CN1338056A - 聚醚氧化膦的熔体聚合物合成 - Google Patents
聚醚氧化膦的熔体聚合物合成 Download PDFInfo
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- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
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Abstract
本发明提供一种生产适于光学应用的聚(芳撑醚氧化膦)的熔体聚合法,该方法包括将双酚的三甲基甲硅烷基衍生物与活化的芳族二卤化物反应,其中的一种反应物为氧化膦。
Description
发明领域
本发明涉及通过熔体聚合合成聚(芳撑醚氧化膦)(PEPO)。本发明的方法减少了危害这些材料的发色体和其它污染物。本发明的方法还减少了生产该材料时流出的废物流。
发明背景
聚芳撑醚是具有高玻璃化转变温度的韧性、硬质、阻燃工程热塑性塑料。因此，这些材料非常适于在光学领域应用。这些聚合物还显示出比其它高温热塑性塑料例如聚酰亚胺更好的耐碱性。
聚醚氧化膦特别适于用在光学领域，因为它们具有高的折光指数。由于在聚合物主链上存在柔性醚键以及带有与磷连接的体积大的苯基，所以PEPO是非晶聚合物。这些特征增加了PEPO在许多普通溶剂中的溶解度。
虽然已经公开有聚(芳撑醚)的熔体合成，但PEPO都是在溶液中通过强碱或弱碱路线合成的。例如，UDEL(Amoco)聚醚砜是通过由Johnson等人的J.Polymer Sci，Part A-1，5，2375(1976)中所述的强碱路线合成的。Riley等人的Polym.Eng.Sci.37，1507-1511(1997)描述了由弱碱路线合成PEPO。该方法生产的产品含有杂质，因而需要额外的提纯步骤来去除杂质。
由溶液法合成PEPO需要大约20小时才能获得30,000克/摩尔的聚合物。在聚合物沉淀前，必须过滤掉弱碱路线中的不溶性盐副产物，例如氟化钾。留在聚合物中的残留盐由于会引起光雾，从而对薄膜的透明度造成不利的影响。
由于在约150℃之上的降解反应和副反应，所以在溶液法中使用的溶剂成为另一污染源。如果能避免在溶液合成时使用酰胺溶剂，例如N，N-二甲基乙酰胺和N-甲基吡咯烷二酮，那么就会提高聚合物的不变黄性能。由于溶剂对环境的潜在影响以及处理易燃材料的危险性，所以对它们要格外的小心。
发明概述
本发明提供一种生产聚醚氧化膦的方法。该方法包括并基本上由反应物的熔体聚合组成，所述反应物包括并基本上由(i)双酚的三甲基甲硅烷基衍生物和(ii)活化的芳族二卤化物组成；其中，(i)，(ii)或(i)和(ii)为氧化膦。
本发明和优选实施方案的详细描述
本发明提供快速、对环境安全的通过熔体合成制备聚醚氧化膦的方法。这些方法不需要聚合物的提纯。在不需要任何溶剂的情况下，反应物在熔体相中聚合。由于不需要任何支持介质或溶剂，所以聚合物产品与初始材料一样纯净。而且，任何缩合副产物生成为易于从反应器中去除的气体。理论上，聚合产物可直接从反应器转移到例如生产眼镜片的最终模具中，这增加了透镜制造过程中的经济效益。
在本发明中用双酚的三甲基甲硅烷基衍生物作为第一反应物。三甲基甲硅烷基衍生物例如可由Kircheldorf等人在Polvmer，25：1151(1984)和Kircheldorf等人在Makromol.Chem.Rapid Commun，10：41-45(1989)中所述由双酚来制备。适合的双酚包括(但不限于此)：氢醌；4，4’-氧二酚；双酚A；联苯酚；4，4’-双(羟苯基)砜；4，4’-双(羟苯基)苯基氧化膦；4，4’-双(羟苯基)硫醚；6F双酚；以及前述的组合。
本发明熔体聚合的第二反应物是活化的芳族二卤化物。适合的活化芳族二卤化物包括(但不限于此)：单体级纯度的双(4，4’-氟苯基)苯基氧化膦(BFPPO)，4，4’-二氯二苯基砜(DDS)以及以BFPPO∶DDS的重量比为约100∶1至约5∶95的组合。
为了使反应体系保持在熔融状态下，本发明的反应要在反应期间温度升至比聚合物产物的Tg高出约50～75℃的温度下在熔体中进行。本发明的反应优选在催化剂的存在下进行。适合的催化剂包括(不限于此)：金属氟化物，例如氟化铯，氟化钾等。优选使用氟化铯。催化剂的有效催化用量为反应物的约0.1～1摩尔％。本发明的熔体聚合可达到高分子量，并且其通常要比溶液聚合快约3～5倍。
单苯基的三甲基甲硅烷基衍生物的加入可保证对端基的控制。适合的单苯基包括(但不限于此)：甲硅烷基化的4-枯基苯酚和甲硅烷基化的苯基乙炔基酚以及前述的组合。
二官能反应物的化学计算补偿可确保对分子量的控制。例如，最终的分子量可用Carother公式预测。使用公式中的通用形式和单官能封端形式来测定单体的化学计算补偿。在下面的B部分将对样品的计算进行说明。优选分子量的范围是约15000～30000g/mol。
由本发明方法生产的聚合物可掺杂金属盐，例如CoCl2或FeCl2。这些掺杂金属的聚合物降低了分散性能并因此在可见光谱例如蓝色和红色可见光中存在较小的折光指数的差异。
下面用实施例来说明本发明，这些实施例并不构成对本发明的限制。
步骤
a.凝胶渗透色谱法(GPC)
在装有并联连接的示差折光率检测器和Viscotek Model100粘度计的Waters150C ALC/GPC色谱仪上测量数均分子量和分子量分布。将15-17mg的样品溶解在含有0.025％P2O5的NMP中得到大约3mg/mL的浓度。在分析前用0.5微米的PTFE滤片对液相进行过滤。
b.示差扫描量热法(DSC)
在Perkin-Elmer DSC7系列仪器上进行DSC。样品被冷压并固定在碾平的铝盘上。在用于去掉任何物理老化样品的第一次扫描期间，将样品以约10℃/分钟的速度从约50℃加热到约300℃并进行骤冷。之后，样品再次以约10℃/分钟的速度从约50℃加热到约300℃，收集数据以测定玻璃化转变温度(Tg)。
c.热解重量分析法(TGA)
在Perkin-Elmer TGA7系列热分析仪上进行TGA。由粉末冷压5-8mg样品并以约10℃/分钟的速度从约30℃加热到约800℃。由生成的温度与重量百分比的关系图来测定5％分解的温度。
d.质子(1H)核磁共振(NMR)
在Varian400MHz仪器上测量质子(1H)NMR光谱。在5mm管中用0.100g固体和0.7mL CDCl3或氘化DMSO(取决于所分析材料的溶解度)来制备样品。对于液体，样品是使用具有mL CDCl3的0.2mL液体制备的。
e.碳(13C)核磁共振(NMR)
用Varian NMR分光计以100MHz的频率获取定量13C NMR光谱。样品是在10mm管中用0.300聚合物和2.0mL CDCl3制备的。
实施例1-Bis A PEPO和6F Bis PEPO的熔体聚合
Bis A PEPO和6F Bis PEPO的熔体合成是以氟化铯为催化剂，基于双酚A或6F双酚和双(4-4’-氟苯基)苯基氧化膦(BFPPO)的甲硅烷基化路线进行的。
还使用了两种单官能封端剂，即甲硅烷基化的4-枯基苯酚和甲硅烷基化的苯基乙炔基酚。
A.单体，装置以及单体和封端剂的甲硅烷基化
在双酚单体，双酚A和6F双酚，以及单官能封端剂，4-枯基苯酚和苯基乙炔基酚上的酚官能团用六甲基二硅氮烷进行甲硅烷基化。
在反应前将双酚A在约80℃，10托～100毫托的真空下干燥16小时。装有磁性搅拌器、冷凝器和氮气入口的500mL三颈圆底烧瓶用作反应器。所有的接口处用PTFE带密封。在具有OMEGA温度控制器的热板/搅拌器上加热的硅油浴保持油浴温度在110℃。将20g(0.876摩尔)的双酚A加入到火焰干燥装置中，紧接着加入40mL甲苯以将双酚A溶解成50％的固体溶液。向每两摩尔酚官能单元中加入2摩尔六甲基二硅氮烷(过量10％以确保完全反应)。向甲苯/双酚A混合物中加入38.8mL(0.1840摩尔)的六甲基二硅氮烷。在加入所有的试剂后，反应器浸渍在加热的油浴中。将氮气打开到低流速以防止甲苯从冷凝器的顶部跑出。在进行约4-5分钟的有力搅拌后，双酚A就可溶解为均匀的溶液。使反应进行约24小时。
反应的进程由质子核磁共振光谱法(1H NMR)监控。在不存在酚质子(9ppm)情况下可证实所有的酚基均被甲硅烷基化。1H NMR表明，大约6小时内就可100％完成甲硅烷基化反应。反应混合物在70℃下循环蒸发以去除残留的甲苯，然后，在120～130℃，300毫托的真空下蒸馏以收集甲硅烷基化的产物。将甲硅烷基化的单体和封端剂保持在氮气的无水环境下。所有的原料均为结晶固体。甲硅烷基化反应产生的甲硅烷基化产物是透明的粘性液体。
在反应前将单体级纯度的BFPPO在80℃的真空下干燥24小时，并且可在不需要进一步提纯的情况下使用。在没有进一步干燥或提纯的情况下，催化剂CsF保存在无水环境中。
在装有金属轴搅拌器、气体入口和气体出口/真空端口的250mL两颈圆底烧瓶中进行全部聚合反应。所有的接口均涂上尽可能少的油脂以避免污染反应。用连接在搅拌器电机上的自耦变压器调节搅拌。反应器浸渍在盐浴(7％NaNO2，43％KNO3，50％NaNO2)中，该盐浴是在热板搅拌器上加热的。用装有J型热电耦的OMEGA电子温度控制器控制浴温。控制器用热电耦监控浴温并因此可计量出热板的电流。在温度上升至反应步骤期间，反应器用氩气吹扫。低流速的氩气从反应器中带走氟化三甲基硅烷并使氧气脱离蒸气空间。在真空步骤中，气体出口用作真空端口并且密封住氩气入口。
B.分子量控制-补偿化学计算法
用Carother公式控制聚合物的分子量。使用公式中的通用形式和单官能封端形式来测定单体的化学计算补偿值。在下面列出了重复单元分子量为502.54826g/ml的30000g/mol聚合物的反应物量。
Na＝Si-BisA的摩尔数
Nb＝BFPPO的摩尔数
Na＝0.03077摩尔Si-BisA＝11.4670g Si-BisA
使用过量的单体级纯度的BFPPO以确保聚合物链具有比硅氧基端基更稳定的氟端基。催化剂浓度是基于甲硅烷基化双酚A(Si-BisA)的摩尔百分比计算的。下面列出了对0.3摩尔％CsF的计算。
C.聚合-30000g/molBis A PEPO的合成合成过程如下所示：
向火焰干燥反应器中加入11.4670g(0.03077摩尔)A部分中制备的甲硅烷基化双酚A(Si-BisA)。通过注射器向称出毛重的反应器中加入Si-Bis A达平衡以测量出准确的重量。基于Si-Bis A的量，用Carother公式计算达到理想分子量所需的单体级纯度的BFPPO的量。在铝箔盘中称出10.0000g(0.03182摩尔)的BFPPO。用一张称重纸作为漏斗，将BFPPO装入反应器中。加入BFPPO后，称量铝箔盘和称重纸两者的重量以确定剩余BFPPO的克数。从初始检测量中减去该量以确定出反应混合物中BFPPO的准确摩尔数。最后，向BFPPO和Si-Bis A混合物中加入0.0149g(9.231×10-5摩尔)的CsF。由于CsF对水极其敏感，所以要快速进行称量和向反应器中添加，以使其重量和计算量的差为0.5-1mg。
一旦所有的反应物都加进了反应器，接口处要用少量的高真空油脂密封并将氩气开到中等流速。烧瓶浸渍在约160℃的盐浴中并吹扫10分钟。在加热和缓慢搅拌3-4分钟后，BFPPO熔融从而产生低粘度的均匀溶液。在初始的10分钟吹扫后，盐浴温度在3小时内升高到约160℃～约300℃。温度上升期间，在约190℃下催化剂会产生小气泡。当生成的气泡变得更加强烈时，在蒸气空间中会看到氟化三甲基硅烷气体。直到约225℃～约230℃，气泡的尺寸和数目才停止增加。此时，在约1小时的反应中，溶液粘度迅速增加并形成泡沫。泡沫变得很粘，当聚合物包裹在搅拌杆上时，缓慢搅拌并最终停止搅拌。一旦反应显示出变缓的迹象，并达到约270℃～约280℃的温度，泡沫就开始消退，这时可进行间歇搅拌。在泡沫消退并且反应在约280℃～约290℃后，密封氩气入口并将反应器排空以去除所有的氟化三甲基硅烷气体。按常规使真空达到200毫托的压力。一旦反应处于完全真空下，浴温要保持在约300℃达两小时并同时缓慢搅拌聚合物。在熔体中不会看到有更多的气泡时，则表明反应已进行完毕。
反应完成后，反应器保持在真空状态下并去除盐浴。一旦聚合物冷却到室温，就除掉真空并加入100mLN，N-二甲基乙酰胺(DMAc)以将聚合物溶解成20％的固体溶液。溶解后，聚合物在高速混合器的2L85/15去离子水/乙酸溶液中析出。通过真空过滤来收集聚合物并在5L去离子水中对其搅拌2-3小时以去除全部的乙酸。再次通过真空过滤收集聚合物并在室温的真空环境下干燥24小时，然后在约150～170℃的真空环境下干燥24小时(这取决于聚合物的分子量)。
D.端基的引入
Carother公式的另一种形式用于控制封端聚合物的分子量。其计算方法如下所示。首先，对所需分子量进行单体化学计算补偿：Na＝Si-BisA的摩尔数Nb＝BFPPO的摩尔数
Na＝0.03077摩尔Si-BisA＝11.4670g Si-BisA下一步，颠倒单体的摩尔比并使用封端剂公式确定用于产生所需端基的封端剂用量。NA＝BFPPO的摩尔数NB＝Si-BisA的摩尔数NB’＝Si-4-枯基苯酚的摩尔数NB’＝0.00321摩尔Si-4-枯基苯酚＝0.6812gSi-4-枯基苯酚
0.00107摩尔Si-4-枯基苯酚＝0.2270gSi-4-枯基苯酚封端聚合物的反应和分离步骤与上述聚合步骤中的相同。
E.分析
a.质子(1H)NMR
用质子(1H)NMR监控甲硅烷基化产物的纯度。在9.1ppm处没有酚质子峰，表明酚官能团被完全甲硅烷基化。光谱显示出清晰、不同的峰值，这些彼此靠近成一体的峰值暗示出甲硅烷基化单体的高纯度。
实施例2-催化剂浓度的作用
用0.1、0.2和0.3摩尔％的催化剂浓度合成聚合物，其化学计算补偿值为30000g/mol。由补偿计算出的推算分子量列在标有推算Mn的栏中(见表1)。由GPC实验测定的数均分子量列在标有实验Mn的栏中。
表1：随催化剂浓度而变化的分子量
| 催化剂浓度(摩尔％) | 推算的Mn(g/mol) | 实验Mn(g/mol)* | 反应程度(％) |
| 0.1 | 29,581 | 8,420 | 96 |
| 0.2 | 30,152 | 11,900 | 98 |
| 0.3 | 30,304 | 33,300 | 100 |
*Mn由GPC在具有0.025％P2O5的NMP中测定
比较推算和实验的分子量以确定完全反应时催化剂的浓度。由两种较低浓度的催化剂可生产出比由化学计算补偿推算出的分子量低的聚合物。为完成反应并得到与化学计算补偿分子量一致的聚合物，需要至少0.3摩尔％的催化剂。此等水平的催化剂浓度看来好象没有影响反应的速率；唯一可看出每种聚合物间差异的是熔体中最终聚合物的粘度。
实施例3-分子量控制
用0.3摩尔％的催化剂合成具有不同分子量的一系列聚合物。表2的第一栏中列出了再用单体的化学计算补偿计算出的推算Mn。由GPC测定的数均分子量(实验Mn)与推算出的分子量一致(见表2)。
表2：用0.3摩尔％CsF的Bis A PEPO的分子量
| 推算Mn(g/mol) | 实验Mn(g/mol) | MWD |
| 30,304 | 33,300 | 2.2 |
| 29,000 | 22,600 | 2.4 |
| 6,216 | 6,700 | 1.6 |
| 溶液控制 | 30,900 | 2.2 |
*Mn由GPC在具有0.025％P2O5的NMP中测定
该数据证明了在熔体中合成的聚合物分子量可由Carother公式控制这一假设的成立。所需分子量可由单体的化学计算补偿来确定。在标有MWD的栏中列出的分子量分布接近2.0，并且具有逐步增长聚合的特性。实施例4-热分析表3列出了一系列聚合物的玻璃化转变温度和5％分解温度
表3：Bis A PEPO的玻璃化转变温度和5％分解温度
| Mn(g/mol) | Tg(℃)** | 5％分解(℃)* |
| 33,000 | 194 | 496 |
| 22,600 | 189 | 500 |
| 6,760 | 163 | 476 |
| 30,900* | 198 | 505 |
*溶液控制
**DSC第二次加热50-300℃；10℃/min
+TGA30-800℃在空气中；10℃/min在每一热性能方面，高分子量聚合物，即33,000g/mol和22,600g/mol，具有与溶液控制相当的效果。而对于6,760g/mol聚合物来说两个值均降低。
带有未反应的苯基端基的6,760g/mol聚合物没有显示出5％分解温度的增加。
实施例5-光谱研究
13C NMR也可用于测定数均分子量。由NMR确定分子量取决于端基中的碳，它显示出与主链中的碳不同的峰值。合成3,610g/mol的苯基乙炔基封端的聚合物并用定量13C NMR确定其分子量。
标有x和y的峰代表乙炔基碳并分别积分为1.56和1.70。季碳峰标为z并积分为8.69。为计算出更精确的分子量，使用两个乙炔基峰的平均积分值1.63。NMR分子量计算如下：
NMR的分子量比GPC分子量高1,750g/mol。由于GPC和NMR方法都存在固有误差，所以这种比较是不确定的。光谱显示出某些端基的引入，但所有的链可能不具有两个乙炔基端基。
实施例证明：对于熔体合成的PEPO和Bis A PEPO来说，可用Carother公式来确定具体的分子量。为了使聚合物的实际分子量与Carother公式计算的分子量一致，CsF的浓度优选基于Si-Bis A为至少0.3摩尔％。甲硅烷基化单体和封端剂的高纯度以及严格的反应步骤可以精确地计算出化学计算的补偿。熔体合成的聚合物的玻璃化转变温度和分解性能与相同分子量的溶液合成聚合物相当。可在Bis APEP主链上引入端基。
可使用典型的反应器。然而，当使用更具挥发性的甲硅烷基化双酚例如6F双酚时，可使部分远离热源，以保持反应器的顶部较冷。
所有上述专利、出版物、申请和测试方法均在这里作为参考引入。根据上述的详细描述，那些本领域中的熟练人员可对本发明进行各种改进。所有这些显而易见的改进均在本发明所附的权利要求书的范围内。
Claims (17)
1.一种生产聚醚氧化膦的方法，所述方法包括使反应物进行熔体聚合，该反应物包括(i)双酚的三甲基甲硅烷基衍生物和(ii)活化的芳族二卤化物，其中(i)，(ii)或(i)和(ii)为氧化膦。
2.根据权利要求1的方法，其中所述聚合是在催化剂的存在下进行的。
3.根据权利要求2的方法，其中所述催化剂为CsF。
4.根据权利要求1的方法，其中所述聚合是在所述聚醚氧化膦的Tg之上约50～约75℃的温度梯度下进行的。
5.根据权利要求1的方法，其中所述聚合是在无溶剂的情况下进行的。
6.根据权利要求1的方法，其中所述聚合是在不存在无机碱的情况下进行的。
7.根据权利要求1的方法，其中所述反应物进一步包括(iii)单酚的三甲基甲硅烷基衍生物。
8.根据权利要求1的方法，其中所述双酚选自氢醌；4，4’-氧二酚；双酚A；联苯酚；4，4’-双(羟苯基)砜；4，4’-双(羟苯基)苯基氧化膦；4，4’-双(羟苯基)硫醚；或前述的任意组合。
9.根据权利要求1的方法，其中所述活化的芳族二卤化物选自双(4，4’-氟苯基)苯基氧化膦(BFPPO)；4，4’-二氯二苯基砜(DDS)；或其组合。
10.根据权利要求10的方法，其中BFPPO与DDS的重量比为约100∶1至约5∶95。
11.根据权利要求2的方法，其中催化剂的用量为反应物总摩尔％的约0.1～1摩尔％。
12.根据权利要求1的方法，其中为了控制所述聚醚氧化膦的分子量，对所述反应物(i)和(ii)的用量进行化学计算补偿。
13.根据权利要求1的方法，其中所述熔体聚合导致可除掉的气态缩合副产物。
14.根据权利要求13的方法，其中所述气态副产物是通过氩气吹扫和抽真空去除的。
15.一种生产双酚A聚醚氧化膦的方法，所述方法包括在氟化铯催化剂存在下将三甲基甲硅烷基化的双酚A和双(4，4’-氟苯基)苯基氧化膦进行熔体聚合。
16.一种生产6F双酚聚醚氧化膦的方法，所述方法包括在氟化铯催化剂存在下将三甲基甲硅烷基化的6F双酚和双(4，4’-氟苯基)苯基氧化膦进行熔体聚合。
17.一种包括由权利要求1方法制备的聚醚氧化膦的眼镜片。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/252,296 | 1999-02-18 | ||
| US09/252,296 US6040416A (en) | 1999-02-18 | 1999-02-18 | Melt polymer synthesis of poly ether phosphine oxides |
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| CN1338056A true CN1338056A (zh) | 2002-02-27 |
| CN1147740C CN1147740C (zh) | 2004-04-28 |
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| US (1) | US6040416A (zh) |
| EP (1) | EP1161695A1 (zh) |
| JP (1) | JP2002537445A (zh) |
| KR (1) | KR100646354B1 (zh) |
| CN (1) | CN1147740C (zh) |
| AU (1) | AU763128B2 (zh) |
| CA (1) | CA2363099A1 (zh) |
| HK (1) | HK1041052A1 (zh) |
| IL (2) | IL144293A0 (zh) |
| MX (1) | MXPA01008359A (zh) |
| MY (1) | MY127932A (zh) |
| RU (1) | RU2221818C2 (zh) |
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| WO (1) | WO2000049429A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6493208B1 (en) | 1999-07-27 | 2002-12-10 | Eikos, Inc. | Triphenyl phosphine oxide polymer capacitors |
| US6288210B1 (en) * | 1999-11-12 | 2001-09-11 | Virginia Tech. Intellectual Properties, Inc. | High refractive index thermoplastic polyphosphonates |
| US9155619B2 (en) | 2011-02-25 | 2015-10-13 | Edwards Lifesciences Corporation | Prosthetic heart valve delivery apparatus |
| KR101882863B1 (ko) * | 2013-01-10 | 2018-08-24 | 삼성전자주식회사 | 고분자, 그 제조방법, 이로부터 형성된 복합체, 이를 포함한 전극과 복합막 및 이를 채용한 연료전지 |
| US10350047B2 (en) | 2015-09-02 | 2019-07-16 | Edwards Lifesciences Corporation | Method and system for packaging and preparing a prosthetic heart valve and associated delivery system |
| US10321996B2 (en) | 2015-11-11 | 2019-06-18 | Edwards Lifesciences Corporation | Prosthetic valve delivery apparatus having clutch mechanism |
| US11033387B2 (en) | 2015-11-23 | 2021-06-15 | Edwards Lifesciences Corporation | Methods for controlled heart valve delivery |
| US10357351B2 (en) | 2015-12-04 | 2019-07-23 | Edwards Lifesciences Corporation | Storage assembly for prosthetic valve |
| US10363130B2 (en) | 2016-02-05 | 2019-07-30 | Edwards Lifesciences Corporation | Devices and systems for docking a heart valve |
| USD867595S1 (en) | 2017-02-01 | 2019-11-19 | Edwards Lifesciences Corporation | Stent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3203186A1 (de) * | 1982-01-30 | 1983-08-11 | Röhm GmbH, 6100 Darmstadt | Phosphorhaltige polyarylenaether |
| US4754225A (en) * | 1987-07-06 | 1988-06-28 | Magnetic Peripherals Inc. | Phase comparator insensitive to clock asymmetry |
| US5143988A (en) * | 1989-11-27 | 1992-09-01 | Virginia Tech Intellectual Properties, Inc. | High refractive-index hybrid material prepared by titanium alkoxide and a phosphine containing oligomer |
| US5079333A (en) * | 1990-07-13 | 1992-01-07 | Virginia Tech Intellectual Properties, Inc. | Novel mine-terminated poly(arylene ether phosphine oxide) oligomer |
| US5407528A (en) * | 1992-07-28 | 1995-04-18 | The Center For Innovative Technology | Oxygen plasma resistant polymeric film and fiber forming macromolecules containing the phosphine oxide moiety |
| US5387629A (en) * | 1992-07-28 | 1995-02-07 | The Center For Innovative Technology | Phosphorus containing poly(arylene ether)s useful as oxygen plasma resistant films and in nonlinear optical applications |
| US5691442A (en) * | 1996-09-17 | 1997-11-25 | The United States Of America As Represented By The Secretary Of The Air Force | Transparent poly(arylene ether) compositions |
| US6008299A (en) * | 1997-08-15 | 1999-12-28 | Innotech, Inc., Johnson & Johnson Vision Care | Optic devices formed from melt processable thermoplastic materials having a high refractive index |
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- 1999-12-07 MY MYPI99005310A patent/MY127932A/en unknown
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- 1999-12-23 AU AU22180/00A patent/AU763128B2/en not_active Ceased
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Also Published As
| Publication number | Publication date |
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| IL144293A0 (en) | 2002-05-23 |
| CA2363099A1 (en) | 2000-08-24 |
| US6040416A (en) | 2000-03-21 |
| KR100646354B1 (ko) | 2006-11-17 |
| KR20010102146A (ko) | 2001-11-15 |
| WO2000049429A1 (en) | 2000-08-24 |
| EP1161695A1 (en) | 2001-12-12 |
| AU763128B2 (en) | 2003-07-10 |
| MY127932A (en) | 2006-12-29 |
| JP2002537445A (ja) | 2002-11-05 |
| MXPA01008359A (es) | 2003-06-06 |
| HK1041052A1 (zh) | 2002-06-28 |
| AU2218000A (en) | 2000-09-04 |
| RU2221818C2 (ru) | 2004-01-20 |
| CN1147740C (zh) | 2004-04-28 |
| TWI238168B (en) | 2005-08-21 |
| IL144293A (en) | 2006-10-05 |
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