【作者】 谢红璐；

【导师】 史铁钧；

【作者基本信息】 合肥工业大学 ， 材料学， 2012， 博士

【摘要】 论文的目标是：首先合成出烷基咪唑型、烯丙基咪唑型离子液体,以它们作为木材液化剂,考察木材原料特性和液化反应条件,探讨离子液体液化木材的机理、离子液体结构与木材液化性能的关系,从而建立离子液体液化木材的方法；然后以该方法液化产物为原料,经磺化、缩合制备出一种悬浮剂,研究其在种衣剂中的悬浮性能及配方应用,以期获得木材液化产物进一步应用的理论和实验依据。主要创新工作如下：1、以1-甲基咪唑与1,2-二氯乙烷为原料,合成出双(1-甲基氯化咪唑)乙烷盐离子液体(Ⅰ)；再与三氯化铝反应,制得三氯化铝双(1-甲基氯化咪唑)乙烷盐离子液体(Ⅱ),经GC-MS分析和FT-IR分析确认产物结构。以所得离子液体为液化剂,液化未经任何预处理的木材,建立了离子液体液化木材的方法,并与传统的苯酚液化方法进行了对比。在液比8：1、反应温度110-120℃、反应时间25min及金属卤化物配比N=0.67条件下,离子液体液化性能明显优于苯酚液化剂,且离子液体可回收并重用于液化反应。2、从金寨、霍山和舒城三个杉木产区取样,考察杉木的化学组成、材性及液化特性。杉木的化学组成受地域影响不大,其中纤维素含量较高,半纤维素和木质素含量接近中等水平。纤维素是最难液化的组分,较木质素需要更高的反应温度和更长的反应时间,显著影响杉木的液化性能。杉木材的纤维素、半纤维素含量高于杉木树皮,而灰分、抽提物含量相对较低,相同条件下液化效率较低,而残渣量较少。3、为降低液化反应温度,以1-丁基咪唑、1-甲基咪唑分别与3-氯丙烯反应,合成出1-丁基-3-烯丙基咪唑氯化物离子液体([BAIM][Cl])和1-甲基-3-烯丙基咪唑氯化物离子液体([MAIM][Cl]),再与三氯化铝混合成盐,经GC-MS分析和FT-IR分析确认产物结构。[BAIM][Cl/AlCl3]和[MAIM][Cl/AlCl3]液化率均优于相应的[BAIM][Cl]和[MAIM][Cl],特别是[BAIM][Cl/AlCl3]在80℃时的残渣率降低到10%左右,相当于离子液体(Ⅱ)在100℃的水平,有效液化温度显著降低。偏光显微镜观察[BAIM][Cl/AlCl3]液化杉木粉发现,60℃时纤维素晶区被部分地破坏,随着反应温度升高及反应时间延长,纤维素结晶逐步消失,此时[BAIM][Cl]主要表现为对木粉表层的润胀,而苯酚则无明显作用。4、以红外光谱吡啶探针法研究了离子液体的酸性与催化性能、离子液体结构与木材液化性能的关系。吡啶探针显示,[Cl/AlCl3]随N值变化而产生不同酸性,当N=0.50-0.67时显Lewis酸性,当N>0.67时则出现Br(?)nsted酸性,这种酸性结构对木材液化具有高催化性能。SnCl2和FeCl3等金属卤化物与前驱体阴离子结合可得到类似于[Cl/AlCl3]的配位结构,对液化反应也具有这种催化作用。依据液化过程中各阶段产物组成,[BAIM][Cl/AlCl3]液化木材机理可认为是纤维素首先发生降解,该步骤是液化的关键,其次是半纤维素和木质素,各步反应速率有较大变化。在离子液体结构与性能上,阴离子[Cl]及金属离子M以及阳离子咪唑环上的烷基、烯丙基有利于木材液化反应；[BPy][Cl]、[BMIM][BF4]和[BMIM][PF6]等中性离子液体基本没有液化性。5、以木材液化产物为原料,确定磺化、缩合及中和的合成路线,制备出一种木材液化物悬浮剂(WLS)。所得较佳反应条件为,磺化、缩合反应温度85℃和90℃,磺化、缩合反应时间2.5h和3.0h,中和反应温度70-80℃,在此条件下产物悬浮率平均达91.1%。研究WLS在4种作物的种衣剂悬浮液中的悬浮性能结果表明：WLS具有一定表面活性,但浓度-表面张力关系曲线上没有明显的转折点,与Tween80混合在Attapulgite中显示出助膨胀性；在二元、三元混合体系中,WLS具有良好配伍性,与非离子表面活性剂等组分产生协同效应,且在室温、高温条件下悬浮性能优良,粘度变化小。三元体系Attapulgite/WLS/Tween80对4种作物的种衣剂悬浮率均达90%以上,优于二元体系和单一组分。经过组分筛选和配方设计,确定悬浮种衣剂的配方组成和用量,制备出一种20%福·克悬浮种衣剂。包衣实验结果表明,配方的各项质量控制指标测定结果均达到质量标准,悬浮性能较为突出；在发芽势、发芽率、发芽指数和活力指数4项指标上较未包衣种子更优,田间播种较为可靠。更多还原

【Abstract】 The objective of this paper is to obtain the following results. First, alkyl imidazole ionic liquids and allyl imidazole ionic liquids are synthesized. By using them as wood liquefacients, the wood raw material characteristics and liquefaction conditions are studied, and the wood liquefaction mechanisms by ionic liquids and the relationship between structures of ionic liquids and properties of wood liquefaction are discussed, thereby the method of wood liquefaction by ionic liquids is established. Secondly, a kind of suspending agent is prepared by sulfonation and condensation using liquefaction products with this method as materials. And its suspension properties and formulation applications in suspending seed coating agent are studied in order to obtain the theoretical and experimental data for the further application of wood liquefaction products.The main innovative works are as follows.1. The bis (1-methylimidazole) ethyl chloride ionic liquid (I) by1-methylimidazole and1,2-dichloroethane, and bis (1-methylimidazole) ethyl chloride aluminum trichloride ionic liquid (II) by ionic liquid (I) and aluminum trichloride were synthesized and confirmed by GC-MS and FT-IR. The method of wood liquefaction by ionic liquids was established by liquefying wood without any pretreatment in ionic liquids liquefacients, contrasting to the traditional liquefaction method of phenol. Under the conditions of liquid/wood ratio20:1,110-120℃,25min and metal halide ratio0.67, the properties of ionic liquids were much more better than those of phenol liquefacient, and the ionic liquid could be recycled and re-used in the liquefaction.2. The chemical composition, properties and liquefaction characteristics of Chinese fir were studied, sampling from the Jinzhai, Huoshan and Shuchen, three Chinese fir-producing areas. The chemical composition of Chinese fir had been less affected by geographic area, wherein, the cellulose content was higher, and hemicellulose and lignin content were close to the middle level. Cellulose was the most difficult to be liquefied in all components, needed higher reaction temperature and longer reaction time than lignin, markedly affecting properties of Chinese fir liquefaction. The cellulose and hemicellulose contents of Chinese fir were higher than those of fir bark, the ash and extractives contents of it were relatively low, the liquefaction efficiency of it was lower, and the amount of residue of it was less under the same conditions.3. In order to reduce the temperature of the liquefaction reaction,1-butyl-3-allyl imidazolium chloride ionic liquid ([BAIM][Cl]) and1-methyl-3-allyl imidazolium chloride ionic liquid ([MAIM][Cl]) were synthesized by1-butylimidazole,1-methylimidazole reacting respectively with3-chloropropene, mixed into salts with aluminum trichloride, and confirmed by GC-MS and FT-IR. The liquefaction rates of [BAIM][Cl/AlC13] and [MAIM][Cl/AlCl3] were better than corresponding [BAIM][Cl] and [MAIM][Cl]. Especially the residue rate of [BAIM][Cl/AlCl3] reduced to about10%at80℃, corresponding to the level of the ionic liquid (Ⅱ) at100℃, and the effective liquefaction temperature was reduced significantly. It was shown that during the course of the observation by polarizing microscope for fir powder liquefaction in [BAIM][Cl/AlCl3], cellulose crystalline region was partially destroyed at60℃and disappeared gradually with the rise of the reaction temperature and the extension of reaction time, the fir powder was mainly swelled in the surface by [BAIM][Cl] at this time, but not significant effect by phenol.4. The acidic and catalytic properties of ionic liquids and the relationship between structures of ionic liquids and properties of wood liquefaction were studied by infrared spectroscopy with pyridine probe. Based on the pyridine probe, it was shown that [Cl/AlCl3] had different acidity with the changes of N, the Lewis acidity was indicated when N was0.50-0.67, the Br(?)nsted acidity was indicated when N was greater than0.67, and this acidic structure for wood liquefaction with high catalytic property. The coordination structure similar to [Cl/AlCl3] could be obtained by the metal halide such as SnCl2and FeCl3combining with the precursor anion, also had such catalysis for liquefaction.According to product composition in various liquefaction stages, the mechanism of wood liquefaction by [BAIM][Cl/AlCl3] could be considered that cellulose was degraded first of all, which was the key of liquefaction, followed by hemicellulose and lignin, and the reaction rate in each step had more changes. The anions [Cl], metal ions M, and alkyl or allyl in the ring of cationic imidazole were in favor of wood liquefaction in the structure and properties of ionic liquids. The neutral ionic liquids such as [BPy][Cl],[BMIM][BF4] and [BMIM][PF6] had basically no liquefaction property.5. A kind of suspending agent, wood liquefaction sulfonation (WLS), had been prepared by the synthetic route of sulfonation, condensation and neutralization with the product of wood liquefaction. The optimum conditions for the reaction were obtained, reaction temperature of sulfonation and condensation were at85℃and90℃, reaction time of sulfonation and condensation were for2.5h and3.0h, reaction temperature of neutralization were at85℃and90℃, under these conditions the average suspension rate of the product was91.1%.The results of WLS suspension properties in seed coating suspension agents of the four kinds of crops showed that, WLS had a certain surface activity, but no apparent turning point on the curve of concentration-surface tension, and produced auxiliary swelling property in Attapulgite system when mixed with Tween80. In the binary and ternary mixtures, WLS had good compatibility, which produced synergistic effect with other components such as non-ionic surfactant, and showed excellent suspension property and little change in viscosity at room or high temperature. The suspension rates of the ternary system Attapulgite/WLS/Tween80to seed coating agent of4crops were more than90%, which were better than those of the binary system and a single component.After component selection and formulation design, the composition and dosage of suspended seed coating formulation had been determined, and then a kind of20%thiram/carbofuran suspended seed coating agent had been prepared. The coating application showed that the measurement results of each quality control index of the formulation could meet quality standards, the suspension properties were more prominent, the samples were better than uncoated seeds in the four indicators including germination potential, germination rate, germination index and vigor index, and field germination was more reliable.更多还原