CN1190428A - 润滑脂 - Google Patents

润滑脂 Download PDF

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Publication number
CN1190428A
CN1190428A CN96195424A CN96195424A CN1190428A CN 1190428 A CN1190428 A CN 1190428A CN 96195424 A CN96195424 A CN 96195424A CN 96195424 A CN96195424 A CN 96195424A CN 1190428 A CN1190428 A CN 1190428A
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CN
China
Prior art keywords
acid metal
zinc
lubricating grease
zinc naphthenate
molybdenumdisulphide
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Granted
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CN96195424A
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English (en)
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CN1053214C (zh
Inventor
R·A·菲勒施
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of CN1190428A publication Critical patent/CN1190428A/zh
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    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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Abstract

一种润滑组合物,该组合物包括矿源和/或合成源的基油与包括二硫化钼、环烷酸锌和一种或多种二硫代磷酸金属盐的减摩擦添加剂混合物以及选择性的一种或多种二硫代氨基甲酸金属盐的组合。包括这种组合物与一增稠剂组合的润滑脂特别适于润滑诸如等速球窝接合之类的等速接合,该增稠剂可为脲化合物、简单锂皂、锂配合物。

Description

润滑脂
本发明涉及润滑组合物,特别涉及含这种组合物的润滑脂,更特别涉及用于等速接合诸如球窝等速接合的润滑脂。
润滑的主要目的是分离相互之间作相对运动的固体表面,以最大程度减少摩擦和磨损。为此目的最常用的材料是油和脂。润滑剂的选择大多数决定于具体应用。
润滑脂用于有重压存在的地方,该处不希望有油从轴承淌流或是接触面的运动不连续因而难于在轴承中保持住隔离膜。因为设计的简化、密封要求的降低和减少维护,润滑脂在润滑电机滚珠轴承和滚柱轴承、家用电器、汽车轮轴承、机床或飞机附件中几乎是普遍给予首先考虑的。润滑脂也用于小齿轮传动装置的润滑和一些低速滑动应用上。
润滑脂主要由流体润滑剂(诸如油)和增稠剂组成。在实质上,配制润滑脂是采用与通常进行油润滑相同类型的油。锂、钙、钠、铝和钡的脂肪酸皂是最常使用的增稠剂。但是增稠剂可以是种种固体材料中的一种,包括粘土、诸如锂配合物的各种配合物以及脲化合物。
基油可以是矿物源或合成源的。矿物源基油可以是矿油,例如溶剂精制或加氢工艺生产的矿油。合成源基油一般可以是C10-50烃聚合物例如α-烯烃的液体聚合物的混合物。它们也可以是常规的酯类,例如多元醇的酯,基油也可以是这些油的混合物。优选的基油是Royal Dutch/Shell集团公司以“HVI”或“MVIN”牌号出售的矿物源基油,是聚α-烯烃,或是二者的混合物。合成的烃基油,例如Royal Dutch/Shell集团公司以“XHVI”(商标)出售的基油,也是可以使用的。
润滑脂可优选地含5-20%(重量)的增稠剂。
用锂皂增稠的润滑脂已经知道了许多年。典型的锂皂得自C10-24优选C15-C18饱和或不饱和脂肪酸或它们的衍生物。氢化蓖麻油是一特殊的衍生物,它是12-羟基硬脂酸的甘油酯。12-羟基硬脂酸是特别优选的脂肪酸。
用配合物增稠剂增稠的润滑脂是众所周知的。在增稠剂中除了脂肪酸的盐外,还掺入了配位剂,配位剂通常是低分子量至中分子量的酸或二元酸或其盐,诸如苯甲酸或硼酸或硼酸锂。
在润滑脂中用作增稠剂的脲化合物包括其分子结构中有脲基(-NHCONH-)的化合物。这些化合物包括单-、二或多脲化合物,决定于脲键的数目。
在润滑脂中可以掺入各种常规的润滑脂添加剂,其量为此应用领域中的常用量,以赋予润滑脂所要求的某种特性,诸如氧化稳定性、粘着性、耐特压性和腐蚀抑制性。适合的添加剂包括一种或多种耐特压/抗磨剂,例如诸如乙烷基或二芳基二硫代磷酸锌之类的锌盐、硼酸盐、取代的噻二唑、例如用二烷氧基胺与取代有机磷酸酯反应制取的聚合氮/磷化合物、胺磷酸盐、天然或合成源的硫化鲸蜡油、硫化猪脂、硫化酯、硫化脂肪酸脂和类似的硫化原料、例如式(OR)3P=0的有机磷酸酯(式中R为烷基、芳基或芳烷基)、以及硫逐磷酸三苯酯(triphenyl phosphorothionate);一种或多种高碱性含金属的洗涤剂,诸如烷基水杨酸钙或镁或烷基芳基磺酸钙或镁;一种或多种无灰分散添加剂,诸如多异丁烯基琥珀酸酐与胺或酯的反应产物;一种或多种抗氧化剂,诸如位阻酚或胺类,例如苯基α-萘胺;一种或多种防锈添加剂;一种或多种摩擦改良剂;一种或多种粘度指数改进剂;一种或多种倾点抑制添加剂;以及一种或多种粘合剂。也可以加入诸如石墨、极细的二硫化钼、滑石粉、金属粉的固体材料和诸如聚乙烯蜡之类的各种聚合物以赋予润滑脂以特别的性能。
为了降低摩擦水平,本技术领域的技术熟练者主要指望使用以有机钼为基础的配方,并且在这种润滑组合物的专利文献中有种种建议。
二硫化钼的使用得知于例如“Solid Lubricant Additives-Effect ofConcentration and Other Additives on Anti-Wear Performance〔固体润滑添加剂-浓度和其它添加剂对耐磨性能的影响〕”Bartz,Wear,17(1971)PP.421-432,当掺入润滑油后具有降低磨损的作用。在“Interelations between Molybdenum Disulfide and Oil SoubleAdditives〔二硫化钼与油溶性添加剂的相互关系〕”,Bartz,NLGISpokesman,Dec.1989)中讨论了二硫化钼与某些二烷基二硫代磷酸锌相组合的应用。然而这种组合显示,它比单独使用这两种添加剂时的磨损更大。很明显,这种相反的作用会使这样的添加剂组合对于降低摩擦水平失去吸引力。
环烷酸锌是衍生自环烷酸(通常是与氧化锌反应)的锌盐形式,环烷酸主要是在精炼各种镏分时得自石油的一元羧酸,可用下列通式定义:
                   R(CH2)nCOOH式中R代表一环烷基,它可被一个或多个低级(例如C1-C10)脂族基团、特别是烷基(例如甲基)取代或未取代。环状核通常是环戊烷,但也可以是环己烷。
环烷酸锌用于润滑组合物作为防锈添加剂以改进抗腐蚀性是已知的,例如美国专利说明书No.3,158,574中记载。在欧洲专利说明书No.508 115 A1的等速接合润滑脂组合物中也有记载,是作为适合的有机锌源用于避免起皮(一种疲劳现象,也称剥蚀或剥落)的。
但是它并不是润滑组合物中普遍使用的添加剂,因为其它的防锈添加剂和有机锌源通常是更多被采用的。
环烷酸锌是粘性物质,通常是用其稀释后的形式以便于处理。常规的环烷酸锌是在矿油中的分散体系,其元素锌的含量为8%(重量),但已知也有其它的浓度,诸如含锌为6%、10%和12%(重量)。环烷酸锌分散体系的粘度和物理性质不只是决定于环烷酸锌在分散体系中的浓度,也决定于稀释矿油的性质和粘度。
欧洲专利说明书No.191608A3涉及用于钻岩机钻头的润滑脂,其实施例公开了含基油、锂配合物皂、二硫化钼和其它添加剂的三种润滑脂的制备和性质,添加剂是二烷基二硫代磷酸锌和环烷酸锌(8%锌)。其中的两种润滑脂含7%(重量)二硫化钼、3%(重量)二硫代磷酸盐和1%(重量)环烷酸锌(8%锌),第三种含15%(重量)二硫化钼、3%(重量)二硫代磷酸盐和1%(重量)环烷酸锌(8%锌)。在每种情况中计算出的净环烷酸锌量为0.6%(重量)。测试三种润滑脂的载重、磨损和流动性,后一性质是特别需要的,因为润滑脂在使用时需用泵送至钻机的钻头。
现已发现,使用组合的二硫化钼和二硫代磷酸金属盐,再在此组合中加入环烷酸锌,事实上就可到意料不到的和增进的低摩擦性能。这种组合当掺入润滑脂并用于等速接合时可让接合在低温下操作,这又可使车辆驱动轴有恒定装配角的设计和/或可使接合尺寸缩小。
本发明提供了用二硫化钼、环烷酸锌和一种或多种二硫代磷酸金属盐、和选择性的一种或多种二硫代氨基甲酸金属盐作为减摩擦添加剂的组合用于包括矿源和/或合成源基油的润滑组合物中。
本发明也提供减摩擦添加剂的组合在包括矿源和/或合成源基油和一增稠剂的润滑脂中的应用。
这一类润滑脂优选地含二硫化钼的量为0.5-10%(重量),更优选1-4%(重量)。润滑脂优选地含(净)环烷酸锌的量为0.05-12%(重量),更优选0.3-2.4%(重量)。润滑脂进一步优选地含所说一种或多种二硫代磷酸金属盐的总量为0.15-10%(重量),更优选1-3%(重量),均基于润滑脂组合物总量计算。
本发明进一步提供了一种润滑组合物,该组合物包括一矿源和/或合成源基油与二硫化钼、环烷酸锌和一种或多种二硫代磷酸金属盐以及选择性的一种或多种二硫代氨基甲酸的金属盐的组合,其中二硫化钼的量与二硫代磷酸金属盐的量的比在1∶0.15-1∶1的范围,二硫代磷酸金属盐量与环烷酸锌量的比在1∶0.2-1∶3.0的范围,二硫化钼量与环烷酸锌量的比在1∶0.1-1∶1.2的范围,环烷酸锌量是以净环烷酸锌计算的。
本发明也延伸涉及包括增稠剂与本发明润滑组合物相组合的润滑脂。
二硫代磷酸金属盐和/或二硫代氨基甲酸金属盐中的金属是优先选自锌、钼、锡、镁、钨和铋。
优选的一种或多种二硫代磷酸金属盐选自二烷基-、二芳基-或烷基芳基二硫代磷酸锌,优选的一种或多种二硫代氨基甲酸金属盐选自二烷基-、二芳基-、或烷基芳基二硫代氨基甲酸锌,其中二硫代磷酸盐和/或二硫代氨基甲酸盐的任何烷基部分都是直链或有支链的,并优选含1-12个碳原子。
环烷酸锌可以其常规的稀释形式使用,是商业上广泛供应的。可述及的适合的分散体系有Manchem 8%Zn、Valirex 8%Zn和Adchem8%Zn(Manchem、Valirex和Addchem均为商品名)。减摩擦效果的提高得自环烷酸锌、二硫化钼和二硫代磷酸金属盐的组合,如果使用不同来源的环烷酸锌也未发现有什么明显变化。
上述润滑脂的增稠剂最好包括一种脲化合物、一种简单锂皂或一配合物锂皂。优选的脲化合物是多脲化合物,这样的增稠剂在润滑脂技术中是众所周知的。
本发明进一步提供润滑等速接合的方法,包括用本发明润滑脂将接合包覆。
本发明更进一步提供用本发明润滑脂包覆的等速接合。
现以下列各实施例对本发明进行说明:
实施例1-20
用下述步骤制备润滑脂。
向冷基油中的氢化蓖麻油或氢化蓖麻油脂肪酸中加入LiOH·H2O和水(1份LiOH·H2O:5份水)的浆液并在密封的高压釜中将混合物加热至150℃,从而制备锂皂润滑脂A、B和E。排放出蒸汽,继续加热至220℃,冷却反应物并搅匀产品。
锂配合物润滑脂D的制备是向油中的氢化蓖麻油脂肪酸、烷基水杨酸钙和辛酸钙中加入LiOH·H2O和硼酸于水中的50%浆液,然后将其加热至210℃,同时搅拌。在缓慢冷却至80℃后,加入配方中需要加入的其它添加剂。在进一步冷却至环境温度时将所得的润滑脂搅拌均匀。
脲润滑脂C的制备是将基油中的5%的4,4′-二苯甲烷二异氰酸酯加热至70℃,然后加入10.8%的硬脂胺。将混合物进一步加热至150℃,然后冷却至80℃,再加入配方中包括的其它添加剂。然后将配制的润滑脂在环境温度下搅匀。
所制备的润滑脂的组分叙述于表1中。
                               表1
                          实施例
    1     2     3   4   5   6   7   8   9   10   11   12
二硫化钼 %W     3     3     3   3   3   3   3   3   3   3   3   3
ZNDTP(1) %W     1     1     1   1   2   1   3   -   -   1   1   1
ZNDTP(2) %W     -     -     -   -   -   1   -   1.2   1.2   -   -   -
环烷酸锌%W      *****     K2.01.2     K0.50.3     K1.00.6   K4.02.4   K2.01.2   K2.01.2   K2.01.2   K2.01.2   K4.02.4   K2.01.2   K2.01.2   K2.01.2
ZNDTC    %W     -     -     -   -   -   -   -   -   -   -   -   -
抗氧化剂 %W类型     0.5X     0.5X     0.5X   0.5X   0.5X   0.5X   0.5X   0.5X   0.5X   -   0.5X   0.5Y
增稠剂     A     A     A   A   A   A   A   A   A   B   B   B
基油     P     P     P   P   P   P   P   P   P   Q   Q   Q
                                        表1(续)
                                             实施例
  13   14   15   16   17   18   *19   20   21   22   23
二硫化钼  %W   3   3   3   3   1   3   3   4   4   4   4
ZNDTP(1)  %W   1   1   1   1   1   1   1   1.3   1.3   1.3   1.3
ZNDTP(2)  %W   -   -   -   -   -   -   -   -   -   -   -
环烷酸锌%W       *****   K0.50.3   K2.01.2   K2.01.2   K2.01.2   K2.01.2   K2.01.2   K2.01.2   K2.71.6   K2.71.6   L1.62.7   M1.62.7
ZNDTC     %W   -   -   -   1   -   -   -   -   -   -   -
抗氧化剂  %W类型   0.5X   0.5X   0.5X   0.5X   0.5X   0.5X   -   0.5Y   0.6Z   0.6Z   0.6Z
增稠剂   C   C   D   D   E   E   D   C   F   F   F
基油   Q   Q   R   R   S   S   T   U   V   V   V
下列的百分数均以重量计:
A=9.15%氢化蓖麻油,1.12%LiOH·H2O,以6-7℃/分钟的速度冷却
B=9%氢化蓖麻油,1.3%LiOH·H2O,以1℃/分钟的速度冷却
C=5% 4,4′-二苯甲烷二异氰酸酯,10.8%硬脂胺
D=7.7%氢化蓖麻油脂肪酸,2.2%硼酸,2.6%LiOH·H2O,1.5%烷基水杨酸钙,1.5%辛酸钙。
E=7.8%氢化蓖麻油,1.1% LiOH·H2O
F=4.7%4,4′-二苯甲烷二异氰酸脂,3.6%辛按,1.4%十二烷胺
K=Manchem 8%Zn(60%环烷酸锌,40%矿油)
L=Valirex 8% Zn
M=Adchem 8% Zn
P=MVIN 170(80%) HVI 170(5%) HVI 105(15%)
Q=HVI 160B(75%) HVI 650(25%)
R=HVI 160B(100%)
S=HVI 160B (78%) MVIN(22%)
T=HVI 160B (67%) HVI650(33%)
U=HVI 160B (70%)聚α-烯烃(30%)
V=MVIN 170 (50%)聚α-烯烃(50%)
X=PAN(苯基α-萘胺)
Y=芳香胺
Z=0.4%芳胺,0.2%位阻酚
ZNDTP(1)=二(4-甲基-α-戊基)二硫代磷酸锌
ZNDTP(2)=二异丁基二硫代磷酸锌
ZNDTC=二戊基二硫代氨基甲酸锌
*   加1.5%硫逐磷酸三苯酯
**  所用工业产品实际量
*** 活性组分环烷酸锌计算量-即13.3%锌
实施例21
摩擦系数测定
所有的摩擦测定均使用Optimol Instruments公司的往复式SRV摩擦测试仪,测试结构是用一个10毫米的球置于一平的磨光表面上。以负荷(200-500牛顿)和温度(40-100℃)范围改变测试条件,整个试验使用的往复频率为50赫兹,行程为1.5毫米。在固定的测试条件下操作2小时后记录摩擦系数。
实施例1-20在SRV摩擦测试仪上以300牛顿测试负荷测定的摩擦系数示于表2。
                 表2
    实施例 摩擦系数(测试负荷300N,100℃)
    1      0.046
    2      0.054
    3      0.048
    4      0.073
    5      0.068
    6      0.073
    7      0.070
    8      0.049
    9      0.068
    10      0.050
    11      0.068
    12      0.048
    13      0.070
    14      0.053
    15      0.048
    16      0.075
    17      0.046*
    18      0.035*
    19      0.068
    20      0.055
    21      0.058
    22      0.053
    23      0.065
*400牛顿测试负荷和100℃
实施例22
为了证明含二硫化钼、二烷基二硫代磷酸锌和环烷酸锌三组分的润滑脂改进了的性能,将实施例1、14和15的润滑脂的摩擦系数和磨痕直径与不合环烷酸锌的类似润滑脂相比较。其结果示于表3、4和5中。
摩擦和磨损测定是用实施例21中所述的往复式SRV摩擦测试仪进行的。磨损是用光学测微尺在2小时试验结束时测定球上的磨痕直径进行估计的。
表3
润滑脂组合物 摩擦系数(100℃,300N测试负荷) 磨痕直径(mm)(100℃,300N测试负荷)
  对比例A     0.100     0.85
  实施例1     0.046     0.51
对比例A含有0.5% PAN,3%二硫化钼,1%二(4-甲基-2-戊基)二硫代磷酸锌和增稠剂A表4
润滑脂组合物 摩擦系数(100℃,300N测试负荷) 磨痕直径(mm)(100℃,300N测试负荷)
  对比例B     0.080     0.67
  实施例14     0.053     0.59
对比例B含有0.5% PAN,3%二硫化钼,1%二(4-甲基-2-戊基)二硫代磷酸锌和增稠剂C表5
润滑脂组合物 摩擦系数(100℃,300N测试负荷) 磨痕直径(mm)(100℃,300N测试负荷)
  对比例C     0.070     0.87
  实施例15     0.048     0.56
比较例C含有0.5% PAN,3%二硫化钼,1%二(4-甲基-2-戊基)二硫代磷酸锌和增稠剂D
可以看出,在所有的三种情况中,将环烷酸锌加入二硫化钼和二烷基二硫代磷酸锌的结果是摩擦系数和磨痕直径显著降低。
实施例23
为了证明与已知的润滑脂相比本发明润滑脂的改进性能,用实施例21的步骤测定了市售基于锂皂的含二硫化钼的润滑脂的摩擦系数。其结果示于表6。为对比的方便,表中也示出了本发明实施例1的摩擦系数。
表6
  润滑脂组合物 摩擦系数(100℃,300N测试负荷)
    实施例1     0.046
    对比例D     0.113
    对比例E     0.118
    对比例F     0.105
对比例D=Molykote VN 2461C对比例E=“Retinax”AM(商标)对比例F=“Glitine 245 MO”(商标)
可以十分清楚地看到,实施例1的摩擦系数大大低于市售各润滑脂的摩擦系数。
如上所指出,本发明的润滑脂配方可包括一种或多种能赋予配方某种所需要特性的添加剂,特别是可包括进一步的耐特压/抗磨剂,诸如硼酸盐、取代的噻二唑、聚合的氮/磷化合物、胺磷酸盐、硫化酯和硫逐磷酸三苯酯。

Claims (10)

1.在包括矿源和/或合成源基油的润滑组合物中二硫化钼、环烷酸锌和一种或多种二硫代磷酸金属盐以及选择性的一种或多种二硫代氨基甲酸金属盐作为减摩擦添加剂组合的应用。
2.权利要求1的应用,其中二硫代磷酸金属盐和/或二硫代氨基甲酸金属盐中的金属选自锌、钼、锡、镁、钨和铋。
3.权利要求2的应用,其中的一种或多种二硫代磷酸金属盐选自二烷基-、二芳基-或烷基芳基二硫代磷酸锌,其中的一种或多种二硫代氨基甲酸金属盐选自二烷基-、二芳基-或烷基芳基二硫代氨基甲酸锌,其中二硫代磷酸盐和/或二硫代氨基甲酸盐的任何烷基部分是直链或有支链的并含有1-12个碳原子。
4.在包括矿源和/或合成源基油和增稠剂的润滑脂中减摩擦添加剂组合的应用。
5.权利要求4的应用,其中二硫化钼的存在量为0.5-10%(重量),和/或环烷酸锌的存在量为0.05-12%(重量),以净环烷酸锌计算,或者一种或多种二硫代磷酸金属盐的存在总量为0.15-10%(重量),均以润滑脂总重量为基础计算。
6.权利要求4或5的应用,其中增稠剂包括脲化合物(优选多脲化合物)、简单锂皂或配合物锂皂。
7.一种润滑组合物,该组合物包括一矿源和/或合成源的基油与二硫化钼、环烷酸锌和一种或多种二硫代磷酸金属盐以及选择性的一种或多种二硫代氨基甲酸金属盐的组合,其中二硫化钼与二硫代磷酸金属盐量的比为1∶0.15-1∶1范围,二硫代磷酸金属盐与环烷酸锌量的比为1∶0.2-1∶3.0的范围,二硫化钼与环烷酸锌量的比为1∶0.1-1∶1.2范围,环烷酸锌是净环烷酸锌或以净环烷酸锌计算。
8.一种包括增稠剂与权利要求7的润滑组合物组合的润滑脂。
9.一种润滑等速接合的方法,包括将其用权利要求8的润滑脂包覆。
10.一种用权利要求8的润滑脂包覆的等速接合。
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CN1102172C (zh) * 1999-05-12 2003-02-26 陈学东 二硫化钼润滑油
CN101578357B (zh) * 2006-12-07 2013-04-24 国际壳牌研究有限公司 制备脲润滑脂的方法和设备
CN104312683A (zh) * 2014-10-29 2015-01-28 任新年 一种炉前辊道润滑脂及其制备方法
CN104312683B (zh) * 2014-10-29 2016-07-13 任新年 一种炉前辊道润滑脂及其制备方法
CN104974818A (zh) * 2015-07-16 2015-10-14 合肥学院 一种抑制碳烟污染导致的酯类润滑油润滑性能下降的方法
CN104974818B (zh) * 2015-07-16 2017-07-28 合肥学院 一种抑制碳烟污染导致的酯类润滑油润滑性能下降的方法
CN111100736A (zh) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 润滑脂组合物及其制备方法

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DE69625074T2 (de) 2003-07-17
MY115642A (en) 2003-08-30
PL324453A1 (en) 1998-05-25
AU705461B2 (en) 1999-05-20
DE69625074D1 (de) 2003-01-09
WO1997003152A1 (en) 1997-01-30
EP0850290A1 (en) 1998-07-01
MX9800311A (es) 1998-07-31
AR002775A1 (es) 1998-04-29
US5650380A (en) 1997-07-22
CA2226734A1 (en) 1997-01-30
BR9609510A (pt) 1999-05-25
EP0850290B1 (en) 2002-11-27
CN1053214C (zh) 2000-06-07
KR100411640B1 (ko) 2004-04-03
ZA965799B (en) 1997-01-27
AU6614896A (en) 1997-02-10
PL187046B1 (pl) 2004-05-31
CO4560490A1 (es) 1998-02-10
JPH11509249A (ja) 1999-08-17
RU2181371C2 (ru) 2002-04-20

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