EP1289651A1 - Produit hydrogel a des fins d'adsorption - Google Patents

Produit hydrogel a des fins d'adsorption

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Publication number
EP1289651A1
EP1289651A1 EP01938915A EP01938915A EP1289651A1 EP 1289651 A1 EP1289651 A1 EP 1289651A1 EP 01938915 A EP01938915 A EP 01938915A EP 01938915 A EP01938915 A EP 01938915A EP 1289651 A1 EP1289651 A1 EP 1289651A1
Authority
EP
European Patent Office
Prior art keywords
cross
support matrix
linked
hydrogel product
polysaccharide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01938915A
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German (de)
English (en)
Inventor
Jerker Porath
Bo Ersson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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Filing date
Publication date
Priority claimed from SE0002152A external-priority patent/SE516594C2/sv
Application filed by Individual filed Critical Individual
Publication of EP1289651A1 publication Critical patent/EP1289651A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/291—Gel sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • B01J20/3219—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond involving a particular spacer or linking group, e.g. for attaching an active group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3251—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulphur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3255—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. heterocyclic or heteroaromatic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds

Definitions

  • the present invention relates to a hydrogel product for adsorption purposes where an in water non-soluble support matrix is cross-linked with polymers which gives rise to an in water swellable adsorbent .
  • a support matrix an organic polymer or a combination of such e.g. polysaccharides such as agar, cellulose, starch etc., protein and components of protein and polysaccharide. Further the cross-linking polymers above have been cross-linked internally.
  • the present invention aims for achieving an improved adsorbent which selectively binds different materials, preferably metals.
  • the invention aims for an adsorbent which may be regenerated with required powerful means, without causing the adsorbent being unusable, e.g. looses its form, e.g. elution with 20% H 2 S0 4 .
  • the invention aims for an adsorbent which effectively may bind and concentrate poisonous compounds and which is cheap enough for making an economically harmless rendering possible of such material through e.g. dumping.
  • the invention aims for an adsorbent, which makes possible economical recycling of small amounts of valuable metals from large quantities of waste.
  • adsorbent according to the invention which in its most common embodiment is based upon a support matrix consisting of polysaccharide, or other material as set out below in the present description, to which different polymers have been cross-linked with other cross-linking agents.
  • the support matrix may also consist of protein or a mixture of protein and polysaccharide .
  • a polysaccharide such as agarose and cellulose may be regarded as thread-shaped molecules consisting of monomer units containing several hydroxyl groups and internal and external ether bonds (acetal bonds) , which taken together give the polysaccharide affinity to water (it is said to be hydrophilic) .
  • Such polymers form in water swellable gels with hydroxyls as targets for substitution.
  • the present invention relates to a product in which adjacent amino groups have been incorporated into the matrix. These amino groups may be alkylated under less drastic conditions (lower alkalinity than the hydroxyls) .
  • the amino groups are part of polyalkylene imines (which actually ought to be called polyalkylene amines) which first are coupled to the polysaccharide. This may be done at a high pH, e.g. 13 to 14. If an oligoethylene imine or polyethylene amine is selected the amino group density will be higher than the hydroxyl density in the original gel network, which is an advantage for the production of the product .
  • the above polyalkylene imines are internally cross-linked through additional addition of cross-linking agents when a suitable amount of layers of polyalkylene imines have been added to the support matrix.
  • our adsorbent differs from these metal adsorbents in that the carbon/protein component (support matrix) may be hydrolyzed with a strong acid without causing the product changing form macroscopically. This component may also be decomposed by oxidation with saturated sodium periodate solution, where the gel thus maintains its form despite these drastic treatments. If the product is being produced in the form of particles these may after acid treatment be packed in beds which allow high filtration velocities . These characteristics are obtained by coupling together a soluble polymer with a carbohydrate-polyamine complex in a non-soluble (gel) form with a cross-linking reagent.
  • organic polymer preferably polysaccharide and/or protein as support matrix or core material .
  • polyethylene imine At least two, often many layers of polyethylene imine are coupled together between themselves and with the support matrix. Further the layers are cross-linked internally through addition of a cross-linking agent.
  • a cross-linking agent e.g. tetraethylene pentamine (TEPA) .
  • TEPA tetraethylene pentamine
  • the cross-linking agent may outweigh the polyethylene amine component in the end product .
  • the glycerol and glycol residues may be activated and thereafter substituted.
  • the polyamine and alcohol components may independently be activated and substituted.
  • One may therefore substitute the polyamine with a metal chelating agent and the alcohol groups with another group, e.g. an aromatic substance and thus obtain an adsorbent with double functions.
  • an adsorbent may be produced which is resistant to a strong acid as well as a base.
  • a hydrogel for adsorption purposes is further described in PCT/SE99/00991 (W099/64149) .
  • a gel is described where you have a support matrix which is cross-linked to the polymers such as TEPA. However, there is no internal cross-linking within the polymers. Because this last-mentioned cross-linking is missing, the rigidity (stability) is reduced in this above-mentioned gel. Further you may suspect that there is a risk for the cross- linkings therein which may counteract through sterical hindrance the metal ion binding. You may thus expect achieving an adsorption maximum and thereafter a gradual lowering of the capacity.
  • Our adsorbent according to the present invention thus differs from these above-mentioned metal adsorbents within the prior art among other things that the carbon/protein component (support matrix) may undergo drastic treatments without the product macroscopically changing shape, and that an internal cross-link is present between/within the polymers which has been added to the support matrix, which gives a more rigid gel. If the product then is manufactured in the form of particles these may after treatment be packed in beds which allow for high filtration velocities .
  • the present invention relates to a hydrogel product for adsorption purposes consisting of an in water non-soluble support matrix and cross-linked polymers, characterized in that the support matrix is substituted with at least one first soluble polymer material which is chemically bound to the support matrix, whereafter optionally further polymer materials are built-in in the primarily synthesized support matrix polymer complex through different kinds of cross-links and that the polymer material is internally cross-linked, wherein optionally the support matrix is present in the form of an acid- and base- stable residue .
  • the present invention relates to a process for the production of this above-mentioned hydrogel product, characterized in that polyalkylene amine chains A x are incorporated into the polysaccharide/protein network (i.e. the support matrix) , which thereafter is activated and at the same time cross-linked with a cross-linking agent X x , where an internal cross-link is obtained, whereupon the product optionally is coupled with one or more new alkylene amine (s) A 2 -A i which thereupon is activated analogously with 2 -Xi whereby additionally one or more internal cross-link (s) is (are) obtained (arise) , whereupon further cross-linking agents X n -X z optionally may be added.
  • polyalkylene amine chains A x are incorporated into the polysaccharide/protein network (i.e. the support matrix) , which thereafter is activated and at the same time cross-linked with a cross-linking agent X x , where
  • support matrix is meant to embrace in the present application a matrix which is built up with a first, in water non-soluble polymer material.
  • the invention is demonstrated in the form of a support matrix consisting of cross-linked spherical agarose particles but the support matrix may also comprise agar particles and polygalactanes (comprising polyglactose units) , agarose or derivatives thereof, laminarine, cellulose (e.g. cotton) or derivatives thereof, cross-linked dextrane or derivatives thereof, and starch or derivatives thereof, and also proteins or a combination of polysaccharide and protein.
  • the support matrix is present as a water-swollen gel when applying the polymers, i.e. e.g. polyethylene amine, most preferred a polyfunctional amine, e.g. polyethylene diamine .
  • the support matrix may instead of a polysaccharide comprise a protein with suitable side chains, which is the case with hair (wool) and silk. They contain e.g. OH from serine and -S-S groups which may be converted into -SH and amino groups . The OH- groups of serine may be converted into SH groups.
  • a polysaccharide comprise a protein with suitable side chains, which is the case with hair (wool) and silk.
  • They contain e.g. OH from serine and -S-S groups which may be converted into -SH and amino groups .
  • the OH- groups of serine may be converted into SH groups.
  • the support matrix may be expanded to other proteins and protein complexes.
  • the protein may be activated with a bifunctional reagent, e.g. a bisepoxide, an epichlorohydrine, a bishalohydrine, divinylsulphone, cyano halides, triazines, mono-, di- or polyaldehydes (e.g. glutaraldehyde) etc., whereupon the polyethylene amine may be coupled thereon later, after optionally a further coupling of polyethylene imine, polyethylene imine (preferably a polyethylene amine) is internally cross-linked in an analogous way as above.
  • a bifunctional reagent e.g. a bisepoxide, an epichlorohydrine, a bishalohydrine, divinylsulphone, cyano halides, triazines, mono-, di- or polyaldehydes (e.g. glutaraldehyde) etc.
  • internally cross-linked is meant to embrace in the present application that the polymer (s) which is bound to the support matrix, preferably polyalkylene imine, is (are) cross-linked either between one of more polymers (preferably polyalkylene imine molecules) or the polymers (preferably polyalkylene imine molecules) are cross-linked within themselves .
  • a support matrix may be built up from both protein and polysaccharide, e.g. by mixing protein particles with agar in a hot solution which thereafter is allowed to congeal into a gel .
  • a polyamine may then be built up around the gel component .
  • the protein and the polysaccharide can separately be enzymatically degraded, alternatively the protein can be degraded in strong alkali, whereupon the polysaccharide can be degraded in acid.
  • the intermediate may be substituted. Such a selective degradation may be valuable for the controlling of the porosity of the end product .
  • the invention may also be present in the shape of a pearl, thread, membrane, or may also be porous and spongy (foam plastic shaped) . Thus, it may be present in a rather arbitrate form.
  • the wording "acid- and base-stable" is meant to embrace in the present application a residue which is formed when treating the support matrix with an acid, a base, an oxidation agent or a reduction agent .
  • the acid may be H 2 S0 4 .
  • the treatment with oxidizing agent may be performed with a saturated periodate solution at pH 7.
  • the reduction agent may be sodium boron hydride .
  • hydrogel product according to the present invention may also be described with the structural formula:
  • Y is a nitrogen, sulphur or oxygen bridge (which originates from the support matrix, or which may have been incorporated into the support matrix in another way) ;
  • X ⁇ ...X n ...X z are the same or different di-, tri- or polyfunctional cross-linking agents
  • a x is a water soluble polymer material, n is a whole number where- -n > 2; and z is 0 or a whole number where z > 0 X
  • hydrogel product according to the present invention may also be described with the structural formula:
  • cross- linking agents which achieve the internal cross-link, may be present in a multiple way on the polymer A ⁇ ) :
  • cross-linking agents which achieve the internal cross-link, may be present in a multiple way on the polymers ⁇ -A :
  • P is the support matrix
  • Y is a nitrogen, sulphur or oxygen bridge (which originates from the support matrix or which may have been incorporated into the support matrix in another way) ;
  • X x ...X t . ..X n ...X z are the same or different di, tri or polyfunctional cross-linking agents
  • Aj_...Ai are water soluble polymer materials, preferably the same or different kinds of cross-linked residues of amines; and n and i are whole numbers where i > 2 and n > 2 and z is 0 or a whole number where z > 0.
  • Agar which may be support matrix comprises OH groups which can be activated with bi- or multifunctional reagents such as bisepoxides and halohydrines .
  • S and N the following reactions may be given:
  • Aj_.. -A ⁇ may be comprised of, one or more, residues of straight or branched oligo or polyalkylene amine (usually called polyalkylene imine) , preferably oligo or polyethylene amine, or of residues from any of the amines NHR X R 2 , wherein R may be identical with or differ from R 2 and R may be H, alkyl, aromatic or heterocyclic alkyl, carboxy alkyl or other amino acid, most preferred a polyalkylene diamine .
  • Preferred among polyalkylene diamines is a polymer of ethylene diamine which is of a high molecular type, most preferred with a molecular weight in the size range > 2000 Da, especially preferred 2,000-100,000 Da
  • the alkylene diamines which may be used for the production of the product in accordance with the present description may further be of low molecular type, e.g. tetraethylene pentamine (TEPA) or high molecular type, e.g. polyethylene imine (PEI) and polypropylene imine (PPI) .
  • TEPA tetraethylene pentamine
  • PEI polyethylene imine
  • PPI polypropylene imine
  • the amine may have a linear molecule structure or it may be branched as e.g. tris (2-aminoethyl) amine, TREN.
  • the invention relates generally to polyalkylene amines wherein polyethylene amine is one example .
  • polypropylene and polybutylene amine give products having characteristics which do not fundamentally differ from polyethylene variants.
  • the latter are somewhat more hydrophilic.
  • polyalkylene diamines are used in the present invention such as polyethylene diamine and polypropylene diamine due to the probable forming of five and six ring structure, respectively
  • Me metal ion, e.g. Cu 2
  • the polyalkylene imines work as a metal adsorbent wherein probably the metal ions are fixed in the polymer network. You may also thus call the gel product according to the present invention a metal chelate forming adsorbent or an ion exchanger.
  • a or Aj_...Ai i.e. the polymer or the polymers above may further also be modified additionally. You may add reactions such as carboxylation, picolylation and so on under the conditions that not all of the sites for attack (for X, i.e. cross-linking agents) on A x or -A..-.A 1 are consumed (i.e. all amino groups) . You may also modify through the addition of hydroxyl containing polymers, such as e.g. polyvinylalcohol, hydroxyethyl cellulose, starch, cellulose or neutral derivatives thereof. You may thus achieve a "protecting" layer for the polyamine or the polyamines . Examples of this may be :
  • the cross-linking agents can be of different kinds. They may be bi-, tri- or polyfunctional . The more activated functions the cross-linking agent possesses, the more efficient both the cross-linking and the activation will be.
  • a trifunctional cross- linking agent as e.g. trihalotriazine or e.g. triepoxide may be working both as cross-linking agent and activator (activating agent) .
  • Cross-linking agents may be halohydrine, epihalohydrine, bishalohydrine, divinyl sulphone, triazine, halodiazine or halotriazine, halohydrine, di-, tri- or polyepoxide, halodiazine or halotriazine, di-, tri- or polyfunctional aldehyde, preferably glutaraldehyde or polymerized glutaraldehyde, di-, tri- or polyaziridine, W x - alkylene-W 2 , wherein W x and W 2 is a halogen, preferably ethylene dibromide, or halogen cyanurate.
  • the cross-linking agents in the product may be of different kinds, wherein one or more cross-links may be broken and leave one or more other cross-links intact.
  • a gel-formed residue product remains after that the support matrix (preferably polygalactane gel) has been broken down by hydrolysis and/or through oxidation.
  • the number of amino groups is at least 10 and the number of cross-links at least 4.
  • an insoluble acid-resistant gel product may be achieved. This gel product may be much more rigid if the number of amino groups in A x .. ,A ⁇ is increased to 1,000. You may thus achieve a grading of the chemical characteristics of the gel product .
  • the metal adsorption capacity increases when the number of amino groups in A . ..A ⁇ is increased and at the same time the stability of the gel is increased.
  • the rigidity and the chemical stability is enhanced with the increased number of cross-links (increasing value as regards X A ) .
  • the invention according to the present description has a considerable stability and it places itself in a preserved, original form also after a powerful chemical influence, e.g. elution, at treatment using a strong acid, e.g. 20% sulphuric acid, treatment using saturated periodate solution at pH 7, or at treatment using sodium boron hydride.
  • a strong acid e.g. 20% sulphuric acid
  • saturated periodate solution at pH 7, or at treatment using sodium boron hydride.
  • sodium boron hydride sodium boron hydride
  • the polyamine is a high molecular polyamine.
  • 100 monomeric units and 10 cross-links a stable residue gel may be obtained.
  • the residue gel may after hydrolysis have (or even alcoholysis) the structures:
  • Polyalkylene imine chains A x are incorporated into the polysaccharide/protein network (support matrix) which thereafter is activated and at the same time is cross-linked with a cross- linking agent X 17 whereupon an internal cross-link is obtained, whereupon the product optionally is coupled with a new alkylene imine A 2 which thereupon is activated with X 2 , whereupon a further internal cross-link is obtained, whereupon further cross-linking agents X 3 -X z may be added. X 3 -X z thus incorporates at least one non-reacted group. Further additional layers of polyalkylene imine chains may be added with an, of course, analogous addition of further cross-linking agents.
  • a cross-linked polyalkylene network is first cross-linked, whereupon it is coupled to the rigid polysaccharide/protein phase (the support matrix) which may be cross-linked polysaccharide/protein with or without polyalkylene imine coupled according to (1) .
  • the processes according to (1) and (2) above may also comprise that the polysaccharide/protein network is subjected to degradation, whereupon an acid- and base-stable residue is obtained.
  • the cross-linking may also be performed in another way, i.e. through the cross-linking agent being built up on the amino units.
  • This may be exemplified by allyl chloride or allyl bromide, e.g.
  • allyl amine is thereafter converted into a reactive form through halogenation, e.g. bromation with bromine water:
  • epoxide In an alkaline solution epoxide is formed.
  • the bromated product may be coupled to amines as polyamines but also thioles This two step activation has certain advantages.
  • the amino groups in the polyethylene imine are adjacent and ring closing comes under better control and a higher capacity may be obtained.
  • the activation and the coupling may be repeated several times or first a polyalkylene network is cross-linked, whereupon it is coupled to a solid polysaccharide/protein phase which may be cross-linked polysaccharide/protein with or without polyalkylene imine coupled according to what has been mentioned above .
  • polyethylene imine - polyethylene imine complex When the thus formed polyethylene imine - polyethylene imine complex in its turn is cross-linked with optionally more polyethylene imine an increasingly higher molecular polyethylene imine complex is formed which through repeatedly similar operations gives an increasingly stable polymer complex.
  • the thus treated particles keep their form and may thus be subjected to extremely drastic treatment such as with strong acid or base without the metal binding capacity being lost under the conditions that the cross-binding (linking) reagents such as epoxides, halohydrines or halogencyanurates have been used.
  • an internal cross-linking according to the present invention is performed on the polyethylene imine - polyethylene imine complex further enhanced stability will be achieved.
  • a sufficient number i.e. at least one or more and optionally more reactions with oligo or polyethylene imine, is performed, wherein you obtain a sufficient number of layers with polyamine, preferably at least one layer on the support matrix, most preferred at least two layers, furthermore more preferred at least three layers.
  • polyamine preferably at least one layer on the support matrix, most preferred at least two layers, furthermore more preferred at least three layers.
  • internal cross-linking of polyamine is performed through addition of one of more cross-linking agents.
  • the characteristics of the product depends on the density of the matrix (agarose concentration in the particles) and are reflected in how molecules of different sizes may penetrate into the matrix. Further the internal cross-linking is affected by the polyamines .
  • the explanations to why the metal ions are being absorbed by the matrix may also e.g. be thanks to the great amount of amino groups in the matrix which may achieve a Z-potential which is powerful enough for the ions to be caught .
  • the free electron pairs in the amino groups may be those who participate actively when catching the ions. Thus, it may depend upon that there is some kind of reciprocal utilization of electrons (electron delocalization) .
  • Covalent bonding may be another explanation to that the invention works, like electrostatic forces.
  • the invention may be present in the form of different particles, e.g. comprising a support matrix NovaroseTM SE 10 (Novarose is a trademark owned by Inovata AB) which preferably is penetrated by protein molecules in average not much greater than 10 000 Dalton, Novarose SE 100 which is penetrated by molecules approximately ten times greater, and Novarose SE 1000 which is penetrated by molecules greater than 1 000 000 Dalton. You may also have a gel which is penetrated by protein molecules with an average size of up to 300 000 Dalton.
  • Application areas for the present invention may e.g. be within the area of environmental technique in order to remove undesirable metal ions from leachate .
  • a concentration of metal ions is obtained at the same time which may be desirable to achieve in other applications such as e.g. extracting of metals.
  • Metallurgical industry may have use of this invention partly for removal of metal ions or partly for concentration of metal ions.
  • the present invention in particular the product, may further be used as support matrix during solid phase synthesis of peptides.
  • the gel according to the present invention may be used for fixing catalysts, e.g. palladium (Pd) or enzymes.
  • Agar-PEI-2000 was produced in an analogous way by coupling of polyethylene amine having a molecular weight of 2000 Da.
  • a 25 ml Erlenmeyer flask (E-flask) was equipped with 10 ml of 0.5 M Na 2 C0 3 , 0.5 ml butane diol-diglycidyl ether (BDG) and 1.5 g Agar-PEI-750000.
  • BDG butane diol-diglycidyl ether
  • the coupling reaction was performed at 60°C during 70 minutes, whereupon the gel was suspended and was was washed on filter with ethanol followed by water.
  • the gel was henceforth called Agaros-PEI-750000-BDG.
  • Agaros-PEI-2000-BDG was produced.
  • 0.5 g of each gel was treated with 1 ml of 30% sulphuric acid at 70°C.
  • Example 2 Analogously with Example 2 both gels were coupled according to Example 1 with 0.5 ml epichlorohydrine instead of BDG.
  • the gels called Agar-PEI-750000-EC and Agar-PEI-2000-EC, respectively, were treated in the same way as in Example 2 with '
  • each of PEI-2000 and PEI-750000 was suspended in a mixture of 0.5 ml of formalin and 10 ml of 1% acetic acid and was heated to 60°C and the reaction was left to continue during 70 minutes, whereupon the gels were collected on filter and washed with water.
  • 0.5 g of each gel was suspended in 30% sulphuric acid and the hydrolysis was left to continue at 70°C.
  • the gels were called Agar-PEI-2000-F and Agar-PEI-750000-F.
  • Sepharose 4B non-cross-linked agarose in particle form obtained from Pharmacia Biotech, Uppsala, Sweden
  • 20 ml of 0.5 M Na 2 C0 3 1 ml of divinyl sulphone (DVS) was added and the reaction was left to go during 20 hours at room temperature .
  • the gel was collected on filter and was washed with ethanol followed by water.
  • the gel was suspended in 10 ml of water and 10 ml of 50% water solution of PEI-750000.
  • the gel called Agarose-DVS-PEI- 750000, was divided into two parts. One part was suspended in 10 ml of water and 10 ml of 50% glutaraldehyde and the reaction was terminated after 1 hour and was further processed. The gel was red coloured. The gel was called Agarose-DVS-PEI-750000-GA. The other part was suspended in 10 ml of 0.5 M Na 2 C0 3 and was equipped with 1 ml of epichlorohydrine . The gel was called Agarose-DVS-PEI-750000-EC. This gel was colourless.
  • Agarose-DVS-PEI-750000 and the two gels cross-linked according to Example 7 were treated over night at room temperature with 2 M NaOH.
  • the gels were collected and washed on filter with distilled water, whereupon they were treated during one week in 50% sulphuric acid at room temperature.
  • Agarose-DVS-PEI-750000 was dissolved and formed a colourless solution in the 50% sulphuric acid.
  • the two other gels, Agarose- DVS-PEI-750000-GA and Agarose-DVS-PEI-750000-EC left gel products having the same macroscopical appearance as the original agarose (Sepharose 4B) but adsorbed an essential amount of copper ions from copper sulphate solution. Further it was established that the gels after hydrolysis did not contain any sulphur. The latter showed that all divinyl sulphon bridges had been dissolved and the residue gels consisted of cross-linked polyethylene imine .

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  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention concerne un produit hydrogel destiné à des fins d'adsorption. Une matrice support insoluble dans l'eau est réticulée avec des polymères pour donner un adsorbant gonflant à l'eau. En outre, les polymères sont réticulés à l'intérieur par au moins agent de réticulation. On utilise comme matrice support un polymère organique ou une association notamment de polysaccharide tel d'agar, de cellulose, d'amidon etc, d'une protéine et de composants protéiques et de polysaccharide. La matrice support est substituée par une première matière polymérique soluble chimiquement liée à la matrice support, des matières polymériques additionnelles étant éventuellement incorporées dans le complexe matrice support tout d'abord synthétisé par différentes sortes de réticulations. Eventuellement la matrice support est présente sous la forme d'un résidu stable en milieu acide et base.
EP01938915A 2000-06-08 2001-06-07 Produit hydrogel a des fins d'adsorption Withdrawn EP1289651A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US20999900P 2000-06-08 2000-06-08
SE0002152 2000-06-08
US209999P 2000-06-08
SE0002152A SE516594C2 (sv) 2000-06-08 2000-06-08 Hydrogelprodukt för adsorptionsändamål
PCT/SE2001/001278 WO2001094007A1 (fr) 2000-06-08 2001-06-07 Produit hydrogel a des fins d'adsorption

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US6821331B2 (en) * 2003-04-09 2004-11-23 Wisconsin Alumni Research Foundation Protein-polysaccharide hybrid hydrogels

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SE512234C2 (sv) * 1998-06-12 2000-02-14 Jerker Porath Hydrogelprodukt för adsorptionsändamål bestående av en vattenolöslig stödmatris som är tvärbunden med polymerer

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