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    • 2. 发明授权
    • X-ray contrast spherical hydrogel particles based on polymer and
copolymers of acrylates and methacrylates and the method for
preparation thereof
    • 基于丙烯酸酯和甲基丙烯酸酯的聚合物和共聚物的X射线对比球形水凝胶颗粒及其制备方法
    • US4622367A
    • 1986-11-11
    • US807281
    • 1985-12-10
    • Daniel HorakMarie MetalovaFrantisek SvecJaroslav DrobnikJaroslav KalalMichail I. KuzinArnold A. AdamianJurij V. MoiseievKlara Z. Gumargalieva
    • Daniel HorakMarie MetalovaFrantisek SvecJaroslav DrobnikJaroslav KalalMichail I. KuzinArnold A. AdamianJurij V. MoiseievKlara Z. Gumargalieva
    • C08F8/00A61B19/00A61K49/04C08F8/30C08F8/32
    • C08F8/30A61B90/39Y10T428/2982
    • 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.
    • 本发明涉及基于丙烯酸酯和甲基丙烯酸酯的聚合物和共聚物的X射线对比球形水凝胶颗粒及其制备方法。 本发明的主题是基于丙烯酸酯和甲基丙烯酸酯的聚合物和共聚物的X射线对比球形水凝胶颗粒,其特征在于直径为0.2至2mm的球形颗粒,其在水中强烈溶胀并含有氨基 - 三碘苯甲酸的衍生物 通式I,其中R 1,R 2是氢,具有1至3个碳原子的酰基或具有1至10个碳原子的烷基,X是卤素,-OH或-NH(CH 2)n NH 2,其中n = 共价键合到聚合物骨架上。 制备根据本发明的X射线对比度水凝胶颗粒的方法,其中将含有位于聚合物骨架的侧链上的羟基或环氧基团的水凝胶颗粒在过量的溶剂中溶胀,所述溶剂选自二恶烷 ,二甲基乙酰胺,二甲基甲酰胺,四氢呋喃和二甲基亚砜,其含有溶解的通式I的氨基 - 三碘苯甲酸的衍生物,任选地与形成的卤化氢反应的化合物,其选自例如叔胺, 将分散体最大程度地加热至100℃,最大限度地反应150小时,分离固相并通过洗涤除去可溶性物质。 根据本发明的方法提供具有X射线对比性质的球形水凝胶,而不改变其在医学实践中应用的实质性的其他性质。
    • 3. 发明授权
    • Polymeric material containing aldehyde groups and the method of its
preparation
    • 含醛基的聚合材料及其制备方法
    • US4093602A
    • 1978-06-06
    • US623964
    • 1975-10-20
    • Jaroslav KalalEva ZurkovaFrantisek Svec
    • Jaroslav KalalEva ZurkovaFrantisek Svec
    • C08F2/00C08F2/18C08F12/00C08F16/00C08F16/34C08F16/38C08F20/00C08F20/10C08F20/42C08F24/00C08F216/34C08G2/00C08G2/26C08G12/04
    • C08F216/34Y10T428/2982
    • 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.
    • 通过醛单体R 1 CH = C(CH = O)的共聚制备具有直径≤3mm并且含有高达40%表现出可测量比表面积的游离醛基的直链形式的三维聚合物材料 )R2,其中R1是H,C1-5烷基,芳基或呋喃基,R2是H,C1-5烷基,卤素,CN,苯基或呋喃基,在水分散相中与交联剂反应。 分散体含有1-25%的降低单体在水中的溶解度的组分,其是碱金属或碱土金属的无机盐或水溶性醇。 用作共聚单体的交联剂是二乙烯基苯,二酯CH2 = C(R1)COOR2OCOC(R1)= CH2(R1 = H,C1-10烷基或卤素; R2 = C1-10亚烷基或羟基亚烷基)或二酰胺CH2 = C( R1)CONHR2NHCOC(R1)= CH2(R1 = H,C1-10烷基或卤素; R2 = C1-10亚烷基或亚苯基)。 该材料可以用于连续柱方法,例如。 在有机合成的催化,胺的分离和含有伯氨基的化合物的固定化。
    • 6. 发明授权
    • Polar polymeric sorbent based on glycidyl esters for gas and liquid
chromatography
    • 用于气相色谱和液相色谱的基于缩水甘油酯的极性聚合物吸附剂
    • US4340483A
    • 1982-07-20
    • US863936
    • 1977-12-23
    • Jaromir LukasJaroslav KalalFrantisek Svec
    • Jaromir LukasJaroslav KalalFrantisek Svec
    • B01J20/285B01J20/22B01J20/281C08F8/00G01N30/88B01D15/08
    • B01J20/26B01J20/264B01J20/267B01J20/285C08F8/00
    • 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.
    • 本发明涉及适用于基于缩水甘油酯的气相色谱和液相色谱的极性聚合物吸附剂。 吸附剂由包含3-70%的具有环氧基的聚合单体单元的大孔共聚物形成,例如 甲基丙烯酸缩水甘油酯或丙烯酸缩水甘油酯单元,和97-30%的交联剂,例如。 二甲基丙烯酸亚烷基酯,二丙烯酸亚烷基酯,二甲基丙烯酸羟基亚烷基酯,二丙烯酸羟基亚烷基酯(含有1-6个C原子的亚烷基)或二乙烯基苯。 吸附剂还可含有至多30%的含有腈基的聚合单体单元,例如 丙烯腈和甲基丙烯腈单元。 根据本发明,吸附剂的极性可以进一步修饰,通过与各种亲核试剂的反应,例如, 水,醇,羧酸及其衍生物,氨,胺,硫醇,丙烯腈。 吸附剂是热和机械稳定的,并用于化合物的复杂混合物的气相色谱和液相色谱分离。 其极性以修改的Rohrschneider指数表示。
    • 8. 发明授权
    • Aldehyde polymers from periodic acid treatment of epoxide polymers
    • 来自环氧化物聚合物的高级酸处理的醛聚合物
    • US4089823A
    • 1978-05-16
    • US679024
    • 1976-04-21
    • Jaroslav KalalFrantisek Svec
    • Jaroslav KalalFrantisek Svec
    • C08F8/00C08F8/06
    • C08F8/06C08F2810/20Y10S528/92
    • 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.
    • 本发明涉及含有可变量醛基并且包含链单元的聚合物材料,其中R1,R2和R3是H,C1-C5烷基,芳基,呋喃基,卤素,腈基或羟基,R4是C1-C20 亚烷基,亚芳基,-COO(CH 2)n - , - O-(CH 2)n - , - CO(CH 2)n CH(OH)CH 2 OCO(CH 2)m - 或 - (CH 2)nOCOR 5 COO(CH 2)m - (n和 m为整数0-20,R5为单键,C1-C20亚烷基或羟基亚烷基或亚芳基)。 该材料可以是具有可测量的比表面积的球形物,并且适用于含有伯氨基或其它胺的生物活性化合物的结合以产生聚合物螯合剂。 本发明还涉及上述材料的制备方法,该方法包括处理包含通式为“IMAGE”的单元的聚合物材料,其中R 1,R 2,R 3和R 4具有上述含义,R 6是H,C 1 -C 20烷基 或芳基与高碘酸水溶液在0〜200℃,压力1Pa〜20MPa。
    • 10. 发明授权
    • Macroporous polymeric membranes for the separation of polymers and a
method of their application
    • 用于分离聚合物的大孔聚合物膜及其应用的方法
    • US4923610A
    • 1990-05-08
    • US411665
    • 1989-09-25
    • Frantisek SvecBoris G. Belenkii
    • Frantisek SvecBoris G. Belenkii
    • B01D71/28B01D15/08B01D67/00B01D71/00B01D71/26B01D71/38B01D71/40B01D71/44B01D71/82B01J20/26B01J20/28B01J20/281C08F2/04C08F2/06C08F12/00C08F20/10C08F26/06C08F26/10C08F212/08C08F220/20C08F226/06C08F226/10C08J9/28C12N9/00G01N30/52
    • B01D67/0006B01D67/0093B01D71/76B01J20/26B01J20/261B01J20/265B01J20/267B01J20/28004B01J20/28026B01J20/28033B01J20/28057B01J20/28085B01J20/285B01J20/3064C12N9/00B01D2323/02B01D2323/30B01D2325/10B01D2325/40B01D71/28B01D71/40B01J2220/54G01N2030/527Y10S264/48Y10S264/62
    • 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.