EP1667789A2 - Utilisation de copolymeres contenant du n-vinyllactame pour produire des membranes fonctionnalisees - Google Patents

Utilisation de copolymeres contenant du n-vinyllactame pour produire des membranes fonctionnalisees

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Publication number
EP1667789A2
EP1667789A2 EP04765159A EP04765159A EP1667789A2 EP 1667789 A2 EP1667789 A2 EP 1667789A2 EP 04765159 A EP04765159 A EP 04765159A EP 04765159 A EP04765159 A EP 04765159A EP 1667789 A2 EP1667789 A2 EP 1667789A2
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EP
European Patent Office
Prior art keywords
alkyl
hydrogen
integer
aryl
alkylaryl
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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Application number
EP04765159A
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German (de)
English (en)
Inventor
Klemens Mathauer
Tanja Schneider
Ralf Widmaier
Andre Kamm
Carl-Martin Bell
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BASF SE
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BASF SE
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Publication of EP1667789A2 publication Critical patent/EP1667789A2/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B01D71/441—Polyvinylpyrrolidone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen

Definitions

  • the present invention relates to the use of copolymers containing N-vinyllactam for the production of membranes and to processes for their production.
  • the present invention furthermore relates to a semipermeable membrane containing the copolymers described according to the invention.
  • Another object of the invention is the use of the polymers for solution diffusion membranes for material separation.
  • Another object of the invention are new copolymers, processes for their preparation and their use according to the invention.
  • membranes are used for a variety of technical applications. With the help of membranes, reverse osmosis can be used to convert sea water into drinking water. Membranes are also suitable for the purification of industrial waste water or for the recovery of valuable materials, for example for the recovery of paints by ultrafiltration of electronic tapes. Membranes are also being intensively investigated and in some cases already used to separate substances, for example in chemical synthesis, as a replacement for known and energy-intensive techniques such as distillation. Membranes are also increasingly used in the areas of food technology, medicine and pharmacy. For example, solutions of different marrow molecules can be fractionated with the help of membranes, or urea and toxins can be removed from the bloodstream during hemodialysis. Membranes can also be used for the skin-controlled delivery of drugs.
  • the surface of the membrane must have a certain have hydrophilicity and thus allow sufficient wetting so that the actual material separation can take place.
  • the separation effect can also be influenced by controlling the surface properties of the membrane.
  • Porous media are very useful in many applications in the field of separation and adsorption of substances such as chromatography.
  • Porous membranes as an example are widely used.
  • the division into microporous and ultrafiltration membranes is based on the pore size, which is generally set in the range between about 0.05 and 10 micrometers for microporous membranes and 0.002 to 0.05 micrometers for ultrafiltration membranes.
  • the pore size refers to circular or approximately circular pores or to characteristic sizes for non-circular pores.
  • the pore size is determined by the size of the smallest particle, molecule, etc. that cannot pass through the membrane above a specified fraction. In general, the limit is considered to be less than 10 percent passage, which corresponds to a 90 percent cut-off or retention. It is also possible to determine the pore size distribution using z. B. Electron microscopy.
  • Microporous membranes are usually used for the separation of particles from liquids and gases, such as sterile filtration for separating bacteria from pharmaceutical solutions or for sterile filtration of gases.
  • Ultrafiltration membranes are generally used to separate smaller particles. Examples include the concentration of proteins in solution in biotechnology, diafiltration to remove salts and low-molecular contaminants in protein solutions or the targeted removal of contaminants from blood, as is also used in hemodialysis for extracorporeal blood purification.
  • pyrogens substances such as lipopolysacccharide complexes, which cause small fever of approximately 0.2 mg / kg body weight in higher animals and in humans after intravenous administration; fever; definition according to Pschyrembel, "clinical Dictionary “, p. 257. Edition, de Gruyter (1994), page 1279
  • the pyrogens are separated off by filtration and / or by adsorption of the pyrogens on the filter medium.
  • Porous membranes can be made from a variety of different materials. Because of the easy to achieve constant product quality, polymers are preferred over naturally occurring materials. Materials or polymers for the production of membranes were classified into the group of reactive or hydrophilic materials and the inert materials (I.
  • Reactive materials either have an intrinsic hydrophilicity or can be modified quite simply hydrophilically, thereby reducing the non-specific binding of proteins to the membrane but generally limited mechanical and thermal properties.Inert materials, on the other hand, have outstanding mechanical, thermal properties and withstand chemical attacks very well, but show a strong hydrophobicity and are therefore susceptible to non-specific binding and thus deposition of proteins with the consequence of Fouling or clogging of the membrane.
  • membranes are usually made from so-called "engineering plastics” such as polyether sulfones, polysulfones, polyvinylidene fluorides, polyethene, polypropene, polytetrafluoroethylene etc. due to their pronounced resistance to thermal, mechanical and chemical loads.
  • engineing plastics such as polyether sulfones, polysulfones, polyvinylidene fluorides, polyethene, polypropene, polytetrafluoroethylene etc.
  • these materials do not have the necessary properties which would enable direct use as membrane material for pharmaceutical or biotechnological purposes, such as a certain hydrophilicity and thus wettability with aqueous solutions, and the high affinity for biomolecules and the strong adsorption also have a negative effect on the desired separation properties.
  • the wettability of the membrane media is necessary to allow the permeation of the substances.
  • the hydrophilicity required for biomolecules can be achieved by using a wetting liquid, the excess of which has to be removed again before use by (expensive) intensive washing. Nevertheless, small residual amounts usually remain in the membrane and can be washed out during use.
  • the extractable material In applications with high purity requirements such as the pharmaceutical industry, in membranes for the medical sector or in the microelectronic industry in the production of e.g. B. Wafers the extractable material must be as low as possible to avoid additional contamination during use.
  • the membranes In addition to permeability and the necessary retention, depending on the application, the membranes must have sufficient mechanical stability to withstand operating conditions such as pressure and temperature. These properties mentioned are usually attempted to be achieved by modifying the membrane surface in order, for. B. to achieve hydrophilization or resistance to the deposition or adsorption of biomolecules.
  • the membrane material can be provided with hydrophilic groups by a chemical reaction or a hydrophilic substance can be applied to the surface.
  • This hydrophilic substance is mostly a polymer due to the problem of washability already mentioned, since polymeric substances are washed out more poorly than low-molecular substances.
  • surface-changing polymers can also be used alone.
  • a thin polymer layer is applied to papers and foils for ink jet applications, which quickly dissipates the moisture (usually water or mixtures of water and oil) of the ink from the surface to prevent smearing of the ink print.
  • the polymer can also be used, for example, to bind the dyes or pigments to the polymer and thus improve the color fixation on the surface.
  • Another application is the application of water-hydrogel-forming polymers to surfaces in order to z. B. to achieve a slidability of the object.
  • the effect of surface modification by polymers and thus the change in surface properties can also be used, for example, to prevent the crystallization of substances in liquid media and thus prevent precipitation or formation of deposits.
  • scale inhibitors are added during water treatment, which prevent the deposition of salts in the systems.
  • polymers are added as alternatives to methanol or glycol, which avoid the crystallization of clathrates or gas hydrates (inclusion of gases in ice), which is always found in the petroleum / natural gas mixture.
  • the organic solvents achieve this effect by lowering the temperature (thermodynamic prevention of ice formation), while the polymers lie on the surface of primarily formed ice crystallites through an interaction with the surface of the ice and thus greatly delay the further growth and coalescence of the crystallites (kinetic inhibition).
  • No. 4,051,300 describes the production of hollow fiber membranes from polysulfone and PVP with a very low molecular weight (Mw at least 2000 g / mol) by producing a spinning solution and then precipitating the membrane and washing it. The low molecular weight of PVP is said to ensure that the PVP is completely washed out of the membrane.
  • EP-A 0 168783 describes asymmetrical microporous hollow fiber membranes for blood treatment.
  • described consist of more than 90% by weight of a hydrophobic polysulfone as the matrix polymer and furthermore contain 1 to 10% by weight of the hydrophilic polyvinylpyrrolidone, are readily wettable with water and have excellent biocompatibility, i.e. that the substances in the body's defense system contained in the blood do not respond to the surface of the membranes.
  • the incompatible hydrophilic polymers serve as pore donors and are washed out of the membrane after solidification, with a small portion remaining for the purpose of hydrophilizing the otherwise hydrophobic membrane.
  • part of the hydrophilic PVP remains in the matrix of the polysulfone by extruding the solution of the two polymers in a narrowly defined viscosity range, with the result that the structure of the extruded hollow-fiber structure is formed until precipitation of the fiber-forming polymer is maintained and the majority of the PVP used is washed out of the spinning mass during the precipitation, but some remains in the membrane.
  • EP-A 0 550798 water-soluble PVP is still present in membranes, such as those obtained according to EP-A 0 168783. According to this, it cannot be avoided that minimal quantities of the medium to be filtered are released from these membranes after repeated reuse. This changes, among other things, the retention behavior of such membranes to less precise separation limits. Possibilities for rendering the PVP contained in polysulfone membranes water-insoluble are described, for example, in EP-A 0 082433 and EP-A 0550 798. Cross-linking by means of chemical cross-linking or cross-linking by means of ionizing radiation is described there.
  • EP-A 0478 842 describes a membrane filter layer made of inert polymeric materials, such as.
  • Example polyethene, polypropene, nylon 6,6, polycaprolactam, polyester or polyvinylidene fluoride, from which membranes for pyrogen removal can be produced, a cationically or anionically modified polymer being preferably used for the pore material of the membrane filter layer, because the deposition performance is hereby tion can be significantly improved.
  • a cationically modified polymer z. B. nylon 6.6 is used, the surface of which is modified with quaternary ammonium-bearing polymers. Carboxy groups are preferred as the source of the negative charge for the anionically modified polymers.
  • EP 683691 describes cationically charged membranes which are suitable for removing endotoxins.
  • the membranes are produced by contacting a hydrophobic polymer membrane, preferably made of polysulfone, polyarylsulfone or polyether sulfone, with a quaternary wetting agent, whereupon at least one agent which modifies the membrane cationically is crosslinked on the membrane.
  • the membrane is cast from a solution containing polyethersulfone, a copolymer of vinylpyrrolidone and a cationic imidazolinium compound, preferably methylvinylimidazolidinium methyl sulfate, and a low molecular weight organic acid, whereby the weight percentages of the acid in the casting solution of 24 to 34% are disclosed ,
  • the parts of the system that come into contact with this casting solution must therefore be acid-resistant, which makes the system more expensive.
  • the equivalent application WO 94/17906 discloses hydrophilic, charge-modified microporous membranes which have a cross-linked structure made of interpenetrating networks (IPN).
  • the membrane consists of a homogeneous matrix of polyethersulfone, polyfunctional glycidyl ether, a polymeric amine such as polyethylene imine (PEI) etc. and polyethylene glycol (PEG).
  • PEI polyethylene imine
  • PEG polyethylene glycol
  • the optional use of N-vinylpyrrolidone homo- or copolymers with dimethylaminoethyl methacrylate or mixtures thereof is particularly preferred, particularly preferably a quaternized copolymer.
  • the membrane has cationic charges and a low proportion of extractable components.
  • EP 054799 describes the fixation of ⁇ -globulin on polyacrylamide, silica, polyvinyl alcohol or polysaccharides for extracorporeal blood purification. All of these carriers have specific disadvantages which have negative effects on body fluids on prolonged contact.
  • GB-B-2092470 discloses the removal of pyrogens from solutions using a nitrogen-containing compound fixed on an insoluble support. selects from polysaccharides, hydroxyalkylpolystyrene and hydroxyalkylpolystyrene-divinylbenzene copolymer. These carriers are not biocompatible.
  • EP 1110596 describes a process for the production of pore-free or preferably porous molded articles for pyrogen retention.
  • the shaped body can be used as an adsorption medium in fine grain in columnar form.
  • porous form it is permeable to at least some of the pyrogens, in particular in the form of a semi-permeable flat, tubular or hollow fiber membrane.
  • the molded body is hydrophilic and consists of a synthetic polymer component and an additive which is a copolymer of vinylpyrrolidone and a vinylimidazole compound in ratios of 90:10 to 10:90, but preferably 50:50. The additive adheres sufficiently well to the synthetic polymer for many applications.
  • hydrophilization of the shaped body can also by wetting with z. B. happen with ethanol, but a permanent hydrophilization is preferred.
  • synthetic polymer component a hydrophilic polymer or a hydrophobic polymer which has been hydrophilized by chemical modification is preferably used, such as. B. various polyamides or sulfonated polyethersulfone.
  • a hydrophobic polymer e.g. B.
  • polysulfone a polysulfone, polyether sulfone, polyaryl ether sulfone, polyacrylonitrile, polycarbonate or polyolefin, and hydrophilic polymer selected from the group of polyvinylpyrrolidones, polyether glycols, polyvinyl alcohols or sulfonated polyether sulfones.
  • EP 0103184 describes biospecific polymers with reactive biomolecules immobilized on them, which can bind factors of the complement system with pathological properties with high activity.
  • the medium consists of a biocompatible terpolymer of glycidyl methacrylate, N-vinylpyprrolidone and hydroxyethyl methacrylate as well as the biomolecules mentioned.
  • the production of such biocompatible polymers on a mechanical support as reinforcement is also disclosed.
  • the extracorporeal cleaning of body fluids such as blood is mentioned as an application.
  • EP 046136 describes the production and use of so-called gradient interpenetrating networks (GIPN), which are formed from a hydrogel-forming polymer and a less permeable condensation polymer by the condensation polymer (polyurethane, polyester, polyamide, polyimide, polyurea or polyimine ) is formed by condensation from the monomers within the hydrogel.
  • the condensation polymer stabilizes the hydrogel mechanically by forming the GIPN and thereby allows the GIPN to be shaped as a membrane in the form of a layer, a film, a tube or a hollow fiber membrane and can in particular be used as the latter for membrane separation processes such as e.g. B. reverse osmosis, dialysis, electrophoresis, solvent-water separation processes as in of wastewater treatment take place.
  • a hydrogel can also be used as an active agent dispenser.
  • WO 98/01208 describes a charge-modified polymer membrane made of a hydrophobic polymer, such as.
  • B. sulfone polymers such as polysulfone, polyarylsulfone or polyethersulfone, which is hydrophilized by means of at least one polymeric wetting agent such as polyvinyl alcohol or a cellulosic polymer with hydrophilic functional groups and at least one cationically modifying agent which is crosslinked on the hydrophobic polymer.
  • These polymeric membranes can be used in the form of a flat membrane, hollow fiber membrane, a cast or meltblown membrane or any other form suitable for use in membrane cartridges. Networking takes place through the influence of energy such as B. by irradiation or heating to 70 to 200 ° C instead or by radical initiators.
  • These membranes can be used in a variety of applications, including the filtration of water or liquids for electronics, pharmaceutical or biological industries, or even blood filtration.
  • the surface coating consists of a terpolymer consisting of vinyl pyrrolidone or derivatives, (meth) acrylamide or derivatives and a crosslinker.
  • membrane materials such as B. polysulfone or polyether sulfone can be used. All common membrane types such as B. hollow fiber flat membranes etc. are disclosed.
  • Another modification can be made by using special monomers such as. B. 2-acrylamido-2-methylpropanesulfonic acid or hydroxymethyldiaceto-neacrylamide can be achieved.
  • No. 4,729,914 describes the production and use of hydrophilic coatings which are difficult to remove from a substrate. This is achieved by coating the substrate which carries free isocyanate groups with a vinylpyrrolidone copolymer, the comonomers of which carry active hydrogen atoms which in turn can react with the isocyanate groups of the substrate, as a result of which the vinylpyrrolidone copolymer is chemically bound to the substrate. This will detach the vinyl pyrrolidone copolymer upon contact with hydrophilic solvents such as e.g. Avoid alcohol or water. Possible comonomers mentioned are e.g. B. monomers containing hydroxyl, imine, carboxy or thiol groups.
  • the present invention was based on the object by a selective modification of the surface of membranes based on polysulfones, zBPolyethersulfon (Ultrason ® E), polysulfone (Ultrason ® S), or polyarylsulfone, lead hamper- reactive groups, in particular a chemical reaction with biomolecules or can have strong interactions in order to achieve a significantly improved separation of material flows, e.g. B. to achieve blood (in the sense of selective removal of toxins or pathogens) without significantly changing the properties of conventional Ultrason ® -PVP polymer blend membranes.
  • the counterions required for charge neutrality are selected from elements of groups 1, 2 or 13 with the proviso that for an element of group 1 there is a residue R4, for an element of the group 2 to two radicals R4 and, in the case of an element of group 13, to three radicals R4, one element from the respective group.
  • R 1 , R 2 , R 3 is hydrogen, CC 4 alkyl, C 6 aryl, C 7 -C 10 alkylaryl or a radical of the general formula III, R 4 is a radical of the general formula III
  • R ⁇ R 2 , R 3 is hydrogen, CC 4 alkyl, C 6 aryl, C 7 -C 10 alkylaryl R 4 is a radical of the general formula IV
  • R 5 d-C ⁇ -alkyl is an integer between 0 and 4 m, 0 or 1 means R 6 C ⁇ -C 4 alkyl
  • R 7 is hydrogen, C r C 4 alkyl and XN (R1) (R2)) or halogen ,
  • R ⁇ R 2 , R 3 is hydrogen, CrC 4 alkyl, C 6 aryl, C 7 -C ⁇ 0 alkylaryl R 4 is a radical of the general formula V.
  • D R3 is hydrogen, CrC alkyl, C 6 aryl, C 7 -C ⁇ 0 alkylaryl, or a radical of the general formula VI
  • R 4 is a radical of the general formula VI (VI)
  • copolymers according to the invention can be prepared by copolymerizing the monomers using customary polymerization processes.
  • graft copolymerization is also possible:
  • further monomers are radically polymerized (grafted) onto an existing polymer, so that polymeric side chains are formed on the existing polymer from the monomer used.
  • non-grafted polymers are also formed.
  • Homopolymers as well as copolymers, terpolymers etc. from the monomers according to the invention can be used as the polymer onto which grafting is carried (polymer backbone).
  • the monomers used for the grafting are selected individually or as a mixture of the monomers a) according to the invention, the monomers b) or as a mixture of two or more monomers from the monomers a) and b).
  • the copolymers obtained by copolymerization according to customary polymerization processes are preferably used.
  • N-vinylamine in contrast to the trisubstituted N, N, N-vinyl-R1-R2-amines, cannot be polymerized as such because it is almost completely in the form of its tautomer, ethylimine.
  • N-vinylamine can be polymerized in the form of its derivative, vinylformamide, by known methods.
  • the resulting vinylformamide polymers can then be partially or completely converted into the corresponding vinylamine polymers by hydrolysis of the formamide groups, as described, for example, in EP 71050 from BASF. The hydrolysis can take place directly after the polymerization in the same reaction vessel or in another, separate reaction step.
  • vinylamine as a monomer always means the use of the corresponding vinylformamide derivatives with subsequent hydrolysis.
  • a copolymer composed of, for example, 50 mol% of vinylformamide and vinylamine consequently means a polymer which was polymerized from 100% vinylformamide, and then 50% of the vinylformamide groups were hydrolyzed to vinylamine.
  • Component a) of the N-vinyllactams or N-vinylamines are preferably N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaproiactam, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole and N-vinylformamide , particularly preferably N-vinylpyrrolidone.
  • the proportion of monomer building blocks a) in the copolymer is in the range from 60 to 99% by weight, preferably 70 to 97% by weight, particularly preferably in the range from 75 to 95
  • the counterions required for charge neutrality are selected from elements of groups 1, 2 or 13 with the proviso that an element from group 1 has a radical R4 and an element from group 2 two residues R4 and, in the case of an element of group 13, there are three residues R4 for each element of the respective group.
  • B1) preferably means glycidyl methacrylate (GMA) or hydroxyethyl methacrylate (HEMA).
  • R 1 , R 2 , R 3 is hydrogen, CC 4 alkyl, C 6 aryl, C 7 -C 10 alkylaryl or a radical of the general formula III, R 4 is a radical of the general formula III
  • B2 preferably means acrylic acid (AS), methacrylic acid (MAS), crotonic acid (CS), dimethylacrylamide (DMAA), 10-undecenoic acid (UDS), 4-pentenoic acid (PS), cinnamic acid (ZS), maleic acid (MS) or maleic anhydride ( MSA), fumaric acid, 3-butenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, citraconic acid, mesaconic acid, itaconic acid.
  • R 1 , R 2 , R 3 is hydrogen, CC 4 alkyl, C 6 aryl, C 7 -C 10 alkylaryl
  • R 4 is a radical of the general formula IV
  • Ci-Cs-alkyl n is an integer between 0 and 4 m, I 0 or 1 means R 6 CC 4 -AlkyI R 7 is hydrogen, CC -AlkyI and XN (R1) (R2)) or halogen.
  • B3) is preferably 4-vinylbenzyl chloride (VBC), 4-aminostyrene, 3-N, N-dimethylaminostyrene, 3-N, N-diethylaminostyrene, 3-N, N-diphenylaminostyrene, 4-N, N-dimethylaminostyrene , 4-N, N-diethylaminostyrene, 4-N, N-diphenylaminostyrene.
  • VBC 4-vinylbenzyl chloride
  • R 1 , R 2 , R 3 is hydrogen, dC 4 alkyl, C 6 aryl, C 7 -C 10 alkylaryl
  • R 4 is a radical of the general formula V.
  • b4) means vinylimidazole (VI) or quaternized vinylimidazole (QVI), 2-methylvinylimidazole, 4-methylvinylimidazole, 5-methylvinylimidazole or their quaternized derivatives.
  • a terpolymer is particularly preferred using vinylimidazole, quaternized vinylimidazole or N-vinyl-1-methylimidazole, N-vinyl-4-vinyl-5-methylimidazole or their quaterinated derivatives.
  • R 1 , R 2 , R 3 is hydrogen, CC 4 alkyl, C 6 aryl, C 7 -C 10 alkylaryl, or a radical of the general formula VI
  • R 4 is a radical of the general formula VI
  • t, u, v, z is a number between 0 and 2 X 0, 1/3, / 2 , 1 and y is an integer between 1 and 3, with the proviso that at least one radical R 1 , R 2 , R 3 and R 4 , but a maximum of 2 radicals mean the general formula VI.
  • B5) preferably means vinylamine (VAm), 2-acrylamido-2-methylpropane sulfonic acid (AMPS), methacrylic acid amidopropyldimethylammonium propylsulfobetaine (SPP), acrylic acid (3-sulfopropyl) ester potassium salt (SPA), ltakonic acid bis- ( 3-sulfopropyl) ester di-potassium salt (SPI), methacrylic acid (3-sulfopropyl) ester potassium salt (SPM), sodium 3-allyloxy-2-hydroxypropane-1-sulfonate (SPAE), vinylbenzenesulfonic acid ( VBS), vinylsulfonic acid (VS), 2-acrylamido-2-methylethanesulfonic acid, methacrylic acid amidomethyldimethylammoniumpropylsulfobetaines, methacrylic acid amidoethyldimethylammoniumethylsulfobetaines, acrylic acid (3-sulfoprop
  • Mixtures of two or more comonomers can of course also be used as long as the sum of the proportions of these comonomers does not exceed 40% by weight.
  • N-vinylpyrrolidone as monomer a) and vinylimidazole or quaternized vinylimidazole as monomer b) provides polymers with good properties.
  • N-vinylpyrrolidone is used as monomer a) and vinylimidazole or quaternized vinylimidazole as monomer b)
  • another monomer or a mixture of further monomers selected from monomers a) and / or b) is used for the copolymerization.
  • a Crd-alkyl radical means a methyl, ethyl, propyl, isopropyl, butyl, isobutyl or a tert-butyl radical.
  • a dC 6 -alkyl radical means methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl radical, pentyl, hexyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 1-dimethylpropyl , 1, 2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl , 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1-ethylmethylpropyl or 1, 2-ethylmethylpropyl radical.
  • a dC- ⁇ 5 alkyl group means methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl group, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl , 1, 2-DimethylpropyI, 2,2-Dimethylpropyl, 1-Ethylpropyl, Hexyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1, 1-Dimethylbutyl, 1, 2-Dimethylbutyl, 1, 3 -Dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1-ethylmethylpropyl, 1, 2-ethylmethylpropyl as
  • a C 6 -C 10 aryl radical is understood to mean phenyl and naphthyl radicals.
  • a C 7 -C 1 -alkylaryl radical is taken to mean mono- and poly-substituted phenyl and naphthyl radicals with the C1-C8-alkyl radicals methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert.
  • a CC alkenyl radical is taken to mean vinyl, allyl, 1-methylvinyl, E-2-propenyl, Z-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2 -Methyl-2-propenyl, 2-methyl-1-propenyl, Z-1-methyl-1-propenyl, E-1-methyl-1-propenyl.
  • Halogen means fluorine, chlorine, bromine and iodine.
  • Group 1 elements are lithium, sodium or potassium.
  • Group 2 elements are magnesium, calcium, strontium or barium.
  • Group 13 elements are aluminum, gallium or indium.
  • the monoethylenically unsaturated carboxylic acids can be used in the form of the free acid and - if present - the anhydrides or in partially or in completely neutralized form in the copolymerization.
  • Alkali metal or alkaline earth metal bases, ammonia or amines e.g. Sodium hydroxide solution, potassium hydroxide solution, soda, potash, sodium bicarbonate, magnesium oxide, calcium hydroxide, calcium oxide, gaseous or aqueous ammonia, triethylene, ethanolamine, diethanolamine, triethanolamine, morpholine, diethylene triamine, amino methyl propanol, 2-amino-2-methyl propanol or tetraethylene pentamine.
  • the membranes can also contain one or more hydrophilic polymers C selected from the group of the polyvinylpyrrolidones, polyethylene glycols, polyglycol monoesters, polyethylene glycol propylene glycol copolymers, water-soluble cellulose derivatives and the polysorbates.
  • hydrophilic polymers C can be used in amounts of 0 to 50% by weight, preferably 0.01 to 40% by weight, particularly preferably 0.1 to 30% by weight, in the production of the membranes.
  • the weight specifications relate to the total mass of the polymers used in membrane production.
  • Polyvinylpyrrolidones are preferably used as polymers C.
  • the membranes according to the invention can also contain one or more polymers selected from the group of the polysulfones, such as polysulfones, polyethersulfones, polyarylethersulfones, polyarylsulfones, polycarbonates, polyolefins, polyimides, polyketopes, polyether ketones, polyether ether ketones, polyesters, polyamides, Polyvinyl chloride, polybutylene terephthalate, hydrophobically modified acrylic acid polymers, polyethers, polyurethanes, polyurethane copolymers or hydrophobically modified polymers such as. B.
  • the polysulfones such as polysulfones, polyethersulfones, polyarylethersulfones, polyarylsulfones, polycarbonates, polyolefins, polyimides, polyketopes, polyether ketones, polyether ether ketones, polyesters, polyamides, Polyvinyl chloride,
  • water-insoluble cellulose derivatives such as cellulose acetates, cellulose senitrates and mixtures thereof.
  • the production of these polymers is generally known. They can be used in the production of the membranes in amounts of 50 to 99% by weight, preferably 60 to 97% by weight, based on the total mass of the polymers used.
  • Polysulfones, polyamides or blends of polysulfones and polyamides are preferably used.
  • the copolymer according to the invention can be used in the production of the membranes in amounts of 1 to 50% by weight, preferably 1 to 40% by weight, based on the total mass of the polymers used.
  • the amounts of polymer C, polymer D and the copolymer according to the invention used are selected such that a sum of 100% by weight of polymer results in the manufacture of the membranes.
  • Copolymers of N-vinylpyrrolidone with vinylamine maleic acid, acrylic acid, methacrylic acid, crotonic acid, 4-pentenoic acid, 10-undecenoic acid, maleic anhydride, glycidyl methacrylate or 2-acrylamido-2-methylpropane sulfonic acid are preferably used.
  • Another object of the invention are also new copolymers obtainable by polymerization of
  • Copolymers obtainable by polymerizing
  • Copolymers obtainable by polymerizing
  • the invention also relates to semipermeable membranes containing the polymers according to the invention.
  • copolymers are prepared by known processes, for example solution, precipitation, emulsion or reverse suspension polymerization using use of compounds which form free radicals under the polymerization conditions.
  • the polymerization temperatures are usually in the range from 30 to 200, preferably 40 to 110 ° C.
  • Suitable initiators are, for example, azo and peroxy compounds and the customary redox initiator systems, such as combinations of hydrogen peroxide and reducing compounds, e.g. As sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxilate and hydrazine and combinations of hydrogen peroxide or organic peroxides with catalytic amounts of metal, metal salts or metal complexes.
  • reducing compounds e.g. As sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxilate and hydrazine and combinations of hydrogen peroxide or organic peroxides with catalytic amounts of metal, metal salts or metal complexes.
  • the copolymers A have K values of at least 20, preferably 25 to 120, particularly preferably 40 to 110.
  • the K values are determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58 to 64 and 71 to 74 (1932) in aqueous or alcoholic or saline solution at 25 ° C, at concentrations that are between 0.1% and 5% depending on the K value range.
  • the average molecular weight of the polymers A used according to the invention is in the range from 30,000 to 10,000,000, preferably 35,000 to 2,000,000, particularly preferably from 40,000 to 1,500,000.
  • the polymer dispersions or solutions obtained can by various drying processes such. For example, spray drying, fluidized spray drying, roller drying or freeze drying can be converted into powder form, from which an aqueous dispersion or solution can be prepared again by redispersing or dissolving in water.
  • the copolymers used according to the invention are suitable for producing a wide variety of wettable membrane types, such as microporous membranes, for example microporous hollow fiber membranes, homogeneous membranes, symmetrical or asymmetrical membranes or solution diffusion membranes for material separation. Microporous or asymmetrical membranes can preferably be produced. Because of their film-forming properties, the copolymers according to the invention can also be used directly for producing membranes such as solution diffusion membranes, in particular after the copolymers have been crosslinked in the film.
  • wettable membrane types such as microporous membranes, for example microporous hollow fiber membranes, homogeneous membranes, symmetrical or asymmetrical membranes or solution diffusion membranes for material separation. Microporous or asymmetrical membranes can preferably be produced. Because of their film-forming properties, the copolymers according to the invention can also be used directly for producing membranes such as solution diffusion membranes, in particular after the copolymers have been crosslinked in the
  • filter nonwovens or filter elements by coating nonwoven fabrics or textile fabrics by means of the copolymers according to the invention and optionally further hydrophilic polymers C and / or hydrophobic polymers D of the above selection possible.
  • Filter elements can be produced from the polymers according to the invention in that the polymers are applied to a multidimensional non-woven material or a multidimensional fabric made of fibers in such a way that the type of coating of the non-woven fabric or of the fabric results in a material that shows filter properties that match those resemble or correspond to a membrane.
  • This can also be achieved in that the structure of the fleece or of the fabric is such that there is a filter effect, the coating with the polymers according to the invention serving to change this filter effect as desired by surface coating, for example the affinity for certain substances to increase or decrease.
  • Membranes or filters according to the invention can be used in the filtering of body fluids or natural or synthetic fluids which are to be introduced into a living organism for the separation of undesired substances.
  • Such liquids include blood, artificially produced blood substitutes or solutions for infusion such as special salt and nutrient solutions.
  • Membranes or filters according to the invention can also be used to free biological or synthetic liquids from undesired substances or to achieve separation of substances. Areas of application for this can be found, for example, in the medical-pharmaceutical field in the preparation of sample liquids such as blood, urine etc. for analytical purposes or in the preparation of solutions or liquids which are used for analytical purposes in the medical-pharmaceutical field, such as, for. B. salt solutions.
  • the polymers according to the invention can also be used for coating surfaces.
  • the polymers can be used as such and, for example, applied to the surface in question from solution.
  • Crosslinking of the polymers before or after application to the surface by known crosslinking techniques can also be used.
  • Crosslinking of the polymers according to the invention by known methods is of course possible and included in the invention.
  • Crosslinking can take place during the polymerization, for example by adding crosslinking agents.
  • the subsequent crosslinking by known methods such as. B. networking using high-energy radiation such. B. UV or gamma radiation or the thermally induced crosslinking.
  • Auxiliaries such as crosslinkers which can be activated thermally or by UV radiation etc. can also be used to strengthen the crosslinking.
  • Another use is the use of the polymers according to the invention to increase the solubility of poorly soluble or crystallization-prone substances in aqueous or organic media.
  • the prevention of crystallization can be used in a variety of ways, for example in crude oil production to prevent the formation of gas hydrates in pipelines or for the formulation of poorly soluble active ingredients that tend to crystallize in the pharmaceutical or agricultural sector.
  • the present invention also includes the binding of substances by chemical reaction or by strong physical interactions with the functional groups of the comonomers in the vinylpyrrolidone copolymer and the use of the properties of the bound substances, e.g. the effect of linked enzymes.
  • copolymers according to the invention e.g. as membranes for technical applications, surface coating, solubilizers, solubilizers, in cosmetics, for pharmaceutical applications, as additives for emulsions or suspensions, as additives for reactive lacquer systems, as kinetic gas hydrate inhibitors etc.
  • the various components are transferred into a solution, with which the shaping is then carried out in a suitable manner, such as casting or spinning.
  • the membranes are produced in a manner known per se, for example by a phase inversion method as described in EP-A 082 433, to which reference is hereby expressly made.
  • Hollow fiber membranes can also be obtained by extrusion and precipitation of a polymer-containing spinning solution. Such a method is described, for example, in EP-A 168 783, which is also incorporated herein by reference.
  • the copolymers produced also have good crosslinkability and adhesion to surfaces, so that a surface coating can be produced.
  • a solubilizer for substances which are poorly soluble in water systems or have a tendency to crystallize.
  • the copolymers also show good compatibility in polymers which can be used for technical membranes such as in solution diffusion membranes for material separation, the use of the copolymers making it possible to improve the separation properties significantly.
  • the copolymers are also suitable directly for producing membranes without the addition of further polymers, in particular after the copolymers have been crosslinked in the film.
  • K value Schott viscometer, type I measuring condition 25 ° C ( ⁇ 0.1 ° C) measuring solution 0.1 to 1 g / 100mL
  • Measurement condition 25 ° C measurement solution: spinning solution (7.5% copolymer, 12.5% polyethersulfone; 80.0% N-methylpyrrolidone)
  • the template was heated to 60 ° C under nitrogen. At 60 ° C., feed 1 was added in 2 hours and feed 2 in 3 hours. The mixture was then heated to 75 ° C. and polymerized for 3 hours. Feed 3 was then added and the mixture was stirred for 30 min.
  • the template was heated to 75 ° C. under nitrogen. Then feeds 1 and 2 were added in 4 hours, feed 3 all at once. After 4 hours, feeds 4, 5, 6 and 7 were added. The mixture was then polymerized for one hour, heated to 90 ° C. and polymerized for a further hour.
  • the template was heated to 70 ° C. under nitrogen.
  • Feed 2 was added at 60 ° C. and feed 1 started and added in 3 hours. After one hour after the start of feed 1, feed 3 was added, after a further hour feed 4, after a further hour feed 5. Then polymerization was continued for 1.5 hours, feed 6 was added, heated to 85 ° C. and post-polymerized for a further two hours. Siert.
  • the template was heated to 70 ° C. under nitrogen. Feed 2 was added and feed 1 started and added in 3 hours. After one hour after the start of feed 1, feed 3 was added, after a further hour feed 4, after a further hour feed 5. Then polymerization was continued for 1.5 hours, feed 6 was added, heated to 85 ° C. and polymerized for a further two hours.
  • the template was heated to 70 ° C. under nitrogen. Feed 2 was added and feed 1 started and added in 3 hours. After one hour after the start of feed 1, feed 3 was added, after a further hour feed 4, after a further hour feed 5. Then polymerization was continued for 1.5 hours, feed 6 was added, heated to 85 ° C. and polymerized for a further two hours.
  • the template was heated to 70 ° C. under nitrogen. Feed 3 was added and feeds 1 and 2 started and added in 3 hours. After one hour after the start of feeds 1 and 2, feed 4 was added, after a further hour of feed 5, after a further hour of feed 6. Then polymerization was continued for 1.5 hours, feed 7 was added, the mixture was heated to 85 ° C. and for a further two hours afterpolymerized. Due to the high viscosity, it was then diluted with 200 ml of water.
  • the template was heated to 70 ° C. under nitrogen. Feed 3 was added and feeds 1 and 2 started and added in 3 hours. After one hour after the start of feeds 1 and 2, feed 4 was added, after a further 1.75 hours of feed 5, after a further 2.5 hours of feed 6. Then polymerization was continued for 2 hours, feed 7 was added, the mixture was heated to 85 ° C. and more post-polymerized for two hours.
  • the template was heated to 70 ° C. under nitrogen. Feed 2 was added and feed 1 started and added in 3 hours. After one hour after the start of feed 1, feed 3 was added, after a further hour feed 4, after a further 1.5 hours feed 5. Then polymerization was continued for 1 hour, feed 6 was added, the mixture was heated to 85 ° C. and for a further 2.5 hours afterpolymerized.
  • the template was heated to 70 ° C. under nitrogen. Feeds 1 and 2 were started and added in 3.5 hours. After one hour, feed 3 was added and polymerization was continued for 2 hours. Due to the high solution viscosity, the mixture was diluted with 100 ml of water.
  • the template was heated to 70 ° C. under nitrogen. Feed 2 was added and feed 1 started and added in 3.5 hours. 1.5 hours after the start of feed 1, feed 3 was added, after a further hour of feed 4, after a further 1.5 hours of feed 5. The mixture was then polymerized for 1.5 hours, feed 6 was added, heated to 85 ° C. and a further 2 Polymerized for 5 hours.
  • Example 11 Vinyl pyrrolidone / acrylic acid (3-sulfopropyl) ester, sodium salt (SPA) 80:20
  • the template was heated to 70 ° C. under nitrogen. Feed 3 was added and feeds 1 and 2 started and added in 3 hours. One hour after the start of feed 1, feed 4 was added, after a further hour feed 5, after a further hour feed 6. Then polymerization was continued for 1.5 hours, feed 7 was added, the mixture was heated to 85 ° C. and polymerized for a further 2 hours.
  • the template was heated to 70 ° C. under nitrogen. Feed 3 was added and feeds 1 and 2 started and added in 3 hours. One hour after the start of feed 1, feed 4 was added, after a further hour feed 5, after a further hour feed 6. Then polymerization was continued for 1.5 hours, feed 7 was added, the mixture was heated to 85 ° C. and polymerized for a further 2 hours.
  • the template was heated to 70 ° C. under nitrogen.
  • Feed 3 was added at 60 ° C., feeds 1 and 2 were started and added in 3 hours.
  • feed 4 was added, after a further hour feed 5, after a further hour feed 6.
  • polymerization was continued for 1.5 hours, feed 7 was added, the mixture was heated to 85 ° C. and polymerized for a further 2 hours.
  • VBS Vinyl pyrrolidone / vinyl benzene sulfonic acid
  • the template was heated to 70 ° C. under nitrogen.
  • Feed 2 was added at 60 ° C. and feed 1 started and added in 3 hours.
  • feed 3 was added, after a further hour feed 4, after a further hour feed 5.
  • polymerization was continued for 1.5 hours, feed 6 was added, the mixture was heated to 85 ° C. and polymerized for a further 2 hours ,
  • the template was heated to 70 ° C. under nitrogen.
  • Feed 2 was added at 60 ° C. and feed 1 started and added in 3 hours.
  • feed 3 was added, after a further hour feed 4, after a further hour feed 5.
  • polymerization was continued for 1.5 hours, feed 6 was added, the mixture was heated to 85 ° C. and polymerized for a further 2 hours ,
  • Intrinsic viscosity membrane functionality - formation of gel particles
  • Example 16 Vinylpyrrolidone / methacrylic acid amidopropyl-dimethyl-ammonium-propyl-sulfobetaine SPP 90:10
  • the template was heated to 70 ° C. under nitrogen. Feed 3 was added at 60 ° C., feeds 1 and 2 were started and added in 3 hours. One hour after the start of feed 1, feed 4 was added, after a further hour feed 5, after a further hour feed 6. Then polymerization was continued for 1.5 hours, feed 7 was added, the mixture was heated to 85 ° C. and polymerized for a further 2 hours. Due to the high solution viscosity, it was diluted with 200 ml of water.
  • the template was heated to 75 ° C under nitrogen.
  • Feed 3 was added and feeds 1 and 2 started and added in 4 hours.
  • feed 4 was added, after a further hour of feed 5, after a further hour of feed 6, after a further hour of feed 7, after a further hour of feed 8.
  • the mixture was then heated to 90 ° C. and for one hour afterpolymerized.
  • the template was heated to 80 ° C. under nitrogen. Feed 3 was added at 70 ° C., feeds 1 and 2 were started and added in 3 hours. One hour after the start of feed 1, feed 4 was added, after a further hour feed 5, after a further hour feed 6. Subsequently, polymerization was continued for 1.5 hours, feed 7 was added, the mixture was heated to 95 ° C. and polymerized for a further 2 hours.
  • the template was heated to 75 ° C under nitrogen. Feeds 1 and 2 were started and added over the course of 2 and 2.5 hours, respectively. The mixture was then polymerized for one hour, feed 3 was added and polymerized for a further 2 hours.
  • the template was heated to 80 ° C. under nitrogen.
  • Feed 2 was added at 70 ° C. and feed 1 started and added in 3 hours.
  • feed 3 was added, after a further hour feed 4, after a further hour feed 5.
  • polymerization was continued for 1.5 hours, feed 6 was added, heated to 95 ° C. and polymerized for a further 2.5 hours ,
  • the initial charge was heated to 70 ° C. under nitrogen and the pH was monitored. At an internal temperature of 70 ° C., feed 1 was added in 3 hours. The pH was checked and controlled by adding feed 2 (increase from 6.2 to 7.4). The polymerization was continued for 3 hours at 70 ° C. and then diluted with feed 3. The mixture was then heated to 80 ° C., feed 4 was added in one hour and the mixture was stirred at 80 ° C. for a further 3 hours for the hydrolysis of vinylformamide to vinylamine. Due to the high solution viscosity, the mixture was diluted with 500 ml of water and the pH was adjusted to 6.9 with feed 5. The product was obtained as a powder after freeze-drying.
  • the hydrolysis can of course also be omitted and the vinylpyrrolidone / vinylformamide copolymer can be isolated.
  • the initial charge was heated to 70 ° C. under nitrogen and the pH was monitored. At an internal temperature of 70 ° C., feed 1 was added in 3 hours. The pH was checked and controlled by adding feed 2 (increase from 6.2 to 7.4). The mixture was postpolymerized at 70 ° C. for 3 hours and then diluted with feed 3. The mixture was then heated to 80 ° C., feed 4 was added in one hour and the mixture was stirred at 80 ° C. for a further 3 hours for the hydrolysis of vinylformamide to vinylamine. Due to the high solution viscosity, the mixture was diluted with 500 ml of water and the pH was adjusted to 6.9 with feed 5. The product was obtained as a powder after freeze-drying.
  • the hydrolysis can of course also be omitted and the vinylpyrrolidone / vinylformamide copolymer can be isolated.

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Abstract

L'invention concerne l'utilisation de copolymères contenant : a) entre 60 et 99 % en poids d'au moins un vinyllactame ou d'une N-vinylamine, sélectionné dans le groupe comprenant : N-vinylpyrrolidone, N-vinylpipéridone, N-vinylcaprolactame ou N-vinylformamide et b) entre 1 et 40 % en poids d'au moins un monomère de formule générale (I).
EP04765159A 2003-09-19 2004-09-14 Utilisation de copolymeres contenant du n-vinyllactame pour produire des membranes fonctionnalisees Withdrawn EP1667789A2 (fr)

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DE10343900A DE10343900A1 (de) 2003-09-19 2003-09-19 Verwendung von N-Vinyllactam enthaltenden Copolymeren zur Herstellung von funktionalisierten Membranen
PCT/EP2004/010243 WO2005032701A2 (fr) 2003-09-19 2004-09-14 Utilisation de copolymeres contenant du n-vinyllactame pour produire des membranes fonctionnalisees

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