Method for producing polyether carbonate polyols

Patent metadata

Field	Value
Publication number	US-10125217-B2
Application number	US-201415030523-A
Country	US
Kind code	B2
Filing date	Oct 20, 2014
Priority date	Oct 23, 2013
Publication date	Nov 13, 2018
Grant date	Nov 13, 2018

Abstract

The invention relates to a process for producing polyether carbonate polyols through an addition reaction of alkylene oxides and carbon dioxide onto one or more H-functional starter substances in the presence of a double metal cyanide catalyst or in the presence of a metal complex catalyst based on the metals zinc and/or cobalt, characterized in that one or more H-functional starter substances containing at least 1000 ppm of component (K) is/are continuously metered into the reactor during the reaction, where component (K) is selected from at least one compound containing a phosphorus-oxygen bond and a phosphorus compound that can form one or more P—O bonds through reaction with OH-functional compounds.

First claim

The invention claimed is:

1. A process for preparing a polyethercarbonate polyol comprising adding alkylene oxides and carbon dioxide onto one or more H-functional starter substance(s) in the presence of a double metal cyanide catalyst or in the presence of a metal complex catalyst based on the metals zinc and/or cobalt, wherein
(γ) one or more H-functional starter substance(s) containing at least 1000 ppm of component K are metered continuously into the reactor during the reaction, component K being selected from at least one compound containing a phosphorus-oxygen bond or a compound of phosphorus that is configured to form one or more P—O bond(s) by reaction with OH— functional compounds, wherein the one or more H-functional starter substance(s) containing at least 1000 ppm of component K and one or more alkylene oxide(s) are metered continuously into the reactor during the reaction in the presence of carbon dioxide, and wherein DMC catalyst is additionally metered continuously into the reactor and the resulting reaction mixture is removed continuously from the reactor; and
(δ) the reaction mixture which is removed continuously in step (γ) and has a content of 0.05% by weight to 10% by weight of alkylene oxide is transferred into a postreactor in which, by way of a postreaction, the content of free alkylene oxide is reduced to less than 0.05% by weight in the reaction mixture.

2. The process as claimed in claim 1 , wherein component K is used in an amount of 1000 ppm to 10 000 ppm.

3. The process as claimed in claim 1 , wherein step (γ) is preceded by initial charging, in a step (α), of a suspension medium containing no H-functional groups together with DMC catalyst and in this step
(α-1) no H-functional starter substance is initially charged in the reactor or
(α-2) a portion of the H-functional starter substance(s) is additionally initially charged in the reactor.

4. The process as claimed in claim 3 , wherein, after step (α) and before step (γ),
(β) a portion of alkylene oxide is added to the mixture from step (α) at temperatures of 90 to 150° C., and wherein the addition of the alkylene oxide compound is then stopped.

5. The process as claimed in claim 3 , wherein the suspension medium used in step (α) is at least one compound selected from the group consisting of 4-methyl-2-oxo-1,3-dioxolane, 1,3-dioxolan-2-one, acetone, methyl ethyl ketone, acetonitrile, nitromethane, dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dioxane, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, ethyl acetate, butyl acetate, pentane, n-hexane, benzene, toluene, xylene, ethylbenzene, chloroform, chlorobenzene, dichlorobenzene, carbon tetrachloride, ε-caprolactone, dihydrocoumarin, trimethylene carbonate, neopentyl glycol carbonate, 3,6-dimethyl-1,4-dioxane-2,5-dione, succinic anhydride, maleic anhydride and phthalic anhydride.

6. The process as claimed in claim 1 , wherein step (γ) is preceded by initial charging, in a step (α), of a portion of the H-functional starter substance(s) together with DMC catalyst.

7. The process as claimed in claim 1 , wherein, in step (γ), the metered addition of the one or more H-functional starter substance(s) containing at least 1000 ppm of component K is ended at a time prior to the addition of the alkylene oxide.

8. The process as claimed in claim 1 , wherein component K is selected from at least one compound from the group consisting of phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, phosphonous acid, phosphinous acid, phosphine oxides and salts, esters, halides and amides of phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, phosphonous acid, phosphinous acid, phosphorus(V) sulfide, phosphorus tribromide, phosphorus trichloride and phosphorus triiodide.

9. The process as claimed in claim 1 , wherein component K is selected from at least one compound from the group consisting of
phosphoric acid,
mono-, di- or trialkyl esters of phosphoric acid,
mono-, di- or triaryl esters of phosphoric acid,
mono-, di- or trialkaryl esters of phosphoric acid,
(NH 4 ) 2 HPO 4 ,
phosphonic acid,
mono- or dialkyl esters of phosphonic acid,
mono- or diaryl esters of phosphonic acid,
mono- or dialkaryl esters of phosphonic acid,
phosphorous acid,
mono-, di- or trialkyl esters of phosphorous acid,
mono-, di- or triaryl esters of phosphorous acid,
mono-, di- or trialkaryl esters of phosphorous acid,
phosphinic acid,
phosphonous acid and
phosphinous acid.

10. The process as claimed in claim 1 , wherein component K is phosphoric acid.

11. The process as claimed in claim 1 , wherein the one or more H-functional starter substance(s) are selected from at least one of the group consisting of ethylene glycol, propylene glycol, propane-1,3-diol, butane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, 2-methylpropane-1,3-diol, neopentyl glycol, hexane-1,6-diol, octane-1,8-diol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, polyethercarbonate polyols having a molecular weight Mn in the range from 150 to 8000 g/mol with a functionality of 2 to 3 and polyether polyols having a molecular weight Mn in the range from 150 to 8000 g/mol with a functionality of 2 to 3.

12. The process as claimed in claim 1 , wherein, in step (γ), the one or more H-functional starter substance(s) are selected from at least one of the group consisting of ethylene glycol, propylene glycol, propane-1,3-diol, butane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, 2-methylpropane-1,3-diol, neopentyl glycol, hexane-1,6-diol, octane-1,8-diol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane and pentaerythritol.

Assignees

• Covestro Deutschland Ag

Inventors

• Hofmann Jörg
• Pirkl Hans-Georg
• Laemmerhold Kai
• Nefzger Hartmut
• Wohak Matthias
• Braun Stefanie
• Gürtler Christoph
• Wolf Aurel
• Langanke Jens

Classifications

• C08G64/34 Primary

  and cyclic ethers · CPC title

• C08G65/2675

  Phosphorus or compounds thereof · CPC title

• C08G65/2663

  Metal cyanide catalysts, i.e. DMC's · CPC title

• C08G65/2603

  the other compounds containing oxygen · CPC title

• C08G65/2609

  containing aliphatic hydroxyl groups · CPC title