Method for producing polyether carbonate polyols

Patent metadata

Field	Value
Publication number	US-10040901-B2
Application number	US-201515323362-A
Country	US
Kind code	B2
Filing date	Jun 30, 2015
Priority date	Jul 3, 2014
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

The invention relates to a method for producing polyether carbonate polyols by binding alkylene oxides and carbon dioxide to one or more H-functional starter substance/s in the presence of a double metal cyanide (DMC) catalyst, characterized in that (y) one or more H-functional starter substance/s and DMC catalyst are continuously metered into the reactor during the binding process, and the free alkylene oxide concentration in the reaction mixture amounts to 1.5 to 5.0 wt %, and the obtained reaction mixture is continuously discharged from the reactor.

First claim

The invention claimed is:

1. A process for preparing polyether carbonate polyols by adding alkylene oxides and carbon dioxide onto one or more H-functional starter substances in the presence of a double metal cyanide (DMC) catalyst, wherein:
(γ) one or more H-functional starter substances and DMC catalyst are metered continuously into the reactor during the addition, and a free alkylene oxide concentration in the reaction mixture is from 1.5% to 5.0% by weight of the reaction mixture, and the resulting reaction mixture is removed continuously from the reactor.

2. The process as claimed in claim 1 , wherein the free alkylene oxide concentration during the addition in step (γ) is from 1.5% to 4.5% by weight of the reaction mixture.

3. The process as claimed in claim 1 , wherein the free alkylene oxide concentration during the addition in step (γ) is from 2.0% to 4.0% by weight of the reaction mixture.

4. The process as claimed in claim 1 , wherein the one or more H-functional starter substances contains at least 1000 ppm of component K, wherein component K is selected from the group consisting of:
at least one compound containing a phosphorus-oxygen bond; and
a compound of phosphorus which can form one or more P—O bond(s) by reaction with OH-functional compounds.

5. The process as claimed in claim 4 , wherein the one or more H-functional starter substances contains from 1000 ppm to 10 000 ppm of component K.

6. The process as claimed in claim 4 , wherein component K is selected from the group consisting of: phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, phosphonous acid, phosphinous acid, phosphine oxides, salts of phosphoric acid, esters of phosphoric acid, halides of phosphoric acid, amides of phosphoric acid, salts of phosphonic acid, esters of phosphonic acid, halides of phosphonic acid, amides of phosphonic acid, salts of phosphorous acid, esters of phosphorous acid, halides of phosphorous acid, amides of phosphorous acid, salts of phosphinic acid, esters of phosphinic acid, halides of phosphinic acid, amides of phosphinic acid, salts of phosphonous acid, esters of phosphonous acid, halides of phosphonous acid, amides of phosphonous acid, salts of phosphinous acid, esters of phosphinous acid, halides of phosphinous acid, amides of phosphinous acid, phosphorus(V) sulfide, phosphorus tribromide, phosphorus trichloride, phosphorus triiodide, and combinations of any thereof.

7. The process as claimed in claim 4 , wherein component K is selected 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, phosphinous acid, and combinations of any thereof.

8. The process as claimed in claim 4 , wherein component K is phosphoric acid.

9. The process as claimed in claim 1 , wherein step (γ) is preceded by an initial charging, in a step (α), of a portion of the one or more H-functional starter substances and/or a suspension medium containing no H-functional groups in a reactor.

10. The process as claimed in claim 9 , wherein at least one suspension medium is used in step (α), wherein the at least one suspension medium is 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, phthalic anhydride, and combinations of any thereof.

11. The process as claimed in claim 9 , wherein step (α) is followed and step (γ) is preceded by:
(β) adding a portion of the alkylene oxide to the mixture from step (α) at temperatures of 90 to 150° C., wherein the addition of the alkylene oxide compound is interrupted.

12. The process as claimed in claim 1 , wherein
(δ) the reaction mixture continuously removed in step (γ) is transferred into a postreactor, wherein, by way of a postreaction, the content of free alkylene oxide is reduced to less than 0.05% by weight in the reaction mixture.

13. The process as claimed in claim 1 , wherein the one or more H-functional starter substances is selected from 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, polyether carbonate polyols having a molecular weight Mn in the range from 150 to 8000 g/mol with a functionality of 2 to 3, polyether polyols having a molecular weight Mn in the range from 150 to 8000 g/mol with a functionality of 2 to 3, and combinations of any thereof.

14. The process as claimed in claim 1 , wherein, in step (γ), the one or more H-functional starter substances is selected from 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, and combinations of any thereof.

15. A process for preparing polyether carbonate polyols by adding alkylene oxides and carbon dioxide onto one or more H-functional starter substances in the presence of a metal complex catalyst, wherein the metal complex catalyst comprises zinc and/or cobalt, and wherein:
(γ) the one or more H-functional starter substances and the metal complex catalyst comprising zinc and/or cobalt, are metered continuously into the reactor during the addition, and wherein a free alkylene oxide concentration in the reaction mixture is from 1.5% to 5.0% by weight of the reaction mixture, and wherein the resulting reaction mixture is removed continuously from the reactor.

16. The process as claimed in claim 9 , wherein the step (α) further comprises an initial charging of DMC catalyst in the reactor.

17. The process as claimed in claim 9 , wherein step (α) is followed and step (γ) is preceded by:
(β) adding a portion of the alkylene oxide to the mixture from step (α) when the mixture is between a temperature of 90° C. to 150° C., wherein the addition of the alkylene oxide compound is interrupted when the mixture is not between a temperature of 90° C. to 150° C.

18. A process for preparing polyether carbonate polyols by adding alkylene oxides and carbon dioxide onto one or more H-functional starter substances in the presence of a double metal cyanide (DMC) catalyst, comprising:
(α) charging a reactor with a portion of the H-functional starter substances and/or a suspension medium containing no H-functional groups together with the DMC catalyst;
(β) adding a portion of alkylene oxide to the mixture from (a) at temperatures of 90 to 1

Assignees

• Covestro Deutschland Ag

Inventors

• Hofmann Jörg
• Braun Stefanie
• Laemmerhold Kai
• Wolf Aurel
• Traving Michael

Classifications

• C08G64/34 Primary

  and cyclic ethers · CPC title

• C08G65/2663

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

• C08G64/403

  Recovery of the polymer · CPC title

• C08G65/2603

  the other compounds containing oxygen · CPC title

• C08G65/2606

  containing hydroxyl groups · CPC title