Use of alcohols which contain at least two urethane groups for producing polyether carbonate polyols

Patent metadata

Field	Value
Publication number	US-10519276-B2
Application number	US-201615573996-A
Country	US
Kind code	B2
Filing date	May 24, 2016
Priority date	May 26, 2015
Publication date	Dec 31, 2019
Grant date	Dec 31, 2019

Abstract

The present invention relates to a method for producing polyether carbonate polyols by attaching alkyloxides and carbon dioxide to H-functional starter compounds, characterized in that at least one alcohol containing at least two urethane groups is used as the H-functional starter compound. The invention further relates to polyether carbonate polyols containing a structural unit of the formula (IV), wherein: R 1 denotes a linear or branched C 2 to C 24 -alkylene, which optionally can be interrupted by heteroatoms of O, S or N and can be substituted, preferably by CH 2 —CH 2 or CH 2 —CH(CH 3 ); R 2 denotes a linear or branched C 2 to C 24 -alkylene, C 3 to C 24 -cycloalkylene, C 4 to C 24 -alkylene, C 5 to C 24 -aralkylene, C 2 to C 24 -alkenylene, C 2 to C 24 -alkynylene, each of which can optionally be interrupted by heteroatoms such as O, S or N and/or can be substituted with alkyl, aryl and/or hydroxyl groups, preferably C 2 to C 24 -alkyls; R 3 denotes 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 can optionally be interrupted by heteroatoms such as O, S or N and/or can each be substituted with alkyl, aryl and/or hydroxyl groups, preferably H; R 4 denotes H, a linear of 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 C24-alkenyl, C2 to C 24 -alkynyl, each of which can optionally be interrupted by heteroatoms such as O, S or N and/or can each be substituted with alkyl, aryl and/or hydroxyl groups, preferably H; R 5 denotes a linear or branched C 2 to C 24 -alkylene, which can optionally be interrupted by heteroatoms such as O, S or N and can be substituted, preferably by CH 2 —CH 2 or CH 2 —CH(CH 3 ); and wherein R1 to R5 can be identical or different to each other.

First claim

The invention claimed is:

1. A process for preparing polyether carbonate polyols comprising adding alkylene oxides and carbon dioxide onto H-functional starter compounds, wherein the H-functional starter compound comprises at least one alcohol containing at least two urethane groups.

2. The process as claimed in claim 1 , wherein the H-functional starter compound comprises at least one alcohol containing two urethane groups.

3. The process as claimed in claim 2 , wherein said at least one alcohol containing two urethane groups corresponds to the formula (II),

wherein
R 1 represents a linear or branched C 2 - to C 24 -alkylene which may optionally be interrupted by heteroatoms which are selected from O, S and/or N and may be substituted,
R 2 represents a linear or branched C 2 - to C 24 -alkylene, C 3 - to C 24 -cycloalkylene, C 4 - to C 24 -arylene, C 5 - to C 24 -aralkylene, C 2 - to C 24 -alkenylene, C 2 - to C 24 -alkynylene, each of which may optionally be interrupted by heteroatoms which are selected from O, S and/or N, and/or each of which may be substituted by alkyl, aryl and/or hydroxyl,
R 3 represents a H atom, a 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 which are selected from O, S and/or N, and/or each of which may be substituted by alkyl, aryl and/or hydroxyl,
R 4 represents a H atom, a 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 which are selected from O, S and/or N, and/or each of which may be substituted by alkyl, aryl and/or hydroxyl,
R 5 represents a linear or branched C 2 - to C 24 -alkylene which may optionally be interrupted by heteroatoms which are selected from O, S and/or N, and may be substituted,
and each of R 1 to R 5 may be identical or different from one another.

4. The process as claimed in claim 3 , wherein
R 1 represents a CH 2 —CH 2 or a CH 2 —CH(CH 3 ),
R 2 represents a C 2 - to C 24 — alkylene,
R 3 and R 4 each represent a H atom, and
R 5 represents a CH 2 —CH 2 or a CH 2 —CH(CH 3 ).

5. The process as claimed in claim 1 , wherein said alcohol containing at least two urethane groups comprises the reaction product of propylene carbonate and/or ethylene carbonate with compounds having at least two amino groups.

6. The process as claimed in claim 1 , wherein said alcohol containing two urethane groups comprises the reaction product of propylene carbonate and/or ethylene carbonate with diamines corresponding to formula (III),
HN(R 3 )—R 2 —NH(R 4 )  (III)

wherein
R 2 to R 4 may be identical or different from one another and

R 2 represents a linear or branched C 2 - to C 24 -alkylene, C 3 - to C 24 -cycloalkylene, C 4 - to C 24 -arylene, C 5 - to C 24 -aralkylene, C 2 - to C 24 -alkenylene, C 2 - to C 24 -alkynylene, each of which may optionally be interrupted by heteroatoms which are selected from O, S and/or N, and/or each of which may be substituted by alkyl, aryl and/or hydroxyl,
R 3 represents a H atom, a 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 which are selected from O, S and/or N, and/or each of which may be substituted by alkyl, aryl and/or hydroxyl,
R 4 represents a H atom, a 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 which are selected from O, S and/or N, and/or each of which may be substituted by alkyl, aryl and/or hydroxyl.

7. The process as claimed in claim 1 , wherein said alcohol containing two urethane groups comprises the reaction product of propylene carbonate and/or ethylene carbonate with at least one compound selected from the group consisting of 1,2-ethanediamine, diaminopropane, diaminopentane, diaminohexane, diaminooctane, diaminodecane, diaminododecane, diaminooctadecane, diaminoeicosane, isophoronediamine, tolylenediamine and methylenedianiline.

8. The process as claimed in claim 1 , wherein adding alkylene oxides and carbon dioxide onto H-functional starter compounds occurs in the presence of at least one DMC catalyst.

9. The process as claimed in claim 1 , wherein adding alkylene oxides and carbon dioxide onto H-functional starter compounds occurs in the presence of a metal complex catalyst based on the metals zinc and/or cobalt.

10. The process as claimed in claim 1 , comprising
(α) initially charging the alcohol containing at least two urethane groups corresponding to formula (II) or a suspension medium and optionally, removing water and/or other volatile compounds by means of elevated temperature and/or reduced pressure (“drying”), wherein DMC catalyst is added to the urethane alcohol corresponding to formula (II) or to the suspension medium before or after drying,
(β) activating said DMC catalyst by adding a portion (based on the total amount of alkylene oxides employed in the activation and copolymerization) of alkylene oxide to the mixture resulting from (α), wherein this addition of a portion of alkylene oxide may optionally be effected in the presence of CO 2 and wherein the temperature spike (“hotspot”) which occurs due to the exothermic chemical reaction that follows and/or a pressure drop in the reactor is then awaited in each case, and wherein (β) for achieving activation may also be effected repeatedly,
(γ) adding alkylene oxide, carbon dioxide and optionally urethane alcohol corresponding to formula (II) to the mixture resulting from (β),
additionally comprising adding in at least one of (α) or (γ) an H-functional starter substance comprising at least one urethane alcohol corresponding to formula (II).

11. The process as claimed in claim 1 , comprising continuously metering an H-functional starter substance comprising one or more urethane alcohols corresponding to formula (II) into the reactor during the reaction.

12. The process as claimed in claim 11 , comprising continuously metering one or more urethane alcohols corresponding to formula (II), one or more alkylene oxides and DMC catalyst into the reactor in the presence of carbon dioxide (“copolymerization”), and continuously removing the resulting reaction mixture (containing the reaction product) from the reactor.

Assignees

• Covestro Deutschland Ag

Inventors

• Rauwald Urs
• Hofmann Jörg
• Klesczewski Bert
• Nefzger Hartmut
• Wolf Aurel
• Langanke Jens

Classifications

• C08G71/04

  Polyurethanes · CPC title

• C08G65/2663

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

• C08G65/2618

  the other compounds containing nitrogen · CPC title

• C08G65/2603

  the other compounds containing oxygen · CPC title

• C08G18/163

  covered by C08G18/18 and C08G18/22 · CPC title