IP Library Granted Patent US 10,611,637
Granted Patent B2
US 10,611,637 · App. 15/995,574 · Granted Apr 7, 2020

Method for the manufacture of cyclododecasulfur

Inventors: Scott Donald Barnicki (Kingsport, TN); Robert Thomas Hembre (Johnson City, TN); Elaine Beatrice Mackenzie (Enfield, CT); Joy Lynn Laningham (Erwin, TN); Michael Richard Laningham (Erwin, TN); Shane Kipley Kirk (Church Hill, TN); Larry Wayne Blair (Gate City, VA); Sumit Chakraborty (Johnson City, TN); Venkateswarlu Bhamidi (Kingsport, TN); Guoxiong Hua (Fife, GB); John Derek Woollins (Fife, GB)
Assignee: Eastman Chemical Company
C01B17/0253C01B17/0243C01B17/12C07D341/00
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Quick Facts
Patent No.
US 10,611,637
App. No.
15/995,574
Granted
Apr 7, 2020
Kind
B2
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.

Claims (35)

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 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 or pseudohalogens.

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 stoichiometric ratio of the oxidizing agent to the metallasulfur derivative is less than one equivalent of the oxidizing agent present for every two M-S bonds in the metallasulfur derivative.

4. The method of claim 1 , wherein X and X′ are one or more of chlorine and bromine.

5. The method of claim 1 , wherein X and X′ are chlorine.

6. The method of claim 1 , wherein X and X′ are bromine.

7. The method of claim 1 , wherein X and X′ comprise one or more of a cyanide, a thiocyanide, a sulfate, a thiosulfate, a sulfonate, or a thiosulfonate.

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, 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 or pseudohalogens.

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.

Assignments (8)
RELEASE OF SECURITY INTEREST Recorded May 23, 2025
From: ROYAL BANK OF CANADA, AS ADMINISTRATIVE AGENT AND AS COLLATERAL AGENT
To: FLEXSYS HOLDINGS, INC.
Reel/Frame 071358/0859 →
RELEASE OF SECURITY INTEREST Recorded May 23, 2025
From: RIVER FINANCE HOLDINGS, LLC, AS COLLATERAL AGENT
To: FLEXSYS HOLDINGS, INC.
Reel/Frame 071210/0337 →
FIRST LIEN PATENT SECURITY AGREEMENT Recorded Dec 27, 2024
From: FLEXSYS HOLDINGS, INC.
To: RIVER FINANCE HOLDINGS, LLC, AS COLLATERAL AGENT
Reel/Frame 069791/0623 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 1, 2022
From: EASTMAN CHEMICAL COMPANY
To: FLEXSYS HOLDINGS, INC.
Reel/Frame 060423/0395 →
SECURITY INTEREST Recorded Nov 1, 2021
From: FLEXSYS HOLDINGS, INC.
To: ROYAL BANK OF CANADA
Reel/Frame 057978/0662 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 4, 2018
From: THE UNIVERSITY COURT OF THE UNIVERSITY OF ST. ANDREWS
To: EASTMAN CHEMICAL COMPANY
Reel/Frame 045972/0263 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 1, 2018
From: 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
To: EASTMAN CHEMICAL COMPANY
Reel/Frame 045962/0152 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 1, 2018
From: HUA, GUOXIONG; WOOLLINS, JOHN DEREK
To: THE UNIVERSITY COURT OF THE UNIVERSITY OF ST. ANDREWS
Reel/Frame 045962/0474 →
Continuity (3)
Continuation 15440056 · Feb 23, 2017
Provisional Application 62302213 · Mar 2, 2016
Related Publication 20180273382A1 · Sep 27, 2018