Methods for producing thiol compounds and sulfide compounds using diphenylamine or a phenol compound

Patent metadata

Field	Value
Publication number	US-10501408-B2
Application number	US-201816210404-A
Country	US
Kind code	B2
Filing date	Dec 5, 2018
Priority date	Sep 12, 2016
Publication date	Dec 10, 2019
Grant date	Dec 10, 2019

Abstract

The present invention discloses processes for producing a thiol compound or a sulfide compound from an olefin compound. Diphenylamine or a phenol compound can be used to increase the rate of conversion of the olefin compound to the thiol compound or the sulfide compound.

First claim

I claim:

1. A process for producing a thiol compound, the process comprising:
i) contacting:
a) an olefin compound;
b) H 2 S;
c) diphenylamine and/or a phenol compound; and
d) a photoinitiator and/or a free radical initiator; and

ii) forming the thiol compound.

2. The process of claim 1 , wherein the phenol is an alkyl phenol.

3. The process of claim 1 , wherein a molar ratio of H 2 S to carbon-carbon double bonds of the olefin compound is from about 2:1 to about 150:1.

4. The process of claim 1 , wherein:
an amount of diphenylamine and/or the phenol compound is in a range from about 0.1 wt. % to about 1 wt. %, based on the weight of the olefin compound; and
an amount of the photoinitiator and/or the free radical initiator is in a range from about 0.05 wt. % to about 5 wt. %, based on the weight of the olefin compound.

5. The process of claim 1 , wherein the thiol compound is formed in the presence of ultraviolet light.

6. The process of claim 1 , wherein the olefin compound comprises ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, 1-dodecene, styrene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, or any combination thereof.

7. The process of claim 1 , wherein the olefin compound comprises limonene, butadiene, isoprene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cyclooctadiene, norbornadiene, vinylcyclohexene, vinylnorbornene, divinylbenzene, cyclopentadiene dimer, trivinylcyclohexane, trivinylbenzene, cycloheptatriene, dimethyl heptatriene, octatriene, cyclooctatriene, cyclododecatriene, cyclooctatetraene, cyclododecatetraene, a polybutadiene, or any combination thereof.

8. The process of claim 1 , wherein the process comprises:
contacting the olefin compound, H 2 S, diphenylamine, and the photoinitiator; and
forming the thiol compound in the presence of ultraviolet light;
wherein a molar percent conversion of the olefin compound is at least about 90%; and
wherein a percent conversion of the olefin compound is greater than a percent conversion obtained by conducting the process without diphenylamine, under the same reaction conditions.

9. The process of claim 1 , wherein the process comprises:
contacting the olefin compound, H 2 S, the phenol compound, and the photoinitiator; and
forming the thiol compound in the presence of ultraviolet light;
wherein a percent conversion of the olefin compound is greater than a percent conversion obtained by conducting the process without the phenol compound, under the same reaction conditions.

10. The process of claim 1 , wherein a molar percent conversion of the olefin compound is at least about 90%.

11. The process of claim 1 , wherein the process further comprises a step of removing at least a portion of the olefin compound, of the H 2 S, of the diphenylamine and/or the phenol compound, of the photoinitiator and/or the free radical initiator, or combinations thereof, from the thiol compound.

12. The process of claim 1 , wherein the thiol compound is formed in the presence of a solvent.

13. The process of claim 1 wherein at least 65% of the carbon-carbon double bonds of the olefin compound react to form a thiol group.

14. A process for producing a sulfide compound, the process comprising:
i) contacting:
a) an olefin compound;
b) a mercaptan compound; and
c) diphenylamine and/or a phenol compound; and

ii) forming the sulfide compound;
wherein an amount of diphenylamine and/or the phenol compound is in a range from about 0.05 wt. % to about 5 wt. %, based on the weight of the olefin compound.

15. The process of claim 14 , wherein a molar ratio of —SH of the mercaptan compound to carbon-carbon double bonds of the olefin compound is in a range from about 2:1 to about 1:2.

16. The process of claim 14 , wherein the mercaptan compound comprises methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, t-butyl mercaptan, n-pentyl mercaptan, phenyl mercaptan, mercaptomethanol, 2-mercaptoethanol, 3-mercaptopropanol, 4-mercaptobutanol, 5-mercaptopentanol, 6-mercaptohexanol, or any combination thereof.

17. The process of claim 14 , wherein the amount of diphenylamine and/or the phenol compound is in a range from about 0.1 wt. % to about 1 wt. %, based on the weight of the olefin compound.

18. The process of claim 14 , wherein the process comprises:
contacting the olefin compound, the mercaptan compound, diphenylamine, and a photoinitiator and/or free radical initiator; and
forming the sulfide compound in the presence of ultraviolet light;
wherein a percent conversion of the olefin compound is greater than a percent conversion obtained by conducting the process without diphenylamine, under the same reaction conditions.

19. The process of claim 14 , wherein the process comprises:
contacting the olefin compound, the mercaptan compound, the phenol compound, and a photoinitiator and/or free radical initiator; and
forming the sulfide compound in the presence of ultraviolet light;
wherein a percent conversion of the olefin compound is greater than a percent conversion obtained by conducting the process without the phenol compound, under the same reaction conditions.

20. A process for producing a sulfide compound, the process comprising:
i) contacting:
a) an olefin compound;
b) a mercaptan compound; and
c) diphenylamine and/or a phenol compound; and

ii) forming the sulfide compound;
wherein a molar percent conversion of the olefin compound is at least about 90%.

21. The process of claim 20 , wherein the process comprises:
contacting the olefin compound, the mercaptan compound, diphenylamine, and a photoinitiator and/or free radical initiator; and
forming the sulfide compound in the presence of ultraviolet light.

22. The process of claim 20 , wherein the process comprises:
contacting the olefin compound, the mercaptan compound, the phenol compound, and a photoinitiator and/or free radical initiator; and
forming the sulfide compound in the presence of ultraviolet light.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Lassen Kenneth M

Classifications

• C07C2601/14

  The ring being saturated · CPC title

• C07C319/04 Primary

  by addition of hydrogen sulfide or its salts to unsaturated compounds · CPC title

• C07C321/04

  of an acyclic saturated carbon skeleton · CPC title

• C07C321/16

  of a saturated carbon skeleton containing rings · CPC title

• C07C319/18 Primary

  by addition of thiols to unsaturated compounds · CPC title