Hydroxy-aminopolymers and method for producing same

Patent metadata

Field	Value
Publication number	US-9994672-B2
Application number	US-201214366342-A
Country	US
Kind code	B2
Filing date	Dec 17, 2012
Priority date	Dec 20, 2011
Publication date	Jun 12, 2018
Grant date	Jun 12, 2018

Abstract

The present invention relates to a process for the preparation of a hydroxy-amino polymer, comprising the steps: a) reacting an H-functional starter compound carrying at least one Zerewitinoff-active H atom with an unsaturated cyclic carboxylic acid anhydride and at least one alkylene oxide compound to give a hydroxyl-group-carrying prepolymer, b) adding a primary amine and/or ammonia to the double bonds of the hydroxyl-group-carrying prepolymer obtained according to step a) to give the hydroxy-amino polymer, wherein the reaction of the H-functional starter compound with the unsaturated cyclic carboxylic acid anhydride and/or the addition of the alkylene oxide compound is carried out using a double metal cyanide catalyst (DMC catalyst). The invention relates additionally to a hydroxy-amino polymer obtainable by the above-mentioned process, wherein the ratio of the amount of alkylene oxide compound to the amount of carboxylic acid anhydride is at least 1.1:1, and further to the use of this hydroxy-amino polymer in the preparation of a polyurethane urea polymer.

First claim

The invention claimed is:

1. A process for the preparation of a hydroxy-amino polymer, comprising:
a) reacting an H-functional starter compound which has at least one Zerewitinoff-active H atom with an unsaturated cyclic carboxylic acid anhydride and one or more of alkylene oxide compounds to form a hydroxyl-group-containing prepolymer,
b) adding a compound selected from the group consisting of primary amine group containing compounds, ammonia and mixtures thereof to the double bonds of the hydroxyl-group-containing prepolymer a) to yield the hydroxy-amino polymer,
wherein
the reaction of said H-functional starter compound with said unsaturated cyclic carboxylic acid anhydride and/or the addition of said alkylene oxide compound is carried out in the presence of a double metal cyanide catalyst (DMC catalyst), said H-functional starter compound contains from 1 to 35 Zerewitinoff-active H atoms,
said alkylene oxide compounds are chosen from alkylene oxides having from 2 to 24 carbon atoms,
said alkylene oxide compounds present in step a) comprise ethylene oxide in an amount greater than 50 wt. % of the total alkylene oxide compounds,
the molar ratio of the amount of alkylene oxide compounds to the amount of carboxylic acid anhydride is at least 1.1:1,
said H-functional starter compound and said DMC catalyst are first placed in a reaction vessel, alkylene oxide compound and optionally comonomer are metered in, and then said unsaturated cyclic carboxylic acid anhydride is added, and after the addition of said unsaturated cyclic carboxylic acid anhydride has taken place, alkylene oxide compound and optionally further comonomer are metered in again, and
said primary amine group containing compound has at least one primary amine group and optionally contains hydroxyl groups, and is selected from the group consisting of aliphatic monoamines, aliphatic diamines, cycloaliphatic monoamines, cycloaliphatic diamines, araliphatic monoamines and araliphatic diamines.

2. The process according to claim 1 , wherein said H-functional starter compound has a number-average molar mass of from 17 to 1200 g/mol.

3. The process according to claim 1 , wherein said unsaturated cyclic carboxylic acid anhydride is an unsaturated cyclic dicarboxylic acid anhydride.

4. The process according to claim 1 , wherein at least one comonomer is additionally reacted in a), and said comonomer is selected from the group consisting of lactones, lactides, saturated cyclic carboxylic acid anhydrides, aromatic cyclic carboxylic acid anhydrides, cyclic carbonates, carbon dioxide and mixtures thereof, wherein the reaction of said comonomer is catalysed by the DMC catalyst.

5. The process according to claim 1 , wherein the ratio of the amount of carboxylic acid anhydride to the number of Zerewitinoff-active H atoms of said H-functional starter compound is approximately from 1:1 to 1.5:1.

6. The process according to claim 1 , wherein said H-functional starter compound and said DMC catalyst are first placed in a reaction vessel, and then said alkylene oxide compound, said cyclic unsaturated carboxylic acid anhydride and optionally said comonomer are added.

7. The process according to claim 1 , wherein said H-functional starter polyol comprises a hydroxyl-group containing prepolymer which is formed by reacting an H-functional starter compound which has at least one Zerewitinoff-active H atom with an unsaturated cyclic carboxylic acid anhydride and at least one alkylene oxide compound.

8. The process according to claim 6 wherein the metering of the cyclic carboxylic acid anhydride is terminated before the alkylene oxide compound is metered in, and in a final metering of alkylene oxide and, optionally a comonomer, more than 1 mol of alkylene oxide compound is metered in per mol of Zerewitinoff-active hydrogen is metered in.

9. The process according to claim 1 , wherein in step a), an H-functional starter polyol and a partial amount of the DMC catalyst are placed in the reactor system; the H-functional compound and further DMC catalyst are fed in continuously together with the alkylene oxide and the unsaturated cyclic carboxylic acid anhydride; wherein the resulting reaction product of a) is continuously removed from the reactor system after a preselectable mean residence time.

10. A hydroxy-amino polymer obtainable by the process according to claim 1 , wherein the ratio of the amount of alkylene oxide compound to the amount of carboxylic acid anhydride is at least 1.1:1, and wherein the hydroxy-amino polymer is not subjected to purification.

11. The hydroxy-amino polymer according to claim 10 , wherein said hydroxy-amino polymer has a structure corresponding to the general formula (VII)

wherein
“starter” represents the radical of the H-functional starter compound,
A represents an aspartate group corresponding to formula (VIIIa) or (VIIIb)

wherein
R2 and R3 independently of one another represent hydrogen, an aliphatic radical, an aromatic radical, or R2 and R3 may be part of a cycloaliphatic ring system,
R1 represents hydrogen, an aliphatic radical which may contain heteroatoms, a cycloaliphatic radical which may contain heteroatoms or an aromatic radical which may also contain heteroatoms,
R4, R5, R6 and R7 independently of one another represent hydrogen, an aliphatic radical, an aromatic radical, or R5 and R6 may be part of a cycloaliphatic ring system,
l represents the number of Zerewitinoff-active hydrogen atoms of the H-functional starter compound,
m, n and o are independent of one another and are integers, wherein n and o=0 or ≥1, and m≥2,
wherein the equivalent molar mass of the compound corresponding to the structure shown in formula VII does not exceed the value of 18,900 g/mol.

12. A polyurethane urea polymer obtainable by reaction of a polyisocyanate with the hydroxy-amino polymer according to claim 10 .

13. The process according to claim 1 , wherein the alkylene oxide compounds further comprise propylene oxide.

14. The process according to claim 1 , wherein the alkylene oxide compounds present in step a) comprise ethylene oxide in an amount greater than 60 wt. % of the total alkylene oxide compounds.

15. The process according to claim 14 , wherein the alkylene oxide compounds further comprise propylene oxide.

Assignees

• Bayer Ip Gmbh
• Covestro Deutschland Ag

Inventors

• Lorenz Klaus
• Hofmann Jorg
• Nefzger Hartmut

Classifications

• C08G18/4252

  derived from polyols containing polyether groups and polycarboxylic acids · CPC title

• C08G18/3821

  Carboxylic acids; Esters thereof with monohydroxyl compounds · CPC title

• C08G18/10 Primary

  Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step · CPC title

• A61K8/817

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6) · CPC title

• A61K8/8147

  Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers · CPC title