Methods of mercaptanizing unsaturated compounds and compositions produced therefrom

Patent metadata

Field	Value
Publication number	US-9944803-B2
Application number	US-201514886146-A
Country	US
Kind code	B2
Filing date	Oct 19, 2015
Priority date	Nov 15, 2012
Publication date	Apr 17, 2018
Grant date	Apr 17, 2018

Abstract

The present invention discloses polythiol compositions containing polythiol molecules having both thiol groups and intermolecular sulfide groups. Processes for producing such polythiol compositions also are described.

First claim

We claim:

1. A polythiol composition comprising polythiol molecules having the structures:

2. The composition of claim 1 , further comprising:

3. The composition of claim 1 , wherein polythiol molecules having at least three SH groups have:
an average thiol sulfur to sulfide sulfur molar ratio in a range from 2:1 to 1000:1;
an average of from 0.1 mole % to 33 mole % sulfide sulfur, based on the total sulfur of polythiol molecules having at least three SH groups;
an average of from 67 mole % to 99 mole % thiol sulfur, based on the total sulfur of polythiol molecules having at least three SH groups;
a mercaptan equivalent weight in a range from 120 to 190 g/eq; or
any combination thereof.

4. The composition of claim 1 , wherein polythiol molecules having at least three SH groups have:
an average thiol sulfur to sulfide sulfur molar ratio in a range from 3:1 to 50:1;
an average of from 2 mole % to 20 mole % sulfide sulfur, based on the total sulfur of polythiol molecules having at least three SH groups;
an average of from 75 mole % to 98 mole % thiol sulfur, based on the total sulfur of polythiol molecules having at least three SH groups;
a mercaptan equivalent weight in a range from 122 to 140 g/eq; or
any combination thereof.

5. An adhesive comprising the polythiol composition of claim 1 .

6. The composition of claim 1 , wherein the composition is produced by a process comprising:
1) contacting:
a) pentaerythritol triallyl ether;
b) H 2 S; and
c) a phosphite compound; and

2) forming the polythiol composition;

wherein a molar ratio of H 2 S to carbon-carbon double bonds of pentaerythritol triallyl ether is in a range from 5:1 to 500:1.

7. The composition of claim 6 , 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.

8. The composition of claim 6 , wherein:
the molar ratio of H 2 S to carbon-carbon double bonds of pentaerythritol triallyl ether is in a range from 5:1 to 100:1; and
a molar ratio of the phosphite compound to carbon-carbon double bonds of pentaerythritol triallyl ether is in a range from 0.0005:1 to 0.10:1.

9. The composition of claim 6 , wherein the polythiol composition is formed in the presence of ultraviolet light.

10. The composition of claim 6 , wherein the polythiol composition is formed in the presence of ultraviolet light and a photoinitiator, wherein the photoinitiator is present at an amount in a range from 0.05 to 5 wt. %, based on the weight of pentaerythritol triallyl ether.

11. The composition of claim 6 , 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.

12. The composition of claim 6 , wherein the process further comprises a step of removing at least a portion of the H 2 S, of the phosphite compound, of pentaerythritol triallyl ether, of compounds having two or less sulfur atoms, or combinations thereof, from the polythiol composition.

13. An article of manufacture comprising the polythiol composition of claim 1 .

14. A coating or paint composition comprising an additive and the polythiol composition of claim 1 .

15. The composition of claim 1 , wherein polythiol molecules having at least three SH groups have an average thiol sulfur to sulfide sulfur molar ratio in a range from 2:1 to 1000:1.

16. The composition of claim 1 , wherein polythiol molecules having at least three SH groups have an average thiol sulfur to sulfide sulfur molar ratio in a range from 3:1 to 50:1.

17. The composition of claim 1 , wherein polythiol molecules having at least three SH groups have an average of from 0.1 mole % to 33 mole % sulfide sulfur, based on the total sulfur of polythiol molecules having at least three SH groups.

18. The composition of claim 1 , wherein polythiol molecules having at least three SH groups have an average of from 2 mole % to 20 mole % sulfide sulfur, based on the total sulfur of polythiol molecules having at least three SH groups.

19. The composition of claim 1 , wherein polythiol molecules having at least three SH groups have an average of from 67 mole % to 99 mole % thiol sulfur, based on the total sulfur of polythiol molecules having at least three SH groups.

20. The composition of claim 1 , wherein polythiol molecules having at least three SH groups have an average of from 75 mole % to 98 mole % thiol sulfur, based on the total sulfur of polythiol molecules having at least three SH groups.

21. The composition of claim 1 , wherein polythiol molecules having at least three SH groups have a mercaptan equivalent weight in a range from 120 to 190 g/eq.

22. The composition of claim 1 , wherein polythiol molecules having at least three SH groups have a mercaptan equivalent weight in a range from 122 to 140 g/eq.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Matson Michael S
• Cameron Colin
• Wright Anthony Colin
• Fletcher Ian David

Classifications

• C09D7/1233 Primary

  Chemistry & Metallurgy · mapped topic

• C07D251/34

  Cyanuric or isocyanuric esters · CPC title

• C09J181/04

  Polysulfides · CPC title

• C07C323/12

  the carbon skeleton being acyclic and saturated · CPC title

• C08G59/66

  Mercaptans · CPC title