公开(公告)号：US4831090A

公开(公告)日：1989-05-16

申请号：US108457

申请日：1987-10-15

申请人： Robert Bachl ,  Guido Funk ,  Konrad Richter ,  Rainer Hemmerich ,  Roland Saive

发明人： Robert Bachl ,  Guido Funk ,  Konrad Richter ,  Rainer Hemmerich ,  Roland Saive

IPC分类号： C08F4/60 ,  C08F4/62 ,  C08F4/639 ,  C08F4/64 ,  C08F4/68 ,  C08F4/685 ,  C08F10/00 ,  C08F10/02

CPC分类号： C08F10/00

摘要： Homopolymerization and copolymerization of ethene are carried out using a Ziegler catalyst system consisting of (1) a transition metal catalyst component prepared by a method in which (1.1) first (1.1.1) an inorganic oxide substance (I) as a carrier and (1.1.2) a solution (II) of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex, (IIb2) a titanium trihalide or titanium trihalide/alcohol complex and, if desired, (IIb3) a zirconium tetrahalide, are combined with formation of a suspension (III), the latter is evaporated down to form a solid-phase intermediate (IV), (1.2) then (1.2.1) the solid-phase intermediate (IV) obtained from (1.1), and (1.2.2) a dissolved organoaluminum compound (V), are combined with formation of a suspension, the resulting suspended substance being a solid-phase product (VI), (2) an organoaluminum catalyst component and (3) an organohalogen catalyst component. In this process, the transition metal catalyst component (1) used is one prepared by a method in which (1.3) in addition (1.3.1) the product (VI) obtained from (1.2) is reacted with (1.3.2) oxygen, the resulting solid-phase end product (VII) being the novel transition metal catalyst component (1).

摘要翻译： 乙烯的均聚和共聚使用齐格勒催化剂体系进行，所述齐格勒催化剂体系由（1）通过以下方法制备的过渡金属催化剂组分：（1.1）第一（1.1.1）作为载体的无机氧化物（I）和（ 1.1.2）（IIa）某种氧杂烃的溶液（II）和（IIb）（IIb1）三氯化钒/醇络合物的混合物，（IIb2）三卤化钛或三卤化钛/醇络合物的混合物，如果需要， （IIb3）四卤化锆与形成悬浮液（III）组合，将其蒸发掉形成固相中间体（IV），（1.2）然后（1.2.1）固相中间体（IV ）和（1.2.2）溶解的有机铝化合物（V）与形成悬浮液结合，得到的悬浮物质为固相产物（VI），（2）有机铝催化剂组分 和（3）有机卤素催化剂组分。 在该方法中，使用的过渡金属催化剂组分（1）是通过（1.3）另外（1.3.1）从（1.2）获得的产物（VI）与（1.3.2）氧气反应的方法制备的 得到的固相终产物（Ⅶ）是新型过渡金属催化剂组分（1）。

公开(公告)号：US06180731B2

公开(公告)日：2001-01-30

申请号：US09000011

申请日：1997-01-22

申请人： Wolfgang Rohde ,  Roland Saive ,  Dieter Lilge ,  Martin Lux ,  Peter Bauer

发明人： Wolfgang Rohde ,  Roland Saive ,  Dieter Lilge ,  Martin Lux ,  Peter Bauer

IPC分类号： C08F442

CPC分类号： C08F10/00 ,  C08F4/61904 ,  C08F4/61912 ,  C08F4/61925 ,  C08F210/16 ,  Y10S526/943 ,  C08F210/14 ,  C08F2500/13 ,  C08F2500/12 ,  C08F2500/07 ,  C08F2500/26 ,  C08F4/63904 ,  C08F4/69

摘要： Polymers of ethylene are obtainable by polymerization of ethylene and, if desired, further comonomers in the presence of a catalyst system comprising as active constituents I) a Phillips catalyst, II) a solid which is different from I) and comprises a component which is derived from the metallocene complexes of the formula (A) in which the substituents and indices have the following meanings:  R1 to R10 are hydrogen, C1-C10-alkyl, 5-to 7-membered cycloalkyl which may in turn bear C1-C6-alkyl groups as substituents, C6-C15-aryl or aryalkyl, where two adjacent radicals may also together form a cyclic group having from 4 to 15 carbon atoms, or Si(R11)3, where R11 is C1-C10-alkyl, C6-C15-aryl or C3-C10-cycloalkyl, or the radicals R4 and R9 together form a group —[Y(R12R13)]m—, where Y is silicon, germanium, tin or carbon, and R12, R13 are hydrogen C1-C10-alky, C3-C10-cycloalyl or C6-C15-aryl, M is a metal of transition groups IV to VIII or a metal of the lanthanide series, Z1, Z2 are fluorine, chlorine, bromine, iodine, hydrogen, C1-C20-alkyl or aryl, —OR14, —OOCR14,  where R14 is hydrogen or C1-C20-alkyl; R15 is C1-C20-alkyl; m is 1,2,3 or 4; n is 0, or 2; r is 0, 1 or 2; the sum n+r is likewise 0, 1 or 2, and, if desired, III) an organometallic component selected from groups IA, IIA, IIB and IIIA of the Periodic Table of the Elements.

摘要翻译： 乙烯的聚合物可以通过在包含作为活性成分的催化剂体系的存在下乙烯和如果需要的情况下进一步的共聚单体获得。I）菲利普斯催化剂，II）与I）不同的固体，并且包含衍生自 式（A）的金属茂络合物，其中取代基和指数具有以下含义：R 1至R 10是氢，C 1 -C 10 - 烷基，5-至7-元环烷基，其也可以含有C 1 -C 6 - 烷基 作为取代基，其中两个相邻基团也可以一起形成具有4至15个碳原子的环状基团的C 6 -C 15 - 芳基或芳烷基，或其中R 11是C 1 -C 10 - 烷基，C 6 -C 15 - 芳基或C 3 -C 10 - 环烷基，或基团R 4和R 9一起形成 - [Y（R 12 R 13）] m - 基团，其中Y是硅，锗，锡或碳，R 12，R 13是氢C1-C10-烷基 C 3 -C 10 - 环烷基或C 6 -C 15 - 芳基，M为Ⅳ〜Ⅷ族金属或镧系金属，Z 1，Z 2为氟， 氯，溴，碘，氢，C 1 -C 20烷基或芳基，-OR 14，-OOCR 14，其中R 14是氢或C 1 -C 20烷基; R 15是C 1 -C 20 - 烷基; m为1,2,3或4; n为0或2; r为0,1或2; 总和n + r同样为0,1或2，如果需要，III）选自元素周期表的IA，IIA，IIB和IIIA族的有机金属组分。

公开(公告)号：US5324697A

公开(公告)日：1994-06-28

申请号：US904924

申请日：1992-06-26

申请人： Hans-Joachim Mueller ,  Rainer Konrad ,  Guenther Schweier ,  Siegfried Weber ,  Roland Saive ,  Peter Koelle

发明人： Hans-Joachim Mueller ,  Rainer Konrad ,  Guenther Schweier ,  Siegfried Weber ,  Roland Saive ,  Peter Koelle

IPC分类号： C08F4/02 ,  C08F4/24 ,  C08F4/60 ,  C08F4/69 ,  C08F10/00 ,  C08F10/02

CPC分类号： C08F10/02

摘要： A novel Phillips catalyst for the homopolymerization of ethylene and the copolymerization of ethylene with .alpha.-olefins contains as catalytically active components a specific chromium catalyst on an aluminum phosphate support and cocatalysts of the formula I to IV, ##STR1## where M is lithium, sodium and potassium,M.sup.1 is magnesium and zinc,M.sup.2 is boron and aluminum,R is C.sub.1 -C.sub.10 -alkyl and C.sub.6 -C.sub.20 -aryl,R.sup.1 is R and C.sub.1 -C.sub.10 -alkoxy and C.sub.6 -C.sub.20 -aryloxy,X is chlorine, bromine and iodine,n is 0, 1 and 2The chromium catalyst on an aluminum phosphate support can be obtained by applying chromium compounds to a finely divided aluminum phosphate with a P:A1 molar ratio near to or equal to 1 and a pore volume of >1 cm.sup.3 /g and activating the resulting intermediate at elevated temperatures in an oxidizing atmosphere. The novel Phillips catalyst has an exceptionally long duration of activity and its productivity can be increased further by adding hydrogen.

摘要翻译： 用于乙烯均聚和乙烯与α-烯烃共聚的新型菲利普斯催化剂在磷酸铝载体上含有特定的铬催化剂和式I至IV的助催化剂，MR（I）M1R2（II）M2R3的催化活性组分 -n1Xn（III）MM2RR31（IV）其中M是锂，钠和钾，M1是镁和锌，M2是硼和铝，R是C1-C10-烷基和C6-C20-芳基，R1是R和C1- C10烷氧基和C6-C20芳氧基，X是氯，溴和碘，n是0,1和2。磷酸铝载体上的铬催化剂可以通过将铬化合物施加到具有P： A1摩尔比接近或等于1，孔体积> 1cm 3 / g，并在氧化气氛中在高温下活化所得中间体。 新型菲利普斯催化剂具有非常长的活性持续时间，并且通过加入氢可以进一步提高其生产率。

公开(公告)号：US5756607A

公开(公告)日：1998-05-26

申请号：US666409

申请日：1996-06-26

申请人： Martin Lux ,  Roland Saive ,  Franz Langhauser ,  Wolfgang Micklitz ,  Hans-Helmut Gortz ,  Dieter Lilge

发明人： Martin Lux ,  Roland Saive ,  Franz Langhauser ,  Wolfgang Micklitz ,  Hans-Helmut Gortz ,  Dieter Lilge

IPC分类号： C08F2/06 ,  C08F2/14 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/64 ,  C08F4/642 ,  C08F4/646 ,  C08F4/6592 ,  C08F10/00 ,  C08F10/02 ,  C08F110/02 ,  C08F210/16

CPC分类号： C08F10/00 ,  C08F10/02 ,  C08F210/16 ,  C08F110/02 ,  C08F4/63912 ,  C08F4/63916 ,  C08F4/6392 ,  Y10S526/943

摘要： Homopolymers of ethylene or copolymers of ethylene with other olefins or mixtures thereof are prepared by suspension polymerization in the presence of catalyst systems by a process in which the catalyst systems used are those which contain, as active components, A) a finely divided carrier treated with trialkylaluminum, B) a metallocene complex, C) an open-chain or cyclic alumoxane compound and D) an alkali metal alkyl or alkaline earth metal alkyl or a mixture thereof.

摘要翻译： PCT No.PCT / EP94 / 04125 Sec。 371日期1996年6月26日第 102（e）日期1996年6月26日PCT 1994年12月13日PCT PCT。 出版物WO95 / 18160 日期1995年7月6日乙烯的共聚物或乙烯与其它烯烃或其混合物的共聚物通过在催化剂体系的存在下通过悬浮聚合制备，其中使用的催化剂体系是含有作为活性组分的A） 用三烷基铝处理的细分载体，B）茂金属络合物，C）开链或环状铝氧烷化合物，和D）碱金属烷基或碱土金属烷基或其混合物。

公开(公告)号：US5188998A

公开(公告)日：1993-02-23

申请号：US671591

申请日：1991-03-19

申请人： Ulrich Bueschges ,  Roland Saive

发明人： Ulrich Bueschges ,  Roland Saive

IPC分类号： C08F4/616 ,  C08F4/622 ,  C08F4/68 ,  C08F10/00

CPC分类号： C08F10/00

摘要： A transition-metal catalyst component for a Ziegler catalyst system, obtainable by1) mixing an inorganic, oxidic carrier with a transition-metal starting component in an organic solvent,2) removing the solvent by evaporation,3) mixing the solid-phase intermediate from step (2) with3.1) an organoaluminum catalyst component of the formula AlR.sub.m X.sub.3-m, whereR is a C.sub.1 - to C.sub.18 -hydrocarbon radical,m is from 1 to 3, andX is OR, chlorine, bromine or hydrogen, and3.2) an organic carboxylate or an organosilicon compound or a mixture thereof in an organic solvent, and4) if desired, isolating the solid-phase intermediate by filtration, washing and drying,and the use thereof for the homopolymerization or copolymerization of ethene are described.

摘要翻译： 一种齐格勒催化剂体系的过渡金属催化剂组分，其可通过以下步骤获得：1）将无机氧化载体与过渡金属起始组分混合在有机溶剂中，2）通过蒸发除去溶剂; 3）将固相中间体 从步骤（2）与3.1）式AlRmX3-m的有机铝催化剂组分，其中R是C 1 -C 18烃基，m为1至3，X为OR，氯，溴或氢，以及 3.2）在有机溶剂中的有机羧酸盐或有机硅化合物或其混合物，以及4）如果需要，通过过滤，洗涤和干燥分离固相中间体，并描述其用于乙烯均聚或共聚的用途 。

公开(公告)号：US5143882A

公开(公告)日：1992-09-01

申请号：US667119

申请日：1991-03-11

申请人： Ulrich Bueschges ,  Roland Saive

发明人： Ulrich Bueschges ,  Roland Saive

IPC分类号： C08F4/685 ,  C08F10/00

CPC分类号： C08F10/00

摘要： A transition-metal catalyst component for a Ziegler catalyst system, obtainable by1) mixing, in a solvent, an inorganic, oxidic carrier with1.1) a vanadium trihalide/alcohol complex of the formula VY.sub.3 nZ-OH, whereY is chlorine or bromine,N is from 1 to 6, andZ is a monovalent, saturated, aliphatic or araliphatic hydrocarbon radical having not more than 10 carbon atoms, and1.2) a titanium trihalide or a titanium trihalide/aluminum trihalide complex, where the halogen can be chlorine and/or bromine, or a titanium trihalide complex of the formula TiY.sub.3. nZ-OH or a mixture thereof, whereY is chlorine or bromine,n is from 1 to 6, andZ is a monovalent, saturated, aliphatic or araliphatic hydrocarbon radical having not more than 10 carbon atoms or a mixture thereof, and1.3) a zirconium tetrahalide, where the halogen can be chlorine and/or bromine,2) removing the solvent by evaporation,3) mixing the solid-phase intermediate from step (2) with3.1) an organoaluminum catalyst component of the formula AlR.sub.m X.sub.3-m, whereR is a C.sub.1 - to C.sub.18 - hydrocarbon radical,m is from 1 to 3, andX is OR, chlorine, bromine or hydrogen, and3.2) an organic carboxylate or an organosilicon compound or a mixture thereof in an organic solvent, and4) if desired, isolating the solid-phase intermediate by filtration, washing and drying.and the use thereof for the homopolymerization or copolymerization of ethane are described.

摘要翻译： 一种用于齐格勒催化剂体系的过渡金属催化剂组分，可通过以下步骤获得：1）在溶剂中将无机氧化载体与1.1）式VY3nZ-OH的三卤化钒/醇络合物混合，其中Y是氯或溴， N为1至6，Z为不大于10个碳原子的单价饱和脂族或芳脂族烃基，和1.2）三卤化钛或三卤化钛/三卤化铝配合物，其中卤素可为氯和 /或溴，或式TiY3的三卤化钛络合物。 nZ-OH或其混合物，其中Y为氯或溴，n为1至6，Z为不大于10个碳原子的一价饱和脂族或芳脂族烃基或其混合物，1.3） 四卤化锆，其中卤素可以是氯和/或溴，2）通过蒸发除去溶剂，3）将步骤（2）的固相中间体与3.1）式AlRmX3-m的有机铝催化剂组分混合， 其中R是C 1 -C 18烃基，m为1至3，X为OR，氯，溴或氢，以及3.2）有机溶剂中的有机羧酸盐或有机硅化合物或其混合物，以及 4）如果需要，通过过滤，洗涤和干燥分离固相中间体。 并描述了其用于乙烷的均聚或共聚的用途。

公开(公告)号：US5143881A

公开(公告)日：1992-09-01

申请号：US667118

申请日：1991-03-11

申请人： Ulrich Bueschges ,  Roland Saive ,  Godofredo Follmer

发明人： Ulrich Bueschges ,  Roland Saive ,  Godofredo Follmer

IPC分类号： C08F4/685 ,  C08F10/00

CPC分类号： C08F10/00

摘要： A transition-metal catalyst component for a Ziegler catalyst system, obtainable by1) mixing, in a solvent, an inorganic, oxidic carrier with1.1) a vanadium trihalide alcohol complex of the formula VY.sub.3.nZ--OH, whereY is chlorine or bromine,n is from 1 to 6, andZ is a monovalent, saturated, aliphatic, aromatic or araliphatic hydrocarbon radical having not more than 10 carbon atoms, and1.2) a titanium halide or a titanium trihalide/aluminum trihalide complex, where the halogen can be chlorine and/or bromine, or a titanium trihalide complex of the formula TiY.sub.3.nZ--OH or mixtures thereof, whereY is chlorine or bromine,n is from 1 to 6, andZ is a monovalent, saturated, aliphatic, aromatic or araliphatic hydrocarbon radical having not more than 10 carbon atoms, and1.3) a compound of the formula BX.sub.n Y.sub.m R.sub.p or SiX.sub.n Y.sub.m R.sub.q or mixtures thereof, whereX is OR,Y is chlorine, bromine or hydrogen, andR is a C.sub.1 - to C.sub.18 -hydrocarbon radical, with the proviso that n>0 and n+m+p=3 or n+m+q=4,2) removing the solvent by evaporation,3) mixing the solid-phase intermediate from step 2) with3.1) an organoaluminum catalyst component of the formula AlR.sub.m X.sub.3-m, whereR is a C.sub.1 - to C.sub.18 -hydrocarbon radical,m is from 1 to 3, andX is OR, chlorine, bromine or hydrogen, and3.2) an organic carboxylate or an organosilicon compound or a mixture thereof in an organic solvent, and4) if desired, isolating the solid-phase intermediate by filtration, washing and drying,and the use thereof for the homopolymerization or copolymerization of ethene are described.

摘要翻译： 用于齐格勒催化剂体系的过渡金属催化剂组分，其可通过以下步骤获得：1）在溶剂中将无机氧化物载体与1.1）式VY3.nZ-OH的三卤化钒醇络合物混合，其中Y是氯或溴 ，n为1-6，Z为不大于10个碳原子的一价饱和脂族芳族或芳脂族烃基，和1.2）卤化钛或三卤化钛/三卤化铝配合物，其中卤素可以 是氯和/或溴，或式TiY3.nZ-OH的三卤化钛配合物或其混合物，其中Y为氯或溴，n为1至6，Z为单价，饱和，脂族，芳族或 具有不超过10个碳原子的芳脂族烃基，和1.3）式BXnYmRp或SiXnYmRq的化合物或其混合物，其中X为OR，Y为氯，溴或氢，R为C1-至C18-烃基 ，条件是n> 0和n + m + p = 3或n + m + q = 4,2） 通过蒸发除去溶剂，3）将来自步骤2）的固相中间体与3.1）式AlRmX3-m的有机铝催化剂组分混合，其中R是C 1 -C 18烃基，m为1至3 ，和X为OR，氯，溴或氢，以及3.2）有机溶剂中的有机羧酸盐或有机硅化合物或其混合物，以及4）如果需要，通过过滤，洗涤和干燥分离固相中间体， 并描述了其用于乙烯的均聚或共聚的用途。