CN1174203A - 聚合物体积浓度至少为50%的低粘度聚合物水分散体的制备 - Google Patents
聚合物体积浓度至少为50%的低粘度聚合物水分散体的制备 Download PDFInfo
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- CN1174203A CN1174203A CN97112790A CN97112790A CN1174203A CN 1174203 A CN1174203 A CN 1174203A CN 97112790 A CN97112790 A CN 97112790A CN 97112790 A CN97112790 A CN 97112790A CN 1174203 A CN1174203 A CN 1174203A
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
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Abstract
一种用于制备低粘度聚合物水分散体的方法,以聚合物分散体为基准计,聚合物体积浓度至少为50%体积,用除卤乙烯和偏二卤乙烯以外的烯键不饱和单体在至少一种引发剂和至少一种起始聚合物存在下的自由基乳液聚合反应制备,其包括在起始聚合物的水分散体中乳化主要部分的单体并将该乳液连续提供给聚合反应。
Description
本发明涉及制备低粘度聚合物水分散体的方法,以该聚合物分散体为基准,聚合物体积浓度至少为50%体积。
由于聚合物水分散体当水分散体介质被蒸发时形成聚合物膜的性质,其被广泛应用。例如作为涂料的粘合剂、作为用于皮革和纸张的涂敷成分、作为织物的修饰层或作为粘胶膜。
高浓度的聚合物水分散体当形成膜或制备聚合物粉末时,具有减少所需蒸发水分散体介质的优点,另一方面,具有所需的较少的运输和储存量的优点。
另一方面,缺点是当聚合物含量提高时,聚合物分散体的粘度也提高了。这导致了在制备过程中(耗散反应的热量)和在加工期间的问题。此外,这种高浓度的聚合物分散体有微凝结(起块)的趋势。由于微凝结的尺寸很小(<40μm),它需要很费力地从聚合物分散体中除去,特别在由聚合物水分散体形成膜时会导致疵点。在此方面,用体积份数表示聚合物浓度(%体积=%wt÷聚合物密度)是合理的,虽然涉及的效果是由于聚合物颗粒在聚合物分散体中的分布原因。
已发现对于给定的固体含量,具有宽型被分散聚合物颗粒分布的聚合物分散体(多分散聚合物)与那些窄型分布的(单分散)相比一般具有较低的粘度。
DE-A-3147008描述了一种用于制备具有双峰型聚合物颗粒分布的高浓缩聚合物水分散体的方法,通过将烯键不饱和单体在两种颗粒大小不同的初始聚合物存在下进行乳液聚合。尽管这个方法得到了聚合物含量高达70%wt(≌64%体积)的聚合物分散体,但两种不同的初始聚合物的使用仍显得复杂。另外,实施例所述的分散体的粘度水平对许多实际的应用太高了。
US-A-4130523涉及一种用于制备聚合物水分散体的方法,其包括将在实际的聚合过程期间连续生成的聚合物水分散体从反应区移出,保存,然后将其作为一种起始聚合物再送入反应区。然而,这种方法显得太复杂,以至无法找到任何大规模的工业应用。
US-A-3424706描述了一种用于制备含70-97%wt共聚形式偏二氯乙烯的聚合物水分散体的方法,通过在一种起始聚合物存在下乳液聚合来制备。这包括计量作为胶乳的起始聚合物以及单体对反应混合物的主要比例。该方法的缺点是它仅限于主要含偏二氯乙烯的单体混合物。另外,只得到了小于50%体积的聚合物体积浓度。
DE-A-4213965描述了一种用于制备高浓缩聚合物水分散体的方法,其中单体和起始聚合物被连续经独立的加料供入聚合釜(polymerizationbatch)。在该方法中,形成微凝结(结块)的问题没有得到完全满意的解决。
因此,本发明的目的在于提供一种允许制备具有高聚合物体积浓度、低粘度和微凝结含量少的聚合物水分散体的方法。另外,本方法应很大程度上不依赖使用的单体的类型。
我们已惊奇地发现这个目的可通过一种用于制备基于聚合物分散体计聚合物体积浓度至少50%体积的低粘度聚合物水分散体的方法达到,即用除卤乙烯和偏二卤乙烯以外的烯键不饱和单体在至少一种引发剂和至少一种起始聚合物存在下的自由基乳液聚合反应,其包括在起始聚合物的水分散体中乳化主要部分的单体并将该乳液连续提供给聚合反应。本发明还涉及用这种新方法制备的聚合物分散体。
根据本发明的乳液聚合这样进行,即在有或没有表面活性物质的帮助下,将要聚合的单体的主要部分、优选至少80%wt、特别是至少90%wt在起始聚合物的水分散体(接种胶乳)中预乳化,该乳液被计量入在反应温度的聚合容器。关于这一点,基于要聚合的单体计,起始聚合物的量优选0.01-10%wt、特别是0.1-2%wt。水对单体的比例在1∶1至1∶9(重量份)的范围。为达到这一点,需要加入额外的水和——如果需要——额外的表面活性剂。在一个优选的实施方案中,在使用前将起始聚合物在单体乳液中溶胀,特别是至少30分钟。
反应优选这样开始,即将一些单体——如果希望的话,与起始聚合物、水和至少一些引发剂一起——加入反应容器中,加热该起始物至反应温度。在接种胶乳中的单体乳液然后被连续提供给聚合反应,即以恒定的供料速度或根据梯度方法。供料速度由在反应中的转化率决定,优选选择使至少80%wt、尤其是90%wt、特别是95%wt的在反应混合物中的单体已被共聚。
在该新方法特别优选的一个实施方案中,单体乳液的供料速度连续或分步提高到希望的值,这个值可由反应中的转化率(见上文)或其它具有特定参数诸如釜的尺寸、反应的加热、混合等的工艺决定并可被保持。
在该新方法另一个优选的变化中,反应开始时,将一些在接种胶乳中的单体乳液计量入已在反应温度并包括至少一些引发剂的起始进料中。在所有情况下,反应进料可包括水、其它乳化剂和其它起始聚合物,并且特别是后者无须与在单体乳液中使用的起始聚合物相同。
引发剂被计量到乳液聚合反应中的方法并不苛刻。它可以被完全包括在聚合反应容器的起始进料里,或也可根据在乳液聚合反应期间引发剂的消耗速度连续地或分步地加入。该工艺取决于引发剂的化学性质和聚合温度两者,可由熟练工人按需选择。
聚合反应的压力和温度同样稍微次要些。后者一般在室温和100℃之间,优选50-95℃。同样可提供升高或降低的压力,这样聚合温度甚至可以超过100℃,并可高到130℃。挥发性较高的单体诸如乙烯或丁二烯优选在升高的压力下聚合。
新方法可用于大量单烯键不饱和单体的反应。这些包括C2-C6链烯,例如乙烯、丙烯、正丁烯和异丁烯;芳族乙烯单体,诸如苯乙烯、α-甲基苯乙烯、邻氯苯乙烯或甲苯乙烯;C1-C12-烷基乙烯基醚,诸如甲基、乙基、正丙基、异丙基、正丁基、异丁基和2-乙基己基乙烯基醚;C1-C18单羧酸的乙烯酯,诸如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、戊酸乙烯酯、己酸乙烯酯、2-乙基己酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯和硬脂酸乙烯酯。α,β-烯键不饱和的C3-C10一或二羧酸与C1-C12-、优选C1-C8-、尤其是C1-C4链烷醇的酯同样适合。这些酸与C5-C8环烷醇的酯也可使用。合适的C1-C12链烷醇的例子是甲醇、乙醇、正丙醇、异丙醇、1-丁醇、2-丁醇、异丁醇和叔丁醇、正己醇和2-乙基己醇。合适的环烷醇的例子是环戊醇和环己醇。丙烯酸、甲基丙烯酸、巴豆酸、马来酸、富马酸和衣康酸的酯是特别合适的。特别的例子是(甲基)丙烯酸甲酯、乙酯、正丁酯、异丁酯和2-乙基己酯,马来酸二甲酯和马来酸二正丁酯。其它合适的单体是α,β-单烯键不饱和羧酸的腈,诸如丙烯腈或甲基丙烯腈。另外,C4-C8共轭二烯也可使用,诸如1,3-丁二烯和异戊二烯。上述单体一般构成主要部分,并优选占要聚合单体的80-99.9%wt、尤其是90-99.9%wt、特别是95-99.7%wt。
作为改善的单体,优选共聚0.1-20%wt、尤其是0.1-10%wt、特别是0.3-5%wt的单体,其均聚物有提高的水溶性。这些改善的单体的例子是α,β-单烯键不饱和的3-10个碳原子的一和二羧酸和它们的酰胺,或烯键不饱和的烷基或芳基磺酸。它们包括丙烯酸、甲基丙烯酸、巴豆酸、马来酸、富马酸和衣康酸、丙烯酰胺或甲基丙烯酰胺、乙烯磺酸、(甲基)丙烯酰氨基-2-甲基丙磺酸和它们的水溶性盐。
另外可以共聚可提高从聚合物乳液形成的聚合物膜的强度的单体。这些单体以较少的量共聚,基于要聚合的单体的总量计,一般至多10%wt、优选至多5%wt、尤其是至多1%wt。这些单体含有环氧基、羟基、N-烷醇基或羰基。这些单体的例子是3-10个碳原子的α,β-单烯键不饱和羧酸的N-羟烷酰胺和N-烷醇酰胺,诸如2-羟乙基(甲基)丙烯酰胺和N-羟甲基(甲基)丙烯酰胺,上述烯键不饱和羧酸的羟烷基酯,诸如丙烯酸和甲基丙烯酸羟乙酯、羟丙酯和羟丁酯。另外的例子是缩水甘油醚和缩水甘油酯,诸如乙烯基、烯丙基和甲代烯丙基缩水甘油醚、丙烯酸缩水甘油酯和甲基丙烯酸缩水甘油酯,上述烯键不饱和酸的二丙酮基酰胺,诸如二丙酮基(甲基)丙烯酰胺,具有所述烯键不饱和酸的上述羟烷基酯的乙酰乙酸的酯,诸如(甲基)丙烯酸乙酰乙酸乙基酯。含两个非共轭烯键不饱和键的化合物也适用,诸如二元醇与C3-C10α,β-单烯键不饱和一羧酸的二酯。这种化合物的例子是二丙烯酸和二甲基丙烯酸亚烷基二醇酯,诸如二丙烯酸乙二醇酯、二丙烯酸-1,3-丁二醇酯、二丙烯酸-1,4-丁二醇酯和二丙烯酸丙二醇酯、二乙烯苯、甲基丙烯酸乙烯酯、丙烯酸乙烯酯、甲基丙烯酸烯丙酯、丙烯酸烯丙酯、马来酸二烯丙酯、富马酸二烯丙酯、亚甲基二丙烯酰胺、丙烯酸环戊二烯酯、(甲基)丙烯酸三环癸烯酯、N,N′-二乙烯基咪唑啉-2-酮和氰尿酸三烯丙酯。
聚合物的分子量可通过加入少量一种或多种调整分子量的物质来调节,基于要聚合单体计,一般加入0.01-5%wt。这些分子量调节剂的例子是巯基化合物,诸如巯基乙醇、巯基丙醇、巯基丁醇、巯基乙酸、巯基丙酸、丁硫醇和叔十二烷基硫醇。这类物质优选与要聚合的单体混合后加入到聚合反应中。
对乳液聚合和制备单体乳液都适合的表面活性物质是通常用于该目的的乳化剂和保护性胶体。基于要聚合单体计,表面活性物质的一般用量为至多10%wt,优选0.5-5%wt,尤其是0.5-3%wt。
适合的保护性胶体的实例是聚乙烯醇、纤维素衍生物和乙烯基吡咯烷酮共聚物。在Houben-Weyl,Methoden der organischen Chemie,VolumeXIV/l,Makromolekulare Stoffe[大分子物质],Georg-Thieme-Verlag,Stuttgart,1961,pp411-420对其它合适的保护性胶体有具体描述。也可使用乳化剂和/或保护性胶体的混合物。作为表面活性物质优选只使用乳化剂,其相对分子量通常低于2000,不象那些保护性胶体的相对分子量。它们性质上可以是阳离子型、阴离子型或非离子型的。当使用表面活性物质的混合物时,各个成分必须相互相溶,在有疑问的情况下,可用一些预先试验来确定。一般的乳化剂的例子是乙氧基化的一、二和三烷基苯酚(EO单元:3-50,C4-C9烷基),乙氧基化脂肪醇(EO单元:3-50,C8-C36烷基),C8-C12烷基硫酸、磺酸的乙氧基化的C12-C18、烷醇(EO单元:4-30)和乙氧基化的烷基苯酚(EO单元:3-50,C4-C9烷基)的半酯、C12-C18磺酸和烷芳基磺酸(C9-C18烷基)的碱金属和铵盐。在Houben-Weyl,loc.cit.,pp.192-208给出了其它适合的乳化剂。
其它适合的阳离子乳化剂是在一个或两个芳环上有C4-C24烷基的双(苯基磺酸)醚和其碱金属和铵的盐。这些化合物是常识的一部分,从例如US-A-4269749可知,并是商业上可获得的,例如作为Dowfax2Al(DowChemical Company的商标)。
适合的自由基聚合引发剂是所有那些适于引发自由基水乳液聚合的引发剂。它们可以是过氧化物,例如过二硫酸碱金属盐,或是偶氮化合物。使用时也是包括至少一种有机还原剂和至少一种过氧化物和/或过氧化氢的联合体系,例如叔丁基氢过氧化物与羟基甲磺酸的钠盐,或过氧化氢与抗坏血酸。也可使用包括少量可溶于聚合介质的金属化合物并且其金属成分可以多种价态存在的联合体系,例如抗坏血酸/硫酸亚铁(II)/过氧化氢,其中抗坏血酸通常被羟基甲磺酸钠盐、亚硫酸钠、亚硫酸氢钠或酸式亚硫酸钠代替,过氧化氢被叔丁基过氧化氢或过二硫酸碱金属盐和/或过二硫酸铵代替。基于要聚合单体的总量计,自由基引发剂体系的用量优选为0.1-2%wt。
在新方法中,起始聚合物用作分散体。起始聚合物的组分单体是推荐的适用于自由基水乳液聚合的上述量的单体。
作为单体,起始聚合物优选含共聚形式的90-99.9%wt、尤其是95-99.7%wt的芳族乙烯单体、共轭的C4-C8二烯、丙烯酸和/或甲基丙烯酸与C1-C12-链烷醇或C5-C8环烷醇的酯或它们的混合物和0.1-10%wt、尤其是0.3-5%wt的α,β-不饱和的C3-C10一或二羧酸、它们的酰胺、N-乙烯基内酰胺和/或它们的混合物。
在一个特殊的实施方案中,使用的起始聚合物是共聚物,含共聚形式的90-99.9%wt、优选95-99.7%wt的苯乙烯、α-甲基苯乙烯、丙烯酸和/或甲基丙烯酸与C1-C12-链烷醇的酯、丁二烯或它们的混合物,和0.1-10%wt、优选0.3-5%wt的(甲基)丙烯酸、(甲基)丙烯腈、(甲基)丙烯酰胺或它们的混合物。
根据本发明加入的起始聚合物的平均颗粒尺寸(d50值,见下文)小于250nm,优选10-200nm,尤其是10-100nm,特别是10-50nm。该分散系的固体含量一般在20-50%wt。
已发现如果作为接种胶乳使用的聚合物具有窄的颗粒尺寸分布是有益的。换句话说,系数 <1,优选<0.75,特别优选<0.5。这个d50值用根据W.Scholtan和H.Langen,Kolloid-Z和Z.-Polymere 250(1972)782-796(见下文)的分析超速离心方法测定的颗粒尺寸的重量平均值定义。超速离心测量给出了一个样品的颗粒直径的积分质量分布,从它可以得到具有等于或小于规定尺寸的直径的颗粒的重量百分比。在这里,d50值代表50%的颗粒在其范围内的颗粒尺寸,d90和d10值具有相似意义。
用已知方法可得到合适的起始聚合物分散体。例如根据Houben-Weyl,Methoden der organischen Chemie,Volume E20,PartI,Markromolekulare Stoffe[大分子物质],Georg-Thieme-Verlag,Stuttgart,1987,pp248-268(更详细的内容参考DE-A-4213965)。例如在低温互相混合水相——可含有调节PH的诸如NaHCO3或氨的碱性化合物、单体、自由基引发剂——基于要聚合起始单体的量,一般为0.1-5%wt、表面活性物质——基于要聚合起始单体的量,为1-50%wt,然后加热该混合物至聚合温度并进行聚合。颗粒尺寸一般随表面活性物质的量的提高而减小。在这里,乳化剂、聚合引发剂和分子量调节剂必须受上述有关乳液聚合内容的支配。但是,用于起始聚合物的水分散体的单体、调节剂和引发剂成分不要求必须与用于制备最终聚合物使用的成分相同。
本发明的方法一般可(但不绝对)包括一个在聚合反应之后用来除去残余单体的步骤(化学和/或物理除臭desodorizing)。例如从EP-A-584458可知,用蒸气汽提可减少聚合物分散体的残余单体含量;EP-A-327006建议常规的蒸馏过程(物理除臭)。化学除臭优选包括接在主聚合反应之后的第二聚合过程。例如在DE-A-3834734、EP-A-379892、EP-A-327006、DE-A-4419518、DE-A-4435422和DE-A-4435423中描述了这种过程,这些公开内容均作为参考引入本文。
新的聚合方法适用于制备聚合物体积含量至少为50%体积、优选至少65%体积的聚合物分散体。其粘度一般小于1000mPa-s,优选小于750mPa-s,特别是小于500mPa-s(DIN53019,23℃)。该方法也以良好的再现性适用于以一种工业上可实行的方法制备固体体积浓度高达75%体积的聚合物分散体。另外,所得分散体只有低粘度并且没有形成微凝结的趋势。
新方法优选适用于制备主要成分包括至少一种上述丙烯酸或甲基丙烯酸的酯、苯乙烯、丁二烯或它们的混合物的聚合物分散体。包括的聚合物特别是那些含70-100%wt共聚形式的丙烯酸和/或甲基丙烯酸与C1-C12-链烷醇的酯、苯乙烯或它们的混合物的、或含70-100%wt共聚形式的苯乙烯、丁二烯或它们的混合物的聚合物。
根据特别的优选,该方法适用于制备聚合物分散体,其中聚合物颗粒包括共聚形式的:95-99.7%wt至少一种丙烯酸和/或甲基丙烯酸与C1-C12-链烷醇的酯,0.3-5%wt丙烯酸和/或甲基丙烯酸,和0-1%wt丙烯酰胺和/或甲基丙烯酰胺。
根据本发明可获得的最终的聚合物分散体特别适用于作为粘合剂,例如用于可刷涂的颜料或薄粘胶膜,用于纸、皮革、纺织的或无纺的纤维制品的涂饰,或作为用于制备涂料和粘结剂的组合物,对于这种组合物,也可习惯上包括添加物质,诸如成膜助剂、填充剂和增塑剂。
实施例1.测定在聚合物分散体中的聚合物颗粒的颗粒尺寸和颗粒数量及粘度和起块程度
通过使用分析超离心的耦合PSD技术方法(见W.Machtle,AngewandteMakromolekulare Chemie,162(1988)35-42(No.2735))测定聚合物颗粒的颗粒尺寸分布。
在聚合物分散体中的聚合物颗粒的浓度相同地用分析超离心通过平均颗粒直径的方式根据W.M chtle,Makromolekulare Chemie,185(1984)1025-1039(见DE-4213965.1)测定。
所得聚合物分散体的粘度在23℃根据DIN53019用487s-1的速度梯度以动态形式测定。
结块程度描述了聚合物分散体中微凝结的比例。为此目的,聚合物分散体规定的参数适用于在60μm厚的涂层的表面透明检测,在干燥后与适合的参照样品进行目视对比。结块程度 检测1 无可见的结块2 局部结块3 一些结块4 很多结块5 特别多结块2.制备起始聚合物的DA1和DA2水分散体
DA1:在室温首先将0.0625kg丙烯酸和0.005kg硫酸亚铁(II)在2kg水中的溶液搅拌着加入到
65.4kg 水、
25kg 丙烯酸正丁酯和
22.25kg 对应于Dowfax2A1的表面活性物质的45%wt的水溶液
的混合物中,然后3分钟内加入2kg水和0.65kg30%wt的过氧化氢水溶液的混合物。随后冷却混合物,加入0.05kg抗坏血酸在1kg水中的混合物,之后每批(batch)搅拌2小时。
如此获得的起始聚合物水分散体有30.2%wt的固体含量,32nm的重均颗粒直径
和1.7×1019颗粒/kg的颗粒浓度。
DA2:1800g 水、
225g 对应于Dowfax2A1的表面活性物质的45%wt的水溶液、
10g 25%wt氨水溶液、
495g 丙烯酸正丁酯和
5g 丙烯酸
的混合物加热到80℃,一次加入25g过二硫酸钠。在冷却到25℃之前混合物保持在80℃1小时。
如此获得的起始聚合物水分散体有26%wt的固体含量,35nm的重均颗粒直径
和1.1×1019颗粒/kg的颗粒浓度。3.制备DE1-DE4不同的新的最终聚合物水分散体
DEl:开始在聚合容器中加入
150g 水、
22g 对应于Dowfax2A1的表面活性物质的20%wt的水溶液和
11g 从1)得到的DA1水分散体
的混合物,边搅拌边加热到85℃。然后保持85℃,连续在5小时期间 加入原料物流II。与原料物流II同时,按下列程序连续加入原料物流I:
4%wt 在40分钟期间,
然后 8%wt 在40分钟期间,
然后 88%wt 在200分钟期间。
在原料物流II加完后,反应混合物保持在85℃1小时。原料物流I:
549g DA1水分散体
1345g 丙烯酸正丁酯
889g 甲基丙烯酸甲酯
46.5g 甲基丙烯酸原料物流II:
160g 水
10g 过二硫酸钠
所得分散体没有微凝结,固体体积浓度为67.8%体积,粘度440mPa-s。结块程度1。
DE2:160g水、
11.2g对应于Dowfax2A1的表面活性物质的20%wt的水溶液和
11g 从1)得到的DA1水分散体
的混合物加到聚合容器中,边搅拌边加热到85℃。保持该温度,连续在5小时期间加入原料物流II。与原料物流II同时,按下列程序加入原料物流I:
4%wt 在40分钟期间,
8%wt 在40分钟期间,
88%wt 在200分钟期间。
在原料物流II加完后,混合物保持在85℃1小时。原料物流I:
549g从1)得到的DA1水分散体
915.2g 丙烯酸正丁酯
114g 丙烯酸乙酯
114g 丙烯酸-2-乙基己酯
114g 甲基丙烯酸甲酯
22.8g 丙烯酸
3.4g 叔十二烷基硫醇原料物流II:
160g 水
10g 过二硫酸钠
所得分散体没有微凝结,固体体积浓度为69.0%体积,粘度360mPa-s。结块程度为1。
DE3:在聚合容器中加入175g水,加热到85℃。然后保持这个温度,加入下述原料物流I和II,开始同时添加它们,进程根据下列程序:
原料物流I:
667g 从1)得到的DA2水分散体
2257.2g 丙烯酸正丁酯
22.8g 丙烯酸
2%wt 在20分钟期间,
4%wt 在20分钟期间,
8%wt 在20分钟期间,
86%wt 在180分钟期间。原料物流II:
79.7g 水
6.0g 过二硫酸钠
20%wt 在5分钟期间,
80%wt 在115分钟期间。
在原料物流II加完后,反应混合物保持在85℃1小时以上,然后冷却。
所得分散体没有微凝结,固体体积浓度为70.0%体积,粘度450mPa-s。结块程度为1-2。
DE4:如同DE3,但原料物流根据下列程序:
原料物流I:
1%wt 在20分钟期间,
2%wt 在20分钟期间,
4%wt 在20分钟期间,
93%wt 在300分钟期间。原料物流II:
5%wt 在60分钟期间,
5%wt 在60分钟期间,
90%wt 在240分钟期间。
所得分散体基本没有微凝结,固体体积浓度为70.0%体积,粘度500mPa-s。结块程度为2。比较分散体VDE1-VDE4的制备VDE1:按DE1制备,但接种分散体DA1和单体用分别进料的方式加入。在按下列顺序:
33.4%wt 在40分钟期间
66.6%wt 在120分钟期间
开始加入单体之后80分钟开始接种加料(按DE1的原料物流I,无接种)。 固体体积浓度 67.6%体积
粘度 460mPa-s
结块程度 4-5VDE2:按DE2制备,但接种分散体和单体用分别进料的方式加入。在按下列 顺序:
26%wt 在80分钟期间
54%wt 在60分钟期间
20%wt 在60分钟期间
开始加入单体之后80分钟开始接种加料(按DE2的原料物流I,无接种)。 固体体积浓度 69.4%体积
粘度 375mPa-s
结块程度 4VDE3:按DE3制备,但接种分散体DA2用分别进料的方式供给聚合反应,与单体的加入同时开始(按DE3的原料物流I,无接种)。接种的加料按下列顺序:
5%wt 在60分钟期间
10%wt 在60分钟期间
85%wt 在120分钟期间
固体体积浓度 69.5%体积
粘度 430mPa-s
结块程度 3-4VDE4:按VDE3制备。接种分散体的加入按下列程序:
1%wt 在5分钟期间
99%wt 在295分钟期间
固体体积浓度 70.3%体积
粘度 510mPa-s
结块程度 4
Claims (15)
1.一种用于制备低粘度聚合物水分散体的方法,以聚合物分散体为基准,聚合物体积浓度至少为50%体积,用除卤乙烯和偏二卤乙烯以外的烯键不饱和单体在至少一种引发剂和至少一种起始聚合物存在下由自由基乳液聚合反应制备,该方法包括在起始聚合物的水分散体中乳化主要部分的单体并将该乳液连续提供给聚合反应。
2.按权利要求1的方法,其中基于要聚合的单体,使用0.01-10%wt的起始聚合物。
3.权利要求1或2的方法,其中起始聚合物的平均粒径(d50值)小于250nm,。
4.利要求1-3任一项的方法,其中使用的起始聚合物含至少一种共聚物,共聚物含共聚形式的90-99.9%wt的芳族乙烯单体、共轭的C4-C8二烯、丙烯酸或甲基丙烯酸与C1-C12-链烷醇或C5-C8环烷醇的酯、或它们的混合物和0.1-10%wt的α,β-不饱和的C3-C10一或二羧酸、它们的酰胺、N-乙烯基内酰胺或它们的混合物,每种情况的重量百分比基于合物总量计
5.权利要求5的方法,其中使用的起始聚合物含至少一种共聚物,共聚物含共聚形式的90-99.9%wt苯乙烯、α-甲基苯乙烯、丙烯酸和/或甲基丙烯酸与C1-C12-链烷醇的酯、丁二烯或它们的混合物和0.1-10%wt的(甲基)丙烯酸、(甲基)丙烯腈、(甲基)丙烯酰胺或它们的混合物。
6.权利要求1-5任一项的方法,其中在加入反应混合物中前起始聚合物至少在单体乳液中溶胀30分钟。
7.权利要求1-6任一项的方法,其中使用的烯键不饱和单体含有80-99.9%wt的至少一种选自α,β-不饱和的C3-C10一或二羧酸与C1-C12-链烷醇或C5-C8环烷醇的酯、C1-C18羧酸乙烯酯、C1-C12-烷基乙烯基醚、C2-C6链烯、芳族乙烯单体、C4-C8共轭二烯、(甲基)丙烯腈或其混合物的组的单体和0.1-20%wt的α,β-单烯键不饱和的C3-C10一或二羧酸、其酰胺、乙烯磺酸(甲基)丙烯酰氨基2-甲基丙磺酸和/或其盐、N-乙烯基吡咯烷酮或它们的混合物及0-10%wt的交联单体,每种情况的重量百分比基于要聚合的单体的总量计。
8.按权利要求1-7任一项的方法,其中在单体乳液中水对单体的数量比例在1∶1至1∶9的范围。
9.权利要求1-8任一项的方法,其中计量加入单体乳液以使在反应混合物中存在的单体的转化率至少为80%。
10.一种聚合物水分散体,按权利要求1-9任一项的方法制备。
11.按权利要求10的聚合物水分散体,其聚合物体积含量大于65%体积。
12.按权利要求10或11的聚合物水分散体,其中粘度小于1000mPa-s。
13.按权利要求10-12任一项的聚合物水分散体,其中聚合物颗粒含有共聚形式的70-100%wt的丙烯酸或甲基丙烯酸与C1-C12-链烷醇的酯、苯乙烯或其混合物、或70-100%wt的苯乙烯、丁二烯或它们的混合物。
14.按权利要求10-13任一项的聚合物水分散体,其中聚合物颗粒含有共聚形式的95-99.7%wt的至少一种丙烯酸和/或甲基丙烯酸与C1-C12-链烷醇的酯、0.3-5%wt的丙烯酸和/或甲基丙烯酸和0-1%wt的丙烯酰胺和/或甲基丙烯酰胺。
15.权利要求10-14任一项的聚合物水分散体,作为用于涂料组合物的粘合剂、胶粘剂、用于涂饰纸、皮革、纺织的或无纺的纤维制品的应用。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19624280A DE19624280A1 (de) | 1996-06-18 | 1996-06-18 | Verfahren zur Herstellung niedrigviskoser, wässriger Polymerisatdispersionen mit Polymervolumenkonzentrationen von wenigstens 50 Vol.-% |
DE19624280.0 | 1996-06-18 |
Publications (1)
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CN1174203A true CN1174203A (zh) | 1998-02-25 |
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CN97112790A Pending CN1174203A (zh) | 1996-06-18 | 1997-06-17 | 聚合物体积浓度至少为50%的低粘度聚合物水分散体的制备 |
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US (1) | US6028135A (zh) |
EP (1) | EP0814103A3 (zh) |
JP (1) | JPH1060022A (zh) |
KR (1) | KR980002084A (zh) |
CN (1) | CN1174203A (zh) |
AU (1) | AU2494097A (zh) |
BR (1) | BR9703612A (zh) |
DE (1) | DE19624280A1 (zh) |
ID (1) | ID17257A (zh) |
TR (1) | TR199700515A2 (zh) |
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KR100518033B1 (ko) * | 1998-09-08 | 2005-12-21 | 주식회사 한솔케미칼 | 종이 도공용 라텍스 조성물 |
US6184287B1 (en) * | 1999-01-26 | 2001-02-06 | Omnova Solutions Inc. | Polymeric latexes prepared in the presence of 2-acrylamido-2-methylpropanesulfonate |
US6525116B2 (en) * | 1999-01-26 | 2003-02-25 | National Gypsum Properties Llc | Gypsum composition with ionic styrene butadiene latex additive |
DE60026076T2 (de) | 1999-12-27 | 2006-09-14 | Arkema | Herstellungsverfahren von einem latex mit hohem feststoffgehalt, mit einer niedrigen viskosität und eine einer bimodalen verteilung |
DE10013733A1 (de) * | 2000-03-21 | 2001-09-27 | Basf Ag | Verfahren zur Herstellung von Kautschukteilchen |
DE10035589A1 (de) * | 2000-07-21 | 2002-02-07 | Wacker Polymer Systems Gmbh | Verfahren zur Herstellun von Polymerdispersionen mi t hohem Feststoffgehalt |
MXPA01008705A (es) * | 2000-09-03 | 2004-08-12 | Rohm & Haas | Sistemas de aditivos polimericos multiples: composiciones, procesos y productos derivados. |
MXPA01008532A (es) * | 2000-09-03 | 2002-08-06 | Rohm & Haas | Sistema de acitivos funcionales de liquidos-solidos; sus composiciones, procesos y productos. |
MXPA01008706A (es) * | 2000-09-03 | 2004-08-12 | Rohm & Haas | Sistemas aditivos polimericos altos en solidos: composiciones, procesos y productos de los mismos. |
US6939922B2 (en) * | 2001-03-30 | 2005-09-06 | Rohm And Haas Company | Coating and coating composition |
US7189767B2 (en) * | 2001-03-30 | 2007-03-13 | Rohm And Haas Company | Colorants, dispersants, dispersions, and inks |
ITMI20011013A1 (it) * | 2001-05-17 | 2002-11-17 | Atofina | Processo per ottenere dispersioni acquose polimeriche |
AU785016B2 (en) * | 2001-06-14 | 2006-08-24 | Rohm And Haas Company | Semi-continuous bimodal emulsion polymerization |
ITMI20011683A1 (it) * | 2001-08-02 | 2003-02-02 | Atofina | Processo per ottenere dispersioni polimeriche acquose |
US20030162890A1 (en) * | 2002-02-15 | 2003-08-28 | Kalantar Thomas H. | Nanoscale polymerized hydrocarbon particles and methods of making and using such particles |
US7244784B2 (en) * | 2002-06-14 | 2007-07-17 | Rohm And Haas Company | Aqueous nanoparticle dispersions |
US20030232916A1 (en) * | 2002-06-14 | 2003-12-18 | Lorah Dennis Paul | Nonaqueous compositions |
EP1517946B1 (de) * | 2002-06-21 | 2006-10-04 | Basf Aktiengesellschaft | Verfahren zur herstellung einer wässrigen polymerdispersion |
JP3999746B2 (ja) * | 2003-05-19 | 2007-10-31 | ローム アンド ハース カンパニー | ポリマーナノ粒子の高固形分調製方法 |
US7504466B2 (en) * | 2004-11-04 | 2009-03-17 | Rohm And Haas Company | High solids preparation of crosslinked polymer particles |
CN107207639A (zh) * | 2015-09-24 | 2017-09-26 | Jsr株式会社 | 乳液组合物及其制造方法、以及层叠体及其制造方法 |
CN114901703B (zh) | 2019-12-31 | 2024-04-23 | 巴斯夫欧洲公司 | 水性聚合物组合物、其制备方法及其作为可移除压敏胶粘剂的用途 |
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US3424706A (en) * | 1966-07-08 | 1969-01-28 | Staley Mfg Co A E | Vinylidene chloride copolymerization in presence of preformed seed latex |
US4130523A (en) * | 1977-07-18 | 1978-12-19 | Union Carbide Corporation | High solids latexes |
US4409355A (en) * | 1980-03-10 | 1983-10-11 | National Distillers And Chemical Corporation | Process for preparing high solids copolymer latices with low viscosity |
DE3147008A1 (de) * | 1981-11-27 | 1983-06-01 | Röhm GmbH, 6100 Darmstadt | Verfahren zur herstellung von waessrigen, hochkonzentrierten bimodalen kunststoffdispersionen |
DE4213969A1 (de) * | 1992-04-29 | 1993-11-04 | Basf Ag | Waessrige polymerisatdispersion |
DE4213968A1 (de) * | 1992-04-29 | 1993-11-04 | Basf Ag | Waessrige polymerisatdispersion |
DE4213965A1 (de) * | 1992-04-29 | 1993-11-04 | Basf Ag | Waessrige polymerisatdispersion |
DE4307683A1 (de) * | 1993-03-11 | 1994-09-15 | Basf Ag | Verfahren zur Herstellung einer wäßrigen Polymerisatdispersion |
US5541253A (en) * | 1994-10-11 | 1996-07-30 | The B. F. Goodrich Company | High solids copolymer dispersion from a latex and its use in sealants |
-
1996
- 1996-06-18 DE DE19624280A patent/DE19624280A1/de not_active Withdrawn
-
1997
- 1997-06-16 AU AU24940/97A patent/AU2494097A/en not_active Abandoned
- 1997-06-16 JP JP9158278A patent/JPH1060022A/ja not_active Withdrawn
- 1997-06-17 CN CN97112790A patent/CN1174203A/zh active Pending
- 1997-06-17 KR KR1019970025144A patent/KR980002084A/ko not_active Application Discontinuation
- 1997-06-17 US US08/877,499 patent/US6028135A/en not_active Expired - Fee Related
- 1997-06-17 EP EP97109873A patent/EP0814103A3/en not_active Withdrawn
- 1997-06-17 BR BR9703612A patent/BR9703612A/pt not_active Application Discontinuation
- 1997-06-17 ID IDP972079A patent/ID17257A/id unknown
- 1997-06-18 TR TR97/00515A patent/TR199700515A2/xx unknown
Also Published As
Publication number | Publication date |
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EP0814103A2 (de) | 1997-12-29 |
ID17257A (id) | 1997-12-11 |
KR980002084A (ko) | 1998-03-30 |
EP0814103A3 (en) | 1998-10-07 |
JPH1060022A (ja) | 1998-03-03 |
TR199700515A2 (xx) | 1998-01-21 |
DE19624280A1 (de) | 1998-01-02 |
US6028135A (en) | 2000-02-22 |
AU2494097A (en) | 1998-01-08 |
BR9703612A (pt) | 1998-11-10 |
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