CN1072683C - 用于乙烯聚合或共聚的催化剂固体组分和催化剂 - Google Patents
用于乙烯聚合或共聚的催化剂固体组分和催化剂 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
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Abstract
用于乙烯(共)聚的催化剂固体组分,它由二氧化硅载体和含钛,镁,氯和烷氧基的催化活性部分组成且由下列步骤获得:
(i)通过与二烷基镁或氯化烷基镁在液体脂肪烃溶剂中的溶液接触来活化二氧化硅载体;(ii)用在液体脂肪或芳族酯中的四氯化钛和烷基钛(二者等分子或几乎等分子)及氯化镁的溶液浸渍活化后的二氧化硅;和(iii)用成比例量的三氯烷基二铝处理步骤(ii)得到的固体。
Description
本发明涉及催化剂固体组分,其制备及其在乙烯聚合和乙烯与α-烯烃共聚方法中的应用。
众所周知,乙烯,或α-烯烃通常可利用低压法在齐格勒-纳塔催化剂上聚合。这些催化剂通常由选自元素周期表付族Ⅳ到Ⅵ的元素(过渡金属化合物)与选自元素周期表Ⅰ到Ⅲ族元素的有机金属化合物或氢化物混合组成。
这些催化剂在本领域是已知的,其中过渡金属化合物被固定到有机或无机性质的可能进行了物理和/或化学处理的固体载体上。固体载体的例子为氧化的二价金属化合物(如氧化物,氧化无机盐和羧酸盐),或二价金属的羟基氯化物或氯化物。
按照美国专利3,642,746,一种催化剂载体是用电子供体处理的二价金属卤化物,按照美国专利4,421,674的描述,一种催化剂载体是通过喷雾干燥氯化镁乙醇溶液获得的固体易流动产品。
特别是按照美国专利4,421,674,固体如二氧化硅的微球状颗粒可悬浮在氯化镁乙醇溶液中以获得球形催化剂载体,该载体由微球形固体和活性氯化镁组成。意大利专利申请21,711A/90(申请日1990年10月11日,以本申请人的名义)描述一种催化剂固体组分,它通过在脂肪酯溶剂中用氯化镁溶液浸渍二氧化硅,然后用氯化烷基铝处理浸渍过的二氧化硅而获得。
按照本发明已经发现,可通过下列步骤改善载在二氧化硅上的催化剂的活性,用氯化镁和等分子或几乎等分子的四氯化钛与四烷氧基钛的混合物在液体酯中的溶液浸渍活化后的二氧化硅,然后用关键量的三氯烷基二基铝处理浸渍后的二氧化硅。特别是,发现催化剂的这些组分在乙烯(共)聚合工艺中有惊人的高活性且能制备有优异流变性的易流动的丸状(共)聚合物。
因此,本发明涉及一个用于乙烯(共)聚合中的催化剂固体组分,该组分包括小颗粒的二氧化硅载体(50-90%(重量))和含有钛、镁、氯、铝和烷氧基的催化活性部分(50-10%(重量)),所述组分由下列步骤获得:
ⅰ)通过与二烷基镁或氯化烷基镁的液态脂肪烃溶液接触而活化二氧化硅载体,
ⅱ)用溶液浸渍这样活化后的二氧化硅,所述溶液是氯化镁和四氯化钛及四烷氧基钛的液态脂肪或芳族酯溶液,其中四氯化钛和四烷氧基钛等分子或几乎等分子,氯化镁和钛化合物之间的摩尔比为1到10;
ⅲ)通过与三氯烷基二铝接触而处理浸渍后的二氧化硅,其中三氯烷基二铝与钛化合物的摩尔比为0.9∶1到2.0∶1;和
(ⅳ)从步骤(ⅲ)的反应产品中回收催化剂固体组分。
宜作催化剂载体的二氧化硅优选微球形硅石(粒径20-100μm),其BET表面积为150-400m2/g,总孔率>80%及平均孔径为50-200。
按照本发明的方法,该二氧化硅在步骤(ⅰ)通过与二烷基镁或氯化烷基镁的液态脂肪烃溶液接触而活化。适于该目的二烷基镁是由通式MgR′R″定义的化合物,其中R′和R″可相同或不同,各自为直链或支链的含1到10个碳原子的烷基。二烷基镁的具体例子是:二乙基镁,乙基丁基镁,二己基镁,丁辛基镁和二辛基镁。相应的卤化物如氯化烷基镁也可使用。适于浸渍的烃溶剂可选自:戊烷,异戊烷,己烷,庚烷或辛烷。通常二烷基镁或卤化烷基镁的量为10-25份重量9以100份重量的二氧化硅为基准)。
步骤(ⅰ)通过二氧化硅与二烷基镁或卤化烷基镁的烃溶液在40到100℃接触0.5到2小时,最好在约60℃下接触1小时。在处理完毕后如用过滤或倾析回收活化的二氧化硅。
在步骤(ⅱ),将活化后的二氧化硅与氯化镁和四氢化钛与四烷氧基钛的液态脂肪或芳族酯溶液接触,其中四氯化钛与四烷氧基钛是等分子或几乎等分子。四烷氧基钛Ti(OR)4可选自:四正丙氧基钛,四正丁氧基钛,四异丙氧基钛和四异丁氧基钛。用于此目的的氯化镁是无水的或基本上无水的(水含量低于1%(重量)。宜作溶剂的酯可选自:氯代或未氯代的低级脂肪羧酸的甲基或乙基酯,或苯甲酸的甲基或乙基酯;如甲酸乙酯,乙酸甲酯,乙酸乙酯,乙酸丙酯,乙酸异丙酯,氯代乙酸乙酯,苯甲酸甲酯和苯甲酸乙酯。优选的溶剂是乙酸乙酯。
在该方法步骤(ⅱ)中,将氯化镁和四氯化钛与四烷氧基钛按上述比例溶在选出的酯中,温度应高于室温以利溶解,将活化后的二氧化硅用这样获得的溶液在50到100℃下浸渍0.5到2小时,最好在70℃下浸渍1小时,在处理结束后,通过减压蒸发溶剂回收浸渍后的二氧化硅。
按照本发明,浸渍后的二氧化硅用三氯烷基二铝在烃溶剂中的溶液处理,以获得高活性催化剂固体组分。溶剂可选自步骤(ⅰ)中所述的液体脂肪烃。更具体地说,将步骤(ⅱ)的浸渍后的二氧化硅与三氯烷基二铝,特别是三氯乙基二铝溶液在10到100℃下,依操作温度可接触10分钟到24小时。在优选的实施方案中,操作温度从20到90℃,时间从15分钟到2小时。特别好的是60-70℃下进行1小时。
在本发明中,从聚合作用中催化剂固体组份的活性来看,在步骤(ⅱ)中所用的三氯化二物的量是关键的。
图1示出了乙烯的产量(以kg聚乙烯/gTi表示)(横座标)与步骤(ⅲ)中三氯烷基化二铝/Ti(纵座标)在使用下列钛组分的可比方式下操作的关系:
--仅用四氯化钛;
--仅用四烷氧基钛;和
--四氯化钛与四烷氧基钛等分子的混合物。
从中可看出,当在步骤(ⅲ)中三氯化二物/Ti的摩尔比为0.9∶1到2.0∶1且较好从1.1∶1到1.7∶1,最好从1.2∶1到1.3∶1时,使用等分子钛化合物的混合物的协同效应。
当步骤(ⅳ)的处理完毕后,回收催化剂固体组分且通常用液体烃溶剂洗涤,直至氯化物从洗液中消失为止,然后尽可能干燥。
本发明的催化剂固体组分是颗粒状固体,它由小颗粒的二氧化硅载体(50-90%(重量))和含钛、镁、氯、铝和烷氧基的催化活性部分(50-10%(重量))组成。在优选的方法中,该催化剂组分含3-5%(重量)的钛,3-5%(重量)的镁,15-20%(重量)的氯,1-5%(重量)的铝和10-50%(重量)的三价钛,其余为四价钛。
本发明也涉及一个用于乙烯(共)聚合的催化剂,该催化剂由上述的催化剂固体组分和一个最好选自三烷基铝,氢化烷基铝及卤化(最好为氯化)烷基铝(其中烷基部分含1到5个碳原子)的助催化剂组成。其中,三烷基铝最好在烷基部分有2到4个碳原子如三乙基铝,三丁基铝和三异丁基铝。
本发明的催化剂,助催化剂中的铝与催化剂固体组分中的钛之间的原子比通常从1到500,且最好从50到200。
本发明也涉及一种使用上述催化剂的乙烯(共)聚合方法。可与乙烯共聚的α-烯烃优选丙烯和1-丁烯,且聚合可在惰性烯释剂悬浮液中或以气相方式在流化床或搅拌床中进行。通常的聚合条件是:温度从50到110℃,总压从5到40巴,氢气分压与乙烯分压比为0到10。在所有情况下可获得高产率稀烃聚合物,后者有优异的流变性特别是以不易碎的丸粒形式存在(粒径通常2000-125μm),没有细粒。
下列的实验例对本发明提供了较好的说明。在这些实施例中微球形二氧化硅用作催化剂中固体组分的载体,其平均直径为40μm且有下列特征:
--表现密度:0.21g/ml
--表面积(BEF):320m2/g
--孔体积:1.6ml/g
--平均孔直径:25
实施例1
(ⅰ)将20ml(17.5毫摩尔)的20%(重量)的Mg(C4H9)1.5(C8H17)0.5的正庚烷溶液和1.7g二氧化硅,在氮气氛下加到500ml的装有回流冷却器、机械搅抖器和温度计的烧瓶中。在搅拌下将混合物加热到60℃保持1小时并经过滤回收活化后二氧化硅。
(ⅱ)将220ml乙酸乙酯,4.96g(14.6毫摩尔)四正丁氧基钛,1.6ml(14.5毫摩尔)四氯化钛和2.79g(29.4毫摩尔)氯化镁在氮气氛下加到另一个500ml装有回流冷却器、机械搅拌器和温度计的烧瓶中、将混合物加热到回流温度(约75℃)保持1小时,直至氯化镁完全溶解。然后将(ⅰ)中所述的活化后的二氧化硅加到这样获得的溶液中。于70℃下接触1小时,然后通过蒸发溶剂将溶液干燥。
(ⅲ)将这样获得的浸渍后的二氧化硅悬浮在300ml正己烷中,然后在25℃下将8.81g(35.6毫摩尔)三氯烷基二铝加到悬浮液中。将温度升到66℃并让悬浮液反应1小时。
(ⅳ)在这一段时间结束后,从悬浮液中回收固体,用无水正己烷洗涤之直至洗液中氯化物消失,最后干燥。
获得28g微球形固体形才的催化剂固体组分,其含4.3%(重量)的钛(其中19%是三价钛),3.8%(重量)的镁,18.4%(重量)的氯和2.2%(重量)的铝。
实施例2
重复实施例1,区别在于在步骤(ⅲ)中使用1.40g三氯乙基二铝。
这样获得28.4g微球形的催化剂固体组分,其含4.25%(重量)的钛(其中12%是三价钛),3.9%(重量)的镁,17%(重量)的氯和1.8%(重量)的铝。
实施例3
重复实施例1,区别在于在步骤(ⅲ)中使用13.2g三氯乙基二铝。
这样获得28.0g微球形的催化剂固体组分,其含4.3%(重量)的钛(其中30%是三价钛),3.4%(重量)的镁,19.3%(重量)的氯和3.5%(重量)的铝。
实施例4(对比例)
重复实施例1,区别在于在步骤(ⅱ)中使用9.92g(29.1毫摩尔)四乙氧基钛且不加四氯化钛。
这样获得28.5g微球形的催化剂固体组分,其含3.7%(重量)的钛(其中43%是三价钛),3.8%(重量)的镁,12.4%(重量)的氯和1.7%(重量)的铝。
实施例5(对比例)
重复实施例1,区别在于在步骤(ⅱ)中使用9.92g(29.1毫摩尔)四丁氧基钛且不加四氯化钛而在步骤(ⅲ)中使用17.6g(71.2毫摩尔)三氯乙基二铝。
这样获得26.6g微球形催化剂固体组分,其含4.4%(重量)的钛(其中51%是三价钛),3.7%(重量)的镁,19.7%(重量)的氯和3.2%(重量)的铝。
实施例6(对比例)
重复实施例1,区别在于在步骤(ⅱ)中使用5.50g(29.0毫摩尔)四氯化钛而不加四丁氧基钛,在步骤(ⅲ)中使用3.03g(12.3毫摩尔)三氯乙基二铝。
这样获得28.2g微球形的催化剂固体组分,其含4.2%(重量)的钛(其中24%是三价钛),3.5%(重量)的镁,17%(重量)的氯和2.1%(重量)的铝。
实施例7(对比例)
重复实施例1,区别在于在步骤(ⅱ)中使用5.50g(29.0毫摩尔)四氯化钛而不加四丁氧基钛,在步骤(ⅲ)中省去三氯乙基二铝处理步骤。
获得23.3g微球形催化剂固体组分,其含4.4%(重量)的钛(100%是四价钛),3.8%(重量)的镁,13.7%(重量)的氯。
实施例8(对比例)
重复实施例1,区别在于在步骤(ⅱ)中使用5.50g(29.0毫摩尔)四氯化钛而不加四丁氧基钛且在步骤(ⅲ)中使用6.03g三氯乙基二铝。
获得24g微球形催化剂固体组分,其含4.1%(重量)的钛(其中35%是三价钛),3.6%(重量)的镁,19.4%(重量)的氯和2.4%(重量)的铝。
实施例9
将实例1-8所制得的催化剂固体组分用于乙烯聚合实验(实验1-8)中。更具体地说,聚合是在内含2升正己烷的6升容积的高压釜中进行。在氢气存在下,操作压力是15巴,氢气和乙烯分压比为0.47/1或0.64/1,温度为90℃,时间为1.5小时,使用三乙基铝作为助催化剂,三乙基铝与固体组分中的钛之间的摩尔比为50/1,实验9-11是用实施例1的固体组分,但聚合时间为3小时。
下列表1示出了每一个实验的氢气压力与乙烯压力比(RP);聚乙烯产量(以kg聚乙烯/g催化剂固体组分表示);相对钛的产量(R/Ti)(以kg聚乙烯/g催化剂固体组分中的钛表示);聚合物密度(D)(ASTMD1505,以g/ml表示);聚合物的熔融流动指数(MFI)(ASTMD1238;2.16kg和21.6kg),以克/10分钟表示;和以g/ml表示的聚合物表观密度(AD)(ASTMD1895)。
表2给出了颗径分布(μ),以在表1所示的聚合实验获得的聚乙烯重量百分数表示。
表1实验 RP 产量 R/Ti D MFI(2.16) MFI(21.6) AD1 0.47 7.9 184 0.9627 6.5 208 0.362 0.47 1.85 44 0.9593 1.15 34.4 0.353 0.64 3.0 70 0.9665 7.0 160 0.324 0.47 4.2 113 0.9630 2.7 78.3 0.345 0.64 2.8 65 0.9641 4.8 137 0.366 0.64 2.2 53 0.9618 3.5 104 0.337 0.47 0.75 17 0.9545 0.82 25.9 0.348 0.64 2.0 48 0.9635 4.0 116 0.339 0.96 7.0 163 0.9673 32.8 ND 0.3510 0.30 18.1 420 0.9638 4.1 129.7 0.3911 0.21 27.4 794 0.9588 0.68 25.2 0.37ND=没测量
表2实验 粒径(μm)号 >2000 2000<>1000 1000<>500 500<>250 250<>125 <1251 0.2 42.9 42.8 9.1 2.8 2.22 0.0 1.1 45.2 41.6 8.6 3.53 0.1 4.5 61.5 31.5 2.0 0.44 0.0 6.6 63.2 24.1 3.1 3.05 1.4 3.2 55.8 32.7 5.4 1.56 0.0 0.9 59.6 34.2 4.1 1.27 0.1 1.2 20.8 58.4 14.8 4.78 0.1 1.0 58.9 35.8 3.1 1.19 0.0 27.9 63.2 8.4 0.3 0.210 0.2 42.9 42.8 9.1 2.8 2.211 3.8 65.1 28.2 2.5 0.2 0.2
Claims (9)
1.用于乙烯聚合或共聚作用的催化剂固体组分,该组分由50-90%(重量)的小颗粒二氧化硅载体和50-10%(重量)的含有钛、镁、氯、铝和烷氧基的催化剂活性部分组成,所述的组分由下列步骤获得:
(ⅰ)通过与在液体脂肪烃溶剂中的二烷基镁或氯化烷基镁的溶液接触来活化二氧化硅载体,其中接触温度为40到100℃,接触时间为0.5到2小时;
(ⅱ)用在液体脂肪或芳族酯中的氯化镁和四氯化钛及四烷氧基钛的溶液浸渍这样活化后的二氧化硅,其中四氯化钛和四烷氧基钛等分子或几乎等分子,氯化镁与钛化合物之摩尔比为1到10,浸渍温度为50到100℃,浸渍时间为0.5到2小时;
(ⅲ)通过与三氯烷基二铝接触来处理浸渍后的二氧化硅,其中三氯烷基二铝与钛化合物的摩尔比为0.9∶1到2.0∶1,接触温度为10到100℃,接触时间为10分钟到2小时;
(ⅳ)从步骤(ⅲ)的反应产品中回收催化剂固体组分。
2.权利要求1的催化剂固体组分,其中步骤(ⅰ)中适宜用作催化剂载体的二氧化硅是粒径20-100μm的微球形二氧二硅,其BET表面积为150到400m2/g,总孔率>80%和平均孔径为50到200埃。
3.权利要求1的催化剂固体组分,其中步骤(ⅰ)中的二烷基镁选自可由通式MgR′R″定义的化合物,其中R′和R″相同或不同,各自为直链或支链的含1到10个碳原子的烷基。
4.权利要求1的催化剂固体组分,其中在步骤(ⅰ)中的液体脂肪烃溶剂选自戊烷、异戊烷、己烷、庚烷或辛烷。
5.权利要求1的催化剂固体组分,其中步骤(ⅱ)中四烷氧基钛选自四正丙氧基钛,四正丁氧基钛,四异丙氧基钛和四异丁氧基钛。
6.权利要求1的催化剂固体组分,其中步骤(ⅱ)中的酯选自氯代或未氯代的低级脂肪羧酸的甲酯或乙酯或苯甲酸的甲酯或乙酯。
7.权利要求1的催化剂固体组分,其中使用三氯烷基二铝烃溶液实施步骤(ⅲ)。
8.权利要求1的催化剂固体组分,该组分含3-5%重量的钛,3-5%重量的镁,15-20%重量的氯,1-5%重量的铝和10-50%三价钛,其余为四价钛。
9.用于乙烯聚合或共聚的催化剂,该催化剂由权利要求1到8任一项的催化剂固体组分和助催化剂-三烷基铝、氢化烷基铝或卤化烷基铝组成,其中助催化剂中的铝和催化剂固体组分中的钛的原子比为50到200。
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ES2342261T3 (es) * | 2002-06-19 | 2010-07-05 | Braskem S.A. | Componente catalitico solido para polimerizacion y copolimerizacion de etileno, y procedimiento para su obtencion. |
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CN102372799B (zh) * | 2010-08-19 | 2013-03-27 | 中国石油化工股份有限公司 | 一种用于烯烃聚合的催化剂组分及其制备方法 |
CN102372802B (zh) * | 2010-08-19 | 2013-03-27 | 中国石油化工股份有限公司 | 一种用于烯烃聚合的催化剂组分及其制备方法 |
JP5981441B2 (ja) * | 2010-11-26 | 2016-08-31 | サウディ ベーシック インダストリーズ コーポレイション | エチレンの重合および共重合のための固体触媒成分を製造するプロセス |
BR102016009378B1 (pt) * | 2016-04-27 | 2021-04-20 | Braskem S.A. | Catalisador heterogêneo de múltiplos sítios, e, processos de preparação do catalisador heterogêneo de múltiplos sítios e de obtenção de poliolefin |
KR20220008669A (ko) * | 2020-07-14 | 2022-01-21 | 주식회사 엘지화학 | 프로필렌의 암모산화용 촉매, 이의 제조 방법, 이를 이용한 프로필렌의 암모산화 방법 |
WO2024132716A1 (en) | 2022-12-20 | 2024-06-27 | Ineos Europe Ag | Process |
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CA920299A (en) * | 1968-08-01 | 1973-01-30 | Mitsui Petrochemical Industries | Process for the polymerization and/or copolymerization of olefins with use of ziegler-type catalytsts supported on carrier |
IT1136627B (it) * | 1981-05-21 | 1986-09-03 | Euteco Impianti Spa | Catalizzatore supportato per la polimerizzazione di etilene |
US4532312A (en) * | 1982-12-15 | 1985-07-30 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
NL8700322A (nl) * | 1987-02-11 | 1988-09-01 | Stamicarbon | Katalysatorsysteem voor (co)polymerisatie van etheen in solutie. |
US5126302A (en) * | 1990-04-30 | 1992-06-30 | Quantum Chemical Corporation | Olefin polymerization catalyst and methods |
IT1248981B (it) * | 1990-06-22 | 1995-02-11 | Enichem Anic Spa | Procedimento per la preparazione di un componente solido di catalizzatore per la (co)polimerizzazione dell'etilene |
IT1252041B (it) * | 1990-10-11 | 1995-05-29 | Enimont Anic Srl | Componente solido di catalizzatore per la (co)polimerizzazione dell'etilene |
-
1991
- 1991-07-12 IT ITMI911938A patent/IT1251465B/it active IP Right Grant
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1992
- 1992-07-07 EP EP92202060A patent/EP0522651B1/en not_active Expired - Lifetime
- 1992-07-07 ES ES92202060T patent/ES2066551T3/es not_active Expired - Lifetime
- 1992-07-07 DE DE69201023T patent/DE69201023T2/de not_active Expired - Fee Related
- 1992-07-07 AU AU19482/92A patent/AU651470B2/en not_active Ceased
- 1992-07-07 AT AT92202060T patent/ATE116340T1/de not_active IP Right Cessation
- 1992-07-07 DK DK92202060.7T patent/DK0522651T3/da active
- 1992-07-08 FI FI923154A patent/FI104083B1/fi active
- 1992-07-08 DZ DZ920087A patent/DZ1597A1/fr active
- 1992-07-09 ZA ZA925140A patent/ZA925140B/xx unknown
- 1992-07-09 NO NO922712A patent/NO179331C/no not_active IP Right Cessation
- 1992-07-10 US US07/911,419 patent/US5298474A/en not_active Expired - Lifetime
- 1992-07-10 TN TNTNSN92058A patent/TNSN92058A1/fr unknown
- 1992-07-10 RU SU925052225A patent/RU2073689C1/ru not_active IP Right Cessation
- 1992-07-10 MX MX9204062A patent/MX9204062A/es not_active IP Right Cessation
- 1992-07-10 CA CA002073644A patent/CA2073644A1/en not_active Abandoned
- 1992-07-11 CN CN92105683A patent/CN1072683C/zh not_active Expired - Fee Related
- 1992-07-11 KR KR1019920012377A patent/KR950001278B1/ko not_active IP Right Cessation
- 1992-07-11 EG EG38392A patent/EG20437A/xx active
- 1992-07-13 BR BR929202665A patent/BR9202665A/pt not_active IP Right Cessation
- 1992-07-13 JP JP4185407A patent/JPH05214024A/ja active Pending
- 1992-10-26 SA SA92130197A patent/SA92130197B1/ar unknown
Also Published As
Publication number | Publication date |
---|---|
NO179331C (no) | 1996-09-18 |
BR9202665A (pt) | 1993-03-23 |
ITMI911938A1 (it) | 1993-01-12 |
KR930002384A (ko) | 1993-02-23 |
TNSN92058A1 (fr) | 1993-06-08 |
ITMI911938A0 (it) | 1991-07-12 |
EP0522651B1 (en) | 1994-12-28 |
DE69201023T2 (de) | 1995-06-22 |
ZA925140B (en) | 1993-04-28 |
MX9204062A (es) | 1993-07-01 |
EP0522651A3 (en) | 1993-03-03 |
ATE116340T1 (de) | 1995-01-15 |
AU651470B2 (en) | 1994-07-21 |
NO179331B (no) | 1996-06-10 |
JPH05214024A (ja) | 1993-08-24 |
FI923154A (fi) | 1993-01-13 |
AU1948292A (en) | 1993-01-14 |
FI104083B (fi) | 1999-11-15 |
DZ1597A1 (fr) | 2002-02-17 |
EP0522651A2 (en) | 1993-01-13 |
KR950001278B1 (ko) | 1995-02-15 |
SA92130197B1 (ar) | 2004-06-23 |
CA2073644A1 (en) | 1993-01-13 |
CN1069031A (zh) | 1993-02-17 |
FI923154A0 (fi) | 1992-07-08 |
RU2073689C1 (ru) | 1997-02-20 |
DK0522651T3 (da) | 1995-04-24 |
NO922712L (no) | 1993-01-13 |
FI104083B1 (fi) | 1999-11-15 |
NO922712D0 (no) | 1992-07-09 |
DE69201023D1 (de) | 1995-02-09 |
US5298474A (en) | 1994-03-29 |
ES2066551T3 (es) | 1995-03-01 |
EG20437A (en) | 1999-04-29 |
IT1251465B (it) | 1995-05-15 |
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