高性能陶瓷聚合物前驱体研究新进展

含硅聚合物是制备高性能陶瓷的重要前驱体。聚合物前驱体热解转化法在非氧化物陶瓷及其复合材料制备方面具有特别优势。本文主要介绍了含不饱和基团聚硅碳烷、线性和超支化聚硼硅氮烷、含过渡金属聚合物等几类前驱体的结构设计和合成新方法,以及其在电磁波吸收材料、锂电池负极材料、特种陶瓷结构3D打印成型方面应用的新进展。     

3D打印用光敏树脂的高性能化及功能化研究进展

3D打印,又称增材制造,是一项新兴的智能制造技术。光固化3D打印技术是增材制造的主要方向之一,具有成型精度高、打印速度快及工艺成熟等优点。处在高速发展之中的光固化3D打印技术对光敏树脂提出了越来越高的要求,3D打印用光敏树脂的高性能及功能化研究受到极大关注。本文综述了高性能光敏树脂的最新研究进展,重点讨论了其用于构筑复杂结构导电导热聚合物、形状记忆聚合物、特殊浸润性聚合物、生物医用聚合物及凝胶材料的设计思路及相应构件所展示的优异功能性,同时对光敏树脂基3D打印材料的发展趋势及应用前景进行了分析和展望。     

聚合物基微纳米功能复合材料3D打印加工的研究

高分子材料3D打印加工可制备传统加工不能制备的形状复杂的高分子制件,是近年来发展很快的先进制造技术。但适用于3D打印加工的高分子材料种类少,结构功能单一,难以制备高分子功能器件。本文介绍了我们在聚合物基微纳米功能复合材料3D打印加工方面的研究工作:通过有机/无机杂化、固相剪切碾磨、超声辐照、分子复合等技术制备适合于选择性激光烧结(SLS)和熔融沉积成型(FDM)的聚合物基微纳米功能复合材料;实现了聚合物基微纳米功能复合粉体的SLS加工和功能复合丝条的FDM加工;研究了3D打印低维构建、层层叠加、自由界面成型、复杂固-液-固转变过程;建立了功能复合粉体球形化技术,发明了直接熔融挤出新型FDM打印机;制备了常规加工方法不能制备的数种形状复杂的功能器件,如尼龙11/钛酸钡压电器件、柔性聚氨酯/碳纳米管传感器、个性化人颌骨模型等,突破了传统加工难以制备复杂形状制品和目前3D打印难以制备功能制品的局限。     

植物纤维及其提取物增强聚合物的3D打印成型研究

3D打印技术作为新型成型技术,近年来受到了巨大的关注,但常见的PLA、ABS等单体打印耗材由于其自身的不同缺点,限制了其进一步的应用。本文综述了植物纤维及其提取物增强聚合物复合材料在3D打印领域的应用研究进展,重点阐述了木纤维、竹纤维,秸秆纤维等常见植物纤维用于3D打印的研究现状,还介绍了纤维素、木质素、半纤维素等植物纤维提取物增强聚合物用于3D打印的研究情况。同时对植物纤维/聚合物材料存在的一些问题及改性方法进行了分析与展望。     

光固化3D打印技术及光敏树脂的开发与应用

光固化3D打印技术因速度快、精度高、环境友好等优势,已成为一类广泛应用的快速成型工艺.光敏树脂作为光固化3D打印的主体材料,对器件的性能与应用有着决定性影响.本文先介绍了几种已普及和新开发的光固化3D打印成型原理;并对光敏树脂的组成、分子结构和器件性能间的构-效关系进行了分析;进而对光固化3D打印及树脂的应用进行分类介...     

光敏树脂合成及3D打印的综合实验教学设计与实践

针对综合实验的特点,结合创新性、趣味性等特性,设计了光敏树脂合成及3D打印综合实验。实验用1,6-己二异氰酸酯(HDI)三聚体和丙烯酸羟乙酯反应,以丙烯酰吗啉(ACMO)为活性溶剂,合成可紫外光固化的预聚体树脂。通过对预聚体树脂的—NCO测定、红外光谱、核磁共振,分析了HDI三聚体和丙烯酸羟乙酯的反应程度,表征预聚体树脂的结构及评价光固化性能,并与其他光固化单体和光引发剂配合制备黏度适宜的光敏树脂。用405 nm波长的桌面级3D打印机打印出测试样条和展示样品,通过对样条性能测试,表明该光敏树脂打印的样条具有较好的力学性能。本实验开设在本科四年级的综合教学实验中,其可以使本科生学到光固化树脂的制备方法,了解化学材料与数字模型及3D打印技术的结合,体会聚合物结构与性能的关系,增强本科生对数据的分析处理能力以及拓展本科生对其他学科的知识水平。     

3D打印用高分子材料及其复合材料的研究进展北大核心CSCD

3D打印技术亦称为增材制造,是基于三维数学模型数据,通过连续的物理层叠加,逐层增加材料来生成三维实体的技术。作为第三次工业革命的代表性技术之一,3D打印材料是影响3D打印技术发展与应用的关健因素。而高分子聚合物在打印材料中占据主要地位,其中高分子复合材料具有明显优势。本文综述了近年来3D打印用高分子材料及其复合材料的研究现状,包括高分子丝材、光敏树脂、高分子粉末、高分子凝胶及其它高分子材料,并对高分子材料在3D打印领域的发展进行了展望。     

3D打印用高分子材料及其复合材料的研究进展

3D打印技术亦称为增材制造,是基于三维数学模型数据,通过连续的物理层叠加,逐层增加材料来生成三维实体的技术。作为第三次工业革命的代表性技术之一,3D打印材料是影响3D打印技术发展与应用的关健因素。而高分子聚合物在打印材料中占据主要地位,其中高分子复合材料具有明显优势。本文综述了近年来3D打印用高分子材料及其复合材料的研究现状,包括高分子丝材、光敏树脂、高分子粉末、高分子凝胶及其它高分子材料,并对高分子材料在3D打印领域的发展进行了展望。     

聚硼硅氮烷陶瓷前驱体分子结构设计和合成*

聚硼硅氮烷是制备高性能硅硼 碳氮（SiBCN）复相陶瓷的主要聚合物前驱体,在耐高温、抗氧化高性能陶瓷领域中具有重要的研究价值。本文分4个方面,即基于硼吖嗪的聚硼硅氮烷、侧基含有环硼氮烷或单硼烷的聚硼硅氮烷、基于多官能硼烷构筑的聚硅氮烷和含硼聚硅基碳化二亚胺,从聚硼硅氮烷分子结构设计、改性、合成及在多维尺寸材料中初步应用的角度综述了该领域国内外研究的新进展,指出了聚硼硅氮烷陶瓷前驱体设计合成研究发展中值得关注的新方向。     

3D打印光敏树脂的研究进展

以光敏树脂为原料的立体快速成形3D打印技术,具有成本低、精度高、成型快等优点,在各个领域得到广泛的应用。但是,与之相适应的光敏树脂价格较高,并被国外的一些大公司所垄断,而国内相关研发起步较晚,能够生产和研发性能优良的3D打印光敏树脂的企业较少。简要阐述了3D打印光敏树脂的成形方式、固化原理和组成,重点讨论了配方设计的基本方法和评价指标,并对该领域进行了展望。     

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%.     

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.     

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.     

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.     

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.     

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.     

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.