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    • 9. 发明授权
    • Preparation of polymers of C.sub.2 -C.sub.10 -alk-1-enes using racemic
metal-locene complexes as catalysts
    • 使用外消旋金属 - 络合物作为催化剂制备C 2 -C 10 - 烷-1-烯的聚合物
    • US5491205A
    • 1996-02-13
    • US330870
    • 1994-10-28
    • Franz LanghauserJurgen KerthGunther SchweierHans-Herbert BrintzingerStefan ManselWerner RoellRobin Kirsten
    • Franz LanghauserJurgen KerthGunther SchweierHans-Herbert BrintzingerStefan ManselWerner RoellRobin Kirsten
    • C08F4/639C08F4/6392C08F4/642C08F4/646C08F4/68C08F10/00C08F110/06C08F4/622
    • C08F110/06C08F10/00C08F4/63912C08F4/63927
    • Polymers of C.sub.2 -C.sub.10 -alk-1-enes are prepared at from 0.5 to 3000 bar and from -50.degree. to 300.degree. C. using a catalyst system by a process in which the catalyst system used is one which contains, as active components:a) a metallocene complex of the general formula I ##STR1## where M is titanium, zirconium, hafnium, vanadium, niobium or tantalum,X is fluorine, chlorine, bromine, iodine, hydrogen, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl or --OR.sup.7,R.sup.7 is C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoraryl, where each alkyl radical is of 1 to 10 carbon atoms and each aryl radical is of 6 to 20 carbon atoms,R.sup.1 to R.sup.6 are each hydrogen, C.sub.1 -C.sub.10 -alkyl, 5-membered to 7-membered cycloalkyl, which in turn may carry C.sub.1 -C.sub.10 -alkyl radicals as substituents, C.sub.6 -C.sub.15 -aryl or arylalkyl, where two adjacent radicals together may furthermore be a cyclic group of 4 to 15, carbon atoms, or Si(R.sup.8).sub.3R.sup.8 is C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl or C.sub.3 -C.sub.10 -cycloalkyl, is silicon, germanium, tin or carbon,Y.sup.1, Y.sup.2 are each ##STR2## R.sup.9 to R.sup.16 are each hydrogen, C.sub.1 -C.sub.10 -alkyl, 5-membered to 7-membered cycloalkyl, which in turn may carry C.sub.1 -C.sub.10 -alkyl radicals as substituents, C.sub.6 -C.sub.15 -aryl or arylalkyl, where two adjacent radicals together may furthermore be a cyclic group of 4 to 15 carbon atoms, or Si(R.sup.17).sub.3,R.sup.17 is C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl or C.sub.3 -C.sub.10 -cycloalkyl andu, v, w are each an integer from 0 to 7, with the proviso that the sum is u+v+w.gtoreq.2, andb) an open-chain or cyclic alumoxane compound of the general formula VI or VII ##STR3## where R.sup.18 is C.sub.1 -C.sub.4 -alkyl and m is an integer from 5 to 30.
    • 使用催化剂体系,通过使用催化剂体系的方法制备C 2 -C 10 - 烷-1-烯的聚合物,其为0.5-3000巴和-50-300℃,其中使用的催化剂体系是含有作为活性组分的催化剂体系 :a)通式I的茂金属络合物,其中M是钛,锆,铪,钒,铌或钽,X是氟,氯,溴,碘,氢,C 1 -C 10 - 烷基, C 15 - 芳基或-OR 7,R 7是C 1 -C 10 - 烷基,C 6 -C 15 - 芳基,烷基芳基,芳基烷基,氟代烷基或氟芳基,其中每个烷基具有1-10个碳原子,并且每个芳基是6-20碳 原子,R 1至R 6各自为氢,C 1 -C 10 - 烷基,5元至7元环烷基,其又可以携带C 1 -C 10 - 烷基作为取代基,C 6 -C 15 - 芳基或芳基烷基,其中两个相邻的基团在一起 另外可以是4〜15个碳原子的环状基团,或Si(R 8)3 R 8是C 1 -C 10 - 烷基,C 6 -C 15 - 芳基或C 3 -C 10 - 环烷基,是硅,锗,锡或碳,Y 1 ,Y2分别为< 图像> R 9至R 16各自为氢,C 1 -C 10 - 烷基,5元至7元环烷基,其又可以携带C1-C10-烷基作为取代基,C6-C15 - 芳基或芳烷基,其中两个相邻的基团 另外可以是4〜15个碳原子的环状基团,或Si(R 17)3,R 17是C 1 -C 10 - 烷基,C 6 -C 15 - 芳基或C 3 -C 10 - 环烷基,u,v,w分别为整数 0至7,条件是该和为u + v + w> / = 2,和b)通式VI或VII的开链或环状铝氧烷化合物,其中R18 是C 1 -C 4 - 烷基,m是5至30的整数。
    • 10. 发明授权
    • Ziegler-Natta catalyst systems modified during their preparation
    • 齐格勒 - 纳塔催化剂体系在制备过程中改进
    • US6156691A
    • 2000-12-05
    • US928394
    • 1997-09-12
    • Stephan HufferUlrich MollIan David McKenzieFranz LanghauserPeter KolleRoland HingmannGunther SchweierRainer HemmerichJurgen Kerth
    • Stephan HufferUlrich MollIan David McKenzieFranz LanghauserPeter KolleRoland HingmannGunther SchweierRainer HemmerichJurgen Kerth
    • C08F4/02C08F4/642C08F4/646C08F4/654C08F4/658C08F10/00B01J31/00
    • C08F10/00
    • In catalyst systems of the Ziegler-Natta type modified during their preparation and comprising as active constituentsa) a titanium-containing solid component which is obtained by reacting a compound of titanium with a compound of magnesium, a halogen, an inorganic oxide as support, a C.sub.1 -C.sub.8 -alkanol and a carboxylic ester as electron donor compound,and also as cocatalystb) an aluminum compound andc) if desired, a further electron donor compound,the titanium-containing solid component a) is prepared by first, in a first stage, admixing an inorganic oxide as support with a solution of a chlorine-free compound of magnesium in an inert solvent, stirring this mixture for from 0.5 to 5 hours at from 10 to 120.degree. C. and subsequently reacting it while stirring continually in an inert solvent with a C.sub.1 -C.sub.8 -alkanol in an at least 1.3-fold excess, based on the compound of magnesium, to give a chlorine-free intermediate, then, without purification or extraction of the intermediate, adding a compound of trivalent or tetravalent titanium and a carboxylic ester as electron donor compound to this intermediate, stirring the resulting mixture for at least 30 minutes at from 20 to 130.degree. C., subsequently filtering off and washing the solid thus obtained and subsequently, in a second stage, extracting the solid obtained from the first stage in an inert solvent comprising at least 5% by weight of titanium tetrachloride and washing it with a liquid alkane.
    • 在其制备过程中改性的齐格勒 - 纳塔型催化剂体系中,包含作为活性成分的含钛固体成分a)通过使钛化合物与镁,卤素,无机氧化物作为载体反应而得到的含钛固体成分, 作为电子给体化合物的C1-C8-链烷醇和羧酸酯,以及作为助催化剂的b)铝化合物,和c)如果需要,另外的电子给体化合物,含钛固体组分a)首先在 第一阶段,将无机氧化物作为载体与无氯化合物的镁在惰性溶剂中的溶液混合,在10至120℃下搅拌该混合物0.5至5小时,随后在持续搅拌下反应 在基于镁化合物的至少1.3倍过量的C 1 -C 8烷醇的惰性溶剂中,得到无氯中间体,然后不经纯化或萃取中间体,加入一种 磅三价或四价钛和羧酸酯作为电子给体化合物,在20至130℃下搅拌所得混合物至少30分钟,随后过滤并洗涤由此获得的固体,随后在 第二阶段,在包含至少5重量%的四氯化钛的惰性溶剂中萃取从第一阶段获得的固体,并用液体烷烃洗涤。