Diels-Alder Addition of Dicyclopentadiene with Cyclopentadiene in Polar Solvents

Diels-Alder addition of dicyclopentadiene and cyclopentadiene in polar solvents has been studied to produce tricyclopentadiene（TCPD） that is a potential high-density fuel precursor. GC and MS analysis shows that the adducts contain two isomers, namely exo- and endo-TCPD. Theoretical simulation shows that although the transition state of endo-TCPD has a lower activation energy, exo-TCPD is thermodynamically preferred. Polar solvents can accelerate the reaction rate and improve the exo/endo ratio of TCPD because the transition state of exo-TCPD has a higher polarity than that of endo-TCPD. The solvent effect follows the order of polarity： benzyl methanol〉cyclohexanone〉toluene. The conversion rises when the temperature ranges from 120 to 150 ℃, but the selectivity of TCPD slightly decreases. Increasing the pressure can improve the conversion but the exo/endo ratio of TCPD is unchanged. The apparent kinetics in different solvents was determined via nonlinear regression. The activation energies are 99.47, 101.15, and 107.32 kJ/mol for benzyl methanol, cyclohexanone, and toluene, respectively. The optimal reaction conditions are as follows： benzyl methanol as solvent, temperature 150 ℃, and pressure 900 kPa. After an 11-hour reaction, a conversion of 58.0%, a TCPD selectivity of 95.7%, and an exo/endo ratio of 1/5.3 has been obtained.

Synthesis of polystyrene-styrene/butadiene diblock copolymers via reversible addition-fragmentation chain transfer miniemulsion polymerization

Polystyrene-styrene/butadiene diblock copolymers were synthesized via reversible addition-fragmentation chain transfer （RAFT） miniemulsion polymerization.During the polymerization process,the molecular weight distribution was narrow and the numerical molecular weight of the copolymers increased with increasing conversion of monomers,which was close to the theoretical.FT-IR and ^1H NMR results indicated that the microstructure of the polymer was mainly 1,4-trans-butadiene with small amount of 1,2-units,and composition in the copolymers was obtained.

Reversible addition-fragmentation chain transfer graft polymerization of acrylonitrile onto PE/PET composite fiber initiated by γ-irradiation

Reversible addition-fragmentation chain transfer(RAFT) mediated grafting of acrylonitrile onto Polyethylene/Poly(ethylene terephthalate)(PE/PET) composite fibers was performed using γ-irradiation as the initial source at ambient temperature. Different initial concentrations of 2-cyanoprop-2-yl dithiobenzonate were used as the chain transfer agent. The kinetics of graft polymerization is in accordance with the living RAFT polymerization. The successful grafting of acrylonitrile is proved by Fourier transform infrared spectroscopy analysis.The results of monofilament tensile test show that mechanical properties of the fibers change slightly after grafting. Scanning electronic microscopy images of the fibers show that the surface of RAFT grafted fibers is smoother than that of fibers grafted conventionally.

Evaluation of the clenbuterol imprinted monolithic column prepared by reversible addition-fragmentation chain transfer polymerization

To make more homogenous organic monolithic structure, reversible addition-fragmentation chain transfer （RAFT） process was employed in the synthesis of the clenbuterol imprinted polymer. In the synthesis, the influence of synthetic conditions on the polymer structure and separation efficiency was studied. The result demonstrated that the imprinted columns prepared with RAFT process have higher column efficiency and selectivity than the columns prepared with conventional polymerization in the present study, which may result from the higher surface area, smaller pore size and the narrower globule size distribution in their structures. The result indicated that RAFT polymerization provided better conditions for the clenbuterol imprinted monolithic polymer preparation. 2009 Xiang Chao Dong. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

High-gravity technology intensified Knoevenagel condensation-Michael addition polymerization of poly (ethylene glycol)-poly (n-butyl cyanoacrylate) for blood-brain barrier delivery

Poly(ethylene glycol)-poly(n-butyl cyanoacrylate)(PEG-PBCA)is a remarkable drug delivery carrier for permeating blood-brain barrier.In this work,a novel high-gravity procedure was reported to intensify Knoevenagel condensation-Michael addition polymerization of PEG-PBCA.A series of PEG-PBCA containing different block ratios were synthesized with narrow molecular weight distribution of polydispersity indexes less than 1.1.Furthermore,the reaction time reduced 60%compared to conventional stirred tank reactor process.Chemical structures of as-prepared polymers were characterized.In vitro drug delivery performance was evaluated.The cytotoxicity of PEG-PBCA to brain microvessel endothelial cells(BMVEC)decreases with the extension of the PEG chain and the shortening of the PBCA chain.The polymer cellular uptake to BMVECs was better after improving hydrophilicity by PEG block.Results of bloodbrain barrier permeability demonstrated that medium length of PBCA chain and short PEG chain are favorable for hydrophobic Nile red permeation,while long PEG chain and short PBCA chain are beneficial to delivery water-soluble doxorubicin hydrochloride(Dox).The average apparent permeability coeffi-cient increased 1.7 and 0.25 times than that of raw Nile red and Dox,respectively.High-gravity intensi-fied condensation polymerization should have great potential in brain drug delivery system.

Two-photon polymerization lithography for imaging optics

Optical imaging systems have greatly extended human visual capabilities,enabling the observation and understanding of diverse phenomena.Imaging technologies span a broad spectrum of wavelengths from x-ray to radio frequencies and impact research activities and our daily lives.Traditional glass lenses are fabricated through a series of complex processes,while polymers offer versatility and ease of production.However,modern applications often require complex lens assemblies,driving the need for miniaturization and advanced designs with micro-and nanoscale features to surpass the capabilities of traditional fabrication methods.Three-dimensional(3D)printing,or additive manufacturing,presents a solution to these challenges with benefits of rapid prototyping,customized geometries,and efficient production,particularly suited for miniaturized optical imaging devices.Various 3D printing methods have demonstrated advantages over traditional counterparts,yet challenges remain in achieving nanoscale resolutions.Two-photon polymerization lithography(TPL),a nanoscale 3D printing technique,enables the fabrication of intricate structures beyond the optical diffraction limit via the nonlinear process of two-photon absorption within liquid resin.It offers unprecedented abilities,e.g.alignment-free fabrication,micro-and nanoscale capabilities,and rapid prototyping of almost arbitrary complex 3D nanostructures.In this review,we emphasize the importance of the criteria for optical performance evaluation of imaging devices,discuss material properties relevant to TPL,fabrication techniques,and highlight the application of TPL in optical imaging.As the first panoramic review on this topic,it will equip researchers with foundational knowledge and recent advancements of TPL for imaging optics,promoting a deeper understanding of the field.By leveraging on its high-resolution capability,extensive material range,and true 3D processing,alongside advances in materials,fabrication,and design,we envisage disruptive solutions to current challenges and a promising incorporation of TPL in future optical imaging applications.

THE EFFECT OF POLAR ADDITIVES ON THE γ RADIATION INDUCED POLYMERIZATION OF STYRENE

The γ induced polymerization of styrene in the presence of polar additives such as tributylphosphate, triethyl amine and ethanol was studied at dose rate of 5.0×10^(17) eV/ml. min. The re-sult shows that radiation induced polymerization of styrene was sensitized by the three kinds ofadditives at the approximate same rate and the experimental results were in agreement with thetheoretical calculation of WAS equation. The cause of sensitization is due to the proton transfer.

Functional additives for solid polymer electrolytes in flexible and high-energy-density solid-state lithium-ion batteries

Solid polymer electrolytes(SPEs)have become increasingly attractive in solid-state lithium-ion batteries(SSLIBs)in recent years because of their inherent properties of flexibility,processability,and interfacial compatibility.However,the commercialization of SPEs remains challenging for flexible and high-energy-density LIBs.The incorporation of functional additives into SPEs could significantly improve the electrochemical and mechanical properties of SPEs and has created some historical milestones in boosting the development of SPEs.In this study,we review the roles of additives in SPEs,highlighting the working mechanisms and functionalities of the additives.The additives could afford significant advantages in boosting ionic conductivity,increasing ion transference number,improving high-voltage stability,enhancing mechanical strength,inhibiting lithium dendrite,and reducing flammability.Moreover,the application of functional additives in high-voltage cathodes,lithium-sulfur batteries,and flexible lithiumion batteries is summarized.Finally,future research perspectives are proposed to overcome the unresolved technical hurdles and critical issues in additives of SPEs,such as facile fabrication process,interfacial compatibility,investigation of the working mechanism,and special functionalities.

Influence of polymer additives on turbulent energy cascading in forced homogeneous isotropic turbulence studied by direct numerical simulations

Direct numerical simulations （DNS） were performed for the forced homogeneous isotropic turbulence （FHIT） with/without polymer additives in order to elaborate the characteristics of the turbulent energy cascading influenced by drag-reducing effects. The finite elastic non-linear extensibility-Peterlin model （FENE-P） was used as the conformation tensor equation for the viscoelastic polymer solution. Detailed analyses of DNS data were carried out in this paper for the turbulence scaling law and the topological dynamics of FHIT as well as the important turbulent parameters, including turbulent kinetic energy spectra, enstrophy and strain, velocity structure function, small-scale intermittency, etc. A natural and straightforward definition for the drag reduction rate was also proposed for the drag-reducing FHIT based on the decrease degree of the turbulent kinetic energy. It was found that the turbulent energy cascading in the FHIT was greatly modified by the drag-reducing polymer additives. The enstrophy and the strain fields in the FH1T of the polymer solution were remarkably weakened as compared with their Newtonian counterparts. The small-scale vortices and the small-scale intermittency were all inhibited by the viscoelastic effects in the FHIT of the polymer solution. However, the scaling law in a fashion of extended self-similarity for the FHIT of the polymer solution, within the presently simulated range of Weissenberg numbers, had no distinct differences compared with that of the Newtonian fluid case.

Polymerization of Norbornene via an Iron-Based Complex/MAO Catalytic System

Polynorbornenes were synthesized in the presence of an iron based catalyst, 2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine iron(Ⅱ) dichloride. The FTIR, 1H NMR and 13C NMR analysis results revealed that the structure of the obtained polynorbornenes consisted of vinyl addition polymer substructures without any ring-opening structures. The polymers were amorphous with a short-range order, displayed in the WAXD(wide angle X-ray diffraction) diagrams. The glass transition temperatures ranged from 200 to 400 ℃. The effects of the polymerization reaction conditions, such as Al/Fe molar ratio and toluene/CH_2Cl_2 volume ratio, on the activity, intrinsic viscosity and T_g were also studied.

A FACILE APPROACH FOR THE SURFACE MODIFICATION OF POLY(VINYLIDENE FLUORIDE) MEMBRANE VIA SURFACE-INITIATED ATOM TRANSFER RADICAL POLYMERIZATION

A novel approach for the surface modification of poly(vinylidene fluoride)(PVDF)membrane was successfully realized through alkaline treatment,UV-induced bromine addition,and followed by surface-initiated atom transfer radical polymerization(ATRP)of methyl methacrylate(MMA).Chemical changes on the PVDF membrane before and after modification were analyzed with attenuated total reflectance Fourier transform infrared spectroscopy(ATR/FT-IR)and X-ray photoelectron spectroscopy(XPS).Primary kinetic study revealed...

Modified Vegetable Oil Based Additives as a Future Polymeric Material—Review

Polymeric materials from renewable resources have attracted a lot of attention in recent years. The development and utilization of vegetable oils for polymeric materials are currently in the spotlight of the polymer and chemical industry, as they are the largest renewable platform due to their universal wide availability, ingrained biodegradability, low cost, and excellent environmental aspects (i.e., low ecotoxicity and low toxicity toward humans). These excellent natural characteristics are now being taken advantage of in research and development, with vegetable oil derived polymers/polymeric materials/composites being used in numerous applications including paints and coatings, adhesives, and nanocomposites. The aim of this review paper is to give a fundamental description of the various vegetable oil applications in polymer materials and its recent developments. Particular emphasis will be placed on study and main application of triglyceride based additive for polymer and to give the reader an insight into the main developments is discussed.

ASSOCIATION OF ETHYLENE VINYL ACETATE COPOLYMER IN DILUTE SOLUTIONS IV. SOLVENT MIXTURE AND ADDITIVE EFFECT ON C_A

Critical association concentration (Ca) of ethylene-vinyl acetate copolymer (EVA) in selective solvent mixtures of 1,2-dichloroethane (DCE) (polar solvent) and cyclohexane (CYH) (non-polar solvent) was investigated. DCE is a good solvent for polyvinyl acetate (PVAc) and a poor solvent for paraffin, whereas CYH is a good solvent for the paraffin and a precipitant for PVAc. Viscosities of EVA in different compositions of the solvent mixture with and without additives were measured. Viscosity results were used to determine the C-A value of the systems. It is shown that C-A was markedly dependent on the composition of the solvent mixture and concentration and structure of the additive. Solvation and competition between hydrogen bonding and micellisation were suggested for qualitative description of the changing of C-A value observed.

Simulation of Rate Retardation in RAFT Polymerization of Styrene with Low RAFT-Initiator Ratio

Bulk polymerizations of styrene (St) were carried out in the presence of three reversible addition fragmentation chain transfer (RAFT) agents benzyl dithiobenzoate (BDB), cumyl dithiobenzoate(CDB), and 1-phenylethyl dithiobenzoate (PEDB) under low ratio of RAFT agent to initiator. The kinetic model was developed to predict polymerization rate, which indicates that the RAFT polymerization of St is a first-order reaction. In the range of experimental conversions, the plots of -ln(1-x) against time t are approximately linear (x is monomer conversion). The kinetic study reveals the existence of strong rate retardation in RAFT polymerization of styrene. A coefficient K_r is defined to estimate the rate retardation in the RAFT system considering the assumption that the retardation in polymerization rate is mainly attributed to slow fragmentation of the intermediate radicals. K_r relates to the structure of RAFT agents as well as the concentrations of RAFT agent and azobis isobutyronitrile (AIBN). For a certain RAFT agent, the value of K_r is enhanced by the increase in the initial concentration of RAFT agent and the higher ratio of RAFT to AIBN. With the same recipe for different RAFT agents, the increasing trend for the values of K_r is BDB<PEDB<CDB.

Large-eddy simulations of a forced homogeneous isotropic turbulence with polymer additives

Large-eddy simulations （LES） based on the temporal approximate deconvolution model were performed for a forced homogeneous isotropic turbulence （FHIT） with polymer additives at moderate Taylor Reynolds number. Finitely extensible nonlinear elastic in the Peterlin approximation model was adopted as the constitutive equation for the filtered conformation tensor of the polymer molecules. The LES results were verified through comparisons with the direct numerical simulation results. Using the LES database of the FHIT in the Newtonian fluid and the polymer solution flows, the polymer effects on some important parameters such as strain, vorticity, drag reduction, and so forth were studied. By extracting the vortex structures and exploring the flatness factor through a high-order correlation function of velocity derivative and wavelet analysis, it can be found that the small-scale vortex structures and small-scale intermittency in the FHIT are all inhibited due to the existence of the polymers. The extended self-similarity scaling law in the polymer solution flow shows no apparent difference from that in the Newtonian fluid flow at the currently simulated ranges of Reynolds and Weissenberg numbers.

Screening of Polymer Additives in Drinking Water Stored in PET Bottles by UHPLC-ESI-IT-TOF MS

In this study, Ultra High Performance Electrospray Ionization Ion Trap Time of Flight Mass Spectrometry （UHPLC-ESI-1T-TOF MS） method is used to screen the polymer additives in drinking water that is stored in Polyethylene Terephthalate （PET） bottles. After directly analyzing the commercially available water samples, 3 polymer additives （chimassorb 81, irgafos 168 and oleamide） were detected. However, after exposure to sunshine for 8 days, two additional polymer additives （antioxidant 2246 and Butylated Hydroxytoluene （BHT）） were detected besides the former three additives.

Drag reduction of flow boiling with polymer additives

The drag reducing effect of polymer additive aqueous solution was investigated in flow boiling, and the polymer additives were two kinds of polyacrylamide (PAM) with relative molecular mass about 2.56×10 6 and 8.55×10 6. The frictional pressure drop was calculated according to the measured total pressure drop. The results show that the flow drag of flow boiling is reduced by adding a small amount of PAM to water when heat flux is in the range of 15.1 kW·m -2 to 47.0 kW·m -2 , when the mass fraction of PAM is higher than 2.0×10 -5 , the drag reducing effect is obvious. Drag reducing effect of PAM, whose relative molecular mass is 8.55×10 6, is slightly better than that of 2.56×10 6 at the same mass fraction, and the greater the flow rate of the additive solution, the better the effect of the drag reduction.

Improved Transfer Process for the Fully Additive Manufacturing of a Conductive Layer-Stacked Polymeric Cantilever

This paper reports on an efficient fabrication process for a polymeric cantilever covered with conductive nano silver. The entire structure can be constructed additively using a printing process, without the use of an etching process or a sacrificial layer. The fabricated cantilever exhibits good linearity and forms a submillimeter-ordered air gap between itself and the substrate surface. Fine operation of a capacitive force gauge was obtained using the capacitance between the conductive cantilever and an electrode on the substrate. This process is expected to make possible the efficient manufacturing of various types of sensors that measure mechanical strain in a cantilever structure.

Application of New Polymeric Additive in Detergent for Automatic Dishwasher

This paper described a new type of multifunctional polymer Noverite^(TM) AD810's calcium ion chelating performance, tinted glass soaking test and its application in containing chlorine or enzyme automatic dishwashing detergent gel and powder. Results showed Noverite^(TM) AD810 has good performance in the final formulation on chelation, anti-filming, and anti-spotting, as well as to prevent the growth of scale crystals.

Molecular Dynamic Simulation on the Absorbing Process of Isolating and Coating of α-olefin Drag Reducing Polymer

The absorbing process in isolating and coating process of α-olefin drag reducing polymer was studied by molecular dynamic simulation method, on basis of coating theory of α-olefin drag reducing polymer particles with polyurethane as coating material. The distributions of sodium laurate, sodium dodeeyl sulfate, and sodium dodeeyl benzene sulfonate on the surface of α-olefin drag reducing polymer particles were almost the same, but the bending degrees of them were obviously different. The bending degree of SLA molecules was greater than those of the other two surfactant molecules. Simulation results of absorbing and accumulating structure showed that, though hydrophobie properties of surfactant molecules were almost the same, water density around long chain sulfonate sodium was bigger than that around alkyl sulfate sodium. This property goes against useful absorbing and accumulating on the surface of α-olefin drag reducing polymer particles; simulation results of interactions of different surfactant and multiple hydroxyl compounds on surface of particles showed that, interactions of different surfaetant and one kind of multiple hydroxyl compound were similar to those of one kind of surfaetant and different multiple hydroxyl compounds. These two contrast types of interactions also exhibited the differences of absorbing distribution and closing degrees to surface of particles. The sequence of closing degrees was derived from simulation; control step of addition polymerization interaction in coating process was absorbing mass transfer process, so the more closed to surface of particle the multiple hydroxyl compounds were, the easier interactions With isoeyanate were. Simulation results represented the compatibility relationship between surfactant and multiple hydroxyl compounds. The isolating and coating processes of α-olefin drag reducing polymer were further understood on molecule and atom level through above simulation research, and based on the simulation, a referenced theoretical basis was provided for practical optimal selection and experimental preparation of α-olefin drag reducing polymer particles suspension isolation agent.