CN101222977A - 含在低渗透率设备中分配的多孔材料内插入的活性相的吸气剂体系 - Google Patents

含在低渗透率设备中分配的多孔材料内插入的活性相的吸气剂体系 Download PDF

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CN101222977A
CN101222977A CNA2006800258712A CN200680025871A CN101222977A CN 101222977 A CN101222977 A CN 101222977A CN A2006800258712 A CNA2006800258712 A CN A2006800258712A CN 200680025871 A CN200680025871 A CN 200680025871A CN 101222977 A CN101222977 A CN 101222977A
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R·詹南托尼奥
C·韦斯科维
L·卡塔尼奥
G·隆戈尼
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Abstract

公开了一种吸气剂体系,它由在多孔材料(12)的孔隙(20,20`,...)内插入的对气体吸附具有活性的相(21,21`,21``,...)组成,所述孔隙转而分散在对待吸附的气体的渗透率低的聚合物设备(11)内。

Description

含在低渗透率设备中分配的多孔材料内插入的活性相的吸气剂体系
本发明涉及含在低渗透率设备中分配的多孔材料内插入的对气体吸附具有活性的相的吸气剂体系。
工业上,吸气剂材料和体系广泛用于其中需要通过吸收痕量非所需气体来维持真空或控制气体氛围组成,或者保护对特定的气体污染物敏感的器件的所有应用上。
广泛用于这一目的的吸气剂材料是多孔材料,例如尤其用于吸附有机物质的活性炭,或者用于吸附小尺寸的气体分子的沸石、二氧化硅或氧化铝。另一类尤其令人感兴趣的化合物由具体地吸附湿气的无水化学干燥剂组成,例如碱土金属的氧化物,或者一些吸湿的盐,例如氯化物(例如氯化钙CaCl2)、高氯酸盐(例如高氯酸镁Mg(ClO4)2)或硫酸盐(例如,硫酸钙CaSO4)。
许多这些材料的常见的一个问题是它们通常为粉末形式,不具有足以形成紧凑物体的内聚力;在干燥剂吸附湿气的情况下,这尤其是事实。这是与几乎所有可预见的工业应用的相关问题,要求不存在游离颗粒。
在一些情况下通过在可渗透的容器(例如,非织造织物外壳,正例如在涉及绝缘面板的专利US4668551中所示的)内部插入吸气剂材料来解决这一问题。
针对这一问题的另一可能的方法是在分散基体内分配吸气剂材料,所述分散基体能在固定的位置内保持吸气剂颗粒,同时使气体朝吸气剂本身流过。在许多文献中列出了第二种解决方法的实例。日本专利申请JP60-132274公开了在聚硅氧烷基体内分散的干燥剂材料;专利US3704806公开了一种干燥剂组合物,它包括在由热固性聚合物(例如环氧树脂等)形成的基体内分散的沸石;专利US4081397公开了一种干燥剂体系,它包括在弹性体聚合物内分散的碱土金属的氧化物颗粒;专利US5304419公开了一种干燥剂组合物,它包括在可由聚硅氧烷、聚氨酯或类似聚合物形成的基体内分散的干燥剂材料;专利US5591379公开了一种干燥剂组合物,它包括在多孔玻璃或陶瓷基体内分散的选自沸石、氧化铝、硅胶、碱土金属氧化物和碱金属碳酸盐中的干燥剂;专利US6226890B1公开了一种干燥剂体系,其中干燥剂材料(例如碱土金属氧化物)分散在聚合物,例如聚硅氧烷、环氧化物、聚酰胺、聚甲基丙烯酸甲酯或其他聚合物等内,该体系据认为在该专利中具有没有降低或者甚至增加通过干燥剂材料的水的吸附速度的性能;专利US6819042B2公开了一种干燥剂体系,它由在树脂,例如聚乙烯、聚丙烯、聚丁二烯或聚异戊二烯树脂内分散的干燥剂材料组成;最后,专利US6833668B1公开了减少湿气对有机发光显示器(OLED)的敏感组分影响的体系,该体系基于含干燥剂粉末的不可渗透的树脂阻挡层;通过作为密封OLED空腔的方式来使用,从而行使这一体系的阻挡功能。
在这些专利中公开的许多体系常见的一个限制是,对气体可渗透或者具有差的渗透率的基于分散基体的这些体系是由于与待吸附的气体反应导致的,吸气剂材料通常经历结构和形态的修正,例如溶胀,尤其在干燥剂的情况下,所述修正可能显著;在吸气剂材料的颗粒周围存在基体可阻碍这些形态的修正并抑制或延迟气体吸附反应。
另外,一些工业应用可强加其他要求到吸气剂体系上。例如,最新一代的OLED要求透明且在器件的整个寿命期间具有恒定的光学性能的吸气剂体系,所述整个寿命亦即就在制造之后不久(当吸气剂材料尚未吸附湿气,但含量最小时),在接近器件寿命的最后(当吸气剂器件已经吸附相对大量的湿气,甚至直到该体系饱和时)以及还在OLED寿命的中间步骤中,亦即当在基体内分散的各种吸气剂颗粒吸附不同量的湿气时;在OLED寿命期间,通过吸气剂颗粒吸收的不同水平的湿气可改变体系的光学性能,例如其透光率或折射指数,因此损害显示器的质量。例如在专利US6465953中讨论了这一问题,它公开了用于OLED的吸气剂体系,所述吸气剂体系由在透明基体内的吸气剂颗粒组成,其中该颗粒具有足够小的尺寸,以致于不与发光辐射线相互作用。考虑到这一应用的重要性,为了阐述本发明吸气剂体系的用途,尤其应当参考在OLED中的用途,但本发明的吸气剂体系具有一般的用途且也可在其他应用中使用。
本发明的目的是提供一种渗透率低的吸气剂体系,它能吸附渗透的气体物种。
根据本发明,采用包括下述物质的吸气剂体系将获得本发明的这一和其他目的:
-对待吸附的气体渗透差的聚合物设备(means);
-在该聚合物设备内分配的多孔材料粉末;
-在多孔材料的孔隙内对吸附一种或更多种气体具有活性的相。
以下参考附图描述本发明,其中:
-图1示出了本发明的吸气剂体系;
-图2示出了多孔材料粉末的一个颗粒;
-图3a和3b图示了在图2的颗粒孔隙内部发生的气体吸附反应。
本发明的吸气剂体系区别于现有技术在于,在气体的吸附中具有活性的材料没有直接分散在基体内,而是存在于“客体(guest)”相的孔隙内部,所述客体相为在基体内分散的粉末形式;这一特征将确保体系的物理性能相对于气体吸附来说基本上不变,例如尽管活性材料在气体吸附过程中可能经历形态修正,但这些修正没有透过单独的多孔颗粒之外,结果多孔颗粒与环境(基体)间的相互作用没有被修正。
关于已知的吸气剂体系,除了以上所列举的差别以外,本发明的体系还提供许多优点。首先,若分散的多孔材料具有良好限定的几何形状特征(例如,在该情况下,它是天然或合成沸石、富勒烯或类似物),则由于产物的位阻效应和/或由于对孔壁产生的尤其高的化学力导致它能将可逆反应或过程转化成不可逆的反应或过程,结果反应产物紧密地保持在孔隙内。另外,除了活性相以外,多孔材料还可接收催化剂,从而确保相互邻近,若活性相和催化剂是固体,则这种相互邻近是尤其明显的优势,和进而若在聚合物设备内自由分配,则它们将具有差的迁移率。最后,在其中多孔材料是沸石的情况下,沸石本身可充当宽泛的各类反应的催化剂(根据路易斯和/或布朗斯台德的酸或碱),从而支持活性相与待吸附的气体之间反应,正如所说明的。
在图1中,以一般的实施方案形式示出了本发明的体系;在这一情况下,以断面图(broken view)示出了短的平行六面体形式的体系10,但该体系可具有任何其他形状,例如带状物、点滴状(drop),或者可直接在必须控制其氛围的器件内表面上形成,例如为薄层形式,或者占据这一表面的凹陷。
吸气剂体系由聚合物设备11组成,其特征在于对待吸附的气体的渗透率低,多孔材料的粉末12分配在所述聚合物设备内。设备11可由对待吸附的气体物种的渗透率差的任何聚合物材料形成,优选这一聚合物显示出粘合剂特征,以便在没有使用额外粘合剂的情况下,它可固定到最终器件的内壁上。
聚合物设备11对气体的渗透率低还便于聚合物设备实现阻挡杂质进入该设备主体内的功能,从而限制必须通过活性相吸附的杂质量,及时延长吸气剂体系的效率和从而延长这种体系在其内使用的器件的寿命。低渗透率拟指渗透率不高于1×10-12(m(STP) 3·m2/bar·m3·s)(m(STP) 3表示在标准温度和压力下测量的气体的立方米)。
可用于本发明目的的适合于形成粉末12的多孔材料;例如是天然或合成沸石、硅质岩(即基本上不具有铝的沸石)、除了沸石以外的硅铝酸盐、富勒烯和有机金属框架(在本领域中更好地称为MOF,参见例如J.L.C.Roswell和O.M.Yaghi的文章“Metal-organic frameworks:a new class of porous materials(金属-有机框架,一组新的多孔材料)”,在“Microporous and Mesoporous Materials”中在线出版,no.73,p.3-14,2004年6月)。
图2图示了颗粒12的放大的截面视图:多孔材料的颗粒显示出对气体吸附具有活性的相在其内排列的孔隙20、20`,…;活性相用沉积物21、21`、21",…形式表示;在附图中,示出了最一般的情况,其中孔隙基本上为具有到达颗粒12表面的可变截面(在不同的孔隙之间以及在相同孔隙内的不同位置内)的通道形式,和沉积物21、21`、21",…粘合到孔隙内壁上;或者,例如在沸石情况下,孔隙具有通过晶体结构坚固地固定的尺寸,正如已知的所述晶体结构可显示出通过减少的截面通道互连的空腔,且活性相可简单地排列在空腔内,并没有键合到同一空腔的内表面上。
图3a和3b图示了本发明的吸气剂体系的操作机理;图3a在进一步放大的视图中示出了颗粒12和尤其活性相的沉积物21、21`,…存在于其内部的孔隙20的细节,同时用30表示待吸附的气体物种分子;在其运动过程中,分子30接触沉积物21、21`,…,并与它们反应,从而根据特定结合的气体分子/活性相的组分性质的不同机理,固定在沉积物上或者通过沉积物固定;通过图3b由“修正”沉积物31、31`,…示出了这一情况,在沸石情况下,如前所述,活性相可以不以沉积物形式存在,而是以“捕获”在沸石空腔内的颗粒形式存在,且与分子30反应的产物转而为捕获在该空腔内的物种形式。
活性相的化学性质取决于待吸附的所需物种。例如,在待吸附的物种为氧气的情况下,活性相可由容易氧化的金属,例如碱金属、碱土金属或其他金属,例如铁、锡和铜;氧化态低的金属氧化物,例如锰或铜的氧化物;具有亚磷酸盐或亚膦酸盐阴离子的盐;或可容易氧化的有机化合物,例如酚类、仲芳胺、硫醚或醛类等形成。在一氧化碳吸附的情况下,可使用与这一气体形成复杂物种的金属,如镍或铁的沉积物,或者在锂基有机金属化合物存在下的链烯烃、胺和酮。在二氧化碳的情况下,活性相可以是碱金属或碱土金属的氢氧化物。在其中需要吸附氮气的(不同寻常的)情况下,可使用无机材料,例如锂、钡或化合物BaLi4或卟啉,亦即能将这一气体固定到络合物的中心金属原子上的金属有机分子。
然而,最常见和重要的情况是除湿。为此,活性物种可选自根据不同吸附机理起作用的广谱材料,正如以下列举物所概述的:
-添加水的材料:属于这一组的有环氧化物;具有双键或三键的有机分子(活化);碱金属氧化物,碱土金属氧化物或假碱土金属(即基本上为镍、锌和镉)的氧化物;有机(例如邻苯二甲酸酐)和无机(例如硼酸酐)酸酐;
-经历水解或亲核取代的材料:属于这一组的有例如一些醇盐(例如醇铝Al(OR)3),一些卤化物,例如AlCl3,通式为RCOX(其中X为卤素原子)的酰卤(和尤其酰氯),或者形成碳阳离子的化合物;
-与水、其分解产物反应和形成或者固体溶液的氧化物和氢化物的材料;这些材料的实例是涉及与水反应的铁,而涉及氢气吸附的是钇、钯或其混合物;
-通过水溶剂化的材料,例如硫酸镁,或存在于沸石内的金属中心,以便补偿因铝导致的损失电荷。
在优选的实施方案中,本发明的吸气剂体系具有在其整个寿命器件对可见光辐射透过的进一步的性能,正如前面所述;按照这一模式,本发明的体系适合于应用到前面援引的OLED类型的屏幕上。
这些优选的吸气剂体系包括:
-对待吸附的气体具有低渗透率的无定形聚合物设备;
-在聚合物设备内分配的多孔材料的粉末,其中粉末颗粒的平均粒度小于100纳米;
-在多孔材料的孔隙内对吸附一种或更多种气体具有活性的相。
在这一优选的实施方案中,作为额外的特征,体系中各组分显示出下述事实:聚合物设备为无定形,而在聚合物设备内分散的多孔材料纳米尺寸化,它由尺寸数量级为小于或等于约100纳米的颗粒形成。这两个额外的要求中的第一个的原因是仅仅若完美结晶或完全无定形,则聚合物透明:由于基本上不可能获得完美结晶的聚合物,特别是在其中粉末必须分散在设备内的本发明的情况下,因此需要求助于完全无定形的聚合物。第二个要求来自于下述事实:尺寸小于可见光辐射波长一半的颗粒不会引起与它的相互作用,于是不会改变聚合物设备的透明度。
适合于制备渗透率低和透明设备的聚合物例如是聚氯乙烯(PVC)、聚苯乙烯(PS)、聚(甲基)丙烯酸甲酯(PMMA)、丙烯腈-丁二烯-苯乙烯的共聚物(ABS)、共聚的环烯烃、聚砜、聚醚砜(PES)和尤其聚芳醚砜、与聚偏氟乙烯的共聚物,与聚六氟异丁烯的共聚物,与聚乙烯的共聚物,与聚全氟二甲基间二氧杂环戊烯的共聚物、氯化聚酰胺、聚酰亚胺(PI)、氟化聚酰亚胺(FPI)、聚碳酸酯(PC)、聚对苯二甲酸乙二酯(PET)、丙烯酸类树脂、环氧树脂、聚氨酯(PU)、聚四氟乙烯(PTFE)和液晶聚合物(LCP)。
一般地,为了获得低渗透率设备,所援引的聚合物及其制造方法优选选自允许获得聚合物设备最小自由体积、聚合物链的最小有序和规则度、最大交联速度、最大堆积密度和与渗透物种最小相互作用的那些。
除了已经援引的组分以外,本发明的体系还可含有改进一些性能或支持实现这些性能的额外的元素。
例如,在多孔材料的孔隙内,可存在能促进待吸收的物种与活性相之间反应的催化剂,例如在不饱和有机分子通过加成到双键或三键上吸附水的情况下,催化剂可以是根据路易斯或布朗斯台德的酸或碱;金属,如铂和钯可催化氢气的吸附,其他金属,如镍、铁、铑、钌、铜或银也可通过形成牵涉有机化合物和/或气体的配位化合物,和通过氧化还原机理,催化其中牵涉有机化合物和气体的各种反应。
为了降低吸气剂体系的渗透率,可添加的其他元素是由无机材料,例如二氧化硅、氧化铝、硅铝酸盐、氧化钨、氧化锌、二氧化锡、氧化钛等形成的纳米尺寸的颗粒以及通常在本领域中称为“小片(platelets)”的颗粒(参见例如,在Materials Science andEngineering,vol.C23(2003),p763-772中出版的H.Fischer的文章“Polymer nanocomposites:from fundamental research to specificapplications”(聚合物纳米复合材料:从基础研究到具体应用));所述纳米尺寸的颗粒的功能是延迟扩散并改进杂质的均匀分布。
可通过在多孔材料内预浸渍活性相,然后在聚合物设备内形成如此浸渍的多孔材料的悬浮液,从而生产本发明的体系,如果其具有足够低粘度的话。或者,可制备浸渍的多孔材料颗粒在溶剂内的悬浮液,其中它还可增溶聚合物。合适的溶剂取决于所选的聚合物且是有机化学中众所周知的;溶剂的实例是氯仿、丙酮、二甲基甲酰胺和二甲亚砜(对于聚亚芳基醚砜来说);硝基苯和三氯乙酸(对于PET来说)。或者,可在活性相预浸渍的多孔材料和聚合物前体(例如,将形成聚合物的低聚物或单体)之间形成悬浮液,并例如通过用UV辐射辐照,引起就地形成聚合物。为了稳定悬浮液,还可向其中添加有机化学中众所周知且不要求进一步说明的合适的表面活性剂。多孔材料的粉末已经存在于其内部的起始溶液(若它含有聚合物或其前体)或低粘度聚合物可倾倒在合适的模具内,或者直接倾倒在最终的外壳内,例如倾倒在OLED屏幕的合适的内表面上;一旦液体混合物倾倒在所需的外壳内,则可通过提取溶剂,就地聚合,使它“硬化”(称为“固体”,在此情况下,材料具有非常高的粘度,以便维持给定形状),或者若通过冷却来维持熔融状态的聚合物,来给予低粘度。

Claims (23)

1.用于吸附一种或更多种气体的吸气剂体系(10),它包括:
-对待吸附的气体渗透性差的聚合物设备(11);
-在聚合物设备内分配的多孔材料的粉末(12);
-在多孔材料的孔隙(20,20`,…)内吸附一种或更多种气体方面具有活性的相(21,21`,21",…)。
2.权利要求1的吸气剂体系,其中所述渗透性差的聚合物设备显示出不高于1×10-12m3(STP)m-3bar-1m2s-1的渗透率值。
3.权利要求1的吸气剂体系,其中多孔材料选自天然或合成沸石、硅质岩、硅铝酸盐、富勒烯和金属有机框架。
4.权利要求1的吸气剂体系,其中当待吸附的气体是氧气时,活性相选自可容易氧化的金属、氧化态低的金属氧化物、具有亚磷酸盐或亚膦酸盐阴离子的盐,和可容易氧化的有机化合物。
5.权利要求4的吸气剂体系,其中所述可容易氧化的金属选自碱金属、碱土金属或其他金属,例如铁、锡和铜。
6.权利要求4的吸气剂体系,其中所述氧化态低的金属氧化物选自锰和铜的氧化物。
7.权利要求4的吸气剂体系,其中所述可容易氧化的有机化合物选自酚类、仲芳胺、硫醚和醛类。
8.权利要求1的吸气剂体系,其中当待吸附的气体是一氧化碳时,活性相选自镍、铁,在锂基有机金属化合物存在下的链烯烃、胺和酮。
9.权利要求1的吸气剂体系,其中当待吸附的气体是二氧化碳时,活性相是碱金属或碱土金属的氢氧化物。
10.权利要求1的吸气剂体系,其中当待吸附的气体是氮气时,活性相选自锂、钡、化合物BaLi4和卟啉。
11.权利要求1的吸气剂体系,其中当待吸附的气体是水时,活性相选自环氧化物;具有双键或三键的有机分子;碱金属氧化物,碱土金属氧化物,或镍、锌和镉的氧化物,和有机或无机酸酐,以及形成碳阳离子的化合物;醇盐;可水解的无机卤化物和酰卤;铁与钇或钯的混合物;和硫酸镁。
12.权利要求1的吸气剂体系,其特征在于当吸附的气体量变化时,维持透明度,它包括:
-对待吸附的气体的渗透性差的无定形聚合物设备;
-在聚合物设备内分配的多孔材料的粉末,其中粉末颗粒的平均粒度小于100纳米;
-在多孔材料的孔隙内吸附一种或更多种气体方面具有活性的相。
13.权利要求12的吸气剂体系,其中所述聚合物设备选自聚氯乙烯(PVC)、聚苯乙烯(PS)、聚(甲基)丙烯酸甲酯(PMMA)、丙烯腈-丁二烯-苯乙烯的共聚物(ABS)、共聚的环烯烃、聚砜、聚醚砜(PES)、与聚偏氟乙烯的共聚物,与聚六氟异丁烯的共聚物,与聚乙烯的共聚物,与聚全氟二甲基间二氧杂环戊烯的共聚物、氯化聚酰胺、聚酰亚胺(PI)、氟化聚酰亚胺(FPI)、聚碳酸酯(PC)、聚对苯二甲酸乙二酯(PET)、聚硅氧烷和液晶聚合物(LCP)。
14.权利要求1或12任何一项的吸气剂体系,它进一步在所述孔隙内含有能加速待吸附的气体和活性相之间反应的催化剂。
15.权利要求1或12任何一项的吸气剂体系,它包括无机材料负载,用于降低所述聚合物设备气体渗透率。
16.权利要求15的吸气剂体系,其中所述负载以纳米尺寸形式置于所述聚合物设备中。
17.权利要求14的吸气剂体系,其中所述催化剂选自铂、钯、镍、铁、铑、钌、铜和银。
18.权利要求14的吸气剂体系,其中所述催化剂是根据路易斯或布朗斯台德的酸或碱。
19.制备权利要求1或12的吸气剂体系的方法,该方法包括下述步骤:在多孔材料内预浸渍活性相;和直接在聚合物设备内形成如此浸渍的多孔材料的悬浮液。
20.制备权利要求1或12的吸气剂体系的方法,该方法包括下述步骤:在多孔材料内预浸渍活性相;在液体内形成如此浸渍的多孔材料的悬浮液,所述液体是聚合物设备的溶剂;在该悬浮液内溶解拟形成聚合物设备所使用的聚合物;和除去溶剂。
21.权利要求20的方法,其中当聚合物是聚亚芳基醚砜时,所述溶剂选自二甲基甲酰胺和二甲亚砜;和当聚合物是PET时,所述溶剂选自硝基苯和三氯乙酸。
22.制备权利要求1或12的吸气剂体系的方法,该方法包括下述步骤:在多孔材料内预浸渍活性相;在液体内形成如此浸渍的多孔材料的悬浮液,所述液体是拟形成聚合物设备所使用的聚合物前体用溶剂;在所述悬浮液内溶解所述前体;引起所述前体在悬浮液内聚合;和除去该溶剂。
23.权利要求20或22任何一项的方法,其中通过添加表面活性剂稳定所述悬浮液。
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KR100979322B1 (ko) 2010-08-31
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