Polymerization of silyl- and fluoro-containing monomers

Patent metadata

Field	Value
Publication number	US-10717820-B2
Application number	US-201615738831-A
Country	US
Kind code	B2
Filing date	Jun 22, 2016
Priority date	Jun 22, 2015
Publication date	Jul 21, 2020
Grant date	Jul 21, 2020

Abstract

Condensation of fluoro-substituted and silyl-substituted monomers provides polymers suitable for use, e.g., as engineering polymers. A monomer composition is condensed in the presence of a bifluoride or poly(hydrogen fluoride) fluoride salt. The monomer composition contains a compound of formula F-X-F and a compound of formula (R1)3Si—Z—Si(R1)3, and forms an alternating X-Z polymer chain and a silyl fluoride byproduct. X has the formula -A(-R2-A)n-; each A is SO2, C(═O), or Het; R2 is an organic moiety; n is 0 or 1; Het is an aromatic nitrogen heterocycle; Z has the formula -L-R3-L-; each L is O, S, or N(R4); and each R3 is an organic moiety, and R4 comprises H or an organic moiety.

First claim

We claim:

1. A polymerization method comprising the step of combining a liquid monomer composition and a catalyst comprising a salt of formula (R + )(F(HF) w − ), wherein R + is an organic cation or a chelated metal cation, and w is 1 or greater to form a polymer therefrom;
wherein the monomer composition comprises at least one compound of formula F-X-F and at least one compound of formula (R 1 ) 3 Si—Z—Si(R 1 ) 3 ;
each R 1 independently is a hydrocarbyl group;
X has the formula -A(-R 2 -A)n-;
each A independently is SO 2 , C(═O), or Het;
R 2 comprises a first organic moiety;
n is 0 or 1;
Het is an aromatic heterocycle comprising at least two carbon atoms and at least one nitrogen atom in a heteroaromatic ring thereof, and when A is Het, the F substituent is attached to a carbon atom of the heteroaromatic ring thereof;
Z has the formula -L-R 3 -L-;
each L independently is O, S, or N(R 4 );
R 3 comprises a second organic moiety;
each R 4 independently is H or a third organic moiety; and
wherein the F and(R 1 ) 3 Si substituents form a silyl fluoride byproduct of formula (R 1 ) 3 Si—F as the respective A and L groups of the monomers condense to form an X-Z polymer chain.

2. The method of claim 1 , wherein R + is selected from an organosulfonium ion, an organophosphonium ion, a quaternary ammonium ion, a quaternized nitrogen heteroaromatic ion, a cationic polymer, and a chelated metal ion.

3. The method of claim 1 , wherein R + comprises an organophosphonium ion.

4. The method of claim 1 , wherein R + comprises a quaternary ammonium ion.

5. The method of claim 1 , wherein R + comprises a quaternized heteroaromatic ion.

6. The method of claim 1 , wherein R + comprises an organosulfonium ion.

7. The method of claim 1 , wherein:
each R 1 independently is an alkyl or aryl group;
X has the formula -A(-R 2 -A)n-;
each A is SO 2 ;
R 2 comprises a first organic moiety;
n is 0 or 1;
Z has the formula -L-R 3 -L-;
each L independently is O; and
R 3 comprises a second organic moiety comprising at least one aryl or heteroaryl group directly bonded to each L.

8. The method of claim 1 , wherein the n is 0.

9. The method of claim 1 , wherein Het is a 1,3,5-triazine.

10. The method of claim 1 , wherein the monomer composition includes a compound in which X includes an additional F substituent on a sulfonyl, carbonyl, or heteroaryl activating group, A, such that the additional F substituent also reacts with a (R 1 ) 3 Si substituent on an oxygen, sulfur or nitrogen atom linking group, L, to form a silyl fluoride, and the activating group condenses with the linking group to introduce a branch point in the polymer.

11. The method of claim 1 , wherein the monomer composition includes a compound in which Z includes an additional silyl substituent, (R 1 ) 3 Si, on an oxygen, sulfur or nitrogen atom linking group, L, such that the additional silyl substituent also reacts with a F substituent on a sulfonyl, carbonyl, or heteroaryl activating group, A, to form a silyl fluoride and the linking group condenses with the activating group to introduce a branch point in the polymer.

12. The method of claim 1 , wherein n is 1; R 2 is -L 1 -R 5 -L 1 -; each L 1 independently is selected from the group consisting of O, S, and N(R 4 ); and each R 4 independently is H or the third organic moiety, and R 5 comprises an organic moiety.

13. The method of claim 1 , wherein n is 1; R 2 is -L-R 5 —; L 1 is selected from the group consisting of O, S, and N(R 4 ); R 4 s H or the third organic moiety; and R 5 is an organic moiety.

14. The method of claim 1 , wherein the catalyst comprises tris(dimethylamino)sulfonium bifluoride.

15. The method of claim 1 , wherein each A is SO 2 .

16. The method of claim 1 , wherein each R 2 comprises an aryl or heteroaryl moiety either directly bonded to an A group or bonded to A via an oxygen atom attached to the aryl or heteroaryl moiety.

17. The method of claim 1 , wherein the X-Z polymer chain is represented by a formula selected from the group consisting of:
(-A(-R 2 -A) n -L-R 3 -L) x -;  Formula (I):

(-A-R 2 -A-L-R 3 -L) y -;  Formula (II):

(-A-L 1 -R 5 -L 1 -A-L-R 3 -L) z -;  Formula (III):

(-A-L 1 -R 5 -A-L-R 3 -L) m -;  Formula (IV):

(-A-L-R 3 -L) p -; and  Formula (V):

(-A-R 2 -A-L-R 3 -L) a -(-A-L 1 -R 5 -L 1 -A-L-R 3 -L) b -(A-L 1 -R 5 -A-L-R 3 -L) c -(-A-L-R 3 -L) d -,  Formula (VI):

wherein:
each A independently is SO 2 , C(═O), or Het;
each L and L 1 independently is O, S, or N(R 4 );
each R 2 and R 5 independently comprises a first organic moiety;
each R 3 comprises a second organic moiety;
each R 4 independently is H or a third organic moiety;
each n independently is 0 or 1;
each Het independently is an aromatic heterocycle comprising at least two carbon atoms and at least one nitrogen atom in a heteroaromatic ring thereof, and when A is Het, the F substituent is attached to a carbon atom of the heteroaromatic ring thereof;
each of x, y, z, m, and p is the average number of repeating units in the polymer and has a value of at least 10; and
each of a, b, c, and d is the average number of respective repeating units, and independently can be 0 or greater, provided the sum of a, b, c, and d is at least 10.

18. The method of claim 12 , wherein one or more of R 1 the R 2 , R 3 , R 4 , and R 5 comprises a moiety selected from the group consisting of a hydrocarbon, a heterocycle, a carbohydrate, an amino acid, a polypeptide, a peptide analog, and a combination of two or more thereof.

19. The method of claim 18 , any one of claims 1 to 18 , wherein one or more of R 1 , R 2 , R 3 , R 4 , and R 5 is substituted by at least one substituent selected from the group consisting of hydroxyl, halogen, nitro, —C(O)R 6 , —C(O)OR 6 , —C(O)N(R 6 ) 2 , —CN, —SO v R 6 , SO v N(R 6 ) 2 , R 6 SO v N(R 6 )—, —N(R 6 )SO v R 6 , —SO 3 R 6 , —N(R 6 ) 2 , —N(R 6 )OR 6 , —N(R 6 )C(O)R 6 , —N(R 6 )C(O)OR 6 , —N(R 6 )C(O)N(R 6 ) 2 , —OC(O)N(R 6 ) 2 , —OC(O)OR 6 , azido, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy, heteroaryl, poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), a fatty acid, a carbohydrate, an amino acid, and a polypeptide; wherein each R 6 independently is H, alkyl, or aryl, and v is 0, 1, or 2.

20. The method of claim 1 , wherein the monomer composition comprises (a) two or more different compounds of formula F-X-F, (b) two or more different compounds of formula (R 1 ) 3 Si—Z—Si(R 1 ) 3 , or (c) c combination of both (a) and (b).

21. The method of claim 20 , wherein the two or more different compounds of formula (R 1 ) 3 Si—Z—Si(R 1 ) 3 differ by the selection of R 1 , Z, or both R 1 and Z.

22. The method of claim 1 , wherein the monomer composition comprises at least one compound of Formula VII and at least one compound of Formula VIII:

wherein each R 1 independently is an alkyl or aryl group, and each R 9 independently is a covalent bond, C(CH 3 ) 2 , C(CF 3 ) 2 , or SO 2 .

23. The method of claim 1 , wherein the liquid monomer mixture comprises a melted mixture of the monomers.

24. The method of claim 1 , wherein the liquid monomer mixture comprises a solution of the monomers in a solvent.

25. The method of claim 24 , wherein the solvent is a polar aprotic solv

Assignees

• Scripps Research Inst

Inventors

• Sharpless K Barry
• Dong Jiajia
• Gao Bing
• Wu Peng
• Wang Hua

Classifications

• C07F9/5407 Primary

  Acyclic saturated phosphonium compounds · CPC title

• C08G75/24

  Polysulfonates · CPC title

• C07F9/5463

  Compounds of the type "quasi-phosphonium", e.g. (C)a-P-(Y)b wherein a+b=4, b>=1 and Y=heteroatom, generally N or O · CPC title

• C08G77/24

  halogen-containing groups · CPC title

• B01J31/0239

  Quaternary ammonium compounds · CPC title