CN1069323C - 气相聚合方法 - Google Patents

气相聚合方法 Download PDF

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CN1069323C
CN1069323C CN95115846A CN95115846A CN1069323C CN 1069323 C CN1069323 C CN 1069323C CN 95115846 A CN95115846 A CN 95115846A CN 95115846 A CN95115846 A CN 95115846A CN 1069323 C CN1069323 C CN 1069323C
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R·J·N·本尼埃
R·L·布伊森
R·C·布朗
L·S·施卡罗拉
G·H·威廉斯
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Union Carbide Chemicals and Plastics Technology LLC
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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

气相聚合方法
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闪蒸为蒸汽。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。
本发明具体包括下列的技术方案1-14：
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述单体的露点。
3．根据技术方案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．根据技术方案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．根据技术方案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．根据技术方案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．根据技术方案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．根据技术方案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．根据技术方案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．根据技术方案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．根据技术方案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。
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仪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，ENB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)* 3Co(acac)* 3Co(acac)* 3Cp2ZrMe2 **助催化剂：三乙基铝 三乙基铝   三乙基铝    MAO***重单体进料速率(1b/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述单体的露点。
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：
ⅰ)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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