CN107250167A - 使烯键式不饱和单体聚合的方法 - Google Patents
使烯键式不饱和单体聚合的方法 Download PDFInfo
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- CN107250167A CN107250167A CN201680010234.1A CN201680010234A CN107250167A CN 107250167 A CN107250167 A CN 107250167A CN 201680010234 A CN201680010234 A CN 201680010234A CN 107250167 A CN107250167 A CN 107250167A
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- acid
- reactor
- fouling inhibitor
- polymerization
- aqueous solution
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
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- 230000002035 prolonged effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C08F2/00—Processes of polymerisation
- C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
- C08F2/004—Scale prevention in a polymerisation reactor or its auxiliary parts by a prior coating on the reactor walls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- 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
- C08F218/00—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
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
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Abstract
本发明涉及在聚合反应器中在水性介质中通过自由基引发的乳液聚合使烯键式不饱和单体聚合的方法,其中在装填所述反应器之前,通过施加积垢抑制剂从而涂覆所述反应器的内壁及任选涂覆所述反应器的内部构件,其特征在于,用酸溶液处理待用积垢抑制剂涂覆的表面。
Description
技术领域
本发明涉及在聚合反应器中在水性介质中通过自由基引发的乳液聚合使烯键式不饱和单体聚合的方法,其中在装填所述反应器之前,通过施加积垢抑制剂涂覆所述反应器的内壁及任选涂覆所述反应器的内部构件。
背景技术
在水中通过自由基引发的乳液聚合制备乙酸乙烯酯均聚物和共聚物时,在此形成的聚合物作为积垢沉淀在聚合反应器的内壁和内部构件上。这些积垢阻碍聚合作用,这是因为沉积物会降低经由反应器壁的热交换效果,还使反应器的冷却变困难。额外地,小块的器壁积垢可能脱离并污染聚合产物。为了消除这些缺点,在每个生产循环之后必须对聚合反应器进行清洁以去除积垢。但是这会导致聚合时间明显延长,因此损害聚合方法的经济性。
由现有技术公开了用积垢抑制剂(防垢剂)涂覆聚合反应器的内壁以及聚合反应器中的内部构件,如搅拌器或冷却装置或计量装置。
EP 0 052 421 A1建议,为了防止在氯乙烯聚合时发生积垢,使用在碱性水溶液中或者在有机溶液中的包含1-萘酚和甲醛的缩合产物的积垢抑制剂。为了改善该抑制剂对反应器壁的粘着性,例如建议添加保护胶体如部分水解的聚乙烯醇,以溶解积垢抑制剂。这些缩合产物的缺点是其发黑的着色。
WO 97/08210 A1建议,为了使着色变淡,将羟基取代的萘化合物和羟基甲烷亚磺酸盐或羟基甲烷磺酸盐的缩合产物作为积垢抑制剂。利用水蒸汽将这些抑制剂喷射在反应器壁上,其中水蒸汽的温度越高,则粘着性应当越好。
为了避免积垢抑制剂发黑的着色,WO 96/35723 A1建议通过使1-萘酚和次硫酸盐、优选羟基甲烷亚磺酸钠的混合物缩合获得的缩合产物。
在WO 96/35724 A1中描述了,为了改善在WO 96/35723 A1中所述的积垢抑制剂的粘着性,其应当利用水蒸汽喷雾在尽可能高的温度下进行喷射。
WO 2013/053895 A1建议,为了改善用作积垢抑制剂的缩合产物的粘着性,将其在与丙烯酸酯聚合物的混合物中喷射在反应器壁上。
为了抑制在涉及氯乙烯或乙酸乙烯酯的聚合过程中形成积垢,WO 98/24820 A1建议了其水溶液形式的醛、苯酚化合物和羟基取代的芳族羧酸的缩合产物。WO 03/085003 A1建议通过将溶液的pH值调节至小于5的pH值,改善这些缩合产物对聚合反应器内壁的粘着性。为此目的,实际上将缩合产物的水溶液在通向聚合反应器的导管中与酸的水溶液混合,在所述反应器中将该混合物喷射在器壁上。缺点在于,在此情况下在导管中可能发生过早的团聚。
发明内容
本发明的目的是提供一种方法,通过该方法使积垢抑制剂迅速沉淀在壁上并形成薄膜,并限制积垢抑制剂由反应器壁流走(Ablaufen),通过该方法可以改善积垢抑制剂对反应器壁的粘着性,不会造成上述缺点。
本发明的一个主题是在聚合反应器中在水性介质中通过自由基引发的乳液聚合使烯键式不饱和单体聚合的方法,其中在装填所述反应器之前通过施加积垢抑制剂从而涂覆所述反应器的内壁及任选涂覆所述反应器的内部构件,其特征在于,用酸溶液处理待用积垢抑制剂涂覆的表面。
合适的积垢抑制剂是在用酸溶液处理时发生沉淀的积垢抑制剂,例如以上作为现有技术讨论的缩合产物。例如是甲醛与萘酚化合物如1-萘酚或1,3-二羟基萘或1,5-二羟基萘或1,7-二羟基萘的缩合产物(EP 0 052 421 A1),或者是萘酚化合物如1-萘酚和次硫酸盐如羟基甲烷亚磺酸钠的缩合产物(WO 97/08210 A1),或者是萘酚化合物如1-萘酚和通过醛与连二亚硫酸盐之间的反应获得的次硫酸盐的缩合产物(WO 96/035723 A1),或者是萘酚化合物如1-萘酚和醛如甲醛和于芳香核羟基化的芳族羧酸如羟基苯甲酸的缩合产物(WO98/24820 A1)。该缩合产物也是可商购获得的,例如以NoxolR的商品名购自AkzoNobel或者以EvicasR的商品名购自INEOS。
所述积垢抑制剂以其水溶液的形式施加。一般而言,所述水溶液包含0.1至20重量%、优选1至10重量%的积垢抑制剂。优选利用水蒸汽喷射积垢抑制剂的水溶液。
一般而言,积垢抑制剂的水溶液的施加量使得反应器中的经处理的表面用0.1至10.0g/m2的量的积垢抑制剂涂覆。为此目的,可以在一个步骤或多个步骤中施加积垢抑制剂的水溶液;积垢抑制剂的水溶液优选施加一至三次。
在根据本发明的方法中,在用聚合混合物的成分装填所述反应器之前且在施加积垢抑制剂之前或之后,例如用无机酸或有机酸的水溶液处理聚合反应器的壁及任选处理聚合反应器的内部构件如搅拌器、冷却装置或进料管线。
合适的酸是pKa值为pKa≤5的无机酸或有机酸。例如是无机酸如盐酸、硫酸或硝酸,或有机酸如甲酸、乙酸、抗坏血酸、柠檬酸、酒石酸或草酸。优选为抗坏血酸或柠檬酸。酸的水溶液的浓度取决于各种酸的pKa值。一般而言,酸的水溶液的浓度为0.1至20重量%。在抗坏血酸或柠檬酸的情况下,水溶液的浓度优选为5至10重量%。
为了将酸溶液施加至待用其处理的表面,借助水蒸汽喷射酸溶液。喷射酸溶液的量使得待用积垢抑制剂处理的区域尽可能完全地用水溶液润湿。喷射的酸溶液的量一般为由1至100.0g/m2。
在用酸的水溶液处理或者施加积垢抑制剂之前,优选将反应器壁加热至40℃至100℃、更优选50℃至70℃的温度。
在此可以首先将酸溶液施加至待涂覆的区域,随后施加积垢抑制剂。也可以相反地,首先施加积垢抑制剂,随后施加酸溶液。在一个优选的实施方案中,首先喷射酸的水溶液,随后将积垢抑制剂喷射至待处理的区域。在施加积垢抑制剂之后,可以使在此形成的涂覆层固化最多30分钟。
在所述实施方案中,可以各自重复施加酸的水溶液和/或积垢抑制剂。该顺序优选实施一至三次。
随后用聚合作用的反应物装填反应器。
所述方法适合于防止在一种或多种选自以下组中的烯键式不饱和单体聚合时发生积垢:具有1至15个碳原子的羧酸的乙烯基酯、羧酸与具有1至15个碳原子的非分支或分支醇的甲基丙烯酸酯或丙烯酸酯、烯烃或二烯烃、乙烯基芳烃或卤乙烯。
优选的乙烯基酯是乙酸乙烯酯、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、新戊酸乙烯酯及具有5至13个碳原子的alpha分支单羧酸的乙烯基酯,例如VeoVa9R或VeoVa10R(Momentive公司的商品名)。特别优选为乙酸乙烯酯。
优选的甲基丙烯酸酯或丙烯酸酯是具有1至15个碳原子的非分支或分支醇的酯,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、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸降冰片基酯。特别优选为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯和丙烯酸2-乙基己酯。
优选的烯烃或二烯烃是乙烯、丙烯及1,3-丁二烯。优选的乙烯基芳烃是苯乙烯和乙烯基甲苯。优选的卤乙烯是氯乙烯。
基于单体的总重量,任选还可以使0.05至50重量%、优选0.1至10重量%辅助单体共聚。辅助单体的例子是烯键式不饱和的单羧酸和二羧酸、烯键式不饱和的羧酰胺、烯键式不饱和的磺酸及其盐、预交联的共聚单体如多烯键式不饱和的共聚单体、后交联的共聚单体如N-羟甲基丙烯酰胺、环氧官能的共聚单体、硅官能的共聚单体。
所述方法优选适合于使乙酸乙烯酯及任选存在的其他可与乙酸乙烯酯共聚的共聚单体聚合。优选使用的单体的例子是乙酸乙烯酯、乙酸乙烯酯与乙烯的混合物、乙酸乙烯酯与乙烯和一种或多种其他乙烯基酯的混合物、乙酸乙烯酯与一种或多种其他乙烯基酯的混合物、乙酸乙烯酯与乙烯和(甲基)丙烯酸酯的混合物、乙酸乙烯酯与乙烯和氯乙烯的混合物、氯乙烯及乙烯及任选存在的一种或多种其他乙烯基酯的混合物。
特别优选为乙酸乙烯酯。
基于单体的总重量,包含乙酸乙烯酯及1至40重量%乙烯的混合物也是特别优选的。
包含乙酸乙烯酯和1至50重量%一种或多种选自以下组中的其他共聚单体及任选存在的1至40重量%乙烯的混合物也是特别优选的:在羧基中具有1至12个碳原子的乙烯基酯如丙酸乙烯酯、月桂酸乙烯酯、具有5至13个碳原子的alpha分支羧酸的乙烯基酯,如VeoVa9R、VeoVa10R、VeoVa11R,其中以重量%给出的数据均是基于单体的总重量并且均加至100重量%。
包含乙酸乙烯酯和1至60重量%具有1至15个碳原子的非分支或分支醇的(甲基)丙烯酸酯,尤其是甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸正丁酯或丙烯酸2-乙基己酯的混合物也是特别优选的,其任选还可以包含1至30重量%月桂酸乙烯酯或具有5至13个碳原子的alpha分支羧酸的乙烯基酯及任选存在的1至40重量%乙烯,其中以重量%给出的数据均是基于单体的总重量并且均加至100重量%。
包含1至60重量%氯乙烯、1至40重量%乙烯及任选存在的一种或多种在羧基中具有1至12个碳原子的乙烯基酯如乙酸乙烯酯、丙酸乙烯酯、月桂酸乙烯酯、具有5至13个碳原子的alpha分支羧酸的乙烯基酯如VeoVa9R、VeoVa10R、VeoVa11R的混合物也是特别优选的,其中以重量%给出的数据均是基于单体的总重量并且均加至100重量%。
被描述为特别优选的单体及单体混合物各自还可以包含所述量的所述辅助单体,其中以重量%给出的数据均加至100重量%。
在通过乳液聚合法进行制备时,聚合温度优选为40℃至120℃,更优选为60℃至90℃。在诸如乙烯、1,3-丁二烯或氯乙烯的气态共聚单体共聚时,还可以在压力下,通常在5巴至100巴下进行。
优选利用乳液聚合常用的水溶性引发剂或氧化还原引发剂组合引发聚合作用。合适的氧化引发剂的例子是过二硫酸的钠盐、钾盐和铵盐,及过氧化氢。基于单体的总重量,所述引发剂的使用量通常为0.01至2.0重量%。合适的还原剂例如是羟基甲烷亚磺酸钠、酒石酸及(异)抗坏血酸。基于单体的总重量,还原剂的量优选为0.015至3重量%。所述氧化剂也可以独自用作热引发剂。
在存在保护胶体和/或乳化剂的情况下进行聚合。聚合作用的优选的保护胶体是聚乙烯醇、水溶性形式的多糖,如淀粉或纤维素及其衍生物。特别优选使用水解度为80至100摩尔%的部分水解或完全水解的聚乙烯醇,尤其是水解度为80至95摩尔%且在浓度为4%的水溶液中的粘度为1至30mPas(法,在20℃下,DIN 53015)的部分水解的聚乙烯醇。
合适的乳化剂是阴离子、阳离子和非离子型乳化剂,例如阴离子表面活性剂,如链长度为8至18个碳原子的烷基硫酸盐(酯)、在疏水基团中具有8至18个碳原子并且具有最多40个环氧乙烷或环氧丙烷单元的烷基或烷基芳基醚硫酸盐(酯)、具有8至18个碳原子的烷基或烷基芳基磺酸盐(酯)、磺基琥珀酸与一元醇或烷基酚的全酯和单酯;或非离子表面活性剂,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。
一般而言,基于单体的总重量,保护胶体和/或乳化剂的使用量为1至5重量%。
可以作为分批过程或半分批过程分批地或者连续地进行聚合。所述单体可以整体作为初装料引入或者按计量添加。基于单体的总重量,优选将0至100重量%、更优选2至50重量%的单体作为初装料引入,并在乳液聚合期间在较晚的时刻按计量添加剩余量的单体。可以(在空间和时间上)分离地按计量添加,或者按计量添加的组份可以完全或部分地以预乳化形式按计量添加。保护胶体和/或乳化剂可以完全或部分地按计量添加,完全或部分地作为初装料引入。以引发乳液聚合开始直至全部所用的烯键式不饱和单体的转化率优选为85重量%至95重量%的时刻,测量乳液聚合的持续时间。
在聚合结束之后,可以采用已知方法进行后期聚合以去除残余单体,通常通过用氧化还原催化剂引发的后期聚合。也可以通过蒸馏,优选在减压下,及任选引导惰性夹带气体如空气、氮气或水蒸汽穿过或经过聚合混合物,从而去除挥发性残余单体。
由此获得的聚合物水分散体的固体含量为30至75重量%,优选为50至60重量%。
可由所述聚合物水分散体获得在水中可再分散的聚合物粉末。为了制备在水中可再分散的聚合物粉末,任选在添加保护胶体作为喷雾助剂之后,例如借助流化床干燥、冷冻干燥或喷雾干燥,对所述水分散体进行干燥。
所述聚合物水分散体和/或由其获得的水中可再分散的分散体粉末可以用于对于此系统典型的应用领域。例如用于建筑化学产品,任选连同水硬性粘结剂,如水泥(波特兰水泥、铝酸盐水泥、火山灰水泥、矿渣水泥、镁氧水泥及磷酸盐水泥)、石膏及水玻璃,用于生产建筑粘合剂,尤其是砖瓦粘合剂及完全绝热粘合剂灰浆、抹平组合物、地板抹平组合物、流平组合物、密封泥浆、填缝砂浆及油漆,及用于混凝土改性。额外地用作涂料的粘结剂及粘合剂,或者用作纺织品和纸张的涂料和/或粘结剂。
通过根据本发明的方法,可以在分批和连续运行时有效地减少在聚合反应器内部沉积物的形成。在反应器内壁上的沉积物特别是表现在对经由反应器外套的传热的限制作用。由此导致,为了对放热聚合进行冷却,随着形成的积垢的增加,必须降低冷却水温度(外套温度)Tm。发现通过根据本发明的方法能够在反应器连续运行的情况下使运行有效范围(Kampagnenreichweite)显著延长。
实施例:
在用于制备用聚乙烯醇稳定化的乙酸乙烯酯-乙烯共聚物水分散体的连续运行的500升反应器中测试所述方法。
通过反应器外套将干净的空反应器加热至70℃。使用60克浓度为10%的抗坏血酸水溶液利用蒸汽对反应器内壁和内部构件进行喷射。随后利用蒸汽使用90克Noxol水溶液(Noxol ETH/S3,购自AkzoNobel)对如此预处理的反应器内壁和内部构件进行喷射。然后用氮气吹洗反应器,并在70℃下保持30分钟。该顺序再重复一次。然后连续地用聚合作用的反应物装填反应器,并连续地提取出聚合产物。
在40天的运行持续时间之后,对聚合作用进行冷却所需的冷却水温度Tm已由23℃下降至6℃。
为了进行比较,实施运行(Kampagne),其中采用相似的过程,区别仅在于,仅使用90克Noxol水溶液(Noxol ETH/S3,购自AkzoNobel)利用蒸汽对反应器内壁和内部构件进行喷射,但是不使用抗坏血酸水溶液进行喷射。
在仅19天的运行持续时间之后,对聚合作用进行冷却所需的冷却水温度Tm已下降至6℃。
这表明,通过根据本发明的酸化作用显著地减少了积垢的形成。与仅施加积垢抑制剂的水溶液的方式相比,通过额外地使反应器内壁酸化可以显著地降低清洁的成本和复杂性。
因此,通过根据本发明的方法,使清洁的间隔时间变长,并且在连续聚合的情况下也使运行有效范围延长。在连续地实施聚合的情况下,使外套温度Tm(冷却水温度)每天的下降量减少,并且相应地增加了运行有效范围,而不会降低每天的产量吨数。
Claims (10)
1.在聚合反应器中在水性介质中通过自由基引发的乳液聚合使烯键式不饱和单体聚合的方法,其中在装填所述反应器之前,通过施加积垢抑制剂从而涂覆所述反应器的内壁及任选涂覆所述反应器的内部构件,其特征在于,用酸溶液处理待用积垢抑制剂涂覆的表面。
2.根据权利要求1的方法,其特征在于,使用选自以下组中的积垢抑制剂:甲醛与萘酚化合物的缩合产物、萘酚化合物和次硫酸盐的缩合产物、萘酚化合物和醛和于芳香核羟基化的芳族羧酸的缩合产物。
3.根据权利要求1或2的方法,其特征在于,在用聚合混合物的成分装填所述反应器之前且在施加积垢抑制剂之前和/或之后,用无机酸或有机酸的水溶液处理所述聚合反应器的壁及任选处理所述聚合反应器的内部构件。
4.根据权利要求1至3之一的方法,其特征在于,使用pKa值为pKa≤5的无机酸或有机酸。
5.根据权利要求1至4之一的方法,其特征在于,在一个步骤或多个步骤中施加积垢抑制剂的水溶液。
6.根据权利要求1至5之一的方法,其特征在于,首先将酸溶液施加至待涂覆的区域然后施加积垢抑制剂,或者首先施加积垢抑制剂然后施加酸溶液。
7.根据权利要求1至6之一的方法,其特征在于,各自重复施加积垢抑制剂和/或施加酸的水溶液。
8.根据权利要求1至7之一的方法,其特征在于,分批地实施聚合。
9.根据权利要求1至7之一的方法,其特征在于,连续地实施聚合。
10.根据权利要求1至9之一的方法,其特征在于,使乙酸乙烯酯及任选存在的其他可与乙酸乙烯酯共聚的共聚单体聚合。
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DE102015202580.2A DE102015202580A1 (de) | 2015-02-12 | 2015-02-12 | Verfahren zur Polymerisation von ethylenisch ungesättigten Monomeren |
DE102015202580.2 | 2015-02-12 | ||
PCT/EP2016/052889 WO2016128502A1 (de) | 2015-02-12 | 2016-02-11 | Verfahren zur polymerisation von ethylenisch ungesättigten monomeren |
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CN1625570A (zh) * | 2002-04-11 | 2005-06-08 | 阿克佐诺贝尔股份有限公司 | 防污剂的涂敷方法 |
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ATE23866T1 (de) | 1980-10-31 | 1986-12-15 | Ici Plc | Vinylchlorid-polymerisationsverfahren. |
IT1280168B1 (it) | 1995-05-12 | 1998-01-05 | Cirs Spa | Anti-incrostante per rivestire i reattori di polimerizzazione e rispettivo prodotto risultante |
IT1281413B1 (it) | 1995-08-29 | 1998-02-18 | Cirs Spa | Anticrosta ecologico per rivestire i reattori di polimerizzazione |
EP2581421A1 (en) | 2011-10-12 | 2013-04-17 | Ineos Europe AG | Additive |
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2015
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- 2016-02-11 WO PCT/EP2016/052889 patent/WO2016128502A1/de active Application Filing
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Patent Citations (6)
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EP0062230A2 (en) * | 1981-03-23 | 1982-10-13 | Shin-Etsu Chemical Co., Ltd. | Method for preventing polymer scale deposition in the polymerization of ethylenically unsaturated monomers |
US5147455A (en) * | 1990-05-25 | 1992-09-15 | Shin-Etsu Chemical Co., Ltd. | Method of preventing polymer scale deposition and polymer scale preventive liquid used therein |
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EP0942936B1 (en) * | 1996-12-04 | 2000-10-18 | 3V SIGMA S.p.A | Build-up suppressor agents, compositions containing them and method of use in polymerization processes |
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CN1625570A (zh) * | 2002-04-11 | 2005-06-08 | 阿克佐诺贝尔股份有限公司 | 防污剂的涂敷方法 |
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US20180002467A1 (en) | 2018-01-04 |
DE102015202580A1 (de) | 2016-08-18 |
WO2016128502A1 (de) | 2016-08-18 |
CN107250167B (zh) | 2019-06-18 |
US9975978B2 (en) | 2018-05-22 |
EP3256497A1 (de) | 2017-12-20 |
SG11201706091VA (en) | 2017-08-30 |
EP3256497B1 (de) | 2018-09-19 |
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