CN86104206A - 汽油组合物 - Google Patents
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Abstract
一种汽油组合物,该组合物包括两部分,占其大部分的为一种适用于火花点火发动机的汽油,小部分为一种琥珀酸衍生物的碱金属盐或碱土金属盐。该琥珀酸衍生物至少在其中一个x-碳原子上有一未取代的或取代的C20-200脂族烃基取代基,或在其中一个x-碳原子上有一未取代的或取代的C20-200脂族烃基取代基而该取代基又通过一C1-6烃部分与另一x-碳原子相连。
Description
本发明涉及一种汽油组合物,该组合物包括两部分,占其大部分的是一种适用于火花点火发动机的汽油,小部分为添加剂(至少一种)。
在火花点火发动机中,当汽油/空气比不足以点火时便会发生故障。因此,如果采用一些能改善贫油的汽油/空气混合物点火状况的汽油添加剂那就有利了。为了确定添加剂对火花塞的效能和对早期点火的影响,人们研究出一种测定火花点火发动机汽缸中火焰速度的试验技术。
人们发现很多加到汽油中的有机或无机的碱金属化合物和碱土金属化合物能促使汽缸中产生早期火焰并提高火焰速度。因此在汽油中使用这些金属化合物能改善贫油的汽油/空气混合物的燃烧状况并从而节约燃油,并且不影响发动机的功能和装有这种发动机的汽车的驾驶性能。
虽然这类金属化合物的上述效应尚未得到公认,但人们知道这类化合物是可以加到汽油中去的。例如,从英国专利说明书No785,196得知,烷基水杨酸或环烷酸等的一价金属盐(包括碱金属盐)能加入到包括汽油在内的燃油中以防止过滤器的腐蚀和堵塞。从英国专利说明书No818,323得知可将碱土金属化合物等加入到汽油之类的轻质烃混合物中。
人们发现,烷基水杨酸的碱金属或碱土金属盐确实能促使火花点火发动机中产生早期火焰,但也发现火花点火发动机的吸入系统被这些添加剂严重沾污堵塞。当汽车在城市的行驶条件(包括停停走走的行驶方式)下行驶时,沉积物尤其积聚在汽车的火花点火发动机的燃油吸入系统中。
现在已发现某些琥珀酸衍生物的碱金属盐或碱土金属盐一方面确实能提高汽缸中的火焰速度,另一方面又不会引起发动机沾污堵塞。因此本发明提供了一种汽油组合物,它包括两部分,占其大部分的是一种适用于火花点火发动机的汽油,小部分为一种琥珀酸衍生物的碱金属盐或碱土金属盐。该琥珀酸衍生物至少在其中一个α-碳原子上有一未取代的或取代的C20-200脂族烃基取代基,或在其中一个α-碳原子上有一未取代的或取代的C20-200脂族烃基取代基而该取代基又通过一个C1-6烃部分与另一α-碳原子相连形成环状结构。
本发明还提供一种操作火花点火内燃机的方法,包括将上述汽油组合物引入该内燃机。
琥珀酸衍生物盐可以是一代盐也可以是二代盐。由于汽油中不能有酸基,因此宜采用那些其留下的羧酸基已转变为酰胺基或酯基的一代盐。但最好还是采用二代盐。
合适的金属盐包括锂盐、钠盐、钾盐、铷盐、铯盐和钙盐。采用碱金属盐时,特别是采用钾盐或铯盐时对贫油混合物的点火影响更大些。考虑到钾盐来源丰富,价格低廉,因此最好采用这种碱金属盐。
琥珀酸衍生物上的取代基的种类是重要的,因为它在很大程度上决定了碱金属盐或碱土金属盐在汽油中的溶解度。脂族烃基宜由单体为2~6个碳原子的聚烯烃衍生。便于采用的聚烯烃有聚乙烯、聚丙烯、聚丁烯、聚戊烯、聚己烯或混合聚合物。最好是由聚异丁烯衍生的脂族烃基。
烃基包括一烷基部分和一链烯基部分。它可以有取代基。其中一个或多个氢原子可被另一原子(如囟素)所取代,或被一非脂族有机基(如取代的或未取代的苯基),羟基,醚基,酮基,醛基或酯基所取代。烃基上的一种非常合适的取代基是至少一种其它金属的琥珀酸盐部分,这样就产生了有两个或两个以上琥珀酸盐部分的烃基。
脂族烃基的链长对于碱金属盐在汽油中的溶解度来说也是重要的。该烃基有20~200个碳原子。当链长少于20个碳原子时,羧基和碱金属离子使分子具有很大的极性,以致不溶于汽油;而当链长大于200个碳原子时则会带来在芳烃型汽油中的溶解度问题。为了避免任何溶解度问题的发生,脂族烃基宜含35~150个碳原子。当用聚烯烃作取代基时,链长通常用数均分子量表示。用渗透压法等测定的取代基的数均分子量最好为400~2000。
琥珀酸衍生物可以有多个结合在一个或两个α-碳原子上的C20-200脂族烃基。最好在琥珀酸的其中一个α-碳原子上有一个C20-200脂族烃基。而在其另一个α-碳原子上最好不含取代基或只有相当短的烃基,如C1-6基。这种短烃基可与C20-200烃基键合形成环状结构。
取代的琥珀酸衍生物的制备方法在技术上是已知的。如用聚烯烃作取代基,制备取代的琥珀酸盐的方便方法是使聚烯烃(如聚异丁烯)与顺丁烯二酸或顺丁酸酐混合,并将氯气通过此混合物,产生盐酸和聚烯烃取代的琥珀酸,例如英国专利说明书No949,981所述。这种酸用金属氢氧化物或金属碳酸盐中和便容易地获得相应的金属盐。
例如,从荷兰专利申请No7412057中得知,烃取代的琥珀酸酐是通过将聚烯烃与顺丁烯二酸酐加热起反应而制得。
取代的琥珀酸的金属盐以很少量加入汽油组合物中时就产生所要求的效果,从经济观点来看,只要能明显地产生所要求的效果,其加入量应尽可能地少。本发明的汽油组合物中,琥珀酸衍生物的碱金属盐或碱土金属盐所含的碱金属或碱土金属量宜为汽油组合物总重的1~100ppmw。
除了上述取代的琥珀酸的金属盐外,汽油组合物还可含其它添加剂。例如可含用作抗爆添加剂的铅化合物,因此本发明的汽油组合物既包括含铅汽油又包括不含铅汽油。当上述琥珀酸金属盐用于不含铅汽油时,出乎意料地发现原来以为含在发动机排气阀阀座处产生的磨损不是大大减少了就是完全消除了。汽油组合物也可含抗氧化剂,如2,6-二叔丁基苯酚之类的苯酚或N,N′-二仲丁基-对苯二胺之类的苯二胺,也可含不是铅化合物的抗爆添加剂或如美国专利说明书No4,477,261和欧洲专利申请No151,621所述的多醚氨基添加剂。
除了琥珀酸衍生物之外,还有一种非常适用于本发明的汽油组合物的组合添加剂,该添加剂如美国专利说明书No4,357,148所述。这种组合添加剂包括一种油溶性脂族多胺和一种烃聚合物。这种组合添加剂降低了辛烷值要求量(ORI)。它之所以能降低ORI值是由于防止了在火花点火发动机的燃烧室内和邻近的表面生成沉积物和/或能从那些地方清除沉积物。虽然可采用各种各样多胺和各种各样聚合物,但最好采用一种由单体含2-6个碳原子的聚烯烃与有C20-200烷基或链烯基的多胺所组成的组合添加剂。因此本发明的汽油组合物最好含有这种组合物添加剂。聚烯烃最好采用含有20~175碳原子的聚异丁烯,尤其是含35~150碳原子的聚异丁烯。多胺最好采用N-聚异丁烯-N′,N′-二甲基-1,3-二氨基丙烷。本发明汽油组合物中聚烯烃的含量最好为100~1200ppmw,含烷基或链烯基的多胺的含量最好为5~200ppmw。该组合物中最好还含有一种非离子表面活性剂,如一种烷基酚或一种烷基烷氧化物,合适的表面活性剂的例子有C4-C18烷基酚和C2-6烷基乙氧基化物或C2-6烷基丙氧基化物,或其混合物。表面活性剂的含量最好为10~1000ppmw。
本发明的汽油组合物的主要部分为一种适用于火花点火花发动机的汽油(基本燃油)。这包括沸点基本上是在汽油的30~230℃沸点范围之内的烃类基本燃油。这些基本燃油可由饱和烃、烯烃和芳烃的混合物组成。它们可由直馏汽油、合成的芳烃混合物、热裂化或催化裂化的烃原料、加氢裂化的石油馏分或用催化剂重整的烃而得。基本燃油的辛烷值并不是关键性的,一般在65以上。汽油中相当大数量的烃可被醇、醚、酮或酯所取代。自然,基本燃油最好是大体上不含水的,因为水会妨碍平稳燃烧。
上述取代的琥珀酸的碱金属盐或碱土金属盐可以单独加入汽油,也可与其它添加剂混合后一起加入汽油。将这些盐加入汽油的较好方法是先制备这些盐的浓缩物,然后将计算出来的所需量的浓缩物加入汽油。
因此本发明又涉及一种适宜于加入汽油中的浓缩物,它包括一种与汽油相容的稀释剂和加在其中的一种琥珀酸衍生物的碱金属盐或碱土金属盐(加入量为稀释剂重量的20~50%),该琥珀酸衍生物至少在其中一个α-碳原子上有一未取代的或取代的C20-200脂族烃基取代基,或在其中一个α-碳原子上有一未取代的或取代的C20-200脂族烃基取代基而该取代基又通过一C1-6烃部分与另一α-碳原子相连形成环状结构。如果在汽油组合物中还需要加入上面述及的聚烯烃和多胺,那么浓缩物中最好再含稀释剂重量的20~80%的、单体碳原子数为2~6的聚烯烃和稀释剂重量的1~30%的、含C20-150烷基或链烯基的多胺。合适的与汽油相溶的稀释剂有烃(如庚烷),醇或醚(如甲醇,乙醇,丙醇,2-丁氧基乙醇或甲基叔丁基醚)。最好的稀释剂是一种芳烃溶剂,如甲苯,二甲苯,甲苯与二甲苯的混合物或者甲苯或二甲苯与一种醇的混合物。浓缩物还可含一种除混浊剂,特别是一种聚醚型乙氧基化烷基酚-甲醛树脂。如果采用除混浊剂,其在浓缩物中的用量为稀释剂重量的0.01~1%。本发明还提供一种琥珀酸衍生物的碱金属盐或碱土金属盐,该琥珀酸衍生物在其中一个α-碳原子上有一未取代的或取代的C20-200脂族烃基取代基,该取代基又通过一C1-6烃部分与另一α-碳原子相连形成环状结构。
这些化合物包括琥珀酸衍生物的金属盐,琥珀酸衍生物包括聚烯烃与顺丁烯二酸酐的狄尔斯-阿德耳加合物。
下面用一些实例对本发明加以说明。
实例1
为了证明贫油混合物的火焰速度得到提高,用一经过改装的1.3升Astra发动机进行试验,改装是指采用了一块有观察窗的板以观察到其中一个汽缸的燃烧室。试验时汽缸的压缩比为5.8。使发动机在近乎理想配比的条件下以2000rpm(每分钟转数)的转速运转。2小时后频繁地测定火焰从火花塞隙到达相距10毫克的激光束处所需的时间(T),并取(T)的平均值。这项技术在Combustion and Flame(燃烧与火焰),49,163-169(1983)中有介绍。试验是用不含钾添加剂的不含铅汽油和含50ppm、20ppm和8ppm钾的不含铅汽油进行的。加入的钾是采用聚异丁烯取代的琥珀酸的二代钾盐,其中聚异丁烯链的数均分子量为930(用渗透压法测定)。本实例及其以后的实例中所采用的聚异丁烯取代的琥珀酸衍生物的结构均为聚异丁烯与琥珀酸的狄尔斯-阿德耳加合物的结构。
试验结果如表Ⅰ所示。
表Ⅰ
钾量 平均(T)(毫秒) 改进率%
(ppmw)
- 1.59 -
50 1.37 14
20 1.45 9
8 1.46 8
实例2
下面的试验表明由于钾添加剂提高了火焰速度而对燃油消耗量产生的影响。将-2.0升Ford Pinto发动机运转一些时间使达到正常状态。当转速达1675rpm时开始加速,至转速达2800rpm时停止加速。如此重复10次。测定加速时的耗油量和平均加速时间。用三种不同馏程的汽油进行试验。不同馏程的汽油的特征用平均沸腾温度(即约50%蒸馏温度)表示,分别为101,109和120℃。所用的添加剂为聚异丁烯琥珀酸钾盐,其中聚异丁烯的数均分子量为1000,其用量为使钾含量达到50ppmw。
采用钾添加剂和不采用钾添加剂的试验结果如表Ⅱ所示。
表Ⅱ
燃油平均 燃油消耗量(毫升) 加速时间(秒)
沸腾温度 无添加剂 有添加剂 变化% 无添加剂 有添加剂 变化%
℃
101 29.3 26.4 -9.8 10.92 10.50 -3.8
109 29.2 28.0 -4.1 11.30 10.84 -4.1
120 30.1 28.3 -6.0 12.18 11.26 -7.5
实例3
用一2升四汽缸Ford Sierra发动机进行42小时循环试验,循环试验包括在载荷调整为2.5Nm、转速为900rpm的情况下运转2分钟,在载荷调整为52Nm转速为3000rpm的情况下运转2分钟。试验结束后将汽缸的进气阀卸下,根据一套由10张代表不同清洁度等级的照片组成的标准(该标准中最清洁的等级以10.0表示,最脏的等级以5.5表示,其间每隔0.5为一等级),目测评定进气阀的清洁度等级。
试验中采用含铅汽油。所用的添加剂为:添加剂Ⅰ:用渗透压法测定的数均分子量为650的聚异丁烯;添加剂Ⅱ:N-聚异丁烯-N′,N-二甲基-1,3-二氨基丙烷,其中聚异丁烯链的数均分子量为750;添加剂Ⅲ:与添加剂Ⅱ相似,但聚异丁烯链的数均分子量为1000;添加剂Ⅳ:烷基水杨酸钠,其中烷基直链含14~18个碳原子;添加剂Ⅴ:聚异丁烯琥珀酸钾,其中聚异丁烯链的数均分子量为930。
表Ⅲ列出四个阀的平均等级,同时列出平均改进率,平均改进率用下式表示:
(目测评定等级-不含添加剂的目测评定等级)/(10.0-不含添加剂的目测评定等级) ×100
(注意添加技Ⅳ和Ⅴ的用量是用碱金属的重量百万分率表示的)
表Ⅲ
添加剂用量(ppmw) 平均等级 平均改进率(%)
Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ
- - - - - 7.77 -
400 18 - - - 8.77 45
400 18 - 4 - 8.37 27
400 18 - 20 - 7.13 -29
400 - 16 - 4 9.02 56
400 18 - - 20 9.32 70
从表Ⅲ可明显地看出,加入添加剂Ⅰ和Ⅱ之后清洁度提高了,如再加入添加剂Ⅴ还能使清洁度进一步提高。但加入添加剂Ⅳ却反而使添加剂Ⅰ和Ⅱ的效果降低了。
实例4
为了评定含碱金属的添加剂的热稳定性,取1.00克所要试验的添加剂,加入一直径为5厘米的圆盘中,置于温度保持在280℃的加热板上(该温度与实例3试验的阀温度相比)。20分钟后将圆盘取下,冷却后再称重以确定剩余物的百分数。
然后进行清洗以模拟汽油在发动机进口的溶剂作用。用50%(重量)二甲苯与50%(重量)石油醚(沸程为80~120℃)所组成的混合物清洗圆盘。称量所剩余的沉积物以确定沉积物在原来的添加剂中所占的百分数。
结果如表Ⅳ所示。
表Ⅳ
添加剂 280℃下20分钟后 清洗后剩下的沉积物
的重量百分数
含C14-18烷链的 25.1%(重量) 16.5%(重量)
烷基水杨酸钾
含有数均分子量为 20.3%(重量) 0.45%(重量)
930聚异丁烯链的
聚异丁烯琥珀酸钾
从表中可明显地看出,琥珀酸盐添加剂在280℃下处理后留下的沉积物比烷基水杨酸盐添加剂留下的少。而且琥珀酸盐的沉积物易于用汽油洗涤。因此,显然,琥珀酸盐添加剂给进气阀带来的污染堵塞比烷基水杨酸盐添加剂带来的少。
实例5
为了证明本发明的汽油组合物对减少排气阀阀座磨损的影响,用一个1.6升Ford Sierra和一个1.1升Ford Fiesta发动机进行了10,000英里(16,000公里)试车。在一组试验中汽车用不含铅的汽油作燃油,在另一组试验中用含有30ppmw的例3的添加剂Ⅱ、400ppmw的例3的添加剂Ⅰ和129ppmw的例3的添加剂Ⅴ(相当于8ppmw钾)的不含铅汽油进行试验。
用不含铅的汽油行驶10,000英里后,阀座出现一些磨损,但用本发明的汽油组合物行驶10,000英里后阀座没有发现磨损。
实例6
环状结构的琥珀酸衍生物的钾盐的制备
在氮气氛中将1000pbw的平均数均分子量为1000的聚异丁烯通入反应器中。再加入167pbw顺丁烯二酸酐,搅拌混合物,同时加热至180℃左右。将氯气通入反应混合物达5小时,直至引入79pbw的氯为止。反应混合物在180℃下保持4小时。然后进行蒸馏,脱除过剩的未起反应的顺丁烯二酸酐。冷却后使琥珀酸衍生物溶于二甲苯并与30%氢氧化钾甲醇溶液混合,使钾与琥珀酸衍生物的摩尔比为2.04左右。此混合物在回流温度(约70℃)下保持3小时。然后,过滤除去可能存在于混合物中的固体,即获得所需要的盐。C13核磁共振测定结果证明了所获得的狄尔斯-阿德耳加合物具有环状结构。
Claims (15)
1、一种汽油组合物,该组合物包括两部分,占其大部分的是一种适用于火花点火发动机的汽油,小部分为一种琥珀酸衍生物的碱金属盐或碱土金属盐,该琥珀酸衍生物至少在其中一个α-碳原子上有一未取代的或取代的C20-200脂族烃基取代基,或在其中一个α-碳原子上有一未取代的或取代的C20-200脂族烃基取代基而该取代基又通过一C1-6烃部分与另一α-碳原子相连形成环状结构。
2、权利要求1所述的汽油组合物,其中应用琥珀酸衍生物的二代盐。
3、权利要求1或2所述的汽油组合物,其中的金属为一碱金属。
4、权利要求1~3中任一权利要求所述的汽油组合物,其中脂族烃基系由单体含2-6个碳原子的聚烯烃衍生。
5、权利要求4所述的汽油组合物,其中脂族烃基系由聚异丁烯衍生。
6、权利要求1~5中任一权利要求所述的汽油组合物,其中脂族烃基含35~150个碳原子。
7、权利要求1~6中任一权利要求所述的汽油组合物,其中琥珀酸衍生物的碱金属盐或碱土金属盐中所含的碱金属或碱土金属量为汽油组合物总量的1~100ppmw。
8、权利要求1~7中任一权利要求所述的汽油组合物,该组合物含少量单体有2~6个碳原子的聚烯烃和少量含C20-150烷基或链烯基的多胺。
9、权利要求8所述的汽油组合物,其中聚烯烃为聚异丁烯,含烷基的多胺为N-聚异丁烯-N′,N′-二甲基-1,3-二氨基丙烷。
10、权利要求8~9所述的汽油组合物,它含有100~1200ppmw的聚烯烃和5~200ppmw的含烷基或链烯基的多胺。
11、一种适用于加入到汽油中的浓缩物,其特征是该浓缩物包括一种与汽油相容的稀释和加在其中的一种琥珀酸衍生物的碱金属盐或碱土金属盐(加入量为稀释剂重量的20~50%),该琥珀酸衍生物至少在其中一个α-碳原子上有一未取代的或取代的C20-200脂族烃基取代基,或在其中一个α-碳原子上有一未取代的或取代的C20-200脂族烃基取代基而该取代基又通过一C1-6烃部分与另一α-碳原子相连。
12、权利要求11所述的浓缩物,其中还含稀释剂重量的20~80%的、单体碳原子数为2~6的聚烯烃和稀释剂重量的1~30%的、含C20-150烷基或链烯基的多胺。
13、权利要求1所述的汽油组合物,基本上如前所述,同时具体参照实例。
14、一种运转火花点火内燃机的方法,它包括将权利要求1~10或13中任一权利要求所述的汽油组合物用于上述发动机。
15、一种琥珀酸衍生物的碱金属盐或碱土金属盐,该琥珀酸衍生物在其中一个α-碳原子上有一未取代的或取代的C20-200脂族烃基取代基,该取代基又通过一C1-6烃部分与另一α-碳原子相连形成环状结构。
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US4448586A (en) * | 1981-11-02 | 1984-05-15 | Ethyl Corporation | Corrosion inhibitor compositions for alcohol-based fuels |
JPS58222190A (ja) * | 1982-06-17 | 1983-12-23 | Nippon Petrochem Co Ltd | 石油中間留出燃料油組成物 |
-
1985
- 1985-06-24 GB GB858515974A patent/GB8515974D0/en active Pending
-
1986
- 1986-06-06 CA CA000510961A patent/CA1258268A/en not_active Expired
- 1986-06-18 ZM ZM58/86A patent/ZM5886A1/xx unknown
- 1986-06-18 LU LU86478A patent/LU86478A1/fr unknown
- 1986-06-19 SE SE8602738A patent/SE464134B/sv not_active IP Right Cessation
- 1986-06-20 PH PH33917A patent/PH21546A/en unknown
- 1986-06-20 IN IN482/MAS/86A patent/IN167283B/en unknown
- 1986-06-20 US US06/876,556 patent/US4765800A/en not_active Expired - Fee Related
- 1986-06-20 OA OA58881A patent/OA08347A/xx unknown
- 1986-06-20 ZA ZA864611A patent/ZA864611B/xx unknown
- 1986-06-20 TR TR324/86A patent/TR22956A/xx unknown
- 1986-06-20 DK DK290786A patent/DK169472B1/da not_active IP Right Cessation
- 1986-06-20 IT IT20877/86A patent/IT1204894B/it active
- 1986-06-20 BR BR8602884A patent/BR8602884A/pt not_active IP Right Cessation
- 1986-06-20 JP JP61144707A patent/JPH0762141B2/ja not_active Expired - Lifetime
- 1986-06-20 ES ES556350A patent/ES8801360A1/es not_active Expired
- 1986-06-20 MA MA20942A patent/MA20715A1/fr unknown
- 1986-06-20 AT AT86201081T patent/ATE74375T1/de not_active IP Right Cessation
- 1986-06-20 DE DE3620651A patent/DE3620651C3/de not_active Expired - Fee Related
- 1986-06-20 PL PL1986260191A patent/PL146028B1/pl unknown
- 1986-06-20 ZW ZW120/86A patent/ZW12086A1/xx unknown
- 1986-06-20 IE IE165786A patent/IE59121B1/en not_active IP Right Cessation
- 1986-06-20 PT PT82805A patent/PT82805B/pt unknown
- 1986-06-20 GR GR861618A patent/GR861618B/el unknown
- 1986-06-20 KR KR1019860004930A patent/KR940006326B1/ko not_active IP Right Cessation
- 1986-06-20 CN CN86104206A patent/CN1013204B/zh not_active Expired
- 1986-06-20 SU SU864027742A patent/SU1568891A3/ru active
- 1986-06-20 DK DK290786D patent/DK290786A/da unknown
- 1986-06-20 AU AU59119/86A patent/AU585994B2/en not_active Ceased
- 1986-06-20 HU HU862605A patent/HU203385B/hu not_active IP Right Cessation
- 1986-06-20 DE DE8686201081T patent/DE3684640D1/de not_active Expired - Fee Related
- 1986-06-20 EP EP86201081A patent/EP0207560B1/en not_active Expired - Lifetime
- 1986-06-20 IL IL79182A patent/IL79182A0/xx not_active IP Right Cessation
- 1986-06-20 DD DD86291511A patent/DD254954A5/de not_active IP Right Cessation
- 1986-06-20 CH CH2504/86A patent/CH671771A5/fr not_active IP Right Cessation
- 1986-06-20 MX MX2884A patent/MX163895B/es unknown
- 1986-06-20 AT AT0168786A patent/AT395015B/de not_active IP Right Cessation
- 1986-06-20 NZ NZ216611A patent/NZ216611A/xx unknown
- 1986-06-20 GB GB08615156A patent/GB2177418B/en not_active Expired
- 1986-06-20 NL NL8601606A patent/NL8601606A/nl not_active Application Discontinuation
- 1986-06-20 BE BE0/216815A patent/BE904971A/fr not_active IP Right Cessation
- 1986-06-20 FR FR8608932A patent/FR2583763B1/fr not_active Expired
- 1986-06-20 NO NO862496A patent/NO167380C/no not_active IP Right Cessation
- 1986-06-23 FI FI862653A patent/FI84359C/fi not_active IP Right Cessation
- 1986-06-23 EG EG381/86A patent/EG17898A/xx active
- 1986-06-24 AR AR86304350A patent/AR244782A1/es active
- 1986-06-24 TN TNTNSN86094A patent/TNSN86094A1/fr unknown
-
1990
- 1990-03-20 SG SG221/90A patent/SG22190G/en unknown
- 1990-05-31 HK HK429/90A patent/HK42990A/xx not_active IP Right Cessation
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