CN103415538A - 在喷射环流反应器中通过乳液聚合或悬液聚合生产聚合物的方法 - Google Patents
在喷射环流反应器中通过乳液聚合或悬液聚合生产聚合物的方法 Download PDFInfo
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- CN103415538A CN103415538A CN2012800124357A CN201280012435A CN103415538A CN 103415538 A CN103415538 A CN 103415538A CN 2012800124357 A CN2012800124357 A CN 2012800124357A CN 201280012435 A CN201280012435 A CN 201280012435A CN 103415538 A CN103415538 A CN 103415538A
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Abstract
本发明提供了通过一种或多种烯属不饱和单体的自由基引发的异相聚合用于制备处于其水分散液或水可再分散性粉剂形式的聚合物的方法并且可选地随后干燥得到的聚合物分散液,其特征在于,在喷射环流反应器中进行所述异相聚合反应。
Description
技术领域
本发明涉及通过烯属不饱和单体的自由基引发的乳液聚合或悬液聚合用于制备处于其水分散液或水可再分散性粉剂形式的聚合物的方法,以及还有以这种方式获得的方法产品在构建化学产品中的用途,尤其是在构建化学产品中作为涂覆组合物或粘合剂。
背景技术
可以通过间歇、半间歇或连续方法来进行烯属不饱和单体的乳液聚合或悬液聚合。通常在搅拌反应器中进行间歇或半间歇方法以及在搅拌容器、管流反应器或环流反应器的级联中进行连续方法。因此,US-A 3551396描述了用于在环流反应器中制备聚乙酸乙烯酯分散液的方法,其中单体和水连续地循环并且将额外的单体和引发剂连续地计量加入并且将形成的聚合物从反应器中连续地取出。US-A 2703794描述了在乳化剂和可选地水互溶的有机溶剂的存在下用于乙酸乙烯酯和乙烯的连续乳液聚合的方法。缺点是振荡的工艺参数以及因此形成具有不同粒径分布的聚合物。DE-A2555142描述了在许多串联连接的聚合反应器中通过乳液聚合方法用于制备烯属不饱和单体的聚合物的连续方法。EP-A 834518描述了间歇聚合方法,其中在具有外部冷却回路的反应器中进行聚合反应,其中使用低剪切泵(low-shear pump)以便不对产品造成不利影响是绝对必要的。WO-A03/006510描述了在具有外部冷却回路的聚合反应器中的间歇聚合方法,其中通过低剪切缸体泵(cylinder pump)或蠕动泵通过泵送来循环该聚合反应批次以便使产物不受剪切的不利影响。WO-A 02/59158描述了在具有外部冷却回路的反应器中的聚合方法,其中通过泵送来循环该聚合反应批次并且至少部分量的单体不得不引入外部回路。间歇聚合方法的缺点(其中必须通过泵送来循环包含分散的聚合物颗粒的大体积批量)是由于通过泵引入的剪切力造成的它们对聚结的敏感性。
然而,为了制备具有不同平均粒径或不同的粒径分布的聚合物,通常需要改变聚合反应组分的配方或在聚合条件或聚合过程中做出显著的改变。
此外,尤其是在连续的乳液聚合或悬液聚合的方法中的情况下,问题在于在聚合反应的整个持续时间内设置恒定的聚合条件,从而防止工艺参数的摆动(振荡),以便在聚合反应的整个持续时间内形成具有相同特性的聚合物。
发明内容
鉴于这个背景,本发明的目的是通过技术简单的测量以目标方式可以改变的聚合物的产品特性(例如平均粒径或粒径分布宽度)提供用于烯属不饱和单体的乳液聚合或悬液聚合的新方法。具体地,甚至在常规方法中给出>1μm的重量平均粒径分布的配方的情况下(根据ISO13320通过激光散射方法来确定),可以获得≤1μm的重量平均粒径分布。此外,可以抑制工艺参数的摆动(振荡)。
通过在喷射环流反应器中进行烯属不饱和单体的乳液聚合或悬液聚合已经出人意料地实现这个目的。
在下文中也将乳液聚合和悬液聚合共同地称为异相聚合(heterophasepolymerization)。
具体实施方式
本发明提供了通过一种或多种烯属不饱和单体的自由基引发的异相聚合反应用于制备处于其水分散液或水可再分散性粉剂形式的聚合物的方法,并且可选地随后干燥得到的聚合物分散液(polymer dispersions),其特征在于,在喷射环流反应器中进行异相聚合反应。
喷射环流反应器的实例是紧凑的、冲击喷射或喷射区域的环流反应器。例如,在P.Zehner,Bubble Columns4.Jet Loop Reactors,Ullmann′sEncyclopedia of Industrial Chemistry,Article Online Posting Date15.06.2000中已知并且描述了喷射环流反应器本身和它们的结构。
通过图1中的实例显示了本发明的方法的优选实施方式。
通常喷射环流反应器(图1)包含一个或多个喷嘴(2),一个或多个插入管(plug-in tube)(3),可选地一个或多个给料管道(4),可选地一个或多个产品出口(9),可选地一个或多个冲击板(impingement plate)(10),可选地一个或多个外部回路(5)以及可选地另外的结构,例如冷却器,尤其是夹套冷却器。外部回路(5)包括例如,一个或多个泵(7),一个或多个计量管路(6)以及可选地一个或多个热交换器(8)。
通常喷嘴(2)是整个地或部分地定位在喷射环流反应器内。通常相对于彼此线性地,优选以垂直对齐方式来设置喷嘴(2)、插入管(3)以及可选地冲击板(10)。由于这种设置,在通过喷嘴(2)引入之后,聚合介质通过插入管(3)输送并且在反应器底部或冲击板(10)的区域中转向,并且该聚合介质进一步流过插入管(3)和反应器壁(1)之间的区域,以便最后在插入管(3)周围的喷射环流反应器内诱导流动。因此,将聚合介质的液体和气体的、溶解的、乳化的或分散的组分在反应器中循环并且因此强力混合以便带来聚合介质的非常均匀的混合。
如果喷射环流反应器具有多个喷嘴(2),优选地将这些喷嘴彼此紧挨地排列,尤其是平行地或者水平地排列。如果存在多个插入管(3),也优选地将这些插入管彼此紧挨地排列,尤其是平行地或者水平地排列。
当从喷射环流反应器中取出部分的聚合介质并且再循环至喷射环流反应器时将一个或多个外部回路(5)连接至喷射环流反应器。可以在喷射环流反应器中的任一点处取出聚合介质。优选地,在喷射环流反应器的底部取出该聚合介质,尤其在冲击板(10)的下面。离开外部回路,优选地该聚合介质通过喷嘴(2)再循环进入喷射环流反应器。以这种方式,可以实现聚合介质的均匀混合。另外的原料,例如一种或多种烯属不饱和单体和/或一种或多种引发剂,可以通过计量管路(6)引入。通过热交换器(8)可以控制存在于外部回路(5)中的聚合介质的温度。通过一个或多个泵(7)可以影响通过外部回路(5)的聚合介质的输送。
在下文中也将外部回路的操作称为再循环。
本发明方法的显著的优点是通过喷射环流反应器的操作参数技术上的简单改变可以影响聚合物的特性(例如平均粒径或粒径分布)。驱动的喷射速度,即聚合介质通过喷嘴(2)的速度优选从3m/s至25m/s并且特别优选从5m/s至15m/s。反应器高度与反应器直径的比率优选从1至15并且特别优选从2至7。反应器直径与喷嘴直径(2)的比率优选从10至1000并且特别优选从20至100。
可以通过间歇、半间歇或连续方法来运行该喷射环流反应器,可选地使用再循环。具体地,在没有再循环的情况下也可以运行该连续方法。
在没有再循环的连续操作中,在异相聚合期间通过进料管路(4)引入原料,具体地是烯属不饱和单体和引发剂,并且通过产品出口(9)排出聚合介质然后可以从这种排放的聚合介质中分离聚合物。在连续操作中,流入的质量流量应当对应于流出的质量流量。在没有再循环的连续操作中,因此优选并不安装外部回路(5)。
在具有再循环的连续操作中,在异相聚合期间通过进料管路(4)或通过计量管路(6)引入原料,具体地是烯属不饱和单体和引发剂,并且通过产品出口(9)排出聚合介质然后可以从这种排出的聚合介质中分离聚合物。在连续操作中,流入的质量流量应当对应于流出的质量流量。
在半间歇方法或间歇方法中,通常将一个或多个外部回路(5)安装在喷射环流反应器上。在半间歇方法的情况下,通过进料管路(4)和/或可选地计量管路(6)引入原料,具体地是烯属不饱和单体和引发剂,但是并不通过产品出口(9)排出聚合介质。在间歇方法的情况下,在异相聚合期间并未通过进料管路(4)引入原料,例如烯属不饱和单体,并且并未通过产品出口(9)排出聚合介质。
优选半间歇方法并且具体地是具有再循环的连续方法。
通常通过喷嘴(2)来将原料加入喷射环流反应器或将原料引入喷射环流反应器。对于喷嘴(2),优选多流体(multifluid)喷嘴,尤其是双流体喷嘴。双流体喷嘴具有两个入口(优选地通过所述两个入口在一个入口运送原料并且在另一个入口运送外部回路(5)的介质)和一个出口(通过所述出口将聚合介质引入喷射环流反应器中)。
可以从产品出口(9)中取出存在于其中的聚合介质和聚合产物。
通过一个或多个热交换器可以进行温度调节,即加热或冷却,可以将所述热交换器安装在外部回路(5)中或直接地连接在喷射环流反应器上。为了这个目的,可能使用传统的热交换器,例如夹套冷却器(jacket cooler)、夹套加热器(jacket heater)、管壳式热交换器(shell-and-tube heat exchanger)或板式热交换器(plate heat exchanger)。
在优选的实施方式中,将喷射环流反应器构建在包含另外的反应器的级联中。因此级联包含至少两个串联连接的反应器。可以在任一点处从第一反应器中取出聚合介质并且在任一点处将其进料至第二反应器中。在喷射环流反应器的情况下,优选地从第一反应器的产品出口(9)中取出聚合介质并且将其输送至第二反应器中。当第二反应器是喷射环流反应器时,优选地通过外部回路(5)的计量管路(6)或可选地通过进料管路(4)将聚合介质引入喷射环流反应器。
优选的级联包含两个或更多个喷射环流反应器;或一个或多个喷射环流反应器和一个或多个喷射区域环流反应器;或一个或多个喷射环流反应器和一个或多个气升式环流反应器(airlift loop reactor);或一个或多个喷射环流反应器和一个或多个搅拌容器。在级联中,可以将每个反应器安装在一个或多个外部回路(5)中。
在开始聚合反应之前,优选地使用聚合物分散液来填充喷射环流反应器至其体积的50%至80%,优选地该聚合物分散液对应于在聚合物组成、保护性胶体的类型与量以及粒径和固体含量方面的聚合反应的终产物。这可以通过间歇聚合通过在喷射环流反应器中生产这类分散液,或用单独产生的分散液填充喷射环流反应器来进行。
通常通过进料管路(4)或计量管路(6)引入聚合批量的各自的原料,例如烯属不饱和单体、引发剂、保护性胶体或晶种(seed particle)。可以单独地或以预先混合的形式,如纯物质或以溶液、悬液或乳液的形式引入这些原材料。优选地在上游混合单元中预混合这些原料。
可以通过进料管路(4)或在外部回路(5)中通过物理地设置在热交换器(8)的上游或下游的一个或多个计量管路(6)引入所有单体和保护性胶体。
通过传统的引发剂,尤其是由氧化组分和还原组分组成的氧化还原系统来引发该聚合反应。优选地通过进料管路(4)以其整体引入还原组分。通常通过引入的引发剂的量来控制单体转化率。
通过设置计量的添加在连续操作中可以自由地选择聚合介质在喷射环流反应器中的停留时间。
可以在环境压力下或在相对于环境的增加的压力下,尤其是在10巴至80巴下进行该聚合反应。
在已经结束聚合反应之后,使用已知的方法,通常通过使用氧化还原催化剂引发的后聚合反应,可以进行后聚合,以便除去剩余单体。
为了这个目的,在聚合反应结束之后,优选使用在超大气压力下运行的反应器和/或在环境压力下运行的环流反应器,尤其是喷射环流反应器或喷射区域环流反应器或喷射环流反应器和气升式环流反应器的级联用于后聚合。
也可以通过蒸馏,优选地在减压下,并且可选地使用惰性的夹带剂气体(如空气、氮气或通过或经过反应混合物的蒸汽)的通过来除去挥发性组分如剩余的单体。
优选地,烯属不饱和单体选自由乙烯基酯、(甲基)丙烯酸酯、乙烯基芳烃、烯烃、1,3-二烯烃和乙烯基卤化物以及可选地可与其共聚的其他单体所组成的组中。
合适的乙烯基酯是例如,具有1至18个碳原子的羧酸的那些。优选乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、乙酸1-甲基乙烯酯、新戊酸乙烯酯和具有9至11个碳原子的α-支链的一元羧酸的乙烯酯,例如或(Resolution的商品名称)。特别优选乙酸乙烯酯。
来自丙烯酸酯和甲基丙烯酸酯的组中的合适的单体是例如,具有1至15个碳原子的无支链或支链的醇的酯。优选的甲基丙烯酸酯或丙烯酸酯是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、丙烯酸2-乙基己酯。特别优选丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯以及丙烯酸2-乙基己酯。
优选的乙烯基芳烃是苯乙烯、甲基苯乙烯和乙烯基甲苯。优选的乙烯基卤化物是氯乙烯。优选的烯烃是乙烯、丙烯,并且优选的二烯烃是1,3-丁二烯和异戊二烯。
基于单体混合物的总重量,按重量计0至10%的辅助单体可以可选地被另外地共聚。优选使用按重量计0.1%至5%的辅助单体。辅助单体的实例是烯属不饱和的一元羧酸和二元羧酸,优选丙烯酸、甲基丙烯酸、富马酸和马来酸;烯属不饱和的甲酰胺和羧基腈类,优选丙烯酰胺和丙烯腈;富马酸和马来酸的单酯和二酯,例如二乙基酯与二异丙酯,以及还有马来酸酐;烯属不饱和的磺酸或其盐,优选乙烯基磺酸,2-丙烯酰胺基-2-甲基丙烷-磺酸。另外的实例是预交联的共聚单体如多重烯属不饱和的共聚单体,例如邻苯二甲酸二烯丙酯、己二酸二乙烯酯、马来酸二烯丙酯、甲基丙烯酸烯丙酯或氰脲酸三烯丙酯、或后交联的共聚单体,例如丙烯酰胺基乙醇酸(AGA)、甲基丙烯酰胺基乙醇酸甲基酯(MMAG)、N-羟甲基丙烯酰胺(NMA)(N-methylolacrylamide)、N-羟甲基甲基丙烯酰胺、N-羟甲基氨基甲酸烯丙酯,烷基醚如异丁氧基醚或N-羟甲基丙烯酰胺的酯、N-羟甲基甲基丙烯酰胺的酯和N-羟甲基氨基甲酸烯丙基酯的酯。环氧化物官能性共聚单体(诸如甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯)也是合适的。另外的实例是硅官能化的共聚单体如丙烯酰基氧基丙基三(烷氧基)硅烷和甲基丙烯酰基氧基丙基三(烷氧基)硅烷、乙烯基三烷氧基硅烷和乙烯基甲基二烷氧基硅烷,其中,例如乙氧基和乙氧基丙二醇醚基团可以作为烷氧基存在。还可以提及具有羟基或CO基团的单体,例如甲基丙烯酸羟基烷基酯和丙烯酸羟基烷基酯,例如丙烯酸或甲基丙烯酸的羟基乙基酯、羟基丙基酯或羟基丁基酯,以及化合物,如双丙酮丙烯酰胺和乙酰基乙酰氧基乙基的丙烯酸酯或甲基丙烯酸酯。
优选地选择来自由以下组成的组中的一个或多个单体:乙烯基酯,乙烯基酯混合物(包含来自由以下组成的组中的一个或多个单体:乙烯基酯、烯烃、乙烯基芳烃、乙烯基卤化物、丙烯酸酯、甲基丙烯酸酯、富马酸和/或马来酸的单酯或二酯);(甲基)丙烯酸酯均聚物,(甲基)丙烯酸酯混合物(包含来自由以下组成的组中的一个或多个单体:甲基丙烯酸酯、丙烯酸酯、烯烃、乙烯基芳烃、乙烯基卤化物、富马酸和/或马来酸的单酯或二酯);二烯烃的单体或单体混合物如丁二烯或异戊二烯以及烯烃的单体或单体混合物如乙烯或丙烯,其中,例如该二烯烃可以与苯乙烯、(甲基)丙烯酸酯或富马酸或马来酸的酯一起共聚;乙烯基芳烃的单体或单体混合物如苯乙烯、甲基苯乙烯、乙烯基甲苯;卤代乙烯化合物的单体或单体混合物如氯乙烯,其中该单体混合物可以额外地包含辅助单体。
特别优选具有按重量计1%至50%乙烯的一种或多种乙烯基酯的单体混合物;具有按重量计1%至50%乙烯以及按重量计1%至50%的来自下组的一种或多种另外的共聚单体的乙烯基酯的单体混合物:在羧酸基团中具有1至12个碳原子的乙烯基酯,例如丙酸乙烯酯、月桂酸乙烯酯、具有9至13个碳原子的α-支链羧酸的乙烯基酯,例如VeoVa9、VeoVa10、VeoVa11;一种或多种乙烯基酯的单体混合物,按重量计1%至50%的乙烯以及优选地按重量计1%至60%的具有1至15个碳原子的无支链或支链的醇的(甲基)丙烯酸酯,尤其是丙烯酸正丁酯或者丙烯酸2-乙基己酯;以及单体混合物,包含按重量计30%至75%的乙酸乙烯酯,按重量计1%至30%的月桂酸乙烯酯或具有9至11个碳原子的α-支链羧酸的乙烯基酯以及按重量计1%至30%的具有1至15个碳原子的无支链的或支链的醇的(甲基)丙烯酸酯,尤其是丙烯酸正丁酯或丙烯酸2-乙基己酯,其另外包含按重量计1%至40%的乙烯;单体混合物,包含一种或多种乙烯酯,按重量计1%至50%的乙烯和按重量计1%至60%的氯乙烯;其中该单体混合物可以另外含有以指示的量提及的辅助单体并且在每种情况下按重量%计的数字合计为按重量计100%。
还特别优选(甲基)丙烯酸酯单体混合物如丙烯酸正丁酯或丙烯酸2-乙基己基酯的单体混合物或甲基丙烯酸甲酯和丙烯酸正丁酯和/或丙烯酸2-乙基己基酯的共聚物;苯乙烯-丙烯酸酯单体混合物,包含来自由以下组成的组中的一种或多种单体:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己基酯;乙酸乙烯酯-丙烯酸乙烯酯单体混合物,包含来自由以下组成的组中的一种或多种单体:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己基酯以及可选地乙烯;苯乙烯-1,3-丁二烯单体混合物,其中该单体混合物可以另外含有指示的量的辅助单体并且在每种情况下按重量%计的数字合计为按重量计100%。
对于氯乙烯单体混合物特别优选的共聚单体的实例是α-烯烃如乙烯或丙烯和/或乙烯基酯如乙酸乙烯酯和/或具有1至15个碳原子的醇的丙烯酸酯或甲基丙烯酸酯,例如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、丙烯酸-2-乙基己基酯、和/或富马酸和/或马来酸的单酯或二酯如马来酸或富马酸的二甲基酯、甲基叔丁基酯、二正丁基酯、二叔丁基酯和二乙基酯。
最优选的单体混合物是包含乙酸乙烯酯和按重量计5%至50%乙烯的单体混合物;或单体混合物,包含乙酸乙烯酯,按重量计1%至50%的乙烯和按重量计1%至50%的具有9至11个碳原子的α-支链的一元羧酸的乙烯基酯;或单体混合物,包含按重量计30%至75%的乙酸乙烯酯,按重量计1%至30%的月桂酸乙烯酯或具有9至11个碳原子的α-支链羧酸的乙烯基酯以及按重量计1%至30%的具有1至15个碳原子的无支链或支链的醇的(甲基)丙烯酸酯以及另外地按重量计1%至40%的乙烯;或单体混合物,包含乙酸乙烯酯,按重量计5%至50%的乙烯和按重量计1%至60%的氯乙烯。
最优选的单体混合物还是氯乙烯-乙烯单体混合物,包含按重量计60%至98%的氯乙烯单元和按重量计1%至40%的乙烯单元,其中按重量%计的数字是基于单体混合物的总重量并且在每种情况下合计为按重量计100%。
通常,进行单体的选择以及按重量计这些共聚单体的比例的选择,从而导致玻璃化转化温度Tg为-50℃至+50℃,优选-20℃至+30℃。通过差示扫描量热法(DSC)以已知方式可以确定聚合物的玻璃转化温度Tg。还可以通过Fox方程预先大致地计算出Tg。根据Fox T.G.,Bull.Am.Physics Soc.1,3,page123(1956):1/Tg=x1/Tg1+x2/Tg2+…+xn/Tgn,其中xn是单体n的质量分数(%按重量/100计)并且Tgn是单体n的均聚物的绝对温度的玻璃转化温度。在Polymer Handbook2nd Edition,JU.Wiley&Sons,New York(1975)中可以找到针对均聚物的Tg值。
通过悬液聚合方法或优选地通过乳液聚合方法来进行聚合反应。通常聚合温度是40℃至100℃,优选60℃至90℃。通过通常用于乳液聚合或悬液聚合的引发剂,尤其是氧化还原引发剂组合来引发聚合反应。合适的氧化引发剂的实例是过氧化二硫酸的钠盐、钾盐和铵盐,过氧化氢,叔丁基过氧化物,叔丁基过氧化氢,异丙基苯过氧化氢,异丙基苯单过氧化氢和偶氮二异丁腈。优选过氧化二硫酸的钠盐、钾盐和铵盐和过氧化氢。通常基于单体的总重量,以按重量计0.01%至2.0%的量使用提及的引发剂。
合适的还原剂是碱金属和铵的亚硫酸盐与亚硫酸氢盐,例如亚硫酸钠、次硫酸的衍生物,例如甲醛次硫酸的锌盐或碱金属盐,例如羟基甲烷亚磺酸钠(sodium hydroxymethanesulfinate)(Brüggolit)和(异)抗坏血酸。优选羟基甲烷亚磺酸钠和(异)抗坏血酸。还原剂的量优选基于单体的总重量,按重量计0.015%至3%。
为了控制分子量,在聚合反应期间有可能使用链转移物质。如果使用链转移剂,通常地基于有待聚合的单体,以按重量计0.01%至5.0%范围的量使用这些(链转移剂)并且单独地引入或与反应组分一起预混合。这类物质的实例是正十二烷基硫醇、叔十二烷基硫醇、巯基丙酸、巯基丙酸乙酯、异丙醇和乙醛。优选不使用任何链转移物质。
优选地在保护性胶体的存在下进行聚合反应。合适的保护性胶体是部分水解的聚乙烯醇;聚乙烯吡咯烷酮;聚乙烯缩醛;处于水溶形式的多糖,例如淀粉(直链淀粉和支链淀粉)、纤维素及其羧甲基衍生物、甲基衍生物、羟基乙基衍生物、羟丙基衍生物;蛋白质,如酪蛋白或酪蛋白酸盐、大豆蛋白、明胶、木素磺酸盐;合成的聚合物,如聚(甲基)丙烯酸,(甲基)丙烯酸酯与羧基官能化的共聚单体单元的共聚物;聚(甲基)丙烯酰胺,聚乙烯基磺酸及其水溶性的共聚物;三聚氰胺(melanine)-甲醛磺酸酯,萘-甲醛磺酸酯,苯乙烯-马来酸和乙烯基醚-马来酸共聚物;阳离子聚合物如聚DADMAC。
优选的保护性胶体是部分水解的或完全水解的聚乙烯醇。特别优选具有80mol%至95mol%的水解度以及从1mPas至30mPas的在4%浓度水溶液中的粘度(在20℃下的方法,DIN53015)的部分水解的聚乙烯醇。还特别优选具有80mol%至95mol%的水解度以及从1mPas至30mPas的在4%浓度水溶液中的粘度的部分水解的、疏水性改性的聚乙烯醇。实例是具有疏水性共聚单体(如乙酸异丙烯酯)的乙酸乙烯酯的部分水解的共聚物、新戊酸乙烯酯、乙基己酸乙烯酯、具有5或9至11个碳原子的饱和的α-支链一元羧酸的乙烯酯、马来酸二烷基酯和反丁烯二酸二烷基酯例如马来酸二异丙基酯和反丁烯二酸二异丙基酯、氯乙烯、乙烯基烷基醚如乙烯基丁基醚、烯烃如乙烯和癸烯。疏水单元的比例优选基于部分水解的聚乙烯醇的总重量,按重量计0.1%至10%。还可能使用所提及的聚乙烯醇的混合物。
进一步特别优选的聚乙烯醇是部分水解的、疏水的聚乙烯醇,通过聚合物类似反应获得该聚乙烯醇,例如通过C1-C4醛类(如丁醛)缩醛化乙烯醇单元。疏水单元的比例优选基于部分水解的聚乙酸乙烯酯的总重量,按重量计0.1%至10%。水解度是从80mol%至95mol%,优选地从85mol%至94mol%,并且粘度(DIN 53015,方法,在20℃下,4%浓度水溶液)是从1mPas至30mPas,优选地从2mPas至25mPas。
最优选具有85mol%至94mol%的水解度以及从3mPas至15mPas的在4%浓度水溶液的粘度(在20℃下的方法,DIN53015)的聚乙烯醇。通过本领域技术人员已知的方法可以获得所提及的保护性胶体。
在聚合反应中,通常加入基于单体的总重量,按重量计1%至20%的总量的聚乙烯醇。
在本发明的方法中,优选地在没有添加乳化剂的情况下进行该聚合反应。在例外情况下,可以有利地使用乳化剂,可选地基于单体的量,按重量计从1%至10%。合适的乳化剂是阴离子型、阳离子型和非离子型乳化剂,例如阴离子表面活化剂如具有8至18个碳原子的链长度的烷基硫酸酯,在疏水基团中具有8至18个碳原子的烷基或烷基芳基醚硫酸酯并且可达40个环氧乙烷或环氧丙烷单元,具有8至18个碳原子的烷基磺酸酯或烷基芳基磺酸酯,磺基琥珀酸与一价醇或烷基酚的酯和单酯或非离子型表面活性剂如具有8至40个环氧乙烷单元的烷基聚乙二醇醚或烷基芳基聚乙二醇醚。
通过本发明的方法可以获得的水分散液具有按重量计从30%至75%,优选按重量计从50%至60%的固体含量。
为了制备水可再分散性聚合物粉剂,可选地在添加保护性胶体作为干燥助剂之后干燥该水分散液,例如通过流化床干燥、冷冻干燥或喷雾干燥。优选地该分散液是喷雾干燥的。在传统的喷雾干燥设备中进行喷雾干燥,通过单流体、双流体或多流体喷嘴或通过转盘能够进行雾化。取决于装置、树脂的Tg和所期望的干燥程度,通常选择的输出温度在45℃至120℃,优选60℃至90℃的范围内。
通常,基于分散液的聚合物组分,以按重量计3%至30%的总量来使用干燥助剂,即在干燥操作之前的保护性胶体的总量应当为基于聚合物的量,按重量计≥3%至30%;优选使用基于聚合物的量,按重量计5%至20%。
合适的干燥助剂是部分水解的聚乙烯醇;聚乙烯吡咯烷酮;聚乙烯醇缩醛;处于水溶形式的多糖,例如淀粉(直链淀粉和支链淀粉)、纤维素及其羧甲基衍生物、甲基衍生物、羟基乙基衍生物、羟基丙基衍生物;蛋白质如酪蛋白或酪蛋白酸盐、大豆蛋白、明胶;木质素磺酸酯;合成的聚合物如聚(甲基)丙烯酸、(甲基)丙烯酸酯与羧基官能化的共聚单体单元的共聚物、聚(甲基)丙烯酰胺、聚乙烯基磺酸及其水溶性共聚物;三聚氰胺-甲醛磺酸酯、萘-甲醛磺酸酯、苯乙烯-马来酸和乙烯基醚-马来酸共聚物;阳离子聚合物如聚DADMAC。除了将聚乙烯醇用作干燥助剂以外,并不优选另外的保护性胶体。
在雾化中,基于原料聚合物(base polymer),按重量计可达1.5%的防沫剂的含量经常发现是有利的。为了通过改善阻断的稳定性来提高保存期限,尤其是在粉末具有低玻璃转化温度的情况下,获得的粉末可以优选地以基于聚合物组分的总重量,按重量计可达30%的量配备有防粘连剂(抗结块剂)。防粘连剂的实例是碳酸钙和碳酸镁、云母、石膏、硅石、高岭土、偏高岭土、硅酸盐,具有优选在10nm至10μm范围内的粒径。
通过固体含量来设置有待雾化的进料的粘度以便获得<500mPas(在20个旋转和23℃下的Brookfield粘度),优选地<250mPas的值。有待雾化的分散液的固体含量通常>35%,优选>45%。
为了提高使用性能,在雾化期间可以添加另外的添加剂。存在于优选实施方式中的分散体粉末组合物的另外的组分是,例如颜料、填充剂、泡沫稳定剂、疏水化剂(hydrophobicizing agent)。
可以将聚合物水分散液与水可再分散的、保护性胶体稳定的聚合物粉剂用于一般用于这类粉末的应用领域中,例如在构建化学产品中,可选地与水力固化的粘合剂结合如水泥(波特兰水泥,铝酸盐,火山土,熔渣,镁砂,磷酸盐水泥)、石膏灰泥和水玻璃,用于生产建筑粘合剂,尤其是砖瓦粘合剂和完全热绝缘粘合剂,灰泥和粉刷剂(render),适于用灰刀填塞的填缝物(knifing filler),地面刮板,自流平组合物,密封的浆液,接缝灰浆和涂料。还可以将它们用作涂层组合物和粘合剂的粘结剂或用作涂料组合物或者用于纺织品和纸张的粘结剂。
使用喷射环流反应器用作异相聚合的显著优点是反应介质的强烈的和快速的混合以及较高的热量和质量传递。
本发明的方法能够通过改变工艺条件将目标方式控制聚合物的平均粒径,例如反应器几何形状或操作参数,例如驱动喷射速度或再循环比率,即技术简单的措施有可能获得具有不同平均粒径的聚合物。聚合物的粒径分布还可以受到所使用的工艺的影响。另一方面,在常规方法中,通常需要改变聚合反应批次的配方用于控制聚合物的平均粒径。
尤其出乎意料的是在来自喷嘴的聚合介质的出口处出现高剪切力不能导致聚合介质的任何凝结,因为当这种高剪切力发生在传统的环流反应器或搅拌釜反应器中时这种情况是不利的。凝结导致反应器积垢或甚至导致管状反应器堵塞。不得不通过过滤从产品中费力地除去凝固物。
以下实施例用来详细地阐明本发明,而不构成任何限制。
实施例1(Ex.1):通过半间歇方法的聚合
使用了在图1中描述的具有450ml体积的喷射环流反应器。该喷射环流反应器具有反应器高度与反应器直径H/D的比率为2以及反应器直径与喷嘴直径d/D的比率为74。在半间歇模式下并且在5m/s的驱动喷射速度下运行该喷射环流反应器。
通过进料管路(4)将120g的具有88mol%的水解度和在20℃下粘度为4mPas的10%浓度聚乙烯醇水溶液以及120g的乙酸乙烯酯和30g的VeoVa10放置在喷射环流反应器中。通过热交换器(8)在大气压下将聚合介质加热至65℃并且通过泵(7)通过双流体喷嘴(2)的喷嘴进料。此时喷射环流反应器填充至其体积的60%。
在4小时的时期内通过进料管路(4)和双流体喷嘴(2)的第二部分随后引入以下的材料:96g的上述聚乙烯醇溶液,20g的0.1%浓度的叔丁基过氧化氢;20g的0.17%浓度的抗坏血酸溶液,10g的VeoVa10和110g的乙酸乙烯酯。
以这种方式获得的聚合物分散液具有55%的固体含量。基于聚合物分散液,剩余单体含量是1.2%。进一步的结果在表1中显示。
比较例2(comp.Ex.2):在搅拌釜反应器中聚合
使用配方进行聚合,即在具有500ml体积的搅拌的实验室容器中如在实施例1中描述的温度和压力以及聚合时间下进行类似于实施例1的初始进料和另外的引入。
基于分散液,以这种方式获得的分散液的剩余单体含量是1.8%。进一步的结果在表中显示。
表1:
从表1中可以看出,与常规方法(comp.Ex.2)相比本发明的方法(Ex.1)导致聚合物具有更小的平均粒径Dw。此外,如从更小的Dw/Dn比率可以看出的,该粒径分布更窄。
实施例3:驱动喷射速度的改变
除了驱动喷射速度是10m/s以外,类似于实施例1。
通过改变在喷射环流反应器的喷嘴(2)处的驱动喷射速度可以显著地影响聚合物的平均粒径Dw。在表2中显示了结果。
表2:
驱动喷射速度 | 平均粒径Dw | |
实施例1 | 5m/s | 0.677μm |
实施例3 | 10m/s | 0.358μm |
实施例4:连续聚合
以类似于实施例1的方式,在喷射环流反应器中通过半批量方法首先制备聚合物分散液。在4小时的聚合时间之后,固体含量是55%。通过计量管路(6)在指示的引入速率下随后引入以下指示的组分并且将喷射环流反应器改换为连续操作模式:
乙酸乙烯酯:84ml/h,
VeoVa10:14.9ml/h,
叔丁基过氧化氢(0.1%浓度):6.6ml/h,
抗坏血酸(0.17%浓度):6.6ml/h。
连续运行该喷射环流反应器8小时。在此期间,在产品出口(9)处取出聚合介质,即聚合物分散液,具有55%的固体含量和0.730μm的平均粒径Dw(根据ISO13320通过测量仪器Beckmann LS确定的)。
比较例5:
在由各自具有500ml体积的两个搅拌容器构成的搅拌容器级联中以类似于实施例4的方式进行聚合。
用来自实施例4的分散液进料搅拌容器并且开始以下进料流:
搅拌容器1:
10%浓度的聚乙烯醇水溶液(具有88mol%的水解度以及在20℃下具有4mPas的粘度):70ml/h,
乙酸乙烯酯:84ml/h,
VeoVa10:14.9ml/h,
叔丁基过氧化氢(0.1%浓度):6.6ml/h,
抗坏血酸(0.17%浓度):6.6ml/h。
搅拌容器2:
叔丁基过氧化氢(0.1%浓度):12.2ml/h,
抗坏血酸(0.17%浓度):12.2ml/h。
连续运行该搅拌容器级联持续8小时。
Claims (9)
1.一种通过一种或多种烯属不饱和单体的自由基引发的异相聚合用于制备处于其水分散液或水可再分散性粉剂形式的聚合物的方法并且可选地随后干燥所得到的聚合物分散液,其特征在于,在喷射环流反应器中进行所述异相聚合反应。
2.根据权利要求1所述的方法,其特征在于,所述喷射环流反应器包含一个或多个喷嘴(2),一个或多个插入管(3),可选地一个或多个进料管道(4),可选地一个或多个产品出口(9),可选地一个或多个冲击板(10),可选地一个或多个外部回路(5)以及可选地另外的结构。
3.根据权利要求1或2所述的方法,其特征在于,驱动喷射速度是从3m/s至25m/s。
4.根据权利要求1至3中任一项所述的方法,其特征在于,通过间歇、半间歇或连续方法运行所述喷射环流反应器,可选地使用再循环。
5.根据权利要求1至4中任一项所述的方法,其特征在于,将所述喷射环流反应器建造在包含以下的反应器级联中:两个或更多个喷射环流反应器;或一个或多个喷射环流反应器和一个或多个喷射区域环流反应器;或一个或多个喷射环流反应器和一个或多个气升式环流反应器;或一个或多个喷射环流反应器和一个或多个搅拌容器。
6.根据权利要求1至5中任一项所述的方法,其特征在于,通过乳液聚合方法或悬液聚合方法进行所述异相聚合反应。
7.根据权利要求1至6中任一项所述的方法,其特征在于,所述烯属不饱和单体选自由乙烯基酯、(甲基)丙烯酸酯、乙烯基芳烃、烯烃、1,3-二烯烃和乙烯基卤化物以及可选地能够与其共聚的另外的单体组成的组中。
8.根据权利要求1至7中任一项所述的方法,其特征在于,在选自由以下组成的组中的保护性胶体存在下进行所述异相聚合反应:聚乙烯醇,聚乙烯吡咯烷酮,聚乙烯基缩醛,处于水溶形式的多糖,纤维素及其羧甲基、甲基、羟基乙基、羟丙基衍生物,蛋白质,聚(甲基)丙烯酸,(甲基)丙烯酸酯和羧基官能化的共聚单体单元的共聚物,聚(甲基)丙烯酰胺,聚乙烯基磺酸及其水溶性共聚物;三聚氰胺-甲醛磺酸酯共聚物,萘-甲醛磺酸酯共聚物,苯乙烯-马来酸共聚物和乙烯基醚-马来酸共聚物,阳离子聚合物。
9.获自权利要求1至8中任一项所述方法的产品在构建化学产品中的用途,可选地与水力固化粘合剂结合。
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CN111164107A (zh) * | 2017-10-04 | 2020-05-15 | 瓦克化学股份公司 | 采用外部冷却的聚合方法 |
CN112912405A (zh) * | 2019-07-25 | 2021-06-04 | 瓦克化学股份公司 | 用于制备水性聚合物分散体的方法 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1174445A1 (de) * | 2000-07-21 | 2002-01-23 | Wacker Polymer Systems GmbH & Co. KG | Verfahren zur Herstellung von Schutzkolloid-stabilisierten Polymerisaten mittels kontinuierlicher Emulsionspolymerisation |
CN1396939A (zh) * | 2000-02-24 | 2003-02-12 | 巴斯福股份公司 | 在多金属氰化物配合物催化剂存在下生产聚醚多元醇的方法 |
CN101778872A (zh) * | 2007-08-14 | 2010-07-14 | 瓦克化学股份公司 | 连续的聚合方法 |
CN101809040A (zh) * | 2007-08-29 | 2010-08-18 | 瓦克化学股份公司 | 保护性胶体稳定的聚合物产品的制备方法和实施该方法的装置 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2703794A (en) | 1951-09-04 | 1955-03-08 | Du Pont | Ethylene/vinyl acetate polymerization process |
US3551396A (en) | 1968-01-05 | 1970-12-29 | Gulf Oil Canada Ltd | Continuous vinyl polymerization process |
IT1026928B (it) | 1974-12-10 | 1978-10-20 | Montedison Spa | Procedimento di polimerizzazione continua in emulsione |
DE3047101A1 (de) | 1980-12-13 | 1982-07-22 | Hoechst Ag, 6000 Frankfurt | Verfahren zum verbessern der gasverteilung in mammut-schlaufenreaktoren |
DE19640793A1 (de) | 1996-10-02 | 1998-04-16 | Basf Ag | Verfahren und Vorrichtung zur Herstellung von Homo- und Copolymeren in Emulsionspolymerisationstechnik |
DE10103709A1 (de) | 2001-01-26 | 2002-08-01 | Basf Ag | Verfahren zur Herstellung einer wässrigen Polymerisatdispersion durch radikalisch initiierte wässrige Emulsionspolymerisation |
DE10134023A1 (de) | 2001-07-12 | 2003-01-23 | Basf Ag | Verfahren und Vorrichtung zur Herstellung von Polymerdispersionen |
KR100452233B1 (ko) * | 2002-07-19 | 2004-10-12 | 한국과학기술연구원 | 젯트루프식 분사형 반응기를 이용한 삼불화질소 제조방법 |
DE10319452A1 (de) | 2003-04-30 | 2004-11-18 | Basf Ag | Kontinuierliches Verfahren zur Herstellung von Methylvinylether |
US7186867B2 (en) | 2004-04-21 | 2007-03-06 | Basf Aktiengesellschaft | Process for preparing reactive polyether polyols having an ethylene oxide end block |
DE102006053380A1 (de) | 2006-11-13 | 2008-05-15 | Wacker Chemie Ag | Verfahren zur Herstellung von chlorierten Carbonylverbindungen in Jet Loop Reaktoren |
-
2011
- 2011-03-10 DE DE102011005388A patent/DE102011005388A1/de not_active Withdrawn
-
2012
- 2012-03-09 CN CN201280012435.7A patent/CN103415538B/zh not_active Expired - Fee Related
- 2012-03-09 WO PCT/EP2012/054162 patent/WO2012120136A1/de active Application Filing
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1396939A (zh) * | 2000-02-24 | 2003-02-12 | 巴斯福股份公司 | 在多金属氰化物配合物催化剂存在下生产聚醚多元醇的方法 |
EP1174445A1 (de) * | 2000-07-21 | 2002-01-23 | Wacker Polymer Systems GmbH & Co. KG | Verfahren zur Herstellung von Schutzkolloid-stabilisierten Polymerisaten mittels kontinuierlicher Emulsionspolymerisation |
CN101778872A (zh) * | 2007-08-14 | 2010-07-14 | 瓦克化学股份公司 | 连续的聚合方法 |
CN101809040A (zh) * | 2007-08-29 | 2010-08-18 | 瓦克化学股份公司 | 保护性胶体稳定的聚合物产品的制备方法和实施该方法的装置 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2607916C1 (ru) * | 2015-12-21 | 2017-01-11 | Владимир Леонидович Письменный | Теплообменник |
CN111164107A (zh) * | 2017-10-04 | 2020-05-15 | 瓦克化学股份公司 | 采用外部冷却的聚合方法 |
CN111164107B (zh) * | 2017-10-04 | 2022-05-24 | 瓦克化学股份公司 | 采用外部冷却的聚合方法 |
CN112912405A (zh) * | 2019-07-25 | 2021-06-04 | 瓦克化学股份公司 | 用于制备水性聚合物分散体的方法 |
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