CN108501164A - 用于制造木质复合材料的方法以及通过该方法可获得的木质复合材料 - Google Patents

用于制造木质复合材料的方法以及通过该方法可获得的木质复合材料 Download PDF

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Publication number
CN108501164A
CN108501164A CN201810162251.8A CN201810162251A CN108501164A CN 108501164 A CN108501164 A CN 108501164A CN 201810162251 A CN201810162251 A CN 201810162251A CN 108501164 A CN108501164 A CN 108501164A
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hmf
resin
oligomer
method described
composite wooden
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CN201810162251.8A
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CN108501164B (zh
Inventor
弗兰乔斯·巴杜
斯特凡·克拉维利茨基
马里安杰拉·莫尔塔托
雷托·弗赖
玛丽-克里斯蒂娜·拉格勒
克里斯托弗·霍尔梅斯
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Avalon Industrial Co Ltd
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Avalon Industrial Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/08—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
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    • B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08—Moulding or pressing
    • B27N3/10—Moulding of mats
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B21/02—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board the layer being formed of fibres, chips, or particles, e.g. MDF, HDF, OSB, chipboard, particle board, hardboard
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    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
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Abstract

本发明涉及用于制造木质复合材料的方法，包括以下步骤：在导致缩聚产物的形成的条件下通过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)反应制备可热固化的树脂，使该树脂与含木质纤维素的材料接触，以及在形成木质复合材料的条件下固化树脂。该方法的特征在于5‑羟甲基糠醛包含至少一种HMF低聚物。本发明还涉及通过该方法可获得的木质复合材料。

Description

用于制造木质复合材料的方法以及通过该方法可获得的木质 复合材料
本发明涉及用于制造木质复合材料的方法。特别地，本发明涉及用于制造木质复合材料的方法，包括以下步骤：
-制备可热固化的树脂，在导致形成缩聚产物的条件下使能够缩聚的酚类化合物和/或氨基塑料成型剂(amino plastic forming agent)与5-羟甲基糠醛(HMF)反应，
-使树脂与含木素纤维素的材料接触，
-固化树脂，形成木质复合材料。
本发明还涉及可通过该方法获得的木质复合材料。
木质复合材料通常由含木质纤维素的材料(如木刨花、木纤维或木屑)和可热固化树脂制成。具有氨基塑料成型剂脲、三聚氰胺和双氰胺的氨基树脂，苯酚树脂或氨基酚树脂可以提及作为可热固化树脂的例子。通常如下获得木质复合材料：使木质纤维素材料与树脂的接触，并在升高的温度下压制，其中树脂固化，其与交联相结合。
使用这些树脂生产的木质复合材料由于其良好的力学性能，如良好的内部结合强度(IB)，对湿度(特别是蒸汽)不敏感，尤其是在家具中找到了它们的实际应用，其中以下列形式使用，例如，胶合板，木纤维复合材料，刨花板，多层板的面板。它们主要用在室内。为此，重要的是，木质复合材料不发散任何有害化合物。这些有害化合物主要源于所使用的树脂。
可热固化的树脂通常通过缩聚酚类化合物和/或氨基塑料成型剂与活性羰基化合物，特别是醛类而得到。基于其较高的反应性，主要是甲醛(其必须被分类为对健康造成危害)用于缩聚。为了促进反应，通常用过量的甲醛(其具有高挥发性)进行反应，因此树脂具有含量较高的游离甲醛。因此，树脂的甲醛排放和由其制造的木质复合材料的甲醛排放也较高。
由于潜在的危害，已经尝试多年以减少甲醛的含量。在这方面的一个措施是在树脂的制备中用其他反应性化合物代替甲醛。5-羟甲基糠醛(HMF)已被认为是用于此目的的非常有前途的候选物，因为它能够形成交联键，难挥发以及几乎无毒，并且可得自可再生原料。
US 4 524 164 A涉及无甲醛的可热固化的粘合剂树脂并且涉及使用该粘合剂树脂用于粘合含木质纤维素的材料的方法，从而形成产品例如胶合板和刨花板面板。首先如下制备液体可熔树脂：在交联剂(其选自脲或苯酚或它们的混合物)连同无机酸或其铵盐和金属离子催化剂存在下加热水性的糖或淀粉溶液。然后，将可熔树脂与有机酸酐混合，涂覆在含木质纤维素的材料的表面上。为了形成产品，如胶合板或刨花板面板，然后将该混合物暴露于热和压力。
在行业杂志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30重量％的甲醛(N.Esmaeili et al.,DOI 10.1007/s0017-016-1072-8)。用该树脂制造的刨花板面板具有≥0.35N/mm2的内部结合强度(IB)，如当前需要的满足根据欧洲标准NEN EN 319用于室内面板的最低标准。仍然，其缺点是树脂和由其制造的刨花板面板仍然含有大量的有毒的甲醛。
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的特征的用于制造木质复合材料的方法来实现该任务。
用于制造木质复合材料的方法，包括以下步骤：
-在导致形成缩聚产物的条件下通过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，制备可热固化的树脂，
-使树脂与含木质纤维素的材料接触，以及
-在形成木质复合材料的条件下固化树脂。
该方法的特征在于，5-羟甲基糠醛包括至少一种HMF的低聚物(5-羟甲基糠醛类化合物包括至少一种HMF的低聚物)。
已经发现，可以完全省去甲醛来制造木质复合材料，条件是HMF(包含HMF低聚物)用于缩聚的制备步骤。这是假设HMF低聚物的反应性大于HMF单体，从而允许在不使用甲醛的情况下制备木质复合材料。
在HMF溶液中出现水溶性直链和支化的HMF低聚物是已知的(例如DE 10 2014 112240 A1)。例如可以通过HPLC分析追踪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/单体的化合物被称为HMF低聚物。通常，HMF低聚物被理解为摩尔质量最高达3000g/mol的化合物。具有低摩尔质量的HMF低聚物(其在选定的反应条件下可溶性地存在或至少以分散形式存在于选择的溶剂中)特别适合本方法。在这个方面，溶解和分散形式之间的过渡可以是连续的，因此在这方面的差别不会出现在本发明中。
用于制备可热固化树脂的缩聚以本身已知的方式进行。适合该反应的溶剂以及适合的反应条件，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低聚物可以存在于各种长度和/或各种交联程度的HMF低聚物的混合物中。另外，可以通过选择HMF低聚物或通过选择不同的HMF低聚物的组合，来匹配由选择性地针对使用的技术目的的制备步骤得到的树脂的性能。
根据该方法的一个有利的配置，制备树脂的反应是在40℃至140℃的范围内，优选50至140℃的范围内，更优选为60℃至100℃的范围内，特别优选80℃至100℃的范围内的温度下进行的。原则上，进行缩聚的温度可以在较宽的范围内变化。然而，已经观察到，更多的反应树脂可通过在较高温度下的反应获得。特别是较高反应性树脂(其需要在后续形成木材材料期间用于固化的较短的压制时间)可以在80℃至100℃的范围内的温度下获得。这是出乎意料的，由于迄今为止猜想HMF的增加的分解将已经从高于50℃的温度开始就发生了。
根据该方法的另一有利的配置，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。摩尔过量的HMF也可以是有利的。相应的酚类化合物，相应的氨基塑料成型剂或酚类化合物和氨基塑料成型剂的混合物的合适的摩尔比可以由本领域技术人员容易地确定。
根据该方法的另一有利的配置，相对于使用的HMF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％；特别优选相对于使用的HMF的总量，HMF低聚物的比例为2wt％至4wt％。由于较高的反应性，即使少量的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，也可以使用较高比例的HMF低聚物。本发明也包含以下事实：相对于使用的HMF的总量，低聚物HMF占比最高达到或最高达到几乎100wt％。
根据该方法的另一个有利的配置，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。具有2至10个单元的HMF低聚物在温和的条件下(是指室温和常压)是容易溶于水的，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低聚物是特别容易溶于水的，因此特别适合用于该反应。
根据该方法的另一优选的配置，用于该反应的HMF低聚物为碳连接的HMF的低聚物。
在本发明的含义中，HMF低聚物被称为碳连接的HMF的低聚物，条件是至少两个HMF单元通过碳-碳键连接，涉及两个HMF单元之一的呋喃环的3或4位的芳族键合的碳原子。具体地，碳连接的HMF低聚物至少含有一个第一单元，其醛基碳原子与第二单元的呋喃环的芳环键合碳原子连接。
本发明人已经发现，除了HMF低聚物(产生自HMF单元的醛和/或羟基的连接，并且具有相应的醚，半缩醛和/或缩醛键)，在酸性条件下和在碱性条件下形成HMF低聚物(其中通过碳-碳键连接这些单元)。例如，这些键可以在亲电攻击第一HMF单体的醛基或第二HMF单体的呋喃环的位置3或4的碳原子的HMF低聚物的HMF单元或HMF低聚物的HMF单元期间形成。
提出了在酸中和碱中形成HMF低聚物的机理，并且在图1和图2中示出。由此，可以清楚的是，除了其他事实，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官能醛和/或羟基基团。由此，获得具有非常(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外，碳连接的HMF低聚物可以还含有其它键，如醚，半缩醛和/或缩醛键。为了提高所得树脂的反应性，当两个HMF单元已经与涉及芳族键合碳原子连接时，这是足够的。特别地，具有2个单元的碳连接的HMF低聚物含有较高比例的游离的官能性反应性基团/HMF低聚物。碳连接的HMF低聚物也可以具有多个这样的碳-碳连接。
此外，除了碳连接的HMF低聚物，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，即使少量的碳连接的HMF低聚物足以制备具有非常(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低聚物占比最高达到或最高达到几乎100wt％。
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：通常用于制造可热固化树脂。
在这个方面，所有含羟基的芳族化合物(在芳族部分具有至少一个碳原子，该碳原子适合于酚类化合物和HMF之间的亲核加成反应)，在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的至少两种的混合物。
有利地，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的至少两种的混合物。
在这个方面，除了提及的组分，还可以存在其他酚类化合物和/或氨基塑料成型剂。
根据酚类化合物和/或氨基塑料成型剂，在准备步骤中pH可在较宽范围内变化。例如，pH范围为6至10的范围内，优选为7至8.5的范围内。
根据该方法的另一有利的配置，制备步骤在溶液中进行，直至溶液达到需要的粘度或反应结束。优选地，进行制备步骤直至溶液达到超过200mPa.s的粘度，特别优选直至溶液达到超过450mPa.s的粘度。
有利的是，如下制备具有非常(高)反应性的可热固化性树脂：通过固化与含木质纤维素的材料的材料接触，产生具有非常好的机械性能的木质复合材料。
优选地，可热固化的树脂包括至少一种聚合物，该聚合物通过酚类化合物和/或氨基塑料成型剂与5-羟甲基糠醛(HMF)的缩聚获得，其中聚合物为酚类化合物和/或氨基塑料成型剂与HMF的低聚物的缩聚产物。
在本发明的含义中，缩聚产物理解为术语聚合物。聚合物通常不溶于水。
特别优选地，该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，其包含与第二HMF单元的芳族键合的碳连接的至少一种第一HMF单元。
在制备步骤中得到的树脂的固体含量可在较宽的范围内变化。固体含量为至少40wt％，优选地，树脂的固体含量范围为45wt％至80wt％，特别优选50wt％至70wt％。
根据该方法的另一个有利的配置，方法包括至少一个另外的步骤，它使得用于制备可热固化树脂的步骤可以使用包括至少一种HMF低聚物的5-羟甲基糠醛。
优选地，使可用的步骤包括将HMF单体和/或HMF低聚物的更高或更低纯的溶液暴露于导致形成HMF低聚物的条件。发明人已经发现例如，由具有水的结晶HMF制备的HMF水溶液老化，伴随形成HMF低聚物。在这个方面，可以使用本领域技术人员熟悉的分析手段如HPLC和NMR光谱法量来确定HMF低聚物的量和分子量。
在温和的条件下(即在常压和室温下)HMF低聚物的形成可以持续数小时，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，条件特别优选包括加热溶液，必要时与酸化或碱化结合。可通过酸化，碱化和加热来加速老化过程。
特别优选的可用步骤的变体包括使得5-羟甲基糠醛可用，其包括在水热条件下通过处理含纤维素的生物质的水悬浮液和/或至少一种己糖的水性碳水化合物溶液和/或一种水性5-羟甲基糠醛溶液的至少一种HMF低聚物。
在用于制备5-HMF的水热条件下，处理碳水化合物或衍生自碳水化合物的化合物的生物质(例如基于植物的原料)是已知的，并且其提供了在水性介质中将起始原料暴露于压力和升高的温度。在水热条件下，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/或水性的5-羟甲基糠醛的溶液期间，形成HMF低聚物。
因为其低成本因素，含纤维素的生物质(其通常作为农业生产的废物而积聚)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℃温度。这具有以下优点：HMF低聚物的形成在数分钟至数小时内完成，这取决于起始原料。
优选地，进行可用步骤直至达到HMF低聚物的需要量或反应停止。
优选地，在可用步骤结束时，HMF(其包括至少一种HMF低聚物)存在于水溶液中。进一步优选影响该低聚物或多种低聚物的含量，尺寸和/或浓度。特别优选地，通过使可用步骤中得到溶液在至少一个过滤装置上进行过滤来影响该低聚物或多种低聚物的含量。例如，在DE 10 2014 112240A1中描述的在水热碳化后处理水性的HMF溶液。
根据该方法的另一有利的配置，含木质纤维素的材料(使其与树脂接触)包括木刨花、木纤维、木绒毛(木毛絮wood flocks)、木屑、木颗粒、木条(wood strips)、木片(woodflakes)和板以及这些的混合物。相对于大量不同的木质复合材料，含木质纤维素的材料可在宽范围内改变。
使树脂与含木质纤维素的材料接触可以通过在本领域技术人员已知的方法进行。通常进行接触取决于树脂的性质和含木质纤维素的材料的配置，例如通过喷涂，刷涂，通过机械搅拌混合，或辊涂。
根据该方法的另一有利的配置，相对于干的含木质纤维素的材料的重量，使含木质纤维素的材料与以2wt％至20wt％的量，优选以5wt％至15wt％的量的树脂接触。树脂量可以在较宽范围内改变，这取决于含木质纤维素的材料的配置，和适用于木质复合材料的要求。此外，可以有利的是使两种或更多种树脂的混合物与含木质纤维素的材料接触。
根据该方法的另一有利的配置，固化树脂包括压制含木质纤维素的材料与树脂。通常使用的压力为1mPa至30mPa，。
优选地，压制发生在120℃至250℃的范围内，特别优选210℃至230℃的范围内的温度下。由于树脂的反应性，甚至少至数分钟足够用于生产具有良好力学性能的木材质材料。优选地，压制时间为3至10分钟的范围内；特别优选，压制时间为5至8分钟的范围内。从生产工程和经济角度看，短的压制时间是有利的。
如果需要的话，树脂的交联能力可通过添加固化剂至树脂来增强。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，非常特别优选相对于树脂的量，在2wt％至3wt％的范围内。固化剂特别地可用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，需要使用仅很少量的固化剂来获得具有高的交联能力的树脂。还可以完全弃用固化剂。
得到的木质复合材料可以最终被后处理，用于在烘箱中或木材干燥机中，在10℃至100℃温度下，在受控的气氛下进行稳定。这可以包括，例如，相对湿度在40％至70％的范围内。
根据另一个方面，本发明涉及木质复合材料，其可用通过以上描述的方法获得。
使用本发明的方法制造木质复合材料的一个优点是木质复合材料无甲醛，并且可基于自然的，可再生原料制造，并且在该过程中，具有非常好的耐湿性，特别是耐蒸汽性。该方法的另一个优点是，由于HMF低聚物的反应性，在数分钟范围内的短的压制时间足以获得具有非常好的机械性能的木质复合材料。从经济性观点看，并相对于木质复合材料的工业生产，这是非常令人期望的。
根据木质复合材料的另一个有利的配置，木质复合材料是胶合板、木纤维复合材料、刨花板或多层板的面板，具有≥0.35N/mm2的内部结合强度(IB)
木质复合材料的优点在于这样的事实：它超过根据欧洲标准NEN EN319的最小标准的要求，也可从以下实施例推断出。
以下实施例仅仅用作解释说明本发明而不旨在以任何方式对其进行限制。
实施例1:
制造刨花板面板
a)制备含有HMF低聚物的HMF溶液：
通过在旋转蒸发仪中在45℃和30毫巴(mbar)下减少体积同时浓缩和老化结晶HMF的16％的水溶液，直至相对于溶液HMF浓度为50％。
b)制备脲-HMF树脂以及性能比较：
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))，使用脲与HMF的比例为1：0.5进行制备。第二树脂(以下称为UH(1:0.25))，使用脲与HMF的比例为1：0.25进行制备。树脂的固体含量为约58％。对于两种树脂，使用来自a)的400mL 50％的HMF溶液。对于两种树脂，首先在pH 2下使脲与HMF反应2.5h并且温度为90℃，然后在20℃的温度下反应数小时。在该过程中，观察到树脂粘度的改变。
表1:作为时间函数的粘度增加
c)压制刨花成刨花板面板：
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)用于随后压制木刨花。将树脂分别与木刨花和六亚甲基四胺混合，然后在220℃压制生产尺寸为250mm×250mm×16mm的面板。相对于木材的量，干燥木材负载为10wt％树脂固体。为了测试不同压制时间和不同固化剂量的影响，使用不同的时间和不同量的六亚甲基四胺生产多个面板。针对具有两种树脂UH(1:0.5)和UH(1:0.25)的刨花板面板获得的值在表2中给出。
为了比较，通过使树脂UH(1:0.5)的组分在较低的温度45℃下反应生成第三树脂UH45(1:0.5)。将树脂UH45(1:0.5)也用于将木刨花压制成尺寸为250mm×250mm×16mm的刨花板。针对这些刨花板面板获得的值也在表2中给出。
使用这些树脂生产的面板的比较表面，原则上，在更长的压制时间下获得内部结合强度更好的值。
在脲与HMF的摩尔比为1:0.5的情况下，面板3和4获得较高值52N/mm2和55N/mm2。这些值可归因于压制时间7.5分钟与用于制备树脂的高温90℃的结合。
面板1和2以及5和6说明在制备树脂期间温度的影响。
当压制时间延长时，即使使用较少量的HMF产生的面板也产生令人满意的结果，如面板7至10所示。
关于固化剂，已经发现不同量的固化剂为稍微显著至不显著，条件是使用一定比例的HMF生产面板，如面板3至6所示。面板7和10(使用较低比例的HMF)显然受到固化剂的量更强的影响。这些值表明，由于使用的HMF低聚物的正面性能，固化剂的需要量可大幅度降低，其中可以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。
对于厚度为13mm至20mm的范围内的刨花板和纤维板，NF EN 319(AFNOR 1993)规定内部结合强度≤0.35N/mm2。
通过切割在c)中产生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℃和相对湿度65％下稳定。
通过热熔粘合剂将面板固定至背衬。根据NF EN 319(AFNOR 1993)，垂直于面板的平面，机械地确定内部结合强度。
表2:刨花板面板的生产参数和刨花板面板的性能
从权利要求和所附的附图可以推断出进一步的优点和有利的配置，
其中，
图1显示了基于两个HMF分子的二聚在酸性条件下的碳-碳键形成的提出的机理，以及
图2显示了基于两个HMF分子的二聚在碱性条件下的碳-碳键形成的提出的机理。
无论单独地及其在彼此任何组合中，本发明的所有特征对于本发明是重要的。

Claims (15)

1.用于制造木质复合材料的方法，包括以下步骤：
-在导致缩聚产物的形成的条件下，通过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)反应制备可热固化树脂，
-使所述树脂与含木质纤维素的材料接触，以及
-在形成木质复合材料的条件下，固化所述树脂，
其特征在于，所述5-羟甲基糠醛包含至少一种HMF低聚物。
2.根据权利要求1所述的方法，其特征在于，用于制备所述树脂的所述反应在40℃至140℃范围内的温度下进行。
3.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HMF的总量，所述HMF低聚物的比例为0.05wt％至10wt％。
4.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。
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低聚物是碳连接的HMF低聚物。
6.根据前述权利要求中一项所述的方法，其特征在于，所述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。
7.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。
8.根据前述权利要求中一项所述的方法，其特征在于，所述制备的步骤在溶液中进行，直至所述溶液达到所需的粘度或反应结束。
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，所述另外的步骤使所述制备的步骤得到包含至少一种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-羟甲基糠醛溶液得到所述5-羟甲基糠醛。
11.根据前述权利要求中一项所述的方法，其特征在于，与所述树脂接触的所述含木质纤维素的材料包括木刨花、木纤维、木绒毛、木屑、木颗粒、木条、木片和板以及它们的混合物。
12.根据前述权利要求中一项所述的方法，其特征在于，相对于干的所述含木质纤维素的材料的重量，使所述含木质纤维素的材料与以2wt％至20wt％的量、优选以5wt％至15wt％的量的树脂接触。
13.根据前述权利要求中一项所述的方法，其特征在于，所述树脂的固化包括所述含木质纤维素的材料与所述树脂的压制。
14.通过根据权利要求1至13中一项所述的方法可获得的木质复合材料。
15.根据权利要求14所述的木质复合材料，其特征在于，所述木质复合材料是具有根据NF EN 319(AFNOR 1993)确定的≥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。
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