CATALYSTS AND METHODS FOR POLYMER SYNTHESIS

• US 20110152497A1
• Filed: 08/24/2009
• Published: 06/23/2011
• Est. Priority Date: 08/22/2008
• Status: Active Grant

• Current Assignee: Saudi Aramco Technologies Company
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: Cherian, Anna E., LaPointe, Robert E., Farmer, Jay J., Simoneau, Chris A., Gridnev, Alexei, Coates, Geoffrey W., Allen, Scott D.
• Granted Patent: US 8,633,123 B2
• Time in Patent Office: Days
• US Class Current: 528/405
• CPC Class Codes: B01J 2531/0238 Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
• CPC Class Codes: B01J 2531/025 Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
• CPC Class Codes: B01J 2531/0252 Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
• CPC Class Codes: B01J 2531/0294 "Non-innocent" or "non-spectator" ligands, i.e. ligands described as, or evidently, taking part in the catalytic reaction beyond merely stabilizing the central metal as spectator or ancilliary ligands, e.g. by electron transfer to or from the central metal or by intra-/intermolecular chemical reactions, e.g. disulfide coupling, H-abstraction
• CPC Class Codes: B01J 2531/31 Aluminium
• CPC Class Codes: B01J 2531/62 Chromium
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 31/0239 Quaternary ammonium compounds
• CPC Class Codes: B01J 31/0259 comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
• CPC Class Codes: B01J 31/0265 Phosphazenes, oligomers thereof or the corresponding phosphazenium salts polyphosphazenes per se C07F9/067
• CPC Class Codes: B01J 31/182 comprising aliphatic or saturated rings
• CPC Class Codes: B01J 31/183 with more than one complexing nitrogen atom, e.g. phenanthroline
• CPC Class Codes: B01J 31/1835 comprising aliphatic or saturated rings
• CPC Class Codes: B01J 31/2243 At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
• CPC Class Codes: C07C 251/24 having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 279/12 being further substituted by nitrogen atoms not being part of nitro or nitroso groups
• CPC Class Codes: C07D 213/53 Nitrogen atoms
• CPC Class Codes: C07D 487/04 Ortho-condensed systems
• CPC Class Codes: C07D 487/22 in which the condensed system contains four or more hetero rings
• CPC Class Codes: C07F 15/065 : without a metal-carbon linkage
• CPC Class Codes: C07F 19/005 : without metal-C linkages
• CPC Class Codes: C07F 9/5355 : Phosphoranes containing the structure P=N-
• CPC Class Codes: C07F 9/6561 : containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
• CPC Class Codes: C08F 4/80 : selected from iron group metals or platinum group metals
• CPC Class Codes: C08G 64/34 : and cyclic ethers

Abstract

The present invention provides unimolecular metal complexes having increased activity in the copolymerization of carbon dioxide and epoxides. Also provided are methods of using such metal complexes in the synthesis of polymers. According to one aspect, the present invention provides metal complexes comprising an activating species with co-catalytic activity tethered to a multidentate ligand that is coordinated to the active metal center of the complex.

Claims

1. A method comprising the step of contacting an epoxide and carbon dioxide with a polymerization catalyst having the structure:

2. The method of claim 1, wherein M is selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni.

3. The method of claim 1, wherein M is selected from the group consisting of:

Co, Al, and Cr.

4. The method of claim 1, wherein M is Co.

7. The method of claim 1, wherein the moiety contains 1-30 atoms including at least one carbon atom, and optionally one or more atoms selected from the group consisting of N, O, S, Si, B, and P.

8. The method of claim 1, wherein the moiety is a C_2-30 aliphatic group wherein one or more methylene units are optionally and independently replaced by —

NR^y—

, —

N(R^y)C(O)—

, —

C(O)N(R^y)—

, —

O—

, —

C(O)—

, —

OC(O)—

, —

C(O)O—

, —

S—

, —

Si(R^y)₂—

, —

SO—

, —

SO₂—

, —

C(═

S)—

, —

C(═

NR^y)—

, or —

N═

N—

, where each occurrence of R^y is independently —

H, or an optionally substituted radical selected from the group consisting of C_1-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10-membered aryl.

9. The method of claim 1, wherein the moiety is selected from the group consisting of:

13. The method of claim 1, wherein the multidentate ligand is selected from the group consisting of:

15. The method of claim 13, wherein

16. The method of claim 15, wherein the polymerization catalyst comprises:

17. The method of claim 1, wherein the polymerization catalyst is selected from the group consisting of:

18. The method of claim 16, wherein the polymerization catalyst is selected from the group consisting of:

19. The method of claim 18, wherein each R^4a, R^4a′

, R^5a, R^5a′

, R^6a, R^6a′

, R^7a, and R^7a′

is independently selected from the group consisting of;

—

H, optionally substituted C_1-20 aliphatic, optionally substituted phenyl, and optionally substituted 8- to 10-membered aryl.

20. The method of claim 18, wherein each R^4a, R^4a′

, R^6a, and R^6a′

is —

H.

21. The method of claim 18, wherein each R^4a, R^4a′

, R^6a, and R^6a′

is —

H and each R^5a, R^5a′

, R^7a, and R^7a′

is independently —

H, or an optionally substituted C_1-20 aliphatic.

26. The method of claim 16, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:

31. The method of claim 26, wherein one or more Z group is independently a neutral functional group selected from the group consisting of amines, phosphines, gaunidines, bis-guanidines, amidines, and nitrogen-containing heterocycles.

32. The method of claim 26, wherein one or more Z group is a cationic moiety independently selected from the group consisting of:

33. The method of claim 26, wherein each linker moiety “

”

is independently selected from the group consisting of;

36. The method of claim 26, wherein M is cobalt.

37. The method of claim 26, wherein X is selected from the group consisting of:

chlorine, bromine, an optionally substituted C_1-12 carboxylate, azide, an optionally substituted phenoxide, a sulfonate salt, and a combination of any two or more of these.

38. The method of claim 26, wherein X is selected from the group consisting of chloride, acetate, trifluoroacetate, azide, pentafluorobenzoate, and a nitrophenolate.

39. The method of claim 1, wherein the polymerization catalyst is selected from Table 1.

42. The method of claim 1, wherein the polymerization catalyst contains a total of 1 to 4 Z groups.

46. The method of claim 1, wherein at least one Z group is

51. The method of claim 1, wherein at least one Z group is selected from the group consisting of:

57. The method of claim 1, wherein at least one Z group is selected from the group consisting of:

58. The method of claim 57, wherein R¹, R^1′

, R^1″

, R², R^2′

, and R³ and are independently —

H or optionally substituted C_1-20 aliphatic.

59. The method of claim 57, wherein R¹, R^1′

, R^1″

, R², R^2′

, and R³ are independently —

H or optionally substituted C_1-10 aliphatic.

60. The method of claim 57, wherein two or more of R¹, R^1′

, R^1″

, R², R^2′

, and R³ are taken together to form one or more optionally substituted rings optionally containing additional heteroatoms.

61. The method of claim 1, wherein at least one Z group is selected from the group consisting of:

62. The method of claim 1, wherein at least one Z group is

66. The method of claim 1, wherein at least one Z group is selected from the group consisting of:

72. The method of claim 1, wherein the epoxide is selected from the group consisting of:

ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, 1,2 octene oxide, 3-vinyl cyclohexene oxide, epichlorohydrin and mixtures of any two or more of these.

5-6. -6. (canceled)

10-12. -12. (canceled)

14. (canceled)

22-25. -25. (canceled)

27-30. -30. (canceled)

34-35. -35. (canceled)

40-41. -41. (canceled)

43-45. -45. (canceled)

47-50. -50. (canceled)

52-56. -56. (canceled)

63-65. -65. (canceled)

67-71. -71. (canceled)

73-77. -77. (canceled)

78. A polymerization catalyst having the structure:

80. The polymerization catalyst of claim 78, wherein

81. The polymerization catalyst of claim 80 having a structure selected from the group consisting of:

82. The polymerization catalyst of claim 78 having a structure selected from the group consisting of:

83. The polymerization catalyst of claim 82, having a structure selected from the group consisting of:

84. The polymerization catalyst of claim 83, wherein each R^4a, R^4a′

, R^5a, R^5a′

, R^6a, R^6a′

, R^7a, and R^7a′

is independently selected from the group consisting of;

—

H, optionally substituted C_1-20 aliphatic, optionally substituted phenyl, and optionally substituted 8- to 10-membered aryl.

86. The polymerization catalyst of claim 83, wherein each R^4a, R^4a′

, R^6a, and R^6a′

is —

H and each R^5a, R^5a′

, R^7a, and R^7a′

is independently —

H, or an optionally substituted C_1-20 aliphatic.

91. The polymerization catalyst of claim 81, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of:

96. The polymerization catalyst of claim 91, wherein one or more Z group is independently a neutral functional group selected from the group consisting of amines, phosphines, gaunidines, bis-guanidines, amidines, and nitrogen-containing heterocycles.

98. The polymerization catalyst of claim 91, wherein each linker moiety “

”

is independently selected from the group consisting of;

101. The polymerization catalyst of claim 91, wherein M is cobalt.

102. The polymerization catalyst of claim 91, wherein X is selected from the group consisting of:

chlorine, bromine, an optionally substituted C_1-12 carboxylate, azide, an optionally substituted phenoxide, a sulfonate salt, and a combination of any two or more of these.

103. The polymerization catalyst of claim 83, wherein the catalyst metal complex has a structure selected from those in Table 1.

104. The polymerization catalyst of claim 78, wherein the catalyst has a structure selected from those in Table 1.

105. The polymerization catalyst of claim 78, wherein the catalyst has a structure selected from those in Table 2.

106. The polymerization catalyst of claim 96, wherein at least one Z group is

107. The polymerization catalyst of claim 96, wherein at least one Z group is selected from the group consisting of:

108. The polymerization catalyst of claim 96, wherein at least one Z group is selected from the group consisting of:

109. The polymerization catalyst of claim 78, wherein at least one Z group is

110. The polymerization catalyst of claim 78, wherein at least one Z group is selected from the group consisting of:

79. (canceled)

85. (canceled)

87-90. -90. (canceled)

92-95. -95. (canceled)

97. (canceled)

99-100. -100. (canceled)