Depolymerization of polyurethanes with organic amine bases

Patent metadata

Field	Value
Publication number	US-2025171607-A1
Application number	US-202318839819-A
Country	US
Kind code	A1
Filing date	Feb 22, 2023
Priority date	Feb 22, 2022
Publication date	May 29, 2025
Grant date	—

Abstract

A hydrolyzing process improves the depolymerization of polyurethanes by contacting the polyurethane with water in the presence of an organic amine base and a phase transfer catalyst. The mild reaction conditions and low salt concentration in the reaction mixture allow to increase the yields of polyether polyol and organic polyamines, respectively.

First claim

1 . A method of hydrolyzing a polyurethane, the method comprising:
contacting said polyurethane with water in the presence of an organic amine base to yield an active hydrogen containing polyether, and an organic polyamine, wherein the organic amine base is an aliphatic amine, and a reaction mixture comprising the polyurethane, water and the organic amine base is a stirred homogeneous or heterogeneous mixture, during hydrolysis, and the organic amine base is separated from the active hydrogen containing polyether, and organic polyamine formed during polyurethane hydrolysis via distillation or extraction or membrane filtration.

2 . The method according to claim 1 ,
comprising: contacting the polyurethane with water in the presence of an organic amine base and a phase transfer catalyst.

3 . The method of claim 1 , wherein the organic amine base comprises one or more tertiary nitrogen atom(s) and/or has a boiling point below that of at least one organic polyamine obtained as product of the polyurethane hydrolysis.

4 . The method of claim 1 , wherein the organic amine base is at least one selected from the group consisting of
a base according to Formula (1)
(((R 3 ) 2 N—R 2 )—(O—R 1 ) x ) y —N(R 4 ) z   (1)

wherein the R 1 groups in the molecule may be identical or different, the R 2 groups in the molecule may be identical or different, the R 3 groups in the molecule may be identical or different, and the R 4 groups in the molecule may be identical or different, and wherein R 1 are identical or different and are independently from each other selected from the group consisting of linear or branched alkylene radicals with 1 to 10 carbon atoms, R 2 are identical or different and are independently from each other selected from the group consisting of linear or branched alkylene or hydroxy alkylene radicals with 1 to 20 carbon atoms and if R 2 is hydroxy alkylene R 2 comprises 1 to 5 hydroxy group(s), R 3 are identical or different and are independently from each other selected from the group consisting of hydrogen, linear or branched alkyl groups with 1 to 6 carbon atoms, linear or branched hydroxy alkyl groups with 1 to 6 carbon atoms, (CH 2 CH 2 O) u H, (CH 2 CH 2 CH 2 O) v H and (CH 2 CH(CH 3 )CH 2 O) w H, most preferred hydrogen, methyl, ethyl, propyl, isopropyl, hydroxymethyl, 2 hydroxyethyl, 3 hydroxypropyl, 2 hydroxypropyl, 2-hydroxyisopropyl, R 4 are identical or different and are independently from each other selected from the group consisting of hydrogen, linear or branched, cyclic or alicyclic alkyl groups with 1 to 20 carbon atoms, linear or branched hydroxy alkyl groups with 1 to 6 carbon atoms and cycloalkyl residues having 6 to 18 carbon atoms, (CH 2 CH 2 O) u H, (CH 2 CH 2 CH 2 O) v H and (CH 2 CH(CH 3 )CH 2 O) w H, and wherein u=1 to 14, v=1 to 14, w=1 to 14, x=0 or 1, y=0 to 3, z=0 to 3, with the proviso that if z=3, at least one of R 4 is not hydrogen, y+z=3, a base according to formula (2)
(((R 6 ) 2 N—R 5 ) a (H) b N) d —CZ—(N(R 7 ) 2 ) c   (2)

wherein the R 5 groups in the molecule may be identical or different, the residues R 6 groups in the molecule may be identical or different and the residues R 7 groups in the molecule may be identical or different, and wherein R 5 are identical or different and are independently from each other selected from the group consisting of linear or branched alkylene radicals with 1 to 10 carbon atoms, wherein one or more CH 2 groups may be replaced by O to form ether bonds, R 6 are identical or different and are independently from each other selected from the group consisting of hydrogen, linear or branched alkyl groups with 1 to 6 carbon atoms, linear or branched hydroxy alkyl groups with 1 to 6 carbon atoms, (CH 2 CH 2 O) u H, (CH 2 CH 2 CH 2 O) v H and (CH 2 CH(CH 3 )CH 2 O) w H, R 7 are identical or different and are independently from each other selected from the group consisting of hydrogen, linear or branched alkyl groups with 1 to 6 carbon atoms, linear or branched hydroxy alkyl groups with 1 to 6 carbon atoms, (CH 2 CH 2 O) u H, (CH 2 CH 2 CH 2 O) v H and (CH 2 CH(CH 3 )CH 2 O) w H, and wherein Z═O or NH, u=1 to 14, preferably 1 to 6 v=1 to 14, preferably 1 to 6 w=1 to 14, preferably 1 to 6 a=0, 1 or 2, b=0, 1 or 2, a+b=2, c=0, 1 or 2, d=0, 1 or 2, c+d=2,
cyclic or bicyclic, non-aromatic, nitrogen comprising organic base comprising 4 to 20 carbon atoms, and 1 to 4 nitrogen atoms, optionally the cyclic or bicyclic, non-aromatic, nitrogen comprising organic base comprises one or more O atoms and/or carries one or more substituents selected from the group consisting of linear or branched alkyl or alkenyl groups with 1 to 6 carbon atoms, linear or branched hydroxy alkyl groups with 1 to 6, carbon atoms, (CH 2 CH 2 O) u H, (CH 2 CH 2 CH 2 O) v H and (CH 2 CH(CH 3 )CH 2 O) w H,
and mixtures thereof.

5 . The method according to claim 4 , wherein the organic amine base is at least one selected from the group consisting of
a trialkylamine according to Formula (3)
NR 4 R 4 ′R 4 ″  (3)

with R 4 , R 4 ′, R 4 ″ are identical or different and are independently selected from the group consisting of hydrogen, linear or branched, cyclic or alicyclic alkyl groups with 1 to 20 carbon atoms, linear or branched hydroxy alkyl groups with 1 to 6 carbon atoms and cycloalkyl residues having 6 to 18 carbon atoms, (CH 2 CH 2 O) u H, (CH 2 CH 2 CH 2 O) v H and (CH 2 CH(CH 3 )CH 2 O) w H,
u=1 to 14,
v=1 to 14,
w=1 to 14,
with the provision at least one of R 4 , R 4 ′ and
R 4 ″ is not hydrogen, a polyamine according to Formula (4)
((R 3 ) 2 N—R 2 ) 3 N  (4),

wherein
R 2 are identical or different and are independently from each other selected from the group consisting of linear or branched alkylene or hydroxy alkylene radicals with 1 to 20 carbon atoms and if R 2 is hydroxy alkyl R 2 comprises 1 to 5 hydroxy group(s),
R 3 are identical or different and are independently from each other selected from the group consisting of hydrogen, linear or branched alkyl groups with 1 to 6 carbon atoms, linear or branched hydroxy alkyl groups with 1 to 6 carbon atoms, (CH 2 CH 2 O) u H, (CH 2 CH 2 CH 2 O) v H and (CH 2 CH(CH 3 )CH 2 O) w H,
u=1 to 14,
v=1 to 14,
w=1 to 14,
a polyamine according to Formula (5)
(((R 3 ) 2 N—R 2 )—(O—R 1 ) x ) y —N(R 4 ) z   (5)

wherein x=0 or 1, y=1 or 2 and z=1 or 2 and y+z=3 and wherein
R 1 are identical or different and are independently from each other selected from the group consisting of linear or branched alkylene radicals with 1 to 10 carbon atoms,
R 2 are identical or different and are independently from each other selected from the group consisting of linear or branched alkylene or hydroxy alkylene radicals with 1 to 20 carbon atoms and if R 2 is hydroxy alkyl R 2 comprises 1 to 5 hydroxy group(s),
R 3 are identical or different and are independently from each other selected from the group consisting of hydrogen, linear or branched alkyl groups with 1 to 6 carbon atoms, linear or branched hydroxy alkyl groups with 1 to 6 carbon atoms, (CH 2 CH 2 O) u H, (CH 2 CH 2 CH 2 O) v H and (CH 2 CH(CH 3 )CH 2 O) w H,
R 4 are identical or different and are independently from each other selected from the group consisting of hydrogen, linear or branched, cyclic or alicyclic alkyl groups with 1 to 6 carbon atoms, linear or branched hydroxy alkyl groups with 1 to 6 carbon atoms, CH 2 CH 2 O) u H, (CH 2 CH 2 CH 2 O) v H and (CH 2 CH(CH 3 )CH 2 O) w H,
u=1 to 14,
v=1 to 14,
w=1 to 14,
a polyaminoalkylurea according to Formula (6)
(((R 6 ) 2 N—R 5 ) a (H) b N) d —CO—(N(R 7 ) 2 ) c   (6)

wherein
R 5 are identical or different and are independently from each other selected from the group consisting of linear or branched alkyle

Assignees

• Evonik Operations Gmbh

Inventors

• Hildebrand Jens
• Terheiden Annegret
• Hinrichs-Tontrup Natalia
• Burdeniuc Juan Jesus
• Schweissinger Emily Clare

Classifications

• C08J2375/14

  Polyurethanes having carbon-to-carbon unsaturated bonds · CPC title

• C08J11/14 Primary

  by treatment with steam or water · CPC title

• C08G65/48

  Polymers modified by chemical after-treatment · CPC title

• C08G18/4244

  containing oxygen in the form of ether groups · CPC title

• C08G18/244

  tin salts of carboxylic acids · CPC title