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EP1232018B1 - Procede d'application d'un polymere sur un support - Google Patents

Procede d'application d'un polymere sur un support Download PDF

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Publication number
EP1232018B1
EP1232018B1 EP00979625A EP00979625A EP1232018B1 EP 1232018 B1 EP1232018 B1 EP 1232018B1 EP 00979625 A EP00979625 A EP 00979625A EP 00979625 A EP00979625 A EP 00979625A EP 1232018 B1 EP1232018 B1 EP 1232018B1
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EP
European Patent Office
Prior art keywords
polymer
solution
layer
crosslinking
reagent
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.)
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EP00979625A
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German (de)
English (en)
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EP1232018A2 (fr
Inventor
Klaus Gottschall
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Instraction GmbH
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Instraction GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers

Definitions

  • the present invention relates to a method in which one or more polymers can be applied in layers to a carrier material.
  • the polymer network which by the inventive Method is available, in a preferred embodiment, the polymer Network is made such that its conformation to one or more Template connections is adjusted.
  • Another aspect of the present invention relates to the use of the polymer produced according to the invention Network in processes in which substances are manufactured, separated, detected or in other substances are converted.
  • Coatings with polymers are described, for example, in Wilfried Plum, dissertation, D 82 (RWTH Aachen), Shaker Verlag, Aachen 1995, G. Schomburg et al, Chromatographia, 18 (1984) 265 and in A. Kurganov et al, Journal of Chromatography A, 660 (1994) 97-111.
  • Suitable polymers are, inter alia, in the German patent applications DE-A 198 55 173.8 and DE-A 199 28 236.6.
  • the present invention relates to a method for applying at least two layers of at least one polymer on a carrier material, thereby characterized in that in at least one step at least one layer of the at least one polymer is bound to the carrier material and in at least a further step at least one further layer of the at least one Polymer on the at least one polymer layer bonded to the carrier material is applied.
  • the stepwise application of the at least one polymer can be carried out in accordance with all suitable procedures are carried out to ensure that at least per step a layer of the polymer is applied so that a layered polymer structure is applied to the carrier material.
  • the solution according to (i) can be brought into contact with the carrier material will have one or more suitable solvents, the at least one polymer dissolved in the solvent or solvent mixture or also colloidally dissolved or suspended, for example in the form of a Nanosuspension.
  • reaction conditions are chosen so that when they are brought into contact the solution with the carrier material does not bind the at least one Polymer is carried out on the carrier material.
  • reaction conditions are, for example adjusted by one or more suitable solvents.
  • solvents are used in which the at least one The polymer is so soluble that it does not bind to the carrier material.
  • reaction conditions can also be selected by suitable temperature can be achieved in which, for example, the solution with the carrier material at so high temperatures is brought into contact that the binding of the at least a polymer on the carrier material is omitted.
  • reaction conditions can also be adjusted by suitable adjustment of the pH the polymer solution can be achieved when the binding of the at least a polymer depends on the pH of the carrier material.
  • reaction conditions under which the solution contained at least a polymer fails can be avoided.
  • a solution containing the at least one polymer comprises to bring into contact with the carrier material.
  • Carrier material first in contact with the at least one solvent bring and then in the at least one solvent the at least one polymer contribute.
  • first cover the substrate with at least one a solvent and then a solution that the comprises at least one polymer.
  • each separately or together with one or more other polymers in a solvent or solvent mixture to solve and the individual solutions, each of which is at least one polymer comprises, together or separately with the carrier material, which optionally already dissolved or colloidally dissolved or suspended in at least one solvent to contact.
  • all carrier materials are suitable within the scope of the present to which the at least one polymer can be applied by bonding can. If two or more different polymers are used, then it is sufficient within the scope of the method according to the invention if one of the Polymers can be applied to the carrier material by binding. Of course, it is of course also conceivable for two or more different ones Polymers can be applied to the carrier material by binding.
  • the carrier materials polymer can no polymer is applied to one or more of them as long as at least one of the carrier materials polymer is applied.
  • Can also other polymers and compounds, such as those commonly used Aids are applied, the binding of the polymer to the carrier material can also be achieved through other interactions and / or processes can.
  • the polymers present in the solution or / and Connections are not applied to the carrier and for example in the Solution remain.
  • at least one of these Polymers applied in a further step to, for example, a carrier material will, before this further step with the solution that this polymer includes, is brought into contact.
  • the reaction conditions become such after contacting changed that the binding of the at least one polymer to the support material he follows.
  • the reaction conditions become such after contacting changed that the binding of the at least one polymer to the support material he follows.
  • a polymer is bound to a carrier material.
  • the bond is temperature dependent, it is conceivable to either increase or decrease the temperature depending on what change favors the bond.
  • the composition of the solution containing the at least one polymer contains, changed or this solution was slowly concentrated.
  • the composition of the Solution changed so that at least one acidic or at least one basic Compound or a mixture of two or more thereof are added, by which the pH of the solution is changed so that the binding at least one of the polymers is enabled.
  • the pH of the solution changed so that the binding at least one of the polymers is enabled.
  • the solution that the least contains a polymer so concentrated that the concentration of at least a polymer that is to be bound to the support material in the Solution remains largely constant.
  • this solution is concentrated by a correspondingly slow one Process control by which the polymer concentration is kept largely constant becomes.
  • the solution containing the at least one polymer Presence of a non-specific or non-selective cross-linking reagent to dryness.
  • the generally is carried out so that the polymer from the solution faster on the support is deposited as it is depleted from solution in particular Deposits avoided when spinning off.
  • the method according to the invention can be carried out such that a solution containing the at least one polymer contains, by a device filled with carrier material, preferably a packed column, passed through, preferably pumped, then a non-specific or non-selective cross-linking reagent by using Carrier filled device is passed through, then again Solution with at least one polymer, the same or different from the first performed polymer can be through the device filled with carrier material is passed through, etc.
  • This embodiment is excellent for the continuous, comparatively time-effective application of polymer layers, especially when the polymer solutions and the crosslinker can be passed one after the other from the respective storage containers.
  • the temperature can be combined in a suitable manner.
  • At least one polymer can be applied to the carrier material, wherein the first layer of the polymer is bound to the carrier material, the second layer of the polymer is bound to the first layer and, if necessary, any further layer of the polymer is bound to the previous layer.
  • anyone can In principle, a single type of polymer or two or more different from one another Include polymers.
  • a solution of the at least a polymer in contact with the support material under reaction conditions is brought, in which the solution of the at least one polymer under theta conditions is present.
  • the application takes place of the at least one polymer on the support material is particularly preferred during the contacting of the solution with the carrier material.
  • a layer of at least one polymer is applied to the carrier material and on this first layer in a second step a second layer and on the second layer, if necessary in a third step a third layer and so on.
  • a layer of at least one polymer is applied to the carrier material and on this first layer in a second step a second layer and on the second layer, if necessary in a third step a third layer and so on.
  • binding all covalently reversible, covalently irreversible and non-covalent interactions understood by which the at least one Polymer with the carrier material and / or with a possibly already on the Carrier material applied or optionally applied to a polymer layer Polymer layer can interact.
  • examples are among others binding via disulfide bridges or via labile esters or imines such as, for example Called Schiff bases or enamines.
  • all polymers can be used in the process according to the invention who are capable of developing these interactions.
  • it can be commercially available or also such polymers, which are produced specifically for the method according to the invention.
  • a commercially available To derivatize polymer in such a way that it has side groups which are used for Training of the desired interaction are needed.
  • the derivatization can by all methods known from the prior art respectively.
  • derivatized polymer in the method according to the invention is that a polymer having at least one functional group with at least one activation reagent or a derivative of an activation reagent is implemented, this implementation being homogeneous or heterogeneous, preferred can be done homogeneously.
  • the activation reagent will usually be chosen so that the at least one functional group of the polymer during the reaction with the activation reagent reacts and thus in its reactivity in a subsequent one Implementation with a derivatization reagent is improved.
  • the polymer having at least one functional group with at least an activated and / or at least one non-activated derivatization reagent and / or an activating reagent at the same time i.e. in the sense of "One-pot reaction" are implemented.
  • selective in this context means that a polymer, for example two or has more functional groups different from one another, for example with two different activation reagents is implemented so that a subsequent reaction with a derivatization reagent for derivatization predominantly to exclusively on the activated functional one or more Groups takes place, which is activated with one of these two activation reagents or are, usually on or with respect to the derivatization reagent more reactive activated functional group (s).
  • the polymer having at least one functional group with different Products from reactions of activation reagents and derivatization reagents implement.
  • a mixture of compounds be reacted with the polymer the mixture being reaction products an activation reagent and two or more different derivatization reagents includes.
  • this is also possible, should this be the case be required to use a mixture that consists of reaction products of two or more different activation reagents and two or more different ones Derivatization reagents.
  • the various reaction products from activation reagent and derivatization reagent not in a mixture, but individually and in the desired order with the at least one to implement functional group-containing polymer.
  • activation reagents known from the literature can be used as activation reagents be used.
  • An overview of a whole series of activation reagents used to activate various functional Groups can be used, for example, the one already cited above Article by P. Mohr, M. Holtzhauer, G. Kaiser, who reference in this regard fully included in the context of the present patent application becomes. Chloroformic acid esters and chloroformic acid esters in particular mentioned with electron-withdrawing residues.
  • the present invention describes a method in which the activating reagent is derived from a compound of the following structure (I): wherein R 1 and R 2 are the same or different and can be straight-chain, branched-chain or bridged to a carbocycle or a heterocycle and are chosen so that the activation reagent or the derivative of the activation reagent are reacted with the polymer having at least one functional group in a homogeneous phase can.
  • R 1 and R 2 are the same or different and can be straight-chain, branched-chain or bridged to a carbocycle or a heterocycle and are chosen so that the activation reagent or the derivative of the activation reagent are reacted with the polymer having at least one functional group in a homogeneous phase can.
  • R 1 and R 2 can be, for example, cycloalkyl, cycloalkenyl, alkyl, aryl or aralkyl radicals having up to 30 carbon atoms.
  • the present invention describes a process in which the activating reagent is derived from a compound of the following structure (I '), where R 3 to R 10 may be the same or different and may represent hydrogen, straight-chain or branched-chain alkyl, aryl, cycloalkyl, heterocyclic and aralkyl radicals having up to 30 carbon atoms, or more of the R 3 to R 10 can in turn be bridged to form a carbocycle or heterocycle and are selected such that the activating reagent or the derivative of the activating reagent can be reacted with the polymer having at least one functional group in a homogeneous phase.
  • R 3 to R 10 may be the same or different and may represent hydrogen, straight-chain or branched-chain alkyl, aryl, cycloalkyl, heterocyclic and aralkyl radicals having up to 30 carbon atoms, or more of the R 3 to R 10 can in turn be bridged to form a carbocycle or heterocycle and are selected such that
  • the present invention further describes a process in which the activation reagent has the following structure (II), wherein R 3 to R 10 are as defined above.
  • the present invention describes a process in which the activating reagent is derived from a compound of structure (II), as indicated above, where R 3 to R 10 are each hydrogen.
  • activation reagents or derivatives of activation reagents as described above can in principle all polymers that have at least one the activation reagents have reactive functional group, implemented become.
  • polymers are preferred in the process according to the invention used which have a group as at least one functional group, which has at least one nucleophilic unit.
  • Examples of preferred functional groups of the polymer having at least one functional group include OH groups, optionally substituted amine groups, SH groups, OSO 3 H groups, SO 3 H groups, OPO 3 H 2 groups, OPO 3 HR 11 Groups, PO 3 H 2 groups, PO 3 HR 11 groups, COOH groups and mixtures of two or more thereof, R 11 being chosen so that the activation reagent or the derivative of the activation reagent with the at least one functional polymer can be implemented in a homogeneous and / or heterogeneous phase.
  • the polymers having at least one functional group can also contain further polar groups, such as, for example, -CN.
  • both natural and synthetic polymers can be used. Any Restrictions in the selection of the polymers result only from the fact that the implementation of the polymer in the process according to the invention in homogeneous phase is made and from the later use of the derivatized polymer.
  • polymer naturally goes without saying equally high molecular weight compounds that are used in polymer chemistry as "Oligomers” are referred to.
  • copolymers not only are homopolymers, but also copolymers and in particular Block copolymers and statistical copolymers are in principle suitable for use in existing methods to be used. Both copolymers are included non-functionalizable fractions such as co-styrene or co-ethylene or also to name copolymers such as co-pyrrolidone.
  • this reaction product can, as also described above can be reacted with a derivatization reagent.
  • reagents that react with the activated polymer can and derivatized directly or indirectly to the desired Polymer lead, are used.
  • Process compounds used as derivatization reagents at least have a nucleophilic group.
  • derivatization reagents which have the general composition HY-R 12 .
  • Y stands for example for O, NH, NR 13 or S, where R 12 and R 13 can generally be chosen freely. For example, they represent an optionally suitable substituted alkyl or aryl radical.
  • nucleophilic chiral compounds examples include: Bomeol, (-) - menthol, (-) - ephedrine, ⁇ -phenylethylamine, adrenaline, dopamine.
  • Another possibility is to activate the activated in the inventive method Polymer with a mono- or polyhydric alcohol containing amino groups or Implement thiol. Will that contain at least one functional group If polymer is activated, for example, with ONB-Cl, the one containing amino groups reacts mono- or polyvalent alcohol or the mono- or polyvalent amino group-containing Thiol selective with the amino group.
  • the thus introduced into the polymer OH or SH groups can then be used again in a further step activate with, for example, one of the activation reagents described above, whereby chain extensions and branches, depending on the value of the originally used alcohols or thiols.
  • the method has at least one functional group Polymer reacted with an activated derivatization reagent, the latter from the reaction of an activation reagent with the derivatization reagent is obtained.
  • these activated derivatization reagents which can be reacted with the polymer having at least one functional group, have the following general structures (III) to (IX): wherein R 3 to R 10 are as defined above and R 14 to R 21 are generally not subject to any restrictions, for example may also have chirality, and are chosen in the process according to the invention in such a way that the reaction with the polymer having at least one functional group in a homogeneous phase can be carried out.
  • the substituents R 14 to R 21 are generally chosen as a function of the desired interaction with the substrate.
  • R 14 to R 21 may be the same or different and represent hydrogen, a straight-chain or branched-chain alkyl, aryl or aralkyl radical having up to 30 C atoms or radicals containing corresponding heteroatoms.
  • Polyvalent amines, alcohols, thiols, carboxylic acids, sulfonic acids, Sulfates, phosphates or phosphonic acids reacted with an activating reagent and this reaction product with the at least one functional Group-containing polymer are implemented, in particular here Polyols should be mentioned.
  • Such multivalent derivatization reagents can be used in the present Invention selectively partially or completely with an activation reagent activated and with the at least one functional group Polymer are implemented.
  • the present invention describes a derivative of the type in question here, the at least one receptor group has a crucial for the binding of a biological substrate Has binding unit.
  • amino acid there is also the use of one or more di- or oligopeptides conceivable, in particular homopeptides that only consist of the same amino acids are constructed, are to be mentioned.
  • An example of a dipeptide is, for example To call hippuric acid.
  • R 0 is a halogen atom or a radical (X ') stands and R 1 ', R 2 ';
  • R 1 "and R 2 " are the same or different and represent hydrogen, straight-chain or branched-chain alkyl, aryl, cycloalkyl, heterocyclic or aralkyl radicals having up to 30 carbon atoms or either R 1 'and R 2 ' or R 1 " and R 2 "or both R 1 'and R 2 ' as well as R 1 " and R 2 "are linked to at least one carbocycle or to at least one heterocycle or to at least one carbocycle and to at least one heterocycle.
  • the derivatization reagent with regard to its chemical Condition among other things with regard to the later binding of the polymer to the carrier material and / or to a further polymer and / or another To design polymer layer.
  • the derivatization reagent Contain groups that are responsible for covalent and / or non-covalent interaction are selective or specific.
  • the polymers are prepared from suitable monomers by a suitable method be, this polymer then optionally according to the above described method can be derivatized.
  • any method that has this polymer is suitable for groups leads.
  • a method for producing the polymer is preferably used in which a condensation compound by reacting at least one functional group of a first low-molecular compound having at least two functional groups with at least one functional group of at least one further second low-molecular compound having at least two functional groups, the may be the same as or different from the first low molecular weight compound, to obtain a condensation compound, the process being characterized in that at least one of the functional groups involved in this reaction is reacted with a compound structure (X) before the reaction as defined above
  • the first layer on the at least one carrier material is applied, bound in such a way that between the polymer layer and the carrier material non-covalent interactions of the be described above.
  • the present invention also relates to a method as described above, characterized in that the binding of the at least one layer of the at least one polymer to the carrier material by non-covalent Interaction of the at least one polymer with the carrier material takes place and the application of the at least one further layer of the at least one Polymers done by covalent crosslinking.
  • covalent crosslinking which, as described, is particularly preferred are all formed between the individual polymer layers suitable, covalently reversible and / or covalently irreversible interactions possible.
  • examples are among others binding via disulfide bridges or via labile esters or imines such as, for example Called Schiff bases or enamines.
  • binding via disulfide bridges or via labile esters or imines such as, for example Called Schiff bases or enamines.
  • labile esters or imines such as, for example Called Schiff bases or enamines.
  • the covalent or / and non-covalent interactions mentioned can between the carrier material and the first polymer layer or between the Single polymer layers are made in such a way that functional groups in the polymer strand of the at least one polymer used and / or in at least a side chain of the at least one polymer are present with the carrier material or at least one functional group of a further polymer, which in turn in the polymer strand or / and in at least one side chain of this polymer interact.
  • the binding of the first polymer layer to the support material and / or Binding of other polymer layers, one polymer layer on each already applied polymer layer is bound using at least one Carry out crosslinking reagent.
  • cross-linking reagent all compounds are understood in the context of the present invention, which have at least two functional groups through which this connection non-covalently and / or covalently reversible or / and covalently irreversible with either the carrier material and at least one polymer or with at least two polymers, the same or different from each other can be interacts.
  • cross-linking reagents come from the state compounds known in the art. Accordingly, networking can for example in a covalently reversible manner, in a covalently irreversible manner or in a non-covalent manner, with crosslinking in a non-covalent manner
  • cross-links via ionic interaction or via charge-transfer interaction.
  • Such cross-linking procedures or reagents include in Han, K.K., et al., Int. J. Biochem., 16: 129 (1984), Ji, T.H., et al., Meth. Enzymol., 91, 580 (1983) and Means, G. and Feeney, R.E., Bioconj.
  • non-covalent crosslinking can, for example take place if in the event that two basic groups of, for example, polyallylamine are crosslinked with each other, a dibasic acid such as Glutaric acid is added, or in the event that two acidic groups of, for example Polyacrylic acid to be cross-linked, a divalent Base such as ethylenediamine is added.
  • a non-covalent cross-linking through complex-forming metal ions or through Metal complexes are formed with free coordination points can do all possible with regard to non-covalent crosslinking Interactions are referred to, which have already been presented above.
  • a covalently reversible crosslinking can be achieved, for example, by forming a sulfur-sulfur bond to form a disulfide bridge between two groups attached to one or two polymer strands or by forming a Schiff base.
  • Crosslinking via ionic interaction can occur, for example, via two residues, one of which as a structural unit is a quaternary ammonium ion and the other as a structural unit, for example ⁇ COO - or ⁇ SO 3 - having.
  • Crosslinking via hydrogen bonds can, for example, be formed between two complementary base pairs, for example via the following structure:
  • non-covalently crosslinkable polymers can be used in terms of Networking points are designed to be complementary, with mutually complementary Structural units are, for example, acid / triamine or uracil / melamine.
  • the crosslinking reagent can also be used for non-covalent crosslinking be complementary to the crosslinking sites on the polymer strand. As an an example this would include an amine group on the polymer strand and a dicarboxylic acid to name as crosslinking reagent.
  • a crosslinking step at least one of the functional groups that are attached to the Networking are involved, so this is essentially after all Methods that are known from the prior art are conceivable.
  • a functional group can be activated according to a method, as described above in the activation and derivatization of polymers is described in detail.
  • cross-linking reagents that can lead to covalently irreversible cross-linking, are among other things two or more functional connections such as To name diols, diamines or dicarboxylic acids.
  • divalent crosslinker with the activated polymer derivative or the at least divalent activated crosslinking reagent with the non-activated polymer derivative.
  • this crosslinking reagent can in particular be a condensation compound which, by reacting at least one functional group of a first low molecular weight compound having at least two functional groups, with at least one functional group of at least one further, at least two functional Group-containing second low molecular weight compound, which may be the same as or different from the first low molecular weight compound, is prepared to give a condensation compound, the method being characterized in that at least one of the functional groups involved in this reaction is reacted with before the reaction a connection structure (X) as defined above
  • a dimeric crosslinker is listed below which is prepared from phenylalanine and leucine by the process described above:
  • reaction routes (A) and (B), in which the remainder BNO represents the following structural unit (XII), are listed as examples of the structure of a condensation compound to be used as a crosslinking reagent by the process according to the invention:
  • all materials are suitable as carrier materials, which like covalent and / or non-covalent interactions described above which can form at least one polymer.
  • the carrier material it is conceivable for the carrier material to be dissolved or colloidally dissolved or suspended.
  • the carrier material is a polymer or a polymer network, as described under other manufactured in the method according to the invention, as described below becomes.
  • the carrier material is a solid, its surface can even, such as plates made of glass or metal, or curved or embedded in porous bodies, for example tubular or sponge-like, such as for example zeolites, silica gel or cellulose beads. They can continue Carrier materials of natural origin or synthetic nature. As an example may include gelatin, collagen or agarose.
  • the first Polymer layer which is applied to the carrier material, via non-covalent Interaction without using a cross-linking reagent on the carrier material bound, and the polymer layers with each other by covalent crosslinking cross-linked using at least one cross-linking reagent.
  • cross-linking reagents it is within the scope of the present invention conceivable that either non-selective / non-specific or / and selective / specific cross-linking reagents are used.
  • selective "specific crosslinking reagent” is used in the context of the present Invention understood a crosslinking reagent, the two or more different has functional groups, of which at least one group in comparison to at least one different group under given reaction conditions with a functional group of another polymer or the carrier material prefers to respond.
  • crosslinking reagents which have two or more identical functional groups, their chemical However, the environment differs and / or the sterically different are arranged and therefore at least one of them under given reaction conditions with a functional group of another polymer or the Carrier material reacts preferentially.
  • This term also includes such cross-linking reagents, the same or different functional groups have that differ in selectivity / specificity because a Part of the functional groups according to a method as described above an activation reagent is activated.
  • one or more of the functional groups with possibly different ones reactive groups must be activated so that the reactivity of a Part of the optionally activated groups on the reactivity of the other Part of the possibly activated groups differs.
  • Combinations of two or more of the influences described that affect specificity / selectivity impact are of course also conceivable.
  • the present invention also relates to a method as described above, characterized in that the covalent crosslinking by at least a non-specific or non-selective cross-linking reagent or at least a specific or selective crosslinking reagent or by a mixture from two or more of them.
  • cross-linking reagents they are all Processes conceivable, at least for the application according to the invention a layer of at least one polymer on the carrier material which, as described, is preferably carried out gradually.
  • a polymer layer is applied to the carrier material or a polymer layer applied to the carrier material or onto a polymer layer polymer layer applied using a selective / specific Crosslinking reagent applied, so in a preferred embodiment proceeded in such a way that the starting material to which the polymer layer was applied with a solution containing the at least one cross-linking reagent and the at least one polymer, which are applied as a polymer layer should be brought into contact.
  • reaction conditions are chosen among which the crosslinking reagent, preferably with the educt or with the one to be applied Polymer reacts.
  • the crosslinking takes place, for example by the reaction product from the polymer to be applied and crosslinking reagent over at least a functional group of the crosslinking reagent reacts with the starting material or, for example, the reaction product of starting material and crosslinking reagent the polymer to be applied reacts.
  • Selective / specific cross-linking reagents are used in the invention The method is preferably used when the carrier material and polymer or Polymer and polymer are cross-linked with each other via functional groups that have the same or similar reactivity.
  • selective / specific Activation reagents include, for example, polyvalent carboxylic acids, Diamines or diols activated with different reactive groups are or of which only a part of the functional groups is activated. Further Examples include connections that are at least two different have functional groups, such as, inter alia, amino acids, Hydroxy acids or amino alcohols, the different functional Groups have different reactivity under given reaction conditions.
  • connections can have two or more have different functional groups, one or more of the functional groups with possibly different reactive groups be activated so that the reactivity of some of the activated, if necessary Groups of the reactivity of the other part of the optionally activated Groups differ, as already described above.
  • non-selective / non-specific cross-linking reagents in the method according to the invention including two preferred procedures to call. Just as with the procedure described above, in which intramolecular cross-linking is avoided and one Polymer layer applied to the support material or another polymer layer is, these preferred procedures are carried out so that the intramolecular networking or / and the intermolecular networking within a polymer layer is largely avoided and a polymer layer is applied becomes. Small cross-links within a polymer layer can contribute to an additional stabilization of the polymer network.
  • method (aa) is like this performed that the cross-linking reagent at temperatures with the last applied Polymer layer is brought into contact, in which the cross-linking reagent statistically even over the existing polymer layer distributed and in which a reaction of the cross-linking reagent with that already existing polymer layer largely
  • the temperatures at which this are usually in the range of 0 to -70 ° C.
  • concentration of crosslinking reagent in the solvent care is taken in this preferred embodiment of the method that the reaction of the cross-linking reagent with the existing polymer layer largely is omitted until the crosslinking reagent is statistically uniform over the already existing polymer layer is distributed.
  • Ways of Networking Like This other can be induced, for example, use of ultrasound or photochemical cross-linking.
  • the next step is to find a solution that at least comprises a polymer which is to be applied as the next polymer layer, with the reaction product from cross-linking reagent and already existing polymer layer brought into contact.
  • the reaction conditions will then be like this changed that the reaction is particularly preferred between the unreacted functional groups of the bound to the existing polymer layer Crosslinking reagent and the polymer to be applied as the next polymer layer he follows.
  • the reaction conditions by adding the solution comprising the at least one polymer which to be applied as the next polymer layer are influenced in such a way that a further change in the reaction conditions no longer has to take place.
  • the specific methods referred to above described can first be applied to the binding of a polymer prevent and stimulate in a further step.
  • the method is also used in a particularly preferred embodiment carried out according to (bb) such that the solution comprising the at least one Cross-linking reagent and the at least one polymer with which was applied last Location of the at least one polymer under reaction conditions Is brought into contact, in which no reaction takes place initially, but both Cross-linking reagent and polymer to be applied are statistically Distribute evenly over the existing polymer layer.
  • this is done Contacting in a preferred embodiment at low temperatures, usually in the range from 0 to -70 ° C.
  • the reaction conditions are then changed in such a way that the crosslinking reagent with both the existing polymer layer as also reacts with the polymer that is applied as the next layer.
  • the crosslinking reagent initially already with the existing polymer layer and then with the polymer to be applied reacted to form the new polymer layer.
  • the cross-linking reagent simultaneously with the already existing polymer layer and the polymer to be applied reacts to form the new polymer layer.
  • the crosslinking reagent to be statistically uniformly distributed first reacted with the statistically evenly distributed polymer and then the reaction product with the existing polymer layer Formation of the new polymer layer reacts.
  • the reactions of the cross-linking reagent take place with the existing polymer layer on the one hand and the polymer to be applied, on the other hand, not at the same time, so it is possible to Varying the reaction conditions first one of the reactions, by further Varying the reaction conditions to perform the other reaction.
  • Polymer layer can be referred to, among other things, the specific methods that as described above can be used to first bind a To prevent polymers and to stimulate them in a further step. Possibilities, Examples of how this crosslinking can be induced include also use of ultrasound or photochemical cross-linking.
  • non-selective / non-specific cross-linking reagents are below other, for example, divalent epoxides, isocyanates, chlorotriazines, amidines or aldehydes. Succinimide are also activated. particularly preferred ONBund N-hydroxy-phthalimide-activated compounds. Amongst other things they also refer to the cross-linking reagents explicitly listed above directed. In a preferred embodiment of the method according to the invention are symmetrical, usually bivalent cross-linking reagents and activated dicarboxylic acids are very particularly preferably used.
  • the chain length of the cross-linking reagents used in any of the embodiments of the method according to the invention is generally arbitrary and adaptable to the requirements of the respective process.
  • the chain itself can be aliphatic or aromatic or araliphatic.
  • The can continue Chain one or more functional groups used to form covalent or are capable of non-covalent interactions.
  • the chain length is preferably in the case of crosslinking reagents which have a carbon chain have, in the range of 2 to 24 carbon atoms, particularly preferably in the range from 4 to 24 carbon atoms and particularly preferably in the range from 8 to 12 carbon atoms.
  • the polymers used in the process according to the invention are subject to essentially only the limitation that they are in at least one location Formation of the interactions as described above on a carrier material can be applied.
  • Polymers are particularly preferably used, which have a molecular weight in the range of 2,000 to 100,000 g / mol. The molecular weights are determined by GPC.
  • the present invention also relates to a method as described above, characterized in that the at least one polymer has a molecular weight in the range of 2,000 to 100,000 g / mol.
  • the at least one polymer is applied in such a way that that it has a largely uncoiled structure, but as close as possible above of the theta point with carrier material and / or already applied polymer layer is brought into contact.
  • the solution in which this at least one polymer dissolved and with carrier material and / or polymer layer is contacted, a solvent or solvent mixture chosen in which the polymer is largely uncoiled of course also by the specific choice of other reaction conditions such as for example, temperature, pressure or pH the uncoiled form of the polymer can be supported.
  • a solvent or solvent mixture chosen in which the polymer is largely uncoiled of course also by the specific choice of other reaction conditions such as for example, temperature, pressure or pH the uncoiled form of the polymer can be supported.
  • Polymers used that have a molecular weight less than about 30,000 have g / mol.
  • the application of is largely monomolecular polymer layers
  • solvents or solvent mixtures or other reaction conditions chosen such that the at least one Polymer in the solution is near above the theta point.
  • solvents or solvent mixtures or other reaction conditions chosen such that the at least one Polymer in the solution is near below the theta point.
  • solvents or solvent mixtures or other reaction conditions chosen such that the at least one Polymer in the solution is near below the theta point.
  • the individual crosslinking steps carried out in the process according to the invention can be done so that an essentially any degree of crosslinking the polymer layers are reached with each other.
  • the method is preferred however, so that the degree of crosslinking of a polymer chain with two other polymers is cross-linked, is in the range of 0.5 to 25%.
  • This Degree of crosslinking is based on the monomer units of a polymer chain that was cross-linked with two neighboring polymer chains. Is particularly preferred this degree of crosslinking in the range of 2 to 10%.
  • the present invention also relates to a method as described above, characterized in that the degree of crosslinking in the range of 0.5 up to 25%, based on the monomer units of one with two adjacent polymer chains cross-linked polymer chain.
  • a carrier material to apply a polymer network, for example, by the covalent cross-linking of the polymer layers with one another has a structure that consists of two- or three-dimensional cells.
  • a cell of the polymer Network is usually by at least one cross-linking reagent, the two polymer layers cross-linked and part of at least one polymer, from which the polymer layers are formed.
  • the at least one cross-linking reagent or the at least one have a polymer used it is conceivable, among other things, that the cells are constructed such that the cell interacts with at least one Template connection is possible.
  • the present invention also describes a method as described above in which a polymeric network is applied at least one polymer layer is formed on at least one carrier material the polymeric network comprising one or more interaction cells, via which the polymer network with at least one template compound in can interact covalently or / and non-covalently.
  • the method according to the invention can do so be performed that the polymeric structure by the application at least of a polymer built up in at least one layer on at least one carrier material with respect to the interaction cells to at least one template connection is adjusted.
  • the present invention describes therefore also a method as described above, characterized in that that the conformation of the polymeric structure by interaction and crosslinking results, during or after application at least one of the layers of the at least one polymer on the carrier material is adapted to at least one template connection.
  • the present invention also describes a method in which the polymer Structure that has been applied and produced on the carrier material, is detached from the carrier material and then used in applications such as for example, are described below.
  • the present invention also encompasses the polymeric network itself, the is obtainable according to a method as described above.
  • the present invention therefore also relates to a polymer network which can be prepared by a method as described above.
  • the polymer network that can be produced by the method according to the invention is distinguished in a particularly preferred embodiment from the fact that it is insoluble, but nevertheless has swellability.
  • the present invention also relates to the use of a method as described above, or a polymeric network, obtainable by a method as described above for producing an at least one Template connection adapted polymeric network.
  • the polymeric networks produced according to the invention can because of their Structure comprising interaction cells, as described above, in a preferred one Embodiment can be used in processes in which, for example Fabrics manufactured, converted into other fabrics or from other fabrics be separated. It is also conceivable that the manufactured according to the invention polymeric networks for the detection of optical, electrical or mechanical Signals are used.
  • the polymer networks are very special suitable for these processes if, as described above, at least a template connection is adapted.
  • silica gel 300 ⁇ , 20 ⁇ m (Daisogel SP 300-15 / 30) (10.02 g) Moved for 30 minutes on a shaker and after suction over a Glass frit washed with dichloromethane (4 ⁇ 50 mL).
  • the coated silica gel became a solution of dodecanedioic acid bis (N-hydroxy-5-norbornene-2,3-dicarboximide) ester (46 mg, 83 ⁇ mol) and Triethylamine (36 mg, 0.35 mmol) in dichloromethane (60 mL) and the Suspension in vacuo (85 mbar, water bath 0 ° C) evaporated to dryness.
  • the coated silica gel was washed with tetrahydrofuran (60 ° C, 4 ⁇ 25 mL), suction filtered and washed with dichloromethane (50 mL).
  • poly (benzyl-N-allyl carbamate) was used with a degree of derivatization of 14% (1.60 g) dissolved in boiling glacial acetic acid (100 mL, approx. 117 ° C), after cooling, diluted with dichloromethane (100 mL, 1.18 mol) and with 100 mL Pyridine (100 mL, 1.26 mol) was added to deteriorate the solubility of the polymer.
  • the coated silica gel was crosslinked again as described above and then, accordingly the second method, covered with a third polymer layer.
  • the coated silica gel was treated with glacial acetic acid (100 mL), the suspension to Boiled, suction filtered, washed with dichloromethane (5 ⁇ 50 mL), dried (110 ° C, 16 h) and sieved over a 45 ⁇ m sieve.
  • the weight was 9.4 g.
  • the coated silica gel obtained was converted into a solution of bis-dodecanedioic acid (N-hydroxy-5-norbomen-2,3-dicarboximide) ester (100 mg, 0.18 mmol) and triethylamine (54 mg, 0.54 mmol) in dichloromethane (80 mL) and the suspension in vacuo (100 mbar, water bath 0 ° C) to dryness concentrated.
  • the coated silica gel was boiled in THF (40 mL) and suction filtered and washed with hot THF (3 x 40 mL) and dichloromethane (2 x 30 mL).
  • poly (benzyl-N-allyl carbamate) was used with a degree of derivatization of 14% (1.66 g) in 100 ml glacial acetic acid at 50 ° C within 30 Dissolved minutes, after cooling with dichloromethane (100 mL) and diluted with Pyridine (100 mL) added to deteriorate the solubility of the polymer. Then dimethylaminopyridine (DMAP, 22 mg, 0.15 mmol) and 13 mL pyridine added. The resulting turbidity was reduced by adding 3 mL Glacial acetic acid removed. To this solution was obtained the crosslinker obtained above reacted, coated silica gel and the batch 30 minutes on a Shaking machine moves.
  • DMAP dimethylaminopyridine
  • the coated silica gel was suspended in a frit in THF (10 mL). By a slow leakage of a solution of diethylamine (0.27 g, 3.7 mmol) in THF (10 mL) were the remaining activated crosslinker groups quenched. The residue was then treated with THF (60 ° C, 4 x 20 mL) and Washed dichloromethane (2 x 10 mL) and sucked dry.
  • the coated silica gel was treated with glacial acetic acid (40 mL), the suspension to Boiled, suction filtered and washed with dichloromethane (4 x 20 mL). Subsequently, a solution of 0.25 ml of pyridine in 15 ml Washed dichloromethane and THF (4 x 20 mL) and dried.
  • the carbon content of the silica gel covered was 7.2%; this corresponds to 111 mg of polymer per gram of silica gel.
  • a 2.5 cm diameter glass column was covered with 300 ⁇ , 20 ⁇ m silica gel (Daisogel SP 300-15 / 30) (5.00 g) packed.
  • Poly (benzyl-N-allyl carbamate) with one Degree of derivatization of 14% (3.20 g) was in 200 ml of water and with addition 1-2 ml of glacial acetic acid dissolved within 2 hours.
  • This polymer solution was made for Pumped in a circle through the glass column with silica gel for 24 hours.
  • the pillar was first with air, then with acetone / water 50:50 vol% (30 ml) and acetone (150 ml) rinsed. According to elemental analysis, the carbon content of the documented was Silica gel on average 2.7%.
  • poly (benzyl-N-allyl carbamate) was used with a degree of derivatization of 14% (3.20 g) in 200 ml of water and with the addition of 1-2 ml Glacial acetic acid dissolved within 2 hours.
  • This polymer solution was for 24 hours pumped in a circle through the glass column with the coated silica gel. The pillar is rinsed first with air and then with acetone / water 50:50 vol% (120 ml).
  • the coated silica gel was treated with glacial acetic acid (50 mL), the suspension to Boil heated, suction filtered and pyridine (20 mL) added. Then was suction filtered, washed with THF (60 ° C, 3 x 50 mL) and dried.
  • the carbon content of the silica gel occupied was average 5.0%.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Materials For Medical Uses (AREA)
  • Silicon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulding By Coating Moulds (AREA)

Claims (10)

  1. Procédé pour l'application d'au moins deux couches d'au moins un polymère sur un matériau de support, caractérisé en ce que dans au moins une étape au moins une couche de l'au moins un polymère est liée au matériau de support et dans au moins une autre étape au moins une autre couche de l'au moins un polymère est appliquée sur l'au moins une couche de polymère liée au matériau de support.
  2. Procédé selon la revendication 1, caractérisé en ce que dans l'au moins une étape dans laquelle l'au moins une couche de l'au moins un polymère est liée au matériau de support,
    (i) on met une solution de l'au moins un polymère en contact avec le matériau de support, dans des conditions réactionnelles dans lesquelles l'au moins un polymère n'est pas lié au matériau de support et on fait varier ensuite les conditions réactionnelles de sorte que l'au moins un polymère est lié au matériau de support, ou
    (ii) on met une solution de l'au moins un polymère en contact avec le matériau de support dans des conditions réactionnelles dans lesquelles la solution de l'au moins un polymère se trouve dans des conditions thêta.
  3. Procédé selon la revendication 2, caractérisé en ce qu'on fait varier les conditions réactionnelles selon (i),
    (a) en modifiant la composition de la solution par variation de l'au moins un solvant ou par addition d'au moins un autre composé, ou
    (b) en concentrant la solution de manière à maintenir pratiquement constante lors de la concentration la teneur en l'au moins un polymère de la solution, ou
    (c) en combinant au moins une méthode selon (a) et la méthode (b).
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la liaison de l'au moins une couche de l'au moins un polymère au matériau de support s'effectue par interaction non covalente de l'au moins un polymère avec le matériau de support et l'application de l'au moins une autre couche de l'au moins un polymère s'effectue par réticulation covalente.
  5. Procédé selon la revendication 4, caractérisé en ce que la réticulation covalente s'effectue au moyen d'au moins un réactif de réticulation non spécifique ou non sélectif ou d'au moins un réactif de réticulation spécifique ou sélectif ou au moyen d'un mélange de deux de ceux-ci ou plus.
  6. Procédé selon la revendication 5, dans lequel on utilise au moins un réactif de réticulation non spécifique ou un réactif de réticulation non sélectif, caractérisé en ce qu'on effectue la réticulation
    (aa) en faisant réagir l'au moins un réactif de réticulation, dans une première étape, avec la couche, appliquée en dernier lieu, de l'au moins un polymère, et, dans une autre étape, en mettant le produit de réaction en contact avec une solution, comprenant l'au moins un polymère, et au moins une autre couche de l'au moins un polymère étant appliquée sur le produit de réaction par réaction de l'au moins un polymère, contenu dans la solution, avec le produit de réaction, ou
    (bb) en mettant une solution, comprenant l'au moins un réactif de réticulation et l'au moins un polymère, en contact avec la couche, appliquée en dernier lieu, de l'au moins un polymère, dans des conditions réactionnelles dans lesquelles la réaction de l'au moins un réactif de réticulation s'effectue aussi bien avec la couche, appliquée en dernier lieu, de l'au moins un polymère qu'avec l'au moins un polymère contenu dans la solution, ou
    (cc) en combinant de façon appropriée les méthodes selon (aa) et (bb).
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'au moins un polymère présente une masse moléculaire dans la plage de 2 000 à 100 000 g/mole.
  8. Procédé selon l'une quelconque des revendications 3 à 7, caractérisé en ce que le degré de réticulation se situe dans la plage de 0,5 à 25 %, par rapport aux motifs monomères d'une chaíne polymère réticulée avec deux chaínes polymères voisines.
  9. Réseau polymère pouvant être obtenu par un procédé selon l'une quelconque des revendications 1 à 8.
  10. Utilisation d'un procédé selon l'une quelconque des revendications 1 à 8 ou d'un réseau polymère selon la revendication 9, pour la fabrication d'un réseau polymère adapté à un assemblage de gabarits.
EP00979625A 1999-11-26 2000-11-27 Procede d'application d'un polymere sur un support Expired - Lifetime EP1232018B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19957018A DE19957018A1 (de) 1999-11-26 1999-11-26 Verfahren zum Aufbringen eines Polymers auf einen Träger
DE19957018 1999-11-26
PCT/EP2000/011841 WO2001038009A2 (fr) 1999-11-26 2000-11-27 Procede d'application d'un polymere sur un support

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EP1232018A2 EP1232018A2 (fr) 2002-08-21
EP1232018B1 true EP1232018B1 (fr) 2003-07-09

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JP (1) JP2003534393A (fr)
AT (1) ATE244610T1 (fr)
AU (1) AU1704901A (fr)
CA (1) CA2390628C (fr)
DE (2) DE19957018A1 (fr)
DK (1) DK1232018T3 (fr)
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JP2008290909A (ja) * 2007-05-24 2008-12-04 Sumitomo Chemical Co Ltd 珪素酸化物含有乾燥ゲルの充填方法
DE102010054766B4 (de) 2010-12-16 2012-08-30 Previpharma Ag Verfahren zur Trennung, Aufkonzentration oder Reinigung eines (Blut)Plasmaproteins oder Virenbestandteils aus einer Mischung
DE102010054767B4 (de) 2010-12-16 2013-02-21 Previpharma Ag Verfahren zur Trennung, Aufkonzentration und/oder Reinigung von (Blut)Plasmaprotein, Viren oder Virenbestandteilen
EP2545989A1 (fr) 2011-07-13 2013-01-16 InstrAction GmbH Matériau composite pour applications chromotographiques
KR20140103893A (ko) 2011-07-13 2014-08-27 인스트랙션 게엠베하 크로마토그라피 응용용 복합 재료
DE102012022234A1 (de) 2012-11-14 2014-05-15 Instraction Gmbh Einstufiges Verfahren zur Reinigung von (Blut)Plasmaproteinen wie Albumin aus Gemischen
DE102012022233A1 (de) 2012-11-14 2014-05-15 Instraction Gmbh Verfahren zur Reinigung eines (Blut)plasmaproteins
BR112021006991A2 (pt) 2018-10-19 2021-07-20 Klaus Gottschall materiais e métodos para a remoção de um contaminante

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JP2844280B2 (ja) * 1992-03-12 1999-01-06 日本ペイント株式会社 メタリック塗装方法
JPH0825551A (ja) * 1994-07-13 1996-01-30 Kawasaki Steel Corp 耐食性およびスポット溶接性に優れた有機複合被覆鋼板
DE19855173C2 (de) * 1998-11-30 2001-03-15 Gottschall Instruction Ges Fue Verfahren zur Herstellung derivatisierter Polymere und Derivate von funktionelle Gruppen aufweisende Polymere sowie Verfahren zur Substratbindung
DE19860972A1 (de) * 1998-11-30 2001-04-26 Gottschall Instruction Ges Fue Verfahren zur Herstellung derivatisierter Polymere
CZ297147B6 (cs) * 1998-11-30 2006-09-13 Dr. Gottschall Instruction Zpusob prípravy polymerní síte, polymerní sít a její pouzití
DE19928236C2 (de) * 1999-06-21 2002-05-16 Gottschall Instruction Ges Fue Verfahren zur Herstellung von Kondensationsverbindungen

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ATE244610T1 (de) 2003-07-15
CA2390628C (fr) 2009-11-10
EP1232018A2 (fr) 2002-08-21
WO2001038009A2 (fr) 2001-05-31
AU1704901A (en) 2001-06-04
DK1232018T3 (da) 2003-10-27
JP2003534393A (ja) 2003-11-18
DE50002864D1 (de) 2003-08-14
ES2203533T3 (es) 2004-04-16
WO2001038009A3 (fr) 2001-12-06
CA2390628A1 (fr) 2001-05-31
DE19957018A1 (de) 2001-06-13

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