CN1003853B - 以烯烃为厚料制备二聚产物的方法 - Google Patents
以烯烃为厚料制备二聚产物的方法 Download PDFInfo
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- CN1003853B CN1003853B CN85109193.8A CN85109193A CN1003853B CN 1003853 B CN1003853 B CN 1003853B CN 85109193 A CN85109193 A CN 85109193A CN 1003853 B CN1003853 B CN 1003853B
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000002253 acid Substances 0.000 claims abstract description 40
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- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 150000003304 ruthenium compounds Chemical class 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims description 29
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 230000007704 transition Effects 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
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Abstract
一种以２～１２碳原子的脂族单烯烃为原料制备二聚产品的方法，在该方法中，使脂族单烯烃在质子惰性的有机溶剂中与催化体系接触。催化体系由钯和（或）钌化合物和除氢卤酸以外的ＰＫａ值小于２的酸结合剂组成。
Description
本发明涉及用一种含钯和（或）钌的催化剂在有机溶剂中，以低分子量的脂族单烯烃为原料制备二聚产物的方法。
已有人提出，乙烯可在含高浓度的强无机酸，如磷酸（浓度14.0摩尔/升，～85%）和硫酸（浓度17.0摩尔/升，～95%）的反应介质中经催化二聚成丁烯类，所用的催化剂是一种具有与钯不太作用或不作用的负离子的钯盐。这种二聚方法是不足取的，因为它应用了一个强腐蚀性的反应介质，同时乙烯生成丁烯的转化率相对钯用量来说也非常低（参见：苏联专利说明书374930（化学文摘，90，22286h））。
此外，也已知道，用就地制备的化合物〔Pd（CH3CN）（PPh3）3〕.（BF4）2或化合物〔Pd（CH3CN）〕（BF4）2·nPPh3（n＝2，3）作催化剂，乙烯可在氯仿中发生二聚（参见：J.Am.Chem.Soc.1034627-4629（1981）和1043520-3522（1982））。但是，这些催化剂需要严格的无水反应条件（参见：《过渡金属催化聚合》;《烯烃和二烯烃》，A部分，R.P.Quirk编，1983 PP341-354）。
本发明提供了一个由每分子含2～12个碳原子的脂族单烯烃制备其二聚产物的方法。该方法是以脂族单烯烃在质子惰性的有机溶剂中与催化体系接触为特征，催化体系是由一种钯和（或）钌化合物和一种PKa值小于2的酸（除氢卤酸外）结合而成。
在本发明方法的催化体系中存在如上定义的酸，由于在质子惰性的有机溶剂中强的活化效应，可以得到非常高的二聚速率。
根据本发明，可用于本方法的每分子中含有2～12个碳原子的脂族单烯烃是直链或支链链烯烃或环烯烃，例如，乙烯、丙烯、1-丁烯、2-丁烯、异构的戊烯类、己烯类、辛烯类和十二碳烯类、环戊烯、环辛烯和环十二碳烯。其它脂族单烯烃的例子有取代的链烯烃，如烯丙醇、丙烯酸和丙烯酸的烷基、芳基、芳烷基酯。较好的烯烃是乙烯和丙烯。
本文中所用的术语“二聚产物”是指两个相同的烯烃相互反应以及两种不同的烯烃相互反应得到的烯烃产物，也指在反应混合物中还分别有水、醇或羧酸存在下就地得到的这些烯烃的醇、醚或酯的衍生物。
根据本发明，均相和非均相催化剂均可应用，但以均相催化剂为。
所以，本发明方法所用的催化剂最好是由可溶于反应混合物中或就地形成可溶性化合物的钯化合物和（或）钌化合物等所组成。
合适的钯化合物的例子是硝酸钯、硫酸钯、卤化钯和钯的羧酸盐类，最好是每个分子含不多于12个碳原子的羧酸的盐类。也可以使用PKa2的酸的钯盐，下文中对这种酸有详细说明。最好使用钯的羧酸盐，特别是醋酸钯。
合适的钯化合物的例子还有钯的络合物，如双（2，4-戊二酸根）合钯、双（吡啶甲酸根）合钯、四（三苯膦）合钯、四氟硼酸四乙腈合钯、醋酸双（三邻甲苯膦）合钯、硫酸双（三苯膦）合钯等。
适合的钌化合物的例子是氯化钌（Ⅲ）、氯化钌（Ⅳ）、氯化钌（Ⅲ）三水合物、钌氧化物、钌的羧酸盐（如醋酸钌或丙酸钌）、三乙酰丙酮酸酸钌（Ⅲ）和带有P和N单齿配位体的有机钌络合物。此外，下文中有详细说明的PKa小于2的酸的钌盐也是合用的。
钯和（或）钌化合物的用量可在较宽的范围内变化，对于每摩尔烯烃原料，该用量通常是在10-6到10-1、最好是在10-6到10-2摩尔钯和（或）钌化合物的范围之内。
本发明方法中所用的PKa小于2的酸包括：有机酸（如羧酸和有机磷酸）和无机酸，这些酸最好具有不配位的阴离子，也就是说，钯和负离子之间的相互作用很小或不发生作用。这种阴离子的典型实例是PI6 -、SbF6 -、BF4 -和ClO4 -。
可用的比较好的酸类是，例如：过氯酸、硫酸、磺酸和那些可以用路易斯酸（例如BF3、AsF5、SbFs、PF5、TaF5或NbF5）与质子酸（Broensted acid）（例如氢卤酸（特别是HF）、氟磺酸、磷酸或硫酸）相互作用而就地形成的酸。上面最后提到的一类酸的特例有氟硅酸、HPF4、HSbF4和HBF4，这些酸是比较好的。可用的磺酸的典型例子是氟磺酸、氯磺酸和有机磺酸类（如甲磺酸、2-羟基丙磺酸、对甲苯磺酸和三氟甲磺酸，其中最后两种酸较好）。
可用的羧酸有三氟醋酸、三氯醋酸和二氯醋酸。
PKa值小于2的酸的用量是，每克原子钯和（或）钌用至少1当量的酸，最好是用至少10当量的酸。
另外，当催化体系中采用含有Va族原子的配位体时，酸相对于配位体的过量会使催化体系大大活化。因而，在本发明方法中，催化体系是由钯和（或）钌化合物、含有至少一个元素周期表中的Va族原子作配位原子的配位体和一个PKa值小于2的酸结合而成，酸用量是配位体中每克原子Va族原子用1当量以上的酸。
本发明方法中可使用的单齿配位体包括含有一个元素周期表中的Va族原子的化合物，特别是含有与至少一个芳烃基团相连的三价N或P原子的化合物，或是含有三价N原子、此N原子是杂芳环上一构环原子的化合物。
由一种含有与至少一个芳烃基团相连的三价N或P原子的化合物构成的合适的单齿配位体的实例有：N，N-二烷基苯胺和膦化合物，例如N，N-二甲基苯胺、N，N-二乙基苯胺、N，N-二丁基苯胺、4-氯-N，N-二甲基苯胺、4-乙氧基-N，N-二甲基苯胺、4-二甲氨基苯磺酸、3-二甲氨基苯磺酸、双（1，1-二甲乙基）苯膦、二甲基苯膦、环己基二苯膦、二丁基苯膦、甲基二苯膦、三苯膦、三（4-氯苯基）膦、三（4-甲氧基苯基）膦、三（2-甲氧基苯基）膦、三（4-丁基苯基）膦、三（4-三氟苯基）膦、三（4-氟苯基）膦和2-羧苯基二苯膦。
由一种含有作为杂芳环一部分的三价N原子的化合物构成的合适的单齿配位体的实例有：吡啶类和喹啉类化合物，例如吡啶、2，6-二甲基吡啶、4-乙基吡啶、2-甲氧基吡啶、2-氯吡啶、3-氯吡啶、2，6-二氯吡啶、2-吡啶羧酸、3-吡啶羧酸、喹啉、2-甲基喹啉和2-氯喹啉。
最好采用一种包括N，N-二甲基苯胺、三苯膦、吡啶或其衍生物的单齿配位体。
可用于本发明方法的螯合配位体包括含有至少两个元素周期表中的Va族原子的化合物，这些原子通过含2～6个碳原子的链相互连接。
适宜的螯合配位体的例子有含两个磷原子的化合物（这两个磷原子通过含有2或3个碳原子的链相连），如1，2-亚乙基双二苯膦、1，2-亚乙烯基双二苯膦、1，2-亚苯基双二苯膦和1，3-亚丙基双二苯膦。
适宜的螯和配位体的例子还包括含两个氮原子的化合物，这两个氮原子通过含有2个碳原子的链相连，特别是分子中含有如下式所示基团的化合物：
例如1，10-菲咯啉、4，7-二甲基-1，10-菲咯啉、4，7-二苯基-1，10-菲咯啉-二磺酸、2，2′-联吡啶，4，4′-二甲基-2，2′-联吡啶和4，4′-二氯-2，2′联吡啶。
在本发明方法中用于催化剂的配位体的量是，每克原子钯和（或）钌至少用1摩尔配位体。
本发明方法是在质子惰性的有机溶剂中进行反应。合用的溶剂实例有烃类（如己烷、环己烷、辛烷、环辛烯、苯、甲苯、三种二甲苯、乙苯和枯烯）、卤代烃类（如氯仿、1，2-二氯乙烷、全氟代烷烃、氯苯和三种二氯苯）。醚类（如四氢呋喃、二甘醇二甲醚、甲基叔丁基醚和二氧六环）以及硝基化合物（如硝基甲烷和硝基苯）。
反应物烯烃也可作为质子惰性溶剂，特别是当使用高级烯烃或取代的烯烃（如丙烯酸的酯类）的时候。
最好是用芳烃或卤代脂族烃作溶剂。
如前所述，在水、醇或羧酸的存在下，由本发明方法制得的二聚产物中可以分别含有就地生成的醇、醚或酯。可以存在的醇类和羧酸最好是低级脂族醇和羧酸，如甲醇、乙醇、丙醇、醋酸、丙酸或己酸。水、醇和羧酸存在的量应以保持反应介质的质子惰性性质为度，即按质子惰性溶剂的量计为50%（体积）以下，最好是20%（体积）以下。
按照本发明，反应可在高达200℃的温度下进行，但最好是在20～135℃的温度范围内进行。反应压力可在1～100巴表压之间，最好是在20～75巴表压之间。
按照本发明，反应可以分批、半连续或连续方式进行。
下面是几个实例，可进一步说明本发明。
实例Ⅰ
在一个300毫升磁力搅拌的Hastelloy C级高压釜中
（“Hastelloy”是商标名），放入50毫升溶剂、0.1毫摩尔醋酸钯或钌（乙酰丙酮酸盐）和PKa小于2的酸作为催化体系。高压釜用乙烯冲洗，在40巴压力下充入乙烯，然后密封，加热到规定的温度，经规定的反应时间后，用气/液相色谱分析高压釜中的成分。
乙烯转化产品（二聚体、三聚体等等）的转化率按摩尔乙烯/克原子钯或钌/小时计。对丁烯的选择性按形成的反应产物中丁烯的摩尔百分数计。
按上述过程进行的试验1～6的数据与结果如表Ⅰ所示。
在不按本发明做的一个实验中，将50毫升甲苯和5毫摩尔三氟甲磷酸加到一个玻璃衬里的高压釜中，高压釜用乙烯冲洗，在40巴压力下充入乙烯，然后加热到70℃，反应5小时后，通过气/液相色谱分析，仅有痕量的二聚体生成。这个实验表明，在基本相同的反应条件下，如果只有PKa小于2的酸，而没有钯或钌的化合物存在的话，二聚反应是不能实现的。
实例Ⅱ
在300毫升磁力搅拌的Hastelloy C级高压釜中（“Hastelloy”是商标名称），装入50毫升溶剂和0.1毫摩尔醋酸钯、一种配位体和PKa小于2的酸作为催化体系。高压釜用乙烯冲洗后，在给定的压力下充入乙烯，然后密封并加热到规定温度，经规定的反应时间后，釜内各成分用气/液色谱进行分析。
乙烯相对于产物（二聚体、三聚体等）的转化率按摩尔乙烯/克原子钯/小时计。
按上述方法进行的实验1～9的数据和结果如表Ⅱ所示。实验2中，对生成的丁烯类产品的组成的分析结果是：1-丁烯24%，反-2-丁烯47.7%，顺-2-丁烯38.3%。实验9中，对生成的丁烯类产品的组成的分析结果是：1-丁烯6.3%，反-2-丁烯63.3%，顺-2-丁烯30.7%。实验4、6和8是不按本发明做的，说明PKa小于2的酸只有过量于配位体才能得到高的转化率。
实例Ⅲ
在300毫升磁力搅拌的Hastelloy C级高压釜中（“Hastelloy”是商标名称），装入溶剂和醋酸钯、一种单齿配位体和PKa小于2的酸作为催化体系。高压釜用丙烯冲洗后，充入40毫升液体丙烯，密封后加热到规定温度，经规定的反应时间后，釜内成分用气/液相色谱进行分析。
丙烯相对于产物（二聚体，三聚体等）的转化率按摩尔丙烯/克原子钯/小时计。对二聚体己烯类产品的选择性按形成的产物中二聚体的摩尔百分含量计。
按上述过程进行的实验1-3的数据和结果如表Ⅲ所示。
实例Ⅳ
在300毫升磁力搅拌的Hastelloy C级高压釜中（“Hastelloy”是商标名称）。装入40毫升甲苯，10毫升醋酸和0.1毫摩尔醋酸钯以及4毫摩尔CF3SO3H作为催化体系。高压釜用乙烯冲洗后，在40巴压力下充入乙烯，密封后加热到70℃，反应1小时后，釜内各成分用气/液相色谱进行分析。
乙烯相对二聚产物的转化率是4800摩尔乙烯/克原子钯/小时，醋酸转化为醋酸仲丁酯的转化率是78%摩尔。
实例Ⅴ
在300毫升磁力搅拌的Hastelloy C级高压釜中（“Hastelloy”是商标名称），装入50毫升丙烯酸甲酯和0.5毫摩尔乙酰丙酮酸钌、0.5毫摩尔1，3-亚丙基双二苯膦和3毫摩尔三氟甲磺酸作为催化体系。高压釜用乙烯冲洗后在40巴压力下充入乙烯，密封并加热到90℃，反应5小时后，釜内成分用气/液相色谱进行分析。
丙烯酸甲酯的转化率是40%摩尔，混合产物的组成是：
戊烯酸甲酯类 30%摩尔
丁烯类 30%摩尔
丙烯酸酯二聚体类 40%摩尔
实例Ⅵ
在300毫升磁力搅拌的Hastelloy C级高压釜中（“Hastelloy”是商标名称），装入50毫升丙烯酸甲酯和0.5毫摩尔醋酸钯、1毫摩尔三苯膦和3毫摩尔三氟甲磺酸作为催化体系。高压釜用乙烯冲洗后，在40巴压力下充入乙烯，密封并加热到70℃。反应1小时后，釜内成分用气/液相色谱进行分析。
丙烯酸甲酯的转化率是30%摩尔，混合产物的组成是：
戊烯酸甲酯类 43%摩尔
丁烯类 46%摩尔
丙烯酸酯二聚体类 1%摩尔
Claims (18)
1、一种以每分子2～12个碳原子的脂族单烯烃为原料制备二聚产品的方法，其特征是使脂族单烯烃在质子惰性的溶剂中与一种催化体系接触，此催化体系是由以下a）、b）、以及取舍任意的c）组成：
a）钯和/或钌化合物，
b）PKa值小于2的酸，氢卤酸除外，对每克原子钯和/或钌而言该酸的量至少为10当量，
c）含有至少一个元素周期表中的Va族原子作配位原子的配位体，其量满足下述条件：对于每当量酸而言Va族原子的克原子数小于2，同时对于每克原子钯和/或钌而言配位体的摩尔数至少是1。
2、按照权利要求1所述的方法，其特征是PKa值小于2的酸是HBF4。
3、按照权利要求1所述的方法，其特征是PKa值小于2的酸是磺酸。
4、按照权利要求3所述的方法，其特征是PKa值小于2的酸是三氟甲磺酸或对甲苯磺酸。
5、按照权利要求1所述的方法，其特征是，配位体是一种单齿配位体，它包括含三价N或P原子的化合物，N或P原子与至少一个芳烃基团相连。
6、按照权利要求5所述的方法，其特征是单齿配位体包括N，N-二甲基苯胺或其衍生物。
7、按照权利要求5所述的方法，其特征是单齿配位体包括三苯膦或其衍生物。
8、按照权利要求1所述的方法，其特征是所说配位体是单齿配位体，包括含有三价N原子的化合物，该N原子是杂芳环的构环原子。
9、按照权利要求8所述的方法，其特征是单齿配位体包括吡啶或其衍生物。
10、按照权利要求1所述的方法，其特征是配位体是螯合配位体，它包括含至少两个元素周期表中的Va族原子的化合物，这两个原子通过含有2～6个碳原子的链相连。
11、按照权利要求1所述的方法，其特征是螯合配位体包括分子中含有式
所示的一种基团的化合物。
12、按照权利要求1所述的方法，其特征是脂族单烯烃是乙烯。
13、按照权利要求1所述的方法，其特征是脂族单烯烃是丙烯。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB848432042A GB8432042D0 (en) | 1984-12-19 | 1984-12-19 | Preparation of dimerization products |
| GB8432042 | 1984-12-19 |
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| Publication Number | Publication Date |
|---|---|
| CN85109193A CN85109193A (zh) | 1986-06-10 |
| CN1003853B true CN1003853B (zh) | 1989-04-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85109193.8A Expired CN1003853B (zh) | 1984-12-19 | 1985-12-17 | 以烯烃为厚料制备二聚产物的方法 |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US4599476A (zh) |
| EP (1) | EP0188830B1 (zh) |
| JP (1) | JPS61145126A (zh) |
| CN (1) | CN1003853B (zh) |
| AR (1) | AR241500A1 (zh) |
| AT (1) | ATE40878T1 (zh) |
| AU (1) | AU584956B2 (zh) |
| BR (1) | BR8506330A (zh) |
| CA (1) | CA1255334A (zh) |
| DD (1) | DD240197A5 (zh) |
| DE (1) | DE3568326D1 (zh) |
| ES (1) | ES8706101A1 (zh) |
| FI (1) | FI81777C (zh) |
| GB (1) | GB8432042D0 (zh) |
| IN (1) | IN169685B (zh) |
| SU (1) | SU1482520A3 (zh) |
| ZA (1) | ZA859603B (zh) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN166314B (zh) * | 1985-08-29 | 1990-04-07 | Shell Int Research | |
| IN168306B (zh) * | 1986-03-05 | 1991-03-09 | Shell Int Research | |
| EP0235866A3 (en) * | 1986-03-05 | 1988-01-27 | Shell Internationale Researchmaatschappij B.V. | Catalyst compositions |
| IN168056B (zh) * | 1986-03-05 | 1991-01-26 | Shell Int Research | |
| CA1271877A (en) * | 1986-03-24 | 1990-07-17 | Johannes A.M. Van Broekhoven | Polymer preparation |
| US4810774A (en) * | 1986-06-24 | 1989-03-07 | Shell Oil Company | Catalytic copolymerization of CO/olefin with ketone additive. |
| US4804739A (en) * | 1986-07-01 | 1989-02-14 | Shell Oil Company | Process for preparing carbon monoxide polymer with quaternary phosphonium compound bidentate ligand |
| EP0254956A3 (de) * | 1986-07-29 | 1988-08-03 | Linde Aktiengesellschaft | Verfahren zur Oligomerisierung von Olefinen |
| US4820802A (en) * | 1987-02-03 | 1989-04-11 | Shell Oil Company | Improved process of preparing carbon monoxide/olefin copolymer with ortho substituted phosphine catalyst composition. |
| GB8704338D0 (en) * | 1987-02-24 | 1987-04-01 | Shell Int Research | Dimerization of olefins |
| GB8711524D0 (en) * | 1987-05-15 | 1987-06-17 | Shell Int Research | Carboxylic acids |
| GB8720379D0 (en) * | 1987-08-28 | 1987-10-07 | Shell Int Research | Preparation of butenes |
| US4857147A (en) * | 1988-03-18 | 1989-08-15 | Shell Oil Company | Method of composite part fabrication |
| DE69325757T2 (de) * | 1992-09-21 | 1999-12-30 | Montell Technology Co. B.V., Hoofddorp | Polymerisationsverfahren |
| US6331502B1 (en) * | 1998-12-09 | 2001-12-18 | Council Of Scientific And Industrial Research | Catalyst system containing a semilabile anionic ligand and a use of such catalyst system to produce α, β, -unsaturated carboxylic acids and their esters |
| US6228797B1 (en) | 1998-12-11 | 2001-05-08 | Phillips Petroleum Company | Oligomerization catalyst system and method of making and method of using such catalyst system in the oligomerization of olefins |
| EP1365004A1 (en) * | 2002-05-23 | 2003-11-26 | ATOFINA Research | Production of olefins |
| JP2007022974A (ja) * | 2005-07-19 | 2007-02-01 | Nissei Kagaku Kogyosho:Kk | ハロメチル芳香族炭化水素の製造方法 |
| US8383869B2 (en) | 2009-09-01 | 2013-02-26 | Shell Oil Company | Olefin oligomer composition |
| WO2014093447A1 (en) * | 2012-12-12 | 2014-06-19 | Uop Llc | Process for the generation of 2,5-dimethylhexene from isobutene |
| JP6178611B2 (ja) | 2013-05-08 | 2017-08-09 | Ｊｘｔｇエネルギー株式会社 | エステル化合物の製造方法 |
| CN107497489B (zh) * | 2016-06-14 | 2020-06-09 | 中国石油化工股份有限公司 | 乙烯合成丙酸甲酯用催化剂组合物及其合成方法 |
| CN113024336B (zh) * | 2021-03-19 | 2022-09-27 | 常州大学 | 催化异戊烯二聚制备异癸烯的方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE573530A (zh) * | 1957-12-03 | |||
| FR1517704A (fr) * | 1966-04-07 | 1968-03-22 | Inst Francais Du Petrole | Dimérisation d'oléfines |
| SU374930A1 (ru) * | 1971-07-07 | 1978-09-25 | Сибирское Отделение Ордена Трудового Красного Знамени Института Катализа Ан Ссср | Гомогенный катализатор димеризации этилена |
| US4487847A (en) * | 1983-07-25 | 1984-12-11 | Phillips Petroleum Company | Ethylene dimerization |
| DE3568037D1 (en) * | 1984-07-30 | 1989-03-09 | Shell Int Research | Process for the dimerization of olefins |
-
1984
- 1984-12-19 GB GB848432042A patent/GB8432042D0/en active Pending
-
1985
- 1985-10-03 US US06/783,706 patent/US4599476A/en not_active Expired - Lifetime
- 1985-11-21 AT AT85201928T patent/ATE40878T1/de not_active IP Right Cessation
- 1985-11-21 DE DE8585201928T patent/DE3568326D1/de not_active Expired
- 1985-11-21 EP EP85201928A patent/EP0188830B1/en not_active Expired
- 1985-11-27 CA CA000496285A patent/CA1255334A/en not_active Expired
- 1985-12-17 CN CN85109193.8A patent/CN1003853B/zh not_active Expired
- 1985-12-17 ZA ZA859603A patent/ZA859603B/xx unknown
- 1985-12-17 FI FI855027A patent/FI81777C/fi not_active IP Right Cessation
- 1985-12-17 ES ES550042A patent/ES8706101A1/es not_active Expired
- 1985-12-17 AR AR85302620A patent/AR241500A1/es active
- 1985-12-17 IN IN1070/DEL/85A patent/IN169685B/en unknown
- 1985-12-17 DD DD85284545A patent/DD240197A5/de not_active IP Right Cessation
- 1985-12-17 JP JP60284190A patent/JPS61145126A/ja active Pending
- 1985-12-17 SU SU853996104A patent/SU1482520A3/ru active
- 1985-12-17 AU AU51329/85A patent/AU584956B2/en not_active Ceased
- 1985-12-17 BR BR8506330A patent/BR8506330A/pt unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AR241500A1 (es) | 1992-07-31 |
| AU5132985A (en) | 1986-06-26 |
| IN169685B (zh) | 1991-12-07 |
| DE3568326D1 (en) | 1989-03-30 |
| DD240197A5 (de) | 1986-10-22 |
| CN85109193A (zh) | 1986-06-10 |
| ZA859603B (en) | 1986-08-27 |
| FI855027A0 (fi) | 1985-12-17 |
| ES550042A0 (es) | 1987-06-01 |
| EP0188830A1 (en) | 1986-07-30 |
| JPS61145126A (ja) | 1986-07-02 |
| EP0188830B1 (en) | 1989-02-22 |
| US4599476A (en) | 1986-07-08 |
| GB8432042D0 (en) | 1985-01-30 |
| SU1482520A3 (ru) | 1989-05-23 |
| FI81777B (fi) | 1990-08-31 |
| FI81777C (fi) | 1990-12-10 |
| ES8706101A1 (es) | 1987-06-01 |
| ATE40878T1 (de) | 1989-03-15 |
| CA1255334A (en) | 1989-06-06 |
| BR8506330A (pt) | 1988-03-01 |
| AU584956B2 (en) | 1989-06-08 |
| FI855027A (fi) | 1986-06-20 |
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