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     

木质素基生物质聚氨酯

聚氨酯材料是由多元醇与异氰酸酯经过聚加成反应得到的一种多功能性的高分子材料,在涂料、弹性体、胶黏剂、泡沫等领域具有非常广泛的应用。但是多元醇与异氰酸酯都来源于石油,随着石油资源的消耗以及环境问题的加剧,寻求可再生原料成为研究热点。目前对于生物基聚氨酯的报道,大多都是针对多元醇的生物质替代,其中利用最多的是植物油和木质素。木质素作为储量丰富的天然有机碳资源,当前利用效率极低,大多被作为燃料而浪费。与植物油相比,在合成聚氨酯方面木质素不存在“与人争粮”问题并且相关产品性能优越,但是木质素的利用仍存在一定缺陷,如分离困难、均一性差、易聚集、位阻大和活性低等,这让木质素的直接利用或改性利用成为关键。本文主要介绍了木质素在生物基聚氨酯合成中的发展现状和最新研究进展。最后,在此基础上展望了木质素基聚氨酯材料在不同领域的发展前景。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.