CN109311750B - 包含水可溶胀的聚合物核和溶胶-凝胶涂层的经涂覆的聚合物颗粒 - Google Patents
包含水可溶胀的聚合物核和溶胶-凝胶涂层的经涂覆的聚合物颗粒 Download PDFInfo
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- CN109311750B CN109311750B CN201780037008.7A CN201780037008A CN109311750B CN 109311750 B CN109311750 B CN 109311750B CN 201780037008 A CN201780037008 A CN 201780037008A CN 109311750 B CN109311750 B CN 109311750B
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Abstract
本发明涉及经涂覆的聚合物颗粒,其包含水可溶胀的聚合物核和包封该核的基本上连续的涂层。所述涂层包含硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物。所述聚合物颗粒在与水或含水液体接触时不显示出瞬间的溶胀,而在合适的时间段后显示出延迟的水吸收。所述经涂覆的聚合物颗粒可用在油田、采矿、建筑化学组合物中或用作活性物质的载体。所述经涂覆的聚合物颗粒通过悬浮液涂覆法或流化床涂覆法进行制备。
Description
本发明涉及经涂覆的聚合物颗粒,其包含水可溶胀的聚合物核和包封该核的基本上连续的涂层,涉及一种制备所述经涂覆的聚合物颗粒的方法以及所述经涂覆的聚合物颗粒在采矿、建筑化学组合物中或作为活性物质的载体的用途。
超吸收剂是能够以相当于其自身重量的许多倍的量吸收流体(例如水或含水流体)的聚合物。即使在受到外部压力的情况下,它们也能保留所吸收的流体。这种聚合物已广泛用于例如吸收性卫生产品,例如尿布、卫生巾等,并且其特征在于,当与含水流体接触时,其立即吸收流体。在超吸收剂中,还制备了盐不敏感的超吸收剂(SISA)(例如通过凝胶聚合)并且其可商购获得。所述SISA例如被用作建筑化学组合物的添加剂。与上述普通的超吸收剂类似,在与水或含水流体接触时,已知的SISA也显示出瞬间吸水性。然而,对于特定的应用而言,瞬间的溶胀是不期望的,例如,在超吸收剂或包含超吸收剂的组合物被放置在其使用的适当目的地之前,不应发生吸水。这例如与采矿中的应用、在建筑化学组合物中的使用或用于活性物质的载体相关。
WO 98/16308 A1记载了包含水可溶胀的聚合物凝胶和无机的电中性材料的复合材料。还记载了通过使用水溶性和水不溶性交联剂获得的核-壳体系。这产生了在整个颗粒中交联并且另外在表面交联的产物。
WO 2005/087181 A2记载了包含用于降低臂下湿度的悬浮产品的化妆品制剂,其包含超吸收性聚合物、倍半萜、氧化锌和挥发性硅氧烷。如果所述制剂为走珠或泵喷雾形式,则其可另外包含硅胶作为悬浮剂。
US 2008/0108524 A1记载了一种吸水性组合物,其包含水可溶胀的材料的核和包围该核的涂层,所述涂层暂时防止了水与水可溶胀的材料接触。该涂层可包括水可降解的材料(例如聚乳酸)和水不可降解的材料(其不包括无机氧化物材料,但可包括天然树胶、多糖、纤维素或蛋白质)。所述水不可降解的材料可通过机械破损或在不为水的液体中降解来除去。
US 2005/0005869 A1记载了包含颗粒形式的吸收材料(例如矿物)和增强性能的活性物质(例如抗菌剂或气味吸收剂或抑制剂)的复合材料。这种活性物质可设置在颗粒表面上的层中。
WO 2011/023536 A1记载了可通过例如烷氧基甲硅烷基化合物后交联的颗粒状超吸收剂。也可将多价金属盐或无机细颗粒(如胶体硅酸溶胶)施用于颗粒状超吸收剂的表面以改善导液性。后交联在颗粒状超吸收剂的表面上进行,而不形成另外的层。无机细颗粒(其例如通过喷雾施用)是通过物理吸附而包含在超吸收剂聚合物基质中的。无机细颗粒在颗粒状超吸收剂表面上形成孤立的岛状物,而不凝结成连续的涂层。
WO 2013/174753涉及一种制备杂化有机-无机核-壳纳米颗粒的方法,其包括以下步骤:a)提供包含合成聚两性电解质的胶态有机颗粒作为模板;b)加入至少一种无机氧化物前体,例如四乙氧基硅烷;和c)在所述模板上由所述前体形成壳层以产生核-壳纳米颗粒。该胶态有机模板颗粒的平均粒径为10至300nm。SiO2与聚两性电解质的经计算的质量比为1.39至2.5。发现该核-壳纳米颗粒的水性分散体显示出非常好的储存稳定性和操作稳定性,这意味着该分散体几乎不显示粘度改变或胶凝的倾向。
本发明所要解决的问题是提供水可溶胀的聚合物颗粒,其在与水或含水液体接触时不显示瞬间溶胀,而是在适当的一段时间后显示出延迟的吸水性。
上述问题已通过包含以下物质的经涂覆的聚合物颗粒解决:
(a)水可溶胀的聚合物核,所述水可溶胀的聚合物核包含共聚物,所述共聚物包含含磺基和/或含季铵基团的结构单元,和
(b)包封所述核的基本上连续的涂层,所述涂层包含硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物,
其中涂层(以氧化物计)与水可溶胀的聚合物核的质量比为0.002至小于1。
本文所用的术语“水可溶胀的聚合物”意指能吸收水或盐的水溶液的聚合物。通常,水可溶胀的聚合物能吸收其自身重量许多倍的液体。吸收能力定义为所吸收的液体的量(以g计)与干燥聚合物的质量(以g计)之比。所述吸收能力根据标准EDANA 440.2-02测定,该标准通过使用1重量%的甲酸钙水溶液替代0.9重量%的氯化钠溶液进行修正。聚合物的吸收能力通常为5至50g/g,优选5至30g/g。
基本上连续的涂层是通过可缩合前体或可水解且可缩合前体的缩聚反应在水可溶胀的聚合物核上形成的。水可溶胀的聚合物核完全被基本上连续的涂层包封。涂层包含硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物。单个经涂覆的颗粒的涂层通过共价键无缝键合和/或交联。术语“无缝键合和/或交联”是指在涂层内提供足够的共价键,以获得包围核的基本上连续的涂层。涂层完全覆盖聚合物核的表面,并且优选不显示出缺陷或未覆盖区域。
涂层(以氧化物计)与(无水)水可溶胀的聚合物核的质量比为0.002至小于1,优选为0.02至0.85。涂层的质量以氧化物计,即,理论上地前体可能的最大缩合状态。例如,如果使用四乙氧基硅烷作为前体,则计算时假定四乙氧基硅烷完全转化为SiO2。
此外,聚合物核与涂层之间的共价键可通过聚合物核的官能团与用于上述涂层的前体的缩合反应来建立。所述官能团可例如包括羧酸基团和/或羟基和/或氨基。
在一个实施方案中,涂层包含二氧化硅、氧化铝、氧化锆、羟基氧化铝、氧化锡、二氧化钛或氧化锡、或其混合物。
在另一实施方案中,涂层包含硅、铝和锆的氧化物。
在另一实施方案中,涂层基本上包含硅的氧化物。
在一个实施方案中,经涂覆的聚合物颗粒的数均直径为10至1000μm,优选为50至500μm。所述平均直径通过电子显微镜测定。
在一个实施方案中,涂层的平均层厚度为100至1000nm,优选为250nm至700nm,更优选为300nm至600nm。平均层厚度通过电子显微镜(SEM:Jeol 7500-TFE(Jeol Ltd.,Tokyo,Japan),在5kV下操作,二次电子(SE)检测器;TEM:透射电子显微镜(TEM):TecnaiG2-F20ST机器(FEI Company,Hillsboro,USA),在200keV下操作)来测定。
在一个实施方案中,经涂覆的聚合物颗粒基本上为球形颗粒,并且平均球度(mSPHT)为至少0.90,优选为至少0.95,更优选为至少0.99。球度(SPHT)定义为SPHT=4πA/U2,其中A表示颗粒的横截面积,U表示颗粒的横截面周长。平均球度可通过图像分析系统如(Retsch Technology GmbH;Haan;Germany)来测定。
涂层暂时阻止了水或含水流体与聚合物核的接触。暂时防止包含的水与聚合物核的接触例如是指至少5分钟、优选至少15分钟、更优选至少60分钟、特别是至少100分钟的时间,其中吸水性聚合物不与聚合物颗粒周围的水或含水流体接触。水或含水流体与吸水性核开始接触的时间可通过层厚度来控制。层的厚度越厚,则水或含水流体扩散穿过层的时间越长。
本发明的经涂覆的聚合物颗粒另外地提供以下有利特征:涂层可借助pH-调节或压力在适当的或限定的时间后除去。涂层在pH值为6至8之间基本上是稳定的。高于和低于所述pH值时,可以通过水解除去涂层。
优选地,水可溶胀的聚合物为所谓的盐不敏感的超吸收性聚合物(SISA)。这些聚合物可以承受建筑材料或无机聚合物中遇到的高碱和高盐负荷。
根据一个实施方案,水可溶胀的聚合物包括共聚物P1和/或共聚物P2,所述共聚物P1包含含磺基和含酰胺基的结构单元,所述共聚物P2包含含季铵基和含酰胺基的结构单元。
根据另一实施方案,共聚物P1包含:
(i)式(I)的含磺酸的结构单元
其中
R1表示氢或甲基,
R2、R3和R4彼此独立地表示氢、C1-C6-烷基或C6-C14-芳基,
M表示氢、金属阳离子或铵阳离子,
a表示1或1/金属阳离子的化合价,优选1/2或1,
(ii)式(II)的含(甲基)丙烯酰胺基的结构单元
其中
R1表示氢或甲基,
R5和R6彼此独立地表示氢、C1-C20-烷基、C5-C8-环烷基或C6-C14-芳基,和
(iii)衍生自具有两个或更多个烯键式不饱和乙烯基的单体的结构单元,和
(iv)任选地,衍生自具有一个烯键式不饱和乙烯基的单体的结构单元,该结构单元不同于结构单元(i)和(ii)。
根据另一实施方案,共聚物P2包含:
(i)式(III)的阳离子结构单元
其中
R1表示氢或甲基,
R7、R8、R9和R10彼此独立地表示氢、C1-C20-烷基、C5-C8-环烷基或C6-C14-芳基,
m表示1至6的整数,
X表示氧或N-R10,
Y- a表示卤素、C1-C4-烷基硫酸根、C1-C4-烷基磺酸根或硫酸根,
a表示1/2或1,和
(ii)式(II)的含(甲基)丙烯酰胺基的结构单元
其中
R1表示氢或甲基,
R5和R6彼此独立地表示氢、C1-C20-烷基、C5-C8-环烷基或C6-C14-芳基,和
(iii)衍生自具有两个或更多个烯键式不饱和乙烯基的单体的结构单元,和
(iv)任选地,衍生自具有一个烯键式不饱和乙烯基的单体的结构单元,该结构单元不同于结构单元(i)和(ii)。
根据另一实施方案,共聚物P1包含:
(i)10至70摩尔%的式(I)的结构单元,
(ii)29.99至89.99摩尔%的式(II)的结构单元,
(iii)0.01至1摩尔%的衍生自具有两个或更多个烯键式不饱和乙烯基的单体的结构单元,和
(iv)0至30摩尔%的衍生自具有一个烯键式不饱和乙烯基的单体的结构单元,
其中组分(i)、(ii)、(iii)和(iv)总计达100摩尔%。
根据另一实施方案,共聚物P2包含:
(i)10至70摩尔%的式(III)的结构单元,
(ii)29.99至89.99摩尔%的式(II)的结构单元,
(iii)0.01至1摩尔%的衍生自具有两个或更多个烯键式不饱和乙烯基的单体的结构单元,和
(iv)0至30摩尔%的衍生自具有一个烯键式不饱和乙烯基的单体的结构单元,
其中组分(i)、(ii)、(iii)和(iv)总计达100摩尔%。
在根据式(I)的含磺酸的结构单元的一个实施方案中,M表示选自碱金属或碱土金属的一价或二价金属阳离子,例如钠、钾、钙或镁。
在根据式(I)的含磺酸的结构单元的另一个实施方案中,M表示铵阳离子,其选自伯、仲、叔C1-C20烷基胺、C1-C20链烷醇胺、C5-C8环烷基胺和C6-C14芳基胺的质子化形式。这样的铵阳离子的实例为甲胺、二甲胺、三甲胺、乙醇胺、二乙醇胺、三乙醇胺、环己胺、二环己胺或苯胺的质子化形式。
在一个实施方案中,C6-C14-芳基为苯基或萘基,特别是苯基。在另一实施方案中,C5-C8-环烷基为戊基或己基。在另一实施方案中,R2和R4为氢,R3为氢或直链或支链的C1-C6-烷基。在另一实施方案中,R7、R8和R9为直链或支链的C1-C6-烷基。R10为氢或直链或支链的C1-C6-烷基。在另一实施方案中,式I和II中的R5和R6为氢或直链或支链的C1-C6-烷基。
在一个实施方案中,根据式(I)的结构单元衍生自选自以下的单体:2-丙烯酰胺基-2-甲基丙磺酸、2-甲基丙烯酰胺基-2-甲基丙磺酸、2-丙烯酰胺基丁磺酸、3-丙烯酰胺基-3-甲基丁磺酸、2-丙烯酰胺基-2,4,4-三甲基戊磺酸、所述酸的相应碱金属或碱土金属盐,及其混合物。在一个优选的实施方案中,根据式(I)的结构单元衍生自2-丙烯酰胺基-2-甲基丙磺酸,其钠、钾、钙或镁盐,或其混合物。
在一个实施方案中,共聚物P1包含10至43摩尔%、优选10至40摩尔%、更优选10至37摩尔%且最优选15至30摩尔%的根据式(I)的含磺酸的结构单元。
在一个实施方案中,式(II)的含(甲基)丙烯酰胺基的结构单元可衍生自选自以下的单体:丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺、N-甲基甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-乙基丙烯酰胺、N,N-二乙基丙烯酰胺、N-环己基丙烯酰胺、N-苄基丙烯酰胺、N,N-二甲基氨基丙基丙烯酰胺、N,N-二甲基氨基乙基丙烯酰胺或N-叔丁基丙烯酰胺或其混合物,优选丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺,N,N-二甲基丙烯酰胺或其混合物。
在一个实施方案中,共聚物P1包含31至88.99摩尔%、优选39至86.99摩尔%、更优选42.92至84.99摩尔%且最优选54.95至79.99摩尔%的式(II)的含(甲基)丙烯酰胺基的结构单元。
在一个实施方案中,共聚物P1包含衍生自具有两个或更多个烯键式不饱和乙烯基的单体的结构单元iii)作为交联剂。
这种单体的实例为(甲基)丙烯酰基官能化的单体,例如二丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,4-丁二醇酯、二丙烯酸1,3-丁二醇酯、二甲基丙烯酸1,3-丁二醇酯、二丙烯酸二乙二醇酯、二甲基丙烯酸二乙二醇酯、二甲基丙烯酸乙二醇酯、乙氧基化的双酚-A-二丙烯酸酯、乙氧基化的双酚-A-二甲基丙烯酸酯、二甲基丙烯酸乙二醇酯、二丙烯酸1,6-己二醇酯、二甲基丙烯酸1,6-己二醇酯、二甲基丙烯酸新戊二醇酯、二丙烯酸聚乙二醇酯、二甲基丙烯酸聚乙二醇酯、二丙烯酸三乙二醇酯、二甲基丙烯酸三乙二醇酯、二丙烯酸三丙二醇酯、二丙烯酸四乙二醇酯、二丙烯酸四乙二醇酯、二甲基丙烯酸四乙二醇酯、五丙烯酸二季戊四醇酯、四丙烯酸季戊四醇酯、三丙烯酸季戊四醇酯、三丙烯酸三羟甲基丙烷酯、三甲基丙烯酸三羟甲基酯、二丙烯酸环戊二烯酯、三(2-羟乙基)异氰脲酸三丙烯酸酯或三(2-羟基)异氰脲酸三甲基丙烯酸酯;单体,例如具有两个或更多个羧酸基团的多羧酸的二乙烯基酯或二烯丙基酯,例如对苯二甲酸三烯丙酯、马来酸二烯丙酯、富马酸二烯丙酯、偏苯三酸三乙烯酯、己二酸二乙烯酯、琥珀酸二烯丙酯;具有多于一个(甲基)丙烯酰胺基的单体,例如N,N'-亚甲基双丙烯酰胺或N,N'-亚甲基双甲基丙烯酰胺;或具有多于一个马来酰亚胺基团的单体,例如六亚甲基双马来酰亚胺;具有多于一个乙烯基醚基团的单体,例如乙二醇二乙烯基醚、三乙二醇二乙烯基醚或环己二醇二乙烯基醚;或其盐。此外,还可使用具有多于一个烯丙基基团的烯丙基氨基化合物或烯丙基铵化合物,例如三烯丙基胺或四烯丙基氯化铵;碱金属或碱土金属盐;或芳族化合物,例如二乙烯基苯。
在上述单体中,优选甲基丙烯酰基官能化的单体、甲基丙烯酰胺基官能化的和烯丙基氨基官能化的单体和二乙烯基苯。特别优选N,N'-亚甲基双丙烯酰胺、N,N'-亚甲基双甲基丙烯酰胺、三烯丙基异氰脲酸酯、三烯丙基胺、四烯丙基氯化铵、碱金属盐或碱土金属盐,或其混合物。
在另一实施方案中,共聚物P1包含衍生自具有一个烯键式不饱和乙烯基的单体的结构单元iv)。优选亲水性单体。这种单体的实例为丙烯腈、甲基丙烯腈、乙烯基吡啶、乙酸乙烯酯、羟乙基丙烯酸、羟乙基甲基丙烯酸、羟丙基丙烯酸、羟丙基甲基丙烯酸、丙烯酸、甲基丙烯酸、乙基丙烯酸、α-氯丙烯酸、α-氰基丙烯酸、β-甲基丙烯酸、α-苯基丙烯酸、β-丙烯酰氧基丙酸、山梨酸、α-氯山梨酸、2'-甲基异巴豆酸、肉桂酸、马来酸、马来酸酐、对氯肉桂酸、衣康酸、柠康酸、中康酸、戊二酸、乌头酸、富马酸、三羧基乙烯、乙烯基磺酸、烯丙基磺酸、苯乙烯磺酸、丙烯酸磺乙酯、甲基丙烯酸磺乙酯、丙烯酸磺丙酯、甲基丙烯酸磺丙酯、2-羟基-3-甲基丙烯酰氧基丙基磺酸或其混合物或其盐。优选(甲基)丙烯酸单体,特别是丙烯酸和甲基丙烯酸及其盐。
交联结构单元iii)的存在量通常为0.01至1摩尔%,更优选0.01至0.08摩尔%,最优选0.01至0.05摩尔%。
结构单元iv)的存在量通常为0至30摩尔%。在一个实施方案中,结构单元iv)的存在量为1至25摩尔%,优选3至20摩尔%,更优选5至20摩尔%且最优选5至15摩尔%。
在另一实施方案中,共聚物P1或P2包含以下量的结构单元i)、ii)、iii)和iv):
结构单元i):10至43摩尔%;
结构单元ii):31至88.99摩尔%;
结构单元iii):0.01至1摩尔%;
结构单元iv):1至25摩尔%
优选:
结构单元i):10至40摩尔%;
结构单元ii):39至86.99摩尔%;
结构单元iii):0.01至1摩尔%;
结构单元iv):3至20摩尔%
更优选:
结构单元i):10至37摩尔%;
结构单元ii):42.92至84.99摩尔%;
结构单元iii):0.01至0.08摩尔%;
结构单元iv):5至20摩尔%
最优选:
结构单元i):15至30摩尔%;
结构单元ii):54.95至79.99摩尔%;
结构单元iii):0.01至0.05摩尔%;
结构单元iv):5至15摩尔%
及其任意组合。
在一个实施方案中,共聚物P2包含根据式(III)的结构单元。所述结构单元例如衍生自以下单体:[2-(丙烯酰氧基)-乙基]-三甲基氯化铵、[2-(丙烯酰氧基)-乙基]-三甲基甲磺酸铵、[2-(甲基丙烯酰氧基)-乙基]-三甲基氯化铵或[2-(甲基丙烯酰氧基)-乙基]-三甲基甲磺酸铵、[3-(丙烯酰基氨基)-丙基]-三甲基氯化铵或[3-(甲基丙烯酰基氨基)-丙基]-三甲基氯化铵或其混合物。在所述单体中,优选[3-(丙烯酰基氨基)-丙基]-三甲基氯化铵和[3-(甲基丙烯酰基氨基)-丙基]-三甲基氯化铵。
在一个实施方案中,共聚物P2包含15至70摩尔%、优选15至60摩尔%、更优选20至50摩尔%的式(III)的结构单元。
在一个实施方案中,共聚物P2包含如上定义的式(II)的结构单元且其摩尔量如上所定义。
在另一实施方案中,共聚物P2包含如上定义的结构单元iii)且其摩尔量如上所定义。
在又一实施方案中,共聚物P2包含如上定义的结构单元iv)且其摩尔量如上所定义。
在一个实施方案中,水可溶胀的聚合物核由共聚物P1表示。
在另一实施方案中,水可溶胀的聚合物核由共聚物P2表示。
在另一实施方案中,水可溶胀的聚合物核包含共聚物P1和P2的混合物,其比例优选为99/1至85/15(摩尔%P1/P2)或1/99至15/85(摩尔%P1/P2)。
包含共聚物P1和/或共聚物P2的水可溶胀的聚合物可通过使适于形成如上所定义的结构单元的单体通过自由基聚合反应进行聚合来制备。以酸形式存在的单体可以游离酸或其盐的形式或以部分中和的形式来聚合。也可以在聚合后进行酸的中和或部分中和。合适的碱为例如氢氧化钠、氢氧化钾、氢氧化钙、氢氧化镁或氨。其他合适的碱为伯、仲或叔C1-C20-烷基胺、C1-C20-链烷醇胺、C5-C8-环烷基胺或C6-C14-芳基胺。可以使用一种或多种碱。
单体可例如通过自由基本体、溶液、凝胶、乳液、分散或悬浮聚合来进行共聚。优选在水相中的聚合、在反相乳液中的聚合或在反相悬浮液中的聚合。在特别优选的实施方案中,反应在有机溶剂中以反相悬浮聚合的方式进行。
共聚反应也可以以绝热聚合的方式进行,并且可通过氧化还原引发剂体系或通过光引发剂引发。此外,两种引发变型的组合也是可行的。氧化还原引发剂体系可以由至少两种组分组成,即有机或无机氧化剂和有机或无机还原剂。合适的为具有过氧化物单元的化合物,例如无机过氧化物,如过硫酸碱金属盐和过硫酸铵、过磷酸碱金属盐和过磷酸铵、过氧化氢及其盐(过氧化钠、过氧化钡);或有机过氧化物,如过氧化苯甲酰、丁基氢过氧化物或过酸如过乙酸。还适合的为氧化剂,例如高锰酸钾、氯酸钠和氯酸钾、重铬酸钾等。作为还原剂,可以使用含硫化合物,例如亚硫酸盐、硫代硫酸盐、亚磺酸、有机硫醇(例如乙硫醇、2-羟基乙烷-硫醇、2-巯基乙基氯化铵、巯基乙酸)等。此外,还合适的为抗坏血酸和例如铜-(I)、锰-(II)或铁-(II)的低价金属盐。也可以使用磷化合物,例如次磷酸钠。
光聚合通常借助UV光引发,其导致光引发剂的分解。合适的光引发剂为例如苯偶姻和苯偶姻衍生物,例如苯偶姻醚、苯偶酰及其衍生物,例如苯偶姻缩酮;丙烯酰重氮盐;偶氮引发剂,如2,2'-偶氮双-(异丁腈)、2,2'-偶氮双(2-脒基丙烷)盐酸盐和/或苯乙酮衍生物。
在氧化还原引发剂体系的情况下,氧化组分和还原组分的重量比范围在每种情况下例如为0.00005至0.5重量%,优选0.001至0.1重量%。在光引发剂的情况下,该范围为例如0.001至0.1重量%,优选0.002至0.05重量%。对于氧化和还原组分以及光引发剂给出的重量百分比,在每种情况下均基于用于共聚的单体的质量计。
共聚可在水溶液中(例如在浓缩水溶液中)进行,既可在聚合容器中间歇进行(间歇方法),又可通过如US-A-4857610中所述的“连续传送带”方法连续进行。
另一种可能性是在连续或不连续操作的捏合反应器中进行聚合。该过程通常在-20至20℃、优选-10至10℃的温度下引发,并且在没有外部加热的情况下在大气压下进行,其中由聚合热得到的最高最终温度(取决于单体含量)为50至150℃。在完成共聚后,可以粉碎聚合物,其以凝胶形式存在。如果共聚以实验室规模进行,则粉碎的凝胶可以在对流干燥烘箱中在70至180℃、优选80至150℃下干燥。在工业规模时,也可以在相同的温度范围内连续进行干燥,例如在带式干燥器或流化床干燥器中进行干燥。
在一个实施方案中,共聚以含单体的水相在有机溶剂中的反相悬浮聚合的方式进行。在这里,如果合适,将已溶解在水中并被中和的单体混合物在有机溶剂的存在下进行聚合,其中含单体的水相是不溶或微溶的。共聚例如在“油包水”乳化剂(W/O乳化剂)和/或保护性胶体的存在下进行,所述乳化剂和/或保护性胶体可以以0.05至5重量%、优选0.1至3重量%的比例使用,基于单体的重量计。W/O乳化剂和保护性胶体也称为稳定剂。可以使用在反相悬浮聚合技术中称为稳定剂的常规化合物,例如,羟丙基纤维素、乙基纤维素、甲基纤维素、混合的乙酸丁酸纤维素醚、乙烯和乙酸乙烯酯的共聚物、苯乙烯和丙烯酸丁酯的共聚物、聚氧乙烯山梨糖醇单油酸酯、单月桂酸酯或单硬脂酸酯以及环氧丙烷与环氧乙烷的嵌段共聚物。
用于反相悬浮聚合的有机溶剂为例如具有6至14个碳原子的直链、支链或环状脂族烃,以及芳族烃,如苯、甲苯或二甲苯。其他合适的溶剂为具有一个、两个或更多个羟基的C1-C12-醇。优选与水形成共沸混合物的有机溶剂。
水可溶胀的共聚物可以初始作为有机介质中的细分散的液滴以溶胀形式获得,并且可以通过除去水而作为有机介质中的固体颗粒被分出。除去有机相并进行干燥而得到粉状固体。反相悬浮聚合的优点在于,可以控制粉末的粒径分布,并且可以通过改变聚合条件(单体和交联剂的选择、交联剂的量、聚合期间的搅拌速度、表面活性剂的量)来获得定制的聚合物核,因此,通常可以避免用于调节粒径分布的另外的处理步骤(研磨步骤)。在一个实施方案中,所得聚合物颗粒基本上是球形的,其中球度如上所定义。
本发明的经涂覆的聚合物颗粒可通过多种方法制备,优选通过悬浮液涂覆法或通过流化床涂覆法。
一方面,本发明涉及一种制备经涂覆的聚合物颗粒的方法,所述方法包括以下步骤:
a)将水可溶胀的聚合物核颗粒悬浮于有机溶剂中,
b)向悬浮液中加入硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物的前体,以使反应性前体在颗粒溶剂相界面处布置,
c)使前体转化为硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物,和
d)获得水可溶胀的聚合物核,其涂覆有包封水可溶胀的聚合物的基本上连续的涂层,
其中步骤b)和c)任选地根据需要重复多次以获得所需厚度的涂层(一次、两次或三次至十次)。
合适的有机溶剂例如选自具有一个、两个或更多个羟基的C1-C12-醇;芳族烃,如苯、甲苯、二甲苯;和脂族烃(包括脂环族烃),优选具有5至14个碳原子的脂族烃,如戊烷、己烷、辛烷、环己烷和甲基环己烷。脂族和脂环族C7至C12烃的混合物被称为石油溶剂油并且是有用的有机溶剂。
步骤a)可以包括通过如上文详述的反相悬浮聚合原位制备悬浮的水可溶胀的聚合物核颗粒。另外的有机溶剂也可加入反相悬浮聚合后获得的悬浮液中。但是,添加另外的有机溶剂不是必须的。
可选地,步骤a)包括向水可溶胀的聚合物颗粒中加入合适的有机溶剂,并将水可溶胀的聚合物核颗粒悬浮于溶剂中。当从悬浮液/分散体中分离出水可溶胀的聚合物时,添加所述有机溶剂是特别重要的。
制备本发明的经涂覆的聚合物颗粒的方法的步骤b)包括向悬浮液中加入硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物的前体,以使反应性前体在颗粒溶剂相界面处布置。合适的前体如下文所定义。
然后,将前体至少部分地转化成硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物,如下文所述。
在一个实施方案中,步骤d)包括从分散体中除去液体上清液,洗涤并干燥经涂覆的聚合物颗粒,例如在20至60℃的温度和环境压力下。所得经涂覆的颗粒的洗涤可以用合适的溶剂(例如丙酮、正戊烷、正己烷、正庚烷或甲苯)进行。
在一个实施方案中,步骤b)和c)任选地重复一次、两次或三次至十次,在各重复之间进行或不进行从悬浮液中分离经涂覆的颗粒。这种重复过程使得形成具有两层、三层或最高达十一层的涂层。
另一方面,本发明涉及一种制备经涂覆的聚合物颗粒的方法,所述方法包括以下步骤:
(a)使水可溶胀的聚合物核颗粒在流化气体料流中流化,
(b)使颗粒与硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物的前体的溶液或分散体接触,以使颗粒涂覆有反应性前体,
(c)使反应性前体转化成硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物,
(d)干燥经涂覆的颗粒。
步骤(b)至(d)可进行两次或更多次以获得具有较厚涂层的颗粒。
在一个实施方案中,干燥步骤(d)与步骤(b)和/或步骤(c)同时进行。
流化床涂覆法可在常规装置中进行,例如购自Glatt GmbH,Binzen,Germany或Bosch Huettlin GmbH,Schopfheim,Germany的那些。选择条件使得颗粒的温度保持在40至100℃、特别是40至80℃的范围内,即,使得流化气体(通常为空气)的出口温度在40至80℃的范围内。为实现这一点,供应气体温度通常选择为60至200℃、特别是80至140℃,而其他参数则必须根据装置的类型和大小以及批量大小来选择。
为了进料前体和其他试剂(如果有的话),可以使用常规喷嘴,例如双物质喷嘴或三物质喷嘴。将水可溶胀的聚合物核颗粒置于流化床装置中并使该装置投入运行。一旦装置的内容物达到操作温度和稳定的流化床,就施用(优选通过喷雾)前体溶液或分散体。
将经涂覆的颗粒干燥至水含量为0.5至5重量%。
适用于上述方法的前体是任选在水解和/或酸化后能够进行缩聚反应以形成硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物的化合物。
合适的前体可选自:
(a)四-C1-C4-烷氧基硅烷、三-C1-C4-烷氧基-C1-C4-烷基硅烷、三苯基氧基-C1-C4-烷基硅烷、三-C1-C4-烷氧基-苯基-硅烷、二-C1-C4-烷氧基二-C1-C4-烷基硅烷、二-苯基-苯基氧基-C1-C4-烷基硅烷、二-C1-C4-烷氧基二-苯基-硅烷;乙烯基三-C1-C4-烷氧基硅烷、乙烯基三苯基氧基硅烷、(甲基)丙烯酰氧基-C1-C4-烷氧基三-C1-C4-烷基硅烷、(甲基)丙烯酰氧基-C1-C4-烷基三-C1-C4-烷基硅烷、(甲基)丙烯酰氧基-C1-C4-烷基二-C1-C4-烷基-C1-C4-烷氧基硅烷、(甲基)丙烯酰氧基-C1-C4-烷基-C1-C4-烷基-C1-C4-二烷氧基硅烷、(甲基)丙烯酰氧基-C1-C4-烷基三-C1-C4-烷氧基硅烷;或其部分预反应或预水解的产物;
(b)铝、锆、锡或钛的卤化物、C1-C4-醇盐、羧酸盐;或其部分预反应或预水解的产物;
(c)碱金属的硅酸盐或偏硅酸盐;或其部分预反应或预水解的产物;
(d)或它们的混合物。
在一个实施方案中,用于涂覆的合适的前体选自四-C1-C4-烷氧基硅烷、三-C1-C4-烷氧基-C1-C4-烷基硅烷、三-苯基氧基-C1-C4-烷基硅烷、三-C1-C4-烷氧基-苯基-硅烷、二-C1-C4-烷氧基二-C1-C4-烷基硅烷、二-苯基-苯基氧基-C1-C4-烷基硅烷、二-C1-C4-烷氧基二-苯基-硅烷;铝、锆、锡或钛的卤化物、C1-C4-醇盐、羧酸盐,例如异丙醇铝、四氯化锆、四氯化钛、四丁醇钛。
其他合适的前体为乙烯基三-C1-C4-烷氧基硅烷、乙烯基三-苯基氧基硅烷、(甲基)丙烯酰氧基-C1-C4-烷氧基三-C1-C4-烷基硅烷、(甲基)丙烯酰氧基-C1-C4-烷基三-C1-C4-烷基硅烷、(甲基)丙烯酰氧基-C1-C4-烷基二-C1-C4-烷基-C1-C4-烷氧基硅烷、(甲基)丙烯酰氧基-C1-C4-烷基-C1-C4-烷基-C1-C4-二烷氧基硅烷,或(甲基)丙烯酰氧基-C1-C4-烷基三-C1-C4-烷氧基硅烷。
可向前体中加入基于前体的重量计1至10重量%的多元醇或碱金属(例如钠)的硅酸盐或偏硅酸盐,所述多元醇具有两个或更多个羟基和2至6个碳原子,例如二乙二醇、季戊四醇、新戊二醇、1,2-己二醇或1,6-己二醇。
对于具有至少两个烷氧基取代基的上述前体,该前体的烷氧基取代基可以相同或不同。对于具有至少两个烷基取代基的前体,烷基取代基可以相同或不同。
在前体的C1-C4-烷氧基取代基中,优选甲氧基、乙氧基和丙氧基。在前体的C1-C4-烷基取代基中,优选甲基、乙基和丙基。
料想水可溶胀的聚合物核颗粒中存在的残余水分足以使前体与颗粒接触时发生前体的水解,随后经水解的前体发生缩合反应,任选地包括与水可溶胀的聚合物核的官能团缩合。以这种方式,获得的水可溶胀的聚合物核通过共价键包覆有基本上连续的涂层,该涂层包封该水可溶胀的聚合物核。当然,可以根据需要添加另外的水。
在上述流化床涂覆法中特别有用的其他前体为碱金属的硅酸盐或偏硅酸盐,或其部分预反应或预水解的产物。
硅酸钠水溶液(Na2O·nSiO3)或硅酸钾水溶液(K2O·nSiO3)(通常为称为水玻璃)为优选的前体。摩尔比SiO2/Na2O或SiO2/K2O分别称为玻璃模量(n)并决定许多物理和化学特性,如溶液的pH和粘度。已发现模量为2至3.5且固含量为30至45重量%的钠水玻璃或模量为2至3.5且固含量为30至45重量%的钾水玻璃是有用的。
向前体中加入酸以最终实现至少部分转化为二氧化硅。合适的酸为pKa(在25℃下)≤5的水溶性(水溶性是指每1L水中溶解度≥100g的酸)无机和有机酸。这些酸的实例为盐酸、氢溴酸、硫酸、磷酸、硝酸、甲磺酸、甲苯磺酸、苯磺酸、甲酸、乙酸等。酸的浓度有利地≤1.5N,特别是≤1.2N。
二氧化硅前体和/或用于将二氧化硅前体转化为二氧化硅的酸通过将它们喷洒到流化床装置中的水可溶胀的聚合物核颗粒上来施用。
前体与酸的结合可有利地根据以下选择进行:
(1)将全部量的酸加入初始前体溶液中。酸的量使得溶液的pH仍在碱性范围(即,“8.5至9.5”)内。这样产生包含一种硅酸盐的预反应前体溶液,该硅酸盐中生成二氧化硅的缩合反应进一步提前,但未完成。然后,将这种前体溶液施用至水可溶胀的聚合物核颗粒,并完成生成二氧化硅网络的缩合反应。
(2)仅将一部分酸加入前体溶液中,然后将前体溶液施用至水可溶胀的聚合物核颗粒。酸的量使得溶液的pH仍在碱性范围(即,“10至12”)内。这实现了碱金属硅酸盐的部分缩合,其与使用全部量的酸的缩合相比缩合水平较低。然后,通过将前体溶液喷洒至运行的流化床装置中而将其施用至水可溶胀的聚合物核颗粒。然后,可通过将第二部分酸喷洒至运行的流化床装置中而使其与酸处理的前体溶液同时施用或随后施用。
(3)将未酸化的前体溶液施用至水可溶胀的聚合物核颗粒上,并通过将酸溶液喷洒到运行的流化床装置中来施用它们。这包括在已开始施用前体溶液之后的任何时间施用酸。在一个实施方案中,首先施用全部量的未酸化的前体溶液,随后施用全部量的酸,并且是在已施用未酸化的前体溶液后立即施用或在短时间后施用。在另一个实施方案中,从未酸化的前体溶液开始间歇地施用未酸化的前体溶液和酸。未酸化的前体溶液和酸可以在彼此之后立即施用或在特定的一段时间之后施用。
优选地,方法中所用酸的量使得前体相对于酸摩尔过量。前体与酸的摩尔比特别为2:1至10:1。
本发明还涉及如上定义的经涂覆的聚合物颗粒在油田、采矿、建筑化学组合物中或作为活性物质的载体的用途。
关于采矿或油田,本发明经涂覆的聚合物颗粒可用于吸收不希望的渗透水。
本发明的经涂覆的聚合物颗粒可用于油田中,例如以防止所谓的水锥进(waterconing)。锥进是一种生产问题,其中例如底部水渗透到近井区域中的孔射区域并且减少了石油产量。当引入至适当的区域时,本发明的经涂覆的聚合物颗粒可用于吸收所述渗透水。当已除去涂层时,例如在通过增加的压力将水扩散至聚合物核中之后,则水可溶胀的聚合物核可开始吸收足够量的水。
本发明的经涂覆的聚合物颗粒还可用于在采油操作期间控制一致性。一致性是在采油驱油操作期间所注入的驱动流体的注水前缘的均匀性以及注水前缘在垂直方向和平面方向上(当其通过储油器传输时)的均匀性的量度。所述一致性可能会受到渗透水的负面影响。本发明的经涂覆的聚合物颗粒可通过吸水有助于阻塞所述渗透通道。
本发明的经涂覆的聚合物颗粒还可以用作建筑化学组合物的添加剂,包括例如需要延时吸水的砂浆、混凝土。这可以有助于进行建筑化学组合物的延时流变学转换。
当引入至混凝土组合物中,本发明的经涂覆的聚合物颗粒可通过在合适的时间吸水而有助于改善抗冻性/抗冻融性。
此外,本发明的经涂覆的聚合物颗粒可在包封前负载作物保护化学品。在将所述负载颗粒沉积在所需区域之后,可以通过涂层的降解,例如通过将水扩散至聚合物核中来引发作物保护化学品的受控释放。
以下图和实施例旨在更详细地阐述本发明。
图1示出了两张本发明的经涂覆的聚合物颗粒(通过悬浮涂覆方法获得)的电子显微镜照片。上方的照片示出了经涂覆的颗粒的全貌,下方的照片示出了通过所述颗粒的横截面并且示出了聚合物核的连续涂层。
图2示出了实施例8的经涂覆的聚合物颗粒的电子显微镜照片。
图3示出了实施例9的经涂覆的聚合物颗粒的电子显微镜照片。
实施例1
共聚物1(阴离子超吸收性共聚物)
将600g石油溶剂油D40(购自Chemie,Germany)加入2L双夹套反应器中。在添加3g80(sorbitane monooleate,购自Sigma Aldrich,Germany)和稳定剂(丙烯酸烷基酯或甲基丙烯酸烷基酯与丙烯酸和甲基丙烯酸的共聚物)后,用氮气吹扫反应器90分钟,同时将混合物在300rpm的转速下搅拌。单体相在单独的容器中制备:向所述容器中加入水(7.2g)和160.81g(21.97摩尔%)2-丙烯酰胺基-2-甲基丙磺酸的钠盐(50重量%的水溶液),依次加入161.29g(70.99摩尔%)丙烯酰胺(50重量%的水溶液)、8.11g(7.01摩尔%)丙烯酸(99.5重量%的浓溶液)和4.04g(0.03摩尔%)亚甲基双丙烯酰胺(2.0重量%的浓溶液),并使用7.93g 50%的氢氧化钠溶液中和,以将pH调节至6.0。另外,将3.60g 4%的V50水溶液(2,2'-偶氮双(2-脒基丙烷)二盐酸盐;WAKO Chemicals)和3.60g 1%的亚硫酸氢钠水溶液加入水相中。将所述水相加入反应器中的油相中,并将油水混合物在300rpm的转速下分散2分钟。通过加入3.6g 0.5%的叔丁基过氧化氢的水溶液来引发聚合反应。将反应混合物搅拌30分钟。然后,共沸蒸馏出水(620rpm,50mPa,60℃)。过滤出所得聚合物珠粒,用丙酮洗涤并在干燥室中于40℃下干燥6小时。
实施例2
共聚物2(阴离子超吸收性共聚物)
在分开的玻璃烧杯中制备油相和水相。为了制备油相,使10.7g80(购自Sigma Aldrich,Germany)、35.6g稳定剂(丙烯酸烷基酯或甲基丙烯酸烷基酯与丙烯酸和甲基丙烯酸的共聚物)和295g石油溶剂油D40(脂族烃混合物,购自Chemie,Germany)混合。为了制备水相,使191.04g(22.01摩尔%)2-丙烯酰胺基-2-甲基丙磺酸的钠盐(50重量%的水溶液)、191.18g(70.94摩尔%)丙烯酰胺(50重量%的水溶液)、0.2gC(50%的二亚乙基三胺五乙酸、五钠盐的溶液,购自BASF SE,Germany)、4.79g(0.03摩尔%)亚甲基双丙烯酰胺(2.0重量%的浓溶液)和9.63g(7.02摩尔%)丙烯酸(99.5重量%的浓溶液)混合,并用23.84g 20%的氢氧化钠溶液中和,以将pH调节至6.0。然后,将5.6g水加入水相中。然后,使油相和水相在一个玻璃烧杯中混合并在10000rpm下均化1分钟。然后,将所得混合物加入2L双夹套反应器中并调节至15℃。在调节温度期间,在300rpm下用氮气吹扫反应器。通过滴加0.16g 0.5%的叔丁基过氧化氢的水溶液和0.16g 1.0%的SO2水溶液来引发聚合反应。以升温不超过1℃/分钟的标准来控制所述添加,直至最高反应温度达到40℃。通过在80℃下添加偶氮双(异丁腈)(24g 4重量%的甲醇溶液)并搅拌来降低未反应的丙烯酰胺的量。然后,共沸蒸馏出水。
实施例3
原位涂覆
将600g石油溶剂油D40(购自Chemie,Germany)加入2L双夹套反应器中。在添加80(3g,sorbitane monooleate,购自Sigma Aldrich,Germany)和稳定剂(丙烯酸或甲基丙烯酸的烷基酯与丙烯酸和甲基丙烯酸的共聚物)后,用氮气吹扫反应器90分钟,同时将混合物在300rpm的转速下搅拌。单体相在单独的容器中制备:向所述容器中加入水(7.2g)和160.81g(21.97摩尔%)2-丙烯酰胺基-2-甲基丙磺酸的钠盐(50重量%的水溶液),依次加入161.29g(70.99摩尔%)丙烯酰胺(50重量%的水溶液)、8.11g(7.01摩尔%)丙烯酸(99.5重量%的浓溶液)和4.04g(0.03摩尔%)亚甲基双丙烯酰胺(2.0重量%的浓溶液),并使用7.93g 50%的氢氧化钠溶液中和,以将pH调节至6.0。另外,将3.60g 4%的V50水溶液(2,2'-偶氮双(2-脒基丙烷)二盐酸盐;WAKO Chemicals)和3.60g 1%的亚硫酸氢钠水溶液加入水相。将所述水相加入反应器中的油相中并将油水混合物在300rpm的转速下分散2分钟。通过加入3.6g 0.5%的叔丁基过氧化氢的水溶液来引发聚合反应。将反应混合物搅拌30分钟。然后,共沸蒸馏出水(620rpm,50mPa,60℃)。
之后,在20℃下加入0.85g新戊二醇。然后注入SiCl4(17mL)并将混合物在300rpm搅拌12小时。过滤出所得经涂覆的聚合物珠粒,用丙酮洗涤并在干燥室中于40℃下干燥6小时。
实施例4
2-步涂覆
通过添加1.25g(购自Dow Chemical Company,USA)和150mL乙醇而将实施例1中获得的聚合物珠粒(5g)再分散于250mL三颈烧瓶中。在轻微搅拌下,加入异丙醇铝(1.25g)和四乙氧基硅烷(0.5mL)。搅拌12小时后,除去上清液,用乙醇洗涤由此获得的经涂覆的聚合物珠粒,并将其转移至装有50mL甲苯的容器中。然后加入SiCl4(5mL)。搅拌5小时(60℃)后,用己烷洗涤所得的具有双涂层的聚合物珠粒并在30℃下干燥。
实施例5
3-步涂覆
通过添加甲苯(50mL)而将实施例1中获得的聚合物珠粒(5g)再分散于250mL三颈烧瓶中。在轻微搅拌下,加入异丙醇铝(0.01g)和SiCl4(0.5mL)。搅拌12小时后,除去上清液,用己烷洗涤由此获得的经涂覆的聚合物珠粒并在30℃下干燥。重复该过程两次,以获得具有三层涂层的聚合物珠粒。
实施例6
保水试验
根据实施例3制备经涂覆的聚合物颗粒,并通过不同的涂覆循环重复次数来获得不同厚度的涂层。向单独的试管中加入所获得的颗粒(粒径:100至200μm,1g)和10mL水(Merck Millipore)并测定层厚度。表1表明增加层厚度提供增加的保水时间。保水时间是指在测量时间段内水可溶胀的聚合物核与周围水的接触被阻止。
保水时间测量:将30mg经涂覆的颗粒与1mL水一起加入试管中。摇动试管直至形成凝胶,这表明SiO2壳的破裂以及随后的SISA核的溶胀。从摇动试管到目测观察到凝胶形成的时间为保水时间。
表1
层厚度[μm] | 保水时间[分钟] |
0.375 | 5 |
0.395 | 8 |
0.416 | 15 |
0.488 | 100 |
0.375μm的层厚度提供5分钟的保水性。层厚度增加至大于400μm提供15分钟(0.416μm)或甚至是100分钟(0.488μm)的保水性。
对比实施例
根据实施例3的聚合方法制备水可溶胀的聚合物核。然而,在聚合反应后不进行涂覆步骤。通过过滤、洗涤和干燥来纯化所得聚合物核。根据实施例6的方法,将所述未涂覆的聚合物核(层厚=0μm)用于对比试验。所述对比试验提供小于1分钟的保水时间。
实施例7
通过反相悬浮聚合制备阳离子的水可溶胀的聚合物
将600g石油溶剂油D40加入2L双夹套反应器中。在添加3g Span80和5.0g MUV后,将混合物在300rpm的转速下用氮气吹扫90分钟。在单独的容器中制备含单体的水相。为此,首先引入23.3g水,并随后加入152.00g(28摩尔%)DIMAPA Quat水溶液(60重量%的水溶液)、161.30g(72摩尔%)丙烯酰胺(50重量%的水溶液)和4g(0.03摩尔%)亚甲基双丙烯酰胺水溶液(2重量%的水溶液),并用7.93g 50%的氢氧化钠溶液中和,以将pH调节至6。此外,将3.60g 4%的V50水溶液和3.60g 1%的亚硫酸氢钠水溶液加入水相中。将该水性溶液与反应器中的油相结合,并将油/水混合物在300rmp的转速下分散2分钟。通过添加3.6g0.5%的叔丁基过氧化氢的水溶液来引发聚合反应。将该批次搅拌30分钟。随后,在620rpm、50mPa和60℃下共沸蒸馏出水。过滤出聚合物珠粒,用丙酮洗涤并在干燥室中于40℃下干燥6小时。
实施例8
通过流化床涂覆法制备经涂覆的聚合物颗粒
使用水可溶胀的聚合物颗粒,其包含45.0重量%2-丙烯酰胺基-2-甲基丙磺酸、5.0重量%丙烯酸、49.9重量%丙烯酰胺和0.2重量%亚甲基双丙烯酰胺。
使用如下水玻璃:钠水玻璃,其包含8.8重量%Na2O、28重量%SiO2和63.2H2O,模量3.4,固含量38.2%;钾水玻璃,其包含12.5重量%K2O、26.7重量%SiO2和60.8重量%H2O,模量3.35,固含量39.2%。
通过使用水稀释上述水玻璃溶液(3份水玻璃,1份水)来制备二氧化硅前体溶液。然后,小心地加入62.5重量%的0.5M盐酸溶液(与先前制备的溶液的量相比)。
将水可溶胀的聚合物颗粒(445g)置于流化床装置(Co.Bosch Huetlin,TypeUnilab 1)中,其中将颗粒加热至80℃。然后,将二氧化硅前体溶液喷洒在颗粒上(进气口温度:80℃;出口温度:60℃;气体体积:160m3/h;微气候0.12巴;喷嘴压力:0.55巴)。总计,将1300g二氧化硅前体喷洒在445g颗粒上。最终,获得硅酸盐涂覆的SISA颗粒。
实施例9
将实施例8中使用的水可溶胀的聚合物颗粒(450g)置于流化床装置(Co.BoschHuetlin,Type Unilab 1)中,其中将颗粒加热至80℃。然后,将实施例8中使用的二氧化硅前体溶液喷洒在颗粒上(进气口温度:80℃;出口温度:55℃;气体体积:160m3/h;微气候0.15巴;喷嘴压力:0.55巴)。总计,将1300g二氧化硅前体喷洒在450g颗粒上。在另外喷洒200mL水用于均化和清洁喷嘴和桶之后,将500mL 1M盐酸以与之前相同的速率喷洒在颗粒上。最后,获得二氧化硅涂覆的水可溶胀的聚合物颗粒。
Claims (17)
1.经涂覆的聚合物颗粒,其包含:
(a)水可溶胀的聚合物核,所述水可溶胀的聚合物核包含共聚物,所述共聚物包含含磺基和/或含季铵基团的结构单元,和
(b)包封所述核的连续的涂层,所述涂层包含硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物,
其中以氧化物计的涂层与水可溶胀的聚合物核的质量比为0.002至小于1。
2.根据权利要求1所述的经涂覆的聚合物颗粒,其中水可溶胀的聚合物核包含共聚物P1和/或共聚物P2,所述共聚物P1包含含磺基和含酰胺基的结构单元,所述共聚物P2包含含季铵基和含酰胺基的结构单元。
3.根据权利要求2所述的经涂覆的聚合物颗粒,其中共聚物P1包含:
(i)式(I)的含磺酸的结构单元
其中
R1表示氢或甲基,
R2、R3和R4彼此独立地表示氢、C1-C6-烷基或C6-C14-芳基,
M表示氢、金属阳离子或铵阳离子,
a表示1或1/金属阳离子的化合价,和
(ii)式(II)的含(甲基)丙烯酰胺基的结构单元
其中
R1表示氢或甲基,
R5和R6彼此独立地表示氢、C1-C20-烷基、C5-C8-环烷基或C6-C14-芳基,和
(iii)衍生自具有两个或更多个烯键式不饱和乙烯基的单体的结构单元,和
(iv)任选地,衍生自具有一个烯键式不饱和乙烯基的单体的结构单元,该结构单元不同于结构单元(i)和(ii),
并且
共聚物P2包含:
(i)式(III)的阳离子结构单元
其中
R1表示氢或甲基,
R7、R8、R9 和R10彼此独立地表示氢、C1-C20-烷基、C5-C8-环烷基或C6-C14-芳基,
m表示1至6的整数,
X表示氧或N-R10,
Y- a表示卤素、C1-C4-烷基硫酸根、C1-C4-烷基磺酸根或硫酸根,
a表示½或1,和
(ii)式(II)的含(甲基)丙烯酰胺基的结构单元
其中
R1表示氢或甲基,
R5和R6彼此独立地表示氢、C1-C20-烷基、C5-C8-环烷基或C6-C14-芳基,和
(iii)衍生自具有两个或更多个烯键式不饱和乙烯基的单体的结构单元,和
(iv)任选地,衍生自具有一个烯键式不饱和乙烯基的单体的结构单元,该结构单元不同于结构单元(i)和(ii)。
4.根据权利要求3所述的经涂覆的聚合物颗粒,其中共聚物P1包含:
(i)10至70摩尔%的式(I)的结构单元,
(ii)29.99至89.99摩尔%的式(II)的结构单元,
(iii)0.01至1摩尔%的衍生自具有两个或更多个烯键式不饱和乙烯基的单体的结构单元,和
(iv)0至30摩尔%的衍生自具有一个烯键式不饱和乙烯基的单体的结构单元,
其中组分(i)、(ii)、(iii)和(iv)总计达100摩尔%,并且
共聚物P2包含:
(i)10至70摩尔%的式(III)的结构单元,
(ii)29.99至89.99摩尔%的式(II)的结构单元,
(iii)0.01至1摩尔%的衍生自具有两个或更多个烯键式不饱和乙烯基的单体的结构单元,和
(iv)0至30摩尔%的衍生自具有一个烯键式不饱和乙烯基的单体的结构单元,
其中组分(i)、(ii)、(iii)和(iv)总计达100摩尔%。
5.根据权利要求2至4中任一项所述的经涂覆的聚合物颗粒,其中水可溶胀的聚合物核包含共聚物P1和P2的混合物,其比例为99/1至85/15,以摩尔% P1/P2计,或1/99至15/85,以摩尔% P1/P2计。
6.根据权利要求1或2所述的经涂覆的聚合物颗粒,其中颗粒的数均直径为10至1000 µm。
7.根据权利要求6所述的经涂覆的聚合物颗粒,其中颗粒的数均直径为50至500 µm。
8.根据权利要求1或2所述的经涂覆的聚合物颗粒,其中涂层的平均层厚度为100至1000 nm。
9.根据权利要求1或2所述的经涂覆的聚合物颗粒,其平均球度为至少0.90,球度定义为SPHT = 4πA/U2,其中A表示颗粒的横截面积,U表示颗粒的横截面周长。
10.根据权利要求1或2所述的经涂覆的聚合物颗粒,其中涂层包含硅、铝、锆、锡或钛的氧化物或水合氧化物或其混合物。
11.根据权利要求10所述的经涂覆的聚合物颗粒,其中涂层包含硅、铝或锆的氧化物或其混合物。
12.一种制备权利要求1至11中任一项的经涂覆的聚合物颗粒的方法,包括以下步骤:
a)将水可溶胀的聚合物核颗粒悬浮于有机溶剂中,
b)向悬浮液中加入硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物的前体,以使反应性前体在颗粒溶剂相界面处布置,
c)将前体转化为硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物,和
d)获得水可溶胀的聚合物核,其涂覆有包封水可溶胀的聚合物的连续的涂层,
其中步骤b)和c)任选地重复一次、两次或三次至十次。
13.根据权利要求12所述的方法,其中有机溶剂选自具有一个、两个或更多个羟基的C1-C12-醇,芳族烃,脂族烃,以及它们的混合物。
14.一种制备权利要求1至11中任一项的经涂覆的聚合物颗粒的方法,包括以下步骤:
(a)使水可溶胀的聚合物核颗粒在流化气体料流中流化,
(b)使颗粒与硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物的前体的溶液或分散体接触,以使颗粒涂覆有反应性前体,
(c)使前体转化成硅、铝、锆、锡或钛的氧化物、氢氧化物或水合氧化物或其混合物,
(d)干燥经涂覆的颗粒。
15.根据权利要求12至14中任一项所述的方法,其中所述前体选自:
(a)四-C1-C4-烷氧基硅烷、三-C1-C4-烷氧基-C1-C4-烷基硅烷、三苯基氧基-C1-C4-烷基硅烷、三-C1-C4-烷氧基-苯基-硅烷、二-C1-C4-烷氧基二-C1-C4-烷基硅烷、二-苯基-苯基氧基-C1-C4-烷基硅烷、二-C1-C4-烷氧基二-苯基-硅烷;乙烯基三-C1-C4-烷氧基硅烷、乙烯基三苯基氧基硅烷、(甲基)丙烯酰氧基-C1-C4-烷氧基三-C1-C4-烷基硅烷、(甲基)丙烯酰氧基-C1-C4-烷基三-C1-C4-烷基硅烷、(甲基)丙烯酰氧基-C1-C4-烷基二-C1-C4-烷基-C1-C4-烷氧基硅烷、(甲基)丙烯酰氧基-C1-C4-烷基-C1-C4-烷基-C1-C4-二烷氧基硅烷、(甲基)丙烯酰氧基-C1-C4-烷基三-C1-C4-烷氧基硅烷;或其部分预反应或预水解的产物;
(b)铝、锆、锡或钛的卤化物、C1-C4-醇盐、羧酸盐;或其部分预反应或预水解的产物;
(c)碱金属的硅酸盐或偏硅酸盐;或其部分预反应或预水解的产物;
(d)或它们的混合物。
16.根据权利要求12至14中任一项所述的方法,其中前体的转化包括(i)通过水解和/或酸化前体来活化前体和(ii)使活化的前体进行缩聚反应。
17.根据权利要求1至11中任一项所述的经涂覆的聚合物颗粒在油田、采矿、建筑化学组合物中或作为活性物质的载体的用途。
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