Polythiols with carbamate groups

Patent metadata

Field	Value
Publication number	US-9469607-B2
Application number	US-201514636747-A
Country	US
Kind code	B2
Filing date	Mar 3, 2015
Priority date	Mar 3, 2015
Publication date	Oct 18, 2016
Grant date	Oct 18, 2016

Abstract

The present invention discloses polythiol compositions containing sulfur-containing compounds with carbamate groups, and to methods for producing such polythiol compositions. These polythiol compositions can be synthesized via the reaction of an isocyanate with an allyl ether alcohol, followed by thiolation with H 2 S, and these polythiol compositions are often used in formulations for adhesives, paints, and coatings.

First claim

We claim:

1. A polythiol composition comprising sulfur-containing compounds having formula (I):

each R independently is a C 3 to C 15 hydrocarbon group;
each R 1 independently is a C 1 to C 30 hydrocarbon group;
n is an integer greater than or equal to 2; and
m is an integer from 0 to 6, wherein an average value of m in the composition is from greater than 0 to 3.

2. The composition of claim 1 , wherein:
each R independently is a C 3 to C 15 alkane group;
each R 1 independently is a substituted or unsubstituted C 5 to C 20 cycloalkane group;
n is an integer from 2 to 4; and
m is an integer from 0 to 4, wherein an average value of m in the composition is from greater than 0 to 2.

3. The composition of claim 1 , wherein:
each R is the same and is a C 3 to C 12 alkane group;
each R 1 is the same and is a substituted or unsubstituted C 6 to C 12 cycloalkane group;
n is an integer from 2 to 4; and
m is an integer from 0 to 3, wherein an average value of m in the composition is from greater than 0 to 1.

4. The composition of claim 3 , wherein n is equal to 2.

5. The composition of claim 1 , wherein the sulfur-containing compounds are characterized by:
an average thiol sulfur to sulfide sulfur molar ratio in a range from 2:1 to 500:1;
an average of from 0.05 wt. % to 10 wt. % sulfide sulfur;
an average of from 12.5 wt. % to 16.2 wt. % thiol sulfur;
a thiol equivalent weight in a range from 198 to 300 g/eq; and
an average thiol functionality in a range from 4.05 to 6.

6. The composition of claim 1 , wherein the sulfur-containing compounds are characterized by:
an average thiol sulfur to sulfide sulfur molar ratio in a range from 3:1 to 100:1;
an average of from 0.1 wt. % to 5 wt. % sulfide sulfur;
an average of from 13 wt. % to 16 wt. % thiol sulfur;
a thiol equivalent weight in a range from 200 to 250 g/eq; and
an average thiol functionality in a range from 4.05 to 5.

7. The composition of claim 6 , wherein n is equal to 2.

8. The composition of claim 1 , wherein the sulfur-containing compounds contain from 5 wt. % to 70 wt. % compounds having a sulfide sulfur group.

9. The composition of claim 1 , wherein the sulfur-containing compounds contain from 30 wt. % to 95 wt. % compounds having a thiol sulfur group and no sulfide sulfur group.

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

11. The article of claim 10 , wherein the article is a coating, a paint, or an adhesive.

12. The composition of claim 1 , wherein the sulfur-containing compounds of the polythiol composition comprise:

13. The composition of claim 12 , further comprising a sulfur-containing compound having the structure

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

15. A process for producing a polythiol composition, the process comprising:
(1) contacting a compound having the formula

with a compound having the formula

to form a reaction mixture comprising a polycarbamate; and
(2) contacting the polycarbamate, H 2 S, and an optional phosphite compound to form the polythiol composition; wherein:
a molar ratio of H 2 S to carbon-carbon double bonds of the polycarbamate is in a range from 2:1 to 500:1; and
the polythiol composition comprises sulfur-containing compounds having formula (I):

each R independently is a C 3 to C 15 hydrocarbon group;
each R 1 independently is a C 1 to C 30 hydrocarbon group;
n is an integer greater than or equal to 2; and
m is an integer from 0 to 6, wherein an average value of m in the composition is from greater than 0 to 3.

16. The process of claim 15 , wherein:
the molar ratio of H 2 S to carbon-carbon double bonds of the polycarbamate is in a range from 10:1 to 150:1; and
the polythiol composition is formed in the presence of ultraviolet light.

17. The process of claim 15 , wherein the polycarbamate comprises a compound having formula (D):

wherein:
each R independently is a C 3 to C 15 hydrocarbon group; and
R 1 is C 1 to C 30 hydrocarbon group.

18. The process of claim 15 , wherein the polycarbamate comprises:

19. The process of claim 15 , wherein:
the compound having formula (A) comprises:

and
the compound having formula (B) comprises:

20. The process of claim 15 , wherein the process further comprises a step of removing at least a portion of the H 2 S, of the optional phosphite compound, of compounds having no sulfur atoms, or combinations thereof, from the polythiol composition.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Upshaw Thomas A
• Matson Michael S

Classifications

• C07C271/24

  with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring · CPC title

• C08G18/6715

  Unsaturated monofunctional alcohols or amines · CPC title

• C07C271/10

  with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms · CPC title

• C08G18/2835

  having less than 5 ether groups · CPC title

• C07C323/12 Primary

  the carbon skeleton being acyclic and saturated · CPC title