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    • 1. 发明专利
    • Production of polymer
    • 生产聚合物
    • JPS59155409A
    • 1984-09-04
    • JP2977083
    • 1983-02-23
    • Toshinobu Higashimura
    • HIGASHIMURA TOSHINOBUMASUDA TOSHIO
    • C08F4/00C08F4/06C08F4/20C08F4/68C08F38/00C08F138/00
    • PURPOSE: To facilitate the formation of a high-MW polymer, by polymerizing a 1-monoalkyl(1W4C)dimethylsilyl-1-propyne in the presence of a specified polymerization catalyst.
      CONSTITUTION: A group V transition metal compound (e.g., tantalum pentachloride or tantalum pentabromide) is used as a catalyst. Namely, a 1-monoalkyl (1W4C)dimethylsilyl-1-propyne of the formula (wherein R is methyl, ethyl, propyl, or butyl) is polymerized at about 50W100°C in the presence of about 0.01W 20mol% above catalyst in a solvent such as benzene, carbon tetrachloride, or cyclohexane.
      COPYRIGHT: (C)1984,JPO&Japio
    • 目的:为了促进形成高分子量聚合物,通过在指定的聚合催化剂存在下聚合1-单烷基(1-4C)二甲基甲硅烷基-1-丙炔。 构成:使用V族过渡金属化合物(例如五氯化钽或五溴化钽)作为催化剂。 即,式(其中R是甲基,乙基,丙基或丁基)的1-单烷基(1-4C)二甲基甲硅烷基-1-丙炔在约50-100℃下在约0.01-20mol 在溶剂如苯,四氯化碳或环己烷中的催化剂上。
    • 2. 发明专利
    • Preparation of trimer of 4c-olefin
    • 4C-OLEFIN的TRIMER的制备
    • JPS5921629A
    • 1984-02-03
    • JP13125982
    • 1982-07-29
    • Toshinobu Higashimura
    • HIGASHIMURA TOSHINOBU
    • C07C2/26B01J31/00B01J31/02C07B61/00C07C1/00C07C11/02C07C67/00
    • Y02P20/52
    • PURPOSE: To obtain the titled compound in high yield in high selectivity, by reacting a mixture of a dimer of a 4C-olefin and a monomer of a 4C-olefin using trifluoromethanesulfonic acid as a catalyst.
      CONSTITUTION: A mixture consisting of 100pts.wt. dimer of a 4C-olefin, such as 2,4,4-trimethylpentene-1,5-methyl-heptene-2, etc. and 10W300pts.wt. monomer of a 4C-olefin, such as pure isobutylene, pure 1-butene, etc. is reacted in the presence of a catalyst of trifluoromethanesulfonic acid optionally in a nonpolar solvent at -40W40°C, preferably at -20W10°C for 3W24hr under pressure or atmospheric pressure. After the reaction is over NaOH, etc. is added to the reaction mixture, and the catalyst is removed to give the desired compound. The amount of the catalyst used is 0.1W10pts.wt., preferably 1W5pts.wt. based on 100pts.wt. total amount of the mixture.
      EFFECT: When it is separated as a product, complicated purification distillation is not required.
      COPYRIGHT: (C)1984,JPO&Japio
    • 目的:通过使用三氟甲磺酸作为催化剂,使4C-烯烃的二聚物与4C-烯烃的单体的混合物反应,以高选择性得到标题化合物。 构成:由100pts.wt。 4,4-烯烃的二聚体,如2,4,4-三甲基戊烯-1,5-甲基 - 庚烯-2等,10-300pts.wt。 在三氟甲磺酸的催化剂存在下,任选在非极性溶剂中,-40-40℃,优选-20-10℃下,使4-烯丙基单体如纯异丁烯,纯1-丁烯等反应 在压力或大气压下进行3-24小时。 反应过程超过NaOH后,加入反应混合物,除去催化剂,得到所需化合物。 所用催化剂的量为0.1-10pts.wt。,优选为1-5pts.wt。 基于100pts.wt 混合物的总量。 效果:当作为产品分离时,不需要复杂的纯化蒸馏。
    • 3. 发明专利
    • Preparation of diarylbenzene from divinylbenzene as raw material
    • 以二乙苯为原料制备二苯并噻吩
    • JPS57120531A
    • 1982-07-27
    • JP598381
    • 1981-01-20
    • Toshinobu Higashimura
    • HIGASHIMURA TOSHINOBUHASEGAWA HIROSHI
    • C07C2/72B01J27/00B01J27/06B01J31/00B01J31/02C07B61/00C07C1/00C07C15/16C07C67/00
    • Y02P20/52
    • PURPOSE: To obtain in high yield a diarylbenzene useful as a plasticizer, a lubricant, and a high energy fuel, by adding a monocyclic aromatic compound to divinylbenzene in the presence of a compound which generates a peroxy acid anion.
      CONSTITUTION: Using a compound (e.g., perchloric acid, acetyl perchlorate, valeryl perchlorate, etc.) which generates a peroxy acid ion, 2mol monocyclic aromatic compound (e.g., styrene, xylene, etc.) is added to 1mol divinylbenzene (e.g., m-divinylbenzene, etc.), to give a diarylbenzene shown by the formula (Ar
      1 and Ar
      2 are monocyclic aromatic group residue). 0.01W10mmol of the compound which generates the peroxy acid ion is present in the reaction system.
      COPYRIGHT: (C)1982,JPO&Japio
    • 目的:通过在产生过氧酸阴离子的化合物存在下,通过在二乙烯基苯中加入单环芳香族化合物,高收率地得到可用作增塑剂,润滑剂和高能燃料的二芳基苯。 构成:使用产生过氧酸离子的化合物(例如高氯酸,乙酰高氯酸,戊酰基高氯酸盐等),将2mol单环芳族化合物(例如苯乙烯,二甲苯等)加入1mol二乙烯基苯(例如,m - 二乙烯基苯等),得到式(Ar1和Ar2为单环芳基残基)所示的二芳基苯。 0.01-10mmol产生过氧酸离子的化合物存在于反应体系中。
    • 4. 发明专利
    • 1-phenyl-1-alkyne polymer
    • 1-苯基-1-烷基聚合物
    • JPS59197410A
    • 1984-11-09
    • JP7212683
    • 1983-04-26
    • Toshinobu Higashimura
    • HIGASHIMURA TOSHINOBUMASUDA TOSHIO
    • C08F38/00C08F138/00
    • PURPOSE: A polymer of weight-average MW (light scattering method) ≥10,000, which is stable in air and soluble in a solvent and has excellent membrane- forming property, prepared by polymerizing a 1-phenyl-1-alkyne by using a specified catalyst.
      CONSTITUTION: A mixture of a reducing agent (e.g., tetraphenyltin) with a niobium (or tantalum) halide (e.g., niobium pentachloride) or a tungsten (or molybdenum) halide (e.g., tungsten hexachloride) is used, as a catalyst. Namely, a 1- phenyl-1-alkyne of the formula (wherein R
      1 is H or an alkyl, and R
      2 is an alkyl other than methyl), e.g., 1-phenyl-1-butyne, is polymerized at about 50W150°C for about several W several tens hr in the presence of about 0.1W5mol%, based on monomer, above catalyst in a solvent such as toluene.
      COPYRIGHT: (C)1984,JPO&Japio
    • 目的:重均分子量(光散射法)≥10000,在空气中稳定,溶于溶剂,具有优异的成膜性,通过使用1-苯基-1-炔烃 指定催化剂。 构成:使用还原剂(例如四苯基锡)与铌(或钽)卤化物(例如五水合铌)或钨(或钼)卤化物(例如六氯化钨)的混合物作为催化剂。 即,通式(其中R 1是H或烷基,R 2是甲基以外的烷基)的1-苯基-1-炔烃,例如1-苯基-1-丁炔,被聚合 在大约0.1-5mol%存在下,在约50-150℃下,基于单体,在催化剂上,在溶剂如甲苯中,存在约数十至几十小时。
    • 5. 发明专利
    • Production of 1-chloro-2-phenylacetylene polymer
    • 1-氯代-2-苯基乙烯聚合物的生产
    • JPS5978218A
    • 1984-05-07
    • JP18973682
    • 1982-10-27
    • Toshinobu Higashimura
    • HIGASHIMURA TOSHINOBUMASUDA TOSHIO
    • C08F4/00C08F4/60C08F4/64C08F4/69C08F38/00C08F138/00
    • PURPOSE: To produce a high-MW linear polymer in good yields, by polymerizing a 1-chloro-2-phenylacetylene with the aid of a catalyst prepared by combining molybdenum pentachloride with a specified organometallic compound.
      CONSTITUTION: Use is made of a catalyst prepared by combining molybdenum pentachloride with an organometallic compound selected from the group consisting of an organotin compound, an organosilicon compound, and an organobismuth compound (e.g., tetra-n-butyltin, phenyldimethylsilane, or triphenylbismuth) at a molar ratio of about 1:0.01W10. Namely, a 1-chloro-2-phenylacetylene of the formula (wherein A is an alkyl, aryl, aralkyl, alkoxy, aryloxy, or a halogen, and n is 0W5) is polymerized at about -10W50°C in the presence of the above catalyst in a solvent (monomer concentration of about 0.1W5mol/l.
      COPYRIGHT: (C)1984,JPO&Japio
    • 目的:为了通过将五氯化钼与特定的有机金属化合物结合制备的催化剂进行聚合,以高产率生产高分子量线性聚合物,通过聚合1-氯-2-苯基乙炔。 构成:使用通过将五氯化钼与选自有机锡化合物,有机硅化合物和有机铋化合物(例如四正丁基锡,苯基二甲基硅烷或三苯基铋)的有机金属化合物组合的催化剂制备,催化剂在 摩尔比约为1:0.01-10。 即,式(其中A为烷基,芳基,芳烷基,烷氧基,芳氧基或卤素,n为0-5)的1-氯-2-苯基乙炔在约-10-50℃聚合 在上述催化剂存在下在溶剂中(单体浓度为约0.1-5mol / l。
    • 6. 发明专利
    • Preparation of hexamer of 4c-olefin
    • 4C-烯烃的六聚体的制备
    • JPS5921628A
    • 1984-02-03
    • JP13126082
    • 1982-07-29
    • Toshinobu Higashimura
    • HIGASHIMURA TOSHINOBU
    • C07C2/26B01J31/00B01J31/02C07B61/00C07C1/00C07C11/02C07C67/00
    • Y02P20/52
    • PURPOSE: To obtain the titled compound useful as a raw material for isoparaffin, etc. in high selectivety in high yield with suppressing the cutting and recombination of C-C bond, by reacting a trimer of a 4C-olefin using trifluoromethanesulfonic acid as a catalyst.
      CONSTITUTION: 100pts.wt. timer of a 4C-olefin is reacted in the presence of 0.1W 20pts.wt., preferably 1W10pts.wt. catalyst of trifluoromethanesulfonic acid optionally in a nonpolar solvent at -40W40°C, preferably -25W10°C under atmospheric pressure, reduced pressure or under pressure. After the reaction is over, a basic substance such as NaOH, etc. is added to the reaction mixture, and the catalyst is removed easily, to give the desired compound. 1-Dodecene, 2- tert-butyl-3,3,4-trimethyl-1-pentene, 2-neopentyl-3-tert-butyl 2-propene, etc. may be cited as the trimer of 4C-olefin.
      USE: A base oil for cosmetic, etc.
      COPYRIGHT: (C)1984,JPO&Japio
    • 目的:通过使用三氟甲磺酸作为催化剂使4C-烯烃的三聚体反应,以高产率获得用作异构烷烃等的原料的标题化合物,抑制C-C键的切割和重结合。 组成:100pts.wt。 在0.1-20pts.wt。,优选1-10pts.wt。的存在下使4C-烯烃的定时器反应。 在-40-40℃,优选-25-10℃,任选在非极性溶剂中,在大气压,减压或压力下,三氟甲磺酸的催化剂。 反应结束后,向反应混合物中加入NaOH等碱性物质,容易除去催化剂,得到所需化合物。 1-十二碳烯,2-叔丁基-3,3,4-三甲基-1-戊烯,2-新戊基-3-叔丁基2-丙烯等可以列举4C-烯烃的三聚体。 用途:化妆品等基础油
    • 8. 发明专利
    • Preparation of diarylbenzene from divinylbenzene as raw material
    • 以二乙苯为原料制备二苯并噻吩
    • JPS57120530A
    • 1982-07-27
    • JP598281
    • 1981-01-20
    • Toshinobu Higashimura
    • HIGASHIMURA TOSHINOBUHASEGAWA HIROSHI
    • C07C2/72B01J27/00B01J27/06B01J31/00B01J31/02C07B61/00C07C1/00C07C15/16C07C67/00
    • Y02P20/52
    • PURPOSE: To obtain in high yield a diarylbenzene useful as a plasticizer, a lubricant, and a raw material for high energy fuel, by adding a monocyclic aromatic compound to divinylbenzene in the presence of a compound preparing a sulfonate anion.
      CONSTITUTION: Using a compound which generates a sulfonate ion[e.g., fluorsulfic acid, chlorosulfonic acid, trifluoromethanesulfonic acid shown by the formula RSO
      3 H(R is F, Cl, or perfluoroalkyl), etc.], 2mol monocyclic aromatic compound (e.g., tolulene, xylene, etc.) is added to 1mol divinylbenzene (e.g., m-divinylbenzene, etc.), to give a diarylbenzene shown by the formula (Ar
      1 and Ar
      2 are monocyclic aromatic group residue). 0.01W1.00mmol/l of the compound which generates sulfonate ions is preferably present in the reaction.
      COPYRIGHT: (C)1982,JPO&Japio
    • 目的:通过在制备磺酸根阴离子的化合物的存在下,通过在二乙烯基苯中加入单环芳香族化合物,高收率地获得可用作增塑剂,润滑剂和高能燃料原料的二芳基苯。 构成:使用产生磺酸根离子的化合物(例如氟磺酸,氯磺酸,式RSO3H(R为F,Cl或全氟烷基)等所示的三氟甲磺酸等),2摩尔单环芳香族化合物(例如甲苯, 二甲苯等)加入到1mol二乙烯基苯(例如间二乙烯基苯等)中,得到式(Ar1和Ar2为单环芳基残基)所示的二芳基苯。 在反应中优选存在0.01-1.00mmol / l的产生磺酸根离子的化合物。
    • 9. 发明专利
    • Production of mono substituted acetylene polymer
    • 单取代乙炔聚合物的生产
    • JPS5731911A
    • 1982-02-20
    • JP10645680
    • 1980-08-04
    • Toshinobu Higashimura
    • HIGASHIMURA TOSHINOBUMASUDA TOSHIO
    • C08F2/00C08F2/50C08F4/00C08F4/06C08F4/22C08F38/00C08F138/00
    • PURPOSE: To obtain a high-MW polymer applicable to a semiconductor, gas adsorbent or polarizing material, by polymerizing a monosubstituted acetylene by use of a catalyst prepared by irradiating a transition metal carbonyl/organic halide mixture with light.
      CONSTITUTION: A mixture of a transition metal carbonyl, e.g., tungsten hexacarbonyl, and an organic halide, e.g., CCl
      4 , is irradiated with light. The irradiation is preferably such that the dosage corresponds to that obtained from a 100WW1kW light source placed about 30cm distant for at least 10min, pref., 30minW1hr. A monosubstituted acetylene of the formula, wherein R is a (substituted) alkyl or a (substituted) arly, e.g., phenylacetylene, is polymerized by use of the above-produced catalyst. The amount of the transition metal carbonyl used is suitably 0.1W 10mol%, based on the monomer of the formula. It is possible to obtain a high-MW polymer in high yields.
      COPYRIGHT: (C)1982,JPO&Japio
    • 目的:通过使用通过用光照射过渡金属羰基/有机卤化物混合物制备的催化剂聚合单取代的乙炔,获得适用于半导体,气体吸附剂或偏振材料的高分子量聚合物。 构成:过渡金属羰基,例如六羰基钨和有机卤化物如CCl 4的混合物用光照射。 照射优选使得剂量对应于从放置在约30cm处至少10分钟,优选30分钟-1小时的100W-1kW光源获得的剂量。 其中R为(取代的)烷基或(取代的)芳基,例如苯基乙炔的下式的单取代的乙炔通过使用上述制备的催化剂进行聚合。 使用的过渡金属羰基化物的量适宜为0.1-10mol%,基于式的单体。 可以以高产率获得高分子量聚合物。