CN1133298A - 气相聚合方法 - Google Patents
气相聚合方法 Download PDFInfo
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- CN1133298A CN1133298A CN95115846A CN95115846A CN1133298A CN 1133298 A CN1133298 A CN 1133298A CN 95115846 A CN95115846 A CN 95115846A CN 95115846 A CN95115846 A CN 95115846A CN 1133298 A CN1133298 A CN 1133298A
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- polymeric segment
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/34—Polymerisation in gaseous state
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
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- A61P25/06—Antimigraine agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P9/00—Drugs for disorders of the cardiovascular system
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1818—Feeding of the fluidising gas
- B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1872—Details of the fluidised bed reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/14—Monomers containing five or more carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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Abstract
本发明提出在气相反应器中制备聚合物的方法,其中将单体物流和气体连续引入聚合反应区,同时将聚合反应区的温度保持在该聚合反应区中存在的至少一种单体的露点温度以下。
Description
本发明涉及一种新的气相法,此方法能可使用液态单体进行有效聚合反应的另一气相方法。
用于生产聚合物,特别是聚烯烃聚合物的气相流化床和搅拌反应器方法的发现,使有可能生产非常理想并改进性能的各种各样的新聚合物。用于生产此类聚合物的这些气相方法,特别是气相流化床方法,与其它常规方法相比,提供一种基本投资费用大幅度降低,并且显著节约能量消耗的生产聚合物的方法。
在常规的气相流化床方法中,将含有一种或多种单体的气态流通入含有在聚合段正在生长的聚合物颗粒床的流化床反应器中,同时将聚合催化剂连续或间歇加入聚合段。所需的聚合物产品全用周知的技术自聚合段卸出、脱气、稳定和包装以便装运。由于聚合反应是放热的,在聚合段产生的大量热必须移走,以防止聚合物颗粒过热和熔融在一起。这是通过将未反应的热气体从聚合段中连续移走,并用较冷的气体代替而实现的。将从聚合段移出的热气体压缩,并在热交换器中冷却、另外补充一定量的单体以取代已聚合的和从反应段中移走的单体,然后循环入反应器底部。循环气体的冷却可在一个或多个热交换器中完成。压缩和冷却顺序根据设计进行选择,但通常优选在冷却之前使热气体压缩。气体流入和流出反应器的流速保持到使聚合物颗粒床维持流化状态的水平。在搅拌床反应器中生产聚合物很相似,主要区别在于所使用的有助于保持聚合物床处于流化状态的机械搅拌装置。
常规的气相流化床树脂生产在现有技术中是众所周知的,例如,在美国专利4379758、4383095和4876320中公开的,这里作为参考被引入。
在气相搅拌反应器中生产聚合物物质在现有技术中也是众所周知的,通过在美国专利3256263中描述的方法和设备来举例说明。
多年来,人们误认为使任何种类的液体进入气相反应器的聚合段将不可避免导致树脂颗粒的附聚、形成大块状聚合物并最终使反应器完全停止运转。基于此,使得气相聚合物生产者小心翼翼避免将进入反应器的循环气流冷却至温度低于聚合反应中使用的任何单体的冷凝温度。
共聚单体如己烯-1、4-甲基戊烯和辛烯-1用于生产乙烯共聚物-聚合物特别有价值。这些较高级α-烯烃具有相当高的冷凝温度。由于人们认为在聚合段的液态单体将导致附聚、结块甚至最终使反应器停止运转,与从聚合段移走热的速度有关的生产速率受到认为需要保持进入反应器的循环气流的温度总高于存在于循环气流中的沸点最高的单体的冷凝温度严格限制。
甚至对于在搅拌反应器中进行聚合反应的情况,也要仔细操作以保持树脂床温高于循环气体流组分的冷凝温度。
为了最大限度地移走热,通常将液体喷雾入或注入聚合物床中或聚合床上,于此液体通过暴露于较热的循环气体流中立即闪蒸为气体状态。用此技术因Joules-Thompson效应实现了有限量的辅助冷却,但并未将循环气体流冷却到可能发生冷凝的程度。此方法通常包含先分别将循环气体流部分冷却为液态单体贮存,然后再分别加入聚合床中或床上的繁琐并且耗能的步骤。这种方法的例子可在美国专利3254070、3300457、3652527和4012573中找到。
后来发现,与人们长期坚持认为的在循环气体流中存在液体会导致附聚和反应器停止运转相反,完全有可能将整个循环气体流冷却至出现大量单体冷凝的温度,当这些液体在与循环气体流平衡的温度下加入反应器中时不会出现想象的可怕结果。冷却整个循环气体使其在相互平衡温度下生成气-液两相混合物,以便在气体流中含有的液体不会立即闲蒸为蒸汽。取而代之的是由于气体和液体总物料都在比以前认为的可能温度显著低的温度下进入聚合段,会产生大量的冷却。此方法对于气相法,特别是使用冷凝温度相当低的共聚单体所生产的聚合物的产率有显著改进。这种方法,通常称为″冷凝模式″操作,在美国专利4543399和4588790中进行了详细描述,这里作为参考被引入。在冷凝模式操作中,将进入聚合段的气液两相混合物十分迅速加热并在进入聚合段后在很短距离内完全汽化。甚至在最大的工业反应器中,所有液体进入聚合段后不久即被完全汽化;接着所有气态循环气流的温度受聚合反应的放热性显著升高。以冷凝模式操作气相反应器的能力被认为有可能由于进入伴有有效恒定返混流化床的反应器中的气液两相流体比两相汽液体循环流进入处之上较短距离内的更迅速加热,在聚合物床中没有液体存在。
我们现在已发现液态单体可以存在于遍及整个聚合物床中,条件是存在于床中的液态单体被吸附在存在于床中的固体颗粒物料上或吸收入固体颗粒物料中,例如这些颗粒物料为存在于床中的生产出来的聚合物或流化助剂,只要进入聚合段处之上短距离内(与冷凝模式操作一样)没有相当大量的游离单体存在。此发现使得有可能在气相反应器中,用冷凝温度比在气相反应器中生产常规聚烯烃的温度高得多的单体生产聚合物。本发明有可能用气相法生产各种以前认为不能用连续气相法生产的聚合物。
虽然本发明不限于任何特定类型或种类聚合反应,但本发明特别适于烯烃聚合反应,包括沸点相当高的单体的均聚反应和共聚反应。
能够进行烯烃聚合反应的沸点较高的单体的例子如下:
A.分子量较高的α烯烃如癸烯-1、十二碳烯-1等和苯乙烯。
B.二烯烃如己二烯、乙烯基环己烯、双环戊二烯、丁二烯、异丁烯、异戊二烯、亚乙基降冰片烯等等。
C.极性乙烯基单体如丙烯腈、马来酸酯、醋酸乙烯酯、丙烯酸酯、甲基丙烯酸酯、乙烯基三烷基硅烷等等。
这些沸点较高的单体可根据本发明,使用惰性气体作为循环于反应器中气液两相混合物的气态组分进行均聚。用于此目的合适的惰性物质包括氮气和在温度低于选取的在聚合段保持的温度下维持气态的饱和烃。
沸点较高的单体还可与一种或多种沸点较低的单体如乙烯、丙烯和丁烯及上面提到的那些沸点较高的其它单体共聚,唯一要求是沸点较高的单体与至少一种沸点较低的单体或惰性物质的冷凝温度之间有明显差别,这样可使循环气体流中存在足够的气体以使进行切实可行的、状态稳定的连续操作。
根据我们的发明,沸点较高的单体可直接加入聚合反应段或与循环气流一起载入聚合反应段。
本发明的实施不限于任何特定类型或种类的催化剂。任何用于进行气相聚合反应的催化剂都适用在本发明的实施中。
常规的Ziegler-Natta催化剂,意即那些由烷基金属或金属氢化物与过渡金属盐反应而形成的,优选用于实施本发明。其中由烷基铝与周期表中第I族至III族金属的盐反应形成的催化剂特别有用。
可用于实施本发明的催化剂举例说明如下:
A.钛基催化剂,如在美国专利4376062、4379758中所叙述的。
B.铬基催化剂,如在美国专利3709853、3709954和4077904中所叙述的。
C.钒基催化剂,如氯氧化钒、乙酰丙酮钒。
D.金属茂催化剂,如在美国专利4530914、4665047、4752597、5218071、5272236和5278272中所叙述的。
E.阳离子型金属卤化物,如三卤化铝。
本发明中特别适于生产聚合物物料的流化床反应体系在附图中进行说明。图标中,反应器10由反应段12和速度降低段14组成。
通常,反应段的高度与直径之比可在约2.7∶1至约4.6∶1范围内变化。当然此范围可以变到较大的或较小的比例,并且取决于所需的生产量。速度降低段14的截面积通常为约2.6至约2.8乘以反应段12的截面积的范围内。
反应段12包括一正在生长的聚合物颗粒、形成的聚合物颗粒和少量催化剂的床,该床被以补充进料形式的可聚合的和改性气体组分及通过反应段的循环流体连续流动而流化。为保持一个能生存的流化床,通过流化床的表面气体速度必须超过流化所需的最小流速,优选至少超过最小流速0.1ft/sec。通常表面气体速度不超过5.0ft/sec,并且一般不大于2.5ft/sec就足够了。
床始终含有颗粒以防止形成局部″热点″,并在整个反应段中截留和分配催化剂。开始时,反应器在气体流动之前通常充满一层特定的聚合物颗粒。这些颗粒可与要形成的聚合物种类相同或不同。当不同时,它们作为第一批产品与形成的所需聚合物颗粒一起卸出。最终,所需聚合物颗粒的流化床取代初始床。
在流化床中使用的部分或完全活化的前体组成和/或催化剂优选贮存于储罐16中并用对贮存材料惰性的气体,如氮气或氩气覆盖备用。
流化通过流体高速循环流入并流过床实现,通常其流速为补充流体进料速度的50倍。流化床具有各个移动颗粒的紧密物料的一般外观,这是由通过床的气体的渗透造成的。通过床的压力降等于或稍大于床的重量除以截面积。所以它取决于反应器的几何形状。
补充流体在18处加入床中。补充流体的组成由气体分析仪21测定。用气体分析仪21测定循环流的组成,并调节补充流的组成以便反应段中保持基本稳定状态的气体组成。
气体分析仪为常规气体分析仪,可按常规方法操作测定循环流的组成以容易保持进料流组分的比例。此仪器可通过很多途径买到。气体分析仪21通常从位于速度降低段14和热交换器24之间的取样点接收气体。
沸点较高的单体可以各种方式加入反应段,包括通过喷嘴(图中没有表示出)直接注入床中或由位于床上部的喷嘴(未表示出)喷在床的顶部,这样通过循环气流可有助于消除一些夹带的粉尘。如消耗速度相当小,较重的单体可简单地通过悬浮于进入反应器底部的循环气流加入反应段。
为确保完全气化,循环流和(需要时)部分补充流通过循环管线22在床的底部26处回到反应器中。优选在回料处之上设一气体分配器板28,以有助于使床流化。循环流通过床时吸收聚合反应产生的反应热。
在床中未反应的部分流化流从聚合段移去,优选使它通过床上面的速度降低段14,在此处将夹带的颗粒可落回床中。
循环流在压缩机30中被压缩后,在回到床中之前通过热交换段移走热量。热交换段通常为一热交换器24,它可以是卧式或立式类型。如果需要,可使用几个热交换器分步降低循环气流的温度。还有可能将压缩机设在热交换器的下游或几个热交换器之间的中间处。循环流经冷却后从反应器底26回到反应器中并通过气体分配器板28进入流化床。气体折流板32优选安装在反应器入口处以阻止所含的聚合物颗粒沉降出并附聚成固体块料,同时防止液体累积在反应器底部,还有助于循环气流中含液体过程与不含液体过程之间及不含液体过程与含液体过程之间易于转化。适于本发明的气体折流板的例子是在美国专利4933149中所述的设备。
选择的床温通过不断移走反应热在稳定状态条件下保持基本恒温。没有出现明显的温度梯度存在于床的上部分。温度梯度会存在于床底部约6至12英寸厚的层中,此即入口流体温度与床的剩余物的温度之间的梯度。
良好的气体分配对于反应器操作起重要作用。流化床中含有正在生长的和已形成的散式聚合物颗粒及催化剂颗粒。由于聚合物颗粒是热的并且可能有活性,必须防止其沉降,因为如果允许静止物料存在,含在其中的任何活性催化剂都可使反应继续并造成熔化。所以,以足以保持整个床处于流化状态的速度使循环流体扩散通过床是重要的。
气体分配板28是一种实现良好气体分配的优选装置,可以是筛子、长眼筛板、孔板、泡罩型板等等。板的元件都可以是固定的,或可用美国专利3298792中所述的活动型板。无论其如何设计,它必须使循环流体扩散通过床底的颗粒以保持床处于流化状态,同时当反应器停止运转时还应起到支撑树脂颗粒静止床的作用。
优选的气体分配器板28的类型为金属的并具有穿过其表面分布的孔。这些孔直径一般为大约1/2英寸。这些孔延伸过板。在每个孔上设一如36标记的三角形角铁,它安装在板28上面。这些角铁起到分配流体沿板表面流动的作用以避免固体滞流段。此外当床沉降时它们可防止聚合物流过孔。
任何对催化剂和反应物惰性的流体也可存在于循环流中。若要使用活化剂化合物,优选将其加入自热交换器24的反应系统下游,在此情况下,活化剂可从给料器38经管线40加入循环系统中。
在本发明实施中,操作温度可为约-100℃至约150℃范围内,其中温度为约40℃至约120℃是优选的。
对于生产聚烯烃树脂,流化床反应器可在压力高达大约1000psi,优选压力为大约100psi至大约350psi条件下操作。在较高压力下操作有利于热交换,原因在于随着压力的增加,气体单位体积热容量也增加。
部分或所有活化的前体组成和/或催化剂(以下统称为催化剂)以与消耗相同的速度从分配器板28上面的42处注入床中。催化剂优选从床中发生聚合物颗粒混合良好之处注入。在分配板上面某处注入催化剂对于令人满意的地操作流化床聚合反应器是一重要特征。将催化剂注入分配器板下的区域,可能那里引起开始聚合并最终造成分配器板堵塞。将催化剂直接注入床中有助于催化剂在整个床中均匀分配并趋于避免形成催化剂浓度高的局部点,这种点会引起"热点″的形成。将催化剂在床上面注入反应器中会导致过量的催化剂夹带进循环管线中,并在此管线中发生聚合可能最终导致管线和热交换器堵塞。
可用各种技术将催化剂注入反应器。然而,优选用如在美国专利3779712中公开的催化剂加料器将催化剂连续加入反应器中。催化剂优选在与反应器壁相距为反应器直径的20%至40%,高度为床高的约5%至约30%处加入反应器中。
对催化剂惰性的气体,如氮气或氩气,优选用于将催化剂载入床中。
床中聚合物生产速率取决催化剂注入速度和循环流中单体的浓度。可方便地通过简单调节催化剂注入速率控制生产速率。
由于催化剂注入速率的任何变化将改变反应速率,因而床中产生热的速率也会改变。将进入反应器中的循环流的温度调高或调低以适当产生热的速率的变化。这就确保了床中的温度基本维持恒定。当然,要用流化床和循环流冷凝系统两者的完备义器检测床中温度的任何变化,以便能使操作器或常规自控系统可适当调节循环流的温度。
在给定的操作条件下,流化床通过按颗粒聚合物产品的形成速率,卸出作为产品部分床以保持其高度基本恒定。由于产生热的速率直接涉及到产品形成速率,如果无可汽化的液体存在于入口流体中,则测量的穿过反应器的流体的温度升高(入口流体温度与出口流体温度之差)表示在恒定流体流速下颗粒聚合物的形成速率。
对于从反应器10中卸出的颗粒聚合物产品,需要并且优选从产品中分离出流体并使流体回到循环管线22中。现有技术中有很多方法完成此过程。一个优选系统如附图所示。所以,流体和产品在44处离开反应器10并经阀门48进入产品卸料罐46中,阀门48设计为球形阀,以便打开时将其对流动的限制减至最小。位于产品卸料罐46上面和下面的阀门为常规阀门50、52,后者适合提供一路线使产品进入产品缓冲罐54中。产品缓冲罐54有一放空装置,如管线56所示,及一进气体装置,如管线58所示。在产品缓冲罐54的底部还设一卸料阀60,当其处于开启的位置时,卸出产品为了输送去贮存。当阀门50处于开启位置时,将流体释放进缓冲罐62。从缓冲罐62出来的流体直接通过过滤吸收器64,然后经过压缩机66后经管线68进入循环管线22。
在典型操作模式中,阀门48开启而阀门50、52处于关闭位置。产品和流体进入产品卸料罐46。将阀门48关闭并使产品沉降于产品卸料罐46中。然后打开阀门50使流体从产品卸料罐46中流入缓冲罐62中,从此将其连续压回循环管线22中。然后阀门50关闭时,打开阀门52使产品卸料罐46中的所有产品流入产品缓冲罐54中。最后关闭阀门52。将产品用惰性气体,优选氮气清洗,惰性气体通过管线58进入产品缓冲罐54并经管线56放空。最后产品从产品缓冲罐54经阀门60卸出并经管线20输送去贮存。
阀门开关的特定时间顺序通过使用现有技术中公知的常规程序控制器实现。此外,阀门通过周期性地将气流直接通过阀门并返回到反应器而基本保持无附聚颗粒。
可替代使用的另一优选产品卸料系统是在Robert G.Aronson于1981年7月28日申请的申请号为287815、名称为流化床卸料系统的尚待批准的美国专利申请中公开并要求保护的系统。此系统使用包括沉降罐和输送罐的至少一(平行)对罐串联排列,并将从沉降罐顶分离出的气相送回反应器中靠近流化床顶的某处。所述替代的优选产品卸料系统免去了需要如附图体系中所示的再压缩管线64、66、68。
流化床反应器中装有适当的放空(未表示出)系统使床在起动和关闭时放空。反应器不需要使用搅拌和/或刮壁。循环管线22和其中的设备(压缩机30、热交换器24)表面应光滑,并且避免不必要的障碍以便不阻碍循环流体流动或不夹带颗粒。
可按照本发明生产的聚合物例子如下:
聚异戊二烯(顺式-1,4-聚异戊二烯)
聚苯乙烯
聚丁二烯
SBR(丁二烯与苯乙烯的共聚物)
ABS(丙烯腈、丁二烯和苯乙烯的聚合物)
Nitrile(丁二烯与丙烯腈的共聚物)
Butyl(异丁烯与异戊二烯的共聚物)
EPR(乙烯与丙烯的共聚物)
EPDM(乙烯与丙烯和二烯如己二烯、双环戊二烯或亚乙基降冰片烯的共聚物)
Neoprene(氯丁橡胶)
Silicone(聚二甲基硅氧烷)
乙烯与乙烯基三甲氧基硅烷的共聚物
乙烯与一种或多种丙烯腈、马来酸酯、醋酸乙烯酯、丙烯酸和甲基丙烯酸酯等等的共聚物。
当需要使用一种或多种沸点都相当高并且在优选用于按照本发明的气相流化床生产的温度和压力条件下为液体的单体生产聚合物或共聚物时,必须使用在选取的流化床中聚合的条件下保持气态的惰性物质。适合此目的的惰性气体如氮气、氩气、氖气、氪气等等。饱和烃如乙烷、丙烷、丁烷等及卤代烷如氟利昂也可使用。在所述条件下保持气态的其它材料如二氧化碳、只要实质上是惰性的并且不影响催化剂的性能,也可使用。
氮气,因其物理性质和价格相对低廉,优选用作由高沸点单体如苯乙烯、乙烯基醋酸、丙烯腈、丙烯酸甲酯、甲基丙烯酸甲酯等等生产聚合物的介质。在相当低的温度下保持气态的烷烃如乙烷、丙烷也是优选的。
防止反应器堵塞和聚合物附聚的常规技术可用于实施本发明。这些技术的例子有加入微小分离的颗粒物料以防止附聚,如在美国专利4994534和5200477中所述的;加入产生负电荷的化学物质以平衡正电压或加入产生正电荷的化学物质以中和负电势,如美国专利4803251中描述的。还可以连续或间歇加入抗静电剂以防止或中和产生的静电荷。
下面的实施例是用于说明本发明的。
实施例1
在本发明方法实施例中,前述流化床反应系统按下面的描述进行操作以生产乙烯-丙烯二烯三元共聚物。在下列反应条件生产聚合物:反应器温度为40℃,压力为290psia。反应器内单体和共聚单体的分压(露点)对乙烯为90psia,对丙烯为198psia。氢气的分压为2.0psia。将亚乙基-降冰片烯(ENB)以0.53Lb/h的速度注入反应器的聚合物。反应器体积为55ft3;反应器内树脂的重量为112Lbs。本实施例中使用的催化剂体系为乙酰丙酮钒,并用氯化二乙基铝作为助催化剂,并用三氯乙酸乙酯作为促进剂。生产速率为20Lb/h。产品的门尼值为55。
注入的ENB有75%通过聚合结合于聚合物中。溶于聚合物中的未反应的ENB为聚合物重量的0.66%。对于反应器内的112Lbs树脂,未反应的ENB总量为O.74Lbs。若未反应的ENB在反应器内完全气化,其分压应为0.6764psia。
在40℃时,乙烯的饱和压力为2187.7psia,丙烯为337.1psia,ENB为0.262psia。由于反应器内乙烯和丙烯的分压比其饱和压力要小得多,不存在冷凝的乙烯或丙烯。然而,计算出反应器内未反应的ENB的分压比其饱和压力大得多。所以ENB必然保持液体状态并被聚合物吸收。
实施例2
按照下列反应条件在上述流化床反应体系中制备乙烯-丙烯二烯三元共聚物:反应器温度40℃,压力363.4psia。反应器内单体和共聚单体的分压对于乙烯为90psia,丙烯为198.2psia。氢气的分压为2.2psia,氮气的分压为72.6。将单体亚乙基降冰片烯(ENB)以0.53Lb/h的速率注入反应器的聚合段。反应器的体积为55ft3。反应器内树脂的重量为112Lbs。本实施例中使用的催化剂体系为乙酰丙酮钒,用氯化二乙基铝作为助催化剂,三氯醋酸乙酯为促进剂。生产速率为20Lb/h。产品的门尼值为55。
注入的ENB有75%通过聚合被结合进聚合物中。溶解于聚合物中的未反应的剩余ENB为聚合物重量的0.66%。反应器内树脂量为112Lbs,未反应的ENB总量为0.74Lbs。若未反应的ENB在反应器内完全气化,其分压应为0.6764psia。
在40℃时,乙烯的饱和压力为2187,7psia,丙烯为337.1psia,ENB为0.262psia。由于反应器内乙烯和丙烯的分压比其饱和压力小得多,因此没有乙烯或丙烯冷凝。然而,计算出的反应器内未反应的ENB的分压比其饱和压力大得多。因此,KNB必然保持液体状态并被聚合物吸收。
实施例3-6
下列实施例以表的形式列出,根据本发明按照表中的操作条件生产各种不同的聚合物。这些实施例使用不同的催化剂体系和不同循环气体组成说明本发明的实施。实施例标号 3 4 5 6产品: 聚丁二烯 SBR ABS 聚苯乙烯反应条件温度(℃) 40 40 40 40压力(psi) 100 110 200 100表面速率 1.75 2.0 1.5 1.5(ft/s)生产速率 30 25 20 40(1b/h)反应器总体积(ft3) 55 55 55 55反应段体积(ft3) 7.5 7.5 7.5 7.5床高(ft) 7.0 7.0 7.0 7.0床直径(ft) 1.17 1.17 1.17 1.17床重(1bs) 112 112 112 112循环气体组成N2 20 27.3 58.0 99.7丁二烯 80 72.5 39.9 -苯乙烯 - 2 0.15 0.3丙烯腈 - - 1.95 -催化剂: Co(acac)* 3 Co(acac)* 3 Co(acac)* 3 Cp2ZrMe2 **助催化剂: 三乙基铝 三乙基铝 三乙基铝 MAO***重单体进料速率(lb/h)丁二烯 46.2 9.62 2.46 -苯乙烯 - 20.83 15.33 44.4丙烯腈 - 7.08 -聚合物组成:丁二烯 100 25 8 -苯乙烯 75 69 100丙烯腈 - 23 -
* 三乙酰丙酮钴
** 二甲基二茂锆
*** 甲基铝噁烷
Claims (14)
1.一种在具有含正在生长的聚合物颗粒床的聚合段的搅拌床或气体流化床反应器中生产聚合物的方法,包括:
1)将包括一种或多种单体及任意一种或多种惰性气体或液体的流体连续加入所述聚合段;
2)将聚合催化剂连续或间歇加入所述聚合段;
3)将聚合物产品从所述聚合段连续或间歇卸出;
4)从所述聚合段连续卸出未反应的气体,压缩和冷却所述气体,同时保持所述聚合段的温度低于存在于所述聚合段的至少一种单体的露点;条件是如果只有一种单体存在于所述气-液流中,也有至少一种惰性气体存在。
2.一种在具有含正在生长的聚合物颗粒床的聚合段的搅拌床或气体流化床反应器中,由两种或多种单体通过放热聚合反应生产聚合物的方法,包括:
1)连续加入包括至少二种单体和任意一种或多种惰性气体或液体的流体流;
2)将聚合催化剂连续或间歇加入所述聚合段;
3)将聚合物产品连续或间歇从所述聚合段卸出;
4)将未反应的气体连续从所述聚合段卸出,并压缩和冷却所述气体;
5)保持所述聚合段的温度低于至少一种所属单体的露点。
3.根据权利要求1的方法,其中所述流体流进入聚合段的速率、所述催化剂加入所述聚合段的速率及所述流体流中单体的浓度应使所述聚合段的温度低于存在于所述流体流中的至少一种单体的露点。
4.根据权利要求1的方法,其中所述聚合段的温度和通过所述聚合段的气体的速度应使所述聚合段中基本不存在液体,由此固体颗粒物上或固体颗粒物里没有吸收液体。
5.一种在具有含正在生长的聚合物颗粒床的聚合段的搅拌床或气体流化床反应器中,由两种或多种单体通过放热聚合反应生产聚合物的方法,包括:
1)将包括至少二种单体和任意一种或多种惰性气体的流体流连续加入所述聚合段;
2)将聚合催化剂连续或间歇加入所述聚合段;
3)将聚合物产品连续或间歇从所述聚合段中卸出;
4)将未反应的气体连续从所述聚合段中卸出;并压缩和冷却所述气体;
5)保持所述聚合段的温度低于至少一种所述单体的露点并且高于至少一种所述单体的气化温度。
6.一种在连续流化床中由两种或多种流体单体,通过在反应条件下在催化剂存在下将气态流通过流化床反应器,卸出聚合物产品和未反应的流体,冷却所述未反应的流体,并将所述冷却后的流体和足够附加单体来代替已聚合的单体及作为产品卸出的一起送回所述反应器,生产聚合物的方法,其改进包括:控制通过所述反应器的气态流中的单体浓度、回到所述反应器的冷却流体的温度和存在于所述反应器中的催化剂的量,使所述反应器内的温度保持低于至少一种所述单体的露点并高于至少一种所述单体的气化温度。
7.根据权利要求1的方法,其中所述聚合方法在惰性颗粒物料存在下进行。
8.根据权利要求1的方法,其中所述方法在一种用于控制静电荷的试剂或设备存在于所述反应器中的条件下进行。
9.根据权利要求1的方法,其中所述反应器中的静电压基本保持中性。
10.一种在具有含正在生长的聚合物颗粒床的聚合段的搅拌床或气体流化床反应器中生产聚合物的方法,包括:
1)将包括一种或多种单体和一种或多种惰性气体的流体流连续加入所述聚合段;
2)将聚合催化剂连续或间歇加入所述聚合段;
3)将聚合物产品连续或间歇从所述聚合段卸出;
4)将未反应的气体从所述聚合段中连续卸出,压缩和冷却所述气体同时使所述聚合段的温度保持低于至少一种所述气体的露点温度。
11.根据权利要求10的方法,其中所述流体流为包括一种惰性气体和一种或多种液体单体的气液两相流。
12.根据权利要求11的方法,其中所述惰性气体为氮气,所述液体单体为丁二烯或氯丁二烯。
13.根据权利要求11的方法,其中所述惰性气体为氮气,所述液体单体为苯乙烯。
14.根据权利要求11的方法,其中所述惰性气体为氮气,所述液体单体为丁二烯、苯乙烯和丙烯腈的混合物。
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Cited By (2)
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CN102667017A (zh) * | 2009-11-25 | 2012-09-12 | 埃克森美孚上游研究公司 | 使用段塞抑制器和/或雾化器的离心湿气压缩或膨胀 |
JP2014047237A (ja) * | 2012-08-29 | 2014-03-17 | Bridgestone Corp | 変性カーボンブラックの製造方法及び変性カーボンブラック |
Families Citing this family (366)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6025448A (en) | 1989-08-31 | 2000-02-15 | The Dow Chemical Company | Gas phase polymerization of olefins |
US6538080B1 (en) | 1990-07-03 | 2003-03-25 | Bp Chemicals Limited | Gas phase polymerization of olefins |
US5733988A (en) * | 1994-06-29 | 1998-03-31 | Union Carbide Chemicals & Plastics Technology Corporation | Process for reducing polymer build-up in recycle lines and heat exchangers during polymerizations employing butadiene, isoprene, and/or styrene |
US5859156A (en) * | 1995-08-31 | 1999-01-12 | The Goodyear Tire & Rubber Company | Vapor phase synthesis of rubbery polymers |
US5652304A (en) * | 1995-08-31 | 1997-07-29 | The Goodyear Tire & Rubber Company | Vapor phase synthesis of rubbery polymers |
CA2190678A1 (en) | 1995-11-22 | 1997-05-23 | Robert Joseph Noel Bernier | Process for preparing elastomeric compounds from granular elastomers and polymers and articles manufactured therefrom |
CA2190301A1 (en) | 1995-11-22 | 1997-05-23 | Robert Joseph Noel Bernier | Curable ethylene-alpha olefin-diene elastomer |
CA2190302A1 (en) | 1995-11-22 | 1997-05-23 | Gregory George Smith | Process for preparing vulcanizable elastomeric compounds from granular elastomer blends and elastomeric articles manufactured therefrom |
CA2191383A1 (en) | 1995-12-01 | 1997-06-02 | Union Carbide Chemicals & Plastics Technology Corporation | Olefin polymerization catalyst compositions |
CA2192862A1 (en) | 1995-12-15 | 1997-06-16 | Frederick John Karol | Process for the production of long-chain branched polyolefins |
EP0814100A1 (en) * | 1996-06-21 | 1997-12-29 | Bp Chemicals S.N.C. | Polymerisation process |
EP0803519A1 (en) * | 1996-04-26 | 1997-10-29 | Bp Chemicals S.N.C. | Polymerisation process |
US6211310B1 (en) | 1997-06-05 | 2001-04-03 | Union Carbide Chemicals & Plastics Technology Corporation | Manufacture of stereoregular polymers |
US5693727A (en) * | 1996-06-06 | 1997-12-02 | Union Carbide Chemicals & Plastics Technology Corporation | Method for feeding a liquid catalyst to a fluidized bed polymerization reactor |
ES2158567T3 (es) | 1996-06-17 | 2001-09-01 | Exxonmobil Chem Patents Inc | Sistemas cataliticos de metales de transicion mixtos para la polimerizacion de olefinas. |
US6759499B1 (en) * | 1996-07-16 | 2004-07-06 | Exxonmobil Chemical Patents Inc. | Olefin polymerization process with alkyl-substituted metallocenes |
US5731381A (en) * | 1996-11-01 | 1998-03-24 | Union Carbide Chemicals & Plastics Technology Corporation | Termination of gas phase polymerizations of conjugated dienes, vinyl-substituted aromatic compounds and mixtures thereof |
US5763541A (en) * | 1996-12-04 | 1998-06-09 | Union Carbide Chemicals & Plastics Technology Corporation | Process for feeding particulate material to a fluidized bed reactor |
JP3710247B2 (ja) * | 1997-04-10 | 2005-10-26 | 三井化学株式会社 | 気相重合装置 |
FI111846B (fi) | 1997-06-24 | 2003-09-30 | Borealis Tech Oy | Menetelmä ja laitteisto polypropeeniseosten valmistamiseksi |
AU8382698A (en) * | 1997-07-08 | 1999-02-08 | Union Carbide Chemicals & Plastics Technology Corporation | Method for reducing sheeting during olefin polymerization |
AU8488198A (en) * | 1997-07-16 | 1999-02-10 | Union Carbide Chemicals & Plastics Technology Corporation | Low bed-level transition, start-up, and reactor residence time control using sound waves |
US6063877A (en) * | 1997-07-31 | 2000-05-16 | Union Carbide Chemicals & Plastics Technology Corporation | Control of gas phase polymerization reactions |
US6001478A (en) * | 1997-08-08 | 1999-12-14 | Union Carbide Chemicals & Plastics Technology Corporation | Resin particle produced by diene polymerization with rare earth and transition metal catalysts |
US6004677A (en) * | 1997-08-08 | 1999-12-21 | Union Carbide Chemicals & Plastics Technology Corporation | Gas phase production of polydienes with pre-activated nickel catalysts |
DE19735794A1 (de) * | 1997-08-18 | 1999-02-25 | Bayer Ag | Neuer Cobalt-Träger-Katalysator, dessen Herstellung sowie seine Verwendung zur Polymerisation ungesättigter Verbindungen |
US5879805A (en) * | 1997-09-09 | 1999-03-09 | Union Carbide Chemicals & Plastics Technology Corporation | Gas phase polymerization of vinylpolybutadiene |
DE59807820D1 (de) | 1997-09-19 | 2003-05-15 | Bayer Ag | Zwei-Komponenten-Trägerkatalysatoren und ihre Verwendung für die Gasphasenpolymerisation |
DE19744710A1 (de) | 1997-10-10 | 1999-04-15 | Bayer Ag | Gasphasenpolymerisation in einem Kelchreaktor |
DE19754789A1 (de) * | 1997-12-10 | 1999-07-01 | Bayer Ag | Katalysator, dessen Herstellung und Verwendung zur Gasphasenpolymerisation von konjugierten Dienen |
DE19801857A1 (de) | 1998-01-20 | 1999-07-22 | Bayer Ag | Katalysatorsystem zur Gasphasenpolymerisation von konjugierten Dienen |
DE19801859A1 (de) | 1998-01-20 | 1999-07-22 | Bayer Ag | Verfahren zur Vermeidung von Instabilitäten bei der Gasphasenpolymerisation von Kautschuk |
AU1320699A (en) * | 1998-03-11 | 1999-09-23 | Union Carbide Chemicals & Plastics Technology Corporation | Reduced sheeting in single-site and single-site like polymerization by employing a chromium containing compound |
US6136914A (en) | 1998-03-13 | 2000-10-24 | Bridgestone Corporation | Anionic polymerization initiators for preparing macro-branched diene rubbers |
US6071847A (en) | 1998-03-13 | 2000-06-06 | Bridgestone Corporation | Gas phase anionic polymerization of diene elastomers |
US6114475A (en) * | 1998-04-06 | 2000-09-05 | Union Carbide Chemicals & Plastics Technology Corporation | Reactor drying by addition of compound that lowers boiling point of water |
CN1191114C (zh) | 1998-05-15 | 2005-03-02 | 埃林纳克股份有限公司 | 气相流化床反应器 |
US6136919A (en) * | 1998-05-27 | 2000-10-24 | The Goodyear Tire & Rubber Company | Rubber composition and tire having tread thereof |
US6245868B1 (en) | 1998-05-29 | 2001-06-12 | Univation Technologies | Catalyst delivery method, a catalyst feeder and their use in a polymerization process |
DE19825589A1 (de) | 1998-06-09 | 1999-12-16 | Elenac Gmbh | Gasphasenwirbelschichtreaktor |
BR9910984A (pt) | 1998-06-09 | 2001-02-13 | Union Carbide Chem Plastic | Processo e equipamento para uma aprimorada fluidez de sólidos mediante a redução da força de consolidação |
US6200509B1 (en) | 1998-06-26 | 2001-03-13 | Union Carbide Chemicals & Plastics Technology Corporation | Form of synthetic rubber |
DE69935815T2 (de) | 1998-07-01 | 2007-12-27 | Exxonmobil Chemical Patents Inc., Baytown | Elastische Mischung mit Kristallpolymeren und kristallisierbaren Polymeren des Propens |
DE19835785A1 (de) * | 1998-08-07 | 2000-02-17 | Bayer Ag | Verfahren zur Polymerisation von Dienen mittels chlorierter Titanverbindungen |
CA2310647A1 (en) * | 1998-09-26 | 2000-04-06 | Montell Technology Company B.V. | Catalyst components for the polymerization of dienes, catalyst obtained therefrom, and process for the preparation of polydienes using the same |
WO2000018808A1 (en) | 1998-09-30 | 2000-04-06 | Exxon Chemical Patents Inc. | Cationic group 3 catalyst system |
US6486088B1 (en) | 1998-10-23 | 2002-11-26 | Exxonmobil Chemical Patents Inc. | High activity carbenium-activated polymerization catalysts |
BR9915199B1 (pt) | 1998-11-02 | 2010-09-08 | interpolìmero de etileno/alfa-olefina de cisalhamento fino, processo de preparação de interpolìmero de etileno/alfa-olefina, artigo manufaturado, composição de mistura de polìmeros e composição vulcanizada termoplástica. | |
US6189236B1 (en) * | 1998-11-05 | 2001-02-20 | Union Carbide Chemicals & Plastics Technology Corporation | Process for drying a reactor system employing a fixed bed adsorbent |
FI111953B (fi) * | 1998-11-12 | 2003-10-15 | Borealis Tech Oy | Menetelmä ja laite polymerointireaktoreiden tyhjentämiseksi |
US6112777A (en) * | 1998-11-19 | 2000-09-05 | Union Carbide Chemicals & Plastics Technology Corporation | Process for bulk handling elastomeric materials via temperature control |
US6441107B1 (en) | 1998-12-18 | 2002-08-27 | Union Carbide Chemicals & Plastics Technology Corporation | Molecular weight control of gas phase polymerized polybutadiene when using a rare earth catalyst |
US6300429B1 (en) * | 1998-12-31 | 2001-10-09 | Union Carbide Chemicals & Plastics Technology Corporation | Method of modifying near-wall temperature in a gas phase polymerization reactor |
US6111034A (en) * | 1998-12-31 | 2000-08-29 | Union Carbide Chemicals & Plastics Technology Corporation | Static control in olefin polymerization |
US6218484B1 (en) | 1999-01-29 | 2001-04-17 | Union Carbide Chemicals & Plastics Technology Corporation | Fluidized bed reactor and polymerization process |
US6313236B1 (en) | 1999-03-30 | 2001-11-06 | Eastman Chemical Company | Process for producing polyolefins |
BR9917247B1 (pt) | 1999-03-30 | 2010-11-30 | processo para a polimerização de uma olefina e/ou uma olefina e pelo menos uma ou mais outra(s) olefina(s), processo para reduzir a carga eletrostática gerada na polimerização de uma olefina e/ou uma olefina e pelo menos uma ou mais outra(s) olefina(s), pelìcula, e, artigo. | |
US6300432B1 (en) | 1999-03-30 | 2001-10-09 | Eastman Chemical Company | Process for producing polyolefins |
US6255411B1 (en) | 1999-04-07 | 2001-07-03 | Union Carbide Chemicals & Plastics Technology Corporation | Reactor product discharge system |
BR0015853A (pt) * | 1999-06-14 | 2002-08-27 | Union Carbide Chem Plastic | Redução de oligÈmero e formação de gel em poliolefinas |
US6255412B1 (en) | 1999-06-29 | 2001-07-03 | Union Carbide Chemicals & Plastics Technology Corporation | Polymerization of a sticky polymer in the presence of a treated carbon black |
US6180738B1 (en) | 1999-06-29 | 2001-01-30 | Union Carbide Chemicals & Plastics Technology Corporation | Production of a sticky polymer using an improved carbon black |
US6187879B1 (en) | 1999-08-31 | 2001-02-13 | Eastman Chemical Company | Process for producing polyolefins |
US6191238B1 (en) | 1999-08-31 | 2001-02-20 | Eastman Chemical Company | Process for producing polyolefins |
BR9917469B1 (pt) | 1999-08-31 | 2008-11-18 | processo para polimerizar uma olefina e/ou uma olefina e pelo menos uma ou mais outras olefinas, filme, e, artigo. | |
EP1083192A1 (en) * | 1999-09-10 | 2001-03-14 | Union Carbide Chemicals & Plastics Technology Corporation | Process for feeding liquid comonomer to a polymerization conducted in a fluidized bed reactor |
FR2799394A1 (fr) | 1999-10-11 | 2001-04-13 | Michelin Soc Tech | Catalyseur solide supporte utilisable pour la polymerisation de dienes conjugues, son procede de preparation et procede de polymerisation de dienes conjugues utilisant ce catalyseur |
US6255420B1 (en) * | 1999-11-22 | 2001-07-03 | Union Carbide Chemicals & Plastics Technology Corporation | Start-up process for gas phase production of polybutadiene |
US6822057B2 (en) * | 1999-12-09 | 2004-11-23 | Exxon Mobil Chemical Patents Inc. | Olefin polymerization catalysts derived from Group-15 cationic compounds and processes using them |
US6489480B2 (en) | 1999-12-09 | 2002-12-03 | Exxonmobil Chemical Patents Inc. | Group-15 cationic compounds for olefin polymerization catalysts |
US6281306B1 (en) | 1999-12-16 | 2001-08-28 | Univation Technologies, Llc | Method of polymerization |
US6444605B1 (en) | 1999-12-28 | 2002-09-03 | Union Carbide Chemicals & Plastics Technology Corporation | Mixed metal alkoxide and cycloalkadienyl catalysts for the production of polyolefins |
US6455644B1 (en) | 2000-02-28 | 2002-09-24 | Union Carbide Chemicals & Plastics Technology Corporation | Polyolefin production using condensing mode in fluidized beds, with liquid phase enrichment and bed injection |
US6472483B1 (en) | 2000-02-28 | 2002-10-29 | Union Carbide Chemicals & Plastics Technology Corporation | Dry product discharge from a gas phase polymerization reactor operating in the condensing mode |
US6815512B2 (en) | 2000-02-28 | 2004-11-09 | Union Carbide Chemicals & Plastics Technology Corporation | Polyolefin production using condensing mode in fluidized beds, with liquid phase enrichment and bed injection |
US6809209B2 (en) | 2000-04-07 | 2004-10-26 | Exxonmobil Chemical Patents Inc. | Nitrogen-containing group-13 anionic compounds for olefin polymerization |
DE60213380T2 (de) | 2001-02-28 | 2007-08-23 | Bridgestone Corp. | Kontinuierliches verfahren zur herstellung von engeren molekulargewichtverteilungen konjugierten dien-polymeren und dadurch hergestellten produkten |
US6723888B2 (en) | 2001-03-14 | 2004-04-20 | Bridgestone Corporation | Humidification of hydrocarbon mixtures for use in polymer synthesis |
WO2002077045A2 (en) * | 2001-03-27 | 2002-10-03 | Union Carbide Chemicals & Plastics Technology Corporation | Gas phase process for polymers with group 4 metal complex catalyst addition |
DE60238049D1 (de) | 2001-04-12 | 2010-12-02 | Exxonmobil Chem Patents Inc | Verfahren zur Polymerisation von Propylen und Ethylen in Lösung |
EP1406761B1 (en) | 2001-06-20 | 2016-11-02 | ExxonMobil Chemical Patents Inc. | Polyolefins made by catalyst comprising a noncoordinating anion and articles comprising them |
US7220801B2 (en) * | 2001-06-22 | 2007-05-22 | Exxonmobil Chemical Patents Inc. | Metallocene-produced very low density polyethylenes or linear low density polyethylenes as impact modifiers |
EP1927617A1 (en) | 2001-07-19 | 2008-06-04 | Univation Technologies, LLC | Polyethylene films with improved physical properties. |
JP4606671B2 (ja) * | 2001-09-25 | 2011-01-05 | 三井化学株式会社 | エチレン・α−オレフィン共重合体の製造方法 |
EP1308464A1 (en) * | 2001-10-19 | 2003-05-07 | BP Chemicals S.N.C. | Process for the gas-phase (co-)polymerisation of olefins in a fluidised bed reactor |
EP1444276A1 (en) | 2001-11-06 | 2004-08-11 | Dow Global Technologies, Inc. | Isotactic propylene copolymers, their preparation and use |
US6927256B2 (en) | 2001-11-06 | 2005-08-09 | Dow Global Technologies Inc. | Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agent |
DE10163154A1 (de) * | 2001-12-20 | 2003-07-03 | Basell Polyolefine Gmbh | Pyrogene Kieselsäuren enthaltender Katalysatorfeststoff zur Olefinpolymerisation |
CN1308357C (zh) * | 2002-01-15 | 2007-04-04 | 高级弹性体系统两合公司 | 热塑性弹性体及其制备方法 |
EP1348719B2 (en) † | 2002-03-25 | 2010-11-17 | Mitsui Chemicals, Inc. | Process for producing polyolefin |
US7943700B2 (en) * | 2002-10-01 | 2011-05-17 | Exxonmobil Chemical Patents Inc. | Enhanced ESCR of HDPE resins |
AU2003302033A1 (en) | 2002-10-15 | 2004-06-15 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
US7223822B2 (en) | 2002-10-15 | 2007-05-29 | Exxonmobil Chemical Patents Inc. | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
US7459500B2 (en) | 2002-11-05 | 2008-12-02 | Dow Global Technologies Inc. | Thermoplastic elastomer compositions |
US7579407B2 (en) | 2002-11-05 | 2009-08-25 | Dow Global Technologies Inc. | Thermoplastic elastomer compositions |
US7365039B2 (en) | 2003-03-21 | 2008-04-29 | Dow Global Technologies Inc. | Morphology controlled olefin polymerization process |
US6759489B1 (en) | 2003-05-20 | 2004-07-06 | Eastern Petrochemical Co. | Fluidized bed methods for making polymers |
AU2004247640B2 (en) * | 2003-05-30 | 2009-12-24 | Univation Technologies, Llc | Gas phase polymerization and method of controlling same |
JP4231357B2 (ja) * | 2003-07-17 | 2009-02-25 | リケンテクノス株式会社 | 熱可塑性エラストマー組成物 |
US7737205B2 (en) * | 2003-07-28 | 2010-06-15 | Dow Global Technologies Inc | Thermoplastic vulcanizates and process to prepare them |
EP1687346B1 (en) | 2003-11-14 | 2012-06-06 | ExxonMobil Chemical Patents Inc. | Propylene-based elastomers and uses thereof |
US7410926B2 (en) * | 2003-12-30 | 2008-08-12 | Univation Technologies, Llc | Polymerization process using a supported, treated catalyst system |
WO2005092503A1 (en) * | 2004-03-16 | 2005-10-06 | Union Carbide Chemicals & Plastics Technology Corporation | Aluminum phosphate-supported group 6 metal amide catalysts for oligomerization of ethylene |
TW200604224A (en) | 2004-03-17 | 2006-02-01 | Dow Global Technologies Inc | Catalyst composition comprising shuttling agent for ethylene copolymer formation |
CA2558251A1 (en) | 2004-03-17 | 2005-09-29 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for ethylene copolymer formation |
JP4879882B2 (ja) | 2004-03-17 | 2012-02-22 | ダウ グローバル テクノロジーズ エルエルシー | より高次のオレフィンマルチブロックコポリマーを形成するためのシャトリング剤を含む触媒組成物 |
US7270791B2 (en) * | 2004-05-17 | 2007-09-18 | Univation Technologies, Llc | Angular flow distribution bottom head |
US7683140B2 (en) * | 2004-05-20 | 2010-03-23 | Univation Technologies, Llc | Method for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring |
WO2005113615A2 (en) | 2004-05-20 | 2005-12-01 | Univation Technologies, Llc | Gas olefin polymerization process |
US7754830B2 (en) | 2004-05-20 | 2010-07-13 | Univation Technologies, Llc | Polymerization reaction monitoring with determination of induced condensing agent concentration for preventing discontinuity events |
GB0411742D0 (en) | 2004-05-26 | 2004-06-30 | Exxonmobil Chem Patents Inc | Transition metal compounds for olefin polymerization and oligomerization |
US7858736B2 (en) * | 2004-06-21 | 2010-12-28 | Exxonmobil Chemical Patents Inc. | Polymer recovery method |
AU2005262843B2 (en) * | 2004-06-21 | 2007-11-15 | Univation Technologies, Llc | Methods for producing polymers with control over composition distribution |
WO2006009945A1 (en) | 2004-06-21 | 2006-01-26 | Exxonmobil Chemical Patents Inc. | Impact copolymers |
US7981984B2 (en) * | 2004-06-21 | 2011-07-19 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2006009942A1 (en) * | 2004-06-21 | 2006-01-26 | Exxonmobil Chemical Patents Inc. | Polymerization process |
US7157531B2 (en) * | 2004-06-21 | 2007-01-02 | Univation Technologies, Llc | Methods for producing polymers with control over composition distribution |
KR101195320B1 (ko) * | 2004-08-09 | 2012-10-29 | 다우 글로벌 테크놀로지스 엘엘씨 | 중합체를 제조하기 위한 지지된비스(하이드록시아릴아릴옥시) 촉매 |
US7253239B2 (en) | 2004-10-29 | 2007-08-07 | Westlake Longview Corporation | Method for preventing or inhibiting fouling in a gas-phase polyolefin polymerization process |
US7399874B2 (en) | 2004-10-29 | 2008-07-15 | Exxonmobil Chemical Patents Inc. | Catalyst compound containing divalent tridentate ligand |
KR20120034235A (ko) | 2004-11-01 | 2012-04-10 | 우베 고산 가부시키가이샤 | 공액 디엔 중합체의 중합용 촉매 및 그를 이용한 공액 디엔 중합체의 제조 방법, 타이어용 고무 조성물 및 골프공용 고무 조성물 |
US7745526B2 (en) | 2004-11-05 | 2010-06-29 | Exxonmobil Chemical Patents Inc. | Transparent polyolefin compositions |
US7829623B2 (en) * | 2004-11-05 | 2010-11-09 | Exxonmobil Chemical Patents Inc. | Thermoplastic vulcanizates having improved fabricability |
ATE404628T1 (de) * | 2004-12-16 | 2008-08-15 | Exxonmobil Chem Patents Inc | Polymerzusammensetzungen einschliesslich ihrer verwendungen und herstellungsverfahren |
US6987152B1 (en) | 2005-01-11 | 2006-01-17 | Univation Technologies, Llc | Feed purification at ambient temperature |
US7803876B2 (en) * | 2005-01-31 | 2010-09-28 | Exxonmobil Chemical Patent Inc. | Processes for producing polymer blends and polymer blend pellets |
US9410009B2 (en) | 2005-03-17 | 2016-08-09 | Dow Global Technologies Llc | Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation |
WO2006101595A1 (en) | 2005-03-17 | 2006-09-28 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for regio-irregular multi-block copolymer formation |
CA2600140A1 (en) | 2005-03-17 | 2006-09-28 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation |
US20060247394A1 (en) * | 2005-04-29 | 2006-11-02 | Fina Technology, Inc. | Process for increasing ethylene incorporation into random copolymers |
US7799882B2 (en) * | 2005-06-20 | 2010-09-21 | Exxonmobil Chemical Patents Inc. | Polymerization process |
US7634937B2 (en) | 2005-07-01 | 2009-12-22 | Symyx Solutions, Inc. | Systems and methods for monitoring solids using mechanical resonator |
TW200722441A (en) | 2005-09-15 | 2007-06-16 | Dow Global Technologies Inc | Catalytic olefin block copolymers via polymerizable shuttling agent |
CA2622599A1 (en) * | 2005-09-15 | 2007-03-29 | Dow Global Technolgies Inc. | Control of polymer architecture and molecular weight distribution via multi-centered shuttling agent |
US7714082B2 (en) * | 2005-10-04 | 2010-05-11 | Univation Technologies, Llc | Gas-phase polymerization process to achieve a high particle density |
US7737206B2 (en) | 2005-11-18 | 2010-06-15 | Exxonmobil Chemical Patents Inc. | Polyolefin composition with high filler loading capacity |
WO2007070041A1 (en) | 2005-12-14 | 2007-06-21 | Exxonmobil Chemical Patents Inc. | Halogen substituted metallocene compounds for olefin polymerization |
EP1803747A1 (en) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
DE102006004429A1 (de) * | 2006-01-31 | 2007-08-02 | Advanced Micro Devices, Inc., Sunnyvale | Halbleiterbauelement mit einem Metallisierungsschichtstapel mit einem porösen Material mit kleinem ε mit einer erhöhten Integrität |
US7714083B2 (en) * | 2006-03-08 | 2010-05-11 | Exxonmobil Chemical Patents Inc. | Recycle of hydrocarbon gases from the product tanks to a reactor through the use of ejectors |
US7696289B2 (en) * | 2006-05-12 | 2010-04-13 | Exxonmobil Chemical Patents Inc. | Low molecular weight induced condensing agents |
KR101397337B1 (ko) | 2006-05-17 | 2014-05-19 | 다우 글로벌 테크놀로지스 엘엘씨 | 고 효율 용액 중합 방법 |
CA2662796A1 (en) * | 2006-09-07 | 2008-03-13 | Univation Technologies, Llc | Methods for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring |
CN101511882B (zh) * | 2006-09-07 | 2011-09-21 | 尤尼威蒂恩技术有限责任公司 | 使用降低熔融起始温度的模型在线测定树脂粘着性程度的方法 |
US8198373B2 (en) * | 2006-10-02 | 2012-06-12 | Exxonmobil Chemical Patents Inc. | Plastic toughened plastics |
BRPI0717152B1 (pt) * | 2006-10-03 | 2018-07-03 | Univation Technologies, Llc. | Método para polimerização de olefina e sistema de reação para polimerização de olefina |
US7754834B2 (en) * | 2007-04-12 | 2010-07-13 | Univation Technologies, Llc | Bulk density promoting agents in a gas-phase polymerization process to achieve a bulk particle density |
US7872090B2 (en) * | 2007-07-12 | 2011-01-18 | Eastman Chemical Company | Reactor system with optimized heating and phase separation |
JP2009024074A (ja) * | 2007-07-19 | 2009-02-05 | Japan Polypropylene Corp | ポリプロピレンの製造方法 |
TW200932762A (en) | 2007-10-22 | 2009-08-01 | Univation Tech Llc | Polyethylene compositions having improved properties |
US7875685B2 (en) * | 2007-11-07 | 2011-01-25 | Exxonmobil Chemical Patents Inc. | Gas phase polymerization and distributor plate passivation treatment |
TW200936564A (en) * | 2007-11-15 | 2009-09-01 | Univation Tech Llc | Methods for the removal of impurities from polymerization feed streams |
US8129485B2 (en) | 2007-11-27 | 2012-03-06 | Univation Technologies, Llc | Integrated hydrocarbons feed stripper and method of using the same |
EP2112173A1 (en) | 2008-04-16 | 2009-10-28 | ExxonMobil Chemical Patents Inc. | Catalyst compounds and use thereof |
BRPI0819573B1 (pt) * | 2007-12-31 | 2019-04-09 | Dow Global Technologies Inc. | Composição e artigo |
WO2010074994A1 (en) | 2008-12-22 | 2010-07-01 | Univation Technologies, Llc | Systems and methods for fabricating polymers |
JP5179899B2 (ja) * | 2008-02-26 | 2013-04-10 | 住友化学株式会社 | 気相流動層装置、気相流動化方法及び重合体の製造方法 |
US20090214395A1 (en) * | 2008-02-27 | 2009-08-27 | The Dow Chemical Company | Raw Material Efficiency Method and Process |
EP2119732A1 (en) | 2008-05-16 | 2009-11-18 | Borealis Technology Oy | Metallocene catalyst compositions with improved properties, process for its preparation and use for preparing polyolefin homo- or copolymers |
US8580902B2 (en) | 2008-08-01 | 2013-11-12 | Exxonmobil Chemical Patents Inc. | Catalyst system, process for olefin polymerization, and polymer compositions produced therefrom |
CN103951769A (zh) | 2008-08-01 | 2014-07-30 | 埃克森美孚化学专利公司 | 催化剂体系和用于烯烃聚合的方法 |
DE102008039218A1 (de) | 2008-08-22 | 2010-02-25 | Woco Industrietechnik Gmbh | Vulkanisierbare Kautschukmischungen sowie Elastomerformteile, erhältlich aus diesen Kautschukmischungen |
JP2009013428A (ja) * | 2008-10-22 | 2009-01-22 | Riken Technos Corp | 熱可塑性エラストマー組成物 |
EP2186831B1 (en) | 2008-11-10 | 2013-01-02 | Borealis AG | Process for the preparation of an unsupported, solid olefin polymerisation catalyst and use in polymerisation of olefins |
EP2186832B1 (en) | 2008-11-10 | 2012-09-12 | Borealis AG | Process for the preparation of an unsupported, solid metallocene catalyst system and its use in polymerization of olefins |
US20100119855A1 (en) * | 2008-11-10 | 2010-05-13 | Trazollah Ouhadi | Thermoplastic Elastomer with Excellent Adhesion to EPDM Thermoset Rubber and Low Coefficient of Friction |
US8202952B2 (en) * | 2008-11-21 | 2012-06-19 | Equistar Chemicals, Lp | Process for making ethylene homopolymers |
EP2361268B1 (en) | 2008-12-22 | 2012-11-07 | Univation Technologies, LLC | Systems and methods for fabricating polymers |
WO2010080870A2 (en) | 2009-01-08 | 2010-07-15 | Univation Technologies,Llc | Additive for polyolefin polymerization processes |
WO2010080871A1 (en) | 2009-01-08 | 2010-07-15 | Univation Technologies, Llc | Additive for gas phase polymerization processes |
RU2011152483A (ru) | 2009-07-23 | 2013-06-27 | Юнивейшн Текнолоджиз, Ллк | Реакционная система для полимеризации |
US8957167B2 (en) | 2009-07-28 | 2015-02-17 | Univation Technologies, Llc | Polymerization process using a supported constrained geometry catalyst |
ES2858349T3 (es) | 2009-07-29 | 2021-09-30 | Dow Global Technologies Llc | Agentes de transporte de cadena de múltiples cabezas y su uso para la preparación de copolímeros de bloques |
US8425924B2 (en) * | 2009-11-24 | 2013-04-23 | Exxonmobil Chemical Patents Inc. | Propylene compositions containing a pyrethroid and products made therefrom |
US8722820B2 (en) | 2009-12-07 | 2014-05-13 | Univation Technologies, Llc | Methods for reducing static charge of a catalyst and methods for using the catalyst to produce polyolefins |
WO2011078923A1 (en) | 2009-12-23 | 2011-06-30 | Univation Technologies, Llc | Methods for producing catalyst systems |
RU2573325C2 (ru) | 2010-02-22 | 2016-01-20 | Инеос Коммершиал Сервисиз Юк Лимитед | Усовершенствованный способ производства полиолефина |
US8058461B2 (en) | 2010-03-01 | 2011-11-15 | Exxonmobil Chemical Patents Inc. | Mono-indenyl transition metal compounds and polymerization therewith |
CN103554324B (zh) | 2010-04-30 | 2016-02-03 | 大林产业株式会社 | α-烯烃的气相聚合 |
US8557906B2 (en) | 2010-09-03 | 2013-10-15 | Exxonmobil Chemical Patents Inc. | Flame resistant polyolefin compositions and methods for making the same |
KR101821026B1 (ko) | 2010-10-21 | 2018-01-22 | 유니베이션 테크놀로지즈, 엘엘씨 | 폴리에틸렌 및 그의 제조 방법 |
WO2012068703A1 (en) | 2010-11-24 | 2012-05-31 | Exxonmobil Asia Pacific Research & Development Co., Ltd. | High filler loaded polymer composition |
CN103228682B (zh) | 2010-11-30 | 2015-07-22 | 尤尼威蒂恩技术有限责任公司 | 用经萃取的金属羧酸盐聚合烯烃的方法 |
SG190429A1 (en) | 2010-11-30 | 2013-06-28 | Univation Tech Llc | Catalyst composition having improved flow characteristics and methods of making and using the same |
CA2734167C (en) | 2011-03-15 | 2018-03-27 | Nova Chemicals Corporation | Polyethylene film |
US9803032B2 (en) | 2011-05-09 | 2017-10-31 | Bridgeston Corporation | Processes for the preparation of high-cis polydienes |
CA2739969C (en) | 2011-05-11 | 2018-08-21 | Nova Chemicals Corporation | Improving reactor operability in a gas phase polymerization process |
CN103534279B (zh) | 2011-05-13 | 2016-08-17 | 尤尼威蒂恩技术有限责任公司 | 喷雾干燥的催化剂组合物及使用其的聚合方法 |
CA2740755C (en) | 2011-05-25 | 2019-01-15 | Nova Chemicals Corporation | Chromium catalysts for olefin polymerization |
SG11201402631YA (en) | 2011-11-30 | 2014-08-28 | Univation Tech Llc | Methods and systems for catalyst delivery |
CA2760264C (en) | 2011-12-05 | 2018-08-21 | Nova Chemicals Corporation | Passivated supports for use with olefin polymerization catalysts |
CN102675513B (zh) * | 2012-06-06 | 2013-08-07 | 吉林众鑫化工集团有限公司 | 溶液法生产三元乙丙橡胶聚合反应器及工艺过程控制方法 |
US9115233B2 (en) | 2012-06-21 | 2015-08-25 | Nova Chemicals (International) S.A. | Ethylene copolymer compositions, film and polymerization processes |
CA2798855C (en) | 2012-06-21 | 2021-01-26 | Nova Chemicals Corporation | Ethylene copolymers having reverse comonomer incorporation |
LU92037B1 (fr) * | 2012-07-06 | 2014-01-07 | Wurth Paul Sa | Dispositif de depressuration d'un reservoir sous pression de stockage de matiere granuleuse ou pulverulente, et installation de distribution de matiere pulverulente par transport pneumatique comportant un tel dispositif |
US9243325B2 (en) | 2012-07-18 | 2016-01-26 | Rohm And Haas Electronic Materials Llc | Vapor delivery device, methods of manufacture and methods of use thereof |
KR102055471B1 (ko) * | 2012-07-30 | 2019-12-12 | 우베 고산 가부시키가이샤 | 변성 시스-1,4-폴리뷰타다이엔 및 그 제조 방법 |
JP6034623B2 (ja) * | 2012-08-29 | 2016-11-30 | 株式会社ブリヂストン | 重合触媒組成物の製造方法及び重合触媒組成物 |
WO2014065989A1 (en) | 2012-10-26 | 2014-05-01 | Exxonmobil Chemical Patents Inc. | Polymer blends and articles made therefrom |
US10221263B2 (en) | 2012-11-01 | 2019-03-05 | Univation Technologies, Llc | Mixed compatible Ziegler-Natta / chromium catalysts for improved polymer products |
WO2014074981A1 (en) | 2012-11-12 | 2014-05-15 | Univation Technologies, Llc | Recycle gas cooler systems for gas-phase polymerization processes |
CN104853917A (zh) | 2012-11-21 | 2015-08-19 | 埃克森美孚化学专利公司 | 包含基于乙烯的聚合物的膜及其制造方法 |
CA2797620C (en) | 2012-12-03 | 2019-08-27 | Nova Chemicals Corporation | Controlling resin properties in a gas phase polymerization process |
CN104837630B (zh) | 2012-12-05 | 2017-02-22 | 埃克森美孚化学专利公司 | 基于乙烯的聚合物和由其制成的制品 |
EP2934889A2 (en) | 2012-12-18 | 2015-10-28 | ExxonMobil Chemical Patents Inc. | Polyethylene films and method of making same |
CA2800056A1 (en) | 2012-12-24 | 2014-06-24 | Nova Chemicals Corporation | Polyethylene blend compositions |
US20150353651A1 (en) | 2013-01-30 | 2015-12-10 | Univation Technologies, Llc | Processes for making catalyst compositions having improved flow |
KR101462466B1 (ko) | 2013-03-07 | 2014-11-17 | 대림산업 주식회사 | 올레핀의 중합 방법 |
CN105209505B (zh) | 2013-05-14 | 2017-04-19 | 埃克森美孚化学专利公司 | 基于乙烯的聚合物和由其制得的制品 |
US20160102429A1 (en) | 2013-07-02 | 2016-04-14 | Exxonmobil Chemical Patents Inc. | Carpet Backing Compositions and Carpet Backing Comprising the Same |
US9433914B2 (en) | 2013-12-20 | 2016-09-06 | Chevron Phillips Chemical Company, Lp | Polyolefin reactor system having a gas phase reactor |
CA2943378C (en) | 2014-04-02 | 2023-09-12 | Univation Technologies, Llc | Continuity compositions and methods of making and using the same |
US10196508B2 (en) | 2014-10-24 | 2019-02-05 | Exxonmobil Chemical Patents Inc. | Thermoplastic vulcanizate compositions |
CA2870027C (en) | 2014-11-07 | 2022-04-26 | Matthew Zaki Botros | Blow molding composition and process |
CA2871463A1 (en) | 2014-11-19 | 2016-05-19 | Nova Chemicals Corporation | Passivated supports: catalyst, process and product |
WO2016094843A2 (en) | 2014-12-12 | 2016-06-16 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system comprising mesoporous organosilica support |
CN107001945B (zh) | 2014-12-12 | 2020-12-18 | 埃克森美孚研究工程公司 | 芳烃氢化催化剂及其用途 |
WO2016094870A1 (en) | 2014-12-12 | 2016-06-16 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system comprising mesoporous organosilica support |
US10155826B2 (en) | 2014-12-12 | 2018-12-18 | Exxonmobil Research And Engineering Company | Olefin polymerization catalyst system comprising mesoporous organosilica support |
CA2874344C (en) | 2014-12-15 | 2021-08-31 | Nova Chemicals Corporation | Spheroidal catalyst for olefin polymerization |
EP3268399B1 (en) | 2015-03-10 | 2021-01-20 | Univation Technologies, LLC | Spray dried catalyst compositions, methods for preparation and use in olefin polymerization processes |
US10195589B2 (en) | 2015-04-20 | 2019-02-05 | Univation Technologies, Llc | Bridged bi-aromatic ligands and olefin polymerization catalysts prepared therefrom |
US10533063B2 (en) | 2015-04-20 | 2020-01-14 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
US10618989B2 (en) | 2015-04-20 | 2020-04-14 | Exxonmobil Chemical Patents Inc. | Polyethylene composition |
EP3274380B1 (en) | 2015-04-20 | 2020-08-19 | ExxonMobil Chemical Patents Inc. | Catalyst composition comprising fluorided support and processes for use thereof |
CN107531601A (zh) | 2015-04-20 | 2018-01-02 | 尤尼威蒂恩技术有限责任公司 | 桥连联芳香基配位体及由其制备的过渡金属化合物 |
EP3288984B1 (en) | 2015-04-27 | 2023-08-09 | Univation Technologies, LLC | Supported catalyst compositions having improved flow properties and preparation thereof |
CA2890606C (en) | 2015-05-07 | 2022-07-19 | Nova Chemicals Corporation | Process for polymerization using dense and spherical ziegler-natta type catalyst |
WO2016182920A1 (en) | 2015-05-08 | 2016-11-17 | Exxonmobil Chemical Patents Inc. | Polymerization process |
DE102015005943A1 (de) * | 2015-05-12 | 2016-11-17 | Dräger Safety AG & Co. KGaA | Festbettreaktor, Verfahren zur Herstellung eines Festbettreaktors und Verwendung eines Festbettreaktors |
CA2891693C (en) | 2015-05-21 | 2022-01-11 | Nova Chemicals Corporation | Controlling the placement of comonomer in an ethylene copolymer |
CA2892552C (en) | 2015-05-26 | 2022-02-15 | Victoria Ker | Process for polymerization in a fluidized bed reactor |
WO2016195824A1 (en) | 2015-05-29 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Polymerization process using bridged metallocene compounds supported on organoaluminum treated layered silicate supports |
EP3303675A4 (en) | 2015-06-05 | 2019-01-09 | ExxonMobil Chemical Patents Inc. | FILES-BONDED FABRICS COMPRISING PROPYLENE-BASED ELASTOMERIC COMPOSITIONS, AND METHODS THEREOF |
US9289748B1 (en) | 2015-06-11 | 2016-03-22 | Chevron Phillips Chemical Company Lp | Treater regeneration |
US9861955B2 (en) | 2015-06-11 | 2018-01-09 | Chevron Phillips Chemical Company, Lp | Treater regeneration |
US10577435B2 (en) | 2015-08-26 | 2020-03-03 | Sabic Global Technologies B.V. | Ethylene gas phase polymerisation process |
EP3350236B1 (en) | 2015-09-17 | 2023-10-04 | ExxonMobil Chemical Patents Inc. | Polyethylene polymers and articles made therefrom |
EP3350258A1 (en) * | 2015-09-17 | 2018-07-25 | Dow Global Technologies LLC | Polymer coatings compositions with reduced ignition sensitivity |
EP3353217A4 (en) | 2015-09-24 | 2018-11-07 | ExxonMobil Chemical Patents Inc. | Polymerization process using pyridyldiamido compounds supported on organoaluminum treated layered silicate supports |
EP3356374A1 (en) | 2015-09-30 | 2018-08-08 | Dow Global Technologies LLC | Multi- or dual-headed compositions useful for chain shuttling and process to prepare the same |
JP6414032B2 (ja) * | 2015-11-25 | 2018-10-31 | 日本ポリプロ株式会社 | プロピレン系重合体の製造方法 |
WO2017139031A1 (en) | 2016-02-10 | 2017-08-17 | Exxonmobil Chemical Patents Inc. | Polyethylene shrink films and processes for making the same |
ES2818733T3 (es) | 2016-03-29 | 2021-04-13 | Univation Tech Llc | Complejos metálicos |
US10790404B2 (en) | 2016-03-30 | 2020-09-29 | Exxonmobil Chemical Patents Inc. | Thermoplastic vulcanizate compositions for photovoltaic cell applications |
US11299607B2 (en) | 2016-04-22 | 2022-04-12 | Exxon Mobil Chemical Patents Inc. | Polyethylene sheets |
US10844529B2 (en) | 2016-05-02 | 2020-11-24 | Exxonmobil Chemicals Patents Inc. | Spunbond fabrics comprising propylene-based elastomer compositions and methods for making the same |
US9803037B1 (en) | 2016-05-03 | 2017-10-31 | Exxonmobil Chemical Patents Inc. | Tetrahydro-as-indacenyl catalyst composition, catalyst system, and processes for use thereof |
EP3452521B1 (en) | 2016-05-03 | 2023-07-12 | ExxonMobil Chemical Patents Inc. | Tetrahydroindacenyl catalyst composition, catalyst system, and processes for use thereof |
EP3464390A1 (en) | 2016-05-27 | 2019-04-10 | ExxonMobil Chemical Patents Inc. | Metallocene catalyst compositions and polymerization process therewith |
WO2017216047A1 (en) | 2016-06-13 | 2017-12-21 | Sabic Global Technologies B.V. | A catalyst for ethylene gas phase polymerization process |
KR101856202B1 (ko) * | 2016-07-12 | 2018-05-10 | 대림산업 주식회사 | 개질된 담체를 포함하는 폴리올레핀 중합 촉매 및 이를 이용한 폴리올레핀의 제조 방법 |
WO2018017180A1 (en) | 2016-07-21 | 2018-01-25 | Exxonmobil Chemical Patents Inc. | Rotomolded compositions, articles, and processes for making the same |
EP3519446B1 (en) | 2016-09-27 | 2021-05-19 | ExxonMobil Chemical Patents Inc. | Polymerization process |
CN109996818B (zh) | 2016-09-27 | 2021-08-06 | 埃克森美孚化学专利公司 | 聚合方法 |
WO2018063767A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063764A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
CN109983036B (zh) | 2016-09-27 | 2021-09-24 | 埃克森美孚化学专利公司 | 聚合方法 |
WO2018063765A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
KR102444560B1 (ko) | 2016-09-30 | 2022-09-20 | 다우 글로벌 테크놀로지스 엘엘씨 | 체인 셔틀링에 유용한 다중 또는 이중 헤드 구성 요소 및 이를 준비하는 과정 |
JP7123040B2 (ja) | 2016-09-30 | 2022-08-22 | ダウ グローバル テクノロジーズ エルエルシー | 連鎖シャトリングに有用な多頭または二頭組成物の調製方法 |
CN109952324B (zh) | 2016-09-30 | 2023-06-09 | 陶氏环球技术有限责任公司 | 适用于链梭移的封端多头或双头组合物和其制备方法 |
US10730038B2 (en) | 2016-10-05 | 2020-08-04 | Exxonmobil Chemical Patents, Inc. | Metallocene catalysts, catalyst systems, and methods for using the same |
WO2018067289A1 (en) | 2016-10-05 | 2018-04-12 | Exxonmobil Chemical Patents Inc. | Sterically hindered metallocenes, synthesis and use |
WO2018071250A1 (en) | 2016-10-14 | 2018-04-19 | Exxonmobil Chemical Patents Inc. | Oriented films comprising ethylene-based and methods of making same |
CN110062777A (zh) | 2016-10-19 | 2019-07-26 | 埃克森美孚化学专利公司 | 混合催化剂体系及其使用方法 |
WO2018075243A1 (en) | 2016-10-19 | 2018-04-26 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and methods of using same |
CN109891221B (zh) | 2016-11-17 | 2023-01-24 | 尤尼威蒂恩技术有限责任公司 | 测量浆料催化剂组合物中的固体含量的方法 |
JP6934518B2 (ja) | 2016-11-18 | 2021-09-15 | エクソンモービル ケミカル パテンツ インコーポレイテッド | クロム含有触媒を利用する重合方法 |
WO2018102080A1 (en) | 2016-12-02 | 2018-06-07 | Exxonmobil Chemical Patens Inc. | Olefin polymerization catalyst systems and methods for making the same |
WO2018102091A1 (en) | 2016-12-02 | 2018-06-07 | Exxonmobil Chemical Patents Inc. | Polyethylene films |
CN110225929B (zh) | 2016-12-20 | 2021-09-24 | 埃克森美孚化学专利公司 | 聚合方法 |
WO2018118155A1 (en) | 2016-12-20 | 2018-06-28 | Exxonmobil Chemical Patents Inc. | Polymerization process |
US10563055B2 (en) | 2016-12-20 | 2020-02-18 | Exxonmobil Chemical Patents Inc. | Carpet compositions and methods of making the same |
CN110267994A (zh) | 2016-12-22 | 2019-09-20 | 埃克森美孚化学专利公司 | 喷雾干燥的烯烃聚合催化剂组合物和使用其的聚合方法 |
HUE054322T2 (hu) * | 2017-01-20 | 2021-08-30 | Basell Poliolefine Italia Srl | Módszer folyadék betáplálására gázfázisú polimerizációt végzõ reaktorba |
US11230614B2 (en) | 2017-02-03 | 2022-01-25 | Exxonmobil Chemical Patent Inc. | Methods for making polyethylene polymers |
CN110431158A (zh) | 2017-02-07 | 2019-11-08 | 埃克森美孚化学专利公司 | 减少齐格勒-纳塔催化剂的催化剂活性损失的方法 |
KR20190112293A (ko) | 2017-02-20 | 2019-10-04 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | 4족 촉매 화합물 및 이의 사용 방법 |
WO2018151904A1 (en) | 2017-02-20 | 2018-08-23 | Exxonmobil Chemical Patents Inc. | Group 4 catalyst compounds and process for use thereof |
WO2018151903A1 (en) | 2017-02-20 | 2018-08-23 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
WO2018151790A1 (en) | 2017-02-20 | 2018-08-23 | Exxonmobil Chemical Patents Inc. | Hafnocene catalyst compounds and process for use thereof |
US11208502B2 (en) | 2017-03-15 | 2021-12-28 | Dow Global Technologies Llc | Catalyst system for multi-block coploymer formation |
KR102631009B1 (ko) | 2017-03-15 | 2024-01-30 | 다우 글로벌 테크놀로지스 엘엘씨 | 다중-블록 공중합체 형성을 위한 촉매 시스템 |
WO2018170056A1 (en) | 2017-03-15 | 2018-09-20 | Dow Global Technologies Llc | Catalyst system for multi-block copolymer formation |
SG11201908414YA (en) | 2017-03-15 | 2019-10-30 | Dow Global Technologies Llc | Catalyst system for multi-block copolymer formation |
ES2954446T3 (es) | 2017-03-15 | 2023-11-22 | Dow Global Technologies Llc | Sistema de catalizador parala formación de copolímero multibloque |
CN110637049B (zh) | 2017-04-06 | 2022-04-05 | 埃克森美孚化学专利公司 | 流延膜及其制造方法 |
WO2018191000A1 (en) | 2017-04-10 | 2018-10-18 | Exxonmobil Chemicl Patents Inc. | Methods for making polyolefin polymer compositions |
CA3060058C (en) | 2017-05-03 | 2020-07-14 | Chevron Phillips Chemical Company Lp | Regeneration of a desiccant in an off-line treater of a polyolefin production process |
ES2939177T3 (es) | 2017-05-10 | 2023-04-19 | Univation Tech Llc | Sistemas catalizadores y procesos para usar los mismos |
CN115487755B (zh) | 2017-05-17 | 2024-01-26 | 巴塞尔聚烯烃股份有限公司 | 具有多个再循环气体入口喷嘴的流化床反应器 |
CA2969627C (en) | 2017-05-30 | 2024-01-16 | Nova Chemicals Corporation | Ethylene copolymer having enhanced film properties |
WO2018226311A1 (en) | 2017-06-08 | 2018-12-13 | Exxonmobil Chemical Patents Inc. | Polyethylene blends and extrudates and methods of making the same |
WO2019022801A1 (en) | 2017-07-24 | 2019-01-31 | Exxonmobil Chemical Patents Inc. | POLYETHYLENE FILMS AND METHODS OF PRODUCING THE SAME |
WO2019027586A1 (en) | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | MIXED CATALYSTS COMPRISING 2,6-BIS (IMINO) PYRIDYL-IRON COMPLEXES AND BRONZED HAFNOCENES |
EP3661984B1 (en) | 2017-08-04 | 2022-01-19 | ExxonMobil Chemical Patents Inc. | Films made from polyethylene compositions and processes for making the same |
WO2019027587A1 (en) | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | POLYETHYLENE COMPOSITIONS AND FILMS PREPARED THEREFROM |
EP3697822A1 (en) | 2017-08-04 | 2020-08-26 | ExxonMobil Chemical Patents Inc. | Mixed catalysts with unbridged hafnocenes with -ch2-sime3 moieties |
JP6986163B2 (ja) | 2017-10-23 | 2021-12-22 | エクソンモービル ケミカル パテンツ インコーポレイテッド | 触媒系およびそれを使用する重合方法 |
EP3710499A1 (en) | 2017-11-13 | 2020-09-23 | ExxonMobil Chemical Patents Inc. | Polyethylene compositions and articles made therefrom |
WO2019094131A1 (en) | 2017-11-13 | 2019-05-16 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions and articles made therefrom |
US11111325B2 (en) | 2017-11-15 | 2021-09-07 | Exxonmobil Chemical Patents Inc. | Polymerization processes |
CN111448226B (zh) | 2017-11-15 | 2023-08-25 | 埃克森美孚化学专利公司 | 聚合方法 |
EP3710501A2 (en) | 2017-11-15 | 2020-09-23 | ExxonMobil Chemical Patents Inc. | Polymerization processes |
CN111356869B (zh) | 2017-11-17 | 2022-02-22 | 埃克森美孚化学专利公司 | Pe-rt管道及其制造方法 |
US10934376B2 (en) | 2017-11-28 | 2021-03-02 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions and films made therefrom |
CN111511781B (zh) | 2017-11-28 | 2023-07-11 | 埃克森美孚化学专利公司 | 催化剂体系和使用其的聚合方法 |
WO2019108327A1 (en) | 2017-12-01 | 2019-06-06 | Exxonmobil Chemical Patents Inc. | Films comprising polyethylene composition |
WO2019108977A1 (en) | 2017-12-01 | 2019-06-06 | Exxonmobil Chemical Patents Inc. | Catalyst systems and polymerization processes for using the same |
US11591417B2 (en) | 2017-12-13 | 2023-02-28 | Exxonmobil Chemical Patents Inc. | Deactivation methods for active components from gas phase polyolefin polymerization processes |
US10202537B1 (en) | 2018-01-12 | 2019-02-12 | Saudi Arabian Oil Company | Cement compositions comprising high viscosity elastomers on a solid support |
WO2019162760A1 (en) | 2018-02-05 | 2019-08-29 | Exxonmobil Chemical Patents Inc. A Corporation Of State Of Delaware | Enhanced processability of lldpe by addition of ultra-high molecular weight high density polyethylene |
US11440979B2 (en) | 2018-02-19 | 2022-09-13 | Exxonmobil Chemical Patents Inc. | Catalysts, catalyst systems, and methods for using the same |
WO2019173030A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Methods of preparing and monitoring a seed bed for polymerization reactor startup |
CN108380141A (zh) * | 2018-03-16 | 2018-08-10 | 安丽华 | 鼓泡床反应器、甲基丙烯酸甲酯生产设备 |
WO2019182968A1 (en) | 2018-03-19 | 2019-09-26 | Exxonmobil Chemical Patents Inc. | Processes for producing high propylene content pedm using tetrahydroindacenyl catalyst systems |
US11518825B2 (en) | 2018-03-23 | 2022-12-06 | Univation Technologies, Llc | Catalyst formulations |
EP3784382A1 (en) * | 2018-04-24 | 2021-03-03 | SABIC Global Technologies B.V. | Method for drying wet polymer composition |
CN112351987B (zh) | 2018-04-26 | 2024-02-02 | 埃克森美孚化学专利公司 | 含有具有大烷基基团的阳离子的非配位阴离子型活化剂 |
US11441023B2 (en) | 2018-04-27 | 2022-09-13 | Exxonmobil Chemical Patents Inc. | Polyethylene films and methods of making the same |
WO2019217173A1 (en) | 2018-05-02 | 2019-11-14 | Exxonmobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
CN112055719B (zh) | 2018-05-02 | 2022-11-25 | 埃克森美孚化学专利公司 | 从中试装置放大到较大生产设施的方法 |
US10792609B2 (en) | 2018-05-07 | 2020-10-06 | Chevron Phillips Chemical Company Lp | Nitrogen conservation in polymerization processes |
CN112154174B (zh) | 2018-05-22 | 2024-02-06 | 埃克森美孚化学专利公司 | 形成膜的方法及其相关的计算装置 |
CN110559845B (zh) * | 2018-06-06 | 2022-06-28 | 中国石油化工股份有限公司 | 一种含有丁二烯组分有机废气的化学处理方法 |
CN110559844B (zh) * | 2018-06-06 | 2022-06-28 | 中国石油化工股份有限公司 | 一种含有苯乙烯组分有机废气的化学预处理方法 |
EP3810666A1 (en) | 2018-06-19 | 2021-04-28 | ExxonMobil Chemical Patents Inc. | Polyethylene compositions and films prepared therefrom |
WO2020046406A1 (en) | 2018-08-30 | 2020-03-05 | Exxonmobil Chemical Patents Inc. | Polymerization processes and polymers made therefrom |
CN111100226B (zh) * | 2018-10-25 | 2023-03-28 | 中国石油化工股份有限公司 | 一种可调节抗冲聚丙烯刚韧平衡的生产方法 |
US20210395404A1 (en) | 2018-11-01 | 2021-12-23 | Exxonmobil Chemical Patents Inc. | In-line trimming of dry catalyst feed |
US11168157B2 (en) | 2018-12-04 | 2021-11-09 | Chevron Phillips Chemical Company Lp | Melt flow index response in polyethylene reactors |
CN113227244A (zh) | 2018-12-27 | 2021-08-06 | 埃克森美孚化学专利公司 | 具有较快结晶时间的基于丙烯的纺粘织物 |
CN113677713A (zh) | 2019-03-21 | 2021-11-19 | 埃克森美孚化学专利公司 | 改进气相聚合的方法 |
EP3941950A1 (en) | 2019-03-21 | 2022-01-26 | ExxonMobil Chemical Patents Inc. | Methods for improving production in gas phase polymerization |
CN113710731A (zh) | 2019-04-17 | 2021-11-26 | 埃克森美孚化学专利公司 | 改进热塑性硫化橡胶的uv耐候性的方法 |
US10717061B1 (en) | 2019-06-26 | 2020-07-21 | X Energy, Llc | Fluidized bed reactor system allowing particle sampling during an ongoing reaction |
US20220267649A1 (en) | 2019-07-17 | 2022-08-25 | Exxonmobil Chemical Patents Inc. | Pressure Sensitive Adhesives Comprising Propylene-Ethylene(-Diene) Copolymers |
US11820841B2 (en) | 2020-01-28 | 2023-11-21 | Exxonmobil Chemical Patents Inc. | Reducing accumulation of C6+ hydrocarbon components in polyolefin gas-phase reactors |
WO2021154442A1 (en) | 2020-01-31 | 2021-08-05 | Exxonmobil Research And Engineering Company | Polyethylene films having high tear strength |
WO2021173362A1 (en) | 2020-02-24 | 2021-09-02 | Exxonmobil Chemical Patents Inc. | Lewis base catalysts and methods thereof |
WO2021173326A1 (en) | 2020-02-26 | 2021-09-02 | Exxonmobil Chemical Patents Inc. | Highly efficient c6 inert vent for gas phase polyethylene production |
US20230159679A1 (en) | 2020-03-18 | 2023-05-25 | Exxonmobil Chemical Patents Inc. | Extrusion Blow Molded Articles and Processes for Making Same |
WO2021188361A1 (en) | 2020-03-20 | 2021-09-23 | Exxonmobil Chemical Patents Inc. | Linear alpha-olefin copolymers and impact copolymers thereof |
CA3168710A1 (en) | 2020-04-07 | 2021-10-14 | Nova Chemicals Corporation | High density polyethylene for rigid articles |
CN111285947B (zh) * | 2020-04-29 | 2021-03-16 | 东莞巨正源科技有限公司 | 绿色环保聚丙烯薄壁注塑料生产工艺及生产线 |
US20230182366A1 (en) | 2020-05-19 | 2023-06-15 | Exxonmobil Chemical Patents Inc. | Extrusion Blow Molded Containers And Processes For Making Same |
KR20230028473A (ko) * | 2020-06-24 | 2023-02-28 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | 저밀도 폴리에틸렌 제조에서 서브시스템의 셧 다운 시간을 단축하는 방법 |
WO2022010622A1 (en) | 2020-07-07 | 2022-01-13 | Exxonmobil Chemical Patents Inc. | Processes for making 3-d objects from blends of polyethylene and polar polymers |
EP4192888A1 (en) | 2020-08-10 | 2023-06-14 | ExxonMobil Chemical Patents Inc. | Methods for delivery of non-aromatic solutions to polymerization reactors |
US20230272195A1 (en) | 2020-08-25 | 2023-08-31 | Exxonmobil Chemical Patents Inc. | High Density Polyethylene Compositions With Exceptional Physical Properties |
US20230322972A1 (en) | 2020-10-08 | 2023-10-12 | Exxonmobil Chemical Patents Inc. | Supported Catalyst Systems and Processes for Use Thereof |
CN116490525A (zh) | 2020-11-19 | 2023-07-25 | 埃克森美孚化学专利公司 | 聚烯烃排放工艺和设备 |
WO2022108971A1 (en) | 2020-11-23 | 2022-05-27 | Exxonmobil Chemical Patents Inc. | Toluene free supported methylalumoxane precursor |
US20240018278A1 (en) | 2020-11-23 | 2024-01-18 | ExxonMobil Technology and Engineering Company-Chem | Improved Process to Prepare Catalyst from In-Situ Formed Alumoxane |
EP4247825A1 (en) | 2020-11-23 | 2023-09-27 | ExxonMobil Chemical Patents Inc. | Metallocene polypropylene prepared using aromatic solvent-free supports |
WO2022122749A1 (en) * | 2020-12-09 | 2022-06-16 | Basell Polyolefine Gmbh | Reactor for a gas-phase olefin polymerization |
CN117412994A (zh) | 2021-06-10 | 2024-01-16 | 陶氏环球技术有限责任公司 | 具有改性活性的催化剂组合物和其制备方法 |
WO2023042155A1 (en) | 2021-09-20 | 2023-03-23 | Nova Chemicals (International) S.A. | Olefin polymerization catalyst system and polymerization process |
CA3231623A1 (en) | 2021-09-20 | 2023-03-23 | Dow Global Technologies Llc | Process of making catalytically-active prepolymer composition and compositions made thereby |
WO2023081577A1 (en) | 2021-11-02 | 2023-05-11 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions, articles thereof, and methods thereof |
CA3221979A1 (en) | 2022-03-22 | 2023-10-05 | Nova Chemicals Corporation | Organometallic complex, olefin polymerization catalyst system and polymerization process |
WO2023244901A1 (en) | 2022-06-15 | 2023-12-21 | Exxonmobil Chemical Patents Inc. | Ethylene-based polymers, articles made therefrom, and processes for making same |
WO2023250240A1 (en) | 2022-06-24 | 2023-12-28 | Exxonmobil Chemical Patents Inc. | Low cost processes of in-situ mao supportation and the derived finished polyolefin catalysts |
WO2024056538A1 (en) | 2022-09-12 | 2024-03-21 | Basell Poliolefine Italia S.R.L. | Fluidized-bed reactor for the gas-phase polymerization of olefins |
WO2024056539A1 (en) | 2022-09-12 | 2024-03-21 | Basell Poliolefine Italia S.R.L. | Fluidized-bed reactor for the gas-phase polymerization of olefins |
Family Cites Families (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE539302A (zh) * | 1954-06-25 | |||
IT567238A (zh) * | 1956-02-08 | 1900-01-01 | ||
NL137126C (zh) * | 1961-09-28 | |||
BE632184A (zh) * | 1962-05-11 | |||
GB1288230A (zh) * | 1968-09-24 | 1972-09-06 | ||
DE1805765C3 (de) * | 1968-10-29 | 1980-09-11 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Polymerisation von Propylen |
US3709954A (en) | 1970-03-16 | 1973-01-09 | Union Carbide Corp | Preparation of liquid polymers of olefins |
AU445455B2 (en) * | 1970-10-02 | 1974-02-06 | Union Carbide Australia Ltd | Continuous process for producing solid particulate polymers of olefinically unsaturated compounds |
US4012573A (en) * | 1970-10-09 | 1977-03-15 | Basf Aktiengesellschaft | Method of removing heat from polymerization reactions of monomers in the gas phase |
US3709853A (en) | 1971-04-29 | 1973-01-09 | Union Carbide Corp | Polymerization of ethylene using supported bis-(cyclopentadienyl)chromium(ii)catalysts |
US3779712A (en) * | 1971-11-26 | 1973-12-18 | Union Carbide Corp | Particulate solids injector apparatus |
US4110525A (en) * | 1975-02-27 | 1978-08-29 | Compagnie Generale Des Etablissements Michelin | Polymerization process |
US4077904A (en) | 1976-06-29 | 1978-03-07 | Union Carbide Corporation | Olefin polymerization process and catalyst therefor |
DE2848964A1 (de) * | 1978-11-11 | 1980-05-22 | Bayer Ag | Katalysator, dessen herstellung und verwendung zur loesungspolymerisation von butadien |
US4383095A (en) * | 1979-02-16 | 1983-05-10 | Union Carbide Corporation | Process for the preparation of high density ethylene polymers in fluid bed reactor |
JPS564608A (en) * | 1979-06-26 | 1981-01-19 | Mitsubishi Petrochem Co Ltd | Vapor-phase polymerization of olefin |
US4376062A (en) | 1979-11-28 | 1983-03-08 | Union Carbide Corporation | Spheroidal polymerization catalyst, process for preparing, and use for ethylene polymerization |
US4379758A (en) * | 1980-12-24 | 1983-04-12 | Union Carbide Corporation | Catalyst composition for polymerizing ethylene |
US4876320A (en) * | 1981-03-26 | 1989-10-24 | Union Carbide Chemicals And Plastics Company Inc. | Process for reducing sheeting during polymerization of alpha-olefins |
JPS5861107A (ja) * | 1981-10-07 | 1983-04-12 | Japan Synthetic Rubber Co Ltd | 共役ジエン重合体の製造方法 |
DZ520A1 (fr) * | 1982-03-24 | 2004-09-13 | Union Carbide Corp | Procédé perfectionné pour accroitre le rendement espace temps d'une réaction de polymérisation exothermique en lit fluidisé. |
US4543399A (en) * | 1982-03-24 | 1985-09-24 | Union Carbide Corporation | Fluidized bed reaction systems |
US4588790A (en) * | 1982-03-24 | 1986-05-13 | Union Carbide Corporation | Method for fluidized bed polymerization |
DE3239883A1 (de) * | 1982-10-28 | 1984-05-10 | Basf Ag, 6700 Ludwigshafen | Verfahren zum kontinuierlichen herstellen von copolymerisaten des ethylens mit hoeheren (alpha)-monoolefinen |
US4530914A (en) | 1983-06-06 | 1985-07-23 | Exxon Research & Engineering Co. | Process and catalyst for producing polyethylene having a broad molecular weight distribution |
US4933149A (en) * | 1984-08-24 | 1990-06-12 | Union Carbide Chemicals And Plastics Company Inc. | Fluidized bed polymerization reactors |
US4575538A (en) * | 1984-12-20 | 1986-03-11 | Phillips Petroleum Company | Olefin polymerization |
US4752597A (en) | 1985-12-12 | 1988-06-21 | Exxon Chemical Patents Inc. | New polymerization catalyst |
US4981929A (en) * | 1986-06-23 | 1991-01-01 | Union Carbide Chemicals And Plastics Company, Inc. | Catalyst productivity in the polymerization of olefins |
US4665047A (en) | 1986-08-15 | 1987-05-12 | Shell Oil Company | Stabilization of metallocene/aluminoxane catalysts |
US4803251A (en) * | 1987-11-04 | 1989-02-07 | Union Carbide Corporation | Method for reducing sheeting during polymerization of alpha-olefins |
FR2634486B1 (fr) * | 1988-07-22 | 1992-07-31 | Bp Chimie Sa | Appareillage et procede de polymerisation d'olefines en phase gazeuse dans un reacteur a lit fluidise, avec introduction d'un compose organometallique |
US5218071A (en) | 1988-12-26 | 1993-06-08 | Mitsui Petrochemical Industries, Ltd. | Ethylene random copolymers |
IT1230756B (it) * | 1989-02-17 | 1991-10-29 | Enichem Elastomers | Metodo per la preparazione di polibutadiene a lavorabilita' migliorata. |
US4994534A (en) * | 1989-09-28 | 1991-02-19 | Union Carbide Chemicals And Plastics Company Inc. | Process for producing sticky polymers |
JPH0415111A (ja) * | 1990-05-07 | 1992-01-20 | Sumitomo Rubber Ind Ltd | 安全タイヤ |
US5272236A (en) | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
DD296496A5 (de) * | 1990-07-12 | 1991-12-05 | Buna Ag,De | Katalysatorsystem fuer die loesungsmittelfreie polymerisation von 1,3-dienen zu polydienen |
JP2923383B2 (ja) * | 1991-10-01 | 1999-07-26 | 出光石油化学株式会社 | スチレン系重合体の製造方法 |
US5200477A (en) * | 1991-02-22 | 1993-04-06 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing sticky polymers |
GB9107378D0 (en) * | 1991-04-08 | 1991-05-22 | Ici Plc | Olefin polymerisation |
US5278272A (en) | 1991-10-15 | 1994-01-11 | The Dow Chemical Company | Elastic substantialy linear olefin polymers |
DE69309726T2 (de) * | 1992-01-23 | 1997-08-21 | Mitsui Petrochemical Ind | Ethylen/Alpha-Olefin/7-Methyl-1,6-Octadien Copolymerisat-Kautschuk und Zusammensetzungen desselben |
US5352749A (en) * | 1992-03-19 | 1994-10-04 | Exxon Chemical Patents, Inc. | Process for polymerizing monomers in fluidized beds |
US5436304A (en) * | 1992-03-19 | 1995-07-25 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
US5317036A (en) * | 1992-10-16 | 1994-05-31 | Union Carbide Chemicals & Plastics Technology Corporation | Gas phase polymerization reactions utilizing soluble unsupported catalysts |
FR2698290B1 (fr) * | 1992-11-23 | 1995-03-24 | Michelin & Cie | Catalyseur de polymérisation de dioléfines, son procédé de préparation et son application à la préparation de polymères. |
US5376743A (en) * | 1993-03-11 | 1994-12-27 | Union Carbide Chemicals & Plastics Technology Corporation | Process for the production of sticky polymers |
WO1994025495A1 (en) * | 1993-05-20 | 1994-11-10 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
DE4334045A1 (de) * | 1993-10-06 | 1995-04-13 | Bayer Ag | Katalysator, dessen Herstellung und Verwendung zur Gasphasenpolymerisation von konjugierten Dienen |
-
1994
- 1994-08-02 US US08284797 patent/US5453471B1/en not_active Expired - Lifetime
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102667017A (zh) * | 2009-11-25 | 2012-09-12 | 埃克森美孚上游研究公司 | 使用段塞抑制器和/或雾化器的离心湿气压缩或膨胀 |
CN102667017B (zh) * | 2009-11-25 | 2015-08-19 | 埃克森美孚上游研究公司 | 使用段塞抑制器和/或雾化器的离心湿气压缩或膨胀 |
JP2014047237A (ja) * | 2012-08-29 | 2014-03-17 | Bridgestone Corp | 変性カーボンブラックの製造方法及び変性カーボンブラック |
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