UNSATURATED TERTIARY ALCOHOLS AS LIGANDS FOR ACTIVE DMC CATALYSTS
The present invention provides an active double metal cyanide (DMC) catalyst made of a non-hexanitrometallate containing double metal cyanide compound, one or more unsaturated tertiary alcohols and about 0 to about 80 wt. %, based on the amount of catalyst, of a functionalized polymer having a number average molecular weight greater than about 200. Also provided are methods of producing the inventive catalysts. The inventive catalysts may find use in the production of polyols.
1 . A double metal cyanide (DMC) catalyst comprising:
a non-hexanitrometallate containing double metal cyanide compound;
one or more unsaturated tertiary alcohols; and
about 0 to about 80 wt. %, based on the amount of catalyst, of a functionalized polymer having a number average molecular weight greater than about 200.
2 . The catalyst according to claim 1 , wherein the double metal cyanide compound is a zinc hexacyanocobaltate.
3 . The catalyst according to claim 1 , wherein the one or more unsaturated tertiary alcohols are of the formula (I),
wherein
R 1 represents a group containing from two to twenty carbon atoms with at least one site of unsaturation, where an unsaturated carbon atom is attached to the hydroxyl-bearing carbon of (I) and wherein atoms other than carbon and hydrogen may be present,
R 2 represents a group containing from two to twenty carbon atoms with at least one site of unsaturation where an unsaturated carbon is attached to the hydroxyl-bearing carbon of (I) or one to twenty carbon atoms free of any sites of unsaturation attached to the hydroxyl-bearing carbon (I) and wherein atoms other than carbon and hydrogen may be present,
R 3 represents a group containing from two to twenty carbon atoms with at least one site of unsaturation where an unsaturated carbon is attached to the hydroxyl-bearing carbon of (I) or one to twenty carbon atoms free of any sites of unsaturation attached to the hydroxyl-bearing carbon (I) and wherein atoms other than carbon and hydrogen may be present.
4 . The catalyst according to claim 1 , wherein the unsaturated tertiary alcohol is 2-methyl-3-butene-2-ol (MBE).
5 . The catalyst according to claim 1 , wherein the unsaturated tertiary alcohol is 2-methyl-3-butyn-2-ol (MBY).
6 . The catalyst according to claim 1 , wherein the functionalized polymer is a polyether polyol having a number average molecular weight of about 1000 to about 10,000.
7 . The catalyst according to claim 1 , wherein the functionalized polymer is a poly(oxypropylene) diol having a number average molecular weight of about 2000 to about 4000.
8 . The catalyst according to claim 1 containing about 5 to about 80 wt. % of the functionalized polymer.
9 . The catalyst according to claim 1 containing about 10 to about 70 wt. % of the functionalized polymer.
10 . The catalyst according to claim 1 containing about 15 to about 60 wt. % of the functionalized polymer.
11 . A method of preparing a double metal cyanide (DMC) catalyst comprising reacting
an aqueous solution of a metal salt, and
an aqueous solution of a non-hexanitrometallate containing metal cyanide salt,
in the presence of
one or more unsaturated tertiary alcohols, and
a functionalized polymer having a number average molecular weight greater than about 200,
wherein the DMC catalyst contains from about 0 to about 80 wt. % of the polymer.
12 . The method according to claim 11 , wherein the DMC catalyst is a zinc hexacyanocobaltate.
13 . The method according to claim 11 , wherein the one or more unsaturated tertiary alcohols are of the formula (I),
wherein
R 1 represents a group containing from two to twenty carbon atoms with at least one site of unsaturation where an unsaturated carbon atom is attached to the hydroxyl-bearing carbon of (I) and wherein atoms other than carbon and hydrogen may be present,
R 2 represents a group containing from two to twenty carbon atoms with at least one site of unsaturation where an unsaturated carbon is attached to the hydroxyl-bearing carbon of (I) or one to twenty carbon atoms free of any sites of unsaturation attached to the hydroxyl-bearing carbon (I) and wherein atoms other than carbon and hydrogen may be present,
R 3 represents a group containing from two to twenty carbon atoms with at least one site of unsaturation where an unsaturated carbon is attached to the hydroxyl-bearing carbon of (I) or one to twenty carbon atoms free of any sites of unsaturation attached to the hydroxyl-bearing carbon (I) and wherein atoms other than carbon and hydrogen may be present.
14 . The method according to claim 11 , wherein the unsaturated tertiary alcohol is 2-methyl-3-butene-2-ol (MBE).
15 . The method according to claim 11 , wherein the unsaturated tertiary alcohol is 2-methyl-3-butyn-2-ol (MBY).
16 . The method according to claim 1 1 , wherein the functionalized polymer is a polyether polyol having a number average molecular weight of about 200 to about 10,000.
17 . The method according to claim 11 , wherein the functionalized polymer is a poly(oxypropylene) diol having a number average molecular weight of about 2000 to about 4000.
18 . The method according to claim 11 , wherein the DMC catalyst contains about 5 to about 80 wt. % of the functionalized polymer.
19 . The method according to claim 11 , wherein the DMC catalyst contains about 10 to about 70 wt. % of the functionalized polymer.
20 . The method according to claim 11 , wherein the DMC catalyst contains about 15 to about 60 wt. % of the functionalized polymer.
21 . A method of preparing a double metal cyanide (DMC) catalyst, said method comprising:
reacting aqueous solutions of a metal salt and a non-hexanitrometallate containing metal cyanide salt, said metal salt being in excess compared with the amount of metal cyanide salt, in the presence of one or more unsaturated tertiary alcohols with efficient mixing to produce a catalyst slurry;
combining the catalyst slurry with a functionalized polymer having a number average molecular weight greater than about 200;
isolating a polymer-containing solid catalyst from the slurry;
washing the polymer-containing solid catalyst with an aqueous solution that contains additional unsaturated tertiary alcohol; and
recovering a double metal cyanide (DMC) catalyst containing about 0 to about 80 wt. %, based on the amount of the DMC catalyst, of the polymer.
22 . The method according to claim 21 , wherein the double metal cyanide catalyst is a zinc hexacyanocobaltate.
23 . The method according to claim 21 , wherein the one or more unsaturated tertiary alcohols are of the formula (I),
wherein
R 1 represents a group containing from two to twenty carbon atoms with at least one site of unsaturation where an unsaturated carbon atom is attached to the hydroxyl-bearing carbon of (I) and wherein atoms other than carbon and hydrogen may be present,
R 2 represents a group containing from two to twenty carbon atoms with at least one site of unsaturation where an unsaturated carbon is attached to the hydroxyl-bearing carbon of (I) or one to twenty carbon atoms free of any sites of unsaturation attached to the hydroxyl-bearing carbon (I) and wherein atoms other than carbon and hydrogen may be present,
R 3 represents a group containing from two to twenty carbon atoms containing at least one site of unsaturation where an unsaturated carbon is attached to the hydroxyl-bearing carbon of (I) or one to twenty carbon atoms free of any sites of unsaturation attached to the hydroxyl-bearing carbon (I) and wherein atoms other than carbon and hydrogen may be present.
24 . The method according to claim 21 , wherein the unsaturated tertiary alcohol is 2-methyl-3-butene-2-ol (MBE).
25 . The method according to claim 21 , wherein the unsaturated tertiary alcohol is 2-methyl-3-butyn-2-ol (MBY).
26 . The method according to claim 21 , wherein the functionalized polymer is a polyether polyol having a number average molecular weight of about 200 to about 10,000.
27 . The method according to claim 21 wherein the polyether is a poly(oxypropylene)diol having a number average molecular weight of about 2000 to about 4000.
28 . The method according to claim 21 , wherein the catalyst slurry is combined with the polyether by low-shear mixing.
29 . The method according to claim 21 , wherein the aqueous solution of unsaturated tertiary alcohol in the step of washing also includes additional polymer.
30 . The method according to claim 29 , wherein, after the step of washing, the catalyst is re-washed with additional unsaturated tertiary alcohol.
31 . The method according to claim 30 , wherein the unsaturated tertiary alcohol further includes a polymer.
32 . In a process for the production of a polyol by polyaddition of alkylene oxides onto starter compounds containing active hydrogen atoms, the improvement comprising conducting the polyaddition in the presence of the double metal cyanide (DMC) catalyst comprising a non-hexanitrometallate containing double metal cyanide compound, one or more unsaturated tertiary alcohols and about 0 to about 80 wt. %, based on the amount of catalyst, of a functionalized polymer having a number average molecular weight greater than about 200.
33 . The process according to claim 32 , wherein the DMC catalyst is a zinc hexacyanocobaltate.
34 . The process according to claim 32 , wherein the one or more unsaturated tertiary alcohols are of the formula (I),
wherein
R 1 represents a group containing from two to twenty carbon atoms with at least one site of unsaturation where an unsaturated carbon atom is attached to the hydroxyl-bearing carbon of (I) and wherein atoms other than carbon and hydrogen may be present,
R 2 represents a group containing from two to twenty carbon atoms with at least one site of unsaturation where an unsaturated carbon is attached to the hydroxyl-bearing carbon of (I) or one to twenty carbon atoms free of any sites of unsaturation attached to the hydroxyl-bearing carbon (I) and wherein atoms other than carbon and hydrogen may be present,
R 3 represents a group containing from two to twenty carbon atoms with at least one site of unsaturation where an unsaturated carbon is attached to the hydroxyl-bearing carbon of (I) or one to twenty carbon atoms free of any sites of unsaturation attached to the hydroxyl-bearing carbon (I) and wherein atoms other than carbon and hydrogen may be present.
35 . The process according to claim 32 , wherein the unsaturated tertiary alcohol is 2-methyl-3-butene-2-ol (MBE).
36 . The process according to claim 32 , wherein the unsaturated tertiary alcohol is 2-methyl-3-butyn-2-ol (MBY).
37 . The process according to claim 32 , wherein the functionalized polymer is a polyether polyol having a number average molecular weight of about 200 to about 10,000.
38 . The process according to claim 32 , wherein the functionalized polymer is a poly(oxypropylene)diol having a number average molecular weight of about 2000 to about 4000.
39 . The process according to claim 32 , wherein the DMC catalyst contains about 5 to about 80 wt. % of the functionalized polymer.
40 . The process according to claim 32 , wherein the DMC catalyst contains about 10 to about 70 wt. % of the functionalized polymer.
41 . The process according to claim 32 , wherein the DMC catalyst contains about 15 to about 60 wt. % of the functionalized polymer.