Polymerization method and polymers formed therewith

1. A polymerization method comprising the step of contacting a liquid monomer composition with a basic catalyst, 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 ; wherein:

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; and wherein the basic catalyst comprises at least one material selected from the group consisting of an amidine, a guanidine, a phosphazene, a nitrogen heterocyclic carbene, a tertiary alkoxide, and a fluoride salt;

and wherein the basic catalyst is selected from the group consisting of:

(a) 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU);

(b) at least one phosphazene selected from the group consisting of 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) and 1-tert-butyl-4,4,4-tris-(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2λ 5 ,4λ 5 -catenadi(phosphazene) (P 4 -t-Bu);

(c) at least one guanidine selected from the group consisting of 1,1,3,3-tetramethylguanidine (TMG), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), and 7-methyl-1,5,7-triazabicyclo-[4.4.0]dec-5-ene (MTBD); and

(d) at least one nitrogen-heterocyclic carbene selected from the group consisting of an imidazole-2-ylidene, a 1,2,4-triazole-5-ylidene, a thiazole-2-ylidene, and an imidazolin-2-ylidene.

2. 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 0; and

R 3 comprises a second organic moiety comprising at least one aryl or heteroaryl group directly bonded to each L.

3. The method of claim 1 wherein the n is 0.

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

5. 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, such that the additional F substituent also reacts with a (R 1 ) 3 Si substituent on an oxygen, sulfur or nitrogen atom linking group, to form a silyl fluoride, and the activating group condenses with the linking group to introduce a branch point in the polymer.

6. 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, such that the additional silyl substituent also reacts with a F substituent on a sulfonyl, carbonyl, or heteroaryl activating group, to form a silyl fluoride and the linking group condenses with the activating group to introduce a branch point in the polymer.

7. 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.

8. The method of claim 1 wherein the basic catalyst comprises is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

9. The method of claim 1 wherein the basic catalyst is at least one phosphazene selected from the group consisting of 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) and 1-tert-butyl-4,4,4-tris-(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2λ 5 ,4λ 5 -catenadi(phosphazene) (P 4 -t-Bu).

10. The method of claim 1 wherein the basic catalyst is at least one guanidine selected from the group consisting of 1,1,3,3-tetramethylguanidine (TMG), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), and 7-methyl-1,5,7-triazabicyclo-[4.4.0]dec-5-ene (MTBD).

11. The method of claim 1 wherein the basic catalyst is at least one nitrogen-heterocyclic carbene selected from the group consisting of an imidazole-2-ylidene, a 1,2,4-triazole-5-ylidene, a thiazole-2-ylidene, and an imidazolin-2-ylidene.

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

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

14. The method of claim 1 wherein the polymer comprises a polymeric chain 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 -A-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 -;  Formula (V)

and

(-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.

15. The method of claim 1 wherein one or more of 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.

16. The method of claim 1 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.

17. 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).

18. The method of claim 17 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.

19. 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 .

20. The method of claim 1 wherein the liquid monomer mixture comprises a mixture of the monomers dissolved in a solvent.

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

22. The method of claim 1 wherein the F—X—F monomer comprises sulfuryl fluoride (FSO 2 F).

23. The method of claim 1 wherein the F—X—F monomer comprises a bisfluorosulfonyl monomer of formula F—SO 2 —CH 2 CH 2 —N(R 11 )—CH 2 CH 2 —SO 2 —F, wherein R 11 comprises an organic moiety.

24. The method of claim 23 wherein R 11 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.

25. The method of claim 23 wherein 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.

26. A polymer comprising a polymeric chain of

(-A(-R 2 -A) n -L-R 3 -L) x -;  Formula (I)

wherein:

A is SO 2 ;

each L independently is O, S, or N(R 4 );

each R 2 is —CH 2 CH 2 —N(R 11 )—CH 2 CH 2 —, wherein R 11 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 is 1;

x is the average number of repeating units in the polymer and has a value of at least 10; and

the polymer includes a group of formula E-A- at one or both ends of the polymer chain, wherein each E independently is fluoro, OR 8 , NHR 8 , N(R 8 ) 2 , azido, CN, or SR 8 , and each R 8 independently is an organic moiety.

27. The polymer of claim 26 wherein one or more of the organic moieties R 3 , R 4 , R 8 and R 11 is 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.

28. The polymer of claim 26 wherein one or more of R 3 , R 4 , R 8 and R 11 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.

29. The polymer of claim 26 wherein R 11 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.

30. The polymer of claim 26 wherein R 11 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.

31. The polymer of claim 26 wherein the polymer has a molecular weight polydispersity index (PDI) of less than about 2.2 based on gel permeation chromatography using polystyrene standards, and includes less than about 5 percent by weight of cyclic oligomers.

32. A method of preparing a transparent, substantially colorless poly(bisphenol A sulfate) film or sheet comprising pelletizing poly(bisphenol A sulfate) into pellets, and consolidating the pellets at an elevated pressure and at a temperature greater than the glass transition temperature thereof, wherein the elevated pressure is at least about 25,000 pounds-per-square inch (psi) and the temperature is in the range of about 200 to 250° C.