Double-metal cyanide catalysts for preparing polyether polyols

Details Double-metal cyanide catalysts for preparing polyether polyols Double-metal cyanide catalysts for preparing polyether polyols

2002-08-28

2003-07-01

Wood, Elizabeth (Department: 1755)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From heterocyclic reactant containing as ring atoms oxygen,...

C502S175000, C502S200000, C502S172000, C502S150000, C528S403000, C528S405000, C528S408000, C528S410000, C528S411000, C528S412000, C528S413000, C528S414000, C528S415000, C528S416000, C549S512000, C549S513000, C549S518000, C549S539000, C568S617000, C568S622000, C568S623000, C568S624000

Reexamination Certificate

active

06586564

ABSTRACT:

TECHNICAL FIELD OF THE INVENTION
The present invention relates to double-metal cyanide (DMC) catalysts for preparing polyether polyols by the polyaddition of alkylene oxides on to starter compounds having active hydrogen atoms.
BACKGROUND OF THE INVENTION
DMC catalysts for the polyaddition of alkylene oxides on to starter compounds having active hydrogen atoms are known. See, for example, U.S. Pat. Nos. 3,404,109; 3,829,505; 3,941,849; and 5,158,922. In comparison to polyether polyols prepared with alkali catalysts such as, for example, alkali metal hydroxides, DMC-catalyzed polyether polyols exhibit a reduction in the content of mono-functional polyethers having terminal double bonds, so-called “mono-ols”. Polyether polyols prepared with DMC catalysts can be used to produce high-grade polyurethanes such as, for example, elastomers, foams and coatings.
DMC catalysts are typically prepared by reacting an aqueous solution of a metal salt with an aqueous solution of a metal cyanide salt in the presence of an organic complexing ligand, for example, an ether. In a typical DMC catalyst preparation, aqueous solutions of zinc chloride (in excess) and potassium hexacyanocobaltate are mixed together to form a suspension. Dimethoxyethane (glyme) is then added to the suspension. The DMC catalyst is then filtered and washed with an aqueous solution of glyme. A DMC catalyst prepared in this manner can be represented by the general formula
Zn
3
[Co(CN)
6
]
2
.x ZnCl
2
.y H
2
O.z glyme
See, for example, EP-A 700 949.
The following references disclose DMC catalysts which use tert-butanol as the organic complexing ligand (by itself or in combination with a polyether) in the preparation of polyether polyols to further reduce mono-ol content: JP 4145123; U.S. Pat. No. 5,470,813; EP 700 949; EP 743 093; EP 761 708; and WO 97/40086. Additionally, the use of these DMC catalysts in the production of polyether polyols reduces the induction time in the polyaddition reaction of alkylene oxides with corresponding starter compounds. Catalytic activity also increases with the use of these DMC catalysts.
There remains, however, a need for DMC catalysts which have increased activity compared to catalysts known in the art which can be used to produce polyether polyols.
SUMMARY OF THE INVENTION
DMC catalysts of the present invention are composed of: a) at least one DMC compound; b) at least one organic complexing ligand which is not a coronand; and c) at least one coronand.
DMC catalysts of the present invention have increased activity compared to catalysts known in the art.
DESCRIPTION OF THE INVENTION
DMC catalysts of the present invention are composed of: a) at least one DMC compound; b) at least one organic complexing ligand which is not a coronand; and c) at least one coronand.
DMC catalysts of the present invention can optionally comprise water, preferably in an amount from 1 to 10 wt. %, based on the total weight of the DMC catalyst. Also, DMC catalysts of the present invention can optionally comprise one or more water-soluble metal salts, preferably in an amount from 5 to 25 wt. %, based on the total weight of the DMC catalyst.
Water-soluble metal salts which can be used in the present invention can be represented by the general formula (I)
M(X)
n
  (I)
wherein
M is selected from Zn(II); Fe(II); Ni(II); Mn(II); Co(II); Sn(II); Pb(II); Fe(III); Mo(IV); Mo(VI); Al(III); V(V); V(IV); Sr(II); W(IV); W(VI); Cu(II); and Cr(III) (preferably, Zn(II), Fe(II), Co(II) and Ni(II));
each X is identical or different, preferably identical, and an anion selected from halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates and nitrates; and
n is 1, 2 or 3.
DMC compounds of the present invention are the reaction products of water-soluble metal salts and water-soluble metal cyanide salts or the corresponding acids of the metal cyanide salts. Examples of water-soluble metal salts which can be used to prepare the DMC compounds of the present invention can be represented by the general formula (I), in which M is selected from Zn(II); Fe(II); Ni(II); Mn(II); Co(II); Sn(II); Pb(II); Fe(III); Mo(IV); Mo(VI); Al(III); V(V); V(IV); Sr(II); W(IV); W(VI); Cu(II); and Cr(III) (preferably, Zn(II), Fe(II), Co(II) and Ni(II)). Each X is identical or different, preferably identical, and an anion selected from halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates and nitrates. The value of n is 1, 2 or 3.
Examples of suitable water-soluble metal salts which can be used in the present invention include zinc chloride; zinc bromide; zinc acetate; zinc acetylacetonate; zinc benzoate; zinc nitrate; iron(II) sulfate; iron(II) bromide; iron(II) chloride; cobalt(II) chloride; cobalt(II) thiocyanate; nickel(II) chloride; and nickel(II) nitrate. Mixtures of water-soluble metal salts can also be used.
Examples of water-soluble metal cyanide salts which can be used to prepare the DMC compounds of the present invention can be represented by the general formula (II)
(Y)
a
M′(CN)
b
(A)
c
  (II)
wherein
M′ is selected from Fe(II); Fe(III); Co(II); Co(III); Cr(II); Cr(III); Mn(II); Mn(III); Ir(III); Ni(II); Rh(III); Ru(II); V(IV); and V(V) (Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II) are preferred) and the water-soluble metal cyanide salt can comprise one or more of these metals;
each Y is identical or different, preferably identical, and is chosen from the group consisting of alkali metal ions and alkaline earth metal ions;
A is identical or different, preferably identical, and is chosen from halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates and nitrates; and
a, and b and c are integers, with the values for a, b and c being chosen so that electroneutrality of the metal cyanide salt is achieved (a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; and c preferably has the value 0).
Examples of water-soluble metal cyanide salts which can be used in the present invention include potassium hexacyanocobaltate(III); potassium hexacyanoferrate(II); potassium hexacyanoferrate(III); calcium (hexacyanocobaltate(III); and lithium hexacyanocobaltate(III).
A preferred DMC compound according to the invention can be represented by the general formula (III)
M
x
[M′
x′
(CN)
y
]
z
  (III)
wherein
M is as defined in formula (I);
M′ is as defined in formula (II); and
x, x′, y and z are integers and are chosen such that electroneutrality of the DMC compound exists.
Preferably,
x=3, x′=1, y=6 and z=2′;
M=Zn(II), Fe(II), Co(II) or Ni(II); and
M′=Co(III), Fe(III), Cr(III) or Ir(III).
Examples of DMC compounds which can be used in the present invention include zinc hexacyanocobaltate(III); zinc hexacyanoiridate(III); zinc hexacyanoferrate(III); and cobalt(II) hexacyanocobaltate(III). Further examples of DMC compounds which can be used in the present invention can be found in, for example, U.S. Pat. No. 5,158,922, the teachings of which are incorporated herein by reference. Zinc hexacyanocobaltate(III) is preferably used in the present invention.
Organic complexing ligands of the present invention are known and described in the following references: U.S. Pat. Nos. 5,470,813; 5,158,922; 3,404,109; 3,829,505; and 3,941,849, the teachings of which are incorporated herein by reference, as well as in EP 700 949; EP 761 708; JP 4145123; EP 743 093; and WO 97/40086. Preferably, organic complexing ligands of the present invention are water-soluble organic compounds having heteroatoms such as oxygen, nitrogen, phosphorus or sulfur which are able to form complexes with the DMC compound. Examples of organic complexing ligands which can be used in the present invention include, for example, alcohols; aldehydes; ketones; ethers; esters; amides; ureas; nitriles; sulfides and mixtures thereof. Preferred organic complexing ligands

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