Traitement en cours

Veuillez attendre...

Paramétrages

Paramétrages

Aller à Demande

1. WO2020160102 - POLYMÉRISATION PAR TRANSFERT DE GROUPE POUR LA PRODUCTION DE MONOMÈRES FONCTIONNELS

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

[ EN ]

CLAIMS

What is claimed is:

1. A method for preparing compounds comprising Formula (V)


V

the method comprising:

(a) contacting an initiating compound comprising Formula (I):


I

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


II

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


III

to prepare a compound comprising Formula (IV):


(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 CFh or C=0;

Ri is selected from substituted or unsubstituted C1-C10OH, substituted or unsubstituted arylOH, substituted or unsubstituted C1-C10COR7, substituted or unsubstituted arylCORy, substituted or unsubstituted CI-CIOOCOCH=CH2, substituted or unsubstituted

arylOCOCH=CH2, substituted or unsubstituted CI-CIOOCOC(CH3)=CH2, substituted or unsubstituted arylOCOC(CH3)=CH2, substituted or unsubstituted CI-CIONHCOCH=CH2, or substituted or unsubstituted arylNHCOCH=CH2;

R3 is CHR8 or O;

R4, R5, and R6 are independently selected from a group consisting of H, Ci-Cs substituted or unsubstituted alkyl, or substituted or unsubstituted aryl;

R7 is selected from a group consisting of hydrogen, or substituted or unsubstituted C1-C10 alkyl; X is CN, COORs or CONR9R10;

R8, R9, and Rio are independently selected from a group consisting of H, C1-C10 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

Rii and R12 are independently selected from a group consisting of H, C1-C10 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 -CH2- or C=0; Ri is selected from substituted or unsubstituted Ci-CoOH, substituted or unsubstituted arylOH, substituted or unsubstituted C1-C6COR7, substituted or unsubstituted arylCORy, substituted or unsubstituted CI-C60C0CH=CH2, substituted or unsubstituted arylOCOCH=CH2, substituted or unsubstituted CI-C60C0C(CH3)=CH2, substituted or unsubstituted arylOCOC(CH3)=CH2, substituted or unsubstituted CI-C6NHCOCH=CH2, or substituted or unsubstituted

arylNHCOCH=CH2; R3 is a CH2 or O; R4, R5, and R6 are independently selected from a group consisting of H, C1-C4 substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; R7 is selected from a group consisting of hydrogen, or substituted or unsubstituted Ci-Cs alkyl; X is COOR8 or CONR9R10; R8, R9, and Rio are independently selected from a group consisting of H, C1-C6 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 Rn and R12 are independently selected from a group consisting of H, C1-C6 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 -CH2- or C=0; Ri is selected from substituted or unsubstituted C1-C4OH, substituted or unsubstituted arylOH, substituted or unsubstituted C1-C4COR4, substituted or unsubstituted arylCOR4, substituted or unsubstituted CI-C40C0CH=CH2, substituted or unsubstituted arylOCOCH=CH2, substituted or unsubstituted CI-C40C0C(CH3)=CH2, substituted or unsubstituted arylOCOC(CH3)=CH2, substituted or unsubstituted CI-C4NHCOCH=CH2, or substituted or unsubstituted

arylNHCOCH=CH2; R3 is a CH2 or O; R4, R5, and R6 are independently selected from a group consisting of C1-C4 substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; R7 is selected from a group consisting of hydrogen, or substituted or unsubstituted Ci-Cs alkyl; X is COOR8 or CONR9R10; and Rs, R9, and Rio are independently selected from a group consisting of H, C1-C4 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 Rii and R12 are independently selected from a group consisting of H, C1-C4 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=0; Ri is selected from a group consisting of -CH2CH2OCOCH=CH2, -CH2CH2OCOC(CH3)=CH2, -CH2CH2NHCOCH=CH2 ; R3 is CH2; R4, R5, and R6 is selected from a group consisting of methyl, tert- butyl, or phenyl; R7 is selected from a group consisting of hydrogen, methyl, or ethyl; X is COORs; Rs is selected from a group consisting of hydrogen, methyl, ethyl, 2-methoxymethyl, «-butyl, iso-butyl, or 2-ethylhexyl; and R11 and Ri2 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 (Mn 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):


IXA IXB

the method comprising:

(a) contacting a compound comprising Formula (VI):


VI

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


VIIA VIIB

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


III

to prepare the compound comprising Formula (VIIIA) and/or (VIIIB):


VIIIA 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:

Ri is selected from substituted or unsubstituted C1-C10OH, substituted or unsubstituted arylOH, substituted or unsubstituted C1-C10COR7, substituted or unsubstituted arylCORy, substituted or unsubstituted CI-CIOOCOCH=CH2, substituted or unsubstituted

arylOCOCH=CH2, substituted or unsubstituted CI-CIOOCOC(CH3)=CH2, substituted or unsubstituted arylOCOC(CH3)=CH2, substituted or unsubstituted CI-CIONHCOCH=CH2, or substituted or unsubstituted arylNHCOCH=CH2;

R2 is selected from a group consisting of hydrogen, substituted or unsubstituted Ci-C10OH, substituted or unsubstituted arylOH, substituted or unsubstituted Ci-CIOOCOC(CH3)=CH2, or substituted or unsubstituted arylOCOC(CH3)=CH2;

R3 is CHR8 or O;

R4, R5, and R6 are independently selected from a group consisting of H, Ci-Cs substituted or unsubstituted alkyl, or substituted or unsubstituted aryl;

R7 is selected from a group consisting of hydrogen, substituted or unsubstituted C1-C10 alkyl;

X is CH, COORs or CONR9R10;

Rs, R9, and Rio are independently selected from a group consisting of H, C1-C10 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

R11 and R12 are independently selected from a group consisting of H, C1-C10 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 Ri is selected from substituted or unsubstituted Ci-CeOH, substituted or unsubstituted arylOH, substituted or unsubstituted C1-C6COR7, substituted or unsubstituted arylCORy, substituted or unsubstituted CI-C60C0CH=CH2, substituted or unsubstituted arylOCOCH=CH2, substituted or unsubstituted CI-C60C0C(CH3)=CH2, substituted or unsubstituted arylOCOC(CH3)=CH2, substituted or unsubstituted Ci-C6NHCOCH=CH2, or substituted or unsubstituted arylNHCOCH=CH2; R2 is selected from a group consisting of hydrogen, substituted or unsubstituted Ci-CeOH, substituted or unsubstituted arylOH, substituted or unsubstituted CI-C60C0C(CH3)=CH2, or substituted or unsubstituted arylOCOC(CH3)=CH2; R3 is CHRs or O; R4, R5, and R6 are independently selected from a group consisting of H, C1-C4 substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; R7 is selected from a group consisting of hydrogen, substituted or unsubstituted Ci-Cs alkyl; X is COOR8 or CONR9R10; R8, R9, and Rio are independently selected from a group consisting of H, C1-C6 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 Rn and R12 are independently selected from a group consisting of H, C1-C6 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 Ri is selected from substituted or unsubstituted Ci-C4OH, substituted or unsubstituted arylOH, substituted or unsubstituted C1-C4COR7, substituted or unsubstituted arylCOR?, substituted or unsubstituted CI-C40C0CH=CH2, substituted or unsubstituted arylOCOCH=CH2, substituted or unsubstituted CI-C40C0C(CH3)=CH2, substituted or unsubstituted arylOCOC(CH3)=CH2, substituted or unsubstituted Ci-C4NHCOCH=CH2, or substituted or unsubstituted arylNHCOCH=CH2; R2 is selected from a

group consisting of hydrogen, substituted or unsubstituted C1-C4OH, substituted or unsubstituted arylOH, substituted or unsubstituted CI-C40C0C(CH3)=CH2, or substituted or unsubstituted arylOCOC(CH3)=CH2; R3 is a CH2 or O; R4, R5, and R6 are independently selected from a group consisting of H, C1-C4 substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; R7 is selected from a group consisting of hydrogen, or substituted or unsubstituted Ci-Cs alkyl; X is COOR8 or CONR9R10; R8, R9, and Rio are independently selected from a group consisting of H, C1-C4 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 Rn and R12 are independently selected from a group consisting of H, C1-C4 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 Ri and R2 are independently selected from a group consisting of -CH2CH2OCOCH=CH2, -CH2CH2OCOC(CH3)=CH2, -CH2CH2NHCOCH=CH2; R3 is CH2; R4, R5, and R6 is selected from a group consisting of methyl, ieri-butyl, or phenyl; R7 is selected from a group consisting of H, methyl, or ethyl; X is COORs; Rs is selected from a group consisting of hydrogen, methyl, ethyl, 2-methoxymethyl, n-butyl, iso-butyl, or 2-ethylhexyl; and R11 and R12 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 any one of the claims 1-10, 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 (Mn 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):


VIIIA VIIIB

wherein:

RI is selected from substituted or unsubstituted C1-C10OH, substituted or unsubstituted arylOH, substituted or unsubstituted C1-C10COR7, substituted or unsubstituted arylCORy, substituted or unsubstituted CI-CIOOCOCH=CH2, substituted or unsubstituted

arylOCOCH=CH2, substituted or unsubstituted CI-CIOOCOC(CH3)=CH2, substituted or unsubstituted arylOCOC(CH3)=CH2, substituted or unsubstituted CI-CIONHCOCH=CH2, or substituted or unsubstituted arylNHCOCH=CH2;

R2 is selected from a group consisting of hydrogen, substituted or unsubstituted Ci-C10OH, substituted or unsubstituted arylOH, substituted or unsubstituted Ci-CIOOCOC(CH3)=CH2, or substituted or unsubstituted arylOCOC(CH3)=CH2;

R3 is CHR8 or O;

R7 is selected from a group consisting of hydrogen, substituted or unsubstituted C1-C10 alkyl;

R8 is selected from a group consisting of H, C1-C10 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

R11 and R12 are independently selected from a group consisting of H, C1-C10 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 Ri is selected from substituted or unsubstituted Ci-CeOH, substituted or unsubstituted arylOH, substituted or unsubstituted C1-C6COR7, substituted or unsubstituted arylCORy, substituted or unsubstituted CI-C60C0CH=CH2, substituted or unsubstituted arylOCOCH=CH2, substituted or unsubstituted CI-C60C0C(CH3)=CH2, substituted or unsubstituted arylOCOC(CH3)=CH2, substituted or unsubstituted Ci-C6NHCOCH=CH2, or substituted or unsubstituted arylNHCOCH=CH2; R2 is selected from a group consisting of hydrogen, substituted or unsubstituted Ci-CeOH, substituted or unsubstituted arylOH, substituted or unsubstituted CI-C60C0C(CH3)=CH2, or substituted or unsubstituted arylOCOC(CH3)=CH2; R3 is CHRs or O; R7 is selected from a group consisting of hydrogen, substituted or unsubstituted Ci-Cs alkyl; Rs is selected from a group consisting of H, C1-C6 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 Rn and R12 are independently selected from a group consisting of H, C1-C6 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 Ri is selected from substituted or unsubstituted Ci-C4OH, substituted or unsubstituted arylOH, substituted or unsubstituted C1-C4COR7, substituted or unsubstituted arylCOR?, substituted or unsubstituted CI-C40C0CH=CH2, substituted or unsubstituted arylOCOCH=CH2, substituted or unsubstituted CI-C40C0C(CH3)=CH2, substituted or unsubstituted arylOCOC(CH3)=CH2, substituted or unsubstituted Ci-C4NHCOCH=CH2, or substituted or unsubstituted arylNHCOCH=CH2; R2 is selected from a group consisting of hydrogen, substituted or unsubstituted C1-C4OH, substituted or unsubstituted arylOH, substituted or unsubstituted CI-C40C0C(CH3)=CH2, or substituted or unsubstituted arylOCOC(CH3)=CH2; R3 is a CH2 or O; R7 is selected from a group consisting of hydrogen, or substituted or unsubstituted Ci-Cs alkyl; Rs is selected from a group consisting of H, C1-C4 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 Rn and R12 are independently selected from a group consisting of H, C1-C4 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 Ri and R2 are independently selected from a group consisting of -CH2CH2OCOCH=CH2, -CH2CH2OCOC(CH3)=CH2, .CH2CH2NHCOCH=CH2; R3 is CH2; R7 is selected from a group consisting of H, methyl, or ethyl; Rs is selected from a group consisting of hydrogen, methyl, ethyl, 2-methoxymethyl, n-butyl, iso-butyl, or 2-ethylhexyl; and R11 and RI2 are H.