8-羟基喹啉铜(Ⅱ)功能化SBA-15的制备、表征及催化性质

利用3-氨丙基功能化的介孔SBA-15(APS-SBA-15)作为载体, 通过C—N共价键将8-羟基喹啉铜(Ⅱ)固定到APS-SBA-15孔道中, 制备了8-羟基喹啉铜(Ⅱ)功能化的SBA-15催化剂[Cu(Ⅱ)-Q-APS-SBA-15], 并将其用于以质量分数30%的过氧化氢为氧化剂的苯酚羟化反应中. 结果表明, Cu(Ⅱ)-Q-APS-SBA-15呈现出较高的苯酚转化率和苯二酚选择性.     

金属酸盐催化剂对苯酚羟基化反应的活性考察

苯酚羟基化联产邻苯二酚和对苯二酚是一条典型的绿色工艺路线.通过对多种金属酸铁酸盐进行筛选,得出以Fe(NO3)3.9H2O为铁源、Cu(CH3COO)2.H2O为铜源,以氨水为沉淀剂,采用共沉淀法制备的Fe-Cu复合金属酸盐催化剂具有最好的催化活性.结果表明,在水作溶剂,催化剂与苯酚的质量比为1∶100,苯酚初始浓度25%,反应温度65℃,苯酚与双氧水的摩尔比为2的条件下,采用Fe-Cu催化剂,苯酚单程转化率可达25%,苯二酚总选择性在90%左右.通过对铁酸盐催化剂的XRD、IR表征,可以看出,Fe-Cu催化剂具有独特的CuFe2O4尖晶石结构,因而具有不同于其它铁酸盐的衍射峰和吸收峰.另外,Fe-Cu催化剂制备简便、原料廉价易得,因此具有良好的工业应用前景.     

苯酚直接羟基化制备苯二酚反应体系中催化剂的设计与性能

邻苯二酚和对苯二酚是重要的工业原料。苯酚一步羟基反应合成苯二酚的方法原子利用率高且节能高效,符合可持续发展的理念。以H_2O_2为氧化剂氧化苯酚合成苯二酚的工艺,流程简单、反应条件温和且绿色环保,成为催化合成领域的研究热点。在该反应中,苯酚的转化率和产物苯二酚的收率高低取决于催化剂的活性。本文综述了近几年在苯酚羟基化制备苯二酚反应中催化剂的研究进展。按照反应体系的不同,催化剂可被分为热催化反应体系中的催化剂和光催化反应体系中的催化剂。催化剂的催化性能主要以苯酚转化率、苯二酚的选择性和稳定性等方面作为评价指标。本文重点介绍了以H_2O_2为氧化剂的液相非均相催化体系中含金属催化剂的研究现状,并在最后对催化剂在苯酚一步羟基化制备苯二酚的反应体系中的制备与应用作了展望。     

催化还原胺类衍生物N-单烷基化反应一锅法合成4,6-二(异丙基氨基)-1,3-苯二酚

以 2-氯-4,6-二硝基-1,3-苯二酚为原料,丙酮为烷基源,氢气为还原剂,研究了在10%Pd/C催化剂上一锅法合成N-单烷基氨基苯酚化合物 4,6-二(异丙基氨基)-1,3-苯二酚的反应工艺. 考察了反应条件如醋酸量、丙酮浓度、氢气压力、催化剂量和反应时间对反应的影响,开发出一条高收率、高选择性制备N-单烷基氨基苯酚化合物的合成路线.     

高选择性的水相苯酚羟基化反应的研究

浸渍法制备负载型氧化铜催化剂,并且采用XRD、氮气物理吸附、扫描电镜、H2-程序升温还原、热失重等手段对所得催化剂进行表征。以30%过氧化氢为氧化剂,负载型氧化铜为催化剂,将苯酚催化氧化成为苯二酚,经高效液相色谱法分析反应产物组分,发现当反应物料的摩尔比为n苯酚∶n双氧水=3∶1时,参加反应的苯酚的转化率达到25.72%,选择性(邻苯二酚)超过74%。     

水相中苯酚的高选择性羟基化反应研究

浸渍法制备负载型氧化铜催化剂,并且采用XRD、氮气物理吸附、扫描电镜、H2-程序升温还原、热失重等手段对所得催化剂进行表征。以30%过氧化氢为氧化剂,负载型氧化铜为催化剂,将苯酚催化氧化成为苯二酚,经高效液相色谱法分析反应产物组分,发现当反应物料的摩尔比为n苯酚∶n双氧水=3∶1时,参加反应的苯酚的转化率达到25.72%,选择性(邻苯二酚)超过74%。     

改性L石催化苯酚羟基化反应的应用

以L沸石为载体,分别采用浸渍法和离子交换法制备了Cu/L催化剂,并应用于苯酚羟基化反应.在苯酚与双氧水摩尔比等于3的条件下详细考察了反应时间、反应温度、L沸石酸碱性以及Cu的负载量和负载方法等因素对反应的影响.结果表明:采用浸渍法制备的催化剂比离子交换法制备的催化剂具有更高的活性,而且增加催化剂酸量或者升高反应温度均有利于提高苯酚转化.在最佳反应条件下,反应2h苯酚转化率为24.0%,苯二酚选择性为71.4%,其中n(邻苯二酚)/n(对苯二酚)为1.22.     

铁改性的HMS分子筛催化苯酚羟基化反应合成二酚

邻苯二酚和对苯二酚是重要的精细化工中间体,在各个行业中具有广泛的应用。苯酚与过氧化氢反应合成苯二酚是一条反应条件温和、环境友好的合成路线,该合成路线的关键是催化剂的选择和反应条件的优化。本文以铁改性的HMS分子筛为催化剂,研究了金属负载量、催化剂使用量、反应温度、反应时间等因素对催化性能的影响,优化了反应条件。以水为溶剂,n(Fe)∶n(Si)=0.04,n(苯酚)∶n(H2O2)=2∶1,反应温度50℃,催化剂用量0.1g,反应4h,苯酚的转化率达45.5%,苯二酚选择性为94.9%。N2吸附-脱附结果表明,Fe/HMS具有良好的介孔结构,铁进入HMS材料的骨架中,并且催化剂具有良好的稳定性,循环使用后骨架保持完整。     

负载型铁基复合氧化物催化苯酚羟基化的研究

在温和条件下对铁基复合氧化物催化苯酚和过氧化氢的羟基化反应进行了研究.结果表明,活性组分、载体以及催化剂/苯酚(质量比)、过氧化氢/苯酚(摩尔比)、反应温度和反应时间等对苯酚羟基化反应具有重要影响.Fe-A催化剂的活性组分形成了α-Fe2O3和尖晶石结构;Fe-B催化剂活性组分以非晶态分布在催化剂上,高度弥散,具有更好的催化性能.溶剂的加入,有助于苯酚和过氧化氢的混合,水是理想的羟基化反应溶剂,可以实现苯酚和过氧化氢水溶液的互溶,有利于·OH的生成.以Fe-B作催化剂,水为溶剂,反应温度65℃,反应时间1h,催化剂/苯酚(质量比)=0.02,水/苯酚(体积比)=2.0,过氧化氢/苯酚(摩尔比)=0.3,苯酚转化率21.6%,苯二酚选择性86.5%.     

Cu/SiO_2结构及其催化苯酚羟基化反应性能的研究

以不同结构的SiO_2为载体,采用传统浸渍法,合成3种负载型的Cu/SiO_2.使用X射线衍射(XRD)、 N_2的等温吸-脱附、紫外漫反射光谱(DR UV-vis)、 X射线电子能谱(XPS)、等离子原子发射光谱(ICP)和H_2的程序升温还原(H_2-TPR)方法对样品进行表征.考察了以H_2O_2为氧化剂,样品对苯酚直接羟基化合成苯二酚的催化性能.结果表明:具有介孔和MFI结构的二氧化硅(MS-1),稳定性强,有利于引入Cu物种在其孔内扩散及分布,形成更多的高分散CuO.一定反应条件下, Cu/MS-1催化活性最高,苯二酚的收率和选择性分别高达38.91%和81.5%. Cu/MS-1催化剂重复使用10次后,苯二酚的收率为37.64%,而Cu含量仅从2.5%变为2.1%,具有较强稳定性;高分散CuO是目标反应的主要活性物种.     

Comparative Thermogravimetric Studies of Poly(ether-ketone/sulfone) Imides and Their Parent Polymers: I. Poly(ether-ketone/sulfone) ethylimide

Thermogravimetry (TG) was employed to study the thermal degradation kinetics of poly(etherketone/sulfone)ethylimide (PEK-IE and PES-IE). The corresponding decomposition activation energies and reaction orders were obtained and the comparison was made with their parent polymerspoly(ether-ketone/sulfone) with Cardo group (PEK-C and PES-C). The results show that the degradation activation energies of PEK-IE and PES-IE were lower than that of PEK-C and PES-C; and two stages of the degradation process were found for all the four polymers. For PEK-IE and PES-IE, the activation energies in the first decomposition stage are much lower than that in the second stage and the two stages can be taken as slow induction and fast degradation, whereas for PEK-C and PES-C the activation energies in the first decomposition stage are larger than that in the second stage, and the two stages can both be taken as two fast degradation stages. The decomposition mechanism of the two stages was also speculated.This revised version was published online in November 2005 with corrections to the Cover Date.     

Drei stereoisomere quadratisch-pyramidale [Ma3b2]-Komplexe: Untersuchungen zur Existenz und zur Struktur kristalliner Dimethylsulfoxid-Komplexe von Antimon- und Bismuttrichlorid

Three Stereoisomeric Square-Pyramidal Complexes [Ma₃b₂]: Investigations of the Existence and the Structures of Crystalline Dimethyl Sulfoxide Complexes of Antimony and Bismuth Trichlorides The formation of solid complexes MCl₃ · n DMSO (M = Sb, Bi; n = 1–4) was reinvestigated. In each system, only two of four presumptive complexes could be isolated as crystalline solids: SbCl₃ · DMSO ( 1 a ) was prepared for the first time, SbCl₃ · 2 DMSO ( 1 b ), BiCl₃ · 2 DMSO ( 2 b ) and BiCl · 3 DMSO ( 2 c ) were reproduced according to literature data. Evidence is presented as to the non-existence of BiCl₃ · 4 DMSO, contrary to previous claims in the literature. A unit cell determination showed 2 c to be structurally identical with the monomeric fac-octahedral complex BiCl₃(DMSO)₃ obtained fortuitously and described elsewhere [Z. anorg. allg. Chem. 620 (1994) 1037]. The compounds 1 a (monoclinic, space group P2₁/c), 1 b (monoclinic, space group P2₁/n) and 2 b (monoclinic, space group C2) represent examples of each of the three possible geometric isomers of a square-pyramidal complex [Ma₃b₂]. In the formally 1/1 adduct 1 a , which is in fact [Sb(1)Cl₃(DMSO)₂ · Sb(2)Cl₃], the Sb(1) atom of the complex unit displays square-pyramidal geometry with the DMSO ligands situated in the apical and one of the basal positions. These units are linked into chains by SbCl₃ molecules acting as Cl-acceptors. Sb(2) forms two chelating chloro-bridges with cis-Cl atoms of one neighbouring complex and a third chloro-bridge with the remaining Cl of the symmetry-related second neighbour. The resulting Cl₆-geometry around Sb(2) is distorted octahedral. 1 b consists of square-pyramidal molecules, in which the DMSO ligands occupy two basal cis-positions; the monomeric units are loosely linked through the apical Cl atoms to form a chain of octahedra sharing trans-vertices. The asymmetric unit of 2b is a square pyramid with trans-basal DMSO ligands. The pyramids are connected by symmetry-equivalent basal chlorine atoms into chains of octahedra sharing cis-vertices. 1a displays remarkably short Sb? O dative bonds (204.7/212.9 pm); the M? O bond distances of 1b and 2b are 223.0/234.6 and 234.5/238.7 pm, respectively.     

On the morphological behavior of ABC miktoarm stars containing poly(cis 1,4-isoprene), poly(styrene), and poly(2-vinylpyridine)

Fundamental understanding of microphase separation in ABC miktoarm copolymers is vital to access a plethora of nonconventional morphologies. Miktoarm stars based on poly(cis 1,4-isoprene) (I), poly(styrene) (S), and poly(2-vinylpyridine) (V) are model systems, which allow systematic studies of the effects of composition, chemical microstructure, and temperature on the thermodynamics of microphase separation. Eleven ISV-x (I:S:V = 1:1:x, v:v:v) miktoarm copolymers were synthesized by anionic polymerization affording well-defined copolymers with a variable V arm. Equilibrium bulk morphologies of all samples, as evidenced by small-angle X-ray scattering, transmission electron microscopy (TEM), and self-consistent field theory, showed a systematic transition from lamellae (x ≈ 0–0.2) to [8.8.4] tiling (x ≈ 0.6–0.9) to cylinders in undulating lamellae (x ≈ 2–4) and, finally, to hexagonally packed core–shell cylinders (x ≈ 5–8). Chemical microstructure of the I arm [poly(cis 1,4-isoprene)] versus poly(3,4-isoprene) is shown to play important role in affecting morphological behavior. To reconcile differences between ISV-x star morphologies reported in the literature and those reported herein, even for the same composition, effects of the microstructure of I arm on the Flory–Huggins parameter between I and V arms were taken into account in a qualitative manner. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1491–1504     

Structural Studies on Dimethyltin(IV) Carboxylates

In order to correlate ¹¹⁹Sn Mössbauer parameters and structural data for dimethyltin(IV) derivatives, the molecular structures of bis(acetato)dimethyltin(IV) and bis(trifluoroacetato)dimethyltin(IV) were determined by single crystal X-ray diffration. Crystals of Me₂Sn(OOCCH₃)₂ are monoclinic, a = 26.282(4), b = 5.282(1), c = 14.434(3) Å, β = 101.17(2)°, Z = 8, space group C2/c, and those of [Me₂Sn(OOCCF₃)₂]_n are monoclinic, a = 8.444(1), b = 17.689(1), c = 15.368(1) Å, β = 93.013(9)°, Z = 8, space group Cc. The structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.025 and 0.027 (R_w = 0.023 and 0.030) for 2 298 and 4 182 reflections with I ≥ 3σ(F²), respectively.     

聚甲基丙烯酸甲酯单分子膜的原子力学显微镜研究

报道了利用原子力显微镜（ＡＦＭ）技术对聚甲基丙烯酸甲酯（ＰＭＭＡ）单分子膜进行分子结构水平的观察研究．由ＡＰＭ图像中得到的ＰＭＭＡ单体所占面积与用π－Ａ曲线中换算出液面上ＰＭＭＡＬａｕｇｍｕｉｒ膜中单体的面积符合得很好．从ＡＦＭ图像中可见ＰＭＭＡＬＢ膜中ＰＭＭＡ的线型碳链是与档板（ｂａｒｒｉｅｒ）平行的紧密排列，与ＬＢ提膜方向相垂直．并由此对ＰＭＭＡＬＢ膜的形成过程进行分析．此外，还观察到了在Ｓｉ基底上ＰＭＭＡ直链的卷绕伸直排列形态，初步分析了其形成原因．     

Biodegradations of block copolymers composed of L- or D,L-lactide and six-membered cyclic carbonates prepared with organolanthanide initiators

Diblock copolymerizations of L - or D,L -lactide (LA) with trimethylene carbonate (TMC) or 2,2-dimethyltrimethylene carbonate (2,2-DTMC) with SmMe(C₅Me₅)₂-(tetrahydrofuran) as an initiator and triblock copolymerizations of L - or D,L -LA/cyclic carbonates/L - or D,L -LA with [Sm(C₅Me₅)₂]₂(PhCCCCPh) as an initiator generated the desired block copolymers. This article describes the comparison of biodegradabilities by proteinase K and a compost and mechanical properties between the resulting di- or triblock copolymers and random copolymers composed of L - or D,L -LA and cyclic carbonates. The scanning electron microscopic profiles of resulting polymers were measured to understand the morphological change during biodegradation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3572–3588, 2003     

A simulation of thermal characteristic parameters with an inverse "S" type curve

A synthetical equation is proposed to characterize the essential features of the inverse "S" type curve on the oasis of summing-up simulation approach of "S" type curve.The two physical variables in the model obtained are discussed and the detailed method used to determine the parameters is given.The model is then presented to describe the crystallization of poly(caryleher ether ketone) (PEEK) and thermal decomposition of poly (amide-imide) (PAl) respectively.It is found that some thermal characteristic parameters can be well estimated from the model simulated in computer.     

Thermal Degradation of Poly(ε-caprolactone), Poly(L-lactic acid) and their Blends with Poly(3-hydroxy-butyrate) Studied by TGA/FT-IR Spectroscopy

Summary: The thermal degradation behavior of poly(ε-caprolactone) (PCL) and poly(L-lactic acid) (PLA) have been studied in different environment. It was found that these polymers undergo completely different degradation processes in nitrogen and oxygen atmosphere. In oxygen environment PCL and PLA mainly decompose to CO₂, CO, water and short-chain acids. In nitrogen atmosphere PCL releases 5-hexenioc acid, CO₂, CO and ε-caprolactone, whereas PLA decomposes to acetaldehyde, CO₂, CO and lactide. The polymer blends of poly(3-hydroxybutyrate) (PHB) with PCL and PLA decompose similar to the individual homopolymers with crotonic acid as the initial decomposition product of PHB.     

氧氟沙星在聚L-色氨酸修饰电极上的电化学行为及测定

氧氟沙星(ofloxacin,OFL)又名氟嗪酸,是第3代喹诺酮类药物,通过作用于细胞DNA螺旋酶的A亚单位,抑制DNA的合成和复制导致细菌死亡,具有高效广谱抗菌作用,是治疗呼吸道、泌尿道、肠道、皮肤、关节及软组织等感染的有效药物,而大剂量的服用可发生结晶尿,若不调整剂量,会使肝、肾功能减退、血药浓度增高等,因此测定药物中OFL的含量有重要意义.     

Step-scan TMDSC and high rate DSC study of the multiple melting behavior of poly(1,3-propylene terephthalate)

The multiple melting behavior of poly(1,3-propylene terephthalate) (PPT) samples after isothermal crystallization from the melt was studied. The step-scan temperature-modulated differential scanning calorimetry (TMDSC) and high rate DSC were used to investigate this behavior in conjunction with standard DSC, wide-angle X-ray diffraction (WAXD) and polarizing light microscopy (PLM). The effect of PPT average molecular weight on the melting was also examined. In general multiple endotherms after isothermal crystallization of PPT were attributed to a continuous crystal perfection process during the subsequent heating scan via melting-recrystallization-remelting. Multiple melting behavior was more pronounced for the low molecular weight PPT. Step-scan TMDSC showed that extensive recrystallization occurs in PPT samples, especially after rapid isothermal crystallization. In fact two recrystallization exothermic peaks were observed. High rate DSC revealed the initial morphology generated during the isothermal step and showed that the low and middle peaks are associated with melting of primary crystals while the high temperature peak should be attributed to melting of recrystallized material.