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公开(公告)号：US5652304A
公开(公告)日：1997-07-29
申请号：US663803
申请日：1996-06-28
IPC分类号： B01J8/10 , B01J8/24 , B01J8/36 , C08F2/06 , C08F2/34 , C08F4/64 , C08F4/70 , C08F36/04 , C08F136/04 , C08F136/06 , C08F136/08 , G09F13/28 , G09F21/06
CPC分类号： B01J8/1827 , B01J8/10 , B01J8/24 , B01J8/36 , C08F136/04 , C08F136/06 , C08F136/08 , C08F36/04 , G09F13/28 , G09F21/06 , B01J2208/00256 , B01J2208/00274 , B01J2219/00108 , B01J2219/182 , Y10S526/901 , Y10S526/903
摘要： By utilizing the vapor phase polymerization techniques of the present invention, numerous distinct and highly beneficial advantages are realized. For instance, cis-1,4-polyisoprene rubber and high cis-1,4-polybutadiene rubber having a consistent and controllable molecular weight can be easily and practically prepared without utilizing a solvent. The subject invention more specifically discloses a method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of:(1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride, preferably in the presence of at least one ether; wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure;(2) allowing said isoprene to polymerize into cis-1,4-polyisoprene at a temperature within the range of about 35.degree. C. to about 70.degree. C.; and(3) withdrawing said cis-1,4-polyisoprene from said reaction zone. It has been determined that gel formation can be reduced by conducting the polymerization of isoprene monomer in the presence of a diarylamine, such as para-styrenated diphenylamine.
摘要翻译： 通过利用本发明的气相聚合技术，实现了许多显着和非常有益的优点。 例如，具有一致和可控分子量的顺式-1,4-聚异戊二烯橡胶和高顺式-1,4-聚丁二烯橡胶可以在不使用溶剂的情况下容易且实际地制备。 本发明更具体地公开了一种将异戊二烯气相聚合成顺式-1,4-聚异戊二烯的方法，包括以下步骤：（1）将反应区中的所述异戊二烯和预制的催化剂体系装入反应区， 有机铝化合物与四氯化钛，优选在至少一种醚存在下进行; 其中所述异戊二烯通过温度和压力的适当组合保持在所述反应区中的气相中; （2）允许所述异戊二烯在约35℃至约70℃的温度范围内聚合成顺式-1,4-聚异戊二烯; 和（3）从所述反应区中取出所述顺式-1,4-聚异戊二烯。 已经确定通过在二芳基胺如对苯二甲酸二苯胺存在下进行异戊二烯单体的聚合可以降低凝胶形成。
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公开(公告)号：US5834573A
公开(公告)日：1998-11-10
申请号：US859984
申请日：1997-05-21
IPC分类号： C08F4/70 , C08F136/06
CPC分类号： C08F136/06 , Y10S526/907
摘要： By utilizing the techniques of this invention, trans-1,4-polybutadiene can be synthesized continuously to a high level of conversion utilizing a low level of a highly active cobalt-based catalyst system. The trans-1,4-polybutadiene made with the cobalt-based catalyst system of this invention also typically has a molecular weight which is acceptable for use in tire applications without the need for employing a molecular weight regulator. It is also not typically necessary to utilize a gel inhibitor, such as carbon disulfide, in the polymerizations of this invention. Since a low level of residual cobalt is present in the trans-1,4-polybutadiene which is made utilizing the catalyst system of this invention, it is much more stable than trans-1,4-polybutadiene made with standard cobalt-based catalyst systems. This invention specifically relates to a process for synthesizing trans-1,4-polybutadiene by polymerizing 1,3-butadiene monomer in the presence of a catalyst system which is comprised of cobalt (III) acetylacetonate, an organoaluminum compound and a para-alkyl-substituted phenol, wherein the cobalt (III) acetylacetonate is mixed with the para-substituted phenol prior to the polymerization. Such polymerizations can be conducted on a batch or a continuous basis.
摘要翻译： 通过利用本发明的技术，反式-1,4-聚丁二烯可以利用低水平的高活性钴基催化剂体系连续合成至高转化率。 用本发明的钴基催化剂体系制备的反式1,4-聚丁二烯也通常具有可用于轮胎应用中的分子量，而不需要使用分子量调节剂。 在本发明的聚合中通常也不需要使用凝胶抑制剂，例如二硫化碳。 由于使用本发明的催化剂体系制备的反式1,4-聚丁二烯中存在低水平的残余钴，因此它比用标准钴基催化剂体系制备的反式1,4-聚丁二烯更稳定 。 本发明具体涉及通过在催化剂体系存在下聚合1,3-丁二烯单体来合成反式1,4-聚丁二烯的方法，所述催化剂体系由乙酰丙酮钴（III），有机铝化合物和对位烷基 - 取代的苯酚，其中在聚合之前将乙酰丙酮钴（III）与对位取代的苯酚混合。 这种聚合可以分批或连续进行。
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3.发明授权Synthesis of cis-1,4-polybutadiene rubber in presence of cobalt containing catalyst system 失效在含钴催化剂体系的存在下合成顺式-1,4-聚丁二烯橡胶
公开(公告)号：US5811499A
公开(公告)日：1998-09-22
申请号：US944399
申请日：1997-10-06
IPC分类号： C08F4/60 , C08F4/70 , C08F36/06 , C08F136/06
CPC分类号： C08F136/06 , Y10S526/903
摘要： It has been determined that 1,3-butadiene monomer can be polymerized into cis-l,4-polybutadiene rubber utilizing a cobalt-based catalyst system which is comprised of (a) an organocobalt compound, (b) a trialkylaluminum compound and (c) hexafluoro-2-propanol. The use of this catalyst system results in extremely fast rates of polymerization. The molecular weight of the cis-1,4- polybutadiene rubber made utilizing this cobalt-based catalyst system can be regulated by conducting the polymerization in the presence of 1,5-cyclooctadiene. This present invention more specifically discloses a catalyst system which is particularly useful for polymerizing 1,3-butadiene monomer into cis-1,4-polybutadiene, said catalyst system being comprised of (a) an organocobalt compound, (b) a trialkylaluminum compound and (c) hexafluoro-2-propanol. The subject invention further discloses a process for synthesizing cis-1,4-polybutadiene rubber which comprises polymerizing 1,3-butadiene in the presence of (a) an organocobalt compound, (b) a trialkylaluminum compound and (c) hexafluoro-2-propanol.
摘要翻译： 已经确定，使用钴基催化剂体系，可以将1,3-丁二烯单体聚合成顺式-1,4-聚丁二烯橡胶，所述钴基催化剂体系包括（a）有机钴化合物，（b）三烷基铝化合物和（c ）六氟-2-丙醇。 使用该催化剂体系导致极快的聚合速率。 使用该钴基催化剂体系制备的顺式-1,4-聚丁二烯橡胶的分子量可以通过在1,5-环辛二烯存在下进行聚合来调节。 本发明更具体地公开了一种特别可用于将1,3-丁二烯单体聚合成顺式-1,4-聚丁二烯的催化剂体系，所述催化剂体系包括（a）有机钴化合物，（b）三烷基铝化合物和 （c）六氟-2-丙醇。 本发明还公开了一种合成顺式-1,4-聚丁二烯橡胶的方法，该方法包括在（a）有机钴化合物，（b）三烷基铝化合物和（c）六氟-2- 丙醇。
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公开(公告)号：US06617406B2
公开(公告)日：2003-09-09
申请号：US09943155
申请日：2001-08-30
IPC分类号： C08F470
CPC分类号： C08F136/06 , C08F4/7096
摘要： This invention is based upon the unexpected discovery that elastomeric trans-1,4-polybutadiene can be made by utilizing a catalyst system that is comprised of an organocobalt compound, an organoaluminum compound, a para-alkyl substituted phenol, and ortho-phenyl phenol wherein the molar ratio of the para-substituted phenol to the organoaluminum compound is within the range of about 1.2:1 to about 1.8:1, and wherein the molar ratio of the ortho-phenyl phenol to the organoaluminum compound is within the range of about 0.7:1 to about 1.3:1. Accordingly, the elastomeric trans-1,4-polybutadiene made by the process of this invention does not need to be heated, such as in a hot-house, before being used in making rubber stocks.
摘要翻译： 本发明基于意想不到的发现，即弹性体反式-1,4-聚丁二烯可以通过利用由有机钴化合物，有机铝化合物，对位烷基取代的苯酚和邻苯基苯酚组成的催化剂体系来制备，其中 对位取代的酚与有机铝化合物的摩尔比在约1.2:1至约1.8:1的范围内，并且其中邻苯基苯酚与有机铝化合物的摩尔比在约0.7的范围内 ：1至约1.3：1。 因此，通过本发明的方法制备的弹性体反式1,4-聚丁二烯在用于制造橡胶原料之前不需要例如在热房中加热。
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公开(公告)号：US6066705A
公开(公告)日：2000-05-23
申请号：US850314
申请日：1997-05-02
IPC分类号： B01J8/10 , B01J8/24 , B01J8/36 , C08F2/06 , C08F2/34 , C08F4/64 , C08F4/70 , C08F36/04 , C08F136/04 , C08F136/06 , C08F136/08 , G09F13/28 , G09F21/06
CPC分类号： B01J8/1827 , B01J8/10 , B01J8/24 , B01J8/36 , C08F136/04 , C08F136/06 , C08F136/08 , C08F36/04 , G09F13/28 , G09F21/06 , B01J2208/00256 , B01J2208/00274 , B01J2219/00108 , B01J2219/182 , Y10S526/901 , Y10S526/903
摘要： By utilizing the vapor phase polymerization techniques of the present invention, numerous distinct and highly beneficial advantages are realized. For instance, cis-1,4-polyisoprene rubber and high cis-1,4-polybutadiene rubber having a consistent and controllable molecular weight can be easily and practically prepared without utilizing a solvent. The subject invention more specifically discloses a method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of:(1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride, preferably in the presence of at least one ether; wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure;(2) allowing said isoprene to polymerize into cis-1,4-polyisoprene at a temperature within the range of about 35.degree. C. to about 70.degree. C.; and(3) withdrawing said cis-1,4-polyisoprene from said reaction zone. It has been determined that gel formation can be reduced by conducting the polymerization of isoprene monomer in the presence of a diarylamine, such as para-styrenated diphenylamine.
摘要翻译： 通过利用本发明的气相聚合技术，实现了许多显着和非常有益的优点。 例如，具有一致和可控分子量的顺式-1,4-聚异戊二烯橡胶和高顺式-1,4-聚丁二烯橡胶可以在不使用溶剂的情况下容易且实际地制备。 本发明更具体地公开了一种将异戊二烯气相聚合成顺式-1,4-聚异戊二烯的方法，包括以下步骤：（1）将反应区中的所述异戊二烯和预制的催化剂体系装入反应区， 有机铝化合物与四氯化钛，优选在至少一种醚存在下进行; 其中所述异戊二烯通过温度和压力的适当组合保持在所述反应区中的气相中; （2）允许所述异戊二烯在约35℃至约70℃的温度范围内聚合成顺式-1,4-聚异戊二烯; 和（3）从所述反应区中取出所述顺式-1,4-聚异戊二烯。 已经确定通过在二芳基胺如对苯二甲酸二苯胺存在下进行异戊二烯单体的聚合可以降低凝胶形成。
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公开(公告)号：US06713565B2
公开(公告)日：2004-03-30
申请号：US10172936
申请日：2002-06-17
申请人： Craig William Burkhart , Michael Lester Kerns , Kenneth Floyd Castner , Michael Joseph Rachita , Michael Paul Mallamaci
发明人： Craig William Burkhart , Michael Lester Kerns , Kenneth Floyd Castner , Michael Joseph Rachita , Michael Paul Mallamaci
IPC分类号： A63B3706
CPC分类号： A63B37/04 , A63B37/0003 , A63B37/0051 , A63B37/0054
摘要： It has been unexpectedly discovered that cis-1,4-polybutadiene that is synthesized utilizing Zeigler-Natta catalyst systems has superior characteristics for utilization in solid golf ball cores if the polymerization is terminated utilizing a carboxylic acid of the structural formula RCOOH, wherein R represents an alkyl group containing from 1 to about 30 carbon atoms.
摘要翻译： 已经意外地发现，使用Zeigler-Natta催化剂体系合成的顺式-1,4-聚丁二烯如果使用结构式RCOOH的羧酸聚合终止，则其具有优异的固体高尔夫球芯的特性，其中R表示 含有1至约30个碳原子的烷基。
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公开(公告)号：US5919876A
公开(公告)日：1999-07-06
申请号：US167600
申请日：1998-10-07
IPC分类号： B01J8/10 , B01J8/24 , B01J8/36 , C08F2/06 , C08F4/649 , C08F36/04 , C08F136/04 , C08F136/06 , C08F136/08
CPC分类号： B01J8/1827 , B01J8/10 , B01J8/36 , C08F136/04 , C08F136/06 , C08F136/08 , C08F36/04 , B01J2208/00256 , B01J2208/00274 , B01J2219/00108 , B01J2219/182
摘要： The synthesis of cis-1,4-polyisoprene by polymerizing isoprene with a catalyst system which is comprised of a titanium tetrahalide, a trialkylaluminum compound and diphenylether is plagued with the formation of gel. This invention is based upon the unexpected discovery that gel formation can be reduced by conducting such polymerizations in the presence of a diarylamine, such as para-styrenated diphenylamine. The subject invention more specifically discloses a process for synthesizing cis-1,4-polyisoprene having a low gel content which comprises polymerizing isoprene in an inert organic solvent with a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrahalide, such as titanium tetrachloride, in the presence of at least one ether, wherein said polymerization is conducted at a temperature which is within the range of about 0.degree. C. to about 100.degree. C., and wherein said polymerization is conducted in the presence of a diarylamine.
摘要翻译： 通过用四卤化钛，三烷基铝化合物和二苯基醚组成的催化剂体系聚合异戊二烯来合成顺式-1,4-聚异戊二烯，形成凝胶。 本发明基于意想不到的发现，即通过在二芳基胺如对苯二甲酸二苯胺存在下进行这种聚合可以降低凝胶形成。 本发明更具体地公开了一种具有低凝胶含量的顺式-1,4-聚异戊二烯的方法，该方法包括在惰性有机溶剂中将异戊二烯与预制的催化剂体系聚合，该催化剂体系是通过使有机铝化合物与四卤化钛 四氯化钛，在至少一种醚的存在下，其中所述聚合在约0℃至约100℃的温度下进行，并且其中所述聚合在二芳基胺 。
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公开(公告)号：US5859156A
公开(公告)日：1999-01-12
申请号：US990251
申请日：1997-12-15
IPC分类号： B01J8/10 , B01J8/24 , B01J8/36 , C08F2/34 , C08F36/04 , C08F136/04 , C08F136/06 , C08F136/08
CPC分类号： B01J8/1827 , B01J8/10 , B01J8/24 , B01J8/36 , C08F136/04 , C08F136/06 , C08F136/08 , C08F36/04 , B01J2208/00256 , B01J2208/00274 , B01J2219/00108 , B01J2219/182 , Y10S526/901 , Y10S526/903
摘要： By utilizing the vapor phase polymerization techniques of the present invention, numerous distinct and highly beneficial advantages are realized. For instance, cis-1,4-polyisoprene rubber and high cis-1,4-polybutadiene rubber having a consistent and controllable molecular weight can be easily and practically prepared without utilizing a solvent. The subject invention more specifically discloses a method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of:(1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride, preferably in the presence of at least one ether; wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure;(2) allowing said isoprene to polymerize into cis-1,4-polyisoprene in said reaction zone at a temperature within the range of about 0.degree. C. to about 100.degree. C. in the presence of a diarylamine, wherein said reaction zone is a horizontal, stirred reactor of substantially circular cross section containing a centrally-located drive shaft extending longitudinally through said reactor to which are attached a plurality of adjacently located paddles, which paddles cause essentially no forward or backward movement of the cis-1,4-polyisoprene contained in said reactor; and(3) withdrawing said cis-1,4-polyisoprene from said reaction zone.
摘要翻译： 通过利用本发明的气相聚合技术，实现了许多显着和非常有益的优点。 例如，具有一致和可控分子量的顺式-1,4-聚异戊二烯橡胶和高顺式-1,4-聚丁二烯橡胶可以在不使用溶剂的情况下容易且实际地制备。 本发明更具体地公开了一种将异戊二烯气相聚合成顺式-1,4-聚异戊二烯的方法，包括以下步骤：（1）将反应区中的所述异戊二烯和预制的催化剂体系装入反应区， 有机铝化合物与四氯化钛，优选在至少一种醚存在下进行; 其中所述异戊二烯通过温度和压力的适当组合保持在所述反应区中的气相中; （2）在二芳基胺的存在下，使所述异戊二烯在所述反应区中在约0℃至约100℃的温度范围内聚合成顺式-1,4-聚异戊二烯，其中所述反应区为 一个基本圆形横截面的水平搅拌的反应器，其包含一个中心定位的驱动轴，其纵向延伸穿过所述反应器，所述反应器附接有多个相邻的桨叶，该桨叶基本上不引起顺式-1,4- 所述反应器中含有的聚异戊二烯; 和（3）从所述反应区中取出所述顺式-1,4-聚异戊二烯。
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公开(公告)号：US06310152B1
公开(公告)日：2001-10-30
申请号：US09694977
申请日：2000-10-24
IPC分类号： C08F470
CPC分类号： C08F136/06 , C08F4/7096
摘要： This invention is based upon the unexpected discovery that elastomeric trans-1,4-polybutadiene can be made by utilizing a catalyst system that is comprised of an organocobalt compound, an organoaluminum compound, a para-alkyl substituted phenol, and ortho-phenyl phenol wherein the molar ratio of the para-substituted phenol to the organoaluminum compound is within the range of about 1.2:1 to about 1.8:1, and wherein the molar ratio of the ortho-phenyl phenol to the organoaluminum compound is within the range of about 0.7:1 to about 1.3:1. Accordingly, the elastomeric trans-1,4-polybutadiene made by the process of this invention does not need to be heated, such as in a hot-house, before being used in making rubber stocks. This invention more specifically discloses a process for synthesizing elastomeric trans-1-4-polybutadiene by polymerizing 1,3-butadiene monomer in the presence of a catalyst system that is comprised of an organocobalt compound, an organoaluminum compound, a para-alkyl substituted phenol, and ortho-phenyl phenol, wherein the molar ratio of the para-substituted phenol to the organoaluminum compound is within the range of about 1.2:1 to about 1.8:1, and wherein the molar ratio of the ortho-phenyl phenol to the organoaluminum compound is within the range of about 0.7:1 to about 1.3:1.
摘要翻译： 本发明基于意想不到的发现，即弹性体反式-1,4-聚丁二烯可以通过利用由有机钴化合物，有机铝化合物，对位烷基取代的苯酚和邻苯基苯酚组成的催化剂体系来制备，其中 对位取代的酚与有机铝化合物的摩尔比在约1.2:1至约1.8:1的范围内，并且其中邻苯基苯酚与有机铝化合物的摩尔比在约0.7的范围内 ：1至约1.3：1。 因此，通过本发明的方法制备的弹性体反式1,4-聚丁二烯在用于制造橡胶原料之前不需要例如在热房中加热。 本发明更具体地公开了一种通过在催化剂体系存在下聚合1,3-丁二烯单体来合成弹性体反式-4-聚丁二烯的方法，所述催化剂体系由有机钴化合物，有机铝化合物，对 - 烷基取代的苯酚 和邻苯基苯酚，其中对位取代的酚与有机铝化合物的摩尔比在约1.2:1至约1.8:1的范围内，并且其中邻苯基苯酚与有机铝的摩尔比 化合物在约0.7:1至约1.3:1的范围内。
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公开(公告)号：US06284844B1
公开(公告)日：2001-09-04
申请号：US09259912
申请日：1999-03-01
IPC分类号： C08F13606
CPC分类号： C08F136/06 , C08K5/09 , C08F4/7096 , C08L9/00
摘要： Syndiotactic 1,2-polybutadiene is a thermoplastic resin which has double bonds attached in an alternating fashion to its polymeric backbone. Films, fibers and molded articles can be made utilizing syndiotactic 1,2-polybutadiene. It can also be blended into rubbers and cocured therewith. It is generally preferred to synthesize syndiotactic 1,2-polybutadiene in an aqueous medium by suspension or emulsion polymerization utilizing a cobalt-based catalyst system. This invention is based upon the unexpected finding that certain substituted benzoic acids can be employed to deactivate such cobalt based catalyst systems. This invention more specifically discloses a process for synthesizing and deactivating syndiotactic 1,2-polybutadiene which comprises (1) polymerizing 1,3-butadiene monomer in the aqueous medium in the presence of a catalyst system which is comprised of (a) transition metal compound, (b) an organoaluminum compound and (c) at least one member selected from the group consisting of carbon disulfide, phenyl isothiocyanate and xanthic acid to produce an aqueous medium which contains the syndiotactic 1,2-polybutadiene; and (2) subsequently adding a substituted benzoic acid to the aqueous medium which contains the syndiotactic 1,2-polybutadiene to deactivate the catalyst system.
摘要翻译： 间同立构1,2-聚丁二烯是一种热塑性树脂，其具有以其聚合物主链交替形式连接的双键。 膜，纤维和模塑制品可以利用间同立构1,2-聚丁二烯制备。 它也可以混合到橡胶中并与其共混。 通常优选通过使用钴基催化剂体系的悬浮或乳液聚合在水性介质中合成间规1,2-聚丁二烯。 本发明基于意想不到的发现，可以使用某些取代的苯甲酸来使这种基于钴的催化剂体系失活。 本发明更具体地公开了间同立构1,2-聚丁二烯的合成和失活的方法，其包括（1）在催化剂体系存在下，在水性介质中聚合1,3-丁二烯单体，所述催化剂体系包含（a）过渡金属化合物 ，（b）有机铝化合物和（c）选自二硫化碳，异硫氰酸苯酯和黄原酸中的至少一种，以产生含有间同立构1,2-聚丁二烯的水性介质; 和（2）随后将含取代苯甲酸加入到含有间同立构1,2-聚丁二烯的水性介质中以使催化剂体系失活。
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