长链醇丙烯酸酯合成方法的研究进展

长链醇丙烯酸酯是支链具有空间立体效应以及亲水性或疏水性的大分子,可以用作多种聚合化合物的有机合成单体。本文综述了长链丙烯酸酯的合成方法,为以后进一步研究其在生物医药、材料、表面活性剂等方面的应用提供依据。     

长链α-烯烃的生产与应用前景

简要地阐述了国内外长链α 烯烃的生产现状及国内市场情况 ,并根据我国国情 ,提出了蜡裂解制取长链α 烯烃的工艺路线。并以 5 4 # 半炼蜡为原料进行蜡裂解试验 ,通过精密分馏将目的烯烃切割成不同馏分 ,进行下游产品的评定试验。试验结果表明 ,以半炼蜡为原料 ,通过裂解工艺 ,可以生产出质量合格的符合下游产品应用要求的长链α 烯烃产品 ,解决了国内部分行业的急需 ,具有很好的社会效益和经济效益     

氯化专用聚氯乙烯树脂颗粒特性的研究——非离子型表面活性剂和链转移剂的影响

水相悬浮法生产氯化聚氯乙烯(CPVC)时,氯化速度和氯化均匀性取决于Cl2在聚氯乙烯(PVC)颗粒中的扩散程度,因而需要有能满足氯化要求的PVC专用树脂。采用以聚乙烯醇(PVA)和羟丙基甲基纤维素(HPMC)为主的复合分散剂,考察Span系列非离子表面活性剂、链转移剂等对PVC颗粒特性的影响。实验结果表明,表面活性剂的加入使PVC树脂增塑剂吸收率、平均粒径和比表面积增大,粒径分布变窄,而表观密度下降;随着链转移剂的加入,PVC树脂增塑剂吸收率、平均粒径和表观密度都增加。     

Effect of Amino Acids on Micellization,Surface Activity and Micellar Properties of Nonionic Surfactant Hexadecyl Alcohol Ethoxylate (25EO) in Aqueous Solutions

The effects of amino acids (dl ‐glycine, dl ‐alanine, dl ‐phenylalanine, dl ‐serine, l ‐leucine, l ‐aspartic acid, l ‐lysine) on the micellization, surface activity, viscometric and aggregation properties of hexadecyl alcohol polyethoxylate (25EO) in aqueous solution were studied. The critical micelle concentration and free energy of micellization were evaluated and discussed. The surface excess concentration, the minimum area per molecule, the surface pressure at the critical micelle concentration and the standard free energy of adsorption were obtained from surface activity studies. On the basis of the determination of the relative viscosities on concentration, the viscosity B‐coefficients of the Jones–Dole semiempirical equation were calculated for the premicellar and postmicellar regions. The method of fluorescence quenching was used for determination of the micellar aggregation number of hexadecyl alcohol polyethoxylate (25EO) in aqueous solution in the presence of amino acids. It was found that among studied amino acids serine shows behavior that is different from that of the other neutral amino acids.     

Statistical Analysis of the Collaborative Study in Support of the Official Method AOCS Ce 1i-07: Determination of Saturated, cis-Monounsaturated and cis-Polyunsaturated Fatty Acids in Marine and Other Oils Containing Long Chain Polyunsaturated Fatty Acids by Capillary GLC

Analysis was done of the statistical results obtained by following recommended AOCS Collaborative Study Procedure M-86 to evaluate the performance of Official Method AOCS Ce 1i-07, which provides a gas–liquid chromatography (GLC) procedure for the determination of the fatty acid composition of oils containing long chain polyunsaturated fatty acids (PUFAs). The method obtains relative between-lab reproducibility (%RSDR) values on the order of 5% or less for most fatty acids that are present above ~0.5% w/w; however, the reproducibility worsens dramatically for analytes below this threshold. Apparently, several participating labs had problems identifying small peaks in the sample chromatograms. They also had problems correctly identifying certain larger peaks that occurred in a congested area of the sample chromatograms, including the 9c-16:1, 9c-11c-22:1, and 6c,9c,12c,15c-16:4 fatty acids. Finally, several analytes with chain lengths between 16 and 18 and between 21 and 22 carbons that were present at moderate concentrations had worse than expected reproducibilities due to severe overlap of these analytes’ peaks. A detailed inspection of the contributed data shows that the relatively poor between-lab reproducibility for analytes in this region is due to differences in the labs’ chromatographic efficiencies and perhaps in their methods of quantifying highly overlapped peaks.     

The Role of Plant Progesterone in Regulating Growth,Development, and Biotic/Abiotic Stress Responses

Progesterone is a steroid hormone that performs important functions in mammals. However, studies on its physiological functions in plants have gradually increased in recent years. Therefore, this review summarizes the regulatory functions of progesterone on plant growth and development, as well as its response to stress. Moreover, the plant metabolic processes of progesterone are also discussed. Overall, progesterone is ubiquitous in plants and can regulate numerous plant physiological processes at low concentrations. Since progesterone shares similar characteristics with plant hormones, it is expected to become a candidate for plant hormone. However, most of the current research on progesterone in plants is limited to the physiological level, and more molecular level research is needed to clarify progesterone signaling pathways.     

Synergistic Behavior and Microstructure Transition in Mixture of Zwitterionic Surfactant,Anionic Surfactant,and Salts in Sorbitol/H<Subscript>2</Subscript>O Solvent: 1. Effect of Surfactant Compositions

The phase behavior and rheological properties of a multi-component system, made of a zwitterionic surfactant cocoamidopropyl betaine (CAPB), an anionic surfactant sodium lauryl sulfate (SLSS), and mixed salts (tetrasodium pyrophosphate, sodium acid pyrophosphate, sacharrin, and sodium fluoride) in sorbitol/H₂O mixed solvent at different mass fraction of SLSS (X _SLSS) were systematically investigated by steady and dynamic rheology, dynamic light scattering, and diffusion ordered spectroscopy (DOSY). When fixing the salt concentration and the mass ratio of sorbitol in mixed solvent (R), the zero-shear viscosity increases first and then decreases showing a maximum with increasing X _SLSS, resulting from the formation and entanglement of wormlike micelles. Especially when X _SLSS is between 0.33 and 0.80, the mixture is dominated by entangled wormlike micelles coexisting with small micelles and separated wormlike micelles, and shows high viscoelasticity. The maximum of the zero-shear viscosity is ca. 5 orders of magnitude larger than that of sorbitol/H₂O mixed solvent or the CAPB/SLSS aqueous solution. The characteristic structural parameters for the micellar solutions at different X _SLSS are also estimated from further analysis of the rheological results, and indicate the stronger network structures of the wormlike micelles are formed in our systems compared with the wormlike micelles formed by a traditional zwitterionic/anionic surfactant aqueous solutions. The great improvements of rheological properties are attributed to the strong screening effects of the mixed salts and the strong solvophobic effect of sorbitol on the electrostatic and hydrophobic interaction between the CAPB and SLSS molecules. The present work has improved our understanding about the aggregation behavior of zwitterionic/anionic mixed surfactants with salts in less polar solvent/H₂O mixture, which would be of widely practical importance to optimize the formulation of products for personal care and household cleaning.     

Rheological Properties and Microstructure Transition in Mixture of Zwitterionic Surfactant,Anionic Surfactant and Salts in Sorbitol/H2O Solvent: 2. Effect of Salts and Sorbitol

The impact of mixed salts and sorbitol on the viscoelastic properties of a multi‐component system, made of a zwitterionic surfactant cocoamidopropyl betaine (CAPB), an anionic surfactant sodium lauryl sulfate (SLSS) and mixed salts (tetrasodium pyrophosphate, sodium acid pyrophosphate, saccharin and sodium fluoride) in sorbitol/H₂O mixed solvent are systematically investigated by steady state and dynamic rheology. As reported previously, the viscosity of the mixed system passes through a maximum with increase in the SLSS mass fraction (X_SLSS) at a fixed total surfactant concentration, salt concentration (C_salt) and mass ratio of sorbitol in mixed solvent (R). The shape of the X_SLSS‐dependent viscosity curve does not change regardless of C_salt and R, but adding salts or sorbitol has different effects on the rheological properties of this system. The former due to a high screening effect plays an important role in the elongation and entanglement of the wormlike micelles, facilitating the enhancement of rheological properties and the formation of Maxwell fluids. The latter has a dual effect on the rheological properties and phase behavior of the mixtures. A certain amount of sorbitol can promote the formation entangled wormlike micelles, while the effect is reversed if the sorbitol content is too large. The electrostatic and hydrophobic interaction between CAPB and SLSS are the prerequisite for the aggregate formation and transition. Meanwhile, the aggregation behaviors are strongly influenced by the balance between low dielectric constant, strong solvophobic interaction and steric effect of sorbitol with the ability to form hydrogen bonds which favors the growth of micelles, and appearance of aqueous two‐phase systems with smaller amounts of wormlike micelles in CAPB‐rich regions which oppose enhancement of rheological properties. Our findings provide a new insight and approach to control and adjust the phase behavior of such a complicated applied multi‐component system.     

Characterization of a Gene Encoding Clathrin Heavy Chain in Maize Up-Regulated by Salicylic Acid,Abscisic Acid and High Boron Supply

Clathrin, a three-legged triskelion composed of three clathrin heavy chains (CHCs) and three light chains (CLCs), plays a critical role in clathrin-mediated endocytosis (CME) in eukaryotic cells. In this study, the genes ZmCHC1 and ZmCHC2 encoding clathrin heavy chain in maize were cloned and characterized for the first time in monocots. ZmCHC1 encodes a 1693-amino acid-protein including 29 exons and 28 introns, and ZmCHC2 encodes a 1746-amino acid-protein including 28 exons and 27 introns. The high similarities of gene structure, protein sequences and 3D models among ZmCHC1, and Arabidopsis AtCHC1 and AtCHC2 suggest their similar functions in CME. ZmCHC1 gene is predominantly expressed in maize roots instead of ubiquitous expression of ZmCHC2. Consistent with a typical predicted salicylic acid (SA)-responsive element and four predicted ABA-responsive elements (ABREs) in the promoter sequence of ZmCHC1, the expression of ZmCHC1 instead of ZmCHC2 in maize roots is significantly up-regulated by SA or ABA, suggesting that ZmCHC1 gene may be involved in the SA signaling pathway in maize defense responses. The expressions of ZmCHC1 and ZmCHC2 genes in maize are down-regulated by azide or cold treatment, further revealing the energy requirement of CME and suggesting that CME in plants is sensitive to low temperatures.     

Role of Klotho in Hyperglycemia: Its Levels and Effects on Fibroblast Growth Factor Receptors,Glycolysis, and Glomerular Filtration

Hyperglycemic conditions (HG), at early stages of diabetic nephropathy (DN), cause a decrease in podocyte numbers and an aberration of their function as key cells for glomerular plasma filtration. Klotho protein was shown to overcome some negative effects of hyperglycemia. Klotho is also a coreceptor for fibroblast growth factor receptors (FGFRs), the signaling of which, together with a proper rate of glycolysis in podocytes, is needed for a proper function of the glomerular filtration barrier. Therefore, we measured levels of Klotho in renal tissue, serum, and urine shortly after DN induction. We investigated whether it influences levels of FGFRs, rates of glycolysis in podocytes, and albumin permeability. During hyperglycemia, the level of membrane-bound Klotho in renal tissue decreased, with an increase in the shedding of soluble Klotho, its higher presence in serum, and lower urinary excretion. The addition of Klotho increased FGFR levels, especially FGFR1/FGFR2, after their HG-induced decrease. Klotho also increased levels of glycolytic parameters of podocytes, and decreased podocytic and glomerular albumin permeability in HG. Thus, we found that the decrease in the urinary excretion of Klotho might be an early biomarker of DN and that Klotho administration may have several beneficial effects on renal function in DN.     

TEMPO and Carboxylic Acid Functionalized Imidazolium Salts/Sodium Nitrite: An Efficient,Reusable, Transition Metal‐Free Catalytic System for Aerobic Oxidation of Alcohols

An effective catalytic system comprising a 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) functionalized imidazolium salt ([Imim‐TEMPO]⁺ X⁻), a carboxylic acid substituted imidazolium salt ([Imim‐COOH]⁺ X⁻), and sodium nitrite (NaNO₂) was developed for the aerobic oxidation of aliphatic, allylic, heterocyclic and benzylic alcohols to the respective carbonyl compounds with excellent selectivity up to >99%, even at ambient conditions. Notably, the catalyst system could preferentially oxidize a primary alcohol to the aldehyde rather than a secondary alcohol to the ketone. Moreover, the reaction rate is greatly enhanced when a proper amount of water is present. And a high turnover number (TON 5000) is achieved in the present transition metal‐free aerobic catalytic system. Additionally, the functionalized imidazolium salts are successfully reused at least four times. This process thus represents a greener pathway for the aerobic oxidation of alcohols into carbonyl compounds by using the present task‐specific ionic liquids in place of the toxic and volatile additive, such as hydrogen bromide, bromine, or hydrogen chloride (HBr, Br₂ or HCl), which is commonly required for the transition metal‐free aerobic oxidation of alcohols.     

Adsorption, oxidation and reduction of crotyl alcohol on platinum: A DEMS and in situ FTIRS study

The electrochemical reactivity of crotyl alcohol (CA) on Pt in acid media has been studied applying electrochemical methods combined with in situ Fourier transform IR spectroscopy (FTIRS) and on-line mass spectrometry (DEMS). Mass spectrometric cyclic voltammograms (MSCVs) and IR spectra, acquired with the alcohol in the solution, point out the formation of CO₂ and crotonaldehyde as oxidation products.On the other hand, spectra recorded during the electroreduction display negative features at 2964, 2934 and 2875 cm⁻¹, which are assigned to the CH₃ and CH₂ asymmetric stretchings and the CH₂ symmetric stretching, respectively. The intensity of these signals confirms that a massive hydrogenation process occurs at E < 0.05 V_RHE with a strong production of hydrocarbons. Accordingly, several reduction compounds (2-butene, butane, propane, propene, ethane and methane) were detected by DEMS.The same products, with the exception of the aldehyde, were established from CA adsorbed species, isolated applying an electrolyte exchange procedure. A feature at 2020 cm⁻¹ due to lineal adsorbed CO develops in the IR spectra. These results allow us to propose a general overview of the electrochemical reactions of CA at Pt.     

Probing the Nature and the Structure of Pores in Silica Xerogels by Water Sorption: The Tetramethyl Orthosilicate-Hydrogen Chloride/Fluoride System

A series of silica xerogels were synthesized in a closed system by hydrolyzing tetramethyl orthosilicate (TMOS) with various concentrations of hydrochloric acid solution but without the addition of alcohol. The molar ratio of H₂O to TMOS was fixed at 4.96. The gels were characterized by water and nitrogen sorption measurements. The gelation time peaked at 50 to 80 h with 5 × 10⁻² to 10⁻¹ M HCl, apparently a consequence of the isoelectric point of silica. Surface area, pore size, and sorption capacity were, however, at a minimum for samples prepared with 5 × 10⁻² to 10⁻¹ M HCl. The BET c constant and hence the net heats of sorption were at a maximum for these samples. Although water sorption of all the samples prepared with HCl exhibited moderate Type I isotherms, the concavity of the isotherms to the P/P ₀ axis increased with increasing concentrations of HCl up to 10⁻¹ M in accordance with the decreased pore size and increased heat of sorption. Addition of F⁻ ions (HF or NaF) in the presence of 10⁻¹ M HCl steadily decreased the gelation time. Addition of F⁻ in the absence of HCl, however, caused rapid gelation and an increase in pore size, nitrogen BET surface area, and hydrophobicity. Consequently, the shape of water isotherms gradually converted to Type IV and/or Type V. Adsorption and desorption measurements on differently activated gels exhibited various types of hystereses as a result of development of hydrophobie sites at as low as 200°C, inelastic distortion induced by adsorption, and chemical reaction and aging of gels when exposed to water vapor.     

Complexation of Surfactant/β‐Cyclodextrin to Inhibit Surfactant Adsorption onto Sand,Kaolin, and Shale for Applications in Enhanced Oil Recovery Processes. Part III: Oil Displacement Evaluation

This proof of concept research evaluates the performance of a surfactant/β‐cyclodextrin (β‐CD) inclusion complex during chemical flooding for enhanced oil recovery. It was hypothesized that the encapsulated surfactant propagates well through the porous media. Sodium dodecyl sulfate (SDS) was used to study the surfactant/β‐CD complexations. Phase behavior analysis was carried out to prepare the most favorable chemical slug formulation. A series of core flooding tests were conducted to determine the efficiency of the SDS/β‐CD inclusion complex in displacing residual oil. Surfactant flooding was conducted as tertiary oil recovery mode (after mature water flooding) by injecting 0.3 pore volume (PV) of the optimum surfactant slug that was chased by 0.3 PV of a polymer slug; followed by continuous water flooding until oil production stopped. The experimental results indicate that the encapsulated surfactant propagates well through the sandpack system and consistently produces higher incremental oil recoveries that range from 40 to 82 % over the incremental oil recovery achieved by conventional surfactant flooding.     

Complexation of Surfactant/β‐Cyclodextrin to Inhibit Surfactant Adsorption onto Sand,Kaolin, and Shale for Applications in Enhanced Oil Recovery Processes. Part II: Dynamic Adsorption Analysis

Surfactant adsorption onto solid surfaces is problematic in some industrial processes, such as in surfactant flooding for enhanced oil recovery. In this work, it was hypothesized that the use of a surfactant delivery system could prevent surfactant adsorption onto solid surfaces. Therefore, the encapsulation of sodium dodecyl sulfate (SDS) into the hydrophobic core of β‐cyclodextrin (β‐CD) to generate a surfactant delivery system (SDS/β‐CD) was evaluated in this work. This complexation was characterized using optical and scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT‐IR). Dynamic adsorption evaluation was applied to determine the effectiveness of the complexation in inhibiting surfactant adsorption onto a variety of solid adsorbents including sand, and mixtures of sand–kaolin and sand–shale. Surfactant adsorption was also evaluated applying the quartz crystal microbalance technology (QCM‐D). The formation and morphology of the complexation was confirmed by optical microscopy, SEM, and FT‐IR. Dynamic adsorption tests demonstrated the effectiveness of the surfactant delivery approach in preventing the adsorption of surfactant (up to 74 % adsorption reduction). The QCM‐D technology confirmed these observations. Several mechanisms were proposed to explain the inhibition of surfactant adsorption including steric hindrance, self‐association of inclusion complexes, hydrophilicity increase, and disruption of hemimicelles formation.     

Complexation of Surfactant/β‐Cyclodextrin to Inhibit Surfactant Adsorption onto Sand,Kaolin, and Shale for Applications in Enhanced Oil Recovery Processes. Part I: Static Adsorption Analysis

Surfactant adsorption onto solid surfaces is a major issue during surfactant flooding in enhanced oil recovery applications; it decreases the effectiveness of the chemical injection making the process uneconomical. Therefore, it was hypothesized that the adsorption of surfactant onto solid surfaces could be inhibited using a surfactant delivery system based on the complexation between the hydrophobic tail of anionic surfactants and β‐cyclodextrin (β‐CD). Proton nuclear magnetic resonance spectroscopy was used to confirm the complexation of sodium dodecyl sulfate (SDS)/β‐CD. Surface tension analysis was used to establish the stoichiometry of the complexation and the binding constant (K_a). Static adsorption testing was applied to determine the adsorption of surfactant onto different solids (sandstone, shale, and kaolinite). The release of the surfactant from the β‐CD cavity was qualitatively evaluated through bottle testing. The formation of the inclusion complex SDS/β‐CD with a 1:1 stoichiometry was confirmed. The K_a of the complexations increases as salinity and hardness concentration increases. The encapsulation of the surfactant into the β‐CD cavity decreases the adsorption of surfactant onto solid surfaces up to 79 %. Qualitative observations indicate that in the presence of solid adsorbents partially saturated with crude oil, the β‐CD cavity releases surfactant molecules, which migrate towards the oil–water interface.     

CO2混合物热物性在CCS研究中的作用:实验数据、理论模型和典型应用

二氧化碳捕集与封存（CCS）各工艺过程的设计、运行都依赖于对CO₂及其混合物热物理性质的深入理解。同时，CCS的规模化发展和商业化进程，对CO₂混合物及其热物性的准确性提出了更高的要求。本文从实验数据、理论模型和典型应用3个方面综述了CO₂及其混合物热物性的发展现状，并尝试对发展趋势进行归纳。在实验研究方面，CO₂混合体系的研究进展视组分不同，差异较大，其中CO₂-N₂、CO₂-CH₄、CO₂-H₂O和CO₂-H₂二元体系已形成较完善的物性数据库，而CO₂-NH₃、CO₂-NO _x 和CO₂-CO体系的物性数据还比较欠缺；在物性估算方面，面向CCS的物性估算模型研究自2008年开始活跃，基于不同理论构架，目前已逐步形成面向CCS的多元化的物性估算体系。物性研究在CCS中的应用主要体现在物性是支撑CCS过程研究的基础，其不准确性在过程模拟或计算中会被“放大”，从而影响过程评估的准确性，本文从物性在循环构建和能效分析中的作用以及CO₂水合物的形成3个方面入手做了说明。文章最后对面向CCS的物性研究趋势进行了梳理，对分子模拟技术、通用性强的物性估算模型和物性在过程设计和循环分析中的角色进行了展望。