CN108503760A - 用于制造可热固化树脂的方法和通过该方法可获得的树脂 - Google Patents
用于制造可热固化树脂的方法和通过该方法可获得的树脂 Download PDFInfo
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Abstract
本发明涉及用于制备可热固化树脂的方法,包括以下步骤:在导致缩聚产物的形成的条件下使能够缩聚的酚类化合物和/或氨基塑料成型剂与5‑羟甲基糠醛(HMF)反应,其特征在于HMF包含至少一种HMF低聚物。本发明还涉及可热固化的树脂并且涉及树脂用于制造木质复合材料的用途。
Description
本发明涉及用于制造可热固化树脂的方法,涉及可热固化树脂并且涉及树脂用于制造木质复合材料的用途。特别地,本发明涉及用于制造可热固化树脂的方法,包含通过酚类化合物和/或氨基塑料成型剂(aminoplastic forming agent)与HMF的缩聚获得至少一种缩聚产物并且涉及通过该方法可获得的可热固化的树脂。本发明还特别涉及可热固化树脂用于制造胶合板,木纤维复合材料,刨花板或多层板的用途。
可热固化的树脂优选通过酚类化合物和/或氨基塑料成型剂与反应性羰基化合物(特别是醛)的缩聚来获得。具有氨基塑料成型剂脲,三聚氰胺和双氰胺的氨基树脂、酚醛树脂或氨基苯酚树脂可以作为实施例来提及。树脂通常通过良好的加工性能例如高反应性来区分。通过随后固化树脂得到热固性塑料材料。
对于木质复合材料的制造,树脂通常与碎木,例如木刨花或木纤维混合,此后在升高的温度下压制,其中树脂通过交联固化。
基于其高反应性,主要用甲醛进行缩聚。为了促进反应,经常用过量的甲醛进行反应,从而树脂具有较高含量的游离甲醛。因此,树脂的甲醛排放较高。
在这个方面,与甲醛相关的健康危害是不利的,因此甲醛的使用受到越来越多的监管。
由于潜在的危害,多年来努力减少甲醛的含量。在这方面的一种措施是在树脂的制造中用其它反应性化合物代替甲醛。5-羟甲基糠醛(HMF)已经被认为是用于此目的的高度有前景的候选物,这是由于其具有形成交联键的能力,不易挥发,几乎无毒,并且可从可再生原料中得到。
在行业杂志欧洲European Journal of Wood Products中,描述了HMF改性的脲-甲醛树脂,其制备需要用纯化的结晶HMF替代最高达约30wt%的甲醛(N.Esmaeili et al.,DOI 10.1007/s0017-016-1072-8)。使用这种树脂制造的刨花板面板具有≥0.35N/mm2的内部结合强度(IB),如目前需要的满足根据欧洲标准NEN EN 319的室内面板的最小标准。然而,缺点是由其制造的树脂和刨花板面板仍含有大量的有毒甲醛。
因此,本发明的任务在于消除上述缺点。
根据本发明的第一方面,通过根据权利要求1的特征的用于制造可热固化树脂的方法来实现。
用于制造可热固化树脂的方法包括在导致缩聚产物形成的条件下使能够缩聚的酚类化合物和/或氨基塑料成型剂与5-羟甲基糠醛(HMF)反应的步骤,其特征在于,HMF包括至少一种HMF低聚物(HMF类化合物包括至少一种HMF低聚物)。
已经发现,可以完全弃用甲醛,条件是包含HMF低聚物的HMF用于缩聚。假定HMF低聚物比HMF单体更具反应性,这允许在不使用甲醛的情况下用于制造可热固化树脂的方法。
在HMF溶液中出现水溶性线性和支化HMF低聚物是已知的(例如,DE 10 2014 112240A1)。例如可以通过HPLC分析来追踪HMF低聚物的形成。
与HMF单体相比,在本发明的含义内,至少两个连接的HMF单元/单体的化合物被指定为HMF低聚物。通常,HMF低聚物被理解为具有最高达3000g/mol的摩尔质量的化合物。具有低摩尔质量的HMF低聚物(在所选择的反应条件下其可溶于或至少以分散形式存在于所选择的溶剂中)特别适合于方法。在这个方面,溶解和分散形式之间的过渡可以是连续的,因此在本发明中不进行这个方面的区别。
以自身已知的方式进行缩聚。适用于反应的溶剂以及合适的反应条件如反应温度和pH原则上是本领域技术人员已知的。优选地,该反应在水溶剂中进行。
在这个方面,本领域技术人员应当清楚的是,至少一种HMF低聚物可以存在于不同长度和/或不同交联程度的HMF低聚物的混合物中。此外,通过选择HMF低聚物或通过选择不同HMF低聚物的组合可以使得到的树脂的性质选择性地与使用的技术目的相匹配。
根据方法的一个有利配置,反应步骤在40℃至140℃的范围内、优选在50℃至140℃的范围内、更优选在60℃至100℃的范围内、特别优选在80℃至100℃的范围内的温度下进行。原则上,用于实施该方法的温度可以在较宽范围内变化。然而,已经观察到,在较高温度下通过反应可获得更多反应性的树脂。特别是高反应性树脂(其需要在后续材料制造过程中用于固化的短的压制时间)可以在80℃至100℃范围内的温度下获得。这是出人意料的,因为迄今为止,假定的是在从高于50℃的温度开始就已经发生HMF的分解增加。
根据方法的另一有利配置,使用的HMF的量与酚类化合物和/或氨基塑料成型剂的总量的摩尔比为0.20:1至3:1、优选摩尔比为0.3:1至1:1、特别优选摩尔比为0.45:1至0.70:1。原则上,使用的HMF的量与酚类化合物和/或氨基塑料成型剂的总量的摩尔比可以在较宽的范围内变化。HMF的摩尔过量也可以是有利的。本领域技术人员可以容易地确定相应的酚类化合物,相应的氨基塑料成型剂,或酚类化合物与氨基塑料成型剂的混合物的合适的摩尔比。
根据方法的另一有利的配置,相对于使用的HMF的总量,HMF低聚物的比例为0.05wt%至10wt%;优选地,相对于使用的HMF的总量,HMF低聚物的比例为0.1wt%至8wt%;特别优选地,相对于使用的HMF的总量,HMF低聚物的比例为2wt%至4wt%。由于高反应性,甚至少量的HMF低聚物足以制备反应性树脂。本领域技术人员应当清楚的是,也可以使用更高比例的HMF低聚物。本发明还包括以下事实:相对于使用的HMF的总量,HMF低聚物占比最高达或最高达几乎100wt%。
根据该方法的另一有利的配置,HMF低聚物具有2至20个单元,优选2至10个单元,特别优选2至4个单元。在温和条件下(即,室温和常压)具有2至10个单元的HMF低聚物容易溶于水,因此可以使用HMF低聚物而没有在水性介质中缩聚的问题。具有2至4个单元的HMF低聚物具有改善的水溶性。具有2个单元的HMF低聚物特别容易溶于水。
能够缩聚的酚类化合物和/或氨基塑料成型剂可以是这样的,从而通常用于制造可热固化树脂。
在这个方面,在芳族部分中具有至少一个碳原子(其适合于酚类化合物和HMF之间的亲核加成反应)的所有含羟基的芳族化合物,原则上可以被认为是能够缩聚的化合物。
有利的是,能够缩聚的酚类化合物是苯酚、木质素、衍生自木质素的酚类化合物、间苯二酚、对苯二酚、羟基醌、邻苯二酚、间苯三酚或这些化合物中至少两种的混合物。
有利的是,氨基塑料成型剂为脲、三聚氰胺、取代的三聚氰胺、取代的脲、乙炔二脲、胍、硫脲、硫脲衍生物、二氨基烷烃(diaminoalkane)、二酰氨基烷烃(diamidoalkane)或这些氨基塑料成型剂中至少两种的混合物。
在这个方面,除了提及的组分之外,还可以存在另外的酚类化合物和/或氨基塑料成型剂。
根据酚类化合物和/或氨基塑料成型剂,pH可以在较宽范围内变化。例如,pH可以在6至10的范围内,优选在7至8.5的范围内。
根据该方法的另一优选配置,用于缩聚的HMF低聚物是碳连接的HMF低聚物。
在本发明的含义中,HMF低聚物被指定为碳连接的HMF低聚物,条件是至少两个HMF单元通过碳-碳键连接,涉及两个HMF单元中的一个的呋喃环的位置3或4处的芳族键合碳原子。特别地,碳连接的HMF低聚物包含至少一个第一单元,其醛基碳原子与第二单元的呋喃环的芳族键合碳原子相连接。
发明人已发现,除了通过连接HMF单元的醛和/或羟基得到的并且具有相应的醚、半缩醛和/或缩醛键的HMF低聚物之外,HMF低聚物(其中通过碳-碳键连接单元)在酸性条件和碱性条件两者下形成。作为实例,这些键可以在亲电攻击第一HMF单体的醛基或第二HMF单体的呋喃环的3或4位中的碳原子上HMF低聚物的HMF单元或HMF低聚物的HMF单元期间形成。
所提出的在酸中和在碱中形成HMF低聚物的机理在图1和2中给出。由此,可以清楚的是,除了其他事实之外,与其中仅通过HMF的醛和/羟基形成键的HMF低聚物相比,具有通过碳-碳键的连接的HMF低聚物同时具有更多的游离的功能醛和/或羟基。由此获得了非常(高)反应性的HMF低聚物,其具有额外的交联能力。
除了与涉及芳族键合碳原子连接的键之外,碳连接的HMF低聚物还可以包含其它键,例如醚、半缩醛和/或缩醛键。为了提高所得树脂的反应性,当这些HMF单元中的两个已经与涉及芳族键合碳原子连接时,就足够了。特别地,具有2个单元的碳连接的HMF低聚物含有相对高比例的游离的官能的反应基团/HMF低聚物。碳连接的HMF低聚物还可以具有多种这样的碳-碳连接。
此外,除了碳连接的HMF低聚物之外,还可以存在具有醚、半缩醛和/或缩醛键的其他HMF低聚物。由于高比例的游离官能团,甚至少量的碳连接的HMF低聚物足以制备非常(高)反应性的低聚物。本发明还包括以下事实:相对于HMF低聚物的总量,碳连接的HMF低聚物占比最高达或最高达约100wt%。
根据方法的另一有利配置,反应步骤在溶液中进行,直至溶液达到所需的粘度或反应结束。优选地,进行反应步骤,直至溶液达到200mPa.s以上的粘度,特别优选直到溶液达到450mPa.s以上的粘度
根据方法的另一有利配置,方法包括至少一个另外的步骤,其可以使得反应步骤利用包括至少一种HMF低聚物的5-羟甲基糠醛。
优选地,制备步骤包括将HMF单体和/或HMF低聚物的更高或更低纯溶液暴露于导致HMF低聚物形成的条件。发明人已发现,例如由结晶HMF和水制备的水性的HMF溶液老化,伴随着HMF低聚物的形成。在这个方面,HMF低聚物的量和分子量,可以使用本领域技术人员熟悉的分析手段来确定,如HPLC和NMR光谱法
在温和的条件下(即,常压和室温)形成HMF低聚物可持续数小时,数天,或数周。
特别优选地,HMF溶液暴露的条件包括溶液的碱化或酸化。同样地,该条件特别优选包括加热溶液,如果需要与酸化或碱化结合。通过酸化,碱化和加热,加速老化过程。
制备步骤的特别优选的变体包括制备5-羟甲基糠醛,5-羟甲基糠醛包括水热条件下通过处理包含纤维素的生物质的水性悬浮液和/或至少一种己糖的水性碳水化合物溶液和/或一种水性的5-羟甲基糠醛溶液的至少一种HMF低聚物。
在水热条件下处理碳水化合物或由碳水化合物衍生的化合物的生物质(例如基于植物的原料),来制备5-HMF(单体)是已知的,并且其提供了在水性介质中将起始材料暴露于压力和高温。在水热条件下在处理含纤维素的生物质的水性悬浮液和/或至少一种己糖的水性碳水化合物溶液和/或一种水5-羟甲基糠醛溶液的过程中,形成HMF低聚物。
由于其低成本因素,含纤维素的生物质(经常作为农业生产的废物累积)是特别优选的。优选的己糖是果糖或葡萄糖,特别地它们可以是果糖或果糖和葡萄糖的混合物。
优选的水热条件是饱和蒸汽压力和150℃至250℃的温度。这具有以下优点:根据起始原料,在数分钟至数小时内完成HMF低聚物的形成。
优选地,进行制备步骤,直至达到所需量的HMF低聚物或反应停止。
优选地,在制备步骤结束时,在水溶液中存在包含至少一种HMF低聚物的HMF。进一步优选的是影响低聚物或多种低聚物的含量、尺寸和/或浓度。特别优选地,通过在至少一个过滤装置上使在前述步骤中获得的溶液进行过滤来影响低聚物或多种低聚物的含量。例如,在DE 10 2014 112240A1中描述了水热碳化后,处理HMF水溶液。
根据另一方面,本发明涉及可通过前文描述的方法获得的可热固化树脂。
优选地,可热固化树脂包含通过缩聚酚类化合物和/或氨基塑料成型剂与5-羟甲基糠醛(HMF)获得的至少一种聚合物,其中聚合物是酚类化合物和/或氨基塑料成型剂与HMF低聚物的缩聚产物。
在本发明的含义中,缩聚的产物理解为术语聚合物。聚合物通常是水不溶性的。
关于优选的酚类化合物和氨基塑料成型剂,可允许参考上述的陈述
树脂的固体含量可以在较宽范围内变化。固体含量为至少40wt%。优选树脂的固体含量为45wt%至80wt%的范围内,特别优选50wt%和70wt%之间。
优选地,在树脂中总HMF量与酚类化合物和/或氨基塑料成型剂的总量的摩尔比为0.20:1至3:1,优选摩尔比为0.3:1至1:1;特别优选摩尔比为0.45:1至0.70:1。
根据树脂的优选配置,聚合物是酚类化合物和/或氨基塑料成型剂与碳连接的HMF低聚物的缩聚产物,碳连接的HMF低聚物包含与第二HMF单元的芳族键合碳连接的至少一个第一HMF单元。
关于碳连接的HMF低聚物,可允许参考上述的陈述。
根据另一个方面,本发明涉及根据本发明的树脂用于制造木质复合材料的用途。
树脂特别适用于从含木质纤维素的材料如木刨花、木纤维或木屑制造复合材料。根据本技术领域中公知的方法进行木质复合材料的制造。通过使木质纤维素材料与树脂接触,然后固化树脂(其与交联相关联)而得到的木质复合材料。
固化优选通过压制提供有含木质纤维素的材料的树脂来进行。通常使用1mPa至30mPa的压力。通常,压制在120℃至250℃的温度下进行。由于树脂的反应性,即使少至几分钟,也足以生产具有良好机械性能的木材材料。优选地,压制时间在3至10分钟的范围内;特别优选地,压制时间在5至8分钟的范围内。从生产工程和经济观点来看,短的压制时间是有利的。
如果需要,可以通过向树脂中加入固化剂来增强树脂的交联能力。优选地,相对于树脂的量,固化剂的量在2wt%至7wt%的范围内,特别优选相对于树脂的量,在2wt%至5.5wt%的范围内,特别优选相对于树脂的量,在2wt%至3wt%的范围内。特别地,固化剂可以是六亚甲基四胺或铵盐如硫酸铵。然而,HMF低聚物的反应性很高,因此仅需使用非常少量的固化剂来获得具有高交联能力的树脂。还可以完全弃用固化剂。
所得的木质复合材料最终可在干燥烘箱或木材干燥机中在控制气氛下在10℃至100℃范围内的温度下进行后处理,用于稳定。例如,可以包括40%至70%范围内的相对湿度。
制造根据本发明的具有可热固化树脂的木质复合材料中的一个优点在于,木质复合材料是无甲醛的,并且可以基于天然的、可再生的原料生产,并且在该过程中对水分,特别是蒸汽具有非常好的抗性。进一步的优点在于,由于树脂的反应性,数分钟内的短的压制时间足以得到具有非常好的机械性能的木质复合材料。
本发明的树脂特别适用于制造具有≥0.35N/mm2的内部结合强度(IB)的胶合板、木纤维复合材料、刨花板或多层板的面板,
基于本发明树脂的产品的另一优点在于以下事实:它们超过了根据欧洲标准NENEN 319的最小标准的要求,也可以从以下实施例中推断出。
以下实施例仅用于解释说明本发明,并不旨在以任何方式限制本发明。
实施例1:
制造刨花板面板
a)制备含有HMF低聚物的HMF溶液:
通过在45℃和30毫巴(mbar)下在旋转蒸发器中减少体积,同时浓缩和老化结晶HMF的16%水溶液,直至相对于溶液,HMF的浓度为50wt%。
b)制备脲-HMF树脂和性能的比较:
制备脲与HMF的摩尔比不同的两种树脂。第一树脂(以下称为UH(1:0.5))以脲与HMF的比例为1:0.5进行制备。第二树脂(以下称为UH(1:0.25))以脲与HMF的比例为1:0.25进行制备。树脂的固体含量为约58%。对于这两种树脂,使用来自a)的400ml的50%HMF溶液。对于这两种树脂,首先使脲在pH 2下与HMF反应2.5小时,温度为90℃,然后在20℃的温度下进行数小时。在该过程中,观察到树脂的粘度变化。
表1:作为时间函数的粘度增加
c)将木刨花压成刨花板面板:
粘度为1275mPa.s的树脂UH(1:0.5)和粘度为65mPa.s的树脂UH(1:0.25)用于后续压制木刨花。将树脂分别与木刨花和六亚甲基四胺混合,然后在220℃下压制用于生产尺寸为250mm×250mm×16mm的面板。相对于木材的量,干木材的负载量为10wt%的树脂固体。为了测试不同压制时间和不同量的固化剂的影响,使用不同的时间和不同量的六亚甲基四胺产生多个面板。对于使用两种树脂UH(1:0.5)和UH(1:0.25)的刨花板面板获得的值列于表2中。
为了比较,通过使树脂UH(1:0.5)的组分在45℃的较低温度下反应制得第三树脂,UH45(1:0.5)。树脂UH45(1:0.5)还用于将木刨花压制成尺寸为250mm×250mm×16mm的刨花板,对于这些刨花板面板所获得的值也在表2中给出。
使用这些树脂生产的面板的比较表明,原则上,在较长的压制时间下获得了较好的内部结合强度值。
在脲与HMF的摩尔比为1∶0.5的情况下,面板3和4的获得较高值52N/mm2和55N/mm2。这些值可归因于7.5分钟的压制时间与用于制备树脂的90℃高温的结合。
面板1和2以及5和6示出了在制备树脂期间温度的影响。
当延长压制时间时,即使用较少量的HMF制造的面板也产生了令人满意的结果,如面板7至10所示。
关于固化剂,发现不同量的固化剂为稍微显著至不显著,条件是用一定比例的HMF制成面板,如面板3至6所示。面板7和10(具有较低比例的HMF)明显地受固化剂的量更强烈地影响。这些值表明,作为使用的HMF低聚物的正向性质的结果,可大幅降低固化剂的需要量,其中可得到具有相同或相当的内部结合强度的产品。
根据NF EN 319(AFNOR 1993)的内部结合强度(IB):
通过下式表示以[N/mm2]计的内部结合强度:
其中Fmax是断裂时的力,a是面板的宽度以及b是面板的长度。
对于具有13mm至20mm厚度的刨花板和纤维板面板,NF EN 319(AFNOR 1993)规定了≤0.35N/mm2的内部结合强度。
通过切割出在c)下生产的面板获得用于研究内部结合强度的面板。它们的尺寸为50mm×50mm。在切割之前,面板在干燥器中在20℃和65%的相对湿度下稳定。
通过热熔粘合剂将面板紧固到背衬上。根据NF EN 319(AFNOR1993),垂直于面板的平面,机械地测定内部结合强度。
表2:刨花板面板的生产参数和刨花板面板的性能
从权利要求和附图中可以推断出进一步的优点和有利的配置,其中
图1示出了基于两个HMF分子二聚在酸性条件下碳-碳键形成的建议机理,以及
图2示出了基于两个HMF分子二聚在碱性条件下碳-碳键形成的建议机理。
无论单独地以及在彼此的任何组合中,本发明的所有特征对于本发明都是必不可少的。
Claims (13)
1.用于制备可热固化树脂的方法,包括以下步骤:在导致形成缩聚产物的条件下进行使氨基塑料成型剂与5-羟甲基糠醛(HMF)的反应,其特征在于,所述HMF包含至少一种HMF低聚物,并且其中相对于使用的HMF的总量,所述HMF低聚物的比例为0.05wt%至100wt%。
2.根据权利要求1所述的方法,其特征在于,所述反应的步骤在20℃至140℃范围内的温度下进行。
3.根据权利要求1或2所述的方法,其特征在于,使用的所述HMF的量与所述氨基塑料成型剂总量的摩尔比为0.20:1至3:1。
4.根据前述权利要求中一项所述的方法,其特征在于,相对于使用的所述HMF的总量,所述HMF低聚物的比例为0.05wt%至10wt%。
5.根据前述权利要求中一项所述的方法,其特征在于,所述HMF低聚物具有2至20个单元。
6.根据前述权利要求中一项所述的方法,其特征在于,所述氨基塑料成型剂为脲、三聚氰胺、取代的三聚氰胺、取代的脲、乙炔二脲、胍、硫脲、硫脲衍生物、二氨基烷烃、二酰氨基烷烃或这些氨基塑料成型剂中至少两种的混合物。
7.根据前述权利要求中一项所述的方法,其特征在于,所述HMF低聚物是碳连接的HMF低聚物。
8.根据前述权利要求中一项所述的方法,其特征在于,所述反应的步骤在溶液中进行,直至所述溶液达到所需粘度或所述反应结束。
9.根据前述权利要求中一项所述的方法,其特征在于,所述方法包括至少一个另外的步骤,所述另外的步骤使得对于所述反应的步骤产生包含至少一种HMF低聚物的5-羟甲基糠醛。
10.根据权利要求9所述的方法,其特征在于,在水热条件下通过处理含纤维素的生物质的水性悬浮液和/或至少一种己糖的水性碳水化合物溶液和/或一种水性5-羟甲基糠醛溶液制备所述5-羟甲基糠醛。
11.通过根据权利要求1至10中一项所述的方法可获得的可热固化树脂。
12.根据权利要求11所述的可热固化树脂用于制造木质复合材料的用途。
13.根据权利要求11所述的可热固化树脂用于制造具有根据NF EN 319(AFNOR 1993)测定的≥0.35N/mm2的内部结合强度(IB)的胶合板、木纤维复合材料、刨花板或多层板的面板的用途。
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EP17158247.1A EP3366468B1 (de) | 2017-02-27 | 2017-02-27 | Verfahren zur herstellung thermisch härtbarer harze sowie durch das verfahren erhältliche harze |
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CN113103380A (zh) * | 2021-04-13 | 2021-07-13 | 桃江县福丰木业有限公司 | 一种不易剥裂的环保木胶板及其制备方法 |
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EP4086295A1 (en) | 2021-05-08 | 2022-11-09 | Prefere Resins Holding GmbH | Resins from aldehydes and organic aldehyde-reactive compounds |
CA3215441A1 (en) | 2021-05-26 | 2022-12-01 | Lignum Technologies Ag | Modified aminoplastic adhesive resin, procedure of its preparation and composite materials prepared using this modified aminoplastic adhesive resin |
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- 2018-02-26 US US15/904,809 patent/US20180244825A1/en not_active Abandoned
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- 2018-02-26 PH PH12018000061A patent/PH12018000061A1/en unknown
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EP3366468A1 (de) | 2018-08-29 |
PH12018000061A1 (en) | 2019-07-24 |
MX2018002378A (es) | 2018-11-09 |
BR102018003743A2 (pt) | 2018-10-30 |
JP2018162444A (ja) | 2018-10-18 |
AU2018201390A1 (en) | 2018-09-13 |
EP3366468B1 (de) | 2022-04-06 |
US20180244825A1 (en) | 2018-08-30 |
CA2996566A1 (en) | 2018-08-27 |
RU2018106891A (ru) | 2019-08-26 |
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