CN103232588B - 两组分液体垫片组合物 - Google Patents

两组分液体垫片组合物 Download PDF

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CN103232588B
CN103232588B CN201310119720.5A CN201310119720A CN103232588B CN 103232588 B CN103232588 B CN 103232588B CN 201310119720 A CN201310119720 A CN 201310119720A CN 103232588 B CN103232588 B CN 103232588B
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索海伯·尔吉米亚比
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Abstract

本发明提供了环氧固化剂和包含环氧固化剂和环氧树脂的两组分组合物以及其在液体垫片中的使用方法。环氧固化剂包含至少一种脂环族聚胺固化剂和至少一种第二固化剂，所述至少一种第二固化剂选自：a)脂肪族聚酰胺型胺；和b)过量的非支化的聚醚二胺与环氧树脂的加合物。

Description

两组分液体垫片组合物
本发明专利申请是国际申请号为PCT/US2010/023597，国际申请日为2010年2月9日，进入中国国家阶段的申请号为201080007247.6，发明名称为“两组分液体垫片组合物”的发明专利申请的分案申请。
相关专利申请的交叉引用
本专利申请要求提交于2009年2月9日的美国临时专利申请No.61/151076的优先权，该专利申请的公开内容以引用方式全文并入本文。
技术领域
本发明涉及固化剂组合物和包含固化剂组分和环氧树脂组分的两组分组合物（其在液体垫片中可能是可用的）以及其使用方法。
背景技术
垫片被用于组装操作的许多方面，以定位和填充组装件之间的间隙。由于严格的公差要求和需要消除在界面处的间隙，在航空航天的组装操作中对填隙的需求特别迫切。用于组装操作的垫片一般分为三种类型。在一些情况下，固体垫片由与交界部件相同的材料制成。可剥离的层合垫片可由金属薄片制成，金属薄片可被逐层移除，直到实现良好的贴合。液体垫片材料在填充不规则的或锥形界面中可能是可用的。液体垫片材料通常用于填充宽度不大于0.7mm的间隙。
发明内容
本发明提供环氧组合物、固化剂组合物、和包含所述环氧组合物和固化剂组合物的两组分组合物（其在液体垫片应用中可能是可用的）以及它们的使用方法。
简而言之，本发明提供环氧固化剂，该环氧固化剂包含至少一种脂环族聚胺固化剂和至少一种第二固化剂，该至少一种第二固化剂选自：a)脂肪族聚酰胺型胺；和b)过量的非支化的聚醚二胺与环氧树脂的加合物。在一些实施例中，该至少一种第二固化剂为脂肪族聚酰胺型胺。在一些实施例中，该至少一种第二固化剂为过量的非支化的聚醚二胺与环氧树脂的加合物。在一些这样的实施例中，该非支化的聚醚二胺为根据式I的化合物：
H2N-[(CH2)xO]y-(CH2)x-NH2 [I]
其中y为1、2、3或4，且其中每一个x都独立地选自2、3或4。在一些这样的实施例中，过量的非支化的聚醚二胺与环氧树脂的加合物为每份环氧树脂介于2份和8份之间的非支化的聚醚二胺的加合物。在一些实施例中，环氧固化剂另外包含至少一种硝酸钙促进剂。在一些实施例中，环氧固化剂不包含粒状金属。
在另一方面，本发明提供填充间隙的方法，该方法包括以下步骤：a)将包含环氧树脂的环氧组分与根据本发明的环氧固化剂混合，以制备混合物；b)用混合物填充间隙；以及c)使混合物固化。在一些实施例中，环氧组分另外包含核壳型冲击改性剂。在一些实施例中，环氧组分包含环氧化间苯二甲胺，特别是当环氧固化剂为脂肪族聚酰胺型胺时。在一些实施例中，环氧组分包含环氧酚醛清漆树脂，特别是当环氧固化剂为过量的非支化的聚醚二胺与环氧树脂的加合物时。
在另一方面，本发明提供通过混合和固化下述物质获得的组合物：a)包含环氧树脂的环氧组分；和b)根据本发明的环氧固化剂。在一些实施例中，环氧固化剂另外包含硝酸钙促进剂。在一些实施例中，环氧组分包含环氧化间苯二甲胺，特别是当环氧固化剂为脂肪族聚酰胺型胺时。在一些实施例中，环氧组分包含环氧酚醛清漆树脂，特别是当环氧固化剂为过量的非支化的聚醚二胺与环氧树脂的加合物时。
具体实施方式
本发明提供环氧组合物、固化剂组合物、和包含所述环氧组合物和固化剂组合物（其在液体垫片中可能是可用的）的两组分组合物。本发明另外提供通过混合本发明所公开的两组分组合物的两种组分获得的组合物。
任何适用的环氧组合物都可以用于本发明的两组分组合物中。通常，使用每个分子具有三个或更多个环氧基团的多官能树脂。在一些实施例中，可以使用环氧酚醛清漆树脂。在一些实施例中，可以使用基于间苯二甲胺的环氧树脂，如ERISYS GA240。环氧组合物另外可以包含添加剂，该添加剂可以包括抗冲改性剂、填料、流变改性剂和/或颜料。
任何适用的固化剂组合物都可以用于本发明的两组分组合物中。固化剂组合物通常包含两种或更多种类的固化剂，该固化剂通常为聚胺。在一些实施例中，固化剂组合物包含至少一种脂环族聚胺。在一些实施例中，固化剂组合物包含至少一种过量的非支化的聚醚二胺与环氧树脂的加合物，通常的过量为超过200%、更通常超过250%、更通常超过280%、更通常超过300%，在一些实施例中超过350%，并且在一些实施例中超过400%。在一些实施例中，固化剂组合物包含至少一种过量的非支化的聚醚二胺与环氧树脂的加合物，其中通常的过量为小于800%、更通常小于700%、更通常小于600%、更通常小于500%、以及更通常小于450%。非支化的聚醚二胺的分子量通常为小于500、更通常小于400、更通常小于300、更通常小于280、更通常小与260、以及更通常小于240。非支化的聚醚二胺的分子量通常为至少130、更通常至少150、更通常至少180、以及更通常至少200。非支化的聚醚二胺具有的醚氧通常为介于一到四之间、更通常为两个或三个。在一些实施例中，非支化的聚醚二胺可以为根据式I的化合物：
H2N-[(CH2)xO]y-(CH2)x-NH2 [I]
其中y为1、2、3或4，更通常为2或3，并且其中每一个x都独立地选自2、3或4，更通常为2或3。在一些实施例中，y为2。在一些实施例中，y为2且每一个x都独立地选自2或3。在一些实施例中，y为3。在一些实施例中，y为3且每一个x都独立地选自2或3。在一些实施例中，非支化的聚醚二胺可以为4,7,10-三氧-1,13-十三烷二胺(TTD)。在一些实施例中，非支化的聚醚二胺可以为4,7-二氧癸烷1,10-二胺，可以商品名EDR176商购获得。
在一些实施例中，固化剂组合物包含非支化的聚醚二胺/环氧树脂加合物和至少一种脂环族聚胺。固化剂组合物另外可以包含硝酸钙作为促进剂，如PCT国际公布专利申请No.WO2008/089410（代理人档案No.62522WO005）中所公开，该专利的公开内容以引用的方式并入本文。固化剂组合物另外可以包含添加剂，该添加剂可以包括抗冲改性剂、填料、流变改性剂和/或颜料。然而，根据本发明的固化剂组合物通常不包含粒状金属填料或添加剂。根据本发明的固化剂组合物通常不包含粒状铝或铝合金填料或添加剂。根据本发明的固化剂组合物通常不包含粒状铁、钢或铁合金填料或添加剂。根据本发明的固化剂组合物通常不包含粒状铜或铜合金填料或添加剂。
在许多实施例中，液体垫片组合物将在室温下24小时到48小时后完全固化并在施用4小时后可用砂纸磨光或钻孔。在许多实施例中，液体垫片组合物将具有约3小时的适用寿命（用于定位和调整的时间）并可以采用温和加热使之加速固化，通常在70℃下在小于30分钟的时间内固化。
在许多实施例中，液体垫片组合物在固化前将显示特性，包括例如可能适用于注射或通过注射器施用的低粘度和施用时低程度的松弛或蠕变的组合。
在许多实施例中，液体垫片组合物在固化后显示特性，包括：无脆性的良好压缩强度、在低温和高温（-55℃至120℃）下的适当的强度性能、对大多数溶剂、油、液压流体、等等的抵抗力。在许多实施例中，本发明的组合物将显示出固化后的玻璃化转变温度Tg为大于120℃、更通常大于140℃、更通常大于160℃、以及更通常大于180℃。在许多实施例中，液体垫片组合物必须满足Airbus AIMS qualification10-07-001的要求。
下面的实例进一步说明本发明的目的和优点，但这些实例中列举的具体材料及其量以及其他条件和细节不应被解释为是对本发明的不当限制。
实例
除非另外说明，否则所有的试剂均得自或可以得自Aldrich Chemical Co.(Milwaukee,WI)、或可以通过已知的方法合成。
环氧树脂组合物
表I中的环氧树脂组合物通过在小型实验室搅拌器中进行混合制成。B4制剂的制备在2l的doppel Z lab mogul（双Z实验室莫古瓶）中完成。将酚醛树脂引入到莫古瓶中并与Kane Ace156混合。混合30分钟后，加入硅胶，然后加入二氧化钛粉末。然后，所有物质在真空下混合至少40分钟。所得为均匀的白色糊剂。
表I
固化剂组合物
表II中给出的固化剂组合物在小型实验室搅拌器中通过混合制成。制剂A1和A2的制备在与B4组分描述的相同的莫古瓶中进行。第一步是引入Ancamine2167和硝酸钙。将它们加热至80℃并搅拌1小时。冷却至室温(RT)后，加入硅胶并混合直至均匀。然后，引入TTD和Epikote828的加合物并在室温下混合约30分钟。然后掺入Minsil和碳黑在真空下混合1小时。TTD和Epikote828的加合物通过使180份TTD和60份Epikote828反应制成。两组分在室温下混合1小时，然后加热至80℃。保持该温度1小时以完成预聚合反应。
表II
树脂/固化剂组合
本发明设想出B组分和A组分的任意组合，包括B1/A0、B1/A1、B1/A2、B2/A0、B2/A1、B2/A2、B3/A0、B3/A1、B3/A2、B4/A0、B4/A1和B4/A2。下面的B组分和A组分的组合以两部分体积B对一份体积A的比例制成：B1/A0、B2/A0、B3/A0、B4/A1和B4/A2。制剂B4/A1和B4/A2在Haake RheoWin仪器上测得的混合粘度为低于600帕斯卡(Pa)。
结果-固化时间
制剂B1/A0、B2/A0和B3/A0的适用寿命由DSC量度（固化度）确定。表III记录了此三种组合的混合后的固化可能性随时间变化的情况。
表III
B1/A0 B2/A0 B3/A0
固化可能性（总） 100% 100% 100%
混合后3小时 90% 70% 73%
混合后3小时+70℃下30分钟 35% 28% 33%
观察到B4/A1的适用寿命为大约120分钟。观察到B4/A2的适用寿命为大约90分钟。
结果-机械测试
机械测试根据Airbus AIMS qualification10-07-001进行。结果见表IV、表V和表VI。
表IV：在铝基底上的交叠剪切强度(MPa)
表V：剥离力
表VI：压缩强度
B1/A0和B4/A2制剂显示出最佳机械特性。对B4/A2制剂的其它特性进行了测试，包括阻流性和老化测试，结果见表VII、表VIII和表IX。
表VII：B4/A2交叠剪切强度(MPa)
条件 持续时间 实验温度℃ 最小值 结果
甲基乙基酮(MEK) 1小时 120 8 10
干热120℃ 7天 120 8,5 18
70℃水 7天 120 7 10
特种液压工作油/水混合物 1000小时 120 7,5 9
特种液压工作油1000小时 1000小时 120 8 13
表VIII：B4/A2剥离力(N)
条件 持续时间 实验温度℃ 最小值 结果
干热120℃ 7天 23 50 107
表IX：B4/A2压缩强度(MPa)
条件 持续时间 实验温度℃ 最小值 结果
相对湿度85%&，70℃ 1000小时 23 55 93
相对湿度85%&，70℃ 1000小时 -55 150 160
相对湿度85%&，70℃ 1000小时 120 18 24
在不背离本发明的范围和原理的前提下，本发明的各种修改和更改对本领域技术人员来说将显而易见，并且应当理解，本发明不应不当地受限于上面示出的示例性实施例。

Claims (6)

1.一种两组分液体环氧组合物，其在室温下固化，其包含一种环氧固化剂组合物，其中环氧固化剂由至少一种脂环族聚胺固化剂和至少一种第二固化剂组成，
所述至少一种第二固化剂为过量的非支化的聚醚二胺与环氧树脂的加合物，其中所述过量为超过200％，其中所述非支化的聚醚二胺为根据式I的化合物：
H2N-[(CH2)xO]y-(CH2)x-NH2 [I]
其中y为1、2、3或4，且其中每一个x都独立地选自2、3或4。
2.根据权利要求1所述的两组分液体环氧组合物，其中所述过量的非支化的聚醚二胺与环氧树脂的加合物为每份环氧树脂介于2份和8份之间的非支化的聚醚二胺的加合物。
3.根据权利要求1或2所述的两组分液体环氧组合物，其中所述环氧固化剂组合物另外包含至少一种硝酸钙促进剂。
4.根据权利要求1或2所述的两组分液体环氧组合物，其中所述环氧固化剂组合物不包含粒状金属。
5.一种填充间隙的方法，该方法包括以下步骤：
a)将包含环氧树脂的环氧组分与根据权利要求1或2中所限定的环氧固化剂组合物混合，以制备混合物；
b)用所述混合物填充所述间隙；以及
c)使所述混合物固化。
6.通过混合下述物质并使其固化获得的组合物：a)包含环氧树脂的环氧组分；和b)根据权利要求1或2中所限定的环氧固化剂组合物。
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