CN112352001A - 清洁聚合反应器的方法 - Google Patents
清洁聚合反应器的方法 Download PDFInfo
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- CN112352001A CN112352001A CN201980044330.1A CN201980044330A CN112352001A CN 112352001 A CN112352001 A CN 112352001A CN 201980044330 A CN201980044330 A CN 201980044330A CN 112352001 A CN112352001 A CN 112352001A
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- polymerization
- aqueous mixture
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- polymerization reactor
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G85/00—General processes for preparing compounds provided for in this subclass
- C08G85/008—Cleaning reaction vessels using chemicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
- C08F18/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
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- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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Abstract
本发明涉及清洁用于在一种或多种保护性胶体和/或乳化剂的存在下通过自由基引发的一种或多种烯键式不饱和单体的乳液聚合而制备聚合物水分散体的聚合反应器的方法,其特征在于首先将水性混合物加入到聚合反应器中,其包含一种或多种烯键式不饱和单体、一种或多种保护性胶体和/或乳化剂且不包含氧化引发剂,其中烯键式不饱和单体的比例基于所述水性混合物的总重量为20至70重量%,然后将所述水性混合物加热至50℃至100℃的温度,然后将聚合反应器用水性混合物处理5分钟至3小时,然后加入一种或多种引发剂和任选其它的原料,然后引发聚合,然后将由此获得的水性聚合物分散体从聚合反应器中除去,并进行后处理以除去在处理期间脱附的壁沉积物。
Description
本发明涉及一种通过自由基引发的可自由基聚合的烯键式不饱和单体的乳液聚合而清洁用于制备水性聚合物分散体的聚合反应器的方法。
聚合物水分散体在广泛应用中用作粘合剂,例如在粘合剂、涂料应用中、在地毯、纺织品和纸张应用中以及在建筑化学产品中用作粘合剂,其中所述建筑化学产品中用在诸如瓷砖粘合剂、抹灰和密封剂中。这些水分散体通常在搅拌聚合反应器中分批地(不连续地)或在搅拌的釜级联中连续地通过水乳液聚合而制备。工艺效率受到通过经由冷却表面散发的散热而限制,其中所述冷却表面例如冷却盘管和反应器壁。
所述散热也受到称为结垢的壁沉积物形成的限制。该壁沉积物基本上由在聚合过程中不充分稳定且沉积在反应器内壁或内部部件的表面上的聚合物组成。为了改善散热,在分批聚合的情况下因此必须在一批或多批之后辛苦地清洗反应器,例如用有机溶剂或者通过在高压下用水高压清洗的纯机械清洗。
为了防止壁沉积,可以如EP 0152115 B1和EP 3256497 B1中所述,将聚合反应器的内部及其内部部件的表面涂覆有防垢剂。此处的缺点是涂覆成本以及防污涂覆剂对聚合产物污染的风险。
已知机械方法用于去除已经形成的壁沉积物。US 6274690 B1提出用喷水器清洗反应器内壁。EP 2689838 A1描述了一种聚合方法,其中将惰性磨料颗粒添加到聚合混合物中以防止在聚合过程中形成沉积物。在EP 2658644 B1的管式反应器中的连续聚合过程中,反应器内表面用刮刀和擦拭器清洁。在WO 98/29186 A1的方法中,使反应器壁振动以防止沉积物的形成。US 2006/0130870 A1描述了一种借助用低频声波进行处理而清洁聚合反应器壁的方法。这些机械方法的缺点是设备费用以及这些方法所需的在反应器内部上形成沉积物的风险。
聚合反应器的内部也可以用化学试剂清洗。在US 4038473中,用热碱性洗涤剂溶液除去在氯乙烯聚合期间形成的壁沉积物。在EP 0057433 A1的方法中,将具有多价金属盐的表面活性剂水溶液用于清洁。EP 0633061 A1描述了在管式反应器中的连续乳液聚合,该反应器使用表面活性剂溶液进行清洁。US 4904309也使用表面活性剂溶液进行清洁。在EP3351612 A1中,用非离子表面活性剂溶液冲洗聚合反应器。EP 1230019 B1描述了在环管反应器中的乳液聚合,其中聚合反应器用水进行清洗,并且将洗涤水再用于聚合中。根据EP0248681 B1,将皂形成剂如碱金属硅酸盐或碱金属磷酸盐、碱如碱金属氢氧化物或碱金属碳酸盐、表面活性剂和有机溶剂如二甲苯或甲苯的组合物,任选与单体的组合物用于清洁反应器内部。化学清洗方法的缺点是清洗所需的时间以及产物被清洗液成分污染的风险。
因此,本发明的目的是提供一种清洁用于制备聚合物水分散体的反应器的改进方法,通过该方法可以有效地去除聚合物壁的沉积物,并确保改善的设备利用率(由于清洁而导致的停机时间更短)以及由于清洁溶液而更少的浪费。
本发明涉及清洁用于在一种或多种保护性胶体和/或乳化剂的存在下通过自由基引发的一种或多种烯键式不饱和单体的乳液聚合而制备聚合物水分散体的聚合反应器的方法,其特征在于首先将水性混合物加入到聚合反应器中,其包含一种或多种烯键式不饱和单体、一种或多种保护性胶体和/或乳化剂,且不包含氧化引发剂,其中烯键式不饱和单体的比例基于所述水性混合物的总重量为20至70重量%,然后将所述水性混合物加热至50℃至100℃的温度,然后将聚合反应器用水性混合物处理5分钟至3小时,然后加入一种或多种引发剂和任选其它的原料,然后引发聚合,然后将由此获得的水性聚合物分散体从聚合反应器中除去,并进行后处理以除去在处理期间脱附的壁沉积物。
借助自由基引发的乳液聚合而制备聚合物水分散体已有多次描述,并且是本领域技术人员已知的;例如在Encyclopedia of Polymer Science and Engineering,第8卷(1987),John Wiley and Sons,第659-677页。
所述烯键式不饱和单体优选选自乙烯基酯、(甲基)丙烯酸酯、乙烯基芳族化合物、烯烃和乙烯基卤化物、以及任选的可与其共聚的其他单体。合适的乙烯基酯是具有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-支化一元羧酸的乙烯基酯,例如或(Hexion的商品名)。特别优选乙酸乙烯酯。合适的丙烯酸酯或甲基丙烯酸酯的单体例如是具有1至15个碳原子的直链或支化醇的酯。优选的甲基丙烯酸酯或丙烯酸酯为丙烯酸甲酯、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、丙烯酸叔丁酯和丙烯酸2-乙基己酯。优选的乙烯基芳族化合物是苯乙烯、甲基苯乙烯和乙烯基甲苯。优选的烯烃是乙烯、丙烯和丁二烯。优选的乙烯基卤化物是氯乙烯。
特别优选包含乙酸乙烯酯和1至40重量%的乙烯的共聚单体混合物;和包含乙酸乙烯酯和1至40重量%乙烯和1至50重量%的一种或多种其他共聚单体的混合物,其中所述其它共聚单体选自在羧酸基团中具有3至15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11个碳原子的α-支链羧酸的乙烯基酯,例如VeoVa9、VeoVa10、VeoVa11;和
包含乙酸乙烯酯、1至40重量%乙烯、优选1至60重量%具有1至15个碳原子的直链或支化醇的丙烯酸酯,特别是丙烯酸正丁酯或丙烯酸2-乙基己酯的混合物;
和包含30至75重量%乙酸乙烯酯、1至30重量%月桂酸乙烯酯或具有9至11个碳原子的α-支化羧酸的乙烯基酯以及1至30重量%具有1至15个碳原子的直链或支化醇的丙烯酸酯,特别是丙烯酸正丁酯或丙烯酸2-乙基己酯的混合物,其另额外包含1至40重量%的乙烯;
和包含乙酸乙烯酯、1至40重量%乙烯和1至60重量%氯乙烯的混合物;其中,该混合物还可以任选包含其他单体,并且其中在每种情况下的重量百分比总计为100重量%。
合适的保护胶体例如为,部分皂化的聚乙烯醇;聚乙烯吡咯烷酮;聚乙烯醇缩醛;水溶性形式的多糖,例如淀粉(直链淀粉和支链淀粉)、纤维素及其羧甲基、甲基、羟乙基、羟丙基衍生物;蛋白质,例如酪蛋白或酪蛋白酸盐、大豆蛋白、明胶、木质素磺酸盐;合成聚合物,例如聚(甲基)丙烯酸、(甲基)丙烯酸酯与羧基-官能共聚单体单元的共聚物、聚(甲基)丙烯酰胺、聚乙烯磺酸及其水溶性共聚物;三聚氰胺甲醛磺酸盐、萘甲醛磺酸盐、苯乙烯马来酸和乙烯基醚马来酸共聚物;阳离子聚合物,例如聚二烯丙基二甲基氯化铵(poly-DADMAC)。优选部分皂化的聚乙烯醇,其水解度为80至95mol%,并且在4%水溶液中的霍普勒粘度为1至30mPas(20℃下的霍普勒方法,DIN 53015)。
合适的乳化剂例如为阴离子和/或非离子乳化剂。阴离子型乳化剂的实例是链长为8至18个碳原子的烷基硫酸盐,疏水基团中具有8至18个碳原子且多至40个氧化乙烯或氧化丙烯单元的烷基或烷基芳基醚硫酸盐,具有8至10个碳原子的烷基或烷基芳基磺酸盐、磺基琥珀酸与一元醇的酯和半酯。非离子型乳化剂的实例是乙氧基化度为2至20个氧化乙烯单元的C12-C14-脂肪醇乙氧基化物。
在预处理或聚合中,所述保护性胶体和/或乳化剂的总用量基于单体的总重量通常为1至20重量%。
在根据本发明的清洁中,首先将水、单体以及保护性胶体和/或乳化剂作为水性混合物加入到聚合反应器中,并且优选在搅拌下在聚合反应器中将该混合物进行搅拌。在每种情况下,在所述水性混合物中的单体含量基于水性混合物的总重量,通常为25至70重量%,优选30至70重量%,特别优选40至70重量%。混合物中的单体含量越高,由于聚合物在单体中的溶胀和溶解,则聚合物壁沉积物溶解得越有效。在此可以设定单体含量的上限,以使乳液并不会从水包油转变为油包水。所述保护性胶体和/或乳化剂优选以聚合所需的量而在初始进料中使用。最初并没有添加氧化引发剂。优选,并不首先加入氧化引发剂和还原引发剂。
在每种情况下,基于反应器的体积,聚合反应器中水性混合物的填充水平通常为40至95体积%,优选50至95体积%,特别优选70至95体积%。
将水性混合物优选在搅拌下加热至50℃至100℃的温度,优选70℃至100℃的温度,特别优选至80至100℃的温度。温度的选自应避免使混合物沸腾并过早聚合。任选,该处理也可以在压力下进行。
达到所需温度后,通常在5分钟至3小时,优选10分钟至2小时,特别优选20分钟至1小时的期间内,优选在搅拌下用所述水性混合物处理(清洗)聚合反应器。
该处理完成以后,可以任选将所述水性混合物冷却。所述混合物可任选用水进行稀释。也可以任选加入单体、保护性胶体和/或乳化剂或其他原料,例如缓冲剂或调节剂。
为了引发聚合,将引发剂加入到水性混合物中,并将所述水性混合物加热至聚合温度。
所述聚合使用用于乳液聚合的常规引发剂进行引发,特别是氧化引发剂和还原引发剂的氧化还原引发剂的组合物。合适的氧化引发剂的实例是过二硫酸的钠、钾和铵盐、过氧化氢和偶氮二异丁腈。优选过氧二硫酸的钠、钾和铵盐和过氧化氢。所提及的氧化引发剂的用量通常基于单体总重量为0.01至2.0重量%。
合适的还原剂(还原引发剂)例如碱金属和铵的亚硫酸盐和亚硫酸氢盐,例如亚硫酸钠;次硫酸的衍生物,例如锌或碱金属甲醛次硫酸盐,例如羟基甲亚磺酸钠(Bruggolite)和抗坏血酸、异抗坏血酸或其盐;或不含甲醛的还原剂,例如2-羟基-2-磺基乙酸二钠盐(Bruggolite FF6)。还原引发剂的量基于单体的总重量优选为0.015至3重量%。
所述聚合在乳液聚合的典型条件下进行。聚合温度优选50℃至110℃。压力取决于要聚合的单体在特定的聚合温度下是液态还是气态,优选1至110巴abs。在气态共聚单体,例如乙烯、1,3-丁二烯或氯乙烯的共聚中,聚合在特别优选10至80巴abs的压力下进行。
在聚合完成后,将产物混合物从聚合反应器中除去,并任选通过脱气、后聚合和/或汽提而进行后处理。由此获得的聚合物分散体包括在清洁过程中脱附的壁沉积物。因此,对聚合物分散体进行后处理,优选进行过滤,以除去脱附的壁沉积物。在后处理之后,所述聚合物分散体优选具有未经预处理而获得的聚合物分散体的规格,并且可以与常规获得的批次混合以储存。
在填充该清洁批次之后,并且任选在用水冲洗之后,聚合反应器处于清洁的状态,并且立即可以再次使用。
用根据本发明的方法进行清洁的频率取决于具体情况,例如反应器内部的体积、产品组合(单体批料的组成)、对污染物的敏感性(取决于所制备聚合物的胶体稳定性或剪切稳定性)。优选,在反应器由聚合物壁沉积物严重污染之前,使用根据本发明的方法,这是因为否则清洁效果将降低并且过滤作用增大。聚合期间或两个或更多个连续聚合期间形成的壁沉积物的程度可以借助聚合反应器的冷却能力的降低而测量。在没有聚合物壁沉积物的干净的聚合反应器的情况下,冷却能力为100%。随着聚合物壁沉积物形成的增加,冷却能力大约成比例地降低。
冷却能力Q*通常至少对应于释放的聚合热,并且以千瓦(kW)测量。冷却能力Q*由以下关系定义:
Q*=α*A*ΔT,其中
α=传热系数[W/(m2K)],A=换热表面[m2],ΔT=温度差[K](反应器温度和冷却水温度之间的差)。交换表面是恒定的,并不会改变。传热系数通常并不精确已知,并且由于壁沉积物的形成而变差。为了再次获得相同的冷却能力,因此若冷却能力变差的话,则ΔT必须相应更大。
因此,ΔT的百分比变化大约对应于由于传热系数α变差所致的冷却能力的变化。例如,如果温度差ΔT从10℃增加到11℃,则冷却能力仅为初始冷却能力的10/11=90.9%,而没有形成壁沉积物。
当聚合反应器由于结垢(壁沉积物的形成)而仅表现出初始冷却能力的50至95%,特别优选仅是初始冷却能力的60至90%时,最优选初始冷却能力的70%至85%时,优选使用本发明的方法。
根据本发明的方法的目的在于,在应用本发明的清洁方法之后,再次获得大于95%的初始冷却能力而没有壁沉积物。
本发明的方法优选适合于清洁用于分批聚合的聚合反应器。在分批聚合的情况下,聚合反应器中填充有反应物,进行聚合,并且将反应器排空。对于下一批次,将聚合反应器重新填充、聚合并当聚合完成时再次排空。在分批聚合方法的一批或多批之后,优选20到30批之后,可以使用本发明的方法用于清洁聚合反应器。
在根据本发明的方法中,将清洁聚合反应器所引起的时间损失减少到最小。另一个优点是没有由于清洁剂所造成的浪费,所述清洁剂例如有机溶剂。特别有利的是,在清洁步骤之后的聚合步骤中也产生产物且不产生废料。
下列实施例用于进一步阐明本发明:
一般聚合步骤(第1批):
在约600升的容积压力反应器中首先加入如下组分:
115kg水,
105kg 20重量%的部分皂化聚乙烯醇的聚乙烯醇溶液,其水解度为88mol%,霍普勒粘度为4mPas(根据DIN 53015的霍普勒方法,在20℃和4%的水溶液中),
11kg 10重量%的部分皂化的聚乙烯醇的聚乙烯醇溶液,其水解度为88mol%,霍普勒粘度为25mPas,
70g 85%甲酸水溶液,
80g 10%硫酸铁铵水溶液。
将反应器排空,然后将220kg乙酸乙烯酯加入到含水初始进料中。然后将反应器加热至55℃,并经受32巴的乙烯压力(相当于28kg的乙烯)。
通过以1.5kg/h的速率加入3重量%过硫酸钾水溶液和以1.5kg/h的速率加入1.5重量%的羟基甲烷亚磺酸钠水溶液(Bruggolite)以开始聚合。观察到聚合反应开始后,在30分钟内将内部温度升高至85℃。从反应开始,将压力升至55巴并保持直至计量加入额外的10kg乙烯。然后关闭乙烯阀并允许压力下降。在达到75℃的聚合温度之后,在2小时的时间内计量加入额外的55kg乙酸乙烯酯,并且引发剂速率增加到2.0kg/h至2.5kg/h的速率。计量加入乙酸乙烯酯后,引发剂再运行60分钟以使该批料聚合。
总聚合时间为约5小时。该聚合的平均热量输出为约28千瓦。为了保持85℃的期望的聚合温度(反应器温度),夹套入口温度(冷却水温度)最低为77℃。因此,温度差ΔT为8℃。
然后将分散体转移至未加压的反应器中以进行分离和固化,在其中通过加入500g10重量%的叔丁基过氧化物水溶液和145g 10重量%的Bruggolite水溶液以进行后聚合。通过加入氢氧化钠水溶液(10重量%水溶液)而将pH调节至然后将压力反应器用15kg水进行冲洗。
产物性质:
重复一般聚合步骤(批次2至20):
将按照一般步骤的聚合重复了19次,在每批之间仅用水冲洗聚合反应器,而没有进一步的清洗。
在第20批之后,观察到夹套入口温度下降至72℃,每批具有相同的聚合时间且每批具有相同的热量输出28kW。因此,与聚合温度的差为ΔT=13℃,并且明显高于ΔT=8℃下的反应器(批料1)的清洁状态。
ΔT由8℃升增加至13℃对应于冷却能力下降至没有壁沉积物的初始冷却能力的8/13=61.5%。
本发明方法的实例:清洁批次(批次21):
如一般步骤所述,将反应器填充有水、聚乙烯醇溶液、甲酸溶液、硫酸铁铵溶液、乙酸乙烯酯和乙烯。然后将反应器中存在的混合物加热至85℃,并在该温度下搅拌30分钟。然后通借助夹套冷却将反应器内容物再次冷却至55℃。
然后通过以1.5kg/h的速率加入3重量%的过硫酸钾水溶液和以1.5kg/h的速率加入1.5重量%的羟基甲烷亚磺酸钠水溶液(Bruggolite)以开始聚合。如一般步骤中所述进行聚合。
通过根据本发明的清洁方法的这种方法,观察到保持85℃期望的聚合温度所需的夹套入口温度最小为76.7℃。因此,存在ΔT=8.3℃的差异,与第1批次的ΔT=8℃的差异相当。该温度行为表明反应器已经通过本发明步骤而恢复到清洁的状态。冷却能力商8/8.3=96.4%表明,在清洗以后,再次获得没有壁沉积物的初始冷却能力的96.4%。这意味着壁沉积物已经通过根据本发明的处理而几乎完全脱附。
由于在该批次中存在脱附的壁沉积物,因此将该批料进行分离并与脱附的反应器壁沉积物仔细过滤。此后获得的产物具有与批次1所述相同的产物性质。然后将该分散体混合到批次1至批次20的产物中。
Claims (6)
1.一种在一种或多种保护性胶体和/或乳化剂的存在下通过一种或多种烯键式不饱和单体的自由基引发的乳液聚合而清洁用于制备聚合物水分散体的聚合反应器的方法,其特征在于在聚合反应器中初始加入水性混合物,其包含一种或多种烯键式不饱和单体、一种或多种保护性胶体和/或乳化剂,并且不包含氧化引发剂,其中烯键式不饱和单体的比例基于所述水性混合物的总重量为20至70重量%,然后将所述水性混合物加热至50℃至100℃的温度,并将聚合反应器用水性混合物处理5分钟至3小时,然后加入一种或多种引发剂和任选存在的其它原料,然后引发聚合反应,将由此获得的水性聚合物分散体从聚合反应器中除去并后处理,以除去在处理期间脱附的壁沉积物。
2.如权利要求1所述的方法,其特征在于在所述水性混合物中初始既没有加入氧化引发剂也没有加入还原引发剂。
3.如权利要求1或2所述的方法,其特征在于当所述聚合反应器具有仅50至95%的冷却能力时进行所述方法,没有壁沉积物。
4.如权利要求1-3所述的方法,其特征在于在间歇聚合方法的一批或多批以后,进行所述方法。
5.如权利要求1-3所述的方法,其特征在于在间歇聚合方法的20-30批次以后,进行所述方法。
6.如权利要求1-5所述的方法,其特征在于使用所述水性混合物处理所述聚合反应器20分钟至1小时。
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