PROCESS FOR PREPARING POLYMERIC IMIDAZOLIUM COMPOUNDS WITHOUT OR WITH LESS MONOALDEHYDE

Abstract

A process for preparing polymeric compounds comprising ionic imidazolium groups (polymeric imidazolium compounds for short) comprising reacting an -dicarbonyl compound, an amino compound having at least two primary amino groups (referred to as oligoamine), a protic acid, less than 1 mol of a compound with only one aldehyde group (referred to as monoaldehyde) per mol of oligoamine and optionally further compounds.

Claims

1. A process for preparing a polymeric compound comprising ionic imidazolium groups, the process comprising reacting a reaction mixture comprising an -dicarbonyl compound, an oligoamine, which is an amino compound comprising at least two primary amino groups, a protic acid, less than 1 mol of a monoaldehyde, which is a compound with only one aldehyde group, per mol of the oligoamine, and optionally further compounds in a reactor.

2. The process according to claim 1, wherein less than 0.1 mol of the mono-aldehyde per mol the oligo-amine is used.

3. The process according to claim 1, wherein no mono-aldehyde is used.

4. The process according to claim 1, wherein the -dicarbonyl compound is a compound or a mixture of compounds of formula I
R1-COCOR2(I) wherein R1 and R2 are each, independently of one another, an H atom, a hydroxy group or an organic radical having from 1 to 20 carbon atoms.

5. The process according to claim 4, wherein R1 and R2 are each, independently of one another, an H atom or a hydroxyl group.

6. The process according to claim 1, wherein the -dicarbonyl compound is glyoxal, glyoxylic acid or a mixture thereof.

7. The process according to claim 1, wherein the oligoamine is a compound of formula II
(NH2).sub.nR3(II) where n is an integer greater than or equal to 2 and R3 is any n-valent organic radical.

8. The process according to claim 1, wherein the oligo-amine is an aliphatic or aromatic diamine or triamine.

9. The process according to claim 1, wherein the oligo-amine is a C2-C20-alkylenediamine.

10. The process according to claim 1, wherein the protic acid is an acid with a pK.sub.a greater than 1.

11. The process according to claim 1, wherein the protic acid is acetic acid.

12. The process according to claim 1, wherein the process is performed in water, a water-miscible solvent, or a mixture thereof.

13. The process according to claim 1, wherein said reacting occurs in a reaction solution with pH value of from 1 to 6.

14. The process according to claim 1, wherein the protic acid is introduced into the reactor first and the oligoamine, the -dicarbonyl compound and optionally the mono-aldehyde are subsequently added in a rate so that temperature of the reaction mixture is kept below 30 C.

Description

EXAMPLES

[0099] The molecular weight of the polymeric imidazolium compounds was determined by Size-exclusion chromatographie (SEC) using poly(2-vinylpyridine as standard and water comprising 0.1 w/w % trifluoracetic acid and 0.1 mol/1 NaCl as effluent. The temperature of the column was 25 C., the injected volume 100 L (liter), the concentration 1.5 mg/mL and the flow rate 0.8 mL/min.

[0100] The weight average molecular weight (Mw), the number average molecular weight (Mn) and the polydispersity PDI (Mw/Mn) of the polymeric imidazolium compounds obtained are specified in the examples.

[0101] The solid content of the product solutions obtained was determined by drying the solution under vacuum at 120 C. for two hours.

[0102] The nuclear magnetic resonance spectra (NMR) wereattaken of the product solutions as such. In the Annexes the NMR spectra of the examples are shown (chemical shift on the x-axis, intensity on the y-axis). The NMR spectra show peaks of the polymer, only. Hence the NMR spectra prove that the solutions obtained do not comprise unreacted starting materials and that all starting materials have reacted to polymer.

Comparison Example

[0103] (Using Mono-Aldehyde According to WO 2010/072571)

[0104] 2 mol acetic acid and 1 mol of 1,4 butane-diamine (dissolved in water) were placed in a flask. A mixture of 1 Mol formaldehyde (49% aq. solution) and 1 Mol glyoxal (40% aq. solution) were added at room temperature (ice bath cooling) to the reaction mixture. After completion of the addition the reaction mixture was heated to 95 C. for one hour.

[0105] An aqueous solution comprising a polymeric imidazolium compound was obtained. The solid content of the solution was 37.5% by weight.

[0106] Mw: 25200 g/mol Mn: 2910 g/mol; PDI: 6.5

Example 1

[0107] (Using Two Mol of Glyoxal, No Mono-Amine)

[0108] 2 mol acetic acid and 1 mol of 1,4 butane-diamine (dissolved in water) were placed in a flask. 2 Mol glyoxal (40% aq. solution) were added at room temperature (ice bath cooling) to the reaction mixture. After completion of the addition the reaction mixture was heated carefully to 75 C. for 50 min. Water was added to the solution and the mixture was cooled to room temperature.

[0109] An aqueous solution comprising a polymeric imidazolium compound was obtained. The solid content of the solution was 17.1% by weight.

[0110] Mw: 12800 g/mol; Mn: 1210 g/mol; PDI: 10.6

Example 2

[0111] (Using 1 Mol Glyoxal and 1 Mol Glyoxylic Acid, No Mono-Amine)

[0112] 2 mol acetic acid and 1 mol of 1,4 butane-diamine (dissolved in water) were placed in a flask. A mixture of 1 Mol glyoxilc acid (50% aq. solution) and 1 Mol glyoxal (40% aq. solution) were added at room temperature (ice bath cooling) to the reaction mixture. After completion of the addition the reaction mixture was heated carefully to 95 C. for 2 h, during this time CO.sub.2 evolved from the reaction mixture.

[0113] An aqueous solution comprising a polymeric imidazolium compound was obtained.

[0114] Mw: 12900 g/mol; Mn: 2190 g/mol; PDI: 5.9

TABLE-US-00001 TABLE compounds used in the examples Formal- Glyoxylic Acetic Diamine dehyde acid Glyoxal acid (mol) (mol) (mol) (mol) (mol) Comparison 1,4-Diamino- 1 mol 1 mol 2 mol example butane 1 mol Example 1 1,4-Diamino- 2 mol 2 mol butane 1 mol Example 2 1,4-Diamino- 1 mol 1 mol 2 mol butane 1 mol

[0115] Attached are three figures:

[0116] FIG. 1: 1H-NMR of polymer from the comparison example

[0117] FIG. 2: 1H-NMR of polymer from example 1

[0118] FIG. 3: 1H-NMR of polymer from example 2