CN100519659C - 连续制造高粘度可交联聚硅氧烷组合物的方法 - Google Patents
连续制造高粘度可交联聚硅氧烷组合物的方法 Download PDFInfo
- Publication number
- CN100519659C CN100519659C CNB2006100774506A CN200610077450A CN100519659C CN 100519659 C CN100519659 C CN 100519659C CN B2006100774506 A CNB2006100774506 A CN B2006100774506A CN 200610077450 A CN200610077450 A CN 200610077450A CN 100519659 C CN100519659 C CN 100519659C
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- Prior art keywords
- organopolysiloxane
- kneading
- kneading chamber
- additive
- viscosity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
本发明涉及连续制造在提高的温度下固化的有机聚硅氧烷组合物(MH)的方法，该有机聚硅氧烷组合物(MH)在25℃下测得的粘度至少为500帕斯卡·秒，在该方法中于具有至少2个彼此相临排列成一行的捏合室的级联捏合器内，将高粘度的有机聚硅氧烷(OH)与交联添加剂(H)加以混合并实施均匀化，这些捏合室均具有两个轴平行的可同向或反向驱动的捏合工具，并通过可横穿捏合工具轴的开孔相互连接，其中第一捏合室具有进料孔，而最后的捏合室具有出料孔，含有该交联添加剂(H)的捏合室内的温度最高为95℃。
Description
技术领域
本发明涉及在级联捏合器内制造于升高的温度下可固化的有机聚硅氧烷组合物的方法。
背景技术
数十年来，于辗压机上，通常为2辊轧机机架上，将对温度敏感的添加剂，如过氧化物或HSi官能的交联剂及铂催化剂，混入长链乙烯基官能的有机聚硅氧烷/填料混合物(HTV橡胶或HCR橡胶)内。即使在高度填充且粘度非常高的聚硅氧烷配制品的情况下，如HTV(又称硬橡胶)，这些易冷却的辗压机可用低温过氧化物制造质量优异的混合物，最终加工者/顾客可将该混合物固化成不同的弹性体。但尤其是在需要混入更多的低粘度如油状的添加剂时，该传统方法需消耗相对更多的时间及人力。
于更大的机器内，如封闭式捏合机，对于最终加工者而言所需的混入添加剂的操作明显更经济(产量更高)。但由于在填充了高粘度HTV橡胶的情况下随总质量的增加而产生的高摩擦热，需要的冷却效率高，或限制适合于大体积的交联剂/促进剂的待混合量及反应性。此外，在实施温度控制的情况下，大型捏合机需要相对更长的装填及卸载时间，这限制了每吨最终产品的产量。
所以早在上世纪90年代就尝试了在螺杆挤出机内连续制造此类聚硅氧烷混合物，如热塑性塑料及部分情况下的有机橡胶。此处可参考DIK-Seminar“连续混合(Kontinuierliches Mischen)”，25.-26.10.1999；尤其是H.Schaarschmidt的有关Berstorff公司的双螺杆挤出机(ZSE)的报告：同步旋转的双螺杆挤出机属于加工热塑性塑料的标准技术，由于摩擦热，在高度填充的HTV橡胶的情况下，产品温度上升得相对较高，尤其是在低于100℃下引发的反应性交联系统的情况下，即使实施迅速冷却，效率比(HTV混合物/时间×挤出机长度)仍非常有限。EP1110696A2描述了优选在140至180℃下(自调节的混合器温度)，于双螺杆挤出机内，将用增强性填料填充的不含交联剂的HTV基础混合物加以混合。此处，在混入不耐热的添加剂之前，需要单独的冷却步骤。
此外，尤其是在用硅石高度填充的坚硬的HTV橡胶的情况下，强烈混合的双螺杆挤出机在金属磨损情况上存在问题，所以即使在中等压力下，仍会产生非期望的“灰色线”。
DE 196 17 606 A描述了一种“连续制造存储稳定的有机聚硅氧烷组合物的方法”，其中在具有一系列相临排列的捏合室的捏合机内，将预先疏水化的硅石混入乙烯基硅封端的聚二甲基硅氧烷内。以ContemaR捏合机为例，用粘度相对较低的聚二甲基硅氧烷(在实施例中为20,000毫帕斯卡·秒)，15分钟后温度已达到100℃。在双螺杆挤出机内，用同样的原料制造基础组合物的类似的比较实验在2分钟后温度已上升至150℃。
在DE 103 13 941 A中，同样在该级联捏合器内，由原料固体聚合物及增强性硅石混合成更高粘度的HTV聚硅氧烷组合物。在此情况下，在6个无加热或冷却装置的捏合室之后，出口温度已达到150℃，而在最优的工作过程中该温度上升至超过200℃。此外，经粉末输送/称重的填料以及HTV聚合物是在超过100℃的温度下按计量加入的，因此粘度明显低于室温，而类似于液体。
发明内容
本发明的目的是提供一种连续的方法，利用该方法可以特别经济的方式制造在提高的温度下固化的可交联的高粘度有机聚硅氧烷组合物。
本发明涉及连续制造在提高的温度下固化的有机聚硅氧烷组合物(MH)的方法，该有机聚硅氧烷组合物(MH)在25℃下测得的粘度至少为500帕斯卡·秒，在该方法中于具有至少2个彼此相临排列成一行的捏合室的级联捏合器内，将高粘度的有机聚硅氧烷(OH)与交联添加剂(H)加以混合并实施均匀化，这些捏合室均具有两个轴平行的可同向或反向驱动的捏合工具，并通过可横穿捏合工具轴的开孔相互连接，其中第一捏合室具有进料孔，而最后的捏合室具有出料孔，含有该交联添加剂(H)的捏合室内的温度最高为95℃。
目前在本领域中，无法于级联捏合器内实现低温输送及交联剂的良好的混入性能。
与上述现有技术相比，在该级联捏合器内，低温输送与交联添加剂(H)及任选的其他添加剂(Z)的良好的混入性能可以更经济地实现：在根据本发明的方法中，非常坚硬的有机聚硅氧烷组合物(MH)以及对温度敏感的添加剂，无需交联系统的部分固化作用即可达到高的物料通量，从而可获得比辗压机、螺杆挤出机或非连续混合器明显更好的产率。
即使在较长的时间后，仍能制得良好地均匀化的可交联有机聚硅氧烷组合物(MH)，所以特定的质量控制成本低于根据现有技术制造的MH混合物。
使用同样的原料时，与在标准混合器或可冷却的捏合器内制造的有机聚硅氧烷组合物相比，尤其是在带式输出形状(Bandlieferformen)的情况下，使存储稳定性提高。
例如通过将少量能量输入混合物内的捏合钩(Knethaken)，通过大的热交换面积或通过使用液态冷却剂的迅速冷却作用，可在级联捏合器内，尤其是含有交联添加剂(H)的捏合室内，保持低温。
该有机聚硅氧烷(OH)与该交联添加剂(H)及任选的其他添加剂(Z)优选以恒定的质量比加以混合并实施均匀化。
该高粘度的有机聚硅氧烷(OH)可为一种有机聚硅氧烷(OH)或为不同有机聚硅氧烷(OH)的混合物。涉及制造HTV组合物、LSR组合物、RTV-1组合物及RTV-2组合物的本领域技术人员已知，可使用所有充分说明的有机聚硅氧烷(OH)。它们包括直链、分支、环状或树脂状的有机聚硅氧烷，这些有机聚硅氧烷可任选含有通常为了可交联性的官能基团。优选使用直链型有机聚硅氧烷(OH)，如聚合度为50至9,000的聚二甲基硅氧烷。该有机聚硅氧烷(OH)的有机基团优选为甲基、苯基、乙烯基及三氟丙基，更优选为甲基。优选存在于聚有机硅氧烷内的官能基团为-SiOH、-SiOR、Si-乙烯基及-SiH，更优选为乙烯基。特别优选的有机聚硅氧烷(OH)是通常用于制造热固性HTV聚硅氧烷组合物的有机聚硅氧烷(O)，其在25℃下测得的Brabender值为200至900daNm，更优选为400至700daNm。
该有机聚硅氧烷(OH)的组成优选对应于平均通式(1)
R1 aR2 bSiO(4-a-b)/2 (1)，
其中
R1代表相同或不同的、选自-H、-OH、-OR的单价硅键结基团，其中R代表C1-C10烃基以及任选被卤素或氰基取代的、任选经二价有机基团与硅键结的、含有至少一个脂族碳碳多键的C1-C10烃基，
R2代表相同或不同的、硅键结的、任选被卤素或氰基取代的、不含脂族碳碳多键的单价C1-C10烃基，
a是0至1的非负数，及
b是1至2.1的非负数。
R1优选为可与SiH官能的交联剂或与过氧化物反应的烯基。通常使用具有2至6个碳原子的烯基，如乙烯基、烯丙基、甲基烯丙基、1-丙烯基、5-己烯基、乙炔基、丁二烯基、己二烯基、环戊烯基、环戊二烯基、环己烯基，优选为乙烯基及烯丙基。
这些烯基可经例如由氧化烯基单元组成的二价有机基团与聚合物链上的硅键结，该氧化烯基单元例如具有通式(2)
-(O)p[(CH2)qO]r- (2)，
其中
p是0或1的值，优选为0，
q是1至4的值，优选为1或2，及
r是1至20的值，优选为1至5。
通式(2)的氧化烯基单元于左侧与硅原子相连。
基团R1可连接在该聚合物链上的任何位置，更优选与末端硅原子相连。
R2优选具有1至6个碳原子，更优选为甲基及苯基。
通式(1)的聚有机硅氧烷的结构可为直链、环状或分支型。导致分支型聚有机硅氧烷的三官能和/或四官能单元的含量通常非常低，即优选为最高20摩尔％，更优选为最高0.1摩尔％。
特别优选使用含有乙烯基的有机聚硅氧烷(OH)，它的分子对应于通式(3)
(ViMe2SiO1/2)c(ViMeSiO)d(Me2SiO)e(Me3SiO1/2)f (3)，
其中，Vi代表乙烯基，而Me代表甲基，非负整数c、d、e及f满足以
下关系式：c+d≥1，c+f＝2，1000<(d+e)<9000，优选为3000<(d+e)<7000，且0<(d+1)/(d+e)<1，优选为0<(d+1)/(d+e)<0.1。
作为交联添加剂(H)，优选为含有铂催化剂或铑催化剂的过氧化物及SiH官能的硅氧烷。优选混入选自以下组中的过氧化物交联剂：过氧化烷基、过氧化缩酮，更优选为反应性更强的过氧化芳酰基。此处特别优选为：2，5-二叔丁基过氧基-2，5-二甲基己烷、过氧化二异丙苯基、1，1-二(叔丁基过氧基)-3，3，5-三甲基环己烷，尤其是过氧化双(4-甲基苯甲酰)及过氧化双(2，4-二氯苯甲酰)。它们优选作为在硅油或有机聚硅氧烷(OH)中的糊状物按计量加入。
作为其他添加剂(Z)，例如可添加促进剂、抑制剂、稳定剂、颜料、染料浆、阻燃或导热性的金属氧化物添加剂、诸如三水合铝的提高电学性能的物质、填料、有机聚硅氧烷改性剂、结构改进剂、加工助剂、分散助剂、诸如硅氮烷的疏水化剂、含有硅烷醇的低聚硅氧烷、改性剂、增塑剂(Weichwalzmittel)、粘合助剂、热稳定剂及抗氧化剂。
SiH官能的硅氧烷连同铂催化剂或铑催化剂的抑制剂优选为乙炔基环己醇。
在该方法中，优选按计量添加染料浆及稳定剂，作为颜料批料或金属氧化物批料或作为炭黑批料，即作为在硅油或有机聚硅氧烷(OH)内的糊状物。该添加剂(Z)/硅氧烷批料的粘度特别优选设定为不超过2000帕斯卡·秒，这是因为与所述粘度更高的有机聚硅氧烷(OH)的进料装置相比，该计量装置的消耗量或成本水平更为有利。以有机聚硅氧烷组合物(MH)为基准，它们的混入量优选为0.2至10％。
作为填料可使用聚硅氧烷组合物中所有常用的填料，还可使用不同填料的混合物。合适的填料例如为：硅石、炭黑、金属氧化物、金属碳酸盐、金属硫酸盐、金属氮化物、硅藻土、粘土、白垩、云母、金属粉末、活性炭、有机塑料粉末等。重要的是：由于含有填料，该含有填料的有机聚硅氧烷组合物(MH)的粘度明显高于以连续的方式混入该含有填料的聚硅氧烷组合物的有机聚硅氧烷(OH)的粘度。优选为增强性填料，即BET比表面积至少为50平方米/克，优选为50至500平方米/克的填料，如热解法制得的硅石，经脱水以获得结构的硅石水凝胶，即所谓的气凝胶，其他类型的沉积二氧化硅及炭黑。特别优选的热解法制得的硅石、沉积硅石及炭黑还可任选实施表面处理，从而例如提高其可分散性。
特别优选为通过疏水化作用获得的碳含量至少为0.5重量％的预先疏水化的氧化物增强性填料。
尤其还可含有在室温下呈固态的纯净的MwDxTyQz型聚硅氧烷树脂的聚硅氧烷树脂。
该有机聚硅氧烷组合物(MH)的填料含量优选为5至80重量％，更优选为10至50重量％。特别优选制造填料含量为20至40重量％的有机聚硅氧烷组合物(MH)。
结构改进剂优选为在25℃下测得的粘度为10至200毫帕斯卡·秒，优选为20至150毫帕斯卡·秒的有机聚硅氧烷。优选为含有硅烷醇的低聚硅氧烷、由三甲基甲硅烷基封端的二甲基低聚硅氧烷或二甲基聚硅氧烷。该结构改进剂的基团优选为选自：甲基、苯基、乙烯基及羟基。
相对于该有机聚硅氧烷(OH)，具有低比表面积的固体添加剂的含量可为低于1％至高于150％。若预期地掺入三水合铝(ATH；BET比表面积为2至9平方米/克)以提高电学性能，则该MH混合物中特别优选含有10至55％。
该方法中，所用的有机聚硅氧烷(OH)可与添加剂(Z)混合。作为待添加的由有机聚硅氧烷(OH)与添加剂(Z)组成的基础混合物，含有乙烯基且不含交联添加剂(H)的所有粘度更高的聚硅氧烷组合物原则上含都是合适的。优选使用粘度范围为1000至100,000帕斯卡·秒或10至150Mooney单位(Mooney终值，在23℃下的ML(1+4分钟)；DIN53523)的HTV聚合物/硅石混合物，该混合物也可商购，尤其是对于辗压混合物及挤出混合物而言，用于混合时的各种不同的用途。如DE 103 13 941 A1所述，这些混合物为Wacker化学公司的HTV型系列的
R(橡胶)。
该级联捏合器优选由最少3个且最多10个捏合室组成，特别优选为最多6个捏合室。此处，最后的捏合室优选具有泵叶片以排出产品。起始原料可以任意顺序按计量添加并混入；还可将起始原料添加至该级联捏合器的一个或更多个捏合室内。优选将所有的有机聚硅氧烷(OH)添加至第一捏合室内。也可将部分有机聚硅氧烷(OH)添加至靠后的捏合室内，例如用于降低来自第一捏合室的有机聚硅氧烷组合物(MH)的粘度。可将预计的交联添加剂(H)及任选的添加剂(Z)添加至所有捏合室内；优选不将填料添加至最后的捏合室内。在此情况下，可将所需填料的总量仅添加至一个/两个或三个前端的捏合室内，但添加剂(H)、填料及任选的添加剂(Z)也可分布在所有捏合室内。
在稳定剂糊状物及染料浆中有效的氧化物可作为粉末添加，优选将其混入该级联混合机前端的捏合室内。对于呈粉末状且易熔化的交联剂，如过氧化二异丙苯基，与添加剂(Z)—硅氧烷批料相比，这是更有利的具体实施方案。
若使用结构改进剂，则优选将它们添加至前端的几个捏合室内，尤其是添加至第一捏合室内。优选不将油状添加剂(Z)添加至最后的捏合室内。
该级联捏合器优选具有至少3个，更优选为至少5个捏合室。单个捏合室或所有捏合室之间均可安装筛网、圆盘刮板或挡板以阻挡该有机聚硅氧烷组合物(MH)。可调节这些元件的位置以及可释放的开孔，从而影响单个捏合室内的停留时间。捏合工具优选为捏合钩、捏合叶片、滚筒或多边形盘。
除第一捏合室的进料口之外，该捏合器内优选还具有导入单个捏合室内或位于两个捏合室之间的其他进料口。优选每个捏合室均具有一个进料口。尤其是第一及第三捏合室的进料口适合于送入固体物质，而其他进料口则适合于送入液体或可压出的糊状物。
因为该级联捏合器内几乎不存在自由的气体空间，所以可省略保护气体。
根据本发明的方法中，该级联捏合器的每个捏合室均优选具有单独的驱动装置，从而可以精确且最优地控制各个捏合室内混合加工的强度。
这些捏合室优选为可加热和/或可冷却的，它们尤其可在不同的温度下单独工作。
在此情况下，前端的捏合室优选为可加热的，例如用于混入可熔化的固体物质。后端的捏合室优选可迅速冷却，以混入对温度敏感的交联添加剂及添加物质(Z)，并用于导出摩擦热。
在根据本发明的方法中，在捏合室内，尤其是在最后的捏合室至出口处，组合物的温度优选为室温至最高150℃，更优选为40至最高95℃。含有交联添加剂(H)的捏合室的温度优选为最高80℃，更优选为最高70℃。
优选以悬臂式安装捏合工具。轴承侧的外壳端壁具有捏合工具的驱动轴所需的开孔。该捏合室的外壳优选具有横穿工具轴排列的分离点，从而使远离该轴承的外壳部件可从这些分离点及捏合工具沿该驱动轴的轴方向移开。如此构成的捏合器特别容易清洗，因此有利于更换产品。EP 807 509 A描述了该捏合器。
该均匀的有机聚硅氧烷组合物(MH)优选经过柔性连接件或传送带在最后的捏合室之后送至成型出料机上。
虽然该有机聚硅氧烷组合物(MH)由于温度低而在该级联捏合器之后表现出优异的存储稳定性，但通过连续且优选为经冷却的滚筒装置的附加连接仍可进一步提高存储稳定性。此处，优选在可迅速冷却的剪切滚筒上出料，其上任选还可混入添加剂(Z)。
该任选位于下游的出料机优选为可产生压力的喂料式挤出机(Fütterextruder)，尤其是具有反向转动的圆锥形进料螺杆和/或齿轮泵的双螺杆挤出机。
在根据本发明的方法中，利用该预压力，由出料孔板之前还可安装滤网以形成预期的输出形状。优选使用带有换筛附件的自润滑齿轮泵。
在另一个优选的具体实施方案中，于出料器下游安装带有旋转刀具的孔板，以连续制造有机聚硅氧烷组合物(MH)的圆柱状小粒。该线上造粒法是特别经济的，这是因为根据标准方法单独实施的造粒步骤可由连续装置的常规人员实施，无需暂时存储(Zwischenlagerung)该有机聚硅氧烷组合物(MH)。
时间上恒定地按计量加入不含交联剂的有机聚硅氧烷(OH)，其任选与尤其是填料的添加剂(Z)混合，在该级联捏合器中优选可使用产生压力的、任选具有下游齿轮泵的喂料式挤出机。任选与添加剂(Z)混合的有机聚硅氧烷(OH)优选在不实施预处理的情况下预成型，如小粒或粉末。为此，优选使用圆锥状多螺杆挤出机，更优选为反向旋转的双螺杆机。
在结合齿轮泵使用双螺杆挤出机时，可与添加剂(Z)保持特别恒定的混合比例。
双螺杆挤出机，如商品名为Moriyama的挤出机，适用于所有聚硅氧烷固体橡胶的方法，而与其形状及粘度无关，并且在硬化(Verstrammung)倾向/脱混倾向的情况下，将用高度分散的硅石强烈或高度填充的触变性非常高的糊状物加以再塑化。
最终加工者为实施固化所需的液体或糊状添加剂(Z)的精确配制的进料工作，可在该方法中同样经过产生压力的计量装置加以实施。为此，取决于有效成分的流动性，优选使用简单的活塞泵、薄膜泵、齿轮泵或具有转子/定子输送装置的出料泵。经过过程控制系统，优选将这些不同的添加泵的配料效率与任选与添加剂(Z)混合的有机聚硅氧烷(OH)向该级联捏合器的第一捏合室内的所述送料过程加以偶合。从而确保正确的配料比例，并由装置操作人员使物料通量的最适化过程更容易进行。
若待混入的固体物质，特别是阻燃或导热性的金属氧化物添加剂(Z)的量更大，则该特别阻燃或导热性的金属氧化物添加剂优选经差动天平按计量添加，并送入一个或更多个捏合室内。
虽然以上并未明确表示，根据本发明的方法中所用的机器可包括其他已知的部件，如计量及输送装置，例如压力、温度及体积流的测量及调节装置，以及阀，通常用于加热或冷却所需的部件，或输送装置及包装装置。
上述通式中的所有符号的定义均是相互独立的。
附图说明
图1所示为用称重装置(4)按计量添加固体的可能性。
具体实施方式
除非另有说明，以下实施例中所有的量及百分率均是基于重量，所有压力均是0.10MPa(绝对)。所有粘度均是在20℃下测得的。
在以下实施例中使用：
HTV橡胶A：高粘度固体橡胶混合物，其包含：基于100份平均聚合度为5500、具有少量可交联的乙烯基的聚二甲基硅氧烷的40份BET比表面积至少为200平方米/克的增强性硅石，以及加工助剂。该HTV混合物的Mooney粘度(ML(1+4分钟)，在23℃下；DIN 53523)约为40，例如用过氧化物实施固化后的肖氏A硬度为60。
HTV橡胶B：高度填充的捏合器中间产物，其包含：基于100份HTV乙烯基固体聚合物(如同橡胶A)的50份BET比表面积约为200平方米/克的增强性硅石，及少量短链的羟基官能的硅氧烷，其额外包含68份石英，Mooney最终粘度约为53。交联后测得的肖氏A硬度约为80。
实施例1：根据本发明的方法(试运行装置)
该方法根据图1进行描述：
使用IKA机械制造Janke & Kunkel GmbH & Co.KG，Staufen出品的级联捏合器(2)实施混合。该级联捏合器(2)具有6个捏合室，每个捏合室的容量为5升且具有独立可调的叶片组。取决于该添加剂中的油含量，总的物料通量为150至250千克/小时。均使用Colmec公司(Mailand/意大利)出品的CTE 75型圆锥形双螺杆挤出机，送入由有机聚硅氧烷(OH)与填料组成的混合物(1)，并实施有机聚硅氧烷组合物(MH)的出料或成型(6)。
在Visco Tec公司(
/德国)出品的鼓式压出装置(
)(3)与偏心螺杆泵及压力监控装置的PLS偶合下，按计量加入添加剂糊状物。
经上述具有下游齿轮泵的CTE 75型挤出机，精确地将170千克/小时的HTV橡胶A压入经水冷的级联捏合器(2)的捏合室内。同时均经过ViscoMT-XS型出料装置精确地将3.06千克/小时的浓度为50％的过氧化二(4-甲基苯甲酰)在硅油中的糊状物(Degussa/过氧化物化学公司)及2.1千克/小时的
FL蓝-5015型染料浆(Wacker化学公司的产品)按计量加入该捏合混合器的第一及第二捏合室内。经冷却的叶片的转速为15至50转/分钟。约10分钟的停留时间之后，在49℃的温度下将均匀地染成蓝色的橡胶混合物经输送带(5)取出，并输送至另一个经冷却的输送挤出机的竖井(6)内。由该产生压力的螺杆机(6)挤压该MH产品通过安装于出口处的边长为60×100毫米的孔板。将该橡胶棒剪切至长度为340毫米之后，将成品装入20千克的纸箱(7)中或进行质量控制测试。
在135℃下实施固化10分钟，制得肖氏A硬度为61的光滑的测试片。在固化计上实施的来自2吨批料的不同中间产品试样的快速测试显示了相同的T90值，这表明该产品具有突出的均匀性。
实施例2：根据本发明的方法，试运行装置
经计量挤出机(1)将220千克/小时的HTV橡胶B代替实施例1的HTV橡胶A送入级联捏合器(2)内，但现在经鼓式压出装置(3)将1.2％的浓度为45％的2，5-二叔丁基过氧基-2，5-二甲基己烷在硅氧橡胶中的糊状物(可购自过氧化物化学公司，商品名为DHBP-45-PSI)。为进行染色，经Flexwall计量装置(Brabender公司)将8.8千克/小时的
FG黑色-9005着色颗粒直接加入第二捏合室的进料漏斗内，其同样于前一捏合室的出口处均匀地混入。
除实施例1之外，在形成产品形状之前，于该锥形喂料式挤出机的出口处安装具有换筛附件的经冷却的GP112型齿轮泵(Colmec/Mailand公司)，因而此处还可安装100微米的滤网。
在低于60℃的温度下，经过10×40毫米的孔板，制得所谓的L8型连续带，依照质量测试的结果其被均匀混合(在165℃下加压10分钟；对该批次的更多试样实施固化计测试：在量测误差范围内的T90值是相等的)。
该高度填充的HTV混合物的耐油性高。
比较例1：非本发明的方法
在迅速冷却的1吨混合器内，如经水冷的Sigma捏合器，将实施例2中所述的交联活性的安全电缆混合物的相同成分加以混合时，所需的混合及清空时间至少为4小时，这是因为内部温度必须保持在低于100℃，以避免发生部分固化。
对于1位装置操作人员而言，1吨混合器的装填时间至少为1小时，而随后的100微米滤网过程的工作时间(1吨至少约为2至3小时)，直至灌装过程的总产量仅为130至140千克/小时。
与此相比，在根据本发明的方法中，在根据实施例2的相对较小的试运行装置的情况下，计算出每位工作人员的包括线上过滤过程的产量超过220千克/小时。
比较例2：非本发明的方法
在用于混入反应性非常高的交联剂的传统方法中，于如同实施例1的两个经水冷的(直径均为550毫米，长度均为2米)钢辊的大型标准辗压机上，将120千克的HTV橡胶A与1.8％的过氧化二(4-甲基苯甲酰)(＝2.16千克的糊状物，浓度为50％，在硅油中)及1.2％的FL蓝色-5015液体染料浆加以混合。由于该添加剂具有油状稠度，必须逐份地将该添加剂添加在滚压薄片(Walzenfell)上，因此使橡胶不会与以不同转速旋转的辊脱离，而产生损耗。至少20分钟的添加时间之后，开始实施额外的15分钟均匀化，然后再取出至下游的滤网挤出机。该100微米的纯化步骤及类似于实施例1的切割成品的包装工作额外耗时25至30分钟，因而局部加热超过该交联系统的临界橡胶温度65℃，即可以避免交联活性的MH产品的部分固化的温度。
所以，使用润滑的添加剂，标准辗压机的平均产率低于125千克/小时。若单位时间的混合物的量更大，则需面临以下风险：产品的不均匀性及挤出应用中，即顾客的加工问题。这还会在质量控制中，尤其是在不同辗压混合物的固化计数值的特定比较(作为快速测试的交联速率)中辨认出来。
相反地，即使在低温交联剂的情况下，根据本发明的连续混合法，如实施例1中所述，仍能使难以处理的添加剂的质量更高，尤其是使该方法的产率显著更高。
Claims (7)
1、连续制造在提高的温度下固化的有机聚硅氧烷组合物(MH)的方法，该有机聚硅氧烷组合物(MH)在25℃下测得的粘度至少为500帕斯卡·秒，其中于具有至少2个彼此相临排列成一行的捏合室的级联捏合器内，将在25℃下测得的Brabender值为200至900daNm的有机聚硅氧烷(OH)与交联添加剂(H)以恒定的质量比加以混合并实施均匀化，使用选自过氧化烷基、过氧化缩酮及过氧化芳酰基的过氧化物交联剂、HSi官能的硅氧烷以及铂催化剂或铑催化剂及抑制剂作为所述交联添加剂(H)，这些捏合室均具有两个轴平行的可同向或反向驱动的捏合工具，并通过可横穿捏合工具轴的开孔相互连接，其中第一捏合室具有进料孔，而最后的捏合室具有出料孔，其中时间上恒定地利用具有安装在下游的齿轮泵的喂料式挤出机按计量加入不含交联剂的有机聚硅氧烷(OH)，含有该交联添加剂(H)的捏合室内的温度最高为95℃。
2、根据权利要求1所述的方法，其中所述有机聚硅氧烷(OH)与所述交联添加剂(H)及其他添加剂(Z)以恒定的质量比加以混合并实施均匀化。
3、根据权利要求2所述的方法，其中所述添加剂(Z)选自：促进剂、抑制剂、稳定剂、颜料、染料浆、阻燃或导热性的金属氧化物添加剂、提高电学性能的物质、填料、有机聚硅氧烷改性剂、分散助剂、疏水化剂、增塑剂、粘合助剂及抗氧化剂。
4、根据权利要求1至3之一所述的方法，其中所述级联捏合器由3至10个捏合室组成。
5、根据权利要求1至3之一所述的方法，其中所述有机聚硅氧烷组合物(MH)的填料含量为5至80重量％。
6、根据权利要求1至3之一所述的方法，其中使用聚二甲基硅氧烷作为有机聚硅氧烷(OH)，它的分子对应于通式(3)
(ViMe2SiO1/2)c(ViMeSiO)d(Me2SiO)e(Me3SiO1/2)f (3)，
其中，Vi代表乙烯基，而Me代表甲基，非负整数c、d、e及f满足以下关系式：c+d≥1，c+f＝2，1000<(d+e)<9000且0<(d+1)/(d+e)<1。
7、根据权利要求1至3之一所述的方法，其中将所述有机聚硅氧烷组合物(MH)在最后的捏合室之后送至成型的出料机上。
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| DE102005019874.0 | 2005-04-28 | ||
| DE102005019874A DE102005019874A1 (de) | 2005-04-28 | 2005-04-28 | Verfahren zur kontinuierlichen Herstellung von hochviskosen vernetzbaren Siliconmassen |
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| CN1854199A CN1854199A (zh) | 2006-11-01 |
| CN100519659C true CN100519659C (zh) | 2009-07-29 |
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| EP (1) | EP1717002B1 (zh) |
| JP (1) | JP2006307219A (zh) |
| KR (1) | KR100798378B1 (zh) |
| CN (1) | CN100519659C (zh) |
| DE (2) | DE102005019874A1 (zh) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7939014B2 (en) | 2005-07-11 | 2011-05-10 | Saint-Gobain Performance Plastics Corporation | Radiation resistant silicone formulations and medical devices formed of same |
| US9133340B2 (en) | 2005-07-11 | 2015-09-15 | Saint-Gobain Performance Plastics Corporation | Radiation resistant silicone formulations and medical devices formed of same |
| US7943697B2 (en) | 2005-07-11 | 2011-05-17 | Saint-Gobain Performance Plastics Corporation | Radiation resistant silicone formulations and medical devices formed of same |
| US20080166509A1 (en) * | 2007-01-08 | 2008-07-10 | Saint-Gobain Performance Plastics Corporation | Silicone tubing formulations and methods for making same |
| DE102007031989A1 (de) | 2007-07-10 | 2009-01-15 | Contitech Vibration Control Gmbh | Vorrichtung zur Herstellung von Elastomermischungen |
| DE102008054536A1 (de) * | 2008-12-11 | 2010-06-17 | Wacker Chemie Ag | Verfahren zur kontinuierlichen Herstellung von hochviskosen Siliconmassen |
| DE102008055035A1 (de) * | 2008-12-19 | 2010-07-01 | Wacker Chemie Ag | Kontinuierliches Verfahren zur Herstellung von Grundmassen für Siliconzusammensetzungen mit verbesserter Stabilität |
| KR101311189B1 (ko) * | 2011-12-23 | 2013-09-26 | 강윤정 | 방화재용 실리콘 고분자 조성물 및 그 제조방법 |
| FI20155022A (fi) | 2015-01-13 | 2016-07-14 | Oy Pro-Hydro Ab | Menetelmä ja laitejärjestely silikonimassan sekoittamiseksi |
| FR3093457A1 (fr) * | 2019-03-06 | 2020-09-11 | Compagnie Generale Des Etablissements Michelin | Machine de Mélangeage et d’Extrusion à Bi-Vis avec Éléments Amovibles |
| CN112123619B (zh) * | 2020-09-08 | 2022-04-05 | 湖南连心科技有限公司 | 一种用于粉末涂料制备的挤出机进料装置 |
| EP4063091A1 (de) * | 2021-03-26 | 2022-09-28 | Starlinger & Co Gesellschaft m.b.H. | Vorrichtung und verfahren zur wärmebehandlung von thermoplastischen kunststoffschmelzen |
| CN114701099B (zh) * | 2022-04-07 | 2023-08-08 | 华南理工大学 | 一种模块化高分子材料双转子泵式输运设备及输运方法 |
| CN115814669A (zh) * | 2023-02-13 | 2023-03-21 | 山东轩友新材料科技有限公司 | 硅酮胶连续化着色系统 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2049256A1 (en) * | 1990-08-22 | 1992-02-23 | Masao Moriyama | Twin conical screw extruder |
| DE4103602A1 (de) * | 1991-02-07 | 1992-08-13 | Wacker Chemie Gmbh | Verfahren zur kontinuierlichen herstellung von htv-siliconmassen |
| ES2192612T3 (es) * | 1995-09-01 | 2003-10-16 | Dow Corning | Perfiles de gel de silicona extruidos. |
| DE19617606A1 (de) * | 1996-05-02 | 1997-11-06 | Wacker Chemie Gmbh | Kontinuierliches Verfahren zur Herstellung lagerstabiler Organopolysiloxanzusammensetzungen |
| JP2001342347A (ja) * | 2000-05-31 | 2001-12-14 | Dow Corning Toray Silicone Co Ltd | 押出成形用シリコーンゴム組成物およびシリコーンゴム押出成形品の製造方法 |
| JP2002294074A (ja) * | 2001-03-29 | 2002-10-09 | Ge Toshiba Silicones Co Ltd | 高電圧電気絶縁体用シリコーンゴム組成物の製造方法 |
| DE10313941A1 (de) * | 2003-03-27 | 2004-10-14 | Wacker-Chemie Gmbh | Verfahren zur kontinuierlichen Herstellung von hochviskosen Siliconmassen |
| JP4997843B2 (ja) * | 2006-06-26 | 2012-08-08 | 富士電機株式会社 | ソフトウェア修正漏れ確認システムおよび方法 |
-
2005
- 2005-04-28 DE DE102005019874A patent/DE102005019874A1/de not_active Withdrawn
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- 2006-03-30 DE DE502006001472T patent/DE502006001472D1/de active Active
- 2006-04-25 US US11/410,683 patent/US20060247406A1/en not_active Abandoned
- 2006-04-27 JP JP2006123117A patent/JP2006307219A/ja active Pending
- 2006-04-27 KR KR1020060038137A patent/KR100798378B1/ko active IP Right Grant
- 2006-04-28 CN CNB2006100774506A patent/CN100519659C/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN1854199A (zh) | 2006-11-01 |
| KR20060113504A (ko) | 2006-11-02 |
| DE502006001472D1 (de) | 2008-10-16 |
| KR100798378B1 (ko) | 2008-01-28 |
| EP1717002A1 (de) | 2006-11-02 |
| DE102005019874A1 (de) | 2006-11-02 |
| US20060247406A1 (en) | 2006-11-02 |
| JP2006307219A (ja) | 2006-11-09 |
| EP1717002B1 (de) | 2008-09-03 |
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