Synthesis and Characterization of Silicone Modified Polyurethane Surfactant Useable at High Temperature

A series of novel silicone modified polyurethane (Si-PU) surfactants were successfully synthesized by using hydroxypropyl-terminated polydimethylsiloxane (HPMS), polyethylene glycol (PEG), dimethylolpropionic acid (DMPA) and isophoronediisocyanate (IPDI). The chemical structure of the surfactant was confirmed by FTIR and ¹H-NMR. TEM photographs showed that the micelles of the Si-PU surfactants dispersed in aqueous solution were spherical with the particle size in the range of 100–400 nm. Surface tension measurements indicated that these surfactants had low surface tension to 29.9 mN·m^?1and a definite critical micelle concentration to, approximately 5.0×10^?4–7.5×10^?4mol·L^?1. When the content of HPMS was 20 wt%, the surfactant's, emulsifying performance was superior to the traditionally available Span80/Tween80 mixed emulsifiers. In addition to that, no phase transition temperature was detected from 20°C to 90°C by fluorescence probe and DSC measurements, confirming the high thermal stability of the micelles.     

Alkane isomers: presence in petroleum ether and complexity

The presence and absence of alkane isomers in petroleum and petroleum derivatives depend on the complexity of these structures. It was assumed that the more complex the structure is the less probable it is that that the molecule can be detected in any petroleum derivative. Complexity is a vague concept, which has not been defined in quantitative terms yet, and therefore there is no experimental method, which could be used to determine ‘complexity’. Mass spectrometry and infrared spectroscopy in combination with gas chromatography were used to identify the various structural isomers of alkanes in petroleum ether. The isomers were categorised in quantitative terms by using topological indices and linear discriminant analysis. It was found that alkanes possessing a more complex, highly branched structure are less probable to be detected in petroleum ether than isomers with a simpler backbone structure. It was proposed that the experimental ‘measure’ of the complexity of isomer_i should be proportional to 1/C_i , where C_i , denotes the concentration of isomer_i in a (primary) petroleum derivative.     

重度原油注空气低温氧化过程研究(英文)

低温氧化反应对现场燃烧(ISC)技术点火的成功有十分重要的影响.采用高压氧化管,研究了不同温度压力下,新疆克拉玛依重度原油的低温氧化过程.结果表明,温度和压力的变化对低温氧化反应的放热程度、持续时间以及气体产物有明显影响.适合油样低温氧化反应的温度和压力分别为150℃和10MPa.此外,采用纯组分替代原油族组分进行低温氧化实验,研究低温氧化反应对原油族组分(饱和烃、芳香烃、胶质、沥青质)含量的影响.结果表明,原油所含族组分中,芳香烃组分最易被氧化,其含量由氧化前的19.17%减少到12.38%(150℃)和9.51%(250℃).随着低温氧化过程的进行,结构复杂的族组分(胶质、沥青质)的含量明显增加.实验数据对油藏实施注空气技术,以及该技术现场实施条件的确定有十分重要的指导意义.     

大豆油煎炸过程理化指标与LF-NMR弛豫特性的相关性研究

在对大豆油无料/薯条煎炸过程[温度:(180±5)℃,持续36 h]中的酸价(AV)、粘度(V)、吸光值(A)及总极性化合物(TPC)含量等及低场核磁共振(LF-NMR)弛豫特性(峰起始时间T21、T22、T23、相应的峰面积比例S21、S22、S23、单组份弛豫时间T2W)变化规律研究的基础上,利用多元回归分析建立了理化指标与其LF-NMR检测结果的相关性模型,并进行验证。结果表明:大豆油的酸价、TPC含量及S21峰面积均随煎炸时间的延长而线性增大,T21、T22峰起始时间及T2W则随煎炸时间的延长而线性减小(r2>0.90),粘度、吸光值随煎炸时间的延长逐渐增加并符合二项式关系(r2>0.90),而T23峰起始时间及S22、S23与煎炸时间之间无明显规律性变化。煎炸薯条后,油样的酸价、粘度、TPC含量、吸光值及S21均较无料煎炸显著增大(P<0.05),而T21、T22峰起始时间及T2W显著缩短。多元回归分析表明,酸价及TPC含量与T2W、T21,粘度与T2W,吸光值与S21间均可建立良好的相关性模型(R2>0.93)。模型验证合理可靠,可通过油样的LF-NMR检测结果有效预测其理化指标的变化。     

甲基苯基含氢硅油的合成及其热稳定性

以甲基含氢硅油为氢源,在浓硫酸催化下经水解共聚缩合合成了甲基苯基含氢硅油(1),其结构和热稳定性经1H NMR,FT-IR和TGA表征。结果表明,1失重5%的温度为337.42℃。     

绿色合成CdSe及制备CdSe-聚氨酯纳米复合发光材料

通过一步法绿色合成了CdSe-聚氨酯(CdSe-PU)纳米复合发光材料.在N2保护下,将单质硒(Se)溶于蓖麻油,以蓖麻油酸作为氧化镉(CdO)的配体,合成硒化镉(CdSe)纳米晶.将聚丙二醇2000和异佛尔酮二异氰酸酯(IPDI)合成的预聚体,加入含CdSe纳米晶的蓖麻油溶液,通过交联作用得到CdSe-PU纳米复合发光材料.采用紫外-可见分光光度计(UV-Vis)、荧光光谱仪(PL)、傅里叶红外光谱仪(FT-IR)、热重分析仪(TGA)、透射电子显微镜(TEM)对CdSe纳米晶和聚氨酯复合材料的结构和性能进行了表征.结果表明:此方法合成的CdSe纳米晶性能良好,能在聚氨酯纳米复合材料中均匀分散且性能稳定,CdSe-PU纳米复合材料耐热性有所提高.     

Application of solid‐phase microextraction to the determination of polycyclic aromatic sulfur heterocycles in Bohai Sea crude oils

A simple and rapid solid‐phase microextraction approach for the isolation of polycyclic aromatic sulfur heterocycles from the aromatic fraction of crude oil is described. 8‐Hydroxyquinoline silica gel impregnated with palladium chloride was used as a sorbent material for extraction. Operational parameters of the extraction solvents have been evaluated and optimized. Benzothiophene, dibenzothiophene, and benzo[b]naphtho[1,2‐d]thiophene and their C₁–C₄ alkyl derivatives were identified and quantified by GC–MS. Under optimum conditions, the limits of detection for benzothiophene, dibenzothiophene, and benzo[b]naphtho[1,2‐d]thiophene were 0.277, 0.193, and 0.597 μg/g oil, respectively. The recoveries for the polycyclic aromatic sulfur heterocycles ranged from 81.5 to 92.1%, and the linear dynamic range was from 10 to 1000 ng/mL. The developed methodology was tested in the characterization of crude oil samples collected at the DY, SZ, ZH, and HC petroleum oil fields of the Bohai Sea. The results proved that SPE coupled with GC–MS is a promising tool for the quantitative analysis of polycyclic aromatic sulfur heterocycles in crude oils, especially for oil samples with low concentrations of polycyclic aromatic sulfur heterocycles.     

Novel combination of non-aqueous capillary electrophoresis and multivariate curve resolution-alternating least squares to determine phenolic acids in virgin olive oil

This paper presents the development of a non-aqueous capillary electrophoresis method coupled to UV detection combined with multivariate curve resolution-alternating least-squares (MCR-ALS) to carry out the resolution and quantitation of a mixture of six phenolic acids in virgin olive oil samples. p-Coumaric, caffeic, ferulic, 3,4-dihydroxyphenylacetic, vanillic and 4-hydroxyphenilacetic acids have been the analytes under study. All of them present different absorption spectra and overlapped time profiles with the olive oil matrix interferences and between them. The modeling strategy involves the building of a single MCR-ALS model composed of matrices augmented in the temporal mode, namely spectra remain invariant while time profiles may change from sample to sample. So MCR-ALS was used to cope with the coeluting interferences, on accounting the second order advantage inherent to this algorithm which, in addition, is able to handle data sets deviating from trilinearity, like the data herein analyzed. The method was firstly applied to resolve standard mixtures of the analytes randomly prepared in 1-propanol and, secondly, in real virgin olive oil samples, getting recovery values near to 100% in all cases. The importance and novelty of this methodology relies on the combination of non-aqueous capillary electrophoresis second-order data and MCR-ALS algorithm which allows performing the resolution of these compounds simplifying the previous sample pretreatment stages.     

New discrimination method combining hit quality index based spectral matching and voting

A new discrimination method, called hit quality index (HQI)-voting, that uses the HQI for discriminant analysis has been developed. HQI indicates the degree of spectral matching between two spectra as known. In this method, a library sample yielding the highest HQI value for an unknown sample was initially searched and a group containing this sample was chosen as the group for the unknown sample. When overall spectral features of two groups are quite close to each other, many library samples with similar HQI values could be available for an unknown sample. In this situation, the simultaneous consideration of multiple votes (several library samples with close HQI values) for final decision would be more robust. In order to evaluate the discrimination performance of HQI-voting, three different near-infrared (NIR) spectroscopic datasets composed of two sample groups were used: (1) domestic and imported sesame samples, (2) domestic and imported Angelica gigas samples, and (3) diesel and light gas oil (LGO) samples. For the purpose of comparison, principal component analysis–linear discriminant analysis (PCA–LDA), partial least squares–discriminant analysis (PLS–DA) as well as k-nearest neighbor (k-NN) were also performed using the same datasets and the resulting accuracies were compared. The discrimination performances improved with the use of HQI-voting in comparison with those resulted from PCA–LDA and PLS–DA. The overall results support that HQI-voting is a comparable discrimination method to that of existing factor-based multivariate methods.     

Development of a manual method for the determination of mineral oil in foods and paperboard

So far the majority of the measurements of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) were obtained from on-line high performance liquid chromatography–gas chromatography–flame ionization detection (on-line HPLC–GC–FID). Since this technique is not available in many laboratories, an alternative method with more easily available tools has been developed. Preseparation on a small conventional liquid chromatographic column was optimized to achieve robust separation between the MOSH and the MOAH, but also to keep out the wax esters from the MOAH fraction. This was achieved by mixing a small portion of silica gel with silver nitrate into highly activated silica gel and by adding toluene into the eluent for the MOAH. Toluene was also added to the MOSH fraction to facilitate reconcentration and to serve as a keeper preventing loss of volatiles during solvent evaporation. A 50 μl volume was injected on-column into GC–FID to achieve a detection limit for MOSH and MOAH below 1 mg/kg in most foods.