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1. US20200239626 - GROUP TRANSFER POLYMERIZATION FOR THE PRODUCTION OF FUNCTIONAL MONOMERS

Note: Texte fondé sur des processus automatiques de reconnaissance optique de caractères. Seule la version PDF a une valeur juridique

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Claims

1. A method for preparing compounds comprising Formula (V)
the method comprising:
(a) contacting an initiating compound comprising Formula (I):

(MOL) (CDX)
in the presence of a silane and a first catalyst to form a compound comprising Formula (II):

(MOL) (CDX)
(b) contacting the compound comprising Formula (II) with a monomer comprising Formula (III), optionally in the presence of a second catalyst:

(MOL) (CDX)
 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 a compound Formula (V);
wherein
A and B are independently selected from CH 2 or C═O;
R 1 is selected from substituted or unsubstituted C 1-C 10OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 10COR 7, substituted or unsubstituted arylCOR 7, substituted or unsubstituted C 1-C 10OCOCH═CH 2, substituted or unsubstituted arylOCOCH═CH 2, substituted or unsubstituted C 1-C 10OCOC(CH 3)═CH 2, substituted or unsubstituted arylOCOC(CH 3)═CH 2, substituted or unsubstituted C 1-C 10NHCOCH═CH 2, or 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 9R 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 11and 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 6OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 6COR 7, substituted or unsubstituted arylCOR 7, substituted or unsubstituted C 1-C 6OCOCH═CH 2, substituted or unsubstituted arylOCOCH═CH 2, substituted or unsubstituted C 1-C 6OCOC(CH 3)═CH 2, substituted or unsubstituted arylOCOC(CH 3)═CH 2, substituted or unsubstituted C 1-C 6NHCOCH═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 9R 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 selected from substituted or unsubstituted C 1-C 4OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 4COR 4, substituted or unsubstituted arylCOR 4, substituted or unsubstituted C 1-C 4OCOCH═CH 2, substituted or unsubstituted arylOCOCH═CH 2, substituted or unsubstituted C 1-C 4OCOC(CH 3)═CH 2, substituted or unsubstituted arylOCOC(CH 3)═CH 2, substituted or unsubstituted C 1-C 4NHCOCH═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 9R 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; Ru is selected from a group consisting of —CH 2CH 2OCOCH═CH 2, —CH 2CH 2OCOC(CH 3)═CH 2, —CH 2CH 2NHCOCH═CH 2; R 3 is CH 2; R 4, R 5, and R 6 is selected from a group consisting of methyl, tent-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 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 the mole ratio of the compounds comprising Formula (III) to the compound comprising Formula (I) in step (b) 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 ratio of the second catalyst to the compound comprising Formula (I) in step (b) 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 a molybdenum catalyst, or an iridium catalyst.
13. The method of claim 1, wherein the ratio of the ring opening metathesis polymerization (ROMP) catalyst to the compound comprising Formula (I) in step (c) 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 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).
18. A method for preparing the compound comprising Formula (IXA) and/or (IXB):
the method comprising:
(a) contacting a compound comprising Formula (VI):

(MOL) (CDX)
in the presence of a silane and a first catalyst to form a compound comprising Formula (VIIA) and/or (VIIB):

(MOL) (CDX)
(b) contacting the compound comprising Formula (VIIA) and/or (VIIB) with a monomer comprising Formula (III) in the presence of a second catalyst:

(MOL) (CDX)
 to prepare the compound comprising Formula (VIIIA) and/or (VIIIB):
and
(c) contacting the compound comprising Formula (VIIIA) and/or (VIIIB) with a ring opening metathesis polymerization (ROMP) catalyst to prepare the compound comprising Formula (IXA) and/or (IXB);
wherein:
R 1 is selected from substituted or unsubstituted C 1-C 10OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 10COR 7, substituted or unsubstituted arylCOR 7, substituted or unsubstituted C 1-C 10OCOCH═CH 2, substituted or unsubstituted arylOCOCH═CH 2, substituted or unsubstituted C 1-C 10OCOC(CH 3)═CH 2, substituted or unsubstituted arylOCOC(CH 3)═CH 2, substituted or unsubstituted C 1-C 10NHCOCH═CH 2, or substituted or unsubstituted arylNHCOCH═CH 2;
R 2 is selected from a group consisting of hydrogen, substituted or unsubstituted C 1-C 10OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 10OCOC(CH 3)═CH 2, or substituted or unsubstituted arylOCOC(CH 3)═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, substituted or unsubstituted C 1-C 10 alkyl;
X is CH, COOR 8 or CONR 9R 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.
19. The method of claim 18, wherein R 1 is selected from substituted or unsubstituted C 1-C 6OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 6COR 7, substituted or unsubstituted arylCOR 7, substituted or unsubstituted C 1-C 6OCOCH═CH 2, substituted or unsubstituted arylOCOCH═CH 2, substituted or unsubstituted C 1-C 6OCOC(CH 3)═CH 2, substituted or unsubstituted arylOCOC(CH 3)═CH 2, substituted or unsubstituted C 1-C 6NHCOCH═CH 2, or substituted or unsubstituted arylNHCOCH═CH 2; R 2 is selected from a group consisting of hydrogen, substituted or unsubstituted C 1-C 6OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 6OCOC(CH 3)═CH 2,or substituted or unsubstituted arylOCOC(CH 3)═CH2; 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 4 substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; R 7 is selected from a group consisting of hydrogen, substituted or unsubstituted C 1-C 8 alkyl; X is COOR 8 or CONR 9R 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.
20. The method of claim 18, wherein R 1 is selected from substituted or unsubstituted C 1-C 4OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 4COR 7, substituted or unsubstituted arylCOR 7, substituted or unsubstituted C 1-C 4000CH═CH 2, substituted or unsubstituted arylOCOCH═CH 2, substituted or unsubstituted C 1-C 4OCOC(CH 3)═CH 2, substituted or unsubstituted arylOCOC(CH 3)═CH 2, substituted or unsubstituted C 1-C 4NHCOCH═CH 2, or substituted or unsubstituted arylNHCOCH═CH 2; R 2 is selected from a group consisting of hydrogen, substituted or unsubstituted C 1-C 4OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 4OCOC(CH 3)═CH 2, or substituted or unsubstituted arylOCOC(CH 3)═CH 2; R 3 is a CH 2 or O; R 4, R 5, and R6 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 9R 10; 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.
21. The method of claim 18, wherein R 1 and R 2 are independently selected from a group consisting of —CH 2CH 2OCOCH═CH 2, —CH 2CH 2OCOC(CH 3)═CH 2, —CH 2CH 2NHCOCH═CH 2; R 3 is CH 2; R 4, R 5, and R 6 is selected from a group consisting of methyl, tent-butyl, or phenyl; R 7 is selected from a group consisting of H, 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.
22. The method of claim 18, wherein the mole ratio of the silane to the compound comprising Formula (VI) in step (a) is ranges from about 1.10:1.0 to about 1.50:1.0.
23. The method of claim 18, wherein the first catalyst is a Lewis Acid catalyst and the mole ratio of the first catalyst to the compound comprising Formula (VI) in step (a) ranges from about 0.001:1.0 to about 0.1:1.0.
24. The method of claim 18, wherein the reaction temperature of (a) ranges from about −10° C. to about 80° C.
25. The method of claim 18, wherein the mole ratio of the compounds comprising Formula (III) to the compound comprising Formula (VI) in (b) ranges from about 10.0:1.0 to about 100.0:1.0.
26. The method of claim 18, wherein the second catalyst is the same or different than the first catalyst, and the ratio of the second catalyst to the compound comprising Formula (VI) in step (b) ranges from about 0.001:1.0 to about 0.1:1.0.
27. The method of claim 18, wherein the reaction temperature of step (b) ranges from about −10° C. to about 80° C.
28. The method of claim 18, wherein the yield of the compound comprising Formula (VIIIA) and/or (VIIIB) after steps (a) and (b) is greater than 60%.
29. The method of claim 18, wherein the ring opening metathesis polymerization (ROMP) catalyst comprises a ruthenium, a molybdenum catalyst, or an iridium catalyst.
30. The method of claim 18, wherein the ratio of the ring opening metathesis polymerization (ROMP) catalyst to the compound comprising Formula (VI) in step (c) ranges from about 0.001 to about 0.1:1.0.
31. The method of claim 18, wherein the reaction temperature of step (c) ranges from about −10° C. to about 80° C.
32. The method of claim 18, wherein the yield of the process from steps (a) to (c) is greater than 60%.
33. The method of claim 18, wherein the number average molecular weight observed (M n obs) for compound comprising Formula (IXA) and/or (IXB) ranges from about 0.5 to about 10.0 kDa.
34. The method of claim 18, wherein weight average molecular weight divided by the number average molecular weight observed ranges from about 1.00 to about 1.50 for the compound comprising Formula (IXA) and/or (IXB).
35. A composition comprising a compound having a Formula (VIIIA) and/or (VIIIB):
wherein:
R 1 is selected from substituted or unsubstituted C 1-C 10OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 10COR 7, substituted or unsubstituted arylCOR 7, substituted or unsubstituted C 1-C 10OCOCH═CH 2, substituted or unsubstituted arylOCOCH═CH 2, substituted or unsubstituted C 1-C 10OCOC(CH 3)═CH 2, substituted or unsubstituted arylOCOC(CH 3)═CH 2, substituted or unsubstituted C 1-C 10NHCOCH═CH 2, or substituted or unsubstituted arylNHCOCH═CH 2;
R 2 is selected from a group consisting of hydrogen, substituted or unsubstituted C 1-C 1OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 10OCOC(CH 3)═CH 2, or substituted or unsubstituted arylOCOC(CH 3)═CH 2;
R 3 is CHR 8 or O;
R 7 is selected from a group consisting of hydrogen, substituted or unsubstituted C 1-C 10 alkyl;
R 8 is 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.
36. The composition of claim 35, wherein R 1 is selected from substituted or unsubstituted C 1-C 6OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 6COR 7, substituted or unsubstituted arylCOR 7, substituted or unsubstituted C 1-C 6OCOCH═CH 2, substituted or unsubstituted arylOCOCH═CH 2, substituted or unsubstituted C 1-C 6OCOC(CH 3)═CH 2, substituted or unsubstituted arylOCOC(CH 3)═CH 2, substituted or unsubstituted C 1-C 6NHCOCH═CH 2, or substituted or unsubstituted arylNHCOCH═CH 2; R 2 is selected from a group consisting of hydrogen, substituted or unsubstituted C 1-C 6OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 6OCOC(CH 3)═CH 2, or substituted or unsubstituted arylOCOC(CH 3)═CH 2; R 3 is CHR 8 or O; R 7 is selected from a group consisting of hydrogen, substituted or unsubstituted C 1-C 8 alkyl; R 8 is 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.
37. The composition of claim 35, wherein R 1 is selected from substituted or unsubstituted C 1-C 4OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 4COR 7, substituted or unsubstituted arylCOR 7, substituted or unsubstituted C 1-C 4OCOCH═CH 2, substituted or unsubstituted arylOCOCH═CH 2, substituted or unsubstituted C 1-C 4OCOC(CH 3)═CH 2, substituted or unsubstituted arylOCOC(CH 3)═CH 2, substituted or unsubstituted C 1-C 4NHCOCH═CH 2, or substituted or unsubstituted arylNHCOCH═CH 2; R 2 is selected from a group consisting of hydrogen, substituted or unsubstituted C 1-C 4OH, substituted or unsubstituted arylOH, substituted or unsubstituted C 1-C 4OCOC(CH 3)═CH 2, or substituted or unsubstituted arylOCOC(CH 3)═CH 2; R 3 is a CH 2 or O; R 7 is selected from a group consisting of hydrogen, or substituted or unsubstituted C 1-C 8 alkyl; R 8 is 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.
38. The composition of claim 35, wherein R 1 and R 2 are independently selected from a group consisting of —CH 2CH 2OCOCH═CH 2, —CH 2CH 2OCOC(CH 3)═CH 2, —CH 2CH 2NHCOCH═CH 2; R 3 is CH 2; R 7 is selected from a group consisting of H, methyl, or ethyl; 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.