Methods of mercaptanizing olefinic hydrocarbons and compositions produced therefrom

Patent metadata

Field	Value
Publication number	US-9340715-B2
Application number	US-201514820610-A
Country	US
Kind code	B2
Filing date	Aug 7, 2015
Priority date	Aug 3, 2010
Publication date	May 17, 2016
Grant date	May 17, 2016

Abstract

The present invention discloses processes for forming polythiol compositions from olefinic hydrocarbons such as cyclooctadiene, cyclododecatriene, and trivinylcyclohexane. The polythiol compositions produced from these processes, including the sulfur-containing compounds of these compositions, also are described.

First claim

We claim:

1. A polythiol composition comprising sulfur-containing compounds, wherein the sulfur-containing compounds of the polythiol composition comprise:
from 30 to 85 wt. % tri(2-mercaptoethyl)cyclohexane; and
from 0.1 to 60 wt. % di(2-mercaptoethyl)vinylcyclohexane.

2. The composition of claim 1 , wherein the polythiol composition comprises less than 10 wt. % trivinylcyclohexane.

3. The composition of claim 2 , wherein the sulfur-containing compounds of the polythiol composition comprise from 20 to 55 wt. % di(2-mercaptoethyl)vinylcyclohexane.

4. The composition of claim 1 , wherein the sulfur-containing compounds of the polythiol composition comprise from 0.1 to 10 wt. % di(2-mercaptoethyl)vinylcyclohexane.

5. The composition of claim 1 , wherein the sulfur-containing compounds of the polythiol composition comprise an average of from 0.3 to 6 wt. % sulfide sulfur.

6. The composition of claim 1 , wherein the sulfur-containing compounds of the polythiol composition comprise less than or equal to 5 wt. % (2-mercapto-ethyl)divinylcyclohexane.

7. The composition of claim 1 , wherein a weight ratio of tri(2-mercaptoethyl)cyclohexane to di(2-mercaptoethyl)vinylcyclohexane in the polythiol composition is in a range from 2:1 to 60:1.

8. The composition of claim 1 , wherein a weight ratio of intermolecular sulfide compounds to intramolecular sulfide compounds in the polythiol composition is in a range from 1:1 to 30:1.

9. The composition of claim 1 , wherein the sulfur-containing compounds of the polythiol composition comprise an average of from 22 to 34 wt. % thiol sulfur.

10. A process for forming the polythiol composition of claim 1 , the process comprising:
1) contacting
a) trivinylcyclohexane;
b) H 2 S; and
c) a phosphite compound; and

2) forming the polythiol composition;

wherein a molar ratio of H 2 S to olefinic double bonds of trivinylcyclohexane is in a range from 10:1 to 500:1.

11. The process of claim 10 , wherein the phosphite compound comprises a compound having the formula:
P(OR 1 ) 3 ;

wherein each R 1 is independently a C 1 -C 10 hydrocarbyl group.

12. The process of claim 10 , wherein the phosphite compound comprises trimethylphosphite, triethylphosphite, tributylphosphite, or any combination thereof.

13. The process of claim 10 , wherein:
the molar ratio of H 2 S to olefinic double bonds of trivinylcyclohexane is in a range from 30:1 to 500:1; and
a molar ratio of the phosphite compound to olefinic double bonds of trivinylcyclohexane is in a range from 0.003:1 to 0.10:1.

14. The process of claim 10 , wherein:
the molar ratio of H 2 S to olefinic double bonds of trivinylcyclohexane is in a range from 40:1 to 250:1; and
a molar ratio of the phosphite compound to olefinic double bonds of trivinylcyclohexane is in a range from 0.006:1 to 0.05:1.

15. The process of claim 10 , wherein the polythiol composition is formed in the presence of ultraviolet light.

16. The process of claim 10 , wherein the polythiol composition is formed in the presence of ultraviolet light and a photoinitiator.

17. The process of claim 10 , wherein the polythiol composition is formed at conditions suitable for a thermal decomposition of a free radical initiator.

18. The process of claim 10 , wherein the polythiol composition is formed in the presence of a hydrocarbon solvent, an aromatic hydrocarbon solvent, a ketone solvent, an alcohol solvent, an ether solvent, or any combination thereof.

19. The process of claim 10 , wherein at least 65% of the olefinic double bonds of trivinylcyclohexane have reacted to form a sulfur-containing group.

20. The process of claim 10 , further comprising a step of separating at least a portion of the H 2 S, of the phosphite compound, of trivinylcyclohexane, of compounds having only one sulfur atom, or combinations thereof.

21. The process of claim 20 , wherein the H 2 S, the phosphite compound, trivinylcyclohexane, the compounds having only one sulfur atom, or combinations thereof, are removed by wiped film evaporation, distillation, short path distillation, or a combination thereof.

Assignees

• Chevron Phillips Chemical Co

Inventors

• Matson Michael S
• Cameron Colin
• Marrion Alastair Robert
• Wright Anthony Colin
• Refvik Mitchell D
• Netemeyer Eric J

Classifications

• C07C321/22

  Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of rings other than six-membered aromatic rings · CPC title

• C07C321/06

  of a saturated carbon skeleton containing rings · CPC title

• C09J201/00

  Adhesives based on unspecified macromolecular compounds · CPC title

• C07C2601/20

  the ring being twelve-membered · CPC title

• C09J11/06

  organic · CPC title