Manufacture of an epoxyethyl ethers or glycidyl ethers

• US 9,145,378 B2
• Filed: 01/26/2011
• Issued: 09/29/2015
• Est. Priority Date: 02/02/2010
• Status: Active Grant

• Current Assignee: Westlake Epoxy Incorporated (TTWF LP)
• Original Assignee: Hexion Incorporated (Hexion Intermediate Holding 2, Inc.)
• Inventors: Muppa, Prasad, Postma, Ron, Schoolderman, Caspar, Rens, Sandra, Stoitsas, Kostas
• Primary Examiner(s): Oh, T. Victor
• Application Number:
  US13/574,704
• Publication Number:
  US 20120330041A1
• Time in Patent Office: 1,707 Days
• Field of Search: 549/524, 549/531, 549/523
• US Class Current: 1/1
• CPC Class Codes: C07D 301/12 with hydrogen peroxide or inorganic peroxides or peracids

Abstract

Processes are provided for the formation of an epoxyethyl ether or a glycidyl ether. In one embodiment, a process is provided for the manufacture of an epoxyethyl ether or glycidyl ether including reacting a vinyl ether or an allyl ether with an oxidant in the presence of a water-soluble manganese complex in an aqueous reaction medium, wherein the water-soluble manganese complex comprises an oxidation catalyst, characterized in that the water-soluble manganese complex is a mononuclear complex of the general formula (I): [LMnX₃]Y (I), or a binuclear complex of the general formula (II): [LMn(μ-X)₃MnL](Y)_n (II), wherein Mn is a manganese; L or each L independently is a polydentate ligand, each X independently is a coordinating species and each μ-X independently is a bridging coordinating species, Y is a non-coordinating counter ion, and wherein the epoxidation is carried out at a pH in the range of from 1.0 to 6.0. The invention also relates to epoxyethyl ethers.

Claims

1. A process for the manufacture of an epoxyethyl ether or a glycidyl ether, comprising:

reacting a vinyl ether or an allyl ether with an oxidant in the presence of a water-soluble manganese complex in an aqueous reaction medium, wherein the water-soluble manganese complex comprises an oxidation catalyst, characterized in that the water-soluble manganese complex is a mononuclear complex of the formula (I);

[LMnX₃]Y 

 

(I)

or a binuclear complex of the formula (II);

[LMn(μ

-X)₃MnL](Y)_n 

 

(II)

wherein Mn is a manganese;

L or each L independently is a polydentate ligand, each X independently is a coordinating species and each μ

-X independently is a bridging coordinating species, wherein Y is an anion, n is 1 or 2, and wherein the reaction is performed at a pH in the range of from 1.0 to 6.0 and the molar ratio of the vinyl ether or the allyl ether to the oxidant is from an excess vinyl ether or the allyl ether to 12;

1, wherein each polydentate ligand is independently selected from acyclic compounds having at least 7 atoms in the backbone or cyclic compounds having at least 9 atoms in the ring, wherein each polydentate ligand having 3 nitrogen atoms with the nitrogen atoms separated by at least two carbon atoms, and wherein the oxidant comprises hydrogen peroxide, dilute hydrogen peroxide, or is selected from group consisting of organic peroxides, peracids, and combinations thereof.

2. The process of claim 1 wherein each X is independently a coordinating species and each μ

-X is independently a bridging coordinating species, selected from the group consisting of;

RO⁻

, Cl⁻

, Br⁻

, I⁻

, F⁻

, NCS⁻

, N₃ ⁻

, I₃⁻

, NH₃, NR₃, RCOO⁻

, RSO₃<sup>−

, RSO</sup>₄⁻

, OH⁻

, O²⁻

, O₂<sup>2−

, HOO−</sup>

, H₂O , SH⁻

, CN⁻

, OCN⁻

, and S₄²⁻

and combinations thereof, wherein R is a C₁-C₂₀ radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof.

3. The process of claim 1, wherein each polydentate ligand is independently selected from triazacyclononane and 1,4,7-trimethyl-1,4,7,-triazacyclononane.

4. The process of claim 1, wherein a binuclear water-soluble manganese complex is used as an oxidation catalyst.

5. The process of claim 1, wherein the catalyst is used in a molar ratio of catalyst (Mn) versus the oxidant of from 1:

10 to 1;

10,000,000.

6. The process of claim 1, wherein the aqueous reaction medium is a water phase, comprising less than 10% by volume of co-solvents.

7. The process of claim 1, wherein the aqueous reaction medium further comprises an organic acid-salt combination buffer system.

8. The process of claim 1, wherein the reaction is carried out at temperatures in the range from −

5°

C. and 40°

C.

9. The process of claim 1, wherein the oxidant comprises hydrogen peroxide and is an aqueous solution in a concentration of from 15% to 98%.

10. The process of claim 1, wherein the vinyl ether or the allyl ether is a mono alcohol, a diol, a triol a tetraol or a polyol molecule having one or more ether groups within the molecule.

11. The process of claim 10, wherein the vinyl ether or the allyl ether is an aliphatic or aromatic alcohol.

12. The process of claim 1, wherein the vinyl ether or the allyl ether having the formulae:

O(CH═

CH₂)₂;

R(OCH═

CH₂)₂;

O(CH₂CH═

CH₂)₂;

R(OCH₂CH═

CH₂)₂;

R′

OCH═

CH₂;

or

R′

OCH₂CH═

CH₂;

wherein R is a radical of 1 to 20 carbon atoms optionally having one or more heteroatoms and R′

is a divalent radical of 1 to 20 carbon atoms.

13. The process of claim 1, wherein the vinyl ether or allyl ether is selected from ethers of aliphatic alcohols, polyglycols, fatty alcohols, carbohydrates, benzyl alcohols, phenol, phenol derivatives, novalac resins, and combinations thereof, wherein the phenol derivatives are selected from the group consisting of phenol, 4-tert-butylphenol, 2,4-dibromophenol, 4-(1,1,3,3)-tetramethylbutylphenol, 4-(2-phenylisopropyl)phenol, nonylphenol, o-cresol, p-methoxyphenol, bisphenol A, tetra-bromo bisphenol A, bisphenol S, bisphenol F, bisphenol P, bisphenol M, p-tert butyl phenol, resorcine, styrenated phenol, tetraphenyloethane, trisphenol, benzyl alcohol, and combinations thereof, hydrogenated versions thereof, and halogenated versions thereof.

14. The process of claim 12, wherein the vinyl ether or allyl ether is selected from the group consisting of divinyl ether, diallyl ether, allyl n-butyl ether, n-butyl vinyl ether, vinyl allyl ether, ethyl vinyl ether, ethylene divinyl diether, and combinations thereof.

15. The process of claim 1, wherein the hydrogen peroxide is added to the aqueous reaction medium at a rate about equal to the reaction rate of the catalytic oxidation.

16. The process of claim 1, wherein the molar ratio of the a vinyl ether or the allyl ether to the oxidant is from 2:

1 to about 12;

1.

18. The process of claim 1, wherein the anion is selected from the group consisting of RO⁻

, Cl⁻

, Br⁻

, I⁻

, F⁻

, SO₄²⁻

, RCOO⁻

, PF₆⁻

, tosylate, triflate (CF₃SO₃ ⁻

) and a combination thereof with R once again being a C₁ to C₂₀ radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combination thereof.

19. The process of claim 1, wherein the aqueous reaction medium has a pH in the range of from 2.0 to 5.0.

17. A process for the manufacture of an N-glycid compound, comprising:

reacting a N-allylamine with an oxidant in the presence of a water-soluble manganese complex in an aqueous reaction medium, wherein the water-soluble manganese complex comprises an oxidation catalyst, characterized in that the water-soluble manganese complex is a mononuclear complex of the formula (I);

[LMnX₃]Y 

 

(I)

or a binuclear complex of the formula (II);

[LMn(μ

-X)₃MnL](Y)_n 

 

(II)

wherein Mn is a manganese;

L or each L independently is a polydentate ligand, each X independently is a coordinating species and each μ

-X independently is a bridging coordinating species, n is 1 or 2, and wherein Y comprises an anion selected from the group consisting of RO⁻

, Cl⁻

, Br⁻

, I⁻

, F⁻

, SO₄²⁻

, RCOO⁻

, PF₆⁻

, tosylate, triflate (CF₃SO₃⁻

) and a combination thereof with R once again being a C₁ to C₂₀ radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combination thereof, wherein the molar ratio of the N-allylamine to the oxidant is from 1;

1 to 12;

1.