Use of urethane alcohols for preparing polyether carbonate polyols

Patent metadata

Field	Value
Publication number	US-9957352-B2
Application number	US-201415104480-A
Country	US
Kind code	B2
Filing date	Dec 12, 2014
Priority date	Dec 17, 2013
Publication date	May 1, 2018
Grant date	May 1, 2018

Abstract

The present invention relates to a method for preparing polyether carbonate polyols by the addition of alkylene oxides and carbon dioxide onto H-functional starter compounds. The method is characterized in that at least one urethane alcohol according to formula (II) is used as an H-functional starter compound, wherein R 1 represents a linear or branched C2 to C24-alkylene which can be optionally interrupted by heteroatoms such as O, S or N and can be substituted; R2 represents a linear or branched C2 to C24-alkylene which can be optionally interrupted by heteroatoms such as O, S or N and can be substituted; R3 represents H, linear or branched C1 to C24-alkyl, C3 to C24-cycloalkyl, C4 to C24-aryl, C5 to C24-arylalkyl, C2 to C24-alkenyl, C2 to 24-alkinyl, that can each be optionally interrupted by heteroatoms such as O, S, or N and/or may each be substituted with alkyl, aryl, and/or hydroxyl.

First claim

The invention claimed is:

1. A process for preparing polyether carbonate polyols, the process comprising an addition of alkylene oxides and carbon dioxide onto H-functional starter compounds comprising at least one urethane alcohol of formula (II)

where
R 1 is linear or branched C 2 - to C 24 -alkylene which may optionally be interrupted by heteroatoms such as O, S or N and may be substituted,
R 2 is linear or branched C 2 - to C 24 -alkylene which may optionally be interrupted by heteroatoms such as O, S or N and may be substituted,
R 3 is H, linear or branched C 1 - to C 24 -alkyl, C 3 - to C 24 -cycloalkyl, C 4 - to C 24 -aryl, C 5 - to C 24 -aralkyl, C 2 - to C 24 -alkenyl, C 2 - to C 24 -alkynyl, each of which may optionally be interrupted by heteroatoms such as O, S or N and/or each of which may be substituted by alkyl, aryl and/or hydroxyl.

2. The process as claimed in claim 1 , wherein
R 1 =CH 2 —CH 2 or CH 2 —CH(CH 3 ),
R 2 =CH 2 —CH 2 or CH 2 —CH(CH 3 ), and
R 3 =H.

3. The process as claimed in claim 1 , wherein the urethane alcohol of formula (II) is obtained by reacting propylene carbonate and/or ethylene carbonate with an alkanolamine of formula (III)
HN(R 3 )—R 2 —OH  (III)

4. The process as claimed in claim 3 , wherein the urethane alcohol is obtained by reacting propylene carbonate and/or ethylene carbonate with at least one amine selected from the group consisting of ethanolamine, diethanolamine, (N-methyl)ethanolamine, isopropanolamine, diisopropanolamine and propanolamine.

5. The process as claimed in claim 1 , wherein the alkylene oxide used is at least one alkylene oxide selected from the group consisting of ethylene oxide and propylene oxide.

6. The process as claimed in claim 1 , wherein the addition is conducted in the presence of at least one DMC catalyst.

7. The process as claimed in claim 1 , wherein the addition is conducted in the presence of a metal complex catalyst based on the metals zinc and/or cobalt.

8. The process as claimed in claim 1 , wherein
(α) the urethane alcohol of formula (II) or a suspension medium is initially charged and any water and/or other volatile compounds are removed by elevated temperature and/or reduced pressure, with addition of the DMC catalyst to the urethane alcohol of formula (II) or to the suspension medium before or after the removal of the water and/or the other volatile compounds, and
(β) adding a portion to activate copolymerization (based on the total amount of alkylene oxides used in the activation and copolymerization) of alkylene oxide to the mixture resulting from step (α), where this portion of alkylene oxide may optionally be added in the presence of CO 2 and where a temperature spike that occurs due to the exothermic chemical reaction that follows and/or a pressure drop in the reactor is awaited in each case, and where step (β) for activation may also be repeated, and
(γ) adding alkylene oxide, carbon dioxide and optionally urethane alcohol of formula (II) to the mixture resulting from step (β),
where at least one urethane alcohol of formula (II) is added as H-functional starter substance at least in one of steps (α) and (γ).

9. The process as claimed in claim 1 , wherein one or more urethane alcohols of the formula (II) are metered continuously into a reactor as H-functional starter substance(s) during the addition.

10. The process as claimed in claim 6 , wherein the one or more urethane alcohols of formula (II), the one or more alkylene oxide(s) and the DMC catalyst are metered continuously into a reactor in the presence of the carbon dioxide and wherein the resulting reaction mixture, which includes the reaction product of the copolymerization, is removed continuously from the reactor.

11. The process as claimed in claim 10 , wherein, in a step (δ), the reaction mixture removed continuously from the reactor with 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.

12. A polyurethane foam prepared by reacting a polyisocyanate with a polyether carbonate polyol containing a structural unit of the formula (IV)

where
R 1 =CH 2 —CH 2 or CH 2 —CH(CH 3 ),
R 2 =CH 2 —CH 2 or CH 2 —CH(CH 3 ),
and where R 1 and R 2 may be identical or different from one another.

Assignees

• Covestro Deutschland Ag

Inventors

• Hofmann Jörg
• Heinz Monika
• Nefzger Hartmut
• Laemmerhold Kai
• Klesczewski Bert
• Müller Thomas E
• Wolf Aurel
• Langanke Jens

Classifications

• C08G65/2603

  the other compounds containing oxygen · CPC title

• C08G64/34 Primary

  and cyclic ethers · CPC title

• C08G18/5045

  containing urethane groups · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C08G64/0208

  saturated · CPC title