Nitroxide‐Mediated Controlled/Living Free Radical Copolymerization of Styrene and Divinylbenzene in Aqueous Miniemulsion

Summary: The nitroxide‐mediated controlled/living free radical copolymerization of styrene and divinylbenzene using a polystyrene‐TEMPO macroinitiator in aqueous miniemulsion and in bulk have been investigated. The crosslink densities were estimated based on the content of pendant vinyl groups as determined by ¹H NMR. Considerably lower crosslink densities were revealed in the miniemulsion than in the corresponding bulk system. The rate of polymerization in the miniemulsion increased with decreasing particle size, and was significantly higher than in bulk.

Crosslink density for the TEMPO‐mediated free radical copolymerization of S(1) and DVB(2) (f = 0.99, f = 0.01) at 125 °C in bulk (□) and in miniemulsions with d_n = 585 nm (○) and 53.3 nm (•).     

Nitroxide‐Mediated Radical Polymerization in Dispersed Systems: Compartmentalization and Nitroxide Partitioning

Compartmentalization and nitroxide partitioning in NMP in dispersed systems have been investigated by modeling and simulations. Compartmentalization comprises the segregation effect on termination and the confined space effect on deactivation. Under certain conditions, it is possible to obtain an improvement in both control and livingness. The particle size threshold for compartmentalization, decreases with any system change that leads to a decrease in the number of propagating radicals and/or nitroxides per particle, and vice versa. There is direct competition between the confined space effect on deactivation and nitroxide exit–the more water‐soluble the nitroxide, the weaker the confined space effect. Nitroxide partitioning leads to an increase in polymerization rate and loss in control/livingness.

     

Nitroxide‐Mediated Radical Polymerization in Miniemulsion at Stationary State: Rationale for Independence of Polymerization Rate on Nitroxide Partitioning Using Oil‐Phase Initiation

Summary: Simulations based on the kinetics and mechanism of nitroxide‐mediated free radical polymerization (NMP) have been carried out in order to understand the hitherto largely unexplained effects (or lack thereof) of nitroxide partitioning in aqueous miniemulsion NMP. The focus has been on the miniemulsion NMP of styrene mediated by TEMPO and 4‐hydroxy‐TEMPO, two nitroxides with very similar activation‐deactivation equilibria, but very different organic phase‐aqueous phase partition coefficients. The general conclusion is that the organic phase propagating radical and nitroxide concentrations are unaffected by the partition coefficient in the stationary state, but the rate of polymerization and the extent of bimolecular termination increase with increasing nitroxide water solubility in the pre‐stationary state region. Specific NMP systems are, therefore, affected differently by nitroxide partitioning depending on whether polymerization predominantly occurs in the stationary state or not, which in turn is governed mainly by the activation‐deactivation equilibrium constant and the rate of thermal initiation.

Simulated organic‐phase propagating radical concentrations in the presence of thermal initiation for TEMPO‐mediated miniemulsion free radical polymerization of styrene for different nitroxide partitioning coefficients at 125 °C.     

Nitroxide‐Mediated Radical Polymerization in Microemulsion

Nitroxide‐mediated polymerizations of styrene in microemulsion have been carried out at 125 °C using the cationic surfactant tetradecyltrimethylammonium bromide and the nitroxides 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy (TEMPO) and N‐tert‐butyl‐N‐[1‐diethylphosphono‐(2,2‐dimethylpropyl)] nitroxide (SG1). TEMPO‐mediated polymerizations were extremely slow, with large particles (d_n = 39–129 nm) and broad molecular weight distributions (MWDs). The origin of the broad MWDs was likely significant alkoxyamine decomposition and differing diffusion rates of monomer and low MW alkoxyamines (and nitroxide) between monomer‐swollen micelles and polymer particles. SG1‐mediated polymerizations proceeded at higher rates, resulting in nanoparticles (d_n = 21–37 nm) and lower than for TEMPO.

     

Compartmentalization in TEMPO‐Mediated Radical Polymerization in Dispersed Systems: Effects of Macroinitiator Concentration

The influence of the initial macroinitiator concentration ([PT]₀) on compartmentalization effects (segregation effects and confined space effects) in 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy (TEMPO)‐mediated radical polymerization of styrene in a dispersed system at 125 °C has been investigated by simulations employing modified Smith‐Ewart equations. The modeling approach accounts for compartmentalization of both propagating radicals and nitroxide, as well as the generation of radicals by thermal initiation of styrene. The manifestation of compartmentalization effects occurs at significantly greater particle diameters (d) for low [PT]₀; at [PT]₀ = 0.002 M , the polymerization rate, control and livingness are affected by compartmentalization for d < 120 nm, whereas the system behaves as in the corresponding bulk system for d > 45 nm at [PT]₀ = 0.2 M . The results are discussed with regards to the specific effects of compartmentalization on deactivation and bimolecular termination.

     

Modeling of Nitroxide‐Mediated Semibatch Radical Polymerization

A mechanistic model is developed for high‐temperature (138 °C) styrene semibatch thermally and conventionally initiated FRP, as well as NMP with a two‐component initiating system (tert‐butyl peroxyacetate, 4‐hydroxy‐TEMPO). The model, using kinetic coefficients from literature, provides a good representation of the FRP experimental results. Implementation of a gel effect correlation to represent the change in the diffusion‐controlled termination rate coefficient with conversion improves the fit to the thermally initiated system, but is not required to represent the production of low molecular weight material ( Dalton) by conventionally initiated FRP or NMP. The low initiator efficiency found in NMP is well explained by a reaction network involving combination of free nitroxide with methyl radicals formed from initiator decomposition.

     

Kinetics of Controlled/Living Radical Polymerization in Emulsified Systems

Summary : For the controlled/living radical polymerization (CLRP) in which the active period during the chain formation is extremely small, ϕ_A < 1, such as the cases of usual SFRP and ATRP, the polymerization rate can be made larger by increasing the average number of monomeric units added during a single active period, . The -value is inversely proportional to the trapping agent concentration [X], and the polymerization rate is controlled by [X]. For small particles, even with a single trapping agent, [X] in the particle could be larger than that in corresponding bulk polymerization, and the polymerization rate decreases with D, where D_p is the particle diameter. On the other hand, for CLRPs whose ϕ_A-value is not very much smaller than unity, say ϕ_A>0.01, such as some of RAFT polymerization systems, the polymerization rate can be made larger by increasing the kinetic chain length for a given initiation frequency. For such reaction systems, the polymerization rate can be enhanced significantly by employing the emulsified polymerization systems.     

Nitroxide‐Mediated Radical Dispersion Polymerization of Styrene in Supercritical Carbon Dioxide Using a Poly(dimethylsiloxane‐block‐styrene) Alkoxyamine as Initiator and Stabilizer

Summary: Nitroxide‐mediated dispersion polymerization of styrene in supercritical carbon dioxide has been performed successfully at 110 °C using a new polymeric so‐called inistab species, which fulfils the dual functions of an initiator and a colloidal stabilizer. The inistab species comprised a poly(dimethylsiloxane) block and a polystyrene block end‐capped with the nitroxide N‐tert‐N‐butyl‐N‐[1‐diethylphosphono‐(2,2‐dimethylpropyl)] nitroxide (SG1). The dispersion polymerization resulted in sub‐micron sized polymer particles and polymers of narrow polydispersity.

TEM micrograph of PS particles prepared in the dispersion polymerization of S in scCO₂ in the presence of PDMS(\overline M _{\rm n} = 6 500)‐b‐PS(\overline M _{\rm n} = 4 500)‐SG1 at 110 °C.     

Thioketone‐Mediated Polymerization of Butyl Acrylate: Controlling Free‐Radical Polymerization via a Dormant Radical Species

It is demonstrated by experiment and simulation that the commercially available thioketone 4,4‐bis(dimethylamino)thiobenzophenone is capable of controlling AIBN‐initiated bulk butyl acrylate polymerization at 80 °C. On the basis of molecular weight data and from monomer conversion versus time curves, the associated rate parameters are estimated. The addition rate coefficient, k_ad, for the reaction of a propagating chain with the thioketone is close to 10⁶ L · mol⁻¹ · s⁻¹ and the fragmentation rate coefficient, k_frag, is around 10⁻² s⁻¹ giving rise to large equilibrium constants in the order of 10⁸ L · mol⁻¹. Furthermore, cross‐ and self‐termination of the dormant radical species are identified to be operational.

     

Monte Carlo Simulation of Controlled/Living Radical Polymerization in Emulsified Systems

A new MC simulation method is proposed for the controlled/living radical polymerization in a dispersed medium, assuming an ideal miniemulsion system. This tool is used to consider the effects of particle size on the polymerization rates and the molecular weight distributions. For NMP, the polymerization kinetics are basically governed by two conflicting factors, (i) the confined space effect that promotes the coupling reaction between a radical and a trapping agent and (ii) the isolation effect of radicals into different particles that suppresses the overall frequency of bimolecular termination. For RAFT polymerization, a significant rate enhancement by reducing the particle size could be observed only for the systems with fast fragmentation of adduct radicals.

     

Kinetics of Stable Free Radical Mediated Polymerization inside Submicron Particles

Controlled/living radical polymerization systems in which the active period is extremely small, ϕ_A ≪ 1, such as the cases of stable free radical mediated polymerization (or nitroxide mediated polymerization) and atom transfer radical polymerization, are considered theoretically. The polymerization rate, R_p, for such systems increases by lowering the trapping agent concentration [X]. When the polymerization is conducted inside small particles, R_p decreases with D below the diameter D_p,SMC at which a single molecule concentration (SMC) is equal to [X]_bulk. On the other hand, when the average number of trapping agents in a particle is smaller than about 10, the fluctuation of n_X among particles is significant, which leads to a larger R_p than in the cases where all particles contain the same n_X. Because of the effects of SMC and fluctuation, R_p may show an acceleration window, D_p,SMC < D_p < D_p,Fluct where R_p is slightly larger than that in bulk.

     

End‐Group Characterization of Poly(acrylic acid) Prepared by Nitroxide‐Mediated Controlled Free‐Radical Polymerization

Summary: A low‐molar‐mass poly(acrylic acid) with a narrow molar‐mass distribution, prepared by SG1 nitroxide‐mediated controlled free‐radical polymerization, was subjected to end‐group analysis to confirm its living nature. ¹H and ³¹P NMR spectroscopy confirmed the presence of the SG1‐based alkoxyamine end group. Furthermore, chain extension with styrene and n‐butyl acrylate demonstrated the ability of the homopolymer to initiate the polymerization of a second block. These results open the door to the synthesis of poly(acrylic acid)‐based block copolymers by direct nitroxide‐mediated polymerization of acrylic acid.

Acrylic acid polymerization using an alkoxyamine initiator based on SG1 (N‐tert‐butyl‐N‐(1‐diethyl phosphono‐2,2‐dimethylpropyl) nitroxide resulting in a homopolymer capable of initiating the polymerization of a second block.     

Particle Size Effects in TEMPO‐Mediated Radical Polymerization of Styrene in Aqueous Miniemulsion

Summary: 2,2,6,6‐Tetramethylpiperidinyl‐1‐oxy (TEMPO)‐mediated radical polymerization of styrene in aqueous miniemulsion at 125 °C using sodium dodecylbenzenesulfonate and poly(vinyl alcohol), respectively, as colloidal stabilizers has been investigated. The particle size had a dramatic effect on the polymerization process. Decreasing particle size led to a markedly higher polymerization rate, but less control and a lower degree of livingness. For particles with diameters greater than approximately 170 nm, the polymerization behavior was essentially the same as in the corresponding bulk system. By varying the particle size within an appropriate range, it is possible to tune the polymerization such that the polymerization rate is increased while still maintaining reasonable control and livingness.

     

Living Nitroxide‐Mediated Radical Terpolymerization: General Concept and Synthetic Possibilities

The general concept for nitroxide‐mediated radical terpolymerization is advanced. This concept is based on activation‐deactivation equilibria for terminal polymer‐nitroxide adducts. Depending on monomer activity and the stability of terminal nitroxide adducts, terpolymerization can be equilibrium living, quasi‐equilibrium (gradient) living, decaying living, decaying gradient, or non‐living. Expressions for the effective activation‐deactivation equilibrium constant, K_ef, and the rate of terpolymerization are derived from theoretical speculations on equilibrium living and decaying living terpolymerization. For quasi‐equilibrium living terpolymerization, various types of gradient terpolymers are predicted. When activity of the active monomer M₁ is, at least, one order of magnitude different from that of the two other monomers, the effective constant K_ef is shown to approach K₁ of the most active monomer. Experimental kinetic and equilibrium constants agree with the advanced concept for the equilibrium living terpolymerization of styrene with methyl methacrylate, and acrylonitrile in the presence of nitroxide SG1, as well as for decaying living terpolymerization in the same system in the presence of nitroxide TEMPO.

     

Modeling of Network Formation in Nitroxide‐Mediated Radical Copolymerization of Vinyl/Divinyl Monomers Using a Multifunctional Polymer Molecule Approach

A mathematical model for the kinetics of copolymerization with crosslinking of vinyl/divinyl monomers in the presence of stable nitroxyl radicals is presented. A reaction scheme considering multifunctional polymer molecules is proposed. The Flory‐Stockmayer theory is used for the post‐gelation period. Average crosslink and cyclization densities are calculated using two different approaches. Good agreement between predicted profiles and experimental data from our and other groups is observed in all cases. Overall monomer concentration, controller/initiator ratio, and crosslinker initial concentration are found to be the governing factors for the development of average crosslink and cyclization densities and therefore for the homogeneity of the resulting polymer network.

     

Nitroxide‐mediated radical polymerization in miniemulsion: Bimolecular termination in monomer‐free model systems

Bimolecular termination in nitroxide‐mediated radical polymerization in miniemulsion has been investigated through the heating of a polystyrene–2,2,6,6‐tetramethylpiperidinyl‐1‐oxy macroinitiator and its 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyl‐1‐oxy analogue in an aqueous toluene dispersion with sodium dodecyl benzenesulfonate as a surfactant at 125 °C. The level of bimolecular termination by combination, evaluated from the high‐molecular‐weight shoulder, was higher in miniemulsion than in solution and increased with decreasing particle size. Quantitative analysis revealed that these results cannot be rationalized solely by nitroxide partitioning to the aqueous phase. The results are explained by an interface effect, by which nitroxide is adsorbed or located at the aqueous–organic interface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4995–5004, 2007     

醋酸乙烯酯的可控/活性自由基聚合

概述了醋酸乙烯酯单体可控/活性自由基聚合的现状.总结了氮氧化合物存在下的聚合、原子转移自由基聚合、可逆加成断裂链转移聚合以及含碘化合物的衰减链转移聚合这四种活性自由基聚合方法用于醋酸乙烯酯聚合的研究结果,并对这四种方法作了简要的比较.     

Studying the Fundamentals of Radical Polymerization Using ESR in Combination with Controlled Radical Polymerization Methods

Electron spin resonance (ESR) spectroscopy can contribute to understanding both the kinetics and mechanism of radical polymerizations. A series of oligo/poly(meth)acrylates were prepared by atom transfer radical polymerization (ATRP) and purified to provide well defined radical precursors. Model radicals, with given chain lengths, were generated by reaction of the terminal halogens with an organotin compound and the radicals were observed by ESR spectroscopy. This combination of ESR with ATRPs ability to prepare well defined radical precursors provided significant new information on the properties of radicals in radical polymerizations. ESR spectra of the model radicals generated from tert-butyl methacrylate precursors, with various chain lengths, showed clear chain length dependent changes and a possibility of differentiating between the chain lengths of observed propagating radicals by ESR. The ESR spectrum of each dimeric, trimeric, tetrameric, and pentameric tert-butyl acrylate model radicals, observed at various temperatures, provided clear experimental evidence of a 1,5-hydrogen shift.     

Kinetics and Molecular Weight Development of Dithiolactone‐Mediated Radical Polymerization of Styrene

Calculations of polymerization kinetics and molecular weight development in the dithiolactone‐mediated polymerization of styrene at 60 °C, using 2,2′‐azobisisobutyronitrile (AIBN) as initiator and γ‐phenyl‐γ‐butirodithiolactone (DTL1) as controller, are presented. The calculations were based on a polymerization mechanism based on the persistent radical effect, considering reverse addition only, implemented in the PREDICI® commercial software. Kinetic rate constants for the reverse addition step were estimated. The equilibrium constant (K = k_add/k_‐add) fell into the range of 10⁵–10⁶ L · mol^?1. Fairly good agreement between model calculations and experimental data was obtained.

     

Atom‐Transfer Radical Batch and Semibatch Polymerization of Styrene

Batch and semibatch styrene polymerizations are carried out using a heterogeneous ATRP catalyst system that provides excellent molecular‐weight control. The observed initiator efficiency is lower for semibatch operation due to the high initiator concentrations required to make a low‐MW polymer. Experiments verified that the insoluble metal complex does not participate in the polymerization and that Cu(I) solubility is an order of magnitude higher than that of Cu(II). A mechanistic model, using kinetic coefficients from literature and the solubility data from this study, provides a good representation of the experimental results.