Miniemulsion copolymerizations of methyl methacrylate and butyl acrylate in the presence of reactive costabilizer

The storage stability and free radical polymerizations of miniemulsions comprising methyl methacrylate (MMA), butyl acrylate (BA), and a reactive costabilizer stearyl methacrylate (SMA) were investigated. The Ostwald ripening rate increases with increasing MMA content in the monomer mixture. Both the pseudo‐two‐component model and empirical equation with one adjustable parameter k adequately predicted the Ostwald ripening rate data. For the empirical model, the least‐squares best fit technique gave a value of k equal to 677.5 and values of Ostwald ripening rate and water solubility equal to (8.8 ± 0.2) × 10^?21 cm³/s and 1.8 × 10^?9 cm³/cm³ for SMA, respectively. These two models were combined to impart some physical insight to the parameter k. The kinetic studies showed that the polymerization rate increased with increasing MMA content. This is closely related to the nature of the constituent monomers MMA and BA and the particle nucleation mechanisms. The reactive costabilizer SMA is not hydrophobic enough to completely eliminate the Ostwald ripening effect, thereby increasing the probability of polymer reactions in the continuous aqueous phase. Thus, in addition to monomer droplet nucleation, particle nuclei can be generated in the aqueous phase via homogeneous nucleation. The extent of homogeneous nucleation increased with increasing MMA content and, as a result, the number of reaction loci available for the major polymerization to take place followed the same trend. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Miniemulsion copolymerizations of styrene and reactive alkyl methacrylate costabilizers

Miniemulsion copolymerizations of styrene (ST) and stearyl methacrylate (SMA) or lauryl methacrylate (LMA) were investigated. Miniemulsions comprising ST and various levels of SMA showed very good storage stability against the diffusional degradation of monomer droplets (Ostwald ripening), whereas miniemulsions comprising ST and various levels of LMA exhibited significant Ostwald ripening. In subsequent miniemulsion copolymerizations of ST and SMA, particle nucleation occurring in the continuous aqueous phase (homogeneous nucleation) plays an important role in the particle formation process in addition to monomer droplet nucleation. The final overall conversion and the individual conversions of ST and SMA all decrease with increasing SMA concentration. Furthermore, at a particular reaction time, the individual conversion of SMA is always greater than that of ST. Monomer droplet nucleation was retarded severely for the monomer pair ST/LMA, presumably due to the very strong Ostwald ripening effect. As a result, relatively slow rates of copolymerization of ST and LMA were attained compared with the ST/SMA counterpart. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Kinetics of reversible addition–fragmentation transfer (RAFT) miniemulsion polymerization of styrene using dibenzyl trithiocarbonate as RAFT reagent and costabilizer

The roles of dibenzyl trithiocarbonate (DBTTC) as both costabilizer and reversible addition–fragmentation transfer (RAFT) reagent in RAFT miniemulsion polymerizations of styrene were investigated. The effectiveness of DBTTC costabilizer in retarding Ostwald ripening involved in the storage stability of miniemulsion is comparable to that of conventional low‐molecular‐weight costabilizers such as cetyl alcohol, but inferior to that of hexadecane. The major variables chosen for studying kinetics of RAFT miniemulsion polymerizations include the type of initiators and levels of DBTTC and surfactant. At a constant level of DBTTC, the rate of polymerization for benzoyl peroxide (BPO)‐initiated polymerization is slower than that for sodium persulfate (SPS)‐initiated polymerization. Furthermore, the polymerization rate decreases with increasing level of DBTTC for polymerizations initiated by BPO (or SPS). It is the monomer droplet nucleation that governs BPO‐initiated polymerizations. In contrast, for SPS‐initiated polymerizations, the probability for homogeneous nucleation to take place is greatly increased, especially for polymerizations with lower levels of DBTTC and higher levels of surfactant. © 2015 Society of Chemical Industry     

Miniemulsion copolymerization of styrene and butyl acrylate initiated by redox system at lower temperature: Reaction kinetics and evolution of particle‐size distribution

The kinetics of the miniemulsion copolymerization of styrene (St) and butyl acrylate (BA) initiated by redox initiators, (NH₄)₂S₂O₈/NaHSO₃, at lower temperature (45°C) was studied. The polymerization rate in miniemulsion copolymerization is lower than that of the corresponding conventional emulsion copolymerization. In regard to the rate of polymerization, the initiator concentration plays a more important role in miniemulsion copolymerization than in conventional emulsion polymerization, while the surfactant concentration has a more important role in conventional emulsion polymerization than in miniemulsion polymerization. These are attributed to their different nucleation mechanisms, which are the same as those found in the miniemulsion polymerization carried out at higher temperatures. While by eliminating nucleation via micelle and ensuring against homogeneous nucleation, miniemulsion polymerization can be carried out by the sole nucleation mechanism—monomer droplet nucleation—at lower temperature. Because of this, the particles become narrower during the polymerization and, finally, monodisperse polymer particles are obtained. The result of the particle numbers indicated that a continuous nucleation will cease at about 60% conversion. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 315–322, 1999     

Kinetics of miniemulsion polymerizations of ethylene glycol dimethacrylate and/or methyl methacrylate

Two types of reactive acrylic microgel particles of methyl methacrylate (MMA)/ethylene glycol dimethacrylate (EGDMA) (66.4/33.6 and 0/100 (mol/mol)) were prepared by miniemulsion polymerization with 2,2′‐azobisisobutyronitrile as the initiator in the temperature range 60–80 °C. Ostwald ripening occurred during the very early stage of polymerization. In addition to the predominant droplet nucleation, homogeneous nucleation was also observed. The polymerization rate for MMA/EGDMA miniemulsion was higher than that for EGDMA miniemulsion. By contrast, comparable apparent limiting conversions were observed for the polymerizations of MMA/EGDMA and EGDMA. The mole fractions of MMA and EGDMA units incorporated into the copolymer product were estimated to be 0.62 and 0.38, respectively, for the polymerization of MMA/EGDMA at 70 °C. The mole fraction of the EGDMA unit containing one ? C?C? within the MMA/EGDMA microgel particle product was estimated to be 0.23, which was comparable to that (0.22) of the EGDMA unit containing one ? C?C? within the EGDMA microgel particle product. © 2015 Society of Chemical Industry     

Miniemulsion polymerization of styrene with polymeric costabilizers

The polymeric costabilizers poly(stearyl methacrylate‐co‐2‐hydroxyethylmethacrylate) (PSH) and poly(lauryl methacrylate‐co‐2‐hydroxyethylmethacrylate) (PLH), composed of a hydrophilic backbone and several hydrophobic alkyl (stearyl or lauryl) side chains, were prepared by the free‐radical copolymerization of stearyl methacrylate (SMA) or lauryl methacrylate (LMA) with 2‐hydroxyethylmethacrylate and evaluated in the miniemulsion polymerization of styrene (ST). For comparison, the reactive costabilizers SMA and LMA were also included in this work. The hydrophobicity of costabilizers in increasing order was PLH < PSH < LMA < SMA. Only a small amount of these comb‐like copolymers was capable of producing kinetically stable ST emulsion droplets. The more hydrophobic the costabilizer was, the more effective was the costabilizer in the retardation of Ostwald ripening. About 30–40% of the monomer droplets were successfully converted into latex particles during the polymerization. The degree of monomer droplet nucleation increased with increasing hydrophobicity of the costabilizer. The formation of particle nuclei in the continuous aqueous phase played a crucial role in the polymerization kinetics. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1961–1969, 2004     

Preparation of Hybrid Nanocomposite Particles via in situ Miniemulsion Polymerization and the Sol‐Gel Process

In this paper, the preparation of polymer/silica nanocomposite particles in a convenient one‐step process, via in situ miniemulsion polymerization and the sol‐gel technique, is described. The products were characterized using differential scanning calorimetry, transmission electron microscopy, and dynamic light scattering. Moreover, the effects of various reaction parameters, including the content of silica and the concentrations of sodium dodecyl sulfate and potassium persulfate, on the particle size and size distribution were also investigated. It is shown that polymer/silica hybrid nanocomposite particles were successfully synthesized in one step by this novel technique.

     

Kinetics of Miniemulsion Polymerization of Styrene in the Presence of Organoclays

The impacts of nanoclays on the miniemulsion polymerization kinetics of styrene were studied. It was found that both R_P and the fractional conversion decreased upon increasing the organoclay content in the miniemulsion system. In the presence of nanoclay the molecular weight of polystyrene nanoclay composite is lower and the particle size polydispersity of the final composite latex is greater than that of pure styrene miniemulsion polymerization. The effect of the nanoclays is mainly caused by the destabilization of the miniemulsion by the organoclay particles. The increase in the monomer viscosity and the decrease in the diffusion rate of the monomer and the living polymer inside the monomer droplet also accounts for the reduction in the polymerization rate.

     

Particle nucleation and growth mechanisms in miniemulsion polymerization of styrene

Styrene miniemulsion polymerizations stabilized by sodium lauryl sulfate in combination with a reactive costabilizer, lauryl methacrylate (LMA) or stearyl methacrylate (SMA), were studied. A small amount of extremely hydrophobic dye was incorporated into monomer droplets (10² nm in diameter) to investigate particle nucleation and growth mechanisms. In addition to monomer droplet nucleation, particle nuclei generated in the aqueous phase (homogeneous nucleation) also play an important role in both LMA‐ and SMA‐containing polymerization systems. The way that these two nucleation mechanisms compete with each other is closely related to the water solubility of the costabilizer (LMA > SMA). The fraction of latex particles originating from homogeneous nucleation increases with decreasing hydrophobicity of the costabilizer. Zeta potential data of latex particles and the molecular weight and molecular weight distribution of emulsion polymers provide supporting evidence for the proposed competitive particle nucleation and growth mechanisms. © 2002 Society of Chemical Industry     

高分子表面活性剂对细乳液聚合的影响

通过分析细乳液聚合过程中的单体乳液稳定性、聚合反应动力学以及聚合所得乳胶粒的特性,讨论了高分子表面活性剂对细乳液聚合的影响,并与普通低分子表面活性剂进行了比较。     

An evaluation of the impact of SG1 disproportionation and the addition of styrene in NMP of methyl methacrylate

A kinetic modeling study is presented for batch nitroxide mediated polymerization (NMP) of methyl methacrylate (MMA; nitroxide: N‐tert‐butyl‐N‐[1‐diethylphosphono‐(2,2‐dimethylpropyl)] (SG1)). Arrhenius parameters for SG1 disproportionation (A = 1.4 10⁷ L mol^?1 s^?1; E_a = 23 kJ mol^?1) are reported, based on homopolymerization data accounting for unavoidable temperature variations with increasing time, that is, nonisothermicity. For low targeted chain lengths (TCLs ≤ 300), this nonisothermicity is also relevant for NMP of MMA with a small amount of styrene. Parameter tuning to copolymerization data confirms a penultimate monomer unit effect for activation (s_a2 = k_a12/k_a22=6.7; 363 K; 1: MMA; 2: styrene). To obtain, for a broad TCL range (up to 800), a dispersity well below 1.3 an initial styrene mass fraction of ca. 10% is required. An interpretation of the comonomer incorporation is performed by calculating the fractions of activation‐growth‐deactivation cycles with a given amount of monomer units and the copolymer composition distribution. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2545–2559, 2018     

Dispersion polymerization of methyl methacrylate: Effect of stabilizer concentration

In dispersion polymerizations of methyl methacrylate (MMA), little difference was found in the polymerization kinetics with varying stabilizer (PVP K‐30) concentration, indicating that in contrast to emulsion polymerization, the kinetics of these dispersion polymerizations are independent of the number of particles. Comparing MMA precipitation and dispersion polymerizations revealed that nuclei formation in the latter results from precipitation polymerization occurring in the continuous phase, which can contribute significantly to the kinetics, and especially to the molecular weight distributions. No change was found in the molecular weight distribution of the PVP during a dispersion polymerization, nor was there any measurable difference between using fresh and recycled stabilizer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Tentative study on kinetics of bulk polymerization of methyl methacrylate in presence of montmorillonite

The kinetics of the bulk polymerization of methyl methacrylate (MMA) in the presence of montmorillonite (MMT) were studied. The effect of MMT on the radical polymerization of MMA was researched by determining the polymerization rate dilatometrically. It was assumed that there were both bimolecular and monomolecular termination processes involved in the termination of the radicals in the polymerization. It was found that a lower benzoyl peroxide (BPO) concentration promotes a higher fraction of monomolecular mode in chain termination. The results show that there is an optimal ratio of MMT to initiator that increases the bulk polymerization rate of MMA. The X‐ray results show that the layer structure of the formed PMMA–MMT composites was also affected by the BPO concentration. With lower initiator concentration, less pronounced layer structure will be observed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3690–3695, 2003     

Solution and quasi‐bulk copolymerizations of styrene and methyl methacrylate in the presence of polybutadiene: Mathematical model

A mathematical model was developed for simulating the batch copolymerization of styrene (St) and methyl methacrylate (MMA) in the presence of polybutadiene (PB). It was adjusted to the measurements of three reactions carried out at 65°C, with initial comonomers ratio at the azeotropic condition, THF as solvent, and benzoyl peroxide as initiator. The measurements included: (a) conversions and grafting efficiencies by gravimetry; (b) molecular weight distributions (MWDs) by size exclusion chromatography; and (c) global mass fractions of St in the co‐ and terpolymer, by UV‐Vis spectroscopy. The model predicts the MWDs of the three polymeric components of MBS: free St‐MMA copolymer, St‐MMA‐g‐PB graft terpolymer (GT), and residual PB. In addition, it predicts the bivariate chain length distributions of the different GT topologies, with each topology characterized by the number of branches per molecule. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanism of seeded dispersion polymerization of methyl methacrylate using submicron polystyrene seed particles

Submicron polystyrene (PS) latex particles were used as seed in seeded dispersion polymerization of methyl methacrylate (MMA) to investigate the particle nucleation and aggregation behavior in this type of polymerization. The PS seed particles were located and tracked during the reaction using a refractive index matching technique. The number of PS seed particles present in the poly(methyl methacrylate) (PMMA) particles was investigated in detail throughout the reaction. The change in the distribution of PMMA particle populations containing different numbers of seed particles indicated that intensive nucleation and aggregation occurred during the early stage of the reaction until a transition point of 8.7% conversion was attained under the reaction conditions studied. The size of the large particles at this point was around 1 μm. These particles were regarded as mature particles that did not aggregate with other mature particles. Meanwhile, immature particle were still generated continuously from the continuous phase. These immature particles could not survive the aggregation process to grow to become mature particle, but instead, were captured by the mature particles. Therefore, the total number of the mature particles remained constant from this point until the end of the reaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of short chain alcohols on the styrene emulsion polymerization

The effects of a series of short chain alcohols, 1‐butanol (C₄OH), 1‐pentanol (C₅OH), and 1‐hexanol (C₆OH), on the styrene (ST) emulsion polymerization mechanisms and kinetics were investigated. The CMC of the ST emulsions stabilized by sodium dodecyl sulfate (SDS) first decreases rapidly and then levels off when the C_iOH (i = 4, 5, or 6) concentration ([C_iOH]) increases from 0 to 72 mM. Furthermore, at constant [C_iOH], the CMC data in decreasing order is CMC (C₄OH) > CMC (C₅OH) > CMC (C₆OH). The effects of C_iOH (i = 4, 5, and 6) on the ST emulsion polymerization stabilized by 6 mM SDS are significant. This is attributed to the reduction in CMC by C_iOH, the different oil–water interfacial properties, the different concentrations of monomer within latex particles, and the different effectiveness of SDS/C_iOH in stabilizing latex particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4406–4411, 2006     

Rapid ambient temperature living radical polymerization of methyl methacrylate and styrene utilizing sodium hypophosphite as reducing agent

A facile, safe, and inexpensive reducing agent, sodium hypophosphite (NaH₂PO₂·H₂O), has been successfully used to perform ambient temperature living radical polymerizations of methyl methacrylate (MMA) and styrene (St). The rapid radical polymerizations were readily obtained at 25°C, i.e., MMA reached a conversion of ca 90% after 2.5 h, and St reached a conversion of ca 80% after 40 h. The polymerizations of MMA and St exhibited excellent living/controlled nature, as evidenced by pseudo first‐order kinetics of polymerization, linear evolution of molecular weights with increasing monomer conversions, and narrow molecular weight distributions. The various experimental parameters—ligand, solvent, and molar ratio of NaH₂PO₂·H₂O to CuSO₄·5H₂O—were varied to improve the control of polymerization, molecular weight, and molecular weight distribution. ¹H NMR analyses and chain‐extension reactions confirm the high chain‐end functionality of the resultant poly(methyl methacrylate) and polystyrene. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42123.     

Effect of the carboxylic acid monomer type on the emulsifier‐free emulsion copolymerization of styrene and butadiene

Carboxylated styrene–butadiene rubber latexes were prepared through the emulsifier‐free emulsion copolymerization of styrene and butadiene with various carboxylic acid monomers. The effects of various carboxylic acid monomers on the particle formation process were investigated. The type of carboxylic acid monomer strongly affected the particle nucleation. The number of particles and thus the polymerization rate increased with the increasing hydrophobicity of the carboxylic acid monomers. There was a significant difference in the polymerization rate per particle. The results showed that particle nucleation and growth were dependent on the hydrophilic nature of the carboxylic acid monomers. The average particle diameter of the carboxylated styrene–butadiene rubber latexes in the dry state was obtained through some calculations using direct measurements of the average particle diameter in the monomer‐swollen state by a dynamic light scattering technique. Several parameters, such as the polymerization rate, number of latex particles per unit of volume of the aqueous phase, and polymerization rate per particle, were calculated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007