Molecular weight distribution in nonlinear emulsion polymerization

A modelistic study of the molecular weight distribution (MWD) formed in emulsion polymerization that involves chain transfer to polymer is conducted, by focusing our attention to the effect of very small reaction volume on the formed MWD. In emulsion polymerization, a polymer radical that causes polymer transfer reaction must choose the partner only within the same particle, which makes the expected size of the polymer molecule to be chosen smaller compared with the corresponding polymerization system that involves an infinitely large number of polymeric species. The usual assumption for homogeneous polymerization that the rate of chain transfer to a particular polymer molecule is proportional to its chain length cannot be used, except when branching frequency is low and particle size is large enough. This fact invalidates the direct use of models developed for homogeneous nonlinear polymerizations to emulsion polymerizations. Model equations that could be used to assess the significance of the limited space effects on the MWD under a given polymerization condition are also proposed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1515–1532, 1997     

Average termination rate coefficients in emulsion polymerization: Effect of compartmentalization on free‐radical lifetimes

A method is presented by which the time‐dependent average termination rate coefficient in an emulsion polymerization may be calculated as an appropriate average of the chain‐length‐dependent termination rate coefficients. The method takes advantage of the fact that the overall termination rate is dominated by terminations between rapidly moving short radicals and much slower long ones. This termination rate coefficient is suitable for use in the Smith–Ewart equations describing the compartmentalization of radicals in an emulsion polymerization. Rate data in emulsion polymerizations can be quantitatively interpreted if the kinetics fall into one of two categories: zero–one (showing compartmentalization; intraparticle termination is not rate‐determining) or pseudo‐bulk (no compartmentalization; intraparticle termination is rate‐determining). The new method can be used to interpret rate data for systems falling between these categories and also can be used to find termination rate coefficients from Monte Carlo simulations of termination kinetics. The latter is especially useful for predicting and understanding kinetics in controlled radical polymerizations in disperse media. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1076–1089, 2005     

Modeling molecular weight distribution in emulsion polymerization reactions with transfer to polymer

A mathematical model was developed for the computation of the dynamic evolution of molecular weight distributions (MWDs) during nonlinear emulsion polymerization reactions. To allow the direct computation of the whole MWD, an adaptive orthogonal collocation technique was applied. The model was validated with experimental methyl methacrylate/butylacrylate (BuA) semicontinuous and vinyl acrylate (VA)/Veova10 continuous emulsion polymerization results. Both systems considered introduce significant chain‐transfer reactions to polymer chains as a result of the presence of BuA and VA, respectively. The model developed was able to represent quite properly the kinetics and MWD of polymer samples during emulsion polymerizations. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3513–3528, 2001     

Dynamic modeling of the morphology of latex particles with in situ formation of graft copolymer

Modification of the polymer–polymer interfacial tension is a way to tailor‐make particle morphology of waterborne polymer–polymer hybrids. This allows achieving a broader spectrum of application properties and maximizing the synergy of the positive properties of both polymers, avoiding their drawbacks. In situ formation of graft copolymer during polymerization is an efficient way to modify the polymer–polymer interfacial tension. Currently, no dynamic model is available for polymer–polymer hybrids in which a graft copolymer is generated during polymerization. In this article, a novel model based on stochastic dynamics is developed for predicting the dynamics of the development of particle morphology for composite waterborne systems in which a graft copolymer is produced in situ during the process. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Copolymerization of sec‐butenyl acetate with styrene via emulsion polymerization

The incorporation of allylic monomers into highly reactive vinyl polymerizations provides a means to control molecular weight, conversion, and Trommsdorff effect to produce copolymers with desirable performance characteristics. The copolymerization behavior of styrene with sec‐butenyl acetate, whose copolymerization properties have not been reported, is investigated. Copolymers were produced via semicontinuous emulsion polymerization and characterized via NMR, gel permeation chromatography, differential scanning calorimetry, dynamic light scattering, and atomic force microscopy. A high degree of chain termination due to allylic hydrogen abstraction was observed, as expected, with resultant decreases in molecular weight and in monomer conversion. However, high conversions were achieved, and it was possible to incorporate high percentages of the allylic acetate comonomer into the polymer chain. Copolymer thermal properties are reported. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3191–3203, 2007     

Effect of dose rate on emulsion and microemulsion polymerization of styrene

Emulsion and microemulsion polymerization of styrene were initiated with a gamma ray to study the effect of dose rate on polymerization. In both systems, there is an apparent plateau of polymerization rate in the curve of reaction rate vs. conversion. It was shown that emulsion polymerization conformed to the Smith–Ewart theory very well. Changing the dose rate in interval 2 had no great influence on polymerization rate, but it changed the average lifetime of radicals in polymer particles and affected the molecular weight of polymer produced. For microemulsion polymerization it was assumed that in the plateau it is the number of growing polymer particles being kept constant, not the number of polymer particles. When the dose rate was changed while the polymerization came into the constant period, the polymerization rate and the molecular weight of the polymer varied with the dose rate. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 257–262, 1998     

Production of micron-sized monodispersed polymer particles by seeded polymerization for the dispersion of highly monomer-swollen particles prepared with submicron-sized polymer seed particles utilizing the dynamic swelling method

For the purpose of extending the size range of polymer seed particles used in “dynamic swelling method” (DSM), first it was verified theoretically that the submicron-sized polymer particles produced by emulsion polymerization can also absorb a large amount of monomer by DSM in both equilibrium and kinetic control states. Next, on the basis of the theoretical results, experimentally about 2.6 μm-sized styrene-swollen polystyrene (PS) particles were prepared utilizing DSM in the presence of 0.64 μm-sized monodispersed PS seed particles produced by emulsifier-free emulsion polymerization. Moreover, 2.5 μm-sized monodispersed PS particles were produced by the addition of cupric chloride as a water-soluble inhibitor to depress the by-production of submicron-sized PS particles in the seeded polymerization at 30°C with 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) initiator. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2513–2519, 1998     

Modeling emulsion polymerization stabilized by polymerizable surfactants

A mathematical model for seeded emulsion polymerization stabilized with polymerizable surfactants (surfmers) was developed. The model accounts for the main features of the process and provides information about surfmer conversion as well as surfmer burying inside the polymer particles. The model was validated by comparing its predictions with the experimental results for the effect of particle size, surface properties of the surfmer, and type of initiator on surfmer conversion. The effect of surfmer reactivity on surfmer incorporation to the polymer backbone is also discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 585–595, 2001     

The effect of Co(II)‐mediated catalytic chain transfer on the emulsion polymerization kinetics of methyl methacrylate

The effect the catalytic chain transfer agent, bis[(difluoroboryl) dimethylglyoximato] cobalt(II) (COBF), on the course of the ab initio emulsion polymerization of methyl methacrylate, and the product properties in terms of the molecular weight distribution were investigated. The emulsion polymerization kinetics have been studied with varying surfactant, initiator, and COBF concentrations. The experimentally determined average number of radicals per particle strongly depends on the concentration of COBF and proves to be in good agreement with the results of model calculations. The apparent chain transfer constant, determined up to high conversion, is in excellent agreement with the predicted value based on a mathematical model based on COBF partitioning and the Mayo equation. The results of this work enhance the fundamental understanding of the influence a catalytic chain transfer agent has on the course of the emulsion polymerization and the control of the molecular weight distribution. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5078–5089, 2009     

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     

AB and ABA type butyl acrylate and styrene block copolymers via RAFT‐mediated miniemulsion polymerization

Two trithiocarbonate reversible addition fragmentation chain transfer (RAFT) agents are compared in miniemulsion polymerization of styrene and butyl acrylate and the formation of seeded emulsion block copolymers. The order of block synthesis and the number of block segments per polymer are discussed. The use of nonionic surfactants is examined and the type of surfactant in relation to the monomer used is found to have a significant affect on latex formation. Conditions are shown by which AB and ABA type block copolymers can be successfully prepared via a seeded RAFT‐mediated emulsion polymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 588–604, 2007     

Catalytic chain transfer for molecular weight control in the emulsion homo- and copolymerizations of methyl methacrylate and butyl methacrylate

The behavior of catalytic chain transfer in semi-batch emulsion polymerization has been studied for two monomers, viz, methyl and n-butyl methacrylate. Two different catalytic chain transfer reagents were used with different water solubilities: cobaloxime boron fluoride (COBF), which was found to partition approximately equally between organic and aqueous phases, and tetra-phenyl cobaloxime boron fluoride (COPhBF), which was found to reside predominantly in the organic phase. The difference in hydrophilicity between the two transfer agents was found to affect the polymerization mechanism. COBF exhibited superior transfer behavior in all cases, whereas the restricted mobility of the COPhBF had a deleterious effect on the efficiency of the transfer mechanism. The best results were achieved under monomer flooded conditions using COBF. MALDI-TOF mass spectrometry analysis shows catalytic chain transfer to be the dominant mechanism initiating and stopping chain growth as none of the chains appear to have initiator fragment end groups. Analysis of copolymers by MALDI-TOF mass spectrometry reveals both molecular weight and composition data. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 859–878, 1997     

The effect of different catalytic chain transfer agents on particle nucleation and the course of the polymerization in ab initio batch emulsion polymerization of methyl methacrylate

The effect a Co(II) based catalytic chain transfer agent (CCTA) has on the course of the polymerization and the product properties of an emulsion polymerization is governed by the intrinsic activity and the partitioning behavior of the catalyst. The effect on the conversion time history, the molecular weight distribution and the particle size distribution is evaluated in batch emulsion polymerization of methyl methacrylate for three different CCTAs, which cover a range of intrinsic activities and partitioning behaviors. It was demonstrated that radical desorption from the particle phase to the aqueous phase preceded by chain transfer is the main kinetic event controlling the course of the polymerization and the product properties in terms of the particle size distribution. The experimental results show that the aqueous phase solubility of the CCTA is the key parameter controlling the course of the polymerization and the particle size distribution. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1038–1048, 2010     

Molecular weight distribution in emulsion polymerization. I. The homopolymer case

A model for evaluating the instantaneous degree of polymerization distribution of homopolymers produced in emulsion, based on the mathematics of the Markov chains, is developed. The model accounts for any number of active chains per particle, as well as for the two fundamental mechanisms of chain termination: mono- and bi-molecular, both by combination and by disproportionation. The core of the model is the so called subprocessmain process treatment, which allows us to correctly evaluate the degree of polymerization of the chains growing in the polymer particles, by distinguishing between the events experienced by the polymer chain which imply a change of its degree of polymerization (subject transitions) and those which imply only a change in the particle state (environment transitions). This is obtained by properly defining the one-step transition probability matrix of the relevant Markov process. Once this is done, the evaluation of the distribution of the degrees of polymerization reduces to a few simple operations among matrices. Explicit expressions for the instantaneous probability density functions and the relative cumulative distributions are obtained. The application of such relationships is facilitated by the numerical procedures reported in the Appendices. The results of the model developed in this work are in agreement with those of earlier models in the range of parameter values of practical interest. In the limit of very low molecular weights, only the model developed in this work provides the correct answer. Moreover, a much more significant result is its applicability to the case of emulsion copolymerization, as it is shown in Part II.     

Molecular weight distribution in emulsion polymerizations

A mathematical formulation is given which describes the evolution of the number distribution of the molecular weight (MWD) of linear polymer chains that grow in emulsion polymerization systems. The resulting set of coupled ordinary differential equations takes into account the microscopic events of free radical entry, exit, chain annihilation, bimolecular termination (by combination and disproportionation), and chain transfer in a mono- or polydisperse system. Simple analytic solutions are presented for systems in which the number of particles, as well as the average number of free radicals per particle, is constant and in which the rate coefficients are size independent. These solutions indicate that compartmentalization of the free radicals in the latex particles results in a significant increase in the polydispersity of the polymer produced by emulsion polymerization, compared with that in bulk systems. The theory shows that significant mechanistic information may be obtained from experimental MWDs and that, in principle, experimental conditions may be prescribed to grow a desired MWD. The MWDs are presented in a novel manner that facilitates the comparison of theory with experiment.     

Emulsion terpolymerization of butyl acrylate/methyl methacrylate/vinyl acetate: Experimental results

A systematic study of the terpolymerization of butyl acrylate/methyl methacrylate/vinyl acetate (BA/MMA/VAc) was conducted. In this stage of the study, batch emulsion terpolymerizations were performed in a 5 L stainless steel pilot plant reactor. The experiments were designed using a Bayesian (optimal) technique. The polymers produced were characterized for conversion, composition, molecular weight, and particle size. Conversion, terpolymer composition, number- and weight-average molecular weight, and average particle size results are discussed in light of the influence of seven factors and the interaction of these factors. The factors studied include monomer feed composition, initiator concentration, chain transfer agent concentration, impurity concentration, initiator type, emulsifier concentration, and temperature. A “two-stage rate” phenomenon, similar to that occurring in bulk co- and terpolymerization and emulsion copolymerization of acrylic/vinyl acetate systems was observed in the conversion, composition and molecular weight data. Furthermore, an interesting yet often ignored effect of impurities on emulsion polymerization kinetics was explained. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1659–1672, 1997     

Polymer coating of carboxylic acid functionalized multiwalled carbon nanotubes via reversible addition‐fragmentation chain transfer mediated emulsion polymerization

In this work, successful polymer coating of COOH‐functionalized multiwalled carbon nanotubes (MWCNTs) via reversible addition fragmentation chain transfer (RAFT) mediated emulsion polymerization is reported. The method used amphiphilic macro‐RAFT copolymers as stabilizers for MWCNT dispersions, followed by their subsequent coating with poly(methyl methacrylate‐co‐butyl acrylate). Poly(allylamine hydrochloride) was initially used to change the charge on the surface of the MWCNTs to facilitate adsorption of negatively charged macro‐RAFT copolymer onto their surface via electrostatic interactions. After polymerization, the resultant latex was found to contain uniform polymer‐coated MWCNTs where polymer layer thickness could be controlled by the amount of monomer fed into the reaction. The polymer‐coated MWCNTs were demonstrated to be dispersible in both polar and nonpolar solvents. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Effect of the number of seed polymer particles on the kinetic behavior of the seeded emulsion copolymerization of styrene and acrylamide

The seeded emulsion copolymerizations of styrene and acrylamide were carried out at 50°C using polystyrene latex particles as the seed and potassium persulfate as the initiator, respectively. It was found that the change in the number of seed particles initially charged causes a drastic change in the kinetic behavior of this seeded emulsion copolymerization system: when the number of seed particles initially charged was less than a certain critical value, both styrene and acrylamide started polymerization from the beginning of the reaction. However, when the number of seed particles was higher than this critical value, an apparent induction period suddenly emerged only for acrylamide polymerization, that is, acrylamide did not start polymerization until the styrene conversion exceeded around 75%, while the styrene polymerization started and continued very smoothly from the beginning of the reaction. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2689–2695, 1997