Miscibility and morphology in crystalline/amorphous blends of poly(caprolactone)/poly(4-vinylphenol) as studied by DSC, FTIR, and C solid state NMR

The miscibility and morphology of poly(caprolactone) (PCL) and poly (4-vinylphenol) (PVPh) blends were investigated by using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and ¹³C solid state nuclear magnetic resonance (NMR) spectroscopy. The DSC results indicate that PCL is miscible with PVPh. FTIR studies reveal that hydrogen bonding exists between the hydroxyl groups of PVPh and the carbonyl groups of PCL. ¹³C cross polarization (CP)/magic angle spinning (MAS)/dipolar decoupling (DD) spectra of the blends show a 1 ppm downfield shifting of ¹³C resonance of PVPh hydroxyl-substituted carbons and PCL carbonyl carbons with increasing PCL content. Both FTIR and NMR give evidence of inter-molecular hydrogen bonding within the blends. The proton spin-lattice relaxation in the laboratory frame, T₁(H), and in the rotating frame, T_1ρ(H), were studied as a function of the blend composition. The T₁(H) results are in good agreement with thermal analysis; i.e. the blends are completely homogeneous on the scale of 50-80 nm. The T_1ρ(H) results indicate that PCL in the blends has both crystalline and amorphous phases. The amorphous PCL phase is miscible with PVPh, but the PCL crystal domain size is probably larger than the spin-diffusion path length within the T_1ρ(H) time-frame, i.e. larger than 2-4 nm. The mobility differences between the crystalline and amorphous phases of PCL are clearly visible from the T_1ρ(H) data.     

INTEGRATING ALBEMARLE RESOLVE DESULFURIZATION TECHNOLOGY WITH NOVEL PETRO-CANADA PROCESS CONCEPTS IN COMMERCIAL FCCU OPERATIONS

The gasoline and distillate sulfur regulations promulgated throughout the world to reduce tail-pipe emissions are now strongly impacting refinery operations and investments. FCC gasoline is recognized as the principal contributor of sulfur to the gasoline pool and has become the focus for meeting the new specifications. The difficulty in removing sterically hindered sulfur species in the fluid catalytic cracking unit (FCCU) cycle oil drives up the hydrogen and investment costs for treating the distillates. Although installation of pre- and post-treatment facilities is planned by many refiners, other non-capital approaches such as undercutting are being evaluated to meet interim and future sulfur levels. Even when expensive treatment facilities are installed, operating costs can be lowered and the flexibility of the facility increased with improvements in the ability to remove sulfur in the FCCU. In this article, we detail Petro-Canada's experience in integrating Albemarle's RESOLVE sulfur reduction technology with a combination of innovative process ideas. These concepts include heavy naphtha recycle, coprocessing of hydrogen donor feeds, and recycle of light cycle oil (LCO) to a specially designed stripper reactor. Special attention is paid to the interaction of deep FCC feed hydrodesulfurization with the FCC performance. The results demonstrate that very low FCC gasoline sulfur levels can be achieved without significant capital investment through novel approaches to recycle, creative integration of cat feed hydrotreating unit (CFHTU)-FCCU designs and operations, and application of state-of-the-art sulfur reduction additive technology. An added benefit of the RESOLVE 950 sulfur reduction technology is the substantial elimination of sulfur oxides in the FCC flue gas. This has been observed in Petro-Canada operations and numerous other RESOLVE 950 applications around the world.     

Separation of Triacylglycerol Species from Interesterified Oils by High-Performance Liquid Chromatography

Using a 1,3-regioselective lipase as a catalyst, soybean oil and olive oil were interesterified with the short-chain triacylglycerol tributyrin (1,2,3-tributyrylglycerol) to produce mixtures of structured triacylglycerols (SL-TAG). The SL-TAG were purified by column chromatography and analyzed by both normal-phase (silica column; NP_SIL) and reversed-phase [octadecyl silane (ODS) column] high-performance liquid chromatography (HPLC). Individual SL-TAG molecular species were detected by evaporative light-scattering detection, and characterized by mass spectrometry. NP_SIL HPLC successfully separated the newly synthesized SL-TAG into two groups of TAG: one composed of one butyryl group and two long-chain fatty acyl groups (from soybean or olive oil); the second was composed of two butyryl groups and one long-chain fatty acyl group. The SL-TAG species were further analyzed by reversed-phase HPLC which gave a more detailed separation of the TAG species present in the two SL-TAG.     

互联网金融平台中高违约风险用户识别算法

在我国金融科技不断创新的背景下,互联网金融平台中通过网络分析技术开展用户风险识别已经成为当前的热点技术发展方向。以某互联网金融平台的用户交易数据为对象,通过分析其中借贷逾期违约的传播行为,提出通过传播特征构建模型算法识别互联网金融平台的高风险用户。在构建基于阈值传播和随机传播的SIS模型和SIR模型基础上,将模型转换为可评价用户风险值的算法,并进一步与实际违约数据进行验证对比。对比结果显示在前5%和10%高风险群体划分条件下,算法具有较高的召回率和良好的结构关联性。     

Synthesis and characterization of new functional poly(urethane‐imide) crosslinked networks

To synthesize new functional poly(urethane‐imide) crosslinked networks, soluble polyimide from 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride, 4,4′‐oxydianiline, and maleic anhydride and polyurethane prepolymer from polycaprolactone diol, tolylene 2,4‐diisocyanate and hydroxyl ethyl acrylate were prepared. Poly(urethane‐imide) thin films were finally prepared by the reaction between maleimide end‐capped soluble polyimide (PI) and acrylate end‐capped polyurethane (PU). The effect of polyurethane content on dielectric constant, residual stress, morphology, thermal property, and mechanical property was studied by FTIR, prism coupler, Thin Film Stress Analyzer (TFSA), XRD, TGA, DMTA, and Nano‐indentation. Dielectric constant of poly(urethane‐imide) thin films (2.39–2.45) was lower than that of pure polyimide (2.46). Especially, poly(urethane‐imide) thin films with 50% of PU showed lower dielectric constant than other poly(urethane‐imide) thin films did. Lower residual stress and slope in cooling curve were achieved in higher PU content. Compared to typical polyurethane, poly(urethane‐imide) thin films exhibited better thermal stability due to the presence of the imide groups. The glass transition temperature, modulus, and hardness decreased with increase in the flexible PU content even though elongation and thermal expansion coefficient increased. Finally, poly(urethane‐imide) thin films with low residual stress and dielectric constant, which are strongly affected by the morphological structure, chain mobility, and modulus, can be suggested to apply for electronic devices by variation of PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 113–123, 2006     

Artificial neural network approaches on composition-property relationships of jet fuels based on GC-MS

The relationships of composition-properties of 80 jet fuels concerning chemical compositions and several specification properties including density, flashpoint, freezing point, aniline point and net heat of combustion were studied. The chemical compositions of the jet fuels were determined by GC-MS, and grouped into eight classes of hydrocarbon compounds, including n-paraffins, isoparaffins, monocyclopraffins, dicyclopraffins, alkylbenzens, naphthalenes, tetralins, hydroaromatics. Several quantitative composition-property relationships were developed with three artificial neural network (ANN) approaches, including single-layer feedforward neural network (SLFNN), multiple layer feedforward neural network (MLFNN) and general regressed neural network (GRNN). It was found that SLFNNs are adequate to predict density, freezing point and net heat of combustion, while MLFNNs produce better results as far as the flash point and aniline point prediction are concerned. Comparisons with the multiple linear regression (MLR) correlations reported and the standard ASTM methods showed that ANN approaches of composition-property relationships are significant improvement on MLR correlations, and are comparable to the standard ASTM methods.     

Binding of several heavy metal ions by polyaspartyl polymers and their application to some Chinese herbal medicines

Water‐insoluble polyaspartyl polymers were synthesized by using water as medium instead of organic medium. Taking Ca²⁺ as a reference, the binding of several heavy‐metal ions, including Pb²⁺, Cd²⁺, Hg²⁺, Cr³⁺, Cu²⁺, and Mn²⁺, by polyaspartyl polymers was studied. The experimental results revealed that polyaspartate is an excellent binding agent for the investigated heavy‐metal ions. These cation ions were bound to polyaspartate polymer by the same mechanism as Pb²⁺, which can be explained by ion exchange model. Since polyaspartate has a protein‐resembling structure that is sensitive to trace heavy metal, it was used to remove some trace heavy‐metal elements in Chinese herbal medicines. It was found that polyaspartate material was an effective agent for the removal of Pb²⁺, Cd²⁺, and Hg²⁺ ions from glycyrrhizin, angelica, and gynostemma pentaphyllum. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Combinatorial chemistry methods for coating development: VI. Correlation of high throughput screening methods with conventional measurement techniques

Combinatorial chemistry has proven to be a valuable tool for the development of new compounds. In the pharmaceutical industry, where combinatorial chemistry began, the approach has been instrumental in the high-speed development of new drugs. Due to the overwhelming success of the combinatorial methodology in the pharmaceutical industry, it has been recently applied to materials development. We have recently developed a combinatorial factory capable of preparing and evaluating on the order of 100 organic clear coatings in a day.

One of the most challenging aspects of the creation of the combinatorial factory was the development of the high throughput screening (HTS) methods for the primary coating properties of interest such as optical clarity, abrasion resistance, adhesion, and weatherability. For each property, an entirely new method was developed that allowed for rapid measurement of these properties on very small samples. This paper describes various aspects of the development of these novel measurement systems including the correlation of the HTS methods with conventional, industry standard measurement methods.     

Platinum-group metal cyclodextrin complexes and their use as command-cure catalysts in silicones

The Command-Cure concept is defined for a curable formulation as one with long work-like at ambient temperature and rapid cure time at elevated temperature. This concept is explored for a curable silicone system, cured via hydrosilylation. CODMCl₂ complexes (COD=1.5-cyclo-octadiene:M=Pt. Pd) are reacted with beta-cyclodextrin (-CD) to make 11 inclusion compounds,M=Pd.2;M=Pt.4. Compounds2 and4 were analyzed by¹H NMR and X-ray powder diffraction. Their catalytic ability was evaluated in a model system as well as a polymeric system that gels upon cure. Surprisingly, the Pd analog2 was a good command-cure catalyst whereas the guest compound CODPdCl₂,1, was not active in the hydrosilylation reaction. The Pt analog,4, was an effective command-cure catalyst while the corresponding guest. CODPtCl₂,3, was too active at low temperature in the hydrosilylation reaction. Additional Pt compounds and one Rh inclusion compound were evaluated as command cure catalysts. These inclusion compounds were: 11 -CD:[CODRhCl]₂,5: 11 -CD:CpPtMe₃,6 (Cp=cyclopentadienyl): 12 -CD:MeCpPtMe₃,7; 12 -CO:CODPtMe₂,8. The effectiveness of4 8 was evaluated in a number of silicone systems.     

Flow distribution in spiral mandrel dies

An analysis of flow of a power law fluid in a spiral mandrel die is presented. The analysis is applied to study the effect of various die design parameters on the flow distribution at the end of the spiral mandrel section. Three variables that have a very strong effect on the flow distribution are the number of grooves, the initial clearance, and the groove helix angle. The distribution is improved by increasing the number of grooves, by using a non-zero initial clearance, and a relatively small helix angle. Two more variables that have a significant effect on the flow distribution are the taper angle and the initial groove depth. The optimum taper angle was found to be between 1 and 3 degrees. The distribution uniformity improves with the initial groove depth, while the pressure drop reduces at the same time.