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1. 发明授权

US4085005A Method of preparation of insoluble biologically active compounds 失效
标题翻译：不溶性生物活性化合物的制备方法
公开(公告)号：US4085005A
公开(公告)日：1978-04-18
申请号：US669866
申请日：1976-03-24
申请人： Miroslav Bleha , Eva Votavova , Zdenek Plichta
发明人： Miroslav Bleha , Eva Votavova , Zdenek Plichta
IPC分类号： C08F8/00 , A61K31/785 , C08F8/06 , C08F8/30 , C08G81/00 , C08G85/00 , C12N11/08 , C07G7/02
CPC分类号： C12N11/08 , Y10S436/817
摘要： The invention relates to biologically active insoluble compounds on a carrier containing in its side chains a p-phenylene-diamine skeleton, where a polymer of the general formula I ##STR1## where R.sub.1 is a polymer residue, R.sub.2 is a lower alkyl group, x = 1-4, is oxidized in the presence of a soluble biologically active compound containing a primary amino group, such as e.g. enzymes, coenzymes, inhibitors of enzymes, hormones, or antigens. The oxidation is carried out by using an oxidation agent which does not disturb the biologically active compounds present in the mixture.
摘要翻译：本发明涉及在其侧链上含有对苯二胺骨架的载体上的生物活性不溶性化合物，其中通式I的聚合物其中R1是聚合物残基，R2是低级烷基， x = 1-4，在含有伯氨基的可溶性生物活性化合物的存在下被氧化，例如，酶，辅酶，酶抑制剂，激素或抗原。通过使用不干扰混合物中存在的生物活性化合物的氧化剂进行氧化。

2. 发明授权

US4166804A Polymeric color indicators and a method of their preparation 失效
标题翻译：聚合颜色指示剂及其制备方法
公开(公告)号：US4166804A
公开(公告)日：1979-09-04
申请号：US842273
申请日：1977-10-14
申请人： Miroslav Bleha , Zdenek Plichta , Eva Votavova , Jaroslav Kalal
发明人： Miroslav Bleha , Zdenek Plichta , Eva Votavova , Jaroslav Kalal
IPC分类号： G01N31/22 , G01N21/08 , C08F8/30 , C08J9/00
CPC分类号： G01N31/221
摘要： Polymeric color pH indicators are prepared which are insoluble in the measured aqueous medium and show a certain range of color change. These polymeric indicators are the product of copolymerization of a hydrophilic comonomer, selected from esters, amides and N-substituted amides of acrylic and methacrylic acid, with 0.1- 30 wt.% of a comonomer. The comonomer forms the pH-indicating color center by a subsequent coupling with a suitable diazonium salt or a passive component. Vinylic monomers comprising an aromatic system in the molecule are suitable as the functional comonomers. The indicators are prepared by radical copolymerization of the comonomers either in a suspension or in a solution, followed by the subsequent coupling with a diazonium compound, or diazotizing and coupling with a passive component, to obtain the pH-indicating sites of polymer. The product is in the form of small spherical macroporous particles suitable for pH indication in flow-through column processes, in small volumes, or on a microscope stage, or in the form of a solution applicable as a paint and indicating the pH of vessels, reactors, etc. coated therewith, or useful for application to inert carriers.
摘要翻译：制备聚合物颜色pH指示剂，其不溶于测量的水性介质并显示一定范围的颜色变化。这些聚合物指示剂是选自丙烯酸和甲基丙烯酸的酯，酰胺和N-取代的酰胺的亲水共聚单体与0.1-30重量％的共聚单体共聚的产物。共聚单体通过与合适的重氮盐或无源组分的后续偶联形成pH-指示颜色中心。分子中包含芳族体系的乙烯基单体适用作为功能性共聚单体。指示剂通过在悬浮液或溶液中共聚单体的自由基共聚制备，随后与重氮化合物偶联，或与无源组分重氮化并偶联，得到聚合物的pH指示位点。该产品是适于在流通柱方法中以小体积或在显微镜载物台上的pH指示的小球形大孔颗粒的形式，或以可用作涂料的溶液形式并指示血管的pH值，反应器等，或者可用于惰性载体。

3. 发明授权

US4180629A Polymers containing a reactive aromatic system based on p-phenylenediamine derivatives 失效
标题翻译：含有基于对苯二胺衍生物的反应性芳族体系的聚合物
公开(公告)号：US4180629A
公开(公告)日：1979-12-25
申请号：US920236
申请日：1978-06-29
申请人： Miroslav Bleha , Zdenek Plichta
发明人： Miroslav Bleha , Zdenek Plichta
IPC分类号： C08F20/34 , C08F220/06 , C08F220/56 , C08F226/02
CPC分类号： C08F20/34
摘要： Polymers containing a reactive aromatic system in the side chain which consist of structural units of the general formula IV: ##STR1## where R.sup.1 is hydrogen or CH.sub.3,R.sup.2 is alkyl containing 1 to 6 carbon atoms,R.sup.3 is an acyl or sulfonic group,Ar is a bifunctional aromatic residue, andX=1 to 4.Said polymers being subject to further treatment consisting of acid hydrolysis and subsequent modification, e.g., with chloroacetic acid, formaldehyde or diazotizing and coupling with a suitable passive component.
摘要翻译：在侧链中含有由通式IV的结构单元组成的反应性芳族体系的聚合物：其中R 1是氢或CH 3，R 2是含有1至6个碳原子的烷基，R 3是酰基或磺酸基基团，Ar是双官能芳族残基，X = 1至4.所述聚合物经受由酸水解和随后的改性（例如用氯乙酸，甲醛或重氮化和与合适的被动组分的偶联）进行的进一步处理。

4. 发明授权

US4127732A Monomers and polymers containing the reactive aromatic system and method for their preparation 失效
标题翻译：含有反应性芳香体系的单体和聚合物及其制备方法
公开(公告)号：US4127732A
公开(公告)日：1978-11-28
申请号：US625317
申请日：1975-10-23
申请人： Miroslav Bleha , Zdenek Plichta
发明人： Miroslav Bleha , Zdenek Plichta
IPC分类号： C08F8/00 , C07C67/00 , C07C231/00 , C07C231/02 , C07C231/12 , C07C233/43 , C07C239/00 , C07C271/00 , C07C301/00 , C07C303/34 , C07C303/40 , C07C307/02 , C08F8/12 , C08F20/00 , C08F20/34 , C08F290/00 , C08F299/00 , C07C69/54
CPC分类号： C08F20/34
摘要： The invention relates to monomers of the general formula I with a reactive aromatic system based on p-phenylenediamine derivatives:Ch.sub.2 .dbd.cr.sup.1 --co--(o--ch.sub.2 --ch.sub.2).sub.x --NR.sup.2 --Ar--NH--R.sup.3 (I),where R.sup.1 is H or CH.sub.3, R.sup.2 is C.sub.1 -C.sub.6 alkyl, R.sup.3 is acyl, carboxylic group or sulfonic group. It further relates to methods for preparation of such monomers by the reaction of p-H.sub.2 NC.sub.6 H.sub.4 N(Et)CH.sub.2 CH.sub.2 OH or p-H.sub.2 NC.sub.6 H.sub.4 N(CH.sub.2 CH.sub.2 OH).sub.2 derivatives with blocked NH.sub.2 groups with chlorides of unsaturated organic acids or by nitrosation, reducing and above mentioned acylation of N-alkylaniline derivatives. It further relates to polymers prepared by polymerization or copolymerization of monomers I, which consist of structural units IV: ##STR1## where R.sup.1, R.sup.2, R.sup.3, Ar and x have the above given meaning, and to methods of their preparation. These methods include the free-radical polymerization or copolymerization with acrylic and methacrylic monomers, as acrylamide, methacrylamide, acrylic and methacrylic acids and their esters, vinyl monomers, as butadiene, isoprene, and styrene, bifunctional monomers, as divinylbenzene, methylenebisacrylamide, ethylene glycol dimethacrylate, and with monomers containing OH groups. The polymerization methods further include polymerization in the presence of polymer solvents and precipitants and a crosslinking copolymerization in a dispersion medium which provides porous polymer particles with large inner surface area. Another objective of the invention are polymers containing structural units V: ##STR2## where R.sup.1, R.sup.2, Ar and x have the above given meaning and R.sup.3, R.sup.4 are H, C.sub.1 -C.sub.4 alkyl or CH.sub.2 COOH or where R.sup.3 + R.sup.4 means .dbd. N-- group, and methods for their preparation from polymers with units IV consisting in acid hydrolysis and subsequent modification, e.g. with chloroacetic acid, formaldehyde or diazotizing and coupling with a suitable passive component.
摘要翻译：本发明涉及具有基于对苯二胺衍生物的反应性芳族体系的通式I的单体：

5. 发明授权

US4952349A Macroporous polymeric membranes for the separation of polymers and a method of their application 失效
公开(公告)号：US4952349A
公开(公告)日：1990-08-28
申请号：US468907
申请日：1990-01-23
申请人： Frantisek Svec , Miroslav Bleha , Tatiana B. Tennikova , Boris G. Belenkii
发明人： Frantisek Svec , Miroslav Bleha , Tatiana B. Tennikova , Boris G. Belenkii
IPC分类号： B01D71/28 , B01D15/08 , B01D67/00 , B01D71/00 , B01D71/26 , B01D71/38 , B01D71/40 , B01D71/44 , B01D71/82 , B01J20/26 , B01J20/28 , B01J20/281 , C08F2/04 , C08F2/06 , C08F12/00 , C08F20/10 , C08F26/06 , C08F26/10 , C08F212/08 , C08F220/20 , C08F226/06 , C08F226/10 , C08J9/28 , C12N9/00 , G01N30/52
CPC分类号： B01D67/0006 , B01D67/0093 , B01D71/76 , B01J20/26 , B01J20/261 , B01J20/265 , B01J20/267 , B01J20/28004 , B01J20/28026 , B01J20/28033 , B01J20/28057 , B01J20/28085 , B01J20/285 , B01J20/3064 , C12N9/00 , B01D2323/02 , B01D2323/30 , B01D2325/10 , B01D2325/40 , B01D71/28 , B01D71/40 , B01J2220/54 , G01N2030/527 , Y10S264/48 , Y10S264/62
摘要： 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.

6. 发明授权

US4889632A Macroporous polymeric membranes for the separation of polymers and a method of their application 失效
标题翻译：用于分离聚合物的大孔聚合物膜及其应用的方法
公开(公告)号：US4889632A
公开(公告)日：1989-12-26
申请号：US281266
申请日：1988-12-07
申请人： Frantisek Svec , Miroslav Bleha , Tatiana B. Tennikova , Boris G. Belenkii
发明人： Frantisek Svec , Miroslav Bleha , Tatiana B. Tennikova , Boris G. Belenkii
IPC分类号： B01D71/28 , B01D15/08 , B01D67/00 , B01D71/00 , B01D71/26 , B01D71/38 , B01D71/40 , B01D71/44 , B01D71/82 , B01J20/26 , B01J20/28 , B01J20/281 , C08F2/04 , C08F2/06 , C08F12/00 , C08F20/10 , C08F26/06 , C08F26/10 , C08F212/08 , C08F220/20 , C08F226/06 , C08F226/10 , C08J9/28 , C12N9/00 , G01N30/52
CPC分类号： B01D67/0006 , B01D67/0093 , B01D71/76 , B01J20/26 , B01J20/261 , B01J20/265 , B01J20/267 , B01J20/28004 , B01J20/28026 , B01J20/28033 , B01J20/28057 , B01J20/28085 , B01J20/285 , B01J20/3064 , C12N9/00 , B01D2323/02 , B01D2323/30 , B01D2325/10 , B01D2325/40 , B01D71/28 , B01D71/40 , B01J2220/54 , G01N2030/527 , Y10S264/48 , Y10S264/62
摘要： 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.

7. 发明授权

US5059220A Composite polymeric membranes for the separation of mixtures of gases and the method of preparation the same 失效
标题翻译：用于分离气体混合物的复合聚合物膜及其制备方法
公开(公告)号：US5059220A
公开(公告)日：1991-10-22
申请号：US438330
申请日：1989-11-15
申请人： Miroslav Bleha , Jan Schauer , Jan Lokaj , Galina A. Polockaja , Jurij P. Kuznecov , Kira A. Romaskova
发明人： Miroslav Bleha , Jan Schauer , Jan Lokaj , Galina A. Polockaja , Jurij P. Kuznecov , Kira A. Romaskova
IPC分类号： B01D69/10 , B01D69/12 , B01D71/40 , B01D71/44 , B01D71/52 , B01D71/64 , B01D71/66 , C08F22/36 , C08F22/40 , C08G73/10 , C08G73/14 , C08J9/42
CPC分类号： C08G73/14 , B01D69/12 , B01D71/64 , B01D71/28 , B01D71/40
摘要： Highly selective membranes for the separation of mixtures He/N.sub.2 and O.sub.2 /N.sub.2, which have suitable mechanical properties and high permeability are dislcosed. They consist of a polymeric porous base from poly-2,6-dimethyl-1,4-phenyleneoxide and a polymeric selective layer formed from polyamidoimide of the general formula I, where R= ##STR1## and n=140-220 ##STR2## or from an interpolymeric equimolar complex of PAI-1 with polyvinylpyrrolidone, or from an aromatic polyimide of the general formula II, where X is --O-- or ##STR3## and n=150-230 ##STR4## or of the general formula III, where n=150-240 ##STR5## or from polymeric imides of the general formula IV, where R=H or CH.sub.3 ##STR6## or also from their copolymers with styrene, methyl methacrylate, methyl acrylate, and dimethylaminoethyl methacrylate. A method for the preparation of composite polymeric membranes consists of saturation of the porous base from poly-2,6-dimethyl-1,4-phenyleneoxide with an organic solvent inert to it, e.g. with C.sub.7 H.sub.16 to C.sub.10 H.sub.22 aliphatic hydrocarbons or their mixtures, drying, and coating with a 1-25 wt.-% solution of the selective polymer in an organic solvent which is incompatible with the organic liquid, e.g. N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or their mixtures.

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