Catalysts for ring opening polymerization

1. A method for ring opening polymerization, comprising contacting a substrate of Formula (I):

wherein,

X is a chemical bond, C(O), or C(O)O;

when X is a chemical bond then Z is a chemical bond or the group —CR 5 R 6 —; and

when X is C(O) or C(O)O then Z is a group —CR 5 R 6 —or a group of the formula —(CH 2 ) Z —, wherein z is an integer from 0-6;

R 1 is selected from Rla, OR 1a , N(R 1a ) 2 , SiR 1a 3 , SR 1a , SO 2 R 1a , SO 2 N(R 1a ) 2 , C(O)R 1a ; C(O)OR 1a , OCOR 1a ; C(O)N(R 1a ) 2 , OC(O)N(R 1a ) 2 , N(R 1a )C(O)N(R 1a ) 2 , F, Cl, Br, I, cyano, and nitro, wherein R 1a is in each case independently selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, aryl, C 1-8 heteroaryl, C 3-8 cycloalkyl, or C 1-8 heterocyclyl;

R 2 is selected from R 2a , OR 2a , N(R 2a ) 2 , SiR 2a 3 , SR 2a , SO 2 R 2a , SO 2 N(R 2a ) 2 , C(O)R 2a ; C(O)OR 2a , OCOR 2a ; C(O)N(R 2a ) 2 , OC(O)N(R 2a ) 2 , N(R 2a )C(O)N(R 2a ) 2 , F, Cl, Br, I, cyano, and nitro, wherein R 2a is in each case independently selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, aryl, C 1-8 heteroaryl, C 3-8 cycloalkyl, or C 1-8 heterocyclyl;

R 3 is selected from R 3a , OR 3a , N(R 3a ) 2 , SiR 3a 3 , SR 3a , SO 2 R 3a , SO 2 N(R 3a ) 2 , C(O)R 3a ; C(O)OR 3a , OCOR 3a ; C(O)N(R 3a ) 2 , OC(O)N(R 3a ) 2 , N(R 3a )C(O)N(R 3a ) 2 , F, Cl, Br, I, cyano, and nitro, wherein R 3a is in each case independently selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, aryl, C 1-8 heteroaryl, C 3-8 cycloalkyl, or C 1-8 heterocyclyl;

R 4 is selected from R 4a , OR 4a , N(R 4a ) 2 , SiR 4a 3 , SR 4a , SO 2 R 4a , SO 2 N(R 4a ) 2 , C(O)R 4a ; C(O)OR 4a , OCOR 4a ; C(O)N(R 4a ) 2 , OC(O)N(R 4a ) 2 , N(R 4a )C(O)N(R 4a ) 2 , F, Cl, Br, I, cyano, and nitro, wherein R 4a is in each case independently selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, aryl, C 1-8 heteroaryl, C 3-8 cycloalkyl, or C 1-8 heterocyclyl;

R 5 , when present, is selected from R 4a , OR 4a , N(R 4a ) 2 , SiR 4a 3 , SR 4a , SO 2 R 4a , SO 2 N(R 4a ) 2 , C(O)R 4a ; C(O)OR 4a , OCOR 4a ; C(O)N(R 4a ) 2 , OC(O)N(R 4a ) 2 , N(R 4a )C(O)N(R 4a ) 2 , F, Cl, Br, I, cyano, and nitro, wherein R 5a is in each case independently selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C2-8alkynyl, aryl, C 1-8 heteroaryl, C 3-8 cycloalkyl, or C 1-8 heterocyclyl;

R 6 , when present, is selected from R 6a , OR 6a , N(R 6a ) 2 , SiR 6a 3 , SR 6a , SO 2 R 6a , SO 2 N(R 6a ) 2 , C(O)R 6a ; C(O)OR 6a , OCOR 6a ; C(O)N(R 6a ) 2 , OC(O)N(R 6a ) 2 , N(R 6a )C(O)N(R 6a ) 2 , F, Cl, Br, I, cyano, and nitro, wherein R 6a is in each case independently selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, aryl, C 1-8 heteroaryl, C 3-8 cycloalkyl, or C 1-8 heterocyclyl;

wherein any two or more of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 may together form a ring;

with a catalyst system comprising a catalyst of Formula II and propagator of Formula III:

wherein

N x is selected from N, P, As, Sn, and Pb;

B x is in each case independently selected from B, Al, Ga, In, and Th;

R b1 , R b2 , R b3 , R b4 , R b5 , R b6 , and R b7 are independently selected from are independently selected from C 1-8 alkyl; wherein any two or more of R b1 , R b2 , and R b3 ; R b4 and R b5 ; or R b6 and R b7 may together form a ring;

R n1 , R n2 , and R n3 are independently selected from hydrogen and C 1-8 alkyl, wherein any two or more of R n1 , R n2 , and R n3 may together form a ring;

R 7 is C 1-8 alkyl, or wherein R 7 may form an C 2-8 alkyl group with one or more of R n1 , R n2 , and R n3 ;

to give a ring opened polymer having the formula:

wherein n is any integer,

wherein the ring opening polymerization is conducted in a polar aprotic solvent, non-polar solvent, polar protic solvent, or a combination thereof.

2. The method according to claim 1 , wherein X is a chemical bond.

3. The method according to claim 1 , wherein X is a chemical bond and Z is a chemical bond.

4. The method according to claim 1 , wherein X is a chemical bond and Z is CR 5 R 6 .

5. The method according to claim 1 , wherein Z is C(O).

6. The method according to claim 1 , wherein Z is C(O) and Z is 1, 2, 3, 4, 5, or 6.

7. The method according to claim 1 , wherein Z is C(O)O.

8. The method according to claim 1 , wherein Z is C(O)O and Z is 1, 2, 3, 4, 5, or 6.

9. The method according to claim 1 , wherein B x is in each case Al.

10. The method according to claim 1 , wherein N x is in each case N.

11. The method according to claim 1 , wherein the catalyst of Formula (II) has the formula:

12. The method according to claim 1 , wherein the mole ratio of the catalyst of Formula II and propagator of Formula III is from 1:1 to 10:1.

13. The method according to claim 1 , wherein R 7 and R n1 together form a C 2-8 alkyl group.

14. The method according to claim 13 , wherein the catalyst system comprises an adduct of Formula (IV):

15. The method according to claim 1 , wherein the ring opening polymerization is conducted in the presence of carbon dioxide.

16. The method according to claim 1 , wherein the ring opening is conducted in the presence of a compound having the formula R—OH, wherein R is C 1-8 alkyl, aryl, C 1-3 alkaryl, or a polymer having the formula:

X′ is a chemical bond, C(O), or C(O)O;

when X′ is a chemical bond then Z′ is a chemical bond or the group —CR 5′ R 6′ —; and

when X′ is C(O) or C(O)O then Z′ is a group —CR 5′ R 6′ — or a group of the formula —(CH 2 ) Z′ —, wherein z′ is an integer from 0-6;

R 1′ is selected from R 1a′ , OR 1a′ , N(R 1a′ ) 2 , SiR 1a′ 3 , SR 1a′ , SO 2 R 1a′ , SO 2 N(R 1a′ ) 2 , C(O)R 1a′ ; C(O)OR 1a′ , OCOR 1a′ ; C(O)N(R 1a′ ) 2 , OC(O)N(R 1a′ ) 2 , N(R 1a′ )C(O)N(R 1a′ ) 2 , F, Cl, Br, I, cyano, and nitro, wherein R 1a′ is in each case independently selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, aryl, C 1-8 heteroaryl, C 3-8 cycloalkyl, or C 1-8 heterocyclyl;

R 2 is selected from R 2a′ , OR 2a′ , N(R 2a′ ) 2 , SiR 2a′ 3 , SR 2a′ , SO 2 R 2a′ , SO 2 N(R 2a′ ) 2 , C(O)R 2a′ ; C(O)OR 2a′ , OCOR 2a′ ; C(O)N(R 2a′ ) 2 , OC(O)N(R 2a′ ) 2 , N(R 2a′ )C(O)N(R 2a′ ) 2 , F, Cl, Br, I, cyano, and nitro, wherein R 2a′ is in each case independently selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, aryl, C 1-8 heteroaryl, C 3-8 cycloalkyl, or C 1-8 heterocyclyl;

R 3 is selected from R 3a′ , OR 3a′ , N(R 3a′ ) 2 , SiR 3a′ 3 , SR 3a′ , SO 2 R 3a′ , SO 2 N(R 3a′ ) 2 , C(O)R 3a′ ; C(O)OR 3a′ , OCOR 3a′ ; C(O)N(R 3a′ ) 2 , OC(O)N(R 3a′ ) 2 , N(R 3a′ )C(O)N(R 3a′ ) 2 , F, Cl, Br, I, cyano, and nitro, wherein R 3a′ is in each case independently selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, aryl, C 1-8 heteroaryl, C 3-8 cycloalkyl, or C 1-8 heterocyclyl;

R 4 is selected from R 4a′ , OR 4a′ , N(R 4a′ ) 2 , SiR 4a′ 3 , SR 4a′ , SO 2 R 4a′ , SO 2 N(R 4a′ ) 2 , C(O)R 4a′ ; C(O)OR 4a′ , OCOR 4a′ ; C(O)N(R 4a′ ) 2 , OC(O)N(R 4a′ ) 2 , N(R 4a′ )C(O)N(R 4a′ ) 2 , F, Cl, Br, I, cyano, and nitro, wherein R 4a′ is in each case independently selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, aryl, C 1-8 heteroaryl, C 3-8 cycloalkyl, or C 1-8 heterocyclyl;

R 5 , when present, is selected from R 5a′ , OR 5a′ , N(R 5a′ ) 2 , SiR 5a′ 3 , SR 5a′ , SO 2 R 5a′ , SO 2 N(R 5a′ ) 2 , C(O)R 5a′ ; C(O)OR 5a′ , OCOR 5a′ ; C(O)N(R 5a′ ) 2 , OC(O)N(R 5a′ ) 2 , N(R 5a′ )C(O)N(R 5a′ ) 2 , F, Cl, Br, I, cyano, and nitro, wherein R 5a′ is in each case independently selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, aryl, C 1-8 heteroaryl, C 3-8 cycloalkyl, or C 1-8 heterocyclyl;

R 6 , when present, is selected from R 6a′ , OR 6a′ , N(R 6a′ ) 2 , SiR 6a′ 3 , SR 6a′ , SO 2 R 6a′ , SO 2 N(R 6a′ ) 2 , C(O)R 6a′ ; C(O)OR 6a′ , OCOR 6a′ ; C(O)N(R 6a′ ) 2 , OC(O)N(R 6a′ ) 2 , N(R 6a′ )C(O)N(R 6a′ ) 2 , F, Cl, Br, I, cyano, and nitro, wherein R 6a′ is in each case independently selected from hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, aryl, C 1-8 heteroaryl, C 3-8 cycloalkyl, or C 1-8 heterocyclyl;

R7′ is selected from H, C 1-8 alkyl, aryl, or C 1-3 alkaryl;

n′ is any integer; and

wherein any two or more of R 1′ , R 2′ , R 3′ , R 4′ , R 5′ , and R 6′ may together form a ring.

17. The method according to claim 16 , wherein the ring opening is conducted in the presence of a compound having the formula R—OH, wherein R is benzyl, and R 7′ is hydrogen or benzyl.

18. The method according to claim 16 , wherein R 1′ , R 2′ , and R 3′ are hydrogen and R 4′ is methyl.