木质素磺酸盐基胶黏剂的合成与表征

以双氧水(H2O2)-硫酸亚铁(FeSO4)为氧化还原引发剂,丙烯酸(AA)和马来酸酐(MAH)为单体,采用原位一步法制备了宽分子量分布的P(MAH-co-AA)。通过测定P(MAH-coAA)和木质素磺酸盐(LS)缩聚反应产物的凝胶含量,研究了P(MAH-co-AA)中单体组成、胶黏剂酸度和添加三乙醇胺(TEA)等因素对交联的影响,比较了木质素磺酸钠(LSS)和木质素磺酸铵(LSA)两种LS的反应活性。结果表明:木质素磺酸盐能代替部分多元醇与共聚物制备低成本无甲醛型木材用胶黏剂;提高共聚物P(MAH-co-AA)中MAH含量、胶黏剂酸度及采用LSA均能提高固化交联的程度。     

生物质液化制备酚醛树脂

探讨生物质液化制备酚醛树脂的液化条件、树脂化条件及其性能,分析了生物质的液化率、残渣率,生物质酚醛树脂的红外谱图、粘度、残余酚含量、复合材料拉伸性能等实验数据。研究结果表明,不同生物质对液化条件的要求各不相同,其中竹粉的最佳液化条件是以苯酚重量5%的硫酸为催化剂,反应时间为60 min;同样液化条件下,生物质液化物合成酚醛树脂的树脂化条件相近,每10 g生物质液化物盐酸催化剂添加量为0.6 mL,反应时间为30 min;在最佳实验条件下,竹粉酚醛树脂的各项综合指标最佳,相对粘度最大、液化率最高、残渣率最低、残余酚含量低,其与玻璃纤维布复合的拉伸弹性模量经向和纬向分别是1 508.56 MPa和1 161.40 MPa,大大提高了基底材料性能,使材料刚度更好;通过红外谱图研究发现,不同生物质液化物制备的酚醛树脂结构相同,说明生物质液化物可替代苯酚作为原料与甲醛进行树脂化反应,大大降低了生产成本,减少了苯酚对环境的污染。     

木质素活化及在木材胶粘剂中的应用进展

木质素是相对分子量较高的天然聚合物,由于具有苯酚结构利于制备木材胶粘剂,但是木质素本身反应活性低,一般都将其活化后再利用.而且,除了以往利用最多的造纸工业产生的木质素外,研究发现木材经过褐腐菌降解后残留主要成分是结构部分发生变化的木质素,这种可再生生物质资源以其自身的结构特点在合成胶粘剂上也有很大的优势,本文结合木质素胶粘剂应用中的问题,重点概述了活化木质素的各种方法及褐腐木质素在木材胶粘剂中的应用.     

有机蒙脱土改性脲醛树脂胶黏剂的制备及结构表征

采用"碱-酸-碱"合成工艺,在各阶段将OMMT(有机蒙脱土)投入反应体系,制备有机蒙脱土改性脲醛树脂胶黏剂,测试胶黏剂的各项性能,用XRD(X射线衍射仪)、FTIR(傅里叶变换红外光谱)、SEM(扫描电镜)、TG(热重分析)对改性胶黏剂结构进行表征.实验结果表明,随着OMMT的加入,胶黏剂的游离甲醛含量降低,胶合强度增加.第一阶段投入OMMT,降醛效果明显,第二阶段投入OMMT,补强效果明显.SEM图显示,改性胶黏剂中被剥离成片层状的OMMT因受基体的包覆或挤压,呈现出蜷曲的形状;XRD图谱显示,OMMT/UF胶黏剂的结晶度低于UF胶黏剂的结晶度,有机蒙脱土的加入,破坏了脲醛树脂中羰基和氨基的规整性排列;FTIR图谱表明,改性脲醛树脂胶黏剂中存在大量游离的尿素,胶黏剂的游离甲醛含量低;TG分析得出,改性胶黏剂的TG曲线移向高温方向,材料的热分解温度提高.     

木质素:一种有潜力的生物质基催化剂来源

木质素是自然界中储量丰富的唯一含芳环生物质可再生资源,但复杂的结构使其难以高效利用,目前大部分被废弃。除通过氧化还原等过程可将其转化为石油化工产品的替代品外,木质素结构中丰富的含氧官能团及制浆过程引入的硫元素等均可提供有效位点,为其作为催化剂基质提供了丰富的可行性。本文从木质素资源的来源和结构分析出发,根据不同催化反应的机理和制备催化剂过程中的结构改性类型,综述了具有不同结构特征的木质素基催化剂分别在生物质平台化合物水解等酸碱催化反应、电催化反应和负载金属纳米粒子催化氧化还原反应等过程中的应用,讨论了木质素类型、制备或活化改性条件对催化材料性能的影响,也指出了当前木质素基催化剂的开发研究难点和未来发展方向。     

木质素磺酸盐表面活性剂的研究和应用进展

论述了木质素磺酸盐结构方面的研究、木质素磺酸盐的分离纯化和化学改性制备表面活性剂的方法、木质素磺酸盐表面活性剂应用取得的进展和研究面临的挑战。最后总结认为:进一步加强木质素磺酸盐结构和性能的基础研究,结合界面化学的最新理论成果和现代分析测试手段,通过改性解决木质素磺酸盐的颜色和活性问题,开发可用于日用领域的新型环保的木质素磺酸盐表面活性剂,是木质素磺酸盐这一绿色资源得到高值化利用的一个重要方向,同时木质素磺酸盐在导电高分子等先进材料制备领域具有重大的研究潜力。     

木质素改性可发性甲阶酚醛树脂的固化动力学研究

以酚醛摩尔比1∶1.7,氧化降解木质素40%替代苯酚制备可发性甲阶酚醛树脂,采用DSC研究其等温条件不同温度下的固化动力学,并运用哈克流变仪研究该树脂的固化活性。结果表明,不同温度下树脂的固化反应焓变基本相同,随着固化温度的升高,固化速率得到较大提高;木质素改性可发性甲阶酚醛树脂的固化动力学方程:dα/dt=2.83×1017×exp(-125.27×103/RT)(1-α)0.84。由该方程模拟的等温聚合反应程度与时间的关系曲线与实际情况基本吻合。     

酚醛树脂研究新进展

酚醛树脂成本低廉、原料易得、生产工艺简单、综合性能优良,应用非常广泛。在能源与环境问题突出的大背景下,酚醛树脂已超出通用树脂的范畴,除高性能化、功能化以外,生态友好化也是其重要发展方向。本文综述了酚醛树脂在这些方面的新进展,介绍了相关的合成、固化及制备方法,如离子液体法、相分离法、Stober法,这些方法与常规方法相比具有独特的优势;同时介绍了木质素、单宁酸、生物油等生物质基酚醛树脂以及实现酚醛树脂回收再利用的物理、化学、生物方法。     

农林废弃生物质吸附材料在水污染治理中的应用

环境污染问题已经成为人类社会可持续发展的巨大挑战之一,化工、冶炼及核燃料循环过程等排放的废水中含大量重金属离子、有机物及放射性核素等,若未经处理即排放会给环境带来了极大的危害。吸附法的效率高、操作简单、低成本且无副产物、可循环利用及无二次污染等优点使其成为废水处理的重要方法之一。由于农林废弃生物质成本低、来源丰富、绿色环保且可再生,以其为原料制备的吸附材料被广泛研究。本文主要针对以农林废弃生物质为原料制备的生物炭、纤维素及木质素为研究对象, 综述了生物炭的制备及改性方法、天然纤维素及木质素的改性方法及其在水污染治理中的应用现状。从原材料、制备工艺、改性方法等方面总结分析了吸附材料的性能对水中污染物吸附的影响,提出了生物质基吸附材料在水污染治理应用中所存在的问题,并展望了未来的发展方向。     

新专利介绍

正1.一种光固化玻璃棉毡及其制备方法公开(公告)号:CN109797549A公开(公告)日:2019.05.24申请(专利权)人:江南大学摘要:一种光固化玻璃棉毡及其制备方法,属于玻璃棉纤维改性技术领域。本发明配方包括玻璃棉毡、改性剂和胶黏剂;所述胶黏剂包括预聚物、活性稀释剂、光引发剂和阻聚剂;所述改性剂包覆在玻璃棉毡的     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.