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CN1058022C - 制备反应器混合物的方法 - Google Patents

制备反应器混合物的方法 Download PDF

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CN1058022C
CN1058022C CN94108568A CN94108568A CN1058022C CN 1058022 C CN1058022 C CN 1058022C CN 94108568 A CN94108568 A CN 94108568A CN 94108568 A CN94108568 A CN 94108568A CN 1058022 C CN1058022 C CN 1058022C
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约翰·尤恩
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Abstract

本发明是关于能用于生产半等规聚合物的催化剂体系中的一种金属茂化合物，该化合物是具有不同的环戊二烯基基团及不具有双侧面对称性的一种桥接的金属茂化合物，该化合物的一种实例是异亚丙基(3-甲基环戊二烯基-1-芴基)二氯化锆。本发明的催化剂可以通过一种离子化试剂，例如甲基铝氧烷被转变在离子金属茂催化剂。用该催化剂所制备的聚合物，其特征在于具有只对每隔一个的不对称碳原子有效的等规结构，在聚丙烯的情况下，每隔一个甲基在用弗歇尔投影来表示的聚合物主链的同一侧，剩余的甲基或者在聚合物主链的同一侧，或者在其相反的一侧。用本发明的催化剂所制备的聚合物可以用作增塑剂。

Description

制备反应器混合物的方法
本申请是原申请日90.10.10、原案申请号90109215.0的发明名称为生产等规聚丙烯的催化剂的分案申请。
本发明一般涉及一种催化剂体系，特别是涉及半等规催化剂。
烯烃，特别是丙烯，可以聚合成多种形式的聚烯烃：等规，间规和无规。等规聚丙烯链中，主要是具有相同构型的重复单元和只有很少的无定的、简单的变型，等规聚丙烯其结构可以用弗歇尔投影，如式(1)来表示：
Figure C9410856800031
按照Bovey的NMR(核磁共振)命名原则，由于其5个连续的甲基是彼此为内消旋的，则该等规结构表示为…mmmm…，即在弗歇尔投影平面的同一侧。
等规聚丙烯是可以具有高熔点和其它所需物理性质的高结晶的聚合物，与元定形(非结晶的)状态聚合物有显著不同。
间规聚合物主要含有完全交替的立体异构体单元，并按弗歇尔投影，用结构式(2)来表示：
Figure C9410856800032
按照Bovey的NMR命名原则，由于其5个连续的甲基是彼此为外消旋的，则该间规结构表示为…rrrr…，即在弗歇尔投影平面上更迭一侧。
显示无规则次序的重复单元构型的聚合物链的是一种无规聚合物。商业上使用的一定百分比的无规聚合物一般是与等规形式一起生产的。
聚合物的结构形式有其它的变化，由M.Farina，G.Disilvestro及P.Sozzani著的题目为“半有规立构聚丙烯：一种新型聚合物立构规整度的实例“中公开了半等规或半有规立构聚丙烯(MacromoLecules，Vol.15，1451-1452，1982)。该半等规聚合物的结构用弗歇尔投影，表示如下：该聚合物的链节为如下所示的结构
Figure C9410856800042
其中，Rs为烃基或非烃基，在式(4)中的第二个碳原子为不对称碳原子，即不是由相同基团所连接的碳原子，因此，称之为“不对称”。
该聚合物结构的特征在于，Rs基团连接到每隔一个的不对称碳原子上，处于用弗歇尔投影来表示的聚合物主链的相同的一侧及Rs基团还连接到剩余的不对称碳原子上，处于与已经连接到每隔一个的不对称碳原子上的Rs基团的相同一侧，或者在相反的一侧。当Rs基团在聚合物主链的同一侧时，该结构是等规的，由于仅仅是每隔一的符合等规结构，因此称之为“半”，该材料是一种非结晶的聚合物。
烯烃的聚合反应主要是用齐格勒-纳塔型催化剂，齐格勒-纳塔型催化剂是用第IV族的金属
Figure C9410856800051
化合物与甲基铝氧烷作为助催化剂，西德专利申请号2608863公开了一种乙烯聚合的催化剂体系，它由双(环戊二烯基)二烃基钛、三烷基铝和水组成，西德专利申请号2608933公开了一种由通式为(环戊二烯基)，ZrY4-n，的锆金属
Figure C9410856800052
(式中Y代表R1CH2AlR2，CH2CH2AlR2和CH2CH(AlR2)2，其R为烷基或金属烷基，及n为1-4数，与三烷基铝助催化剂和水结合在一起所组成的乙烯聚合催化剂体系。
在乙烯和其它α-烯烃的共聚合中，使用金属作为催化剂在现有技术中是已知的，Kaminsky等人在美国专利号4542199中公开了一种烯烃聚合方法，特别是用于制备聚乙烯及聚乙烯与其它α-烯烃的共聚物的方法，所公开的催化剂体系包括一种分子式为(环戊二烯基)2MeRHal的催化剂，分子式中的R是卤素、环戊二烯基或C1-C6烷基、Me是过渡金属．特别是金属锆、及Hal是卤素，特别是氯。该催化剂体系还包括一种通式为Al2OR4(Al(R)-O)n的线型分子和/或为(Al(R)-O)n+2的环状分子的铝氧烷，其中，n是4-20的数，R是甲基或乙基。在美国专利号4404344中公开了一种类似的催化剂体系。
美国专利号45309l4公开丁一种将乙烯聚合成具有宽分子量分布及特别是具有双峰或多峰分子量分布的聚乙烯的催化剂体系，该催化剂体系禽有至少二种不同的金属
Figure C9410856800053
和铝氧烷，该专利公开了具有在二个环戊二烯基环之间的桥接的，用该桥接来使那些环为主体刚性的金属
Figure C9410856800061
欧洲专利公开号0185918公开了一种烯烃聚合的立体刚性的、手性锆金属 催化剂，该申请没有表示可以用铪来代替锆并被用来生产有用的聚合物产品。在环戊二烯基之间的桥接，被公开为1-4个碳原子的直链烃或为3-6个碳原子的环状烃。
欧洲专利申请0-277003涉及由Turner所进行的、通过质子化作用的方法制备的催化剂的工作。为一种双(环戊二烯基)金属化合物与一种具有能给予质子的阳离子及具有许多硼原子的阴离子的化合物相结合，例如，用下列反应来说明此发明：
双(环戊二烯基)二甲基铪十N，N-二甲基苯胺双(7，8-二氨癸烷硼酸盐)钴酸盐(III)→
[CP2HfMe][B]+CH4+N，N-二甲基苯胺
其中[B]为7，8-二氨癸烷硼烷。
欧洲专利申请0-277-004也涉及由Turner所进行的、用质子化作用的方法制备的一种催化剂的工作，为一种双(环戊二烯基)金属化合物与一种离子化合物相结合，该离子化合物具有阳离子和阴离子，该阳离子可以与金属化合物上的配位体进行不可逆反应：而该阴离子在金属或准金属离子周围有许多亲脂基团，例如，可用下列反应来说明此发明：
三(正丁基)胺四(五氟苯基)硼+双(环戊二烯基)二甲基踏→[CP2ZrMe][Bph4]+CH4+(正丁基)3N
在“用可溶性4B族的金属 /甲基铝氧烷催化剂进行丙烯聚合反应中的立体化学控制机理”(J.Am.Chem.Soc.，Vol.106，pp.6355-64，1984)的文章中，介绍了一种用钛或锆金属催化剂及铝氧烷助催化剂生产等规聚丙烯的体系，该文章揭示：由乙烯桥接的茚基衍生物的外消旋对映体所得到的手性催化剂，通过由立体化学控制模式的对映(结构)体一模型新预示的通常的结构可以生成等规聚丙烯，然而，乙烯桥接的钛茚基非对映体的内消旋非手性形式及非手性锆衍生物，生产出完全是无规结构的聚丙烯。
按照本发明，提供了一种通式为
R″(CPRn)(CPR′m)MHal2           (5)的金属
Figure C9410856800071
化合物，式中每个R和R′是1-20个碳原子的烃基，可相同或不同，并且要进行选择以使该CPR′m与CPRn是在空间不同的环，从而导致化合物中的双侧面对称的缺乏。R″是给予化合物以立体刚性的桥接的结构，M是第4族金属。n是0至4，m是0至4，及Hal是卤素。这种化合物的一种实例是异丙基(3-甲基环戊二烯基-1-芴基)二氯化锆，该化合物是一种具有不同环戊二烯基及没有双侧面对称的桥接的金属茂化合物。
这些化合物的一种用处是用在金属茂催化剂体系中，上述定义的金属茂化合物可通过任意已知的金属茂催化剂制备方法，被活化以用作催化剂。
用本发明的催化剂生产的聚合物具有被称之为“半等规”的结构，半等规聚丙烯的特征为用弗歇尔投影所表示的其甲基每隔一个地处于聚合物主链的同一侧，其剩余的甲基或者在聚合物主链的同一测或在相反一侧。
聚合物链的增长导致丙烯链节由头一尾键合以这种方式形成下列结构：
在费歇尔投影中表示，该奇数次甲基单元就其相互间来说，是内消旋的，偶数次甲基碳具有无规空间(排列)的构型，半等规聚丙烯是非结晶的，这是由于这些无规基团的无序和不规则性所致。
本发明是有关一种新型的金属茂化合物，它是用来生产称之为半等规聚合物催化剂的催化剂前体。用一种离子化试剂将该金属茂化合物转变成金属茂催化剂，该离子化试剂将中性的金属茂化合物转化成起催化剂作用的金属茂阳离子。该离子化试剂可以是一种助催化剂化合物例如甲基铝氧烷(MAO)。
本发明的较好的应用是可用下列分子式表示的单体的半等规聚合，
CH2＝CH-Rs          (7)式中R3是烃基或非烃基取代基。本发明中可以使用的单体是C3 +α-烯烃、1-丁烯、1-二烯类，例如1，3-丁二烯、取代的乙烯化合物，例如乙烯、及苯乙烯，优选应用是乙烯的不饱和单体，此处用“乙烯的不饱和单体”是指其特征为其未端为乙烯基的(CH2＝CH-)一种烃或取代烃化合物，在本发明中所使用的最好的乙烯的不饱和化合物为至少具有3个碳原子的，一个特殊的实例是丙烯。
用于生产半等规烯烃的催化剂是具有下列通式的金属茂化合物，R″(CPRn)(CPR′m)MeHal2，式中CP为环戊二烯基或取代的环戊二烯基、每个R和R′是1-20个碳原子的烃基、可相同或不同，并且要进行选择以使该CPR′m与CPRn是在空间不同的环，从而导致化合物的双侧面对称的缺乏，R″是给予化合物以立体刚性的桥接的结构，M是第4族金属，优选是钛、锆、铪。n是0至4，m是0至4，Hal是卤素，优选是氯。
化合物双侧面对称的缺点是按照以下的条件来定义的，一种金属茂化合物具有一个没有取代基的非环戊二烯基配位位置的、或者在环戊二烯基环一侧上有一个或多个取代基都在配位位置的上面和下面，以及在环戊二烯基环的另一侧上有一个或多个取代基，它在其配位位置的上面或者下面。这种化合物的一种实例是异亚丙基(3-甲基环戊二烯基-1-芴基)二氯化锆、简写为ipr(3MeCP-1-Flu)ZrCl2，该化合物的配位体的说明如下所示：
Figure C9410856800091
该双侧面对称的缺乏可通过以下情况来说明，由于一个甲基在环戊二烯基环的右侧，并在同一环戊二烯基环的左侧上没有取代基，则图示的右侧不同于左侧。
该ipr(3MeCP-1-Flu)ZrCl2化合物可以通过以下步骤来制备：裂解甲基环戊二烯二聚体，制备3，6，6-三甲基亚甲基环戊二烯，用异亚丙基桥接二个环戊二烯化合物并与锆和氯形成配位化合物，最后在四氢呋喃(THF)和在二氯甲烷(MeCl2)中进行反应，使用MeCl2以使ipr(3MeCP-1-Flu)ZrCl2以纯的形式而被离析出来。
烯烃的聚合可以通过用金属茂催化剂使烯烃聚合的任意已知的方式来完成，例如：本体聚合、淤浆聚合或气相中聚合。对于聚丙烯，聚合温度的范围为从-80℃到150℃，优选是25℃到90℃，最优选是从500℃到80℃。
非结晶的半等规聚丙烯用作间规或等规聚丙烯的增塑剂，增塑剂是掺入到塑料中以增加可加工性及挠曲性或伸长性的一种材料，添加增塑剂可以降低熔体粘度、二次转化温度，或塑料的弹性模量。将塑料与增塑剂紧密的混合(这是最普通的作法)，混合是通过加热直至将塑料溶入增塑剂中，反之亦然。另外，塑料和增塑剂可以通过溶解于普通溶剂中，不必加热而加以混合，随之，通过蒸发而除去溶剂。
半等规聚合物是非结晶的，并且由于其具有部分有规立构的结构，因而具有增塑剂的性质。半等规聚合物作为增塑剂的一个具体实例是一种半等规聚丙烯和间规聚丙烯的反应器混合物，该混合物是通过使丙烯同时与iPr(3MeCp-1-Flu)ZrCl2和异亚丙基(环戊二烯基-1-芴基)二氯化锆(简写为iPr(Cp-1-Flu)ZrCl2)或其它任何间规催化剂前体进行聚合制得的。半等规聚丙烯和等规聚丙烯的一种反应器混合物可以通过使丙烯同时与iPr(3MeCp-1-Flu)ZrCl2和亚乙基双(四氢茚基)二氯化锆(简写为Et(IndH4)2ZrCl2)或其它任何等规催化剂前体进行聚合而得到。在与等规或间规聚丙烯的混合物中半等规聚丙烯的用量可以在1-90％(重量)的范围内，但要取决于被增塑的塑料所需的物理性质。优选的是在与等规或间规聚丙烯的混合物中半等规聚丙烯的用量在5-50％(重量)的范围内。更好的是在与等规或间规聚丙烯的混合物中半等规聚丙烯的用量大约为10％(重量)。
已对本发明作了一般性的说明，下列实施例将给出本发明的部分实施方案及实施实例及其优点，通过说明，可理解所给出的这些实例，并且不意味着以任何方式的对说明书或其后的权利要求的限制。
                实施例1
A.制备3，6，6-三甲基亚甲基环戊二烯
150毫升的甲基环戊二烯二聚体与100毫升矿物油在60℃进行分级蒸馏，并在0℃加以收集。在0℃，将500毫摩尔的甲基锂(1.4M；在乙醚中)逐滴加入到500毫摩尔的新蒸馏的甲基环戊二烯和137毫升的干燥丙酮中。将此溶液在25℃搅拌1小时，在用100毫升的饱和的NH4Cl水溶液萃取，并在MgSO4进行干燥之后，由通过真空蒸馏而得有机层中收集8℃(收率为85％)的3，6，6-三甲基亚甲基环戊二烯。B.制备ipr(3-MeCP-1-Flu)
将1摩尔3，6，6-三甲基亚甲基环戊二烯溶于100毫升的四氢呋喃中，并将其逐滴地加到含有1摩尔的溶于大约100毫升四氢呋喃和714毫升的乙醚中的芴基阴离子的锂盐冷(-78℃)溶液中。将混合物加热至室温，通过用NH4Cl水溶液进行萃取、在MgSO4上进行干燥。在真空下过滤浓缩得到一油状物，再溶于氯仿中，沉淀，并用过量甲醇洗涤，从所得有机层中得到作为单一异构件的18克的白色粉末。1HNMR(核磁共振)CO2Cl2，Int.ref.Me4Siδ＝0ppm：7.7d，7.3t，7.2d和7.1t(8)(Flu C6环)：6.5t和5.6d(2)(CP乙烯基)；4.1S(1)(Flu C5环次甲基)；2.95S(2)(CP亚甲基)；2.2d(3)(CP甲基)；1.0S(6)(异丙基甲基)。(1立体异构体：CP亚甲基作为单一的信号出现，因为该亚甲基同时在ipr桥接和CP甲基的α位上)。
Cl在二氯甲烷中制备异亚丙基(3-甲基环戊二烯基-1-芴基)二氯化锆。
将2当量的甲基锂(1.4M，在乙醚中)在-78℃，逐滴加入到溶于100毫升的四氢呋喃中的5克异亚丙基(3-甲基环戊二烯-1-芴)中，加热至25℃，搅拌12小时，通过在真空下蒸发溶剂而分离出红色的二锂盐，然后通过用每分150毫升的干的、脱氧的戊烷(该戊烷随之被除去)洗涤二次以加以纯化，将二阴离子在-78℃溶于二氯甲烷中，并将等当量的在-78℃、125毫升CH2Cl2中成淤浆的ZrCl4快速加入到含有可溶性二阴离子的烧瓶中，搅拌混合物并慢慢地加热至25℃，并搅拌12小时。一种白色的固体物被过滤出来。通过在真空下浓缩二氯甲烷、冷却至-20℃，冷却时间为12小时，并取走浮在上层的部分，而得到对空气有一定程度的敏感性的、3克橙色粉末。将该产品用二氯甲烷进行重结晶而加以纯化，其ZrCl2C22H20，理论值为：C，59；H，4.5。测定值为：C，56；H，4.4。1H NMR(核磁共振)(δ，ppm)CO2Cl2，Int.ref.TMSδ＝0ppm：8.15-8.10 2d(2)，7.87-7.78 2d(2)，7.55-7.48 2t(2)，7.27-7.21m(2)(Flu C6环)；5.93t(1)，5.63t(1)，5，42t(1)(CP乙烯基)；2，4d(6)(异丙烯甲基)；2.0S(3)(CP甲基)。C2，在四氢呋喃中制备异亚丙基(3-甲基环戊；烯-1-芴基)二氯化锆。
在搅拌下于25℃，将34毫摩尔在乙醚(1.4摩尔)中的甲基锂，逐滴地加入到5克异亚丙基(3-甲基环戊二烯基-1-芴)配位体中，然后将其溶于75毫升的四氢呋喃中(它预先装在被装有侧臂和滴液漏斗的园底烧瓶中)，当气体停止放出之后，将此暗橙色/红色的溶液搅拌数小时。将6.41克的ZrCl4·2四氢呋喃在40℃溶于100毫升的四氢呋喃中，在25℃，将上述的二阴离子装入含有ZrCl4·2四氢呋喃的烧瓶中，将该混合物搅拌18小时。然后再将该溶液装入一烧瓶中，并冷却到-20℃，以得到结晶产品，另外，在真空下蒸发出四氢呋喃。将5毫升的LiCl/ipr[3MeCP-1-Flu]ZrCl2混合物加到甲基铝氧烷中，用于聚合试验。
                实施例II
将1.4毫升的甲基铝氧烷(MAO)与5毫克如按实施例1在四氢呋喃中制备的ipr(3MeCP-1-Flu)ZrCl2混合，并溶于10-20毫升甲苯中。该MAO为37％(重量)(Scherring)。把1.2升的丙烯加入反应器中，将此混合物搅拌10分钟，反应温度保持在60℃。
将催化剂溶液加到50毫升不锈钢钢瓶中，把200毫升丙烯通过钢瓶泵入反应器中，将反应器中的内装物被搅拌60分钟。
反应产物在真空下干燥。称重聚合物，并进行分子量分布分析其结果示于表1中。
                  实施例III
重复实施例II的程序，用1.4毫升的甲基铝氧烷、1.2升的丙烯、5毫升的ipr(3MeCp-1-Flu)ZrCl2反应温度为30℃，反应运行时间为60分钟，所得结果示于表1中。
                  实施例IV
重复实施例II的程序，用1.4毫升的甲基铝氧烷、1.2升的丙烯、5毫克按实施例I在MeCl2中所制得的ipr(3MeCP-1-Flu)ZrCl2，反应器温度为65℃，运行时间为60分钟，所得结果示于表1中。
由本实验的聚合物、得到C-13核磁共振谱按“半有规立构聚丙烯(一种新型立构规整度聚合物的实例)的方法为基础计算半等规聚丙烯的内消旋和外消旋聚合物结构的特定序列所出现的几率。
把计算值与观察值作为核磁共振谱的相对强度的函数的结果示于表II中。
                   实施例V
将5.0毫升的甲基铝氧烷与5毫克如按上述实施例在二氯甲烷中制备的ipr(3MeCP-1-Flu)ZrCl2混合，并溶于10-20毫升的甲苯中。该甲基铝氧烷为10％(重量)(SCherring)。将1.4升的丙烯加到反应器中，搅拌混合物10分钟，反应器温度被保持在60℃。
将0.4毫克的异亚丙基(环戊二烯基-1-芴基)二化锆(简写为ipr(CP-1-Flu)ZrCl2)，单独地溶于10-20毫升的甲苯中，再把二种催化剂溶液混合在一起，并加到50毫升的不锈钢钢瓶中，将200毫升的丙烯经钢瓶泵入到反应器中。将反应器的内容物搅拌60分钟。
将反应产物在真空下干燥，称重聚合物并测定其熔点，其结果示于表1中。
所有一般合成程序都在惰性气氛下，使用真空气氛手套箱或Schlenk技术设备来进行的。甲苯、戊烷、及四氢呋喃溶剂都是在氮气氛下，在红紫钠/二苯甲酮一羰游基的存在下进行蒸馏的，二氯甲烷是在氮气氛下从新鲜的氢化钙中蒸馏出来。
下列结果是使用本发明的方法，由上述进行的实验中所得到的结果。
                 表1实施例      金属茂化合物         甲基铝氧烷      丙烯      温度
            毫克             毫升数          升         ℃
   ipr(3MeCP-1-Flu)ZrCl22                5               1.4             1.2        603                5               1.4             1.2        304                5               1.4             1.2        65
   ipr(3MeCP-1-Flu)ZrCl2/
   ipr(CP-1-Flu)ZrCl25                5/0.4           5.0             1.4        60
            时间             收率   重均分子量/数均分子量实施例          分钟             克2                60              184             1.93                60              324                60              297             3.45                60              162
                          表II序列       计算值      测量值mmmm       0.15        0.14mmmr       0.11        0.12rmmr       0.07        0.06mmrr       0.25        0.21xmrx       0.00        0.05mrmr       0.00        0.00rrrr       0.23        0.19rrrm       0.14        0.14mrrm       0.06        0.08
本发明已经采用一种已知的具有双侧面对称性的间规催化剂前体，并在一个环戊二烯基基团上引入一个甲基以消除其双侧面对称性。由于聚丙烯中的甲基每隔一个的处于上述的弗歇尔投影平面的上部，则该新的催化剂制备出了被称之为半等规聚丙烯结构，半等规聚丙烯是非结晶的，并可以与间规和等规聚丙烯一起用作增塑剂。
显然，借助于上述的介绍，对本发明进行许多改进和其他是可能的。应该理解，在本发明权利要求的范围内，除了本文所作的特殊说明之外，本发明是可以实施的。

Claims (5)

1.一种制备反应器混合物的方法，所述反应器混合物包括：1)半等规聚丙烯；2)等规聚丙烯或间规聚丙烯，
所述方法的特征在于在单一反应器中，在两种催化剂的存在下聚合丙烯，其中一种催化剂包括：
a)一种下列通式的中性金属茂化合物：
R″(CpRn)(CpR’m)MHal2
式中Cp是环戊二烯基，每个R和R’是具有1-20个碳原子的烃基，可相同或不同，并且要进行选择以使CpR’m与CpRn是在空间上是不同的环，从而导致该化合物缺乏双侧面对称性，R″是给予化合物立体刚性的桥接结构，M是第3族、第4族、第5族或第6族金属，n为0至4，m为0至4，及Hal是卤素；
b)一种将所述的中性金属茂化合物转化成起催化剂作用的金属茂阳离子的离子化试剂；
另一种催化剂为间规催化剂或等规催化剂。
2.按照权利要求1所述的方法，其中，组分2)是间规聚丙烯。
3.按照权利要求2所述的方法，其中，半等规聚丙烯的用量是1-90％(重量)。
4.按照权利要求3所述的方法，其中，半等规聚丙烯的用量是5-50％(重量)。
5.按照权利要求4所述的方法，其中，半等规聚丙烯的用量是10％(重量)。
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DE69033715D1 (de) 2001-04-19
JPH03193796A (ja) 1991-08-23
GR3036018T3 (en) 2001-09-28
ES2155909T3 (es) 2001-06-01
ATE199722T1 (de) 2001-03-15
EP0742227A3 (en) 1997-01-22
CA2027124C (en) 2001-09-04
DK0423101T3 (da) 2000-07-17
CA2027124A1 (en) 1991-04-11
US6369175B1 (en) 2002-04-09
GR3033307T3 (en) 2000-09-29
DE69033435T3 (de) 2006-10-19
CN1100733A (zh) 1995-03-29
ES2142303T3 (es) 2000-04-16
CN1051735A (zh) 1991-05-29
ATE189226T1 (de) 2000-02-15
US5036034A (en) 1991-07-30
EP0423101B1 (en) 2000-01-26
EP0742227A2 (en) 1996-11-13
ES2142303T5 (es) 2006-12-01
DE69033435T2 (de) 2000-07-20
KR0181495B1 (ko) 1999-05-15
KR910007973A (ko) 1991-05-30
DE69033435D1 (de) 2000-03-02
EP0423101B2 (en) 2006-05-03
EP0423101A2 (en) 1991-04-17
DK0742227T3 (da) 2001-06-05
DK0423101T4 (da) 2006-08-21
EP0423101A3 (en) 1991-08-07
EP0742227B1 (en) 2001-03-14
CN1028532C (zh) 1995-05-24

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