TW201249529A - Nanofiltration membrane - Google Patents

Abstract

The invention relates to a nanofiltration membrane having a porous support membrane, the surface of the support membrane being coated with polymer particles which are prepared by emulsion polymerization and which have an average particle diameter of less than 70 nm, preferably between 30-60 nm, more preferably between 40 - 50 nm.

Description

201249529 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a nanofiltration membrane having a porous support membrane, a method for producing such a membrane, and uses thereof. [Prior Art] In the chemical industry, the food industry, the beverage industry, the electronics industry, and the pharmaceutical industry, for example, a membrane for separating a solid/liquid mixture and a liquid is used. In the context of environmental technology, these membranes are also used to purify wastewater and produce potable water. A variety of membrane separation techniques are known in the art. They include microfiltration, ultrafiltration, and nanofiltration, as well as reverse osmosis. These techniques can be classified as mechanical separation methods. These separation mechanisms are governed by different membrane structures. The structures are separated by membrane pores having a diameter smaller than the diameter of the particles to be separated. In addition to the steric hindrance effect, another key mechanism in the separation between the nanofiltration membrane and the reverse osmosis membrane is the electrostatic interaction of the ions in the solution or the separation of the decomposed hydrocarbons and the corresponding charged groups on the membrane surface of the aqueous solution. Electrostatic interaction. This interaction allows for the separation of two species having similarly sized particle radii but different charge or official abilities. Similarly, in the case of a membrane having corresponding pores, such as for nanofiltration or reverse osmosis, separation may be based, for example, on the difference in the tendency of substances present in the solution to diffuse through the membrane. 201249529 Known methods for treating liquids under pressure are microfiltration, ultrafiltration and nanopellets. For nanofiltration, ultrafiltration, and microfiltration, the pore size of the membrane is approximately 0.001 μηη to 10·0 μιη. In order to characterize the membrane, a cut-off R for a substance is usually employed. [%] W (feed) - w (permeate), W (feed) where W is the mass fraction of a particular substance. Interception describes the percentage of the concentration of a separated material in the permeate (from the Latin "permeare" = pass) relative to the concentration in the feed. It depends not only on the temperature but also on the transmembrane pressure or flow rate and the concentration of the starting solution. The retentate (from the Latin "retenere" = retention) constitutes the wave of the substance to be separated, which is increased compared to the feed. This shows the difficulty in assessing the separation characteristics of a film. The crude classification of the membrane is typically obtained from cut-off molecules along with the flow rate. This entrapment is synonymous with a molar mass system having at least 90% entrapment for its membrane, and can be very different, particularly within the nanofiltration range, depending on the molecular configuration of the material to be separated. The retention of the nanofiltration membrane is typically &lt; 1500 g/mol. Ultrafiltration membranes typically have a cutoff of <about 150,000 g/mol. Also known are organic polymer based membranes which are used for separation at the molecular level, such as gas separation, for example and also for full evaporation and/or water vapor permeation. However, a disadvantage of such polymeric films is their short lifetime due to the sensitivity of the polymeric film to solvents. 201249529 The solvent destroys the film material or causes it to swell. In addition, the relatively low temperature tolerance of σ species poses a problem. (iii) Polymeric ceramic membranes are also frequently used, they have a relatively long life because, depending on their composition, they are very inert to organic compounds, acids or bases and in addition they have a greater temperature than polymeric materials. Tolerance. Therefore, they can also be used for separation tasks in chemical operations, such as in steam infiltration. These types of ceramic crucibles/type crucibles are produced by a sol-gel method or by dip coating method to produce a multi-layered system of ceramic layers having a material thickness and pore size on such a square wire. The top layer that performs the actual separation task has the smallest holes and is constructed to be as thin as possible. Due to the low elasticity of the ceramic material, Tao Lai is sensitive to mechanical loads and the valley is easily broken. In contrast to polymer films, in order to make space-saving wound modules, they cannot be rolled up. A book can explain that 'for all known membrane synthesis methods, one main, the problem is to determine the shape of the separation active pores, and thus produce a very narrow pore X for a wide pH range. And for many applications, polymer membranes made from a very wide variety of materials can be obtained at a very favorable cost: 2 in most cases lacking tolerance to organic solvents, shaking. Very high and/or very low enthalpy levels are also lacking tolerance. 'Permanent temperature stability above 80 〇c is almost unremarkable. Although there are many methods for improving these properties of polymer membranes 201249529' Usually, one of the above requirements is not met. Moreover, at very high temperatures, most polymers are plastically deformable. This results in the films being pressed together when they are operated under pressure at very high temperatures. This compaction causes the pore microstructure of the membrane to be fully compressed, thereby causing a sharp increase in resistance to filtration. This causes a reduction in flow. Another disadvantage of conventional polymeric materials is the poor tolerance to organic solvents and oils, as well as the plasticizing action of oils on polymers. This adversely affects the separation ability of the membranes. Membrane technology is quite important in the separation of liquid mixtures. In the recovery of drinking water from brine by reverse osmosis, and in the purification of the product, in particular, ultrafiltration and nanofiltration techniques and reverse osmosis membranes are increasingly used. In summary, in the thin film method, the diluted solution is concentrated and the organic solvent, aqueous solution or salt solution is separated. Thus, concentrated and potentially low salt solutions result in valuable compounds or contaminant compounds that make subsequent storage, transportation, disposal, and further processing more cost effective. Particularly in wastewater treatment, the purpose of membrane treatment is to recover the largest portion of the permeate in a form that is free of contamination or only slightly contaminated. The concentrated retentate can be separated and purified at a lower cost and effort to replenish the remaining compound, or can be disposed more cost effectively in this concentrated form, such as by burning. The field of membrane technology includes a wide variety of different methods. Therefore, there are also different membranes and different technical designs for these membranes. Technically relevant membrane separation techniques operate primarily as a cross-flow. Due to the high flow rate and specific membrane volume configuration, the high shear rate is intended to reduce membrane fouling and reduce concentration polarization. Commercially available nanofiltration membranes are composite crucibles formed by phase interface condensation as described in U.S. Patent 5,049,167. However, such known membrane systems are very expensive and inconvenient to produce, and are only produced in safety measures with cost implications because of the use of carcinogenic diamines and highly reactive acrylonitrile chlorides. An example of a reactant. The film can have a variety of configurations, such as in the form of a flat film module, a box module, a spiral wound module, or an empty fiber module. In addition, commercial filtration membranes can generally be used only at process temperatures up to about 80 °C. SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a high performance nanofiltration membrane that exhibits high thermal load carrying capacity, in organic and inorganic solutions, and also in high and low based on suitable surface modification. Good stability at pH level and in addition good separation characteristics. Another object of the invention is to provide a method by which it is possible to produce a defined pore size for the membrane in question. It is known from the prior art that the polymer particles can be placed on a porous substrate having a relatively wide pore size distribution in order to obtain a composite membrane having a narrow pore size distribution. The cavity between the particles forms a 201249529 hole that can be separated from the liquid by the holes. The composite film obtained in this manner can be used, for example, as an ultrafiltration and microfiltration membrane. Therefore, in order to achieve this object, there is provided a nanofiltration membrane having the form indicated at the beginning, wherein the surface of the support membrane is coated with polymer particles which are produced by emulsion polymerization and It has an average particle diameter of &lt; 70 nm, preferably between 30 nm and 65 nm, more preferably between 40 nm and 50 nm. Here, a distinction is made between the filtration quality of a membrane (e.g., characterized by entrapment) and the construction of the filtration membrane. The following reference frames for nanofiltration membranes use polymer particles in the particle size range of S 100 nm for the production of such membranes. The term "nanofiltration membrane" does not have any meaning for its separation characteristics. Separation effects, separation characteristics, and separation behavior are used as synonyms. The separation effect is defined by the above-described entrapment. Polymer particles and nanoparticles are used synonymously herein. The use of polymer particles made by emulsion polymerization and having an average particle size of &lt;70 nm, preferably between 30 nm and 65 nm, more preferably between 40 nm and 50 nm, provides superior to other polymers The various advantages of the particles, because the chemical and physical properties of the polymer particles (such as particle size, particle morphology, swelling behavior, catalytic activity, hardness, dimensional stability, axial properties, surface energy, ageing resistance, and impact toughness) can Adjusted. This aspect is achieved by a production process, more specifically by a polymer process, and also by selecting a suitable base monomer, and on the other hand by selecting a suitable functional group, in the polymer particles. The concentration and occupancy of these functional groups can be customized or adjusted within a wide range. Therefore, the separation active film is produced using polymer particles which are produced by emulsion polymerization and have an average particle diameter of &lt; 70 nm, preferably between 30 nm and 65 nm, more preferably between 40 nm and 50 nm. The membrane is also referred to as the polymer layer of the nanofiltration membrane of the present invention. By emulsion polymerization it is more particularly meant a process which is known per se and which is generally used in the reaction medium in which the monomers used are polymerized in the presence or absence of emulsifiers and radical-forming substances. Usually an aqueous polymer latex. (See, among other things, R0mpp Lexikon der Chemie, Volume 2, 10th Edition, 1997; PA Lovell, MS El-Aasser, Emulsion Polymerization and Emulsion Polymers, John Wiley &amp; Sons, ISBN: 0 471 96746 7; H. Gerrens, Fortschr. Hochpolym. Forsch. 1,234 (1959)). Unlike suspension polymerization or dispersion polymerization, emulsion polymerization typically produces relatively fine particles which allow for a smaller void diameter and thus a smaller pore size in the separation of the active layers. Particles having a particle size of less than 500 nm are generally not obtainable by suspension polymerization or dispersion polymerization, and thus such particles are generally unsuitable for the purposes of this patent application. Surprisingly, it has been found that due to the selection of the determined polymer particles, there is no longer any need to use additional thermal or chemical means to stabilize the nanofiltration membrane of the present invention. The choice of monomer is used to adjust the glass transition temperature of the polymer particles as well as the width of the glass transfer. The glass transition temperature (Tg) of the polymer particles and the width (ATg) of the glass transition are determined by differential scanning 201249529 calorimetry (DSC), preferably as described below. Two cooling/heating cycles were performed to confirm Tg and ATg'. Ts and Δ&amp; were determined in the second thermal cycle. In the sample from Perkin-Elmer, the assay used approximately 10-12 mg of selected polymer particles. The first D S C shield ring was stored by first cooling the sample to -10 ° C with liquid nitrogen and then heating it to +150% at a rate of 20 K/min. The second DSC cycle begins by cooling the sample as soon as the sample temperature of +15 〇〇C is reached. In the second heating cycle, the sample was again heated to +15 〇C) C as in the first cycle. The heating rate in the second cycle was again 20 K/min. Tg and ΔΑ are determined graphically on the Dsc curve of the second heating process. For this purpose, three straight lines are placed on the DSC curve. Place the first line on the DSC curve, on the Tg portion, place the second line on the curve through the two branches of Tg, with an inflection point, and place the third line on the same Tg as the DSC curve. The location. In this way, two straight lines with two intersections are obtained. Each of these two intersections is marked by a characteristic temperature. The glass transition temperature &amp; is obtained as the average of these two temperatures, and the width A of the glass transition is obtained from the difference between these two temperatures. The polymer particles preferably have a temperature of from -85 ° C to 150 ° C, more preferably from -75 ° C to UyC ' very preferably _7 〇. 〇 to the glass transition temperature (Tg) of 9〇〇c. The width of the glass transfer /m degree of the polymer particles used in accordance with the invention is preferably greater than 5 ° C, more preferably greater than 1 ° C. 201249529 The polymer particles prepared by emulsion polymerization are preferably rubbery. The rubbery polymer particles are preferably based on conjugated dienes (for example, butyl dichloride, isoprene, 2-butadiene and 2, 3). -dichlorobutane dilute), vinyl acetate, styrene or its derivatives, 2-vinylpyridine and 4-vinylpyridine, acrylonitrile, acrylamide, mercaptopropenamide, tetraethylene, vinylidene fluoride And hexafluoropropylene, and those of the trans-group, epoxy, amine, carbonyl and ketone compounds containing a double bond. Preferred monomers or combinations of monomers include the following: butadiene, isoprene, acrylonitrile, styrene, alpha-mercaptostyrene, chloroprene, 2,3-dioxadiene, Butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate, acrylic acid, diacetone acrylamide, tetrafluoroethylene, vinylidene fluoride and hexamethacrylate . "Based on" is meant herein that the polymer particles preferably comprise, by weight, more than 60%, more preferably more than 70%, and most preferably more than 90% by weight of said monomers. Crosslinked or non-crosslinked. These polymeric particles may more particularly be particles based on homopolymers or random copolymers. The term homopolymer or random copolymer is known to those skilled in the art. And is described, for example, in Vollmert, Polymer Chemistry, Springer 1973. 201249529 As a polymer base of rubbery crosslinked or non-crosslinked polymer particles comprising functional groups, more specifically the following: BR: poly Butadiene, ABR: Butadiene/Ci·4 alkyl acrylate copolymer, IR: Polyisodecadiene, SBR: Random styrene-butadiene copolymer 'with styrene content by weight 1 _60%, preferably 5-50% FKM: fluorinated rubber, ACM: acrylate rubber, nbr: polybutadiene-acrylonitrile copolymer, having an acrylonitrile content of 5-60%, preferably 10-60% by weight , CR: polybutadiene, EAM: ethylene /Acrylate copolymer EVM: Ethylene/vinyl acetate copolymer. Other preferred polymer particles are thermoplastic and based on methacrylate, more specifically decyl methacrylate, styrene, alpha methyl styrene and Acrylonitrile. The polymer particles preferably have an approximately spherical geometry. The polymer particles used according to the invention have a particle size of less than 70 nm, preferably between 30 nm and 65 nm, more preferably between 40 nm and 50 nm. The average granules are determined by ultracentrifugation using water (iv) milk from emulsion polymerized polymer particles. This method gives the average of the particle size (considering any agglomerates) (HG Miiller (1996) ) Gel 12 201249529 Colloid Polymer Science 267: 1113-1116 and W. Scholtan, Η Lange (1972) Kolloid-Zu. Z. Polymer (Polymere 250: 782). The ultracentrifugation method has The advantage is that all particle size distributions are characterized, and different average numbers (such as number average and weight average) can be calculated from the distribution curve. The average diameter number used according to the invention refers to the weight average It is possible to use the number of diameters such as d5 〇 and dS(). These numbers refer to particles having 10%, 50% and 80% by weight, respectively, by weight, having a diameter smaller than the corresponding value. The diameter of the light scattering is determined to be on the latex. Conventional laser systems operate at 633 nm (red light) and at 532 nm (green light). Dynamic light scattering produces an average of the particle size distribution curves. The average number of diameters used in accordance with the present invention is related to this average. 5 m ~, the team comes to σ wood to take 侑, with the change of reactants and also the emulsification degree, the concentration of the initiator, the liquid phase of the organic phase, the ratio of hydrophilic monomer to hydrophobic monomer, six ^ The amount of =, the polymerization temperature, etc., in the range of - wide diameter = after the polymerization, the latex is treated by vacuum evaporation or by stripping with steam, in order to remove volatiles, more specifically ^ The monomer of the reaction. The polymer particles prepared from the pure form do not require any additional differentiation, for example by coagulation. 201249529 In a preferred embodiment, the polymer particles prepared by emulsion polymerization and used in accordance with the invention are at least partially crosslinked. The crosslinking of the polymer particles prepared by emulsion polymerization is preferably achieved by adding a polyfunctional monomer to the polymerization reaction, for example,

By the addition of a compound having at least two, preferably 2 to 4, copolymerizable c=C double bonds, such as diisopropenylbenzene, divinylbenzene, diethion, monoethylidene, ortho-benzene Diethyl propyl vinegar, triallyl cyanurate, triallyl isocyanurate, 1,2-polybutadiene, n, N, · stupid base maleimide, 2,4-A Phenyl bis(maleimide), triallyl phthalate, glycidyl methacrylate, polyhydroxy acrylates of the following materials, and mercapto acrylates (preferably 2 to 4-membered) C2 to C10 alcohols such as ethylene glycol, propanol, 2-diol, butanediol, hexanediol, polyethylene glycol having 2 to 20, preferably 2 to 8, oxyethylene units , neopentyl glycol, bicinch A, glycerol, triterpene methylpropanol, pentaerythritol, sorbitol; and also aliphatic diols and polyols with maleic acid, fumaric acid, and/or itacon Acidic unsaturated polyacetate. The polymer particles may be directly crosslinked in the emulsion polymerization, such as by copolymerization with a polyfunctional compound having crosslinking activity, or by subsequent crosslinking as described below. Direct cross-linking during emulsion polymerization is preferred. Preferred polyfunctional comonomer systems have at least two, preferably 2 to 4, copolymerizable oc: double bond compounds such as diisopropenylbenzene, divinylbenzene, divinyl ether, divinyl fluorene, ortho Diallyl phthalate, triallyl cyanurate, isocyanurate 201249529 acid trilute propyl vinegar, 1,2-polybutylene dilute, N,N'-m-phenyl-maleimide, 2,4-Methylphenyl bis(maleimide), and/or triallyl trimethacrylate. Also contemplated are acrylates and mercapto acrylates of the following materials: aliphatic amines, epoxides and polybasic, preferably two to four membered C2-C10 alcohols, such as ethylene glycol, propane-1,2 -diol, butanediol, hexanediol, polyethylene glycol having from 2 to 20, preferably from 2 to 8 oxyethylene units, neopentyl glycol, bisphenol A, glycerol, trimethylpropanol, Pentaerythritol, sorbitol; and also unsaturated polyesters derived from aliphatic diols and polyols with maleic acid, fumaric acid, and/or itaconic acid. Crosslinking during the emulsion polymerization can also be carried out by continuing the polymerization to high conversion or by reacting with the highly internally converted polymer during the monomer feed. An alternative possibility is to carry out the emulsion polymerization in the absence of a chain transfer regulator. In order to crosslink the polymer particles which are not crosslinked or only slightly crosslinked after the emulsion polymerization, it is preferred to use the latex obtained in the emulsion polymerization. Examples of suitable chemicals having crosslinking activity include organic peroxides, For example, dicumyl peroxide, tertiary butyl peroxy oxime, bis (tertiary butyl peroxyisopropyl) stupid, di- or tertiary butyl peroxy^, 2,5-didecyl hexene Dioxane, 2,5· dimethyl ίH peroxide, bismuth peroxide, bis (2,4 yl i peroxide, benzoic acid tertiary vinegar, and organic money) The noodles, such as the money nitrile nitrile, and the even 15 201249529 nitrogen dicyclohexanenitrile, and also the dinonyl and polydecyl compounds, such as dibenzylethane, 1,6-dimercaptohexane, 1,3 , 5-trimercaptotriazine, and thiol-terminated polysulfide rubber, such as the product of a sulphur-terminated reaction of bischloroethylformal with sodium polysulfide. Optimum temperature for post-crosslinking It is of course dependent on the reactivity of the crosslinker and can optionally be carried out at elevated pressures from room temperature to about 180 ° C ( In this respect, reference is made to Houben-Weyl, Methoden der organischen Chemie, 4th Edition, Volume 14/2, page 848. A particularly preferred crosslinking agent is a peroxide. The rubber containing C=C double bonds is crosslinked to form a polymerization. The particles may also be carried out in a dispersion or in an emulsion, with a C=C double bond by hydrazine (or optionally, other hydrogenating agents, such as organometallic hydride complexes) simultaneously, partially, optionally Fully hydrogenated, as described in US 5,302,696 or US 5,442,009. It is possible to optionally carry out particle expansion by coacervation before, during or after postcrosslinking. Crosslinked polymers used in accordance with the invention The granules advantageously have a portion (gel content) which is insoluble at 23 ° C, which is at least about 70% by weight, more preferably at least about 80% by weight, more preferably 90% by weight, Even more preferably at least about 98% by weight. This insoluble benzene-based fraction is determined at 23% in toluene. In this assay, 250 mg of polymer 16 201249529 is granulated at 25 ml. In benzene by shaking at 23 ° C The expansion was carried out for 24 hours. After centrifugation at 20000 rpm, the insoluble portion was separated and dried. The gel content was obtained as a ratio of the dry residue to the initial mass, and expressed as a percentage by weight. The polymer particles also advantageously have an expansion index in toluene of less than about 80, more preferably less than 60, still more preferably less than 40 at 23 ° C. Thus, the swelling index (Qi) of the polymer particles may preferably be at 1 - Between 20 and 1 - 10. The swelling index was calculated from the weight of the solvent-containing polymer particles (after centrifugation at 20,000 rpm) which was swollen in toluene at 23 ° C for 24 hours, and the weight of the dried polymer particles:

Qi = wet weight of polymer particles / dry weight of polymer particles. To determine the expansion index, 250 mg of polymer particles were swollen under vibration for 24 hours in 25 ml of toluene. The gel was recovered by centrifugation and weighed and then dried to constant weight at 70 ° C and weighed again. The support film is preferably composed of an inorganic or organic material. Furthermore, the support film is advantageously chemically and/or mechanically stable. It is pH-stable and is also in organic solvents such as aldehydes, ketones, monohydric and polyhydric alcohols, benzene derivatives, hydrocarbons, ethers, esters, carboxylic acids, cyclic hydrocarbons, amines, guanamines. Among the classes, intrinsic amines, lactones, sulfoxides, alkanes and alkenes. Preferably, a support film which is chemically stable in the following solvents is selected: acetone, toluene, benzene, water, tetrahydrofuran, dimercapto 17 201249529 formamide, dimethyl sulfoxide, N-methylpyrrolidone, N -ethylpyrrolidone, pyridine, decyl alcohol, ethanol, propanol, isopropanol, butanol, isobutanol, pentane, hexane, gamma, cinnabar, teriyaki, terpene, decyl ethyl ketone, Diethyl ether, dichloromethane, tetrachloroethane, tetra-carbonized carbon, methyl tertiary butyl ether, chlorobenzene, di-benzene, tri-benzene, nitrobenzene, acetic acid, and hexene. It has been found that the nanofiltration membrane of the present invention is also particularly stable in the pH range of 10-14 and/or 1-4. Further, for the application of the film, it is useful that the support film is composed of a material which is temperature-stable at room temperature and at a typical application process temperature. Temperature sensitivities between 50 ° C and 200 ° C, more preferably between 70 ° C and 150 ° C and also between 80 ° C and 120 ° C are also conceivable. As inorganic permeable support films, it is for example possible to use non-woven glass microfiber fabrics, non-woven metal fabrics, densely woven glass microfiber fabrics or woven metal fabrics, as well as woven or non-woven ceramics or Carbon fiber fabric. It is clear to those skilled in the art that it is also possible here to use all other known, preferably flexible, materials of correspondingly sized openings or openings as support material. It is also possible to use a ceramic-ceramic composite material such as an inorganic support material made of, for example, an oxide selected from the group consisting of A?2?, titanium oxide, zirconium oxide or cerium oxide. The inorganic support film is preferably also characterized by a material selected from the group consisting of ceramic, SiC, Si3N4, carbon, glass, metal or semi-metal. In addition, organic polymer materials with sufficient chemical and thermal stability are likely to be used as support films, such as polyimine, polytetrafluoroethylene, polybiathral 201249529 difluoroethylene, polyetherimine, polyetherketone , polyetheretherketone, polyethersulfone, polybenzimidazole, polyamine. The support film preferably has a pore size of less than 500 nm. It is especially preferred that they have a pore size of less than 100 nm, and very preferably less than 50 nm. The pore diameter of the support film is preferably smaller than the average diameter of the polymer particles. The thickness of the support film is preferably from 5 μm to 100 μm, more preferably from 20 μm to 80 μm, and very preferably from 30 μm to 60 μm. The polymer particles prepared by emulsion polymerization are preferably at least partially functionalized by the addition of a polyfunctional monomer in the polymerization. In this context, the polyfunctional monomers may be selected from the group consisting of compounds having at least two, preferably from 2 to 4, copolymerizable C=C double bonds, for example, two. Isopropenylbenzene, divinylbenzene, divinyl ether, divinyl sulfone, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, 1,2-poly Butadiene, anthracene, anthracene---phenyl-phenyleneimine, 2,4-anthracene-phenylene (maleimide), triallyl trimellitate, acrylates of the following substances Classes and mercapto acrylates: aliphatic amines, epoxides and polybasic are preferably two to four membered C2-C10 alcohols, such as polyethylene glycol, 1,2-propanediol, butanediol, a diol, polyethylene glycol having 2 to 20, preferably 2 to 8 oxyethylene units, neopentyl glycol, bisphenol A, glycerin, tri-propyl mercapto, neopentyl alcohol, sorbitol, and There are also aliphatic diols and unsaturated polyesters of polyhydric alcohols with maleic acid, fumaric acid, and/or itaconic acid. 19 201249529 The separation active layer of the nanofiltration membrane of the present invention preferably has at least one monolayer of polymer particles having an average particle diameter of &lt; 70 nm, preferably between 30 nm and 65 nm, More preferably between 40 nm and 50 nm. A preferred embodiment of the nanofiltration membrane of the present invention has a separation active layer having a thickness of from 0.1 μm to 20 μm, wherein a plurality of polymer particle layers are located on each other. The thickness of the separation active layer is preferably not more than the thickness of the support film. Another invention is a method for producing a nanofiltration membrane of the present invention, wherein a dispersion (latex) of polymer particles prepared by emulsion polymerization is applied to the support film, and a support film is formed on the support film. Polymer layer (separating the active layer). It has been determined that the dispersion used is substantially very monodisperse, i.e. according to dynamic light scattering, 95.4. /. The polymer particles are present in a size scale with a deviation of ± 7 nm. The method is preferably carried out continuously. The aqueous dispersion of shai preferably comprises 2 average diameter polymer particles having &lt; 70 nm, preferably between 30, and 65 nm, more preferably between 4 〇 nm and 50 nm and dried after polymerization The rubber content is at least 20%, preferably at least 25%, more preferably at least 30°/. Based on the total volume of the polymer. Based on the total volume of the polymer, a latex concentration of not more than 65% of the dry rubber content is also available for this production. 20 201249529 The dry rubber content is determined as follows: The dry rubber content is determined using a halogen humidity measuring instrument such as the Mettler Toledo Halogen Humidity Analyzer HG63. Here, a latex was dried at a temperature of 140 ° C and subjected to continuous weighing. When the weight loss is less than 1 mg/50 sec, the measurement is considered to have reached the end point. The dry rubber content after the polymerization is preferably not more than 65% based on the total volume of the polymer. Preferably, the latex having the polymer particles is applied to the support film by a nozzle. In a downstream step, the nanofiltration membrane formed in this manner is dried. It is conceivable for the nanofiltration membrane thus formed to be additionally crosslinked, wherein the polymer particles are attached to each other and/or their results are attached to the support membrane. Chemical (covalent and/or ionic) and also physical cross-linking modes are typically employed, initiated by electromagnetic (e.g., UV), thermal, and/or radioactive Korean shots. All conventional crosslinking aids can be used. As a result, the pore diameter is still further lowered and the filtration characteristics are improved. Another invention uses polymer particles prepared by emulsion polymerization for producing a nanofiltration membrane having an average particle diameter of &lt; 70 nm, preferably between 30 nm and 65 nm, more It is preferably between 40 nm and 50 nm. Another invention uses nanofiltration membranes for the food, chemical, and biochemical industries. This list is not limited. 21 201249529 [Embodiment] The present invention will be described in more detail by way of examples of use. EXAMPLES: Preparation of Polymer Particle Types and 2 Polymer particles were prepared using the following reactants. In Table 1, the formulation ingredients are based on 100 parts by weight of the monomer mixture. Monomer from butadiene from Germany (Lanxess Deutschland GmbH) (99% form, unstabilized) Azironitrile from Merck KgaA (99% form, with hydroquinone) Ether-stable) 3) Styrene (98% form) from KMF Laboratories of Chemie Handels GmbH 4) Trihydroxydecylpropane acrylate (96% form) from Aldrich; product No. 24684-0; (abbreviation: TMPTMA) 5) Mercaptopropionic acid via base group (97% from Arcos; abbreviation: HEMA) emulsifier 6) Deuterated resin acid (abbreviated as RS) - as Calculation of the free acid starting from the amount of Dresinate® 835 (Abieta Chemie GmbH; D-86358 Gersthofen) 22 201249529 The Dresinate® 835 batch used is characterized by its solids content and also with sodium salt, free An emulsifier component in the form of an acid, as well as a neutral form. The solid content is determined according to the instructions published by Maron, S. H.; Madow, BP; Borneman, E: "The effective equivalent weights of some rosin acids and soaps", Rubber Age, 1952, April, 71-72. The average value determined from the three aliquots of the Dresinate® 835 batch used was 71% solids by weight. The emulsifier fraction in the form of the sodium salt and in the form of the free acid is determined by titration analysis according to the method described below: Maron, S. H" Ulevitch, IN, Elder, Μ. E. "Fat And rosin acid, soap and mixtures thereof" (Fatty and Rosin Acids, Soaps, and Their Mixtures), Analytical Chemistry, Vol. 21, 6, 691-695. For this assay (in an example), 1.213 g

Dresinate® 835 (71% form) was dissolved in a mixture of 200 g of distilled water and 200 g of distilled isopropanol, an excess of sodium hydroxide solution (5 ml of 0.5 N NaOH) was added, and back-titrated with 0.5 N hydrochloric acid. The process of titration is monitored by pH measurement of the potentiometric method. The titration curve was evaluated as described in Analytical Chemistry, Vol. 21, 6, 691-695. 23 201249529 The average values obtained for the three aliquots of the Dresinate® 835 batch used are as follows: Total emulsifier content: Na salt: Free acid: 2.70 mmol/g at 2.42 mmol/g Dry t 0.28 mmol/g Dry $ by means of the molar mass (324 g/mol) of the Na salt of disproportionated rosin acid and the molar mass (302 g/mol) of the free disproportionated rosin acid, calculated using the Dresinate® 835 batch Weight fraction of Na salt, free acid and uncaptured fraction: Sodium salt of disproportionated resin acid: 78.4% by weight Free disproportionated resin acid: 8.5% by weight Uncaptured part (neutral) by weight 13.1% In the following formulation, the amount of Dresinate® 835 used for the polymerization was converted to the free acid (abbreviated as RA) and expressed as a weight fraction relative to the monomer of 100 parts by weight. In this transformation, the neutral body is not considered. To illustrate the conversion of the amount of disproportionated rosin acid (RA) shown in Table 1, based on the amount of Dresinate 835® used, 'attach the following Table 1: 24 201249529 Table 1:

Initial mass of Dresinate® 835 [g dry weight] r —' — - Calculated amount of disproportionated rosin acid (no neutral) [g dry weight] 0.25 0.20 0.5 0.41 1.0 0.82 1.5 1.22 2.0 1.63 2.5 2.04 3.0 2.45 3.5 2.86 4.0 3.26 4.5 3.67 4.75 3.87 5.0 4.08 7) Partially hydrogenated animal fatty acids - abbreviated as fa (from Edenor® HtiCT N from Cognis Oleo Chemicals) Emulor® HtiCT N batch emulsifier content and The weight average molecular weight is determined by titration analysis by the following methods: Maron, SH, Ulevitch, IN, Elder, Μ. E.: ''fat and rosin acid, soap and mixtures thereof' (Fatty and Rosin Acids, Soaps, and Their Mixtures), Analytical Chemistry » Vol. 21, 6, 691-695; Maron, SH; Madow, s 25 201249529 BP; Borneman, E.: “Efficient equal weight of some rosin acids and soaps” ( The effective equivalent weights of some rosin acids and soaps), Rubber Age, (1952), 71 71-2). In this titration (in one example), 1.5 g of Edenor® HTiCT N was dissolved in a mixture of 200 g of distilled water and 200 g of distilled isopropanol, 15 ml of excess NaOH (0.5 mol/1) was added, and back-titration was carried out using 〇·5 Μ hydrochloric acid. The average values found for the Edenor® HTiCT(R) batches of the three aliquots used are as follows: Total emulsifier content·· 3.637 mmol/g dry weight MoE Dong (free acid): 274.8 mg/mmol In the following formulation, the partially hydrogenated tallow fatty acid used (as commercially available) was expressed as "free acid == fa'. The amount required for the degree of neutralization reported in the setup table is based on the magnitude of the different components of the Dresinate® 835 and Edenor® HTiCT N batches determined by the Drip Analysis method. The degree of neutralization was set using potassium hydroxide. Chain Transfer Regulator 〖From Chevron Phillips Chemical Company (chevr〇n phillips

Chemical Company LP) (Sulfole® 120) Terephthalic thiol The polymer granules were prepared by emulsion polymerization in a 20 liter autoclave with a stirrer. For the polymerization batch, 4 3 kg of monomer having 0.34 26 201249529 g of 4_曱oxylate (Arcos Organics, product No. 1-2-2, 1〇〇〇, 99%) was used. In each case, the total emulsifier and total water stalk reported in the table were introduced into the da da (reduced the amount of water required to prepare the aqueous premix solution and the chloral peroxide solution). The following), together with the required amount of emulsifier and sodium hydroxide. The reaction mixture was adjusted at 15. (After the next, for each listed polymerization minus '5 〇% freshly prepared aqueous premixed solution (4% concentration) was bowed into the high pressure dad. The composition of the premixed solution was: 0.284 g ethylenediaminetetraacetic acid (Fluka, product number, 0.238 g iron (II) sulfate * 7H2 〇 (Riedd such as Haen, product number 12354) (not counting crystal water) W76gR〇ngalit c, formaldehyde-sodium sulfoxylate 2 hydrate (Merck-Schuchardt, product No. 8. 〇6455) (without crystallization water), and 0.874 g of disodium sulphate*12 h2 〇 (Acr〇s, product number 2〇652〇〇1〇) (not counting crystal water) In order to initiate the listed polymerization, 5 g of thin tank hydroperoxide is used for the type containing styrene and L7 g is used for the burning of hydroperoxide (Trig〇n for the type containing acrylonitrile) 〇x from Akz〇-Degussa) and emulsified in 200 ml of emulsifier solution prepared in reaction β. When the field reaches 30% conversion, the remaining 5% premixed solution is measured. 27 201249529 Borrow The temperature in the polymerization reaction is managed by setting the amount of the coolant and the temperature of the coolant. The temperature range is shown in the table below. When a polymerization conversion of more than 85% (typically 9〇% to 100%) is reached, by adding an aqueous solution of 2.35 g of diethylhydroxylamine (DEHA, Aldrich, product number 03620) The polymerization reaction is stopped. The volatile component of the volatile component is removed from the latex by subjecting it to steam distillation at atmospheric pressure. The polymer particles prepared in this manner are used in the present invention. Meter filtration film. Table 2 shows the formulation of the prepared polymer particles; the index used is as follows: diced dilute (unstable) 2) acrylonitrile from Germany's Merck KgaA (99%) Form, stabilized with hydroquinone monohydric ether) 3) Phenyl bromide (consistent with 1 to 150 ppm of 4-tert-butyl butyl) 2) Trihydroxymercaptopropane trimethacrylate (96% form, from Aldrich) 5) Hydroxyethyl methacrylate (97% form, from Arc〇s) 6) Amount of disproportionated resin acid calculated from the amount of Dresinates 835 used (abbreviated RA 7) Edenor from Oil Chemicals (Oleo Chemicals)

HtiCT N (abbreviated as FA) 28 201249529 8) The properties of the particles prepared by tertiary dodecyl mercaptan (Sulfol® 120 from Chevron Phillips) are listed in Table 3. 29 201249529 ^- Li [%] 006 ΙΛ6 als 繁 οοε bol

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Particle size [nm] in \〇VO 1 η ►γΗ 〇Bist 1 | 20.0 1 Acid value [mg KOH gel 1 1 in Expansion index 1/5 1 11.3 ! Gel content [% by weight] 00 〇\ ' sO ON latex pH (after monomer removal) 00 irj gold present ' &lt; (rO ^ 0, &gt; 28.8 28.3 polymer particle type - (S 201249529 Production of the invention with polymer particle type 1 and polymer particle type 2 The support lanthanide used in the nanofiltration membrane is a highly crosslinked polyimine. The membrane is coated with an aqueous dispersion of type 1 or 2 rubbery polymer particles by a bead coating method using a slit die. The film of the branch was transferred to the die at a speed of 2 m/min. The distance between the die and the support film was μιη. The wet film thickness of the latex layer was estimated to be 3 μm, thus giving The dry thickness of the separated active layer was about 10 μm. It was dried at atmospheric pressure for about 30 minutes at room temperature. A nanofiltration membrane type j (using type 1 polymer particles) and a nanofiltration membrane type 2 (using type) were produced. 2 polymer particles). In the case of the nanofiltration membrane type 2 of the present invention, The crosslinking of the polymer particles is additionally carried out after drying. The crosslinking agent used is hexamethylene diisocyanate (HDI). First, all the membranes are washed with propylene and then with n-hexane. 2% by weight of HDI in the alkane and 2% by weight of dioctyltin laurate were applied to the film. After a reaction time of 20 minutes at 25 ° C, the reaction solution was removed and the film was removed. Washing with acetone. Filtration, Characterization The filtration characteristics of the nanofiltration membrane of the present invention were measured in a different solvent using a polystyrene oligomer model system. The oligomer had a molecular weight of 230 g/mol. Between 11 〇〇g/mol. After passing a sufficiently large amount of permeate, the sample is taken from the retentate and permeate, and the corresponding oligomer concentration is determined by HPLC using HPLC. From each oligomerization The concentration of the generated substances makes it possible to determine their entrapment through the membrane and thus the molecular weight cut-off. 31 201249529 The filtration characteristics of the nanofiltration membrane type 1 of the present invention Table 4 shows the type 1 for the nanofiltration membrane of the present invention. The value of the polystyrene oligomer is retained, wherein the separation active layer is composed of type 1 polymer particles which are not additionally crosslinked. The solvent selected is acetone. Separation of the styrene oligomer occurs. The flow rate was determined to be 11 l/(m2h) at 25 ° C. Table 4: Molecular weight / g / mol Interception / % 236 21 295 38 395 56 495 67 595 74 685 81 795 83 895 87 995 90 Thus, in the test system defined herein, the nanofiltration membrane of the present invention has a cutoff of about 1000 g/mol because the cutoff measured here is 90%. This membrane is therefore suitable for use in nanofiltration. The filtration characteristics of the nanofiltration membrane type 2 of the present invention Table 5 contains values for the entrapped polystyrene oligomer of the nanofiltration membrane type 2 of the present invention, wherein the separation active layer is composed of the type 2 poly 32 201249529 In the case of particles, the particles are additionally crosslinked by 1,6-hexamethylene diisocyanate. Values for filtration were reported in three different solvents (acetone, tetrahydrofuran (thf), and stupid). The flow rate of 7 to 丨丨1/(m2 h) was measured at a temperature of 25 ° C and a pressure of 3 Torr. Table 5: Molecular Weight / g / mol Solvent: Toluene Interception /% Solvent: THF Retention /% Solvent: Acetone Interception /% 236 - 42 34 295 ------ 52 50 45 395 73 71 66 495 -~^ 82 79 76 595 88 85 84 _695 91 87 87 795 93 89 89 _895 95 89 91 995 96 90 92 1095 96 91 93 From the measurements shown here, it is obvious that the film is retained after cross-linking of the polymer particles. The system is located between 700 g/mol and 800 g/mol, which means that the ruthenium can be used for nano 谑. These data are only slightly dependent on the solvent chosen. The film of the present invention did not show any signs of dissolution in all solvents used. 33 201249529 [Simple description of the diagram] None [Key component symbol description] None 34

Claims (1)

201249529 VII. Patent application scope: 1. A nanofiltration membrane having a porous support membrane, characterized in that the surface of the support membrane is coated with emulsion polymerization and has a thickness of less than 70 nm, preferably 30 - 65 nm. More preferably, the polymer particles have an average particle diameter of between 40 and 50 nm. 2. The nanofiltration membrane of claim 1, wherein the support membrane is composed of an inorganic or organic material. 3. A nanofiltration membrane according to claim 2, characterized in that the pore size of the support membrane is less than 500 nm, preferably less than 100 nm and more preferably less than 50 nm. 4. The nanofiltration membrane of claim 3, wherein the pore size of the support membrane is less than the average particle diameter of the polymer particles. 5. The nanofiltration membrane of claim 4, wherein the thickness of the membrane is from 5 to 100 μm, preferably from 20 to 80 μm and very preferably from 30 μm to 60 μm. 6. The nanofiltration membrane of claim 5, wherein the polymer particles prepared by emulsion polymerization are rubbery. 7. The nanofiltration membrane of claim 6, wherein the rubbery polymer particles are based on a conjugated diene such as butadiene, isoprene, 2-chlorobutadiene and 2 , 3-dichlorobutadiene, vinyl acetate, styrene or its derivatives, 2-vinyl pyridine and 4-ethylene ratio, acrylonitrile, acrylamide, mercapto acrylamide, tetrafluoro Granules of ethylene, vinylidene fluoride, hexafluoropropylene, and hydroxyl-containing, epoxy, amine, carboxyl, and ketone compounds containing double bonds. 35 201249529 8. 9. 10. 11. The nanofiltration membrane of item 7 of the scope, characterized by Μ. The 5 particles have a temperature of -85 ° C to 150. 〇 is preferably -750C: iio °c, more preferably. c to &quot;〇〇c glass turn (Tg). The nanofiltration, film according to item 8 of the patent application, characterized in that the polymer particles prepared by the recording of the polymerization are at least partially crosslinked. A nanofiltration membrane according to item 9 of the patent scope, characterized in that the polymer particles prepared by emulsion polymerization are at least partially functionalized by the addition of a polyfunctional monomer in the polymerization reaction. For example, the application of the full-circle 1G item of nanometer hearing is characterized in that 'these township functional single systems are selected from the group consisting of: having at least two, preferably from 2 to 4 copolymerizable C= c double bond compound, for example, diisopropenylbenzene, divinylbenzene, divinyl ether, divinyl fluorene, diallyl phthalate, triallyl cyanurate, isocyanurate Allyl ester, 1,2-polybutadiene, N,N'-meta-phenyleneimine, 2,4-methylphenylene (maleimide), trimellitic acid Allyl esters, acrylates of the following materials, and mercapto acrylates, aliphatic amines, epoxides and polybasic are preferably two to four membered C2-C10 alcohols, such as ethylene glycol, propane-1 , 2-diol, butanediol, hexanediol, polyethylene glycol having 2 to 2, preferably 2 to 8 oxyethylene units, neopentyl glycol, bisphenol A, glycerol, trimethylol Propane, neopentyl alcohol, sorbitol, and also unsaturated polyesters of aliphatic diols and polyols with maleic acid, fumaric acid, and/or itaconic acid. 36 201249529 • In the Xiangdu film, the characteristics of the patent range: the knife weight loss is at least about 7〇%, more preferably, more: choose ί ΐ about 8〇%, more preferably 90% by weight, or even More preferably, it is at least about 98% by weight. 14. The nanometer (4) film characterized in that the ruthenium particles have a swelling index of less than 6 Å, (4), more preferably less than 4, at 23 ° C in the case. 15. The nano-paste film according to item 14 of the present invention, characterized in that the layer thickness of the non-pervious film has at least one monolayer of the polylayer, and the average particle size of the polymer mask is 70 nm, preferably Between 3 〇 nm and 65 (10), more preferably between 4 〇 nm and 50 nm (separating the active layer). 16. The nano-pass film according to claim 15 of the patent application, characterized in that the layer has a layer thickness of from ιμηη to 2 〇 from the active layer. 17. The nanofiltration membrane of claim 16, wherein the separation active layer has a thickness no greater than a thickness of the support film. And a method for producing a nanofiltration membrane having a pore support crucible according to any one of the above claims, characterized in that the dispersion of the polymer particles prepared by emulsion polymerization is fine. The support film is used, and a polymer layer (separation active layer) is formed on the support crucible. 37 18. 201249529 19. The method of claim 18, characterized in that the method is carried out continuously. 20. The method of claim 19, wherein the dispersion system is monodisperse. 21. The method of claim 20, characterized in that the dispersion comprises less than 70 nm, preferably between 30 nm and 60 nm, more preferably at 40 nm, based on the total volume of the polymer. The average diameter of the polymer particles between 50 nm has a dry rubber content after polymerization of at least 20%, preferably at least 25%, more preferably at least 30%. 22. The method of claim 21, wherein the dry rubber content after polymerization is not more than 65% based on the total volume of the polymer. 23. The method of claim 22, wherein the polymer particles are applied by a nozzle. 24. The method of claim 23, wherein the nanofiltration membrane is dried in a downstream step. 25. The method of claim 24, wherein the separation active layer of the nanofiltration membrane is additionally crosslinked. 26. Polymer particles prepared by emulsion polymerization and having an average particle size of less than 70 nm, preferably between 30 and 60 nm, more preferably between 40 and 50 nm, for production as in the scope of the above patent application The use of any of the nanofiltration membranes. 27. A nanofiltration membrane according to any one of the above claims, for use in the food, chemical or biochemical industries. 38 201249529 IV. Designated representative map: (1) The representative representative of the case is: (No). (2) A brief description of the symbol of the representative figure: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None