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1. 发明授权

US3649607A Process for manufacturing butadiene-isoprene copolymer 失效
标题翻译：制备丁二烯 - 异丙苯共聚物的方法
公开(公告)号：US3649607A
公开(公告)日：1972-03-14
申请号：US3649607D
申请日：1969-05-06
申请人： BRIDGESTONE TIRE CO LTD
发明人： FURUKAWA JUNJI , SAEGUSA TAKEO , ONISHI AKIRA , ISHIKAWA TAKAO , ANZAI SHIRO , IRAKO KOICHI , NARUMIYA TSUNEAKI , ISHIZUKA YUZO
IPC分类号： C08F236/04 , C08D1/12 , C08D3/08 , C08D3/12
CPC分类号： C08F236/04 , C08F4/7095
摘要： BUTADIENE-ISOPRENE COPOLYMER HAVING A BUTADIENE UNIT OF AT LEAST 90% OF CIS-1,4 STRUCTURE AND AN ISOPRENE UNIT OF AT LEAST 95% OF 1,4-STRUCTURE IS PRODUCED BY COPOLYMERIZING BUTADIENE AND ISOPRENE BY MEANS OF THREE COMPONENT CATALYST CONSISTING OF (A) A COMPOUND SELECTED FROM THE GROUP CONSISTING OF AN ORGANIC CARBOXYLIC ACID SALT AND AN ORGANIC COMPLEX COMPOUND OF NICKEL, (B) A COMPOUND SELECTED FROM THE GROUP CONSISTING OF BORON TRIFLUORIDE AND ITS COMPLEX COMPOUND WITH AN OXYGENCONTAINING ORGANIC COMPOUND AND (C) AN ORGANOMETALLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF TRIALKYLALUMINUM, DIALKYLZINC, ALKYLLITHIUM AND DIALKYLALKOXYALUMINUM, BUTADIENE/ISOPRENE FEED RATIO BEING IN THE RANGE OF 90/10-70/30 (MOLE RATIO), THE MOLE RATIO OF SAID (C)-COMPONENT TO SAID (A)-COMPONENT BEING AT LEAST 0.5 AND THE MOLE RATIO OF SAID (C)-COMPONENT TO SAID (B)-COMPONENT BEING WITHIN THE RANGE OF 0.5 TO 2.0.

2. 发明授权

US3590024A Method of producing random copolymers of a conjugated diene and an alpha-olefin 失效
标题翻译：生产偶联二烯和ALPHA-OLEFIN的随机共聚物的方法
公开(公告)号：US3590024A
公开(公告)日：1971-06-29
申请号：US3590024D
申请日：1969-08-20
申请人： BRIDGESTONE TIRE CO LTD
发明人： ISHIZUKA YUZO , IRAKO KOICHI
IPC分类号： C08F236/04 , C08D3/02 , C08F15/04
CPC分类号： C08F236/04 , C08F4/68 , C08F4/6421
摘要： A METHOD OF PRODUCING RANDOM COPOLYMERS OF A CONJUGATED DIENE AND AN A-OLEFIN BY CONTACTING A MIXTURE OF SAID CONJUGATED DIENE AND SAID A-OLEFIN WITH A CATALYST SYSTEM CONSISTING OF A COMPONENT (A) OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF CHLORIDES AND BROMIDES OF TITANIUM, AND OXYCHLORIDES OF VANADIUM, AND A COMPONENT (B) OF AN ORGANOALUMINUM COMPOUND HAVING THE GENERAL FORMULA AIR3, WHEREIN R REPRESENTS A HYDROCARBON RADICAL, IN THE PRESENCE OF A HIGH MOLECULAR WEIGHT POLYETHER, WHICH PROMOTES THE COPOLYMERIZATION REACTIVITY OF THE A-OLEFIN.

3. 发明专利

DE1570293B1 未知
公开(公告)号：DE1570293B1
公开(公告)日：1970-02-05
申请号：DEB0083393
申请日：1965-08-23
申请人： BRIDGESTONE TIRE CO LTD
发明人： FURUKAWA JUNJI , SAEGUSA TAKEO , ONISHI AKIRA , ISHIKAWA TAKAO , ANZAI SHIRO , IRAKO KOICHI , NARUMIYA TSUEAKI , ISHIZUKA YUZO
IPC分类号： C08F236/04 , C08D1/12
摘要： Diolefin copolymers containing a butadiene unit having a high cis-1,4-structure are made by copolymerizng butadiene and a hydrocarbon-radical-substituted butadiene in which the substituents are selected from alkyl, aryl, or cycloalkyl radicals, in the presence of a diluent, at a temperature in the range of -30 DEG C. to 150 DEG C. and under a pressure sufficient to maintain the reaction system in the liquid phase, and a three-component catalyst. The catalyst consists of (A) a metal salt of an organic carboxylic acid of the formula where R is a hydrocarbon radical, M is a metal, and n the valency of the metal, or a hydroxyketone metal complex, or a hydroxy ester metal complex, or a hydroxyaldehyde metal complex, or a hydroxyacid metal complex, or a diketonedioximo metal complex, or an 8-hydroxyquinoline metal complex, or a cyclodiolefin metal complex, or a carbonyl metal complex, and in all cases the metal is nickel or cobalt, (B) boron trifluoride or its complexes with oxygen-containing organic compounds, and (C) an organometallic compound selected from alkyllithiums, dialkylzincs, trialkylaluminiums, and dialkylalkoxy-aluminium compounds. The mole ratio of the (C) component to the (A) component is at least 0.5, and the mole ratio of the (C) component to the (B) component being within the range of 0.1 to 5.0. All or two of the catalyst components are soluble in organic solvents. The comonomer may be isoprene, 2,3-dimethylbutadiene, or 1,3-pentadiene. The copolymers may be made by normal or block techniques. Both of these types of copolymers are exemplified. The copolymerization is preferably effected in a hydrocarbon solvent or diluent. Recovery of the copolymer is by conventional techniques. The Specification contains long lists of catalyst components. Exemplified catalysts are (1) nickel naphthenate, boron trifluoride etherate, and triethyl aluminium, (2) as (1) but nickel salt replaced by acetylacetone nickel, (3) as (1) but nickel salt, nickel 2-ethylhexoate, (4) as (1) but acetylacetone cobalt used instead of Ni salt, (5) as (1) but instead of Ni salt, the ethyl acetoacetonate salt of Ni or Co used, (6) tetracarbonyl Ni, (C2H5)3Al, and BF3 etherate, (7) as (6) but Ni compound replaced by salicylaldehyde Co or Ni, nickel benzoate, or nickel stearate, and (8) acetylacetone Ni, or Ni naphthenate, BF3 etherate, and butyl lithium or diethyl zinc, or diethylmonoethoxy aluminium. The copolymers may be vulcanized.

4. 发明专利

CA831103A PROCESS FOR MANUFACTURING CONJUGATED DIOLEFIN COPOLYMERS 未知
公开(公告)号：CA831103A
公开(公告)日：1969-12-30
申请号：CA831103D
申请人： BRIDGESTONE TIRE CO LTD
发明人： ANZAI SHIRO , NARUMIYA TSUNEAKI , ONISHI AKIRA , ISHIZUKA YUZO , ISHIKAWA TAKAO , IRAKO KOICHI , SAEGUSA TAKEO , FURUKAWA JUNJI

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