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1. 发明授权

US4385162A Preparation of homopolymers and copolymers of .alpha.-mono-olefins by means of a Ziegler-Natta catalyst system 失效
公开(公告)号：US4385162A
公开(公告)日：1983-05-24
申请号：US256129
申请日：1981-04-21
申请人： James F. R. Jaggard , Peter Klaerner , Guenther Schweier
发明人： James F. R. Jaggard , Peter Klaerner , Guenther Schweier
IPC分类号： C08F4/64 , C08F10/00
CPC分类号： C08F10/00 , Y10S526/906
摘要： A process for the preparation of homopolymers and copolymers of .alpha.-monoolefins by means of a Ziegler-Natta catalyst system comprising (1) a titanium-III component, which is prepared by subjecting (1.1) a titanium trichloride/aluminum trichloride compound (a) and (1.2) an ester (b) to a certain type of milling treatment in which (A) a vibratory ball mill providing a relatively high milling acceleration is used, (B) the mill is first charged with the titanium-containing compound (a) and, if appropriate, is run for a certain period, thereafter (C) the ester (b) is added at a certain rate while milling the charge, thereupon (D) the charge is kept at +15.degree. C. or above for a certain period, while continuing the milling, hereupon (E), if appropriate, the product obtained from (D) is milled further for a certain period at +5.degree. C. or below, then (F), if appropriate, but advantageously so, the product obtained from (D) or (E) is kept at +20.degree. C. or above for a certain period, without milling, and thereafter (G), if appropriate, the product obtained from (F) is milled further for a certain period at +5.degree. C. or below, (2) an aluminum-alkyl component containing a chlorine bonded to the aluminum, and (3), if appropriate, a phenolic compound of a certain category, in which process a titanium-III component (1) is employed, in the preparation of which additionally .sup.- (H) a suspension is prepared from (H.sub.1) the product obtained according to (D), (E), (F) or (G), (H.sub.2) a liquid hydrocarbon (c) and (H.sub.3) an oxygen-containing compound (d), consisting of (d.sub.1) an ether of a certain category and/or (d.sub.2) an ester of a certain category, thereafter (I) the suspension obtained according to (H) is kept at an elevated temperature for a certain period, with vigorous agitation, and is then cooled, hereupon (J), if appropriate, the solid is isolated from the suspension obtained according to (I), and, if desired, is washed with a liquid hydrocarbon and dried, the novel titanium-III component (1) being the solid, in suspended form, obtained according to (I) or the solid, in isolated form, obtained according to (J). Using this Ziegler-Natta catalyst system, polymers with relatively high stereo-regularity and advantageous morphological properties can be obtained in relatively high yield.

2. 发明授权

US4761461A Preparation of homopolymers and copolymers of propylene by means of a Ziegler-Natta catalyst system 失效
标题翻译：通过齐格勒 - 纳塔催化剂体系制备丙烯的均聚物和共聚物
公开(公告)号：US4761461A
公开(公告)日：1988-08-02
申请号：US930529
申请日：1986-11-14
申请人： James F. R. Jaggard , Rainer A. Werner , Wolfgang Gruber
发明人： James F. R. Jaggard , Rainer A. Werner , Wolfgang Gruber
IPC分类号： C08F2/02 , C08F4/02 , C08F4/58 , C08F4/60 , C08F4/64 , C08F4/658 , C08F10/00 , C08F10/06
CPC分类号： C08F10/06 , Y10S526/901
摘要： Polymers of polypropylene are prepared by means of a Ziegler-Natta catalyst system comprising (1) a titanium component which contains titanium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component, wherein the (1) used is obtained by (1.1) first reacting with one another (1.1.1) in a liquid hydrocarbon, (1.1.2) a finely divided magnesium halide, (1.1.3) an alkanol, (1.1.4) a phthalic acid ester and (1.1.5) titanium tetrachloride under certain conditions, (1.2) then extracting the solid intermediate obtained from (1.1) with titanium tetrachloride until the remaining solid substance has become significantly richer in magnesium, and (1.3) finally washing the solid substance remaining in (1.2) with an alkane in a certain manner.
摘要翻译：聚丙烯的聚合物通过齐格勒 - 纳塔催化剂体系制备，该系统包括（1）钛，镁，氯和苯甲酸衍生物的钛组分，（2）铝组分和（3）硅烷组分，其中（1.1）通过（1.1）在液体烃中首先反应（1.1.1）获得，（1.1.2）细碎的卤化镁，（1.1.3）链烷醇，（1.1.4）a 邻苯二甲酸酯和（1.1.5）四氯化钛，（1.2），然后用四氯化钛萃取由（1.1）得到的固体中间体，直到剩下的固体物质变得更加富镁，（1.3）最后洗涤残留在（1.2）中的固体物质以某种方式与烷烃反应。

3. 发明授权

US4385160A Preparation of homopolymers and copolymers of .alpha.-monoolefins by means of a Ziegler-Natta catalyst system 失效
标题翻译：通过齐格勒 - 纳塔催化剂体系制备α-单烯烃的均聚物和共聚物
公开(公告)号：US4385160A
公开(公告)日：1983-05-24
申请号：US267923
申请日：1981-05-28
申请人： James F. R. Jaggard , Peter Klaerner , Guenther Schweier
发明人： James F. R. Jaggard , Peter Klaerner , Guenther Schweier
IPC分类号： C08F4/64 , C08F10/00
CPC分类号： C08F10/00 , Y10S526/906
摘要： Alpha-olefins are polymerized with a catalyst containing (1) TiCl.sub.3 /AlCl.sub.3 and (2) aluminum dialkyl chloride wherein (1) is prepared by milling the TiCl.sub.3 /AlCl.sub.3 with a particular phosphorous compound under special conditions and then treating with a liquid hydrocarbon and an ether and/or ester.
摘要翻译： α-烯烃与含有（1）TiCl 3 / AlCl 3和（2）二烷基二烷基锡的催化剂聚合，其中（1）通过在特殊条件下用特定的磷化合物研磨TiCl 3 / AlCl 3，然后用液体烃和醚和/或酯。

4. 发明授权

US4250283A Titanium trihalide composition 失效
标题翻译：三卤化钛组成
公开(公告)号：US4250283A
公开(公告)日：1981-02-10
申请号：US549301
申请日：1975-02-12
申请人： Anthony D. Caunt , James F. R. Jaggard
发明人： Anthony D. Caunt , James F. R. Jaggard
IPC分类号： C08F4/00 , B01J31/00 , C01G23/02 , C08F4/16 , C08F4/60 , C08F4/64 , C08F10/00 , C08F4/66 , C08F10/06
CPC分类号： C08F10/00
摘要： A titanium trihalide component of an olefine polymerization catalyst is prepared by reacting together a titanium tetrahalide and an organo-aluminium compound, and treating the solid reaction product with a hydrocarbon solution of an alkyl aluminium dihalide. It is preferred that the solid reaction product is treated with a complexing agent, particularly an ether such as di-isoamyl ether before contacting with the alkyl aluminium dihalide. The titanium trihalide can then be used together with an organo-metallic compound to polymerize an olefine monomer, particularly propylene. The catalyst system may include further components in addition to the titanium trihalide and organo-metallic compound.
摘要翻译：烯烃聚合催化剂的三卤化钛组分通过使四卤化钛与有机铝化合物反应并用二烷基铝的烃溶液处理固体反应产物来制备。优选在与烷基铝二卤化物接触之前，用络合剂，特别是醚如二异戊醚处理固体反应产物。然后可以将三卤化钛与有机金属化合物一起使用以使烯烃单体，特别是丙烯聚合。除了三卤化钛和有机金属化合物之外，催化剂体系可以包括另外的组分。

5. 发明授权

US4260710A Process for the preparation of homopolymers and copolymers of .alpha.-monoolefins 失效
标题翻译：制备α-单烯烃均聚物和共聚物的方法
公开(公告)号：US4260710A
公开(公告)日：1981-04-07
申请号：US72984
申请日：1979-09-06
申请人： Gerhard Staiger , James F. R. Jaggard , Paul Schneider
发明人： Gerhard Staiger , James F. R. Jaggard , Paul Schneider
IPC分类号： C08F4/64 , C08F10/00 , C08F4/66 , C08F10/06
CPC分类号： C08F10/00 , Y10S526/906
摘要： A process for the preparation of homopolymers and copolymers of .alpha.-monoolefins by means of a Ziegler-Natta catalyst system comprising (1) a titanium halide of the formulaTiCl.sub.3.m AlCl.sub.3where m is a number from 0 to 0.5, (2) an oxygen compound of the formula ##STR1## where R.sup.1 is hydrogen, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy, R.sup.2 is C.sub.1 -C.sub.4 -alkyl and n is an integer from 0 to 3, and (3) an appropriate conventional aluminum-alkyl, the titanium halide (1) and the oxygen compound (2) having been milled together before use, wherein the catalyst system employed contains, as a further component (4), a phenolic compound of the formula ##STR2## where R.sup.3 is C.sub.1 -C.sub.6 -alkyl, R.sup.4 is hydrogen or C.sub.1 -C.sub.6 -alkyl, R.sup.5 is hydrogen or a saturated hydrocarbon radical of not more than 30 carbon atoms which may also contain not more than a total of 6 ether groups and/or ester groups, R.sup.6 is C.sub.2 -C.sub.24 -alkyl and o is an integer from 1 to 6.
摘要翻译：一种通过齐格勒 - 纳塔催化剂体系制备α-单烯烃的均聚物和共聚物的方法，包括（1）式TiCl 3·m AlCl 3的卤化钛，其中m为0至0.5的数，（2）其中R 1是氢，C 1 -C 4 - 烷基或C 1 -C 4 - 烷氧基，R 2是C 1 -C 4 - 烷基，n是0-3的整数，和（3）适当的常规铝 - 烷基，卤化钛（1）和氧化合物（2）在使用前已被研磨在一起，其中所用的催化剂体系包含作为另外的组分（4）的式（I）的酚类化合物，（II）其中R3是C1-C6-烷基，R4是氢或C1-C6-烷基，R5是氢或不超过30个碳原子的饱和烃基，其也可以含有不超过总共 6个醚基和/或酯基，R6是C 2 -C 24 - 烷基，o是1至6的整数。

6. 发明授权

US4154700A Manufacture of a titanium-containing component for catalysts of the Ziegler-Natta type 失效
标题翻译：制造齐格勒 - 纳塔型催化剂的含钛组分
公开(公告)号：US4154700A
公开(公告)日：1979-05-15
申请号：US855876
申请日：1977-11-30
申请人： Heinz Mueller-Tamm , Hans Schick , James F. R. Jaggard , Johann Nickl
发明人： Heinz Mueller-Tamm , Hans Schick , James F. R. Jaggard , Johann Nickl
IPC分类号： C08F4/00 , C01G23/02 , C08F4/60 , C08F4/64 , C08F10/00
CPC分类号： C08F10/00
摘要： A process for the manufacture of a titanium-containing component of a catalyst for the polymerization of monoolefins by the Ziegler-Natta method by milling (a) a particular titanium-containing compound, viz. a titanium trichloride/aluminum trichloride complex and (b) a particular ether with one another, in which process (1) a vibratory ball mill producing a particular milling acceleration is used, (2) the mill is first charged with the titanium-containing compound (a) and may or may not then be run for some time in the absence of diluents, (3) while milling, the ether (b) is added at a particular rate, continuously or in small portions, and in the absence of diluents, thereafter (4) the grist is brought to an elevated temperature, while milling, and is kept at this temperature until from 6 to 85% of the aluminum trichloride originally present in a bonded form in the titanium-containing compound (a) have been eliminated from the said compound (a), after which (5) the product obtained according to (4) is washed with a hydrocarbon and then (6) the product obtained in accordance with (5) is dried and milled for a certain length of time at a low temperature in the absence of a diluent. Polyolefins of high stereoregularity can be obtained in a high specific yield by means of the catalyst component manufactured according to the invention.
摘要翻译：用于通过齐格勒 - 纳塔法通过研磨（a）特定的含钛化合物制造用于单烯烃聚合的催化剂的含钛组分的方法，三氯化钛/三氯化铝配合物和（b）特定的醚，其中使用生产特定研磨加速度的振动球磨机，（2）首先将研磨机装入含钛化合物（a），并且在没有稀释剂的情况下可以运行一段时间，（3）在研磨时，以特定速率，连续地或以小部分加入乙醚（b），并且在没有稀释剂的情况下（4）在研磨时将砂轮升至高温，并保持在该温度下，直到含钛化合物（a）中最初以粘合形式存在的三氯化铝的6至85％为从所述化合物（a）中除去，然后（5）将根据（4）获得的产物用烃洗涤，然后（6）将根据（5）获得的产物干燥并研磨一定长度的在不存在稀释剂的情况下在低温下进行。可以通过根据本发明制备的催化剂组分以高比产率获得高立构规整性的聚烯烃。

7. 发明授权

US4745164A Preparation of homopolymers and copolymers of propylene by means of a Ziegler-Natta catalyst system 失效
标题翻译：通过齐格勒 - 纳塔催化剂体系制备丙烯的均聚物和共聚物
公开(公告)号：US4745164A
公开(公告)日：1988-05-17
申请号：US930528
申请日：1986-11-14
申请人： Guenther Schweier , James F. R. Jaggard , Rainer A. Werner , Wolfgang Gruber
发明人： Guenther Schweier , James F. R. Jaggard , Rainer A. Werner , Wolfgang Gruber
IPC分类号： C08F4/02 , C08F4/58 , C08F4/60 , C08F4/64 , C08F4/654 , C08F10/00 , C08F10/06
CPC分类号： C08F10/06 , Y10S526/901
摘要： Polymers of propylene are prepared by means of a Ziegler-Natta catalyst system comprising (1) a titanium component which contains titanium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component, wherein the (1) used is obtained by (1.1) first reacting with one another (1.1.1) in a liquid hydrocarbon, (1.1.2) a finely divided magnesium halide, (1.1.3) an alkanol, (1.1.4) a phthalic acid ester and (1.1.5) titanium tetrachloride under certain conditions, (1.2) then extracting the solid intermediate obtained from (1.1) with a liquid alkylbenzene until the remaining solid substance has become significantly richer in magnesium, and (1.3) finally washing the solid substance remaining in (1.2) with an alkane in a certain manner.
摘要翻译：丙烯聚合物通过齐格勒 - 纳塔催化剂体系制备，包括（1）钛，镁，氯和苯甲酸衍生物的钛组分，（2）铝组分和（3）硅烷组分，其中（1.1）通过（1.1）在液体烃中首先反应（1.1.1）获得，（1.1.2）细碎的卤化镁，（1.1.3）链烷醇，（1.1.4）a 邻苯二甲酸酯和（1.1.5）四氯化钛，（1.2），然后用液体烷基苯提取从（1.1）得到的固体中间体，直到剩下的固体物质变得更加富镁，（1.3）最后洗涤残留在（1.2）中的固体物质以一定的烷烃形式存在。

8. 发明授权

US4120823A Manufacture of a titanium-containing component for catalysts of the Ziegler-Natta type 失效
标题翻译：制造齐格勒 - 纳塔型催化剂的含钛组分
公开(公告)号：US4120823A
公开(公告)日：1978-10-17
申请号：US855874
申请日：1977-11-30
申请人： Heinz Mueller-Tamm , Hans Schick , James F. R. Jaggard , Johann Nickl
发明人： Heinz Mueller-Tamm , Hans Schick , James F. R. Jaggard , Johann Nickl
IPC分类号： C08F4/00 , C01G23/02 , C08F4/60 , C08F4/64 , C08F10/00
CPC分类号： C08F10/00
摘要： A process for the manufacture of a titanium-containing component of a catalyst for the polymerization of monoolefins by the Ziegler-Natta method by milling (a) a titanium trichloride/aluminum trichloride complex and (b) a particular ether with one another, in which process (1) a vibratory ball mill producing a particular milling acceleration is used, (2) until from 6 to 85% of the aluminum trichloride originally present in a bonded form in the titanium-containing compound (a) have been eliminated from the said compound (a). Polyolefins of high stereoregularity can be obtained in a high specific yield by means of the catalyst component manufactured according to the invention.
摘要翻译：一种用于通过齐格勒 - 纳塔法通过研磨（a）三氯化钛/三氯化铝配合物和（b）彼此的特定醚来制造用于单烯烃聚合的催化剂的含钛组分的方法，其中方法（1）使用产生特定研磨加速度的振动球磨机，（2）直到来自含钛化合物（a）中最初以粘结形式存在的三氯化铝的6至85％从所述化合物（a）。可以通过根据本发明制备的催化剂组分以高比产率获得高立构规整性的聚烯烃。

9. 发明授权

US4455405A Preparation of propylene/ethylene block copolymers 失效
标题翻译：丙烯/乙烯嵌段共聚物的制备
公开(公告)号：US4455405A
公开(公告)日：1984-06-19
申请号：US438278
申请日：1982-11-01
申请人： James F. R. Jaggard , Guenther Schweier , Peter Klaerner
发明人： James F. R. Jaggard , Guenther Schweier , Peter Klaerner
IPC分类号： C08F297/08
CPC分类号： C08F297/083
摘要： Propylene/ethylene block copolymers are prepared by a process in which, in an agitated bed comprising small polymer particles, first (I) propylene is homopolymerized from the gas phase, in a first polymerization zone, by feeding in a Ziegler-Natta catalyst comprising (1) a titanium(III) component and (2) a dialkyl-aluminum chloride component, with or without (3) a further catalyst component, and then (II) the product obtained in the first polymerization zone is fed into a second polymerization zone, where a mixture of propylene and ethylene is polymerized with the propylene homopolymer present in this product.In this process, the Ziegler-Natta catalyst employed contains a titanium(III) component (1) which is prepared by subjecting (1.1) a titanium-containing compound (a) of the formula TiCl.sub.3. nAlCl.sub.3 and (1.2) an electron donor (b), consisting of (b.sub.1) an ester of a particular class or (b.sub.2) a phosphorus-containing compound of a particular class, to a special milling procedure, the particular features of which are special metering and temperature conditions, suspending the resulting intermediate in a mixture of a liquid hydrocarbon (c) and an oxygen-containing compound (d), comprising (d.sub.1) an ether of a certain class and/or (d.sub.2) an ester of a certain class, and then heating the suspension obtained. The solid remaining in suspension is the titanium(III) component (1) which is to be employed for the polymerization. The polymer obtained has improved morphological properties.
摘要翻译：丙烯/乙烯嵌段共聚物是通过一种方法制备的，其中在包含小聚合物颗粒的搅拌床中，第一（I）丙烯在气相中在第一聚合区域中通过进料齐格勒 - 纳塔催化剂进行均一聚合，该齐格勒 - 纳塔催化剂包含 1）钛（III）组分和（2）二烷基氯化铝组分，具有或不具有（3）另外的催化剂组分，然后（II）将在第一聚合区中获得的产物进料到第二聚合区，其中丙烯和乙烯的混合物与本产品中存在的丙烯均聚物聚合。在该方法中，使用的齐格勒 - 纳塔催化剂含有通过（1.1）式TiCl 3的含钛化合物（a）制备的钛（III）组分（1）。 nAlCl 3和（1.2）电子给体（b），由（b1）特定类别的酯或（b2）特定类别的含磷化合物组成的特殊研磨程序，其特征是特殊的计量和温度条件，将所得中间体悬浮在液体烃（c）和含氧化合物（d）的混合物中，其包含（d1）一定类的醚和/或（d2）一定的酯类，然后加热获得的悬浮液。残留在悬浮液中的固体是用于聚合的钛（III）组分（1）。获得的聚合物具有改善的形态特性。

10. 发明授权

US4229318A Manufacture of a titanium-containing component for catalysts of the Ziegler-Natta type 失效
公开(公告)号：US4229318A
公开(公告)日：1980-10-21
申请号：US935948
申请日：1978-08-23
申请人： Heinz Mueller-Tamm , James F. R. Jaggard , Hans Schick
发明人： Heinz Mueller-Tamm , James F. R. Jaggard , Hans Schick
IPC分类号： C08F4/00 , C07F7/00 , C08F4/60 , C08F4/64 , C08F10/00 , B01J31/02
CPC分类号： C08F10/00 , C07F7/006 , Y10S526/906
摘要： A process for the manufacture of a titanium-containing component of a catalyst for the Ziegler-Natta polymerization of .alpha.-monoolefins, by (a) milling a titanium-containing compound of the general formula TiCl.sub.3.nAlCl.sub.3 (where n is a number from 0.01 to 1) with (b) an ether of a particular type or an ester of a particular type, wherein (1) a vibratory ball mill giving a relatively high milling acceleration is used, (2) the mill is first charged with the titanium-containing compound (a), after which it may or may not be run for a certain period, thereafter (3) while milling, the amount of the ether or ester (b) which corresponds to a particular molar ratio of aluminum in the titanium-containing compound (a) to ether or ester (b) is added continuously or in small portions, then (4) the batch is milled for a certain period, after which (5) the product obtained from stage (4) may or may not be washed with a hydrocarbon and dried, and following which (6) the product obtained from stage (4) or (5) may or may not be milled for a certain period at a low temperature, next (7) the product obtained from stage (4), (5) or (6) is brought together with a liquid silicon compound of a particular type or a liquid tin compound of a particular type (these compounds acting as promoters) and the batch is left for a certain period and is then separated into a solid-phase product and into a liquid-phase product, and thereafter (8) the solid-phase product obtained from stage (7) is washed with a hydrocarbon or with one of the promoters mentioned under (7) and is dried, following which (9) the product obtained from stage (8) may or may not be milled for a certain period at a low temperature.Using the titanium-containing catalyst components thus obtainable makes it possible to produce polymers, having a high stereoregularity, in high specific yields.

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