公开(公告)号：US5618895A

公开(公告)日：1997-04-08

申请号：US121465

申请日：1993-09-16

申请人： Juergen Kerth ,  Peter Koelle ,  Ralf Zolk ,  Harald Schwager

发明人： Juergen Kerth ,  Peter Koelle ,  Ralf Zolk ,  Harald Schwager

IPC分类号： C08F2/34 ,  C08F4/642 ,  C08F4/648 ,  C08F210/06

CPC分类号： C08F210/06 ,  Y10S526/901 ,  Y10S526/916

摘要： Copolymers of propylene with other 1-alkenes, obtainable by gas-phase polymerization of a mixture of propylene and another 1-alkene in the absence of a liquid reaction medium under a pressure of from 15 to 30 bar, at from 60.degree. to 90.degree. C. and with an average holdup time of the polymer of from 1 to 5 hours, with the aid of a Ziegler-Natta catalyst system which, besides a titanium-containing solid component, contains an aluminum component and an electron donor, with the temperature being chosen so that, under the preset pressure, no condensation of the monomer mixture takes place in the gas space and, moreover, the ratio of the partial pressures of propylene and the other 1-alkene is adjusted to from 5:1 to 100:1, are particularly suitable for producing sheets and shaped articles.

摘要翻译： 丙烯与其它1-烯烃的共聚物，可通过在不存在液体反应介质的情况下，在15至30巴，60至90度的压力下，将丙烯与另一种1-烯烃的混合物气相聚合而得到。 并且借助于齐格勒 - 纳塔催化剂体系，聚合物的平均保持时间为1至5小时，除了含钛固体组分外，还含有铝组分和电子给体，温度 使得在预设压力下，在气体空间中不发生单体混合物的冷凝，此外，将丙烯和其它1-烯烃的分压比例调节至5:1至100:1。 1，特别适用于生产片材和成形制品。

公开(公告)号：US5536789A

公开(公告)日：1996-07-16

申请号：US427273

申请日：1995-04-24

申请人： Harald Schwager ,  Peter Koelle ,  Rueger Schlund ,  Ralf Zolk ,  Juergen Kerth ,  Guenther Schweter ,  Klaus-Dieter Hungenberg ,  Werner Schoene

发明人： Harald Schwager ,  Peter Koelle ,  Rueger Schlund ,  Ralf Zolk ,  Juergen Kerth ,  Guenther Schweter ,  Klaus-Dieter Hungenberg ,  Werner Schoene

IPC分类号： C08F4/654 ,  C08F2/34 ,  C08F2/38 ,  C08F4/60 ,  C08F4/649 ,  C08F10/06 ,  C08F110/00 ,  C08F110/06 ,  C08L23/10 ,  C08L23/12 ,  C08F255/02 ,  C08F297/08

CPC分类号： C08F110/06 ,  C08F10/06 ,  C08L23/12 ,  C08L2205/02 ,  C08L23/10

摘要： Propylene polymers have a molecular weight ratio Q (M.sub.w /M.sub.n) of from 6 to 30 and are obtainable by Ziegler-Natta polymerization in the presence of hydrogen as molecular weight regulator and are particularly suitable for the production of films and moldings.

摘要翻译： 丙烯聚合物的分子量比Q（＆upbar＆Mw /＆Upbar＆Mn）为6至30，可通过齐格勒 - 纳塔聚合在氢气存在下作为分子量调节剂获得，特别适用于制备薄膜和模制品。

公开(公告)号：US5166113A

公开(公告)日：1992-11-24

申请号：US759980

申请日：1991-09-17

申请人： Harald Schwager ,  Peter Koelle ,  Juergen Kerth ,  Ralf Zolk

发明人： Harald Schwager ,  Peter Koelle ,  Juergen Kerth ,  Ralf Zolk

IPC分类号： C08F10/00

CPC分类号： C08F10/00

摘要： Ziegler-Natta-type catalyst systems containing, as active constituents,a) a titanium-containing solid component which also contains magnesium, halogen and a carboxylic acid ester, and, as cocatalyst,b) an aluminum compound,wherein the carboxylic acid ester in the solid component is a diester of a carboxylic acid of the formula Ia or Ib ##STR1## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical or different and are hydrogen, C.sub.1 - to C.sub.15 -alkyl, C.sub.7 - to C.sub.15 -alkylaryl, or 5- to 7-membered cycloalkyl, which may itself carry C.sub.1 - to C.sub.10 -alkyl groups, are particularly suitable for the preparation of polypropylene and copolymers of propylene containing minor amounts of other .alpha.,.beta.-unsaturated olefinic compounds having from 2 to 12 carbon atoms.

摘要翻译： 含有作为活性成分的齐格勒 - 纳塔型催化剂体系a）含镁，卤素和羧酸酯的含钛固体组分，和作为助催化剂的b）铝化合物，其中羧酸酯在 固体组分是式Ia或Ib的羧酸的二酯（Ia）其中R 1，R 2，R 3和R 4相同或不同，为氢，C 1至C 15 - 烷基 可以自身携带C1-至C10烷基的C 7 -C 15烷基芳基或5-至7-元环烷基特别适用于制备聚丙烯和含有少量其它α，β- 具有2至12个碳原子的不饱和烯烃化合物。

公开(公告)号：US5147928A

公开(公告)日：1992-09-15

申请号：US660252

申请日：1991-02-25

申请人： Juergen Kerth ,  Harald Schwager ,  Ralf Zolk

发明人： Juergen Kerth ,  Harald Schwager ,  Ralf Zolk

IPC分类号： C08F2/34 ,  C08F10/00 ,  C08F210/06 ,  C08F297/08

CPC分类号： C08F297/083

摘要： Propylene-ethylene copolymers are prepared in an agitated bed of solids by first polymerizing propylene from the gas phase in a first polymerization zone at 20-40 bar and 60.degree.-90.degree. C. by addition of a Ziegler-Natta catalyst system, and copolymerizing in a second polymerization zone at 7-35 bar and 40.degree.-70.degree. C. the finely divided polymer from the first polymerization zone with a mixture of olefins a process which comprises copolymerizing in the second polymerization zone with a mixture of propylene, ethylene and a further .alpha.-olefin of from 4 to 10 carbon atoms, setting the ratio of the partial pressures between propylene and ethylene within the range from 100:20 to 100:120 and that of the partial pressures between propylene and the further .alpha.-olefin within the range from 100:1 to 100:20, setting the pressure in the second polymerization zone at at least 5 bar below the pressure in the first polymerization zone, and determining the weight ratio between the monomers reacted in the first polymerization zone and those reacted in the second polymerization zone in such a way that said weight ratio is within the range from 100:10 to 100:50.

摘要翻译： 丙烯 - 乙烯共聚物在搅拌的固体床中通过首先在20-40巴和60-90℃的第一聚合区中通过加入齐格勒 - 纳塔催化剂体系在气相中聚合丙烯来制备，并共聚合 在7-35巴和40-70℃的第二聚合区中，来自第一聚合区的细分聚合物与烯烃混合物的方法，该方法包括在第二聚合区中与丙烯，乙烯和 另外的4-10个碳原子的α-烯烃使丙烯和乙烯之间的分压比在100:20至100:120的范围内，丙烯与其它α-烯烃之间的分压比 范围为100:1至100:20，将第二聚合区中的压力设定在第一聚合区内的压力以下至少5巴，并测定单体之间的重量比 在第一聚合区和第二聚合区中反应的那些，使得所述重量比在100:10至100:50的范围内。

公开(公告)号：US5773537A

公开(公告)日：1998-06-30

申请号：US579890

申请日：1995-12-28

申请人： Patrik Mueller ,  Klaus-Dieter Hungenberg ,  Juergen Kerth ,  Ralf Zolk

发明人： Patrik Mueller ,  Klaus-Dieter Hungenberg ,  Juergen Kerth ,  Ralf Zolk

IPC分类号： C08F4/646 ,  C08F10/00 ,  B01J31/00 ,  B01J37/00 ,  C08F4/02 ,  C08F4/60

CPC分类号： C08F10/00

摘要： Catalyst systems of the Ziegler-Natta type contain, as active components a) a titanium-containing solid component in whose preparation a titanium compound, a compound of magnesium, a halogenating agent and an electron donor component are used, b) an aluminum compound and c) as a further electron donor component, an organosilicon compound of the formula (I) R.sup.1 R.sup.2 Si(OR.sup.3).sub.2 (I) where R.sup.1 is C.sup.1 -C.sub.10 -alkyl or C.sub.3 -C.sub.8 -cycloalkyl, excluding sec-butyl, R.sup.2 is sec-butyl and R.sup.3 is C.sub.1 -C.sub.8 -alkyl. The catalyst systems are particularly suitable for the preparation of polymers of C.sub.2 -C.sub.10 -alk-1-enes.

摘要翻译： 齐格勒 - 纳塔型催化剂体系包含作为活性组分的a）其中使用钛化合物，镁化合物，卤化剂和电子给体组分的含钛固体组分，b）铝化合物和 c）作为另外的电子给体组分，式（I）的有机硅化合物R1R2Si（OR3）2（Ⅰ）其中R1是C1-C10-烷基或C3-C8-环烷基，不包括仲丁基，R2是仲 - 丁基，R 3为C 1 -C 8 - 烷基。 催化剂体系特别适用于制备C 2 -C 10 - 烷-1-烯的聚合物。

公开(公告)号：US4977210A

公开(公告)日：1990-12-11

申请号：US389818

申请日：1989-08-04

申请人： Juergen Kerth ,  Rainer A. Werner ,  Ralf Zolk ,  Klaus-Dieter Ruempler ,  Guenther Schweier ,  Rudolf Mueller-Mall ,  Wolfgang Gruber

发明人： Juergen Kerth ,  Rainer A. Werner ,  Ralf Zolk ,  Klaus-Dieter Ruempler ,  Guenther Schweier ,  Rudolf Mueller-Mall ,  Wolfgang Gruber

IPC分类号： C08F2/34 ,  C08F4/02 ,  C08F4/58 ,  C08F4/60 ,  C08F4/64 ,  C08F4/642 ,  C08F297/08

CPC分类号： C08F297/083

摘要： Propylene/ethylene block copolymers are prepared by a continuous process in which, in each case in an agitated fixed bed of finely divided polymer from the gas phase, first (I) in a first polymerization zone, propylene is homopolymerized by feeding in a Ziegler-Natta catalyst system consisting of (1) a titanium component which contains titanium, magnesium, chlorine and a phthalic acid derivative, (2) an aluminumalkyl component and (3) a silane component, and (II) in a second polymerization zone, a mixture of propylene and ethylene is polymerized with the propylene homopolymer present in the reaction mixture obtained in the first polymerization zone by feeding in the said reaction mixture. In the process, (A) a titanium component (1) is used which is obtained by a method in which (1.1) first, (1.1.1) in a liquid hydrocarbon, (1.1.2) a finely divided magnesium halide, (1.1.3) an alkanol, (1.1.4) a certain phthalic acid derivative and (1.1.5) titanium tetrachloride are reacted with one another under certain conditions, (1.2) the solid intermediate obtained from (1.1) is extracted with titanium tetrachloride or a liquid alkylbenzene until the remaining solid substance has become substantially richer in magnesium, and (1.3) finally, the solid substance remaining in (1.2) is washed with an alkane in a certain manner, (B) a specific silane is used as (3), and (C) specifically selected polymerization parameters are employed, with relationships between the first and second polymerization zones.

摘要翻译： 丙烯/乙烯嵌段共聚物通过连续方法制备，其中在每种情况下，在来自气相的搅动的细分散聚合物的固定床中，在第一聚合区中的第一（I），丙烯通过进料齐格勒 - 纳塔催化剂体系（1）钛，镁，氯和邻苯二甲酸衍生物的钛成分，（2）铝烷基成分和（3）硅烷成分，（II）在第二聚合区中的混合物 的丙烯和乙烯通过在所述反应混合物中进料而与在第一聚合区中获得的反应混合物中存在的丙烯均聚物聚合。 在该方法中，（A）使用通过以下方法获得的钛组分（1）：（1.1）第一，（1.1.1）在液体烃中，（1.1.2）细碎的卤化镁， 1.1.3）链烷醇（1.1.4）某些邻苯二甲酸衍生物和（1.1.5）四氯化钛在一定条件下彼此反应，（1.2）从（1.1）得到的固体中间体用四氯化钛 或液态烷基苯，直到残留的固体物质变得更加富镁，（1.3）最后，以（某种）方式用烷烃洗涤残留在（1.2）中的固体，（B）使用特定的硅烷作为（ 3），和（C）具体选择的聚合参数，与第一和第二聚合区之间的关系。

公开(公告)号：US5162465A

公开(公告)日：1992-11-10

申请号：US646493

申请日：1991-01-28

申请人： Juergen Kerth ,  Ralf Zolk ,  Rainer Hemmerich

发明人： Juergen Kerth ,  Ralf Zolk ,  Rainer Hemmerich

IPC分类号： C08F4/58 ,  C08F4/60 ,  C08F4/64 ,  C08F4/658 ,  C08F10/00 ,  C08F10/06

CPC分类号： C08F10/06 ,  Y10S526/901

摘要： Polymers of propene are prepared using a Ziegler-Natta catalyst system consisting of (1) a titanium component which is based on a finely divided, shape-imparting silica gel and contains, in addition to titanium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component. In this process, a titanium component (1) is used which is obtained by a method in which (1.1) first (I) a carrier is prepared from (Ia) a silica gel, (Ib) an alkanol, (Ic) an organomagnesium compound and (Id) a gaseous chlorinating agent by a procedure in which (1.1.1) first (Ia) is reacted with (Ib), (1.1.2) then the mixture obtained in (1.1.1) is combined with (Ic), (1.1.3) then (Id) is passed into the mixture obtained in (1.1.2) and (I) is isolated, (1.2) thereafter a solid-phase intermediate is prepared from (I), (II) an alkanol, (III) titanium tetrachloride and (IV) a phthalic acid drivative by a procedure in which (1.2.1) first (I) is reacted with (II), (1.2.2) then (III) is introduced into the mixture resulting from (1.2.1), with the proviso that (IV) is also introduced during (1.2.1) and/or (1.2.2), (1.3) then the solid-phase product resulting from (1.2) is extracted with titanium tetrachloride and (1.4) finally the solid-phase product resulting from (1.3) is washed with a liquid hydrocarbon.

摘要翻译： 丙烯聚合物使用齐格勒 - 纳塔催化剂体系制备，该催化剂体系由以下组成：（1）基于精细分散的形状赋予硅胶的钛组分，除钛，镁，氯和苯甲酸衍生物外， （2）铝成分和（3）硅烷成分。 在该方法中，使用通过以下方法获得的钛组分（1）：其中（1.1）第一（I）载体由（Ia）硅胶制备，（Ib）烷醇，（Ic）有机镁 化合物和（Id）气态氯化剂，其中（1.1.1）第一（Ia）与（Ib），（1.1.2）反应，然后将（1.1.1）中获得的混合物与（Ic ），（1.1.3）然后（Id）进入（1.1.2）中获得的混合物中，（I）分离，（1.2）之后，从（I），（II）制备固相中间体 链烷醇，（III）四氯化钛和（IV）通过其中（1.2.1）第一（I）与（II），（1.2.2）然后（III）反应的方法将邻苯二甲酸驱动物引入混合物 （1.2.1）产生，条件是在（1.2.1）和/或（1.2.2），（1.3）中也引入了（IV），则从（1.2）得到的固相产物用 四氯化钛和（1.4）最后由（1.3）产生的固相产物用液体洗涤 加油

公开(公告)号：US5006620A

公开(公告)日：1991-04-09

申请号：US400350

申请日：1989-08-30

申请人： Ralf Zolk ,  Juergen Kerth ,  Rainer Hemmerich

发明人： Ralf Zolk ,  Juergen Kerth ,  Rainer Hemmerich

IPC分类号： C08F4/658 ,  C08F4/02 ,  C08F4/58 ,  C08F4/60 ,  C08F4/64 ,  C08F4/646 ,  C08F10/00 ,  C08F10/06

CPC分类号： C08F10/00 ,  C08F10/06 ,  Y10S526/909

摘要： Polymers of propene are prepared by means of a Ziegler-Natta catalyst system composed of (1) a titanium component based on a finely divided shape-dictating silica gel and containing titanium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component, the titanium component (1) being obtained by (1.1) first preparing (I) a carrier material from (Ia) a silica gel, (Ib) an organomagnesium compound (Ic) a gaseous chlorinating agent and (Id) a specific phthalic acid derivative by (1.1.1) first reacting (Ia) with (Ib), then (1.1.2) passing (Ic) into the product of (1.1.1) together with the phthalic acid derivative (Id) and isolating (I), (1.2) preparing a solid-phase intermediate from (I), (II) an alkanol and (III) titanium tetrachloride by (1.2.1) first reacting (I) with (II), then (1.2.2) introducing (III) into the product resulting from (1.2.1), then (1.3) extracting the solid-phase result from (1.2) with titanium tetrachloride or a titanium tetrachloride/ethylbenzene mixture, and finally (1.4) washing the solid-phase result from (1.3) with a liquid hydrocarbon.

摘要翻译： 丙烯聚合物通过齐格勒 - 纳塔催化剂体系制备，该催化剂体系由（1）基于精细分散形状的硅胶组成的钛组分，含有钛，镁，氯和苯甲酸衍生物，（2）铝 组分和（3）硅烷组分，钛组分（1）通过（1.1）首先制备（I）载体材料从（Ia）硅胶获得，（Ib）有机镁化合物（Ic），气态氯化剂 和（Id）通过（1.1.1）首先使（Ia）与（Ib）反应的（1.1.1）特定的邻苯二甲酸衍生物，然后（1.1.2）将（Ic）与（1.1.1）的产物一起与邻苯二甲酸衍生物 （I）和（II），（I）与（II）反应制备（I），（1.2）从（I），（II）烷基醇和（III）四氯化钛制备固相中间体（1.2.1） 然后（1.2.2）将（III）引入到由（1.2.1）得到的产物中，然后（1.3）从（1.2）中提取四氯化钛的固相或 四氯化钛/乙苯混合物，最后（1.4）用液态烃洗涤（1.3）的固相结果。

公开(公告)号：US4857613A

公开(公告)日：1989-08-15

申请号：US236213

申请日：1988-08-25

申请人： Ralf Zolk ,  Juergen Kerth ,  Rainer Hemmerich

发明人： Ralf Zolk ,  Juergen Kerth ,  Rainer Hemmerich

IPC分类号： C08F4/58 ,  C08F4/60 ,  C08F4/64 ,  C08F10/06

CPC分类号： C08F10/06

摘要： Polymers of propene are prepared using a Ziegler-Natta catalyst system consisting of (1) a titanium component which is based on a finely divided, shape-imparting silica gel and contains titanium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component. In the process, a titanium component (1) is employed which is obtained by (1.1) first preparing (I) a carrier from (Ia) a silica gel which has a relatively high moisture content, (Ib) an organomagnesium compound and (Ic) a gaseous chlorinating agent by a method in which (1.1.1) first (Ia) is reacted with (Ib), (1.1.2) then (Ic) is passed into the mixture obtained in (1.1.1), and (I) is isolated, (1.2) thereafter a solid-phase intermediate is prepared from (I), (II) an alkanol, (III) titanium tetrachloride and (IV) a phthalic acid derivative by a procedure in which (1.2.1) first (I) is reacted with (II), (1.2.2) then (III) is introduced into the mixture resulting from (1.2.1), with the proviso that (IV) is also introduced during (1.2.1) and/or (1.2.2), (1.3) then the solid-phase product resulting from (1.2) is extracted with titanium tetrachloride or a titanium tetrachloride/hydrocarbon mixture, and (1.4) finally the solid-phase product resulting from (1.3) is washed with a liquid hydrocarbon.

摘要翻译： 丙烯聚合物使用齐格勒 - 纳塔催化剂体系制备，该催化剂体系由（1）基于精细分散的形状赋予硅胶并含有钛，镁，氯和苯甲酸衍生物的钛组分组成，（2） 铝成分和（3）硅烷成分。 在该方法中，使用钛成分（1），其通过（1.1）首先制备（I）来自（Ia）具有较高水分含量的硅胶的载体（Ib）有机镁化合物和（Ic） ）气态氯化剂，其中（1.1.1）第一（Ia）与（Ib），（1.1.2）反应，然后将（Ic）转化为（1.1.1）中获得的混合物和（ I）分离，（1.2）之后，通过（I），（II）烷醇，（III）四氯化钛和（Ⅳ）邻苯二甲酸衍生物，通过步骤（1.2.1）制备固相中间体， 第一（I）与（II），（1.2.2）反应，然后将（III）引入由（1.2.1）得到的混合物中，条件是在（1.2.1）期间引入（IV）和 /或（1.2.2），（1.3），然后用四氯化钛或四氯化碳/烃混合物萃取由（1.2）得到的固相产物，（1.4）最后由（1.3）得到的固相产物 用液体水溶液洗涤 碳。

公开(公告)号：US4843132A

公开(公告)日：1989-06-27

申请号：US176861

申请日：1988-04-01

申请人： Rainer A. Werner ,  Ralf Zolk

发明人： Rainer A. Werner ,  Ralf Zolk

IPC分类号： C08F4/02 ,  C08F4/58 ,  C08F4/60 ,  C08F4/64 ,  C08F10/00 ,  C08F10/06

CPC分类号： C08F10/00

摘要： Polymers of propene are prepared using a Ziegler-Natta catalyst system consisting of (1) a titanium component which contains titanium, magnesium, chlorine and a benzenecarboxylic acid derivative on a carrier, (2) an aluminum component and (3) a silane component. The process employs a titanium component (1) which is obtained by a method in which (1.1) first a solid-phase intermediate is prepared from (I) magnesium chloride, (II) an alkanol, (III) a carrier which in turn consists of a finely divided inorganic oxide carrier material which has been pretreated with an alkylchlorosilane, (IV) titanium tetrachloride and (V) a phthalic acid derivative, in such a way that (1.1.1) first (I) is reacted with (II), (1.1.2) then the carrier (III) is introduced into the substance resulting from (1.1.1), (1.1.3) thereafter the solid-phase substance resulting from (1.1.2) is reacted with (IV) in a liquid hydrocarbon, with the proviso that (V) is also introduced in (1.1.1) or (1.1.2) or (1.1.3), the (1.2) the solid-phase substance resulting from (1.1) is extracted with titanium tetrachloride, and finally the solid-phase substance resulting from (1.2) is extracted with a liquid hydrocarbon.

摘要翻译： 丙烯的聚合物使用由（1）钛，镁，氯和苯甲酸衍生物在载体上的钛组分，（2）铝组分和（3）硅烷组分组成的齐格勒 - 纳塔催化剂体系制备。 该方法采用通过以下方法获得的钛组分（1）：其中（1.1）首先由（I）氯化镁，（II）烷醇制备固相中间体，（III）载体，其又包含 （I）与（II）反应的已经用烷基氯硅烷，（IV）四氯化钛和（V）邻苯二甲酸衍生物预处理的细分无机氧化物载体材料， ，（1.1.2）然后将载体（III）引入到（1.1.1），（1.1.3）所得的物质中，其后由（1.1.2）得到的固相物质与（IV）在 液态烃，条件是（V）也被引入到（1.1.1）或（1.1.2）或（1.1.3）中，（1.2）由（1.1）得到的固相物质用 四氯化钛，最后用液体烃提取由（1.2）得到的固相物质。