POLY(OXIRANE)S AND PROCESSES AND CATALYSTS FOR MAKING THEM
A catalyst composition for polymerizing oxiranes is provided that yields high molecular weight poly(oxiranes). The catalyst composition comprises: a hydrophobically modified particulate inorganic oxide; an aluminum alkyl complex; and a compound containing a Lewis basic free electron pair. Polymerization methods and poly(oxirane) polymers are also provided.
1 . A catalyst composition for polymerizing an epoxide, the composition comprising:
a hydrophobically modified particulate inorganic oxide;
an aluminum alkyl complex; and
a compound containing a Lewis basic free electron pair;
wherein the hydrophobically modified particulate inorganic oxide is hydrophobically modified fumed silica.
2 . The catalyst composition of claim 1 wherein the hydrophobically modified particulate inorganic oxide is finely divided and has an average surface area of 50 m 2 /g or greater.
3 . (canceled)
4 . (canceled)
5 . The catalyst composition of claim 1 comprising about 0.001 to about 20 mmol of hydrophobic groups per gram of inorganic oxide.
6 . The catalyst composition of claim 1 comprising about 0.01 to about 50 mmol of aluminum alkyl complex per gram of inorganic oxide.
7 . The catalyst composition of claim 1 wherein the molar ratio of the aluminum alkyl complex to the compound containing a Lewis basic free electron pair is about 0.1 to about 100.
8 . The catalyst composition of claim 1 wherein the aluminum alkyl complex is of the formula AlR 2 R 3 x (OR 4 ) (2-x) , wherein R 2 and R 3 are independently hydrogen or C 1 -C 8 alkyl, R 4 is C 1 -C 20 alkyl or aryl, and x is 0, 1, or 2.
9 . The catalyst composition of claim 1 wherein the compound containing a Lewis basic free electron pair is of the formula ER 5 R 6 R 7 , wherein E is a nitrogen or phosphorus atom and R 5 , R 6 , and R 7 are each independently H, C 1 -C 20 alkyl, aryl, or two or three of R 5 , R 6 , and are linked to form a cyclic amine or phosphine with the E group.
10 . An oxirane polymerization process comprising: reacting an oxirane containing compound with itself, or with itself and with other oxiranes, in the presence of the catalyst composition of claim 1 .
11 . The process of claim 10 wherein the reaction is conducted in a diluent.
12 . The process of claim 10 wherein the oxirane containing compound is selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, and mixtures thereof.
13 . (canceled)
14 . A catalyst composition for polymerizing an epoxide, the composition comprising:
a hydrophobically modified particulate inorganic oxide;
an aluminum alkyl complex; and
a compound containing a Lewis basic free electron pair, wherein the hydrophobically modified particulate inorganic oxide comprises an inorganic oxide functionalized with monofunctional groups of the formula —(SiR 2 O) n SiR 3 , difunctional groups of the formula —(SiR 2 O) n SiR 2 —, or mixtures thereof, wherein n at each occurrence is independently 0 to 20, R is independently H or C 1 -C 8 alkyl, and wherein each monofunctional and difunctional group is bound to the inorganic oxide through one or more oxygen atoms.
15 . A The catalyst composition of claim 14 wherein the hydrophobically modified particulate inorganic oxide is finely divided and has an average surface area of 50 m 2 /g or greater.
16 . The catalyst composition of claim 14 comprising about 0.001 to about 20 mmol of hydrophobic groups per gram of inorganic oxide.
17 . The catalyst composition of claim 14 comprising about 0.01 to about 50 mmol of aluminum alkyl complex per gram of inorganic oxide.
18 . The catalyst composition of claim 14 wherein the molar ratio of the aluminum alkyl complex to the compound containing a Lewis basic free electron pair is about 0.1 to about 100.
19 . The catalyst composition of claim 14 wherein the aluminum alkyl complex is of the formula AlR 2 R 3 x (OR 4 ) (2-x) , wherein R 2 and R 3 are independently hydrogen or C 1 -C 8 alkyl, R 4 is C 1 -C 20 alkyl or aryl, and x is 0, 1, or 2.
20 . The catalyst composition of claim 14 wherein the compound containing a Lewis basic free electron pair is of the formula ER 5 R 6 R 7 , wherein E is a nitrogen or phosphorus atom and R 5 , R 6 , and R 7 are each independently H, C 1 -C 20 alkyl, aryl, or two or three of R 5 , R 6 , and are linked to form a cyclic amine or phosphine with the E group.
21 . An oxirane polymerization process comprising: reacting an oxirane containing compound with itself, or with itself and with other oxiranes, in the presence of the catalyst composition of claim 14 .
22 . The process of claim 21 wherein the reaction is conducted in a diluent.
23 . The process of claim 21 wherein the oxirane containing compound is selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, and mixtures thereof.