回收聚乙烯醇缩丁醛/二氧化硅复合材料的制备与性能研究

利用硅烷偶联剂KH560对气相法SiO2进行表面改性,对改性前后SiO2的堆积密度、表面结构与形貌进行了分析。而后采用熔融共混法将SiO2添加到回收PVB膜片中,比较SiO2改性前后复合材料的力学性能、微观形貌及动态流变行为。结果表明:改性后SiO2表面接枝上KH560,其堆积密度明显增加;改性SiO2与PVB之间存在明显的相互作用,可显著降低回收PVB膜片加工黏附性;SiO2改性前后复合材料拉伸性能与回收PVB膜片相比均稍有降低,而撕裂强度有所增加。     

聚乙烯醇缩丁醛的甲苯-乙醇溶液及其非溶剂诱导相分离研究

在片式多层陶瓷电容器（MLCC）的流延工艺中,甲苯-乙醇混合溶剂是黏合剂聚乙烯醇缩丁醛（PVB）广泛采用的溶剂体系。本文探讨了甲苯与乙醇的体积比、PVB浓度以及流延成膜的相对湿度等因素对溶液中PVB构象以及凝聚态膜片结构的影响。PVB中存在由烷侧链排列形成的玻璃区以及由链缠结而成的无定形区。乙醇是PVB的良性溶剂,通过溶胀玻璃区,使得PVB链更加舒展;甲苯可以有效降低PVB与溶液的摩擦,并通过“成核-生长”机制发生粗化聚并,导致分子间相互作用逐渐增大。较高湿度会造成膜片缺陷;混合溶剂中乙醇的体积分数过高易形成缺陷;缺陷几乎不影响膜的有效模量以及热力学性能。     

废旧锂离子电池正极材料资源化回收与再生

随着电子设备的普及和电动汽车行业的迅速崛起,作为提供能量来源的锂离子电池发挥着重要的作用。以钴酸锂、磷酸铁锂以及三元正极材料为代表的锂离子电池产销量不断增加;与此同时,为了提供更长的续航时间以及续航稳定性,新型锂离子电池材料的研究工作也在不断推进。在此背景下,锂离子电池正极材料的失效、废弃以及资源化回收再生的过程就显得愈发重要,如何在下游解决报废锂离子电池处理的问题也逐渐提上日程。基于此,本文分别从湿法和火法再生两个角度对废旧锂离子电池正极材料的回收和再生过程进行了介绍,包括回收条件优化的方法、较为新颖的回收再生方法以及再生材料的性能等,并总结了回收再生过程的杂质元素,包括铝、铜等元素对再生材料结构和性能的影响以及工业上常用的回收废旧锂离子电池的方法和环境影响。最后对锂离子电池回收的方法进行总结并进行展望。     

基于高温化学转化的废旧锂离子电池资源化技术

鉴于废旧锂离子电池的环境危害性和资源化价值的双重属性,对其进行无害化处理并对其中的有价资源进行回收再利用具有十分重要的意义。目前电池资源化技术主要通过高温或常温条件下的化学转化实现。高温条件下,废旧锂离子电池中有价元素化学转化速率快、回收流程短、物料适应性强,易于实现工业应用,相关技术成为废旧锂离子电池资源化研究热点之一。本文基于物相化学转化方式的差异,系统分析了高温化学还原、熔盐化学焙烧以及短程材料再生等方法的物理化学机理、技术特征及研究现状,并对比了不同技术的优势和存在的问题。在此基础上,提出今后高温化学转化方法实现废旧锂离子电池资源化研究中需要考虑材料的短程清洁循环再生、深入研究其化学转化机理。基于绿色化学原理的工艺设计开发出低能耗、环境友好的资源化工艺路线,真正实现废旧锂离子电池的绿色处理和循环利用。     

国内外PVB材性研究

主要介绍了国内外研究PVB(聚乙烯醇缩丁醛)材性的现状。国内外研究表明,PVB是应变率及温度敏感材料。应变率增加,弹性模量变大;温度升高,弹性模量和剪切模量均下降。同时,国内外进行了少量的实验,研究PVB的本构模型。总结发现,PVB的本构模型可描述为线弹性、弹塑性、线性粘弹性和非线性粘弹性四种,但本质上PVB是非线性粘弹性材料,不同的环境条件与计算要求可选择不同的本构模型。目前,国内外学者比较认可的是用超弹性考虑其非线性,用Maxwell模型考虑其粘弹性。     

BTF变色对其热安定性和与PVB等相容性的影响

通过光照制备了一定量的变色苯并三呋咱氧化物（BTF）,再分别采用差热（DTA）,差示扫描量热（DSC）,真空安定性试验（VST）等热分析方法,对变色前后的BTF进行了热安定性研究及与聚乙烯醇缩丁醛（PVB）等接触材料的相容性研究,并通过热重－红外等仪器分析手段,初步探讨了BTF与PVB之间的作用机理。     

PVB掺杂有机无机复合SiO2增透膜的制备和表征

以聚乙烯醇缩丁醛(PVB)为有机掺杂剂,正硅酸乙酯为前驱体,氨水为催化剂,利用溶胶-凝胶法制备出了一种新型的有机无机复合二氧化硅增透膜。采用红外光谱、X射线衍射、粒度分析、紫外分光光度法、椭偏测定、原子力显微镜、静滴接触角测量等对膜层性质进行了表征。结果表明：PVB分子的引入并没有引起增透膜结构的变化。在相同的实验条件下,未经PVB掺杂的SiO₂增透膜在720 nm处的峰值透过率为99.8％,而PVB掺杂后的SiO₂复合膜在840 nm处的峰值透过率在99.9%以上。掺杂膜层变厚,峰值透过率朝长波方向移动。掺杂前后增透膜对水的接触角从29°增加到71°,膜层的疏水性得到明显提高。     

废旧锂离子电池正极材料有价金属回收研究进展

锂电池新能源汽车行业快速发展,大量含有贵金属的废旧锂电池(LIBs)进入退役期。目前废旧LIBs预处理及有价金属回收技术面临能源消耗量大、电池种类泛化性弱等问题。本文介绍了LIBs生命周期、组成及失效机理,综述了国内外废旧LIBs预处理及有价金属回收技术现状;总结了目前预处理技术中放电、破碎及分选工艺的不足,分析了有价金属回收再利用技术中湿法冶金和火法冶金回收工艺的优缺点;提出了废旧LIBs预处理方法和有价金属回收技术的研究方向。     

涤纶化学降解单体产物的高效结晶提纯研究

为了解决废旧涤纶(PET)纺织品乙二醇醇解法循环利用中存在的醇解产物对苯二甲酸二乙二醇酯(BHET)纯化困难的问题，通过研究BHET晶体的独特的相变性质，发展了BHET纯化新技术.实验结果表明，对结晶的、醇解反应产物BHET使用减压升华操作，在1.33 kPa,130℃的条件下，可获得纯度达99.7%，收率达86.4%，白度(L^*值)达99.8的纯化BHET.回收所得的BHET可再缩聚制备再生PET.该再生PET在相同条件下与由石油基BHET缩聚所制得的PET具有类似的性质，包括白度、分子量及分子量分布等.本文还验证了该种醇解法回收废旧涤纶纺织品的技术的普适性：考察各种含有不同成分及颜色的涤纶纺织品样品的醇解行为及产物分离纯化效果.所研究的BHET纯化方法步骤短、产物纯度高、不额外使用有毒化学试剂，并有效地克服了粉末状BHET在加热纯化时容易发生缩聚的关键难题，为高品质回收废旧涤纶纺织品提供了一种新的路径.     

废旧锂离子电池正极材料及电解液的全过程回收及再利用

作为发展势头迅猛的新型储能形式,锂离子电池缓解了能源领域对化石燃料的依赖,同时减轻了日益严峻的环境压力,但是数量巨大的废旧锂离子电池具有危险废弃物和高附加值可用资源的双重属性。因此,通过不同技术手段的创新和组合,实现组成成分日益多样化的废旧锂离子电池的高效回收和再利用具有巨大的挑战和特殊重要的现实意义。本文从预处理工艺出发,详细阐述了放电失活、分类拆解、粉碎筛分、酸浸除杂等一系列过程的技术手段和要求;从原料再生、结构修复以及再制备三个方面探讨了具有代表性的再利用思路,分析了各技术方法的优势和存在的问题。此外,对废旧电解液的无害化处理和回收进行了专题讨论,重点介绍了超临界CO₂萃取工艺。最后,针对现阶段存在的问题提出展望,为后续开展废旧锂离子电池回收的相关研究及工业应用提供参考。     

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%.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.