Epoxidation process with improved heterogeneous catalyst

Claim 2

A PROCESS FOR THE EPOXIDATION OF AN OLEFINICALLY UNSATURATED COMPOUND WHICH COMPRISES REACTING THE OLEFINICALLY UNSATURATED COMPOUND IN THE LIQUID PHASE WITH AN ORGANIC HYDROPEROXIDE AT A TEMPERATURE OF FROM ABOUT 25*C TO ABOUT 200*C IN THE PRESENCE OF A CATALYST PREPARED BY REACTING AN OLEFIN EPOXIDATION CATALYST COMPRISING AN INORGANIC SILICEOUS SOLID IN CHEMICAL COMBINATION WITH AN OXIDE OR HYDROXIDE OF TITANIUM WITH AN ORGANIC SILYLATING AGENT AT AN ELEVATED SILYLATION TEMPERATURE IN THE RANGE FROM ABOUT 100* TO ABOUT 450*C FOR FROM ABOUT 0.1 TO 48 HOURS.

Claim 3

A process for the epoxidation of an olefinically unsaturated compound which comprises reacting the olefinically unsaturated compound in the liquid phase with an organic hydroperoxide at a temperature of from about 25*C to about 200*C in the presence of a catalyst prepared by reacting an olefin epoxidation catalyst comprising an inorganic siliceous solid in chemical combination with an oxide or hydroxide of titanium for a time period of from 0.1 to 48 hours, at a temperature from about 100*C to about 450*C, with an organic silylating agent selected from the group consisting of (a) trihalomonohydrocarbylsilanes, dihalo-dihydrocarbylsilanes and mono-halotrihydrocarbylsilanes wherein the halo substituents are selected from the group consisting of chloro, bromo, and iodo, and (b) organodisilazanes having the structural formula

Claim 4

A process for the epoxidation of an olefinically unsaturated compound which comprises reacting the olefinically unsaturated compound in the liquid phase with an organic hydroperoxide at a temperature of from about 25*C to about 200*C in the presence of a catalyst prepared by reacting an olefin epoxidation catalyst comprising an inorganic siliceous solid in chemical combination with an oxide or hydroxide of titanium for a time period of from 0.1 to 48 hours, at a temperature from about 100*C to about 450*C, with an organic silylating agent selected from the group consisting of (a) trihalomonohydrocarbylsilanes, dihalo-dihydrocarbylsilanes and mono-halotrihydrocarbylsilanes wherein the halo substituents are selected from the group consisting of chloro, bromo, and iodo, and (b) organodisilazanes having the structural formula

Claim 5

The process of claim 2 wherein the olefinically unsaturated compound is an alkene of from 3 to 20 carbon atoms and the organic hydroperoxide is selected from the group consisting of tertiary alkyl hydroperoxides and aralkyl hydroperoxides.

Claim 6

The process of claim 3 wherein the alkene is a linear alkene of from 3 to 10 carbon atoms, the hydrocarbyl substituents in the halosilanes each have from one to four carbon atoms and all the R''s in said organodisilazanes are lower alkyl groups of one to four carbon atoms.

Claim 7

The process of claim 4 wherein the alkene is propylene.

Claim 8

The process of claim 2 wherein the silylating agent is chosen from the group consisting of trihalomonohydrocarbylsilane, dihalodihydrocarbylsilane, and monohalotrihydrocarbylsilane; the halo substituents are selected from the group consisting of chloro, bromo and iodo; the hydrocarbyl substituents each have from 1 to 4 carbon atoms; the silylation reaction time is from about 1 to 48 hours; and the silylation reaction temperature is from about 300*C to 450*C.

Claim 9

The process of claim 6 wherein the organic silylating agent is chlorotrimethylsilane.

Claim 10

The process of claim 6 wherein said unsaturated compound is propylene.

Claim 11

The process of claim 2 wherein the silylating agent is an organodisilazane

Claim 12

The process of claim 9 wherein every R is methyl.

Claim 13

The process of clam 9 wherein said unsaturated compound is propylene.

Claim 14

The process of clam 9 wherein said unsaturated compound is propylene.

Claim 15

The process for the epoxidation of a linear alpha alkene of from 3-20 carbon atoms which comprises reacting the linear alpha alkene with an organic hydroperoxide in the presence of a catalyst prepared by reacting an olefin epoxidation catalyst comprising an inorganic siliceous solid containing a major portion of silica in chemical combination with from 0.2 to 10% by weight of total catalyst of titanium oxide or hydroxide for from 0.1 to 48 hours at a temperature of from 100*C to about 450*C with an organic silylating agent selected from the group consisting of (a) trihalomonohydrocarbylsilanes, dihalo-dihydrocarbylsilanes and monohalotrihydrocarbylsilanes wherein the halo substituents are selected from the group consisting of chloro, bromo, and iodo and the hydrocarbyl substituents each have from 1 to 4 carbon atoms and (b) organodisilazanes having the structural formula

Claim 16

The process for the epoxidation of a linear alpha alkene of from 3-20 carbon atoms which comprises reacting the linear alpha alkene with an organic hydroperoxide in the presence of a catalyst prepared by reacting an olefin epoxidation catalyst comprising an inorganic siliceous solid containing a major portion of silica in chemical combination with from 0.2 to 10% by weight of total catalyst of titanium oxide or hydroxide for from 0.1 to 48 hours at a temperature of from 100*C to about 450*C with an organic silylating agent selected from the group consisting of (a) trihalomonohydrocarbylsilanes, dihalo-dihydrocarbylsilanes and monohalotrihydrocarbylsilanes wherein the halo substituents are selected from the group consisting of chloro, bromo, and iodo and the hydrocarbyl substituents each have from 1 to 4 carbon atoms and (b) organodisilazanes having the structural formula

Claim 17

The process of claim 12 wherein said alkene is propylene and said silylating agent is chlorotrimethylsilane.

Claim 18

The process of claim 12 wherein said alkene is propylene and said silylating agent is an organodisilazane of the formula

Claim 19

The process of claim 14 wherein every R is methyl.

Claim 20

A process for the epoxidation of an olefinically unsaturated compound which comprises reacting the olefinically unsaturated compound in the liquid phase with an organic hydroperoxide at a temperature of from about 25*C to about 200*C in the presence of a catalyst prepared by reacting an olefin epoxidation catalyst comprising an inorganic siliceous solid in chemical combination with an oxide or hydroxide of titanium for a time period of from 0.1 to 48 hours, at a temperature from about 100*C to about 450*C, with an organic silylating agent selected from the group consisting of (a) tetrasubstituted silanes having from 1 to 3 hydrocarbyl substituents wherein the halo substituents are selected from the group consisting of chloro, bromo, and iodo and (b) organodisilazanes having the structural formula

Claim 21

A process for the epoxidation of an olefinically unsaturated compound which comprises reacting the olefinically unsaturated compound in the liquid phase with an organic hydroperoxide at a temperature of from about 25*C to about 200*C in the presence of a catalyst prepared by reacting an olefin epoxidation catalyst comprising an inorganic siliceous solid in chemical combination with an oxide or hydroxide of titanium for a time period of from 0.1 to 48 hours, at a temperature from about 100*C to about 450*C, with an organic silylating agent selected from the group consisting of (a) tetrasubstituted silanes having from 1 to 3 hydrocarbyl substituents wherein the halo substituents are selected from the group consisting of chloro, bromo, and iodo and (b) organodisilazanes having the structural formula

Claim 22

The process for the epoxidation of propylene which comprises reacting propylene with ethylbenzene hydroperoxide, cumene hydroperoxide or tertiary butyl hydroperoxide at a temperature of from about 25*C to about 200*C in the presence of a catalyst prepared by reacting an olefin epoxidation catalyst comprising an inorganic siliceous solid containing at least 99% silica in chemical combination with from 0.2 to 10% by weight of total catalyst of titanium oxide or hydroxide for a time period of from 1 to 48 hours at a temperature of from about 300*C to about 425*C with chlorotrimethylsilane as silylating agent.

Claim 23

The process for the epoxidation of propylene which comprises reacting propylene with ethylbenzene hydroperoxide, cumene hydroperoxide or tertiary butyl hydroperoxide at a temperature of from about 25*C to about 200*C in the presence of a catalyst prepared by reacting an olefin epoxidation catalyst comprising an inorganic siliceous solid containing at least 99% silica in chemical combination with from 0.2 to 10% by weight of total catalyst of titanium oxide or hydroxide for a time period of from 1 to 48 hours at a temperature of from about 300*C to about 425*C with chlorotrimethylsilane as silylating agent.

Claim 24

The process for the epoxidation of propylene which comprises reacting propylene with ethylbenzene hydroperoxide, cumene hydroperoxide or tertiary butyl hydroperoxide at a temperature of from about 25*C to about 200*C in the presence of a catalyst prepared by reacting an olefin epoxidation catalyst comprising an inorganic siliceous solid containing at least 99% silica in chemical combination with from 0.2 to 10% by weight of total catalyst of titanium oxide or hydroxide for a time period of from about 0.1 to 5 hours at a temperature of from about 150*C to 300*C with hexamethyldisilazane as silylating agent.

Claim 25

The process for the epoxidation of propylene which comprises reacting propylene with ethylbenzene hydroperoxide, cumene hydroperoxide or tertiary butyl hydroperoxide at a temperature of from about 25*C to about 200*C in the presence of a catalyst prepared by reacting an olefin epoxidation catalyst comprising an inorganic siliceous solid containing at least 99% silica in chemical combination with from 0.2 to 10% by weight of total catalyst of titanium oxide or hydroxide for a time period of from about 0.1 to 5 hours at a temperature of from about 150*C to 300*C with hexamethyldisilazane as silylating agent.