CN102822282B - 用于木材部分的乙酰化的方法 - Google Patents

用于木材部分的乙酰化的方法 Download PDF

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CN102822282B
CN102822282B CN201180009580.5A CN201180009580A CN102822282B CN 102822282 B CN102822282 B CN 102822282B CN 201180009580 A CN201180009580 A CN 201180009580A CN 102822282 B CN102822282 B CN 102822282B
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CN102822282A (zh
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米歇尔·马斯
贝诺·波尔
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Titan Wood Ltd
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Abstract

一种包括乙酰化木材部分的复合材料木制品，其特征在于，在经受25次如表II中所述的湿干/冻融循环后，厚度膨胀的平均值不超过5％。可替代的特性包括弹性模量和断裂模量、以及抗弯强度。也描述了用于木材部分的乙酰化的两个阶段方法。

Description

用于木材部分的乙酰化的方法
技术领域
本发明涉及未装饰或装饰的板材和/或嵌条，具体地说，涉及由木材刨花、木材碎料、木纤维和/或纤维素纤维压制成单或多重叠芯层(lapcorelayer)在建筑物中的室内或室外应用，其中木材部分被乙酰化，用作为粘合剂的合成树脂浸渍，加热固化并压制。为了方便起见，这些板材/嵌条将称为“复合材料”，通常包括主要来自例如云杉或松木的软木原料的工程木制品，例如中密度纤维板、定向刨花板以及碎料板。
背景技术
包括这样复合材料的制品可用于建筑物的外部正面覆层；外部壁板的应用；在隔离和支撑中的结构性应用；围墙、屋顶以及地板、阳台的覆层；或护墙板或围墙板；或也可用于墙壁或家具的内衬壁，或湿室或实验室设备的内壁衬。
复合材料的表面可未装饰，或由涂层或层压胶合板组成的装饰层完成。
现有技术公开了由木屑以及木纤维与合成树脂或粘合剂的基体制成的板材。该板材通常具有均匀的密度，且通常不适用于在潮湿条件下的外部应用或内部应用。这种类型的板材即不是免维护，且通常由于通过边缘或表面的严重水吸收而需要在所有侧面上进行后处理。水吸收会引起严重的膨胀，伴随有板材尺寸的增加以及材料的机械强度的显著损失。
这些材料的耐气候性也不令人满意。在耐气候性测试中，数周后发生水分的强吸收以及随之发生的周围膨胀和芯分裂，因此会发生表面裂缝。
当进行抗生物侵蚀测定时，现有的板材与由乙酰化木材部分(element)制成的板材相比也显示出较差的耐久性。
发明内容
因此，本发明的目的在于提供一种木基复合材料，该木基复合材料在变化的气候条件影响下不会显示出上述不足，而是将显示出有利且降低的膨胀性质。
本发明的另一个目的在于提供一种木基复合材料，该木基复合材料寿命长且是耐用的，即该木基复合材料在天气和生物侵蚀的影响下将不会腐烂、腐败或破裂。
本发明的另一个目的在于提供一种木基复合材料，该木基复合材料在环境温度下浸入水中且与其平衡相当长的时间后，与现有复合材料相比时将显示出机械强度性能例如断裂模量和弹性模量显著少的降低。“相当长的时间”表示几个星期或几个月。
本发明的另一个目的在于提供一种木基复合材料，该木基复合材料在浸湿或底漆涂装后具有仍然光滑的表面，基本上纤维或木材部分不会变得松动或从表面上竖起。这就使得涂层和油漆更有效地涂布，因此有效地花费成本。此外，与改善的尺寸稳定性结合的此性能产生显著长的涂层使用寿命以及因此较低的维护成本。通常，纤维和木材部分可能会从复合材料的表面上竖起1至2mm，使得表面有“毛刺的感觉”。
本发明的另一目的在于提供一种生产乙酰化木材部分作为用于生产根据本发明的木基复合材料的基础原料的方法。通常，根据本发明适用于乙酰化的木材部分在下表I中描述：
表I
合适的乙酰化木材部分可通过乙酰化大的几何部分(即大片刨花)，然后将该几何元素进一步尺寸减小至所需的最终几何构形，或通过在乙酰化前首先直接转换生材(greenwood)至所需的最终几何构形来制备。
因此，本发明包括一种包括乙酰化木材部分的复合材料木制品，其特征在于，在经受25次如表II所示的湿干/冻融测试循环后，所述复合材料木制品的厚度膨胀的平均值不超过5％。
或者，包括乙酰化木材部分的复合材料的特征在于，在经受25次如表II所示的湿干/冻融测试循环后，所述复合材料还可保持平均值至少为其90％的弹性模量。
此外，在可替代的包括乙酰化木材部分的复合材料中，其特征在于，在经受25次如表II所示的湿干/冻融测试循环后，所述复合材料还可保持平均值至少为其90％的抗弯强度。
此外，包括乙酰化木材部分的复合材料的特征在于，在环境温度下的水中浸泡48小时后，所述复合材料还可保持至少为其70％的断裂模量。
包括乙酰化木材部分的复合材料的特征在于，所述复合材料还可具有两种或更多种上述产品性能。
本发明还包括用于木材部分的乙酰化的两阶段方法，其中，(a)在30℃至190℃的温度下，大气压力至15巴的压力下，用乙酸酐处理部分至多80分钟，以及(b)随后用可混合有乙酸酐、或乙酸酐和乙酸的混合物的惰性气体在1至5巴的压力下加热至150℃至190℃，并持续5至300分钟。
阶段(a)和(b)可容易地在合适的压力反应器中实施。
优选地，木材部分在乙酰化之前通过常规方法干燥至2wt％至10wt％的含水量。
优选地，在阶段(a)之前，对部分施加真空以去除存在的气体。
然后乙酰化部分可方便地在大气压下干燥或真空下干燥或在这两个条件下干燥。
在阶段(a)中，乙酸酐的使用优选在60℃至130℃的温度下，在8至12巴的压力下持续5至20分钟，而在阶段(b)中，优选使用惰性气体(例如氮气)在130℃至145℃的温度下持续2至4小时。在该阶段中，反应器中的压力可升至1至3巴，且惰性气体变得由乙酸酐和乙酸完全饱和。
具体实施方式
在本发明的方法的实施例中，将源自于云杉的且具有4wt％至10wt％的含水量的木屑(约40mmx40mmx10mm)置于金属丝网壁篮(wiremeshwalledbaskets)中(以使流体容易通过)，并置于压力反应器中。然后对木屑施加-0.95巴的真空并持续5分钟。然后，将130℃下预热的乙酰化流体(包括95％的乙酸酐和5％乙酸的混合物)引入反应器中，该反应器施加10巴的压力并持续10分钟。然后，排尽反应器，且将木屑暴露在加热至145℃的循环氮气中并持续60分钟。在该方法的此部分期间，反应器中的压力可升至1至2巴。在释放了压力之后，在-0.92巴下真空干燥乙酰化的木屑并冷却5至10小时，通常总共为6-7个小时(即干燥和冷却)。乙酰化水平约为20％的乙酰基含量(通过高效液相色谱/近-红外光谱测定)。
然后，将乙酰化的木屑通过常规纤维分离机破碎成纤维，与pMDI粘合剂结合(详见下面)，且通过采用高温和高压转化成复合材料平板或复合材料板。然后这种板的样品与由未乙酰化的云杉木纤维制成的板一起经受表II所述的湿干和冻融测试程序(DINEN12467/12)。
表II
在25次湿干和冻融循环测试后，与包括未乙酰化木纤维的板的厚度膨胀的平均值是27％相比，乙酰化纤维板的厚度膨胀的平均值是3％，从而很容易证明由乙酰化的木屑制成的板的优越价值。
下面表III至X进一步详述了包括根据本发明的乙酰化木材部分的复合材料(平板)的优越性能。
使用两种不同的粘合剂来制备平板。它们是酚醛树脂粘合剂(PF，HexionGmbH，标号：‘BakelitePF1279HW’)和聚二苯基甲烷二异氰酸酯(pMDI，BayerAG，标号：‘Desmodur1520A20’)。后者是优选的粘合剂。厚度膨胀
环境温度下，在水中浸泡24小时后测量下述平板。
表III
MDF-中密度纤维板
OSB-定向刨花板
应注意的是，包括乙酰化木材部分的板样品产生1.2％至2.2％的最小厚度膨胀。
此外，下表IV详细描述了根据本发明的方法由木纤维、木屑或刨花制成的复合材料样品A-F，并转化成中密度纤维板和定向刨花板。
表IV
SYP-南方黄松
下表V示出了在25次如表II中所述的循环湿干/冻融测试后，平均厚度膨胀中变化的影响。这些结果进一步证明了通过使用乙酰化材料对厚度膨胀的有利影响。
表V
断裂模量和弹性模量
环境温度下在水中浸泡48小时后，测量由云杉纤维制成的MDF平板。
表VI
MOR-断裂模量
MOE-弹性模量
应注意的是，当使用pMDI粘合剂时，由乙酰化木材部分制成的MDF平板对MOR和MOE的影响最小。
弹性模量和抗弯强度
下表VII和VIII示出了在25次如表II中所述的循环湿干/冻融测试后各自的弹性模量和抗弯强度的平均值变化的影响。
表VII
注意：(i)乙酰化的MDF样品C、B和A与未乙酰化的样品D相比产生最小模量损失，以及
(ii)乙酰化的OSB样品E相比未乙酰化的样品F产生相类的最小模量损失。
表VIII
注意：(i)乙酰化的MDF样品B、A和C相比未乙酰化的样品D产生最小强度损失，以及
(ii)乙酰化的OSB样品E与未乙酰化的样品F中的损失相比强度增加。
表面粘附力
本发明的另一个优点是，对包括乙酰化木材部分的复合材料的表面粘附力的有利效果，该效果可通过简单测试证明。在样品A的表面上贴上一段铝胶带，随后进行25次湿干压力循环时，事实上在胶带剥离时未发现纤维粘附在胶带上。在样品B的情况下，少量的纤维粘附在胶带上，但相比之下，当胶带从样品D上剥离后，近乎100％的粘附表面覆盖有未乙酰化木纤维。
乙酰化样品的表面在浸润后发现仍保持光滑，而不同于未乙酰化样品的表面。
生物降解
下面两个表IX和X中记录的结果证明了复合材料(平板)产品的生产中使用乙酰化木材部分在防止微生物侵蚀中的进一步的有利效果。
众所周知，暴露在某些真菌和/或细菌中的木材会非常快速地劣化，通常伴随着相当大的重量和/或强度的损失，这就严重限制了复合材料产品的利用。在这些实验中使用已知的测试方法，其中在控制的温度和湿度条件下将未乙酰化板的样品和乙酰化板的样品部分埋入土壤床中。随后在长达72个月的期间检查样品的劣化迹象。
表IX
表X

Claims (15)

1.一种用于制造复合材料木制品的方法，包括木材部分的乙酰化和由乙酰化的木材部分制备复合材料木制品，其中，所述乙酰化的特征在于，(a)在30℃至190℃的温度、大气压力至15巴的压力下，用乙酸酐处理所述部分至多80分钟，以及(b)随后用混合有乙酸酐、或乙酸酐和乙酸的混合物的惰性气体在1至5巴的压力下加热至150℃至190℃的温度，并持续5至300分钟。
2.如权利要求1所述的方法，其特征在于，所述木材部分包括云杉或松木。
3.如权利要求1或2所述的方法，其特征在于，所述木材部分在乙酰化之前干燥至2wt％至10wt％的含水量。
4.如权利要求1或2所述的方法，其特征在于，在阶段(a)之前对所述部分施加真空以去除存在的气体。
5.如权利要求1或2所述的方法，其特征在于，在阶段(a)中，所述温度为60℃至130℃，所述压力为8至12巴，且时间为5至20分钟。
6.如权利要求1或2所述的方法，其特征在于，在阶段(b)中，所述压力为1至3巴，且时间为2至4小时。
7.如权利要求6中所述的方法，其特征在于，在阶段(b)中，所述压力为1至2巴。
8.如权利要求1或2所述的方法，其特征在于，所述惰性气体是氮气。
9.如权利要求8所述的方法，其特征在于，所述氮气被乙酸酐和乙酸完全饱和。
10.一种利用权利要求1的方法制得的复合材料木制品，所述复合材料木制品包括乙酰化木材部分，其特征在于，在经受25次根据DINEN12467/12所测量的湿干/冻融循环后，所述复合材料木制品的厚度膨胀的平均值不超过5％，其中，一次湿干循环由在20℃的温度下的水中将尺寸为500mm×500mm×12mm的测试样品储藏18小时并随后在60℃的温度和20％的相对湿度的烘箱中干燥所述测试样品6小时组成，且一次冻融循环由在20℃的温度下的水中将尺寸为500mm×500mm×12mm的所述测试样品储藏3小时并随后在-20℃的温度下冷冻所述测试样品3小时。
11.一种利用权利要求1的方法制得的复合材料木制品，所述复合材料木制品包括乙酰化木材部分，其特征在于，在经受25次根据DINEN12467/12所测量的湿干/冻融循环后，所述复合材料木制品保持平均值至少为90％的弹性模量，其中，一次湿干循环由在20℃的温度下的水中将尺寸为500mm×500mm×12mm的测试样品储藏18小时并随后在60℃的温度和20％的相对湿度的烘箱中干燥所述测试样品6小时组成，且一次冻融循环由在20℃的温度下的水中将尺寸为500mm×500mm×12mm的所述测试样品储藏3小时并随后在-20℃的温度下冷冻所述测试样品3小时。
12.一种利用权利要求1的方法制得的复合材料木制品，所述复合材料木制品包括乙酰化木材部分，其特征在于，在经受25次根据DINEN12467/12所测量的湿干/冻融循环后，所述复合材料木制品保持平均值至少为90％的抗弯强度，其中，一次湿干循环由在20℃的温度下的水中将尺寸为500mm×500mm×12mm的测试样品储藏18小时并随后在60℃的温度和20％的相对湿度的烘箱中干燥所述测试样品6小时组成，且一次冻融循环由在20℃的温度下的水中将尺寸为500mm×500mm×12mm的所述测试样品储藏3小时并随后在-20℃的温度下冷冻所述测试样品3小时。
13.一种利用权利要求1的方法制得的复合材料木制品，所述复合材料木制品包括乙酰化木材部分，其特征在于，在环境温度下的水中浸泡48小时后，所述复合材料木制品保持至少70％的断裂模量。
14.一种利用权利要求1的方法制得的复合材料木制品，所述复合材料木制品包括乙酰化木材部分，其特征在于，所述复合材料木制品具有权利要求10至13中的所述制品的两个或更多个性能。
15.如权利要求10至13中任一项所述的复合材料木制品，其特征在于，使用聚二苯基甲烷二异氰酸酯粘合剂。
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