CN1509298A - 多功能自动修复的复合材料 - Google Patents

多功能自动修复的复合材料 Download PDF

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CN1509298A
CN1509298A CNA02808120XA CN02808120A CN1509298A CN 1509298 A CN1509298 A CN 1509298A CN A02808120X A CNA02808120X A CN A02808120XA CN 02808120 A CN02808120 A CN 02808120A CN 1509298 A CN1509298 A CN 1509298A
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matrix material
capsule
polymkeric substance
polymerizing agent
catalyst
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斯科特·R·怀特
R
南茜·R·索托斯
H
菲利普·H·格贝尔
S���¶�
杰弗里·S·穆尔
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苏雷什·R·斯里拉姆
迈克尔·R·凯斯勒
N
埃里克·N·布朗
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University of Illinois
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Abstract

复合材料包含聚合物、聚合剂、聚合剂的相应催化剂和许多胶囊。聚合剂在胶囊中。复合材料是自修复的。

Description

多功能自动修复的复合材料
联邦政府赞助研究或开发
本申请课题部分由美国空军(Air Force)(AFOSR Grant No.F49620-00-1-0094/White)资助。政府对本发明拥有部分权利。
技术领域
本发明涉及自修复复合材料。
背景技术
在从微电子领域到复合材料飞机机翼中广泛使用的热固性聚合物很容易受裂纹的损害。通常这些裂纹在结构的深层形成，很难检测出，并且事实上不可能修复。在纤维增强聚合物复合材料中，纤维基质界面剥离、脱层和单纯基质裂化形式的裂纹会导致材料的降解。在微电子领域中，聚合物胶囊和聚合物基复合印刷电路板也会遭受相似形式的损害，但是除了机械故障外，裂纹还会引起元件的电学故障。由热或机械疲劳诱发的微小裂纹在聚合物添加剂中是一个长期存在的问题。不考虑应用，一旦裂纹已经在聚合物材料中形成，就会明显危害结构的完整性。典型地，先前报道的成功修复裂纹的方法需要某种形式的手动干预。
建议的自修复方法在以下文献中已有描述：“Self-HealingComposites Using Embedded Microspheres”D.Jung et al. Composites and Functinnally Gradde Materials vol.MD-80，in Proceedings of theASME International Mechanical Engineering Conference and Exposition，265-275(1997)。所提出的方法使用聚甲醛脲(PMU)微球来储存要释放入裂纹中并且再粘接裂纹面的裂纹填充剂。修复机理使用在聚酯基质网络中天然存在的官能位置来引发修复行为。特别研究了添加反应性组分来引发裂纹填充剂固化的方法在内含环氧化物组分和内含氨基的情况，并且发现氨基不会保留足够的活性，因此确定这种方法是不可行的。所使用的PMU微胶囊含有环氧化物单体。
发明内容
第一方面，本发明涉及一种包含聚合物、聚合剂、聚合剂的相应催化剂和许多胶囊的复合材料。聚合剂在胶囊中。
第二方面，本发明涉及一种包含聚合物、聚合剂、聚合剂的相应活化剂和许多胶囊的复合材料。聚合剂在胶囊中，并且相应的活化剂没有自然活化部分。
第三方面，本发明涉及一种制备上述复合材料的方法，包括将胶囊和相应催化剂或活化剂分散到聚合物中。
定义
聚合剂是指与该聚合剂的相应活化剂接触时形成聚合物的组合物。聚合剂的实例包括聚合物的单体，例如苯乙烯、乙烯、(甲基)丙烯酸酯和双环戊二烯(DCPD)；多元聚合物的单体，例如二醇、二胺和环氧化物，以及预聚物，例如仍能进一步聚合的部分聚合单体。
活化剂是与聚合剂接触或混合时形成聚合物的任何物质。活化剂的实例是催化剂、引发剂和天然的活化片段。聚合剂的相应活化剂是指与特定聚合剂接触或混合时形成聚合物的活化剂。
催化剂是指引发可聚合组合物聚合的化合物或片段，并且每次引发聚合时并不总是消耗。这一点不同于引发剂和天然活化片段。催化剂的实例包括开环聚合(ROMP)催化剂，例如Grubbs催化剂。聚合剂的相应催化剂是指与特定聚合剂接触或混合时形成聚合物的催化剂。
引发剂是引发可聚合组合物聚合的化合物，并且每次引发聚合时并不总是消耗。引发剂的实例是过氧化物(形成自由基引发不饱和单体聚合)；多单体聚合物的单体，例如二醇、二胺、环氧化物和胺(与环氧化物形成聚合物)。聚合剂的相应引发剂是指与特定聚合剂接触或混合时形成聚合物的引发剂。
天然活化片段是与聚合剂混合或接触时形成聚合物的聚合物片段，并且每次引发聚合时并不总是消耗。天然活化片段的实例是胺的片段(与环氧化物形成聚合物)。
化合物指包含至多100个重复单元的分子，这不同于包含多于100个重复单元的聚合物。
胶囊指长径比为1∶1到1∶10的中空封闭体。胶囊的长径比指最短轴与最长轴的比，这些轴都是垂直的。胶囊可以是在该长径比范围内的任何形状，例如球形、环形，或者不规则的变形形状。胶囊的表面可以是任何结构，例如粗糙或平滑。
附图说明
本发明的许多其它目标、特征和伴随的优点将从结合相关附图的详细说明中变得更容易理解，附图中，参照特征指出了贯穿几个视角的类似或相应部分，其中：
图1说明了自修复复合材料的一个实施方案。
图2表示复合材料的裂纹修复效率。
具体实施方式
由发表了“Self-Healing Composites Using EmbeddedMicrospheres”的研究组进行的进一步研究发现使用天然的功能性实际上是不可行的。先前已经排除的途径被再次考虑，导致发现不使用相应天然活化片段的体系可以是一种自修复复合材料。优选地，使用向聚合物中添加催化剂的体系。不仅可以修复复合材料的损害，而且在某些情况下实现的修复强度高于原始基质材料的强度。
本发明包括在聚合物中包含胶囊的复合材料。胶囊包含聚合剂并且复合材料包括不是相应天然活化片段的催化剂。优选地，活化剂是聚合剂的相应催化剂。当裂纹在复合材料中形成时，一些胶囊被打破，聚合剂进入裂纹中，随之与引发剂接触并形成聚合物，从而修复了裂纹。
胶囊包含聚合剂。聚合剂包含可聚合的化合物，例如单体或预聚物，并且任选包含其它组分，例如其它单体和/或预聚物、稳定剂、溶剂、诸如聚合物的粘度改性剂、增香剂、着色剂和染料、起泡剂、抗氧化剂，以及共催化剂。优选地，聚合剂是液体。
聚合物包含胶囊和聚合剂的相应活化剂。优选地，活化剂是催化剂或引发剂。可聚合化合物的实例是环烯烃，优选地含有4-50个碳原子并且任选地含有杂原子，例如DCPD、取代的DCPD、降冰片烯、取代的降冰片烯、环辛二烯和取代的环辛二烯。它们的相应催化剂是开环异位聚合(ROMP)催化剂，例如Schrock催化剂(Bazan，G.C.；Schrock，R.R.；Cho，H.-N.；Gibson，V.C.Macromolecules 24，4495-4502(1991))和Grubbs催化剂(Grubbs，R.H.；Chang，S.Tetrahedron 54，4413-4450(1998))。
可聚合化合物的另一个实例是内酯如己内酯以及内酰胺，它们在聚合时分别形成聚酯和尼龙。这些化合物的相应催化剂是环酯聚合催化剂和环酰胺聚合催化剂，例如三氟磺酸钪。
此外，聚合剂可以包含可聚合的化合物和双组分催化剂的一组分，同时相应的引发剂是双组分催化剂的另一组分。举例来说，可聚合化合物可以是环烯烃，双组分催化剂之一可以是钨化合物，例如有机铵的钨酸盐、有机鉮的钨酸盐，或有机鏻的钨酸盐，或者可以是钼的化合物，例如有机铵的钼酸盐、有机鉮的钼酸盐，或有机鏻的钼酸盐。双组分催化剂的第二组分可以是烷基铝化合物，例如烷氧基烷基卤化铝、芳氧基烷基卤化铝，或者金属氧烷基卤化铝，其中化合物中金属是锡、铅或铝；或者有机锡化合物，例如四烷基锡、三烷基锡的氢化物或三芳基锡的氢化物。
在另一种体系中，可聚合化合物可以是不饱和化合物，例如丙烯酸酯、丙烯酸、丙烯酸烷基酯、烷基丙烯酸、苯乙烯、异戊二烯和丁二烯。在此情况下，可以使用原子转移自由基聚合(ATRP)，其中两组分之一与可聚合化合物混合，并且另一个起引发剂的作用。一个组分是有机卤化物，例如1-氯-1-苯乙烷，而另一组分可以是铜(I)源，例如铜(I)的联吡啶络合物。或者，一个组分可以是过氧化物，例如过氧化苯甲酰，而另一组分可以是硝酰基前体，例如2，2，6，6-四甲基哌啶基-1-氧(TEMPO)。这些体系在文献Malcolm P.Stevens；PolymerChemistry：An Introduction，3rd Edition；New York：Oxford UniversityPress，1999，p.184-186中描述。
在另一种体系中，可聚合化合物可以包含带有羟基官能团(-OH)的异氰酸酯官能团(-N＝C＝O)。对于这类体系，举例来说可聚合材料可以是含有异氰酸酯基团和羟基基团的化合物，或者是两种不同化合物，一个含有至少两个异氰酸酯基团而另一个至少含有两个羟基基团。异氰酸酯基团与羟基基团发生反应，在化合物间形成氨基甲酸酯连接(-N-C(＝O)-O-)，可能释放出二氧化碳。二氧化碳可用于生产可膨胀的聚氨酯泡沫，任选地聚合剂可以包含起泡剂，例如诸如二氯甲烷的挥发性液体。在此情况下，可以使用缩聚，两组分之一与可聚合化合物混合，另一个起着引发剂的作用。举例来说，一个组分可以是诸如2-乙基己酸亚锡的烷基锡化合物，而另一组分是诸如二氮杂双环[2.2.2]辛烷(DABCO)的四级胺。这些体系在文献Malcolm P.Stevens；Polymer Chemistry：An Imtroduction，3rd Edition；New York：OxfordUniversity Press，1999，p.378-381中描述。
任选地，活化剂，例如催化剂或引发剂可以在胶囊的隔离体中。此外，这种胶囊的隔离体可以包含稳定剂、溶剂、诸如聚合物的粘度改性剂、增香剂、着色剂和染料、起泡剂、抗氧化剂，以及共催化剂。任选地，胶囊体中可以包含一种或多种添加组分，例如稳定剂、溶剂、诸如聚合物的粘度改性剂、增香剂、着色剂和染料、起泡剂、抗氧化剂，以及共催化剂。
胶囊包含聚合剂。优选地，胶囊具有10nm到1mm的平均直径，优选地为30-500μm，最优选地为50-300μm。胶囊具有1∶1到1∶10的长径比，优选地为1∶1到1∶5，更优选地1∶1到1∶3，甚至更优选地为1∶1到1∶2，并且最优选地为1∶1到1∶1.5。
胶囊的壁厚优选地为100nm到3μm。胶囊壁厚的选择取决于复合材料中的聚合物。举例来说，太厚的胶囊壁在裂纹接近时不会破裂，而壁太薄的胶囊在加工期间会破裂。
胶囊和复合材料的聚合物间的粘附将影响在存在裂纹时胶囊是否破裂或脱粘。为了促进聚合物和胶囊壁间的粘附，可以使用许多硅烷偶合剂。典型地，它们是通式为R-SiX3的化合物。其中R优选地是由丙烯基与硅隔开的反应性基团R1，并且X是烷氧基(优选地是甲氧基)，例如R1CH2CH2CH2Si(OCH3)3。实例包括购自DOW CORNING的硅烷偶合剂(带有后面圆括号内的反应基团)：Z6020(二氨基)、Z6030(甲基丙烯酸酯)、Z6032(苯乙烯胺阳离子)、Z6040(环氧基)和Z6075(乙烯基)。
为了增加复合材料中胶囊和聚合物间的粘附，胶囊可以通过在偶合剂溶液中洗涤的方法来处理。举例来说，脲-甲醛胶囊可以在硅烷Z6020或Z6040和己烷的溶液(1∶20wt.)中洗涤，接着向聚合物中加入硅烷Z6032(1％wt.)。
胶囊可以由许多技术和由许多材料来制备，例如下列文献所述：Microencapsulation：Methods and Industrial Applications Ed.Benita，Simon Marcel Dekker，New York，1996；Microencapsulation：Processesand Applications Ed.Vandegaer，J.Plenum Press，New York，1974；andMicrocapsule Processing and Technology Kondo，A.Marcel Dekker，New York，1979。制备胶囊的材料和制备技术的实例包括：脲-甲醛，由原位聚合形成；明胶，由络合物凝聚形成；聚脲，由异氰酸酯与联胺或三胺反应形成，取决于所要的交联度(交联程度也确定胶囊的脆性)，以及聚酰胺，由使用适当的酸性氯化物和水溶性三胺形成。
聚合物可以是任何可以分散入胶囊内的聚合材料。其实例包括聚酰胺如尼龙；聚酯如聚(对苯二甲酸乙二酯)和聚己内酯；聚碳酸酯；聚醚如环氧化物；聚酰亚胺如聚均苯四酰亚胺(例如KAPTAN)；酚醛树脂(例如BAKELITE)；胺甲醛树脂如三聚氰胺树脂；聚砜；聚(丙烯腈-丁二烯-苯乙烯)(ABS)；聚氨基甲酸酯；聚烯烃如聚乙烯、聚苯乙烯、聚丙烯腈、乙烯类聚合物、聚氯乙烯、聚(DCPD)和聚(甲基丙烯酸甲酯)；聚硅烷，比如聚(碳硼烷-硅氧烷)；以及聚磷腈。
胶囊和活化剂(例如催化剂或引发剂)可以通过在胶囊和活化剂周围形成聚合物的方法分散到聚合物中，例如通过聚合单体来与混合入单体中的胶囊和活化剂形成聚合物。尤其是在催化剂的情况下，催化剂可以用作聚合物的催化剂以及胶囊中聚合剂的相应活化剂。此体系的实例包括DCPD作为聚合剂，聚合物是聚(DPCD)，而且Grubbs催化剂用于形成聚(DPCD)并在胶囊中用作DCPD的活化剂；以及己内酯作为聚合剂，聚合物是聚(己内酯)，而且三氟磺酸钪在胶囊中用作己内酯的活化剂。
或者，聚合物可以先形成，而后混合胶囊和活化剂。举例来说，聚合物可以溶解在溶剂中并且将胶囊和活化剂混合到溶液中，接着除去溶剂。在将胶囊分散入聚合物前，活化剂可以涂布到胶囊上。另外，可以向聚合物中加入其它的组分，例如纤维、填料、粘附改性剂、起泡剂、抗氧化剂、着色剂和染料，以及增香剂。
图1说明了自修复复合材料的一个实施方案。邻近的裂纹使内含的胶囊(图中称作微胶囊)破裂，从而通过毛细管作用向裂纹平面释放聚合剂(图中称作修复剂)。修复剂的聚合可以通过与活化剂(此处是催化剂)接触来引发，从而粘合裂纹表面。损害诱导引发的机理提供了修复的位置特异性自动控制。如图1所示，内嵌的修复剂被包含在含有能聚合修复剂的催化剂的结构复合基质中：(i)基质中裂纹在损伤发生的地方形成，(ii)裂纹使微胶囊破裂，通过毛细作用向裂纹平面释放修复剂，(iii)修复剂与引发聚合的催化剂接触，引发聚合使裂纹平面粘接并闭合。
实施例
下面提供的实施例和制备方法仅是用来进一步说明本发明的。
本发明的范围并不是仅由下面的实施例构成。
由原位聚合制备胶囊的一般程序
在600毫升的烧杯中，将脲(0.11摩尔，7.0克)、接着将间苯二酚(0.5克)和氯化铵(0.5克)溶解在水中(150毫升)。向反应混合物加入乙烯马来酐共聚物的5wt.％溶液(100毫升)，并且用10％的NaOH溶液调节反应混合物的pH值到3.5。反应混合物在454rpm的转速下搅拌，并且向搅拌的溶液中加入60毫升的二环戊二烯，得到平均200μm大小的液滴。向搅拌的微乳液中加入37％的甲醛(0.23摩尔，18.91克)溶液，并且升高反应混合物的温度到50℃并维持2小时。2小时后，向反应混合物中加入200毫升水。4小时后，反应混合物被冷却至室温，并且分离胶囊。胶囊的浆料用另外200毫升的水稀释并用水(3×500毫升)洗涤。胶囊真空过滤分离，并在空气中干燥，产率：80％。平均尺寸：220μm。
复合环氧树脂试样的生产
环氧基质复合材料通过混合100份EPON 828(Shell ChemicalsInc.)环氧化物与12份DETA(二亚乙基三胺)固化剂(Shell ChemicalsInc.)来制备。复合环氧树脂试样通过混合2.5％(重量比)Grubbs催化剂和10％(重量比)带有上述树脂混合物的胶囊来制备。然后，树脂被倒入硅橡胶模中并在室温下固化24小时，接着在40℃进行后固化处理24小时。
实例
DCPD填充的带有脲甲醛壳的胶囊(50-200μm的平均直径)使用标准的微囊包封技术来制备。胶囊的壳层在催化剂和DCPD间提供了保护层，从而在制备复合材料间阻止其聚合。
DCPD的聚合反应机理如下所示
为了评价这些复合材料的裂纹修复效率，使用锥形双悬臂梁(TDCB)试样进行断裂试验(图2)。制备自修复复合材料和对照样品。对照样品由下列组成：(1)不含Grubbs催化剂或胶囊的纯环氧树脂，(2)含Grubbs催化剂但不含胶囊的环氧树脂，(3)含胶囊但不含Grubbs催化剂环氧树脂。通过将剃刀片轻敲入模制起始物切口中的方法产生尖的前裂纹。如图2所示，用销负荷夹具在垂直于前裂纹(模式I)的方向施加负荷。从裂纹蔓延和试样损坏的临界负荷来确定初始断裂韧度。损坏后，移去负荷并且允许裂纹在室温下修复而无人工干预。在48小时后重复断裂试验来定量修复的量。
典型的负荷-位移曲线如图2所示，表明约75％的初始断裂负荷恢复了。在大量的对照试验中，所有三种类型的对照样品没有表现出修复并且在重新加负荷时不能加载任何负荷。一组四个独立制备的自修复复合材料样品表明平均的修复效率为60％。当相对于初始的纯树脂对照(图2中的上水平线)的临界负荷来计算修复效率时，得到略大于100％的值。含有胶囊及Grubbs催化剂的初始自修复复合材料的平均临界负荷比纯环氧树脂对照样品的平均值高20％，表明添加胶囊和催化剂增加了环氧树脂的内在韧度。
明显地，本发明的大量修改和变化都可能在上述的教导中。因此应理解成在附加权利要求的范围内，本发明可以由本文具体说明之外的方式来实施。

Claims (23)

1、一种复合材料，其包括：
(i)聚合物，
(ii)聚合剂，
(iii)所述聚合剂的相应催化剂，以及
(iv)许多胶囊，
其中聚合剂在胶囊中。
2、如权利要求1的复合材料，其中所述聚合剂包括选自以下组中的至少一种单体：环烯烃、内酯、内酰胺、丙烯酸酯、丙烯酸、丙烯酸烷基酯、烷基丙烯酸、苯乙烯、异戊二烯及丁二烯。
3、如权利要求1的复合材料，其中所述聚合剂包括环烯烃。
4、如权利要求1的复合材料，其中所述聚合物包括选自以下组中的至少一种物质：聚酰胺、聚酯、聚碳酸酯、聚醚、聚酰亚胺、酚醛树脂、胺甲醛树脂、聚砜、聚(丙烯腈-丁二烯-苯乙烯)、聚氨基甲酸酯、聚烯烃和聚硅烷。
5、如权利要求1的复合材料，其中所述聚合物包括选自以下组中的至少一种物质：聚酯和聚醚。
6、如权利要求1的复合材料，其中所述聚合剂的相应催化剂包括选自以下组中的至少一种单体：ROMP催化剂和环酯聚合催化剂。
7、如权利要求1的复合材料，其中所述聚合剂的相应催化剂包括ROMP催化剂。
8、如权利要求1的复合材料，其中所述胶囊具有1∶1到1∶2的长径比，并且平均直径为10nm到1mm。
9、如权利要求1的复合材料，其中所述胶囊包括脲及甲醛的聚合物、明胶、聚脲和聚酰胺。
10、如权利要求1的复合材料，其中：
所述聚合剂包括DCPD，
所述聚合物包括环氧树脂，
所述聚合剂的相应催化剂包括Grubbs催化剂，
所述胶囊具有1∶1到1∶1.5的长径比和30-300μm的平均直径，以及
所述胶囊包括脲和甲醛的聚合物。
11、如权利要求1的复合材料，其中：
所述聚合剂包括DCPD，
所述聚合物包括聚(DCPD)，
所述聚合剂的相应催化剂包括Grubbs催化剂，
所述胶囊具有1∶1到1∶1.5的长径比和30-300μm的平均直径。
12、如权利要求1的复合材料，其中：
所述聚合剂包括己内酯，
所述聚合物包括聚(己内酯)，
所述聚合剂的相应催化剂包括三氟磺酸钪，
所述胶囊具有1∶1到1∶1.5的长径比和30-300μm的平均直径。
13、一种复合材料，其包括：
(i)聚合物，
(ii)聚合剂，
(iii)所述聚合剂的相应活化剂，以及
(iv)第一种许多胶囊，
其中所述聚合剂在胶囊中，且
相应的活化剂不是天然活化片段。
14、如权利要求13的复合材料，其中所述相应活化剂是第一种聚合剂的相应引发剂。
15、如权利要求13的复合材料，其进一步包括第二种许多胶囊，其中所述活化剂在第二种许多胶囊中。
16、如权利要求14的复合材料，其中所述相应活化剂是单体。
17、如权利要求13的复合材料，其中所述聚合剂包括单体和双组分催化剂的第一组分，而且
所述相应活化剂是双组分催化剂的第二组分。
18、如权利要求13的复合材料，其中所述聚合物包括选自以下组中的至少一种物质：聚酰胺、聚酯、聚碳酸酯、聚醚、聚酰亚胺、酚醛树脂、胺甲醛树脂、聚砜、聚(丙烯腈-丁二烯-苯乙烯)、聚氨基甲酸酯、聚烯烃和聚硅烷。
19、如权利要求13的复合材料，其中所述聚合物包括选自以下组中的至少一种物质：聚酯和聚醚。
20、如权利要求13的复合材料，其中所述胶囊具有1∶1到1∶2的长径比，并且平均直径为10nm到1mm。
21、如权利要求13的复合材料，其中所述胶囊包括脲及甲醛的聚合物、明胶、聚脲和聚酰胺。
22、一种制备权利要求1的复合材料的方法，其包括将胶囊和相应催化剂分散入聚合物中。
23、一种制备权利要求13的复合材料的方法，其包括将胶囊和相应活化剂分散入聚合物中。
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