Method for preparing metal cyanide catalysts using polymerizable complexing agents
Complexes of a metal cyanide polymerization catalyst and certain monomer complexing agents provide a method whereby heterogeneous, active metal cyanide catalysts can be prepared. The catalysts are useful alkylene oxide polymerization catalysts that are easily separated from the polymerization product and recycled.
1. A catalyst complex comprising a water insoluble metal cyanide catalyst that is complexed with a monomer complexing agent that has at least one polymerizable site of carbon-carbon unsaturation.
2. The catalyst complex of claim 1 , which is represented by the structure
M b [M 1 (CN) r (X) t ] c [M 2 (X) 6 ] d .zL.nM 3 x A y
wherein M is a metal ion that forms an insoluble precipitate with the M 1 (CN) r (X) t group; M 1 and M 2 are transition metal ions that may be the same or different;
each X independently represents a group other than cyanide that coordinates with an M 1 or M 2 ion;
M 3 x A Y represents salt of metal ion M 3 and anion A, wherein M 3 is the same as or different than M;
b and c are positive numbers that, together with d, reflect an electrostatically neutral complex;
d is zero or a positive number;
x and y are numbers that reflect an electrostatically neutral salt;
r is from 4 to 6; t is from 0 to 2;
n is a positive number indicating the relative quantity of M 3 x A y ;
L represents the complexing agent and z is a positive number representing the relative quantity of complexed L molecules.
3. The catalyst complex of claim 2 , which is a zinc hexacyanocobaltate catalyst complex wherein M 3 is zinc.
4. The catalyst complex of claim 1 , wherein the monomer complexing agent is a vinyl monomer containing a nitrogen or oxygen atom.
5. The catalyst complex of claim 4 , wherein the monomer complexing agent is vinyl acetate, vinyl ethyl ether, vinyl 2-ethylhexanoate, vinyl isobutyl ether, vinyl methyl ketone, 1-vinyl-2-pyrrolidinone or a mixture of two or more thereof.
6. The catalyst complex of claim 1 , wherein the monomer complexing agent is acrylamide, methacrylamide, an N,N-dialkyl acrylamide or an N,N-dialkyl methacrylamide.
7. The catalyst complex of claim 1 , wherein the monomer complexing agent is an acrylic or methacrylic ester.
8. The catalyst complex of claim 7 , wherein the acrylic or methacrylic ester has one or more ether and/or alcohol groups in the ester portion of the molecule.
9. The catalyst complex of claim 8 , wherein the acrylic or methacrylic ester is represented by the structure
R 1 [—O—C( 0 )—CR═CH 2 ] x
where R is hydrogen or methyl, x is a number that is at least 1 and R 1 is (1) the residue of a compound having from 1–8 aliphatic hydroxyl groups, (2) the residue of a phenol or bisphenol.
10. The catalyst complex of claim 9 , wherein the acrylic or methacrylic ester is
(A) an ester of one or more moles of acrylic or methacrylic acid and a mole of propylene glycol, ethylene glycol, trimethylolpropane, neopentyl glycol, pentaerythritol, glycerine, dipropylene glycol, diethylene glycol or an ethoxylated and/or propoxylated derivative of any of the foregoing,
(B) a complex ester of one or more moles of acrylic or methacylic acid and (a) one or more moles of a C 6 –C 24 straight chain saturated or unsaturated carboxylic acid and (b) propylene glycol, ethylene glycol, trimethylolpropane, neopentyl glycol, pentaerythritol, glycerine, dipropylene glycol, diethylene glycol or an ethoxylated and/or propoxylated derivative of any of the foregoing; or
(C) a mixture of two or more of (A) and/or (B).
11. A polymer having dispersed therein a metal cyanide catalyst that is complexed with said polymer, formed by subjecting the catalyst complex of claim 1 to conditions sufficient to polymerize the monomer complexing agent.
12. A polymer having dispersed therein a metal cyanide catalyst that is complexed with said polymer, formed by subjecting the catalyst complex of claim 3 to conditions sufficient to polymerize the monomer complexing agent.
13. A polymer having dispersed therein a metal cyanide catalyst that is complexed with said polymer, formed by subjecting the catalyst complex of claim 4 to conditions sufficient to polymerize the monomer complexing agent.
14. A polymer having dispersed therein a metal cyanide catalyst that is complexed with said polymer, formed by subjecting the catalyst complex of claim 5 to conditions sufficient to polymerize the monomer complexing agent.
15. A polymer having dispersed therein a metal cyanide catalyst that is complexed with said polymer, formed by subjecting the catalyst complex of claim 6 to conditions sufficient to polymerize the monomer complexing agent.
16. A polymer having dispersed therein a metal cyanide catalyst that is complexed with said polymer, formed by subjecting the catalyst complex of claim 7 to conditions sufficient to polymerize the monomer complexing agent.
17. A polymer having dispersed therein a metal cyanide catalyst that is complexed with said polymer, formed by subjecting the catalyst complex of claim 9 to conditions sufficient to polymerize the monomer complexing agent.
18. A polymer having dispersed therein a metal cyanide catalyst that is complexed with said polymer.
19. The polymer of claim 18 , wherein the polymer is a polymer of a vinyl monomer containing a nitrogen or oxygen atom.
20. The polymer of claim 19 , wherein the polymer is a polymer of acrylamide, methacrylamide, an N,N-dialkyl acrylamide or an N,N-dialkyl methacrylamide.
21. The polymer of claim 19 , wherein the polymer is a polymer of an acrylic or methacrylic ester.
22. The polymer of claim 18 , wherein the polymer is a polymer of
(A) an ester of one or more moles of acrylic or methacrylic acid and a mole of propylene glycol, ethylene glycol, trimethylolpropane, neopentyl glycol, pentaerythritol, glycerine, dipropylene glycol, diethylene glycol or an ethoxylated and/or propoxylated derivative of any of the foregoing,
(B) a complex ester of one or more moles of acrylic or methacylic acid and (a) one or more moles of a C 6 –C 24 straight chain saturated or unsaturated carboxylic acid and (b) propylene glycol, ethylene glycol, trimethylolpropane, neopentyl glycol, pentaerythritol, glycerine, dipropylene glycol, diethylene glycol or an ethoxylated and/or propoxylated derivative of any of the foregoing; or
(C) a mixture of two or more of (A) and/or (B).
23. A method of making a polymerization catalyst, comprising
a) treating a metal cyanide catalyst with a complexing agent having at least one site of polymerizable carbon-carbon unsaturation, and
b) subjecting said treated catalyst to conditions sufficient to polymerize said complexing agent to form a polymer containing the metal cyanide catalyst dispersed within it.
24. The method of claim 23 , wherein the metal cyanide catalyst is represented by the structure
M b [M 1 (CN) r (X) t ] c [M 2 (X) 6 ] d .zL.nM 3 x A y
wherein M is a metal ion that forms an insoluble precipitate with the M 1 (CN) r (X) t group;
M 1 and M 2 are transition metal ions that may be the same or different;
each X independently represents a group other than cyanide that coordinates with an M 1 or M 2 ion;
M 3 x A y represents salt of metal ion M 3 and anion A, wherein M 3 is the same as or different than M;
b and c are positive numbers that, together with d, reflect an electrostatically neutral complex;
d is zero or a positive number;
x and y are numbers that reflect an electrostatically neutral salt;
r is from 4 to 6; t is from 0 to 2;
n is a positive number indicating the relative quantity of M 3 x A y ;
L represents the complexing agent and z is a positive number representing the relative quantity of complexed L molecules.
25. The method of claim 24 , wherein the polymerization is performed in the presence of a free radical initiator.
26. The method of claim 24 , wherein the metal cyanide catalyst is precipitated from starting solutions or suspensions, and step b) is conducted simultaneously with the precipitation of the catalyst.
27. The method of claim 25 , wherein the free radical initiator is an azo-type initiator.
28. The method of claim 23 , wherein the monomer complexing agent is a vinyl monomer containing a nitrogen or oxygen atom.
29. The method of claim 23 , wherein the monomer complexing agent is vinyl acetate, vinyl ethyl ether, vinyl 2-ethylhexanoate, vinyl isobutyl ether, vinyl methyl ketone, 1-vinyl-2-pyrrolidinone or a mixture of two or more thereof.
30. The method of claim 23 , wherein the monomer complexing agent is acrylamide, methacrylamide, an N,N-dialkyl acrylamide or an N,N-dialkyl methacrylamide.
31. The method of claim 23 , wherein the monomer complexing agent is an acrylic or methacrylic ester.
32. The method of claim 31 , wherein the acrylic or methacrylic ester has one or more ether and/or alcohol groups in the ester portion of the molecule.
33. The method of claim 32 , wherein the acrylic or methacrylic ester is represented by the structure
R 1 [—O—C(O)—CR═CH 2 ] x
where R is hydrogen or methyl, x is a number that is at least 1, and R 1 is (1) the residue of a compound having from 1–8 aliphatic hydroxyl groups, (2) the residue of a phenol or bisphenol.
34. The method of claim 33 , wherein the acrylic or methacrylic ester is
(A) an ester of one or more moles of acrylic or methacrylic acid and a mole of propylene glycol, ethylene glycol, trimethylolpropane, neopentyl glycol, pentaerythritol, glycerine, dipropylene glycol, diethylene glycol or an ethoxylated and/or propoxylated derivative of any of the foregoing,
(B) a complex ester of one or more moles of acrylic or methacylic acid and (a) one or more moles of a C 6 –C 24 straight chain saturated or unsaturated carboxylic acid and (b) propylene glycol, ethylene glycol, trimethylolpropane, neopentyl glycol, pentaerythritol, glycerine, dipropylene glycol, diethylene glycol or an ethoxylated and/or propoxylated derivative of any of the foregoing; or
(C) a mixture of two or more of (A) and/or (B).
35. The method of claim 23 , wherein volatiles are stripped from the catalyst prior to polymerization of the monomer complexing agent.
36. The method of claim 23 , wherein volatiles are stripped from the catalyst simultaneously with the polymerization of the monomer complexing agent.
37. The method of claim 23 , wherein step b is performed in the presence of a support.
38. The method of claim 37 , wherein the support is a particulate silica, silica chips, alumina particulates or spheres, porous alumina spheres or particulates, polyacrylate or styrene/divinylbenzene copolymer particles or catalyst substrate spheres.
39. A method of making a polyether, comprising subjecting a mixture of an alkylene oxide and an initiator compound to conditions sufficient to polymerize the alkylene oxide while in the presence of the polymer of claim 11 .