Group transfer polymerization for the production of functional monomers
The present invention provides efficient processes for preparing brush polymers. In general, the process comprises three distinct reaction steps utilizing two separate catalysts. In the first step, the initiating compound comprising norbornene is contacted with a silane in the presence of a catalyst, thereby forming a silated intermediate. This silated intermediate is then contacted with a monomer in the presence of a catalyst via Group Transfer Polymerization (GTP). The resulting compound from GTP is contacted with a ring opening metathesis polymerization (ROMP) catalyst to prepare the brush polymer. Surprisingly, the brush polymers obtained from the above process are accessed in an efficient and rapid GTP methodology as compared to prior methods.
1. A method for preparing a compound comprising Formula (V)
the method comprising:
(a) contacting an initiating compound comprising Formula (I):
in the presence of a silane and a first catalyst to form a compound comprising Formula (II):
(b) contacting the compound comprising Formula (II) with a monomer comprising Formula (III), optionally in the presence of a second catalyst:
to prepare a compound comprising Formula (IV):
and
(c) contacting the compound comprising Formula (IV) with a ring opening metathesis polymerization (ROMP) catalyst to prepare the compound comprising Formula (V);
wherein
A and B are independently selected from CH 2 or C═O;
R is selected from substituted or unsubstituted C 1 -C 10 OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1 -C 10 COR 7 , substituted or unsubstituted arylCOR 7 , substituted or unsubstituted C 1 -C 10 OCOCH═CH 2 , substituted or unsubstituted arylOCOCH═CH 2 , substituted or unsubstituted C 1 -C 10 OCOC(CH 3 )═CH 2 , substituted or unsubstituted arylOCOC(CH 3 )═CH 2 , substituted or unsubstituted C 1 -C 10 NHCOCH═CH 2 , or substituted or unsubstituted arylNHCOCH═CH 2 ;
R 1 is the residue of a group selected from the group consisting of a substituted or unsubstituted C 1 -C 10 OH, a substituted or unsubstituted arylOH, a substituted or unsubstituted C 1 -C 10 COR 7 , a substituted or unsubstituted arylCOR 7 , a substituted or unsubstituted C 1 -C 10 OCOCH═CH 2 , a substituted or unsubstituted arylOCOCH═CH 2 , a substituted or unsubstituted C 1 -C 10 OCOC(CH 3 )═CH 2 , a substituted or unsubstituted arylOCOC(CH 3 )═CH 2 , a substituted or unsubstituted C 1 -C 10 NHCOCH═CH 2 , and a substituted or unsubstituted arylNHCOCH═CH 2 ;
R 3 is CHR 8 or O;
R 4 , R 5 , and R 6 are independently selected from a group consisting of H, C 1 -C 8 substituted or unsubstituted alkyl, or substituted or unsubstituted aryl;
R 7 is selected from a group consisting of hydrogen, or substituted or unsubstituted C 1 -C 10 alkyl; X is CN, COOR 8 or CONR 9 R 10 ;
R 8 , R 9 , and R 10 are independently selected from a group consisting of H, C 1 -C 10 substituted or unsubstituted alkyl optionally substituted with at least one heteroatom on the alkyl chain, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and
R 11 and R 12 are independently selected from a group consisting of H, C 1 -C 10 substituted or unsubstituted alkyl optionally substituted with at least one heteroatom on the alkyl chain, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.
2. The method of claim 1 , wherein A and B are independently selected from —CH 2 -or C═O; R 1 is selected from substituted or unsubstituted C 1 -C 6 OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1 -C 6 COR 7 , substituted or unsubstituted arylCOR 7 , substituted or unsubstituted C 1 -C 6 OCOCH═CH 2 , substituted or unsubstituted arylOCOCH═CH 2 , substituted or unsubstituted C 1 -C 6 OCOC(CH 3 )═CH 2 , substituted or unsubstituted arylOCOC(CH 3 )═CH 2 , substituted or unsubstituted C 1 -C 6 NHCOCH═CH 2 , or substituted or unsubstituted arylNHCOCH═CH 2 ; R 3 is a CH 2 or O; R 4 , R 5 , and R 6 are independently selected from a group consisting of H, C 1 -C 4 substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; R 7 is selected from a group consisting of hydrogen, or substituted or unsubstituted C 1 -C 8 alkyl; X is COOR 8 or CONR 9 R 10 ; R 8 , R 9 , and R 10 are independently selected from a group consisting of H, C 1 -C 6 substituted or unsubstituted alkyl optionally substituted with at least one heteroatom on the alkyl chain, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and R 11 and R 12 are independently selected from a group consisting of H, C 1 -C 6 substituted or unsubstituted alkyl optionally substituted with at least one heteroatom on the alkyl chain, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.
3. The method of claim 1 , wherein A and B are independently selected from —CH 2 -or C═O; R 1 is a residue of a group selected from substituted or unsubstituted C 1 -C 4 OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1 -C 4 COR 4 , substituted or unsubstituted arylCOR 4 , substituted or unsubstituted C 1 -C 4 OCOCH═CH 2 , substituted or unsubstituted arylOCOCH═CH 2 , substituted or unsubstituted C 1 -C 4 OCOC(CH 3 )═CH 2 , substituted or unsubstituted arylOCOC(CH 3 )═CH 2 , substituted or unsubstituted C 1 -C 4 NHCOCH═CH 2 , or substituted or unsubstituted arylNHCOCH═CH 2 ; R 3 is a CH 2 or O; R 4 , R 5 , and R 6 are independently selected from a group consisting of C 1 -C 4 substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; R 7 is selected from a group consisting of hydrogen, or substituted or unsubstituted C 1 -C 8 alkyl; X is COOR 8 or CONR 9 R 10 ; and R 8 , R 9 , and R 10 are independently selected from a group consisting of H, C 1 -C 4 substituted or unsubstituted alkyl optionally substituted with at least one heteroatom on the alkyl chain, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; and R 11 and R 12 are independently selected from a group consisting of H, C 1 -C 4 substituted or unsubstituted alkyl optionally substituted with at least one heteroatom on the alkyl chain, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.
4. The method of claim 1 , wherein A and B are C═O; R 1 is selected from a group consisting of CH 2 CH 2 OCOCH═CH 2 , CH 2 CH 2 OCOC(CH 3 )═CH 2 , —CH 2 CH 2 NHCOCH═CH 2 ; R 3 is CH 2 ; R 4 , R 5 , and R 6 is selected from a group consisting of methyl, tert-butyl, or phenyl; R 7 is selected from a group consisting of hydrogen, methyl, or ethyl; X is COOR 8 ; R 8 is selected from a group consisting of hydrogen, methyl, ethyl, 2-methoxymethyl, n-butyl, iso-butyl, or 2-ethylhexyl; and R 11 and R 12 are H.
5. The method of claim 1 , wherein the mole ratio of the silane to the compound comprising Formula (I) in step (a) ranges from about 0.95:1.00 to about 1.50:1.00.
6. The method of claim 1 , wherein the first catalyst is a Lewis Acid catalyst, and the mole ratio of the first catalyst to the compound comprising Formula (I) in step (a) ranges from about 0.001:1.0 to about 0.1:1.0.
7. The method of claim 1 , wherein the reaction temperature of step (a) ranges from about −10° C. to about 80° C.
8. The method of claim 1 , wherein in step (b) the monomer comprising Formula (III) is present in an amount such that the mole-to-mole ratio of the monomer comprising Formula (III) present in step (b) to the compound comprising Formula (I) present in step (a) ranges from about 10.0:1.0 to about 100.0:1.0.
9. The method of claim 1 , wherein step (b) is performed in the presence of a second catalyst, which is the same or different from the first catalyst, and the second catalyst is present in an amount such that the mole-to-mole ratio of the second catalyst present in step (b) to the compound comprising Formula (I) present in step (a) ranges from about 0.001:1.0 to about 0.1:1.0.
10. The method of claim 1 , wherein the reaction temperature of step (b) ranges from about −10° C. to about 80° C.
11. The method of claim 1 , wherein the yield of the compound comprising Formula (IV) after steps (a) and (b) is greater than 60%.
12. The method of claim 1 , wherein the ring opening metathesis polymerization (ROMP) catalyst comprises a ruthenium catalyst, a molybdenum catalyst, or an iridium catalyst.
13. The method of claim 1 , wherein in step (c) the ring opening metathesis polymerization (ROMP) catalyst is present in an amount such that the mole to mole ratio of the ring opening metathesis polymerization (ROMP) catalyst present in step c to the compound comprising Formula (I) present in step (a) ranges from about 0.001 to about 0.1:1.0.
14. The method of claim 1 , wherein the reaction temperature of step (c) ranges from about −10° C. to about 80° C.
15. The method of claim 1 , wherein the yield of the process from steps (a) to (c) is greater than 60%.
16. The method of claim 1 , wherein the number average molecular weight observed (M n obs ) for the compound comprising Formula (V) ranges from about 0.5 to about 10.0 kDa.
17. The method of claim 1 , wherein weight average molecular weight divided by the number average molecular weight observed ranges from about 1.0 to about 1.50 for the compound comprising Formula (V).