Structure-rheology relationships of long-chain branched polypropylene: Comparative analysis of acrylic and allylic coagent chemistry

The relationship between product structure and melt-state rheological properties is established for series of branched PP derivatives prepared by the radical-mediated grafting of tri-functional coagents. Peroxide-initiated, solvent-free additions of linear PP to triallyl trimesate (TAM), trimethylolpropane triacrylate (TMPTA) and triallyl phosphate (TAP) at high temperature are shown to produce bimodal molecular weight and branching distributions. Low-frequency dynamic shear viscosities as well as extensional viscosities are shown to be highly responsive to a hyper-branched chain population, whose abundance and molecular weight correlate with the kinetic chain length of the grafting process, and the propensity of a coagent to oligomerize.     

A rheology theory and method on polydispersity and polymer long-chain branching

Model calculations were performed to investigate the sensitivity of zero-shear melt viscosity (η₀ or Eta0) on the molecular weight (MW) polydispersity of linear polymers. Simulated MW distributions (MWD) were generated with the generalized exponential (GEX) distribution function for various levels of polydispersity M_w/M_n and M_z/M_w. For linear entangled polymeric chains in the melt, the linear viscoelastic properties were predicted by using the double reptation blending rule and the so-called BSW relaxation time spectrum, named after the authors: Baumgaertel, Schausberger and Winter [Baumgaertel M, Schausberger A, Winter HH. Rheol Acta 1990;29:400-8]. Published rheological parameters appropriate for polyethylene were used in the calculations. It was found that Eta0 depended mostly on M_w, but it also significantly depended on the extent of high-MW polydispersity M_z/M_w. A revision to the fundamental MW dependency of Eta0 was proposed to compensate for this polydispersity effect. To offset the polymer polydispersity differences, we propose a new MW average (M_HV or M_x with x = 1.5) to replace M_w in the historical rheological power-law equation of Eta0 ∝ M_w^a, where the literature value of exponent “a” ranges from 3.2 to 3.6. The use of M_HV instead of M_w in the power-law equation made the calculated Eta0 independent of the sample high-MW polydispersity. With the removal of the complication from polydispersity effect, the new Eta0 power law can now provide a more robust base for studying polymer long-chain branching (LCB). A new LCB index is thus proposed based on this new melt-viscosity power law. The values of M_HV in the new power law can be calculated for polymer samples from the conventional gel permeation chromatographic (GPC) slice data.     

SEC-MALS method for the determination of long-chain branching and long-chain branching distribution in polyethylene

This paper systematically describes a LCB determination method that can quantify both LCB content and LCB distribution across the molecular weight distribution in polyethylene homopolymers as well as copolymers. Coupling size-exclusion chromatography with multi-angle light scattering (SEC-MALS), this method quantifies molecular weights (MW) and radii of gyration (R_g) simultaneously. The number of LCB per molecule and LCB frequency as a function of MW can be calculated by comparing R_g of a branched polymer with that of a linear control at the same MW using the Zimm-Stockmayer approach. Because the presence of short-chain branching in copolymers results in changes in R_g of the copolymers, their LCB contents cannot be obtained before the short-chain branching (SCB) effect is corrected. Using well-characterized linear PE copolymers as standards, an empirical method is successfully established in this paper to correct the SCB effect. Consequently, this method can be applied to determine LCB in PE copolymers as well. Some practical aspects, such as the selection of formalism for data processing, the LCB detection sensitivity and precision, and long-term reproducibility of this method are also discussed. Finally, examples are given to demonstrate how this method is applied to determine LCB and LCB distribution in practical PE homopolymers and copolymers.     

Crystalline and viscoelastic properties of branched polyethylenes synthesized using bidentate nickel (II) catalyst

In this work, five branched polyethylenes with different branching units were synthesized using bidentate nickel (II) catalyst containing -diimine ligands. For comparison, one linear polyethylene was also prepared using tridentate iron (II) catalyst containing -diimine ligand. The crystalline structure of the polyethylenes was investigated using X-ray diffraction (XRD) and polarized optical microscope. The crystalline properties were also measured by differential scanning calorimeter (DSC). Viscoelastic properties of the polyethylenes were investigated using rheometric dynamic analyzer. The DSC and XRD results showed that highly branched polyethylenes exhibit no melting points and no predominating crystalline forms, while the linear polyethylene exhibits clear orthorhombic (110) and (200) reflections on XRD pattern and a clear melting point at 118 °C. The viscoelastic properties of the branched polyethylenes were very complicated due to the combined effect of the molecular weight difference and the degree of chain branching as well as the branching structure.     

Rheological and thermal properties of blends of a long-chain branched polypropylene and different linear polypropylenes

Blends of a long-chain branched polypropylene (LCB-PP) and four linear polypropylenes (L-PP) having different molecular weights were prepared using a twin screw extruder. The linear viscoelastic properties suggested the immiscibility of the high molecular weight L-PP based blends, and the miscibility of the low molecular weight L-PP based blends. In addition, the Palierne emulsion model showed good predictions of the linear viscoelastic properties for both miscible and immiscible PP blends. However, as expected, the low-frequency results showed a clear effect of the interfacial tension on the elastic modulus of the blends for the high molecular weight L-PP based blends. A successful application of time-temperature superposition (TTS) was found for the blends and neat components. Uniaxial elongational properties were obtained using a SER unit mounted on an ARES rheometer. A significant strain hardening was observed for the neat LCB-PP as well as for all the blends. The influence of adding LCB-PP on the crystallinity, crystallization temperature, melting point, and rate of crystallization were studied using differential scanning calorimetry (DSC). It was found that the melting point and degree of crystallinity of the blends first increased by adding up to 20 wt% of the branched component but decreased by further addition. Adding a small amount of LCB-PP caused significant increase of the crystallization temperature while no dramatic changes were observed for blends containing 10 wt% LCB-PP and more. Furthermore, the crystalline morphology during and after crystallization of the various samples was monitored using polarized optical microscopy (POM). Compared to the neat linear polymers, finer and numerous spherulites were observed for the blends and LCB-PP. Dynamic mechanical (DMA) data of the blends and pure components were also analyzed and positive deviations from the Fox equation for the glass transition temperature, T_g, were observed for the blends.     

Synthesis of a branched poly(phenylene ethylene) with bromomethyl groups as an organosoluble and functional parylene

We synthesized a branched poly(phenylene ethylene) (BPPE) with bromomethyl groups from 1,3,5‐tris(bromomethyl)benzene derivatives via the Wurtz coupling reaction. In the case of 1,3,5‐tris(bromomethyl)‐2,4,6‐trimethoxybenzene as a monomer, the obtained polymer (M_n = 6100, M_w/M_n = 1.9) had bromomethyl groups. The ¹HNMR analysis showed that a very large number of unreacted bromomethyl groups (Ph‐CH₂Br) remained in the BPPE; the reaction of this polymer with phenolic hydroxyl groups proceeded quantitatively. This suggested that BPPEs can be functionalized using unreacted bromomethyl groups, making them a very attractive starting point for the creation of functionalized BPPEs with further enhanced processability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Ethylene polymerization with hybrid nickel diimine/Cp2TiCl2 catalyst: a new method to prepare blends of linear and branched polyethylene

Blends of linear polyethylene (LPE) and branched polyethylene (BPE) display very good mechanic properties that can be beneficial for various applications such as shear thinning and melt elasticity. LPE, BPE and amorphous polyethylene can be produced using nickel diimine (DMN) catalyst under various polymerization conditions, while LPE can be obtained using metallocene catalyst. Thus, LPE/BPE blends can be achieved by in situ polymerization using a hybrid DMN/metallocene catalyst. A novel hybrid catalyst made of DMN and Cp₂TiCl₂ was designed and used for ethylene polymerization. A synergistic effect of the two active sites in the hybrid DMN/metallocene catalyst was observed. Blends of linear and low branched polyethylene were synthesized when polymerization was conducted at low temperature (0 °C), while blends of linear and highly branched polyethylene were obtained at high temperature (50 °C). However, the miscibility of the polymers obtained at 50 °C was dramatically reduced as compared to those obtained at 0 °C. Mesoporous particles (MCM‐41) consisting of aluminosilicate with cylindrical pores were used to support the hybrid catalyst, in which MCM‐41 provides sufficient nanoscale pores to facilitate the polymerization in well‐controlled confined spaces. Blends of LPE and BPE were synthesized by in situ polymerization without adding comonomer and characterized. The miscibility of the polymer blends can be improved by supporting the hybrid catalyst on MCM‐41. Copyright © 2009 Society of Chemical Industry     

支化聚合物皮革复鞣填充剂的制备及应用

以甘油(Gly)和马来酸酐(MA)为原料合成马来酸甘油酯(MG),作为多官能度烯类支化单体与丙烯酸(AA)单体,通过自由基共聚法制备水性支化聚合物皮革复鞣填充剂(BPMG)。通过1HNMR对支化单体和聚合物的结构进行了表征。通过正交实验考察了单体配比、引发剂用量、支化单体类型和投料方式对MG双键转化率的影响。结果表明,MG-30为支化单体,n(AA)∶n(MG)=6∶1,w(过硫酸铵)=6%时,以单体滴加的方式,聚合温度85℃,聚合时间2.5h的条件下,具有较高的双键转化率。应用结果显示支化聚合物可以提供皮革较好的填充性能和力学性能。SEM结果表明,支化聚合物对皮革纤维具有明显的分散作用。     

Synthesis of branched polyethylene by ethylene homopolymerization with a novel (α‐diimine)nickel complex in the presence of methylaluminoxane

Branched polyethylene (PE) was prepared with a novel (α‐diimine)nickel(II) complex of 2,3‐bis(2,6‐dimethylphenyl)‐butanediimine nickel dichloride {[2,6‐(CH₃)₂C₆H₃? N?C(CH₃)C(CH₃)?N? 2,6‐(CH₃)₂C₆H₃]NiCl₂} activated by methylaluminoxane in the presence of a single ethylene monomer. The influences of various polymerization conditions, including the temperature, Al/Ni molar ratio, Ni catalyst concentration, and time, on the catalytic activity, molecular weight, degree of branching, and branch length of PE were investigated. According to gel permeation chromatography, the weight‐average molecular weights of the polymers obtained ranged from 1.7 × 10⁵ to 6.0 × 10⁵, with narrow molecular weight distributions of 2.0–3.5. The degree of branching in the polymers rapidly increased with the polymerization temperature increasing; this led to highly crystalline to totally amorphous polymers, but it was independent of the Al/Ni molar ratio and catalyst concentration. At polymerization temperatures greater than 20°C, the resultant PE was confirmed by ¹³C‐NMR to contain significant amounts of not only methyl but also ethyl, propyl, butyl, amyl, and long branches (longer than six carbons). The formation of the branches could be illustrated by the chain walking mechanism, which controlled their specific spacing and conformational arrangements with one another. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1123–1132, 2002; DOI 10.1002/app.10398     

Copper (I) ion stabilized on fe3o4‐core ethylated branched polyethyleneimine‐shell as magnetically recyclable catalyst for ATRP reaction

Branched polyethyleneimine (bPEI) was used to modify the surface of Fe₃O₄ nanoparticles coated with silica layer, and then, it was treated with ethyl iodide to prepare Fe₃O₄@SiO₂@Ethylated‐bPEI. In the next step, the yolk–shell structure was gained by selectively etching the SiO₂ middle layer. Finally, copper(I) was introduced to the yolk–shell Fe₃O₄@Ethylated‐bPEI and the activity of the catalyst was evaluated for atom transfer radical polymerization (ATRP) of styrene, led to obtain the well‐defined polymer with relatively low polydispersity. The toxicity of the residual copper in the polymer product was a limiting issue for applicability of ATRP reactions especially for biological purposes. In this report, the copper content in the polymer was reduced to the excellent value of 1.1 ppm. Moreover, the magnetic isolation, recyclability, and remove the need for an external ligand were other advantages of the synthesized catalyst which makes it suitable for employing in ATRP reactions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42337.     

Using the discrete element method to analyze the breakage rate in a centrifugal/vibration mill

The grinding characteristics of a centrifugal mill with varying G/D (gyration/mill diameter) ratios were investigated using the population balance model and the discrete element method (DEM). A series of grinding tests were conducted on illite samples using a centrifugal mill under various conditions, and the breakage parameters were calculated. Three-dimensional DEM simulations were also conducted. It was found that the specific rates of breakage estimated for various grinding conditions correlated well with the impact energy calculated from DEM simulations. This information was used to develop scale-up functions for the centrifugal mill in terms of G/D ratio, rotational speed, mill diameter, grinding media diameter, and ball loading.     

Using a new approach to analyze a depth profile of double bond conversion in model formulations

A new approach of analyzing the depth profile of double bond conversion as a function of film depth has been studied. By using a combination of statistical calculation and traditional FTIR, a new approach to analyze the depth profile of conversion “layer by layer” in the characterization of photopolymerization was explored. Utilizing a formula (X₁ + X₂ +  + X_n)/n = average conversion, n = 1, 2, 3, n is a number of layers (μm), an average conversion of any 5 μm depth could be calculated from the prior 5 μm conversion and the total average conversion. More detailed information of photopolymerization, such as the depth profile of conversion and a difference in conversion between the top 5 μm and the bottom 5 μm in a 25 μm film as a function of film depth, was obtained. This investigation was accomplished using a variation of film depth, non-photo bleaching photo initiator [PhI] as well as the concentration of PhIs in the presence of air and in the absence of air. Results of analyzing double bond conversion between traditional FTIR and the new approach (statistical calculation/FTIR) were compared.     

Double-layer capacity measurements as a method to characterize porous fuel cell electrodes

Growing interest in porous Teflon-bonded carbon and catalyst carbon electrodes has resulted in increasing research efforts to improve performance and lifetime of these electrodes. The impedance method is demonstrated as a useful instrument to investigate these semihydrophobic electrodes. The double-layer capacity, derived by rather simple calculations from impedance spectra, is correlated with important parameters such as Teflon content, fabrication pressure and drying temperature of the electrode as well as to the deterioration processes which are still limiting the lifetime of the electrode. Information needed for improving these electrodes can be deduced from C_D measurements. Further interpretation of the impedance spectra and calculation of kinetic data are possible with the aid of appropriate equivalent circuits.     

A Branched Tripeptide with an Anion-Binding Motif as a New Delivery Carrier for Efficient Gene Transfection

Branched and dendrimeric cationic peptides have shown better transfection efficiency than linear peptides, owing to their superior capacity for inducing DNA condensation. We have designed and synthesized two analogously guanidinocarbonylpyrrole-substituted (GCP-substituted) branched cationic tripeptides that provide extremely strong electrostatic attraction towards DNA. Both ligands 1 and 2 can bind to DNA and form condensed complexes, owing to the branched structure and high positive charges, as demonstrated by isothermal titration calorimetry (ITC), ζ potential and atomic force microscopy (AFM). After the replacement of the carboxylate group by an amide group, binding of ligand 2 to DNA shows exothermic enthalpy and positive entropy changes relative to ligand 1 . Rational interpretation would suggest that ligand 2 might aid the translocation of plasmid pF143 to HEK 293T cells, showing high gene transfection efficiency. This work therefore provides a facile way, by modifying a branched cationic tripeptide with GCP, to turn a peptide even a tripeptide into an efficient gene transfection vector.     

Evaluation of Swab and Related Tests as a Bioassay for Assessing Responses by Squamate Reptiles to Chemical Stimuli

The ability of squamates to detect chemical cues from adaptively important sources including prey, predators, and conspecifics has been tested frequently by presenting stimuli on cotton-tipped swabs or ceramic tiles. In many such studies the primary response variable is tongue-flicking, which is widely interpreted to indicate sampling for vomerolfaction. I review the basic experimental method and consider limitations regarding its application and interpretation and ways to overcome them. Effects of experimenter proximity and the assumed invisibility of chemical stimuli are considered, as are use of cologne as a pungency control, senses used in making chemical discriminations, and interpretation of results when there are no significant response differences among stimulus classes. Although the assumption that tongue-flicking reveals vomerolfactory sampling and the necessity of an intact vomeronasal system for normal responses to pheromones have been demonstrated where tested, very few species have been examined. In some squamates for which these assumptions have not been examined experimentally, especially eublepharid geckos, attacks on swabs bearing prey chemicals and performance of antipredatory displays in response to predator chemicals occur with no prior tongue-flicking. Not only are assays based on tongue-flicking useless in such cases, but the discriminations are likely based on olfaction. Issues specific to the study of responses to prey chemicals, predator chemicals, and pheromones are discussed. For many purposes, swab tests provide rapid, conclusive assays of ability to respond differentially to biologically relevant stimuli. However, other methods may be superior for studying some responses, and swab tests are not always applicable.     

试井资料确定平面压力分布场方法研究

本文以数值试井技术为依托进行试井资料确定平面压力分布场方法研究,形成了一种以数值试井为主、集动静态分析和油藏工程方法于一体的综合分析方法,解决了中低渗砂岩油藏开发中注采对应关系、水驱开发状况确定等难题。在介绍数值试井基本特点的基础上,阐述了数值试井的技术原理和参数敏感性分析,并介绍了该技术在中原油田的应用实例和效果。     

Possibilities of tar addition to coal as a method of improving coke strength

Tests carried out in a pilot oven, in individual 19-t ovens and for a short time, in a 4.5 m high 54 oven battery, showed that addition of a certain amount of tar directly to any coal mix can improve the coke properties. The experimental procedure adopted for tar addition and the determination of the coke properties are highlighted.