Liquid purification or separation – Processes – Ion exchange or selective sorption
Patent
1996-12-20
1999-06-22
Raymond, Richard L.
Liquid purification or separation
Processes
Ion exchange or selective sorption
210638, 210674, 210679, 210684, 210688, 502159, 502164, 502167, 502401, B01D 1504, B01D 1508
Patent
active
059140445
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
THIS INVENTION relates to immobilised branched polyalkyleneimines, methods for preparation of such imines, and uses of the imines. Specifically the invention is directed towards solid phase ligands comprising immobilised branched polyalkyleneimines.
BACKGROUND ART
Simple linear amines such as ethylenediamine and diethylenetriamine have long been known as excellent coordinating ligands towards a range of transition and other heavy metal ions. The resulting metal complexes, being metal chelates, are usually significantly thermodynamically more stable than corresponding unidentate amine complexes of, for example, ammonia or methylamine.
In the past, various ligands including linear amines, have been attached to organic polymers supports. However, these are often difficult to synthesise in a manner that maintains the ion co-ordination properties of the ligand because of the inherent lipophilicity of the organic backbone. Organic polymer substrates are generally expensive which tends to make organic-polymer-bound ligands relatively expensive.
Amines have also been attached to inorganic supports. A range of simple amines, including ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine have been immobilised by chemically binding them via spacer groups to silicate surfaces to produce insoluble particles that will form complexes with and retain selected cations.
Techniques for binding these simple amines to inorganic supports such as silicon dioxide or silica gel (and other silicon containing substances, including glass), to aluminas and to other insoluble elemental oxides have been described. For example, the amine may be reacted with a spacer group such as (3-chloropropyl)-trimethoxysilane, (3-chloropropyl)-triethoxysilane or a range of other related functionalised alkylsilanes, such that the product is capable of attachment to silicon dioxide via one or more covalent bonds. This is one of several methods for immobilising simple ligands on a solid support. The above reaction sequence may be changed so that the spacer group is first attached to the solid support followed by immobilisation of the amine ligand by reaction with the free terminal group of the spacer. Specifically, the immobilisation of tetraethylenepentamine by this technique is known from Czech Patent No. 177,563 to Vynalezu. Further examples of this type are disclosed in U.S. patents of Bradshaw et al (U.S. Pat. No. 4,952,321), Hancock and Howell (U.S. Pat. No. 4,203,952) and Plueddemann (U.S. Pat. No. 4,071,546). These workers claim the attachment of a number of linear chain derivatives to solid substrates such as silica gel at one end of the linear chain using between one and three bonds to the silica.
Linear polyethyleneimines may be represented by the formula H.sub.2 This linear chain material is expected to also bind certain metal ions strongly. A chromatographic column packing for the purification and separation of anions and more specifically, anionic protein species has been described in Ramsden, U.S. Pat. No. 4,450,486. This patent discloses the preparation of a product that consists of linear non-crosslinked polyethyleneimine bound by a silane reagent to silica gel. The product, however, is limited to the use of silica gel having an average particle diameter of about three to seventy microns.
A related disclosure is found in European Patent No. 403,700 to Crane and Kakodkar, in which linear non-crosslinked polyethyleneimine of molecular weight 400 to 1800, is covalently bound to a silica-based solid-phase support. This product serves as an affinity chromatography matrix. The preparation of surface modified silica materials for use as ion-exchangers is disclosed in Jansen et al., "Absorption of Proteins on Porous and Non-Porous Poly(ethyleneimine) and tentacle-Type Anion Exchangers (Journal of Chromatography, vol. 522, 1990, 77-93).
A known application of immobilised simple linear amines is the retention by complexation of ions, such as the generally toxic ions of bismuth, cobalt,
REFERENCES:
patent: 4071546 (1978-01-01), Plueddemann
patent: 5066395 (1991-11-01), Rameden et al.
patent: 5120443 (1992-06-01), Bruening et al.
patent: 5190660 (1993-03-01), Lindoy et al.
patent: 5244856 (1993-09-01), Bruening et al.
patent: 5304638 (1994-04-01), Marshall et al.
patent: 5334316 (1994-08-01), Bruening et al.
Patent Abstract, AU-A-61034/90, Australian Patent Office, Norman B. Rainer, 1990.
Patent Abridgment, AU-B1-26 731/77, The British Petroleum Co., Ltd., 1977.
Alldredge Robert Louis
Eaglen Peter Lewis
Lindoy Leonard Francis
Metre-International Inc.
Raymond Richard L.
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