阅读说明：本技术 催化剂络合物 (Catalyst complex ) 是由 D·K·斯蒂尔曼 D·A·巴布 J·德皮克尔 J·库吉佩尔 M·S·罗斯 于 2018-05-10 设计创作，主要内容包括：实施例涉及制造改性的双金属氰化物络合物的方法；制造一元醇或多元醇的方法,其包括提供所述改性的双金属氰化物络合物；环氧烷聚合方法,其包括提供所述改性的双金属氰化物络合物；分批、半分批或连续制造方法,其包括提供所述改性的双金属氰化物络合物；以及使用所述分批、半分批或连续制造方法制备的聚醚多元醇,所述分批、半分批或连续制造方法包括提供所述改性的双金属氰化物络合物。(Embodiments relate to methods of making modified double metal cyanide complexes; a method of making a monol or a polyol comprising providing the modified double metal cyanide complex; an alkylene oxide polymerization process comprising providing the modified double metal cyanide complex; a batch, semi-batch, or continuous manufacturing process comprising providing the modified double metal cyanide complex; and polyether polyols prepared using the batch, semi-batch or continuous manufacturing process comprising providing the modified double metal cyanide complex.)

1. A method for making a catalyst complex, the method comprising:

a) forming a starting solution comprising i) a solvent comprising at least one of water and a liquid fatty alcohol, said solvent having ii) M dissolved therein²Cyanometallate compounds of metal cyanometallates and iii) M¹Metal salt of said M¹Reacting a metal salt with the cyanometallate compound to form water-insoluble M¹A metal cyanometallate, said starting solution further comprising 0.01 to 10 moles per mole of cyanometallate compound of iii) at least one other than said M¹M of metal salt³A metal compound of said M³M in which the metal compound is not titanium³A compound of a metal, said M³The metal is selected from one or more of magnesium, group 3-group 15 metals except titanium or lanthanide series metals, and M is³The metal is bonded to at least one alkoxide anion, aryloxide anion, carboxylate anion, acyl anion, pyrophosphate anion, phosphate anion, thiophosphate anion, dithiophosphate anion, phosphate anion, thiophosphate anion, amide anion, oxyanion, siloxide anion, hydride anion, carbamate anion, or hydrocarbon anion, and the M is a metal, a metal³The metal compound does not contain a halogen anion;

b) reacting said cyanometallate compound with M¹The metal salt reacts to form a water-insoluble catalyst complex comprising M¹Metal cyanometallates.

2. The method of claim 1, further comprising step c) washing the water-insoluble catalyst complex with a washing liquid comprising at least one of water and a liquid complexing agent.

3. The method of claim 1 or 2, further comprising step d) drying the catalyst complex to form a solid.

4. The method of any one of the preceding claims, wherein M¹Is zinc and the cyanometallate compound is a hexacyanocobaltate compound.

5. The method of any one of the preceding claims, wherein M³Not titanium, barium, antimony or calcium.

6. The method of any one of the preceding claims, wherein M³Not titanium, barium, antimony, calcium, tin or zinc.

7. The method of any one of the preceding claims, wherein M³Is not titanium, barium, antimony, calcium, tin, zinc, iron, vanadium, magnesium, tungsten or scandium.

8. The method of any one of the preceding claims, wherein M³Is one or more of aluminum, hafnium, indium, manganese or gallium.

9. The method of any one of the preceding claims, wherein the M is³The metal compound is selected from the group consisting of: (a) m³Precursors of metal oxides which react under the conditions of step a) and/or step b) to form M³A metal oxide; and (b) granular M³A metal oxide.

10. The method of any one of the preceding claims, wherein the M is³The metal compound being M³A metal oxide.

11. The method of any preceding claimThe method of (1), wherein said M³The metal compound being M³A metal alkoxide.

12. The method of any one of the preceding claims, wherein the starting solution contains per mole of the M³The metal compound is at least 5 moles of water.

13. The process of any preceding claim, wherein the liquid fatty alcohol in step a) comprises a C3-C6 alkanol.

14. The process according to any one of the preceding claims, wherein the liquid fatty alcohol in step C) is selected from the group consisting of C3-C6 alkanols and polyether alcohols having a number average molecular weight of up to 8,000 g/mol.

15. A catalyst complex formed in the method of any one of claims 1 to 14.

16. The water-insoluble catalyst complex of claim 15, containing per mole of M²0.002 to 10 moles of metal of M³A metal.

17. The water-insoluble catalyst complex according to claim 15 or 16, corresponding to the formula:

M¹ _b[M²(CN)_r(X¹)_t]_c[M⁵(X²)₆]_d·nM⁴ _xA¹ _y·pM³ _wA² _z

wherein:

M¹and M⁴Each represents a metal ion independently selected from: zn²⁺、Fe²⁺、Co⁺²⁺、Ni²⁺、Mo⁴⁺、Mo⁶⁺、Al⁺³⁺、V⁴⁺、V⁵⁺、Sr²⁺、W⁴⁺、W⁶⁺、Mn²⁺、Sn²⁺、Sn⁴⁺、Pb²⁺、Cu²⁺、La³⁺And Cr³⁺；

M²And M⁵Each represents a metal ion independently selected from: fe³⁺、Fe²⁺、Co³⁺、Co²⁺、Cr²⁺、Cr³⁺、Mn²⁺、Mn³⁺、Ir³⁺、Ni²⁺、Rh³⁺、Ru²⁺、V⁴⁺、V⁵⁺、Ni²⁺、Pd²⁺And Pt²⁺；

M³Represents at least one magnesium, group 3-group 15 metal or lanthanide metal ion, with the exception of titanium;

X¹represents and said M²Ionically coordinating groups other than cyanide ions;

X²represents and said M⁵Ionically coordinating groups other than cyanide ions;

A¹denotes halogen, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, alkanesulfonate, arylenesulfonate, trifluoromethanesulfonate or C_1-4A carboxylate radical;

A²represents at least one alkoxy anion, aryloxide anion, carboxylate anion, acyl anion, pyrophosphate anion, phosphate anion, thiophosphate anion, amide anion, oxygen anion, siloxy anion, hydrogen anion, carbamate anion, or hydrocarbon anion;

b. c and d are each numbers reflecting complexes that are electrostatically neutral, provided that b and c are each greater than zero;

x and y are equilibrium metal salts M³ _xA¹ _yAn integer of the charge in (1);

r is an integer from 4 to 6;

t is an integer of 0 to 2;

n is a number of 0 and 20;

p is 0.002 to 10; and

w and z are equilibrium metal salts M³ _zA² _zProvided that w is 1 to 4.

18. The water-insoluble catalyst of claim 17, wherein M¹And M⁴Is zinc; m²And M⁵Is cobalt and M³Selected from the group consisting of aluminum, gallium, hafnium, indium and manganese.

19. A water-insoluble catalyst complex corresponding to the formula:

M¹ _b[M²(CN)_r(X¹)_t]_c[M⁵(X²)₆]_d·nM⁴ _xA¹ _y·pM³ _wA² _z

wherein:

M¹and M⁴Each represents a metal ion independently selected from: zn²⁺、Fe²⁺、Co⁺²⁺、Ni²⁺、Mo⁴⁺、Mo⁶⁺、Al⁺³⁺、V⁴⁺、V⁵⁺、Sr²⁺、W⁴⁺、W⁶⁺、Mn²⁺、Sn²⁺、Sn⁴⁺、Pb²⁺、Cu²⁺、La³⁺And Cr³⁺；

M²And M⁵Each represents a metal ion independently selected from: fe³⁺、Fe²⁺、Co³⁺、Co²⁺、Cr²⁺、Cr³⁺、Mn²⁺、Mn³⁺、Ir³⁺、Ni²⁺、Rh³⁺、Ru²⁺、V⁴⁺、V⁵⁺、Ni²⁺、Pd²⁺And Pt²⁺；

M³Represents at least one magnesium, group 3-group 15 metal or lanthanide metal ion, with the exception of titanium;

X¹represents and said M²Ionically coordinating groups other than cyanide ions;

X²represents and said M⁵Ionically coordinating groups other than cyanide ions;

A¹denotes halogen, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, alkanesulfonate, arylenesulfonate, trifluoromethanesulfonate or C_1-4A carboxylate radical;

A²represents at least one alkoxy anion, aryloxide anion, carboxylate anion, acyl anion, pyrophosphate anion, phosphate anion, thiophosphate anion, amide anion, oxygen anion, siloxy anion, hydrogen anion, carbamate anion, or hydrocarbon anion;

b. c and d are each numbers reflecting complexes that are electrostatically neutral, provided that b and c are each greater than zero;

x and y are equilibrium metal salts M³ _xA¹ _yAn integer of the charge in (1);

r is an integer from 4 to 6;

t is an integer of 0 to 2;

n is a number of 0 and 20;

p is 0.002 to 10; and

w and z are equilibrium metal salts M³ _zA² _zProvided that w is 1 to 4.

20. The water-insoluble catalyst complex of claim 19, wherein M¹And M⁴Is zinc; m²And M⁵Is cobalt and M³Selected from the group consisting of aluminum, gallium, hafnium, indium and manganese.

21. A water-insoluble particulate catalyst complex comprising a compound having M¹ _b[M²(CN)_r(X¹)]_cPhase sum M³Mixed particles of metal oxide phases, in which

M¹Represents a metal ion independently selected from: zn²⁺、Fe²⁺、Co⁺²⁺、Ni²⁺、Mo⁴⁺、Mo⁶⁺、Al⁺³⁺、V⁴⁺、V⁵⁺、Sr²⁺、W⁴⁺、W⁶⁺、Mn²⁺、Sn²⁺、Sn⁴⁺、Pb²⁺、Cu²⁺、La³⁺And Cr³⁺；

M²Represents a metal ion independently selected from: fe³⁺、Fe²⁺、Co³⁺、Co²⁺、Cr²⁺、Cr³⁺、Mn²⁺、Mn³⁺、Ir³⁺、Ni^{2 +}、Rh³⁺、Ru²⁺、V⁴⁺、V⁵⁺、Ni²⁺、Pd²⁺And Pt²⁺；

M³Represents at least one magnesium, group 3-group 15 metal or lanthanide metal ion, with the exception of titanium;

X¹represents and said M²Ionically coordinating groups other than cyanide ions;

b and c are each a number reflecting a complex which is electrostatically neutral;

r is an integer from 4 to 6; and

t is an integer of 0 to 2.

22. The water-insoluble particulate catalyst complex of claim 21, wherein the M¹ _b[M²(CN)_r(X¹)_t]_cThe phases are zinc hexacyanocobaltate phases.

23. The water-insoluble particulate catalyst complex according to claim 21 or 22, wherein M³Selected from the group consisting of aluminum, gallium, hafnium, indium and manganese.

24. The water-insoluble particulate catalyst complex of any one of claims 21 to 23, containing 0.0-2 to 10 moles of the M2 metal per mole of the M2 metal³A metal.

25. A catalyst complex comprising water-insoluble zinc hexacyanocobaltateParticles and M³Physical mixture of metal oxide particles, said M³The metal oxide particles are present in an amount to provide 0.002 to 10 moles M of cobalt per mole provided by the zinc hexacyanocobaltate³A metal, and further wherein said M is measured as using a gas adsorption method³The surface area of the metal oxide particles is at least 1m²/g。

26. A method for making polycarbonate, the method forming a reaction mixture comprising a hydroxyl-containing starter, at least one alkylene oxide, carbon dioxide, and the catalyst complex of any of claims 15-25.