CN101679536B - 制备水性聚合物分散体的方法 - Google Patents
制备水性聚合物分散体的方法 Download PDFInfo
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- CN101679536B CN101679536B CN2008800195619A CN200880019561A CN101679536B CN 101679536 B CN101679536 B CN 101679536B CN 2008800195619 A CN2008800195619 A CN 2008800195619A CN 200880019561 A CN200880019561 A CN 200880019561A CN 101679536 B CN101679536 B CN 101679536B
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- polymerization
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Abstract
本发明涉及一种制备具有近似粒度分布的细粒聚合物分散体的方法。
Description
本发明涉及一种制备水性聚合物分散体的方法,其通过在至少一种分散剂和至少一种引发剂的存在下的烯键式不饱和单体的自由基水性乳液聚合而进行,其中使用
0.1-10重量%的在20℃和1atm(绝对压力)下溶解度≥200g每1000g软化水的至少一种烯键式不饱和单体[单体A],和
90-99.9重量%的在20℃和1atm(绝对压力)下溶解度≤100g每1000g软化水的至少一种烯键式不饱和单体[单体B]
进行乳液聚合,且所述单体A和B总和为100重量%(单体总量);首先仅将
所述至少一种单体B的总量的0.1-10重量%
引入一种水性聚合介质中并进行聚合(聚合阶段1),随后在聚合条件下,将全部量的所述至少一种单体A和剩余量的所述至少一种单体B添加至所述水性聚合介质中并进行聚合(聚合阶段2)。
本发明还涉及可通过本发明方法得到并具有窄粒度分布的水性聚合物分散体,和可由所述水性聚合物分散体得到的聚合物粉末,及所述水性聚合物分散体和所述聚合物粉末的用途,特别是在用于木材涂料的透明制剂中用作组分的用途。
水性聚合物分散体是公知的。它们为流体体系,含有在水性分散介质中作为分散相以分散性分布形式存在的、由许多缠绕的聚合物链组成的聚合物球体,即所称的聚合物基质或聚合物颗粒。聚合物颗粒的平均直径通常在10-1000nm的范围内,特别是在50-600nm的范围内。许多工业应用中均使用水性聚合物分散体作粘合剂。
在水性介质中进行烯键式不饱和单体的自由基乳液聚合的方法被经常描述并因此充分为本领域技术人员所熟知[参见以下文献中的乳液聚合:Encyclopedia of Polymer Science and Engineering,第8卷,第659页及其后各页(1987);D.C.Blackley,in High Polymer Latices,第1卷,第35页及其后各页(1966);H.Warson,The Applications of Synthetic Resin Emulsions,第5章,第246页及其后各页(1972);D.Diederich,Chemie inunserer Zeit 24,第135-142页(1990);Emulsion Polymerisation,Interscience Publishers,New York(1965);DE-A 4003422和Dispersionen synthetischer Hochpolymerer,F. Springer-Verlag,Berlin(1969)]。自由基水性乳液聚合反应通常以如下方式实现:烯键式不饱和单体在同时使用分散剂的情况下以单体液滴的形式分散于水性介质中,并通过自由基聚合引发剂而聚合。
如果待通过自由基水性乳液聚合而制备的聚合物颗粒的粒度以一种有目标的方式预先设定,则通常使用一种所谓的聚合物晶种,所述晶种用其他单体另行预先制备(异质聚合物晶种),或通过待聚合单体的部分聚合而原位产生。
使用一种原位聚合物晶种制备水性聚合物分散体为本领域技术人员所熟知(参见,例如DE-A 196 09 509、EP-A 690882、EP-A 710 680、EP-A 1 125 949、EP-A 1 294 816、EP-A 1 614 732、WO-A 03/29300),并通常以如下方式实现:首先将用于乳液聚合的单体混合物的一小部分在实际乳液聚合之前添加至水性聚合介质中,并在大量乳化剂的存在下进行自由基聚合。
但是,原位聚合物晶种的使用证明,只要用于乳液聚合的单体混合物还含有易溶于水的单体,都有利于狭窄的粒度分布。
因此本发明的一个目标是提供一种制备具有狭窄粒度分布的水性聚合物分散体的方法,其通过使用易溶于水的烯键式不饱和单体的自由基水性乳液聚合进行。
令人惊讶地,该目标已通过开篇说明的方法而实现。
为制备水性聚合物分散体,可使用洁净水,优选饮用水且特别优选软化水,各自基于水性聚合物分散体计,所用水的总量为30-90重量%并且有利地为40-60重量%。重要的是,在聚合阶段1中,首先将水总量的至少一部分、有利地为水总量的≥25重量%且特别有利地为≥35重量%作为水性聚合介质中的一种组分与单体B一起引入聚合容器中。在聚合阶段2中,可将任意剩余量的水——特别是作为水性单体乳液中的一种组分——以一份或多份分批地、或以恒定或改变的流速连续地添加至 聚合介质中。
适宜的单体A为所有在20℃和1atm(绝对压力)下溶解度为≥200g、优选≥300g且特别优选≥500g每1000g软化水的烯键式不饱和单体。通常地,单体A在软化水中具有无限溶解度。特别地,适宜的单体A为具有至少一个酸基、特别是一个羧基或磺基、一个羟烷基、一个氨基、一个亚乙基脲基或一个乙酰乙酰氧基的烯键式不饱和单体。单体A特别有利地选自丙烯酸、甲基丙烯酸、2-丙烯酰氨基-2-甲基丙磺酸(AMPS)、乙烯基磺酸、丙烯酰胺、甲基丙烯酰胺、N-(2-甲基丙烯酰氧基乙基)亚乙基脲(UMA)、N-(2-丙烯酰氧基乙基)亚乙基脲、丙烯酸2-乙酰乙酰氧基乙酯、甲基丙烯酸2-乙酰乙酰氧基乙酯(AAEM)、双丙酮丙烯酰胺(DAAM)、丙烯酸2-羟乙酯、丙烯酸羟丙酯、甲基丙烯酸2-羟乙酯和甲基丙烯酸羟丙基酯。特别优选丙烯酸、甲基丙烯酸、丙烯酰胺和/或AMPS。当然,单体A还包括具有一个酸基、特别是一个羧基或磺基的上述单体的碱金属盐和铵盐。
适宜的单体B为所有在20℃和1atm(绝对压力)下溶解度为≤100g、优选≤60g且特别优选≤20g每1000g软化水的烯键式不饱和单体。
特别适宜的单体B为可以一种简单方式与单体A进行自由基共聚的烯键式不饱和化合物,例如烯烃,如乙烯或丙烯;乙烯基芳香族单体,如苯乙烯、α-甲基苯乙烯、邻氯苯乙烯或乙烯基甲苯;乙烯基卤化物,如氯乙烯或1,1-二氯乙烯;乙烯醇与具有1-18个碳原子的一元羧酸的酯,如乙酸乙烯酯、丙酸乙烯酯、正丁酸乙烯酯、月桂酸乙烯酯和硬脂酸乙烯酯;优选具有3-6个碳原子的α,β-单烯键式不饱和一元和二元羧酸(例如,特别是丙烯酸、甲基丙烯酸、马来酸、富马酸和衣康酸)与通常具有1-12个、优选1-8个且特别是1-4个碳原子的烷醇的酯,例如,特别是丙烯酸及甲基丙烯酸的甲酯、乙酯、正丁酯、异丁酯、戊酯、己酯、庚酯、辛酯、壬酯、癸酯和2-乙基己酯,富马酸和马来酸的二甲酯或二正丁酯;α,β-单烯键式不饱和羧酸的腈,例如丙烯腈、甲基丙烯腈、反丁烯二腈或顺丁烯二腈;和共轭的C4-8二烯类,例如1,3-丁二烯(丁二烯)和异戊二烯。所述单体通常为以单体B的总量计,共占≥80重量%、优选≥90重量%且特别优选≥95重量%、乃至构成单体B的总量的主要单体。
通常能增加聚合物基质薄膜的内部强度的单体B通常具有至少一个环氧基团或至少两个非共轭的烯键式不饱和双键。其实例为具有两个乙烯基的单体、具有两个亚乙烯基的单体和具有两个链烯基的单体。此处,二元醇与α,β-单烯键式不饱和一元羧酸的二酯是特别有利的,在所述一元羧酸中,优选丙烯酸和甲基丙烯酸。所述具有两个非共轭的烯键式不饱和双键的单体的实例为亚烷基二醇二丙烯酸酯和二甲基丙烯酸酯,例如乙二醇二丙烯酸酯、1,2-丙二醇二丙烯酸酯、1,3-丙二醇二丙烯酸酯、1,3-丁二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯和乙二醇二甲基丙烯酸酯、1,2-丙二醇二甲基丙烯酸酯、1,3-丙二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯,和二乙烯基苯、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、丙烯酸环戊二烯基酯、氰脲酸三烯丙酯或异氰脲酸三烯丙酯。上述交联单体B的通常用量各自基于单体B的总量计为≤10重量%、但优选≤5重量%。但是,通常地,完全不使用所述交联单体B。
有利地,在本发明方法中使用单体混合物作为单体B,所述混合物含有
-50-100重量%的丙烯酸和/或甲基丙烯酸与具有1-12个碳原子的烷醇的酯,和/或苯乙烯,或
-50-100重量%的苯乙烯和丁二烯,或
-50-100重量%的氯乙烯和/或1,1-二氯乙烯,或
-40-100重量%的乙酸乙烯酯、丙酸乙烯酯和/或乙烯。
单体B特别有利地选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯、丙烯酸2-丙基庚酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸2-丙基庚酯、苯乙烯、乙烯基甲苯、2-甲基苯乙烯、4-甲基苯乙烯、2-正丁基苯乙烯、4-正丁基苯乙烯、4-正癸基苯乙烯、乙酸乙烯酯、丙酸乙烯酯、丙烯腈和甲基丙烯腈。
在本发明方法中使用0.1-10重量%、有利地1-8重量%且特别有利地2-6重量%的至少一种单体A和相应地90-99.9重量%、有利地92-99重量%且特别有利地94-98重量%的至少一种单体B。
为本发明方法的目的,本发明同时使用分散剂,其保持单体液滴和所得聚合物颗粒以分散形式存在于在水性介质中,并从而确保生成的水性聚合物分散体的稳定性。适宜的分散剂既可为通常用于进行自由基水性乳液聚合的保护胶体,也可为乳化剂。
适宜的保护胶体为例如聚乙烯醇;聚亚烷基二醇;聚丙烯酸和聚甲基丙烯酸的碱金属盐;明胶衍生物;或含有丙烯酸、甲基丙烯酸、马来酸酐、2-丙烯酰氨基-2-甲基丙磺酸和/或4-苯乙烯磺酸的共聚物,和其碱金属盐;以及含有N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、N-乙烯基咔唑、1-乙烯基咪唑、2-乙烯基咪唑、2-乙烯基吡啶、4-乙烯基吡啶、丙烯酰胺、甲基丙烯酰胺、含氨基的丙烯酸酯、甲基丙烯酸酯、丙烯酰胺和/或甲基丙烯酰胺的均聚物和共聚物。对其他适宜的保护胶体的详细描述参见Houben-Weyl,Methoden der organischen Chemie,第XIV/1卷,Makromolekulare Stoffe,Georg-Thieme-Verlag,Stuttgart,1961,第411-420页。
当然,也可使用保护胶体和/或乳化剂的混合物。通常地,只使用与保护胶体相比相对分子量通常低于1000的乳化剂作为分散剂。它们可以是阴离子型、阳离子型或非离子型。当然,在使用表面活性物质的混合物的情况下,各组分必须彼此相容,如果不确定,可通过少量的预备实验进行检验。通常地,阴离子乳化剂彼此相容并与非离子乳化剂相容。这同样也适用于阳离子乳化剂,而阴离子乳化剂和阳离子乳化剂通常互不相容。适宜乳化剂的概述参见Houben-Weyl,Methoden derorganischen Chemie,第XIV/1卷,Makromolekulare Stoffe,Georg-Thieme-Verlag,Stuttgart,1961,第192-208页。
但是,本发明特别使用乳化剂作为分散剂。
常规的非离子乳化剂为例如,乙氧基化的单烷基酚、二烷基酚和三烷基酚(乙氧基化度:3-50,烷基基团:C4-C12)和乙氧基化的脂肪醇(乙氧基化度:3-80,烷基基团:C8-C36)。这些物质的实例为购自BASF AG的 A商品(C12C14脂肪醇乙氧基化物,乙氧基化度:3-8)、 AO商品(C13C15氧代醇乙氧基化物,乙氧基化度:3-30)、 AT商品(C16C18脂肪醇乙氧基化物,乙氧基化度:11-80)、 ON商品(C10氧代醇乙氧基化物,乙氧基化度:3-11)和 TO商品(C13氧代醇乙氧基化物,乙氧基化度:3-20)。
常规的阴离子乳化剂为例如,以下物质的碱金属盐和铵盐:烷基硫酸酯(烷基基团:C8-C12)、乙氧基化烷醇(乙氧基化度:4-30,烷基基团:C12-C18)及乙氧基化烷基酚(乙氧基化度:3-50,烷基基团:C4-C12)的硫酸单酯、烷基磺酸(烷基基团:C12-C18)及烷基芳基磺酸(烷基基团:C9-C18)。
通式(I)的化合物已进一步被证明适宜作为其他的阴离子乳化剂。
其中R1和R2为H原子或C4至C24烷基并且不同时为H原子,并且M1和M2可为碱金属离子和/或铵离子。在通式(I)中,R1和R2优选为具有6-18个碳原子、特别是具有6、12和16个碳原子的直链或支链的烷基基团,或氢,R1和R2两者不同时为H原子。M1和M2优选为钠、钾或铵,特别优选钠。特别有利的是这样的化合物(I),其中M1和M2为钠,R1为一个具有12个碳原子的支链烷基基团,并且R2为一个H原子或者为R1。通常使用含有50-90重量%比例的单烷基化产物的工业混合物,例如 2A1(Dow Chemical Company的商品)。化合物(I)通常已知于例如US-A 4269749,并可商购得到。
适宜的阳离子活性乳化剂通常为具有一个C6至C18烷基、C6至C18烷基芳基或杂环基的伯、仲、叔或季铵盐、烷醇铵盐、吡啶鎓盐、咪唑啉鎓盐、噁唑啉鎓盐、吗啉鎓盐和噻唑啉鎓盐,以及氧化胺的盐、喹啉鎓盐、异喹啉鎓盐、 鎓盐、锍盐和鏻盐。可作为实例提及的有十二烷基乙酸铵或相应的硫酸盐、各种2-(N,N,N-三甲铵)乙基石蜡酸酯的硫酸盐或乙酸盐、N-十六烷基吡啶鎓硫酸盐、N-十二烷基吡啶鎓硫酸盐和N-十六烷基-N,N,N-三甲基硫酸铵、N-十二烷基-N,N,N-三甲基硫酸铵、N-辛基-N,N,N-三甲基硫酸铵、N,N-二硬脂基-N,N-二甲基硫酸铵和双子表面活性剂(Gemini surfactant)N,N’-(十二烷基二甲基)亚乙基二硫酸二胺、乙氧基化动物脂肪烷基-N-甲基硫酸铵和乙氧基化油胺(例如购自BASF AG的 A,约12个环氧乙烷单元)。其它多种实例参见H.Stache,TensidTaschenbuch,Carl-Hanser-Verlag,Munich,Vienna,1981,以及McCutcheon’s,Emulsifiers & Detergents,MC Publishing Company,GlenRock,1989。有利的是,阴离子性相反基团具有尽可能低的亲核性,所述阴离子性相反基团例如高铝酸根、硫酸根、磷酸根、硝酸根和羧酸根(如乙酸根、三氟乙酸根、三氯乙酸根、丙酸根、草酸根、柠檬酸根和苯甲酸根),及有机磺酸的共轭阴离子,如甲基磺酸根、三氟甲基磺酸根和对甲苯磺酸根,此外还有四氟硼酸根、四苯基硼酸根、四(五氟苯基)硼酸根、四[二(3,5-三氟甲基)苯基]硼酸根、六氟磷酸根、六氟砷酸根或六氟锑酸根。
各自基于单体总量计,优选用作分散剂的乳化剂有利地以≥0.1且≤10重量%、优选≥0.1且≤5重量%、特别是≥0.5且≤4重量%的总量使用。
各自基于单体总量计,除乳化剂外的或代替乳化剂的用作分散剂的保护胶体的总量通常为≥0.1且≤10重量%,并且常常为≥0.2且≤7重量%。
但是,优选使用阴离子和/或非离子乳化剂作为分散剂,并且特别优选阴离子乳化剂。
根据本发明,在聚合阶段1中,首先将至少一部分分散剂与部分单体B一起引入水性聚合介质中,并在聚合阶段2中,将任意剩余量——特别是作为含有全部量单体A与剩余量单体B的水性单体乳液的组分——以一份或多份分批地、或以恒定或改变的流速连续地计量加入至水性聚合介质中。在聚合阶段1中,对分散剂、特别是乳化剂的量进行选择,从而使其≥2mmol,优选≥5mmol并且特别优选≥10mmol每10g单体B。
自由基水性乳液聚合的引发通过自由基聚合引发剂(自由基引发剂)而实现。其主要可为过氧化物和偶氮化合物。当然氧化还原引发剂体系也是适宜的。可使用的过氧化物主要为无机过氧化物,例如过氧化氢或过二硫酸盐,例如过二硫酸的单碱金属盐或二碱金属盐,例如其单钠盐和二钠盐、单钾盐和二钾盐,或其铵盐;或有机过氧化物,例如烷基氢过氧化物,如过氧化氢叔丁基、对 基或异丙苯基,以及二烷基或二芳基过氧化物,如过氧化二叔丁基或过氧化二异丙苯基。主要使用2,2’-偶氮二(异丁腈)、2,2’-偶氮二(2,4-二甲基戊腈)和2,2’-偶氮二(脒基丙基)二盐 酸盐(AIBA,相应于购自Wako Chemicals的V-50)作为偶氮化合物。用于氧化还原引发剂体系的适宜氧化剂主要为上述过氧化物。可用作相应还原剂的为具有低氧化态的硫化合物,例如碱金属亚硫酸盐,如亚硫酸钾和/或亚硫酸钠;碱金属亚硫酸氢盐,如亚硫酸氢钾和/或亚硫酸氢钠;碱金属偏亚硫酸氢盐,如偏亚硫酸氢钾和/或偏亚硫酸氢钠;甲醛化次硫酸盐,如甲醛化次硫酸钾和/或甲醛化次硫酸钠;亚磺酸的碱金属盐,尤其是钾盐和/或钠盐;和碱金属硫化氢盐,如硫化氢钾和/或硫化氢钠;多价金属盐,例如硫酸亚铁(II)、硫酸亚铁(II)铵、磷酸亚铁(II);烯二醇,如二羟马来酸、苯甲酸和/或抗坏血酸;及还原性糖,如山梨糖、葡萄糖、果糖和/或二羟基丙酮。通常地,基于单体总量计,所用自由基引发剂的量为0.01%-5重量%,优选0.1-3重量%并且特别优选0.2-1.5重量%。根据本发明,可将全部量的自由基引发剂在聚合阶段1的聚合反应引发之前先引入水性聚合介质中。但是,如果合适,也可在聚合阶段1中的聚合反应引发之前,先将一部分自由基引发剂引入水性聚合介质中,然后再在聚合阶段1和聚合阶段2的本发明自由基乳液聚合过程中,在聚合条件下的消耗速率下,将全部量或任意剩余量以一份或多份分批地、或以恒定或变化的流速连续地加入。
聚合反应的引发应理解为意指在通过自由基引发剂形成自由基后,存在于水性聚合介质中的单体的聚合反应的开始。聚合反应的引发可通过在聚合条件下向聚合容器中的水性聚合介质中添加自由基引发剂而实现。但是,也可在不适宜引发聚合反应的条件下(例如在较低温度下),在聚合阶段1中将一部分或全部量的自由基引发剂添加至水性聚合介质中——该介质含向聚合容器中初始添加的单体B,然后调节该水性聚合介质中的聚合条件。聚合条件通常应理解为意指自由基水性乳液聚合以充分的聚合速率发生时的温度和压力。它们特别取决于所用的自由基引发剂。对自由基引发剂的类型和用量、聚合温度和聚合压力进行有利选择,以始终能够得到足够的引发自由基来引发或维持聚合反应。
0-170℃的全部范围均适宜作为本发明自由基水性乳液聚合的反应温度。通常使用50-120℃、常常60-110℃且经常70-100℃的温度。本发明的自由基水性乳液聚合可在小于、等于或大于1atm(大气压)的压力下进行,从而可使聚合温度超过100℃并最高可达170℃。优选地,易 挥发单体,例如乙烯、丁二烯或氯乙烯,在高压下聚合。所述压力可为1.2、1.5、2、5、10或15bar(绝对压力)或甚至可采用更高的值。如果乳液聚合在低压下进行,则压力设定为950mbar、常常900mbar且经常850mbar(绝对压力)。有利地,本发明的自由基水性乳液聚合在无氧的情况下例如在一种惰性气体氛围例如氮气或氩气下在1atm下进行。
水性反应介质还可主要含有少量的(≤5重量%)水溶性有机溶剂,例如甲醇、乙醇、异丙醇、丁醇或戊醇、以及丙酮等。但是,本发明方法优选在无所述溶剂的情况下进行。
除上述组分外,在本发明方法中还可任选地使用链转移化合物,从而减小或控制通过聚合得到的聚合物的分子量。所述链转移化合物主要使用脂肪族和/或非脂肪族(araliphatic)的卤素化合物,例如正丁基氯、正丁基溴、正丁基碘、二氯甲烷、二氯乙烷、氯仿、溴仿、溴三氯甲烷、二溴二氯甲烷、四氯化碳、四溴化碳、苄基氯或苄基溴;有机硫代化合物,例如脂肪族伯、仲或叔硫醇,例如乙硫醇、正丙硫醇、2-丙硫醇、正丁硫醇、2-丁硫醇、2-甲基-2-丙硫醇、正戊硫醇、2-戊硫醇、3-戊硫醇、2-甲基-2-丁硫醇、3-甲基-2-丁硫醇、正己硫醇、2-己硫醇、3-己硫醇、2-甲基-2-戊硫醇、3-甲基-2-戊硫醇、4-甲基-2-戊硫醇、2-甲基-3-戊硫醇、3-甲基-3-戊硫醇、2-乙基丁硫醇、2-乙基-2-丁硫醇、正庚硫醇及其异构体化合物、正辛硫醇及其异构体化合物、正壬硫醇及其异构体化合物、正癸硫醇及其异构体化合物、正十一硫醇及其异构体化合物、正十二硫醇及其异构体化合物、正十三硫醇及其异构体化合物;取代硫醇,例如2-羟基乙硫醇,芳香族硫醇,例如苯硫醇、或者邻甲基苯硫醇、间甲基苯硫醇或对甲基苯硫醇;及Polymerhandbook第3版,1989,J.Brandrup和E.H.Immergut,John Wiley&Sons,第II部分,第133-141页中所述的所有其他硫化合物;以及脂肪族和/或芳香族醛,例如乙醛、丙醛和/或苯甲醛;不饱和脂肪酸,例如油酸;具有非共轭双键的二烯类,例如二乙烯基甲烷或乙烯基环己烷;或具有易取代(abstractable)的氢原子的烃类,例如甲苯。但是,也可使用不会相互影响的上述链转移化合物的混合物。
基于单体总量计,在本发明方法中任选使用的链转移化合物的总量 通常为≤5重量%,经常≤3重量%且常常≤1重量%。
通常有利的是将一部分或全部量的任选使用的链转移化合物在聚合阶段1中的自由基乳液聚合的引发之前添加至水性聚合介质中。但是,特别有利的是将一部分或全部量的任选使用的链转移化合物在聚合阶段2中与单体A和单体B一起添加至水性聚合介质中。
对本发明而言重要的是,在聚合阶段1中,首先仅将所述至少一种单体B的总量的0.1-10重量%、有利地≥1且≤8重量%并且特别有利地≥2且≤6重量%添加至水性聚合介质中并聚合,其后在聚合阶段2中,在聚合条件下将全部量的所述至少一种单体A和剩余量的所述至少一种单体B添加至水性聚合介质中并聚合。
在聚合阶段2中,全部量的单体A和剩余量的单体B的计量加入可以一份或多份分批地、或以恒定或变化的流速连续地实现。单体A和B的计量加入优选以恒定的流速连续地实现。此外,全部量的单体A和剩余量的单体B可以独立的单独物流的形式或以单体混合物的形式计量加入。优选地,全部量的单体A和剩余量的单体B以单体混合物、特别有利地以水性单体乳液的形式计量加入。重要的是,根据本发明,还可包括方法的变型方案,其中在聚合阶段2中,各单体A和/或单体B的组合物以例如本领域技术人员熟知的梯度法或阶段法(step procedure)变化。有利地,聚合阶段2中单体A和/或单体B的添加通常通过梯度法或阶段法、且特别有利地通过阶段法而实现。
特别有利地,本发明方法以如下方式实现:单体B在聚合阶段1中或者单体A和B在聚合阶段2中进行反应至转化率≥95重量%、有利地≥98重量%且特别有利地≥99重量%。通常有利的是将聚合阶段2结束后得到的水性聚合物分散体进行后处理以降低残留单体含量。所述后处理通过化学方法、例如使用一种更有效的自由基引发剂体系完成聚合反应(所谓的后聚合),和/或物理方法、通过例如用蒸气或惰性气体对水性聚合物分散体进行汽提而实现。
相应的化学和/或物理方法为本领域技术人员所熟知[参见,例如EP-A 771 328,DE-A 196 24 299、DE-A 196 21 027、DE-A 197 41 184、DE-A 197 41 187、DE-A 198 05 122、DE-A 198 28 183、DE-A 198 39 199、DE-A 198 40 586和198 47 115]。化学方法及物理方法结合进行后处理的 优点为,除未转化的烯键式不饱和单体外,还可将其他麻烦的易挥发性有机组分(所谓的VOC[挥发性有机化合物])从水性聚合物分散体中除去。
通过有目的地改变单体A和B的类型和数量,本领域技术人员还可根据本发明制备其聚合物的玻璃化转变温度或熔点在-60至270℃范围内的水性聚合物分散体。当然,还可制备具有多个玻璃化转变温度的阶段聚合物(step polymer)或多相聚合物。根据水性聚合物分散体的有计划使用,制备具有至少一个聚合物相且玻璃化转变温度为≥-60且≤10℃(粘合剂)、≥10且≤100℃(涂料制剂的基料)或≥80℃(硬质成品薄膜)的聚合物。
玻璃化转变温度Tg意指依照G.Kanig(Kolloid-Zeitschrift &Zeitschrift für Polymere,第190卷,第1页,方程1)得出的随着分子量的增加玻璃化转变温度所趋向的极限值。所述玻璃化转变温度或熔点通过DSC方法(示差扫描量热法,20K/mm,中点测量,DIN 53765)测定。
根据Fox(T.G.Fox,Bull.Am.Phys.Soc.1956[Ser.II]1,第123页,和根据Ullmann’s der technischen Chemie,第19卷,第18页,第4版,Verlag Chemie,Weinheim,1980),以下为计算大多数弱交联共聚物的玻璃化转变温度的良好近似法:
1/Tg=x1/Tg 1+x2/Tg 2+....xn/Tg n,
其中x1、x2、......xn为单体1、2、......n的质量分率,并且Tg 1、Tg 2、......Tg n分别为只包括单体1、2、......n之一的聚合物的玻璃化转变温度,以开尔文温度计。大多数单体的均聚物的Tg值为已知,并在例如Ullmann’s Encyclopedia of Industrial Chemistry,第5卷,第A21卷,第169页,VCH,Weinheim,1992中提及;均聚物玻璃化转变温度的其他来源有例如J.Brandrup,E.H.Immergut,Polymer Handbook,第1版,J.Wiley,New York,1966、第2版,J.Wiley,New York,1975和第3版,J.Wiley,New York,1989。
各自基于水性聚合物组合物计,根据本发明得到的水性聚合物分散体通常具有的聚合物固体含量为≥10且≤70重量%、常常≥20且≤65重量%,经常≥40且≤60重量%。
通过本发明方法得到的水性聚合物分散体的聚合物颗粒具有窄粒度分布,并且重均直径Dw的范围为≥10且≤500nm、优选≥20且≤200nm、且特别优选≥30nm至≤100nm。重均颗粒直径的测定为本领域技术人员所已知,并通过例如分析超速离心法实现。在本申请文件中,重均颗粒直径应理解为意指通过分析及超速离心法测得的重均值Dw50(对此参见S.E.Harding et al.,Analytical Ultracentrifugation in Biochemistry andPolymer Science,Royal Society of Chemistry,Cambridge,Great Britain,1992,第10章,Analysis of Polymer Dispersions with anEight-Cell-AUC-Multiplexer:High Resolution Particle Size Distributionand Density Gradient Techniques,W. 第147-175页)。
在本申请文件中,窄粒度分布应理解为意指通过分析超速离心法测得的重均颗粒直径Dw50和数均颗粒直径DN50的比值[Dw50/DN50]≤2.0、优选≤1.5并特别优选≤1.2或≤1.1。
可通过本发明方法得到的具有窄粒度分布并且重均颗粒直径Dw≤100nm的水性聚合分散体具有出乎意料高的透明度,因此特别适宜在用于木材涂料的透明水性制剂中作为基料。此处,通常具有的优点是例如对提供一定粘度的增稠剂的需求降低、使用着色颜料的着色良好且浓郁、制剂渗入木材表面的能力良好或对木材纹理的美化良好。此外,与非本发明的相应水性聚合物分散体相比,本发明的水性聚合物分散体还具有改进的过滤性。
当然,可通过本发明方法得到的本发明水性聚合物分散体可作为组分用于粘合剂、封口剂、塑料打底(plastic render)、涂布纸带(papercoating slip)、纤维网、油漆以及用于有机衬底和用于矿物粘合剂的改性的涂布材料中。
此外,相应的聚合物粉末可以一种简单方式(例如冷冻干燥或喷雾干燥)由本发明水性聚合物分散体获得。可根据本发明得到的这些聚合物粉末同样可作为组分用于粘合剂、封口剂、塑料打底、涂布纸带、纤维网、油漆以及用于有机衬底和用于矿物粘合剂的改性的涂布材料中。
将参照以下非限制性实施例对本发明进行说明。
实施例
a)水性聚合物分散体的制备
实施例1(E1)
首先于20-25℃(室温)在氮气气氛下向装配有计量装置和温度调节器的聚合容器中引入
307.0g软化水,和
168.0g 15重量%浓度的十二烷基硫酸钠水溶液
并搅拌加热至87℃。达到该温度时,添加25g甲基丙烯酸甲酯并进行半分钟乳化。其后,添加2.9g物料3并聚合5分钟,同时保持温度不变。其后,同时开始地,用120分钟连续地计量加入物料1,并与其平行地用165分钟以恒定流速计量加入剩余量的物料3。物料1供给完成后,物料2进行45分钟恒定流速的连续计量加入。
物料1(以下物质的均相混合物):
578.4g软化水
34.0g 15重量%浓度的十二烷基硫酸钠水溶液
492.0g丙烯酸正丁酯
184.2g甲基丙烯酸甲酯
8.4g 50重量%浓度的丙烯酰胺水溶液
7.5g甲基丙烯酸和
47.1g 25重量%浓度的甲基丙烯酸脲基酯的甲基丙烯酸甲酯a)溶液
物料2(以下物质的均相混合物):
118.3g软化水
12.0g 15重量%浓度的十二烷基硫酸钠水溶液
6.8g甲基丙烯酸
30.1g 25重量%浓度的甲基丙烯酸脲基酯的甲基丙烯酸甲酯a)溶液,和
203.1g甲基丙烯酸甲酯
物料3(以下物质的均相溶液):
26.6g软化水,和
2.0g过二硫酸钠
物料2和3供给完成后,使聚合混合物在87℃再反应30分钟。其后,同时开始地,通过独立的供给线,将16g 5重量%浓度的过氧化氢水溶液和1.4g抗坏血酸与67g软化水的溶液以恒定流速经过60分钟连续地计量加入至聚合混合物中。
其后,将得到的水性聚合物分散体冷却至室温,用8.4g 25重量%氨水溶液中和并用125μm过滤器过滤。
得到的水性聚合物分散体具有42.2重量%的固体含量。聚合物颗粒的重均颗粒直径为44nm;测得多分散性DW50/DN50为1.07。用软化水稀释至固体含量为40重量%的该水性聚合物分散体具有26%的透光率。
固体含量通常通过将确定量的水性聚合物分散体(约1g)在内径约5cm的铝坩埚中在干燥箱中于140℃干燥至恒重而测得。进行两次单独的测量。本实施例中的所述值为两次测量结果的平均值。
重均颗粒直径和多分散性的测定通常通过分析超速离心法而实现(对此,参见S.E.Harding et al.,Analytical Ultracentrifugation inBiochemistry and Polymer Science,Royal Society of Chemistry,Cambridge,Great Britain,1992,第10章,Analysis of PolymerDispersions with an Eight-Cell-AUC-Multiplexer:High ResolutionParticle Size Distribution and Density Gradient Techniques,W. 第147-175页)。
透光率通常在将水性聚合物分散体的一个样品用软化水稀释至40重量%的聚合物固体含量后,用购自Hach,Germany的DR/2010分光光度计测定。
对照实施例1(C1)
对照实施例1的制备类似于实施例1的制备,不同在于,首先引入的混合物中的水量为287.0g,而不是307.0g,物料1中的水量为599.4g,而不是578.4g,物料1中的甲基丙烯酸甲酯的量为209.2g,而不是184.2g,并且首先引入的是46g由此得到的物料1,而不是25g纯甲基丙烯酸甲酯。
得到的水性聚合物分散体的固体含量为42.3重量%。聚合物颗粒的 重均颗粒直径为42nm;测得的多分散性DW50/DN50为1.11。用软化水稀释的水性聚合物分散体具有11%的透光率。
实施例2(E2)
实施例2的制备类似于实施例1,不同在于,首先引入
304.7g软化水,和
50.0g 15重量%浓度的十二烷基硫酸钠水溶液
并搅拌加热至87℃,并在达到该温度时,添加25g甲基丙烯酸甲酯并进行半分钟乳化,以恒定流速用165分钟连续计量加入
物料1(以下物质的均相混合物):
736.3g软化水
46.0g 15重量%浓度的十二烷基硫酸钠水溶液
8.2g 50重量%浓度的丙烯酰胺水溶液
14.6g丙烯酸
77.2g 25重量%浓度的甲基丙烯酸脲基酯的甲基丙烯酸甲酯溶液
471.2g甲基丙烯酸甲酯,和
407.9g丙烯酸2-乙基己酯。
得到的水性聚合物分散体具有45.2重量%的固体含量。聚合物颗粒的重均颗粒直径为57nm;测得的多分散性DW50/DN50为1.09。用软化水稀释的水性聚合物分散体具有12%的透光率。
对照实施例2(C2)
对照实施例2的制备类似于实施例2,不同在于,首先引入42.5g物料1,而不是25g甲基丙烯酸甲酯,并在物料1中使用496.2g甲基丙烯酸甲酯,而不是471.2g。
得到的水性聚合物分散体具有45.2重量%的固体含量。聚合物颗粒的重均颗粒直径为62nm;测得的多分散性DW50/DN50为1.20。用软化水稀释的水性聚合物分散体仅具有2%的透光率。
实施例3(E3)
首先在室温下在氮气气氛下向装配有计量装置和温度调节器的聚合容器中引入
593.0g软化水,和
117.0g 15重量%浓度的十二烷基硫酸钠水溶液
并搅拌加热至82℃。在达到该温度时,添加35g丙烯酸正丁酯并进行半分钟乳化。其后,在保持该温度的同时,添加40g 7重量%浓度的过二硫酸钠水溶液,并聚合5分钟。其后,用120分钟以恒定流速连续计量加入物料1。物料1供给完成后,用45分钟以恒定流速连续计量加入物料2。
物料1(以下物质的均相混合物):
623.8g软化水
23.3g 15重量%浓度的十二烷基硫酸钠水溶液
10.9g 50重量%浓度的丙烯酰胺水溶液
9.8g甲基丙烯酸
339.0g甲基丙烯酸甲酯,和
661.0g丙烯酸正丁酯
物料2(以下物质的均相混合物):
152.9g软化水
8.4g 15重量%浓度的十二烷基硫酸钠水溶液
99.3g 50重量%浓度的丙烯酰胺水溶液
14.0g甲基丙烯酸,和
332.0g甲基丙烯酸甲酯
物料供给完成后,将聚合混合物在82℃再反应30分钟。其后,同时开始地,通过独立的供给线,将22.4g 5重量%浓度的过氧化氢水溶液和2.0g抗坏血酸与93.8g软化水的溶液以恒定流速用60分钟连续地计量加入至该聚合混合物中。
其后,将得到的水性聚合物分散体冷却至室温,用9.5g 25重量%浓度的氨水溶液中和并用125μm过滤器过滤。
得到的水性聚合物分散体具有43.1重量%的固体含量。聚合物颗粒的重均颗粒直径为44nm;测得多分散性DW50/DN50为1.08。用软化水稀 释的该水性聚合物分散体具有33%的透光率。
对照实施例3(C3)
对照实施例3的制备类似于实施例3的制备,不同在于,首先引入的混合物中的水量为570.6g,而不是593.0g,物料1中的水量为646.2g,而不是623.8g,物料1中的丙烯酸正丁酯的量为696.0g,而不是661.0g,并且初始引入的是57.5g由此得到的物料1,而不是35g纯丙烯酸正丁酯。
得到的水性聚合物分散体具有42.6重量%的固体含量。聚合物颗粒的重均颗粒直径为45nm;测得的多分散性DW50/DN50为1.12。用软化水稀释的水性聚合物分散体具有15%的透光率。
b)性能特征的研究
用软化水将各水性聚合物分散体稀释至固体含量为37.5重量%。在室温下分别将163g所述经稀释的水性聚合物分散体作为基料添加至可刷性原釉制剂(raw brushable glaze formulation)中并均匀混合,所述可刷性原釉制剂由以下物质组成
22.4g软化水
将得到的可刷性釉料用具有300μm辊隙(nip)的涂布器在室温下均匀并一致地涂至未处理的、预先砂磨的15cmx7cm松木板(厚度:0.5cm)的表面。然后将由此得到的上釉的板在23℃和50%相对湿度的调节室内干燥24小时。涂至木质表面的可刷涂性釉料的颜色深度和颜色 亮度在潮湿状态和干燥状态下肉眼进行评估。所述评估根据以下等级体系而进行,1为极好,2为良好,3为满意,4为尚可,5为不满意。将各次评估所得结果列于下表中:
实施例 | E1 | C1 | E2 | C2 | E3 | C3 |
颜色深度 潮湿 | 1-2 | 3-4 | 3 | 4-5 | 1 | 3 |
颜色亮度 潮湿 | 1-2 | 4 | 3-4 | 5 | 1 | 3 |
颜色深度 干燥 | 1-2 | 2 | 1-2 | 2 | 1-2 | 1-2 |
颜色亮度 干燥 | 1-2 | 2 | 2 | 2 | 1-2 | 2 |
注解 (潮湿情况下的应 用) | 无色 透明 | 淡黄色 浑浊 | 无色 透明 | 色条 浑浊 | 无色 透明 | 淡黄色 浑浊 |
从结果清楚可知,使用本发明的水性聚合物分散体制备的色釉的颜色深度和颜色亮度基本都被评估为较好,特别是在潮湿状态下。
Claims (13)
1.一种制备水性聚合物分散体的方法,其通过在至少一种分散剂和至少一种引发剂的存在下的烯键式不饱和单体的自由基水性乳液聚合来进行,其中使用
0.1-10重量%的在20℃和1atm的绝对压力下溶解度≥200g每1000g软化水的至少一种烯键式不饱和单体——单体A,和
90-99.9重量%的在20℃和1atm的绝对压力下溶解度≤100g每1000g软化水的至少一种烯键式不饱和单体——单体B
进行乳液聚合,且所述单体A和B的总和为100重量%,首先仅将
所述至少一种单体B的总量的0.1-10重量%
引入一种水性聚合介质中并进行聚合——聚合阶段1,其后在聚合条件下,将全部量的所述至少一种单体A和剩余量的所述至少一种单体B添加至水性聚合介质中并进行聚合——聚合阶段2。
2.权利要求1的方法,其中所述单体A和B在聚合阶段2中连续地计量加入。
3.权利要求1和2中任一项的方法,其中在聚合阶段2中,所述单体A和B作为单体混合物而计量加入。
4.权利要求1-2中任一项的方法,其中在聚合阶段1中,首先引入所述至少一种单体B的总量的≥1且≤8重量%并聚合。
5.权利要求1-2中任一项的方法,其中聚合阶段1中分散剂的量≥2mmol每10g单体B。
6.权利要求1-2中任一项的方法,其中所述单体A选自丙烯酸、甲基丙烯酸、2-丙烯酰氨基-2-甲基丙磺酸、乙烯基磺酸、丙烯酰胺、甲基丙烯酰胺、N-(2-甲基丙烯酰氧基乙基)亚乙基脲、N-(2-丙烯酰氧基乙基)亚乙基脲、丙烯酸2-乙酰乙酰氧基乙酯、甲基丙烯酸2-乙酰乙酰氧基乙酯、双丙酮丙烯酰胺、丙烯酸2-羟乙酯、丙烯酸羟丙酯、甲基丙烯酸2-羟乙酯和甲基丙烯酸羟丙酯。
7.权利要求1-2中任一项的方法,其中所述单体B选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯、丙烯酸2-丙基庚酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸2-丙基庚酯、苯乙烯、乙烯基甲苯、2-甲基苯乙烯、4-甲基苯乙烯、2-正丁基苯乙烯、4-正丁基苯乙烯、4-正癸基苯乙烯、乙酸乙烯酯、丙酸乙烯酯、丙烯腈和甲基丙烯腈。
8.权利要求1-2中任一项的方法,其中使用乳化剂作为分散剂。
9.权利要求1-2中任一项的方法,其中使用非离子和/或阴离子乳化剂作分散剂。
10.权利要求1-2中任一项的方法,其中在聚合阶段2中,所述单体A和/或所述单体B的添加通过梯度法或阶段法进行。
11.通过权利要求1-10中任一项的方法得到的水性聚合物分散体。
12.一种聚合物粉末,通过干燥权利要求11的水性聚合物分散体得到。
13.权利要求11的水性聚合物分散体或权利要求12的聚合物粉末在制备粘合剂、封口剂、塑料打底、涂布纸带、纤维网、油漆以及用于有机衬底的涂布材料和用于矿物粘合剂的改性的涂布材料中的用途。
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MX2017003650A (es) | 2014-09-19 | 2017-07-13 | Basf Se | Polimeros de emulsion acuosa finamente divididos y su uso para recubrimientos hidrofobos. |
ES2641752T3 (es) * | 2014-11-04 | 2017-11-13 | Basf Se | Procedimiento para la preparación de una dispersión acuosa de polímero |
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- 2008-06-09 WO PCT/EP2008/057161 patent/WO2008152017A1/de active Application Filing
- 2008-06-09 AU AU2008263946A patent/AU2008263946B2/en not_active Ceased
- 2008-06-09 CN CN2008800195619A patent/CN101679536B/zh not_active Expired - Fee Related
- 2008-06-09 PT PT87607263T patent/PT2158226E/pt unknown
- 2008-06-09 US US12/663,713 patent/US8153721B2/en not_active Expired - Fee Related
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WO2008152017A1 (de) | 2008-12-18 |
US20100204394A1 (en) | 2010-08-12 |
ES2392571T3 (es) | 2012-12-11 |
US8153721B2 (en) | 2012-04-10 |
CN101679536A (zh) | 2010-03-24 |
JP2010529272A (ja) | 2010-08-26 |
AU2008263946B2 (en) | 2013-05-02 |
AU2008263946A1 (en) | 2008-12-18 |
PT2158226E (pt) | 2012-12-27 |
EP2158226B1 (de) | 2012-09-12 |
EP2158226A1 (de) | 2010-03-03 |
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