CN1283670C - 降低过早终止的自由基聚合方法和进行此方法的设备 - Google Patents
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Abstract
本发明揭示了通过自由基聚合机理进行的聚合方法、由此形成的产物以及进行此方法的设备。通过基本上恒定的射线来照射所述将要通过自由基聚合机理进行聚合的组合物,上述射线基本上没有脉冲。使用基本上恒定的没有脉冲的射线来降低聚合反应的过早终止。所述基本上恒定的射线可以由灯提供,该灯由恒定电流、直流电源提供能量。
Description
技术领域
本发明涉及一种聚合方法,其中所述聚合反应通过自由基聚合机理产生;并涉及用于这种方法的设备以及通过这一方法制得的聚合产物,特别是降低了聚合反应的过早终止。本发明适用于物质的聚合反应,其中,所述聚合机理是自由基聚合,对要聚合的物质没有限制,例如,它适于具有C=C双键的物质的聚合反应,在此,所述聚合反应按照自由基聚合反应机理通过例如用光(如紫外光)辐照来引发。
在常规光引发的自由基聚合过程中,使用例如微波驱动、无电极紫外灯,利用整流交流电或者脉冲电源来产生微波。这些微波产生来自无电极紫外灯的脉冲紫外光,作为用于光引发的光。即所述整流交流电或者脉冲电源产生来自灯的脉冲光线输出,用于光引发所述聚合反应。但是,这种常规方法形成不良的分子量低的产物,并且其产率也低。
因此,要求按照自由基聚合反应机理以高产率制得分子量高的聚合反应产物,并且形成的产物(聚合物)的分子量分布较窄,同时以相对较高的速度形成。即要求改进按照自由基聚合反应机理通过辐照(例如,光如紫外光)引发所形成的产物,提高其产率(产率高)和所形成产物的分子量(分子量增大),并降低所形成产物的分布(范围)。
发明揭示
本发明人已经发现所述自由基聚合反应过早终止会导致产率低,并且所形成产物的分子量低,其原因是提供自由基聚合反应光引发的脉冲光输出。以这一发现为基础,本发明在聚合过程中始终提供恒定辐照(例如,光),例如恒定的光强,由此来引发聚合反应(提供光引发),并维持所述聚合反应。
此外在本发明中,通过使用恒定的输出(暂时)、直流电源来获得恒定的光输出。例如(不限于此),可以使用恒定输出(例如,恒定电流)的直流电源来产生微波,用于驱动由微波提供能量的灯,由此始终产生恒定(均匀)、连续的光输出,用于光引发,从而降低过早终止。在本发明中,例如可以使用所述恒定(均匀)电流的直流电源,始终提供恒定电流,使磁控管产生驱动所述灯的微波(例如),微波通过灯(无电极灯)产生恒定的光输出,由此进行聚合反应。通过提供恒定的光输出(恒定强度,没有波动),降低了过早的终止,并且至少降低由于过早终止引起的不利影响。
在另一个例子中,可以使用恒定输出(例如,恒定电流)的直流电源为弧光灯提供能量,由此始终产生恒定(均匀)、连续的光输出(恒定强度、没有波动),用于光引发,由此降低过早的终止。
因此,可以形成改进的聚合产物,所述产物性能提高,并且其分子量更高,分子量分布(范围)降低,并且可以以更高的速度制备所述聚合产物(例如,当形成片材时,可以以更高的线速度形成所述固化产物)。
附图简要说明
图1(a)图示了常规技术中,使用微波驱动的紫外灯提供引发聚合反应的能量,以及使用整流交流电或者脉冲直流电源产生微波,来固化(聚合)聚合物的***;图1(b)显示了用于产生微波驱动紫外灯所需微波的电源的电流输出与时间的函数关系;图1(c)显示了所述灯的紫外光输出与时间的函数关系。
图2(a)图示了本发明说明性实施方式中,使用微波驱动的紫外灯提供引发聚合反应的能量,以及使用直流电源产生微波,来固化(聚合)聚合物的***;图2(b)显示了用于产生微波驱动紫外灯所需微波的电源的电流输出时间的函数关系;图2(c)显示了所述灯的紫外光输出与时间的函数关系。
图3是直流电源的电路图,在本发明说明性实施方式中,可用于产生微波驱动的灯所需的微波,所述灯产生恒定的光输出,由此引发聚合反应。
本发明最佳实施方式
虽然将结合具体和优选的实施方式来说明本发明,但是应理解,这决不是将本发明限制在那些实施方式中。相反,这是用于覆盖所有的替换方式、改动以及等价方式,它们包括在所附的权利要求书所述的本发明精神和范围内。
在整个说明书中,当认为物质、方法和设备包括或包含具体组分或结构或具体工艺步骤时,本发明人认为本发明的物质、方法和设备也基本上由所述的组分或结构或所述的工艺步骤组成。
在本发明的说明部分中,本发明通过自由基聚合方法、设备来进行所述方法并改进所形成的产物。在本发明的说明性方法中,在使组合物进行聚合反应的时间内,用基本上恒定的射线(基本上没有脉冲)照射所述组合物,由此引发并维持所述自由基聚合反应,所述组合物包含通过自由基聚合反应进行聚合的物质(例如,单体或者低聚物)。这种工艺产生改进的产物,它具有高性能,并且可以以更高的速度(更高的生产量)制得所述产物。而且,用于产生基本上恒定的射线的设备包括产生基本上恒定的射线且基本上没有脉冲的辐照源(例如,但不限于光源,如紫外光),以及例如直流电源,它输出恒定电流,用于产生基本上恒定且基本上没有脉冲的射线。举例说明,所述辐照源可以是微波驱动的紫外灯,它具有将恒定电流施加到微波发生器而产生用于驱动所述紫外灯的微波的直流电源。通过使用基本上恒定且没有脉冲的射线,至少可以降低自由基聚合反应的过早终止。
过早的终止描述了在通过自由基聚合机理形成聚合物的过程中通过来自光引发剂光解作用的小的初级自由基来终止增长的高分子自由基的情况。这在脉冲辐照下产生,此时,所述脉冲频率比达到“稳态”(稳态是指自由基形成速度等于终止的速度(自由基与自由基之间偶合的速度)的状态)所需的时间还短。增长的高分子自由基(增长态),其终止速度较低,其原因是聚合介质的粘度以及高分子自由基尺寸增大得很快所导致的迁移性限制。在光线第一脉冲之后,大多数的初级自由基将促进增长,并伴随着自由基聚合反应,加入到所述双键中(例如,丙烯酸酯双键,在此聚合的单体物质是丙烯酸酯)。在更短脉冲情况下,所残留的未光解的光引发剂开始产生新的初级小自由基,相比增长的高分子自由基来说,其迁移性高得多。因此大体上,这些由随后光引发剂光解(由脉冲紫外光引发)刚刚产生的初级小自由基将促进通过和增长的高分子自由基偶合的双自由基终止,由此和引发新链增长相竞争,从而导致聚合反应过早终止。
本发明中,始终通过避免脉冲光,并使用恒定的没有脉冲的光输出,来降低优先终止聚合反应的光引发剂的光解作用。此外,通过使用恒定电流DC电源为提供光照的灯提供能量(例如,产生用于驱动所述灯的微波,在此,该灯是微波驱动的无电极灯;或者为弧光灯提供能量),可以有效地获得恒定光强(例如,恒定紫外光输出),降低上述过早的终止,并至少降低不良的影响。
虽然本发明结合使用由紫外光活化的光引发剂的自由基聚合反应来进行说明,但是本发明并不限于此。即,根据需要用于活化所述自由基聚合反应(例如,但不限于活化用于引发自由基聚合反应的引发剂)的能量(例如,光能),本发明包括使用恒定光输出(基本上没有脉冲或波动)、使用其它类型的光(例如,可见光、红外光等)、使用其它类型的辐射。
图1(a)显示了用于组合物自由基聚合反应的常规技术,所述组合物形成工件的表面7(例如,基材上的涂层)。这种常规技术使用整流交流电或者脉冲直流电源1提供产生微波驱动紫外灯3所需的微波,产生紫外光11来活化形成工件表面7的组合物中的光引发剂。图2(a)描述了本发明中,使用DC电源5来驱动微波驱动紫外灯13,产生紫外光15,来活化形成工件表面7的组合物中的光引发剂,由此引发自由基聚合反应。图1(b)和2(b)各自显示了电源1和5产生的电流与时间的函数关系,在图1(c)和2(c)中显示了常规技术和本发明各自产生的,施加到工件表面7上的光输出11,15与时间的函数。标号9所示箭头指明了工件表面7经过灯3、13的移动方向。
如图1(b)所示,在常规技术中,电源1产生脉冲电流,并从图1(c)可见,由灯3产生的紫外光11是脉冲的。如上所述,这种脉冲的光会导致自由基聚合反应过早终止。
从图2(b)和2(c)可见,本发明中由电源5提供恒定电流,并由紫外灯13始终产生恒定光输出15,施加到工件表面上;如上所述,这降低了过早终止,至少降低了不利的影响,并且其产率提高,产物分子量更高。
在图3中显示了可用于本发明各方面的DC电源。这种DC电源是可用于本发明的一种说明性的电源,并不是用于限制本发明的。这种电源将始终具有恒定电流的高电压输出施加到例如磁控管上,在此,所述灯是微波驱动的无电极灯。所述磁控管产生用于驱动所述灯的微波,该灯始终产生恒定的光输出。所述DC电源也可以用来为弧光灯提供能量。
更具体地是,图3显示了一种三相AC线电压,在流经线性滤波器和触头之后通过三相电桥20进行整流。所述三相电桥20可以将DC电压施加到H电桥30上。在所述三相电桥20和H电桥30之间可以设置预充电继电器(和相关电阻器)25和电容器27。所述预充电继电器(和相关电阻器)25可以防止由为电容器27充电的冲击电流所引起的损害。电桥30可以包括四个设置成H状的绝缘的栅双极晶体管(IGBT)。在运行中,所述H电桥30的对角晶体管在一个半开关循环中同时导电,然后,H电桥30的其它对角晶体管在剩下的一个半开关循环中导电。这种运行可以将交流电施加到高压变压器和整流(HVTR)组件40中。所述晶体管在高频率(如约20kHz)下运行,由此可降低所述高压变压器的大小和重量。当使用更高的运行频率时,也可以减少用于使施加到磁控管上的电流平整的滤波部件。
移相器/脉冲宽度调制器50可以用于控制IGBT晶体管。移相器/脉冲宽度调制器50的输入可以是磁控管电流和电压,它们在HVTR组件40上测量。移相器/脉冲宽度调制器50可以调节晶体管的控制信号,使它调节HVTR组件40输出时的电流或电压。这种方法可以称为反馈控制。
HVTR组件40可以包括多输出的变压器。各输出可以用单独的整流器和滤波器电器进行整流。所述滤波器电路可以包括储能元件(如感应器和电容器),消除所述高频脉冲,为磁控管提供基本上为DC的电流。所述各整流器输出可以串联产生磁控管所需的高电压。
若需要的话,引擎控制电路60可以监视和控制整个电源。所述引擎控制电路包括程序控制微处理器,它具有必要的输入/输出电路,用于监控内部电压和电流。
本发明不限于任何具体类型单体(例如,丙烯酸酯类)的聚合反应,并且可以用于通过自由基聚合反应机理进行的聚合反应(即,自由基体系)。例如,不论分子中的其它结构,任意类型的可自由基聚合的C=C双键或多或少的容易过早终止,并且本发明使用施加到要聚合的组合物上的恒定光输出来降低这种过早的终止。
以下将讨论本发明适用的各种物质。但是应强调的是,以下仅仅是例如容易过早终止的市售反应体系的实施例,这是因为它们进行自由基聚合反应,且本发明并不限于这些反应体系。
本发明适用的第一类物质是那些通过自由基聚合反应,即链增长型的均聚反应形成均聚物的物质。在这种情况下,仅使用一种类型的双键,但是所述双键可以化学连接到任何主链上,并且,可以将任意数量的C=C双键连接到任意主链上。典型的例子是丙烯酸酯类和甲基丙烯酸酯类。在本发明中,苯乙烯和苯乙烯衍生物、N-乙烯基酰胺和乙烯酯也是C=C结构的典型例子,它们可以通过自由基聚合反应进行聚合,并得益于始终提供恒定光输出的恒定直流电源的使用。
本发明适用的第二类物质是那些由链增长型共聚反应形成共聚物的物质。它可以如均聚反应中所述的,使用不同的单体或低聚物。可以以任何比例以及上述任意类型的C=C双键使用任意数量的不同单体或低聚物的混合物,这取决于各单体/低聚物的反应活性比例,所形成的共聚物具有很不同的性质。典型的例子是丙烯酸酯/甲基丙烯酸酯、丙烯酸酯/不饱和聚酯以及丙烯酸酯/N-乙烯基酰胺。
本发明适用的第三类物质是通过交替共聚反应形成共聚物的物质。在这种情况下,任意数量和任意比例的任意受体型(A)单体或其混合物可以和任意数量和任意比例的任意给体型(D)单体或其混合物混合(接近1∶1的摩尔比),进行交替共聚反应。对于这种情况,以上并未提及额外量包含C=C键的具有取代基的潜在和市售单体和低聚物。这些包括A和D型单体,它们并不能进行上述均聚反应。在美国专利No.5,446,073(Jonsson等)中,说明了各种受体型和给体型单体,其内容全部参考引用于此。典型的实施例是延胡索酸酯/乙烯醚、马来酸酯/乙烯醚以及马来酰亚胺/乙烯醚。
如上所述,按照自由基聚合反应进行的许多不同类型的聚合反应都将受益于本发明。以上所述类型并不是仅能使用的物质,可以使用其它类型的物质,只要聚合反应按照自由基聚合反应进行。
本发明适用于任何按照自由基聚合反应进行的聚合反应技术。本发明聚合反应中可以聚合单体和低聚物。本发明中可以聚合的单体包括至少包含一个C=C的分子,它可以通过自由基聚合反应进行聚合。这种单体可以以任意比例包含各种类型的任意数量的C=C键,它能进行自由基聚合反应。
以下将列出本发明各方面的实施例,并进行比较,表明本发明所获得的效果更佳。本发明的这些实施例使用恒定电流(始终)、直流电源,并提供照射到要聚合的组合物上的恒定光输出,并和使用可变电源的实施例比较,所述可变电源提供存在波动(脉冲光)的照射光。所述组合物受到照射,由此进行自由基聚合反应,形成厚度为15-25微米的薄膜,这是通过Teflon隔片或者绕线刮棒来控制的。所述涂膜在空气存在下以及没有空气的条件下均能固化。下表1中列出了以所述速度(fpm:英尺/分钟)经过照射灯的各涂膜。所述组合物包含作为光引发剂的Irgacure 184,它是1-羟基环己基苯基酮。所述组合物包含以下所述量的Irgacure 184,并包含作为单体的丙烯酸异冰片酯、HDDA(己二醇二丙烯酸酯)或者丙烯酸乙氧基化壬基苯酚酯,它们通过自由基聚合反应进行聚合。在光引发剂体系的自由基聚合反应中也可以使用CHVE(环己烷二甲醇二乙烯醚)和EMI(N-乙基马来酰亚胺)作为单体。
本发明中,以下的实施例使用“OMNI”DC电源(见图3的电源图示)来为微波驱动的紫外灯提供恒定电流,它始终用恒定的紫外光输出照射所述组合物。对于比较技术,所述“VPS-3”电源提供脉冲电流,当所述电流施加到微波驱动的紫外灯时,产生脉冲(波动的)紫外光输出。
从以下结果可见,本发明固化制剂的双键(C=C)转化率约比使用比较技术获得的高7%。如以下结果可见,本发明获得的有利结果在其上具有涂膜的基材经过照射光的移动速度更高时尤其显著。
表1
A.均聚--包含0.25%Irgacure 184的丙烯酸异冰片酯
25fpm | 50fpm | 100fpm | 150fpm | 200fpm | |
VPS-3平均OMNI平均 | 91%91%92%91%92%92%91%92% | 89%90%90%90%91%91%91%91% | 84%82%84%83%85%85%85%85% | 69%67%69%68%73%72%73%73% | 51%44%44%52%48%55%55%53%44%52% |
表2
B.均聚--包含2%Irgacure 184的丙烯酸异冰片酯
25fpm | 50fpm | 100fpm | 150fpm | |
VPS-3平均OMNI平均 | 96%96%96%96%96%96%97%96% | 95%95%96%95%95%95%95%95% | 91%92%92%92%92%92%91%92% | 87%88%86%87%90%90%90%90% |
表3
C.均聚--包含0.125% Irgacure 184的己二醇二丙烯酸酯(HDDA)
25fpm | 50fpm | 100fpm | 150fpm | |
VPS-3平均OMNI平均 | 85%87%86%86%86%86%86% | 80%81%83%81%84%83%84%84% | 65%62%60%62%66%68%66%67% | 42%45%39%41%42%46%49%46%53%49% |
表4
D.均聚--包含0.3% Irgacure 184的丙烯酸乙氧基化壬基苯酚酯
使用OMNI和VPS-3以不同固化速度进行双键转化的差异
75fpm | 100fpm | 125fpm | 150fpm | |
VPS-3平均OMNI平均 | 78.1%77.6%80%78.6%76%78.1%74.8%77.9%81.2%85.9%78.4%79.6% | 62.5%66.7%67.1%68.2%63.9%65.7%63.8%72.2%71.7%69%66.4%68.6% | 57.4%53.9%58.6%58.5%52.9%56.3%59%63.6%62.2%62.5%57.3%60.9% | 53.3%50.5%47.6%45.9%49.9%49.4%50.3%50.1%50.9%52.6%52.7%51.3% |
表5
E.共聚--包含0.2% Irgacure 184的丙烯酸异冰片酯/1,6-HDDA(1∶1摩尔比)
使用OMNI和VPS-3以不同固化速度进行双键转化的差异
50fpm | 75fpm | 100fpm | 125fpm | 150fpm | |
VPS-3平均OMNI平均 | 89.6%89.9%88.9%87.3%91.4%89.4%90.9%90.4%90.9%90.7% | 83.9%84.9%84.3%86.3%86.8%85.2%83.8%86.9%87.8%85.7%89.5%86.7% | 80.4%73.6%79.1%77.7%79.7%78.1%82.8%83.3%82.1%80.9%82.1%82.2% | 70.2%71.1%67.4%58%61.2%65.6%71%77.3%72.6%76.5%64%72.3% | 54%50.9%50.4%46.9%41.1%48.7%59%54.6%50.6%49.2%47.9%52.3% |
表6
F.交替共聚-环己烷二甲醇二乙烯基醚/N-乙基马来酰亚胺(1∶2摩尔比)
使用OMNI和VPS-3以不同固化速度进行双键转化的差异
75fpm | 100fpm | 125fpm | |
VPS-3(马来酰亚胺)平均VPS-3(乙烯基醚)平均OMNI(马来酰亚胺)平均OMNI(乙烯基醚)平均 | 86.3%88.8%70.7%80.5%79.8%81.2%61.0%59.2%51.6%56.3%55.5%56.7%91%94.6%78.2%89.9%82.7%87.3%64.5%68.8%60%65.1%62.2%64.1% | 76.4%79.9%74.4%88.6%63%76.5%57%57%56%67.7%44.2%56.4%79.2%82.9%73.8%94%81.8%82.3%61.8%65.4%53.6%63.1%60.4%60.9% | 73.5%74.2%69.2%77.1%73.5%n/a74.7%82.5%82.8%76.2%79.1%57.5%59.4%59.8%58.9%58.9% |
在表7和8中显示了对本发明使用“OMNI”电源固化的样品和使用“VPS-3”电源的比较样品所作出的凝胶渗透色谱(GPC)测量的比较。所得分子量(Mw)分布清楚地表明使用“OMNI”电源固化的样品的分布窄得多。这是由于使用“OMNI”电源时,短的聚合物链部分少得多。
表7
G.丙烯酸异冰片酯/Irgacure 184(0.25%)的GPC结果,它以不同固化速度在隋性氮气中固化
停留时间(min) | Mw | Mw* | d(峰宽) | |
VPS-3/HP6(10fpm)OMNI/HP6(10fpm)VPS-3/HP6(200fpm)OMNI/HP6(200fpm) | 15.39215.450n/an/a | 9417790079n/an/a | 106889103974230923197038 | 3.12803.06394.87244.7655 |
Mw是保留时间下的平均分子量。
Mw*是整个平均分子量分布。
表8
H.丙烯酸异冰片酯/Irgacure 184(2%)的GPC结果,它以不同固化速度在空气中固化
停留时间(min) | Mw | Mw* | d(峰宽) | |
VPS-3/HP6(10fpm)OMNI/HP6(10fpm)VPS-3/HP6(20fpm)OMNI/HP6(20fpm)VPS-3/HP6(200fpm)OMNI/HP6(200fpm) | 15.94515.99016.18616.23917.24017.237 | 624056035752193501822388923942 | 680896840856010558425047143293 | 2.29142.17932.28482.21502.49882.2061 |
Mw是保留时间下的平均分子量。
Mw*是整个平均分子量分布。
因此,本发明中使用恒定输出的辐照(例如,恒定输出光,如紫外光,但不限于此;可以使用其它辐照光如红外光和可见光),可以降低聚合反应的过早终止。而且,可以提高单体向聚合物的转化,尤其当所述组合物高速经过照射光时;可以提高(增大)所得聚合物的分子量,并降低聚合产物中分子量的分布(范围),以及提高所得聚合物的物理和其它性质。
Claims (18)
1.一种自由基聚合方法,所述方法包括:
提供一种组合物,所述组合物包含可进行自由基聚合反应的物质;
用由灯产生的射线照射所述组合物,由此引发所述自由基聚合反应,其中,在所述照射过程中,所述组合物用恒定的、没有脉冲的射线照射。
2.权利要求1所述的方法,其特征在于,用紫外光照射所述组合物,由此引发所述自由基聚合反应。
3.权利要求2所述的方法,其特征在于,所述紫外光由无电极的灯产生。
4.权利要求3所述的方法,其特征在于,所述无电极的灯由微波发生器产生的微波驱动,并且所述微波发生器由恒定电流、直流电源提供能量。
5.权利要求4所述的方法,其特征在于,所述组合物也包含光引发剂。
6.权利要求2所述的方法,其特征在于,所述紫外光由弧光灯产生。
7.权利要求6所述的方法,其特征在于,所述弧光灯由恒定电流、直流电源提供能量。
8.权利要求1所述的方法,其特征在于,所述组合物也包含光引发剂。
9.权利要求1所述的方法,其特征在于,所述可进行自由基聚合反应的物质具有能自由基聚合的C=C双键。
10.权利要求1所述的方法,其特征在于,所述可进行自由基聚合反应的物质是单体或者单体的混合物。
11.权利要求1所述的方法,其特征在于,所述通过辐照引发的自由基聚合反应是均聚反应。
12.权利要求1所述的方法,其特征在于,所述通过辐照引发的自由基聚合反应是共聚反应。
13.权利要求12所述的方法,其特征在于,所述可进行自由基聚合反应的物质包含受体单体和给体单体。
14.权利要求13所述的方法,其特征在于,所述物质以1∶1的摩尔比包含所述受体单体和给体单体。
15.权利要求1所述的方法,其特征在于,所述可进行自由基聚合反应的物质包含丙烯酸酯类和甲基丙烯酸酯类中的至少一种物质。
16.一种进行自由基聚合反应的设备,所述设备包括:
支承结构,用于保持所述可进行自由基聚合反应的组合物;
灯,用于用射线照射所述组合物,由此引发自由基聚合反应,所述灯用于始终提供恒定的,没有脉冲的射线输出,用于辐照所述组合物。
17.权利要求16所述的设备,其特征在于,所述灯是微波驱动的灯,而用于驱动所述灯的微波由恒定电流、直流电源产生。
18.权利要求16所述的设备,其特征在于,所述灯是弧光灯,而用于使所述弧光灯运行的能源来自恒定电流、直流电源。
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US30081601P | 2001-06-27 | 2001-06-27 | |
US60/300,816 | 2001-06-27 | ||
US09/983,208 US6908586B2 (en) | 2001-06-27 | 2001-10-23 | Free radical polymerization method having reduced premature termination, apparatus for performing the method and product formed thereby |
US09/938,208 | 2001-10-23 |
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CNB2006101536045A Division CN100537611C (zh) | 2001-06-27 | 2002-05-29 | 降低过早终止的自由基聚合方法形成的产物 |
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CN1283670C true CN1283670C (zh) | 2006-11-08 |
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US (3) | US6908586B2 (zh) |
EP (1) | EP1476475B1 (zh) |
JP (1) | JP2005505641A (zh) |
CN (1) | CN1283670C (zh) |
HK (1) | HK1105154A1 (zh) |
WO (1) | WO2003002615A1 (zh) |
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- 2002-05-29 JP JP2003508995A patent/JP2005505641A/ja active Pending
- 2002-05-29 WO PCT/US2002/016652 patent/WO2003002615A1/en active Application Filing
- 2002-05-29 CN CNB028165403A patent/CN1283670C/zh not_active Expired - Fee Related
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- 2004-08-31 US US10/929,556 patent/US7037460B2/en not_active Expired - Lifetime
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EP1476475A1 (en) | 2004-11-17 |
US20060116436A1 (en) | 2006-06-01 |
US6908586B2 (en) | 2005-06-21 |
US7037460B2 (en) | 2006-05-02 |
WO2003002615A1 (en) | 2003-01-09 |
EP1476475A4 (en) | 2006-10-04 |
CN1547593A (zh) | 2004-11-17 |
HK1105154A1 (en) | 2008-02-01 |
US7407617B2 (en) | 2008-08-05 |
US20050032926A1 (en) | 2005-02-10 |
JP2005505641A (ja) | 2005-02-24 |
WO2003002615A9 (en) | 2003-03-20 |
EP1476475B1 (en) | 2014-02-12 |
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