Versatility of a succinimidyl‐ester functional alkoxyamine for controlling acrylonitrile copolymerizations

Styrene/acrylonitrile (S/AN) and tert‐butyl methacrylate/acrylonitrile (tBMA/AN) copolymers were synthesized in a controlled manner (low polydispersity $ {{\overline M _w } / {\overline M _n }} $ with linear growth of number average molecular weight $ \overline M _n $ vs. conversion X) by nitroxide mediated polymerization (NMP) with a succinimidyl ester (NHS) terminated form of BlocBuilder unimolecular initiator (NHS‐BlocBuilder) in dioxane solution. No additional free nitroxide (SG1) was required to control the tBMA‐rich copolymerizations with NHS‐BlocBuilder, a feature previously required for methacrylate polymerizations with BlocBuilder initiators. Copolymers from S/AN mixtures (AN molar initial fractions f_AN,0 = 0.13–0.86, T = 115°C) had $ {{\overline M _w } / {\overline M _n }} $ = 1.14–1.26 and linear $ \overline M _n $ versus conversion X up to X ≈ 0.6. tBMA/AN copolymers (f_AN,0 = 0.10–0.81, T = 90°C) possessed slightly broader molecular weight distributions ( $ {{\overline M _w } / {\overline M _n }} $ = 1.23–1.50), particularly as the initial composition became richer in tBMA, but still exhibited linear plots of $ \overline M _n $ versus conversion X up to X ≈ 0.6. A S/AN/tBMA terpolymerization (f_AN,0 = 0.50, f_S,0 = 0.40) was also conducted at 90°C and revealed excellent control with $ \overline M _n $ = 13.6 kg/mol, $ {{\overline M _w } / {\overline M _n }} $ = 1.19, and linear $ \overline M _n $ versus conversion X up to X = 0.54. Incorporation of AN and tBMA in the final copolymer (molar composition F_AN = 0.47, F_tBMA = 0.11) was similar to the initial composition and represents initial designs to make tailored, acid functional AN copolymers by NMP for barrier materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Lewis acid–base properties of cellulose acetate phthalate‐polycaprolactonediol blend by inverse gas chromatography

The net retention volumes, V_N, of n‐alkanes and five polar probes are determined on cellulose acetate phthalate–polycaprolactonediol blend column by inverse gas chromatography in the temperature range 323.15–363.15 K. The dispersive surface energy, $\gamma _{\bf S}^{\bf d}$ , of the blend has been calculated using the V_N values of n‐alkanes and the $\gamma _{\bf S}^{\bf d}$ at 333.15 K is 12.6 mJ/m². The $\gamma _{\bf S}^{\bf d}$ values are decreasing linearly with increase of temperature. The V_N values of the five polar solutes are used to calculate the specific component of the enthalpy of adsorption, ${\Delta }{H}_{\bf a}^{\bf S}$ . The Lewis acid–base parameters, K_a and K_b, are derived using ${\bf \Delta }{H}_{\bf a}^{\bf S}$ values and are found to be 0.019 and 0.403, respectively. The K_a and K_b values indicate that the blend surface contain more basic sites and interact strongly with the acidic probes. The acid–base parameters have been used to analyze the preferential interaction of the solid surface with acidic and basic probes. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Tailoring the Degree of Polymerization of Low Molecular Weight Cellulose

The degradation of cellulose to lmw samples with $\overline {DP} _{{\rm w}} $ varying from 15 to 130 is investigated. Cellulose samples prepared from the hydrolysis of regenerated cellulose fibers in dilute HCl possess $\overline {DP} _{{\rm w}} $ = 50. Applying homogenous degradation of microcrystalline cellulose in H₃PO₄ at RT for 3 weeks, samples with $\overline {DP} _{{\rm w}} $ = 35 and a PDI of 1.58 are obtained. Decreasing the hydrolysis temperature to 8 °C results in lmw cellulose with $\overline {DP} _{{\rm w}} $ > 70. Fractionation in DMA/LiCl provides samples with $\overline {DP} _{{\rm w}} $ = 12 to 130, together with a narrow molecular weight distribution. Detailed structural analysis by 2D NMR spectroscopy reveals that the prepared lmw celluloses are suitable as mimics for cellulose.

     

Effect of Processing Variables on the Morphology of Electrospun Poly[(lactic acid)‐co‐(glycolic acid)] Nanofibers

A systematic study of the effects of , flow rate, voltage, and composition on the morphology of electrospun PLGA nanofibers is reported. It is shown that changes of voltage and flow rate do not appreciably affect the morphology. However, the of PLGA predominantly determines the formation of bead structures. Uniform electrospun PLGA nanofibers with controllable diameters can be formed through optimization. Further, multi‐walled carbon nanotubes can be incorporated into the PLGA nanofibers, significantly enhancing their tensile strength and elasticity without compromising the uniform morphology. The variable size, porosity, and composition of the nanofibers are essential for their applications in regenerative medicine.

     

Correlation of Sequence Block Lengths and Degree of Randomness with Melt Rheological Properties in PET/PEN Blends

PET/PEN blends were prepared over the full composition range via a melt mixing process under various processing conditions. This resulted in transesterification reactions and formation of copolymer structures with various average sequence block lengths and degree of randomness (RD) determined by ¹H NMR. It was seen that with an increase in time and temperature of mixing copolymer content (TEN%) and RD increased, whereas the , values were decreased. The differences in the extent of transreactions arising from different processing histories showed their systematic influence on rheological characteristics. Moreover due to progress of transreactions during the rheological measurements, convergence was seen in all the rheological characteristics at terminal zones in the high frequency regions. Similar convergence in the copolymer structural parameters was also obtained by NMR analysis. An increase in TEN% led to a systematic increase in viscosity of the blends. A decrease in the , values results in an increase in elasticity and relaxation time due to improvement of blend interface with increase in extent of copolymer formation.

     

Correlations between the Shape of Viscosity Functions and the Molecular Structure of Long‐Chain Branched Polyethylenes

The viscosity functions of long‐chain branched metallocene‐catalyzed ethene homopolymers and copolymers (LCB‐mPE) were described by an extended Carreau‐Yasuda model. The two characteristic relaxation times, λ₁ and λ₂, and the slope of the viscosity function between these two characteristic relaxation times can be correlated to the zero shear‐rate viscosity, η₀, and the molar mass . The characteristic relaxation times, λ₁ and λ₂ (describing the main curvatures of the viscosity function) exhibit a power law dependency on the molar mass, . The parameterization of the viscosity function can be used for a molecular characterization and flow simulations of various kinds.

     

Hybrid organic/inorganic dendritic triblock copolymers: Synthesis,nanostructure characterization,and micellar behavior

A new class of amphiphilic dendritic ABA triblock copolymers, which is based on organic linear polyethylene oxide (PEO) and inorganic dendritic carbosiloxane (CSO) was synthesized. The strategy used in synthesizing these materials is based on divergent method using hydrosilylation‐alcoholysis cycles. The reaction conditions and structural features of dendrimers were analyzed by different physicochemical techniques such as: GPC, NMR, UV spectroscopy, DSC, and viscometry. The generational limit of dendrimer after the first generation, OSC‐D‐PEO‐D‐CSO, forced us to employ HSiCl₂CH₃ as branching reagent. Also further hydrosilylation of the third generation yielded an irregular structure species. Self‐assembling and morphological studies of first, OSC‐D‐PEO‐D‐CSO, and second, OSC‐D‐PEO‐D‐CSO, generations in aqueous medium were monitored by using fluorescence, TEM and DLS techniques. However, the dendritic block copolymer with third generation, OSC‐D‐PEO‐D‐CSO, could not be dispersed in aqueous phase. The diameters of denderitic micelles had a narrow distribution in the ranges of 69 and 88 nm, respectively. Although the micelles were stable even in first generation, partition equilibrium constants of pyrene and critical micelle concentration in both of dendritic micelles imply that the micellar behaviors of the supramolecules strongly depend on the hydrophobic block's size in which increasing generation effectively promoted the micelle formation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical and surface properties and hydrolytic stability of cycloaliphatic polyester‐based waterborne polyurethanes modified with fluoro oligomer

Polyurethane dispersions (PUDs) have been designed and synthesized based on different types of soft segments, namely, poly(2,4‐diethyl‐1,5‐pentamethylene adipate) glycol (PDPAD; = 1000) and poly(2,4‐diethyl‐1,5‐pentamethylene‐1,4‐cyclohexane dicarboxylate) glycol (PDPCD; = 1000), and were subsequently modified with fluoro oligomer (BA‐N fluoroalcohol). It was found that the PDPCD segments improved the hydrolytic stability, whereas the contact angle with water drop was significantly increased with the addition and increasing amount of Zonyl for PDPAD‐based PU and it was marginally increased with PDPCD‐based PU. In addition, the PDPCD provided PUD with enhanced mechanical properties compared with the PDPAD. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Determination of crystallinity ratio and some physicochemical properties of poly(4‐methyl‐1‐pentene)

It was determined that the thermal stability of poly(4‐methyl‐1‐pentene) (P4MP) was maintained up to 424°C in an inert atmosphere by thermogravimetric analysis. The retention diagrams of ethyl acetate, tert‐butyl acetate, and benzene on P4MP were plotted at temperatures between 30 and 280°C by inverse gas chromatography (IGC) technique. Melting temperature of the polymer was determined as 230 and 239.5°C by IGC and differential scanning calorimetry (DSC), respectively. The percent crystallinity of P4MP was obtained from the retention diagrams at temperatures below melting point. The percent crystallinity obtained by IGC is in good agreement with the ones obtained by DSC. Then, specific retention volume, V, weight fraction activity coefficient, Ω, Flory‐Huggins polymer‐solvent interaction parameter, χ, equation‐of‐state polymer‐solvent interaction parameter, χ, and effective exchange energy parameter, X_eff of octane, nonane, decane, undecane, dodecane, tridecane, n‐butyl acetate, isobutyl acetate, isoamyl acetate with P4MP, were determined between 240 and 280°C by IGC. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Characteristics of anthraquinone hydrogenation catalysts in a liquid‐solid fluidized bed

The fluidization characteristics of anthraquinone hydrogenation catalysts were investigated in a liquid–solid fluidized bed. The effects of the initial bed conditions such as particle size, bed depth‐to‐column diameter ratio and liquid density and viscosity on the fluidization behaviour, bed expansion and applicability of the Richardson–Zaki equation were studied. The results reveal a strong particle size effect on the Richardson–Zaki (R‐Z) expansion index which in general decreased as the particle diameter increased. One type of particles exhibited two distinct bed expansion behaviours, depending mainly on the bed depth‐to‐column diameter ratio, with an experimentally established boundary at . This behaviour could be attributed to increasing wall friction and a tendency to exhibit slugging. The dependence of the Richardson–Zaki exponent on the liquid dynamic viscosity confirms the classic result .     

Synthetic Inhibitors of Extended Helix–Protein Interactions Based on a Biphenyl 4,4′‐Dicarboxamide Scaffold

Turn Bak : We present rationally designed scaffolds that mimic the spatial projection of the i, i+4, i+7, and i+11 residues of an α‐helix. A library of biphenyl derivatives was shown by competition fluorescence polarization and ITC to mimic Bak and disrupt the Bak/Bcl‐x_L protein–protein interaction. ¹⁵N HSQC experiments confirmed that the surface of Bcl‐x_L normally occupied by Bak was the target area of our new synthetic inhibitors.

     

Effect of microstructure on crazing onset in polyethylene under tension

The influence of microstructure on dilatation onset is analyzed in polyethylene (PE) under tension. Tests are performed by means of a video‐controlled testing system that gives access to true stress σ₃₃—true strain ε₃₃ curve and records volume strain ε_v during stretching. The results indicate that the strain ε (and the corresponding stress σ) from which viscoplastic dilatation begins depends on microstructural properties of PE. At microscopic scale, materials having a low ε are characterized by inhomogeneous deformation mechanisms leading to pronounced crazing phenomena in amorphous layers. On the contrary, materials having a high ε involve homogeneous deformation mechanisms that limit crazing. These observations are discussed on the basis of crystallinity and tie molecules density. A simple model predicting ε is developed from these microstructural aspects. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Adsorptive removal of nitrate and phosphate anions from aqueous solutions using functionalised SBA‐15: Effects of the organic functional group

Adsorption of nitrate and monovalent phosphate anions from aqueous solutions on mono, di‐ and tri‐ammonium‐functionalised mesoporous SBA‐15 silica was investigated. The adsorbents were prepared via a post‐synthesis grafting method, using either 3‐aminopropyltrimethoxysilane (N‐silane) or [1‐(2‐aminoethyl)‐3‐aminopropyl]trimethoxysilane (NN‐silane) or 1‐[3‐(trimethoxysilyl)‐propyl]‐diethylenetriamine (NNN‐silane), followed by acidification in HCl solution to convert the attached surface amino groups to positively charged ammonium moieties. The nominal loading of amino moieties on the SBA‐15 surface was varied from 5% to 20% as organoalkoxysilane/silica molar ratio. The adsorption experiments were conducted batchwise at room temperature. Results showed that adsorption capacity increased with increasing the concentration of monoammonium groups on the SBA‐15 adsorbent. Nitrate adsorption capacity increased from 0.34 to 0.66 mmol ${\rm NO}_{3}^{{-} } /{\rm g}$ adsorbent while phosphate adsorption capacity increased from 0.34 to 0.63 mmol ${\rm H}_{2} {\rm PO}_{4}^{{-} } /{\rm g}$ adsorbent when the molar ratio organoalkoxysilane/silica was varied from 5% to 20%, respectively. Also, for the same organoalkoxysilane/silica molar ratio of 10%, the adsorption capacity increased with the increase of the number of protonated amines in the functional groups. Therefore, maximum adsorption capacities of 0.80, 1.16 and 1.38 mmol ${\rm NO}_{3}^{{-} } /{\rm g}$ adsorbent and 0.72, 0.82 and 1.17 mmol ${\rm H}_{2} {\rm PO}_{4}^{{-} } /{\rm g}$ adsorbent were obtained using mono‐, di‐ and triammonium functionalised SBA‐15 adsorbents, respectively. © 2011 Canadian Society for Chemical Engineering     

Poly[ethylene‐co‐(vinyl alcohol)]‐graft‐poly(ε‐caprolactone) Synthesis by Reactive Extrusion, 1 ‐ Structural and Kinetic Study

Chemical modification of EVOH in the molten state at 185 °C by a grafting from process of poly(ε‐caprolactone) in batch was studied. ¹H NMR was used to characterize the structure evolutions of PCL grafts. In addition to grafting reactions, dynamic covalent transesterification reactions between EVOH residual alcohols and the polyester grafts led to a redistribution of the PCL grafts length. up to 27 and SR up to 80% were obtained. Experiments made in a corotating mini twin‐screw extruder also confirmed these results. The effect of the alcohol to caprolactone ratio and catalyst concentration (SnOct₂) on kinetic evolution showed that few minutes were necessary to complete the polymerization. A kinetic model was proposed and adequate conditions for the synthesis by reactive extrusion were defined.

     

Solution and diffusion properties of cyclohexane,cyclohexanol, and cyclohexanone in poly(ethylene glycol) by inverse gas chromatography

The solution and diffusion properties of cyclohexane, cyclohexanol, and cyclohexanone in poly(ethylene glycol) (PEG) and crosslinked PEG have been studied in the temperature range of 368.15 to 403.15 K using inverse gas chromatography (IGC) technique. The infinite dilute activity coefficient (Ω) and diffusion coefficient (D) have been determined for the above solvent/polymer systems. Accordingly, several thermodynamic functions, the diffusion pre‐exponential factor, and activation energy have been attained. The results showed a decrease in Ω and an increase in D with rising temperature. The order of the relative magnitude of Ω and D of the solvents were explained by comparing their interactions with the polymer and their collision diameters, respectively. Moreover, Ω and D in crosslinked PEG were smaller than those in PEG at various temperatures. The analysis of Ω, the infinite dilute selectivity and capacity showed the possibility of using crosslinked PEG as an appropriate membrane material for the separation of cyclohexane, cyclohexanol, and cyclohexanone mixture. A thermodynamic study also implied that the solvent sorptions in the polymers were all enthalpically driven in the experimental range. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Preparation and characterization of polystyrene modified single‐walled carbon nanotube

A halogen atom terminated Polystyrene (PSt) was prepared by means of atom transfer radical polymerization. Then, the halogen atom was converted into ‐N₃ group and a ‐N₃ terminated PSt was obtained. Finally PSt was grafted onto the surface of single walled carbon nanotube (SWNT) by the reaction of azide group with SWNT. Comparison of X‐ray photoelectron spectrometer of N1s electron belonging to ‐N₃ and the surface of SWNT demonstrated that three‐membered rings were formed by releasing N₂ from ‐N₃ during the reaction. The structure of PSt modified SWNT was characterized by FTIR, UV, Raman spectrum, and TEM. The experimental results showed that the PSt was connected assuredly to SWNT by the covalent bond. TGA data showed that the amount of PSt on the surface of SWNT firstly increased with growing of PSt and then decrease when continues to grow. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Ring‐opening metathesis polymerization of bicyclo[2.2.1]hepta‐2,5‐diene (norbornadiene) initiated by new ruthenium(II) complex

The polymerization of norbornadiene (NBD) initiated by a novel ruthenium (Ru)(II) complex ( 3 ) containing 1,1′‐pyridine‐2,6‐diylbis[3‐(dimethylamino)prop‐2‐en‐1‐one] ( 1 ) as ligand has been investigated. Ru complexes exhibit more catalytic activity in the ring‐opening metathesis polymerization (ROMP) of NBD when activated with trimethylsilyldiazomethane (TMSD). The influence of the various experimental parameters such as reaction time and temperature, nature of the solvent and catalyst, ratio of the NBD/Ru, and TMSD addition has been investigated. The polymers have been obtained in high yields with a relatively low polydispersity index for ROMP and a high $ \bar M_n $ and $ \bar M_w $ values in a monomodal distribution. Their structures have been determined by means of FTIR and ¹H‐NMR spectroscopy. Thermal properties have been determined via thermogravimetric analysis and DTG methods. The NBD polymerization results that initiated by Ru‐based catalyst coordinated to amine ligand have been compared to initiated by [RuCl₂(p‐cymene)]₂. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Experimental Correlation between Mechanical Non‐Linearity in LAOS Flow and Capillary Flow Instabilities for Linear and Branched Commercial Polyethylenes

An experimental correlation between the non‐linear behaviour of commercial polyethylene melts in LAOS flow, and the pressure fluctuations associated with melt flow instabilities developed in capillary rheometry are presented. Polyethylene melts with enhanced non‐linear behaviour under LAOS conditions present larger pressure fluctuations during capillary extrusion, and consequently, larger surface distortions on the extrudate. The combination of both methods can be a tool to predict the development of melt flow instabilities in the extrusion process of polyethylene melts, and can elucidate their correlation with material structural properties ( , MWD and topology).

     

Liquid–solid mass transfer for cocurrent gas–liquid upflow through solid foam packings

This article presents the liquid–solid mass transfer characteristics for cocurrent upflow operated gas–liquid solid foam packings. Aluminum foam was used with 10, 20, and 40 pores per linear inch (PPI), coated with 5 wt % Pd on γ‐alumina. The effects of gas velocity (u_g = 0.1?0.8 m m s^?1) and liquid velocity (u_l = 0.02 and 0.04 m m s^?1) are studied using the Pd/Bi catalyzed oxidation of glucose. The volumetric liquid–solid mass transfer coefficient, k_lsa_ls, is approximately the same for 10 PPI and 20 PPI solid foams, ranging from 2 × 10^?2 to 9 × 10^?2 m m s^?1. For 40 PPI solid foam, somewhat lower values for k_lsa_ls were found, ranging from 6 × 10^?3 to 4 × 10^?2 m m s^?1. The intrinsic liquid–solid mass transfer coefficient, k_ls, increases with increasing liquid velocity and was found to be proportional to u. Initially, k_ls decreases with increasing gas velocity and after reaching a minimum value increases with increasing gas velocity. The values for k_ls range from 5.5 × 10^?6 to 8 × 10^?4 m m s^?1, which is in the same range as found for random packings and corrugated sheet packings. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Rheological Features and Flow‐Induced Crystallization of Branched Poly[ethylene‐co‐(1,4‐cyclohexanedimethylene terephthalate)] Copolyesters

A set of amorphous poly[ethylene‐co‐(1,4‐cyclohexanedimethylene terephthalate)] (PECT) copolymers containing 25 and 30% of 1,4‐cyclohexane dimethylene (CHDM) units and small amounts of branching agent pentaerythritol (PER) is investigated. The level of long chain branching was estimated by analyzing the positive deviation from law. Branching also produced melt elasticity enhancement which is desirable for certain processing methods. Capillary extrusion experiments at 180 °C generated flow‐induced crystallization in PECT containing 25% of CHDM. Crystallization increased with the amount of PER added, which was explained by the favorable effect of branching to increase elongational rate at the entrance of the capillary. Linear and branched PECTs containing 30% of CHDM did not crystallize.