Determination and Temperature Dependence of Plateau Modulus for Polymerization of Propylene to Isotactic Polypropylene with Ultra-high Molecular Weight under Catalysis of Ziegler-Natta Catalyst

The viscoelastic behavior of isotactic polypropylene with ultra-high molecular weight(UHPPH) and broad molecular weight distribution(MWD), produced in the presence of Ziegler-Natta catalyst, was investigated by means of oscillatory rheometry at 180 and 200 ℃, whose loss modulus(G″) plots at 180 and 200 ℃ versus the natural logarithm of angular frequency(ω) present a pronounced maximum at 34.35 and 69.21 rad/s, respectively, and do not show a maximum peak at 0.01-100 rad/s for Ziegler-Natta catalyzing ethylene-propylene random copolymerization(PPR) with a conventional molecular weight and broad MWD. The fact indicates that the high molecular weight is responsible for a maximum peak of G″(ω) vs. lnω curves for UHPPH. This makes it possible to determine the plateau modulus(G 0_N) of UHPPH from a certain experimental temperature G″(ω) curve directly. For UHPPH, the G 0_N determined to be 4.28×10 5 and 3.62×10 5 Pa at 180 and 200 ℃, respectively, decreases with the increase of temperature and is independent of the molecular weight, which directly confirms reputation theoretical prediction that the G 0_N has no relation to the molecular weight.

Enhancement of Adhesive Strength of Ultrahigh Molecular Weight Polyethylene Fibers Prepared by Polar Polymer Implantation

A new technique was proposed to enhance the adhesive strength of ultrahigh molecular weight polyethylene （UHMWPE） fibers. Polar polymer was implanted into UHMWE gel fibers during extracting process and can then be trapped on the surface of the fibers after subsequent ultra-drawing. The physical and chemical changes in the fiber structure were examined with scanning electron microscopy （SEM） and Fourier transform infrared （FTIR） spectroscopy. The mechanical and interfacial adhesion properties of UHMWPE fibers were investigated with tensile testing. The results showed that there were polar groups on the smface of pretreated UHMWPE fiber. The interracial shear strength of UHMWPE fibers with epoxy resin was greatly improved without sacrificing the excellent mechanical p^perties of fibers. After pretreated with ethylene/vinyl acetate copolymer （EVA）, the shear strength of the interface between fiber and epoxy resin increased from 1.06 to 2.49 MPa, while the integrated mechanical properties d the pretreated UHMWPE fibers were still optimal.

Structure and Properties of Self-reinforced Material Made from Ultra-high Molecular Weight Polyethylene-montmorillonite Nanocomposite

High-strength and high-modulus ultra-high molecular weight polyethylene(UHMWPE), named self-reinforced material, was obtained by the elongation of UHMWPE-montmorillonite nanocomposite at melting temperature. According to the scanning electron microscope(SEM) analysis, a great deal of fibrillar texture formed in the direction of elongation, and the tensile fractured surface was similar to that of highly oriented fiber. The transmission electron microscope(TEM) and selective area electron diffraction(SAED) analyses reveal that the reinforced phase of the self-reinforced material is an extended chain crystal and its size is about 50_200 nm wide and several microns long, and the montmorillonite layers are broken up to pieces in the size from 100 to 10 nm. The broken layers which have a huge surface area interacting strongly with macromolecules reduces the entanglement density of UHMWPE and induces the chain orientation in flow field. It is supposed that the astriction of montmorillonite layers to polyethylene chains is not only end-tethered but also side-tethered. The differential scan calorimetry(DSC) analysis shows that there are two endothermal peaks for the self-reinforced material, of which the peak at a higher temperature(136.4 ℃) is ascribed to the melting of the reinforced phase.

Effect of Molecular Weight on Thermoelectric Performance of P3HT Analogues with 2-Propoxyethyl Side Chains

By replacing hexyl chains in poly(3-hexylthiophene)(P3HT)with 2-propoxyethyls,four poly(3-(2-propoxyethyl)thiophene)(P3POET)homopolymers with comparable polydispersity indexes(PDI)and regioregularities were prepared herein in addition with step increment of about 7 kDa on numberaverage molecular weight(M_(n))from around 11 to 32 kDa(accordingly denoted as P11k,P18k,P25k,and P32k).When doped in film by FeCl_(3)at the optimized conditions,the maximum power factor(PF_(max))increases greatly from 4.3μW·m^(-1)·K^(-2)for P11k to 8.8μW·m^(-1)·K^(-2)for P18k,and further to 9.7μW·m^(-1)·K^(-2)for P25k,followed by a slight decrease to 9.2μW·m^(-1)·K^(-2)for P32k.The close Seebeck coefficients(S)at PF_(max)are observed in these doped polymer films due to their consistent frontier orbital energy levels and Fermi levels.The main contribution to this PF_(max)evolution thus comes from the corresponding conductivities(σ).Theσvariation of the doped films can be rationally correlated with their microstructure evolution.

Preparation of Ultra-High Molecular Weight Polypropylene Using Ziegler-Natta Catalyst via Combining Internal Electron Donor and Cocatalyst Loading

Due to the development of the new energy industry,polypropylene with ultra-high molecular weight plays a crucial role for battery isolation membrane.This work investigated the effect of internal electron donor of Ziegler-Natta catalyst system on the molecular weight of the obtained polypropylene.The scanning electron microscope(SEM)and Canon camera were used to characterize the surface morphologies of catalyst particles and polymer particles,respectively.Compared with the polypropylene particles featuring a spherical shape,these study results confirmed that the morphology duplication theory from the catalyst particle to the morphology of polymer particle was exhibited.The gel permeation chromatography(GPC)results revealed that the obtained polypropylene has a much higher average molecular weight than those prepared by conventional method.The Fourier transform infrared spectrometry(FT-IR)and X-ray photoelectron spectroscopy(XPS)revealed that the carbonyl oxygen atom on ester group was preferentially bound to Mg and Ti,as compared to the ether oxygen atom.The XPS results showed that the ratio of Ti^(3+)/Ti^(4+)could be changed by internal electron donors.When Ti3+content was nearly 99%in the Ziegler-Natta catalyst system,isotactic polypropylene with an ultra-high molecular weight of up to 1.42×10^(6)g/mol was obtained by Cat.3.This result implied that internal electron donor ID3 could reduce theβ-hydride elimination reaction to further increase the molecular weight of the obtained polymer.

Ultra-High Molecular Weight Polyethylene Tape Applied for Distal Humeral Condyle Fracture around Total Elbow Arthroplasty in Patients with Rheumatoid Arthritis: Report of Two Cases

Managing fractures of distal humerus in patients with rheumatoid arthritis (RA) is technically challenging. Total elbow arthroplasty (TEA) is one of the treatment options for these fractures. While elbow motion is largely regained by TEA, comminuted condyle fragments are often ignored. Although numerous approaches for repair of condylar fragments around TEA are described, any universal fixation strategy for these fractures has not been established. This report describes, for the first time, application of an ultra-high molecular weight polyethylene (UHMWPE) tape for the treatment of distal humerus fracture in 2 patients with rheumatic elbow arthropathy. The post-operative clinical courses were good. Radiographs showed bony union of the condylar fragments without loosening in two cases. Because of its flat configuration, softness, and flexibility, UHMWPE tape is a promising material for stabilizing fracture of the distal humerus associated with TEA.

PREPARATION AND CHARACTERIZATION OF ULTRA-HIGH MOLECULAR WEIGHT POLY(ETHYLENE TEREPHTHALATE)(PET)FIBER

This paper reports the spinning and drawing behavior of Ultra-high Molecular Weight polyethylene Terephthalate) (UHMW-PET) fibers. The as-spun fibers were produced by dry-jet wet spinning of a 15%-17% solution in 50:50(v:v) trifluroroacetic acid and dichloromethane. Both molecular weight and polymer solution concentration have marked effect on the drawability of the as-spun-fibers. The maximum extension drawing ratio (EDRmax) of as-spun fiber increases with increasing molecular weight, whereas optimal concentration to achieve the EDRmax of as-spun fibers decreases with increasing molecular weight. Drawing speed and temperature during the first step have remarkable effect on the drawability of these fiber during the second step. Relatively lower drawing temperature and drawing speed (19 ℃ , 60 mm/min) during the first drawing step was beneficial to mechanical properties of ultimate fibers. At the range of 210 ℃ to 230 ℃, the draw ratio (DR) during the second step increases with increasing temperature.

Influence of Molecular Weight of Ultra-high Molecular Weight Polyacrylonitrile on Its Rheological Behavior in Dimethylsulfoxide

Ultra-high molecular weight polyacrylonitrile (UHMW PAN ) was prepared by aqueous suspension polymerization, and the effect of molecular weight on its rheological behaviors in dimethylsulfoxide (DMSO) and the spinning stability were investigated. It shows that,compared with common polyacrylonitrile (C-PAN),UHMW- PAN/DMS0 solution has smaller non- Newtonian index, larger structural viscosity index, much longer maximum relaxation time, and no first- Newtonian region appears in the flow curves under the same experimental conditions. The explanations for these phenomena are given in the view of chain- entanglements. The optimal technology of preparing UHMW-PAN fibers and hollow fiber membranes could be obtained based on the theological study.

Temperature Effect on the Conformation Transition of Ultra-high Molecular Weight Polyethylene/Polypropylene Blends Undergoing Continuous Volume Extensional Flow:A Mesoscopic Simulation

Due to the multiformity and complexity of chain conformation under external flow and the challenge of systematically investigating the transient conformation and dynamic evolution process of polymer chains at the molecular level by means of present experimental techniques,a universal description of both chain conformation and dynamics with respect to continuous volume extensional flow(CVEF)is still absent.Taking into account the temperature effect,we performed dissipative particle dynamics(DPD)simulations with the particles corresponding to the repeat units of polymers over a wide temperature range and analyzed the correlation with the conformational properties of ultra-high molecular weight polyethylene/polypropylene(UHMWPE/PP)blend in response to the CVEF.With time evolution,the polymer chains become highly oriented parallel to the flow direction instead of the initial random coiling and self-aggregation.It is found that a high temperature is necessary for more substantial compactness to take place than low temperature.The low-k plateau and low-k peak in structure factor S(k)curves suggest a low degree of conformational diversity and a high degree of chain stretching.It is also concluded that the intra-molecular C-C bond interaction is the main driving force for the dynamics process of the chain conformations undergoing CVEF,where the motion of the alkyl chains is seriously restricted owing to the increase in bond interaction potential,resulting in a reduction of the difference in diffusion rates among alkyl chains.

Surface Treatment of UHMWPE Fibers for Adhesion Promotion in Epoxy Polymers

Surface of Ultra-high molecular weight polyethylene （UHMWPE） fiber were treated by chromic acid chemical etching, pyrrole chemical vapour phase deposition and the complex of these two methods, respectively. The change of surface properties and structure of fibers were discussed by Fiour Transform Infrared Spectroscope （FTIR）, Dynamic Mechanical Analysis （DMA） and Scanning Electron Microscope （SEM）. The results show that some new oxygenous groups could be found on surface of UHMWPE fiber after chromic acid chemical etching, which enhanced intemolecular interaction with polypyrrcle. The adhesion of the fiber and resin natrix increased after pyrrole chemical vapour deposition. When chromic acid etching combined with pyrrole chemical vapor deposition, the treated fiber not only has the same properties as original fiber bat also outstanding adhesion to epoxy resin matrix, and its composites have better mechanic properties shear strength）, resulting from intemolecular interaction treated fiber and polypyrrole.

INFLUENCE OF MOLECULAR WEIGHT OF CHITIN AND ITS THREE DERIVATIVES ON CRITICAL CONCENTRATION OF LYOTROPIC LIQUID CRYSTALLINE PHASE TRANSITION

The critical concentration of lyotropic liquid crystalline phase transition for chitin derivatives was determined using a polarization microscope. The influence of molecular weight on critical concentration of liquid crystalline solution for chitin, chitosan, cyanoethyl chitosan and propionyl chitin successively increases as the chain rigidity decreases. Therefore it can be used as an indicator of the chain rigidity.

Rheological behavior of hydrolyzed polyacrylamide solution flowing through a molecular weight adjusting device with porous medium

The separate-layer injection in different interlayers and the injection of the same-molecular-weight polymer so- lution in a layer are necessary in the polymer flooding process because of heterogeneous multilayer sandstone reservoirs in EOR projects. To alleviate the matching problems between the layer permeability and the injected polymer molecular weight, a molecular weight adjusting device with porous medium was designed on the basis of mechanical degradation principle. In terms of four variables （polymer concentration, pore diameter, length of shear component and flow rate ）, the theological behavior of hydrolyzed polyacrylamide （HPAM） solu- tion flowing through the device was investigated in detail. The change of these variables is able to control the shear rate of HPAM solutions through ceramic foam, and achieve the desired degree of shear degradation and the final theological parameters-viscosity loss, viscoelasticity and pressure drop. Therefore, a linear relationship between viscosity loss and shearing rate was established so as to obtain the targeted viscosity easily. Field tests in the Daqing Oil Field showed that the polymer molecular weight could drop 20% to 50%. In a word, the results could guide the industrial application of the novel device and the further study of polymer degradation flowing through the porous medium.

Investigation of the Low Molecular Weight Thiol Composition in a Metastatic Prostate Cancer Cell Line (LNCaP) by LC-UV-MS and NMR after Labelling with the Ellman Reagent

The low molecular weight thiols present in the deproteinized extract of a prostate cancer cell line (LNCaP-FGC) were analysed after derivatization with the Ellman reagent (ESSE). The mixed disulphides formed (RSSE) were fractionated, characterized and quantified by liquid chromatography on a C-18 column using UV detection. This revealed the presence, in femtomoles per cell, of glutathione (8.30 ± 0.73), cysteine (2.71 ± 0.04) and cysteinylglycine (0.83 ± 0.10), accounting for the bulk of the thiol present. Further analysis of the cell extracts using a novel and sensitive mass spectrometry technique allowed the detection of low level of an additional derivative which was identified as cysteinylglycerate using NMRspectroscopy.

The New Methods for Characterization of Molecular Weight of Supramolecular Polymers

Supramolecular polymers,as a type of dynamic polymers,are subordinate to the interdisciplinary field of polymer chemistry and supramolecular chemistry,whose development has greatly promoted the prosperity of new materials.Notably,molecular weight is one of the most important parameters of supramolecular polymers,which affects the physical/chemical properties and processing applications of materials.Developing new methods for characterizing the molecular weight of supramolecular polymers is crucial for advancing the development of supramolecular polymers.In this review,we elaborate and summarize three strategies for characterizing the molecular weight of supramolecular polymers that recently reported by our research group according to the characteristics of supramolecular polymers,including(1)the molecular weight distinction corresponding to variable fluorescence colors,(2)matching different molecular weights with different fluorescence lifetime,(3)transforming supramolecular polymers into mechanically interlocked polymers or covalent polymers.Besides,we also discuss the limitations of current methods for characterizing supramolecular polymers.We hope that this review can promote the development of supramolecular polymers and significantly inspire to exploit new methods to characterizing molecular weight of supramolecular polymers.

A Simple Method for Synthesizing Ultra-high-molecular-weight Polystyrene through Emulsion Polymerization Using Alkyl-9-BBN as an Initiator

Styrene emulsion polymerization using an alkyl-9-BBN, synthesized by reacting 9-BBN（9-borabicyclo-[3.3.1]-nonane） and styrene, in an aqueous sodium dodecyl sulfate（SDS） solution was studied. Ultra-high-molecular-weight（〉 1.0 × 10~7） polystyrene was synthesized using a radical initiator formed through the aerobic oxidation of this alkyl-9-BBN in a high yield（〉 80%）. The kinetics of this emulsion polymerization of styrene with the alkyl-9-BBN was investigated. We confirmed that in the initial stage of the polymerization, the initial reaction rate followed first-order kinetics. The activation energy for this emulsion polymerization of styrene was approximately 56.2 kJ/mol.

Cyclic Pulsating Pressure Enhanced Segregating Structuration of Ultra-High Molecular Weight Polyethylene/Graphene Composites as High-performance Light-Weight EMI Shields

Currently,the enhancement in electromagnetic interference(EMI)performance of polymeric composite generally relies on either improving electrical conductivity(σ)for stronger electromagnetic(EM)reflections or tailoring structure for higher EM resonances.Herein,we proposed a novel technique called cyclic pulsating pressure enhanced segregating structuration(CPP-SS),which can reinforce these two factors simultaneously.The structural information was supplied by optical microscopy(OM)and scanning electron microscopy(SEM),both of which confirmed the formation and evolution of segregate structured ultra-high molecular weight polyethylene(UHMWPE)/graphene composites.Then,the result showed that CPP-SS can significantly improve theσof samples.Ultimately,advanced specific EMI shielding efficiency of 31.1 d B/mm was achieved for UHMWPE/graphene composite at 1-mm thickness and a low graphene loading of 5 wt%.Meanwhile,it also confirmed that the intrinsic disadvantage of poor mechanical properties of conventional segregated structure composites can be surpassed.This work is believed to provide a fundamental understanding of the structural and performance evolutions of segregated structured composites prepared under CPPSS,and to bring us a simple and efficient approach for fabricating high-performance,strong and light-weight polymeric EMI shields.

Anionic polymerization initiated by lithium amides for preparing high molecular weight polyacrylonitrile

Lithium amides have been proved to be effective anionic initiators for the anionic polymerization of acrylonitrile to get high molecular weight polyacrylonitrile in this study. Polyacrylonitrile with weightaverage molecular weight ranging from 1.02 × 10~6 g/mol to 1.23 ×10~6 g/mol (M_w/M_n= 1.9-2.2) could be prepared utilizing lithium amides derived from diisopropylamine, diethylamine, hexamethyldisilazane,dicyclohexylamine, and 2,2,6,6-tetramethylpiperidine as initiators. The polymerization of acrylonitrile proceeded in a homogeneous manner in N,N-di methyl for mamide and insignificant contribution of side reactions was confirmed.

Structural, Pasting, and Thermal Properties of Ultra-high Pressure-treated Lotus Seed Starch

Lotus seed starch （15%, w/w） was subjected to ultra-high pressure （UHP） at 500 MPa for 10～60 min. The effects of UHP on the structural, pasting, and thermal properties of starch were investigated using solid-state 13C CP/MAS NMR, differential scanning calorimetry （DSC）, HPSEC-MALLS-RI, and a rapid visco analyzer. The 13C CP/MAS NMR results revealed a reduction in the relative crystallinity and peak intensity of the crystalline state with increasing the UHP time. The molecular weight of native starch was 1.433 × 107 Da, which was higher than that of the UHP-treated starch. Viscograms of UHP-treated starch revealed an increase in paste viscosity, peak time, and pasting temperature and a reduction in breakdown and setback viscosity compared to the native starch. Furthermore, the DSC results showed a reduction in gelatinization temperature and gelatinization enthalpy with increasing the UHP time.

Separation/enrichment of the low-content high molecular weight natural protein using protein-imprinted polymers with ARPCs

We introduce a new method for separation/enrichment of the low-content cellular protein in high mo-lecular weight on the basis of molecular imprinting. The template protein, bacterial cloned immu-noglobulin binding protein (BiP), was selectively assembled with assistant recognition polymer chains (ARPCs) from their library, which consists of numerous limited length polymer chains with randomly distributed recognition and immobilizing sites. The assemblies of proteins and ARPCs were adsorbed by porous polymeric beads and immobilized by cross-linking polymerization. After the template was removed, the synthesized imprinted polymer was used to adsorb authentic BiP from endoplasmic re-ticulum (ER) extract, and its proportional content was enriched 45 times. It is the first time that the low-content cellular natural protein, whose molecular weight reaches 78 kDa, is enriched by molecular imprinting.

Tuning Aggregation Behavior of Polymer Donor via Molecular-Weight Control for Achieving 17.1%Efficiency Inverted Polymer Solar Cells

Main observation and conclusion Recently,the polymer solar cells(PSCs)based on the PM6 and small molecular acceptor(SMA)Y6 have attracted considerable attention in this community for their outstanding photovoltaic performance.