Method for the manufacture of cyclododecasulfur

Patent metadata

Field	Value
Publication number	US-10011485-B2
Application number	US-201715440056-A
Country	US
Kind code	B2
Filing date	Feb 23, 2017
Priority date	Mar 2, 2016
Publication date	Jul 3, 2018
Grant date	Jul 3, 2018

Abstract

The present invention relates to a method for the manufacture of cyclododecasulfur, a cyclic sulfur allotrope wherein the number of sulfur (S) atoms in the allotrope's homocyclic ring is 12. The method includes reacting a metallasulfur derivative with an oxidizing agent in a reaction zone to form a cyclododecasulfur-containing reaction mixture.

First claim

The invention claimed is:

1. A method for the manufacture of cyclododecasulfur, comprising reacting a metallasulfur derivative with an oxidizing agent in a reaction zone to form a cyclododecasulfur-containing reaction mixture containing cyclododecasulfur, wherein the oxidizing agent does not add sulfur from its composition to the cyclododecasulfur being produced in the process.

2. The method of claim 1 , wherein the metallasulfur derivative is characterized by the formula:

wherein
L is a monodentate or polydentate ligand species which may be the same or different when x>1;
x is the total number of ligand species and is from 0 to 6 inclusive;
M is a metal atom;
y is the total number of metal atoms and is from 1 to 4 inclusive;
S is a sulfur atom;
z is the number of sulfur atoms, and is from 1 to 12 inclusive;
u represents the charge of the metallasulfur derivative and may be from −6 to +6 inclusive;
v is the number of metallasulfur derivative units in an oligomeric or polymeric structure;
I is an ionic atom or group and may be cationic or anionic;
and w is the number of cationic or anionic atoms or groups, as required to provide charge neutrality.

3. The method of claim 1 , wherein the oxidizing agent is characterized by the formula:
X—X′

wherein X and X′ are the same or different and are selected from the group consisting of halogens and pseudohalogens.

4. The method of claim 1 , wherein the oxidizing agent comprises one or more of SO 2 Cl 2 and SO 2 Br 2 .

5. The method of claim 1 wherein the oxidizing agent comprises one or more of O 2 , H 2 O 2 , an alkyl peroxide, and an acyl peroxide.

6. The method of claim 1 , wherein the stoichiometric ratio of the oxidizing agent to the metallasulfur derivative is selected so that less than one equivalent of the oxidizing agent is present for every two M-S bonds in the metallasulfur derivative.

7. The method of claim 3 , wherein X and X′ are one or more of chlorine and bromine.

8. The method of claim 1 , further comprising a step of reacting elemental sulfur with a sulfur templating agent to form the metallasulfur derivative prior to the step of reacting the metallasulfur derivative with the oxidizing agent.

9. The method of claim 8 , wherein the reacting the elemental sulfur with a sulfur templating agent to form the metallasulfur derivative is carried out in the presence of water.

10. The method of claim 1 , further comprising a step of isolating the cyclododecasulfur from the cyclododecasulfur-containing reaction mixture.

11. The method of claim 10 , wherein the step of isolating the cyclododecasulfur from the cyclododecasulfur-containing reaction mixture comprises one or more steps chosen from dissolving, heat treating, drying, acid treating, solvent washing, crystallizing, and sedimentation.

12. The method of claim 10 , wherein the step of isolating the cyclododecasulfur comprises treating the cyclododecasulfur with a solvent for the cyclododecasulfur to form a dissolution liquor.

13. The method of claim 10 , further comprising removing metal and metal-containing compounds from the cyclododecasulfur by sedimentation of the metal and the metal-containing compounds.

14. The method of claim 1 , further comprising isolating cyclododecasulfur by heating a cyclododecasulfur-containing mixture in the presence of a solvent to decompose and dissolve in the solvent impurities that are present.

15. The method of claim 1 , further comprising isolating cyclododecasulfur by treating a cyclododecasulfur-containing mixture with an acid to remove any metal or metal-containing compounds that are present.

16. The method of claim 12 , further comprising crystallizing cyclododecasulfur from the dissolution liquor.

17. A method for the manufacture of cyclododecasulfur, the method comprising:
(i) reacting cyclooctasulfur, tetramethylethylenediamine, and zinc to form a tetramethylethylenediamine/Zn(S 6 ) complex; and
(ii) reacting the complex with an oxidizing agent.

18. The method of claim 17 , wherein the step of reacting the cyclooctasulfur, the tetramethylethylenediamine, and the zinc to form a tetramethylethylene-diamine/Zn(S 6 ) complex is carried out in the presence of water.

Assignees

• Eastman Chem Co

Inventors

• Barnicki Scott Donald
• Hembre Robert Thomas
• Mackenzie Elaine Beatrice
• Laningham Joy Lynn
• Laningham Michael Richard
• Kirk Shane Kipley
• Blair Larry Wayne
• Chakraborty Sumit
• Bhamidi Venkateswarlu
• Hua Guoxiong
• Woollins John Derek

Classifications

• C07F3/06

  Zinc compounds · CPC title

• C07D341/00

  Heterocyclic compounds containing rings having three or more sulfur atoms as the only ring hetero atoms · CPC title

• C01B17/12

  Insoluble sulfur (mu-sulfur) · CPC title

• C01B17/0253 Primary

  from non-gaseous sulfur compounds other than sulfides or materials containing such sulfides · CPC title

• C01B17/0243

  Other after-treatment of sulfur · CPC title