POLYETHERAMINES WITH LOW MELTING POINT

Abstract

Described herein are substituted polyetheramines with a low melting point which are obtainable by condensation of at least two N-(hydroxyalkyl)amines to obtain a polyetheramine and subsequent reaction of at least one remaining hydroxy group and/or, if present, at least one secondary amino group of said polyetheramine with ethylene oxide and at least one further alkylene oxide to obtain a substituted polyetheramine. Uses of such substituted polyetheramines in fields of cosmetic formulations, as crude oil emulsion brakers, in pigment dispersions of ink jets, in electro paintings, or in cementitious compositions as well as methods wherein said substituted polyetheramines are used in said fields are described herein.

Claims

1. Substituted polyetheramine obtainable by (a) Condensation of at least two N-(hydroxyalkyl)amines, wherein said N-(hydroxyalkyl)amines are independently selected from the group consisting of N-(hydroxyalkyl)amines according to formula Ia and Ib, respectively: ##STR00003## wherein A is independently selected from the group consisting of linear C.sub.1-alkylene, branched C.sub.1-alkylene, linear C.sub.2-alkylene, branched C.sub.2-alkylene, linear C.sub.3-alkylene, branched C.sub.3-alkylene, linear C.sub.4-alkylene, branched C.sub.4-alkylene, linear C.sub.5-alkylene, branched C.sub.5-alkylene, linear C.sub.6-alkylene, and branched C.sub.6-alkylene, R.sup.3, R.sup.3*, R.sup.4, R.sup.4*, R.sup.5, R.sup.5*, R.sup.6, R.sup.6*, R.sup.7, R.sup.7* and R.sup.8 are independently selected from the group consisting of H; linear substituted alkyl; branched substituted alkyl; linear non-substituted alkyl; branched non-substituted alkyl; substituted acycloalkyl; non-substituted acycloalkyl; substituted aryl; and non-substituted aryl to obtain a polyetheramine; and (b) Reacting at least one of the following: (i) at least one remaining hydroxy group and, (ii) at least one secondary amino group of the polyetheramine obtained in (a) with ethylene oxide and at least one further alkylene oxide selected from the group consisting of propylene oxide, butylene oxide, and pentene oxide to obtain a substituted polyetheramine which is substituted with at least one alkylenoxy unit E, wherein E is an alkylenoxy unit according to formula II: ##STR00004## wherein R.sup.1 is independently selected from the group consisting of 1,2-propylene, 1,2-butylene, and 1,2-pentene; R.sup.2 is independently selected from the group consisting of H, any of C.sub.1 to C22 alkyl, and any of C.sub.7 to C.sub.22 aralkyl m is an integer independently selected from values in the range of from 5 to 18; n is an integer independently selected from values in the range of from 1 to 5; and p is an integer independently selected from values in the range of from 2 to 14.

2. Substituted polyetheramine according to claim 1, wherein said substituted polyetheramine is further modified by at least one of quaternization, protonation, sulfation, transsulfation, and phosphation.

3. Substituted polyetheramine according to claim 1, wherein A is a C.sub.1-alkylene.

4. Substituted polyetheramine according to claim 1, wherein N-(hydroxyalkyl)amines according to formula la and not hydroxyalkyl)amines according to formula Ib are condensed.

5. Substituted polyetheramine according to claim 1, wherein at least one of R.sup.3, R.sup.3*, R.sup.4, R.sup.4*, R.sup.5, R.sup.5*, R.sup.6, R.sup.6*, R.sup.7 and R.sup.7* is independently selected from the group consisting of H, methyl and ethyl.

6. Substituted polyetheramine according to claim 1, wherein R.sup.8 is selected from the group consisting of H, methyl, ethyl, and butyl.

7. Substituted polyetheramine according to claim 1, wherein R.sup.1 is 1,2-propylene.

8. Substituted polyetheramine according to claim 1, wherein R.sup.2 is one of H, C.sub.1 alkyl, C.sub.2 alkyl, C.sub.3 alkyl, and C.sub.4 alkyl.

9. Substituted polyetheramine according to claim 1, wherein m is 10 to 12.

10. Substituted polyetheramine according to claim 2, wherein said substituted polyetheramine is further modified by at least one of quaternization and quaternization with additional sulfation.

11. Substituted polyetheramine according to claim 1, wherein R.sup.3*, R.sup.4*, R.sup.5* R.sup.6*, and R.sup.7* are H, and R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 are one of H and methyl.

12. (canceled)

13. Substituted polyetheramine according to claim 1, wherein n is 2 to 3.

14. Substituted polyetheramine according to claim 1, wherein p is 8 to 9.

Description

EXAMPLES p In the examples, the following abbreviations are used:

[0046] EO ethylene oxide

[0047] PO propylene oxide

[0048] x EO/OH x moles ethylene oxide per mole of hydroxyl groups in the polyetheramine

[0049] y PO/OH y moles propylene oxide per mole of hydroxyl groups in the polyetheramine

[0050] Melting points are determined according to DIN 51007 with a differential scanning calorimeter 823/700/229 from Mettler Toledo.

Example 1: Polytriethanolamine+11 EO/OH+2 PO/OH+8 EO/OH

[0051] 1 (a) Polytriethanolamine

[0052] A four-neck flask equipped with stirrer, distillation bridge, gas inlet tube, and internal thermometer was charged with 1500 g triethanolamine and 20 g of a 50% by weight aqueous solution of H.sub.3PO.sub.2. The mixture was heated under nitrogen to 200° C. The reaction mixture was stirred at 200° C. over a period of 15.5 h during which the condensate formed in the reaction was removed by means of a moderate stream of N.sub.2 as stripping gas via the distillation bridge. Toward the end of the reaction time indicated, the temperature was lowered to 140° C. Residual low molecular weight products were removed under a pressure of 100 mbar. Then the reaction mixture was cooled to ambient temperature, and polytriethanolamine (OH number: 585 mg KOH/g, amine number: 423 mg KOH/g, dynamic viscosity at 60° C.: 431 mPas, Mn=4450 g/mol, Mw=8200 g/mol was obtained. Molecular weight was determined by gel permeation chromatography using a refractometer as the detector. The mobile phase used was hexafluoroisopropanol (HFIP), the standard employed for determining the molecular weight being polymethylmethacrylate (PMMA).

[0053] 1 (b) Polytriethanolamine+11 EO/OH+2 PO/OH+8 EO/OH

[0054] In a 2 l autoclave, 90.0 g polytriethanolamine obtained in example 1 (a) and 3.9 g potassium hydroxide (50% aqueous solution) were mixed and stirred under vacuum (<10 mbar) at 120° C. for 2 h. The autoclave was purged with nitrogen and heated to 140° C. 453.8 g ethylene oxide was added within 5 h, followed by the addition of 108.7 g propylene oxide within 1 h and afterwards 330.0 g ethylene oxide within 3 h. To complete the reaction, the mixture was allowed to post-react for additional 10 hat 140° C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80° C. 984.0 g of a light brown liquid was obtained (melting point: 14.6° C.).

Example 2: Polytriethanolamine+11 EO/OH+3 PO/OH+8 EO/OH

[0055] In a 2 l autoclave, 90.0 g polytriethanolamine obtained in example 1 (a) and 4.2 g potassium hydroxide (50% aqueous solution) were mixed and stirred under vacuum (<10 mbar) at 120° C. for 2 h. The autoclave was purged with nitrogen and heated to 140° C. 453.8 g ethylene oxide was added within 5 h, followed by the addition of 163.1 g propylene oxide within 1 h and afterwards 330.0 g ethylene oxide within 3 h. To complete the reaction, the mixture was allowed to post-react for additional 10 h at 140° C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80° C. 1038.0 g of a light brown liquid was obtained (melting point: 13.5° C.).

Comparative Example 1: Polytriethanolamine+20 ethylene oxide/OH

[0056] In a 2 l autoclave, 66.0 g polytriethanolamine obtained in example 1 (a) and 2.7 g potassium hydroxide (50% aqueous solution) were mixed and stirred under vacuum (<10 mbar) at 120° C. for 2 h. The autoclave was purged with nitrogen and heated to 140° C. 605.6 g ethylene oxide was added within 6 h. To complete the reaction, the mixture was allowed to post-react for additional 10 h at 140° C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80° C. 653.6 g of a light brown solid was obtained (melting point: 33.0° C.).