Highly active catalysts for alkylene oxide polymerization
View Patent ↗The reaction product of the reaction product of A.) a ligand of the formula (I), wherein R 1 , R 2 , R 3 , and R 4 in each occurrence independently are the same or different hydrocarbyl substituents of 1 to 20 carbon atoms, hydrogen, halogen, or alkoxy groups of 1 to 8 carbon atoms; X in each occurrence independently is CR 6 with R 6 being hydrogen or an alkyl group of 1 to 8 carbon atoms; and R 5 is an organic divalent group of 4 to 40 carbon atoms with the proviso that the two nodes X are not bound to the same atom or to vicinal atoms in the group R 5 ; B.) an aluminum compound of the formula AlR 7 R 8 R 9 , wherein R 7 , R 8 and R 9 each independently is a C 1 to C 12 hydrocarbyl group, hydrogen, halogen, or an alkoxy group of 1 to 20 carbon atoms; and C.) a Lewis base selected from the group consisting of amines, phosphines, amides, nitriles, isonitriles, and alcohols is useful as a polymerization catalyst, particularly for the homopolymerization or copolymerization of an alkylene oxide.
1. A polymerization catalyst comprising the reaction product of
A.) a ligand of the formula I,
wherein
R 1 , R 2 , R 3 , and R 4 in each occurrence independently are the same or different hydrocarbyl substituents of 1 to 20 carbon atoms, hydrogen, halogen, or alkoxy groups of 1 to 8 carbon atoms;
X in each occurrence independently is CR 6 with R 6 being hydrogen or an alkyl group of 1 to 8 carbon atoms; and
R 5 is an organic divalent group of 4 to 40 carbon atoms and optionally substituted with the proviso that the two nodes X are not bound to the same atom or to vicinal atoms in the group R 5 ; and
B.) an aluminum compound of the formula AlR 7 R 8 R 9 , wherein R 7 , R 8 and R 9 each independently is a C 1 to C 12 hydrocarbyl group, hydrogen, halogen, or an alkoxy group of 1 to 20 carbon atoms; and
C.) a Lewis base selected from the group consisting of amines, phosphines, amides, nitriles, isonitriles, and alcohols.
2. The polymerization catalyst of claim 1 wherein the divalent group R 5 is aromatic.
3. The polymerization catalyst of claim 1 wherein the divalent group R 5 comprises a heteroatom selected from the group consisting of O, N, S, Se and P.
4. The polymerization catalyst of claim 1 wherein R 1 is t-butyl, 1,1,3,3-tetramethylbutyl, 1-methylcyclohexyl, 1-adamantyl, or α, α-dimethylbenzyl.
5. The polymerization catalyst of claim 1 wherein the ligand A) has the formula II
wherein
R 10 , R 11 , R 12 , R 13 , and R 14 in each occurrence independently are the same or different hydrocarbyl substituents of 1 to 20 carbon atoms or hydrogen,
R 15 in each occurrence independently is an alkyl group of 1 to 8 carbon atoms or hydrogen, and
E is selected from the group consisting of O, S, NR 16 , PR 16 and C(R 16 ) 2 , wherein R 16 in each occurrence independently is a hydrocarbyl substituent of 1 to 8 carbon atoms or hydrogen.
6. The polymerization catalyst of claim 5 wherein R 12 , R 13 , R 14 , and R 15 are hydrogen and E is sulfur.
7. The polymerization catalyst of claim 1 wherein the ligand A) has the formula III
wherein
R 17 , R 18 and R 19 in each occurrence independently are the same or different hydrocarbyl substituents of 1 to 20 carbon atoms or hydrogen,
R 20 is a hydrocarbyl substituent of 1 to 20 carbon atoms, hydrogen or an alkoxy group of 1 to 20 carbon atoms,
R 21 in each occurrence independently is an alkyl group of 1 to 8 carbon atoms or hydrogen, and
R 22 is hydrogen or a group OR 23 , SR 23 ,N(R 23 ) 2 , or P(R 23 ) 2 , wherein R 23 in each occurrence independently is hydrogen or a hydrocarbyl group of 1 to 8 carbon atoms.
8. The polymerization catalyst of claim 7 wherein R 19 in each occurrence independently is hydrogen, R 20 is hydrogen, methyl, t-butyl, or methoxy, R 21 and R 23 in each occurrence independently are the same or different and are hydrogen or methyl and R 22 is a hydroxyl or methoxy group.
9. The polymerization catalyst of claim 1 wherein the molar ratio of the aluminum atoms from the aluminum compound (B) to the OH groups from the ligand (A) is from 0.25:1 to 1:1.
10. The polymerization catalyst of claim 1 wherein the molar ratio of the aluminum from the aluminum compound (B) to the Lewis base (C) is from 5:1 to 1.25:1.
11. A process for homopolymerization or copolymerization of an alkylene oxide comprising the step of contacting one or more alkylene oxides with a catalytic amount of a reaction product of at least:
A.) a ligand of the formula I,
wherein
R 1 , R 2 , R 3 , and R 4 in each occurrence independently are the same or different hydrocarbyl substituents of 1 to 20 carbon atoms, hydrogen, halogen, or alkoxy groups of 1 to 8 carbon atoms;
X in each occurrence independently is CR 6 with R 6 being hydrogen or an alkyl group of 1 to 8 carbon atoms; and
R 5 is an organic divalent group of 4 to 40 carbon atoms with the proviso that the two nodes X are not bound to the same atom or to vicinal atoms in the group R 5 ; and
B.) an aluminum compound of the formula
AlR 7 R 8 R 9 , wherein R 7 , R 8 and R 9 each independently is a C 1 to C 12 hydrocarbyl group, hydrogen, halogen, or an alkoxy group of 1 to 20 carbon atoms; and
C.) a Lewis base selected from the group consisting of amines, phosphines, amides, nitriles, isonitriles, and alcohols.
12. The process of claim 11 wherein the polymerization is conducted in an aliphatic hydrocarbon medium.
13. The process of claim 11 wherein the alkylene oxide is ethylene oxide.
14. The process of claim 11 wherein the alkylene oxide is propylene oxide.