Reversible addition–fragmentation transfer (RAFT) copolymerization of methyl methacrylate and styrene in miniemulsion

In the reversible addition–fragmentation transfer (RAFT) copolymerization of two monomers, even with the simple terminal model, there are two kinds of macroradical and two kinds of polymeric RAFT agent with different R groups. Because the structure of the R group could exert a significant influence on the RAFT process, RAFT copolymerization may behave differently from RAFT homopolymerization. The RAFT copolymerization of methyl methacrylate (MMA) and styrene (St) in miniemulsion was investigated. The performance of the RAFT copolymerization of MMA/St in miniemulsion was found to be dependent on the feed monomer compositions. When St is dominant in the feed monomer composition, RAFT copolymerization is well controlled in the whole range of monomer conversion. However, when MMA is dominant, RAFT copolymerization may be, in some cases, out of control in the late stage of copolymerization, and characterized by a fast increase in the polydispersity index (PDI). The RAFT process was found to have little influence on composition evolution during copolymerization. The synthesis of the well‐defined gradient copolymers and poly[St‐b‐(St‐co‐MMA)] block copolymer by RAFT miniemulsion copolymerization was also demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6248–6258, 2004     

Role of the charge in continuous beds in the chiral separation of hydroxy acids by ligand-exchange capillary electrochromatography

This paper deals with the chiral separation of hydroxy acids using diallyl-dimethylammonium chloride as a positive charge-providing agent in the continuous bed. The chiral continuous bed was prepared by in situ copolymerization of monomers, including an L-4-hydroxyproline derivative as a chiral selector. This phase was applied to the chiral separation of hydroxy monocarboxylic acids and hydroxy dicarboxylic acids, respectively. The influence of both the selector concentration and the charge-providing agent on retention and separation was investigated.     

Mathematical modeling of seeded miniemulsion copolymerization for oil-soluble initiator

A mathematical model of seeded miniemulsion copolymerization of styrene-methyl methacrylate for oil-soluble initiator is presented. The mathematical model includes the mass transfer, from the miniemulsion droplets to the polymer particles, by both molecular diffusion and collision between miniemulsion droplets and the polymer particles. The mathematical model also includes the calculation of both the distribution of partices with i radicals and the average number of radicals per particle in the miniemulsion copolymerization using oil-soluble initator. Studies were carried out on the mass transfer coefficients of monomers across the interface between the miniemulsion droplet and the aqueous phase, hexadecane concentration in the miniemulsion droplets, the miniemulsion droplet sizes, and the collision between miniemulsion droplets. The results indicated that the copolymerization of styrene-methyl methacrylate was not a mass transfer controlled process. The mass transfer by collision between miniemulsion droplets and polymer particles plays an important role and was included in the model in order to predict the experimental data of seeded miniemulsion copolymerization.     

Triblock copolymer synthesis via controlled radical polymerization in solution using S‐tert‐alkyl‐N,N‐alkoxycarbonylalkyldithiocarbamate RAFT agents

This paper presents the solution homopolymerization, random and block copolymerization of acrylic monomers, mediated using an S‐(1,4‐phenylenebis(propane‐2,2‐diyl)) bis(N,N‐butoxycarbonylmethyldithiocarbamate) RAFT agent. Fair to good control was obtained over the solution homopolymerization of various acrylic monomers. Although inhibition periods were observed, nearly no retardation was found to occur. Satisfactory control was also obtained over the solution copolymerization of n‐butyl acrylate with methacrylic acid, mediated using this RAFT agent. Finally, triblock copolymer synthesis, starting from the macromolecular intermediates produced in the homo‐ and copolymerization experiments, was studied, and was shown to be successful. The observed relatively broad molar mass distributions could be explained by a partial decomposition of the dithiocarbamate‐based RAFT agent during synthesis and/or polymerization, for which strong indications were obtained by performing a careful MALDI‐ToF MS analysis. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6419–6434, 2006     

Effect of a new hydrophobically modified polyampholyte on the formation of inverse microemulsions and the preparation of gold nanoparticles

A new regular polyampholyte, namely poly-(N,N-dially-N,N-dimethylammonium-alt-N-octyl-maleamic carboxylate), was synthesized by alternating free radical copolymerization. The influence of the added polymer on the range of the inverse micellar region (L(2) phase) of a SDS-based system was investigated. The phase behavior as well as conductivity measurements indicate that the polymer, which forms hydrophobic microdomains, is located more in the water core of the microemulsion droplets rather than at the interface of the surfactant film. The polyampholyte proved to be an efficient reducing and stabilizing agent for the formation of gold colloids. The process of nanoparticle formation was investigated in the absence of any other reducing agent, in water as well as in the microemulsion template phase. In both cases, nanoscalic gold particles can be synthesized, while the adsorption of the polymer on the particle surface prevents their aggregation due to electrosteric stabilization.     

Heterogeneous copolymerization of acrylamide with maleic acid in dioxane

Heterogeneous copolymerization of acrylamide with maleic acid has been investigated. The process was carried out at 70°C in 1,4-dioxane. The polarographic method of analysis was applied. The analysis of the experimental and theoretical composition distribution curves has shown an anomalously large composition polydispersion for the experimental distribution curves. This is attributed to the heterogeneity of the copolymerization process.     

Pegylated thermally responsive block copolymer micelles and nanogels via in situ RAFT aqueous dispersion polymerization

A very straightforward approach was developed to synthesize pegylated thermoresponsive core‐shell nanoparticles in a minimum of steps, directly in water. It is based on RAFT‐controlled radical crosslinking copolymerization of N,N‐diethylacrylamide (DEAAm) and N,N′‐methylene bisacrylamide (MBA) in aqueous dispersion polymerization. Because DEAAm is water‐soluble and poly(N,N‐diethylacrylamide) (PDEAAm) exhibits a lower critical solution temperature at 32 °C, the initial medium was homogeneous, whereas the polymer formed a separate phase at the reaction temperature. The first macroRAFT agent was a surface‐active trithiocarbonate based on a hydrophilic poly(ethylene oxide) block and a hydrophobic dodecyl chain. It was further extented with N,N‐dimethylacrylamide (DMAAm) to target macroRAFT agents with increasing chain length. All macroRAFT agents provided excellent control over the aqueous dispersion homopolymerization of DEAAm. When they were used in the radical crosslinking copolymerization of DEAAm and MBA, the stability and size of the resulting gel particles were found to depend strongly on the chain length of the macroRAFT agent, on the concentrations of both the monomer and the crosslinker, and on the process (one step or two steps). The best‐suited experimental conditions to reach thermosensitive hydrogels with nanometric size and well‐defined surface properties were determined. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2373–2390, 2009     

In Line Monitoring of VAc-BuA Emulsion Polymerization Reaction in a Continuous Pulsed Sieve Plate Reactor using NIR Spectroscopy

Summary: This work deals with the in line and in situ monitoring of the changes in residual monomer concentrations and polymer particle size in the process of emulsion copolymerization of vinyl acetate (VAc) and butyl acrylate (BuA) over the sections of a novel tubular reactor (pulsed sieve plate continuous reactor, PSPC) using NIR spectroscopy. Off-line measurements (gas chromatographic, gravimetric and dynamic light scattering) were used as reference for the development of the multivariate PLS calibration model. All NIR spectra were on-line collected with an IFS 28/N Bruker spectrometer using a probe (transflectance mode) immersed into the reaction medium. The calibration model and validation data were analyzed using the OPUS/QUANT software. The results indicated that there exists a good agreement between values from the NIR calibration models and the off-line reference measured experimental data. Moreover, the on-line NIR can detect efficiently the occurrence of disturbances during the polymerization reaction, a useful tool for the improving the process safety.     

Modeling Particle Size Distribution (PSD) in Emulsion Copolymerization Reactions in a Continuous Loop Reactor

A detailed dynamic mathematical model that describes the evolution of particle size distributions (PSDs) during emulsion copolymerization reactions in a continuous loop reactor was developed and compared with experimental data. The model is based on the assumption that two distinct particle populations exist: precursor particles and stable latex particles. Precursor particles are colloidally unstable and therefore may undergo coagulation with other precursors and be absorbed by stable latex particles. It is shown that the kinetic model is able to reproduce the rather complex dynamic behavior of the vinyl acetate/Veova10 emulsion copolymerization in a continuous loop reactor, including the development of oscillatory responses of PSDs during reaction start‐up. It is also shown that, for the studied polymerization system, oscillatory responses are obtained only when both particle populations are assumed to exist and when both coagulative and micellar particle nucleations are simultaneously considered.     

A Joint Experimental/Theoretical Investigation of the Statistical Olefin/Conjugated Diene Copolymerization Catalyzed by a Hemi‐Lanthanidocene [(Cp*)(BH4)LnR]

Statistical copolymerization of ethylene and isoprene was achieved by using a borohydrido half‐lanthanidocene complex. Under copolymerization conditions, activation of [(Cp*)(BH₄)₂Nd(thf)₂] (Cp*=η⁵‐C₅Me₅) by an appropriate alkylating agent affords trans‐1,4‐poly‐isoprene‐co‐ethylene. Analysis of the microstructure of the copolymer revealed the presence of successive short sequences of ethylene/ethylene, trans‐1,4‐isoprene/ethylene, and trans‐1,4‐isoprene/trans‐1,4‐isoprene. A small amount of 1,2‐insertion of isoprene was observed, and no cyclic structures within the chain were characterized. Test runs showed that these catalysts are unable to copolymerize α‐olefins (such as hex‐1‐ene) with isoprene. The probable initial steps in the copolymerization have been computed at the DFT level of theory. Analysis of the energy profile provides insight into the catalyst’s activity and selectivity. Our theoretical results highlight the key role played by the allyl intermediate, in which diene insertion, and to a lesser extent olefin insertion, is the rate‐determining step of the process. These results also illustrate the coordination behavior of the allyl ligand during the insertion of an incoming monomer, which directly inserts, after pre‐coordination to the metal center, into the η³‐allyl ligand without inducing an η³ to η¹ haptotropic shift. Finally, the inactivity of this family of catalysts towards the copolymerization of hex‐1‐ene was rationalized on the basis of the free‐energy profile of the copolymerization.     

Determination of kinetic constants of the cationic copolymerization of isobutylene with isoprene

A theoretical kinetic model has been developed for cationic isobutylene–isoprene copolymerization in methyl chloride with an AlCl₃ catalyst. Kinetic constants of this process have been derived from experimental data available on copolymerization kinetics (isobutylene conversion curve) and on molecular weight characteristics of the isobutylene–isoprene copolymer (butyl rubber). The adequacy of the theoretical kinetic model of the isobutylene–isoprene copolymerization process has been demonstrated by comparing the calculated molecular weight characteristics and degree of unsaturation of butyl rubber to the corresponding independent experimental data.     

Investigation of cationic copolymerization of styrene with p-benzoquinone

The kinetics of copolymerization of styrene with p-benzoquinone in the presence of BF₃OEt₂ is investigated. The rate constants and activation energy of the copolymerization process are determined. The reaction orders for monomer and catalyst are estimated. It is found that the rate of styrene and quinone copolymerization increase and the induction period decreases owing to addition of the latter. It is shown that the copolymerization rate achieves its maximum at an equimolal ratio of monomers. This phenomenon is explained by formation of active molecular complex between styrene and p-benzoquinone. On the basis of obtained data the course of copolymerization is interpreted and the cationic mechanism of copolymerization process is proposed.     

An Emulsifier‐Free RAFT‐Mediated Process for the Efficient Synthesis of Cerium Oxide/Polymer Hybrid Latexes

Hybrid latexes based on cerium oxide nanoparticles are synthesized via an emulsifier‐free process of emulsion polymerization employing amphiphatic macro‐RAFT agents. Poly(butyl acrylate‐co‐acrylic acid) random oligomers of various compositions and chain lengths are first obtained by RAFT copolymerization in the presence of a trithiocarbonate as controlling agent. In a second step, the seeded emulsion copolymerization of styrene and methyl acrylate is carried out in the presence of nanoceria with macro‐RAFT agents adsorbed at their surface, resulting in a high incorporation efficiency of cerium oxide nanoparticles in the final hybrid latexes, as evidenced by cryo‐transmission electron microscopy.     

Polyiodized‐PCL as multisite transfer agent: Towards an enlarged library of degradable graft copolymers

Poly(ε‐caprolactone)‐based graft copolymers were prepared via a “grafting from” technique derived from iodine transfer polymerization. This copolymerization was done thanks to a poly(ε‐caprolactone‐co‐α‐iodo‐ε‐caprolactone) (PCL‐I), which was used as a multisite transfer agent. Styrene (Sty) and n‐butyl acrylate (n‐BuA) were firstly used as model monomers to establish the feasibility of using PCL‐I as multisite transfer agent, and investigate some general properties of the polymerization. The formation of PCL‐g‐PSty and PCL‐g‐P(n‐BuA) copolymers was confirmed by SEC and NMR analyzes of the copolymers before and after degradation of the PCL backbone. This method was extended to an acrylamide monomer, namely (N,N‐dimethyl) acrylamide (DMA), to prepare original amphiphilic copolymers with PCL as hydrophobic backbone and amido‐functionalized hydrophilic grafted chains. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5006–5016, 2009     

Controlled Free-Radical Copolymerization of N-vinyl succinimide and n-Butyl acrylate via a Reversible Addition–Fragmentation Chain Transfer (RAFT) Technique

Summary : Copolymerization of N-vinyl succinimide and n-butyl acrylate in the presence of dibenzyl trithiocarbonate as a reversible addition-fragmentation chain transfer agent was investigated. The linear dependence of molecular mass on conversion and low values of polydispersity index confirmed pseudo-living mechanism of the process. For the first time the soluble copolymers of N-vinyl succinimide and n-butyl acrylate with high composition homogeneity have been synthesized by copolymerization in bulk. The copolymerization kinetics was studied by NMR ¹H spectroscopy; the reactivity ratios were determined: r_VSI = 0.11, r_BA = 2.54. The copolymer microstructure was estimated; it was shown that in conditions of RAFT polymerization gradient copolymers enriched with BA on the tails of the macromolecule and with VSI in the middle can be obtained. The method of elimination of trithiocarbonate fragment by the reaction with an excess of AIBN was proposed leading to formation of the simplest gradient structure of N-vinyl succinimide – n-butyl acrylate copolymer.     

Controlled radical copolymerization of β‐pinene and acrylonitrile

The feasibility of the radical copolymerization of β‐pinene and acrylonitrile was clarified for the first time. The monomer reactivity ratios evaluated by the Fineman–Ross method were r_β‐pinene = 0 and r_{acrylonitrile} = 0.66 in dichloroethane at 60 °C with AIBN, which indicated that the copolymerization was a simple alternating copolymerization. The addition of the Lewis acid Et₂AlCl increased the copolymerization rate and enhanced the incorporation of β‐pinene. The first example for the synthesis of an almost perfectly alternating copolymer of β‐pinene and acrylonitrile was achieved in the presence of Et₂AlCl. Furthermore, the possible controlled copolymerization of β‐pinene and acrylonitrile was then attempted via the reversible addition–fragmentation transfer (RAFT) technique. At a low β‐pinene/acrylonitrile feed ratio of 10/90 or 25/75, the copolymerization with 2‐cyanopropyl‐2‐yl dithiobenzoate as the transfer agent displayed the typical features of living polymerization. However, the living character could be observed only within certain monomer conversions. At higher monomer conversions, the copolymerizations deviated from the living behavior, probably because of the competitive degradative chain transfer of β‐pinene. The β‐pinene/acrylonitrile copolymers with a high alternation degree and controlled molecular weight were also obtained by the combination of the RAFT agent cumyl dithiobenzoate and Lewis acid Et₂AlCl. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2376–2387, 2006     

Model‐based design and synthesis of gradient MMA/tBMA copolymers by computer‐programmed semibatch atom transfer radical copolymerization

Methyl methacrylate (MMA)/tert‐butyl methacrylate (tBMA) gradient copolymers having linear and hyperbolic composition profiles were synthesized. These special copolymer products were achieved via a model‐based computer‐controlled semibatch atom transfer radical copolymerization (ATRcoP) process. A simple ATRcoP model was developed based on the terminal model. The equilibrium constants in the ATRP of MMA and tBMA were estimated by the data correlation. The model was verified by batch experiments and was found to give good correlation for the polymerization rate, molecular weight, and copolymer composition data. The model coupled with a reactor model was then applied to the semibatch ATRcoP and was used to calculate comonomer feeding rates for the targeted gradient composition profiles. It was found that the experimental monomer conversion, molecular weight, and cumulative copolymer composition were in good agreement with their targeted theoretical values. The gradient copolymers had low polydispersities close to 1.1. This work demonstrated the feasibility of the model‐based semibatch ATRcoP in fine‐tuning gradient copolymer composition profiles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 69–79, 2009     

Reaction kinetics in anionic copolymerization: A revisit on Mayo-Lewis equation

Reactivity ratio is a traditional parameter quantifying the reaction kinetics in copolymerization, which is important for potentially controlling microstructures of polymers and guiding the copolymerization process. Our recent experiments using tube-NMR technique enable us to in situ monitor the concentration profiles of the co-monomers during the anionic copolymerization process. This motivates us to revisit the Mayo-Lewis(ML) equation, which is the basis for derivation of reactivity ratio and has been extensively utilized in addition copolymerization. We found that although an explicit ML expression is desirable for ease of calculation and correlation with experimental data, it fails in our anionic copolymerization experiment as well as some data available in the literature. The origin is ascribed to the validity of the steady state assumption which is essential in the ML equation. This assumption can be released in anionic copolymerization and replaced by the fact that the overall concentration of the living chain ends keeps constant throughout the copolymerization. Alternative numerical method has been utilized to obtain the rate constants and consequently the reactivity ratios. Our work suggests that the ML equation should be applied with caution.     

Improved Kinetic Rate Constants for Nylon 6, Nylon 6,6, and Nylon 6/6,6 Copolymer

Nylon 6 and 6,6 literature data are collected over a wide range of water concentrations and temperatures (0 ≤ [W]₀ ≤ 40.8 wt%, 200 ≤ T ≤300 °C) and used to fit parameters in an updated batch reactor model. The resulting copolymerization model uses side reactions to account for the complex influence of water on kinetics and reaction equilibria. The proposed parameter estimates result in a significant improvement in the fit to the data, corresponding to a 73% reduction in the weighted‐least‐squares objective function compared to when the parameters of Arai et al. are used. Copolymerization simulations are conducted at industrially relevant conditions, shedding light on the complex influence of water and on the potential to include waste nylon 6 cyclic dimer in the feedstock. The model and parameter estimates will be helpful in future models of nylon 6/6,6 copolymerization in continuous reactor systems.