CN1054135C - 制备柱形链状硅酸盐粘土的方法和制备聚合物的方法 - Google Patents
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Abstract
本发明涉及一种可用于α-烯烃聚合，含铬柱形链状硅酸盐粘土催化剂的制备方法。本发明制备方法的具体步骤包括：一、将含海泡石和坡缕石的固体粘土柱形化，制得柱形的链状硅酸盐粘土，即第一种产物；二、将所得的第一种产物先后在惰气或氧化气氛中进行加热处理活化制得第二种产物，即催化剂。上述催化剂组成或它与有机金属化合物组成的催化体系可用来进行α-烯烃，主要具乙烯的聚合或共聚合。
Description
本发明涉及一种用于α-烯烃聚合催化体系的粘土催化剂的制备方法。本发明的一个形态涉及一种新型聚合催化剂。本发明另一个形态涉及α-烯烃的聚合方法。本发明又一个形态涉及α-烯烃的新型聚合物。
我们从U.S.P4,665,045；4,742,033已经知道可以通过蒙脱石型粘土和适当的金属(如铝、钛、锆和铬)的聚合型阳离子羟基金属络合物水溶液的反应来制取柱形夹层粘土组合物。Pinnavaia等人进而又在U.S.P4,665,045中报导用铬制得的这种柱形夹层粘土组合物可以用来进行烯烃聚合。
然而，即使现在也需要开发一种制备柱形夹层粘土的新方法以制取不同的催化剂。同样重要的是需要开发一种可以大规模生产有效催化剂的方法。进而需要对这类粘土中的重要差异有更好的了解，这样才能对生成的聚合物类型的特殊和优异的性能进行探索。
本发明提出一种用于α-烯烃聚合的高效新催化剂组合物的新的制备方法。它是通过制备柱形链状硅酸盐粘土来实现的，它包括以下步骤：
(a)，将铬盐和碱溶于水中制得水解的第一种溶液，将此溶液加热至约20-100℃，同时不断地搅拌直至溶液的PH值达到约1.5-2.5，由此得到一种母料；
(b).将上述母料用水稀释制得稀释的第二种溶液，加热稀释的第二种溶液得到加热的第二种溶液；
(c).在上述加热的第二溶液中加入选自 海泡石和坡缕石
的带状硅酸盐粘土，並继续加热；
(d).回收上述柱形化的链状硅酸盐粘土；和
(e).干燥上述柱形化的链状硅酸盐粘土得到第一种产物。
在另一个实施方案中提供了上述粘土的活化方法，它包括下述步骤：
(a).在惰性气氛中，于大约150-500℃将上述第一种产物加热大约30分钟到10小时；
(b).此后，在氧化气氛中，于约500-900℃再次加热上述第一种产物约1-50小时，回收该催化剂组合物。
本发明进一步提供了一种改进的α-烯烃聚合方法，结果生成新型聚合物组合物。这方法包括：用上述催化剂与至少一种每分子含2到8个碳原子的单-1-烯烃接触；也可以是与每分子中含3到8个碳原子的共聚单体进行共聚合；上述催化剂也可以与有机金属助催化剂并用。
铬—柱形粘土的一般制备方法
本发明采用了坡缕石和海泡石粘土，它们在形态上与过去用来柱形化的那些粘土不同。坡缕石和海泡石两者都是链状粘土，其中二氧化硅具有三层结构，一层八面体被夹在二层四面体之间。但是，二氧化硅的八面体层是不连续的，而四面体层是保持连续的而且含有逆转了的四面体的交替链段。八面体的不连续性发生在每一个转化点上。这种反常的排列在它们带状的形态上得到反映。此外，由于自然界的丰富资源和市场上买得到使得粘土可以成为目前在烯烃聚合中使用的昂贵的合成二氧化硅的廉价代用品。
本发明对Pinnavaia等在U.S.P.4,655,045中所报导的方法进行了重大的改进。区别之一是Pinnavaia只局限于“选自蒙脱石、蛭石和氟锂蒙脱石的具有层状晶格的粘土水浆…”。本发明采用了坡缕石和海泡石粘土，由于它们的独特的结构，在文献中尚未见到可以使它们柱形化的报导。海泡石和坡缕石属于粘土。它们含有三层结构，其中二氧化硅以二层四面体层夹着中间一层八面体层的三明治方式排列。但是，二氧化硅的八面体层是不连续的，而四面体层是保持连续的而且含有逆转了的四面体的交替链段。八面体的不连续性发生在每一个转化点上。这种反常的排列在它们带状的形态上得到反映。它们是纤维状的矿物质。与蒙脱石不同，除去表面的吸附水，坡缕石和海泡石在因不连续性而形成的通道中还包含有分子水或沸石水。
本发明提出了一种用以往认为不能柱形化的粘土来制备柱形化的链状硅酸盐粘土的新方法。本发明方法的第一步是将铬盐和碱溶解在水中制得水解了的第一种溶液。将这第一种溶液加热至约20-约100℃，同时在连续搅拌下加热直至溶液PH值达到约1.5-约2.5止，由此制得一种母料。在恰当的时间内加热可使铬的水解齐聚变得容易，同时PH值可以指示什么时候停止加热能使多羟基铬齐聚物具有最佳浓度。采用上述第一种溶液的PH值来决定加热是否充分是一种新的实施方法，这相当于以往专利中所说的“陈化”。在约90℃，连续搅拌下加热上述第一种溶液直至PH值达到约2.3是较可取的条件。
上述的碱可选自碳酸钠、碳酸铵、氢氧化钠和氢氧化铵，而以碳酸钠较好。上述的盐可选自硝酸铬、氯化铬和乙酸铬，而以硝酸铬较好。
本发明的第二步是用水稀释上述母料得到一个稀释了的第二种溶液，加热上述稀释了的第二种溶液以得到经过加热的第二种溶液。我们发现在对上述母料进行稀释的同时达到了大规模生产柱形化链状硅酸盐粘土的目的。
Pinnavia报导了用来与铬溶液接触用的粘土浆液的制备方法。本发明的制备方法是将上述含铬的母料溶液进行稀释，然后加入干的即粉状或能自由流动的粘土。当大量地制备柱形链状硅酸盐粘土时，浆液所需要的液体体积量是如此之大以至没有实用价值。但意想不到的是用本发明的稀释上述母料的方法代替上述浆料化的粘土时所需的液体体积可以减少到其它方法所需要体积的1/4以下。
稀释步骤还可以提供一个控制催化剂的最终铬含量的方法。当用已知的方法来制取柱形硅酸盐粘土时，最终的粘土产物中含有高的铬含量；当它被用作聚合催化剂时，那么在聚合物中将会含有超过允许的高的Cr(VI)含量。采用本发明的方法，由于对最初的Cr含量进行了控制，所以就可以消除Cr(VI)对健康带来的危害。
上述的稀释是这样进行的，即第一种溶液按每1毫升母料加约0.5至约10毫升水的比例进行稀释。较合适的稀释比是每1毫升母料加约4毫升水。上述第二种溶液被加热到约20-约100℃较可取的是加热到约90℃。
本发明的第三步是将选自海泡石和坡缕石的固体粘土加到上述经过加热的第二种溶液中。以固体形式加入粘土是为了防止过量。上述第二种溶液的液体体积是每1克粘土约0.5-约20毫升，且每1毫升上述第二种溶液含铬量为约0.001至约0.01克。上述第二种溶液较适宜的液体体积为每1克粘土约9毫升，且每1毫升上述第二种溶液的含铬量为约0.002克。
新的柱形链状硅酸盐粘土可以用本专业的人都知道的常规方法来进行回收。然而用下述方法来处理是可取的，即将上述柱形链状硅酸盐粘土先用水进行一系列的洗涤和离心干燥，随后再用醇进行一系列的洗涤和离心干燥。用醇的目的是在最终干燥前除去过量的水，由此得到第一种产物。然后，用本专业的人都知道的任何方法，如烘箱或真空干燥等进行干燥。也可以用恒沸干燥、喷雾干燥、冷冻干燥以及其它任何方法来进行干燥。
铬—柱形粘土的一般活化
已经干燥的柱形粘土可以按下述步骤进行活化而得到催化体系，它包括以下步骤：
(a).在惰性气氛下，于大约150-约500℃下加热上述第一种产物30分钟至约10小时，较适宜的加热温度为约500℃时间约1小时；
(b).然后在氧化气氛中，于大约500-约900℃将上述第一种产物再加热约1-约50小时，得到第二种产物。较合适的再加热温度为约650℃，时间约3小时。
活化也可以进一步包括一个冷却步骤，即将上述第二种产物在还原气氛下冷却到约300-约500℃，时间是约1分钟到约5小时。较适宜的温度为约350℃，时间为约30分钟。比起一步连续加热法来，二步法加热过程可以得到生产率更高的烯烃聚合催化剂。
使用新型催化剂体系的一般聚合方法
本发明的聚合方法需要至少一种每分子中含2-8个碳原子的烯烃与上述新型催化剂接触。上述烯烃可选自乙烯、丙烯、戊烯-1，己烯-1和辛烯-1，上述烯烃中较适宜的主要是指乙烯。
可以使用一种共聚单体与乙烯共聚以制取乙烯共聚物。上述共聚单体可以选自丙烯、丁烯-1、戊烯-1、己烯-1和辛烯-1。较好的共聚物是由乙烯和选自C4-C12的单烯烃共聚而得，其中共聚单体的含量为0.4-1(重量)％，共聚单体以己烯最为合适。
另外，上述新型催化体系还可以和一种有机金属催化剂并用。有机金属助催化剂可以选自三乙基铝、三乙基硼和二乙基硅烷。较好的助催化剂是三乙基铝。
带状硅酸盐柱形粘土的制备实施例1
采用由西班牙Vallecas提供的粘土制备了一系列的含铬海泡石粘土催化剂。由销售者提供的分析数据表明粘土包含下列化合物已折算成氧化物形式)：54.89％SiO2；22.03％MgO32.41％Al2O3；0.62％FeO；0.15％CaO；1.32％K2O+Na2O；0.07％TiO和11.9％H2O(以上数值均指重量百分数)。阳离子交换容量8.3毫克当量/100克。氮孔径分布测量表明它的表面积为137米2/克，孔体积为0.52毫升/克。
母料的制备：将1333克(3.33克分子)的Cr(NO3)3.9H2O溶于13.3升去离子水中。将用353克(3.33克分子)的Na2CO3和6.7升去离子水配成的溶液在搅拌下慢慢地加到上述溶液中。在不断地搅拌下将此混合物于90-95℃加热15-24小时，並随时补充因蒸发而损失的水。冷却所得混合物並在室温下贮存。
在1升母料中加入2.0升去离子水，然后加热至90-95℃，在不断地搅拌下于15分钟内加入454克Pangel粘土。加完粘土后，将溶液在搅拌下加热3小时並随时补充因蒸发而损失的水。将粘土液体混合物分装至4-8个1升的离心瓶中。每一批进行离心分离和洗涤6次，每次用去离子水600毫升。紧接着用甲醇进行洗涤和离心分离4次，每次用甲醇600毫升。将各批产物收集在一起，然后置于真空烘箱中在50-100℃，氮气流下干燥过夜。将干燥后的柱形粘土用Wiley磨进行研磨，用50目筛网过筛得到产物A。
活 化实施例II
将20-25克产物A在一实验室规模的流化床(48毫米外径石英管)中进行高温活化。活化是依次先在400℃用干燥的氮气流处理1小时，随即在650℃用干燥的空气流处理3小时。活化之后，催化剂(A1)在干燥的氮气流下冷却至室温，回收并在干燥的氮气中贮存备用。
实施例III
以实施例II制取A1同样的方法对A进行活化，只是在空气氧化之后将催化剂在氮气冷却至350℃，并且在此温度下将干燥的CO气流通过催化床30-45分钟。然后将它冷却至室温，与此同时用干燥的氮气冲洗置换CO。回收所得产物作为催化剂A2，並按上述实施例II中所述方法进行贮存。分析结果(重量％)：铬(1.9)，镁(17.0)
聚 合实施例IV
乙烯或乙烯和共聚单体己烯-1的聚合是在一只2.6升的不锈钢夹套反应器中以颗粒状方式进行的。在将干净的反应器用干燥的氮气和干燥的异丁烷蒸汽进行冲洗之后，加入1升干燥的液态异丁烷作为稀释剂。将封闭的反应器加热至予定的温度，然后加入所需量的催化剂(0.03-1克)，必要时再加入约1.0-2.0毫升含量为0.5(重量)％的有机金属化合物溶液作为助催化剂。上述有机金属化合物可以是三乙基铝，三乙基硼和二乙基硅烷或者是它们的混合物。然后用乙烯将反应器升压至550Psig。在此压力下可根据聚合反应速度来调节乙烯流量使它在整个反应期间保持恒压。聚合时间通常为1小时，将每小时得到的干燥反应器产物重量除以催化剂用量，所得的值即为产率，用克(聚合物)/克(催化剂)·小时来表示。由于在各种不同聚合条件下用这些粘土催化剂进行烯烃聚合时聚合时间不是正好都等于60分钟，为此需将观察到的稳定的聚合速度折算成以60分钟计的值。事实上就是将得到的未校正的产率值乘以60再除以真实的聚合时间(分钟)。
催化剂，聚合条件，结果和所得聚乙烯的有关性能列于表1中。表1 聚合结果和聚乙烯的性能催化剂 温度 己烯-1 辅助剂 产率 HIMI 密度No (℃) (重量)％ (PPm) g/g/hr g/c.c
**A1 88 TEA(5) 2020A1 88 TEA(5) 1560A1 95 3170A1 105 2580 0.3A1 105 1.1 2070 0.7 0.944A1 105 TEA(5) 2480* 2.8 0.951A1 105 2050 1.4A1 105 1.1 1100 0.7 0.946A1 105 TEA(5) 3560* 2.9 0.953A2 105 1920 0.1A2 105 TEA(3) 2300* 6.1 0.948A2 95 1600A2 95 1.1 TEA(5) 1500* 8.0
注：*.反应器中含5克分子％的氢
**.TEA为三乙基铝实施例V
柱形化的坡缕石粘土的制备
所用的坡缕石是双八面体粘土的一种，它是美国佐治亚产品。分析表明它的表面积为126米2/克，孔体积为0.64毫升/克，阳离子交换容量为1.67毫克当量/100克。它的组成(已折算成氧化物形式)：62.0％SiO2；10.3％Al2O3；9.8％MgO；1.9％CaO；3.5％FeO；1.1％K2O+NaO2和10.0％H2O(以上数值均指重量百分数)。
将160毫升母料溶液加热至90-95℃。在不断地搅拌下加入6.5克坡缕石粘土(佐治亚)並加热1小时，在将混合物冷却至室温后将它转移至1升的离心瓶中。将此混合物用去离子水洗涤和离心分离6次，每次用600毫升去离子水。随后再用甲醇洗涤分离4次，每次用甲醇600毫升。将所得的柱形化粘土在100-110℃真空烘箱中，氮气流下干燥24小时。所得样品在实验室磨中研磨，通过5号筛网得到产物A′。实施例VI
将52毫升去离子水加到18毫升的母料中。将此溶液加热至90-95℃。在不断地搅拌下加入7.0克坡缕石粘土。加完粘土后，在搅拌下将此混合物加热1小时。分离含铬柱形化坡缕石粘土，用实施例V中同样的方法进行洗涤、干燥和研磨，得到产物B′。实施例VII
将产物A′和B′用实施例II中所述的同样方法进行活化，得到产物A1′和B1′。实施例VIII
乙烯聚合是在2.6升不锈钢夹套反应器中，用A1′或B1′为催化剂，以颗粒状方式进行的。在将清洁的反应器用干燥氮气和干燥的异丁烷蒸汽冲洗后，加入1升干燥的液态异丁烷作为稀释剂。将封闭后的反应器加热到予定温度，然后加入所需的催化剂(0.03-1克)。必要时可再加入1.0-2.0毫升含量为0.5(重量)％的有机金属化合物溶液作为助催化剂。上述有机金属化合物可以是三乙基铝、三乙基硼和二乙基硅烷或是它们的混合物。然后用乙烯将反应器升压至550PSig。根据聚合速度来调节乙烯流量使它在整个聚合过程中保持恒压。聚合时间通常为1小时。将每小时得到的干燥反应器产物除以催化剂用量，所得的值即为产率，用克(聚合物)/克(催化剂)。小时来表示。由于在各种不同聚合条件下用这些粘土催化剂进行烯烃聚合时聚合时间不是正好都等于60分钟，为此需将观察到的稳定的聚合速度折算成以60分钟计的值。事实上就是将得到的未校正的产率值乘以60再除以真实的聚合时间(分钟)。
催化剂、聚合条件、结果和所得聚乙烯的性能列于表II中。表II 聚合结果和聚乙烯性能催化剂 温度 辅助剂 产率No ℃ (PPm) g/g/hrA1′ 95 TEA*(5) 3600B1′ 95 TEA(5) 2450
注：*TEA为三乙基铝
Claims (28)
1.一种制备柱形链状硅酸盐粘土的方法，该方法包括：
(a).先将铬盐和碱溶于水中制得水解的第一溶液，将此溶液加热至20-100℃，与此同时不断地搅拌直至溶液的pH值达到1.5-2.5为止，即制得母料；
(b).用水稀释上述母料制得稀释的第二溶液，加热该溶液得到加热后的第二种溶液；
(c).将一种固体形式的海泡石或坡缕石的粘土加到上述加热后的第二溶液中，并继续加热；
(d).回收上述柱形化的链状硅酸盐粘土；和
(e).干燥上述柱形链状硅酸盐粘土生成第一种产物。
2.按照权利要求1的方法，其中所用的碱是碳酸钠，碳酸铵，氢氧化钠或氢氧化铵。
3.按照权利要求2的方法，其中所用的碱是碳酸钠。
4.按照权利要求1-3中任一项所述方法，其中所用的铬盐是硝酸铬，氯化铬或乙酸铬。
5.按照权利要求4的方法，其中所用的铬盐是硝酸铬。
6.按照权利要求1-3中任一项所述方法，其中第一种溶液的加热是在90℃进行，且同时不断地搅拌直至该第一溶液的pH值达到2.3为止。
7.按照权利要求1-3中任一项所述方法，其中以每1毫升的母料加0.5-10毫升的水的比例对第一种溶液进行稀释。
8.按照权利要求7的方法，其中以每1毫升母料加4毫升水的比例对第一种溶液进行稀释。
9.按照权利要求1-3中任一项所述的方法，其中第二种溶液是在90℃进行加热。
10.按照权利要求1-3中任一项所述的方法，其中被用来加到上述第二种溶液中的粘土是固体海泡石。
11.按照权利要求1-3中任一项所述的方法，其中被用来加到上述第二种溶液中的粘土是固体坡缕石。
12.按照权利要求1-3中任一项所述的方法，其中上述第二种溶液的液体体积为每克粘土0.5-20毫升，且每毫升上述第二溶液含铬0.001-0.01克。
13.按照权利要求12的方法，其中上述第二溶液的液体体积为每克粘土9毫升，且每毫升上述第二溶液含铬0.002克。
14.按照权利要求1-3中任一项所述的方法，其中所述的柱形链状硅酸盐粘土的回收过程包括对上述第二种溶液的洗涤和离心分离。
15.按照权利要求1所述的方法，进一步包括对上述柱形链状硅酸盐粘土第一种产物进行活化从而得到一个催化剂体系。
16.按照权利要求15所述的方法，其中上述活化过程包括：
(a).在惰性气氛中于150-550℃加热上述第一种产物30分钟至10小时。
(b).然后在氧化气氛中于500-900℃将上述第一种产物再加热1小时-50小时，然后回收作为第二种产物。
17.按照权利要求16所述的方法，其中第一种产物先在500℃加热1小时，然后再在650℃加热3小时。
18.按照权利要求16所述的方法，该法还包括将上述第二种产物在还原气氛中冷却到300-500℃并保持1分钟到5小时。
19.按照权利要求18所述的方法，其中上述第二种产物被冷却到350℃并保持30分钟。
20.按照权利要求15所述的方法，其中还包含一种有机金属助催化剂，与上述催化剂体系并用。
21.按照权利要求20所述的方法，其中上述助催化剂是三乙基铝，三乙基硼或者二乙基硅烷。
22.按照权利要求21所述的方法，其中所述的助催化剂是三乙基铝。
23.一种制备聚合物的方法，它包括用按照权利要求15-22的任何一项中所述方法制得的催化剂体系，与至少一种每个分子含2-8个碳原子的烯烃接触。
24.按照权利要求23所述的方法，其中上述至少一种烯烃是乙烯、丙烯、戊烯-1、己烯-1或辛烯-1。
25.按照权利要求24所述的方法，其中上述至少一种烯烃是乙烯。
26.按照权利要求25所述的方法，其中选自C4-C12的单烯烃与乙烯进行共聚以生成乙烯共聚物。
27.按照权利要求26所述的方法，其中上述共聚单体可以是丙烯、丁烯-1、戊烯-1、己烯-1或辛烯-1。
28.按照权利要求27所述的方法，其中所述的共聚单体是己烯-1。
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| ATE290045T1 (de) * | 1998-03-16 | 2005-03-15 | Dow Global Technologies Inc | Verfahren zur herstellung von polyolefin- nanocompositen |
| US6495638B2 (en) * | 1998-12-30 | 2002-12-17 | Phillips Petroleum Company | Process to produce polymers |
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| US3008943A (en) * | 1955-12-01 | 1961-11-14 | Exxon Research Engineering Co | Polymerization catalyst |
| US4060480A (en) * | 1971-09-03 | 1977-11-29 | Chevron Research Company | Hydrocarbon hydroconversion process employing hydroxy-aluminum stabilized catalysts supports |
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| US3844979A (en) * | 1972-12-01 | 1974-10-29 | Chevron Res | Layered clay minerals, catalysts, and processes for using |
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| IL50548A (en) * | 1976-09-23 | 1979-10-31 | Yissum Res Dev Co | Process for preparation of molecular sieves |
| US4248739A (en) * | 1979-09-04 | 1981-02-03 | W. R. Grace & Co. | Stabilized pillared interlayered clays |
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| FR2652079B1 (fr) * | 1989-09-18 | 1991-12-13 | Rhone Poulenc Chimie | Procede de preparation d'argiles pontees et argiles pontees obtenues selon ce procede. |
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| US5192726A (en) * | 1991-09-03 | 1993-03-09 | Uop | Beidellite clay and process for preparing the clay |
| US5376311A (en) * | 1993-12-06 | 1994-12-27 | Deguzman; Vel | Apparatus for mixing gas and liquid |
-
1992
- 1992-09-30 AU AU26060/92A patent/AU650787B2/en not_active Ceased
- 1992-10-08 TW TW081108007A patent/TW215431B/zh active
- 1992-10-16 MX MX9205960A patent/MX9205960A/es unknown
- 1992-10-30 AR AR92323555A patent/AR247533A1/es active
- 1992-11-04 KR KR1019920020608A patent/KR0181518B1/ko not_active Expired - Fee Related
- 1992-11-04 CN CN92112754A patent/CN1054135C/zh not_active Expired - Fee Related
- 1992-11-05 JP JP4295731A patent/JPH05238722A/ja active Pending
- 1992-11-05 ZA ZA928534A patent/ZA928534B/xx unknown
- 1992-11-05 BR BR929204298A patent/BR9204298A/pt not_active Application Discontinuation
- 1992-12-04 CA CA002084605A patent/CA2084605C/en not_active Expired - Fee Related
- 1992-12-08 NO NO924749A patent/NO180590C/no unknown
- 1992-12-08 DK DK92120904.5T patent/DK0546499T3/da active
- 1992-12-08 AT AT92120904T patent/ATE138831T1/de not_active IP Right Cessation
- 1992-12-08 HU HU9203881A patent/HU211063B/hu not_active IP Right Cessation
- 1992-12-08 HU HU9203881A patent/HU9203881D0/hu unknown
- 1992-12-08 EP EP92120904A patent/EP0546499B1/en not_active Expired - Lifetime
- 1992-12-08 ES ES92120904T patent/ES2087414T3/es not_active Expired - Lifetime
- 1992-12-08 DE DE69211302T patent/DE69211302T2/de not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| ATE138831T1 (de) | 1996-06-15 |
| NO180590B (no) | 1997-02-03 |
| DE69211302T2 (de) | 1996-10-02 |
| JPH05238722A (ja) | 1993-09-17 |
| MX9205960A (es) | 1993-06-01 |
| DE69211302D1 (de) | 1996-07-11 |
| CA2084605A1 (en) | 1993-06-10 |
| HU9203881D0 (en) | 1993-03-29 |
| GR3020737T3 (en) | 1996-11-30 |
| EP0546499A1 (en) | 1993-06-16 |
| BR9204298A (pt) | 1993-06-15 |
| TW215431B (zh) | 1993-11-01 |
| ZA928534B (en) | 1993-05-05 |
| HUT64983A (en) | 1994-03-28 |
| US5502265A (en) | 1996-03-26 |
| NO924749L (no) | 1993-06-10 |
| CN1073182A (zh) | 1993-06-16 |
| CA2084605C (en) | 1999-04-06 |
| NO180590C (no) | 1997-05-14 |
| EP0546499B1 (en) | 1996-06-05 |
| NO924749D0 (no) | 1992-12-08 |
| ES2087414T3 (es) | 1996-07-16 |
| US5376611A (en) | 1994-12-27 |
| DK0546499T3 (da) | 1996-06-24 |
| HU211063B (en) | 1995-10-30 |
| AU650787B2 (en) | 1994-06-30 |
| AU2606092A (en) | 1993-06-10 |
| KR0181518B1 (ko) | 1999-04-15 |
| AR247533A1 (es) | 1995-01-31 |
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