聚乙二醇活化处理重质碳酸钙粉体的研究

采用单因素考察法考察了聚乙二醇湿法活化处理重质碳酸钙粉体的工艺条件,重点考察了活化温度、活化时间、活化剂用量对沉降体积的影响.采用正交试验对其工艺条件进行了优化,得到重质碳酸钙粉体活化处理的优化条件为:活化温度为70℃,活化时间为43min,活化剂用量为1.6mg·g-1重质碳酸钙粉体,在此条件下重质碳酸钙粉体的沉降体...     

端炔基聚乙二醇的合成及固化

针对NEPE推进剂中端羟基聚醚和多异氰酸酯固化体系对水敏感的缺点,为获得新的固化体系,依据点击化学反应(click-chemistry)原理,以聚乙二醇400和丙炔溴为原料,四氢呋喃为溶剂,在催化剂叔丁醇钾存在下,温度30℃,反应时间24 h,分离产物并真空干燥后,得到黏稠状液态端炔基聚乙二醇,产率为86.1%。用红外、核磁共振和元素分析对端炔基聚乙二醇进行了表征。研究了端炔基聚乙二醇与叠氮类化合物的固化反应,表明其有望用作新的复合固体推进剂的固化体系。     

Amination of Polyethylene Glycol to Polyetheramine over the Supported Nickel Catalysts

Surface nickel (NiO _x ) species, surface NiAl _x O _y compound, and NiO crystallites are present on the Ni/Al₂O₃ catalysts, and the ratio of these nickel species is dependent on the nickel loading. Surface nickel interacts with the TiO₂ support to form a surface nickel titanate compound (NiTiO _x ) which has a lower reducibility. The weak interaction between the surface nickel and the silica support results in the formation of NiO crystallites on the SiO₂ surface. The Ni/Al₂O₃ and Ni/TiO₂ catalysts contain new surface Lewis acid sites and the amount of surface Lewis acid sites increases with increasing nickel concentration. The Ni/SiO₂ catalysts have no sign of the presence of the surface Lewis acid sites. Only the Ni/Al₂O₃ catalysts have shown the ammonia adsorption at temperature of 200°C. Supported nickel on alumina catalysts possess the highest amination conversion, and the amine yield increases with increasing nickel loading up to 15% and starts to level off. By comparing amination catalysis with quantitatively TPR studies of the H₂ consumed of the Ni/Al₂O₃ catalysts, it appears that the dispersed nickel species are the active sites for amination. In addition, the amination product is mainly the secondary amine due to the presence of water.     

Palladium‐Catalyzed Telomerization of Butadiene with Starch

In order to modify the hydrophilic properties of native starch for its incorporation in polymers, the telomerization of butadiene with native starch was investigated. Low to moderate degrees of substitution (DS=0.04–0.52) were obtained depending upon experimental conditions, particularly, reaction time, temperature and solvent. With 0.3‰ water‐soluble palladium catalyst (Pd/TPPTS), the reaction occurred in i‐PrOH/NaOH 0.1 N solvent mixture even at 50 °C and after 3 h reaction the DS reached 0.08, a value suitable for the application.     

Effect of Aqueous Polyethylene Glycol on 1,3‐Dipolar Cycloaddition of Benzoylnitromethane/Ethyl 2‐Nitroacetate with Dipolarophiles: Green Synthesis of Isoxazoles and Isoxazolines

A 1:1 mixture of water‐polyethylene glycol (PEG) facilitated the 1,3‐dipolar cycloaddition of benzoylnitromethane/ethyl 2‐nitroacetate with terminal alkynes or alkenes leading to isoxazoles or isoxazolines under green conditions. The methodology is free from the use of any base, catalyst, dehydrating agent or hazardous solvent.

     

A Microfluidic Approach to the Rapid Screening of Palladium‐Catalysed Aminocarbonylation Reactions

The evaluation and selection of the most appropriate catalyst for a chemical transformation is an important process in many areas of synthetic chemistry. Conventional catalyst screening involving batch reactor systems can be both time‐consuming and expensive, resulting in a large number of individual chemical reactions. Continuous flow microfluidic reactors are increasingly viewed as a powerful alternative format for reacting and processing larger numbers of small‐scale reactions in a rapid, more controlled and safer fashion. In this study we demonstrate the use of a planar glass microfluidic reactor for performing the three‐component palladium‐catalysed aminocarbonylation reaction of iodobenzene, benzylamine and carbon monoxide to form N‐benzylbenzamide, and screen a series of palladium catalysts over a range of temperatures. N‐Benzylbenzamide product yields for this reaction were found to be highly dependent on the nature of the catalyst and reaction temperature. The majority of catalysts gave good to high yields under typical flow conditions at high temperatures (150 °C), however the palladium(II) chloride‐Xantphos complex [PdCl₂(Xantphos)] proved to be far superior as a catalyst at lower temperatures (75–120 °C). The utilised method was found to be an efficent and reliable way for screening a large number of palladium‐catalysed carbonylation reactions and may prove useful in screening other gas/liquid phase reactions.     

New Synthesis of Aryl and Heteroaryl N‐Acylureas via Microwave‐Assisted Palladium‐Catalysed Carbonylation

A new, practical synthesis of aryl and heteroaryl N‐acylureas has been developed via palladium‐catalysed carbonylation of aryl or heteroaryl halides in the presence of urea nucleophiles. A range of reactions illustrating the wide scope of this reaction was carried out under microwave irradiation, using either carbon monoxide gas in a vessel equipped with a gas inlet adapter, or molybdenum hexacarbonyl as the carbon monoxide source in standard microwave vials. The reactions proceeded in good to excellent yields. To illustrate the usefulness of this method a one‐step synthesis of the important insecticide diflubenzuron is reported.     

A Facile Route to Benzo[a]fluorenes via a Palladium‐Catalyzed Reaction of 2‐Alkynylbromobenzene with 2‐(2‐Alkynylphenyl)malonate

A palladium‐catalyzed reaction of 2‐alkynylbromobenzenes with 2‐(2‐alkynylphenyl)malonates gives rise to benzo[a]fluorenes in good yields. This tandem process is efficient with the formation of three bonds from easily available starting materials.     

Optimization of Serine Protease Purification from Mango (Mangifera indica cv. Chokanan) Peel in Polyethylene Glycol/Dextran Aqueous Two Phase System

Mango peel is a good source of protease but remains an industrial waste. This study focuses on the optimization of polyethylene glycol (PEG)/dextran-based aqueous two-phase system (ATPS) to purify serine protease from mango peel. The activity of serine protease in different phase systems was studied and then the possible relationship between the purification variables, namely polyethylene glycol molecular weight (PEG, 4000-12,000 g·mol(-1)), tie line length (-3.42-35.27%), NaCl (-2.5-11.5%) and pH (4.5-10.5) on the enzymatic properties of purified enzyme was investigated. The most significant effect of PEG was on the efficiency of serine protease purification. Also, there was a significant increase in the partition coefficient with the addition of 4.5% of NaCl to the system. This could be due to the high hydrophobicity of serine protease compared to protein contaminates. The optimum conditions to achieve high partition coefficient (84.2) purification factor (14.37) and yield (97.3%) of serine protease were obtained in the presence of 8000 g·mol(-1) of PEG, 17.2% of tie line length and 4.5% of NaCl at pH 7.5. The enzymatic properties of purified serine protease using PEG/dextran ATPS showed that the enzyme could be purified at a high purification factor and yield with easy scale-up and fast processing.     

Synthesis and Characterization of Xylan Grafted with Polyethylene Glycol in Ionic Liquid and Their Use as Moisture‐Absorption/Retention Biomaterials

The objective of this study is to broaden the application of xylan as moisture‐absorption/retention biomaterials by grafting polyethylene glycol (PEG) on xylan backbone. Ionic liquid 1‐allyl‐3‐methylimidazolium chloride ([Amim]Cl) and 4,4‐diphenylmethane diisocyanate are used as reaction media and coupling reagent, respectively. FT‐IR, ¹H‐NMR, and gel permeation chromatography analyses indicate the successful occurrence of the grafting reaction. Thermogravimetric analysis/derivative thermogravimetry indicates that the thermal stability of xylan increases after the grafting of the PEG side chains. With an increase of the degree of substitution of xylan‐g‐PEG, the molecular weight (M_w) of PEG side chains (1000 and 5000 g mol^?1), and the relative humidity of environment, the moisture‐absorption/retention ratio of xylan‐g‐PEG increases. To evaluate the biodegradability/biocompatibility of this promising material, the ratio of biochemical oxygen demand to chemical oxygen demand of xylan‐g‐PEG and the cytotoxicity are tested on the samples. The results indicate that PEG‐modified xylan has great potential as moisture‐absorption/retention biomaterials.

     

Organocatalytic anti‐Mannich Reactions with Dihydroxyacetone and Acyclic Dihydroxyacetone Derivatives: A Facile Route to Amino Sugars

The first primary amine‐containing amino acid‐catalyzed anti‐Mannich reactions of dihydroxyacetone and acyclic dihydroxyacetone derivatives with a variety of imines have been developed. This approach complements proline‐based strategies in the preparation of amino sugars.     

Solvent-Free Formation of Cyclodextrin-Based Pseudopolyrotaxanes of Polyethylene Glycol: Kinetic and Structural Aspects

Pseudopolyrotaxanes (PPRs) are supramolecular structures consisting of macrocycles able to thread on a linear polymer chain in a reversible, non-covalent way, often referred to in the literature as “molecular necklaces”. While the synthesis and reaction mechanisms of these structures in solution have been widely described, their solvent-free production has received little attention, despite the advantages that this route may offer. We propose in this work a kinetic mechanism that describes the PPR formation in the solid phase as a process occurring in two consecutive stages. This mechanism has been used to investigate the spontaneous formation of a PPR that occurs when grinding α-Cyclodextrin (α-CD) with polyethylene glycol (PEG). In the threading stage, the inclusion of the polymer and subsequent release of the water molecules lodged in the cavity of the macrocycle cause vibrational changes that are reflected in the time-dependence of the FTIR-ATR spectra, while the further assembly of PPRs to form crystals produces characteristic reflections in the XRD patterns, due to the channel-like arrangement of CDs, that can be used to track the formation of the adduct in crystalline form. The effects that working variables have on the kinetics of the reaction, such as temperature, feed ratio, molar mass of the polymer and the introduction of an amorphous block in the polymer structure, have been investigated. The rate constants of the threading step increase with the temperature and the activation energy of the process increases at lower proportions of CD to PEG. This is attributed to the lower degree of covering of the polymer chain with CDs that reduces the hydrogen-bonding driven stabilization between adjacent macrocycles. The formation of crystalline PPR, which takes place slowly at room temperature, is markedly promoted at higher temperatures, with lower proportions of CD favoring both the formation and the growth of the crystals. The molar mass of the polymer does not modify the typical channel-like arrangement of packed PPRs but the conversion into crystalline PPR diminishes when using PEG1000 instead of PEG400. At a microscopic level, the crystals arrange into lamellar structures, in the order of hundreds of nm, embedded in an amorphous-like matrix. The introduction of a polypropylene oxide block in the structure of the polymer (Pluronic L62) renders poorer yields and a considerable loss of crystallinity of the product of the reaction. The methodology here proposed can be applied to the general case of inclusion complexes of CDs with drugs in the solid phase, or to multicomponent systems that contain polymers as excipients in pharmaceutical formulations along with CDs.     

Synthesis and characterization of novel block copolymer from trans‐4‐hydroxy‐L‐proline and poly(ethylene glycol)

A series of novel ABA‐type block copolymers were synthesized by polymerization of trans‐4‐hydroxy‐L ‐proline (HyP) in the presence of various molecular weight poly(ethylene glycol)s (PEGs), a bifunctional OH‐terminated PEG using stannous octoate as catalyst. The optimal reaction conditions for the synthesis of the copolymers were obtained with 5 wt % stannous octoate at 140°C under vacuum (20 mmHg) for 24 h. The synthesized copolymers were characterized by IR spectroohotometry, proton nuclear magnetic resonance, differential scanning calorimetry, and Ubbelohde viscometer. The glass transition temperature (T_g) of the copolymers shifted to significantly higher temperature with increasing the number average degree of polymerization and HyP/PEO molar ratio. In contrast, the melting temperature (T_m) decreased with increasing the HyP/PEO molar ratio. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1581–1587, 2001     

Preparation of superhydrophobic silica‐based films by using polyethylene glycol and tetraethoxysilane

Preparation of superhydrophobic silica‐based films via sol‐gel process by adding polyethylene glycol (PEG4000) in the silica sol precursor solution has been developed. The casting films were prepared by casting the above solution on the glass and adding poor solvent on it or not. Surface roughness of the films was obtained by removing polymer from the films at high temperature. Then, the hydrophobic group on the surfaces was obtained by reaction with hexamethyldisilazane (HMDS). Characteristic properties of the as‐prepared surface of the films were analyzed by contact angle measurement, scanning electron microscopy (SEM), atomic force microscope (AFM), Fourier transform infrared (FT‐IR) spectrophotometer, and X‐ray photoelectron spectrometer (XPS). The results showed that the contact angles of the films were varied with the PEG weight fraction of the films, the solvent for the PEG solution, the reaction temperature and time, and adding poor solvent (n‐hexane) or not. However, the surface roughness has been controlled by adjusting the experimental parameters during the early period. The contact angle of the film that prepared by spraying the poor solvent (n‐hexane) onto each coating layer for four times after casting process was greater than 150°. It was difficult to obtain superhydrophobic surface without adding n‐hexane onto any coating layer in this system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

An Efficient Route to 3‐Amidylindoles via a Palladium‐ Catalyzed Tandem Reaction of 2‐Alkynylanilines with Isocyanides

A palladium‐catalyzed reaction of 2‐alkynylaniline, isocyanides, and silver acetate is described, leading to 3‐amidylindoles in moderate to good yields. During the process, five new bonds are formed with high reaction efficiency in one‐pot procedure.     

聚乙二醇／聚乙烯醇固一固相变材料等温结晶动力学及熔融行为研究

采用接枝共聚法将聚乙二醇（PEG）接枝到聚乙烯醇（PVA）主链上,得到了系列性能稳定的PEG／PVA高分子固固相转变材料,利用DSC法对PEG在受限状态下等温结晶及结晶后的熔融行为进行了研究。结果表明：PEG和共聚体系的Avrami指数n在2左右,说明结晶生长方式是二维生长,速率常数Z随温度升高而减小,样品的成核属非均相依热成核方式。结晶后的等温熔融行为表明PEG出现熔融双峰,共聚体系只显示一个与PEG低温峰相对应的吸收峰,该峰的高温侧出现肩峰,且随T0升高而变得明显。     

Palladium‐Catalyzed Suzuki Carbonylative Reaction of α‐Halomethyl Oxime Ethers: A Regioselective Route to Unsymmetrical 1,3‐Oxyiminoketones

The three‐component reaction of α‐halomethyl oxime ethers, boronic acids and carbon monoxide at atmospheric pressure catalyzed by tetrakis(triphenylphosphine)palladium(0) gives efficiently unsymmetrical β‐alkoxyimino carbonyl compounds with total control of the regioselectivity, in high yield and atomic economy. Simple commercially available starting materials are used in this synthetic procedure. The three components assembly takes place preferentially versus the competing direct coupling or other possible side reactions. The mechanism of the transformation was investigated by NMR and intermediate palladium(II) complexes were detected.

     

Catalytic System for Inhibition of Amination‐Type Reaction and Palladium‐Catalysed Direct Arylation using Non‐Protected Pyrazole Derivatives

The palladium‐catalysed direct arylation at C‐4 of non‐protected 5‐aminopyrazoles was found to proceed in high yields using a variety of aryl bromides. The choice of potassium acetate as the base was found to be crucial to inhibit the amination reaction and to promote the direct arylation.     

An Efficient Palladium‐NHC (NHC=N‐Heterocyclic Carbene) and Aryl Amination Pre‐Catalyst: [Pd(IPr*)(cinnamyl)Cl]

The well‐defined [Pd(IPr*)(cinnamyl)Cl] complex is reported as one of the best N‐heterocyclic carbene (NHC)‐based pre‐catalysts for the Buchwald–Hartwig amination reaction. This catalytic system displays high efficiency for the coupling of numerous (hetero)aryl chlorides, with a wide range of amines, at room temperature or at extremely low catalyst loading (as low as 0.025 mol%).