Emulsion Polymerization Research Articles

Damping and acoustic properties of nanosilica filled poly(styrene-acrylate) interpenetrating polymer networks (IPNs): Effect of nanocomposite preparation method

Research on noise pollution reduction has focused on utilizing damping coatings and polymer nanocomposites to enhance sound absorption. Nanosilica/poly(styrene-acrylate) nanocomposites as a water-based coating were prepared through in-situ emulsion polymerization and direct mixing methods at varying concentrations of 1, 2, and 3 wt% of nanosilica. Fourier transform infrared (FTIR) spectroscopy revealed that the inclusion of surfactant-containing micelles and a more extended synthesis period in the in-situ synthesis technique enhanced the interaction between silica nanoparticles and polymer chains. Dynamic light scattering (DLS) analysis showed a unimodal distribution and an acceptable range of polydispersity index (PDI) for neat and nanocomposite latexes. The addition of silica nanoparticles enhanced the stability of latex particles, especially evident in the direct mixing method. The field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) images confirmed the better dispersion of nanoparticles within the polymer matrix in the in-situ method. The addition of nanosilica resulted in a significant increase in pseudoplastic behavior and viscosity, notably in the in-situ synthesis. In both the in-situ synthesis and direct mixing techniques, the addition of 1 wt% of nanosilica resulted in an increase in the damping factor of nanocomposite films to about 2. However, when the nanosilica content was further increased to 3 wt%, the damping factor decreased. Acoustic tests demonstrated improved sound absorption with silica nanoparticles, yielding noise reduction coefficient (NRC) values of 0.49 and 0.46 for in-situ synthesis and direct mixing. The direct mixing method notably enhanced tensile properties at all nanoparticle content levels. Dried nanocomposite films exhibited superior UV-blocking capabilities compared to neat polymer films.

POSSIBILITIES OF SYNTHESIS OF UNCHARGED STABLE LATEX PARTICLES FOR IMMUNOANALYSIS

Objective: The objective of this study is to find a method for synthesizing uncharged polystyrene latex particles whose surface can be easily modified. Theoretical basis: The main method of latex synthesis is emulsion polymerization. Latexes for a specific purpose can be obtained by polymerization in heterogeneous monomer-water systems, without the use of emulsifiers, both with intensive mixing of the system and under static conditions. In this work, polymerization was carried out without the use of emulsifiers in a static monomer-water system. Method: To achieve the set goal, the possibility of obtaining latex particles using a hydrophobic initiator - ditrile of azoisobutyric acid - was investigated by carrying out polymerization in a diffusion mode in a three-phase system monomer - water - initiator. Results and discussion: The results of the study showed that the latex obtained in the three-phase system is stable. It is assumed that the stability is due to the presence of hydroxyl end groups groups of polymer molecules on the surface of the latex particles, which are formed as a result of the reaction of the initiator with water and initiate polymerization. The synthesized latexes retained stability for a year. Practical value: Latexes can be used in all those areas of science and technology where the absence of a charge on the surface of latex particles is required. Originality/value: The originality of the work lies in the fundamental simplicity of the synthesis and the unambiguity of the results obtained.

Fully Atom-Efficient Solvent-Mediated Biopolymer Manufacturing: A Base Case Illustrated with Macromolecular Surfactants Tailored to Stable Polymer-Water Interfaces.

This work introduces a novel 1-pot, 0-waste, 0-VOC methodology for synthesizing polymeric surfactants using acrylated epoxidized soybean oil and acrylated glycerol as primary monomers. These macromolecular surfactants are synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, allowing for tunable hydrophilic-lipophilic balance (HLB) and ionic properties. We characterize the copolymers' chemical composition and surface-active properties, and evaluate their effectiveness in forming and stabilizing emulsions of semiepoxidized soybean oil and poly(acrylated epoxidized high oleic soybean oil). Comprehensive analyses, including gel permeation chromatography, nuclear magnetic resonance spectroscopy, dynamic light scattering, particle size distribution, zeta potential, and critical micelle concentration, provide detailed insights into the copolymers and the emulsions they form. The results demonstrate that the RAFT-polymerized surfactants offer long-lasting stability and effectively disperse both common oil-in-water emulsions and highly viscous and hydrophobic polymer latexes. These surfactants outperform traditional small molecule surfactants by reducing particle size and preventing phase separation, even over extended storage periods. Stable polymer-water interfaces are achieved through HLB control, tailored by monomer composition, and the final product requires no additional purification since polymerization occurs in liquid surfactants. While small molecules contribute to rapid micelle formation, the polymeric components enhance long-term stability through steric repulsion and slower dynamics. This method enables even the emulsification of polymers with submicron particle size, which ordinarily requires emulsion polymerization. Integrating biobased polymeric surfactants with advanced polymer processing techniques opens new possibilities for transforming highly hydrophobic polymers into latexes, facilitating downstream applications. This innovation enhances the environmental sustainability of surfactant production and broadens the potential for polymer emulsification technologies. Additionally, the integrated solution-processing approach demonstrated here can be applied to other emerging polymers, where judiciously selected nonvolatile solvents facilitate the polymerization and play a role in the final application.

Kinetic Investigation of the Emulsion Polymerization of Vinylidene Fluoride

AbstractPoly(vinylidene fluoride) (PVDF) is among the most produced fluoropolymers, second only to polytetrafluoroethylene. Despite its popularity, the complex microstructural properties achieved during the polymerization are not well documented in the literature. In particular, available models only track the chain length distribution of the polymer, while neglecting the distribution of other important properties, affecting the final behavior of the product. In this work, a 2D kinetic model, evaluating not only the chain length but also the number of terminal double bonds (TDBs) per chain, is developed. The numerical solution of the model is achieved by fractionating the population of polymer chains into classes with a specific number of TDBs and using the method of moments for each class. The model results are compared with experimental evidences for the amount of produced polymer, moles of main chain‐ends, number, and weight average molecular weight as well as full molecular weight distribution. Based on this comparison, kinetic parameters are estimated by optimization using genetic algorithm. The model reliability is finally verified using additional experimental data at different temperatures and amounts of initiator.

Hyperbranched Organosilicon Surfactants as Emulsifiers for the Emulsion Polymerization of Methyl Methacrylate

This report is devoted to the investigation of the emulsion polymerization of methyl methacrylate in the presence of PEGylated hyperbranched polymethylethoxysiloxane as an emulsifier. It is shown that its use in the amount of 1–5 wt % affords stable 25–50% poly(methyl methacrylate) dispersions with the controlled particle sizes from 300 to 800 nm and a narrow particle size distribution.

Monomer Transport via Collision in Emulsion Polymerization

AbstractOne of the questions still remaining regarding emulsion polymerization is the issue of mass transfer versus reaction limitation since, by its nature, emulsion polymerization requires monomer transport across an aqueous phase. This question is brought into focus lately by the growing use of miniemulsion polymerization in which the monomer transport step is much less important. This paper will explore the possible rate of monomer transport via collision and ratio this to the maximum rate of polymerization using the Damkohler analysis formality. Results indicate that systems relying on monomer transport by collision will be almost universally monomer‐transport‐limited, thus exhibiting lower‐than‐expected rates of polymerizations.

Synergistic Radical Taming by Concurrent Degenerative Transfer and Atom Transfer Radical Polymerization in Emulsion

Synergistic Radical Taming by Concurrent Degenerative Transfer and Atom Transfer Radical Polymerization in Emulsion

Advancing Sustainability: Geraniol-Enhanced Waterborne Acrylic Pressure-Sensitive Adhesives without Chemical Modification.

The escalating global emphasis on sustainability, coupled with stringent regulatory frameworks, has spurred the quest for environmentally viable alternatives to petroleum-derived materials. Within this context, the adhesives industry has been actively seeking renewable options and eco-friendly synthesis pathways. This study introduces geraniol, a monoterpenoid alcohol, in its unmodified form, as a key component in the production of waterborne pressure-sensitive adhesives (PSAs) based on acrylic latex through emulsion polymerization. Multiple formulations were developed at varying reaction times. The adhesives underwent comprehensive chemical characterization employing techniques such as Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Nuclear Magnetic Resonance (NMR), Gel Permeation Chromatography (GPC), and dynamic light scattering (DLS). The viscosities of the formulations were measured between 4000 and 5000 cP. Adhesion tests showed peel strength values of 0.52 N/mm on cardboard and 0.32 N/mm on painted steel for the geraniol-based formulations. The results demonstrate the potential for geraniol-based PSAs to offer a sustainable alternative to petroleum-derived adhesives, with promising thermal and adhesive properties.

Distributed optical fiber sensors for real-time tracking of fouling buildup for tubular continuous polymerization reactors

Early online fouling detection is expected to be a real step forward in the operation of continuous tubular reactors. As an online technology, the Rayleigh backscatter based Distributed Optical Fiber Sensor (DOFS) technology was evaluated with respect to temperature measurement resolution, reproducibility and the best online calibration method. Different coatings and terminations were characterized for emulsion polymerization reactors. Commercially available sensors with acrylate primary coatings, dual acrylate coatings, and polyimide coatings were all compared with each other. It is shown that the presence of a secondary coating significantly alters sensor behaviour. Sensors with only a primary coating showed a temperature resolution of 0.1 °C. Online calibration for temperature readout was carried out and validation tested on segments of fiber integrated in a 3D-printed reactor channel (diameter 1.5 mm). Acrylate coated sensors showed a deviation of 20 % for the calibration coefficients when inside the reactor channel compared to the online calibration, leading to errors in temperature measurement. Polyimide coated sensors showed a deviation of just 0.6 % in this validation test, demonstrating good capabilities for online calibration with accurate temperature measurements. The possibility of spatial and temporal monitoring of fouling buildup through a heat exchanging wall equipped with DOFS was evaluated.

Research and Evaluation of a Nanometer Plugging Agent for Shale Gas Horizontal Wells.

Due to the low permeability of shales, drilling fluid filtrate is very likely to intrude into the formation along the nanomicron pore joints of shale, leading to microfracture expansion and causing a well wall destabilization phenomenon. Based on the characteristics of the formation shale, a new nano plugging agent, styrene (St)/2-acrylamido-2-methylpropanesulfonic acid (AMPS)/ethyl acrylate (EA), was synthesized by emulsion polymerization using St, EA, and AMPS as reaction monomers. The analysis results using infrared spectroscopy and transmission electron microscopy showed that the product met the expected design. The particle size of the nano plugging agent St/AMPS/EA was mainly concentrated in the range of 50-130 nm. Thermogravimetric analysis revealed that the initial thermal decomposition temperature of St/AMPS/EA is 363.8 °C, indicating strong thermal stability. At a 3% concentration, the permeability of the mud cake decreased by 87.35%, and the maximum differential stress of the shale increased from 141.7 to 174.4 MPa. Stability analysis showed that the plugging agent maintained good plugging performance under various pH values and salinity conditions with fluid loss consistently around 3.2 mm. This nano plugging agent significantly improves wellbore stability, making it suitable for drilling in the Longmaxi Formation shale with developed microfractures, and provides valuable insights for similar formations.

Synthesis of polymeric nanoparticles with different functionalities to produce new biocatalysts

AbstractThis study aimed to synthesize functionalized nanosupports via emulsion polymerization to develop new promising nanobiocatalyts via enzyme immobilizations. The co‐monomers methyl methacrylate, divinylbenzene and the epoxy monomer glycidyl methacrylate (GMA) were used. The performance of the nanobiocatlysts was evaluated in hydrolysis and esterification reactions after the immobilization of lipase B from Candida antarctica (CAL B). Firstly, the nanosupports functionalized in situ with 25% and 50% w/w of GMA were successfully synthesized. In esterification reactions, the nanobiocatalysts containing 25% (w/w) of GMA were more active, achieving 254 U.g−1, or an enzyme activity per area of 2.8 U.m−2; such value was higher than the one obtained when the commercial matrix Octadecyl Sepabeads was used (328 U.g−1, 2.4 U.m−2). Such results point out that there is an optimum concentration of GMA epoxide groups that should be incorporated into the supports. The greater enzymatic activity obtained for 25% of GMA nanobiocatalyst was achieved not only because of their textural properties, but also due to a favorable interaction between the epoxide groups and CAL B. These results highlight the potential use of the heterofunctional matrices for the synthesis of new market‐competitive biocatalysts.

Compatibilizing and toughening of the styrene and acrylonitrile copolymer and core‐shell impact modifier obtained by agglomerate technologies

AbstractParticle size distribution and the compatibility of core‐shell impact modifiers play a crucial role in determining the mechanical properties of the resin. This study presents the synthesis of a core‐shell impact modifier, a copolymer of polybutadiene grafted with styrene and acrylonitrile (PBL‐g‐SAN), using emulsion polymerization to enhance the mechanical properties of SAN resin. Polymer agglomeration technologies were employed to increase the particle size of polybutadiene latex, resulting in particles approximately 300 nm in diameter. Moreover, the effects of core‐shell modifiers with different constitutions on the mechanical properties of ABS resin were investigated. By optimizing the grafting polymerization process, improvements in impact strength of ABS resin were observed. When the St/AN ratio of the core‐shell modifier is 75/25, with a core‐shell ratio of 60/40 and MMA content at 2.5%, the impact strength of ABS resin reaches its peak while maintaining high tensile strength. The incorporation of methyl methacrylate improved the dispersion of core‐shell modifiers in SAN resin. Compared to commercial ABS resins with the same SAN and rubber content, the modified resin demonstrated a nearly 20% improvement in impact performance, and significant reductions in both production time and costs due to the polymer agglomeration method.Highlights The 300 nm polybutadiene latex was synthesized by polymer agglomeration technology. The relationship between the composition of these core‐shell modifiers and the mechanical properties of ABS resin was explored. The ABS resin with impact strength exceeding 20% of commercial material is prepared.

Synthesis and properties of superhydrophobic monomer stearyl methacrylate-modified polyacrylate latex pressure sensitive adhesives

Hybrid surfactants of long carbon chain hydrophobic nonionic emulsifier N-390 and conventional anionic emulsifier CO-436 were utilized in this study to enable successful emulsion polymerization of super-hydrophobic monomer stearyl methacrylate (SMA) together with butyl acrylate (BA), acrylic acid (AA), and 2-hydroxyethyl acrylate (HEA). The influences of SMA on the resulting latex and film properties were thoroughly investigated. Both FTIR and 1H NMR were used to confirm the successful participation of SMA in the emulsion polymerization. The results indicated that with introduction of SMA, the roughness of the latex film increases, while the light transmission decreases. It was also found that with the addition of SMA, contact angle of the latex PSA film increased from 115.1° to 127.2°, while water absorption decreased from 5.76 to 2.89 wt%. DSC curves demonstrated that SMA has participated more in the homopolymerization reaction than in the copolymerization reaction. TGA results showed that the initial decomposition temperature (T5%) of the latex film was increased from 302.8 to 332.7 °C with the increase of SMA dosage from 0 to 20 wt%. Finally, adhesion properties results indicated that loop tack and 180° peel force of the PSA films were decreased from 11.51 to 1.88 N/25 mm and 6.36 to 3.44 N/25 mm, respectively, while shear strength was increased from 732 to 2865 min.

Synthesis of silane-modified styrene-acrylic ester emulsion and its inhibition mechanism on whitening of calcium aluminate cement mortar

A new polymer, triethoxyvinylsilane-modified styrene-acrylic ester emulsion (TMSA), was synthesized through emulsion polymerization. The effect of TMSA on the whitening of calcium aluminate cement (CAC) mortar was investigated. The results showed that TMSA had an excellent inhibition effect on the whitening of the CAC mortar with only 0.8 % - 1.6 % addition. Analysis of the micro-morphology and Raman spectra revealed that the white deposits on the surface of the mortar were C4AC(_)H11 and CaCO3, whereas TMSA addition effectively inhibited the formation of C4AC(_)H11 and reduced the occurrence of CaCO3. Through investigating the hydration, Ca2+ concentration, capillary water absorption and pore structure, it was found that the effect of the CAC hydration on the whitening of the mortars was inessential, whereas there was a strong link among whitening, capillary water absorption and macro-capillary pores. The addition of TMSA not only reduced the concentration of Ca2+ which was the source of the whitening, but also reduced the formation of macro-capillary pores in the CAC mortar that led to a significant reduction in the capillary water absorption, thus weakening the mobility of pore solution in the mortar and hindering the migration of Ca2+ to the mortar surface. Based on these two aspects, TMSA effectively inhibited the whitening of the CAC mortar.

Preparation of a Porous Spherical Adsorbent by Oil-In-Water-In-Oil Emulsion Polymerization for Phycocyanin Adsorption

ABSTRACT Phycocyanin is a protein with potential in food and medical applications. A porous spherical adsorbent was prepared by oil-in-water-in-oil emulsion polymerization. Oil and water phases containing surfactants and monomers, respectively, were emulsified, and the prepared emulsion was added to the oil phase to polymerize the porous spherical adsorbent. The concentration ratio of N,N-dimethylacrylamide and 2-dimethylaminoethylmethacrylate (DMAEMA) in the water phase was changed. The obtained spherical adsorbent had a size of about 150 μm and a water content of 90%, with macropores of several micrometers. Phycocyanin (20 kDa) of Nostoc commune was leached by the freeze and thaw method to prepare the solution. The adsorption data of the batch and column modes were evaluated by ordinary differential and partial differential equations, respectively, considering competitive adsorption, to obtain parameters of the mass transfer coefficient and saturated adsorption capacity. In the b\ sfer coefficient of phycocyanin decreased by about one-third, but the saturated adsorption capacity increased three-fold. In the continuous flow column, leached biomacromolecules other than phycocyanin had greater parameters of mass transfer and capacity. To prepare an adsorbent for the biomacromolecules, selective adsorption sites in the polymer matrix should be designed and prepared.

Enhancement of interaction between Shenhua coal and GON-based dispersant with “surface-to-surface” adsorption by regulating the oxidation degree of GON: Experiments and simulations

The present study focuses on the synthesis of several graphene oxide nanosheet (GON)-based dispersants with an adsorption mode of “surface-to-surface” for the preparation of Shenhua coal (SC) water slurry (SCWS), achieved by grafting allyl polyoxyethylene ether (APEG) onto GON edges with varying degrees of oxidation using emulsion polymerization and esterification techniques. The impacts of the oxidation degree of GON on its structural characteristics and the performance of GON-based dispersants in SCWS were comprehensively assessed through a range of experimental techniques, alongside molecular dynamics (MD) simulations. Results demonstrated that with the increase in oxidation degree, there was an elevation of oxygen-containing groups, in which the content of COH decreased while the content of COC increased. Among all dispersants, GA-2, which was synthesized using GON-2 as the raw material with a graphite-to-KMnO4 mass ratio of 1:2.5, exhibited superior viscosity-reducing and stabilizing abilities compared to other dispersants. All SCWSs demonstrated pseudoplastic fluid behavior and showed good agreement with the Herschel-Bulkley model. After the adsorption of dispersants in SC, both the Zeta potential and surface wettability of SC significantly improved, especially with GA-2. The interaction mechanism between the dispersant and SC was analyzed by establishing and employing three adsorption models (M-1, M-2, and M-3). The interfacial adsorption structure confirmed that the dispersant exhibited “surface-to-surface” mode on coal through hydrophobic interaction, hydrogen bonding, and π–π interaction. Energy studies revealed that M-2 with the highest Eads (−105.31 kcal/mol) demonstrated superior adsorption strength compared to M-1 and M-3. Investigations into water molecule mobility revealed that the interaction between the GON-based dispersant and SC resulted in a reduction of water molecule mobility, thereby promoting water molecule aggregation to facilitate the formation of hydration films and enhance SCWS stability. In summary, an optimal oxidation degree of GON was found to be crucial for enhancing the performance of GON-based dispersants; higher oxidation levels may hinder dispersant adsorption on coal surfaces by converting hydroxyl and carboxyl groups into epoxide groups, thus impairing the conjugated structure.

Development of a Water‐Based Pressure‐Sensitive Adhesive via Emulsion Polymerization for Packaging Tape Applications

Development of a Water‐Based Pressure‐Sensitive Adhesive via Emulsion Polymerization for Packaging Tape Applications

PH- and temperature-dual responsive polymer emulsion for rapid release of drag reducer

Slick water fracturing fluid is widely used in major oil fields due to its low cost and high drag reduction. Polyacrylamide emulsions drag reducers play a decisive role in slick water fracturing. The dissolution rate of polymer emulsions drag reducers was increased by adding hydrophilic surfactants, but the stability of the emulsions is poor, which limits its wide application. In order to solve the contradiction between the stability of polymer emulsion and rapid release of drag reducer. Here, a P(AA-AM-AMPS) polymer emulsion drag reducer with dual stimulation response of pH and temperature was designed. Surfactant (D400/OA) with dual responses to pH and temperature is synthesized by using oleic acid (HOA) and polyether amine 400 (D400). D400/OA shows a remarkable pH- and temperature-responsive behavior due to the pH- and temperature-induced structural transformation of D400/OA. Interestingly, D400/OA-stabilized monomer emulsion exhibits an obvious pH- and temperature-induced structural transformation. Meanwhile, The D400/OA-stabilized monomer emulsion has remarkable stability, which benefits the inverse emulsion polymerization of P(AM-AA-AMPS) polymer. The obtained P(AM-AA-AMPS) polymer emulsion maintain stability whose particle size nearly unchanged by storing for 15 days. Interestingly, P(AM-AA-AMPS) polymer emulsion can be released completely by changing the pH or temperature of the aqueous solution. The apparent viscosity of P(AM-AA-AMPS) polymer, in either the alkaline (pH=10.31) solution of 25±2 °C or neutral (pH=7) solution of 70±2 °C, respectively required 40 s and 8 min to reached a maximum value of 96 mPa·s. The release rate of P(AM-AA-AMPS) polymer emulsion is further enhanced under the dual responsive of temperature (70±2 ℃) and pH (10.31) and it takes only 20 s, In addition, the drag reduction rate of P(AM-AA-AMPS) polymer emulsion is 72 % when completely released under the dual responsive of temperature and pH, showing a remarkable drag reduction property. The D400/OA-stabilized P(AM-AA-AMPS) polymer emulsion are expected to meet the demand for the production enhancement of the oil and gas reservoirs.

Synthesis of magnetic polystyrene nanocomposite by emulsion polymerization using a photo-responsive emulsifier for efficient crude oil absorption

Both human health and marine life are seriously threatened by crude oil spills into bodies of water. For effective crude oil spill cleaning, we created a magnetic polystyrene (m-PS) nanocomposite. The use of magnetic nanoparticles makes crude oil absorption more environmentally friendly by making it easier to collect and recycle using an external magnetic field. To make Fe3O4 nanoparticles compatible with the hydrophobic styrene monomer used in emulsion polymerization, they were treated using a hydrophobic surface modification reaction. This alteration facilitated the grafting of polystyrene (PS) chains onto the nanoparticles, which then underwent emulsion polymerization. As an emulsifier, a light-responsive amphiphilic block copolymer containing coumarin was created via reversible addition-fragmentation chain transfer polymerization. This allowed for regulated emulsification and demulsification in response to UV stimulation. The synthesized m-PS nanocomposite demonstrated a crude oil absorption capacity of up to 2.31 times of its own weight, indicating its high efficiency for crude oil spill cleanup. The synthetic emulsifier exhibited a significantly lower critical micelle concentration compared to the commercial P105 emulsifier (0.0976 against 0.354 mg/mL, respectively), indicating higher efficiency and reduced environmental impact. For a more thorough comprehension of the reported results, we also assessed the Hofmeister effect in PS produced using commercial and synthetic emulsifiers.

Effect of dispersions on vapour permeation resistance of acrylic sealants

Currently, acrylic sealants are widespread due to their environmentally friendly materials, ease of use, and low cost. Their compositions are constantly being improved. It allows ones to improve their quality and reduce the cost by selecting new substances for their manufacture. We obtained acrylic sealants with changing polymer base. The authors used acrylic and styrene acrylic dispersions obtained by emulsion polymerisation. The basis for sealants production is the mechanical mixing of the components and their further dispersion in the Dispermat VLOK dissolver. The main parameter to be determined is the vapour permeability resistance of the material layer. According to research results, the nature of the polymer base, degree of its bonding, type and amount of the filler used affected on vapour permeability of the sealing material. Moreover, increasing in film former temperature, viscosity, and pH causes increasing in tensile strength. By comparing the sealant samples on the basis of dry residue, we found increasing of the Shore hardness in samples with lower % index.