公开(公告)号：US20130023638A1

公开(公告)日：2013-01-24

申请号：US13637764

申请日：2011-03-29

申请人： Kikuo Furukawa ,  Toshiharu Yamashita ,  Yoshio Nishimura

发明人： Kikuo Furukawa ,  Toshiharu Yamashita ,  Yoshio Nishimura

IPC分类号： C07C69/54 ,  C08F220/68 ,  C07C67/08 ,  C08F20/68

CPC分类号： C07C69/54 ,  C07C2603/74 ,  C08F220/18 ,  C08F220/28 ,  G03F7/0397

摘要： Provided according to the present invention are an adamantyl (meth)acrylate represented by formula (1), having a formazin standard turbidity of less than 1.7 NTU (Nephelometric Turbidity Unit) in methylethylketone or tetrahydrofuran, and also a (meth)acrylic copolymer comprising the adamantyl (meth)acrylate as a repeating unit: (in the formula, R1 represents hydrogen or a methyl group; R2 through R4 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having a carbon number of 1 to 3, an aryl group, an alkoxy group, an aryloxy group, a halogen group, an alkyl halide group, or a hydroxyalkyl group; and n1 represents 0 or 1).

摘要翻译： 根据本发明提供的是由式（1）表示的（甲基）丙烯酸金刚烷酯，甲基乙基酮或四氢呋喃中具有小于1.7NTU（比浊法浊度单位）的甲萘醌标准浊度，以及包含 金刚烷基（甲基）丙烯酸酯作为重复单元：（式中，R1表示氢或甲基; R2至R4各自独立地表示氢原子，羟基，碳数为1至3的烷基， 芳基，烷氧基，芳氧基，卤素基，烷基卤基或羟烷基; n1表示0或1）。

公开(公告)号：US08846840B2

公开(公告)日：2014-09-30

申请号：US13637764

申请日：2011-03-29

申请人： Kikuo Furukawa ,  Toshiharu Yamashita ,  Yoshio Nishimura

发明人： Kikuo Furukawa ,  Toshiharu Yamashita ,  Yoshio Nishimura

IPC分类号： C08F220/18 ,  C08F220/28 ,  C07C69/54 ,  C07C67/48 ,  C07C67/08 ,  G03F7/039 ,  C08F4/04

CPC分类号： C07C69/54 ,  C07C2603/74 ,  C08F220/18 ,  C08F220/28 ,  G03F7/0397

摘要： Provided according to the present invention are an adamantyl (meth)acrylate represented by formula (1), having a formazin standard turbidity of less than 1.7 NTU (Nephelometric Turbidity Unit) in methylethylketone or tetrahydrofuran, and also a (meth)acrylic copolymer comprising the adamantyl (meth)acrylate as a repeating unit: (in the formula, R1 represents hydrogen or a methyl group; R2 through R4 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having a carbon number of 1 to 3, an aryl group, an alkoxy group, an aryloxy group, a halogen group, an alkyl halide group, or a hydroxyalkyl group; and n1 represents 0 or 1).

摘要翻译： 根据本发明提供的是由式（1）表示的（甲基）丙烯酸金刚烷酯，甲基乙基酮或四氢呋喃中具有小于1.7NTU（比浊法浊度单位）的甲萘醌标准浊度，以及包含 金刚烷基（甲基）丙烯酸酯作为重复单元：（式中，R1表示氢或甲基; R2至R4各自独立地表示氢原子，羟基，碳数为1至3的烷基， 芳基，烷氧基，芳氧基，卤素基，烷基卤基或羟烷基; n1表示0或1）。

公开(公告)号：US20050158662A1

公开(公告)日：2005-07-21

申请号：US11032095

申请日：2005-01-11

申请人： Kikuo Furukawa ,  Minoru Kakuda ,  Yoshio Nishimura ,  Toshiaki Yamada

发明人： Kikuo Furukawa ,  Minoru Kakuda ,  Yoshio Nishimura ,  Toshiaki Yamada

IPC分类号： C07C69/00 ,  C08F220/28 ,  G03C1/76 ,  G03F7/039

CPC分类号： C07C69/54 ,  C07C2603/74 ,  C08F220/28 ,  G03F7/0397

摘要： The adamantane derivatives of the present invention which are represented by the general formula (1): wherein X is a hydrogen atom, alkyl, halogen-containing alkyl, halogen, or hydroxyl-, halogen-, nitrile- or ether-containing hydrocarbyl, and a plurality of X groups, if any, may be the same or different from each other; n1 is an integer of 1 to 14; R1 to R4 may be the same or different from each other and are independently alkyl or halogen-containing alkyl; and Y1 and Y2 may be the same or different from each other and are independently a hydrogen atom or a group represented by the general formula (2): wherein R5 to R7 may be the same or different from each other and are independently a hydrogen atom, alkyl, halogen or halogen-containing alkyl, are excellent in optical properties, heat resistance and acid-dissociating property, and useful as crosslinking-type resins, optical materials such as optical fibers, light wave guides, optical disk substrates and photoresists as well as raw materials thereof, intermediate products of medicines or agricultural chemicals, and various other industrial products.

摘要翻译： 由通式（1）表示的本发明的金刚烷衍生物：其中X是氢原子，烷基，含卤素的烷基，卤素或羟基，卤素，腈或醚的烃基，和 多个X组（如果有的话）可以相同或不同; n 1是1至14的整数; R 1至R 4可以彼此相同或不同，并且独立地为烷基或含卤素的烷基; 和Y 1和Y 2可以彼此相同或不同，并且独立地为氢原子或由通式（2）表示的基团：其中R' R 5和R 7可以相同或不同，并且独立地为氢原子，烷基，卤素或含卤素的烷基，光学性能，耐热性均优异 和酸解离性，并且可用作交联型树脂，光学材料如光纤，光波导，光盘基片和光致抗蚀剂以及其原料，药物或农药的中间产物，以及各种其它工业产品 。

公开(公告)号：US07078562B2

公开(公告)日：2006-07-18

申请号：US11032095

申请日：2005-01-11

申请人： Kikuo Furukawa ,  Minoru Kakuda ,  Yoshio Nishimura ,  Toshiaki Yamada

发明人： Kikuo Furukawa ,  Minoru Kakuda ,  Yoshio Nishimura ,  Toshiaki Yamada

IPC分类号： C07C69/62

CPC分类号： C07C69/54 ,  C07C2603/74 ,  C08F220/28 ,  G03F7/0397

摘要： The adamantane derivatives of the present invention which are represented by the general formula (1): wherein X is a hydrogen atom, alkyl, halogen-containing alkyl, halogen, or hydroxyl-, halogen-, nitrile- or ether-containing hydrocarbyl, and a plurality of X groups, if any, may be the same or different from each other; n1 is an integer of 1 to 14; R1 to R4 may be the same or different from each other and are independently alkyl or halogen-containing alkyl; and Y1 and Y2 may be the same or different from each other and are independently a hydrogen atom or a group represented by the general formula (2): wherein R5 to R7 may be the same or different from each other and are independently a hydrogen atom, alkyl, halogen or halogen-containing alkyl, are excellent in optical properties, heat resistance and acid-dissociating property, and useful as crosslinking-type resins, optical materials such as optical fibers, light wave guides, optical disk substrates and photoresists as well as raw materials thereof, intermediate products of medicines or agricultural chemicals, and various other industrial products.

摘要翻译： 由通式（1）表示的本发明的金刚烷衍生物：其中X是氢原子，烷基，含卤素的烷基，卤素或羟基，卤素，腈或醚的烃基，和 多个X组（如果有的话）可以相同或不同; n 1是1至14的整数; R 1至R 4可以彼此相同或不同，并且独立地为烷基或含卤素的烷基; 和Y 1和Y 2可以彼此相同或不同，并且独立地为氢原子或由通式（2）表示的基团：其中R' R 5和R 7可以相同或不同，并且独立地为氢原子，烷基，卤素或含卤素的烷基，光学性能，耐热性均优异 和酸解离性，并且可用作交联型树脂，光学材料如光纤，光波导，光盘基片和光致抗蚀剂以及其原料，药物或农药的中间产物，以及各种其它工业产品 。

公开(公告)号：US07067692B2

公开(公告)日：2006-06-27

申请号：US10825118

申请日：2004-04-16

申请人： Kikuo Furukawa ,  Minoru Kakuda ,  Yoshio Nishimura ,  Takehiko Isobe ,  Mitsuharu Suzuki

发明人： Kikuo Furukawa ,  Minoru Kakuda ,  Yoshio Nishimura ,  Takehiko Isobe ,  Mitsuharu Suzuki

IPC分类号： C00C67/26

CPC分类号： C07C67/03 ,  C07C2603/74 ,  C07C69/54

摘要： In the present invention, an adamantyl acrylate compound is produced by a process comprising a first step and a second step without using acid halide. In the first step, a 2-adamantanone compound is reacted with a hydrocarbyl halide in the presence of lithium metal to form an adamantanolate intermediate that is then reacted with an acrylic ester compound in the second step to produce the aimed adamantyl acrylate compound.

摘要翻译： 在本发明中，通过包括不使用酰卤的第一步骤和第二步骤的方法制备丙烯酸金刚烷基酯化合物。 在第一步中，在金属锂存在下，使2-金刚烷酮化合物与烃基卤化物反应，形成金刚烷醇酸盐中间体，然后在第二步中与丙烯酸酯化合物反应，生成目标金刚烷基丙烯酸酯化合物。

公开(公告)号：US20100168464A1

公开(公告)日：2010-07-01

申请号：US12639530

申请日：2009-12-16

申请人： Kikuo Furukawa ,  Yoshihisa Arai

发明人： Kikuo Furukawa ,  Yoshihisa Arai

IPC分类号： C07C69/00

CPC分类号： C07C67/14 ,  C07C67/58 ,  C07C2603/74 ,  C07C69/54

摘要： The present invention provides an efficient production method suitable to industrial-scale production not requiring column purification for adamantyl (meth)acrylates having an adamantane skeleton and useful as monomers for use for resins excellent in optical properties, etc. A method for producing adamantyl (meth)acrylates of formulae (3) and (4), includes a reaction step of reacting a compound of formula (1) with a (meth)acryloyl halide or a (meth)acrylic anhydride in a reaction solution to give a mixture of compounds of formulae (2) to (4), and a separation step of separating the mixture of compounds of formulae (2) to (4), wherein the separation step comprises an extraction step of extracting compounds of formulae (2) and (3) from the reaction solution with a mixed solvent of water and a polar organic solvent, thereby giving a water/polar organic solvent solution containing the compounds of formulae (2) and (3) and the mixed solvent, and a back-extraction step of back-extracting the compound of formula (3) from the water/polar organic solvent solution with a non-polar organic solvent: wherein X's are the same or different, each representing a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group, a nitrile group, or an ether group; n indicates an integer of 14; R1 to R4 are the same or different, each representing an alkyl group or a halogen-containing alkyl group; and Y1 and Y2 are the same or different, each representing a hydrogen atom, lithium, sodium, or a magnesium halide group, wherein X's are the same or different, each representing a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group, a nitrile group, or an ether group; n indicates an integer of 14; and R1 to R4 are the same or different, each representing an alkyl group or a halogen-containing alkyl group, wherein X's are the same or different, each representing a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group, a nitrile group, or an ether group; n indicates an integer of 14; R1 to R4 are the same or different, each representing an alkyl group or a halogen-containing alkyl group; and R5 represents a hydrogen atom or a methyl group, wherein X's are the same or different, each representing a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group, a nitrile group, or an ether group; n indicates an integer of 14; R1 to R4 are the same or different, each representing an alkyl group or a halogen-containing alkyl group; and R5 and R6 are the same or different, each representing a hydrogen atom or a methyl group.

公开(公告)号：US08198475B2

公开(公告)日：2012-06-12

申请号：US12639530

申请日：2009-12-16

申请人： Kikuo Furukawa ,  Yoshihisa Arai

发明人： Kikuo Furukawa ,  Yoshihisa Arai

IPC分类号： C07C67/48 ,  C07C67/58 ,  C07C69/54

CPC分类号： C07C67/14 ,  C07C67/58 ,  C07C2603/74 ,  C07C69/54

摘要： The present invention provides an efficient production method suitable to industrial-scale production not requiring column purification for adamantyl (meth)acrylates having an adamantine skeleton having utility in crosslinked resins, optical fibers, optical waveguides, optical disc substrates and other optical materials.

摘要翻译： 本发明提供了一种适用于工业规模生产的高效生产方法，不需要对具有在交联树脂，光纤，光波导，光盘基片和其它光学材料中使用的金刚烷骨架的金刚烷基（甲基）丙烯酸酯进行柱纯化。

公开(公告)号：US06570042B2

公开(公告)日：2003-05-27

申请号：US09955077

申请日：2001-09-19

申请人： Minoru Kakuda ,  Takashi Onozawa ,  Hiroshi Kurata ,  Kikuo Furukawa

发明人： Minoru Kakuda ,  Takashi Onozawa ,  Hiroshi Kurata ,  Kikuo Furukawa

IPC分类号： C07C3522

CPC分类号： C07C29/48 ,  C07C2603/74 ,  C07C35/37

摘要： Adamantanediols are produced by the hydroxylation of adamantane compounds in a water/organic solvent two-phase system in the presence of a ruthenium compound and a hypochlorite. Throughout the hydroxylation, the hypochlorite concentration in the water phase is regulated within a narrow limited range, for example, by monitoring the pH of the reaction system. With such a control of the hypochlorite concentration, the adamantanediols are produced in a high selectivity and a high yield.

公开(公告)号：US06521781B2

公开(公告)日：2003-02-18

申请号：US10003276

申请日：2001-12-06

申请人： Minoru Kakuda ,  Yoshihisa Arai ,  Kikuo Furukawa ,  Takehiko Isobe

发明人： Minoru Kakuda ,  Yoshihisa Arai ,  Kikuo Furukawa ,  Takehiko Isobe

IPC分类号： C07C6963

CPC分类号： C07C67/03 ,  C07C67/08 ,  C07C2603/74 ,  C07C69/54

摘要： A 2-hydrocarbyl-2-adamantyl acrylate compound represented by the following Formula 6: is produced easily and stably with high yields by reacting a 2-adamantanone compound represented by the following Formula 1: with at least one organometallic compound represented by the following Formula 2 or 3: R1MgX  (2) R1Li  (3) and at least one acrylic compound represented by the following Formula 4 or 5: wherein, R1, R2, R3, X, Y and n in the above formulae being as defined in the disclosure.

摘要翻译： 由下式6表示的2-烃基-2-金刚烷基丙烯酸酯化合物通过使由下式1表示的2-金刚烷酮化合物与至少一种由下式表示的有机金属化合物反应，以高收率容易且稳定地制备： 2或3：和由下式4或5表示的至少一种丙烯酸类化合物：其中，上式中的R 1，R 2，R 3，X，Y和n如本公开内容所定义。