EP1368120A1 - Verfahren zur herstellung von gelförmigen kationenaustauschern - Google Patents

Verfahren zur herstellung von gelförmigen kationenaustauschern

Info

Publication number
EP1368120A1
EP1368120A1 EP02702299A EP02702299A EP1368120A1 EP 1368120 A1 EP1368120 A1 EP 1368120A1 EP 02702299 A EP02702299 A EP 02702299A EP 02702299 A EP02702299 A EP 02702299A EP 1368120 A1 EP1368120 A1 EP 1368120A1
Authority
EP
European Patent Office
Prior art keywords
weight
seed polymer
monomer mixture
seed
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02702299A
Other languages
German (de)
English (en)
French (fr)
Inventor
Wolfgang Podszun
Ulrich Schnegg
Reinhold Klipper
Claudia Schmid
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1368120A1 publication Critical patent/EP1368120A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/14—Purification of sugar juices using ion-exchange materials
    • C13B20/144—Purification of sugar juices using ion-exchange materials using only cationic ion-exchange material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters

Definitions

  • the invention relates to a method for producing gel-like cation exchangers with high stability and purity.
  • Cation exchangers can be obtained by functionalizing crosslinked styrene bead polymers.
  • seed a monodisperse polymer (“seed”) is swollen in the monomer and this is then polymerized.
  • EP 0 describes 098 130 B1, the production of gel-like styrene polymers by a seed / feed process, in which the feed is added under polymerizing conditions to a seed crosslinked with 0.1-3% by weight divinylbenzene
  • EP-0 101 943 B1 discloses one Seed / feed process in which several feeds with different compositions are added to the seed in succession under polymerizing conditions
  • US 5 068 255 describes a seed / feed process in which a first monomer mixture up to a conversion of 10 to 80 % polymerized and then mixed with a second monomer mixture essentially free of radical initiator as feed under polymerizing conditions nt is ..
  • EP-A 1 000 659 describes the production of acrylonitrile-containing copolymers by a seed / feed process and their functionalization with sulfuric acid to form cation exchangers.
  • An advantage of EP-A 1 000 659 is that the acrylonitrile-containing copolymers can be functionalized without swelling agents.
  • the nitrile groups are saponified to carboxylic acid groups and sometimes also to amide groups.
  • the presence of amide groups in the cation exchanger is disadvantageous in several ways: the amide groups have no exchange function and thus reduce the capacity of the exchanger.
  • the amide groups can release traces of ammonia or ammonium compounds during use, which can be disadvantageous for some applications.
  • handling acrylonitrile requires considerable technical effort because of its toxic potential.
  • Cation exchange beads can break down when diluted after sulfonation by the osmotic forces that occur.
  • the exchangers in the form of pearls must retain their habit and must not be partially or completely degraded or broken down into fragments during use. Fragments and pearl polymer fragments can get into the solutions to be cleaned during cleaning and contaminate them themselves.
  • the presence of damaged bead polymers is essential for the functioning of those used in column processes
  • Cation exchanger itself unfavorable. Splinters lead to an increased pressure loss in the column system and thus reduce the throughput of liquid to be cleaned through the column.
  • the object of the present invention is to provide a simple, robust method for producing gel-type cation exchangers with high stability and purity.
  • Purity in the sense of the present invention primarily means that the cation exchangers do not bleed out. The bleeding manifests itself in an increase in the conductivity of water treated with the ion exchanger.
  • the present invention relates to a process for the preparation of gel-like cation exchangers with high stability and purity, characterized in that
  • a) forms a suspension of seed polymer in a continuous aqueous phase, b) allows the seed polymer to swell in an activated monomer mixture, c) polymerizes the activated monomer mixture in the seed polymer, d) and functionalizes the copolymer formed by sulfonation in the absence of a swelling agent with the proviso .
  • the seed polymer is a spherical polymer which is composed of vinyl monomers and crosslinking agents.
  • Preferred compounds of this type include aromatic monomers such as, for example, vinyl and vinylidene derivatives of benzene and naphthalene, such as, for example, vinyl naphthalene, vinyl toluene, ethylstyrene, ⁇ -methylstyrene, chlorostyrenes, styrene, and non-aromatic vinyl and vinylidene compounds, such as, for example, acrylic acid, methacrylic acid, acrylic acid-Cj-Cg-alkyl ester, methacrylic acid-Ci-Cg-alkyl- ester, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride or vinyl acetate.
  • the crosslinking of the seed polymer is based on a proportion of polymerized compounds which contain two or more, preferably two to four, free-radically polymerizable double bonds per molecule. Examples include:
  • Divinylbenzene is preferred.
  • the proportion of compounds polymerized in the seed polymer, in particular divinylbenzene is preferably 0.5 to 6% by weight, particularly preferably 0.8 to 5% by weight.
  • the particle size of the seed polymer is 5 to 500 ⁇ m, preferably 20 to 400 ⁇ m, particularly preferably 100 to 300 ⁇ m.
  • the shape of the particle size distribution curve must correspond to that of the desired cation exchanger. to
  • Production of a narrowly distributed or monodisperse ion exchanger accordingly uses a narrowly distributed or monodisperse seed polymer.
  • a monodisperse seed polymer is used.
  • Monodisperse in the context of the present invention means that the quotient of the 90% value and the 10% value of the volume distribution function is less than 2, preferably less than 1.5, particularly preferably less than 1.25.
  • the seed polymer is microencapsulated.
  • all materials known for this purpose can be used, in particular polyesters, natural and synthetic polyamides, polyurethanes, polyureas.
  • Gelatin is particularly suitable as a natural polyamide. This is used in particular as a coacervate or complex coacervate. Under gelatin-containing complex coacervates in the sense of the present
  • Suitable synthetic polyelectrolytes are copolymers with built-in units of, for example, maleic acid, acrylic acid, methacrylic acid, acrylamide and methacrylamide.
  • Capsules containing gelatin can be coated with conventional hardening agents such as e.g. Formaldehyde or glutardialdehyde can be cured.
  • the preparation of spherical polymers, suitable as seed polymers, is described in detail in EP-0 046 535 B1, for example.
  • the microencapsulation with gelatine! Complex coacervate is preferred.
  • the seed polymer is suspended in an aqueous phase, the ratio of polymer and water being between 2: 1 and 1:20. Preference is 1: 2 to 1:10.
  • the suspension can be carried out, for example, using a normal stirrer, using low to medium shear forces. In laboratory reactors with 4 1 volumes, for example, 80 to 300 rpm (revolutions per minute) are used.
  • activated monomer mixture of vinylaromatic, divinylbenzene and methyl acrylate is added to the suspended seed polymer, the monomer mixture swelling into the seed polymer.
  • activated means that the monomer mixture contains a radical initiator.
  • the monomer mixture can be added both at a low temperature and at for example at room temperature and at an elevated temperature at which the radical initiator used is active.
  • the rate of addition is not critical at low temperature.
  • the monomer mixture is metered in over a period of 0.5 to 10 hours. It is possible to vary the rate of addition and / or the composition of the monomer mixture during the addition.
  • vinylaromatic means a free-radically polymerizable aromatic compound.
  • examples include styrene, vinyl naphthalene, vinyl toluene, ethyl styrene, ⁇ -methyl styrene and chlorostyrenes. Styrene is preferred.
  • the proportion of vinyl aromatics in the monomer mixture is 71 to 95.95% by weight, preferably 79.2 to 92.9% by weight.
  • the proportion of divinylbenzene in the monomer mixture is 3 to 20% by weight, preferably 5 to 14% by weight, based on the monomer mixture.
  • Methyl acrylate is used in amounts of 1 to 8% by weight, preferably 2 to 6% by weight, based on the monomer mixture.
  • Free radical initiators suitable for the process according to the invention are, for example, azo compounds, such as, for example, 2,2'-azobis (isobutyronitrile) or 2,2'-azobis (2-methylisobutyronitrile), or peroxy compounds, such as dibenzoyl peroxide, dialauryl peroxide, bis (p-chlorobenzoyl peroxide ), Dicyclohexyl peroxydicarbonate, tert.-
  • azo compounds such as, for example, 2,2'-azobis (isobutyronitrile) or 2,2'-azobis (2-methylisobutyronitrile)
  • peroxy compounds such as dibenzoyl peroxide, dialauryl peroxide, bis (p-chlorobenzoyl peroxide ), Dicyclohexyl peroxydicarbonate, tert.-
  • Butyl peroctoate 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane or tert-amylperoxy-2-ethylhexane.
  • the radical initiators are generally used in amounts of 0.05 to 1% by weight, preferably 0.1 to 0.8% by weight, based on the monomer mixture.
  • the ratio of seed polymer to the added monomer mixture is generally 1: 0.5 to 1:12, preferably 1: 1 to 1: 8, particularly preferably 1: 1.5 to 1: 6.
  • the added Mixture swells in the seed polymer.
  • feed The maximum amount of the monomer mixture referred to as "feed", which is completely absorbed by the seed, depends to a large extent on the crosslinker content of the seed. Given the particle size of the seed polymer, the seed / feed ratio can be used to set the particle size of the resulting copolymer or ion exchanger.
  • the swollen seed polymer is polymerized to the copolymer in the presence of one or more protective colloids and, if appropriate, a buffer system.
  • Protective colloids for the purposes of the present invention are natural or synthetic water-soluble polymers, such as, for example, gelatin, starch, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid or copolymers of (meth) acrylic acid or (meth) acrylic acid esters.
  • Cellulose derivatives, in particular cellulose esters or cellulose ethers such as carboxymethyl cellulose or hydroxyethyl cellulose, are also very suitable. Cellulose derivatives are preferred as a protective colloid.
  • the amount of protective colloids used is generally 0.05 to 1% by weight, based on the water phase, preferably 0.1 to
  • the polymerization is carried out in the presence of a buffer system.
  • Buffer systems are preferred which adjust the pH of the water phase at the beginning of the polymerization to a value between 14 and 6, preferably between 13 and 9.
  • slit colloids with carboxylic acid groups are wholly or partly present as salts. In this way, the effect of the protective colloids is favorably influenced.
  • Particularly preferred buffer systems within the scope of the present invention contain phosphate or borate salts.
  • An inhibitor can optionally be added to the aqueous phase.
  • inorganic and organic substances are suitable as inhibitors.
  • inorganic inhibitors are nitrogen compounds such as hydroxylamine, hydrazine, sodium nitrite or potassium nitrite.
  • organic inhibitors are phenolic compounds such as
  • Hydroquinone hydroquinone monomethyl ether, resorcinol, pyrocatechol, tert-butyl pyrocatechol, condensation products from phenols with aldehydes.
  • Other organic inhibitors are nitrogen-containing compounds such as diethyl hydroxylamine or isopropyl hydroxylamine.
  • the concentration of the inhibitor is 5-1000, preferably 10-500, particularly preferably 20-250 ppm, based on the aqueous phase.
  • the ratio of organic phase to water phase in the polymerization of the swollen seeds is 1: 0.6 to 1:10, preferably 1: 1 to 1: 6.
  • the temperature during the polymerization of the swollen seed polymer depends on the decomposition temperature of the initiator used. It is generally between 50 to 150 ° C, preferably between 60 and 130 ° C.
  • the polymerisation takes 1 to a few hours. It has proven useful to use a temperature program in which the polymerization is started at a low temperature, for example 60 ° C., and the reaction temperature is increased as the polymerization conversion progresses. In this way, for example, the requirement for a safe course of the reaction and a high polymerization conversion can be met very well.
  • the method according to the invention is preferably carried out in a process-controlled system.
  • the copolymer can be isolated using customary methods, for example by filtration or decanting and, if appropriate, dried after one or more washes and sieved if desired.
  • the copolymers are converted to the cation exchanger by sulfonation.
  • Suitable sulfonating agents are sulfuric acid, sulfur trioxide and chlorosulfonic acid. Sulfuric acid is preferred with a concentration of 90 to 100%, particularly preferably from 92 to 98%.
  • the temperature in the sulfonation is generally from 50 to 200 ° C., preferably from 90 to 150 ° C.
  • copolymers according to the invention can be sulfonated without the addition of swelling agents (such as chlorobenzene, dichloropropane or dichloroethane) and thereby deliver homogeneous sulfonation products.
  • swelling agents such as chlorobenzene, dichloropropane or dichloroethane
  • reaction mixture is stirred.
  • stirrers such as blade, anchor, grid or turbine stirrers can be used.
  • the sulfonation takes place according to the so-called “semi-batch process”.
  • the copolymer is metered into the temperature-controlled sulfuric acid. It is particularly advantageous to do this in portions.
  • reaction mixture of sulfonation product and residual acid is cooled to room temperature and first diluted with decreasing concentrations of sulfuric acids and then with water.
  • the cation exchanger obtainable according to the invention can be treated in the H form for cleaning with deionized water at temperatures of 70-145 ° C., preferably 105-130 ° C.
  • the present invention therefore also relates to the monodisperse gel-like cation exchangers obtainable by
  • the cation exchangers produced according to the invention from the acid form into the sodium form.
  • This transfer is carried out, for example, with sodium hydroxide solution at a concentration of 10-60%, preferably 40-50%.
  • the cation exchangers can be treated with deionized water or aqueous salt solutions, for example with sodium chloride or sodium sulfate solutions, for further purification. It was found that the treatment at 70-150 ° C., preferably 120-135 ° C., is particularly effective and does not reduce the capacity of the cation exchanger.
  • the cation exchangers obtainable by the process according to the invention are notable for particularly high stability and purity. Even after prolonged use and repeated regeneration, they show no defects in the ion exchange balls and no bleeding (leaching) of the exchanger.
  • cation exchangers Because of their high purity and the low leaching behavior that they entail, there are a large number of different types of cation exchangers according to the invention. different applications. They can be used, for example, in drinking water treatment, in the production of ultrapure water (necessary for microchip production for the computer industry), for the chromatographic separation of sugars, especially glucose and fructose, or as catalysts for various chemical reactions (such as in bisphenol A production
  • Phenol and acetone are used.
  • the cation exchangers perform their intended functions without releasing contaminants that may arise from their manufacture or that arise from polymer degradation during use.
  • Water is noticeable in that the conductivity and / or the content of organic carbon (TOC content) in the water is / are increased.
  • the present invention therefore also relates to processes for the production of microchips, for bisphenol A synthesis, for the production of ultrapure water or for the separation of sugar, in particular glucose and fructose, characterized in that the cation exchangers according to the invention are used during these processes.
  • 1,960 ml of deionized water are placed in a 4 1 glass reactor.
  • 630 g of a microencapsulated mixture of 1.0% by weight of divinylbenzene, 0.6% by weight of ethylstyrene (used as a commercially available mixture of divinylbenzene and ethylstyrene with 63% of divinylbenzene), 0.5% by weight of tert-butyl peroxy are incorporated therein -2-ethyl hexanoate and 97.9% by weight of styrene, the microcapsule consisting of a formaldehyde-hardened complex coacervate of gelatin and an acrylamide / acrylic acid copolymer.
  • the average particle size is 231 ⁇ m.
  • a solution of 2.4 g of gelatin, 4 g of sodium hydrogenphosphate dodecahydrate and 100 mg of resorcinol in 80 ml of deionized water is added to the mixture, which is slowly stirred and polymerized at 75 ° C. for 10 hours while stirring. Polymerization is then carried out by increasing the temperature to 95.degree. The approach is about one
  • Methyl acrylate, 85.9 g of divinylbenzene (80.6% by weight), 3.3 g of tert-butyl peroxy-2-ethylhexanoate and 2.3 g of tert-butyl peroxybenzoate were added.
  • the mixture is stirred for 60 min at room temperature, the gas space being flushed with nitrogen.
  • a solution of 2.4 g of methylhydroxyethyl cellulose in 120 g of deionized water is then added.
  • the batch is then heated to 63 ° C. and left at this temperature for 11 hours, then the batch is placed in an autoclave transferred and heated to 130 ° C for 3 hours.
  • the batch is then heated to 63 ° C. and left at this temperature for 11 hours, after which the batch is transferred to an autoclave and heated to 130 ° C. for 3 hours. After cooling, the mixture is washed thoroughly over a 40 ⁇ m sieve with deionized water and then dried in a drying cabinet at 80 ° C. for 18 hours. 1186 g of a spherical copolymer with a particle size of 420 ⁇ m are obtained.
  • the batch is then heated to 63 ° C. and left at this temperature for 11 hours, then the batch is transferred to an autoclave and heated to 130 ° C. for 3 hours. After cooling, the mixture is washed thoroughly over a 40 ⁇ m sieve with deionized water and then dried in a drying cabinet at 80 ° C. for 18 hours. 1186 g of a spherical copolymer with a particle size of 420 ⁇ m are obtained.
  • a 4 l glass reactor is initially charged with 1989.6 g of deionized water, 1.9 g of methylhydroxyethyl cellulose and 8.5 g of sodium hydrogenphosphate dodecahydrate.
  • 300 rpm repetitions per minute
  • a mixture of 712.8 g of styrene, 37.2 g of divinylbenzene (S0.6% by weight) and 5.55 g of dibenzoyl peroxide (75% by weight) was metered in. It is polymerized for 6 hours at 66 ° C, 15 minutes. the heating time, the gas space is flushed with nitrogen, and then polymerized at 95 ° C., then cooled.
  • a dispersant solution consisting of 497.4 g of deionized water, 0.48 g of methylhydroxyethyl cellulose, 2.13 g of sodium hydrogenphosphate dodecahydrate and 0.25 g of resorcinol is added. After a further hour at 50 ° C., the polymerization is carried out at 66 ° C. for 6 hours and the polymerization is carried out at 95 ° C. for 4 hours. After cooling, the batch is thoroughly washed with deionized water on a 315 ⁇ m sieve and dried in a drying cabinet overnight. The yield in the target size range of 315-630 ⁇ m is 1189.1 g of spherical copolymer.
  • 162 ml of the cation exchanger - H form are transferred to a column with a glass frit. 600 g of a sodium hydroxide solution (4% by weight) are rapidly dripped through. Then slowly, then faster, deionized water is allowed to drip through. Finally, it is backwashed with deionized water from below so that the fine fraction is classified.
  • the yield of cation exchanger in the Na form is 150 ml.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Catalysts (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Graft Or Block Polymers (AREA)
EP02702299A 2001-02-05 2002-01-23 Verfahren zur herstellung von gelförmigen kationenaustauschern Withdrawn EP1368120A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10105103A DE10105103A1 (de) 2001-02-05 2001-02-05 Verfahren zur Herstellung von gelförmigen Kationenaustauschern
DE10105103 2001-02-05
PCT/EP2002/000612 WO2002062472A1 (de) 2001-02-05 2002-01-23 Verfahren zur herstellung von gelförmigen kationenaustauschern

Publications (1)

Publication Number Publication Date
EP1368120A1 true EP1368120A1 (de) 2003-12-10

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ID=7672877

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02702299A Withdrawn EP1368120A1 (de) 2001-02-05 2002-01-23 Verfahren zur herstellung von gelförmigen kationenaustauschern

Country Status (10)

Country Link
US (1) US20020153323A1 (zh)
EP (1) EP1368120A1 (zh)
JP (1) JP2004518016A (zh)
CN (1) CN1231509C (zh)
DE (1) DE10105103A1 (zh)
HU (1) HUP0302855A2 (zh)
MX (1) MXPA03006961A (zh)
RU (1) RU2003127386A (zh)
UA (1) UA74050C2 (zh)
WO (1) WO2002062472A1 (zh)

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DE10122896A1 (de) * 2001-05-11 2002-11-14 Bayer Ag Verfahren zur Herstellung von monodispersen gelförmigen Kationenaustauschern
US6750259B2 (en) * 2002-07-08 2004-06-15 Bayer Aktiengesellschaft Process for preparing gel-type cation exchangers
DE10237601A1 (de) * 2002-08-16 2004-02-26 Bayer Ag Verfahren zur Herstellung von monodispersen gelförmigen Ionenaustauschern
DE102007060790A1 (de) * 2007-12-18 2009-06-25 Lanxess Deutschland Gmbh Verfahren zur Herstellung von Kationenaustauschern
JP2011098301A (ja) * 2009-11-06 2011-05-19 Mitsubishi Chemicals Corp カチオン交換樹脂及びビスフェノール化合物の製造方法
WO2016137787A1 (en) * 2015-02-27 2016-09-01 Rohm And Haas Company Chromatographic separation of saccharides using cation exchange resin beads with rough outer surface
WO2016137786A1 (en) * 2015-02-27 2016-09-01 Dow Global Technologies Llc Chromatographic separation of saccharides using whole cracked beads of gel-type strong acid exchange resin

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Also Published As

Publication number Publication date
MXPA03006961A (es) 2004-05-05
DE10105103A1 (de) 2002-08-08
UA74050C2 (en) 2005-10-17
CN1496282A (zh) 2004-05-12
WO2002062472A1 (de) 2002-08-15
HUP0302855A2 (hu) 2004-04-28
US20020153323A1 (en) 2002-10-24
JP2004518016A (ja) 2004-06-17
CN1231509C (zh) 2005-12-14
RU2003127386A (ru) 2005-03-27

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