Method for producing epoxy compound and catalyst composition for epoxidation reaction

Patent metadata

Field	Value
Publication number	US-9650353-B2
Application number	US-201414502206-A
Country	US
Kind code	B2
Filing date	Sep 30, 2014
Priority date	Mar 30, 2012
Publication date	May 16, 2017
Grant date	May 16, 2017

Abstract

A method of producing an epoxy compound, which comprises reacting hydrogen peroxide with a compound having a carbon-carbon double bond, in the presence of at least one of a tungsten compound and a molybdenum compound; and an onium salt comprising 20 or more carbon atoms and one or more of substituents convertible to a functional group containing an active hydrogen or a salt thereof.

First claim

The invention claimed is:

1. A method for producing an epoxy compound, the method comprising:
reacting hydrogen peroxide with a compound having a carbon-carbon double bond in a two-phase reaction system having an organic phase and an aqueous phase, the two-phase reaction system comprising:
at least one compound selected from the group consisting of a tungsten compound and a molybdenum compound; and
an onium salt having 20 or more carbon atoms and containing one or more substituents convertible to an active hydrogen-containing functional group or a salt thereof,

to obtain an epoxy compound;
after the reacting, converting the one or more substituents contained in the onium salt to an active hydrogen-containing functional group or a salt thereof; and
separating the onium salt from the epoxy compound.

2. The method of claim 1 , wherein said active hydrogen-containing functional group is a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a sulfonic acid group or a phosphoric acid group.

3. The method of claim 1 , wherein the two-phase reaction system further comprises at least one acid selected from the group consisting of a phosphoric acid and a phosphonic acid, excluding an onium salt.

4. The method of claim 1 , wherein the aqueous phase of the two-phase reaction system has a pH of from 2 to 6.

5. The method of claim 1 , wherein said onium salt is an ammonium salt, a pyridinium salt, an imidazolinium salt or a phosphonium salt.

6. The method of claim 1 , wherein the converting is achieved by hydrolyzing said one or more substituents with a basic compound.

7. The method of claim 1 , further comprising: washing said compound having a carbon-carbon double bond with an acidic aqueous solution prior to the reacting.

8. The method of claim 1 , further comprising: washing said compound having a carbon-carbon double bond with an aqueous chelating agent solution prior to the reacting.

9. The method of claim 1 , wherein the two-phase reaction system further comprises a chelating agent.

10. A method for producing an epoxy resin, the method comprising:
producing an epoxy compound by the method claimed in claim 1 ; and
polymerizing the epoxy compound.

11. The method of claim 1 , wherein the onium salt is represented by formula (8) to (10), (12) or (31):

wherein R 20 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom, a phenyl group, a phenoxy group, a benzyl group, an alkoxycarbonyl group, an N-alkylcarbamoyl group or an N-alkylsulfamoyl group; each of R 21 to R 23 independently represents an alkyl group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom, or a benzyl group; R 20 to R 23 optionally combine in the same compound to form a ring; k represents an integer of 1 to 4;
each of R 31 and R 32 independently represents a divalent aliphatic hydrocarbon group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom;
R 33 represents a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom, or a monovalent aromatic hydrocarbon group having a carbon number of 4 to 25, which optionally has a substituent;
provided that a plurality of k, R 20 or R 31 present in the same compound is optionally the same or different and the total number of carbon atoms contained in the cation moiety in the formulae is 20 or more; and
X − represents a monovalent anion.

12. The method of claim 1 , wherein, during the reacting, the onium salt does not contain an active hydrogen-containing functional group or a salt thereof.

13. The method of claim 1 , wherein the active hydrogen-containing functional group is a hydroxyl group.

14. The method of claim 1 , wherein the active hydrogen-containing functional group is a carboxyl group.

15. The method of claim 1 , wherein the onium salt is an ammonium salt.

16. The method of claim 1 , wherein the onium salt is a pyridinium salt.

17. The method of claim 1 , wherein the onium salt is an imidazolinium salt.

18. The method of claim 1 , wherein the onium salt is a phosphonium salt.

19. A method for producing an epoxy compound, the method comprising:
reacting hydrogen peroxide with a compound having a carbon-carbon double bond in the presence of
at least one compound selected from the group consisting of a tungsten compound and a molybdenum compound; and
an onium salt having 20 or more carbon atoms and containing one or more substituents convertible to an active hydrogen-containing functional group or a salt thereof,

wherein said one or more sub substituents contained in the onium salt is an alkoxycarbonyl group or an acyloxy group.

20. The method of claim 19 , further comprising, after the reacting, converting the one or more substituents contained in the onium salt to an active hydrogen-containing functional group or a salt thereof, wherein the converting is achieved by hydrolyzing said one or more substituents with a basic compound.

21. A method for producing an epoxy compound, the method comprising:
reacting hydrogen peroxide with a compound having a carbon-carbon double bond in the presence of
at least one compound selected from the group consisting of a tungsten compound and a molybdenum compound; and
an onium salt having 20 or more carbon atoms and containing one or more substituents convertible to an active hydrogen-containing functional group or a salt thereof,

wherein said onium salt is a compound represented by any one of formulae (1) to (3):

wherein each of any one or more of R 1 to R 4 , any one or more of R 5 to R 10 and any one or more of R 11 to R 15 independently represents —Y—CO—O—Z or —Y—O—CO—Z,
Y represents a direct bond or a divalent aliphatic hydrocarbon group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom and which optionally has a substituent, and Z represents a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom, or a monovalent aromatic hydrocarbon group having a carbon number of 4 to 25, which optionally has a substituent,
each of R 1 to R 5 , R 11 and R 13 , when these are not —Y—CO—O—Z or —Y—O—CO—Z, independently represents an alkyl group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom and which optionally has a substituent, or a benzyl group,
each of R 6 to R 10 , R 12 ,R 14 and R 15 , when these are not —Y—CO—O—Z or —Y—O—CO—Z, independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom and which optionally has a substituent, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group or an N-alkylsulfamoyl group,
R 1 to R 15 optionally combine in the same compound to form a ring,
provided that the total number of carbon atoms contained in

Assignees

• Mitsubishi Chem Corp

Inventors

• Hosokawa Akemi
• Kusaka Haruhiko

Classifications

• B01J27/16

  containing oxygen {, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr} · CPC title

• C07D213/04

  having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom · CPC title

• C08G59/02

  Polycondensates containing more than one epoxy group per molecule · CPC title

• C07D303/27

  having all hydroxyl radicals etherified with oxirane containing compounds · CPC title

• B01J2231/72

  Epoxidation · CPC title