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1. 发明授权

US5574116A Process for the preparation of a catalyst for the polymerization of olefins 失效
标题翻译：制备烯烃聚合催化剂的方法
公开(公告)号：US5574116A
公开(公告)日：1996-11-12
申请号：US214691
申请日：1994-03-18
申请人： Karel Bujadoux , Jean-Michel Brusson , Francis Petit , Andre Mortreux
发明人： Karel Bujadoux , Jean-Michel Brusson , Francis Petit , Andre Mortreux
IPC分类号： C08F4/654 , C08F10/00
CPC分类号： C08F10/00
摘要： A process is disclosed for the polymerization of olefins, using (i) a catalyst and (ii) an organometallic activator from Groups I, II or III of the Periodic Table at temperatures between 20.degree. and 250.degree. C., and pressure up to 200 bar, in solution, or in suspension in an inert liquid hydrocarbon, at temperatures between 160.degree. and 350.degree. C., under pressures of between 400 and 3000 bar, in a continuous manner in a reactor where the mean residence time of the catalyst is between 1 and 150 seconds. The catalyst comprises at least one titanium compound, at least one halogen-containing organoaluminum compound and at least one inorganic magnesium compound in suspension in at least one .alpha.,.omega.-dihaloalkane. The titanium compound is essentially a titanium (III) compound, the total content of titanium (II) and titanium (IV) being less than or equal to 15% of the total content of titanium. The catalyst is obtained by a process comprising, in a first step, the reduction of a titanium (IV) compound in an .alpha.,.omega.-dihaloalkane by means of a molar excess of at least one halogen-containing organoaluminum compound, in the absence of an ether, and, in a second step, the addition to the reaction mixture of a compound which forms a magnesium halide in situ without supplementary reduction of the titanium compound obtained in the first step. Molar ratios of the .alpha.,.omega.-dihaloalkane, the titanium compound, halogen-containing organoaluminum, and the compound which forms a magnesium halide in situ are also described.
摘要翻译：公开了一种用于烯烃聚合的方法，其使用（i）催化剂和（ii）在20℃至250℃之间的元素周期表第I，II或III族的有机金属活化剂，压力高达200 在惰性液体烃中，160-150℃的温度下，在400-3000巴的压力下，在反应器中连续地在惰性液体烃中悬浮或悬浮，其中催化剂的平均停留时间为 1到150秒之间。催化剂包含至少一种钛化合物，至少一种含卤素的有机铝化合物和至少一种α，ω-二卤代烷烃中的悬浮液中的至少一种无机镁化合物。钛化合物基本上是钛（III）化合物，钛（II）和钛（IV）的总含量小于或等于钛总含量的15％。该催化剂是通过一种方法获得的，该方法包括在第一步骤中，通过摩尔过量的至少一种含卤素的有机铝化合物在α，ω-二卤代烷烃中还原钛（IV）化合物，醚，并且在第二步中，在没有补充还原第一步中获得的钛化合物的情况下向原位形成镁卤化物的化合物的反应混合物加入。还描述了α，ω-二卤代烷烃，钛化合物，含卤素的有机铝和原位形成卤化镁的化合物的摩尔比。

2. 发明授权

US5320994A Process for preparing a catalyst for the polymerization of olefins 失效
标题翻译：制备烯烃聚合催化剂的方法
公开(公告)号：US5320994A
公开(公告)日：1994-06-14
申请号：US844931
申请日：1992-03-04
申请人： Karel Bujadoux , Jean-Michel Brusson , Francis Petit , Andre Mortreux
发明人： Karel Bujadoux , Jean-Michel Brusson , Francis Petit , Andre Mortreux
IPC分类号： C08F4/654 , C08F10/00
CPC分类号： C08F10/00
摘要： The process comprises, in a first step, the reduction of a titanium (IV) compound in an .alpha.,.omega.-dihalogenoalkane using a molar excess of at least one halogenated organoaluminium compound in the absence of an ether, and then in a second step, the addition of a reaction mixture of a compound capable of forming a magnesium halide in-situ, without additional reduction of the titanium compound obtained in the first step. The catalyst contains at least one titanium compound, at least one halogenated organoaluminium compound and at least one inorganic magnesium compound in suspension in at least one .alpha.,.omega.-dihalogenoalkane; the titanium cmpound is essentially a titanium (III) compound, the total titanium (II) and titanium (IV) content being less than or equal 15% to the total titanium content. It may also contain at least one vanadium compound, an inert solvent, at least one partially polymerized .alpha.-olefin and at least one organometallic activator from groups I to II of the Periodic Classification. Also described is a process for polymerization of olefins in the presence of said catalyst.
摘要翻译：该方法在第一步中包括在不存在醚的情况下使用摩尔过量的至少一种卤化有机铝化合物还原α，ω-二卤代烷烃中的钛（IV）化合物，然后在第二步中，加入能够原位形成卤化镁的化合物的反应混合物，而不需要额外还原在第一步中获得的钛化合物。催化剂在至少一种α，ω-二卤代烷烃中含有至少一种钛化合物，至少一种卤化有机铝化合物和悬浮液中的至少一种无机镁化合物; 钛化合物基本上是钛（III）化合物，总钛（II）和钛（IV）含量小于或等于总钛含量的15％。它还可以含有至少一种钒化合物，惰性溶剂，至少一种部分聚合的α-烯烃和至少一种有机金属活化剂，其定期分类来自I至II组。还描述了在所述催化剂存在下烯烃聚合的方法。

3. 发明授权

US5068014A Catalytic composition for the polymerization of olefins and its process of preparation 失效
标题翻译：用于烯烃聚合的催化组合物及其制备方法
公开(公告)号：US5068014A
公开(公告)日：1991-11-26
申请号：US369229
申请日：1989-06-22
申请人： Jean M. Brusson , Karel Bujadoux , Francis Petit , Jean M. Fuchs , Andre Mortreux
发明人： Jean M. Brusson , Karel Bujadoux , Francis Petit , Jean M. Fuchs , Andre Mortreux
IPC分类号： C08F4/60 , C08F4/62 , C08F4/642 , C08F4/655 , C08F10/00
CPC分类号： C08F10/00
摘要： Process for the preparation of a catalytic composition for the polymerization of olefins. At least partial electrochemical oxidation of aluminum in a solvent of .alpha.,.omega.-dihalogeno-alkane and simultaneously the electrochemical reduction of a compound of titanium (IV) occur in process.The catalytic composition comprises at least one titanium compound, at least one halogenated organo-aluminum compound and at least one inorganic magnesium compound in suspension in at least one .alpha.,.omega.-dihalogeno-alkane. The titanium compound is essentially a titanium (III) compound. The overall content of titanium (II) and titanium (IV) is less than or equal to 15% of the total titanium content.
摘要翻译：制备烯烃聚合催化组合物的方法。在α，ω-二卤代烷烃的溶剂中铝的至少部分电化学氧化，同时发生钛（IV）化合物的电化学还原。所述催化剂组合物包含至少一种钛化合物，至少一种卤化有机铝化合物和至少一种α，ω-二卤代烷烃中悬浮液中的至少一种无机镁化合物。钛化合物基本上是钛（III）化合物。钛（II）和钛（IV）的总含量小于或等于总钛含量的15％。

4. 发明授权

US5492983A Catalysts and process for the preparation of catalysts which may be used for the polymerization of ethylene 失效
标题翻译：用于制备可用于乙烯聚合的催化剂的催化剂和方法
公开(公告)号：US5492983A
公开(公告)日：1996-02-20
申请号：US244679
申请日：1994-06-07
申请人： Xavier Olonde , Karel Bujadoux , Andre Mortreux , Francis Petit, deceased
发明人： Xavier Olonde , Karel Bujadoux , Andre Mortreux , Francis Petit, deceased
IPC分类号： C08F4/42 , C08F4/54 , C08F4/62 , C08F10/00 , C08F10/02 , C08F4/14
CPC分类号： C08F10/02 , Y02P20/544
摘要： This catalyst consists of the reaction product, with at least one organomagnesium compound and/or organolithium compound R.sup.1 Li (R.sup.1 =alkyl) or ArLi (Ar=phenyl or benzyl), of the reaction product of (Cp).sub.2 MX.sub.2 Li(OR.sub.2).sub.2 (M=lanthanide, Sc, Y; (Cp)=optionally substituted cyclopentadienyl; and R=alkyl), with at least one bidentate ligand, such as .beta.-diketone or .beta.-keto imine CZ.sub.3 COCHZCDCZ.sub.3, Z selected from halogen, alkyl and H, D=O, NH or NR.sup.3 (R.sup.3 =alkyl or aryl); and phosphorus ylid R.sup.2.sub.3 P.dbd.CA--CO--R.sup.2, R.sup.2 chosen from alkyl and aryl; A=alkyl or H. It advantageously takes the form of a solution at least partially containing an aromatic hydrocarbon. The process for the polymerization of ethylene may be carried out at 20.degree.-250.degree. C. at a pressure which may range up to approximately 200 bars, in solution or in suspension in an at least C.sub.6 inert hydrocarbon or may be carried out continuously, in at least one autoclave or tubular reactor, at 150.degree.-300.degree. C., at 400-2000 bars, the reaction medium being in the supercritical state.
摘要翻译： PCT No.PCT / FR93 / 00996 Sec。 371日期：1994年6月7日 102（e）日期1994年6月7日PCT提交1993年10月8日PCT公布。第WO94 / 09044号公报该催化剂由（Cp）的反应产物与至少一种有机镁化合物和/或有机锂化合物R1Li（R1 =烷基）或ArLi（Ar =苯基或苄基）组成，具有至少一个二齿配位体，例如β-二酮或β-酮亚胺CZ 3 COCHZCDCZ 3，Z选自：（2）M 2镧（OR 2）2（M =镧系元素，Sc，Y;（Cp）=任选取代的环戊二烯基; R = 卤素，烷基和H，D = O，NH或NR 3（R 3 =烷基或芳基）; 和磷叶立德R23P = CA-CO-R2，R2选自烷基和芳基; A =烷基或H.它有利地是至少部分含有芳族烃的溶液的形式。乙烯聚合的方法可以在20-250℃下进行，压力范围可达200巴，溶液中或在至少C6惰性烃中的悬浮液中，或连续进行，在至少一个高压釜或管式反应器中，在150-300℃，400-2000巴条件下，反应介质处于超临界状态。

5. 发明授权

US5356848A Catalytic composition for the polymerization of olefins and its process of preparation 失效
标题翻译：用于烯烃聚合的催化组合物及其制备方法
公开(公告)号：US5356848A
公开(公告)日：1994-10-18
申请号：US117319
申请日：1993-09-07
申请人： Jean M. Brusson , Karel Bujadoux , Francis Petit , Jean M. Fuchs , Andre Mortreux
发明人： Jean M. Brusson , Karel Bujadoux , Francis Petit , Jean M. Fuchs , Andre Mortreux
IPC分类号： C08F4/60 , C08F4/62 , C08F4/642 , C08F4/655 , C08F10/00 , B01J31/00
CPC分类号： C08F10/00
摘要： Process for the preparation of a catalytic composition for the polymerization of olefins. At least partial electrochemical oxidation of aluminum in a solvent of .alpha.,.omega.-dihalogeno-alkane and simultaneously the electrochemical reduction of a compound of titanium (IV) occur in process.The catalytic composition comprises at least one titanium compound, at least one halogenated organo-aluminum compound and at least one inorganic magnesium compound in suspension in at least one .alpha.,.omega.-dihalogeno-alkane. The titanium compound is essentially a titanium (III) compound. The overall content of titanium (II) and titanium (IV) is less than or equal to 15% of the total titanium content.
摘要翻译：制备烯烃聚合催化组合物的方法。在α，ω-二卤代烷烃的溶剂中铝的至少部分电化学氧化，同时发生钛（IV）化合物的电化学还原。所述催化剂组合物包含至少一种钛化合物，至少一种卤化有机铝化合物和至少一种α，ω-二卤代烷烃中悬浮液中的至少一种无机镁化合物。钛化合物基本上是钛（III）化合物。钛（II）和钛（IV）的总含量小于或等于总钛含量的15％。

6. 发明授权

US5264088A Catalytic composition for the polymerization of olefins and its process of preparation 失效
标题翻译：用于烯烃聚合的催化组合物及其制备方法
公开(公告)号：US5264088A
公开(公告)日：1993-11-23
申请号：US741621
申请日：1991-08-07
申请人： Jean M. Brusson , Karel Bujadoux , Francis Petit , Jean M. Fuchs , Andre Mortreux
发明人： Jean M. Brusson , Karel Bujadoux , Francis Petit , Jean M. Fuchs , Andre Mortreux
IPC分类号： C08F10/00 , C25B3/00 , C07C2/02
CPC分类号： C08F10/00
摘要： Process for the preparation of a catalytic composition for the polymerization of olefins. At least partial electrochemical oxidation of aluminum in a solvent of .alpha., .omega.-dihalogeno-alkane and simultaneously the electrochemical reduction of a compound of titanium (IV) occur in process.The catalytic composition comprises at least one titanium compound, at least one halogenated organs-aluminum compound and at least one inorganic magnesium compound in suspension in at least one .alpha.,.omega.-dihalogeno-alkane. The titanium compound is essentially a titanium (III) compound. The overall content of titanium (II) and titanium (IV) is less than or equal to 15% of the total titanium content.
摘要翻译：制备烯烃聚合催化组合物的方法。在α，ω-二卤代烷烃的溶剂中铝的至少部分电化学氧化，同时发生钛（IV）化合物的电化学还原。催化剂组合物包含至少一种钛化合物，至少一种卤化器官 - 铝化合物和至少一种α，ω-二卤代烷烃中的悬浮液中的至少一种无机镁化合物。钛化合物基本上是钛（III）化合物。钛（II）和钛（IV）的总含量小于或等于总钛含量的15％。

7. 发明授权

US6063882A Long-chain dialkylmagnesium, its preparation process and applications 失效
标题翻译：长链二烷基镁，其制备方法和应用
公开(公告)号：US6063882A
公开(公告)日：2000-05-16
申请号：US106120
申请日：1998-06-29
申请人： Jean-Francois Pelletier , Karel Bujadoux , Xavier Olonde , Emmanuel Adisson , Andre Mortreux , Thomas Chenal
发明人： Jean-Francois Pelletier , Karel Bujadoux , Xavier Olonde , Emmanuel Adisson , Andre Mortreux , Thomas Chenal
IPC分类号： C07C51/15 , C07F3/02 , C08F4/44 , C08F4/60 , C08F10/00 , C08F20/06 , C08F110/02 , C08F118/02 , C08F210/00 , C08F210/02 , C08F11/02
CPC分类号： C07F3/02 , C07C51/15 , C08F10/00 , C08F110/02 , C08F210/02
摘要： This dialkylmagnesium is represented by the formula R--(CH.sub.2 --CH.sub.2).sub.n --Mg--(CH.sub.2 --CH.sub.2).sub.n' --R', (E--O--E').sub.x, where R and R' each independently represent a C.sub.1 -C.sub.20 hydrocarbon residue, branched or not, substituted or not, of the alkyl, cycloalkyl or aralkyl type; n and n', identical or substantially identical, represent an average number of --CH.sub.2 --CH.sub.2 -- linkages such that the average number of carbon atoms in each of the two chains borne by Mg is greater than 20; E and E', identical or different, each represent an alkyl radical, linear or cyclical, branched or not; and 0.ltoreq.x.ltoreq.2, x being the average value of the number of moles of E--O--E' ether complexed to the dialkylmagnesium. In order to prepare a dialkylmagnesium of this type, ethylene is polymerized in an anhydrous, de-oxygenated hydrocarbonaceous solution by means of a catalyst Cp*.sub.2 MCl.sub.2 Li(OEt.sub.2).sub.2 (Cp*=a pentamethylcyclopentadienyl ligand; M=scandium, yttrium or a metal of the lanthanide series; Et=ethyl), in the presence of a dialkylmagnesium, soluble in the solvent, of the formula R--Mg--R', (E--O--E').sub.x, where R, R', E, E' and x are as defined above, as a chain-transfer agent, and the reaction is stopped before the polydispersity of the polymer product obtained exceeds 2, preferably before it exeeds 1.5.
摘要翻译：该二烷基镁由式R-（CH 2 -CH 2）n-Mg-（CH 2 -CH 2）n'-R'，（EO-E'）x表示，其中R和R'各自独立地表示C1-C20烃烷基，环烷基或芳烷基的残基，支链或非取代的; n和n'相同或基本上相同，表示-CH2-CH2-键的平均数，使得由Mg承载的两个链中的每个链中的平均碳原子数大于20; E和E'相同或不同，各自表示直链或环状，支链或不支链的烷基; 和0≤x≤2，x是与二烷基镁络合的E-O-E'醚的摩尔数的平均值。为了制备这种二烷基镁，乙烯通过催化剂Cp * 2MCl2Li（OEt2）2（Cp * =五甲基环戊二烯基配体; M =钪，钇或金属）在无水，脱氧的含烃溶液中聚合的镧系元素; Et =乙基），在可溶于溶剂的二烷基镁存在下，式R-Mg-R'（EO-E'）x，其中R，R'，E，E' 和x如上所定义，作为链转移剂，并且在获得的聚合物产物的多分散性超过2之前优选在其超过1.5之前停止反应。

8. 发明授权

US5779942A Long-chain dialkylmagnesium, its preparation process and applications 失效
标题翻译：长链二烷基镁，其制备方法和应用
公开(公告)号：US5779942A
公开(公告)日：1998-07-14
申请号：US628373
申请日：1996-04-05
申请人： Jean-Fran.cedilla.ois Pelletier , Karel Bujadoux , Xavier Olonde , Emmanuel Adisson , Andre Mortreux , Thomas Chenal
发明人： Jean-Fran.cedilla.ois Pelletier , Karel Bujadoux , Xavier Olonde , Emmanuel Adisson , Andre Mortreux , Thomas Chenal
IPC分类号： C07C51/15 , C07F3/02 , C08F4/44 , C08F4/60 , C08F10/00 , C08F20/06 , C08F110/02 , C08F118/02 , C08F210/00 , C08F210/02
CPC分类号： C07F3/02 , C07C51/15 , C08F10/00 , C08F110/02 , C08F210/02
摘要： This dialkylmagnesium is represented by the formula R--(CH.sub.2 --CH.sub.2).sub.n --Mg--(CH.sub.2 --CH.sub.2).sub.n' --R', (E--O--E').sub.x, where R and R' each independently represent a C.sub.1 -C.sub.20 hydrocarbon residue, branched or not, substituted or not, of the alkyl, cycloalkyl or aralkyl type; n and n', identical or substantially identical, represent an average number of --CH.sub.2 --CH.sub.2 -- linkages such that the average number of carbon atoms in each of the two chains borne by Mg is greater than 20; E and E', identical or different, each represent an alkyl radical, linear or cyclical, branched or not; and 0.ltoreq.x.ltoreq.2, x being the average value of the number of moles of E--O--E' ether complexed to the dialkylmagnesium. In order to prepare a dialkylmagnesium of this type, ethylene is polymerized in an anhydrous, de-oxygenated hydrocarbonaceous solution by means of a catalyst Cp*.sub.2 MCl.sub.2 Li(OEt.sub.2).sub.2 (Cp*=a pentamethylcyclopentadienyl ligand; M=scandium, yttrium or a metal of the lanthanide series; Et=ethyl), in the presence of a dialkylmagnesium, soluble in the solvent, of the formula R--Mg--R', (E--O--E').sub.x, where R, R', E, E' and x are as defined above, as a chain-transfer agent, and the reaction is stopped before the polydispersity of the polymer product obtained exceeds 2, and preferably before it exceeds 1.5.
摘要翻译：该二烷基镁由式R-（CH 2 -CH 2）n-Mg-（CH 2 -CH 2）n'-R'，（EO-E'）x表示，其中R和R'各自独立地表示C1-C20烃烷基，环烷基或芳烷基的残基，支链或非取代的; n和n'相同或基本上相同，表示-CH2-CH2-键的平均数，使得由Mg承载的两个链中的每个链中的平均碳原子数大于20; E和E'相同或不同，各自表示直链或环状，支链或不支链的烷基; 和0≤x≤2，x是与二烷基镁络合的E-O-E'醚的摩尔数的平均值。为了制备这种二烷基镁，乙烯通过催化剂Cp * 2MCl2Li（OEt2）2（Cp * =五甲基环戊二烯基配体; M =钪，钇或金属）在无水，脱氧的含烃溶液中聚合的镧系元素; Et =乙基），在可溶于溶剂的二烷基镁存在下，式R-Mg-R'（EO-E'）x，其中R，R'，E，E' 和x如上所定义，作为链转移剂，并且在获得的聚合物产物的多分散性超过2，优选超过1.5之前停止反应。

9. 发明授权

US4585839A Catalyst containing an aromatic silicon compound for the polymerization of ethylene 失效
标题翻译：含有用于乙烯聚合的芳香族硅化合物的催化剂
公开(公告)号：US4585839A
公开(公告)日：1986-04-29
申请号：US743936
申请日：1985-06-12
申请人： Karel Bujadoux , Jean-Marie Neyer
发明人： Karel Bujadoux , Jean-Marie Neyer
IPC分类号： C08F4/00 , C08F4/60 , C08F4/64 , C08F10/00 , C08F10/02
CPC分类号： C08F10/00
摘要： A catalyst for the polymerization of ethylene comprising at least one halogenated compound of a transition metal of Groups IV to VI of the Periodic System and at least one aromatic silicon compound having the formula .phi..sub.n Si(OH).sub.4-n, in which .phi. is a substituted or unsubstituted aromatic or polyaromatic ring compound having from 6 to 15 carbon atoms and 1.ltoreq.n.ltoreq.3, said silicon compound being present in a molar ratio of between 0.2 and 2 inclusive with respect to said transition metal. Polymerization of ethylene may be carried out under a pressure of between 200 to 2500 bars and at a temperature of between 170.degree. and 300.degree. C. with the catalyst of this invention.
摘要翻译：一种用于乙烯聚合的催化剂，其包含至少一种周期系的第Ⅳ至Ⅵ族过渡金属的卤代化合物和至少一种具有式Ⅺi（OH）4-n的芳族硅化合物，其中phi为取代或未取代的具有6至15个碳原子且1≤n≤3的芳族或多芳族环化合物，所述硅化合物相对于所述过渡金属以相对于所述过渡金属的摩尔比在0.2和2之间存在。乙烯的聚合可以在200至2500巴的压力和170至300℃的温度下与本发明的催化剂进行。

10. 发明授权

US4474703A Grignard reagents and processes for making and using them 失效
标题翻译： Grignard试剂和制备和使用它们的方法
公开(公告)号：US4474703A
公开(公告)日：1984-10-02
申请号：US421499
申请日：1982-09-22
申请人： Karel Bujadoux , Jean-Marie Neyer , Jean-Pierre Houzeaux
发明人： Karel Bujadoux , Jean-Marie Neyer , Jean-Pierre Houzeaux
IPC分类号： C01F5/30 , C01G23/02 , C07F3/00 , C07F3/02 , C07F7/28 , C01G15/00
CPC分类号： C01F5/30 , C01G23/02 , C07F3/00 , C07F3/02
摘要： An organometallic halide having the formula:(RMX) (MX.sub.2).sub.a (MR.sub.2).sub.b (MH.sub.2).sub.cwherein a.ltoreq.0.45, b.ltoreq.0.15, and c.ltoreq.0.30, X is a halogen, R is a hydrocarbon radical, and M is a metal selected from the group consisting of magnesium, zinc, beryllium, and calcium is prepared by a continuous dry process by reacting an organic monohalide RX and a metal M in the form of convex solid grains of a size between 1 and 15 mm. The reaction temperature is lower than the temperature at which decomposition of the organometallic halide RMX begins and at least 10.degree. C. higher than the boiling point of the organic monohalide. The reaction may also take place in the presence of an organometallic derivative comprising a hydroxy group or an enolysable ketone group. The resulting organometallic halide may be used for the synthesis of anhydrous magnesium halide or for the reduction of titanium tetrachloride.
摘要翻译：具有式（RMX）（MX2）a（MR2）b（MH2）c的有机金属卤化物，其中a

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