CN1186080A - 氢化开环复分解聚合物的生产方法 - Google Patents
氢化开环复分解聚合物的生产方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
使用通式(Ⅰ)的钌-碳烯络合物作为聚合阶段的催化剂,由环烯烃生产氢化开环复分解(共)聚合物的方法,其中该催化剂可选地在聚合后,通过加入改性剂进行改性,聚合产物作为溶液(可选用与用聚合期间相同的惰性溶剂或用另一惰性溶剂稀释)氢化,不加入额外的氢化催化剂,温度为0—200℃,最好为35—150℃,氢气压为2—200巴,最好为10—50巴,其中至少60%、最好至少95%的烯双键被饱和,式(Ⅰ)示于右上方。
Description
本发明涉及氢化开环复分解聚合物(ROMP聚合物)的生产方法。由该方法可获得的材料表现出特别高的纯度和良好的热稳定性和光稳定性。由降冰片烯或四环十二碳烯衍生物制备的大多数氢化开环复分解聚合物为具有巨大应用潜力的非晶形热塑性聚合物。
由环应力环烯烃(诸如降冰片烯衍生物、四环十二碳烯衍生物之类)制备的开环复分解聚合物是已知的(例如EP-A002 277)。然而,由于聚合物骨架中的碳-碳双键,它们为热不稳定的和光化学不稳定的。因此,根据这类不饱和聚合物的预定应用,需要或者全部或者部分氢化这类不饱和聚合物。
开环复分解聚合(ROMP)的聚合物氢化产物是已知的。EP-317262和DE4139476描述了由具有酯基的四环十二碳烯衍生物(例如7-甲基-7-甲酯基四环十二碳烯)制备的氢化ROMP聚合物。所述单体通过六氯化钨催化,经过开环聚合,在三异丁基铝或氯化二乙基铝存在下用仲醛改性。然后将产生的聚合物在加压氢气下氢化,其中环烷酸镍、铑-碳、钯-硅藻土、RuHCl(CO)(Ph3)3等可以用作氢化催化剂。EP-303246描述了例如在三氯化二乙基铝存在下,二环戊二烯和甲基四环十二碳烯用五氯化钼催化的开环共聚。产生的聚合物通过氧化铝上的镍催化氢化。
现有技术中描述的聚合和氢化方法使用双组分或多组分聚合催化剂和另一氢化催化剂。催化剂残留物在产物中累积。这些催化剂残留物可能含有金属残留物(W、Ti、Mo、Re、Ru、Al等)、卤素、磷、硅等,这些残留物严重地损害了聚合物的性质,诸如透明度、稳定性、可加工性等。这增加了聚合物合成后的纯化需要。
因此产生了一个目的,即提供一种方法,其中氢化ROMP聚合物的生产只加入含金属并具有较高聚合和氢化活性的的单一催化剂。
US-P5312940和US-P4342909特别描述了通式(I)的钌-碳烯络合物及其作为环烯烃开环复分解聚合催化剂的用途,其中R1和R2相互独立,是指氢、C2-C20链烯基、C1-C20烷基、芳基、C1-C20
羧酸根、C1-C20烷氧基、C2-C20链烯氧基、芳氧基、C2-C20烷氧
羰基、C1-C20烷巯基,它们可以可选地被C1-C5烷基、卤素、C1-C5
烷氧基取代,或被可选地被C1-C5烷基、卤素、C1-C5烷氧基取代
的苯基取代;X1和X2相互独立,是指任何所需的阴离子配位体;L1和L2相互独立,是指任何所需的中性电子给体,
此外,X1、X2、L1和L2中的2个或3个可以一起形成一个多配
位基螯合配位体。
本发明提供使用上述钌-碳烯络合物作为聚合阶段催化剂,由环烯烃生产氢化开环复分解(共)聚合物的方法;其特征在于,该催化剂可选地在聚合后,通过加入改性剂进行改性,聚合产物作为溶液(可选用与用聚合期间相同的惰性溶剂或用另一惰性溶剂稀释)氢化,不加入额外的氢化催化剂,温度为0-200℃,最好为35-150℃,氢气压为2-200巴,最好为10-50巴,其中至少60%、最好至少95%的烯双键被饱和。
C5羧酸根、C1-C5烷氧基、苯氧基、C2-C5烷氧羰基,它们可以
可选地被C1-C5烷基、卤素、C1-C5烷氧基取代,或被可选地被
C1-C5烷基、卤素、C1-C5烷氧基取代的苯基取代;X1和X2相互独立,是指来自Cl、Br、C1-C5羧酸酯、苯氧基、C1-
C5烷氧基、C1-C5烷巯基的一个阴离子配位基,它们可以可选地
被C1-C5烷基、卤素、C1-C5烷氧基取代,或被可选地被C1-C5烷
基、卤素、C1-C5烷氧基取代的苯基取代;L1和L2相互独立,是指来自芳基或C1-C10烷基膦的中性配位基,它们
可以可选地被C1-C5烷基、卤素、C1-C5烷氧基取代,或被可选地
被C1-C5烷基、卤素、C1-C5烷氧基取代的苯基取代。
推荐的催化剂为通式(I)的钌/碳烯络合物,其中R1和R2相互独立,是指氢、甲基、乙基、苯基、可选地被甲基、乙基或苯基取代的乙烯基;X1和X2相互独立,是指Cl、Br;L1和L2相互独立,是指三甲基膦、三乙基膦、三苯基膦或三环己基膦。
可以使用的环烯烃单体为单环或多环单烯烃、二烯烃、三烯烃或四烯烃,它们可以具有多个极性官能,例如卤素、氰基、羧酸酯、羧酰胺、羧酸酐、羧酰亚胺、醚氧基、羰基等。推荐的单体为具有至少一个降冰片烯结构的多环环应变烯烃。
上述单体为有机化学文献中已知的化合物。
特别推荐的单体或共聚单体为例如:
2-降冰片烯,
5-甲酯基-2-降冰片烯,
5-甲基-5-甲酯基-2-降冰片烯,
5-氰基-2-降冰片烯,
5-甲基-5-氰基-2-降冰片烯,
5,5-二氰基-2-降冰片烯,
1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6-甲基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6-甲基-6-甲酯基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6-甲酯基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6-氰基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6-乙基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6-亚乙基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6,7-二甲基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
二环戊二烯,
三环戊二烯,
四环戊二烯,
1,4-二桥亚甲基-1,4,4a,9a-四氢芴。
在聚合条件下为惰性的有机溶剂、质子性溶剂或水性溶剂可以考虑作为溶液聚合的溶剂。实例为芳烃、卤代烃、醚类、脂肪烃、醇类、水或它们的混合物。推荐的实例为苯、甲苯、二氯甲烷、二氯乙烷、氯苯、二氯苯、乙醚、四氢呋喃、己烷和环己烷。
聚合可以在0-100℃下进行,最好在25-45℃下进行。
链转移剂可以加入聚合阶段中,以调节产物的分子量。开环复分解聚合的适宜链转移剂为具有碳-碳双键的开链化合物。链转移剂的实例为C1-C12链烯、乙酸烯丙酯、烯丙基·烷基醚、苯乙烯、1,4-二甲氧基-2-丁烯。通过在1∶50-1∶10000之间,最好在1∶100-1∶1000之间改变链转移剂与单体的摩尔比,可以调节产物的分子量。
烷基·乙烯基醚用作可选加入的改性剂,以将催化剂改性。烷基·乙烯基醚将钌-碳烯络合物转化为钌-烷氧基碳烯络合物,因此显著降低复分解反应的速率。催化剂与改性剂的摩尔比在1∶1-1∶100之间、最好在1∶1-1∶10之间变化。
催化剂与单体的摩尔比可以在1∶5-1∶100000之间变化,最好在1∶1000-1∶50000之间变化。
按照本发明的方法最好按以下方式进行:通常将单体溶于惰性溶剂中。单体浓度可以为5-60%,浓度最好为5-30%。然后需要时分配链转移剂,然后分配催化剂。该反应的进行没有明显的放热效应。反应时间可以变化,为几分钟至几个小时。然后需要时加入改性剂。聚合溶液可选地用与聚合期间相同的溶剂或用另一惰性溶剂稀释为1-50%的浓度,最好为5-30%的浓度,然后在高压釜中氢化。氢化时间可以为1-24小时。
氢化产物可以用已知方法分离,例如通过用低级脂族醇从聚合物溶液中沉淀,或通过将聚合物溶液导入热水中(汽提)进行分离。
聚合和氢化都可以例如在搅拌槽级联中或在反应挤塑机中分批进行或连续进行。
按照本发明的氢化ROMP聚合物的重均分子量(通过用聚苯乙烯校准的凝胶渗透色谱测定)为5000-1000000,最好为5000-150000。分子量取决于加工参数,特别是取决于单体/催化剂之比和单体/链转移剂之比,通过改变这些参数,可以将分子量调至所需值。
按照本发明方法的产物的催化剂残留物含有特别低。大多数应用不再需要纯化。需要时,通过将氢化产物与有机酸/无机酸(诸如甲酸、乙酸、丙酸和盐酸等)接触,或与活性固体吸收剂(诸如硅胶、硅藻土、活性炭或氧化铝等)接触,可以有效地除去微量的元素(诸如氯、钌和磷等)。
与现有技术相比,按照本发明的方法的特殊区别在于,
1.它只需要一种催化剂成分,
2.它在单体中耐受许多极性溶剂,
3.所得产物的金属残留物含量特别低,使得大多数应用不需要单独的纯化阶段。
通过以下实施例说明本发明,但本发明不限于这些实施例。实施例:实施例1:
由2-降冰片烯制备的氢化开环复分解聚合物
于室温、氮气下,将4.7g(50mmol)2-降冰片烯、58mg(0.5mmol)1,4-二甲氧基-顺-2-丁烯在15ml甲苯中的溶液滴加到1ml(0.01mmol)0.01M的氯化双(三环己基膦)-亚苯基钌的甲苯溶液和10ml甲苯的混合物中。将反应混合物再搅拌3小时,用0.2ml乙基·乙烯基醚终止聚合。产生的粘性溶液用50ml甲苯稀释,于120℃、50巴的氢气压下氢化12小时。将反应混合物冷却至室温,将该溶液滴加到甲醇中。抽滤和干燥后,获得4.7g聚合物。1H和13C-NMR表明,90%的烯双键被氢化。实施例2:
由7-甲基-7-甲酯基四环十二碳烯制备的氢化开环复分解聚合物
于室温、氮气下,将27.8g(120mmol)7-甲基-7-甲酯基四环十二碳烯、14mg(0.6mmol)1-己烷在100ml四氢呋喃中的溶液滴加到33mg(0.04mmol)氯化双(三环己基膦)-亚苯基钌在30ml四氢呋喃中的溶液中。将反应混合物再搅拌3小时,用0.2ml乙基·乙烯基醚终止聚合。产生的粘性溶液用500ml四氢呋喃稀释,于120℃、50巴的氢气压下氢化12小时。将反应混合物冷却至室温,将该溶液滴加到甲醇中。抽滤和干燥后,获得26g聚合物,其重均分子量为96700,其数均分子量为41500(通过用聚苯乙烯校准的凝胶渗透色谱测定)。1H和13C-NMR表明,96%的烯双键被氢化。实施例3:
由7-亚乙基四环十二碳烯制备的氢化开环复分解聚合物
于室温、氮气下,将4.52g(24.3mmol)7-亚乙基四环十二碳烯、11mg(0.12mmol)烯丙基·乙基醚在5ml甲苯中的溶液滴加到20mg(0.024mmol)氯化双(三环己基膦)-亚苯基钌在30ml甲苯中的溶液中。将反应混合物再搅拌3小时,用0.2ml乙基·乙烯基醚终止聚合。产生的粘性溶液用200ml甲苯稀释,于120℃、50巴的氢气压下氢化12小时。将反应混合物冷却至室温,将该溶液滴加到甲醇中。抽滤和干燥后,获得4.3g聚合物,其重均分子量为122000,其数均分子量为48100(通过用聚苯乙烯校准的凝胶渗透色谱测定)。1H和13C-NMR表明,多于98%的烯双键被氢化。
通过将粗产物溶于二甲苯中,将该溶液与20g硅藻土混合,回流搅拌悬浮液30分钟,抽滤温悬浮液,在甲醇中再沉淀聚合物,纯化粗产物。比较例1:
由7-亚乙基四环十二碳烯制备的氢化开环复分解聚合物
(1)将3.8ml(3.8mmol)1M的三乙基铝、1.4ml(10mmol)三乙
胺和1.0ml(1.0mmol)1M的四氯化钛的甲苯溶液,按所述
顺序加入22.3g(120mmol)的7-亚乙基四环十二碳烯、2ml
(1mmol)0.5M 1-己烷的甲苯溶液和110ml甲苯的混合物
中。将反应混合物再搅拌3小时,用1ml甲醇终止聚合。
将产生的粘性溶液滴加到甲醇中。通过在真空下抽滤和干
燥,取出沉淀的产物。获得22g聚合物,其重均分子量为
79700,其数均分子量为35100。
(2)在高压釜中,将阶段(1)获得的22g产物溶于200ml甲苯
中。高压釜备有惰性氮气氛围。加入50mg
RuH2(CO)(Ph3)3,混合物于120℃、50巴的氢气压下氢化
12小时。将反应混合物冷却至室温,将该溶液滴加到甲醇
中。抽滤和干燥后,获得21.4g聚合物。1H和13C-NMR
表明,多于98%的烯双键被氢化。实施例4:
于室温、氮气下,将1.9g(16mmol)5-氰基-2-降冰片烯和3.84mg(24mmol)的四环十二碳烯在5ml甲苯中的溶液滴加到33mg(0.04mmol)氯化双(三环己基膦)-亚苯基钌在25ml甲苯中的溶液中。将反应混合物再搅拌6小时,用0.2ml乙基·乙烯基醚终止聚合。产生的粘性溶液用200ml甲苯稀释,于120℃、50巴的氢气压力下氢化12小时。将反应混合物冷却至室温,将该溶液滴加到甲醇中。抽滤和干燥后,获得4.8g聚合物,其重均分子量为33700,其数均分子量为9100(通过用聚苯乙烯校准的凝胶渗透色谱测定)。1H和13C-NMR表明,多于98%的烯双键被氢化,并且保留氰基基团。比较例2:
由5-氰基-2-降冰片烯与四环十二碳烯(摩尔比为40∶60)制备的氢化开环复分解共聚物
(1)将3.97g(10mmol)氯化钨(VI)在氮气下溶于70ml甲苯中。
将2.36g(20mmol)乙醛/二乙基乙缩醛在30ml甲苯中的溶
液于20-25℃下,滴加到该溶液中,同时进行搅拌。将如
此生成的氯化氢在3小时内用氮气干蒸汽吹扫。产生的溶
液中的钨含量大约为0.1mol/L。
(2)将阶段(1)获得的3.3ml(0.33mmol)催化剂溶液和1.3ml
(2.3mmol)1.8M的氯化二乙基铝的甲苯溶液加入4.76g(40
mmol)的5-氰基降冰片烯、2ml(1mmol)的0.5M烯丙基·
乙基醚的二氯甲烷溶液和80ml四氢呋喃的混合物中。然后
在2小时内,滴加9.6g(60mmol)的四环十二碳烯的40ml
四氢呋喃溶液。将反应混合物再搅拌3小时,用1ml甲醇
终止聚合。产生的粘性溶液含有大约12g聚合物/100ml,
可以用于氢化。将该溶液滴加到甲醇中,以分离聚合物。
通过在真空下抽滤和干燥,取出沉淀的产物。获得13.7g
聚合物,其重均分子量为30800,其数均分子量为12600(通
过用聚苯乙烯校准的凝胶渗透色谱测定)。
(3)将阶段(2)获得的溶液(大约120ml)导入备有机械搅拌器的
高压釜中。高压釜备有惰性氯气氛围。加入50mg
RuHCl(CO)(P(C6H5)3)3,并导入氢气。将温度升至120℃,
同时进行搅拌。在该温度下,压力为50巴。反应混合物在
该温室下搅拌10小时。将反应混合物冷却至室温,将该溶
液滴加到甲醇中。抽滤和干燥后,获得12.5g聚合物。1H
和13C-NMR表明,超过98%的烯双键被氢化,并且保留氰
基基团。
Claims (5)
1.使用通式(I)的钌-碳烯络合物作为聚合阶段催化剂,由环烯烃生产氢化开环复分解(共)聚合物的方法,其中该催化剂可选地在聚合后,通过加入改性剂进行改性,聚合产物作为溶液(可选用与用聚合期间相同的惰性溶剂或用另一惰性溶剂稀释)氢化,不加入额外的氢化催化剂,温度为0-200℃,氢气压为2-200巴,其中至少60%的烯双键被饱和,其中R1和R2相互独立,是指氢、C2-C20链烯基、C1-C20烷基、芳基、C1-C20
羧酸根、C1-C20烷氧基、C2-C20链烯氧基、芳氧基、C2-C20烷氧
羰基、C1-C20烷巯基,它们可以可选地被C1-C5烷基、卤素、C1-C5
烷氧基取代,或被可选地被C1-C5烷基、卤素、C1-C5烷氧基取代
的苯基取代;X1和X2相互独立,是指任何所需的阴离子配位体;L1和L2相互独立,是指任何所需的中性电子给体,
此外,X1、X2、L1和L2中的2个或3个可以一起形成一个多配
位基螯合配位体。
2.权利要求1的方法,其中催化剂是通式(I)的钌-碳烯络合物,其中R1和R2相互独立,是指氢、甲基、乙基、苯基、可选地被甲基、乙基或苯基取代的乙烯基;X1和X2相互独立,是指Cl、Br;L1和L2相互独立,是指三甲基膦、三乙基膦、三苯基膦或三环己基膦。
3.权利要求1的方法,其中所用的单体为具有至少一个降冰片烯亚结构的多环环应变烯烃,可以含有卤素、氰基、羧酸酯、羧酰胺、羧酸酐、羧酰亚胺、醚氧基、羰基等
4.权利要求1的方法,其中所用的单体或单体组合物选自
2-降冰片烯,
5-甲酯基-2-降冰片烯,
5-甲基-5-甲酯基-2-降冰片烯,
5-氰基-2-降冰片烯,
5-甲基-5-氰基-2-降冰片烯,
5,5-二氰基-2-降冰片烯,
1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6-甲基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6-甲基-6-甲酯基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6-甲酯基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6-氰基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6-乙基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6-亚乙基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
6,7-二甲基-1,4,5,8-二桥亚甲基-1,4,4a,5,6,7,8,8a-八氢萘,
二环戊二烯,
三环戊二烯,
四环戊二烯,
1,4-二桥亚甲基-1,4,4a,9a-四氢芴。
5.权利要求1的方法,其中至少95%的烯双键被饱和。
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DE196540747 | 1996-12-23 | ||
DE19654074A DE19654074C2 (de) | 1996-12-23 | 1996-12-23 | Verfahren zur Herstellung hydrierter ringgeöffneter Metathesepolymeren |
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US (1) | US5932664A (zh) |
EP (1) | EP0850966B1 (zh) |
JP (1) | JPH10195182A (zh) |
KR (1) | KR19980064464A (zh) |
CN (1) | CN1186080A (zh) |
DE (2) | DE19654074C2 (zh) |
ES (1) | ES2151219T3 (zh) |
TW (1) | TW460501B (zh) |
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-
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- 1996-12-23 DE DE19654074A patent/DE19654074C2/de not_active Expired - Fee Related
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1997
- 1997-12-03 TW TW086118130A patent/TW460501B/zh not_active IP Right Cessation
- 1997-12-10 EP EP97121708A patent/EP0850966B1/de not_active Expired - Lifetime
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- 1997-12-10 ES ES97121708T patent/ES2151219T3/es not_active Expired - Lifetime
- 1997-12-16 US US08/991,721 patent/US5932664A/en not_active Expired - Fee Related
- 1997-12-17 JP JP9363779A patent/JPH10195182A/ja active Pending
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Cited By (4)
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CN104822769B (zh) * | 2012-12-07 | 2017-09-29 | 太阳控股株式会社 | 交联型树脂组合物、固化物及其制造方法 |
CN110776618A (zh) * | 2019-11-15 | 2020-02-11 | 无锡阿科力科技股份有限公司 | 一种环烯烃共聚物及其制备方法和应用 |
CN110776618B (zh) * | 2019-11-15 | 2022-06-10 | 无锡阿科力科技股份有限公司 | 一种环烯烃共聚物及其制备方法和应用 |
CN115386044A (zh) * | 2021-05-21 | 2022-11-25 | 中国石油化工股份有限公司 | 酯基改性三元乙丙橡胶及其制备方法 |
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TW460501B (en) | 2001-10-21 |
DE59702344D1 (de) | 2000-10-19 |
EP0850966B1 (de) | 2000-09-13 |
JPH10195182A (ja) | 1998-07-28 |
US5932664A (en) | 1999-08-03 |
EP0850966A1 (de) | 1998-07-01 |
ES2151219T3 (es) | 2000-12-16 |
DE19654074C2 (de) | 2001-01-25 |
DE19654074A1 (de) | 1998-06-25 |
KR19980064464A (ko) | 1998-10-07 |
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