Method for preparing polyarylene sulfide (PAS) monomer

Patent metadata

Field	Value
Publication number	US-10377705-B2
Application number	US-201615388215-A
Country	US
Kind code	B2
Filing date	Dec 22, 2016
Priority date	Jan 11, 2016
Publication date	Aug 13, 2019
Grant date	Aug 13, 2019

Abstract

A method for preparing a cationic sulfoxide intermediate having the following formula

wherein Ar 1 and Ar 2 are substituted or unsubstituted aryl groups that are the same or different, includes reacting hydrogen peroxide with (i) a compound having the following formula (2) or sulfonic acid R′SO 3 H, wherein R′ is CH 3 , CF 3 , phenyl, toluene, or OH, and (ii) a cationic thioether intermediate having the following formula (4) to obtain the cationic sulfoxide intermediate:

wherein R is a substituted or unsubstituted C 1 -C 6 alkyl group; and

wherein Ar 1 and Ar 2 are as defined above and Y is an anion.

First claim

The invention claimed is:

1. A method for preparing a polyarylene sulfide monomer having the following formula (7):

wherein Ar 1 and Ar 2 are substituted or unsubstituted aryl groups that are the same or different, comprising:
reacting hydrogen peroxide with (i) R′SO 3 H, wherein R′ is CH 3 , CF 3 , phenyl, or toluene, or OH, and (ii) a cationic thioether intermediate having the following formula (4)
to obtain a cationic sulfoxide intermediate having the following formula (1):

wherein Ar 1 and Ar 2 are as defined above and Y is an anion; and
demethylating the cationic sulfoxide intermediate to obtain the polyarylene sulfide monomer.

2. The method of claim 1 , wherein the cationic thioether intermediate is prepared by the method comprising:
reacting a compound having the following formula (5):

and a compound having the following formula (6):

in acidic conditions wherein Ar 1 and Ar 2 are substituted or unsubstituted aryl groups that are the same or different.

3. A method for preparing a polyarylene sulfide having the following formula (8):

comprising:
polymerizing a polyarylene sulfide monomer prepared by the method according to claim 1 ;
wherein Ar 1 and Ar 2 are substituted or unsubstituted aryl groups that are the same or different and n is 1 to 1000.

4. The method according to claim 1 , wherein Ar 1 and Ar 2 are phenyl groups.

5. The method according to claim 1 , wherein R is a methyl group.

6. The method according to claim 1 , wherein the method does not use a halogen.

7. The method of claim 2 , wherein the compound having the formula (5) is thioanisole or methyl biphenyl sulfide.

8. The method of claim 2 , wherein the compound having the formula (6) is methylphenyl sulfoxide.

9. The method of claim 2 , wherein the acidic conditions are produced by adding methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, sulfuric acid, or trifluoromethane sulfonic acid.

10. The method of claim 1 , wherein a molar ratio of hydrogen peroxide to R′SO 3 H is 2:1 to 4:1.

11. The method according to claim 1 , wherein said method consists of:
reacting the hydrogen peroxide with (i) R′SO 3 H, and (ii) the cationic thioether intermediate having formula (4) to obtain the cationic sulfoxide intermediate; and
demethylating the cationic sulfoxide intermediate to obtain the polyarylene sulfide monomer.

12. The method according to claim 1 , wherein the hydrogen peroxide is reacted with R′SO 3 H, wherein R′ is CH 3 , CF 3 , phenyl, or toluene.

Assignees

• Ind Tech Res Inst

Inventors

• Ho Po-Hsien
• Lin Chih-Hsiang
• Chen Meng-Hsin
• Fan Cheng-Hsing
• Kao Hsin-Ching
• Chang Yih-Her

Classifications

• C07C319/14 Primary

  of sulfides · CPC title

• C08G75/025

  Preparatory processes · CPC title

• C08G75/0204

  Polyarylenethioethers · CPC title

• C07C381/12 Primary

  Sulfonium compounds · CPC title

• C07C323/65

  containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton · CPC title