Mercaptanized Vinylnorbornene Compositions and Methods of Making Same

Patent metadata

Field	Value
Publication number	US-2016222155-A1
Application number	US-201514608782-A
Country	US
Kind code	A1
Filing date	Jan 29, 2015
Priority date	Jan 29, 2015
Publication date	Aug 4, 2016
Grant date	—

Abstract

The present invention discloses polythiol compositions containing intermolecular sulfide compounds and at least one of 5-(2-mercaptoethyl)norbornane-2-thiol and 5-(2-mercaptoethyl)norbornane-3-thiol. These polythiol compositions can be derived from 5-vinylnorborn-2-ene, and are often used in formulations for adhesives and other end-use applications.

First claim

We claim:

1 . A polythiol composition comprising sulfur-containing compounds, the sulfur-containing compounds comprising:
(i) 5-(2-mercaptoethyl)norbornane-2-thiol and/or 5-(2-mercaptoethyl)norbornane-3-thiol; and (ii) one or more sulfide molecules having only two thiol sulfur groups (—SH), only one intermolecular sulfide group (—S—), and only two groups independently selected from a 5-(ethyl-2-yl)norborn-2-yl group and a 5-(ethyl-2-yl)norborn-3-yl group.

2 . The composition of claim 1 , wherein the sulfur-containing compounds further comprise one or more sulfide molecules having only two thiol sulfur groups, only two intermolecular sulfide groups, and only three groups independently selected from a 5-(ethyl-2-yl)norborn-2-yl group and a 5-(ethyl-2-yl)norborn-3-yl group.

3 . 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 1.5:1 to 1000:1; an average of from 0.1 wt. % to 10 wt. % sulfide sulfur; an average of from 20 wt. % to 34 wt. % thiol sulfur; and a mercaptan equivalent weight in a range from 95 to 150 g/eq.

4 . 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 40:1; an average of from 1 wt. % to 8 wt. % sulfide sulfur; and an average of from 22 wt. % to 32 wt. % thiol sulfur.

5 . The composition of claim 1 , wherein:
the polythiol composition contains less than 1 wt. % 5-vinylnorborn-2-ene; and the sulfur-containing compounds contain less than 1 wt. % mono-sulfur compounds.

6 . The composition of claim 1 , wherein the sulfur-containing compounds contain from 50 wt. % to 95 wt. % 5-(2-mercaptoethyl)norbornane-2-thiol and 5-(2-mercaptoethyl)norbornane-3-thiol, in total.

7 . The composition of claim 1 , wherein the sulfur-containing compounds contain from 5 wt. % to 35 wt. % intermolecular sulfide compounds.

8 . The composition of claim 1 , wherein the sulfur-containing compounds have a weight ratio of 5-(2-mercaptoethyl)norbornane-2-thiol and 5-(2-mercaptoethyl)norbornane-3-thiol, in total, to intermolecular sulfide compounds in a range from 1.2:1 to 8:1.

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

10 . The article of claim 9 , wherein the article further comprises a substrate.

11 . A polythiol composition comprising sulfur-containing compounds, the sulfur-containing compounds comprising:
5-(2-mercaptoethyl)norbornane-2-thiol and/or 5-(2-mercaptoethyl)norbornane-3-thiol; wherein the sulfur-containing compounds of the polythiol composition have a weight percentage of intermolecular sulfide compounds in a range from 2 wt. % to 90 wt. %.

12 . The composition of claim 11 , wherein:
the polythiol composition contains less than 1 wt. % 5-vinylnorborn-2-ene; and the sulfur-containing compounds contain less than 1 wt. % mono-sulfur compounds and from 5 wt. % to 35 wt. % intermolecular sulfide compounds.

13 . An article of manufacture comprising the polythiol composition of claim 11 .

14 . A polythiol composition comprising sulfur-containing compounds, the sulfur-containing compounds comprising:
5-(2-mercaptoethyl)norbornane-2-thiol and/or 5-(2-mercaptoethyl)norbornane-3-thiol; wherein the sulfur-containing compounds of the polythiol composition have an average thiol sulfur to sulfide sulfur molar ratio in a range from 1.5:1 to 1000:1.

15 . The composition of claim 14 , wherein the sulfur-containing compounds are characterized by:
an average thiol sulfur to sulfide sulfur molar ratio in a range from 2:1 to 40:1; an average of from 1 wt. % to 8 wt. % sulfide sulfur; and an average of from 22 wt. % to 32 wt. % thiol sulfur.

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

17 . A process for producing a polythiol composition, the process comprising:
1) contacting:
a) 5-vinylnorborn-2-ene;
b) H 2 S; and
c) optionally, a phosphite compound; and
2) forming the polythiol composition;
wherein a molar ratio of H 2 S to carbon-carbon double bonds of the 5-vinylnorborn-2-ene is in a range from 2:1 to 500:1.

18 . The process of claim 17 , wherein:
the molar ratio of H 2 S to carbon-carbon double bonds of the 5-vinylnorborn-2-ene is in a range from 3:1 to 50:1; and the polythiol composition is formed in the presence of ultraviolet light.

19 . The process of claim 17 , wherein the process further comprises a step of removing at least a portion of the H 2 S, of the optional phosphite compound, of the 5-vinylnorborn-2-ene, of compounds having only one sulfur atom, or combinations thereof, from the polythiol composition.

20 . The process of claim 19 , wherein the H 2 S, the optional phosphite compound, the 5-vinylnorborn-2-ene, 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 Lp

Inventors

• Matson Michael S
• Cameron Colin
• Marrion Alastair R
• Wright Anthony C

Classifications

• C08G75/02

  Polythioethers · CPC title

• C08L81/00

  Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers · CPC title

• C09J181/00

  Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers · CPC title

• C08L81/02

  Polythioethers; Polythioether-ethers · CPC title

• C08G75/00 Primary

  Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule · CPC title