Carboxyl terminated polyamide 12 chain extension by reactive extrusion using a dioxazoline coupling agent. Part I: Extrusion parameters analysis

Condensation reaction between a carboxyl terminated polyamide 12 (CTPA) (Mn = 2000 g mol^?1) and a dioxazoline [2,2′‐(1,3‐phenylene)‐bis(2‐oxazoline)] (OO) was achieved by reactive extrusion. Extrusion parameters effects on the process were analyzed through residence time distribution (RTD) and conversion distribution (CD) evolutions. RTD was measured using ultraviolet and ultrasonic detectable tracers. RTD measured along the extruder screws showed a decrease of the dimensionless variance (σ) with the reaction progress. Comparing measured molar masses and dispersity with those calculated using CD, competition between condensation and chain scission was detected. Effects of barrel temperature, screw profile, rotation speed and viscous dissipation on the reactive system evolution were analyzed and used for the process optimization. It was shown that a polyester amide with a Dp _n 12 can be obtained using this dioxazoline coupling agent by reactive extrusion.     

In the melt,grafting of polycarbonate onto polystyrene‐block‐poly(ethylene‐butylene)‐block‐polystyrene‐grafted‐maleic anhydride: Reactive extrusion

The use of reactions between polycarbonate (PC) and polystyrene‐block‐poly(ethylene‐butylene)‐block‐polystyrene‐ grafted‐maleic anhydride (SEBS‐g‐MAH) is a convenient way to create SEBS‐g‐PC. Grafting was realized by reactive extrusion at three temperatures using SnOct₂ or TBD catalysts. SEC analyses showed the apparition of a double distribution when the TBD was used. The mean residence time widely increased when this catalyst was used, and the rheological curves depicted a percolation effect of the SEBS nodules in the PC matrix. No explicit evolution was found with the use of SnOct₂. The thermal analyses showed the disappearance of the PC phase transition temperature. The Van Gurp‐Palmen plots confirmed the efficiency of the TBD catalyst and that 260°C was the optimal reactive extrusion temperature. POLYM. ENG. SCI., 54:2660–2668, 2014. © 2013 Society of Plastics Engineers     

Electron spin resonance study and reactive extrusion of polyacrylamide and polydiallyldimethylammonium chloride

In this article we report results from an experimental investigation on reactive extrusion of water‐soluble polymers. A polymer system containing homopolymers of diallyldimethylammonium chloride (PolyDADMAC) and acrylamide (PAM) was chosen for this study. Reactive extrusion was performed in a counter‐rotating, tangential twin screw extruder using glycerol as a plasticizer and 2,5‐dimethyl‐2,5‐di‐(t‐butylperoxy) hexene‐3 (Lupersol 130) as an initiator. The effects of three processing parameters (polyDADMAC/PAM weight ratio, extrusion temperature, and residence time) on grafting efficiency and degree of grafting of polyDADMAC on PAM were examined. We found the grafting efficiency of polyDADMAC onto PAM decreased with increasing extrusion temperature, polyDADMAC/PAM weight ratio, and residence time. The degree of grafting of polyDADMAC increased with increasing polyDADMAC/PAM weight ratio, but decreased with increasing extrusion temperature and residence time. The insoluble gel fraction in the extruded copolymer increased with increasing extrusion temperature and residence time, but decreased with increasing polyDADMAC/PAM weight ratio. The chemistry and free radical mechanism of PAM‐peroxide and polyDADMAC‐peroxide systems were studied for three different peroxides using an electron spin resonance technique. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1154–1164, 2000     

Esterification in reactive extrusion

A condensation type reaction has been studied for reactive extrusion in a twin-screw extruder. The esterification reaction is to graft a nonylphenyl-ethoxylate (NP8) onto a pre-maleated ethylene-propylene (EPR_MA). The kinetics were initially characterized in the static mixture using a thermally controlled call in a FTIR spectrometer. These were then used to predict the conversion along the length of the extruder screws, having determined the residence time distribution at various sampling locations. A reasonable fit with the data was obtained, although the kinetics seem to be slightly faster in the flowing medium than those predicted. Over short screw distances, the equilibrium rapidly approached equilibrium. Moreover, the NP8 was shown to penetrate the EPR_MA within screw distance of less than 1.3 L/D, despite using conveying elements known for their minimal mixing capacity. Within the molten medium, a mixing model showed that obtaining the expected conversion in a product does not imply that the reactants in the product have in fact been well mixed.     

Kinetic and rheokinetic study of dicarboxylic fatty acid chain extension using a dioxazoline coupling agent

A kinetic and rheokinetic study of the condensation reaction of a dicarboxylic fatty acid, Pripol®1009 (C36), and a dioxazoline coupling agent (1,3‐Phenylene)‐bis(2‐Oxazoline) (OO) was made. The kinetic study showed a similar reactivity of the two acid groups of C36 and also a similar reactivity of the two oxazoline groups of OO. The reaction kinetics can be described using a second‐order kinetic model. A kinetic constant k = 16.1 × 10⁻⁴ mol⁻¹ s⁻¹ at 156°C with an activation energy E_a = 80.6 kJ mol⁻¹ was calculated. A rheological evaluation of the reactants and the obtained polymers showed that the reactive system had Newtonian behavior during all the reaction times for shear rates lower than 100 s⁻¹. Using this kinetic modeling and measured viscosity evolution of the reactive system at different temperatures, rheokinetic models were proposed for viscosity evolution with the molar mass evolution of the synthesized polymer and the reaction time and conversion. Viscosity evolution of the reactive system during the first 10 min, corresponding to a typical mean residence time in reactive extrusion, were calculated using the proposed rheokinetic model. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1017–1024, 1999     

Preparation and reaction kinetics of polypropylene‐graft‐cardanol by reactive extrusion and its compatibilization on polypropylene/polystyrene

Polypropylene‐graft‐cardanol (CAPP) was prepared by reactive extrusion with polypropylene (PP) and natural renewable cardanol, which improved the inherent defects of PP such as its chemical inertness and hydrophobicity. Moreover, the cardanol grafted onto PP resolved the degradation of PP during reactive extrusion and use. The effects of reactive extrusion on the change of the molecular structure of PP, the change in the free‐radical concentration during processing, and the compatibilization of CAPP on the PP/polystyrene (PS) composite materials were examined in this study. The constants of the grafting reaction rate at the beginning of reactive extrusion were also deduced. The results show that cardanol was grafted onto PP, and the p–π conjugate system in cardanol was observed to stabilize free radicals. The grafting reaction rate (R_g) at the initial stage of the grafting reaction process was calculated through the equation R_g = k_g[M·][Cardanol], where k_g is the constant of the apparent grafting reaction rate and [M·] is the concentration of free radicals in the reaction system. k_g first increased with the growth of temperature and then began to decrease when the temperature exceeded the critical temperature of 200°C. The mechanical properties showed almost no change after the samples were aged for 72 h. This was due to CAPP, which changed PP/PS to a ductile material from a brittle one. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39911.     

Telomerization of Butyl Methacrylate and 1‐Octadecanethiol by Reactive Extrusion

Butyl methacrylate and 1‐octadecanethiol telomers were prepared by radical reactive extrusion. The main advantages of the use of this processing technique are that mass reactions can be conducted and continuous production is achieved within a reduced reaction time and a correct temperature control. Preliminary studies concerned the choice of the reactants for the telomerization reaction and the adaptation of the telomerization reaction to the reactive extrusion process. The transfer constant to C₁₈H₃₇SH was measured, and then experimental studies were conducted to verify that the hypothesis and approximations made for kinetic modeling are realistic. Particularly, it was shown that the use of relatively high chain‐transfer agent to monomer concentration ratio had no perceptible effect on the monomer conversion kinetic. These results allowed the choice of reactive extrusion conditions. Telomers were prepared using a laboratory co‐rotating twin‐screw extruder. The effect of reaction conditions (temperature, 1‐octadecanethiol to monomer concentration ratio) and of processing conditions (throughput, screw rotation speed) on the residence time distributions, molar mass and monomer conversions were examined. This study allowed the continuous synthesis of butyl methacrylate telomers having variable controlled molar masses and complete monomer conversion.

Screw profile used in reactive extrusion telomerization.     

Reactive extrusion vs. batch preparation of starch–g–polyacrylonitrile

Acrylonitrile (AN) was graft polymerized onto unmodified cornstarch by a continuous reactive extrusion process and, for comparison, by a typical batch reaction process. The effect of AN/starch weight ratios, level of ceric ammonium nitrate (CAN) initiator, starch in water concentration, reaction temperature, reaction time, and extruder screw speed in the reactive extrusion process was studied. Add-on, reaction efficiency, grafting frequency, weight average molecular weight (MW) and MW distribution of polyacrylonitrile (PAN), and water absorbency of the saponified copolymers were determined. Processing times in the twin-screw extruder (ZSK) were 2–3 min, and total reaction time was about 7 min before reaction of the extruded material was terminated, compared to a reaction time of 2 h used in the typical batch procedure. The continuous reactive extrusion process was found to be a rapid and efficient means of preparing St-g-PAN with high add-on (% PAN of the grafted product). For example, 42% add-on was achieved within the 7-min reaction period using an AN/starch weight ratio of 1.0 (3.5% CAN, starch weight basis), as compared to 38–49% for the 2-h batch process (0.75–1.5 AN/starch ratio). Percentages of homopolymer of the copolymers were low for both extrusion and batch processes. Grafting frequencies were substantially higher while MWs were significantly lower for grafts from the extrusion process. Water absorbency of the saponified St–g–PAN products was somewhat greater for the products prepared by the batch process.     

Preparation of highly filled wood flour/recycled high density polyethylene composites by in situ reactive extrusion

Highly filled wood flour/recycled high density polyethylene (WF/RHDPE) composites were directly prepared by in situ reactive extrusion using a twin‐screw/single‐screw extruder system. The effects of dicumyl peroxide (DCP) content on extrusion pressure, rheological behavior, mechanical properties, fractured surface morphology of the composites, and melting temperature of RHDPE in the composites were investigated. The extrusion pressure and torque of WF/RHDPE composite melt increased with DCP content. Mechanical property tests and scanning electron microscopy analysis results confirmed that the interfacial interaction of the composites was improved by in situ reaction. The composites show lower melting peak temperature (T_m) than RHDPE. The cooling in profile extrusion shortened the crystallization time, resulting in decrease of crystalline order of RHDPE in the composites. There are no noticeable changes of T_m values with increasing DCP content. Comparative study on composites with maleic anhydride grafted polyethylene as compatibilizer demonstrated that mechanochemical treatment with DCP and maleic anhydride was an effective method to improve interfacial adhesion for WF/RHDPE composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effect of extrusion processing conditions on EVOH/clay nanocomposites at low organo‐clay contents

Ethylene vinyl alcohol (EVOH) copolymer is studied as a host for low concentrations, up to 1 wt%, of organically treated clay. The clay develops a high interaction level with EVOH and thus high torque levels accompany the structuring process leading to the formation of nanocomposites. Extrusion residence time, successive extrusion passes, screw rotational speed, and processing temperature were all found to affect the morphology and the thermal and mechanical properties of the resulting composites. The extrusion compounded composites were subsequently injection molded. A subtle balance of processing parameters is required to achieve improved properties. Long extrusion residence times were found important for good clay dispersion in some cases, whereas in other cases an exfoliated structure was obtained already after the first extrusion pass. Two organically treated clay types processed at the same conditions were examined, and found to result in different morphology and mechanical behavior. Compression molding of extrusion compounded materials, under several extrusion conditions, was studied to illustrate the effect of shear level on the resulting morphology. The delamination level was higher after compression molding compared to that after injection molding. EVOH thermal properties and thermal stability of the related composites were also examined using differential scanning calorimetry and thermal gravimetric analysis. Higher extrusion processing temperature (220 compared to 200°C) was found to change the crystallization process of EVOH in the presence of clay, leading to significant decrease in T_m and T_c compared to that of the neat EVOH. POLYM. COMPOS., 26:343–351, 2005. © 2005 Society of Plastics Engineers     

Process Intensification of Living Cationic Polymerization of Isobutylene by a Flow Reaction System

Increasing the reaction temperature of the living cationic polymerization of isobutylene is crucial for industrial production due to the cost of refrigeration. The reaction temperature increase was achieved with an accelerated reaction rate using a flow reaction system. The polymerization conditions, including the flow reactor design, were based on the results of kinetic studies. Utilizing a milli‐scale flow reactor, polyisobutylene, which has a narrow molecular weight distribution, was obtained within a considerably short residence time at a high temperature. Furthermore, it was confirmed that the value of M_w/M_n correlates with the product of the Reynolds number and the angle of collision.     

Reactive extrusion to synthesize intumescent flame retardant with a solid acid as catalyst and the flame retardancy of the products in polypropylene

Reactive extrusion and solid acid catalysis technologies were adopted in the pentaerythritol–melamine phosphate (PER‐MP) reaction to synthesize intumescent flame retardant, melamine salt of pentaerythritol phosphate (MPP), which was applied in flame retardant polypropylene (PP). This environment‐friendly synthesis method provided a solution to the problems of conventional methods. On one hand, reactive extrusion in a twin screw extruder can effectively mix and transfer viscous materials that usually results in a tough stir in a conventional reactor, and achieve a continuous synthesis process. On the other hand, the solid acid, silicotungstic acid (STA) serving as a catalyst, can maintain a satisfactory conversion even with a low extrusion temperature and a short residence time, thus effectively suppressing foaming in the process of the reaction. Furthermore, without removal like other catalysts in general chemical reactions, STA was kept in produced MPP to constitute a synergism flame retardant system, therefore further improved the flame retardancy. LOI and UL94 test showed that the STA‐catalyzed MPP (by reactive extrusion) possessed much better flame retardancy in PP when compared with the noncatalyzed MPP (by reactive extrusion), as well as present commercial MPP (by POCl₃ method). In our investigation, the catalytic and synergistic effects of STA, as well as the related factors of the reactive extrusion affecting the conversion of the PER‐MP reaction, flame retardancy and mechanical performance of the corresponding flame retardant PP, were systematically investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly[ethylene‐co‐(vinyl alcohol)]‐graft‐Poly(ε‐caprolactone) by Reactive Extrusion, 2 – Parameter Analysis

EVOH‐g‐PCL were prepared by a solvent‐free reactive extrusion process using a co‐rotating twin screw extruder. Kinetic simulations were made of selected reaction conditions at 185 °C. Changes in the screw rotation rate resulted in evolution of the residence time distribution and slightly changed the monomer conversion. An increase of the [OH]₀/[Cl]₀ ratio made the reactive system more viscous and decreased the overall pumping capacities of the extruder. Increase of the mean residence time, combined with a positive kinetic effect of [OH]₀ increase, leaded to an important increase in conversion. For all the conducted experiments, equivalent distribution dispersions and good agreements between calculated conversion and those measured were obtained. An increase in temperature from 185 to 200 °C resulted in total conversion.

     

Reactive extrusion of in-situ composite based on PET and LCP blends

The “in-situ” compatibilization for a PET/LCP blend via transesterification reactions in a twin-screw extruder having a very short residence time is investigated through thermal, rheological, and mechanical studies. Inclusion of a small amount of liquid crystalline polymer (LCP) enhanced the crystallization rate of the poly(ethylene terephthalate) (PET) matrix. It acted as a nucleating agent. LCP lowered the blend viscosity above T_cn (crystalline-nematic transition temperature), working as a processing aid. However, the addition of dibutyltindilaurate (DBTDL) as a reaction catalyst was found to increase the viscosity of the blends, diminish the size of the dispersed phase, enhance its adhesion with the matrix, and lead to an increase of mechanical properties of two immiscible phases. Hence DBTDL is helpful in producing a reactive compatibilizer by reactive extrusion at the interface of this polyester blend system. The optimum catalyst amount turned out to be about 500 ppm when the reaction proceeds in 90/10 PET/LCP polyester blend systems. Its effect on the mechanical properties is discussed in detail. The structural change of reactive blend was identified by H¹ NMR and wide angle X-ray diffraction patterns.     

Characteristic analysis on a reactive extrusion process for the imidization of poly(styrene-co-maleic anhydride) with aniline

The imidization of poly(styrene-co-maleic anhydride) (SMA) with aniline by reactive extrusion is investigated in a co-rotating twin-screw extruder. During this reactive extrusion, the process temperature is much higher than the boiling point of the aniline. Accordingly, most of the aniline should be vaporized immediately after being fed into the extruder, occupies the unfilled part of the extruder, and is transferred to the melt phase where it is consumed through the reaction. Based on the mechanism of this vapor-melt heterogeneous process and experimental data for residence time distribution (RTD) in the extruder, a continuous process model is developed. The effects of operating conditions including temperature, throughput, and screw rotation speed on the reaction kinetics are discussed by both experimental data and model simulation. The results indicate that the residence time and the mass transport of aniline from vapor to melt phase should play significant roles in this heterogeneous reactive extrusion process.     

Reactive extrusion of acrylic acid grafted polypropylene with hexadecylamine

To study the possibility of the production of branched polypropylene (PP) by a reactive extrusion (REX) route, side chains were introduced on the backbone of a polypropylene material by reacting hexadecylamine with acrylic acid grafted PP. Experiments were carried out both in solution and in the melt, and the products were analyzed by FTIR, elemental analysis, dynamic mechanical, and rheological techniques. Analysis of the FTIR spectra of the samples produced in the solution reactions, at an equal molar ratio of [ –NH₂]/[–COOH] without catalyst addition and without removal of the by-product, revealed that the formation of imide was increased with increasing the reaction time up to 10 h, while a further increase in reaction time resulted in a reversal of the reaction. In the REX experiments, FTIR analysis showed that the imide formation increased with the [–NH₂]/[–COOH] molar ratio. At a molar ratio of one, more imide was present in the REX product than the in-solution one. Elemental analysis suggested that the nitrogen content in the products initially increased with [–NH₂]/[–COOH] molar ratio and then reached an almost constant value at molar ratio values of about unity. The glass transition temperature (T_g) was measured by dynamic mechanical analysis (DMA), and it was found that the attachment of the alkyl chains caused a reduction in T_g of the products. Finally, rheological measurements showed that the shear viscosity of the products increased with the amine/carboxyl molar ratio at low shear rates and that their moduli were enhanced as a result of the attachment of the alkyl side chains.     

Continuous Methanolysis of Palm Oil Using a Liquid–Liquid Film Reactor

A system for the continuous methanolysis of palm oil using a liquid–liquid film reactor (LLFR) was developed and characterized. This reactor is a co-current, constant diameter (0.01 m), custom-made packed column where the mass transfer area between the partially miscible methanol-rich and vegetable oil-rich phases is created in a non-dispersive way, without the intervention of mechanical stirrers or ultrasound devices. An increase in contact area between phases enhances reaction rate while the absence of small, dispersed droplets of one phase into the other diminishes the settling time at the end of the reaction. In this study variations on the concentration of catalyst (sodium hydroxide), flow rate of palm oil and normalized length of the reactor (L/L _max) were explored, keeping constant both the methanol to oil molar ratio and the temperature of the reaction (6:1 and 60 °C). The best experimental results with a reactor of 1.26 m (L/L _max = 1.0) showed a conversion of palm oil of 97.5% and a yield of methyl esters of 92.2% of the theoretical yield, when the mass flow rate and the residence time of the palm oil were 9.0 g min⁻¹ and 5.0 min, respectively. To determine the mean residence time and the degree of axial mixing in the reactor, a residence time distribution (RTD) study was performed using a step-function input. The dispersion model appears to fit well the RTD experimental data.     

Proposal and verification of a kinetic mechanism model for NOx removal with hydrazine hydrate

A relatively precise kinetic mechanism of NO_x reduction using N₂H₄·H₂O in a selective non‐catalytic reduction process was proposed and verified by experiment in this study. The dominant radicals and reactions were confirmed, and the proper ranges of key parameters were determined through sensitivity analysis. Both experimental and simulation results show that the effective temperatures exhibit a bimodal distribution with the optimum temperatures being approximately 893 and 1248 K and the lower temperature window falling in the range of 848–973 K. The optimum residence time of the reaction was 0.2–0.35 s under the research conditions, and a longer residence time would lead to the regeneration of NO_x. The normalized stoichiometric ratio (NSR) of 3.0 corresponded to the lowest temperature window, and a higher NSR value would make the temperature window shift to a higher temperature range. This kinetic mechanism model for the N₂H₄·H₂O‐based De‐NO_x process will serve its precise application. © 2014 American Institute of Chemical Engineers AIChE J, 61: 904–912, 2015     

Synthesis and characterizations of poly(ethylene-co-vinylalcohol)-grafted-poly(3-hydroxybutyrate-co-hydroxyvalerate) copolymers

Poly(ethylene-co-vinylalcohol)-grafted-poly(3-hydroxybutyrate-co-hydroxyvalerate) (EVOH-g-PHBV) was prepared by a catalyzed grafting of PHBV onto immiscible EVOH. These reactions were performed at high temperature in the molten state. The choices of Tin(II) bis(2-ethylhexanoate) (Sn(Oct)₂) and 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), as catalyst, were justified by a first study in an internal mixer. The catalyst quantity, reaction temperature and reaction time were optimized to apply them in the conditions of a reactive extrusion process with a co-rotating twin screw extruder. High reaction temperature, from 180 °C to 220 °C, associated to intensive mixing led to efficient grafting of PHBV onto EVOH, compatible with short residence times required.Rheological, thermal and morphological analyses were conducted to characterize the obtained copolymers. Molecular weights were determined by SEC. SEM imaging were made on cryo-fractured surfaces of blends extruded with and without catalyst. In most of reaction conditions, a compatible blend was obtained with a fine micro phase separation. Grafted copolymers were only obtained when well defined and controlled conditions are applied.     

Radiation-induced polymerization of ethylene in pilot plant. IV. Kinetic analysis

The kinetics of the radiation-induced polymerization of ethylene in a flow system using tert-butyl alcohol aqueous solution as a medium were studied. The polymerization was carried out in a large-scale pilot plant with a 50-liter central source-type reactor at various mean residence times and does rates under constant pressure of 300 kg/cm², temperature of 30°C, and ethylene molar fraction of ca. 0.4. The reaction mixture in the reactor was back-mixed flow from the residual polymer concentration in the reactor. The results of the polymerization were analyzed by kinetic treatment based on a reaction mechanism with both first-and second-order terminations for the propagating radical. The apparent rate constants, except for that of second-order termination (k_t2), were consistent with those determined by small-scale batch experiments. The k_t2 is 20 to 40 times larger than that in the batch experiments. The k_t2 increases with decrease in mean residence time and with agitation, probably because of mobility of the propagating radical.