Ceskoslovenska Akademie Ved

Other

Boehringer Mannheim Gmbh

Akademia Nauk Sssr

Ceskoslovenska Akademive Ved and Akademia Nauk Sssr

Tschechoslowakische Academie Der Wissenschaften

Frantisek Svec

Jaroslav Kalal

Boris G Belenkii

Jiri Coupek

Jaroslav Drobnik

Miroslav Bleha

Karel Bouchal

Tatiana B Tennikova

Eva Zurkova

Hans-Georg Batz

Jan Peska

Manfred Baier

Milan Benes

Svatopluk Pokorny

Vladimir Saudek

Jiri Labsky

Marie Metalova

Paul Tanswell

Arnold Aramovich Adamian

Jaromir Lukas

Bohumil Bednar

Jaromir Zachoval

Jiri Petr

Zdenek Pelcbauer

Michail I Kuzin

Daniel Horak

Klara Z Gumargalieva

Jurij V Moiseiev

Zedenek Plichta

Jiri Lenfeld

A method for preparation of macroporous polymeric membranes consisting in placing a mixture of monomers and a radical initiator, dissolved in a porogenic inert organic solvent selected from the group comprising alcohols, estes of carboxylic acids, ketones, and their mixtures, into a space of an adapted shape formed by two temperature-controlled plates and a distance insert having the thickness corresponding to the required thickness of membrane and heating up to 80.degree. C. for 24 hours at utmost in order to carry out the radical polymerization. Azo-bis-isobutyronitrile is advantageously used as an initiator in the amount 0.05-2 wt. % related to monomers in the polymerization mixture. Cyclohexanol or its mixture containing up to 20 vol. % dodecanol are advantageously used as a porogenic solvent in the amount 40-60 vol. % in the polymerization batch. Also included is the method of application of macroporous membranes, where a sector made from the membrane is placed on a base fixing its position and enabling the outlet of liquid passing through the membrane, which base create a wall of a chamber. The chamber is filled with a solution of polymer or polymer mixture, the solution passes through the membrane under pressure up to 1 MPa, the polymer or polymers are sorbed in the membrane, and then a solvent with properties changing according to the purposeful program is introduced into the chamber and individual components of the separated mixture are eluted and detected and/or collected.

Macroporous polymeric membranes for the separation of polymers and a

An object of the invention are macroporous polymeric membranes, suitable above all for the separation of polymers, which consists of the copolymer of a monovinyl monomer, selected from the group comprising acrylates, methacrylates, vinylpyridine, N-vinylpyrrolidone, vinyl acetate, and hydroxystyrene, with a divinyl monomer, selected from the group comprising alkylene and hydroxyalkylene diacrylates and dimethacrylates, divinylbenzene, and divinylpyridine, at the ratio of monomers of both types ranging from 5:95 to 95:5 wt. %. The membranes are formed from polymeric globular entities which have the size 0.05 to 0.5 .mu.m and are interconnected by covalent bonds, whereas communicating voids--pores occur between the globuli. The total thickness of membranes is 0.2 to 15 mm. and their specific surface area, which is measurable also in the dry state, may attain 400 m.sup.2 /g. Glycidyl methacrylate is advantageously used as the monovinyl monomer in the amount 5-80 vol. % related to the total volume of monomers. Ethylene dimethacrylate is advantageously used in the amount 20-95 vol. % related to the volume of monomers as the divinyl monomer. The membranes contain on their inner surface covalently bound allyl, hydroxyl, amine, sulfonate, hydrogensulfonate, thiol, and/or alkyl groups containing up to 18 carbon atoms and may be reinforced in their whole cross-section with an insert. Another object of the invention is the method for preparation of macroporous polymeric membranes consisting in placing a mixture of monomers and a radical initiator, dissolved in a porogenic inert organic solvent selected from the group comprising alcohols, esters of carboxylic acids, ketones, and their mixtures, into a space of an adapted shape formed by two temperature-controlled plates and a distance insert having the thickness corresponding to the required thickness of membrane and heating up to 80.degree. C. for 24 hours at utmost in order to carry out the radical polymerization. Azo-bis-isobutyronitrile is advantageously used as an initiator in the amount 0.05-2 wt. % related to monomers in the polymerization mixture. Cyclohexanol or its mixture containing up to 20 vol. % dodecanol are advantageously used as a porogenic solvent in the amount 40-60 vol. % in the polymerization batch. Further object of the invention is the method of application of macroporous membranes, where a sector made from the membrane is placed on a base fixing its position and enabling the outlet of liquid passing through the membrane, which base create a wall of a chamber. The chamber is filled with a solution of polymer or polymer mixture, the solution passes through the membrane under pressure up to 1 MPa, the polymer or polymers are sorbed in the membrane, and then a solvent with properties changing according to the purposeful program is introduced into the chamber and individual components of the separated mixture are eluted and detected and/or collected. The properties of solvent changing according to the program may be pH, ionic strength, temperature, or concentration of an organic solvent miscible with water.

An object of the invention are macroporous polymeric membranes, suitable above all for the separation of polymers, which consist of the copolymer of a monovinyl monomer, selected from the group comprising acrylates, methacrylates, vinylpyridine, N-vinylpyrrolidone, vinyl acetate, and hydroxystyrene, with a divinyl monomer, selected from the group comprising alkylene and hydroxyalkylene diacrylates and dimethacrylates, divinylbenzene, and divinylpyridine, at the ratio of monomers of both types ranging from 5:95 to 95:5 wt.%. The membranes are formed from polymeric globular entities which have the size 0.05 to 0.05 .mu.m and are interconnected by covalent bonds, whereas communicating voids - pores occur between the globuli. The total thickness of membranes is 0.2 to 15 mm and their specific surface area, which is measurable also in the dry state, may attain 400 m.sup.2 /g. Glycidyl methacrylate is advantageously used as the monovinyl monomer in the amount 5-80 vol.% related to the total volume of monomers. Ethylene dimethacrylate is advantageously used in the amount 20-95 vol.% related to the volume of monomers as the divinyl monomer. The membranes contain on their inner surface covalently bound allyl, hydroxyl, amine, sulfonate, hydrogensulfonate, thiol, and/or alkyl groups containing up to 18 carbon atoms and may be reinforced in their whole cross-section with an insert.

The invention pertains to a method for the production of bead dextran materials for gel chromatography. The subject of the invention is a method for the production of bead dextran materials for gel chromatography, wherein dextran is, before or during the suspension process or in both stages, subjected to reduction in an alkaline solution, advantageously by the action of sodium borohydride, whereas the density of crosslinking is controlled above all by variation of the concentration of the initial dextran solution and the resulting gel may be optionally subjected to the additional crosslinking in a separate subsequent operation. The procedure according to the invention provides the product of higher quality with a lower content of carboxylic groups and substantially facilitates the preparation of gels with a very high and a very low crosslink density.

Method for the production of bead dextran materials for gel

The invention pertains to X-ray contrast spherical hydrogel particles based on polymers and copolymers of acrylates and methacrylates and to a method of their preparation. The subject of this invention are X-ray contrast spherical hydrogel particles based on polymers and copolymers of acrylates and methacrylates characterized by the particles of spherical form with diameter 0.2 to 2 mm, which strongly swell in water and contain a derivative of amino-triiodobenzoic acid of general formula I, ##STR1## where R.sup.1,R.sup.2 is hydrogen, acyl group with 1 to 3 carbon atoms or alkyl with 1 to 10 carbon atoms and X is halogen, --OH or --NH(CH.sub.2).sub.n NH.sub.2, where n=1-6, covalently bonded to the polymer skeleton. A method for preparation of X-ray contrast hydrogel particles according to the invention in which hydrogel particles, containing hydroxyl or epoxide groups localized on side chains of the polymer skeleton, are allowed to swell in an excess of a solvent chosen from the group comprising dioxane, dimethylacetamide, dimethylformamide, tetrahydrofuran and dimethylsulfoxide, which contains the dissolved derivative of amino-triiodobenzoic acid of the general formula I, optionally together with a compound reacting with hydrogen halogenide formed, which is selected, for example, from the group comprising tertiary amines, the dispersion is heated to 100.degree. C. at utmost and allowed to react for 150 hours at utmost, the solid phase is separated and freed of soluble substances by washing. The procedure according to the invention provides spherical hydrogels with X-ray contrast properties without changing their other properties substantial for application in medical practice.

X-ray contrast spherical hydrogel particles based on polymer and

Hydrophilic latex particles consisting of a homo- or co-polymer of monomers which are sparingly soluble in water, which hydrophilic latex particles can be prepared by emulsion polymerization in the presence of a water-soluble, radical-forming initiator but without an addition of an emulsifier, stabilizer or wetting agent. A process for the preparation of these hydrophilic latex particles, wherein a monomer which is sparingly soluble in water or several monomers which are sparingly soluble in water are dispersed in water and, with the exclusion of oxygen, for example in an inert atmosphere, are homo- or co-polymerized by emulsion polymerization in the presence of a water-soluble, radical-forming initiator but without any addition of an emulsifier, stabilizer or wetting agent. A diagnostic agent containing these hydrophilic latex particles as carrier and biologically and/or immunologically active substances covalently bound to this carrier either directly or via a coupling agent as a bridge.

Hydrophilic latex particles and use thereof

The invention relates to the polar polymeric sorbent applicable in gas and liquid chromatography, which is based on glycidyl esters. The sorbent is formed by the macroporous copolymer containing 3-70% of polymerized monomeric units with epoxy groups, e.g. glycidyl methacrylate or glycidyl acrylate units, and 97-30% of a crosslinking agent, e.g. alkylene dimethacrylate, alkylene diacrylate, hydroxyalkylene dimethacrylate, hydroxyalkylene diacrylate (alkylene containing 1-6 C atoms), or divinylbenzene. The sorbent may further contain up to 30% of polymerized monomeric units containing nitrile groups, e.g. acrylonitrile and methacrylonitrile units. The polarity of sorbent can be further modified, according to the invention, by the reaction with various nucleophilic agents, e.g. water, alcohols, carboxylic acids and their derivatives, ammonia, amines, thioalcohols, acrylonitrile. The sorbent is thermally and mechanically stable and was used for the gas-chromatographic and liquid-chromatographic separation of complex mixtures of compounds. Its polarity was expressed in terms of modified Rohrschneider indices.

Polar polymeric sorbent based on glycidyl esters for gas and liquid

The invention relates to a negative electron resist for application in electron lithography. It consists of an organic copolymer formed by copolymerization of butadiene or isoprene with glycidyl acrylate or glycidyl methacrylate. The resist exhibits the high sensitivity to irradiation by electrons and, at the same time, a good adhesion to the base and a resistance towards common etching agents. The copolymer is advantageously prepared by radical polymerization and a high purity of the product does not require further purification. The electron resist manufactured in this way has the long-term workability.

Electron resist

The invention relates to a solid insoluble carrier which is activated for bonding of nucleophilic groups and to a method of its preparation. The carrier contains active groups --O.CO.O.R, where R is the residue selected from the group comprising nitrophenyl, dinitrophenyl, trichlorophenyl, pentachlorophenyl, N-succinimidyl, N-phthalimidyl, and 8-quinolinyl. Active groups are bonded to polysaccharides, phenol-formaldehyde resins, polyacrylates, or polyacrylamides. The invention further relates to a method for preparation of the polymeric carrier, which consists in treatment of polymers carrying hydroxyl functions and selected from the group comprising polysaccharides, phenol-formaldehyde resins, polyacrylates, and polyacrylamides, with esters of chloroformic acid which contain the above mentioned active groups.

Activated solid carrier and a method of its preparation

Three-dimensional polymeric material in the form of spherical particles of diameter .ltoreq.3 mm and containing up to 40% of free aldehyde groups which exhibits a measurable specific surface area is prepared by copolymerization of an aldehyde monomer R.sub.1 CH.dbd.C(CH.dbd.O)R.sub.2, where R.sub.1 is H, C.sub.1-5 alkyl, aryl or furyl and R.sub.2 is H, C.sub.1-5 alkyl, halogen, CN, phenyl or furyl, with a crosslinking agent in the aqueous dispersion phase. The dispersion contains 1 - 25% of a component reducing the monomer solubility in water, which is either an inorganic salt of alkali metal or alkaline earth metal or a water-soluble alcohol. The crosslinking agent used as comonomer is divinylbenzene, diester CH.sub.2 .dbd.C(R.sub.1)COOR.sub.2 OCOC(R.sub.1).dbd.CH.sub.2 (R.sub.1 .dbd. H, C.sub.1-10 alkyl or halogen; R.sub.2 .dbd. C.sub.1-10 alkylene or hydroxyalkylene), or diamide CH.sub.2 .dbd.C(R.sub.1)CONHR.sub.2 NHCOC(R.sub.1).dbd.CH.sub.2 (R.sub.1 .dbd. H, C.sub.1-10 alkyl or halogen; R.sub.2 .dbd. C.sub.1-10 alkylene or phenylene). The material may be used in continuous column processes, e.g. in catalysis of organic syntheses, separation of amines, and immobilization of compounds which contain primary amino groups.

Polymeric material containing aldehyde groups and the method of its

The invention relates to polymeric materials containing variable amounts of aldehyde groups and comprising the chain units ##STR1## where R.sup.1, R.sup.2 and R.sup.3 are H, C.sub.1 - C.sub.5 alkyl, aryl, furyl, halogen, nitrile group or hydroxyl and R.sup.4 is C.sub.1 - C.sub.20 alkylene, arylene, --COO(CH.sub.2).sub.n --, --O--(CH.sub.2).sub.n --, --COO(CH.sub.2).sub.n CH(OH)CH.sub.2 OCO(CH.sub.2).sub.m -- or --(CH.sub.2).sub.n OCOR.sup.5 COO(CH.sub.2).sub.m -- (n and m are integers 0 - 20 and R.sup.5 is the single bond, C.sub.1 - C.sub.20 alkylene or hydroxyalkylene or arylene). The material may be in the form of globules with a measurable specific surface area and is suitable for bonding of biologically active compounds containing primary amino groups or other amines to produce polymeric chelating agents. The invention further relates to the method for preparation the above materials which consists in treatment of the polymeric materials comprising units of the general formula ##STR2## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the aforesaid meaning and R.sup.6 is H, C.sub.1 - C.sub.20 alkyl or aryl, with the aqueous solution of periodic acid at 0.degree. - 200.degree. C and the pressure 1 Pa to 20 MPa.

Aldehyde polymers from periodic acid treatment of epoxide polymers

Organic three-dimensional polymeric gel-like materials containing covalently bonded phosphoric acid or a derivative thereof and a method for their manufacture. The bonding is accomplished by the reaction of the free hydroxy or epoxide groups in the homogeneous or macroporous gel-like matrix with the H.sub.3 PO.sub.4, P.sub.2 O.sub.5, phosphorus pentahalide and oxyhalide. The halide containing groups may then be hydrolyzed to form acid groups which then may be modified to form complex compounds by reaction with Lewis acids. The gel material may serve as a strongly acidic cation exchanger, catalyst or polymer reagent.

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Hrebec, Czechoslovakia

Frantisek Svec