CN108504034A - 新型hmf低聚物 - Google Patents

新型hmf低聚物 Download PDF

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CN108504034A
CN108504034A CN201810162862.2A CN201810162862A CN108504034A CN 108504034 A CN108504034 A CN 108504034A CN 201810162862 A CN201810162862 A CN 201810162862A CN 108504034 A CN108504034 A CN 108504034A
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hmf
carbon
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弗兰乔斯·巴杜
斯特凡·科勒
马里安杰拉·莫尔塔托
斯特凡·克拉维利茨基
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Avalon Industrial Co Ltd
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Abstract

本发明涉及一种新型碳连接的5‑羟甲基糠醛(HMF)低聚物，其至少包含一种第一HMF单元和一种第二HMF单元，并且其特征在于，第一HMF单元和第二HMF单元通过碳‑碳键连接，涉及第一HMF单元的呋喃环的位置3或4处的芳香键合碳原子。本发明还涉及该新型HMF低聚物在基于酚类化合物和/或氨基塑料成型剂制备可热固化树脂中以及在制备木材复合材料产品中作为反应性羰基化合物的用途。

Description

新型HMF低聚物
本发明涉及新型HMF低聚物及其制备方法。本发明特别地涉及新型碳连接的HMF低聚物。这些低聚物在基于酚类化合物和/或氨基塑料成型剂制备可热固化树脂中以及在制备木材复合材料中可以用作反应性羰基化合物。
5-羟甲基糠醛(HMF)
是一种重要的平台化学物质，并且作为众多合成的起始化合物具有显著的意义。此外，已知，在基于酚类化合物和/或氨基塑料成型剂制备可热固化树脂中，反应性羰基化合物例如甲醛(其对健康有害)可至少部分地被HMF代替。在行业杂志European Journal ofWood Products中，描述了HMF改性脲-甲醛树脂，为了制备它，最高达约30wt％的甲醛被纯化的结晶HMF替代(N.Esmaeili et al.,DOI 10.1007/s0017-016-1072-8)。
HMF溶液中的线性和支化低聚物的出现是已知的(例如，DE 10 2014 112 240A1)。在其它实施例中，在水热条件下在由碳水化合物和含碳水化合物的生物质制造HMF期间形成HMF低聚物，并且可通过NMR、IR和质谱法检测。此外，可以通过HPLC分析追踪它们的形成。
来自HMF的已知的低聚化合物是获得自单独的HMF单体或单独单体的醛和/或羟基与由HMF单体组成的HMF低聚物的连接。HMF单体最终代表形成的HMF低聚物的单元。HMF低聚物是线性或更多或更少高度支化的，并且具有醚、半缩醛和/或缩醛键。在酸性条件下以及在碱性条件下均可形成HMF低聚物。
线性HMF低聚物通常包括包含以下各项的结构元件：通过醚键连接的类型的单元，
和/或通过形成半缩醛连接的类型单元
此外，支化HMF低聚物可以含有具有连接以形成缩醛的类型单元的结构元件
在这些连接中，曲线表示所示结构元件是HMF低聚物的一部分。HMF低聚物通常具有所示类型的多个相同或不同的结构元件。末端HMF单元通过醛或羟甲基基团结合。
发明人已发现，除了带有醚，半缩醛和/或缩醛键的HMF低聚物之外，碳连接的HMF低聚物(其中单元通过碳-碳键连接)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。
因此，本发明的主题是新型碳连接的HMF低聚物，其包括至少一个第一HMF单元和(至少)一个第二HMF单元，并且其特征在于，第一HMF单元和第二HMF单元通过碳-碳键连接，该碳-碳键连接涉及(包含，条件是，with involvement of)第一HMF单元的呋喃环的位置3或4处的芳香键合碳原子。
与HMF单体相比，来自至少两个链接的HMF单元/单体的化合物在本发明的含义内被指定为"HMF低聚物"。在上下文中，HMF低聚物和HMF聚合物之间的过渡是连续的。在本发明的含义内，"HMF低聚物"被理解为具有最高达3000g/mol的摩尔质量的化合物。
在本发明的含义内，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，该碳-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处的芳香键合碳原子。
根据本发明的有利配置，第一单元的芳香族键合碳原子与第二HMF单元的醛碳原子相连。
所提出的用于形成碳-碳键的机理是，碳-碳键形成涉及在酸中和在碱中芳香键合的碳原子和醛碳原子，如在图1和2中给出。由此，可以清楚的是，除了别的事实之外，与仅通过HMF的醛和/羟基形成键的HMF低聚物相比，具有通过碳-碳键连接的HMF低聚物同时也具有更多的游离的官能醛基和/或羟基。这解释了基于额外的碳-碳键的较高交联程度也是有利的，由此在HMF低聚物中可获得较高密度的游离醛基和羟基。
根据本发明的另一有利的配置，碳连接HMF低聚物具有2至20HMF单元，优选2至10个HMF单元，特别优选2至4个HMF单元。具有2至10个单元的HMF低聚物在温和条件下(这意味着室温和常压)容易溶于水。
根据本发明的另一有利配置，除了涉及芳香键合的碳的连接的第一和第二HMF单元，碳连接的HMF低聚物包含至少一个另外的单元，其以醚半缩醛或缩醛键的形式连接到HMF单元。
本发明的另一个主题是制备碳连接的HMF低聚物的方法，其中该方法包括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/或一种水性5-羟甲基糠醛溶液。
在用于制备5-HMF(单体)的水热条件下，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)是已知的，并且其提供了将起始材料暴露于含水介质中的压力和高温。发明人已经发现，在处理含纤维素的生物质的含水悬浮液和/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(在水热条件下)的过程中形成碳连接的HMF低聚物。
由于其低成本因素，含纤维素的生物质(其经常作为农业生产的废物来积累)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。
本发明的另一个主题是制备碳连接的HMF低聚物的方法，其中该方法包括将HMF单体和/或HMF低聚物的更高或更低纯的溶液暴露于导致HMF低聚物的形成的条件。优选地，HMF溶液暴露的条件包括溶液的碱化或酸化和/或加热。
发明人已发现，例如通过用水由结晶HMF制备的水性HMF溶液老化，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光谱法来确定HMF低聚物的量和分子量。
在温和条件下(即，常压和室温)形成HMF低聚物可以持续数小时，数天或数周。可通过酸化，碱化，和加热来加速老化过程。
优选地，进行制造过程直到达到碳连接的HMF低聚物的所需量，或反应停止。
在这个方面，本领域技术人员应当清楚的是通过水热处理制备碳连接的HMF低聚物可与通过老化制备碳连接HMF低聚物结合。因此，例如，然后可以在常压下老化由水热处理获得的水溶液。
优选地，至少一种碳连接的HMF在制备结束时存在于水溶液中。
进一步优选的是影响碳连接的HMF低聚物或碳连接的HMF低聚物的含量、尺寸和/或浓度。特别优选地，通过在至少一种过滤装置上对含有碳连接的HMF低聚物的溶液进行过滤来影响碳连接的HMF低聚物或碳连接的HMF低聚物的含量。例如，在DE 10 2014 112 240A1中描述了在水热碳化之后处理(通过过滤)HMF水溶液。
碳连接的HMF低聚物非常适合作为可热固化树脂中的组分，其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而获得。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。通过随后固化树脂来得到热固性塑料材料。
碳连接的HMF低聚物具有非常(高)的反应性并且具有额外的交联能力。它们在可热固化树脂中作为反应性羰基化合物是非常有效的。所获得的树脂通过特别好的加工性能，例如非常高的反应性来区分。使用碳连接的HMF低聚物来制备可热固化的树脂的主要优点是反应性羰基化合物如甲醛(其对健康有危害)可以完全省去。
通过缩聚制备可热固化树脂是以本身已知的方式进行的。合适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。优选地，在含水溶剂中进行反应。
碳连接的HMF低聚物可用于与其他反应性羰基化合物的混合物中。优选地，将至少一种HMF低聚物用于与至少一种HMF单体的混合物中和/或与含有醚，半缩醛和/或缩醛键的至少一种其他HMF低聚物的混合物中。甚至少量的碳连接HMF低聚物足以制备具有非常(高)的反应性的羰基化合物。
碳连接的HMF低聚物特别适合由含木质纤维素的材料，例如刨花、木纤维或木屑制备复合材料。根据本技术领域中公知的方法制备木材复合材料。木材复合材料可以如下获得：通过使含木质纤维素的材料与含有碳连接的HMF低聚物的可热固化树脂接触，然后固化树脂(其与交联相关)。优选通过压制提供有含木质纤维素的材料的树脂来进行固化。
以下实施例仅仅用作对本发明的解释说明，并不旨在以任何方式限制本发明。
实施例1:
实施例1显示了含有结构元件的碳连接的HMF低聚物的一部分，结构元件包括碳-碳键，该碳-碳键涉及第一HMF单元的呋喃环的芳香键碳原子和第二HMF单元的醛基碳原子。
为了清楚起见，如曲线所示，示出了碳连接HMF低聚物的一部分。实施例1中未示出的末端HMF单元优选通过醛或羟甲基基团结合。
实施例2:
刨花板面板的制造
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)脲-HMF树脂的制备和性能比较：
制备脲与HMF的摩尔比不同的两种树脂。第一树脂(以下表示为UH(1:0.5))以脲与HMF的比例为1:0.5进行制备。第二树脂(以下表示为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400ml的来自a)的50％的HMF溶液。对于这两种树脂，首先脲在pH 2下与HMF反应2.5小时，温度为90℃，然后在20℃的温度下反应数小时。在该过程中，观察到树脂粘度的变化。
表1:作为时间函数的粘度增加
树脂UH(1:0.5)(粘度为1275mPa.s)和树脂UH(1:0.25)(粘度为65mPa.s)用于后续压制刨花。将树脂分别与刨花和六亚甲基四胺混合，然后在220℃下压制以生产尺寸为250mm×250mm×16mm的面板。相对于木材的量，干木材的负载量为10wt％树脂固体。为了测试各种压制时间和各种固化剂的量的影响，使用不同时间和不同量的六亚甲基四胺产生多个面板。使用两种树脂UH(1:0.5)和UH(1:0.25)的刨花板面板所获得的值列于表2中。
为了比较，通过在45℃的较低温度下使树脂UH(1:0.5)的组分反应来制备第三树脂(UH45(1:0.5))。树脂UH45(1:0.5)还用于将刨花压制成尺寸为250mm×250mm×16mm的刨花板，这些刨花板面板所获得的值也在表2中给出。
用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粘合强度值。
使用脲与HMF的摩尔比为1:0.5，面板3和4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高温90℃相关联。
面板1和2以及5和6示出了在制备树脂期间的温度的影响。
即使使用较少量的HMF生产的面板在延长了压制时间时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是稍微明显至不明显，条件是使用一定比例的HMF制成面板，如面板3至6所示。通过固化剂的量明显地更强烈地影响面板7和10(使用较低比例的HMF)。这些值表明，作为使用的HMF低聚物的阳性性质的结果，可大幅降低固化剂的需要量，可得到具有相同或相当的内部粘结强度的产品。
根据NF EN 319(AFNOR 1993)的内部粘合强度(IB)：
通过下式表示以[N/mm2]计的内部粘合强度
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
对于具有在13mm至20mm范围内的厚度的刨花板和纤维板面板，NF EN 319(AFNOR1993)规定了≤0.35N/mm2的内部粘合强度。
通过切割出在c)下生产的面板，获得用于对内部粘合强度进行研究的面板。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(AFNOR 1993)，垂直于面板的平面，机械地进行内部粘合强度的测定。
表2：刨花板的生产参数和刨花板的性能
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分子的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分子的二聚在碱性条件下碳-碳键形成的建议机理。
无论是单独地以及彼此的任何组合中，本发明的所有特征对于本发明都是重要的。

Claims (8)

1.新型碳连接的HMF低聚物，包含至少一种第一HMF单元和一种第二HMF单元，其特征在于，第一HMF单元和第二HMF单元通过碳-碳键连接，所述碳-碳键涉及所述第一HMF单元的呋喃环的位置3或4处的芳香键合的碳原子。
2.根据权利要求1所述的HMF低聚物，其特征在于，所述第一HMF单元的芳香键合的碳原子与所述第二HMF单元的醛碳原子相连。
3.根据权利要求1或权利要求2所述的HMF低聚物，其特征在于，所述碳连接的HMF低聚物具有2至20个HMF单元，优选2至10个HMF单元，特别优选2至4个HMF单元。
4.根据前述权利要求中一项所述的HMF低聚物，其特征在于，除了涉及芳香键合的碳的连接的所述第一HMF单元和所述第二HMF单元外，所述碳连接的HMF低聚物含有至少一种另外的单元，所述至少一种另外的单元通过形成醚、半缩醛或缩醛键连接到HMF单元。
5.用于制造HMF低聚物的方法，其中所述方法包括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/或一种水性5-羟甲基糠醛溶液。
6.用于制造HMF低聚物的方法，其中所述方法包括在正常压力下将HMF单体和/或HMF低聚物的更高或更低纯的溶液暴露于导致HMF低聚物形成的条件。
7.根据权利要求1至4中一项所述的HMF低聚物用于制造可热固化树脂的用途。
8.根据权利要求1至4中一项所述的HMF低聚物用于由含木质纤维素的材料制造复合材料的用途。
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