CN1127002A - 1-烯烃的均聚物和共聚物的制备方法 - Google Patents

1-烯烃的均聚物和共聚物的制备方法 Download PDF

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CN1127002A
CN1127002A CN94192743A CN94192743A CN1127002A CN 1127002 A CN1127002 A CN 1127002A CN 94192743 A CN94192743 A CN 94192743A CN 94192743 A CN94192743 A CN 94192743A CN 1127002 A CN1127002 A CN 1127002A
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W·罗德
R·塞夫
H·H·戈茨
G·施怀尔
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Abstract

本发明涉及利用吸附在无机氧化物载体上的双(环戊二烯基)铬-II化合物(I)通过1-烯烃的聚合来制备聚1-烯烃的方法，在所述化合物中环戊二烯基环可带有惰性有机基团，其特征在于在I至III主族的金属的有机金属化合物或一种金属氢化物、尤其是正丁基锂的存在下进行该聚合反应。

Description

1-烯烃的均聚物和共聚物的制备方法
本发明涉及一种制备聚-1-烯烃的改进的方法，尤其是涉及用吸附在无机氧化物载体上的双(环戊二烯基)铬-II化合物
Figure A9419274300031
通过1-烯烃的聚合来制备聚乙烯和乙烯与C3-C10-1-烯烃的共聚物的方法，在所述化合物中环戊二烯基环可带有惰性有机基团。
本发明还涉及按该方法获得的沉淀聚合物。
由US-A3709853已知，用包括无机氧化物载体材料(尤其是二氧化硅)和双(环戊二烯基)铬-II(一般称为茂铬(chromocene))，的载体催化剂通过乙烯或乙烯与C3-C10-1-烯烃的混合物的聚合来制备聚乙烯及乙烯与C3-C10-1-烯烃的共聚物。
由US-A3879368还已知用硅烷或烷基硅烷预处理的这类催化剂。
此外，在DE-A3634534中建议，用二氧化硅/三氧化铬-载体催化剂和烷基锂进行乙烯和乙烯与其它1-烯烃的聚合反应。
然而，这些方法中使用的催化剂的缺点是它使聚合物具有宽分子量分布(DE-A3634534)或其产率相当低(US-A3709853)，因此，它仅有条件地适合于大工业方法。
因此，发明了一种制备聚-1-烯烃的改进方法，该方法利用吸附在无机氧化物载体上的双(环戊二烯基)-铬-II化合物
Figure A9419274300041
聚合1-烯烃来实施，在所述化合物中环戊二烯基环可带有惰性有机基团，其特征在于在I至III主族金属的有机金属化合物或这些金属的氢化物存在下进行该聚合反应。
作为聚合催化剂的活性组分首先考虑的是双(环戊二烯基)铬-II，此外还可是其衍生物，其中环戊二烯基基团可以带有C1-C6烷基和/或C6-C15芳基作为取代基团。另外，稠合的环戊二烯基如茚和芴也是适用的，它们同样可用上述基团取代。
金属氧化物如Si、Al或Zr的氧化物适于作为载体材料，其中优选二氧化硅或铝和硅的混合氧化物。例如在DE-A3634534中记载了这类载体的制备。该载体应优选具有高内表面积，大约为50至1000m2/g，由此吸附的茂铬具有对烯烃尽可能高的接触面积。平均孔隙直径为1至100nm。特别优选的市售产品是例如Grace公司的硅胶332。
在载带茂铬之前必须活化载体材料，以便脱除吸附的水。因此将它在惰性气氛中加热到200至900℃大约1至30小时。
已述多种技术可使用活性组分加载载体。
因此，可通过升华进行干燥载体材料的加载，为此，在惰性气氛中混合茂铬和载体材料并接着减压到一定程度，使茂铬蒸发并吸附在载体材料上。
还可以下述方法制造载体催化剂：先将茂铬溶解在溶剂中，并让该溶液在载体材料上作用若干小时。适用的溶剂是烃类如戊烷、正己烷、环己烷、苯和二甲苯。溶剂用量应能够完全润湿载体材料。如果需要粉末状产物，则要从悬浮液中脱除溶剂。
载体催化剂中铬的量以载体材料为基准计一般为0.1～10％(重量)。
用本发明方法可生产的聚合物主要是聚乙烯以及乙烯与C3～C10、优选与C3～C6-1-烯烃的共聚物。此外，该方法还适合于定义的其它1-烯烃的共聚合。
以所用载体催化剂用量为基准计，1-烯烃的用量在100和10,000g/g之间，优选在1000和200,000g/g之间。
本发明方法的区别特征是在1-烯烃聚合时除茂铬载体催化剂外还使用金属氢化物或有机金属化合物，其中有机金属化合物的金属属于I至III主族。
有机金属化合物和金属氢化物含有I至II主族的金属。除用锂作为金属外，还可考虑钠、钾、铍、镁、钙、钡、硼和铝。
有机金属化合物中优选烷基金属和芳基金属。作为烃基可以考虑具有1至6个碳原子的脂族基团和具有6至15个碳原子的芳族基团。其中特别优选的是锂化合物，例如正丁基锂、仲丁基锂和苯基锂。
适用的金属氢化物是例如氢化钠和氢化钙，混合的氢化物如氢化锂铝和硼氢化钠以及硼氢化合物。
对于茂铬催化剂来说，本发明所用的有机金属化合物或金属氢化物的用量比例为每摩尔铬优选0.1至100、特别优选1至20当量金属。在总的聚合过程中通过相应地添加金属有机化合物或金属氢化物保持该比例关系是有利的。
对此，一般可采用例如在“Ullmanns Encyklopdie dertechnischen Chemie”，19卷，4版中所述的工艺技术。
优选在溶剂中进行沉淀聚合反应，其中单体而不是聚合物是可溶的。适宜的溶剂尤其是脂族烃，主要是C4～C10烷烃。
为了避免在反应器壁上形成敷层，一般使用抗静电剂。为此涉及到例如由水杨酸烷基酯铬盐、含磺基的丁二酸二辛酯或丁二酸二癸酯的钙盐和吖丙啶与不饱和羧酸的离子共聚物组成的混合物，如在DE-A2302962中所述。
在沉淀聚合中，在正丁基锂存在下可得到细颗粒形式的聚合物，除去溶剂后出人意料地得到比按已知方法例如US-PS3709853的方法得到的聚合物具有更高的堆积密度。该聚合物的优点是不用再造粒即可用于制造模制件。
本发明的方法总体上提供了特别高产率的优点，即，与目前所用催化剂相比较，生产一定量的聚合物需用更少量的催化剂。这可能是由于本发明所用的添加剂捕捉了活性氢或有氧化作用的杂质，并因此保护了敏感的催化剂。
实施例A.制造连续聚合用的载体催化剂
将100g上述载体材料悬浮于3.5g双(环戊二烯基)铬-II在500ml正庚烷中的溶液中。将该悬浮液搅拌8小时并接着直接使用。
按上述方法制造载有加倍量的双(环戊二烯基)铬-II的另一种载体催化剂，不同的是使用7.0g双(环戊二烯基)铬-II在500ml正庚烷中的溶液。B.制造用于非连续聚合用的载体催化剂
将15g硅胶(Grace公司的SG 332)悬浮在1.04g双(环戊二烯基)铬-II在200ml正庚烷中的溶液中，该硅胶已在800℃焙烧24小时，其粒度为20至45μm，比表面积为320m2/g，孔体积为1.75ccm/g。在室温搅拌2小时后，滤出载体材料，用正庚烷洗涤，并在室温下真空干燥成松散的粉末。实施例1(本发明)连续聚合反应
在200l带封闭循环的环形反应器中以异丁烷作溶剂，在温度为88℃和40巴压力下使乙烯连续聚合，其中在整个实验期间保持乙烯浓度为18％(体积)。在反应器中还要各通入恒定量的151/小时氢和0.14g/小时抗静电剂。向反应器中以恒量添加2.8g/小时载有1％(重量)铬的茂铬/SiO2载体催化剂(相当于0.5×10-3molCr/小时)和0.1g/小时正丁基锂(1.5×10-3mol/小时)，得到19kg/小时聚乙烯，相当于产率为每克催化剂生产6800g聚乙烯。所得聚乙烯的堆积密度为440g/l(按DIN 53 468测定)。实施例IV/1(比较用)
该实验与实施例1的不同之处在于载有1％(重量)铬的茂铬/SiO2载体催化剂的添加量提高到5.6g/小时(相当于1.1×10-3molCr/小时)，但不加正丁基锂。获得14kg/小时聚乙烯，相当于产率为每克催化剂2500g聚乙烯。所得聚乙烯的堆积密度为360g/1(按DIN 53 468测定)。实施例IV/2(比较用)
该实验与实施例1的不同之处在于添加含加倍量铬(2％(重量))的茂铬/SiO2载体催化剂和不加正丁基锂。获得23kg/小时聚乙烯，相当于产率为每克催化剂6600g聚乙烯。所得聚乙烯的堆积密度为375g/l(按DIN 53 468测定)。实施例2～5非连续聚合反应(本发明)
在1升高压釜中在氩气氛下供入400ml用氩气清扫过的无水庚烷并混入一摩尔正丁基锂在庚烷中的溶液。此后在70℃用0.2巴氢和30巴乙烯将总压加压到30巴，并接着将100mg(3.8×10-2molCr)茂铬/SiO2载体催化剂加到反应器中，接着立刻进行乙烯的聚合反应。在70℃恒温下保持30巴压力90分钟，之后通过高压釜的减压终止聚合反应并从生成的悬浮液中蒸出庚烷。
在实施例5至7中改变该实验，不同之处在于氢分压和丁基锂的量以及用三乙基铝(ATE)代替丁基锂(见表1)。
这些实施结果列在下表中。
                  实施例
             2      3      4      5丁基锂[mg]       40     30     -      -三乙基铝[mg]     -      -      30     30H2压力[巴]      0.2    0.5    0.2    0.5产率1)          2.5    1.2    1.5    1.2堆积密度(g/l)    390    360    315    300
1)kg聚合物/g催化剂

Claims (5)

1.一种聚1-烯烃的制备方法，该方法利用吸附在无机氧化物载体上的双(环戊二烯基)铬-II化合物
Figure A9419274300021
通过1-烯烃的聚合来进行，在所述化合物中环戊二烯基环可带有惰性有机基团，其特征在于在I至III主族金属的金属有机化合物或这些金属的氢化物存在下进行该聚合反应。
2.根据权利要求1的方法，其特征在于用烃基锂化合物作为金属有机化合物。
3.根据权利要求2的方法，其特征在于用正丁基锂作为烃基锂化合物。
4.根据权利要求1至3中任一项的方法，其特征在于该方法用于乙烯或乙烯与一种或多种C3-C10-1-烯烃的混合物的聚合。
5.根据权利要求1至4中任一项的方法，其特征在于按沉淀聚合法进行聚合反应。
CN94192743A 1993-07-10 1994-06-23 聚－1－烯烃的制备方法 Expired - Fee Related CN1078893C (zh)

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DE4323192A DE4323192A1 (de) 1993-07-10 1993-07-10 Verfahren zur Herstellung von Homo- und Copolymerisaten von Alk-1-enen
DEP4323192.6 1993-07-10

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Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO960350A (no) † 1996-01-26 1997-04-28 Borealis As Fremgangsmåte og katalysatorsystem for polymerisering av etylen, eventuelt sammen med <alfa>-olefiner, og fremstilt polymermateriale
DE19645939A1 (de) * 1996-11-07 1998-05-14 Buna Sow Leuna Olefinverb Gmbh Verfahren zur Herstellung von ultrahochmolekularem Polyethylen und Methode zur Aktivierung des Katalysatorträgers
US6174953B1 (en) * 1998-02-19 2001-01-16 E. I. Du Pont De Nemours And Company Low molecular weight (meth) acrylate copolymer emulsions
DE19833858C2 (de) 1998-07-28 2000-06-08 Elenac Gmbh Geruchsarme Polyethylen-Blends
US6337297B1 (en) * 1998-10-12 2002-01-08 Tosoh Corporation Catalyst for trimerization of ethylene and process for trimerizing ethylene using the catalyst
US6818585B2 (en) * 1998-12-30 2004-11-16 Univation Technologies, Llc Catalyst compounds, catalyst systems thereof and their use in a polymerization process
EP1041085B1 (en) 1999-04-01 2002-08-14 Japan Polyolefins Co., Ltd. Catalyst for the production of ethylene polymer and process for producing ethylene polymer
GB0021301D0 (en) * 2000-08-30 2000-10-18 Borealis Tech Oy Supported catalyst
DE10314369B4 (de) * 2003-03-28 2005-08-25 Otto-Von-Guericke-Universität Magdeburg Polymerisationskatalysatoren auf Porenbetonbasis, Verfahren zu ihrer Herstellung und ihre Verwendung
PT2544679T (pt) 2010-03-12 2019-07-11 Omeros Corp Inibidores de pde-10 e composições e métodos relacionados
NZ716494A (en) 2014-04-28 2017-07-28 Omeros Corp Processes and intermediates for the preparation of a pde10 inhibitor
NZ630803A (en) 2014-04-28 2016-03-31 Omeros Corp Optically active pde10 inhibitor
US9879002B2 (en) 2015-04-24 2018-01-30 Omeros Corporation PDE10 inhibitors and related compositions and methods
US9920045B2 (en) 2015-11-04 2018-03-20 Omeros Corporation Solid state forms of a PDE10 inhibitor

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3013002A (en) * 1960-04-05 1961-12-12 Hercules Powder Co Ltd Polymerization of ethylene with dicyclopentadienyl chromium-metal alkylcatalysts
CA995396A (en) * 1971-03-18 1976-08-17 Robert N. Johnson Catalyst modified with strong reducing agent and silane compounds and use in polymerization of olefins
US3709853A (en) 1971-04-29 1973-01-09 Union Carbide Corp Polymerization of ethylene using supported bis-(cyclopentadienyl)chromium(ii)catalysts
US3806500A (en) * 1972-07-21 1974-04-23 Union Carbide Corp Polymerization with thermally aged catalyst
US4015059A (en) * 1975-12-29 1977-03-29 Union Carbide Corporation Fused ring catalyst and ethylene polymerization process therewith
US4803253A (en) * 1982-03-30 1989-02-07 Phillips Petroleum Company Ethylene polymer produced using a catalyst comprising a phosphate and with a bis-(cyclopentadienyl)chromium(II) compound
US4424139A (en) * 1982-03-30 1984-01-03 Phillips Petroleum Company Catalyst comprising a phosphate and with a bis-(cyclopentadienyl)chromium(II) compound
DE3634534A1 (de) 1986-10-10 1988-04-14 Basf Ag Verfahren zum herstellen von homo- sowie copolymerisaten des ethens mittels eines chromtrioxid-katalysators
DE3635363A1 (de) 1986-10-17 1988-04-21 Basf Ag Verfahren zur neutralisation von reaktionsgemischen, die durch beckmann'sche umlagerung von cyclohexanonoxim erhalten worden sind
GB8919925D0 (en) * 1989-09-04 1989-10-18 Bp Chem Int Ltd Chromium-containing complex polymerisation catalyst

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NO310364B1 (no) 2001-06-25
EP0708787B1 (de) 1999-01-20
FI960098A7 (fi) 1996-01-09
DE59407708D1 (de) 1999-03-04
DE4323192A1 (de) 1995-01-12
FI960098L (fi) 1996-01-09
US6197901B1 (en) 2001-03-06
JPH08512339A (ja) 1996-12-24
CN1078893C (zh) 2002-02-06
FI960098A0 (fi) 1996-01-09
EP0708787A1 (de) 1996-05-01
NO960089D0 (no) 1996-01-09
WO1995001999A1 (de) 1995-01-19
NO960089L (no) 1996-01-09
JP3776929B2 (ja) 2006-05-24
ES2126765T3 (es) 1999-04-01
KR960703947A (ko) 1996-08-31

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