CN108239507B - 用于结构粘合剂的固化剂制剂中作为构成单元的apcha - Google Patents
用于结构粘合剂的固化剂制剂中作为构成单元的apcha Download PDFInfo
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- CN108239507B CN108239507B CN201711401468.1A CN201711401468A CN108239507B CN 108239507 B CN108239507 B CN 108239507B CN 201711401468 A CN201711401468 A CN 201711401468A CN 108239507 B CN108239507 B CN 108239507B
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Abstract
本发明涉及结构粘合剂组合物,并且更具体地涉及双组份(2K)结构粘合剂组合物。所述两种组份发生化学反应以粘接结构表面。已经发现N‑(3‑氨基丙基)环己基胺(APCHA)是用于与在2K粘合剂组合物中的环氧树脂一起使用的改进的固化剂。APHCA表现出有利的特征,所述特征包括粘度、适用期和反应性,和在与环氧树脂一起固化后的粘合和热性能。这些特征及其独特的化学允许在用于结构粘合剂(特别是风力涡轮机叶片粘合剂)的固化剂制剂中使用APCHA。APCHA解决了采用常用的胺制剂不能解决的关于粘度积累、工作时间、穿透固化、相容性和粘合性能的问题。
Description
背景技术
近年来,作为环境安全的和相对廉价的替代能源,风力涡轮机已经受到了增加的关注。正在进行相当大的努力以开发可靠和有效的风力涡轮机。通常,风力涡轮机包括具有多个风力涡轮机叶片的转子。所述风力涡轮机叶片的形状为细长的翼型,其被构造以对风响应地提供旋转力。制造风力涡轮机叶片的一个目前的方案是将每个叶片要么制备为两个半壳和一个翼梁,要么制备为两个具有集成翼梁的半壳。在两种情况下,将所述两个半壳沿着它们的边缘用粘合剂材料粘接以形成完整的叶片。典型地,所述粘合剂材料是双组份(2K)结构粘合剂材料,其包括两种组分,所述两种组分当在环境条件下混合时发生化学反应(即交联)以将所述半壳粘接在一起。
用于将所述风力涡轮机叶片的两半耦合的粘合剂必须能够耐受在使用过程中施加到每个叶片上的离心力,并且在恒定的热循环和环境攻击下能够保持粘接强度持续所述叶片的寿命。另外,这些粘合剂材料应当相对容易施加。因此,对于2K粘合剂,适用期是一个重要的考虑因素。术语“适用期”,如在粘合剂领域中普通技术人员认识的那样,可被定义为其中所述粘合剂组合物充分地是液体使得其可被施加到待被粘接的基底材料上的时间段。具有较短适用期的粘合剂材料是其中所述两种组分反应较快的材料,和具有较长适用期的粘合剂材料是其中所述两种组分反应较慢的材料。
特别由于对于较长叶片的需求增长,另一个要考虑的方面是开放时间。术语“开放时间”可被定义为在一个半壳上施加所述粘合剂和将第二个半壳放置在所述粘合剂粘接线上之间的时间段。甚至在长的开放时间之后仍提供良好粘合剂性质的粘合剂材料是优选的。要考虑的另一个方面是将所述半壳粘接在一起所处的环境条件、温度和湿度。理想地,粘合剂材料是在宽范围的条件下耐用的,并且对不利的环境条件不敏感。
由于对较大的叶片的需求,风力涡轮机叶片制造商正受到挑战。在过去,最大的运转的风力涡轮机具有小于100米的转子直径。所述转子直径大约是所述叶片长度的两倍,因此在这些转子上的最大叶片小于50米。目前,一些陆上风力涡轮机转子直径为大到130米,并且一些海上涡轮机具有170米的转子直径。然而,由于所述叶片变得较长,目前可用的粘合剂导致加工问题。
基于环氧化物的粘合剂用于粘接风力涡轮机叶片壳是公知的。典型相关的技术可在例如DE102011113395和US2012128499中找到。现有技术的粘合剂不具有充分长的适用期,对于长的开放时间是敏感的和/或不具有符合由增加的叶片尺寸导致的需求的在升高的温度下的正确反应性。
图1显示了与具有190的环氧当量(EEW)的双酚A的二缩水甘油醚(DGEBA)型液体环氧树脂一起使用标准风机叶片粘合剂参比环氧固化剂产生的拉伸数据。在正常条件下(没有开放时间),拉开两个基底所需的力为在约1%的伸长率下的8MPa。使用相同的固化剂和基底,但采用在23℃和70%相对湿度下1小时的开放时间,拉开所述基底所需的力下降到在仅0.3%的伸长率下的2MPa(75%降低)。
由于如上讨论的缺点,叶片制造商已经面临叶片故障,使得在所述两个壳之间的粘合剂失败。因此,本领域中需要如下粘合剂组合物,其具有长的适用期,在长开放时间后良好粘接能力和在变化的环境条件下的有效性。
发明内容
发明概述
本发明涉及粘合剂组合物,该粘合剂组合物提供充分的粘接强度,易于施加,当在长开放时间条件下使用时不敏感,并具有充分长的适用期用于将基底材料粘接在一起,所述基底材料例如风力涡轮机叶片。
在本发明的一个方面,所述粘合剂组合物包含环氧树脂组分,其采用包含N-(3-氨基丙基)环己基胺(APCHA)的固化剂组分固化。
附图说明
下文中将结合附图描述本发明,其中同样的数字指代同样的元件:
图1是显示使用采用示例性的现有技术固化剂固化的粘合剂组合物制造的风机叶片的拉伸强度的图。
图2是总结了本发明的制剂的组成和性质的表。
图3是显示使用采用固化剂制剂UMX-126D固化的粘合剂组合物制造的风机叶片的拉伸强度的图。
图4是列举了在本发明的固化剂的优选实施方案中使用的胺制剂的组成的表。
发明详述
随后的详述仅提供优选的示例性实施方案,并且不意欲限制本发明的范围、应用性或构造。相反,随后对优选示例性实施方案的详述将给本领域技术人员提供一种用于实施本发明的优选示例性实施方案的能实现的说明。在元件的功能和布置方面可进行各种改变,而不背离如在所附权利要求书中阐述的本发明的主旨和范围。
在所述权利要求书中,字母可用于确认要求保护的方法步骤(例如a、b和c)。这些字母用于辅助提及所述方法步骤,而不意欲指明其中实施所要求保护的步骤所依的顺序,除非在所述权利要求书中具体说明这样的顺序,并且仅到该程度。
本发明涉及结构粘合剂组合物,并且更具体地涉及2K结构粘合剂组合物。本发明还涉及2K结构粘合剂组合物,其包含环氧树脂组分和基于胺的固化剂组合物。本发明的一个方面涉及基于胺的固化剂,其包含含有APCHA的胺制剂。
APCHA是一种胺固化剂,其具有特定的希望的特征,例如粘度和反应性,和在与环氧树脂一起固化后的良好的粘合和热性能。这些特征及其独特的化学允许在用于结构粘合剂(特别是风机叶片粘合剂)的固化剂制剂中使用APCHA。APCHA解决了采用常用的胺制剂不能解决的关于粘度积累、工作时间、穿透固化(through-cure)、相容性和粘合性能的问题。
上述的性能损失的问题通过改变所述环氧体系的组成,特别是所述固化剂制剂的组成而得到解决。风机叶片固化剂的典型组成使得可能出现相容性问题。APCHA,由于其化学结构,不产生这些问题。令人惊奇地,可使用APCHA设计固化剂制剂,所述APCHA不仅提供良好的粘合性能,而且还具有良好的作为结构粘合剂固化剂制剂的一般性能。
如本领域中已知的,环氧体系包含环氧树脂组分和固化剂组分。任何合适的制剂可用于所述环氧树脂组分。DGEBA型液体环氧树脂已经被发现是特别合适的。合适的环氧树脂组分的一个实例由64%的DGEBA-型液体环氧树脂(EEW 190)、34.5%的滑石和1.5%的热解法二氧化硅组成。环氧树脂组分对固化剂组分的比例优选在按重量计100/65至100/85的范围内,和更优选按重量计100/70至100/80范围内。按重量计100/76的比例已经被发现对于图2的制剂UMX-126D特别有效。
在一个示例性实施方案中,所述固化剂组分的胺制剂包含APCHA、至少一种聚酰胺、至少一种脂环族胺、至少一种聚醚二胺和至少一种醚二胺。这些组分中的每一种的可接受范围(作为重量%表示)在图4的“范围”栏中示出。优选的范围(作为重量%表示)在图4的“优选范围”栏中示出。含有胺官能度的反应性液体聚合物,例如胺封端的丁二烯-丙烯腈共聚物,例如Hycar ATBNX16,可任选存在于所述固化剂组分中。然而,这样的共聚物不是如由本公开定义的胺制剂的一部分。
本公开的合适的聚酰胺包括但不限于3030(A3030)。本公开的合适的脂环族胺包括但不限于4,4’-亚甲基双环己胺(PACM)。本公开的合适的聚醚二胺包括但不限于α-(2-氨基甲基乙基)-ω-(2-氨基甲基乙氧基)(230,D-400)。本公开的合适的醚二胺包括但不限于异十三烷氧基丙基-1,3-二氨基丙烷(Tomamine DA-17)。是Evonik Corp的注册商标。是Huntsman Petrochemical LLC的注册商标。
示例性的固化剂组分包含制剂UMX-126D(参见图4)。这种固化剂组分由如下物质组成:制剂UMX-126D(36重量%);Hycar ATBNX16(11%);铝(15.5%);滑石(36%);热解法二氧化硅(1.5%)。
实验数据证实了在固化剂制剂中使用APCHA的确解决了在不利条件下在长的开放时间后的性能损失的问题。图3显示了使用图2的制剂UMX-126D产生的拉伸数据。该图表明,至少一种基于本发明的制剂,UMX-126D,显示了在粘合性能方面的显著改进。特别地,在暴露1小时(开放时间)后,发现绝对值是更高的,并且在性能方面的降低也是显著较小的(60%),这与在图1中示出的现有技术制剂中的性能方面的75%的降低形成对比。
环氧树脂组分
所述环氧树脂组分可由单一树脂组成,或者其可以是彼此相容的环氧树脂的混合物。所述环氧树脂可包括但不限于双官能环氧化物,例如双酚A和双酚F树脂。如本文中使用的多官能环氧树脂描述了每个分子含有两个或更多个1,2-环氧基团的化合物。这种类型的环氧化合物是本领域技术人员公知的并且描述在Y.Tanaka,“Synthesis andCharacteristics of Epoxides”中,在C.A.May编辑的,Epoxy Resins Chemistry andTechnology(Marcel Dekker,1988)中,其通过引用以其全部内容并入本文中。
适合于在所述环氧树脂组分中使用的一类环氧树脂包含多元酚的缩水甘油醚,包括二元酚的缩水甘油醚。示例性的实例包括但不限于如下物质的缩水甘油醚:间苯二酚、氢醌、双(4-羟基-3,5-二氟苯基)-甲烷、1,1-双-(4-羟基苯基)-乙烷、2,2-双-(4-羟基-3-甲基苯基)-丙烷、2,2-双-(4-羟基-3,5-二氯苯基)丙烷、2,2-双-(4-羟基苯基)-丙烷(商业上称为双酚A)、双-(4-羟基苯基)-甲烷(商业上称为双酚F,并且其可含有变化量的2-羟基苯基异构体)和类似物,或它们的任意组合。另外,在本公开中,式(1)结构的高级二元酚也是有用的:
其中m是0至25,和R是二元酚(例如如上列举的那些二元酚)的二价烃基团。
根据式(1)的材料可通过如下方式制备:将二元酚和表氯醇的混合物进行聚合,或将二元酚的二缩水甘油醚和所述二元酚的混合物升级(advancing)。尽管在任何给定的分子中m的值是整数,但所述材料不变地是可由m的平均值表征的混合物,所述m的平均值不必定是整数。在本公开的一个方面中可使用具有在0和约7之间的m的平均值的聚合物材料。在其它实施方案中,所述环氧组分可以是多缩水甘油基胺,其得自2,2’-亚甲基二苯胺、4,4’-亚甲基二苯胺、间二甲苯二苯胺、乙内酰脲和异氰酸酯中的一种或多种。
所述环氧树脂组分可以是脂环族的(脂环的)环氧化物。合适的脂环族环氧化物的实例包括二羧酸的脂环族酯的二环氧化物,例如草酸双(3,4-环氧基环己基甲基)酯,己二酸双(3,4-环氧基环己基甲基)酯,己二酸双(3,4-环氧基-6-甲基环己基甲基)酯,乙烯基环己烯二环氧化物;苧烯二环氧化物;庚二酸双(3,4-环氧基环己基甲基)酯;二环戊二烯二环氧化物;和其它合适的脂环族环氧化物。二羧酸的脂环族酯的其它合适的二环氧化物例如描述在专利申请公开号WO2009/089145 A1中,该文献通过引用以其全部内容并入本文中。
其它环脂族环氧化物包括3,3-环氧基环己基甲基-3,4-环氧基环己烷羧酸酯,例如3,4-环氧基环己基甲基-3,4-环氧基环己烷羧酸酯;3,3-环氧基-1-甲基环己基-甲基-3,4-环氧基-1-甲基环己烷羧酸酯;6-甲基-3,4-环氧基环己基甲基甲基-6-甲基-3,4-环氧基环己烷羧酸酯;3,4-环氧基-2-甲基环己基-甲基-3,4-环氧基-3-甲基环己烷羧酸酯。其它合适的3,4-环氧基环己基甲基-3,4-环氧基环己烷羧酸酯例如描述在美国专利2,890,194中,其通过引用以其全部内容并入本文中。在其它实施方案中,所述环氧组分可包括多元醇多缩水甘油醚,其得自聚乙二醇、聚丙二醇或聚四氢呋喃或它们的组合。
在另一个方面,根据本公开,可将作为酚醛清漆树脂的缩水甘油醚的环氧酚醛清漆树脂用作多官能环氧树脂。在又一个方面,所述至少一种多官能环氧树脂是双酚A的二缩水甘油醚(DGEBA),DGEBA的高级的或更高分子量变体,双酚F的二缩水甘油醚,环氧酚醛清漆树脂,或它们的任意组合。通过升级工艺制备DGEBA的更高分子量变体或衍生物,其中过量的DGEBA与双酚-A反应以产生环氧基封端的产物。这些产物的环氧当量重量(EEW)的范围为约450至3000或更高。由于这些产物在室温下是固体,它们经常被称为固体环氧树脂。
DGEBA或高级的DGEBA树脂由于它们的低成本和通常高性能性质的组合而经常用于结构制剂。商业级的具有范围为约174至约250和更通常约185至约195的EEW的DGEBA是可容易获得的。在这些低分子量下,所述环氧树脂是液体,并且经常被称为液体环氧树脂。本领域技术人员理解的是,大部分级别的液体环氧树脂是轻度聚合的,因为纯DGEBA具有174的EEW。通常也通过所述升级工艺制备的具有在250和450之间的EEW的树脂被称为半固体环氧树脂,因为它们在室温下是固体和液体的混合物。通常,在本公开中,具有约160至约750的EEW的基于固体的多官能树脂是有用的。在另一方面,所述多官能环氧树脂具有在约170至约250范围内的EEW。
本发明的方面例如如下所述:
<1>一种粘合剂组合物,其包含环氧树脂组分和固化剂组分的反应产物,所述环氧树脂组分包含至少一种环氧树脂,所述固化剂组分包含胺制剂,其中所述胺制剂包含第一胺组分和第二胺组分,所述第一胺组分由N-(3-氨基丙基)环己基胺组成,所述第二胺组分由选自聚酰胺、脂环族胺、聚醚二胺和醚二胺的至少一种组成。
<2>根据<1>的粘合剂组合物,其中所述第一胺组分是所述胺制剂的5重量%至50重量%。
<3>根据<1>的粘合剂组合物,其中所述第一胺组分是所述胺制剂的5重量%至15重量%。
<4>根据<2>至<3>的任一项的粘合剂组合物,其中所述胺制剂包含至少一种聚酰胺。
<5>根据<4>的粘合剂组合物,其中所述至少一种聚酰胺是所述胺制剂的10重量%至60重量%。
<6>根据<4>的粘合剂组合物,其中所述至少一种聚酰胺是所述胺制剂的30重量%至50重量%。
<7>根据<2>至<3>的任一项的粘合剂组合物,其中所述胺制剂包含至少一种脂环族胺。
<8>根据<7>的粘合剂组合物,其中所述至少一种脂环族胺是所述胺制剂的10重量%至40重量%。
<9>根据<7>的粘合剂组合物,其中所述至少一种脂环族胺是所述胺制剂的10重量%至20重量%。
<10>根据<2>至<3>的任一项的粘合剂组合物,其中所述胺制剂包含至少一种聚醚二胺。
<11>根据<10>的粘合剂组合物,其中所述至少一种聚醚二胺是所述胺制剂的10重量%至50重量%。
<12>根据<10>的粘合剂组合物,其中所述至少一种聚醚二胺是所述胺制剂的10重量%至30重量%。
<13>根据<2>至<3>的任一项的粘合剂组合物,其中所述胺制剂包含至少一种醚二胺。
<14>根据<13>的粘合剂组合物,其中所述至少一种醚二胺是所述胺制剂的最高至30重量%。
<15>根据<13>的粘合剂组合物,其中所述至少一种醚二胺是所述胺制剂的10重量%至20重量%。
<16>根据<1>的粘合剂组合物,其中所述第一胺组分是所述胺制剂的10重量%。
<17>根据<16>的粘合剂组合物,其中所述胺制剂包含至少一种聚酰胺,其中所述至少一种聚酰胺是所述胺制剂的40重量%。
<18>根据<17>的粘合剂组合物,其中所述胺制剂进一步包含至少一种脂环族胺,其中所述至少一种脂环族胺是所述胺制剂的15重量%。
<19>根据<18>的粘合剂组合物,其中所述胺制剂进一步包含至少一种聚醚二胺,其中所述至少一种聚醚二胺是所述胺制剂的20重量%。
<20>根据<19>的粘合剂组合物,其中所述胺制剂进一步包含至少一种醚二胺,其中所述至少一种醚二胺是所述胺制剂的15重量%。
<21>根据<1>至<20>的任一项的粘合剂组合物,其中所述至少一种环氧树脂包含双酚A二缩水甘油醚。
<22>根据<21>的粘合剂组合物,其中所述双酚A二缩水甘油醚是所述环氧树脂组分的40重量%至90重量%。
<23>根据<21>的粘合剂组合物,其中所述双酚A二缩水甘油醚是所述环氧树脂组分的55重量%至75重量%。
<24>根据<21>的粘合剂组合物,其中所述双酚A二缩水甘油醚是所述环氧树脂组分的64重量%。
<25>根据<1>至<20>的任一项的粘合剂组合物,其中所述胺制剂是所述固化剂组分的10重量%至60重量%。
<26>根据<1>至<20>的任一项的粘合剂组合物,其中所述胺制剂是所述固化剂组分的25重量%至45重量%。
<27>根据<1>至<20>的任一项的粘合剂组合物,其中所述胺制剂是所述固化剂组分的36重量%。
<28>根据<1>至<20>的任一项的粘合剂组合物,其中所述环氧树脂组分对所述固化剂组分的重量比例为100/65至100/85。
<29>根据<1>至<20>的任一项的粘合剂组合物,其中所述环氧树脂组分对所述固化剂组分的重量比例为100/70至100/80。
<30>根据<1>至<20>的任一项的粘合剂组合物,其中所述环氧树脂组分对所述固化剂组分的重量比例为100/76。
<31>根据<1>至<20>的任一项的粘合剂组合物,其中所述固化剂组分进一步包含选自滑石、热解法二氧化硅、铝和胺封端的丁二烯-丙烯腈共聚物的至少一种。
<32>根据<1>至<20>的任一项的粘合剂组合物,其中所述环氧组分进一步包含选自滑石和热解法二氧化硅的至少一种。
<33>一种风力涡轮机叶片,其包含第一部分,该第一部分通过粘合剂组合物粘附于第二部分,所述粘合剂组合物布置在所述第一部分和所述第二部分之间,其中所述粘合剂组合物包含环氧树脂组分和固化剂组分的反应产物,所述环氧树脂组分包含至少一种环氧树脂,其中所述固化剂组分包含第一胺组分,所述第一胺组分由N-(3-氨基丙基)环己基胺组成。
<34>根据<33>的风力涡轮机叶片,其中所述风力涡轮机叶片进一步具有叶片长度,其中所述叶片长度大于30米。
<35>根据<33>的风力涡轮机叶片,其中所述风力涡轮机叶片进一步具有叶片长度,其中所述叶片长度大于50米。
<36>形成风力涡轮机叶片的方法,该方法包括(a)将环氧树脂组分与固化剂组分混合以形成粘合剂组合物,所述环氧树脂组分包含至少一种环氧树脂,所述固化剂组分包含胺制剂,其中所述胺制剂包含第一胺组分,该第一胺组分由N-(3-氨基丙基)环己基胺组成;(b)将所述粘合剂组合物施加到风力涡轮机叶片的第一部分上;(c)在步骤(b)之后,将所述风力涡轮机叶片的第一部分通过如下方式耦合至所述风力涡轮机叶片的第二部分:使所述第二部分与施加到所述风力涡轮机叶片的第一部分上的粘合剂组合物接触;和(d)将所述风力涡轮机叶片的第一部分和第二部分压在一起持续充分的时间段以使得所述粘合剂组合物固化。
<37>根据<36>的形成风力涡轮机叶片的方法,其中步骤(b)进一步包括将所述粘合剂组合物施加到所述风力涡轮机叶片的第二部分上。
<38>根据<36>的形成风力涡轮机叶片的方法,其中在步骤(c)之后,加热所述风力涡轮机叶片的第一部分和第二部分以辅助所述固化过程。
具体实施方式
实施例
图2显示了大量的固化剂制剂,编码为UMX-126B至H,其是使用APCHA开发的。将所述制剂与DGEBA环氧树脂混合并测试凝胶时间,到10Pa.s的时间,到凝胶点的时间和差示扫描量热法。这些制剂,编码为UMX-126B至H,显示了与风机叶片粘合剂固化剂参比制剂(UMX-126A)相比良好的性能。
尽管如上已经与优选的实施方案相关联地描述了本发明的原理,但要清楚理解的是,仅举例做出了这种说明,并且这种说明不作为本发明的范围的限制。
Claims (15)
1.一种粘合剂组合物,其包括如下物质的反应产物:
环氧树脂组分,其包含至少一种环氧树脂;和
固化剂组分,其包含胺制剂,其中所述胺制剂包含第一胺组分和第二胺组分,所述第一胺组分由N-(3-氨基丙基)环己基胺组成,所述第二胺组分由至少一种聚酰胺、至少一种脂环族胺、至少一种聚醚二胺和至少一种醚二胺组成,其中所述第一胺组分是所述胺制剂的5重量%至50重量%。
2.权利要求1的粘合剂组合物,其中所述至少一种聚酰胺是所述胺制剂的10重量%至60重量%。
3.权利要求1的粘合剂组合物,其中所述至少一种脂环族胺是所述胺制剂的10重量%至40重量%。
4.权利要求1的粘合剂组合物,其中所述至少一种聚醚二胺是所述胺制剂的10重量%至50重量%。
5.权利要求1的粘合剂组合物,其中所述至少一种醚二胺是所述胺制剂的最高至30重量%。
6.权利要求1的粘合剂组合物,其中所述第一胺组分是所述胺制剂的10重量%。
7.权利要求6的粘合剂组合物,其中所述至少一种聚酰胺是所述胺制剂的40重量%。
8.权利要求7的粘合剂组合物,其中所述至少一种脂环族胺是所述胺制剂的15重量%。
9.权利要求8的粘合剂组合物,其中所述至少一种聚醚二胺是所述胺制剂的20重量%。
10.权利要求9的粘合剂组合物,其中所述至少一种醚二胺是所述胺制剂的15重量%。
11.权利要求1的粘合剂组合物,其中所述至少一种环氧树脂包含双酚A二缩水甘油醚。
12.权利要求11的粘合剂组合物,其中所述双酚A二缩水甘油醚是所述环氧树脂组分的40重量%至90重量%。
13.权利要求1的粘合剂组合物,其中所述胺制剂是所述固化剂组分的10重量%至60重量%。
14.权利要求1的粘合剂组合物,其中所述环氧树脂组分对所述固化剂组分的重量比例为100/65至100/85。
15.权利要求1的粘合剂组合物,其中所述固化剂组分进一步包含选自滑石、热解法二氧化硅、铝和胺封端的丁二烯-丙烯腈共聚物的至少一种。
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