Unseeded semibatch emulsion polymerization of butyl acrylate: Bimodal particle size distribution

Unseeded semibatch emulsion polymerization of butyl acrylate (BA) using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator was carried out at the conditions where secondary nucleation was probable. This was achieved by using no emulsifier in the initial reactor charge. The effects of changes in monomer emulsion feed rate, initiator concentration and distribution, emulsifier concentration in the feed, and temperature on the evolution of particle size averages and distribution were investigated. Bimodal particle size distributions (PSD) were obtained for most of the latexes. Inhibition effects were found to be important in the development of PSD. Primary particle formation occurred through micellar nucleation, whereas secondary nucleation probably occurred through homogenous nucleation. The polydispersity index (PDI) of the latexes increased with the decreasing monomer emulsion feed rate. The application of a larger amount of initiator to the reactor charge or using a higher temperature, reduced the formation of secondary particles and resulted in a formation of an unimodal PSD. The overall steady‐state rate of polymerization was found to approach the rate of monomer addition (R_p ≈ R_a ), if the emulsifier concentration in the aqueous phase was appreciable. This is different from the correlation 1/R_p = 1/K + 1/R_a obtained for the BA semibatch process with neat monomer feed. This suggests that different rate expressions can be used for BA semibatch emulsion polymerization at different conditions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 528–545, 2000     

Particle formation and coagulation in the seeded semibatch emulsion polymerization of butyl acrylate

Particle formation and coagulation in the seeded semibatch emulsion polymerization of butyl acrylate were studied under monomer‐starved conditions. To investigate the importance of the kinetics of the water phase in the nucleation process, the monomer feed rate was used as a variable to alter the monomer concentration in the aqueous phase. The emulsifier concentration in the feed was employed to alter the particle stability. Particle formation and coagulation were discussed in terms of critical surface coverage ratios. Particle coagulation occurred if the particle surface coverage dropped below θ_cr1 = 0.25 ± 0.05. The secondary nucleation occurred above a critical surface coverage of θ_cr2 = 0.55 ± 0.05. The number of particles remained approximately constant if the particle surface coverage was within θ_cr1 = 0.25 < θ < θ_cr2 = 0.55. This surface coverage band is equivalent to the surface tension band of 42.50 ± 5.0 dyne/cm that is required to avoid particle formation and coagulation in the course of polymerization. The kinetics of the water phase was shown to play an important role during homogeneous and micellar nucleations. For any fixed emulsifier concentration in the feed and above θ_cr2, the number of secondary particles increased with monomer concentration in the aqueous phase. Moreover, the presence of micelles in the reaction vessel is not the only perquisite for micellar nucleation to occur, a sufficient amount of monomer should be present in the aqueous phase to enhance the radical capture by partially monomer‐swollen micelles. The rate of polymerization increased with the surfactant concentration in the aqueous phase. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3612–3630, 2000     

Kinetics of the styrene emulsion polymerization using n‐dodecyl mercaptan as chain‐transfer agent

The kinetics of the styrene emulsion polymerization using n‐dodecyl mercaptan as chain‐transfer agent was studied. It was found that the chain‐transfer agent (CTA) had no effect on polymerization rate but substantially affected the molecular weight distribution (MWD). The efficiency of the CTA in reducing the MWD was lowered by the mass‐transfer limitations. The process variables affecting CTA mass transfer were investigated. A mathematical model for the process was developed. The outputs of the model include monomer conversion, particle diameter, number of polymer particles, and number‐average and weight‐average molecular weights. The model was validated by fitting the experimental data. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4490–4505, 2000     

Cross‐linking emulsion copolymerization of butyl acrylate with diallyl maleate

The emulsion copolymerization of butyl acrylate (BA) with a trifunctional cross‐linker, diallyl maleate (DAM), was investigated. The effect of the monomer feeding time and the amount of cross‐linker on the microstructural properties (branching, cross‐linking, gel formation, and sol MWD) of the seeded semicontinuous emulsion copolymerization of BA with DAM was investigated. It was found that the gel content was not significantly affected by increasing feeding time, but the level of quaternary carbons (an indication of the branching density) increased. On the other hand, increasing the amount of DAM in the feed composition caused gel content, level of quaternary carbons, and the cross‐linking density to increase. Interestingly, the level of quaternary carbons and the cross‐linking density sharply increased during the cooking period. The molecular weight of the sol decreased as DAM increased in the feed. In addition, the effect of process type, batch versus semibatch, was also considered and important differences in the level of quaternary carbons, cross‐linking, and gel content were found. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4684–4694, 2005     

Influence of the isomeric structures of butyl acrylate on its single‐electron transfer‐degenerative chain transfer living radical polymerization in water Catalyzed by Na2S2O4

The aim of this work is to the study the influence of the isomer structures of butyl acrylate monomer on the single‐electron transfer/degenerative chain transfer mediated living radical polymerization (SET‐DTLRP). The kinetic of isobutyl acrylate is determined for the first time by SET‐DTLRP in water catalyzed by sodium dithionite. The plots of number‐average molecular weight versus conversion and ln([M]₀/[M]) versus time are linear, demonstrating a controlled polymerization. The influence of the isomer t‐butyl, i‐butyl, and n‐butyl on the kinetics, properties, and stereochemistry of the reactions was assessed. To the best of our knowledge, there is no previous report dealing with the synthesis of PiBA by any LRP approach in aqueous medium. The results presented in this work suggest that the stability provided by the acrylate side group has an important influence in the polymerization process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6542–6551, 2008     

Rate enhancement for nitroxide stable free radical polymerization of n‐butyl acrylate by dodecylbenzenesulfonic acid

Dodecylbenzenesulfonic acid, DDBSA, was chosen as a new rate‐accelerating additive for 2,2,6,6,‐teramethyl‐1‐piperidinyloxy (TEMPO)‐mediated stable free radical polymerization of n‐butyl acrylate (n‐BA) monomers with 2,2′‐azobisisobutyronitrile (AIBN). It was found that the number‐average molecular weight of polymers could reach about ten thousand with a narrow polydispersity index (PDI) of 1.4 in a few minutes, which was faster than other systems reported previously. But, at higher conversion, the molecular weight distribution of polymers became broad, and a bimodal distribution occurred. The macro‐initiators isolated from the former polymers with narrow PDI could be extended by polymerization with monomers by the addition of DDBSA. Furthermore, a proposed kinetic model demonstrated that the decay of the concentration of DDBSA would reduce the living polymer concentration and retard the growth of the polymers, which could be further propagated by the supplement of DDBSA. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 42–49, 2005     

Mechanisms of n‐butanol formation in butyl acrylate latexes

The mechanisms involved in the formation of n‐butanol during the synthesis of butyl acrylate containing latices were investigated. The experimental results showed that neither the hydrolysis of butyl acrylate nor of the ester bond in the butyl acrylate segments of the polymer played a major role in the formation of n‐butanol, which was mainly generated from the polymer backbone, by transfer reactions to polymer chain followed by cyclization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5838–5846, 2007     

Single electron transfer–degenerative chain transfer living radical polymerization of N‐butyl acrylate catalyzed by Na2S2O4 in water media

Living radical polymerization of n‐butyl acrylate was achieved by single electron transfer/degenerative‐chain transfer mediated living radical polymerization in water catalyzed by sodium dithionate. The plots of number–average molecular weight versus conversion and ln[M]₀/[M] versus time are linear, indicating a controlled polymerization. This methodology leads to the preparation of α,ω‐di(iodo) poly (butyl acrylate) (α,ω‐di(iodo)PBA) macroinitiators. The influence of polymerization degree ([monomer]/[initiator]), amount of catalyst, concentration of suspending agents and temperature were studied. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right‐angle light scattering (RALLS), a differential viscometer (DV), and refractive index (RI). The methodology studied in this work represents a possible route to prepare well‐tailored macromolecules made of butyl acrylate in an environmental friendly reaction medium. Moreover, such materials can be subsequently functionalized leading to the formation of different block copolymers of composition ABA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2809–2825, 2006     

The application of copper(II) deactivator on the single‐electron transfer living radical polymerization of tert‐butyl acrylate

We demonstrate the living radical polymerization of tert‐butyl acrylate (tBA) applying the SET mechanism, employing methyl 2‐bromopropionate (MBP) as initiator in dimethyl sulfoxide (DMSO) at ambient temperature. It is observed that introducing copper bromide into the catalyst system is necessary for controlling on the SET‐LRP polymerization of tBA. In this work, we make major investigation for the effect of the different stoichiometry quantity of copper bromide on the polymerization. Experiments show that the polymerization achieves better control with increasing the stoichiometry quantity of copper(II) deactivator. The structural analysis of the resulting polymers by ¹H NMR demonstrates the successful synthesis of poly(tBA)s by SET‐LRP in DMSO. Moreover, this work is helpful to the SET‐LRP of other monomers and is expected to expand the application of SET‐LRP. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2793–2797, 2010     

Emulsion polymerization of butyl acrylate: Spin trapping and EPR study

The propagating radical in the emulsion polymerization reaction of butyl acrylate was detected by Electron Paramagnetic Resonance (EPR) spectroscopy using two spin-trapping agents, 2-methyl-2-nitrosopropane (MNP) and α-(4-pyridyl 1-oxide)-N-tert-butylnitrone (PyOBN). Through analysis of hyperfine structure of the spectra obtainedfrom the trapped radicals, the propagating radical is inferred to be the well known acrylate radical, ? [CH₂? CH(COOC₄H₉)]_n? CH₂? CH(COOC₄H₉)? . © 1994 John Wiley & Sons, Inc.     

Atom transfer radical polymerization of n‐butyl acrylate catalyzed by CuBr/N‐(n‐hexyl)‐2‐pyridylmethanimine

The homogeneous atom transfer radical polymerization (ATRP) of n‐butyl acrylate with CuBr/N‐(n‐hexyl)‐2‐pyridylmethanimine as a catalyst and ethyl 2‐bromoisobutyrate as an initiator was investigated. The kinetic plots of ln([M]₀/[M]) versus the reaction time for the ATRP systems in different solvents such as toluene, anisole, N,N‐dimethylformamide, and 1‐butanol were linear throughout the reactions, and the experimental molecular weights increased linearly with increasing monomer conversion and were very close to the theoretical values. These, together with the relatively narrow molecular weight distributions (polydispersity index ～ 1.40 in most cases with monomer conversion > 50%), indicated that the polymerization was living and controlled. Toluene appeared to be the best solvent for the studied ATRP system in terms of the polymerization rate and molecular weight distribution among the solvents used. The polymerization showed zero order with respect to both the initiator and the catalyst, probably because of the presence of a self‐regulation process at the beginning of the reaction. The reaction temperature had a positive effect on the polymerization rate, and the optimum reaction temperature was found to be 100 °C. An apparent enthalpy of activation of 81.2 kJ/mol was determined for the ATRP of n‐butyl acrylate, corresponding to an enthalpy of equilibrium of 63.6 kJ/mol. An apparent enthalpy of activation of 52.8 kJ/mol was also obtained for the ATRP of methyl methacrylate under similar reaction conditions. Moreover, the CuBr/N‐(n‐hexyl)‐2‐pyridylmethanimine‐based system was proven to be applicable to living block copolymerization and living random copolymerization of n‐butyl acrylate with methyl methacrylate. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3549–3561, 2002     

Reversible addition–fragmentation chain transfer polymerization of 2‐naphthyl acrylate with 2‐cyanoprop‐2‐yl 1‐dithionaphthalate as a chain‐transfer agent

The reversible addition–fragmentation chain transfer (RAFT) polymerizations of 2‐naphthyl acrylate (2NA) initiated by 2,2′‐azobisisobutyronitrile were investigated with 2‐cyanoprop‐2‐yl 1‐dithionaphthalate (CPDN) as a RAFT agent at various temperatures in a benzene solution. The results of the polymerizations showed that 2NA could be polymerized in a controlled way by RAFT polymerization with CPDN as a RAFT agent; the polymerization rate was first‐order with respect to the monomer concentration, and the molecular weight increased linearly with the monomer conversion. The polydispersities of the polymer were relatively low up to high conversions in all cases. The chain‐extension reactions of poly(2‐naphthyl acrylate) (P2NA) with methyl methacrylate and styrene successfully yielded poly(2‐naphthyl acrylate)‐b‐poly(methyl methacrylate) and poly(2‐naphthyl acrylate)‐b‐polystyrene block polymers, respectively, with narrow polydispersities. The P2NA obtained by RAFT polymerization had a strong ultraviolet absorption at 270 nm, and the molecular weights had no apparent effect on the ultraviolet absorption intensities; however, the fluorescence intensity of P2NA increased as the molecular weight increased and was higher than that of 2NA. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2632–2642, 2005     

Kinetics of the seeded semicontinuous emulsion copolymerization of methyl methacrylate and butyl acrylate

The effect of a chain‐transfer agent (CTA) on the kinetics and molecular weight distribution of the methyl methacrylate/butyl acrylate semicontinuous emulsion polymerization was investigated. The dodecanethiol had a slight effect on the reaction rate but significantly affected the secondary nucleation. The effect of the CTA concentration on the gel formation and the effect of the reaction conditions on the mass‐transfer limitations of the CTA are discussed. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 367–375, 2000     

Chain‐transfer reaction in the radical polymerization of di‐n‐butyl itaconate at high temperatures

Radical polymerizations of di‐n‐butyl itaconate were investigated. Unexpected resonances (C resonances) were observed in ¹³C NMR spectra of C?O of poly(di‐n‐butyl itaconate)s [poly(DBI)s] obtained at temperatures higher than 60 °C, although two kinds of carbonyl groups showed splittings due to triad tacticities in the spectra of polymers obtained at lower temperatures. The poly(DBI)s formed by the different kinds of initiators or formed in the presence of chain‐transfer agents showed hardly any changes in the intensities of the C resonances; this indicated that the C resonances were not due to the structures formed through initiating and terminating reactions. The poly(DBI)s obtained at different yields showed only a slight increase in the intensities of the C resonances with the yield, which suggested that the C resonances were not attributable to the intermolecular chain‐transfer reaction to the monomer and/or polymer. However, the intensities of the C resonances significantly increased with a decreasing feed monomer concentration; this suggested that intramolecular chain‐transfer reactions took place at high temperatures. Furthermore, a Cu complex‐catalyzed atom transfer radical polymerization mechanism was revealed to be effective for suppressing the intramolecular chain‐transfer reaction at 60 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2415–2426, 2002     

Kinetics of methyl methacrylate and n‐butyl acrylate copolymerization mediated by 2‐cyanoprop‐2‐yl dithiobenzoate as a RAFT agent

The RAFT (co)polymerization kinetics of methyl methacrylate (MMA) and n‐butyl acrylate (BA) mediated by 2‐cyanoprop‐2‐yl dithiobenzoate was studied with various RAFT concentrations and monomer compositions. The homopolymerization of MMA gave the highest rate. Increasing the BA fraction f_BA dramatically decreased the copolymerization rate. The rate reached the lowest point at f_MMA ～ 0.2. This observation is in sharp contrast to the conventional RAFT‐free copolymerization, where BA homopolymerization gave the highest rate and the copolymerization rate decreased monotonously with increasing f_MMA. This peculiar phenomenon can be explained by the RAFT retardation effect. The RAFT copolymerization rate can be described by 〈R_p〉/〈R_p〉₀ = (1 + 2(〈k_c〉/〈k_t〉)〈K〉)[RAFT]₀)^?0.5, where 〈R_p〉₀ is the RAFT‐free copolymerization rate and 〈K〉 is the apparent addition–fragmentation equilibrium coefficient. A theoretical expression of 〈K〉 based on a terminal model of addition and fragmentation reactions was derived and successfully applied to predict the RAFT copolymerization kinetics with the rate parameters obtained from the homopolymerization systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3098–3111, 2007     

Preparation of block copolymers of polystyrene and poly (t‐butyl acrylate) of various molecular weights and architectures by atom transfer radical polymerization

Block copolymers of polystyrene and poly(t‐butyl acrylate) were prepared using atom transfer radical polymerization techniques. These polymers were synthesized with a CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine catalyst system and had predictable molecular weights based on the degree of polymerization, as calculated from the initial ratio of monomer to initiator. The final polydispersities were low (1.10 < M_w /M_n < 1.3) for all the homopolymers and block copolymers. Polymers of various chain architectures were prepared, ranging from linear AB diblocks to three‐armed stars composed of AB diblocks on each arm. The key to controlled synthesis with this catalyst system was the choice of the solvent, temperature, and concentrations of catalyst and deactivator. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2274–2283, 2000     

Particle formation under monomer‐starved conditions in the semibatch emulsion polymerization of styrene. I. Experimental

Particle formation and particle growth compete in the course of an emulsion polymerization reaction. Any variation in the rate of particle growth, therefore, will result in an opposite effect on the rate of particle formation. The particle formation in a semibatch emulsion polymerization of styrene under monomer‐starved conditions was studied. The semibatch emulsion polymerization reactions were started by the monomer being fed at a low rate to a reaction vessel containing deionized water, an emulsifier, and an initiator. The number of polymer particles increased with a decreasing monomer feed rate. A much larger number of particles (within 1–2 orders of magnitude) than that generally expected from a conventional batch emulsion polymerization was obtained. The results showed a higher dependence of the number of polymer particles on the emulsifier and initiator concentrations compared with that for a batch emulsion polymerization. The size distribution of the particles was characterized by a positive skewness due to the declining rate of the growth of particles during the nucleation stage. A routine for monomer partitioning among the polymer phase, the aqueous phase, and micelles was developed. The results showed that particle formation most likely occurred under monomer‐starved conditions. A small average radical number was obtained because of the formation of a large number of polymer particles, so the kinetics of the system could be explained by a zero–one system. The particle size distribution of the latexes broadened with time as a result of stochastic broadening associated with zero–one systems. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3940–3952, 2001     

Kinetics and electron spin resonance study of the radical polymerization of n‐butyl acrylate mediated by a nitroxide precursor: C‐phenyl‐N‐tert‐butylnitrone

The C‐phenyl‐N‐tert‐butylnitrone/azobisisobutyronitrile pair is able to impart control to the radical polymerization of n‐butyl acrylate as long as a two‐step process is implemented, that is, the prereaction of the nitrone and the initiator in toluene at 85 °C for 4 h followed by the addition and polymerization of n‐butyl acrylate at 110 °C. The structure of the in situ formed nitroxide has been established from kinetic and electron spin resonance data. The key parameters (the dissociation rate constant, combination rate constant, and equilibrium constant) that govern the process have been evaluated. The equilibrium constant between the dormant and active species is close to 1.6 × 10^?12 mol L^?1 at 110 °C. The dissociation rate constant and the activation energy for the C? ON bond homolysis are 1.9 × 10^?3 s^?1 and 122 ± 15 kJ mol^?1, respectively. The rate constant of recombination between the propagating radical and the nitroxide is as high as 1.2 × 10⁹ L mol^?1 s^?1. Finally, well‐defined poly(n‐butyl acrylate)‐b‐polystyrene block copolymers have been successfully prepared. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6299–6311, 2006