Preparing chloride-free polyethyleneimines

Patent metadata

Field	Value
Publication number	US-9481763-B2
Application number	US-201314100440-A
Country	US
Kind code	B2
Filing date	Dec 9, 2013
Priority date	Dec 12, 2012
Publication date	Nov 1, 2016
Grant date	Nov 1, 2016

Abstract

In a method of preparing polyalkyleneimines from alkyleneimines in the presence of a liquid solvent, and a catalyst, the preparing is effected semi-discontinuously in one reaction container. The preparing is optionally effected in the presence of further additives.
Polyalkyleneimines obtained by such methods and formulations thereof likewise form part of the subject matter of the invention, especially those having a low proportion of chloride-containing compounds. Such polyalkyleneimines have uses in the field of medical technology, printing media, wastewater treatment, surface treatment, cosmetics, laundry detergents, biotechnology, packaging, electronics, paper, building construction chemistry, textiles, chromatography, ion exchangers, oil industry, ceramics, glass, membrane technology, catalysts, electroplating, biocides or wood protection. Further possible uses include as corrosion inhibitor, dispersant, additive in oils, for formulation of drugs, haircare products, scents and aromas, for preparing gene vectors, for functionalizing and modifying surfaces in electroplating and medical technology or for preparing cleaning systems for the semiconductor industry and lithium batteries.

First claim

We claim:

1. A method of producing a polyalkyleneimine having a degree of branching of more than 50% from an alkyleneimine, the method comprising semi-discontinuously reacting at least one alkyleneimine in the presence of an aqueous solvent and carbon dioxide as a catalyst in one reaction container to produce a polyalkyleneimine,
wherein:
the at least one alkyleneimine is metered into an initial charge comprising the aqueous solvent, the carbon dioxide, and an additive selected from the group consisting of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and 3,3-dimethylaminopropyl amine; and
the carbon dioxide is a sole catalyst in the reaction.

2. The method according to claim 1 , wherein the polyalkyleneimine is produced from the alkyleneimine in the presence of ethylenediamine as the additive.

3. The method according to claim 1 , wherein the polyalkyleneimine is produced from the alkyleneimine in the absence of a chlorine-containing compound.

4. The method according to claim 1 , wherein the alkyleneimine is ethyleneimine, 2-methylaziridine, 1-(2-hydroxyethyl)aziridine, 1-(2-amino ethyl)aziridine, or a combination thereof.

5. The method according to claim 1 , wherein the additive is selected from the group consisting of dimethylamine, ethylamine, diethylamine, propylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and 3,3-dimethylaminopropyl amine.

6. A polyalkyleneimine obtained by the method according to claim 1 .

7. The polyalkyleneimine according to claim 6 , wherein the polyalkyleneimine has a number average molecular weight Mn of 300 to 500 000 g/mol and a polydispersity of 1.3 to 5.

8. The polyalkyleneimine according to claim 6 , wherein the polyalkyleneimine has a degree of branching ranging from 55 to 95%.

9. The polyalkyleneimine according to claim 6 , comprising not more than 0.5 wt % of chlorine-containing impurities of not more than 0.5 wt % based on a total amount of the polyalkyleneimine.

10. A method, comprising contacting the polyalkyleneimine according to claim 9 with an article of manufacture.

11. The method according to claim 10 , wherein the article of manufacture is a component of a medical device, a printing media, an article for wastewater treatment, an article for surface treatment, a cosmetic, a laundry detergent, an article of biotechnology, an article of packaging, an electronic article, a paper, an article of building construction, a textile, an article of chromatography, an ion exchanger, an oil, a ceramic, a glass, an article of membrane technology, a catalyst, an article of electroplating, a biocide or an article of wood protection.

12. The method according to claim 10 , wherein the polyalkyleneimine is adapted to function as a corrosion inhibitor, a dispersant, or an additive suitable for an application selected from the group consisting of formulating an oil, formulating a drug, formulating a haircare product, formulating a scent, formulating an aroma, preparing a gene vector, functionalizing and modifying a surface in electroplating, functionalizing and modifying a surface in a medical technology, preparing a cleaning system for semiconductor industry, and for preparing a lithium battery.

13. A formulation comprising the polyalkyleneimine according to claim 6 .

14. A method, comprising contacting the formulation according to claim 13 with an article of manufacture.

15. The method according to claim 14 , wherein the article of manufacture is a component of a medical device, a printing media, an article for wastewater treatment, an article for surface treatment, a cosmetic, a laundry detergent, an article of biotechnology, an article of packaging, an electronic article, a paper, an article of building construction, a textile, an article of chromatography, an ion exchanger, an oil, a ceramic, a glass, an article of membrane technology, a catalyst, an article of electroplating, a biocide or an article of wood protection.

16. The method according to claim 14 , wherein the formulation is adapted to function as a corrosion inhibitor, a dispersant, or an additive suitable for an application selected from the group consisting of formulating an oil, formulating a drug, formulating a haircare product, formulating a scent, formulating an aroma, preparing a gene vector, functionalizing and modifying a surface in electroplating, functionalizing and modifying a surface in a medical technology, preparing a cleaning system for semiconductor industry, and for preparing a lithium battery.

17. The method of claim 1 , wherein the polydispersity of the polyalkyleneimine ranges from 1.4 to 1.8.

18. The method of claim 1 , wherein the proportion of chlorine-containing impurities in the polyalkyleneimine is not more than 0.5 wt % based on the amount of the polyalkyleneimine.

19. The method of claim 1 , wherein the proportion of chlorine-containing impurities in the polyalkyleneimine is not more than 0.1 wt % based on the amount of the polyalkyleneimine.

20. The method of claim 1 , wherein the at least one alkyleneimine is metered into an initial charge consisting of the aqueous solvent, the carbon dioxide, and the additive selected from the group consisting of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and 3,3-dimethylaminopropyl amine.

21. The method of claim 1 , consisting of semi-discontinuously reacting the at least one alkyleneimine in the presence of the aqueous solvent and the carbon dioxide as the sole catalyst in the one reaction container to produce the polyalkyleneimine,
wherein the at least one alkyleneimine is metered into an initial charge consisting of the aqueous solvent, the carbon dioxide, and the additive selected from the group consisting of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and 3,3-dimethylaminopropyl amine.

Assignees

• Basf Se

Inventors

• Hueffer Stephan
• Kramer Andreas
• Dietsche Frank

Classifications

• C08G73/0213 Primary

  Preparatory process · CPC title

• C08G73/0206

  Polyalkylene(poly)amines · CPC title