CN114835921B - 一种低共熔溶剂及其制备方法与应用 - Google Patents
一种低共熔溶剂及其制备方法与应用 Download PDFInfo
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Abstract
本发明属于生物质溶剂的技术领域，公开一种高效溶解纤维素的低共熔溶剂的制备方法及其在生物质材料方面的应用。该低共熔溶剂由氢键受体和氢键供体组成，首先将超碱基团进行接枝改性，制备一种新型的季铵盐，其次将制备的季铵盐作为低共熔溶剂的氢键受体，加入不同类型和不同比例的氢键供体，经过一定的温度加热，形成低共熔溶剂，对纤维素、木质素等有着优异的溶解效果。
Description
技术领域
本发明属于生物质溶解领域，具体涉及一种低共熔溶剂及其制备方法与应用。
背景技术
低共熔溶剂是在离子液体的基础上研究开发的一种新型的生物质溶剂，该溶剂是由氢键供体和氢键受体，氢键供体来源广泛，种类繁多，相对价格较低，从而使得整个溶剂具有成本优势，黏度也因为氢键供体的加入而大幅度降低。使得低共熔溶剂除了具备离子液体非挥发、安全稳定等优势之外，在黏度、成本、制备方法等方面也具有明显的优势。所以低共熔溶剂作为潜在的生物质溶剂体系引起广泛关注。此外还有以氢氧化胆碱为氢键受体的低共熔溶剂，配合不同的氢键供体形成溶剂后也能够溶解纤维素，但缺少相应的材料开发。因此，开发一种新型的低共熔溶剂，该溶剂必须要简化制备过程，回收率要提高和回收的溶剂的溶解性能也要保持，溶解再生的生物质基材料性能要优越，通过和不同氢键供体组合出的溶剂能够满足不同制备条件下的要求。
发明内容
本发明的目的提供一种低共熔溶剂及其制备方法与应用。本发明提供的生物质溶剂制备方便，溶解性能可控，绿色环保，且溶解再生后的生物质材料性能优越。
为了实现上述目的，本法通过以下方法实现：
一种低共熔溶剂，其结构通式为AB型：
其中A为氢键受体，B为氢键供体；所述氢键受体选自以下结构：
上述阴离子X-为氯离子(Cl-)、溴离子(Br-)、醋酸根离子(Ac-)和氢氧根(OH-)中一种；上述结构中R基团选自甲氧基乙基(CH3OCH2CH2-)、甲氧基丙基(CH3OCH2CH2CH2-)、异丙基氧甲基((CH3)2CHOCH2-)中的一种；
所述氢键供体选自有机酸类、醇类、酰胺类、酚类、唑类、脲类等中的一种。
进一步的，所述有机酸类为醋酸、丙酸、丁酸、丙烯酸、L-乳酸、D-乳酸、甲氧基乙酸、丙酮酸、草酸、丁二酸、顺丁烯二酸、戊二酸、己二酸、L-精氨酸、D-精氨酸、L-脯氨酸、D-脯氨酸、L-天冬氨酸、D-天冬氨酸等中的至少一种；所述醇类为乙二醇和/或丙三醇；所述酚类为愈创木酚和/或苯酚等；所述酰胺类为2-吡咯烷酮、2-唑烷酮、2-氮己环酮、2-咪唑烷酮和己内酰胺等中的至少一种；所述脲类为尿素、二甲基脲、甲基脲、甲基硫脲、二乙基硫脲等中的至少一种；唑类为吡唑、咪唑和三氮唑等中的至少一种。
一种制备上述低共熔溶剂的方法，由氢键供体和氢键受体混合，在50℃～90℃加热至澄清透明，即可得到低共熔溶剂。
所述氢键供体和氢键受体的摩尔比为4～1：1。
上述低共熔溶剂作为生物质溶剂中的应用。所述生物质为木质素、纤维素和半纤维等。
本发明相对于现有技术，具有如下的优点及有益效果：
相对于现有的低共熔溶剂，本发明所提提供的低共熔溶剂较大提高了生物质的溶解度，特别是对于木质素，均能达到70％以上。
附图说明
图1为本发明的氢键受体的核磁氢谱图，其中(a)为[DBNMOE][Cl]，(b)为[DBUMOE][Cl]。
图2为发明的低共熔溶剂的核磁氢谱图(a)及实物图(b)。
图3为本发明低共熔溶剂溶解微晶木质素前(左)后(右)的显微镜图片。
图4为本发明低共熔溶剂溶解阔叶木浆(DP＝650)的图片，其中左图为未溶解的阔叶木浆显微镜照片，右图为溶解后的显微镜图片；
图5为溶解再生后纤维素膜的照片。
具体实施方式
下面结合具体实施例对本发明做进一步说明。
实施例1：低共熔溶剂中氢键受体的合成：
在500毫升烧瓶中，加入超碱原料超碱原料1,5-二氮杂双环[4,3,0]壬-5-烯62.1g(0.5mol,1.0eq.)，并滴加(0.5mol,1.0eq.)47.25g氯乙基甲基醚。滴加完成后在60℃下反应6h。反应结束后，得到黄色固体107.5g，产率为98.1％。核磁谱图如图1(a)所示。
实施例2：低共熔溶剂中氢键受体的合成：
在500毫升烧瓶中，加入超碱原料超碱原料1,8-二氮杂二环[5.4.0]十一碳-7-烯76g(0.5mol,1.0eq.)，并滴加(0.5mol,1.0eq.)47.25g氯乙基甲基醚。滴加完成后在60℃下反应6h。反应结束后，得到黄色固体120.9g，产率为98.1％。核磁谱图如图1(b)所示。
实施例3：本发明低共熔溶剂的制备：
将制备的[DBNMOE][Cl]3g(0.01mol)加入40ml瓶中，另加吡咯烷酮(PyO)1.19g(0.01mol)，在90℃下搅拌均匀后呈现黄色透明液体，如图2所示。改变氢键供体的种类和配比，能够获得不同溶解性能的低共熔溶剂。
其他低共熔溶剂的制备方法与以上方法一致，表1列举所形成的低共熔溶剂对生物质原料的溶解。
本测试例采用微晶纤维素(国药)、木磨木质素、木聚糖(源自玉米芯)测定低共熔溶剂对于纤维素、木质素、木聚糖的溶解性能。
表1本发明部分低共熔溶剂对生物质原料的溶解性能
由上表可知本发明的低共熔溶剂体系相较于纤维素和半纤维，对木质素具有较高的溶解度，纯氢键受体[DBUMOE][Cl]对木质素的溶解度虽然有所下降但仍能满足溶解需求，并且能够大幅度降低溶剂成本。溶剂编号及比例为[DBNMOE][Cl]/Pyo-1:1的这一组中溶解微晶木质素前后的对比照片如图3所示。
实施例4：本发明所得低共熔溶剂体系再生纤维素膜的制备
采用实施例3中的低共熔溶剂对阔叶木浆制备再生纤维素膜的制备。
取用已制备的低共熔溶剂([DBNMOE][Cl]/Pyo-1:1)10g，加热至90℃加入0.2g阔叶木浆，搅拌溶解2h。取样用显微镜观察溶解后，倒入培养皿流延成膜。加入去离子水再生，多次洗涤后除去溶剂后干燥成膜。如图4所示，溶解液在显微镜下的照片，可以看出纤维素已经完全溶解。如图5所示纤维素膜表面光滑，有很好的透光性。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (5)
1.一种低共熔溶剂，其特征在于其结构通式为AB型：
其中A为氢键受体，B为氢键供体；
所述氢键受体选自以下结构：
上述阴离子X-为氯离子、溴离子、醋酸根离子和氢氧根中一种；上述结构中R基团选自甲氧基乙基、甲氧基丙基和异丙基氧甲基中的一种；
所述氢键供体选自有机酸类、醇类、酰胺类、酚类、唑类、脲类中的一种；
所述有机酸类为醋酸、丙酸、丁酸、丙烯酸、L-乳酸、D-乳酸、甲氧基乙酸、丙酮酸、草酸、丁二酸、顺丁烯二酸、戊二酸、己二酸、L-精氨酸、D-精氨酸、L-脯氨酸、D-脯氨酸、L-天冬氨酸和D-天冬氨酸中的至少一种；所述醇类为乙二醇和/或丙三醇；所述酚类为愈创木酚和/或苯酚；所述酰胺类为2-吡咯烷酮、2-唑烷酮、2-氮己环酮、2-咪唑烷酮和己内酰胺中的至少一种；所述脲类为尿素、二甲基脲、甲基脲、甲基硫脲、二乙基硫脲中的至少一种；唑类为吡唑、咪唑和三氮唑中的至少一种；
所述低共熔溶剂由氢键供体和氢键受体混合，在50℃～90℃加热至澄清透明制得；所述氢键供体和氢键受体的摩尔比为1：1。
2.一种制备权利要求1所述低共熔溶剂的方法，其特征在于由氢键供体和氢键受体混合，在50℃～90℃加热至澄清透明，即可得到低共熔溶剂。
3.根据权利要求1所述低共熔溶剂作为生物质溶剂中的应用。
4.根据权利要求3所述的应用，其特征在于所述生物质为木质素、纤维素和半纤维。
5.根据权利要求3所述的应用，其特征在于所述生物质为木质素。
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