CN102066067B - 用于挤压塑性物质的方法 - Google Patents
用于挤压塑性物质的方法 Download PDFInfo
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- CN102066067B CN102066067B CN200980123347.2A CN200980123347A CN102066067B CN 102066067 B CN102066067 B CN 102066067B CN 200980123347 A CN200980123347 A CN 200980123347A CN 102066067 B CN102066067 B CN 102066067B
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Classifications
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Abstract
本发明涉及一种用于也在混合诸如固体、液体、气体之类的其他材料或其他聚合物或其他具有改善的光学特性的聚合物共混物的情况下借助于具有特别的螺杆几何形状的多轴挤压机来挤压塑性物质、尤其是聚合物熔体和聚合物熔体、特别是热塑性塑料和弹性体的混合、尤其优选地聚碳酸酯和聚碳酸酯混合料的方法。
Description
本发明涉及一种用于也在混合诸如固体、液体、气体之类的其他材料或其他聚合物或其他具有改善的光学特性的聚合物共混物的情况下借助于具有特别的螺杆几何形状的多轴挤压机来挤压塑性物质、特别是聚合物熔体和聚合物熔体、特别是热塑性塑料和弹性体的混合、特别优选地是聚碳酸酯和聚碳酸酯混合料的方法。
挤压是在制备、预加工(Aufbereitung)和处理聚合物时的已知方法。这里和以下将挤压理解为在如以包含在[1]中的方式所述的同向旋转的双螺杆或多轴挤压机中处理材料或材料混合物([1]＝Kohlgrüber.“DerDoppelschneckenextruder”，Hanser Verlag München 2007)。
在挤压期间对塑性物质的处理包括输送、熔化、分散、混合、压榨液体成分、脱气和压力建立等方法操作中的一个或多个。
在制备聚合物时，挤压例如用于从聚合物中去除如单体和剩余溶剂之类的挥发性成分([1]，第192至212页)，用于在加聚和缩聚反应时反应以及必要时用于熔化和批量生产聚合物以及必要时将添加剂与聚合物混合。
在预加工聚合物时通过挤压特别是制备聚合物与添加剂和附加料和加固剂以及染料的混合以及例如在化学组成、分子量或分子结构方面不同的各种聚合物的混合(例如参见[1]，第59至93页)。这种也称为复合(Compoundierung)的方法用于聚合物预加工，以便在使用通常熔化的塑料原料、在添加和混合填充和/或加固剂、柔软剂、增附剂、润滑剂、稳定剂等与聚合物的情况下制备成品塑料造型材料(复合物)。预加工通常还包括去除挥发性成分例如空气和水。预加工还可以化学反应，例如接枝、改变官能团或通过有针对性地建立或减少分子量来改变分子量。
如普遍公知的和例如在[1]中在第169至190页上所述的那样，可以将混合划分成分布式和分散式混合。分布式混合被理解为以所考虑的容量均匀地分布不同的分量。分布式混合例如在混合同类聚合物的情况下存在。在分散式混合时，固体微粒、液滴或气泡首先被分散。为了分散，必须施加足够大的切力，以便例如克服在聚合物熔体和添加剂之间的界面处的表面张力。下面总是将混合理解为分布式和分散式混合。
在出版物[1]中在第73页及以下对熔体输送和压力建立予以了描述。熔体输送区用于将产品从一个工艺区传送到下一工艺区以及吸入填充剂。熔体输送区通常被部分填充，例如在将产品从一个向另一工艺区传送时，在脱气时和在停留时间区中时。
在处理聚合物时，使聚合物优选地以半成品、即可使用的产品或部件的形式来提供。处理例如可以通过注塑、挤压、吹膜、拉膜或纺丝(Verspinnen)产生。处理也可以例如包括聚合物与填充剂和附加料和添加剂的混合以及化学改性，例如硫化。
如技术人员所公知的，对聚合物的挤压有利地在具有两个或必要时多个轴的螺杆机上进行。
其转子互相精密刮削的同向旋转的两轴机或必要时多轴机很久以来已经是公知的(DE 862668)。在聚合物的制备、后处理和处理中，以精密刮削的型线的原理为基础的螺杆机得到多种多样的使用。这种螺杆机众所周知具有良好的混合作用、良好的脱气作用和用于熔化聚合物的良好作用。提供以此制备的产品的质量方面的优点，因为聚合物熔体附着于表面上并且在通常的处理温度下随着时间降解，这通过精密刮削的螺杆的自洁作用来禁止。用于产生精密刮削的螺杆型线的规则例如在Klemens Kohlgrüber的“DerDoppelschneckenextruder”(Hanser Verlag München 2007，第96及以下)[1]中得以描绘。在那里，单导程、双导程和三导程型线的设计被描述。
技术人员公知的是，在螺杆齿领域中在熔化中消耗特别多的能量，这在产品中局部地导致强烈过热。这例如在[1]中在第160及以下上予以描绘。该局部过热可能导致产品方面的受损，例如气味、颜色、化学成分或分子量方面的改变或者导致产品中不均匀性的形成，例如凝胶体或斑点。特别是大的顶锥角(Kammwinkel)在此情况下是有害的。
现代双螺杆挤压机具有积木式系统，其中可以把不同的螺杆元件安排在核芯轴上。对此，技术人员可以使双螺杆挤压机匹配于相应的任务要求。通常，目前使用具有两导程和三导程型线的螺杆元件，因为单导程螺杆型线由于其大的顶锥角而具有高太多的能量输入。
按照现有技术[1](例如参见第101页)，精密刮削的螺杆元件的几何形状通过不相关的参量即螺纹头数Z、轴距A和外壳直径(对应于精密刮削的轮廓的直径DE)的说明确定。螺纹头数在此情况下是每个元件的圆弧的数目，所述圆弧净化(abreinigen)外壁。这种圆弧的与回转中点有关的角度被称为顶锥角KW0。在顶锥角的范围中，型线的外半径等于外壳半径。KW0按照现有技术不是可调且可与任务要求相匹配的参量，而是从方程式1得出：
其中KW0是以弧度为单位的精密刮削的型线的顶锥角，π是圆周率(π≈3.14159)。紧密啮合的元件对SKW0的两个元件的顶锥角之和必然得出
技术人员公知的是，直接刮削的螺杆型线不能直接被应用于双螺杆挤压机，相反，螺杆元件和外壳之间和/或螺杆本身之间的间隙是必要的。技术人员基于精密刮削的螺杆的轮廓利用如例如在[1]中所示的已知方法获得所实施的螺杆几何形状的几何数据。对于输送元件，在[1]中在第28页及以下描述了不同的可能策略。在使用在那里所说明的纵向或空间等距线时，实际所实施的螺杆的顶锥角KWA0(例如在[1]第100页所示)与角度KW0相比减小。尤其螺杆之间大的间隙导致KWA0减小。但是用于减小顶锥角的螺杆之间的大间距是不利的，因为由此螺杆的相互自洁的效应被减少并且在螺杆元件的表面上出现长的停留时间，所述长的停留时间导致局部产品损坏并从而导致产品的质量下降。对技术人员还已知的是，由于间隙的增大而消极地影响在输送作用和压力建立方面螺杆元件的效果，使得为实现给定的工艺任务而不允许将间隙选择得太大。
因此存在找到用于挤压聚合物的方法的任务，所述方法将由于自洁而少量凝胶形成的质量优点与低温的质量优点相结合。
出人意外地，该任务通过以下方式来解决，即，使用紧密啮合、同向的脱气挤压机，其中使用具有特别几何形状的螺杆元件。
因此，本发明的主题是用于也在混合诸如固体、液体、气体之类的其他材料或其他聚合物或其他聚合物共混物的情况下在使用同向、紧密啮合的脱气挤压机的情况下在使用具有两个或更多螺杆导程的成对同向和成对精密刮削的螺杆轴的情况下来处理塑性物质、尤其是聚合物熔体和聚合物溶液特别是热塑性塑料和弹性体的混合物、特别优选地是聚碳酸酯和聚碳酸酯混合料的方法，其特征在于，元件对的所有顶锥角之和(SKW)可自由选择地大于0并且小于
其中Z是螺纹头数，A是两个螺杆元件之间的轴距，和DE是螺杆元件的外直径。在本发明螺杆元件的情况下，在推式(schiebend)和挽式(ziehend)齿面上的几何形状按照需求可以单独地被设计并且构成齿边界的棱按照需求被倒圆。
在此，本发明不局限于由螺杆元件和核芯轴组成的螺杆的目前常见模块结构类型的螺杆元件，而是也可应用于实体结构类型的螺杆。因此，概念“螺杆元件”也可以被理解为实体结构类型的螺杆。
本发明螺杆元件的螺纹头数Z优选地为2、3、4、5、6、7或8；所述螺纹头数Z特别优选地为2至4。
螺杆型线的外半径为RE＝DE/2，内直径DK和内半径RK＝DK/2。因此，A＝RE+RK始终适用。
本发明螺杆元件的用来产生的和被产生的型线(“螺杆型线(Schneckenprofil)”)优选地由圆弧组成，所述圆弧以切线的方式过渡到彼此。本发明螺杆元件的用来产生的和被产生的型线由至少6*Z个圆弧组成。
圆弧的大小通过其中心角和其半径的说明给出。下面，圆弧的中心角被简称为圆弧的角度。圆弧的位置通过其圆心点的位置和通过其两个端点的位置给出。
本发明螺杆元件的型线的特征在于，一个或多个圆弧能够具有0大小的半径。在这种情况下，型线具有一个或多个弯折(Knicke)。
双螺杆挤压机的第一轴上的预先给定的螺杆型线(“用来产生的(erzeugende)”)明确地确定相邻的第二轴上的螺杆型线(“被产生的(erzeugte)”)。双螺杆挤压机的第一轴上的螺杆型线因此被称为用来产生的螺杆型线，而双螺杆挤压机的相邻第二轴上的螺杆型线被称为被产生的螺杆型线。在多轴挤压机的情况下，在相邻轴上总是交替地使用用来产生的螺杆型线和被产生的螺杆型线。
本发明螺杆型线始终是闭合的和凸状的。每个元件的各个圆弧的角度之和始终是2π。
本发明螺杆元件的特征在于，被产生的螺杆型线的圆弧分别与用来产生的螺杆型线的圆弧相对应。“对应”被理解为
●相对应的圆弧的角大小相同，
●相对应的圆弧的半径之和等于轴距，
●用来产生的螺杆型线的圆弧的圆心点和其端点之间的连接线中的每一个平行于被产生的螺杆型线的相对应的圆弧的圆心点和其端点之间的连接线中的每一个，
●用来产生的螺杆型线的圆弧的端点从圆弧的圆心点出发所在的方向与被产生的螺杆型线的相对应的圆弧的端点从被产生的螺杆型线的圆弧的圆心点出发所在的方向分别相反，
●用来产生的螺杆型线的圆弧的圆心点与被产生的螺杆型线的相对应的圆弧的圆心点具有间距，该间距对应于轴距，
●用来产生的螺杆型线的圆弧的圆心点和被产生的螺杆型线的相对应的圆弧的圆心点之间的连接线平行于用来产生的螺杆型线的回转点和被产生的螺杆型线的回转点之间的连接线，
●为了与被产生的螺杆型线的相对应的圆弧的圆心点重合而必须将用来产生的螺杆型线的圆弧的圆心点移动的方向，是为了与被产生的螺杆型线的回转点重合而必须将用来产生的螺杆型线的回转点移动的相同方向。
图1示出两个相对应的圆弧的例子。用来产生的螺杆的回转中点是DR，被产生的螺杆的回转中点是DL。在该图中圆弧1是用来产生的圆弧和圆弧1’式被产生的圆弧。
本发明螺杆元件的用来产生的螺杆型线具有Z个圆弧，其半径等于RE并且其圆心点与回转中点重合(“齿弧”)。
本发明螺杆元件的用来产生的螺杆型线具有Z个圆弧，其半径等于RK并且其圆心点与回转中点重合(“槽弧”)。相对应的被产生的螺杆型线同样具有Z个齿弧和Z个槽弧。
本发明用来产生的螺杆型线的齿弧和槽弧的角度之和可自由选择，大于0并且小于
被产生的和用来产生的螺杆型线的所有齿弧的角度之和等于用来产生的螺杆型线的顶锥角和槽角之和并且根据本发明大于0并且小于
在如本发明方法中所使用的螺杆元件的优选实施方案中，如此布置齿弧和槽弧，使得所述齿弧和槽弧在环绕型线运行时交替地出现，也就是说，在运行时在每个齿弧之后是槽弧，在每个槽弧之后是齿弧。由此对于被产生的螺杆型线强制性地得出，齿弧和槽弧如此被布置，使得所述齿弧和槽弧在环绕型线运行时交替地出现，也就是说，在运行时，每个齿弧之后是槽弧，每个槽弧之后是齿弧。
在优选实施方案中，根据本发明所使用的螺杆元件在两个轴上具有相同的型线，除了对于偶数Z围绕型线的相应回转中点旋转π/Z之外。
在另一优选实施方案中，根据本发明所使用的螺杆元件关于型线的相应回转点是点对称的，但不是镜像对称的。
在另一优选实施方案中，根据本发明所使用的螺杆元件关于通过齿弧和槽弧的中心的线对称。螺纹头数Z的螺杆元件于是具有2*Z个对称线。
优选地，螺杆元件作为输送元件被使用。众所周知，输送元件的特征在于(例如参见[1]，第227-248页)，螺杆型线在轴向上连续地螺旋形地被扭转和继续。在此，输送元件可以是右或左旋的。输送元件的螺距优选地处于轴距的0.1倍至10倍的范围中，其中螺距被理解为轴向长度，其对于螺杆型线的完全旋转是必要的，并且输送元件的轴向长度优选地处于螺杆直径的0.1倍至10倍的范围中。
对于本发明螺杆元件的螺杆型线可以使用关于螺杆型线的直径在0.1至0.001范围内的间隙，优选地0.002至0.05和特别优选地0.004至0.02。如技术人员所公知的，间隙在螺杆和外壳之间和在螺杆和螺杆之间可以大小不同或相同。所述间隙也可以是恒定的，或者在所说明的界限内是可变的。也可能在间隙内移动螺杆型线。用于基于预先给定的、精密刮削的螺杆型线得出具有间隙的螺杆型线的方法对技术人员是已知的。为此已知的方法例如是轴距增大、纵切面等距线和空间等距线的在[1]中在第28页及以下所述的可能性，其中所述轴距增大、纵切面等距线和空间等距线均对技术人员是已知的。在轴距增大的情况下，具有较小直径的螺杆型线被构造并且被分离螺杆之间间隙的大小。在纵切面等距线的方法的情况下，将纵向型线曲线(平行于相应元件的回转轴)垂直于型线曲线向内、朝向回转轴的方向移动螺杆-螺杆间隙的一半。在空间等距线的方法的情况下，从空间曲线(在所述空间曲线上净化螺杆元件)出发将螺杆元件在垂直于精密刮削的型线的面的方向上缩小螺杆和螺杆之间间隙的一半。优选地使用纵切面等距线和空间等距线，特别优选地使用空间等距线。
图2以横截面的方式示出两导程的按照现有技术已知的螺杆元件的型线。轴距为48mm，螺杆型线的外直径为58mm，内直径对应于38mm和顶锥角KW0以弧度为单位为0.3788(相当于21.7°)。所有顶锥角之和SKW0以弧度为单位为1.5152。
图3a和3b以横截面的方式以示意图示例性地示出根据本发明所使用的两导程螺杆元件的用来产生的螺杆型线的部分型线X和被产生的螺杆型线的与之相对应的部分型线Y。部分型线X通过圆弧1、2、3、4、5和6构成。部分型线Y通过与部分型线X的相应圆弧相对应的圆弧1’、2’、3’、4’、5’和6’构成。圆弧通过其相应的圆心点M1、M2、...、M6和M1’、M2’、...、M6’、其相应的角度和半径明确地被定义(参见图3a)。
在本例子中，轴距为48mm，螺杆型线的外直径为58mm和内直径为38mm。圆弧1是用来产生的部分型线的齿弧，圆弧6是槽弧。圆弧2具有半径0，也就是说，用来产生的型线在齿弧处具有弯折。
在图3b中，为了清楚明了起见，圆弧和圆心点的附图标记被去除。部分型线X和Y与在图3a中所示的部分型线相同。
图4以横截面的方式示意性地示出具有点对称螺杆型线的根据本发明所使用的螺杆元件，如果在图3a和3b中所示的部分型线点对称地被继续，则所述点对称螺杆型线从图3a或3b得出。所有顶锥角是相同的并且等于0.17454(10°)。例如顶锥角KW被绘出。所有顶锥角之和SKW为0.698，小于按照现有技术的元件的一半。这与现有技术相比是显著的优点。该螺杆型线还具有以下优点，即与挽式侧相比，在顺时针的旋转方向时推式齿面与外壳构成大得多的角度，这在部分填充的情况下再次导致小得多的能量输入。同样，也可以使旋转方向相反，这导致齿的提高的延伸。
图5以横截面的方式示意性地具有镜像和点对称螺杆型线的根据本发明所使用的螺杆元件。在本例子中，轴距为48mm，螺杆型线的外直径为58mm，内直径对应于38mm并且顶锥角中的每一个均为0.175(10°)。例如顶锥角KW被绘出。所有顶锥角之和SKW为0.69813，小于按照现有技术的元件的顶锥角之和的一半。在此情况下，优点在于较小的能量消耗。
图9a示出本发明点对称和镜像对称螺杆元件的例子的两个相对应的(用来产生的螺杆型线的)部分型线X1和(被产生的螺杆型线的)Y1。部分型线X1通过圆弧1、2和3构成。部分型线Y1通过相应相对应的圆弧1’、2’和3’构成。回转点的间距被标准化到1。圆弧3与直线FP相切。在表1中说明了半径、角度、圆弧的起始点和圆弧的圆心点。
表1：在图9a、9b和9c中所示的本发明螺杆元件的部分型线X和Y的几何大小
半径 角度 x坐标 y坐标 x坐标 y坐标
起始点 起始点 圆心点 圆心点
0.6 0.0799 0.6 0 0 0
0 0.3943 0.5981 0.0479 0.5981 0.0479
0.9 0.3112 0.5981 0.0479 -0.2026 -0.3631
图9b示出从图9a通过根据本发明镜像、继续和旋转得出的精密刮削的型线。精密刮削的螺杆轮廓的顶锥角KW为0.1598。所有顶锥角之和SKW为0.3196。按照现有技术精密刮削的轮廓具有0.399的顶锥角KW0和0.799的所有顶锥角之和SKW0.
图9c示出以在图9b中的精密刮削的型线为出发点按照空间等距线的方法构造的型线。外壳直径为0.61和在外壳和螺杆之间的间隙δ和在螺杆和螺杆之间的间隙s分别为0.02。螺距为1.2。
该型线的所实施的顶锥角为KWA＝0.208。所有所实施的顶锥角之和SKWA为0.319。
图9d示出根据现有技术具有与在图9c中相同的间隙和相同的螺距的型线。该型线具有0.329的所实施的顶锥角KWA0和0.658的所实施的顶锥角之和。
根据本发明能够在同时保护产品的情况下以高效率被挤压的塑性物质例如是悬浮液、糊剂、玻璃、陶瓷物质、熔体形式的金属、塑料、塑料熔体、聚合物溶液、弹性体和橡胶物质。
优选地使用塑料和聚合物溶液，特别优选地使用热塑性聚合物。作为热塑性聚合物优选地使用由聚碳酸酯、聚酰胺、聚酯、尤其是聚对苯二甲酸丁二酯和聚对苯二甲酸乙二酯、聚交酯、聚醚、热塑性聚氨酯、聚缩醛、含氟聚合物、尤其是聚偏1，1，-二氟乙烯、聚醚砜、聚烯烃、尤其是聚乙烯和聚丙烯、聚酰亚胺、聚丙烯酸酯、尤其是聚(甲基)丙烯酸甲酯(Poly(methyl)methacrylat)、聚苯醚、聚苯硫醚、聚醚酮、聚芳醚酮、苯乙烯聚合物、尤其是聚苯乙烯、苯乙烯共聚物、尤其是苯乙烯-丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯嵌段共聚物和聚氯乙烯构成的系列中的至少一种。同样优选地使用由所实施的塑料制成的所谓共混物，技术人员将其理解为由两种或更多种塑料的组合。特别优选地是聚碳酸酯和包含聚碳酸酯的混合物，相当特别优选地是例如按照相界面方法或熔体酯交换方法(Schmelzeumesterungsverfahren)获得的聚碳酸酯。
其他优选的给料材料是橡胶。作为橡胶优选地使用由苯乙烯-丁二烯橡胶、天然橡胶、丁二烯橡胶、异戊二烯橡胶、三元乙丙橡胶、乙丙橡胶、丁腈橡胶、氢化腈橡胶、丁基橡胶、卤化丁基橡胶、氯丁二烯橡胶、乙烯-醋酸乙烯酯橡胶、聚氨酯橡胶、热塑性聚氨酯、古塔胶、丙烯酸酯橡胶、氟橡胶、硅橡胶、硫化橡胶、氯磺酰基聚乙烯橡胶构成的系列中的至少一种。所实施的橡胶中的两种或更多种的组合、或者一种或多种橡胶与一种或多种塑料的组合当然也是可能的。
所述热塑性塑料和弹性体能够以纯的形式或者作为与填充和加固剂(如尤其是玻璃纤维)的混合物、作为彼此或与其他聚合物的混合或者作为与常见的聚合物添加剂的混合使用。
在优选的实施形式中，将添加剂掺入塑性物质、尤其是聚合物熔体和聚合物熔体的混合物。这可以作为固体、液体或溶液与聚合物一起被提供到挤压机中，或者添加剂的至少一部分或所有添加剂通过侧流(Seitenstrom)被输送给挤压机。
添加剂能够给予聚合物各种各样的特性。例如可以是染料、颜料、处理助剂、填充剂、防氧化剂、加固剂、UV吸收剂和光稳定剂、金属减活化剂、过氧化物清除剂、基础稳定剂、成核剂、用作稳定剂或防氧化剂的苯并呋喃和吲哚啉酮、分型剂、阻燃添加剂、抗静电剂、着色剂和熔体稳定剂。对于这些示例性地是炭黑、玻璃纤维、粘土、云母、石墨纤维、二氧化钛、碳纤维、碳纳米管、离子液体和天然纤维。
在使用用于不同的聚合物的方法时得出的优点根据挤压工艺的类型和塑性物质的类型而不同。
在挤压聚乙烯和聚乙烯共聚物时在太高的温度时表现出分子量的增加、支化和交联。此外，聚乙烯和聚乙烯共聚物在技术人员公知的自氧化循环中与空气氧反应([2]Hepperle，J.：beiPolymeren，Polymeraufbereitung 2002，VDI-K，VDI-Verlag GmbH，[3]Zweifel，H.：Stabilization of Polymeric Materials，Berlin：Springer 1997，[4]Schwarzenbach，K.et al.：Antioxidants，in Zweifel，H.(出版者)：PlasticsAdditives Handbook，München：Hanser 2001，[5]Cheng，H.N.，Schilling，F.C.，Bovey，F.A.：13C Nuclear Magnetic Resonance Observation of theOxidation of Polyethylene，Macromolecules 9(1976)第363-365页)，形成气味浓烈的和从而有干扰的低分子分量(例如酮、醛、羧酸和醇)。
在挤压基于聚乙烯和醋酸乙烯酯的共聚物时在太高温度时附加地形成气味强烈的和腐蚀性的醋酸。
在挤压聚丙烯和聚丙烯共聚物时，太高的温度导致分子量的减少。此外，聚丙烯和聚丙烯共聚物还与空气氧在自氧化循环中反应，形成气味强烈的并从而干扰的低分子成分(例如酮、醛、羧酸和醇)。
在挤压聚氯乙烯时在太高的温度时在使腐蚀性盐酸气体变色的情况下解离，其中盐酸又以催化的方式在盐酸的进一步解离时起作用。
在挤压聚苯乙烯时，在太高的温度时随着分子量减少并且机械特性相应地变差形成有害健康的苯乙烯以及二聚体和三聚体苯乙烯。
在挤压聚苯乙烯-丙烯腈共聚物(SAN)时，产品在热负荷下向黄色变色，这导致减少的透明度，并且在分子量减少和机械特性变差情况下形成致癌单体丙烯腈以及苯乙烯。
在挤压芳香族聚碳酸酯时，在太高的热负荷下、尤其在氧影响下向黄色变色，这导致减少的透明度，并且尤其在水的影响下表现出分子量减少。在提高的温度下单体(例如双酚A)也被裂解。
在挤压诸如聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚对苯二甲酸1，3-丙二酯或聚交酯之类的聚酯时，在太高的温度和水影响下得出分子量减少和分子中端基位移。这特别是在回收聚对苯二甲酸乙二酯时是有问题的。聚对苯二甲酸乙二酯在高温时解离乙醛，这例如可能导致饮料瓶的内容中味道的改变。
在挤压用二烯橡胶、尤其用丁二烯橡胶抗冲击改性的热塑性塑料、尤其抗冲击改性的聚苯乙烯类(HIPS)和抗冲击改性的SAN(丙烯腈-丁二烯-苯乙烯，ABS)时，在太高的温度下解离出致癌的丁二烯以及有毒的乙烯基环己烯。此外，二烯橡胶交联，使得发生产品的机械特性变差。
在挤压聚缩醛时，在太高的温度下解离出有毒的甲醛。
在挤压如聚酰胺6、聚酰胺6，6、聚酰胺4，6、聚酰胺11和聚酰胺12的聚酰胺时，太高的温度导致产品变色以及分子量减少以及重新形成单体和二聚体并且从而特别在水存在的情况下导致机械特性变差。
在挤压热塑性聚氨酯时，太高的温度由于聚氨酯基交换反应(Umurethanisierung)而导致分子结构的改变，并且在水存在的情况下导致分子量减少。两者均以不希望的方式影响热塑性聚氨酯的特性。
在挤压聚甲基丙烯酸甲酯时，在太高的热负荷下在分子量减少的情况下甲基丙烯酸甲酯解离，这导致嗅觉妨碍和变差的机械特性。
在挤压聚苯硫醚时，在太高的温度时含硫的有机和无机化合物被解离，这可能导致嗅觉妨碍并且导致挤压模具的腐蚀。在此情况下，低分子低聚体和单体也被形成并且分子量被减少，这使聚苯硫醚的机械特性变差。
在挤压聚苯砜时，在太高的温度时，有机化合物特别是在水存在的情况下被解离。分子量也减少，由此使机械特性变差。
在挤压聚苯醚时，在太高的温度时低分子有机化合物被解离，其中分子量减少。这导致产品的机械特性变差。
在挤压二烯橡胶(例如聚丁二烯(BR)、天然橡胶(NR)和合成聚异戊二烯(IR)、丁基橡胶(IIR)、氯化丁基橡胶(CIIR)、溴化丁基橡胶(BIIR)、丁苯橡胶(SBR)、聚氯丁二烯(CR)、丁腈橡胶(NBR)、部分氢化的丁腈橡胶(HNBR)以及三元乙丙胶(EPDM))时，在太高的温度时通过交联形成凝胶，这导致由此制备的部件的机械特性变差。在氯化和溴化丁基橡胶时，在提高的温度下腐蚀性的盐酸或氢溴酸气体可能被解离，这又催化聚合物的进一步分解。
在挤压包含诸如硫或过氧化物之类的硫化剂的橡胶混合物时，由于太高的温度而导致提前的硫化。这导致不再能够由所述橡胶混合物来制备产品。
在挤压由一种或多种聚合物组成的混合物时，在太高的温度时相应出现对各个聚合物的挤压的缺点。
在制备时对聚合物脱气的部分工艺在所谓的脱气挤压机上被执行。脱气挤压机在原理上对于技术人员是公知的并且例如在[1]中予以了描述。所谓的脱气罩说明了脱气挤压机的特征。这是具有开口的外壳，通过所述开口能够泄漏产生的蒸气混合物。如果产品在脱气罩之间被堵住，众所周知，不同的脱气罩可以在不同的压力下运行，从而在不同的压力之间形成密封。
本发明螺杆元件优选地在部分填充的区和特别优选地在脱气区中被使用。
根据产生聚合物的方式可以以不同的方式给本发明脱气挤压机装载产品。在优选的变型方案中，给挤压机装载液相，所述液相除了聚合物之外还可以包含溶剂和必要时剩余单体。在反应和必要时提前蒸发之后产生聚合物的形式对于技术人员是已知的。对此的例子是：
●具有剩余苯乙烯和可能乙苯、甲苯、二甲苯、丁酮或其他溶剂的聚苯乙烯
●具有剩余苯乙烯、剩余丙烯腈和可能乙苯、甲苯、二甲苯、丁酮或其他溶剂的苯乙烯和丙烯腈共聚物
●线型低或高密度聚乙烯，具有如己烷、工业己烷、丙烷、异丁烷之类的溶剂和如丙烯、1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯之类的单体的分支聚乙烯(利用悬浮液的工艺是：MitsuiChemicals的CX工艺(己烷)、Basell的Hostalen工艺(己烷)、Chevron Philips USA(异丁烷)、Borealis(丙烷)Belgien的Borstar工艺以及DSM在溶剂工艺中使用己烷)。对此的细节在[6](ComparatiVe Analysis of Various Polyethylene ProductionTechnologies，Chem.& Petroleum Eng.Vol.44，Nos.7-8，2008)中得以描述。
●具有诸如氯苯和二氯甲烷的溶剂的聚碳酸酯
●具有单体、即甲基丙烯酸甲酯的聚甲基丙烯酸甲酯
在优选的变型方案中，将产品输送给具有所谓反向脱气的以流体方式装载的脱气挤压机。在此，必要时预先加热的聚合物溶液被引进双螺杆挤压机中并且在那里起泡沫。气体于是通过双螺杆挤压机的导程反向被排出到脱气罩。通常，这种反向脱气是现有技术并且例如在[1]中在第193-195页上得以描述。溶液的聚碳酸酯的浓度在该情况下在进入挤压机时优选地在55质量百分比(Masse-％)至95质量百分比之间，特别优选地在65质量百分比至90质量百分比之间。
在另一优选的变型方案中，将产品输送给以流体方式装载的脱气挤压机，在于在挤压机的进口处的闪蒸。优选地直接在挤压机上方闪蒸，使得部分脱气的熔体直接落在螺杆轴上。在闪蒸时产生的蒸气混合物优选地从同样位于挤压机上方的分离容器借助于一个或多个蒸气混合物线路被吸出。聚合物溶液的温度优选地在180℃至300℃的范围中，特别优选地在200℃和250℃之间。闪蒸优选地在0.3bar abs至6bar abs之间的压力范围中运行，特别优选地在0.5bar abs和2bar abs之间。
在另一优选变型方案中，将产品输送给以流体方式装载的脱气挤压机，在于在挤压机的进口处的管束式换热器，所述管束式换热器被布置在挤压机的轴之上，使得从管中出来的部分脱气的聚合物溶液可以直接落在轴上。在管束式换热器的出口和挤压机轴之间还有分离容器，在所述分离容器中，蒸气混合物和聚合物溶液被彼此分开并且所述分离容器具有至少一个用于蒸气混合物的排出口。聚合物溶液通过在下降管蒸发器的上端处的进口开口被引入并且通过分配器底被输送给多个管，所述管从外被加热。优选地通过冷凝水蒸汽、冷凝有机载热体或通过流体有机载热体进行加热。通过管的热表面将用于蒸发溶剂的热能引入聚碳酸酯熔体中。在此，溶剂成分蒸发并且构成两相气液混合物。因此有针对性地避免聚合物熔体过热。泄漏的蒸气形式的溶剂引起聚合物熔体的不断混匀和表面更新，这引起其有效的浓缩。明显更高浓缩的聚碳酸酯熔体被输送给蒸发挤压机，使得不仅能量输入而且在挤压机中聚碳酸酯熔体的停留时间能够较少，以便引起聚碳酸酯熔体的相同的或甚至更高的剩余脱气。优选地，在管束式换热器中在出口中聚合物溶液的浓度在50至80重量百分比(Gew.％)之间。管的加热温度为240℃至360℃，优选地为250℃至340℃并且甚至特别优选地为260℃至300℃。在挤压机中在出口处的聚合物浓度在80至99重量百分比之间，优选地为90至99重量百分比。在分离容器中的压力优选地在0.3bar abs至6bar abs之间，特别优选地在0.5bar abs至2barabs之间。
给以流体方式装载的脱气挤压机装载产品的另一优选方式，在于例如在EP1 740 638中针对聚碳酸酯所描述的泡沫蒸发器。泡沫蒸发器可以例如由管束或由喷嘴板组成。聚合物熔体从泡沫蒸发器的开口起泡沫并且除了少量剩余含量之外摆脱剩余溶剂。
该泡沫蒸发器优选地如此被布置在挤压机的轴之上，使得从管中溢出的聚合物溶液可以直接落到轴上。在管束式换热器的出口和挤压机轴之间还有分离容器，在所述分离容器中，蒸气混合物和聚合物溶液被彼此分开并且所述分离容器具有用于蒸气混合物的至少一个排出口。
特别优选地，作为聚合物溶液使用聚碳酸酯溶液。
在该情况下，在泡沫蒸发器的进口中聚碳酸酯溶液的浓度在90重量百分比和99.95重量百分比之间。可选地，还给聚碳酸酯溶液添加起泡剂，例如氮气、CO2。起泡剂与剩余溶剂一起的蒸气压力为0.1至100bar，优选地为0.5至60bar并且特别优选地为1至40bar。在分离器中的压力为通过泡沫蒸发器的开口将聚合物溶液分成在0.1和20mbar之间的部分流。聚合物溶液的温度在250℃和340℃之间。在分离容器中的压力优选地在0.1和20mbar之间。
图6示出本发明脱气挤压机。在区A中，聚碳酸酯溶液通过闪蒸管1被添加给挤压机。蒸气混合物在脱气容器2中与聚碳酸酯溶液分离。区C、E、G J和L是脱气区。在那里变为自由的蒸气混合物在脱气罩3中被吸出。区B、D、F和H是止流区(Stauzone)，其中通过止流元件产生产品塞(Produktpropfen)，所述产品塞能够在分别相邻的区中调整不同的压力。在区K中，附加地添加携带剂，以便在区L中更有效地进行脱气。在区M中，将具有侧流的聚合物与添加剂混合并且建立压力用于过滤和喷嘴，其在挤压机之后。
图7示出本发明另一脱气挤压机。在区A中，聚碳酸酯溶液通过垂直的预热器1被添加给挤压机。蒸气混合物在脱气容器2中与聚碳酸酯溶液分开。区C、E、G J和L是脱气区。在那里变为自由的蒸气混合物在脱气罩3中被吸出。区B、D、F和H是止流区，其中通过止流元件产生产品塞，所述产品塞能够在分别相邻的区中调整不同的压力。在区K中，附加地添加携带剂，以便在区L中更有效地进行脱气。在区M中将具有侧流的聚合物与添加剂混合并且建立压力用于过滤和喷嘴，其在挤压机之后。
图8示出在进口处具有泡沫蒸发器的另一本发明脱气挤压机。在区A中，聚碳酸酯溶液通过泡沫蒸发器1被添加给挤压机。蒸气混合物在分离器2中与聚碳酸酯溶液分开。在区B、D、F和H中分别添加和分散携带剂。在区C、E、F、G和J中，挥发性组分与聚合物分开。在区K中，将具有侧流的聚合物与添加剂和必要时其他聚合物混合并且建立压力用于过滤和喷嘴，其在挤压机之后。
在制备聚合物时也可以用微粒装载本发明两或多轴挤压机。在该情况下，本发明的挤压机特别是用于熔化、浓缩和用于与添加剂混合。在反应和必要时提前蒸发或沉淀之后产生聚合物的形式对于技术人员是公知的。对此的例子是
●聚丙烯，其中在最后反应之后产生粉末形式的聚合物
●来自气相或料浆工艺的高密度聚乙烯
●在沉淀和必要时干燥之后的乳液聚合物，例如丙烯腈-丁二烯-苯乙烯
在后处理(Aufarbeitung)时，本发明双或多轴挤压机特别适用于具有脱气的任务。在此在从瓶装物直接后处理循环的聚对苯二甲酸乙二酯时得出特别的优点，所述后处理在最小温度负荷情况下实现脱气。
特别优选地，本发明方法被应用于制备和复合聚碳酸酯。在此情况下，特别是在聚碳酸酯的颜色方面提供优点，所述颜色在非染色的聚碳酸酯情况下利用黄度指数(YI)测量。本发明螺杆元件在此情况下特别优选地在脱气区中被使用。
用于制备聚碳酸酯的对本发明方法适用的二酚在现有技术中多次被描述。
适用的二酚例如是对苯二酚、间苯二酚、二羟基联苯、双-(羟基苯基)-链烷烃、双-(羟基苯基)-环烷烃、双-(羟基苯基)-硫化物、双-(羟基苯基)-醚、双-(羟基苯基)-酮、双-(羟基苯基)-砜、双-(羟基苯基)-亚砜、α，α′-双-(羟基苯基)-二异丙苯以及其烷基化、芳环上烷基化、芳环上卤代的化合物。
优选的二酚是4，4′-二羟基联苯、2，2-双-(4-羟基苯基)-苯基-丙烷、1，1-双-(4-羟基苯基)-苯基-乙烷、2，2-双-(4-羟基苯基)丙烷、2，4-双-(4-羟基苯基)-2-甲基丁烷、1，3-双-[2-(4-羟基苯基)-2-丙基]苯(双酚M)、2，2-双-(3-甲基-4-羟基苯基)-丙烷、双-(3，5-二甲基-4-羟基苯基)-甲烷、2，2-双-(3，5-二甲基-4-羟基苯基)-丙烷、双-(3，5-二甲基-4-羟基苯基)-砜、2，4-双-(3，5-二甲基-4-羟基苯基)-2-甲基丁烷、1，3-双-[2-(3，5-二甲基-4-羟基苯基)-2-丙基]-苯和1，1-双-(4-羟基苯基)-3，3，5-三甲基环己烷(双酚TMC)。
特别优选的二酚是4，4′-二羟基联苯、1，1-双-(4-羟基苯基)-苯基-乙烷、2，2-双-(4-羟基苯基)-丙烷、2，2-双-(3，5-二甲基-4-羟基苯基)-丙烷、1，1-双-(4-羟基苯基)-环己烷和1，1-双-(4-羟基苯基)-3，3，5-三甲基环己烷(双酚TMC)。
在均聚碳酸酯(Homopolycarbonate)的情况下仅使用一种二酚，在共聚碳酸酯的情况下使用多种二酚，其中当然所使用的二酚、还有所有添加到合成物中的其他化学试剂和助剂都可能被来自其自身的合成、处理和贮存的杂质污染，尽管值得期望的是用尽可能干净的原料工作。
用于调节分子量所需要的单功能链终止剂(例如酚或烷基酚、尤其是苯酚、对叔丁基苯酚、异辛基苯酚、枯基苯酚、其氯甲酸酯或单羧酸的酰氯或这些链终止剂的混合物)或者与双酚盐或双酚盐类一起被引入反应或者在每一任意时刻被添加到合成，只要在反应混合物中还存在光气或氯甲酸端基，或者在酰氯和氯甲酸酯作为链终止剂的情况下，只要形成的聚合物的足够的酚端基可供使用。但是，所述一种或多种链终止剂优选地在光气化之后在某地点或在某时刻被添加，其中不再存在光气，但是催化剂仍不被分配剂量。可替代地，所述链终止剂也可以在催化剂之前、与催化剂一起或并行地被分配剂量。
以相同的方式，必要时支化剂或支化剂混合物被添加到合成物中。但是通常支化剂在链终止剂之前被添加。通常，使用三苯酚、四联苯或者三或四羧酸的酰氯或者多酚或酰氯的混合物。具有三或大于三酚属羟基的作为支化剂适用的化合物中的一些例如是间苯三酚、4，6-二甲基-2，4，6-三-(4-羟基苯基)-庚-2-烯、4，6-二甲基-2，4，6-三-(4-羟基苯基)-庚烷、1，3，5-三-(4-羟基苯基)-苯、1，1，1-三-(4-羟基苯基)-乙烷、三-(4-羟基苯基)-苯基甲烷、2，2-双-(4，4-双(4-羟基苯基)-环己基]-丙烷、2，4-双-(4-羟基苯基-异丙基)-酚、四-(4-羟基苯基)-甲烷。
其他三官能化合物中的一些是2，4-二-羟基苯甲酸、均苯三酸、氰尿酰氯和3，3-双-(3-甲基-4-羟基苯基)-2-氧代-2，3-二氢吲哚。
优选的支化剂是3，3-双-(3-甲基-4-羟基苯基)-2-氧代-2，3-二氢吲哚和1，1，1-三-(4-羟基苯基)-乙烷。
在聚碳酸酯的相界面合成中优选使用的催化剂是叔胺、尤其是三乙胺、三丁胺、三辛胺、N-乙基哌啶、N-甲基哌啶、N-异/正-丙基哌啶、如四丁铵-、三丁基苄基铵-、四乙基铵-氢氧化物、-氯化物、-溴化物、-硫酸氢盐、-四氟硼酸盐之类的季铵盐以及对应于铵化合物的鏻化合物。所述化合物在文献中作为典型的相界面催化剂被描述，在商业上可得到并且对技术人员而言是常见的。催化剂可以单独地、以混合物形式或者也可以同时和相继地被添加到合成物中，必要时也可以在光气化之前，但是优选地，分配剂量在引入光气之后，除非鎓类化合物或鎓类化合物的混合物被用作催化剂。在这种情况下，优选在光气分配剂量之前添加。对所述一种催化剂或多种催化剂分配剂量可以在本体中、在惰性溶剂、优选地聚碳酸酯合成物溶剂中或者也作为水溶液、在叔胺(tert.Amine)的情况下则作为其与酸、优选矿物酸、尤其是盐酸的铵盐来进行。在使用多种催化剂或对催化剂总量的部分量分配剂量的情况下，当然也可以在不同的地点或在不同的时间进行不同的分配剂量方式。所使用的催化剂的总量相对于所使用的双酚摩尔数为0.001至10摩尔百分比(Mol-％)，特别优选地为0.01至8摩尔百分比，特别优选地为0.05至5摩尔百分比。
可以连续地或不连续地进行聚碳酸酯合成。因此，该反应可以在搅拌釜、管式反应器、复循环泵反应器或搅拌釜级联或其组合中进行。在此，通过使用已经提及的混合设备保证，只有当合成混合物已经反应完，也就是说不再含有光气或氯甲酸酯的可皂化氯时，水相和有机相才尽可能脱混。
在引入光气之后有利地可混匀有机相和水相一定的时间，必要时在支化剂之前，只要所述支化剂不与双酚盐一起被分配剂量，链终止剂和催化剂被添加。这种再反应时间在每个分配剂量之后可能是有利的。所述再搅拌时间处于10秒至60分钟，优选地30秒至40分钟，特别优选地1至15分钟。
有机相可以由溶剂或多种溶剂的混合物组成。适当的溶剂是氯化碳氢化合物(脂肪族的和/或芳香族的)，优选地是二氯甲烷、三氯乙烯、1，1，1-三氯乙烷、1，1，2-三氯乙烷和氯苯和其混合物。但是也可以使用如苯、甲苯、间/对/邻-二甲苯之类的芳香族碳氢化合物或者如苯甲醚之类的芳香族醚，单独地或以与氯化烃类混合或附加到其中的方式使用。合成的另一实施形式使用不溶解聚碳酸酯而只是使聚碳酸酯溶胀的溶剂。因此也可以与溶剂组合地使用用于聚碳酸酯的非溶剂。在此，如果溶剂伙伴形成第二有机相，则作为溶剂也可以使用在水相中可溶的溶剂如四氢呋喃、1，3/1，4-二氧杂环己烷或1，3-二氧戊环。
反应完的至多还包含微量(＜2ppm)氯甲酸酯的至少两相反应混合物可以沉降用于相分离。碱性水相可能完全地或部分地作为水相被引回到聚碳酸酯合成中或者被输送给废水后处理，其中溶剂和催化剂分量被分离和反馈。在后处理的另一变型方案中，在分离有机杂质、尤其是溶剂和聚合物剩余物之后和必要时在例如通过添加氢氧化钠溶液调整确定的pH值之后，盐被分离，所述盐例如可以被输送给氯碱电解质，而水相必要时又被输送给合成。
包含聚碳酸酯的有机相现在可以经净化以除去碱性的、离子的或催化类型的所有污物。有机相也在一个或多个沉降过程之后仍包含微滴形式的碱性水相成分以及催化剂，一般是叔胺。沉降过程必要时可以通过以下方式被支持，即有机相经历沉降釜、搅拌釜、聚结器或分离器或其组合，其中必要时水在每个或几个分离步骤中可能在使用有源或无源混合设备的情况下被分配剂量。
在碱性水相的所述粗略分离之后，有机相利用稀释酸、矿物酸、羧酸、羟基羧酸和/或磺酸一次或多次被洗涤。优选含水矿物酸、尤其是盐酸、亚磷酸和磷酸或所述酸的混合物。所述酸的浓度应该处于0.001至50重量百分比、优选0.01至5重量百分比的范围中。
此外，有机相利用脱盐的或蒸馏的水重复地被洗涤。在各个洗涤步骤之后分离必要时与水相的部分分散的有机相借助于沉降釜、搅拌釜、聚结器或分离器或其组合来实现，其中洗涤水可以在洗涤步骤之间必要时在使用有源或无源混合设备的情况下被分配剂量。
在所述洗涤步骤之间或者也在洗涤之后必要时可以添加优选地溶解在聚碳酸酯溶液所基于的溶剂中的酸。这里优选地使用氯化氢气体、磷酸或亚磷酸，其必要时也可以作为混合物被使用。
所述净化的溶液于是可以在下面的步骤中被输送给具有特别螺杆几何形状的本发明蒸发挤压机。
按照本发明方法所获得的聚碳酸酯可以被配备常见的添加剂和添加物(例如助剂和加固剂)用于改变性质。添加剂和附加料的附加用于延长使用持续时间(例如水解或分解稳定剂)、改善颜色稳定性(例如热和UV稳定剂)、简化处理(例如脱模剂、助流剂)、改善气味特性(例如抗静电剂)、改善火焰保护、影响光学印象(例如有机染料、颜料)或使聚合物特性与确定的负荷匹配(抗冲改性剂、细碎的矿物质、纤维材料、石英粉、玻璃纤维和碳纤维)。
下面根据示出实施例的图1更详细地阐述本发明。
聚合物溶液通过输送1被输送给向下开口的管束式换热器2。管束式换热器利用加热介质被加热，所述加热介质在3被供应和在4被引出。在管末端，聚合物溶液减压(entspannen)到分离容器5中，所述分离容器直接布置在挤压机上方。所释放的气体通过蒸气混合物线路6被引出。产品直接落进挤压机的喂入区7中并且通过密封区8被输送给第一脱气区9，所述第一脱气区9具有脱气罩10。之后是其他止流区8和脱气区9。在最后的脱气罩之前，在捏和区11中通过添加点12添加氮。在添加点13时还添加添加剂和必要时熔化的聚合物，所述聚合物在压力建立和混合区14中与聚合物流混合。
下面的例子用于示例性地阐述本发明并且不应被理解为限制。
聚碳酸酯的相对粘度被确定为聚碳酸酯溶液的粘度与纯溶剂的粘度之比。所述相对粘度通常在二氯甲烷中每升溶剂在5g聚合物的浓度时在25℃时被确定。
比较例1
6750kg/h具有65％聚碳酸酯的溶液被馈入按照图6的脱气挤压机中。在闪蒸之前溶液的温度为230℃。所有区根据现有技术利用螺杆元件被实施。区A至L利用两导程元件来实施，区M利用三导程元件实施。聚碳酸酯的相对溶液粘度为1.295。挤压机的转速为350/min。在进口(区A)处的压力为1.4bar abs，在区C、E、G、J和L中的压力逐步地从1bar abs下降到5mbar abs。在区K中，每小时15千克氮作为携带剂被添加和分散。
在蒸发挤压机之后的温度是398.4℃，氯苯的剩余含量小于400ppm。黄度指数为1.9。
例2
6750kg/h具有65％聚碳酸酯的溶液被馈入按照图6的脱气挤压机中。在闪蒸之前溶液的温度为230℃。区A、B、C、D、E、F、G和M根据现有技术利用螺杆元件被实施。区J、K和L被装备有本发明螺杆元件。聚碳酸酯的相对溶液粘度为1.295。挤压机的转速为350/min。在进口(区A)处的压力为1.4bar abs，在区C、E、G、J和L中的压力逐步地从1bar abs下降到5mbar abs。在区K中，每小时15千克氮作为携带剂被添加和分散。
在蒸发挤压机之后的温度是386.7℃，氯苯的剩余含量小于400ppm。黄度指数为1.5。
比较例3
7500kg/h具有65％聚碳酸酯的溶液被馈入按照图7的脱气挤压机中。溶液在挤压机中在进口之前利用管束式换热器1预热。所有区根据现有技术利用螺杆元件被实施。区A至L利用两导程元件来实施，区M利用三导程元件实施。聚碳酸酯的相对溶液粘度为1.295。挤压机的转速为350/min。在进口(区A)处的压力为1.4bar abs，在区C、E、G、J和L中的压力逐步地从1bar abs下降到5mbar abs。在区K中，每小时15千克氮作为携带剂被添加和分散。
在蒸发挤压机之后的温度是399.2℃，氯苯的剩余含量小于400ppm，和黄度指数为2.2。
例4
7500kg/h具有65％聚碳酸酯的溶液被馈入按照图6的脱气挤压机中。在闪蒸之前溶液的温度为230℃。区A、B、C、D、E、F、G和M根据现有技术利用螺杆元件被实施。区J、K和L被装备有本发明螺杆元件。聚碳酸酯的相对溶液粘度为1.295。挤压机的转速为350/min。在进口(区A)处的压力为1.4bar abs，在区C、E、G、J和L中的压力逐步地从1bar abs下降到5mbar abs。在区K中，每小时15千克氮作为携带剂被添加和分散。
在蒸发挤压机之后的温度是388℃，氯苯的剩余含量小于400ppm，和黄度指数为1.7。
Claims (24)
1.用于在使用具有成对同向和成对精密刮削的螺杆轴、具有两个或更多个螺杆导程、具有轴距A和外直径DE的多轴螺杆机的螺杆元件的情况下挤压塑性物质的方法，其特征在于，元件对的顶锥角之和大于0并且小于
其中Z是每个元件的净化外壁的圆弧的数目，并且所述顶锥角是所述圆弧之一的与回转中点有关的角度。
2.根据权利要求1所述的方法，其特征在于，用来产生的和被产生的螺杆型线的螺杆元件的型线分别由6*Z或更多个具有大于或等于零并且小于或等于A的半径的圆弧组成，其中所述圆弧在其端点处以切线的方式过渡到彼此。
3.根据权利要求2所述的方法，其特征在于，被产生的和用来产生的螺杆型线的所谓相对应的圆弧的螺杆元件对分别通过以下方式来表征，即
-相对应的圆弧的角度大小相同，
-相对应的圆弧的半径之和等于轴距，
-用来产生的螺杆型线的圆弧的圆心点和其端点之间的连接线中的每一个平行于被产生的螺杆型线的相对应的圆弧的圆心点和其端点之间的连接线中的每一个，
-用来产生的螺杆型线的圆弧的端点从圆弧的圆心点出发所在的方向与被产生的螺杆型线的相对应的圆弧的端点从被产生的螺杆型线的圆弧的圆心点出发所在的方向分别相反，
-用来产生的螺杆型线的圆弧的圆心点与被产生的螺杆型线的相对应的圆弧的圆心点具有间距，该间距相应于轴距，
-用来产生的螺杆型线的圆弧的圆心点和被产生的螺杆型线的相对应的圆弧的圆心点之间的连接线平行于用来产生的螺杆型线的回转点和被产生的螺杆型线的回转点之间的连接线，
-为了与被产生的螺杆型线的相对应的圆弧的圆心点重合而必须将用来产生的螺杆型线的圆弧的圆心点移动的方向，是为了与被产生的螺杆型线的回转点重合而必须将用来产生的螺杆型线的回转点移动的相同方向。
4.根据前述权利要求之一所述的方法，其特征在于，具有半径0的圆弧紧接着螺杆元件的型线的至少一个齿弧。
5.根据权利要求1至3之一所述的方法，其特征在于，具有半径＞0并且小于0.1乘以螺杆直径的圆弧紧接着螺杆元件的型线的至少一个齿弧。
6.根据权利要求1至3之一所述的方法，其特征在于，螺杆元件的齿弧和槽弧在循环时绕型线进行交替。
7.根据权利要求1至3之一所述的方法，其特征在于，螺杆元件具有数个对称轴，该数目相应于螺纹头数的数目。
8.根据权利要求1至3之一所述的方法，其特征在于，螺杆元件具有点对称性，但不具有镜像对称性。
9.根据权利要求1至3之一所述的方法，其特征在于，螺杆元件被实施为输送元件。
10.根据权利要求1至3之一所述的方法，其特征在于，螺杆元件在脱气或输送区中被使用。
11.根据权利要求1至3之一所述的方法，其特征在于，在螺杆元件和外壳之间和/或在相邻的螺杆元件之间具有关于螺杆型线的直径在0.1至0.001的范围中的间隙。
12.根据权利要求1至3之一所述的方法，其特征在于，塑性物质是热塑性塑料或弹性体。
13.根据权利要求12所述的方法，其特征在于，作为热塑性塑料使用聚碳酸酯、聚酰胺、聚酯、聚醚、热塑性聚氨酯、聚缩醛、含氟聚合物、聚醚砜、聚烯烃、聚酰亚胺、聚丙烯酸酯、聚苯醚、聚苯硫醚、聚醚酮、聚芳醚酮、苯乙烯聚合物、苯乙烯共聚物、丙烯腈-丁二烯-苯乙烯嵌段共聚物、聚氯乙烯或所述热塑性塑料的至少两种的共混物。
14.根据权利要求13所述的方法，其特征在于，聚酯是聚对苯二甲酸丁二酯和聚对苯二甲酸乙二酯。
15.根据权利要求13所述的方法，其特征在于，含氟聚合物是聚偏1，1，-二氟乙烯。
16.根据权利要求13所述的方法，其特征在于，聚烯烃是聚乙烯和聚丙烯。
17.根据权利要求13所述的方法，其特征在于，聚丙烯酸酯是聚(甲基)丙烯酸甲酯。
18.根据权利要求13所述的方法，其特征在于，苯乙烯聚合物是聚苯乙烯。
19.根据权利要求13所述的方法，其特征在于，苯乙烯共聚物是苯乙烯-丙烯腈共聚物。
20.根据权利要求13所述的方法，其特征在于，作为热塑性塑料使用聚碳酸酯或聚碳酸酯与其他聚合物的共混物。
21.根据权利要求20所述的方法，其特征在于，聚碳酸酯根据相界面方法或熔体酯交换方法被制备。
22.根据权利要求12所述的方法，其特征在于，作为弹性体使用苯乙烯-丁二烯橡胶、天然橡胶、丁二烯橡胶、异戊二烯橡胶、乙丙橡胶、丁腈橡胶、氢化腈橡胶、丁基橡胶、卤化丁基橡胶、氯丁橡胶、乙烯-醋酸乙烯酯橡胶、聚氨酯橡胶、热塑性聚氨酯、古塔胶、丙烯酸酯橡胶、氟橡胶、硅橡胶、硫化橡胶、氯磺酰基聚乙烯橡胶或所述弹性体的至少两种的组合。
23.根据权利要求22所述的方法，其特征在于，乙丙橡胶是三元乙丙橡胶。
24.根据权利要求13所述的方法，其特征在于，填充或加固剂或聚合物添加剂或者有机或无机颜料或其混合被添加给聚合物。
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2008
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- 2009-05-30 US US12/999,810 patent/US9944008B2/en active Active
- 2009-05-30 SG SG2013047279A patent/SG191688A1/en unknown
- 2009-05-30 JP JP2011513903A patent/JP5640000B2/ja active Active
- 2009-05-30 RU RU2011101757/05A patent/RU2513427C9/ru not_active IP Right Cessation
- 2009-05-30 CN CN200980123347.2A patent/CN102066067B/zh not_active Expired - Fee Related
- 2009-05-30 KR KR1020107028461A patent/KR101614176B1/ko active IP Right Grant
- 2009-05-30 ES ES09765528T patent/ES2403287T3/es active Active
- 2009-06-09 WO PCT/EP2009/004121 patent/WO2009152973A1/de active Application Filing
- 2009-06-09 EP EP09765553A patent/EP2291270B1/de active Active
- 2009-06-09 CN CN200980123296.3A patent/CN102066066B/zh active Active
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- 2009-06-09 JP JP2011513914A patent/JP5646467B2/ja active Active
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Also Published As
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| CA2728440A1 (en) | 2009-12-23 |
| ES2403287T3 (es) | 2013-05-17 |
| CN102066067A (zh) | 2011-05-18 |
| DE102008029305A1 (de) | 2009-12-24 |
| TWI492834B (zh) | 2015-07-21 |
| WO2009152973A1 (de) | 2009-12-23 |
| US20110233818A1 (en) | 2011-09-29 |
| SG191688A1 (en) | 2013-07-31 |
| RU2522624C2 (ru) | 2014-07-20 |
| JP2011524279A (ja) | 2011-09-01 |
| US8979355B2 (en) | 2015-03-17 |
| BRPI0914295A2 (pt) | 2015-11-03 |
| KR101614176B1 (ko) | 2016-04-20 |
| EP2291270B1 (de) | 2013-01-30 |
| RU2513427C2 (ru) | 2014-04-20 |
| JP5640000B2 (ja) | 2014-12-10 |
| CN102066066B (zh) | 2014-08-27 |
| US20110141843A1 (en) | 2011-06-16 |
| JP2011524281A (ja) | 2011-09-01 |
| EP2291270A1 (de) | 2011-03-09 |
| RU2011101756A (ru) | 2012-07-27 |
| RU2522624C9 (ru) | 2015-02-20 |
| US9944008B2 (en) | 2018-04-17 |
| JP5646467B2 (ja) | 2014-12-24 |
| ES2401333T3 (es) | 2013-04-18 |
| RU2513427C9 (ru) | 2014-09-20 |
| RU2011101757A (ru) | 2012-07-27 |
| KR20110019747A (ko) | 2011-02-28 |
| TW201016440A (en) | 2010-05-01 |
| CN102066066A (zh) | 2011-05-18 |
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