Heterogeneous alkoxylation using anion-bound metal oxides

• US 5,025,094 A
• Filed: 06/13/1989
• Issued: 06/18/1991
• Est. Priority Date: 07/10/1985
• Status: Expired due to Fees

• Current Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Original Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Inventors: King, Stephen W.
• Primary Examiner(s): McFarlane, Anthony
• Application Number:
  US07/365,359
• Time in Patent Office: 735 Days
• Field of Search: 568/606, 568/613, 568/620, 568/618, 568/622, 568/867, 568/623, 568/616, 568/624
• US Class Current: 568/623
• CPC Class Codes: C07C 41/03 by reaction of oxirane rings with hydroxy groups
• CPC Class Codes: C07C 43/11 Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10
• CPC Class Codes: C07C 43/13 containing hydroxy or O-metal groups C07C43/11 takes precedence
• CPC Class Codes: C07C 43/132 both carbon chains being substituted by hydroxy or O-metal groups
• CPC Class Codes: C08G 65/266 Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
• CPC Class Codes: C08G 65/2693 Supported catalysts

Abstract

Active-hydrogen compounds, for example, primary and secondary alcohols or diols, are alkoxylated, for example, ethoxylated, using solid anion-bound metal oxide catalysts, such as, zirconium oxysulfate catalyst. Hydrous zirconium oxide is treated with solutions of sulfate phosphate, nitrate or tetrafluoroborate and calcined in air at 300° to 950° C. to produce highly active heterogeneous alkoxylation catalysts. The amorphous catalysts afford narrow molecular weight products. The catalyst can be removed from the product by filtration and reused with no significant loss in activity. Reaction temperatures of 50° to 140° C. are employed for alkoxylation.

Claims

1. Process comprising reacting at least one molecule of a liquid or solid epoxide compound having the formula:

##STR10## wherein R₁, R₂, R₃ and R₄ are each H or --(CH₂)_n CH₃, and wherein n is 0 to 3, with the proviso that R₁, R₂, R₃ and R₄ are the same or different, with at least one other molecule of said epoxide compound in the presence of catalytic amount of at least one solid anion-bound metal oxide heterogeneous catalyst, wherein said anion in said anion-bound metal oxide heterogeneous catalyst is SO₄, BF₄, CO₃, BO₃, HPO₄, SeO₄, MoO₄, B₄ O₇ or PF₆, and the metal oxide is zirconium oxide, nickel oxide, aluminum oxide, tin oxide, magnesium oxide, iron oxide, titanium oxide, thorium oxide, hafnium oxide or rubidium oxide, said anion-bound metal oxide heterogeneous catalyst being an amorphous or primarily amorphous compound, and said molecules of said epoxide compound being the same epoxide compound or different epoxide compounds.

2. Process as claimed in claim 1 wherein 0.5 to 50 weight percent, based on the total weight of said epoxide compound, of said anion-bound metal oxide catalyst is used.

3. Process as claimed in claim 1 wherein said anion-bound metal oxide catalyst is an anion-bound zirconium oxide catalyst, an anion-bound nickel oxide catalyst, an anion-bound aluminum oxide catalyst, an anion-bound tin oxide catalyst, an anion-bound calcium oxide catalyst, an anion-bound magnesium oxide catalyst, an anion-bound rubidium oxide catalyst, an anion-bound titanium oxide catalyst, an anion-bound thorium oxide catalyst, an anion-bound hafnium oxide catalyst, or an anion-bound iron oxide catalyst.

4. Process as claimed in claim 1 wherein said catalyst is a solid anion-bound zirconium oxide catalyst.

5. Process as claimed in claim 4 wherein said solid anion-bound zirconium oxide catalyst contains about 2 to about 3 weight percent, based on the total weight of said catalyst, of said anion.

6. Process as claimed in claim 5 wherein said catalyst is an anion-bound thorium oxide catalyst.

7. Process as claimed in claim 1 wherein said catalyst is a solid sulfate-bound hafnium oxide catalyst.

8. Process as claimed in claim 1 wherein said catalyst is supported on an inert carrier.

9. Process as claimed in claim 1 wherein an inert liquid diluent is also present.

10. Process as claimed in claim 1 wherein the epoxide compound is ethylene oxide, or propylene oxide.

11. Process as claimed in claim 1 wherein said reaction is continuously conducted in a fluidized reactor.

12. Process as claimed in claim 1 wherein said anion-bound metal oxide is removed from the reaction site and is regenerated by calcination in air or oxygen at a temperature of 300°

to 950°

C. for a period of 1 to 4 hours.