Kinetics of the batch cationic emulsion polymerization of styrene: A comparative study with the anionic case

An in‐depth study on the kinetics of the cationic emulsion polymerization of styrene in a batch reactor is presented. This study is focused on the effect of the amount of the cationic surfactant dodecyltrimethylammonium bromide (DTAB), using two different cationic initiators: 2,2′‐azobisisobutyramidine dihydrochloride (AIBA), 2,2′‐azobis (N,N′‐dimethyleneisobutyramidine) dihydrochloride (ADIBA), on kinetics and colloidal features such as conversion, number of particles, number average of radicals per particle, mean particle diameter, and particle size distribution (PSD) of the polystyrene latices obtained by emulsion polymerization in a batch reactor. Furthermore, the results of the cationic emulsion polymerization were compared with its homologous anionic case. Using DTAB as cationic surfactant an expected increase in the total rate of polymerization was observed when the DTAB concentration increased. However, the total number of particles increased much more than in the anionic system. On the other hand, a dependence on the particle size of the rate of polymerization per particle together with the average number of radicals per particle was found. These differences between cationic and anionic emulsion polymerizations were explained taking into account the limited particle coagulation observed with cationic surfactants, and the high rate of radical formation of cationic initiators. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4461–4478, 2006     

Which are the mechanisms governing in cationic emulsion polymerization?

The cationic emulsion polymerization of styrene in a batch reactor using different concentrations of dodecyltrimethylammonium bromide (DTAB) and hexadecyltrimethyl-ammonium bromide (HDTAB) as cationic surfactants, and 2,2′-azobisisobutyramidine dihydrochloride (AIBA), and 2,2′-azobis (N,N′-dimethyleneisobutyramidine) dihydrochloride (ADIBA) as cationic initiators has been studied. In the preliminary study, the best conditions to obtain stable cationic latexes at high conversions were identified. When the surfactant concentration was above its cmc, latexes with high conversions were achieved for the two cationic surfactants studied (DTAB and HDTAB). Cationic latexes with less coagulum were obtained using ADIBA as cationic initiator due to its superior resistance to hydrolysis. AIBA is hydrolyzed to amide at basic pHs and in this way, the concentration of radicals formed in the aqueous phase decreases. On the other hand, a stronger effect of the particle size on the kinetics of the cationic emulsion polymerization of styrene using HDTAB as cationic surfactant was observed than using DTAB. Furthermore, different kinetic behaviors were observed with the two cationic initiators (ADIBA and AIBA) using HDTAB as cationic surfactant, due to the lower stabilizing effect of the cationic radicals provided by AIBA.     

Characterization and study of microwave activation effects on the polystyrene tacticity

¹³C Nuclear magnetic resonance proved to be an advantageous tool to determine the stereoregularity of polystyrene polymers. The latter was achieved through the analysis of the signal of the quaternary carbon and that of the carbon-p in the aromatic ring too. Styrene was polymerized through microwaves and conventional heating activation using two different polymerization techniques: emulsion and bulk. Microwave activation was performed in a mono-modal type device under the following experimental conditions: various initiator concentrations, an average irradiation power of 50?W, temperature of 70°C, and using a batch reactor for emulsion and bulk experiments. The results obtained in these experiments were compared with those obtained by conventional heating activation polymerization under the same initiator concentration and temperature conditions. Microwave-activated reactions resulted in shorter reaction times and higher yields. The tacticity of the polymer samples was not significantly altered, which lead to the conclusion that, in this case, the stereoregularity of polystyrene was not influenced by microwave irradiation.     

Polymerization of epoxide with hydroxylamides as thermally latent initiators

A new class of thermally latent initiators for the ring‐opening polymerization of epoxides has been developed. The latent initiators developed herein were the hydroxylamides 1a , 1b , and 1c , which were synthesized from phthalide, 3‐isochromanone, and cis‐cyclohexahydrophthalide, respectively, by their ring‐opening reactions with pyrrolidine. These hydroxylamides were designed so that their hydroxyl groups could attack the amide moiety intramolecularly upon heating, leading to ring closure and formation of the corresponding lactones while releasing pyrrolidine, the initiator for the anionic ring‐opening polymerization of an epoxide. The temperatures at which this thermal dissociation occurred were strongly dependent on the hydroxylamide molecular structure. When using the hydroxylamides as thermally latent initiators, the polymerizations of bisphenol‐A diglycidyl ether were investigated at various temperatures. This investigation clarified that the threshold temperature, that is, the temperature at which polymerization was initiated, increased in the order of 1a , 1b , and then 1c . © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2611–2617     

Microemulsion Polymerization: An Undergraduate Experiment in the Synthesis of Nanosized Polystyrene Particles

The synthesis of polystyrene nanoparticles through microemulsion polymerization is presented as an undergraduate advanced organic laboratory exercise. The resultant polymers molecular weight and particle size are studied as a function of monomer and initiator concentration. A comparison of cationic vs. anionic surfactants, and their effects on the polymer produced through microemulsion polymerization are also investigated. A direct relationship is observed between molecular weight and monomer concentration. A direct relationship is also found for the particle size of the latex produced. An inverse relationship is observed for molecular weight and particle size as the initiator concentration was raised. Comparison of molecular weight and latex size for cationic and anionic surfactants demonstrates that the anionic surfactant produces both a higher molecular weight and a larger latex size over the entire monomer and initiator concentration ranges.     

Synthesis of amphoteric polystyrene particles using mixed initiators

The synthesis of amphoteric polystyrene latex particles, using a mixture of cationic (amidinium based) and anionic (carboxylic acid based) initiators in a surfactant-free emulsion polymerization reaction is investigated; this extends work described in an earlier paper by Bolt et al. Electrophoretic mobility measurements show the effect of the initiator concentration ratio on the isoelectric point (IEP) of the particles. A good correlation with theoretical predictions is obtained. Particle size and polydispersity are determined as a function of the lag time between the addition of each initiator. An increase in particle size and polydispersity is observed at short lag times. It is shown that this is due to the ratio of the cationic to anionic surface charge approaching unity during the reaction. At long lag times an increase in polydispersity may occur due to late-stage, secondary nucleation upon addition of the second initiator. Increasing the reaction pH to reduce the degree of ionization of the cationic initiator greatly reduces the polydispersity and has a significant effect on the IEP of the particles. This effect is ascribed to the burial of a fraction of the neutral amidine groups below the particle surface due to their increased solubility in the monomer. Slow addition of the second initiator was found to reduce the polydispersity of the particles, while maintaining an IEP value consistent with that expected for the ratio of initiators added.     

Comparative study of classical surfactants and polymerizable surfactants (surfmers) in the reversible addition–fragmentation chain transfer mediated miniemulsion polymerization of styrene and methyl methacrylate

Cationic and anionic amphiphilic monomers (surfmers) were synthesized and used to stabilize particles in miniemulsion polymerization. A comparative study of classical cationic and anionic surfactants and the two surfmers was conducted with respect to the reaction rates and molecular weight distributions of the formed polymers. The reversible addition–fragmentation chain transfer process was used in the miniemulsion polymerization reactions to control the molecular weight distribution. The reaction rates of the surfmer‐stabilized miniemulsion polymerization of styrene and methyl methacrylate were similar (in most cases) to those of the classical‐surfactant‐stabilized miniemulsion polymerizations. The final particle sizes were also similar for polystyrene latexes stabilized by the surfmers and classical surfactants. However, poly(methyl methacrylate) latexes stabilized by the surfmers had larger particle sizes than latexes stabilized by classical surfactants. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 427–442, 2006     

微波辐照制备无皂阳离子PMMA胶乳粒子

在微波辐照条件下 ,用偶氮二异丁基脒盐酸盐 (AIBA)引发甲基丙烯酸甲酯的均聚 ,制得窄分散的无皂阳离子胶乳粒子 .讨论了引发剂的浓度、单体的浓度、离子强度等对粒子大小、分散性和乳液稳定性的影响 .对微波辐照和水浴加热进行比较 ,发现微波辐照反应速度快、反应无恒速阶段 ,所得粒子的粒径小 ,粒子数目多 ,这为通过改变反应条件制备适宜的窄分散的胶乳粒子提供了一条途径 .     

Anionic hydrogen‐transfer polymerization of N‐isopropylacrylamide under microwave irradiation

Anionic hydrogen‐transfer homopolymerization of N‐isopropylacrylamide (NIPAAm) was carried out using t‐BuOK as an initiator in DMF under microwave irradiation. After 100 W of microwave was irradiated to the reaction mixture at 140°C for 6 h in the temperature control mode, corresponding polymer was obtained in 10% yield. In the case of conventional oil bath heating, by contrast, corresponding polymer was not obtained in similar anionic polymerization conditions. With 100 W and 2.45 GHz of microwave irradiation, formation of the polymer was obtained. Microwave‐assisted anionic hydrogen‐transfer copolymerization of NIPPAm and acrylamide (AAm) led to the formation of thermo‐sensitive copolymers whose thermo‐sensitivity was controlled by the NIPAAm/AAm unit ratio. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2415–2419     

Preaparation of cationic latexes of poly(styrene-CO-butyl acrylate) and their properties evolution in latex dilution

Cationic latexes were prepared through emulsion copolymerization of styrene(St) and butyl acrylate(BA) with a cationic surfactant,cetyl trimethyl ammonium bromide(CTAB).Latex properties,including particle size,size distribution,ζpotential,surface tension and monomer conversion,were determined for latexes prepared with different CTAB amounts. Evolution of these properties during emulsion polymerization was followed in order to understand the mechanism of the particles formation.Results showed that both particle size andζpotential were function of polymerization time and latex solids.Parallel emulsion polymerizations with cationic,anionic charged initiator and charge-free initiators were also carried out,the latex properties were determined at different polymerization time.All these results were attentively interpreted based on the mechanisms of emulsion polymerization,surfactant adsorption and latex particle stabilization.     

Microwave‐assisted nitroxide‐mediated radical polymerization of acrylamide in aqueous solution

The present work describes a combination of microwave irradiation as a heating source and water as a solvent for carrying out a living/controlled polymerization of acrylamide. Reasonable results were obtained for a nitroxide‐mediated radical polymerization (NMP) with a combination of a conventional hydrosoluble radical initiator and a β‐phosphonylated nitroxide. The microwave enhancement of the polymerization was found to depend on the mode of irradiation, i.e., either a dynamic (DYN) mode or an pulse (SPS) mode. The former mode corresponded to a dynamic control of the temperature by way of a high initial microwave power, and in this case, no specific microwave effect was observed. On the other hand, in the SPS mode, which is a pulsed power mode, the result showed a strong acceleration of the polymerization process (>50 times) without the loss of the living/controlled polymerization characteristics, which is relevant with a reinitiation of the polyacrylamide macroinitiator even after 100% of conversion. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

复合微乳液聚合制备P(MMA-UA)纳米乳胶粒子的研究

将聚氨酯预聚体可聚合乳化剂 (APUA)和甲基丙烯酸甲酯 (MMA)的复合微乳液体系 ,分别用水溶性过硫酸钾 (K2 S2 O8)和油溶性偶氮二异丁腈 (AIBN)作引发剂 ,进行微乳液聚合研究 ,制备了P(MMA UA)复合纳米乳胶粒子 .研究了APUA用量、聚合温度对聚合动力学的影响 ;用透射电子显微镜 (TEM)观察了不同乳化剂浓度及引发剂体系对胶粒形态、大小及分布的影响 .结果表明 ,用可聚合乳化剂APUA可制得稳定性很好的P(MMA UA)纳米级核 壳型乳胶粒子 ,乳胶粒径在 5 0nm左右 .随着乳化剂用量增加 ,粒子变小 ;不同类型的引发剂对胶乳的性质有较大影响 ,以APUA为乳化剂 ,K2 S2 O8为引发剂 ,在聚合反应过程中或在聚合反应后的放置中 ,会出现P(MMA UA)的纳米水凝胶 (Nanogel)现象 .     

Microwave-assisted asymmetric organocatalysis. A probe for nonthermal microwave effects and the concept of simultaneous cooling

A series of five known asymmetric organocatalytic reactions was re-evaluated at elevated temperatures applying both microwave dielectric heating and conventional thermal heating in order to probe the existence of specific or nonthermal microwave effects. All transformations were conducted in a dedicated reactor setup that allowed accurate internal reaction temperature measurements using fiber-optic probes. In addition, the concept of simultaneous external cooling while irradiating with microwave power was also applied in all of the studied cases. This method allows a higher level of microwave power to be administered to the reaction mixture and, therefore, enhances any potential microwave effects while continuously removing heat. For all of the five studied (S)-proline-catalyzed asymmetric Mannich- and aldol-type reactions, the observed rate enhancements were a consequence of the increased temperatures attained by microwave dielectric heating and were not related to the presence of the microwave field. In all cases, in contrast to previous literature reports, the results obtained either with microwave irradiation or with microwave irradiation with simultaneous cooling could be reproduced by conventional heating at the same reaction temperature and time in an oil bath. No evidence for specific or nonthermal microwave effects was obtained.     

微波辐照下丙烯酰胺的原子转移自由基共聚合

在微波辐射下,以水为反应介质,2-氯丙酰胺为引发剂,氯化亚铜/2,2′-联吡啶为催化体系,自制的磺基甜菜碱两性离子功能单体3-(2-甲基丙烯酰氧乙基二甲胺基)丙磺酸盐(DMAPS)与丙烯酰胺(AM)单体进行原子转移自由基共聚合反应,得到磺基甜菜碱型两性离子聚合物P(AM-DMAPS)。 讨论了微波功率、反应时间、单体用量、引发剂用量、催化剂和配体用量等因素对聚合反应的影响,并与相应的热聚合法进行了对照。 结果表明,微波辐射功率240 W,反应时间为1250 s时,微波辐射下共聚合的表观速率常数(Kappp)为热聚合法4.5倍,此时AM与DMAPS在水介质中的最佳合成条件为:单体总浓度4 mol/L(其中功能性单体DMAPS在混合单体中所占摩尔分数为1.0%),引发剂浓度0.015 mol/L,催化剂浓度0.01 mol/L。 此时转化率为40.15%,Mn为46410。     

Initiator effect on the cationic ring‐opening copolymerization of 2‐ethyl‐2‐oxazoline and 2‐phenyl‐2‐oxazoline

The aim of this research was to study the effect of the initiator on the resulting monomer distribution for the cationic ring‐opening copolymerization of 2‐ethyl‐2‐oxazoline (EtOx) and 2‐phenyl‐2‐oxazoline (PhOx). At first, kinetic studies were performed for the homopolymerizations of both monomers at 160 °C under microwave irradiation using four initiators. These initiators have the same benzyl‐initiating group but different leaving groups, Cl^?, Br^?, I^?, and OTs^?. The basicity of the leaving group affects the ratio of covalent and cationic propagating species and, thus, the polymerization rate. The observed differences in polymerization rates could be correlated to the concentration of cationic species in the polymerization mixture as determined by ¹H NMR spectroscopy. In a next‐step, polymerization kinetics were determined for the copolymerizations of EtOx and PhOx with these four initiators. The reactivity ratios for these copolymerizations were calculated from the polymerization rates obtained for the copolymerizations. This approach allows more accurate determination of the copolymerization parameters compared to conventional methods using the composition of single polymers. When benzyl chloride (BCl) was used as an initiator, no copolymers could be obtained because its reactivity is too low for the polymerization of PhOx. With decreasing basicity of the used counterions (Br^? > I^? > OTs^?), the reactivity ratios gradually changed from r_EtOx = 10.1 and r_PhOx = 0.30 to r_EtOx = 7.9 and r_PhOx = 0.18. However, the large difference in reactivity ratios will lead to the formation of quasi‐diblock copolymers in all cases. In conclusion, the used initiator does influence the monomer distribution in the copolymers, but for the investigated system the differences were so small that no difference in the resulting polymer properties is expected. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4804–4816, 2008     

Emulsion polymerization of methyl methacrylate under pulsed microwave irradiation

Emulsion polymerization of methyl methacrylate (MMA) under pulsed microwave irradiation (PMI) with higher peak pulse power was studied. The effects of various parameters of PMI on the polymerization were analyzed and compared with that under conventional heating (CH) process. The results were summarized, as compared with that under CH, as follows. The amount of initiator used to reach constant conversion reduced by 50% at the same polymerization time; at the same initiator concentration 0.15 and 0.2 wt.%, the polymerization rate increased by 131% and 163%, respectively. The molecular weight of polymer obtained was 1.1-2.0 times larger than that under CH; at the same irradiation energy, the conversion achieved using a lower pulse power was greater than that using a higher pulse power. There seemed to be a factor of the irradiation energy efficiency; in other words, for the monomer conversion, the irradiation energy of low pulse power had a higher efficiency. The conversion achieved using a 3.5 μs pulse width was almost the same as that using a 1.5 μs pulse width. The results indicated that PMI had a significant non-thermal effect on the emulsion polymerization of MMA so as to effectively enhance the polymerization rate. The glass transition temperature (T_g), the polydispersity index (PDI) and the regularity of the polymer obtained using two processes were similar, indicating that the physical properties and microstructure of the polymer were not modified by the use of microwaves.     

Relation between the reactivities of vinyl monomers in ionic polymerizations and their 1H NMR spectra

¹H NMR chemical shifts of the protons in the vinyl groups of monomers are correlated with their reactivities in anionic, coordinated anionic, and cationic polymerizations. The relative reactivities of styrenes in anionic addition reactions with living polystyrene increase linearly with the chemical shift of the proton trans to the substituent (δ_H1). Only the plot for 2,4,6-trimethylstyrene deviates very much from the linear relation because of the large steric hindrance. The relative reactivities of methacrylates in anionic copolymerizations increase with increasing chemical shifts of protons attached to the β-carbon of methacrylates. In cationic polymerizations of styrenes, the relative reactivities decrease with increasing δ_H1. The relative reactivities in coordinated anionic polymerizations with Ti-containing Ziegler initiators show a typical feature of cationic polymerization, and those with V-containing initiators show a typical feature of anionic polymerization, indicating the importance of the coordination process in the propagation reaction with Ti-containing initiator systems. From the results, it can be concluded that the chemical shifts of the protons attached to the β-carbon of vinyl monomers can be used as a practical measure of the reactivity of vinyl monomers in ionic polymerizations and also as a tool for understanding the mechanism of polymerization. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2134–2147, 2002     

Ring opening polymerization of epoxides with urea‐derivatives of 4‐aminopyridine as thermally latent anionic initiator

In this study, a series of urea‐derivatives of 4‐aminopyridine (4AP) were evaluated as thermally latent initiators for the anionic ring‐opening polymerization of diglycidyl ether of bisphenol A (DGEBA). The urea‐derivatives were synthesized by the reactions of 4AP with the corresponding iso(thio)cyanates (phenyl isocyanate, tert‐butyl isocyanate, methylene diphenyl diisocyanate, and phenyl isothiocyanate). The ability of the urea‐derivatives as latent initiators was investigated with differential scanning calorimetry (DSC): Upon heating formulations comprised of DGEBA and the urea‐derivatives in a heating rate at 10 °C/min, the resulting DSC profiles indicated exothermic peaks to confirm that DGEBA underwent the polymerization efficiently. The corresponding DSC‐peak top temperatures (T_{peak top}) was higher than that observed for the formulation comprised of DGEBA and pristine 4AP, to clarify that the urea are useful initiators with thermal latency. A possible mechanism for the initiation step involves the thermal dissociation of the urea into 4AP and the corresponding isocyanates. 4AP thus generated readily initiated the ring‐opening polymerization of epoxide. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2518–2522     

Semicontinuous seeded cationic emulsion polymerization of styrene: The effects of the concentration and type of cationic surfactant

The objective of this work was to analyze the effects of the concentration and type of cationic surfactant on the kinetic features (instantaneous and overall conversions) and colloidal characteristics [mean particle diameter, particle size distribution (PSD), and surface charge density] in the semicontinuous seeded cationic emulsion polymerization of styrene. 2,2′‐Azobis(N,N′‐dimethyleneisobutyramidine)dihydrochloride was used as an initiator. The surfactants were dodecyltrimethylammonium bromide (DTAB) and hexadecyltrimethylammonium bromide (HDTAB). So that the evolution of some polymeric and colloidal characteristics of the synthesized latices could be followed, the overall and instantaneous conversions were defined and determined gravimetrically. The PSDs and average particle diameters were determined by transmission electron microscopy and photon correlation spectroscopy. The surface charge density was determined by conductimetric titration. The evolution of the instantaneous conversions, the total number of particles, and the PSDs of the different reactions were related to the nucleation, growth, and coagulation processes taking place in the semicontinuous seeded emulsion polymerizations. The PSDs obtained from the reactions carried out with the emulsifier DTAB, at a concentration equal to its critical micelle concentration (cmc) and at a concentration twice its cmc, presented more and smaller particles than those obtained by the addition of HDTAB to the polymerization recipe. At lower emulsifier concentrations equal to half of the cmc, the system had lower colloidal stability with DTAB. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2322–2334, 2003     

Comparison of oil-soluble and water-soluble initiation of styrene polymerization in a three-component microemulsion

The polymerization of styrene in three-component oil-in-water microemulsions made with the cationic surfactant dodecyltrimethylammonium bromide is studied by dilatometry and quasielastic light scattering as a function of type and concentration of initiator. Fast polymerization rates, high conversions, and high molecular weight polymers are achieved with both oil-soluble (AIBN) and water-soluble (potassium persulfate) initiators. The rate of polymerization shows initiation and termination intervals, but no constant-rate interval is observed. Stable monodisperse microlatexes are obtained with both types of initiators. For both AIBN and potassium persulfate, polystyrene molecular weight is proportional to initiator concentration [I]^–0.4 and particle radii decrease as [I]^–0.2. Polymerization initiation occurs in or at the microemulsion droplets, and polymer particles grow by recruiting monomer and surfactant from uninitiated swollen micelles.