This work aims at deriving analytical solutions for the molecular architecture of multi‐block polymer synthesized in a dual‐catalyst single CSTR. While the relevant equations are developed for homopolymerization, they can easily be extended to copolymerization. Special emphasis is placed on the quantities associated with each catalyst rather than the overall ones. However, if all rate parameters are available, the expressions can be used to calculate the properties of the material made by each catalyst as well as the overall ones under various process conditions. Given the reasonable assumption of large residence time, the solutions are simplified to elucidate the kinetics of chain‐shuttling involving two catalysts. It is shown that systems with low chain‐shuttling ability, if DPPn,0 ≠ DPQn,0, may exhibit significant deviation from Flory's most probable distribution. Furthermore, systems with high chain‐shuttling ability produce macromolecules with more uniform architecture and polydispersity index close to 2.
Cellulose nanocrystals (CNCs) are renewable, nontoxic and naturally available organic nanoparticles derived from cellulosic resources such as cotton and wood pulp. Poly(n‐butyl acrylate‐co‐methyl methacrylate)/CNC latexes are successfully synthesized via in situ emulsion polymerization. The effect of CNC loading on overall conversion, polymer particle size, glass transition temperature (Tg), gel content, latex viscosity, and storage and loss moduli of dried latex are studied. While the effect of CNC content on overall conversion, polymer particle size, and Tg of the resulting latexes is negligible, significant increase in gel content, latex viscosity, and storage and loss moduli are observed.
ArF candidate photoresist polymers have been synthesized by nitroxide mediated polymerization (NMP). Statistical copolymerizations of α‐gamma butyrolactone methacrylate, 3‐hydroxy‐1‐adamantyl methacrylate, and 2‐methyl 2‐adamantyl methacrylate with 5–10 mol% of controlling comonomers (i.e., styrene, p‐acetoxystyrene, 2‐vinyl naphthalene, acrylonitrile, and pentafluorostyrene), which are necessary for controlled polymerization of methacrylates by NMP with the unimolecular alkoxyamine initiator BlocBuilder, have been used. As little as 5 mol% controlling comonomer in the feed is demonstrated to be sufficient to produce linear evolution of number average molecular weight against conversion (X) up to X = 0.7 for relatively low target degrees of polymerization. All of the resulting copolymers have relatively low dispersities and show relatively low absorbance at 193 nm, comparable to other 193 nm candidate photoresists reported previously, with the exception of VN‐containing copolymer.
The present article reveals important roles of metal alkyl activators in tuning the performance of the Phillips catalyst in ethylene polymerization. The addition of aluminum alkyl aids the activation of the catalyst, while excess addition leads to the loss of the activity. The balance between the activation and deactivation depends on the type of employed aluminum alkyl, and tri‐n‐octylaluminum offers the most efficient catalyst usage by preferentially suppressing the deactivation. The passivation of aluminum trialkyl with a hindered phenol mildens not only the deactivation but also chain transfer reactions, leading to an increment of high molecular weight fractions.
The preparation of forced gradient polymers has received considerable attention using batch reactors, while the preparation of usable quantities of forced gradient copolymers using continuous flow reactors has been hampered by the need to vary the composition of the monomer feedstock continuously during the reaction. A reactor that allows for addition of a monomer feedstock continuously at all points along the length of the reactor tubing allows for the preparation of forced gradient copolymers in continuous flow reactors, allowing for the scale‐up and bulk preparation of these polymers. This study reports here the initial investigation of preparing forced gradient copolymers using the reversible addition–fragmentation chain transfer methodology in tube‐in‐tube continuous flow reactors.
The reactivity ratios for the bulk free‐radical copolymerization of n‐butyl acrylate (BA)/n‐butyl methacrylate (BMA) are estimated at 80 °C. By performing a series of low conversion runs including replicate runs, the reactivity ratios are estimated as rBA = 0.460 and rBMA = 2.008. Runs to high conversions are then conducted at three different feed compositions (fBMA = 0.2, 0.5, and 0.8) to validate the reactivity ratios. The composition data from the high conversion experiments show good agreement with the estimated reactivity ratios in the integrated form of the Mayo–Lewis model. The molecular weight, gel content, and glass transition temperature of BA/BMA copolymers are also determined.
The effect of prepolymerization on ethylene homopolymerization and ethylene/1‐hexene copolymerization with a commercial TiCl4/MgCl2 catalyst was investigated and the apparent homo‐ and copolymerization rate constants were estimated by varying polymerization temperature, pressure, time, and 1‐hexene/ethylene molar ratio during the prepolymerization. The apparent rate constants for activation, propagation, and deactivation depend on the prepolymerization conditions, showing that the prepolymerization stage strongly regulates the behavior of the catalyst in the main polymerization. Interestingly, the surface morphology of the prepolymer particles correlates to and explains these changes in polymerization kinetics behavior.
Significant progress has been made over the past 20–30 years in terms of the ability to develop and solve mechanistic models of emulsion polymerization processes, and in particular models for prediction of the particle size distribution. However, this does not imply that modeling of these economically important processes is by any means a “solved problem,” or that it is no longer necessary to perform fundamental research in this area. There are a number of areas where strong scientific work would increase the understanding of the process, including events in the aqueous phase, radical entry into growing particles, monomer partitioning, and especially the mechanisms and modeling of particle coagulation.
Strategies have been successfully developed for the monitoring of the homo and copolymerization of styrene and butyl acrylate in a miniemulsion system using near‐infrared (NIR) spectroscopy. Different concentrations of costabilizer, stearyl methacrylate, are tested to obtain the best stabilization condition. The spectral data are associated with the properties of the reaction medium, such as particle average diameter, conversion, number, and surface area of particles, through linear regression based on partial least squares. It is observed that the NIR spectrophotometer is sensitive to the dynamics of miniemulsion polymerization reactions, thus confirming the promising aspect of NIR technology for monitoring the latex properties.
Various MgCl2‐supported Ziegler–Natta (ZN) catalysts are synthesized with the intention to influence polymerization performance and 1‐butene incorporation in an ethylene copolymer. Modifications are introduced during different steps in the synthesis process, namely support preparation, titanation, and catalyst workup. While multiple different effects are observed upon modification, heat treatment during titanation shows the greatest impact. Increasing the heat‐treatment temperature increases polymerization activity. More importantly, the 1‐butene distribution can be shifted toward a more homogeneous profile. The amount of 1‐butene incorporated is similar to both for short‐ and for very long‐chain molecules. This behavior has so far been known only from metallocene‐based polyethylene and suggests that active sites are distributed more homogeneously in the ZN catalyst.
A novel vanadium‐modified (SiO2/MgO/MgCl2)·TiClx Ziegler–Natta ethylene polymerization catalyst with much better catalytic performance is successfully developed. The catalyst is prepared by co‐impregnation of aqueous solution of water‐soluble magnesium and vanadium compounds on SiO2, and a supported thin layer of magnesium and vanadium oxides is formed over the surface of SiO2 after high temperature calcination in dry air, followed by further reaction with titanium tetrachloride to synthesize the magnesium dichloride carrier in situ and to support the titanium species simultaneously. By characterization of the catalysts and the polymers and investigation of the polymerization behaviors, it is found that compared with the original (SiO2/MgO/MgCl2)·TiClx ZN catalyst, the introduction of vanadium species induce improved catalytic performance with 27% higher activity, 48% higher hydrogen response, and 60% higher 1‐hexene incorporation ability with better short chain branch distribution.
The effects of monomer solubility and different types of initiators are for the first time reported for a reversible addition–fragmentation chain transfer (RAFT) inverse microemulsion polymerization system. 2‐(dimethylamino)ethyl methacrylate is selected as monomer due to its solubility in several solvents. A nonionic surfactant, cyclohexane, and a trithiocarbonyl RAFT chain transfer agent (CTA) are also used as main components. The reactions are performed adjusting the dispersed aqueous phase with selected pH values (5, 7, and 10), using an oil‐soluble or a water‐soluble initiator. In this microemulsion system, the RAFT process is especially influenced by the monomer content in the dispersed aqueous phase, directly related to the final pH. It is suggested that monomer diffusion and changes in the monomer/CTA ratio at the polymerization loci are the primary reasons for the different behaviors observed, specially those related to the molar mass properties.
This article proposes a method to quantify the polymerization kinetics of ethylene and α‐olefins with commercial TiCl4/MgCl2 Ziegler–Natta catalysts. The method determines the leading apparent polymerization kinetic constants for each active site in a Ziegler–Natta catalyst by simultaneously fitting the instantaneous polymerization rate, cumulative polymer yield, and polymer molecular weight distribution measured at different times during a series of semi‐batch polymerization experiments. This approach quantifies the behavior of olefin polymerization with multisite catalysts using the least number of adjustable parameters needed to consistently model polymerization kinetics and polymer microstructural data.
SiO2‐supported Cr–V bimetallic catalyst can be used for producing bimodal polyethylene which can be applied for high‐performance pipe material. Alkyl aluminum are used to prereduce the bimetallic catalysts, and the effects of alkyl aluminum for the bimetallic catalyst are fully studied by catalyst characterization, polymerization kinetics, and the properties of polymer product by the comparison with the catalyst without prereduction. The result shows that the optimum polymerization activity is almost double after the catalyst is prereduced by triisobutylaluminum (TIBA), and the needed dosage of alkyl aluminum also is decreased significantly. The alkyl aluminum of the prereduced catalyst can also act as a chain transfer agent, significantly reducing the molecular weight of the polymer. The diethylaluminum chloride (DEAC) is mostly deactivating the Cr species during the ethylene polymerization. The synthesized catalysts, prereduced by TIBA, triethylaluminum (TEA), and DEAC, all exhibited good hydrogen response and comonomer interposition ability, which will be favorable for the further application of the bimetallic catalyst in the industrial field.
The synthesis of poly(acrylic acid) (PAA) of low molar mass under safe conditions is difficult due to the high polymerization rate of acrylic acid (AA) and the fast heat generation. The aqueous‐solution “semibatch” polymerization of non‐ionized AA in almost starved conditions involves high initiator loads when low molar masses are required. This article proposes the simultaneous feeding of AA and nonconventional chain transfer agents (CTA) as a strategy aimed at controlling both the molar masses and the generated heat rate. Three CTAs are investigated: 2‐mercaptoethanol, thioglycolic acid, and isopropyl alcohol. Even when PAA of relatively low molar mass can be produced by adequately selecting the flow rates and concentrations of both AA and CTA, it is found that the nature of CTA can have a significant effect on the polymerizations kinetics. The mechanisms responsible for these effects are discussed with the help of a representative mathematical model.
In this study a framework consisting of a computational fluid dynamics simulation coupled to a population balance model for the modeling of emulsion polymerizations is proposed. The combined approach is used to understand the impact of changing length and time scales, as well as mixing conditions on the particle size distribution (PSD) of a polymer latex under different conditions. It is shown that the effect of agitation rate can have a profound impact on the distribution of ionic species in the reactor, and thus on the evolution of the PSD.
Chain‐shuttling polymerization with dual catalysts has introduced a new class of polyolefins called olefin block copolymers (OBCs). A dynamic Monte Carlo model to describe the kinetics of chain‐shuttling copolymerization in a semi‐batch reactor is developed, and used it to study how the microstructure of OBCs with different numbers of blocks per chain evolves during polymerization. The model also describes how chain‐shuttling rate constants and concentration of chain‐shuttling agent affect populations of OBCs with different numbers of blocks per chain. These model predictions are useful to make OBCs with precisely designed microstructures.
Amphiphilic block copolymers of 2,3,4,5,6‐pentafluorostyrene (PFS) and methacrylic acid (MAA) are synthesized via nitroxide‐mediated polymerization (NMP). It is established that to obtain a controlled copolymerization a minimum of 40 mol% of PFS is required, which is significantly greater than other copolymerization systems such as using 4.5–8 mol% styrene or 1 mol% of 9‐(4‐vinylbenzyl)‐9H‐carbazole to control the copolymerization of methacrylates. It is surmised that this lack of control is due to the reactivity ratios that favor the addition of MAA rather than PFS (rPFS = 0.14, rMAA = 6.97). However this reactivity ratio pair suggests that a one‐shot delayed injection approach can be utilized to synthesize almost pure block copolymers in one pot. Therefore, poly(PFS)‐b‐(PFS‐ran‐MAA) block copolymers are synthesized by a one‐shot delayed addition of MAA. While the concentration of irreversibly terminated chains is evident these results suggest a promising route to the synthesis of fluorinated amphiphilic block copolymers by NMP.
The authors apply the method of moments to the study of network formation in continuous flow stirred reactors when chain transfer to polymer and coupling are present in the reaction scheme. This approach leads to analytical solutions for the various moments involved. The authors start by assuming that the rate of coupling is proportional to the length of dead chains, which allow them to review and extend previous work in this area. This is followed by similar derivations when a coupling agent is present and the rate of coupling is proportional to the number of coupling groups that such agent leaves in dead polymer molecules, demonstrating that higher values of second order moments can be reached at lower levels of unreacted coupling agent.
Phillips catalyst is one of the most significant industrial ethylene polymerization catalysts. Chemical modifications have been carried out to tune the Phillips catalyst performance and improve the polyethylene properties. After the modification of the catalyst by fluorine, the polyethylene product with higher molecular weight (MW) and narrower molecular weight distribution (MWD) is suitable for producing automobile fuel tanks. Vanadium containing Phillips catalyst enhances α‐olefin incorporation and MW regulation. In present work, fluorine modified and unmodified chromium–vanadium (Cr–V) bimetallic catalysts are prepared and explored. Compared with the fluorine‐free catalyst, the activities of F‐modified bimetallic catalysts slightly decrease with the increasing MW of the product and the hydrogen response increases slightly. Due to the synergistic effect of the chromium, vanadium and fluorine on the silica gel support, the short‐chain branch distribution (SCBD) of copolymers from F‐modified Cr–V bimetallic catalyst (Cr–V–F)600 is more beneficial than that of Cr–V bimetallic catalyst (Cr–V)600 and F‐modified Cr–V bimetallic catalyst (Cr–V–F)500. The fluorination of Cr–V bimetallic catalysts has not only preserved the high polyethylene activity of bimetallic active sites but also produced the advantage of the high MW ability from fluorine.
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