CN102458827A - 包含两个或更多个叠置的仿木材料层的复合材料 - Google Patents
包含两个或更多个叠置的仿木材料层的复合材料 Download PDFInfo
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- CN102458827A CN102458827A CN2010800289647A CN201080028964A CN102458827A CN 102458827 A CN102458827 A CN 102458827A CN 2010800289647 A CN2010800289647 A CN 2010800289647A CN 201080028964 A CN201080028964 A CN 201080028964A CN 102458827 A CN102458827 A CN 102458827A
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- Prior art keywords
- composite
- bamboo
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- prepolymer
- weight
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Abstract
本发明涉及包含两个或更多个叠置的仿木材料层的复合材料。所述层借助包含具有NCO基的预聚物的单组分聚氨酯粘合剂接合在一起，且所述仿木材料为单子叶植物。
Description
本发明涉及包含两个或更多个叠置的仿木材料层的复合材料，该复合材料的用途以及由该复合材料形成的集装箱或拖车底板。
复合材料具有非常广泛的应用领域。
对于可持续使用的资源，来自可再生原料的复合材料特别具有吸引力。目前，仅集装箱地板每年就使用大约800000m3的热带硬木(特别是克隆木等)，这相当于大约560km2面积(等于华盛顿特区面积的大约3倍)的热带雨林每年为此被砍伐。相应的限制和配额限定已极大限制了这些热带雨林木料的可用性，因此正大力寻求替代材料。
US 2007/0088103公开了一种特别具有两个层的复合材料，这两个层由基于氨基甲酸酯改性的异氰酸酯的未发泡的聚氨酯粘合剂粘结。该复合材料层可以是木质纤维层，特别是软木、木材、草或稻草。
然而，该文献未描述来自具有低密度以及高机械负载能力和回弹性的可再生原料的复合材料。
众所周知层压材料可由竹子制成，各个层由酚醛树脂粘合剂彼此粘结(例如参见Journal of Forestry Research，13(2)，151-156页(2002))。然而，事实上由酚醛树脂粘合剂制成并包含竹子的层压材料有时具有0.8-1.0kg/l或甚至＞1kg/l的较高密度，这是不利的。然而，特别不利的是静态效率不足，特别是其动态效率不足。这都导致在静负载下由于破裂而过早破坏(Institute of International Container Lessors(IILC)，Technical Bulletin(TB)001，2002年9月1日，Short Span Test)，尤其是由其制成的层压材料的各个层分层，所述层由酚醛树脂和/或聚乙酸乙烯酯粘合。这种由酚醛树脂粘合的层压材料特别是在高温下，例如在80℃下，也呈现其不足的性能。
因此，本发明的目的是提供一种基于仿木材料的复合材料，其具有优异的机械性能和动态性能，特别是高静态和动态负载能力和高回弹性，以及基本＜1kg/l的低密度，并且即使在高温下也保持其高性能水平。
该目的通过包含两个或更多个叠置的仿木材料层的复合材料实现，该层由包含具有游离NCO基的预聚物的单组分聚氨酯粘合剂彼此粘结，该仿木材料为单子叶植物。
单子叶植物(具有单个子叶的植物)不同于双子叶植物(具有两个子叶的植物)，因为它们的维管束没有形成层，它们在厚度方面没有次生生长。
结果发现，通过使用包含具有游离NCO基的预聚物的单组分聚氨酯粘合剂粘结由单子叶植物形成的层，可获得基于木质化巨型禾本科植物的复合材料，其具有优异的机械性能，同时具有低密度。
单子叶植物优选为木质化巨型禾本科植物。
木质化巨型禾本科植物属于禾本科(Gramineae)并具有年年生长的木质化的杆。
优选使用的木质化巨型禾本科植物为竹子。例如，竹子的结构和性能描述在www.bambus.rwth-aachen.de中。
一般而言，术语竹子被理解为意指具有多年生、木质化或侧生的杆的树状或丛状禾本种。竹子组织的木质化细胞结构及其工艺性能与真实的木材组织非常相似，但还是具有显著差异。
竹子是尺寸、轻度和强度性能的极端产物。结构和性能与现代高科技材料的相当：其稳定，但由于其空腔、极轻和有回弹性而通过隔节变硬，并具有有时优于其它材料(如木材、混凝土或钢)的物理性能。尽管木材具有硬芯并沿向外的方向而逐渐变软，但竹子却是外硬内软-一种更加稳定的结构。
世界范围内存在约500种不同的竹科(Bambusae)，其有时具有数百种亚种，在热带南美洲包括2500种。仅在哥伦比亚，大约25种不同的巨竹被用在艺术品、手工艺品和建筑构造中。
由von Humboldt和Kunt命名的“狭叶瓜多竹(Guadua Angustifolia)”以称为Guadua Macana和Guadua Castilla的两种亚种生长在海平面以上1800m，其通常沿河流生长在小规模的森林中，而且也生长在草地和斜坡上。其达到大约20-25m的高度和将近18cm的直径。每个杆从网状根系处长出来，在一年内达到其完整高度并在6-8年内木质化，直到脉管堵塞。
通过竹节间的筒状壁截面呈现装饰图案，所述图案包含维管束纤维和基本组织纤维。维管束从内向外连续聚集。更强壮的维管束纤维束大多数是致密的，其中与钢筋混凝土构造中的钢筋类似，边缘带的静态应力最大。
在增强材料的情况下，现代材料技术使用术语纤维复合材料。将高强度纤维嵌入填充的基体材料(基质)中。混凝土研究的一个分支同样集中于具有纤维增强的混凝土。
在植物领域中，该发展产生有效的轻质构造。薄壁截面随着元件变硬而定形，以使弯曲方向的总惯性矩尽可能大。
竹筒为仿生方案(即大自然中的问题的技术方案)的主要实例。竹子具有精细的轻质结构：高弹性纤维平行于最外部的硅化边缘层中的轴蔓生，其具有高达40kN/cm2的拉伸强度，这甚至超过结构钢的拉伸强度(37kN/cm2)。
在节间中的筒状竹壁的无限制纵向易分裂性是由绝对平行的纤维导致。然而，在节中，它们四面八方交叉。这些具有高硅化隔膜的增强节使筒的分劈强度和抗弯强度增加。
竹子组织没有象双子叶植物的髓射线一样的径向纤维方向以及没有形成层，这就是在地面之上厚度不增加的原因。整个茎截面为单“年轮”。根据该机理，我们知道，在相同的材料比例下，圆柱形筒的抗弯强度是实心圆杆的四倍。因此早期的植物已死去。它们沿轴仅具有一个强化组织束作为加强件。
因此，大自然逐渐创造了中空体。所有随后的改进不包括新结构单元，仅仅是这些单元的改进和精细的排列：细胞-所有生物体的最小单元。
茎或杆不仅具有静态效果，也用作复杂的器官。它将水和营养物从根输送到最远的叶梢，并将有机化合物从叶梢输送回根。因此轴向材料不应仅仅是粗结构材料，其具有最佳的拉伸、压缩和抗弯强度。
分子物种系统的植物细胞壁由非常复杂的结构组成。在这些之中，纤维素占最重要的比例。通过与其它分子(木质素)结合，可以分化的方式使细胞壁变硬。纤维素和部分半纤维素用作骨架物质，木质素作为粘结剂和填充物。因此，纤维素的比例决定抗弯强度和拉伸强度，木质素含量决定组织的压缩强度。
细胞束称为纤维。维管组织(输送组织)的纤维束结合成维管束。维管束的形态、方向、数目和分布表征竹子组织的解剖结构。这些也可用作微观测定竹子种类和竹材。
根据植物生理特征的生殖结构测定物种通常不成功。
维管束的显著的解剖差异更加清晰。Kratzsch将竹子的筒状壁截面分成四个区。维管束的形状从筒状壁外侧至筒状壁内侧具有显著变化。在I和II区中，两个不等大小的镰状韧皮围绕两个孔纹导管和环纹导管排列。从III区至IV区，镰状韧皮围绕筛部、孔纹导管和环纹导管缓慢形成，内侧镰状韧皮消失并使其周界减少，以致普通竹子的完整的维管束最终具有五个韧皮纤维部分。
所有竹子物种的维管束形状呈现类似的变化。它们的结构、密度和分布对材料性能和整个筒或I-IV区切片的潜在用途具有直接影响。相反地，工件的竹子部分可通过其外观特性在显微镜下诊断，从其起源可在截面区中测定相关竹子物种并可将其分级。I区和II区的分劈条坚硬、刚硬、纤细光滑；III区和IV区的条柔和、柔软、粗糙并产生碎片。此外，茎底部、中部或梢部的其它部分决定材料差异，无论建筑材料或工程材料来源于幼小的、一年生、多年生、薄壁的、厚壁(＞14)的筒。因此，对于各材料切片和片段具有不同预定用途。
关于竹子的压缩强度：在平行于纤维的压力下，具有节的筒切片的强度值仅比不具有节的筒切片高约8％。在垂直于纤维的压力下，与不含节的筒切片相比，节导致强度增加高达45％。
关于竹子的拉伸强度：竹子的外壁的拉伸强度显著高于内皮，就截面区域而言，细筒优于厚筒。这些结果还解释了薄筒比厚筒具有更大弯曲强度的原因；在厚筒的情况下，每一单元面积具有更高拉伸强度的外皮纤维的比例低于总截面。茎上部三分之一的竹材的拉伸强度比茎底部的材料低约12％。节点在拉伸应力下具有降低强度的效果。
关于竹子的回弹性：就截面区域而言，薄壁的细竹筒或竹杆的强度值高于较厚的材料。就回弹性而言，其与拉伸、剪切或弯曲应力相同，在外壁区积聚高强度纤维束也具有加强效应。就实心木材而言，竹子的弹性模量还随着应力增加而降低(5-10％)。对于结构的计算值，可使用2000kN/cm2的弹性模量。
特别地，竹子的优点还在于其为非常有效的高持久性材料：不同建筑材料的能量平衡(即为了生产具有某些建筑能力的建筑材料元件而必需的能量)：木材比竹子大约2.5倍，混凝土比竹子大八倍，钢比竹子大50倍(参见论文：Janssen，J.A.，Bamboo in Building Structures，DissertatieDrukkerij Wibro，Helmond，5月19日，1981)。
更优选地，将棕榈用作单子叶植物。
根据本发明的复合材料优选具有5-31个叠置的层。
叠置的层优选由小而平的竹片或竹条形成，所述竹片或竹条通过如下方式获得：将竹子分劈成厚度为0.4-6mm的同心空筒，将由分劈获得的空筒沿径向分割和使分段的空筒产物变平，小而平的竹片或竹条以这样一种方式排列：在各种情况下，在复合材料的两个最外层中，它们具有沿复合材料的主负载方向的纤维方向，并且在各种情况下，在相邻层中的纤维方向以相对于彼此20-90°，优选90°的角度旋转排列。
叠置的层优选由小而平的竹片或竹条形成，所述竹片或竹条通过如下方式获得：将竹子分劈成厚度为0.4-6mm的同心空筒，将由分劈获得的空筒沿径向分割和使分段的空筒产物变平，小而平的竹片或竹条以这样一种方式排列：在各种情况下，在复合材料的两个最外层中和在复合材料中的直接存在于下方的其它1-6层的每层中，它们具有沿复合材料主负载方向的纤维方向，并且在各种情况下，在相邻层中的纤维方向以相对于彼此20-90°，优选90°的角度旋转排列。
在叠置的层中使用的小而平的竹片或竹条优选没有竹子外皮。
在各种情况下优选将仍具有竹子外皮的小而平的竹片或竹条用于叠置层的两个最外层，在各种情况下在叠置的复合材料的两个最外层中的竹子外皮面向外
除了两个或更多个叠置的仿木材料层之外，可提供有一个或多个塑料层，特别是外部聚氨酯/聚脲层。
除了两个或更多个叠置的单子叶植物层之外，可提供有一个或多个木材层。
更优选地，除了两个或更多个叠置的仿木材料层之外，可提供有一个或多个由玻璃纤维网、天然纤维网、玻璃纤维毡或天然纤维毡形成的层。
复合材料也可被塑料层完全包裹。
根据本发明，两个或更多个单子叶植物(特别是木质化巨型禾本科植物，优选竹子)层由包含具有游离NCO基的预聚物的单组分聚氨酯粘结剂粘结。
优选地，该单组分聚氨酯粘合剂包含比例高达99重量％的具有游离NCO基的预聚物，该预聚物可由至少一种具有对异氰酸酯呈反应性的化合物的组分A和至少一种具有异氰酸酯的组分B获得，
-0.1-40重量％，优选0.1-30重量％的填料，其包含至少一种纤维和至少一种除纤维以外的非纤维填料物质，
-0-20重量％的常用添加剂和助剂，
-0-20重量％的活化剂，
所述至少一种纤维的直径为5-100μm，长度为0.02-6mm。
在另一优选的实施方案中，使用单组分聚氨酯粘合剂，不添加包含纤维的填料。特别地，该单组分聚氨酯粘合剂包含比例高达99.999重量％的预聚物，该预聚物可由至少一种具有对异氰酸酯呈反应性的化合物的组分A和至少一种具有异氰酸酯的组分B获得，该单组分聚氨酯粘合剂包含如下组分：
-0-20重量％的常用添加剂和助剂，和
-0.001-20重量％的至少一种活化剂，其选自一种或多种下列物质：4-甲基吗啉、4-乙基吗啉、4-环己基吗啉、2，2’-二吗啉基二乙基醚或二吗啉基聚乙二醇，
a)该预聚物具有下列特征：
i)基于预聚物计5-30重量％的NCO含量，
ii)在25℃下300-15000MPa.s的粘度，
b)组分A具有下列特征：
i)组分A包含至少一种二醇，
ii)组分A中的OH数为10-500KOH/g，
该单组分聚氨酯粘合剂包含填料，并且在25℃下的粘度为300-15000MPa.s。
上述优选的单组分聚氨酯粘合剂描述在EP 1072620和EP 1072621中。
在制备单组分聚氨酯粘合剂的预聚物时，优选以获得预聚物的上述性能，特别是NCO含量和粘度的比例使用组分A和B。另外，可使用助剂和添加剂或催化剂来制备该预聚物。
用于制备该预聚物组合物和粘合剂组合物的其它原料或组分以举例的方式描述如下：
合适使用的对异氰酸酯呈反应性的化合物(即组分A)可以是具有2-8，优选2-6的官能度和60-10000分子量的化合物，其以羟基、巯基和/或伯和/或仲氨基作为对异氰酸酯呈反应性的基团。例如，已证实有用的是多元醇，其选自聚醚多元醇和聚酯多元醇、含羟基的聚硫醚多元醇和聚缩醛和含羟基的脂族聚碳酸酯、聚碳酸酯二醇和聚己内酯二醇以及至少两种所述多元醇的混合物。优选使用聚酯多元醇和/或聚醚多元醇。多羟基化合物的羟基数通常为20-850mg KOH/g，优选为25-500mg KOH/g。
作为对异氰酸酯呈反应性的化合物，在本发明的方法中还可以使用分子量为60至＜400的二醇和/或三醇作为增链剂和/或交联剂。然而，为了改进机械性能，例如硬度，以及为了增加预聚物的稳定性，可证实添加增链剂、交联剂或任选其混合物是有利的。增链剂和/或交联剂优选具有60-300g/mol的分子量。例如，适合用作起始剂分子的是具有2-14个，优选4-10个碳原子的脂族、脂环族和/或芳脂族二醇，例如乙二醇、1，3-丙二醇、1，10-癸二醇、邻-、间-和对二羟基环己烷、二甘醇、二丙二醇，优选1，4-丁二醇、1，6-己二醇和双(2-羟乙基)氢醌，三醇如1，2，4-和1，3，5-三羟基环己烷、甘油和三羟甲基丙烷，以及含羟基且基于氧化乙烯和/或1，2-氧化丙烯及上述二醇和/或三醇的低分子量聚氧化烯。
作为多元醇组分，通常还可使用高官能多元醇作为起始剂分子，特别是基于高官能醇、糖醇和/或糖的聚醚多元醇。然而，优选地，将基于甘油和/或三羟甲基丙烷和/或二醇的双官能和/或三官能聚醚多元醇或聚酯多元醇用作起始剂分子或用作要酯化的醇。聚醚多元醇由已知的技术制备。用于制备多元醇的合适的氧化烯是例如四氢呋喃、氧化乙烯、1，3-氧化丙烯、1，2-或2，3-氧化丁烯、氧化苯乙烯，优选氧化乙烯和1，2-氧化丙烯。该氧化烯可单独使用、接连交替使用或作为混合物使用。在根据本发明的粘合剂组合物的预聚物中特别优选使用的聚醚多元醇是在烷氧基化末由氧化乙烯烷氧基化并因此具有伯羟基的那些。
合适的起始剂分子的实例为：水，二醇如乙二醇、丙二醇、1，4-丁二醇和1，6-己二醇，胺如乙二胺、己二胺和4，4’二氨基二苯甲烷以及氨基醇如乙醇胺或三乙醇胺。
该聚醚多元醇的官能度优选为2-6，特别是2-3，分子量为400-10000，优选1000-7000。该聚醚多元醇可以单独使用或作为混合物使用。
聚碳酸酯二醇同样是合适的。合适的聚碳酸酯二醇是包含芳族二羟基化合物(例如基于4，4’-二羟基二苯基-2，2-丙烷)的那些，或基于脂族二羟基化合物(例如1，6-己二醇)的那些。其摩尔质量为500-4000，优选1000-2000。
作为多元醇组分的合适的聚酯多元醇例如可以由具有2-12个碳原子的有机二羧酸，优选具有4-6个碳原子的脂族二羧酸和具有2-12个碳原子，优选2-6个碳原子的多羟基醇(优选二醇)或者通过聚合具有3-20个碳原子的内酯而制备。例如，可使用的二羧酸是戊二酸、庚二酸、辛二酸、癸二酸、十二烷二酸，优选己二酸、丁二酸和邻苯二甲酸。二羧酸可以单独使用或作为混合物使用。对于制备聚酯多元醇，可有利地使用相应的酸衍生物(如羧酸酐或酰氯)代替二羧酸。合适的芳族二羧酸是对苯二甲酸、间苯二甲酸或其与其它二羧酸(例如联苯酸、癸二酸、丁二酸和己二酸)的混合物。合适的二醇的实例为二甘醇、1，5-戊二醇、1，10-癸二醇和2，2，4-三甲基戊-1，5-二醇。优选使用1，2-乙二醇、1，4-丁二醇、1，6-己二醇和2，2-二甲基丙-1，3-二醇；1，4-二羟甲基环己烷；1，4-二乙醇环己烷、2，2-双(4-羟基-亚苯基)丙烷(双酚A)的乙氧基化/丙氧基化产物。根据所希望的聚氨酯的性能，多元醇可单独使用或作为不同比例的混合物使用。用于制备聚酯多元醇的合适的内酯是例如α，α-二甲基-β-丙内酯、γ-丁内酯，优选ε-己内酯。聚酯多元醇的官能度优选为2-4，特别是2-3，分子量为1200-3000，优选1500-3000，特别是1500-2500。
特别地，已经证实多元醇混合物可用于该预聚物。这种多元醇混合物优选具有至少一种二醇，优选聚丙二醇，以及至少一种三醇，优选聚醚三醇。特别合适的二醇的平均分子量为500-3000，优选700-1500，特别优选800-1500，除此之外优选800-1200。已证实平均分子量为1000-8000，优选2000-6000，特别优选3000-5000的三醇可用作三醇。特别优选多元醇混合物的OH数为30-140mg KOH/g，优选50-90mg KOH/g，特别优选60-80mgKOH/g。上述二醇和三醇不仅可作为多元醇混合物而且在各种情况下可独立地用于制备预聚物。
在预聚物的另一实施方案中，已证实使用优选具有伯羟基的聚醚多元醇是合适的，所述聚醚多元醇的OH数为10-60mg KOH/g，优选20-40mgKOH/g，特别优选25-35mg KOH/g。
如果使用增链剂、交联剂或其混合物来制备预聚物，则基于对异氰酸酯呈反应性的所有使用的化合物的重量计，其合适的用量为0-20重量％，优选0.5-5重量％。
合适的组分B的异氰酸酯或聚异氰酸酯是本身已知的脂族、脂环族、芳脂族和/或芳族异氰酸酯，优选二异氰酸酯，如果需要，其可通过通常已知的方法缩二脲化或异氰脲酸酯化。可特别地以举例的方式提到下列：在亚烷基中具有4-12个碳原子的亚烷基二异氰酸酯如十二烷-1，12-二异氰酸酯、2-乙基四亚甲基-1，4-二异氰酸酯、2-甲基五亚甲基-1，5-二异氰酸酯、四亚甲基-1，4-二异氰酸酯、赖氨酸酯二异氰酸酯(LDI)、六亚甲基-1，6-二异氰酸酯(HDI)、环己烷-1，3-和/或1，4-二异氰酸酯、六氢甲苯-2，4-和2，6-二异氰酸酯和相应的异构体混合物、二环己基甲烷-4，4’-、2，2’-和2，4’-二异氰酸酯和相应的异构体混合物、1-异氰酸酯基-3，3，5-三甲基-5-异氰酸酯基甲基环己烷(IPDI)、甲苯-2，4-和/或2，6-二异氰酸酯、二苯基甲烷-4，4’、2，4’和/或2，2’-二异氰酸酯(单体的MDI)、聚苯基聚亚甲基聚异氰酸酯(聚合物MDI)以及萘-1，5-二异氰酸酯(1，5-NDI)和甲苯二异氰酸酯(TODI＝2，7-二甲基二苯基-1，6-二异氰酸酯)和对苯二异氰酸酯(PPDI)和/或包含至少两种所述异氰酸酯的混合物。包含酯、脲、脲基甲酸酯、碳化二亚胺、脲二酮和/或氨基甲酸酯基的二-和/或聚异氰酸酯也可用于本发明的方法中。
MDI，如聚合物MDI或优选单体MDI，特别是4，4’-MDI或2，4’-MDI和4，4’-MDI的混合物，特别优选用于制备粘合剂组合物的预聚物。
在一个实施方案中，已证实使用聚合物MDI对于预聚物是特别合适的，所述聚合物MDI的平均官能度为1-5，优选1.5-4，特别优选2-3.5，粘度为100-400MPa.s，优选150-300MPa.s，特别优选160-260MPa.s。
可使用的催化剂是极大促进异氰酸酯与对异氰酸酯呈反应性的化合物的反应的通常已知的化合物，基于所有使用的对异氰酸酯呈反应性的化合物的重量计，优选使用的总催化剂含量为0.01-8重量％，特别是0.1-5重量％。例如，可使用下列化合物：三乙基胺、三丁基胺、二甲基苄基胺、二环己基甲基胺、二甲基环己基胺、N，N，N’，N’-四甲基二氨基二乙基醚、双(二甲基氨基丙基)脲、N-甲基-或N-乙基吗啉、N，N’-二吗啉基二乙基醚(DMDEE)、N-环己基吗啉、N，N，N’，N’-四甲基乙二胺、N，N，N’，N’-四甲基丁二胺、N，N，N’，N’-四甲基己烷-1，6-二胺、五甲基二亚乙基三胺、二甲基哌嗪、N-二甲基氨基乙基哌啶、1，2-二甲基咪唑、N-羟基丙基咪唑、1-氮杂双环[2.2.0]辛烷、1，4-二氮杂双环[2.2.2]辛烷(Dabco)和烷醇胺化合物如三乙醇胺、三异丙醇胺、N-甲基-和N-乙基二乙醇胺、二甲氨基乙醇、2-(N，N-二甲基氨基乙氧基)乙醇、N，N’，N-三(二烷基氨基烷基)六氢三嗪例如N，N’，N-三(二甲基氨基丙基)-S-六氢三嗪、氯化铁(II)、氯化锌、辛酸铅，优选锡盐，如二辛酸锡、二乙基己酸锡、二月桂酸二丁锡和/或二丁基二月桂基锡硫醇盐，2，3-二甲基-3，4，5，6-四氢嘧啶、四烷基氢氧化铵如四甲基氢氧化铵，碱金属氢氧化物如氢氧化钠，碱金属醇化物如甲醇钠和异丙醇钾，和/或具有10-20个碳原子和任选OH侧基的长链脂肪酸的碱金属盐。此外可提及三聚化催化剂，如碱金属或碱土金属的乙酸盐，优选乙酸钾。除了吗啉衍生物用作活化剂，上述催化剂也可用作活化剂。因此，在制备预聚物时将催化剂本身引入其中，在该预聚物作为本发明的粘合剂组合物的另外组分的情况下，将活化剂引入所述组合物中。此外，已证明Ti化合物，特别是Ti(IV)-O-烷基化合物，所述烷基如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、2-戊基、3-戊基，优选乙基、正丙基、异丙基、正丁基、异丁基、叔丁基，特别优选丁醇钛(IV)可用作催化剂或活化剂。
如果合适，可向用于制备预聚物的反应混合物中添加其它助剂和/或添加剂。可以举例的方式提到表面活性物质、稳定剂、细胞调节剂、染料、颜料、阻燃剂、水解稳定剂、杀虫剂、抑霉剂或抑菌剂。表面活性物质和稳定剂防止粘合剂组合物的表面在面对空气时“结膜”。此外，表面活性物质和稳定剂改进粘合剂组合物的水平和粘合剂组合物的蠕变性及其脱挥发性。合适的表面活性物质例如是用作促进原料均化的化合物。可以举例的方式提到乳化剂，如蓖麻油硫酸酯或脂肪酸的钠盐或脂肪酸与胺的盐，例如二乙胺与油酸、二乙醇胺与硬脂酸和二乙醇胺与蓖麻酸的盐，磺酸盐，例如十二烷基苯磺酸或二萘甲烷二磺酸和蓖麻酸的碱金属盐或铵盐；稳定剂，如硅氧烷-氧化烯共聚物及其它有机聚硅氧烷、乙氧基化烷基酚、乙氧基化脂肪醇、液体链烷烃、蓖麻油酯或蓖麻酸酯、土耳其红油和花生油，以及细胞调节剂，如链烷烃、脂肪醇和二甲基聚硅氧烷。此外，上述具有聚氧亚烷基和氟代烷基团作为侧基的低聚丙烯酸酯适于改进预聚物的乳化效果、泡孔结构和/或稳定作用。如果要减少或避免形成泡沫，则优选将磷酸三烷基酯作为防沫剂。这些烷基优选为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、2-戊基、3-戊基，优选乙基、正丙基、异丙基、正丁基、异丁基、叔丁基。基于所有使用的对异氰酸酯呈反应性的化合物的100重量％计，表面活性物质的用量通常为0.01-5重量％。
合适的阻燃剂例如为磷酸三甲苯酯、磷酸三(2-氯乙基)酯、磷酸三(2-氯丙基)酯、磷酸三(1，3-二氯丙基)酯、磷酸三(2，3-二溴丙基)酯、二磷酸四(2-氯乙基)亚乙基酯、二甲基甲烷膦酸酯、二乙醇氨基甲基膦酸二乙基酯和市场上可买到的含卤素的防火多元醇。除了上述卤素取代的磷酸酯，还可以使用无机或有机阻燃剂，如红磷，三水合氧化铝，三氧化锑，五氧化二砷，聚磷酸铵和硫酸钙，膨胀石墨或氰尿酸衍生物，例如三聚氰胺，或至少两种阻燃剂的混合物，例如聚磷酸铵和三聚氰胺，以及如果合适玉米淀粉或聚磷酸铵、三聚氰胺和膨胀石墨，和/或如果合适芳族聚酯，用于增加该预聚物或粘合剂组合物的耐火性。一般而言，已证实基于所有使用的对异氰酸酯呈反应性的化合物的重量计，使用5-50重量％，优选5-25重量％的所述阻燃剂是有利的。
在进一步的优选实施方案中，使用具有填料的单组分聚氨酯粘合剂，所述填料包含至少一种纤维。
该单组分聚氨酯粘合剂优选具有至少一种下列主特征(i)-(iii)：
(i)该预聚物具有至少一种下列子特征(a)和(b)：
(a)基于预聚物计5-30重量％的NCO含量，
(b)在25℃下300-150000MPa.s的粘度，
(ii)组分A具有至少一种下列子特征(c)和(d)：
(c)组分A包含至少一种二醇或多元醇，优选一种二醇或三醇，特别优选二醇和三醇，
(d)组分A的OH数为10-500mg KOH/g，
(iii)填料具有至少一种下列子特征(e)和(f)：
(e)纤维由至少一种纤维聚合物组成，
(f)除了纤维之外，填料由至少一种非纤维的填料物质组成。
如果粘合剂组合物是可泵抽的，则预聚物在25℃下的粘度优选为300-15000MPa.s，优选500-10000MPa.s。另一方面，如果打算将粘合剂组合物以糊状、浆料的形式使用，则该预聚物在25℃下的粘度优选为＞15000-150000MPa.s，特别优选20000-100000MPa.s。
此外，优选粘合剂组合物具有低溶剂含量。这种情况是指粘合剂组合物中的溶剂存在量＜10重量％，优选＜5重量％，特别优选＜2重量％。根据本发明，溶剂为有机和无机液体，其适合用作粘合剂组合物的其它组分的载体并且不与至少一部分其它组分硬化。
优选地，粘合剂组合物不含溶剂。
在粘合剂组合物的有利的实施方案中，实现了该预聚物的上述主特征(i)和组分A的主特征(ii)。
在粘合剂组合物的另一实施方案中，满足了组分A的主特征(ii)和填料的主特征(iii)。
在粘合剂组合物的另一实施方案中，满足了所有的三个主特征(i)-(iii)。
粘合剂组合物的优选实施方案是其中在各种情况下满足预聚物、组分A和填料的子特征(a)和(b)或(c)和(d)或(e)和(f)的那些。
在粘合剂组合物的另一优选实施方案中，满足所有的主特征(i)-(iii)和所有的子特征(a)-(f)。
在粘合剂组合物的又一个实施方案中，除了特征(i)-(iii)，满足至少一个特征(iv)和(v)：
(iv)纤维聚合物为至少一种聚酰胺，
(v)填料物质由至少一种无机材料组成。
优选粘合剂组合物的纤维聚合物主要由有机或无机填料形成。对于纤维聚合物，合适的有机材料特别是缩聚物和加聚物，其优选不为聚氨酯，优选缩聚物。特别合适的缩聚物为聚碳酸酯、聚酯、聚酰胺、聚酰亚胺和蜜胺-甲醛树脂。
加聚物特别是聚丙烯酸酯、聚甲基丙烯酸酯、聚苯乙烯、聚丙烯腈、聚乙烯、聚丙烯、聚乙烯醇和至少两种上述均聚物单体的共聚物和至少其两种的共混物。
特别优选将聚酰胺用作粘合剂组合物中的纤维聚合物。为此，本领域技术人员已知的所有市场上可买到的聚酰胺是合适的。然而，已证实聚酰胺如尼龙，特别是尼龙-6，6或尼龙-6，以及芳族聚酰胺是特别有用的。
此外，纤维可基于天然有机纤维聚合物，例如纤维素、棉、黄麻、纤维胶和剑麻，或由其组成。另外，纤维也可以由无机材料形成。优选的无机纤维聚合物为碳、玻璃和矿棉纤维。此外，例如可通过纺丝从不同的材料获得纤维。
优选使用的纤维直径为5-100μm，优选10-60μm，特别优选10-30μm，长度为0.02-6mm，优选0.05-4mm，特别优选0.1-2mm。
另外，该粘合剂组合物具有由至少一种无机材料组成的非纤维填料物质。原则上，作为固体存在的所有本领域技术人员已知的无机材料，特别是市场上可获得的无机材料，都适于根据本发明的粘合剂。无机材料必须以固体形式存在，特别是在处理本发明的粘合剂组合物并随后使用粘合的制品的温度范围内。该温度范围优选从-50℃至高达+160℃。
已证实硅或铝或镁或其至少两种(其另外任选具有其它元素)的含氧化合物是特别合适的无机材料。特别合适的是硅酸盐和氧化铝，例如粘土，如陶土，以及石英化合物或硅酸。
非纤维填料物质优选为颗粒。80％的颗粒填料物质的粒度为0.01-50μm，优选0.1-10μm，特别优选0.2-8μm。
根据本发明使用的填料可包含纤维或另外的填料物质。如果填料兼具纤维和填料物质，则优选至少刚好与纤维同样多的填料物质存在于填料中，优选填料物质过量。
填料存在于粘合剂组合物中，特别用于改进其各种用途的物理性能。为此，粘合剂组合物必须形成无气泡的粘合剂层，其在固化后尽可能致密，并且衬底间的接合尽可能被完全填充。为了增加粘性，该粘合剂组合物应部分渗入衬底表面。然而，在粘合剂组合物固化以得到粘合剂后，该渗入或收缩不应导致任何空腔，所述空腔可不利地影响内聚。特别是在大于0.1-1mm，优选0.2-1mm的较厚接合处，通过将上述组合物中的填料引入粘合剂组合物中可特别容易地满足这些需求。
在粘合剂组合物中存在填料的情况下，已证实基于填料计，其含水量小于5重量％，优选小于1重量％，特别优选小于0.1重量％是特别有用的。特别是对于制备根据本发明的粘合剂组合物，其是有利的。
粘合剂组合物的活化剂由至少一种吗啉衍生物组成。特别合适的吗啉衍生物是4-甲基吗啉、4-乙基吗啉、4-环己基吗啉、2，2’-二吗啉基二乙基醚或二吗啉基聚乙二醇或其至少两种。此外，除了吗啉衍生物，可使用其它具有活化效应的化合物，例如Becker/Braun，Kunststoffhandbuch 7(1993)中描述的聚氨酯催化剂，优选吗啉衍生物的比例占大多数。
已证实触变助剂是有利的，特别是对于储存期限。特别优选的触变助剂为膨润土、高岭土、藻酸和硅酸，特别优选硅酸。除了或代替上述由固体组成的触变助剂之外，优选可通过例如在胺的存在下的异氰酸酯的反应获得的可溶性触变助剂，如公开文献EP 300388A1、DD 156480、DD 211689、DD 211930和DD 211931所描述的。
触变助剂是小颗粒物质，即使当将其以少量添加或释放至液体中时，例如基于液体计至多不超过10重量％，它也使液体增稠。这些小颗粒的表面优选具有硅醇基，所述硅醇基与其分散的液体相互作用，形成氢桥键，由此导致该液体增稠。当通过强力混合适当地小心分散时，在相同数量下，典型的触变助剂的增稠效果随着粒度的降低而增加。此外，触变助剂具有不从分散的液体沉淀出来的优点。此外，触变助剂阻止或延迟填料沉淀出来。优选的触变助剂材料是蒙脱土、Mg/Al硅酸盐、Al/Na硅酸盐、膨润土、锂皂石、Na/Mg硅酸盐、煅制二氧化硅、水合二氧化硅、角闪石-温石棉、温石棉-石棉、温石棉-硅酸和细粉形式的沉淀MgO，优选例如可作为Aerosil从Degussa-Hüls AG获得的煅制二氧化硅和可作为Bentone从Kronos Titan GmbH Leverkusen获得的硅酸镁，特别优选Aerosil。
本发明还涉及上述复合材料在建筑工程、土木工程、造船业、车辆构造、发电厂构造、采矿或家具构造中的用途。
可优选将该复合材料用作承载元件，特别是用作地板、中间地板、墙壁或屋顶元件。此外，可将该复合材料用作支承元件和/或模板元件。
特别优选将上述复合材料用作集装箱底板或拖车底板。
优选用作卡车、客车、拖车、飞机、火车、轮船或轮渡中的结构元件。
本发明的复合材料还特别适于加固空气涡轮叶片或发电厂的其它部件。
还特别优选在建筑构造和土木工程中用于混凝土模板及其它结构，其中重要的是良好的负载能力，特别是从其它建筑材料(特别是塑料或混凝土)的良好分离效应。
本发明还涉及由上述复合材料形成的集装箱底板或拖车底板。
尽管没有完全弄清楚相互关系，据推测，根据本发明，通过将木质化巨型禾本科植物(特别是竹子)与包含具有游离NCO基的预聚物的单组分聚氨酯粘合剂组合，经由该预聚物的游离NCO基实现了粘合剂对木质化巨型禾本科植物层基质的改进的化学粘结，因为它们与木质化巨型禾本科植物，特别是淀粉或纤维素或木质素以及特别是在外层中的含硅酸的衍生物组分的游离OH基反应，以及与木质化巨型禾本科植物的残余水分反应。
集装箱底板和拖车底板必须符合某些必需的规格：将材料用作板材，其通常尺寸为2.40m×1.16m×28mm(长度×宽度×厚度)。例如，在各种情况下20f集装箱地板由四个上述尺寸的板组成，所述板平行且成对排列，一个在另一个和两个另外的一半上述长度的板之后。然而，它们的用途不局限于这些尺寸。特别地，在本发明中描述的复合材料不局限于这些尺寸范围或密度范围。根据设计和应用领域，密度应为0.8±0.1kg/l，也可以为0.8±0.2kg/l。
标准IICL(国际集装箱出租商协会)，TB 001，2002年9月1日，用于在三点弯曲测试中的静态弯曲强度的“小跨度测试”(250mm“跨度剪切力测试”)，将损坏的力标准化为至少6900N。测试步骤和测试样品的尺寸(长度30.5cm、宽5cm、厚28mm，测试样品放置在具有250mm间隔的两个接触点支架上)详细描述在IICL TB 001中。在此，不但将由于破裂导致的破坏而且特别将层间的剥离评定为损坏，其特别在粘结不足的情况下发生。测试在标准气候条件(23℃和55％相对湿度)下进行。
这些要求由当前主要使用的热带木材克隆木、梅兰蒂木、马拉斯木、海棠木等来满足：包含克隆木并以酚醛树脂作为粘合剂的层压材料(通常也称作层板)在23℃/55％相对湿度下的静态三点弯曲测试中具有约0.8-0.9kg/l的密度和约7000-7300N的负载极限。
然而，由于不可再无限量地获得热带硬木如克隆木等，必须找寻替代方案，其同样满足上述所需的规格或显著超过替代层压材料(“层板”)的迄今性能水平，所述替代层压材料包含其它材料，例如竹子。
市场上可获得并包含其它材料的复合材料“层板”主要不满足上述要求：通常由酚醛树脂粘合的含竹层的复合材料以及包含其它木材(如山毛榉、松树、落叶松、桦树、桉树等)的复合材料、单板或层压材料(包含不同单板的混合物如与竹层的混合物的“层板”)，其在各种情况下由酚醛树脂和/或聚乙酸乙烯酯等粘合，并不满足上述用作集装箱底板的要求和根据IICL TB 001的集装箱底板的认证测试。在各种情况下，这种层压材料在23℃和55％相对湿度下的最大破坏力为5400-6600N。取决于所用的结构以及材料和粘合剂，这些层压材料甚至呈现高达0.9kg/l的密度，有时甚至高达＞1kg/l。
另一方面，根据本发明的复合材料具有例如集装箱底板所需的不超过0.8±0.1kg/l的低密度。
表1：在23℃/55％相对湿度下根据IICL TB 001的各种材料的基本表
征数据
在根据IICL TB 001的集装箱底板认证测试中，由酚醛树脂(PF)粘合的含几乎不可再获得的热带雨林木材克隆木的材料呈现最大7506N的力，因此满足规格。正如由酚醛树脂(PF)粘合的竹子(最大力6558N)一样，由酚醛树脂粘合的替代材料层板未充分地满足集装箱底板的规格，其最大破坏力水平为6282N。
本发明的复合材料，由1-C PU粘合剂粘合的竹子，具有显著低的密度(与1.05kg/l相比为0.8kg/l)，其令人惊讶地具有12363N的最大力，因此其高达迄今为止的材料的两倍。
在测定这种用于集装箱底板的材料的静态效率的测试(所述测试在此进行描述)中，此外由测量的测试数据测定最大弯曲应力(例如测量的σ，MPa)，其由规定样品几何形状(根据IICL TB 001)和测试中测量的最大破坏力产生。所述不可再获得的热带硬木克隆木的弯曲应力为71.6MPa，替代材料层板为66.5MPa，竹子为64.8MPa。另一方面，本发明的复合材料的最大弯曲应力为129MPa，因此其同样为对比材料的两倍大。弯曲应力描述在Dubbel，Taschenbuch für Maschinenbau中。
作为材料的典型特性，弹性模量通常是本领域技术人员已知的。对于本文描述的材料，由本文进行的测量获得的挠曲弹性模量对于热带雨林木材克隆木为6562MPa，层板为5323MPa和竹子为5974MPa。
另一方面，本发明的复合材料(具有1-C的竹子)的挠曲弹性模量为8010MPa，因此显著高于对比材料，所述对比材料本身显示比本发明材料显著更高的强度。
尽管上述特性描述了该材料在23℃/55％相对湿度下以及在集装箱底板严格规格(IICL TB 001)中所需的机械-静态性能水平，然而，对于在地球上各区域的集装箱中必然存在的高温性能，它们没有任何问题。
下列测量值表明在高温下也确保了室温下的高性能水平。表2显示了在80℃下根据IICL TB 001的相应测量，尽管本说明书中不需要或未描述这种测量。
表2：在80℃下根据IICL TB 001的各材料的基本表征数据
为此，将各测试样品在80℃下储存，直到它们被完全加热透并测量。
表2所列的数据表明，与所有上述的对比材料相比，本发明的复合材料具有显著更好的性能水平。特别明显的是本发明的且包含竹子与1-C PU的复合材料的最大力和最大弯曲应力的高性能水平几乎为具有酚醛树脂(PF)的对比竹子的两倍。
另外，本发明的复合材料还具有优异的动态性能：为此，进行以下测量方法来测定动态负载极限。记录所谓的曲线。
曲线描述在例如Dubbel，Taschenbuch für Maschinenbau中。为此，用最大弯曲应力以10Hz的频率对各材料样品进行周期性负载并在各种情况下将负载减少至该最大弯曲应力的10％，所述样品如上述IICL TB 001描述和使用，其长度为30.5cm、宽度为5cm，厚度为28mm。将循环的最大负载与最小负载比表示为R。在这些测试中，R＝0.1。周期性负载处理的频率以Hz测量，并表示每秒中以所述参数进行多少次循环。因为最大弯曲应力由IICL TB 001“小跨度测试”测定，在所述最大弯曲应力下测试样品负载一次就毁坏，这些动态测试从相应地较低弯曲应力开始，其中以10次/秒对测试样品进行负载并将负载减少至10％，如果在一定的循环数(10Hz)之后样品在一定的弯曲应力下毁坏，则以稍微较低的弯曲应力测试相同材料的新测试样品，并测量由其获得完整的循环数，其中该测试样品也被毁坏。之后，用新的测试样品和稍微较低的弯曲应力重复该过程。只有当在大量的完整循环之后(大于1百万)测试样品不再毁坏，才可获得材料的动力性耐力性能水平。因此，在不损坏(层压材料破裂或剥离)的情况下以相应的负载(各弯曲应力)完成的循环数提供了有关各材料在其用作集装箱底板期间的预期动态性能水平或疲劳特性。在不损坏的情况下完成的循环数越大和其中引入的最大弯曲应力越高，材料的动态性能越高，由此对于各集装箱底板的真实寿命也是如此。如表1所概括的，根据IICL TB 001的破坏时的最大弯曲应力用作测定在各种情况下使用的最大弯曲应力。因为这是最大破坏弯曲应力，即各材料在负载一次而破坏的弯曲应力，相应地为
曲线选择较低的弯曲应力。如上所述，最大弯曲应力逐渐降低，直到材料样品可以10Hz周期性地负载/卸载而不发生破坏。图1显示了对比材料和本发明的材料(具有1-C PU粘合剂的竹子)的
曲线。
本发明的复合材料的特征还特别在于弹性可逆能量吸收，并且其还具有能量消散效果。这形成各种潜在的用途，特别是用于需要高能量吸收的领域中，例如防弹元件，或者用于存在爆炸风险的环境中，例如采矿厂或化工厂。
以下参考附图更详细地描述本发明。
说明：
图1显示了本发明的复合材料(由单组分聚氨酯粘合剂粘结的竹子)和对比复合材料(特别是由酚醛树脂粘合的竹子和由酚醛树脂粘合的层板)的
曲线，
图2显示了与图1相同的复合材料的落锤测试结果，
图3显示了包含由单组分聚氨酯粘合剂粘结的多个竹层的本发明的复合材料的光学显微照片，
图4显示了包含竹子和单组分聚氨酯粘合剂的本发明的复合材料的光学显微照片的放大图，
图5显示了竹子的光学显微照片，
图6显示了竹子的光学显微照片的放大图。
在23℃、55％相对湿度和10Hz频率的负载下记录图1所示的
曲线，最小与最大弯曲应力的比例R等于0.1。沿纵坐标绘制弯曲应力σ(MPa或N/mm2)并沿横坐标绘制循环数。包含竹子与单组分聚氨酯粘合剂的本发明的复合材料的值以正方形表示，包含竹子与酚醛树脂粘合剂的对比材料的值以菱形表示，具有酚醛树脂粘合剂的层板的值以三角形表示。在各种情况下，材料仍完整时的值以空心正方形、三角形或菱形表示，材料损坏时的值以实心正方形、三角形或三角形表示。
图1中的图形表明，由酚醛树脂粘合的对比材料层板(由三角形表示)在所有高于30MPa的最大弯曲应力的负载下毁坏。只有当最大弯曲应力降低至约30MPa时，样品才完成约2百万次循环而不毁坏。由酚醛树脂粘合的对比材料竹子(由菱形表示)在相同的循环数时可承受约40-42MPa的最大弯曲应力。比较起来，本发明的材料(由单组分聚氨酯粘合剂粘合的竹子)(由正方形表示)可承受75MPa的最大弯曲应力，甚至在5百万次循环之后也完全没有疲劳或损坏的迹象。在70MPa的最大弯曲应力下，由于缺少时间而在一千万次循环后停止测试，因此此时也完全没有可检测到的疲劳迹象。
考虑到其最大弯曲应力和循环数，因此本发明的材料的动态性能水平比对比材料显著高2.5或5倍。
据推测，因为根据本发明选择的粘合剂未渗入木质化巨型禾本科植物(特别是竹子)的封闭腔中，而保持其完整，实现了本发明复合材料的低密度和同时显著改进的机械性能。
相反，使用现有技术已知的竹子粘合剂，特别是酚醛树脂，粘合剂至少部分渗入木质化巨型禾本科植物(特别是竹子)结构中，因此不利地影响密度(使其增加)以及机械和动态性能。
事实上，也显然根据本发明使用的材料具有显著更高的动态性能水平，其在相应的落锤测试中具有相当高的且可逆的弹性能量吸收。在此，将测量为32cm×32cm且具有如表1和2所示的各厚度并包含各材料的板拧在8cm高的钢架上，四个角点使用四个M8螺钉，钢支架的距离为26cm。该板没有其它的支架/下层，因此该测试安排非常真实地反映了集装箱的实际安装情况。然后通过使99kg重的圆柱形半球从0.624m的高度自由落在无支撑的测试样品上，对该板进行落锤测试。这里描述的引入落锤测试的能量在各种情况下为609J，其等于在这些条件下3.5米/秒的冲击速度。
图2显示了落锤测试图，使用直径为100mm且重量为99kg的半球，落差为0.624m。因此，能量的引入量为609J。在该图中，沿横坐标绘制形变V(mm)，沿纵坐标绘制力F(kN)。本发明的复合材料(由单组分聚氨酯粘合剂粘结的竹子)的值由正方形表示，包含竹子与酚醛树脂粘合剂的对比材料的值由三角形表示，包含层板与酚醛树脂粘合剂的对比材料的值由菱形表示。
包含层板复合材料(由菱形表示)的板在测试中完全毁坏，其相当于不可逆的能量吸收。该板呈现永久形变或14mm的负载压缩特性，相当于初始板厚度的50％。
包含竹子与酚醛树脂粘合剂的复合材料(由三角形表示)的板在测试中也完全毁坏，其相当于不可逆的能量吸收。这呈现永久形变或7-8mm的负载压缩特性，相当于初始板厚度的约30％。
在该测试中板对能量引入的抗性以材料响应时测量的力表示。
在层板的情况下，响应力或抗毁坏性为约25kN，在竹子/酚醛树脂材料的情况下为约30kN至不超过35kN。
令人惊讶地，包含本发明的材料(竹子/1C PU粘合剂)的板(由正方形表示)仍十分完整并完全没有恒载压缩特性。总能量吸收是可逆的并在测试板不经受任何损坏的情况下弹性散失。最大响应力为约50kN，其高达层板/酚醛树脂的两倍，或比竹子/酚醛树脂的对比材料高66％。
因此，这些测试另外呈现本发明材料(竹子/1-C PU)的显著更高的动态性能水平，这也特别由其无毁坏的能量吸收加以证明，并且这有效支持了由其制成的承载部件(如这里特别是集装箱底板)的所述更高效力。
图3显示了包含竹子与单组分聚氨酯粘合剂的本发明的复合材料的光学显微照片。
该光学显微照片清楚地表明正交的层状结构，即在中空竹层之间，这里其出现在背景中并在截面中可见，纵向的竹层与其以直角(90°的角度)排置。竹子的细胞结构完全完整并且是未填充的。
图4显示了分辨率相当于图3的光学显微照片，但仅是竹子，不添加粘合剂。
图5显示了包含竹子与单组分聚氨酯粘合剂的本发明的复合材料的非常放大的显微照片(在该显微照片右下角的比例尺对应200μm)。明显地看到，竹子的细胞结构十分完整并没有渗入所用的1-C PU粘合剂乃至被其填充。
图6显示了具有与图5相同分辨率的非常放大的显微照片(该显微照片右下角的比例尺对应200μm)，但仅仅是竹子。
从图4、5和6的比较可清楚地看到，相对于不含粘合剂的竹子自身，由单组分聚氨酯粘合剂粘合地竹子的细胞结构(如图4所示)十分完整并且未改变。
Claims (19)
1.包含两个或更多个叠置的仿木材料层的复合材料，所述层由包含具有游离NCO基的预聚物的单组分聚氨酯粘合剂彼此粘结，其中所述仿木材料为单子叶植物。
2.根据权利要求1的复合材料，其中所述单子叶植物为木质化巨型禾本科植物。
3.根据权利要求2的复合材料，其中所述木质化巨型禾本科植物为竹子。
4.根据权利要求1的复合材料，其中所述单子叶植物为棕榈。
5.根据权利要求1-4中任一项的复合材料，其中所述单组分聚氨酯粘合剂包含比例高达99.9重量％的具有游离NCO基的预聚物，所述预聚物可由至少一种具有对异氰酸酯呈反应性的化合物的组分A和至少一种具有异氰酸酯的组分B获得，
-0.1-40重量％，优选0.1-30重量％的填料，其包含至少一种纤维和至少一种除纤维以外的非纤维填料物质，
-0-20重量％的常用添加剂和助剂，
-0-20重量％的活化剂，
所述至少一种纤维的直径为5-100μm，长度为0.02-6mm。
6.根据权利要求1-4中任一项的复合材料，其中所述单组分聚氨酯粘合剂包含比例高达99.999重量％的预聚物，所述预聚物可由至少一种具有对异氰酸酯呈反应性的化合物的组分A和至少一种具有异氰酸酯的组分B获得，所述单组分聚氨酯粘合剂包含如下组分：
-0-20重量％的常用添加剂和助剂，和
-0.001-20重量％的至少一种活化剂，其选自一种或多种下列物质：4-甲基吗啉、4-乙基吗啉、4-环己基吗啉、2，2’-二吗啉基二乙基醚或二吗啉基聚乙二醇，
a)所述预聚物具有下列特征：
i)基于预聚物计5-30重量％的NCO含量，
ii)在25℃下300-15000MPa.s的粘度，
b)组分A具有下列特征：
i)组分A包含至少一种二醇，
ii)组分A中的OH数为10-500KOH/g，
所述单组分聚氨酯粘合剂包含填料，并且在25℃下的粘度为300-15000MPa.s。
7.根据权利要求1-6中任一项的复合材料，其中所述复合材料具有5-31个叠置的木质化巨型禾本科植物层。
8.根据权利要求3或5-7中任一项的复合材料，其中叠置的层由小而平的竹片或竹条形成，所述竹片或竹条通过如下方式获得：将竹子分劈成厚度为0.4-6mm的同心空筒，将由分劈获得的空筒沿径向分割和使分段的空筒产物变平，小而平的竹片或竹条以这样一种方式排列：在各种情况下，在复合材料的两个最外层中，它们具有沿复合材料的主负载方向的纤维方向，并且在各种情况下，在相邻层中的纤维方向以相对于彼此20-90°，优选90°的角度旋转排列。
9.根据权利要求3或5-7中任一项的复合材料，其中叠置的层优选由小而平的竹片或竹条形成，所述竹片或竹条通过如下方式获得：将竹子分劈成厚度为0.4-6mm的同心空筒，将由分劈获得的空筒沿径向分割和使分段的空筒产物变平，小而平的竹片或竹条以这样一种方式排列：在各种情况下，在复合材料的两个最外层中和在复合材料中的直接存在于下方的其它1-6层的每层中，它们具有沿复合材料主负载方向的纤维方向，并且在各种情况下，在相邻层中的纤维方向以相对于彼此20-90°，优选90°的角度旋转排列。
10.根据权利要求8或9的复合材料，其中在叠置的层中使用的小而平的竹片或竹条没有竹子外皮。
11.根据权利要求8或9的方法，其中在各种情况下将仍具有竹子外皮的小而平的竹片或竹条用于叠置层的两个最外层，在各种情况下在叠置的复合材料的两个最外层中的竹子外皮面向外。
12.根据权利要求1-11中任一项的复合材料，其中除了两个或更多个叠置的仿木材料层之外，还提供有一个或多个塑料层，特别是外部聚氨酯/聚脲层。
13.根据权利要求1-12中任一项的复合材料，其中除了两个或更多个叠置的单子叶植物层之外，还提供有一个或多个木材层。
14.根据权利要求1-13中任一项的复合材料，其中除了两个或更多个叠置的仿木材料层之外，还提供有一个或多个由玻璃纤维网、天然纤维网、玻璃纤维毡或天然纤维毡形成的层。
15.根据权利要求1-14中任一项的复合材料在建筑构造、土木工程、造船业、车辆构造、发电厂构造、采矿或家具构造中的用途。
16.根据权利要求15的用途，其用作支承元件，特别是用作地板、中间地板、墙壁或屋顶元件。
17.根据权利要求16的用途，其用作集装箱底板或拖车底板。
18.根据权利要求1-14中任一项的复合材料作为防弹结构元件，特别是门、墙壁或天花板元件的用途。
19.由根据权利要求1-14中任一项的复合材料形成的集装箱底板或拖车底板。
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| EP09159158.6 | 2009-04-30 | ||
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| PCT/EP2010/055584 WO2010125038A1 (de) | 2009-04-30 | 2010-04-27 | Verbundwerkstoff umfassend zwei oder mehrere übereinander angeordnete schichten eines holzartigen werkstoffes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104903376A (zh) * | 2012-12-14 | 2015-09-09 | 阿德科产品公司 | 具有反应性粘合剂的屋面接缝 |
| CN109735278A (zh) * | 2019-02-01 | 2019-05-10 | 北京同益中新材料科技股份有限公司 | 一种水性环氧胶粘剂及其在高性能纤维防弹板粘接中的应用 |
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| US9126386B2 (en) | 2011-03-04 | 2015-09-08 | Basf Se | Composite elements |
| CN102416964A (zh) * | 2011-10-14 | 2012-04-18 | 安徽金诚汽车科技有限公司 | 一种卫生间地板及其制备方法 |
| CN102731990B (zh) * | 2012-06-07 | 2014-06-11 | 广东省宜华木业股份有限公司 | 一种增强型聚氨酯仿木材料的制造方法 |
| EP3335847B1 (en) | 2016-12-16 | 2020-09-30 | Mayfair Vermögensverwaltungs SE | Floor panel for a shipping container |
| CN109517135A (zh) * | 2017-09-19 | 2019-03-26 | 科思创德国股份有限公司 | 聚氨酯复合材料集装箱底板板材及其制造方法和用途 |
| CN114369373B (zh) * | 2022-01-21 | 2023-04-07 | 益阳桃花江竹业发展有限公司 | 一种集装箱底板用耐磨高强度竹塑复合材料 |
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| CN109735278A (zh) * | 2019-02-01 | 2019-05-10 | 北京同益中新材料科技股份有限公司 | 一种水性环氧胶粘剂及其在高性能纤维防弹板粘接中的应用 |
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| BRPI1014644A2 (pt) | 2016-04-12 |
| WO2010125038A1 (de) | 2010-11-04 |
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