondary alcohol is α-methyl benzyl alcohol.
Claim 26
Dependent Claim
15 words
The method of claim 19 wherein step (a) is carried out in the liquid phase.
Claim 27
Dependent Claim
23 words
The method of claim 19 wherein the concentration of hydrogen peroxide in the oxidant stream is from about 1 to 10 weight percent.
Claim 28
Dependent Claim
241 words
An integrated process for the production of an epoxide comprising the steps of (a) contacting α-methyl benzyl alcohol with molecular oxygen in the liquid phase under conditions effective to form an oxidant mixture comprised of at least about 30 weight percent α-methyl benzyl alcohol, acetophenone, from about 1 to 10 weight percent hydrogen peroxide, and water; (b) contacting the oxidant mixture with a C 2 -C 30 olefin and an organorhenium oxide catalyst having the general formula (R.sup.2 Re).sub.d O.sub.e R.sup.3.sub.f ·L.sub.g wherein d is 1 or 2, e is an integer of from 1 to 3·d, f is 0 or an integer of from 1 ti 2·d, g is an integer of from 1 to 3·d, Re has a valence of from 5 to 7, R 2 is alkyl or aralkyl, R 3 is alkyl, aralkyl, or aryl, and L is a ligand containing from 1 to 3 heteroatoms selected from O and N and coordinated to Re at a temperature of from about -30° C. to 100° C. to form an epoxide, the molar ratio of hydrogen peroxide:olefin being from about 1:10 ti 10:1, and the molar ratio of Re in the organorhenium oxide catalyst to hydrogen peroxide being from about 0.01:100 to 1:100; (c) separating the epoxide form the α-methyl benzyl alcohol and acetophenone; and (d) reacting the acetophenone with hydrogen in the presence of a transition metal hydrogenation catalyst to convert the acetophenone to α-methyl benzyl alcohol.
Claim 29
Dependent Claim
241 words
An integrated process for the production of an epoxide comprising the steps of (a) contacting α-methyl benzyl alcohol with molecular oxygen in the liquid phase under conditions effective to form an oxidant mixture comprised of at least about 30 weight percent α-methyl benzyl alcohol, acetophenone, from about 1 to 10 weight percent hydrogen peroxide, and water; (b) contacting the oxidant mixture with a C 2 -C 30 olefin and an organorhenium oxide catalyst having the general formula (R.sup.2 Re).sub.d O.sub.e R.sup.3.sub.f ·L.sub.g wherein d is 1 or 2, e is an integer of from 1 to 3·d, f is 0 or an integer of from 1 ti 2·d, g is an integer of from 1 to 3·d, Re has a valence of from 5 to 7, R 2 is alkyl or aralkyl, R 3 is alkyl, aralkyl, or aryl, and L is a ligand containing from 1 to 3 heteroatoms selected from O and N and coordinated to Re at a temperature of from about -30° C. to 100° C. to form an epoxide, the molar ratio of hydrogen peroxide:olefin being from about 1:10 ti 10:1, and the molar ratio of Re in the organorhenium oxide catalyst to hydrogen peroxide being from about 0.01:100 to 1:100; (c) separating the epoxide form the α-methyl benzyl alcohol and acetophenone; and (d) reacting the acetophenone with hydrogen in the presence of a transition metal hydrogenation catalyst to convert the acetophenone to α-methyl benzyl alcohol.
Claim 30
Dependent Claim
15 words
The method of claim 25 wherein the C 2 14 C 30 olefin is propylene.
Claim 31
Dependent Claim
17 words
The method of claim 25 wherein the organorhenium oxide catalyst has a methyl group attached to Re.
Claim 32
Dependent Claim
25 words
The method of claim 25 wherein L is selected from the group consisting of tertiary amines, tertiary amine oxides, aromatic azacycles, and aromatic azacycle oxides.
Claim 33
Dependent Claim
16 words
The method of claim 25 wherein the temperature is from about 20° C. to 60° C.
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