CN104718227B - 用于制备具有微细颗粒尺寸的水性乳化剂稳定的乙酸乙烯酯‑乙烯共聚物分散体的方法 - Google Patents
用于制备具有微细颗粒尺寸的水性乳化剂稳定的乙酸乙烯酯‑乙烯共聚物分散体的方法 Download PDFInfo
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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
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
一种用于制备具有重均颗粒尺寸范围为100nm至300nm的水性乳化剂稳定的乙酸乙烯酯‑乙烯共聚物分散体的方法,包括乳液聚合包含以下的反应混合物:a)乙酸乙烯酯和乙烯,b)基于单体和共聚单体的总重量,0.05重量百分数至1重量百分数的至少一种官能化共聚单体,该官能化共聚单体选自由烯属不饱和磺酸或它们的盐以及具有至少一个磷酸酯基团或膦酸基团或它们的盐的烯属不饱和单体组成的组,c)基于单体和共聚单体的总重量,0.5至5重量百分数的至少一种阴离子乳化剂和可选的一种或多种非离子乳化剂,以及d)基于单体和共聚单体的总重量,可选的至多0.5%的保护性胶体。该方法反应器使用外部热交换回路。
Description
技术领域
本发明涉及在具有装备有泵和热交换器的外部热交换器回路的反应器中通过乳液聚合制备具有微细颗粒尺寸的水性乳化剂稳定的乙酸乙烯酯-乙烯共聚物分散体的方法。
背景技术
乙酸乙烯酯-乙烯共聚物的乳化剂稳定的水性分散体用于广泛的应用,例如,在粘合剂组合物和涂料组合物中作为胶粘剂(binder,粘合剂)。这些是大体积的应用,因此需要生产工业规模的大量的这类分散体。缩短聚合乳化剂稳定的乙酸乙烯酯-乙烯共聚物分散体的循环时间会产生相当大的经济优势。同时,为了获得用于这种应用的高品质的胶粘剂的关键问题是需要生产具有微细颗粒尺寸的分散的乙酸乙烯酯-乙烯共聚物颗粒。
在乳液聚合中使用外部冷却回路用于增强冷却能力以实现更短的反应时间在本领域是公知的。在US 6,660,814 B1中公开了使用结合有外部冷却单元的聚合反应器用于缩短聚合时间,该外部冷却单元装备了低剪切泵和具有层流剖面的热交换器。EP 2 106849 A1教导了用于乳液聚合的方法。为了改善除热,聚合反应器结合了外部冷却回路,其装备有低剪切泵和板框式热交换器。为了防止聚合混合物的凝结,板框式热交换器具有6至18mm间隙宽度。US 6,320,000 B1涉及在乳化剂的存在下进行乳液聚合。聚合在装备有包括泵和热交换器的外部冷却回路的反应器中发生。为了改善冷却能力并且防止凝胶形成,将聚合混合物通过热交换器泵送并返回至聚合反应器中。US 2005/0261423 A1的目的是提供更短反应时间的聚合方法。目标据说可以通过以下方法实现,其中,将聚合混合物转移至外部回路,其来自并且返回至聚合反应器中,并且其包括低剪切泵和热交换器。US 2011/0112218 A1中描述了用于生产保护性胶体稳定的聚合物水性分散体的方法。为了改善热耗散从而缩短反应时间,安装包括泵和热交换器的外部回路。该方法使用特定类型的热交换器,即,静态混合热交换器。
具有微细颗粒尺寸的水性乳化剂稳定的乙酸乙烯酯-乙烯共聚物分散体的一个问题是它们通常差的剪切稳定性。这个问题传统上防止了在使用外部热交换回路(其通常产生高剪切力)的聚合反应器中产生这种分散体。在具有外部热交换器的反应器中,为了制备乙酸乙烯酯-乙烯共聚物分散体,必须找到增加分散体剪切稳定性同时仍然保持微细颗粒尺寸和在油漆以及由分散体制成的其它涂料中的良好的耐刮擦性一些方法。
US 2008/0262104 A1中公开了具有高剪切稳定性的的聚乙酸乙烯酯分散体,其在乙酸乙烯酯共聚物中具有0.05至5重量百分数的(甲基)丙烯酸单元。US 2007/0244238 A1描述了据说有很好的剪切稳定性的聚合物分散体。这些聚合物分散体包括具有至少10℃的Tg差异的两种共聚物,用包含至少一种芳基取代的苯酚亚烷氧基醚非离子乳化剂稳定。
EP 1 300 448 A2和EP 1 801 168公开了在具有高颜料体积浓度的涂料组合物中用作粘合剂的水性乙酸乙烯酯-乙烯分散体。为了改善耐刮擦性,推荐使用在聚合过程中用于稳定的磷酸酯官能化的乳化剂和保护性胶体的组合。
尽管前述的努力,但仍然难以在采用外部热交换器的设备中制备具有微细颗粒尺寸的乙酸乙烯酯乙烯共聚物分散体。因此,该领域的进步在行业内是值得欢迎的补充。
发明内容
在一方面,本发明提供了用于制备具有微细颗粒尺寸的水性乳化剂稳定的乙酸乙烯酯-乙烯共聚物分散体的方法。该方法包括乳液聚合含有以下的反应混合物:
a)乙酸乙烯酯和乙烯,
b)基于单体和共聚单体的总重量,0.05至1重量百分数的至少一种官能化共聚单体,该官能化共聚单体选自由烯属不饱和磺酸或它们的盐以及具有至少一个磷酸酯基团或膦酸基或它们的盐的烯属不饱和单体组成的组。
c)基于单体和共聚单体的总重量,0.5至5重量百分数的至少一种阴离子乳化剂和可选地一种或多种非离子乳化剂,以及
d)基于单体和共聚单体的总重量,可选的至多0.5%的保护性胶体。
在具有包括泵和热交换器的外部热交换回路的反应器中进行乳液聚合,并且在乳液聚合期间,反应混合物通过外部热交换回路循环。该共聚物分散颗粒的重均颗粒尺寸(Dw)的范围为100nm至300nm。
具体实施方式
本发明的目的是提供用于制备具有微细颗粒尺寸、以及高剪切稳定性的水性乳化剂稳定的乙酸乙烯酯-乙烯共聚物分散体的方法。当在涂料组合物中使用时,还期望实现可以提供高耐刮擦性的聚合物分散体。现已发现这种结果可通过以下方法实现,该方法至少部分依赖于在采用外部热交换回路的反应器中,在一种或多种特定类型的阴离子乳化剂的存在下,与乙酸乙烯酯和乙烯共聚的一种或多种特定类型的官能化共聚单体的引入。如本文使用的术语“微细颗粒尺寸”是指重均颗粒尺寸(Dw)的范围为100nm至300nm,优选为150至250nm的分散于水介质中的乙酸乙烯酯-乙烯共聚物颗粒,如通过毛细管流体动力学分级(CHDF)来测定的。根据本发明制备的分散体含有非常少的凝固物,即保留在100目(149μm)筛上的材料。通常情况下,基于水性共聚物分散体的重量,凝结物的量将小于1000ppm,或小于500ppm,或小于100ppm。现在将详细描述用于制造根据本发明的这样的分散体的组合物和制备方法。
分散体的组合物
一般地,基于单体和共聚单体的总重量,乙酸乙烯酯以高达95重量百分数的量存在于共聚物中。优选地,基于单体和共聚单体的总重量的每一种情况下,乙酸乙烯酯含量为70至95重量百分数的范围,更优选乙酸乙烯酯含量为80至95重量百分数的范围。
一般地,在基于单体和共聚单体的总重量的每一种情况下,乙烯是以≥5重量百分数,优选5至30重量百分数,最优选5至20重量百分数的量存在于共聚物中。
一般地,基于单体和共聚单体的总重量的每一种情况下,官能化共聚单体是以0.05至1重量百分数,优选0.05至0.8重量百分数,更优选为0.2至0.6重量百分数的量共聚。
优选的包含具有至少一个磷酸基团或膦酸基团或它们的盐的烯属不饱和单体的官能化共聚单体是2-羟乙基甲基丙烯酸酯磷酸酯、羟丙基(甲基)丙烯酸酯磷酸酯、4-羟丁基丙烯酸酯磷酸酯、2-羟丁基丙烯酸酯磷酸酯、乙烯基膦酸、2-甲基丙烯酰氨基-2-甲基丙烷膦酸、丙烯-2-膦酸、α-膦酰基苯乙烯。
优选的包含烯属不饱和磺酸或它们的盐的官能化共聚单体是乙烯基磺酸、苯乙烯磺酸、2-丙烯酰氨基-2-甲基丙磺酸、磺丙基甲基丙烯酸酯或它们的盐。
如果使用盐代替游离酸,碱金属盐(例如,钠盐或钾盐)或铵盐是优选的。
更优选的官能化共聚单体是烯属不饱和磺酸或它们的碱金属盐。特别优选的官能化共聚单体是乙烯基磺酸或2-丙烯酰氨基-2-甲基丙磺酸或它们的碱金属盐。
在一些实施方式中,在每种情况下基于单体和共聚单体的总重量,共聚物可以包含0至30重量百分数,优选0至10重量百分数的来自由氯乙烯、乙烯基酯和(甲基)丙烯酸酯组成的组的其他非官能化单体单元。适合的其它乙烯基酯是具有3至12个碳原子的羧酸的那些,如丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、乙酸1-甲基乙烯基酯、新戊酸乙烯酯;以及具有9至11个碳原子的α-支链一元羧酸的乙烯基酯,如VeoVaTM9R、VeoVaTM10R或VeoVaTM11R(可从Hexion Specialty Chemicals,Inc.Columbus,OH获得)。合适的甲基丙烯酸或丙烯酸酯是具有1至15个C原子的直链或支链醇的酯,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、丙烯酸丁酯(正、异和叔)、甲基丙烯酸正丁酯,2-乙基己基丙烯酸酯和丙烯酸降冰片酯。优选丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸丁酯、以及2-乙基己基丙烯酸酯。可以引入一种或多种这类非官能化单体用于,例如,调节玻璃化转变温度或疏水性的程度。
最优选的共聚物是没有进一步的非官能化单体的乙烯和乙酸乙烯酯的那些。
为调节某些聚合物性能如交联,或者为改善与某些基材的粘合性,也可以共聚某些辅助单体。合适的辅助单体是预交联共聚单体,如聚烯属不饱和共聚单体,实例是己二酸二乙烯基酯、马来酸二烯丙酯、甲基丙烯酸烯丙酯或氰尿酸三烯丙酯,或者是后交联共聚单体,实例为丙烯酰胺乙醇酸(AGA)、甲基丙烯酰胺甘醇酸甲酯(MAGME)、N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺(NMMA)、N-羟甲基烯丙基氨基甲酸酯、烷基醚如异丁氧基醚或N-羟甲基丙烯酰胺的酯或N-羟甲基甲基丙烯酰胺的酯或N-羟甲基烯丙基氨基甲酸酯的酯。
也适合作为辅助单体的是烯属不饱和的可水解的硅化合物。例如通式R1SiR0-2(OR2)1-3的化合物,其中,R是C1至C3烷基,C1至C3烷氧基或卤素(例如,Cl或Br),R1是CH2=CR3-(CH2)0-1或CH2=CR3CO2(CH2)1-3,R2是具有1至12个C原子的直链或支链的,可选取代的烷基或酰基,其可选地由醚基中断,并且R3是H或CH3。优选的是具有C1至C12烷氧基基团和可选地C1至C3烷基基团的γ-丙烯酰基和γ-甲基丙烯酰氧基丙基三(烷氧基)硅烷、乙烯基烷基二烷氧基硅烷,和乙烯基三烷氧基硅烷,以及还是α-硅烷。示例性的C1至C12的烷氧基包括甲氧基、乙氧基、甲氧基乙烯、乙氧基乙烯、甲氧基丙二醇醚和/或乙氧基丙二醇醚基团。最优选的烯属不饱和可水解的硅化合物是乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三乙氧基硅烷和α-甲基丙烯酰氧基甲基-三乙氧基硅烷。
此外,辅助单体的实例是包含环氧基团的烯属不饱和化合物,例如,甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯、烯丙基缩水甘油醚、乙烯基缩水甘油醚、乙烯基环己烷氧化物、苧烯氧化物、月桂烯氧化物、石竹烯氧化物、和芳族部分上由缩水甘油基基团取代的苯乙烯和乙烯基甲苯,以及在芳族部分上由缩水甘油基团取代的乙烯基苯甲酸酯。优选的是丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、烯丙基缩水甘油醚、乙烯基缩水甘油醚。其他有用的辅助性单体包括含有烯丙基或α,β-不饱和羰基团基团,例如丙烯酸酯、甲基丙烯酸酯或马来酸基团的脲基官能化单体。可商购的实例包括由Rhodia Inc.销售的WAM烯丙基/脲基单体,以及由Rhodia,Inc作为WAM II销售的甲基丙烯酰胺乙基乙撑脲与20%含量的甲基丙烯酸的共混物。
如果这种辅助性单体共聚,在每一种情况下基于单体和共聚单体的总重量,优选使用0.1至3重量百分数。
单体和共聚单体的总和,即乙酸乙烯酯、乙烯、官能化共聚单体和可选地非官能化单体以及可选地辅助性单体等于100重量百分数。
优选选择单体和共聚单体以产生具有-20℃至+20℃,优选-10℃至+20℃,更优选为0℃至15℃的玻璃化转变温度Tg的共聚物。共聚物的玻璃化转变温度Tg可以通过差示扫描量热法(DSC)以已知的方式来确定。还可以通过Fox方程来预先计算出近似的Tg。根据FoxT.G.,Bull.Am.Physics Soc.1,3,page 123(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的均聚物的玻璃转化温度(以开尔文计)。在Polymer Handbook 2nd Edition,J.Wiley&Sons,New York(1975)中可以找到针对均聚物的Tg值。
合适的阴离子乳化剂的实例是具有12至20个C原子的直链脂族羧酸的钠盐、钾盐和铵盐;羟基十八烷基磺酸钠盐;具有12至20个C原子的羟基脂肪酸的钠盐、钾盐和铵盐和其磺化和/或乙酰化产物;烷基硫酸酯的钠盐、钾盐、铵盐和三乙醇胺盐,和每一种情况下具有10至20个C原子的烷基磺酸酯的钠盐、钾盐和铵盐以及具有12至20个C原子的烷基芳基磺酸酯的钠盐、钾盐和铵盐;具有8至18个C原子的二甲基二烷基-氯化铵及其磺化产物;具有4至16个C原子的饱和脂肪族一元醇的磺基琥珀酸酯的钠盐、钾盐和铵盐,以及具有10个到12个C原子的脂肪族一元醇的聚乙二醇醚的磺基琥珀酸4-酯,更特别是它们的二钠盐,以及具有聚乙二醇壬基苯基醚的磺基琥珀-4-酯的钠盐、钾盐和铵盐,更特别是其钠盐,和双环己基磺基琥珀酸酯的钠盐、钾盐和铵盐,更特别是其钠盐;木质素磺酸以及它的钙、镁、钠和铵盐;树脂酸以及氢化和脱氢的树脂酸,以及它们的碱金属盐。其它有用的阴离子表面活性剂包括醇乙氧基化物的磷酸酯,例如十三烷基醇乙氧基化物的磷酸酯作为RS-610商购自Rhodia。
最优选的阴离子乳化剂是在每一种情况下具有10至20个C原子的烷基硫酸酯和烷基磺酸酯的钠盐、钾盐和铵盐,以及具有12至20个C原子的烷基芳基磺酸酯的钠盐、钾盐和铵盐,以及具有4至16个C原子的脂肪族饱和一元醇的磺基琥珀酸酯的钠盐、钾盐和铵盐。
除了一种或多种阴离子乳化剂,可以加入一种或多种非离子乳化剂。合适的非离子乳化剂是,例如,酰基、烷基、油基和烷基芳基的乙氧基化物。这些产品是可商购的,例如,以商品名Genapol(R)或Lutensol(R)。它们包括乙氧基化的单-、二-和三-烷基酚,优选具有3至50个环氧乙烷单元和C4至C12的烷基基团的乙氧基化程度。合适的非离子乳化剂也是乙氧基化的支链或直链脂肪醇(脂肪族醇),优选具有3至80个环氧乙烷单元和C6至C36烷基基团的乙氧基化程度。合适的非离子乳化剂也是具有3至30个环氧乙烷单元的乙氧基化程度的C13-C15羰基合成醇乙氧基化物,具有11至80个环氧乙烷单元的乙氧基化程度的C16-C18脂肪醇乙氧基化物,具有3至11个环氧乙烷单元的乙氧基化程度的C10羰基合成醇乙氧基化物,具有3至20个环氧乙烷单元的乙氧基化程度的C13羰基合成醇乙氧基化物,具有20个环氧乙烷基团的聚氧乙烯失水山梨醇单油酸酯,具有至少10重量百分数的最低含量的环氧乙烷的环氧乙烷和环氧丙烷的共聚物,具有4至20个环氧乙烷单元的乙氧基化程度的油醇的聚环氧乙烷醚,以及具有4至20个环氧乙烷单元的乙氧基化程度的壬基酚的聚环氧乙烷醚。
优选的是乙氧基化的支链或非支链的脂肪族醇,特别是具有3至80个环氧乙烷单元以及C8至C36烷基的乙氧基化程度。优选的非离子型乳化剂也是具有3至30个环氧乙烷单元的乙氧基化程度的C13至C15羰基合成醇乙氧基化物,以及具有11至80个环氧乙烷单元的乙氧基化程度的C16-C18脂肪醇乙氧基化物。特别优选的是具有3至20个环氧乙烷单元的乙氧基化程度的C12-C14脂肪醇乙氧基化物。
在每一种情况下基于单体的总重量,乳化剂的总量典型地是从0.5%至5重量百分数,优选1至3重量百分数的范围。一种或多种阴离子乳化剂通常构成至少25wt%,或至少35wt%,或至少45wt%,或至少55wt%,或至少65wt%的总乳化剂,以及一种或多种非离子乳化剂构成余量。一种或多种阴离子乳化剂可以构成全部的乳化剂,或至多95wt%,或至多85wt%,或至多75wt%。
可选地,除了一种或多种乳化剂之外可以使用一种或多种保护性胶体。合适的保护性胶体是聚乙烯醇;聚乙烯缩醛;聚乙烯吡咯烷酮;水中可溶形式的多糖,如淀粉(淀粉酶和支链淀粉)、纤维素及其羧甲基、甲基、羟乙基、羟丙基衍生物;蛋白质,如酪蛋白或酪蛋白酸盐、大豆蛋白、明胶;木质素磺酸盐;合成聚合物如聚(甲基)丙烯酸、(甲基)丙烯酸酯与羧基官能化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-甲醛磺酸盐;萘甲醛磺酸盐;苯乙烯-马来酸共聚物和乙烯基醚-马来酸共聚物。
如果使用保护性胶体,优选使用部分水解或完全水解的聚乙烯醇,更优选的是具有80至95mol%水解程度和在4%浓度(strength,强度)的水溶液中的1至30mPas的粘度(20℃ 法,DIN53015)的部分水解的聚乙烯醇。最优选具有85至94%(摩尔)水解程度的聚乙烯醇和在4%浓度的水溶液中,3至25mPas的粘度(20℃ 法,DIN53015)的聚乙烯醇。指出的保护性胶体是可商购的或者可以通过本领域技术人员已知的方法获得。
如果加入保护性胶体,每一种情况下基于单体的总重量,它们通常是0.05至0.5重量百分数,更优选0.05至0.1重量百分数的量。在优选的实施方式中,不使用保护性胶体。
分散体的制备
可以通过乳液聚合使用常规乳液聚合方法制备水性共聚物分散体,通常在40℃至150℃,更特别地50℃至120℃,最特别为60℃至100℃的温度范围。取决于乙烯进料,聚合压力通常为40至100巴之间,更典型地45至90巴之间,并可能更具体地在45至85巴之间发生变化。
如按照惯例,可以使用如常用于乳液聚合的氧化还原引发剂组合来启动聚合。合适的氧化剂的实例有过二硫酸的钠盐、钾盐和铵盐、过氧化氢、叔丁基过氧化物、叔丁基过氧化氢、过氧化二磷酸钾、过氧化新戊酸叔丁酯、过氧化氢枯烯、异丙基苯单过氧化氢、偶氮二异丁腈。优选的是过氧二硫酸的钠盐、钾盐和铵盐以及过氧化氢。基于单体的总重量,通常规定的引发剂的使用量为0.01重量百分数至2.0重量百分数。
这些前述氧化剂,尤其是过氧二硫酸的盐,也可以使用其自身作为热引发剂。
合适的还原剂是碱金属和铵的亚硫酸盐和重亚硫酸氢盐,例如亚硫酸钠、次硫酸衍生物,如次硫酸锌或碱金属甲醛次硫酸盐,例如羟基甲烷亚磺酸钠(Brüggolit)。优选使用非甲醛生产的氧化还原引发体系。在一般情况下,合适的非甲醛生产的还原剂的氧化还原对包括,作为非限制性的例子,基于抗坏血酸或它的盐的那些,或异抗坏血酸(赤藻糖酸)或它的盐,或酒石酸或它的盐,或重硫酸盐,特别是本领域已知的亚硫酸氢钠,或本领域已知的羟基甲烷亚磺酸钠,由Brueggeman Chemical of Heilbronn,Germany制造的FF6M的可商购的还原剂。基于单体的总重量,还原剂的量优选是0.015%至3重量百分数。
在聚合期间可以通过使用调节物质来控制分子量。如果使用调节剂,基于待聚合的单体的总重量,使用的调节剂的量为0.01至5.0重量百分数,且单独计量或作为与反应组分的预混合物。这类物质的例子是正十二烷基硫醇、叔十二烷基硫醇、巯基丙酸、巯基丙酸甲酯、异丙醇,和乙醛。优选不使用任何调节物质。
所有单体可形成初始加料,或者所有单体可形成进料,或单体的部分可形成初始加料,并且聚合开始之后,其余可以形成进料。该进料可以是独立的(空间上和时间上),或所有的或一部分的组分预乳化后再进料。在一个优选的实施方式中,单体的至少一部分在初始加料时加入,优选5至50重量百分数的单体中在初始加料中加入。
所有的乳化剂可形成初始加料,或者所有的乳化剂可形成进料,或者乳化剂的一部分可形成初始加料,以及聚合反应开始之后,其余可形成进料。该进料可以是单独的(空间上和时间上),或所有的或一部分的组分预乳化后再进料。
聚合过程一旦结束,可以使用已知的方法除去残留的单体,一种合适的方法的一个实例是通过氧化还原催化剂引发的后聚合。也可以通过蒸馏,优选地在低于大气压下,并且在适当的条件下可选地通过使惰性夹带的气体(如空气、氮气或水蒸汽),穿过或通过材料除去挥发性残留单体。
水性共聚物分散体的固体含量通常在45重量百分数至75重量百分数的范围。
根据本发明,适当地确定用于制备根据本发明的乳化剂稳定的乙酸乙烯酯-乙烯共聚物分散体的合适的反应器(设计用于高压用途的钢反应器)的尺寸,并且其具有常规的搅拌器设备,测量和控制设备,以及用于引入起始材料并且用于排出产品的管线。
该反应器装备有包括泵和热交换器的外部热交换回路。“外部热交换回路”是指热交换器、泵和管线,其从反应器将反应混合物运输至热交换器并将其返回反应器。构建的管线和热交换器的材料对于本发明并不是关键的。典型地,可以使用不锈钢。
合适尺寸的管道的外部热交换回路装备了集成泵和热交换器。用于将聚合混合物抽出至外部热交换回路的连接器的位置是正常在反应器的下部三分之一内,优选在反应器的底部。用于将聚合混合物从外部热交换回路返回至反应器的连接器是在不同于用于将混合物抽出的连接器的位置,并且通常是在反应器的上三分之一处,优选在反应器的顶部。
热交换器的类型不是关键的。混合热交换器可以是壳管式、板框式、板片式、螺旋热交换器或静态混合器热交换器。构建的热交换器的材料对本发明不是关键的。通常可以使用不锈钢。
使用的泵的类型不是关键的。合适的泵的实例是非堵塞(non-chokable)泵(涡流)或活塞泵(排代泵,displacement pump)。优选的是活塞泵,并且特别优选的是螺杆泵,例如,旋转式螺杆泵。泵的尺寸优选使得其可承受高达100巴,优选40至100巴的压力。
除了外部热交换回路,反应器可任选地装备有内部加热/冷却***,诸如夹套加热/冷却或加热/冷却盘管。在优选的实施方式中仅使用外部热交换回路用于冷却或加热反应混合物。
分散体的使用
水性乳化剂稳定的乙酸乙烯酯-乙烯共聚物分散体适用于在通常的应用中使用,例如作为粘合剂用于油漆和其它涂料以及粘合剂组合物中,或作为涂料或粘合剂用于纺织品或纸张。
该分散体可被用来制造包含与一种或多种颜料和/或一种或多种填料混合的共聚物分散体的涂料组合物。该分散体可以,例如用于聚合物乳液涂料、砌筑涂料或内部涂料,以及聚合物分散体粉刷剂(render)。用于聚合物乳液涂料和聚合物分散体粉刷剂的合适的制剂对于本领域技术人员是已知的,并且通常包括5重量百分数至50重量百分数的水性共聚物分散体,5重量百分数至35重量百分数的水,5重量百分数至80重量百分数的一种或多种填料,5重量百分数至30重量百分数的一种或多种颜料,以及还有0.1重量百分数至10重量百分数的其它添加剂,制剂中的重量百分数的数字总计达100重量百分数。
合适的填料的实例包括碳酸盐,如方解石、白垩、大理石的形式的碳酸钙,并且还有白云石的形式的碳酸镁钙。其它实例是硅酸盐,如滑石形式的硅酸镁,微细粉碎的石英,石英砂,高度分散的二氧化硅,长石和/或硅铝酸盐,如壤土和粘土。同样合适的是纤维填料。在实际应用中,经常使用不同填料的混合物。聚合粉刷剂通常包括比乳胶漆包含更粗颗粒的填料,经常在0.2和5.0mm之间。否则,聚合物粉刷剂可以包含相同的添加剂,如乳胶漆。
合适的颜料的例子包括二氧化钛、氧化锌、氧化铁和炭黑作为无机颜料,以及常见的有机颜料。基于该制剂的总重量,其它添加剂的实例是通常为0.1重量百分数至0.5重量百分数的份数的润湿剂。合适的特定的实例是多磷酸钠和多磷酸钾、聚丙烯酸及其盐。添加剂也可以包括增稠剂,基于该制剂的总重量,其通常用量为0.01重量百分数至2.0重量百分数。通常的增稠剂是纤维素醚、淀粉,或无机增稠剂,例如膨润土。另外的添加剂可以包括防腐剂、消泡剂和冻融稳定剂。
为了生产粘合剂和涂覆材料,混合共聚物分散体并且在合适的混合器中均质化其它配方成分、填料,以及其他佐剂。如果期望的产物具有糊状稠度,通常先引入水部分,然后加入分散体,并最终在搅拌下引入固体。
着色涂料的材料,如聚合物乳液涂料的颜料体积浓度(PVC)通常位于10%到90%的范围内,并且根据下式进行计算:
PCV(%)=(VP+F×100)/(VP+F+VB)其中,VP+F=颜料和填料的体积的总和,VB=粘合剂的体积。当PVC≥50%,涂料材料被称为高填充。
下面的实施例用于进一步解释本发明的各方面。
实施例
实施例1
使用装备有搅拌器的压力反应器,仅采用外部热交换回路用于加热/冷却。该热交换器是壳管式热交换器,并且热交换回路的体积是该反应器的约44%。外部热交换回路中的泵是旋转螺杆泵。
向该反应器中加入46.71份去离子水(DI)、1.47份MA-25I(二己基磺基琥珀酸钠)、0.027份乙酸钠、0.0026份硫酸亚铁铵。用0.029份乙酸将电荷的pH调节至4.4。开始搅拌并且加入13.67份乙酸乙烯酯。
初始加料后,将反应器加热至55℃,完全通过泵送将反应混合物泵送通过外部热交换回路。然后,加入13.66份乙稀。为引发聚合反应,以每小时1.01份进料5.5%的过硫酸钠和3.3%的碳酸氢钠的水溶液,以及也以每小时1.01份进料3.3%异抗坏血酸钠的第二水溶液。有明显的放热后,开始另外的两份进料:90分钟内加入72.67份乙酸乙烯酯并且在90分钟内均匀地进料由11.35份水、1.52份L64(由BASF提供的环氧乙烷/环氧丙烷嵌段共聚物),0.505份丙烯酰胺甲基丙磺酸(由Lubrizol作为50%的钠盐溶液以商品名2403供给),1.01份RS-610(由Rhodia公司提供的十三烷基醇乙氧基化物的磷酸酯)和0.12份50%氢氧化钠组成的水性进料。当开始单体进料时,45分钟内将温度从55℃升高到85℃,然后在反应的剩余部分保持85℃。
90分钟的时间内过硫酸钠和异抗坏血酸钠溶液的加入速率保持恒定同时加入乙酸乙烯酯单体进料。乙酸乙烯酯进料完成后,逐渐增加过硫酸盐和异抗坏血酸溶液的加入速率,直到单体的转化基本完成。在整个期间,将总共3.0份的两种溶液加入至反应器。
然后经由泵送其通过外部热交换器泵将反应混合物冷却至35℃。然后将其转移到第二容器,其中,允许排出残留的乙烯,将压力降低至接近大气压的条件。在该点上,加入0.89份670(由Rhodia提供的专有消泡剂组合物)以减少起泡。为进一步完成乙酸乙烯酯的转化,将1.3份的8%异抗坏血酸钠水溶液和1.05份的7%叔丁基过氧化氢的第二水溶液,在15分钟期间分别进料。
得到的胶乳的物理性质是:
*颗粒尺寸Dw通过使用由Matec Applied Sciences of Northborough MA10532USA供给的CHDF 2000单位的毛细管流体动力学分级(CHDF)来测定。凝结物材料保留在100目的(149μm)滤网上。
比较例2
本反应过程在实施例1中,除了使用装备有搅拌器的压力反应器,通过反应器而不使用外部热交换回路直接提供加热/冷却。
得到的胶乳的物理性质是:
比较例3
该方法如比较例2,但由1.01份(即,两倍的量)的丙烯酸代替0.505份的丙烯酰胺甲基丙磺酸。
得到的胶乳的物理性质是:
比较例4
该方法如比较例3中,但仅使用0.505份,而不是1.01份的丙烯酸以匹配实施例1中使用的丙烯酰胺甲基丙磺酸的量。获得的分散体含有很多凝结物判断其不可用。
实施例1和比较例2和比较例3中制备的分散体配制成使用以下配方的涂料。
研磨成分
直接成分(Let-Down Ingredients)
将研磨混合物进行高速混合,并且一旦颜料分散,加入并且混合直接混合物(Let-Down mixture)。
根据用于墙壁涂料耐刮擦性标准测试方法的ASTM D2486-06测试方法B评估在每种情况下所获得的涂料的耐刮擦性(湿磨),并作以下修改:使用3 mil(76μm)Bird Bar代替7 mil(178μm)Dow Bar。使用在恒定的温度和湿度条件下(设定在50%相对湿度和72°F时,即,22℃)3天的固化代替环境条件下规定7天的固化。测定循环次数(cycle)直至故障。结果如下。
刮擦循环次数
实施例1 2252
比较例2 2240
比较例3 416
用实施例1的分散体制备的涂料(其仅用外部热交换回路由冷却/加热产生)产生了与比较例2的分散体(其使用直接反应器冷却/加热)基本相同的耐刮擦性,。但用比较例3的分散体制备的涂料(其用两倍水平的丙烯酸取代了磺酸单体2403)仅产生416次刮擦循环直至故障。因此,即使在低剪切条件下采用直接反应器的温度调节,用丙烯酸取代磺酸导致性能的极大降低。但出人意料的是,在实施例1中使用外部热交换器导致的高剪切处理并没有使由单体/共聚单体和乳化剂的组合使用制成的分散体的稳定性。
尽管在本文中参考具体实施方式说明和描述了本发明,但本发明并不旨在限于所示出的细节。相反地,在没有背离本发明的情况下,可以在本发明权利要求的等价物的范畴和范围内做出细节的多种改变。
Claims (10)
1.一种用于制备具有微细颗粒尺寸的水性乳化剂稳定的乙酸乙烯酯-乙烯共聚物分散体的方法,包括乳液聚合包含以下的反应混合物:
a)乙酸乙烯酯和乙烯,
b)基于单体和共聚单体的总重量,0.05至1重量百分数的至少一种官能化共聚单体,所述官能化共聚单体选自由烯属不饱和磺酸或它们的盐以及具有至少一个磷酸酯基团或膦酸基团或它们的盐的烯属不饱和单体组成的组,
c)基于所述单体和共聚单体的总重量,0.5至5重量百分数的至少一种阴离子乳化剂和可选地一种或多种非离子乳化剂,以及
d)基于所述单体和共聚单体的总重量,可选的至多0.5重量百分数的保护性胶体,
其中,所述乳液聚合在具有包括泵和热交换器的外部热交换回路的反应器中进行,并且在所述乳液聚合期间,所述反应混合物循环通过所述外部热交换回路,并且
其中,所述共聚物分散体颗粒的重均颗粒尺寸DW的范围为100nm至300nm,并且
其中,所形成的所述共聚物分散体含有小于1000ppm的凝结物。
2.根据权利要求1所述的方法,其中,基于所述单体和共聚单体的总重量,所述乙酸乙烯酯构成70至95重量百分数的范围,以及所述乙烯构成5至20重量百分数,其中所述单体和共聚单体的总重量是100重量百分数。
3.根据权利要求1所述的方法,其中,所述至少一种官能化共聚单体选自由烯属不饱和磺酸和它们的盐组成的组。
4.根据权利要求1-3中任一项所述的方法,其中,基于所述单体和共聚单体的总重量,至少一种所述官能化共聚单体构成0.05至0.8重量百分数的范围。
5.根据权利要求1-3中任一项所述的方法,其中,所述阴离子乳化剂包含选自由以下组成的组中的一个或多个成员:每一种情况下具有10至20个C原子的烷基硫酸酯或烷基磺酸酯的钠盐、钾盐或铵盐,具有12至20个C原子的烷基芳基磺酸酯的钠盐、钾盐或铵盐,以及具有含4至16个C原子的脂肪族饱和一元醇的磺基琥珀酸酯的钠盐、钾盐或铵盐。
6.根据权利要求1-3中任一项所述的方法,其中,所述反应混合物包含所述一种或多种非离子乳化剂。
7.根据权利要求1-3中任一项所述的方法,其中,基于所述单体和共聚单体的总重量,所述阴离子乳化剂和可选的非离子乳化剂的总量是1至3重量百分数。
8.根据权利要求1-3中任一项所述的方法,其中,所述反应混合物不含保护性胶体。
9.根据权利要求1-3中任一项所述的方法,其中,基于所述单体和共聚单体的总重量,所述保护性胶体以0.05至0.5重量百分数的量存在。
10.一种涂料或粘合剂组合物,包含与一种或多种颜料和/或一种或多种填料混合的由权利要求1-9中任一项所述的方法制备的共聚物分散体。
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