CN1009933B - 在水分散液中氟化单体的聚合方法 - Google Patents
在水分散液中氟化单体的聚合方法Info
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- CN1009933B CN1009933B CN87103869A CN87103869A CN1009933B CN 1009933 B CN1009933 B CN 1009933B CN 87103869 A CN87103869 A CN 87103869A CN 87103869 A CN87103869 A CN 87103869A CN 1009933 B CN1009933 B CN 1009933B
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Abstract
本发明是关于在水分散液中，氟化单体聚合或共聚合的方法是使用游离基引发剂和氟化的表面活性剂，其特征在于该聚合是在具有中性末端基的全氟聚醚中完成的，并且在水的微乳液的形式中制备的，这是为了增加聚合速率增加方法的可重现性和使用上述全氟聚醚的耗量减至最少。
Description
本发明是关于在水分散液中並在游离基引发剂存在下，氟化单体的聚合和共聚合方法，其特征尤其在于，其聚合速度比按已知方法並在相似条件下所获得的任何一种聚合速度都高得多。
众所周知，氟代烯烃在聚合过程中呈现出各自不同的反应活性，与四氟乙烯（TFE）相比较，它们中的一些具有非常低或没有反应性，在这方面，可引证C3F6作为一例。
也有一些全氟乙烯基醚对于其它的氟代烯烃，特别是对于TFE（见U·S·P·3，132，123）在聚合中表现出很低的反应活性。
这一情况引起的后果是，当由彼此反应活性相差很大的共聚单体制备共聚物时，聚合反应需要在低反应活性单体的高浓度条件下进行操作，並且还需要在上述共聚单体的很高分压的条件下进行操作。
要制备C3F6含量为5～25%（按重量计）的FEP（热塑性共聚物C2F4-C3F6）时，必须在气相中使用高浓度的C3F6进行操作，而对应的单体的总压力是在35～40公斤/厘米2绝对压力（abs.）范围内（参见U·S·P·3，132，124）。
因此，有必要探索增加低反应活性单体的聚合速度，为的是避免在很高的压力条件下进行操作，同时减少聚合时间。
与本文申请同名的意大利专利申请号为20，256A/86的主题是在水分散液中使用游离基引发剂和氟化表面活性剂，並在具有中性未端基的、在聚合条件下是液体並且是一种水乳液形式的全氟聚
醚存在下使氟化单体进行聚合或共聚合的方法。与没有全氟聚醚存在时的常规聚合相比较，这种方法显示了很多优点。但是，当使用大容积高压釜操作时，而且就乳液的重现性而言，又出现了一些问题，这种方法要求使用大量的全氟聚醚，这样在聚合速度方面才能获得显著的效果，众所周知，这将导致成本的大幅度增加，此外，乳液必须在（使用）瞬间配制，並且由于全氟聚醚乳液的使用期所限它不能被长期贮藏。
目前已意外地发现，通过在水性微（滴）乳液形式中制备全氟聚醚，就能够克服这些问题。
使用术语“微（滴）乳液”指的是一种体系，在这种体系中具有中性末端基的全氟聚醚被表面活性剂所溶解，从而提供一种单相的溶液，该溶液在不提供分散能量的条件下长期保存也是稳定的。
事实上，该微（滴）乳液是将各种成分：水、具有中性末端基的全氟聚醚和氟化的表面活性剂，特别是具有端羧基或阳离子末端基的全氟聚醚型的表面活性剂简单的混合而制成的。在本发明中所利用的微（滴）乳液的详细介绍是由意大利专利申请号为20，910A/86的相同申请给出的。
微（滴）乳液的制备是可以重现的，是不受体积因素的影响並提供一个涉及领域很宽的体系：这样将可以使聚合配方从实验室规模过渡到工业化规模，是没有问题的，並且在相同聚合动力学的情况下，可明显地减少存在于聚合介质中全氟聚醚的量。
全氟聚醚加入到聚合介质中的一瞬间以微乳液的形式存在是很重要的，而且这种形式一旦形成就一定不能再被高压釜中的溶液所稀释。
含有全氟氧化烯单元链区的任何一种全氟聚醚都能很好的被使用。
全氟聚醚的平均分子量，其值可以在大约从500开始的一个很宽的范围内变化。
但是，在本发明的方法中，最好是使用分子量范围从600到3000的全氟聚醚。
例如，适用的全氟聚醚为以下类型中的一种：
1）
带有无规分布的全氟-氧化烯单元，其中Rf和R′ f是彼此相同或不相同的，为-CF3、-C2F5、-C3F7，m、n、P具有满足上述有关平均分子量条件的各种数值;
2）RfO（CF2CF2O）n（CF2O）mR′ f
带有无规分布的全氟-氧化烯单元，其中Rf和R′ f是彼此相同或不相同的，为-CF3或-C2F5，m和n具有满足上述条件的各种数值;
3）
带有无规分布的全氟-氧化烯单元，其中Rf和R′ f彼此是相同或不相同的，为-CF3、-C2F5，或C3F7，m、n、P、q具有满足上述条件的各种数值;
4）
其中Rf和R′ f是彼此相同或不相同的，为-C2F5或-C3F7，n为具有满足上述条件的数值;
5）RfO（CF2CF2O）nR′ f
其中Rf和R′ f是彼此相同或不相同的，为-CF3、-C2F5，n为具有满足上述条件的数值;
6）RfO（CF2CF2CF2O）nR′ f
其中Rf和R′ f是彼此相同或不相同的，为-CF3或-C2F5或-C3F7，n为具有满足上述条件的数值;
7）
其中，Rf和R′ f是全氟烷基，R″ f是氟或全氟烷基，n为具有满足上述条件的数值。
类型1）的全氟聚醚是工业上已知的，其商标为Fomblin
Y或Galden
;类型2）的一些全氟聚醚其商标为Fomblin
Z，它们都是由Montedison生产的。
类型4）的工业上已知的产品有Krytox
〔杜邦（Du POnt）〕，类型5）的产品在美国专利4，523，039或美国化学会志（J·Am·Chem·Soc·1985，107，1197-1201）中已有介绍，类型6）的产品在欧洲专利EP148，482中已由Daikin叙述过了。
类型3）的产品是按USP3，665，041制备的，
类型7）的产品在PCT专利申请W087/00538中已有介绍。
全氟聚醚在本发明方法中的用量是很低的，其用量数量级是每升聚合水溶液中有0.05～2毫升，较好的用量为每升0.4～1.5毫升。
作为游离基引发剂，可以使用对于氟化单体在水分散液中进行聚合时所使用过的各种已知类型的引发剂。
通常，无机或有机的两类过氧化物都是适用的：其前者中有钾或铵的过硫酸盐是特别适用的，作为适用的有机过氧化物有：溶于水的，例如，过氧化丁二酰和不溶于水的，例如（见EP75，312）两种。也可以使用已知的偶氮类化合物的游离基引发剂，例如，在USP2，515，628和2，520，338中所叙述过的那些。当希望在低聚合温度（如从10℃到50℃）下进行操作时，可以使用氧化还原引发剂。
通常用于氟化烯烃聚合中的游离基引发剂的用量范围为聚合单体总量的0.003%到2%（按重量计）。
游离基引发剂-按情况-或把氧化还原体系的各组分在聚合开始时全部加入到聚合反应器中，或者可以在聚合过程中逐渐地加入。
对于稳定乳液颗粒所需要的表面活性剂被部分的或全部的包含在中性全氟聚醚微乳液中，通常，含在微乳液中的表面活性剂足以满足聚合过程的需要。
已知的合适的表面活性剂是由全氟化合物组成的，特别是那些具有6-11个碳原子的羧酸或磺酸类。
更适合的表面活性剂是那些具有一个或两个酸末端基的全氟聚醚类。
后一类表面活性剂是比较好的，因为它可以使之含有中性末端基
的全氟聚醚具有良好溶解效果的优点。
全氟聚醚微乳液在聚合开始时必须导入到水相中：无法设想全氟聚醚的分散程度，但是在聚合过程中微乳液被稀释以后：它还能够以微乳液的形式或以极细微的颗粒状态存在。然而，或许全氟聚醚的分散程度会比采用与本申请同名的意大利专利申请No 20，256A/86的方法所获得的分散程度要高得多。然后再加入其他成分（单体、引发剂、分子量调节剂）。
按本发明在水分散液中进行聚合的方法特别是用于下面制备C2F4的各类共聚物中是很有利的：
-“改性”型的聚四氟乙烯，也就是含有少量，如低于0.5%（按重量计）的一种或多种共聚单体，例如：全氟丙烯、全氟烷基-全氟乙烯基醚、1，1-二氟乙烯、六氟异丁烯和一氯三氟乙烯;
-C2F4的热塑性共聚物，包括含有7～27%（按重量计）的C3F6（由杜邦生产的FEP型）的共聚物、含有0.5～10%，最好是2～4%（按重量计）的全氟烷基全氟乙烯基醚（PFA型）的一些共聚物、含有高含量C2H4加少量氟代类第三单体（杜邦生产的Tefzel
）的共聚物类。
-弹性共聚物，该类共聚物含有20%～50%（按摩尔计）的全氟烷基全氟乙烯基醚（或全氟烷氧基全氟乙烯基醚），和一种有固化部位的单体（杜邦公司生产的Kalrez）;
-CF2＝CH2/C2F4/C3F6和CF2＝CH2/C2F4/PFVE之类的三元弹性共聚物。
我们还可以引证ClFC＝CF2/乙烯（Halar）的热塑性共聚物作为有效地利用本发明聚合方法的另外一种情况。
按照本发明的方法，除了提供上述各种优点之外，还提供一些相同于意大利申请的申请号为20256A/86中所述的氟化单体的共聚合时所展示的各种优点，例如，可以在比现有技术中任何一种聚合压力都低的聚合压力下进行聚合操作;形成本发明目的方法的特征是获得了含氟聚合物的水分散液，而该分散液又是以每升颗粒的数目极高和颗粒的直径极小为特征的，每升聚合物颗粒数目的典型例子是0.5～5×1018数量级。
构成本发明目的方法的另一个特征在于，在聚合动力学相同的情况下，所利用的全氟聚醚的用量比意大利专利申请号为No20256A/86的申请所指出的例子范围要低大约一个数量级，这就产生了上述优点。
下面给出的例子仅仅是按照本发明的方法的几个具体应用的说明。
下面的分析方法和特性可以用来测定在各例中所获得的聚合物材料的性质。
a）测定熔融的开始温度，熔融峰温度和熔融终了的温度，该测量是用差示量热法来完成的，使用的是DSC Ⅳ·型Perkin-Elmer量热器，並把大约10克共聚物由室温一直加热到350℃，加热速度为10℃/分。
再将聚合物以10℃/分的降温速度冷却到室温，然后再次以相同的加热速度加热到350℃。相对于熔融吸热的最大值的温度，在下面被称为第二熔融峰值。
b）C2F4/C3F6共聚物中HPF的含量是通过使用20SXB型Nicolet分光镜的FTIR光谱法，並在340℃温度下挤压成型的薄膜（0.05mm～0.01mm）上进行测
定的，HFP的特性谱带的吸收度983Cm-1与参比谱带的吸收度2353Cm-1之间的比例值在下文中被称做吸收度特性比率，HFP的百分含量（按重量计）是通过由差示质量天平得到的正确标定进行计算的，是将吸收度特性比率值乘以4.5。
c）为了测量熔融粘度或熔融流动指数（MFI），使用的仪器设备除了筒体、活塞和排气喷咀是由抗腐蚀的材料制备的之外，其余的都是按ASTM D-1238-65T标准中介绍的进行制造，排气喷咀的长度为8毫米，它的内径是2.0955毫米，筒体的直径为0.95厘米。一定量的聚合物在筒体内被熔融，並在372℃的温度下保持大约10分钟，然后将熔融聚合物在维持活塞上的挤出压力为一恒定值（5公斤）的压力下通过喷咀而被挤出。MFI的值是根据通过喷咀10分钟所挤出的聚合物的克数来计算的，为获得以泊表示的熔融表观粘度，是充分地用MFI值除以53，500。
d）挥发度指数（V·I·），是通过称重10克树脂在铝板上来进行测定的，此铝板放到和真空系统相连的玻璃管（形）瓶中並在该瓶中产生真空（2mmHg），一旦达到平衡就将瓶加热到380℃，然后记录下来瓶内与时间相关的压力，挥发性指数用下式计算：
V·I·＝ (（P40－P0）V)/10
其中P0和P40分别是在时间为零和40分钟后管形瓶内的压力（以毫米汞柱表示的），V是管形瓶的体积，为121±0.2cm3。
e）颗粒的平均直径是通过采用莱塞光散射的犁刀（Coulter）毫微分粒机的设备测定的，乳液样品从1稀释到100，並以1.0微米的微孔过滤器进行过滤，然后进行6次测定，去掉最大值和最小值，如此得到的算术平均值被定为颗粒的平均直径值，该数据与以前用发射电子显微镜得到的数据相一致，这是可利用来测定平均直径的另一种方法。
f）聚合物树脂在Brabender挤压机（PL 651型塑度计）中挤压，制得直径为大约3.5mm，厚度为1.5～3mm的颗粒。颗粒的颜色的测定方法如下：使发射的白光通过样品，再使所引起的反射光通过滤光器的位置並进行测量，最后测定光强度。反射的绿色光的百分率越高表示颗粒的白度也越高，使用的是XL10A型加纳尔（Gardner）色度计。
例1
将5份具有属于类型1的全氟聚醚结构的，其中R′ f为-CF2CooH或-CooH，酸滴定的分子量为632的酸、3份带有全氟烷基並且PM为800的类型1的全氟聚醚、5份10%的氢氧化铵水溶液和10份水加入到玻璃容器内。
产生的分散液在轻微的搅拌下加热到75℃，制得完全透明的溶液，然后将其冷却到室温则使溶液分离成两相，但是，该体系对于加热呈现可逆性，並且发现，该体系在60～90℃的温度范围内微乳液是稳定的。在75℃下将含有2毫升上述中性全氟聚醚的15.3毫升微乳液，加入到装在预先已形成真空並附有机械搅拌的4.2升AISI316号钢制高压釜中的2升充分脱气的水中。
高压釜中的温度在搅拌（600rpm）下升至95℃，用含有
63%摩尔C3F6和37%摩尔C2F4的气体混合物使表压升至20公斤/厘米2，然后将0.73克过硫酸铵（（NH4）2S2O8）和0.73克过硫酸钾（K2S2O8）溶解在500毫升水中制得的水溶液62毫升加入到高压釜中，高压釜中的压力一开始下降，就通过空气压缩机将含有5.8%摩尔六氟丙烯的C3F6/C2F4混合物送入高压釜中，使釜压再恢复到原来的压力。15分钟以后，将上述过硫酸盐溶液在88毫升/小时的流速下进料，在反应器中搅拌持续60分钟，此后停止反应並放出气体混合物。获得含有224克/升聚合树脂的水分散液。
通过电子显微镜测定的分散液颗粒的平均直径等于0.041μm，每升水（Np/1）的颗粒数目等于2.9×1018。
通过机械搅拌使水分散液凝聚，过滤，固体产物用蒸馏水反复洗涤，在200℃的鼓风冷却干燥箱中干燥，产品具有的M·F·I（熔融流动指数）为0.65克/10分钟，第二熔融峰为262.4℃，生成的粉沫在Brabender单螺杆挤压机中挤压，得到规整的和完全白色的粉粒，产品不需要任何再稳定化和脱色处理，热挥发度指数为59，白度为71。
例2
操作与例1相同，使用11毫升含有1.43毫升按照例1的中性全氟聚醚的微乳液。
反应在65分钟后停止，排出胶乳，制得含225克/升的聚合树脂的水分散液，用电子显微镜测得颗粒的平均直径等于0.046μm，相对应的每升水的颗粒数目为2.2×1018。
凝聚粉粒的熔融流动指数为0.92，吸收度特性比率为3.5。
例3（比较实验）
将8毫升例1的带有全氟烷基末端基的全氟聚醚加入到250毫升蒸馏水中，使用IKA Werke制造的T65型（10，000rpm）Ultraturrax
搅拌机将悬浮液搅拌5分钟，再向其中加入含有4克具有等当量酸滴定分子量为690的
水熔液，该乳液是通过5分钟的进一步均化作用而获得的。将该分散液加入到容积为4.2升的AISI316号钢制高压釜中，高压釜已预先形成了真空，加入蒸馏水直到使总体积达到2000毫升为止，使高压釜升温到95℃，用含有62%摩尔C3F6和38%摩尔C2F4的气体混合物使高压釜的表压升至20公斤/厘米2，然后把0.73克的（NH4）2S2O8和0.73克的H2S2O8溶解在500毫升水中制备的水溶液62毫升加入到高压釜中，高压釜中的压力一开始下降，就通过空气压缩机将含有6.7%摩尔全氟聚醚的C3F6/C2F4混合物送入到高压釜中，使釜压再升至开始时的压力。15分钟之后，上述过硫酸盐溶液在88毫升/小时的速度下进料，在反应器中搅拌65分钟，此后停止反应，排出反应器中的内容物。
得到含有230克/升的聚合物树脂的水分散液。
水分散液用机械搅拌凝聚，过滤，固体产物用蒸馏水反复洗涤，在空气循环的干燥箱内200℃下干燥，产物的熔融特性粘度为1.063×106泊，熔融流动指数（M·F·I·）为0.5克/10分钟，在264.9℃出现第二熔融峰，生成的粉末在Brabender单螺杆挤压机中挤出，获得规整的和完全白色的粉粒，
产品不需要再稳定化和脱色处理，热挥发度指数为60，白度为71。
例4
4.7毫升具有属于类型1）的全氟聚醚结构和其平均分子量为632的羧酸，用5毫升10%的NH3中和，再加入10毫升水和3毫升例1的具有全氟烷基末端基的全氟聚醚油。
加热到70℃，获得透明而稳定的单相体系，生成了全氟聚醚的微乳液。
在75℃时，将如此制备的微乳液加入到3升充分脱气的並已装入在附有机械搅拌的4.2升AISI316号钢制高压釜中的水中，高压釜已预先形成了真空。
高压釜中的温度在机械搅拌（600rpm）下升至95℃，用含有11.57%摩尔全氟甲基乙烯基醚（C3F6O）和88.43%摩尔C2F4的气体混合物使高压釜表压升至20公斤/厘米2。
把124毫升含有0.362克/升的K2S2O8和0.362克/升的（NH4）2S2O8的溶液导入高压釜中。
高压釜中的压力一开始下降，就通过空气压缩机把含有2.71%摩尔C3F6O的C3F6O/C2F4混合物送入到高压釜中，使釜压恢复原状，15分钟以后，把上面规定的过硫酸盐溶液以88毫升/小时的速度加料。
搅拌60分钟之后，中断反应，气体混合物被排出。
制得含214克/升聚合物的水分散液。
用差示质量天平测定C3F6O在聚合物中的平均含量为3.1%摩尔。
例5
本例的操作与例1所述的操作相同，使用10毫升其中所述的含有1.3毫升中性全氟聚醚的微乳液。
高压釜中的温度达到30℃，此后加入100毫克（NH4）2S2O8，並通过加入TFE和全氟甲基乙烯基醚（PFMVE）（1.6%摩尔的PFMVE共聚单体）的混合物，使压力升至20个大气压。
然后把含有30毫克莫尔（Mohr）盐的水溶液加入到高压釜中，高压釜中的压力一开始下降，就通过加入C2F4的办法使釜压恢复到原来的压力，在反应中反应温度逐渐上升直至60℃，75分钟之后，停止搅拌並排出气体混合物，由此获得含有200克/升聚合物的水分散液，用电子显微镜测定的分散颗粒的平均直径为0.070微米。
每升水（Np/1）颗粒数目等于5.2×1017。
凝聚聚合物的共聚单体含量（PFMVE）是用质量天平和FTIR光谱（Spectroscopy）测定的，其结果为0.62%（按重量计）。
Claims (7)
1、氟化单体在水分散液中使用游离基引发剂和氟化表面活性剂进行的聚合和共聚合的方法，其特征在于，该聚合是在以水微乳液形式制备的並具有中性末端基的全氟聚醚存在下进行操作的，所说的全氟聚醚在聚合条件下是液体。
2、按照权利要求1，在水分散液中，氟化单体的聚合和共聚合的方法，其中全氟聚醚的平均分子量不低于500，全氟聚醚的用量为每升聚合物溶液中不低于0.05毫升。
3、按权利要求2的方法，其中全氟聚醚是选自下列各种类型：
带有无规分布的全氟-氧化烯单元，其中Rf和R′ f是彼此相同和不相同的为-CF3、-C2F5、-C3F7，n、m、P具有满足上述有关平均分子量条件的各种数值，
2）RfO（CF2CF2O）n（CF2O）mR′ f
带有无规分布的全氟-氧化烯单元，其中Rf和R′ f是彼此相同或不相同的，为-CF3或-C2F5，m和n具有满足上述条件的各种数值，
带有无规分布的全氟-氧化烯单元，其中Rf和R′ f是彼此相同或不相同的，为-CF3、-C2F5或-C3F7，m、n、p、q具有满足上述条件的各种值，
其中Rf和R′ f是彼此相同或不相同的，为-C2F5或-C3F7，n具有满足上述条件的数值，
5）RfO（CF2CF2O）nR′ f
其中Rf和R′ f是彼此相同或不相同的，为-CF3、-C2F5，n具有满足上述条件的数值，
6）RfO（CF2CF2CF2O）nR′ f
其中Rf和R′ f是彼此相同或不相同的，为-CF3、或-C2F5或-C3F7，n具有满足上述条件的数值，
7）
其中Rf和R′ f是全氟烷基，R″ f是氟或全氟烷基，n具有满足上述条件的数值。
4、按照权利要求1的方法，其中表面活性剂属于具有酸末端基的全氟聚醚类。
5、按照权利要求1的方法，其中C2F4和C3F6的共聚合配比应使所得共聚物中含有7%到27%（按重量计）的C3F6。
6、按照权利要求1的方法，其中C2F4与全氟烷基全氟乙烯基醚的共聚合配比，应使所得共聚物中含有低于0.5%（按重量计）的全氟烷基全氟乙烯基醚。
7、按照权利要求1的方法，其中C2F4与全氟烷基全氟乙烯基醚的共聚合配比，应使所得共聚物中含有0.5～10%（按重量计）的全氟烷基全氟乙烯基醚。
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| IT1263955B (it) * | 1993-02-23 | 1996-09-05 | Ausimont Spa | Processo di (co) polimerizzazione radicalica di monomeri olefinici fluorurati |
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| US2559752A (en) * | 1951-03-06 | 1951-07-10 | Du Pont | Aqueous colloidal dispersions of polymers |
| US3635926A (en) * | 1969-10-27 | 1972-01-18 | Du Pont | Aqueous process for making improved tetrafluoroethylene / fluoroalkyl perfluorovinyl ether copolymers |
| US3864322A (en) * | 1973-04-12 | 1975-02-04 | Du Pont | Perfluorocarbon copolymer powders and preparation by spray drying |
| US4342675A (en) * | 1978-06-16 | 1982-08-03 | E. I. Du Pont De Nemours And Company | Process for preparing aqueous dispersion of polytetrafluoroethylene |
| DE2908001C2 (de) * | 1979-03-01 | 1981-02-19 | Hoechst Ag, 6000 Frankfurt | Verfahren zur Herstellung konzentrierter Dispersionen von Fluorpolymeren |
| US4523039A (en) * | 1980-04-11 | 1985-06-11 | The University Of Texas | Method for forming perfluorocarbon ethers |
| CA1191678A (en) * | 1982-02-02 | 1985-08-13 | Memorex Corporation | Lubrication of magnetic recording media |
| US4482685A (en) * | 1982-09-30 | 1984-11-13 | Allied Corporation | Copolymerization of ethylene and chlorotrifluoroethylene in an aqueous emulsion |
| US4513128A (en) * | 1983-06-23 | 1985-04-23 | E. I. Du Pont De Nemours And Company | Fluorinated vinyl ether copolymers having low glass transition temperatures |
| JPS6076516A (ja) * | 1983-09-12 | 1985-05-01 | Daikin Ind Ltd | ポリテトラフルオロエチレン水性分散体の製法 |
| US4564661A (en) * | 1985-03-12 | 1986-01-14 | E. I. Du Pont De Nemours And Company | Tertiary perfluoroalkoxides as surfactants in PTFE dispersion polymerization |
| JPS61223007A (ja) * | 1985-03-28 | 1986-10-03 | Daikin Ind Ltd | フルオロエラストマ−の乳化重合法 |
| IT1189092B (it) * | 1986-04-29 | 1988-01-28 | Ausimont Spa | Processo di polimerizzazione in dispersione acquosa di monomeri fluorurati |
| IL82308A (en) * | 1986-06-26 | 1990-11-29 | Ausimont Spa | Microemulsions containing perfluoropolyethers |
| IT1215418B (it) * | 1987-04-10 | 1990-02-08 | Ausimont Spa | Perfluoroalcani ottenuti mediante fluorurazione fotochimica e loro impiego come iniziatori di polimerizzazione. |
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1986
- 1986-06-26 IT IT20909/86A patent/IT1204903B/it active
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1987
- 1987-04-23 US US07/041,525 patent/US4864006A/en not_active Expired - Lifetime
- 1987-04-23 IL IL82309A patent/IL82309A/xx not_active IP Right Cessation
- 1987-04-23 ZA ZA872891A patent/ZA872891B/xx unknown
- 1987-04-27 IN IN334/CAL/87A patent/IN167721B/en unknown
- 1987-04-28 CZ CS873010A patent/CZ279451B6/cs unknown
- 1987-04-28 NO NO871771A patent/NO167986C/no unknown
- 1987-04-28 DD DD87302214A patent/DD262433A5/de not_active IP Right Cessation
- 1987-04-28 CA CA000535850A patent/CA1281489C/en not_active Expired - Lifetime
- 1987-04-28 RU SU874202519A patent/RU2026308C1/ru active
- 1987-04-28 AU AU72177/87A patent/AU601408B2/en not_active Ceased
- 1987-04-28 JP JP62103435A patent/JP2562890B2/ja not_active Expired - Lifetime
- 1987-04-28 GR GR870659A patent/GR870659B/el unknown
- 1987-04-29 BR BR8702109A patent/BR8702109A/pt not_active Application Discontinuation
- 1987-04-29 EP EP87106253A patent/EP0250767B1/en not_active Expired - Lifetime
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- 1987-04-29 KR KR1019870004170A patent/KR940010337B1/ko not_active IP Right Cessation
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- 1987-04-29 ES ES198787106253T patent/ES2025574T3/es not_active Expired - Lifetime
- 1987-04-29 CN CN87103869A patent/CN1009933B/zh not_active Expired
- 1987-04-29 FI FI871902A patent/FI89373C/fi not_active IP Right Cessation
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