Polyether carbonate polyol production method

Patent metadata

Field	Value
Publication number	US-9273183-B2
Application number	US-201314424171-A
Country	US
Kind code	B2
Filing date	Aug 23, 2013
Priority date	Aug 27, 2012
Publication date	Mar 1, 2016
Grant date	Mar 1, 2016

Abstract

The invention relates to a method for producing polyether carbonate polyols by attaching alkylene oxides and carbon dioxide to one or more H-functional starters in the presence of a double-metal cyanide catalyst, characterized in that (alpha) a suspending agent which contains no H-functional groups and is selected from among one or more compounds from the group consisting of aliphatic lactones, aromatic lactones, lactides, cyclic carbonates comprising at least three optionally substituted methylene groups between the oxygen atoms of the carbonate group, aliphatic cyclic anhydrides, and aromatic cyclic anhydrides, is provided in a reactor; (ss) optionally, a moiety of alkylene oxide is added to the mixture from step (alpha) at temperatures of 90 to 150 DEG C., and the addition of the alkylene oxide compound is then interrupted; and (gamma) one or more H-functional starters are continuously metered into the reactor during the reaction.

First claim

The invention claimed is:

1. A process for the preparation of a polyether carbonate polyol by addition of alkylene oxide and carbon dioxide to one or more H-functional starter substance in the presence of a double metal cyanide catalyst, comprising
(α) placing a suspending agent that does not contain H-functional groups and is selected from one or more compound from the group consisting of aliphatic lactones, aromatic lactones, lactides, cyclic carbonates having at least three optionally substituted methylene groups between the oxygen atoms of the carbonate group, aliphatic cyclic anhydrides and aromatic cyclic anhydrides in a reactor, and
(γ) metering into the reactor one or more H-functional starter substance, one or more alkylene oxide and optionally carbon dioxide simultaneously or sequentially, wherein the one or more H-functional starter substance is metered into the reactor continuously during the reaction.

2. The process according to claim 1 , wherein in step (α) the suspending agent that does not contain H-functional groups and is selected from one or more compound from the group consisting of aliphatic lactones, aromatic lactones, lactides, cyclic carbonates having at least three optionally substituted methylene groups between the oxygen atoms of the carbonate group, aliphatic cyclic anhydrides and aromatic cyclic anhydrides is initially placed in the reactor, and no H-functional starter substance is thereby initially placed in the reactor.

3. The process according to claim 1 , wherein in step (α) the suspending agent that does not contain H-functional groups and is selected from one or more compound(s) from the group consisting of aliphatic lactones, aromatic lactones, lactides, cyclic carbonates having at least three optionally substituted methylene groups between the oxygen atoms of the carbonate group, aliphatic cyclic anhydrides and aromatic cyclic anhydrides, and additionally a partial amount of the H-functional starter substance are initially placed in the reactor.

4. The process according to claim 1 , wherein in step (α) the suspending agent that does not contain H-functional groups and is selected from one or more compound(s) from the group consisting of aliphatic lactones, aromatic lactones, lactides, cyclic carbonates having at least three optionally substituted methylene groups between the oxygen atoms of the carbonate group, aliphatic cyclic anhydrides and aromatic cyclic anhydrides is initially placed in the reactor together with DMC catalyst.

5. The process according to claim 4 , wherein, following step (α),
(β) adding a partial amount of alkylene oxide to the mixture from step (α) at temperatures of from 90 to 150° C.

6. The process according to claim 5 , wherein step (β) is carried out under an inert gas atmosphere, under an atmosphere of an inert gas/carbon dioxide mixture or under a carbon dioxide atmosphere.

7. The process according to claim 5 , wherein in step (β)
(β1) in a first activation step the addition of a first partial amount of alkylene oxide under an inert gas atmosphere takes place, and
(β2) in a second activation step the addition of a second partial amount of alkylene oxide under a carbon dioxide atmosphere takes place.

8. The process according to claim 1 , wherein in step (γ) one or more H-functional starter substance, one or more alkylene oxide are metered in continuously in the presence of carbon dioxide.

9. The process according to claim 1 , wherein in step (γ) the metered addition of the one or more H-functional starter substance is ended, in terms of time, before the addition of the alkylene oxide.

10. The process according to claim 8 , wherein in step (γ) DMC catalyst is metered into the reactor continuously and the resulting reaction mixture is removed from the reactor continuously.

11. The process according to claim 10 , wherein the DMC catalyst is added continuously in suspension in H-functional starter compound.

12. The process according to claim 10 , wherein
(δ) the reaction mixture removed continuously in step (γ) having a content of from 0.05 wt. % to 10 wt. % alkylene oxide is transferred into a post-reactor in which the content of free alkylene oxide is reduced to less than 0.05 wt. % in the reaction mixture in the course of a post-reaction.

13. The process according to claim 1 , wherein in step (α) the suspending agent is at least one compound selected from the group consisting of
a compound of formula (II), (III), (IV), and (V)

wherein
R1, R2, R3 and R4 independently of one another represent hydrogen, a linear or branched C1 to C22 alkyl radical, a linear or branched C1 to C22 alkenyl radical or a C6 to C18 aryl radical, or can be members of a 4- to 7-membered ring or polycyclic system optionally containing ether groups,
wherein the compounds of formula (II) can also be substituted by chlorine, bromine, nitro groups or alkoxy groups,
m is an integer greater than or equal to 1,
and R3 and R4 in repeating units (m>1) can be different,
and n and o independently of one another are an integer greater than or equal to 1, preferably 1, 2, 3 or 4,
and R1 and R2 in repeating units (n>1) and R3 and R4 in repeating units (o>1) can be different,
or a compound of formula (VI)

wherein
R5, R6, R7, R8, R9 and R10 independently of one another represent hydrogen, a linear or branched C1 to C22 alkyl radical, a linear or branched C1 to C22 alkenyl radical or a C6 to C18 aryl radical, or can be members of a 4- to 7-membered ring or polycyclic system,
p is an integer greater than or equal to 1, preferably 1, 2 or 3,
and R9 and R10 in repeating units (p>1) can be different,
and wherein the compounds of formula (VI) can also be substituted by chlorine, bromine, nitro groups or alkoxy groups,
or a compound of formula (VII), (VIII) or (IX)

wherein
R11 and R12 represent hydrogen, halogen, C1-C22-alkyl, C1-C22-alkenyl or C6-C18-aryl, or R11 and R12 can be members of a 4- to 7-membered ring or polycyclic system, preferably R11 and R12 together form a benzene ring,
R13, R14, R15 and R16 represent hydrogen, C1-C22-alkyl, C1-C22-alkenyl or C6-C18-aryl, or can be members of a 4- to 7-membered ring or polycyclic system,
R17, R18, R19, R20, R21 and R22 represent hydrogen, C1-C22-alkyl, C1-C22-alkenyl or C6-C18-aryl, or can be members of a 4- to 7-membered ring or polycyclic system,
and wherein the compounds of formulae (VII) and (VIII) and (IX) can also be substituted by chlorine, bromine, nitro groups or alkoxy groups.

14. The process according to claim 1 , wherein in step (α) the suspending agent is selected from the group consisting of ε-caprolactone, dihydrocoumarin, trimethylene carbonate, neopentyl glycol carbonate, 3,6-dimethyl-1,4-dioxane-2,5-dione, succinic anhydride, maleic anhydride, phthalic anhydride, and mixtures of two or more of those suspending agents.

15. The process according to claim 1 , wherein the H-functional starter substance is selected from at least one of the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, dipropylen

Assignees

• Bayer Materialscience Ag
• Covestro Deutschland Ag

Inventors

• Müller Thomas Ernst
• Gürtler Christoph
• Wohak Matthias
• Hofmann Jörg
• Subhani Muhammad Afzal
• Leitner Walter
• Peckermann Ilja
• Wolf Aurel

Classifications

• C08G64/34 Primary

  and cyclic ethers · CPC title

• C08G18/4833

  Polyethers containing oxyethylene units · CPC title

• C08G65/2663

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

• C08G65/2603

  the other compounds containing oxygen · CPC title

• C08G64/305 Primary

  and alcohols · CPC title