CN1207314C - 丙烯均聚物或共聚物的制备方法 - Google Patents

丙烯均聚物或共聚物的制备方法 Download PDF

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CN1207314C
CN1207314C CNB018141099A CN01814109A CN1207314C CN 1207314 C CN1207314 C CN 1207314C CN B018141099 A CNB018141099 A CN B018141099A CN 01814109 A CN01814109 A CN 01814109A CN 1207314 C CN1207314 C CN 1207314C
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G·维尔特尔
A·哈曼
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Abstract

气相制备丙烯均聚物或共聚物的方法包括：将气态或液态单体输入聚合区，聚合区的压力和温度保持在符合气态单体要求的范围内，从聚合区中排出的气态、未经聚合消耗掉的单体，进行液化和再将液态单体输入聚合区。通过连续地测定所述温度和因温度改变而引起的输送到反应区中的单位时间单位内的液态单体数量的变化来调节聚合区的温度。另外，在多个、相互垂直位置测定聚合区的温度和由测定值计算各种情况下的平均值，将该平均值与计算的预设的额定值进行对比，根据测定差值来改变输送到聚合区的单体数量。

Description

丙烯均聚物或共聚物的制备方法
本发明涉及权利要求1概括的丙烯均聚物或共聚物的制备方法。
由DE 196 45 947 C1已知这种方法。
在又出自EP 38 478 B1的这种已知方法中，气相制备丙烯均聚物或共聚物的方法包括：将气态或液态单体输入聚合区，进行聚合，聚合区的压力和温度保持在符合气态单体要求的范围内。从聚合区中排出的气态、未经聚合消耗掉的单体，进行液化，再将液态单体输入聚合区。通过连续地测定所述温度和输送到聚合区中的单位时间单位内的液态单体数量的改变来调节聚合区的温度，所述的数量改变是因温度改变引起的。
本发明的目的是实施该已知方法，该方法还可以比较成功地实现，特别是改善了聚合物特性的时效稳定性和进一步提高了反应器的产量。
为了实现该目的，在多个、相互垂直位置测定聚合区的温度和由测定值计算各种情况下的平均值，将该平均值与计算的预设的额定值进行对比，根据测定差值的数量和符号来改变输送到聚合区的单体数量。
因此，可以使聚合区的搅拌粉末床中的反应温度基本上一致。特别理想地是利用图3所示的聚合物排料管的测定温度。聚合物排料管配有多个彼此垂直设置的热电偶并在一个细粉状、特别强烈搅拌的聚合物的移动位置插入粉末床中。
根据本发明的另一特点，借助一个进入循环的冷凝单体用的缓冲容器使聚合区的压力保持恒定。按该方法，可以根据反应器的压力调节循环丙烯冷凝物的料位，这单靠自动控制技术装置不能保证。
在本发明方法的另一优选实施方案中，使丙烯和/或C2至C8烃的混合物在第二聚合区中与从聚合区中取出的聚合物进行聚合，聚合压力为10-30巴，温度为30-90℃，以改变或改善聚合物的物理特性。
下面借助于附图详细说明本发明。
在一个聚合区(2)中配有由下部驱动的螺旋搅拌器的搅拌反应器(1)中，在由颗粒大小为0.05-10毫米的固态聚合物颗粒组成的搅拌床中借助一种齐格勒-纳塔催化剂体系进行丙烯均聚物或共聚物的气相聚合。催化剂组分分别在(3)和(4)中计量加入聚合区中。用在(15)中计量加入反应器中的氢控制聚合物的分子量。反应器的压力一般为10-50巴，优选为25-35巴，聚合温度为40-150℃，优选60-90℃。利用过量的单体通过蒸发致冷带走聚合热，其中每吨聚合的丙烯大约需6-7吨单体经多股分流输入搅拌床中并与聚丙烯粉末强烈混合。
借助工艺必备的与14连接的聚合物排料管(40)，用热电偶(41)测定搅拌床中细粉状聚合物急速移动的某一位置的聚合温度为40～150℃。
根据反应器的冲量和需聚合的聚合物类型用计算机确定进行温度测定的任选数量和调节经蒸发排出聚合热的液态单体分流的平均温度。
未经聚合消耗的夹带粉尘状聚合物颗粒的单体以最高0.5米/秒的速度流经反应器园顶(5)中的反应器顶部的开口，在开口处通过包括分离出的共聚单体和在(6)处计量加入的新丙烯在内的液态循环丙稀使其温度调至冷凝温度，释放出一部分夹带的粉尘状聚合物。为了彻底地除尘，使蒸汽状单体经过旋风分离器(7)输送到过滤器(8)中，接着在循环气体冷凝器(9)中在竖管中冷凝，而为调节分子量加入的氢大部分溶解在冷凝的丙烯中。未溶解的部分氢靠喷射器(10)返回反应器(1)中。
采用一个容器和一个调节阀将反应器的压力调节到20-40巴。例如，如果要靠加快聚合速度来增大反应器中的压力，那么循环冷凝器(9)应具有较大的热交换面积。调节阀12释放出大量的来自冷凝器的带走聚合热所需的液态单体。容器(11)中的液态单体的液面升高，循环气体冷凝器(9)中的液面下降，冷凝面积增大。可以象往常一样，在较窄的范围内调节反应器的压力。
靠泵(13)将带走聚合热的单体重新返回到反应器中。一部分单体通过第二个泵(14)处在较高的压力水平下，借助喷射器(10)作为动力流从循环气体冷凝器(9)中吸出氢。
共聚单体经调节流量(16)供入反应器(1)。新丙烯料流(17)通过测定容器(11)的液面来调节。在反应器(1)的搅拌床(2)中形成的细粉状干燥聚合物在停留50-70分钟后通过插在搅拌床中同时用作测定反应温度的排料管(40)和通过定期打开的开关(18)与10-25％未转变的单体一起输入容器(19)中。由反应器(1)上的放射状粉末料位测量控制开关(18)的定期开放。
在容器(19)中，从减压的单体中分离出聚合物，对单体作进一步处理，经叶轮阀门(20)将聚合物输送到容器(21)中，在该容器(21)中，使聚合物在供入叶轮阀门(22)进行挤压前先与逆流的氮接触，释放出剩余的单体，接触时间为60分钟。
图2和2A示出了由两个前后连接、搅拌床体积分别为75米3的反应器构成的串联反应器。
在第一个反应器中聚合的丙烯均聚物或共聚物与丙烯或丙烯-共聚单体混合物一起几乎连续地通过定期打开的开关(18)输入反应器(27)中。输送的单体数量为输送的聚合物数量的10-25％(重量)。在反应器(27)中生产丙烯均聚物时，不仅由第一反应器输送的丙烯进行聚合，而且还向该反应器中供入额外量的丙烯(25)。
在生产共聚物时，可加入附加量的丙烯和C2-或C4-C8-烃。与在第一反应器(1)中一样，用氢(26)调节反应器(27)中的摩尔量。
随聚合物加入的催化剂具有很高的活性，以便在生产几乎所有类型的聚合物时无需再添加催化剂。更确切地说，在计量加入诸如乙烯类的共聚单体时，必需通过添加异丙醇(24)来调节催化剂的活性。未转变的带走聚合热的单体流向反应器的园顶(30)，接着进入旋风分离器(33)和过滤器(34)，与夹带的细粉状聚合物分离，压入压缩机(36)中，在循环气体冷却器(38)中靠冷却水或冷却剂冷却或部分进行液化并将带走聚合热的大部分，两相单体经调节阀(39)返回反应器中。
聚合温度的测量和调节和聚合物的排出同样是靠插在排料管(40)中的热电偶(41)进行的。在搅拌容器(19)中单体与聚合物的分离、聚合物的脱气和聚合物向挤压区的迁移与图1的工艺流程雷同。
采用本发明的方法，主要提高了反应器的产量和改善了聚合物特性的时效稳定性。例如由两个容积为25米3、产量为4吨/小时的反应器构成的串联反应器的产量提高到高于12吨/小时。

Claims (2)

1.丙烯均聚物或共聚物的制备方法，该方法包括在催化剂的存在下，在40-150℃的温度和10-50巴的压力下，气相聚合相应的单体，其中将气态或液态单体输入聚合区和从聚合区排出聚合物，其中聚合区的压力和温度保持在符合气态单体要求的范围内，从聚合区中排出的气态、未经聚合消耗掉的单体，在一个冷凝器中进行液化、贮存并再将液态单体输入聚合区，通过连续地测定所述温度和单位时间单位内输入的在聚合区中蒸发的液态单体数量因温度改变而引起的变化来调节聚合区的温度，加入新单体补充因聚合消耗掉的单体，其特征在于：在多个、相互垂直位置测定聚合区的温度和由测定值计算各种情况下的平均值；将该平均值与计算的预设的额定值进行对比，根据测定差值的数量和符号来改变输送到聚合区的单体数量，其中
借助一个进入循环冷凝单体用的缓冲容器使聚合区的压力保持恒定，通过该单体可以调节冷凝器的热交换面积。
2.根据权利要求1的方法，其特征在于：使丙烯和/或C2至C8烃的混合物在第二聚合区中与从聚合区中排出的聚合物进行聚合，聚合压力为10-30巴，温度为30-90℃。
CNB018141099A 2000-07-03 2001-06-28 丙烯均聚物或共聚物的制备方法 Expired - Fee Related CN1207314C (zh)

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DE3015089A1 (de) * 1980-04-19 1981-10-22 Basf Ag, 6700 Ludwigshafen Verfahren zum herstellen von homopolymerisaten oder copolymerisaten des propylens
DE3832082A1 (de) 1988-09-21 1990-03-29 Basf Ag Verfahren zum herstellen von homopolymerisaten oder copolymerisaten des propylens
DE4004087A1 (de) * 1990-02-10 1991-08-14 Basf Ag Copolymerisate des propylens
JP2797603B2 (ja) * 1990-02-13 1998-09-17 東ソー株式会社 ポリプロピレンの製造方法
DE19522283A1 (de) 1995-06-20 1997-01-02 Basf Ag Vorrichtung zurGasphasenpolymerisation von C¶2¶-C¶8¶-Alk-1-enen
DE19645947C1 (de) * 1996-11-07 1998-04-16 Basf Ag Verfahren zur Herstellung von Homopolymerisaten oder Copolymerisaten des Propylens
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JP3770736B2 (ja) * 1997-10-03 2006-04-26 三井化学株式会社 流動層型重合装置及びオレフィンの重合方法
TW474949B (en) * 1997-10-03 2002-02-01 Mitsui Chemicals Inc A fluidized bed polymerization apparatus and an olefin polymerization process
JP2001278903A (ja) * 2000-03-31 2001-10-10 Mitsui Chemicals Inc 重合系の異常検出方法、重合方法および重合装置

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JP2004502798A (ja) 2004-01-29
CN1447821A (zh) 2003-10-08
EP1299431A1 (de) 2003-04-09
WO2002002656A1 (de) 2002-01-10
US20040030063A1 (en) 2004-02-12
DE10031392A1 (de) 2002-01-17

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