Radical Emulsion Polymerization Research Articles

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

Synthesis of novel acrylate emulsions and examination of their synergistic effects with nanocellulose on paper strengthening

AbstractWith the development of the “paper instead of plastic” trend, the investigation into high‐density, heavy‐weight paper has emerged as a point of interest in both academic and industrial realms. Regrettably, the paper‐strengthening agents that are commercially available fall short of meeting the strength specifications for such papers. To rectify this shortcoming, a water‐based acrylate paper‐strengthening agent (AA) was developed through radical emulsion polymerization. The most stable acrylate emulsion was obtained by amalgamating the anionic emulsifier allyloxyammonium oxymethyl sulfate nonylphenol ethoxy sulfate (DNS‐86) with the nonionic emulsifier nonylphenol polyoxyethylene ether (OP‐10) at a proportion of 1:0.6, with a dosage of 3%. Substituting the conventional strengthening agent (styrene‐butadiene latex) with the synthesized acrylate emulsion in wet‐end addition markedly improved the paper strength, registering a 54.8% increase to 29.4 MPa. The introduction of carboxylated cellulose nanofibers (C‐CNF) further bolstered the mechanical properties of the paper, achieving a tensile strength of 41.44 MPa and an elongation at a break of 3.55%. These results underscore the efficacy of acrylate as a paper‐strengthening agent and the crucial role of C‐CNF in enhancing the structural integrity of paper materials.

Fabrication of cationic microgels doped MnO2/Fe3O4 nanocomposites, and study of their photocatalytic performance and reusability in organic transformations

AbstractThis article reports, the fabrication of cationic microgel doped MnO2/Fe3O4 nanocomposites (CM@MnO2/Fe3O4) via free radical emulsion polymerization technique, and an economical and environmental friendly approach to some organic transformations, such as heterogeneous photocatalytic reduction of methylene blue (MB, toxic dye), para‐nitro phenol (PNP, harmful pollutant) and dimethyl amino benzaldehyde (DMAB, skin allergic reagent) in presence of UV light (38 W). First of all, three different crosslinked grades of cationic microgels (CMs) have been synthesized by using styrene, dimethyl acrylamide, cyclohexyl methacrylate, [2‐(acryloyloxy)ethyl] trimethylammonium chloride and N‐hydroxymethyl acrylamide monomers by taking different amounts of N‐hydroxymethyl acrylamide, and keeping the other monomers in fixed quantities. Further, all the grades of CMs have been doped by bimetallic MnO2/Fe3O4 nanoparticles, through hydrothermal method. Fabrication of CMs and CM@MnO2/Fe3O4 nanocomposites has been confirmed by the characteristic peaks observed in FT‐IR spectral analysis and their thermal stability has been evidenced by thermogravimetric analysis. TEM and DLS analyses have revealed their particular size. The surface morphology of CMs and CM@MnO2/Fe3O4 nanocomposites has been visualized by scanning electrode microscope analysis. The nanocomposites have effectively and efficiently catalyzed the reduction reactions of MB, PNP, and DMAB, in presence of UV light, by 98%, 98%, and 86%, respectively. The photocatalysts have been reused up to eight cycles without any loss of their catalytic activity. The photocatalytic reductions have also been studied for their kinetics, and exhibited pseudo first order kinetics (kapp, 10−2 min−1).

Acrylates-based hydrophilic co-polymeric nanobeads as nanocarriers for imaging agents

Acrylates-based co-polymeric nanoparticles (PNPs) are widely used in nanomedicine applications due to their tunable hydrophilic surface, physical and chemical versatility. Particularly attracting is their use as nanocarriers for imaging agents. Herein, methyl methacrylate (MMA) and N,N-dimethylacrylamide (DMAA) monomers were used to synthesize hydrophilic p(MMA-co-DMAA) nanoparticles in the 200–600 nm size range via surfactant-free radical emulsion polymerization technique. Different MMA/DMAA molar ratios, temperatures, and reaction times were investigated to evaluate their role in determining the average particle size, polydispersity, and optimizing surface properties of PNPs. Nanoparticles formation, stability (in water and culture medium for cell growth), swelling behavior, structural features and molecular weights were assessed by spectroscopic, non-spectroscopic, and chromatographic techniques. Morphological profiles confirming spherical-shaped NPs were obtained at solid state via microscopies (FESEM, AFM). To use such colloids as potential imaging agents, PNPs were loaded with Y3+(aq) ions by the addition of aqueous solutions of YCl3 at different concentrations, and results compared with p(MMA-co-AA)-DTPA NPs (AA = acrylic acid) functionalized with DTPA chelating agent. Yttrium ions loading percentage was ca. 90% for both p(MMA-co-DMAA) and p(MMA-co-AA)-DTPA, with negligible release (<15%) over a month. Parallelly, optical imaging nanoprobes were obtained by physical encapsulation of fluorescein isothiocyanate isomer I (FITC) dye during the synthesis process, and the spontaneous FITC incorporation was evaluated by spectroscopic studies and fluorescence microscopy. Cytotoxicity studies on pristine and yttrium-loaded nanoparticles were done in vitro on human glioblastoma T98G cell line within 24 h of treatment. Transmission electron microscopy (TEM) studies on cancer cells treated with NPs confirmed an active uptake of PNPs through multiple endocytic pathways to reach the perinuclear region of the cell. Overall, this work elucidated the role of synthetic parameters for a rational design of hydrophilic PNPs as nanocarriers for imaging agents with potential applications in theranostics.

Preparation of Fluorine Certified Reference Material for Fluoroether Rubber

High-pressure free radical emulsion polymerization was used to prepare the fluorine certified reference material candidates for fluoroether rubber. Ion chromatography method and high performance liquid chromatography were adopted for the determination of the certified reference material, and various sources of uncertainty in the determination process were analyzed and calculated to gain the expanded uncertainty by synthesis. The homogeneity of the certified reference material was checked by F test and the stability was investigated by t test. The results show that the prepared fluorine certified reference material for fluoroether rubber has accurate value and good homogeneity and stability.

High Water Resistance and Enhanced Mechanical Properties of Bio-Based Waterborne Polyurethane Enabled by in-situ Construction of Interpenetrating Polymer Network

In this study, acrylic acid was used as a neutralizer to prepare bio-based WPU with an interpenetrating polymer network structure by thermally induced free radical emulsion polymerization. The effects of the content of acrylic acid on the properties of the resulting waterborne polyurethane-poly (acrylic acid) (WPU-PAA) dispersion and the films were systematically investigated. The results showed that the cross-linking density of the interpenetrating network polymers was increased and the interlocking structure of the soft and hard phase dislocations in the molecular segments of the double networks was tailored with increasing the content of acrylic acid, leading to enhancement of the mechanical properties and water resistance of WPU-PAA films. Notably, with the increase in content of acrylic acid, the tensile strength, Young’s modulus, and toughness of the WPU-PAA-110 film increased by 3 times, and 8 times, and 2.4 times compared with WPU-PAA-80, respectively. The WPU-PAA-100 film showed the best water resistance, and the water absorption rate at 96 h was only 3.27%. This work provided a new design scheme for constructing bio-based WPU materials with excellent properties.

Synthesis of poly(methyl methacrylate)-b-polyethylene (PMMA-b-PE) block copolymers via conventional emulsion polymerization

Block copolymers can be obtained by combining catalytic chain transfer polymerization (CCTP) and conventional free radical emulsion polymerization of ethylene.

Preparation and characterization of cross-linked poly (vinyl alcohol-co-methyl methacrylate) colloidal nanoparticles from hydrolysis of poly (vinyl acetate-co-methyl methacrylate) as a promising cancer drug delivery system

Amphiphilic cross-linked poly (vinyl alcohol-methyl methacrylate) (PVA-PMMA) copolymer nanoparticles (NPs) were prepared using a two-step process. Unlike other polymers, which are typically produced via direct polymerization, PVA is produced from the hydrolysis of polyvinyl acetate (PVAc). Therefore, in the first part of the project, copolymeric PVAc-PMMA NPs were prepared by using the radical emulsion polymerization method in different concentrations of BDOD (0–10% mol.) and water: methanol compositions. Conversion degree, morphology, particle size, and polymerization rate of non-agglomerated samples were evaluated. The optimal sample that synthesized in water: methanol % (90:10) as polymerization medium and 2.5% mol. crosslinker was hydrolyzed by 0.6 M NaOH solution. To confirm the hydrolysis reaction, FE-SEM, FT-IR, DLS, 1H NMR, and TGA tests were performed. The optimal sample was loaded by methotrexate (MTX), and drug release investigated at different times by UV-vis spectrophotometry. The sustained and pH-responsive profile of drug release in vitro was observed, and 47.24% of the drug was released at pH = 7.4 and 65.39% at pH = 5.8 after 96 h. Also, the MTT assay and dual-fluorescent acridine orange/propidium iodide assay showed that drug-loaded nanocarriers exhibited anticancer activity as applied to MCF-7 cells.

Synthesis of green thermo-responsive amphoteric terpolymer functionalized silica nanocomposite derived from waste vegetable oil triglycerides for enhanced oil recovery (EOR)

Despite the high efficiency of polymer flooding as a chemical enhanced oil recovery (CEOR) technique, the low thermal stability and poor salt resistance of widely applied partially hydrolyzed polyacrylamide (HPAM) limited the application of this technique in oil reservoirs at harsh reservoir conditions of high–temperature and high–salinity (HTHS). These inadequacies of HPAM, result in the urge for an environmentally friendly polymer with good viscosifying properties and a substantial effect on mobility ratio at HTHS reservoir conditions. In this research, a high oleic acid waste vegetable oil (WVO) is utilized to synthesize a novel environmentally benign, thermo-responsive amphoteric nanocomposite for EOR applications at HTHS reservoir conditions. A green route transesterification reaction has been utilized to synthesize a novel thermo-sensitive monomer from WVO. The existence of unsaturated fatty acids isolated double bonds and acryloyl functional groups in the synthesized monomer has been confirmed using different characterization methods. The reactive acryloyl double bond in the synthesized monomer has been copolymerized with acrylamide, acrylacyloxyethyltrimethyl ammonium chloride, and 2-acrylamide-2-methylpropane sulfonic acid in presence of dimethylphenylvinylsilane via free radical emulsion polymerization. The synthesized nanocomposite has been characterized by FTIR, 1H NMR, SEM, EDX, TEM, and DLS. The thermal stability of the nanocomposite has been evaluated by TGA and DTA analysis. The results indicated that nanocomposite solution exhibited a pouncing thermo-thickening behaviour and superior viscosifying properties even at an ultra-low polymer concentration of 0.04 wt% as the temperature increased from 25 to 100 °C, with increasing salinity from 10,000 to 230,000 ppm as well as salt-free solutions. Flooding experiments demonstrated that the oil recovery factor reached 15.4 ± 0.1 % using low nanocomposite concentrations of 0.04 wt%, 22.6 ± 0.3 % using nanocomposite concentrations of 0.06 wt% and 25 ± 0.2 % using 0.1 wt% nanocomposite concentrations evaluated under hostile conditions of 100 °C and salinity of about 230,000 ppm. This research offers a new direction for the synthesis of a novel green, high molecular weight thermoresponsive nanocomposite for EOR application at extremely harsh reservoir conditions via WVO valorization.

Influence of Metal Oxide Nanoparticles as Antimicrobial Additives Embedded in Waterborne Coating Binders Based on Self-Crosslinking Acrylic Latex

This article deals with the simple preparation of environmentally friendly acrylic latex binders, which are functionalized with nanoparticles of metal oxides, namely MgO, ZnO, La2O3 and combinations of MgO and ZnO, serving as functional components to achieve antimicrobial properties, but also to improve physical–mechanical properties and chemical resilience. The incorporation of uncoated powder nanoparticles was performed during the synthesis, using the two-stage semi-continuous emulsion radical polymerization technique, to obtain latexes containing 0.5%–1.3% nanoparticles relative to the polymer content. Changes in latex performance due to nanoparticles were compared from the point of view of the type and concentration of metal oxide nanoparticles in latex. The results of the tests showed that all types of nanoparticles showed very promising properties, while with increasing concentration of nanoparticles there was an improvement in properties. The nanoparticles in latex provided interfacially crosslinked transparent smooth coating films with high gloss and good physical–mechanical properties. Latexes containing the highest concentration of nanoparticles provided coatings with significant antimicrobial activity against all tested bacterial and fungal strains, but also in-can preservative stability of liquid latex. Furthermore, the coatings were resistant to solvents, and in addition, latexes with MgO nanoparticles showed a significant decrease in the minimum film-forming temperature, and latex with a concentration of about 1.3% MgO did not show any flash corrosion under the coating film cast on a steel substrate. The latexes containing MgO and La2O3 nanoparticles provided coatings that were very resistant to water bleaching.

Synthesis and characterization of dual-responsive poly(N-vinylcaprolactam-co-N-methylolacrylamide) nanogels

ABSTRACT This article reports the synthesis of poly(N-vinylcaprolactam-co-N-methylolacrylamide) (P(NVCL-co-NMA)) nanogels and investigates their thermo-/pH-responsive behavior. The formation of nanogels was synthesized using free radical emulsion polymerization by varying the monomer composition of NVCL:NMA, and their molecular structure was characterized by 1H-NMR and FTIR. It was found that the nanogels were successfully prepared, and the nanogels exhibited LCST-type phase transition behavior. Cloud point transition temperature (Tc) was studied as a function of copolymer composition, MBA concentration, and pH of the solution by exploring their changes in turbidity using UV–vis spectrophotometer. Our studies reveal that Tc nanogels increased with increasing concentration of NMA, which is due to the hydrophilicity of NMA. Our research also demonstrated that the increase in MBA percentage could decrease the Tc of the synthesized nanogels. Interestingly, P(NVCL-co-NMA) nanogels showed not only a thermoresponsive behavior but also a pH response with increasing Tc in a strong acidic environment owing to the H-bonds within the polymer chains. The results show that nanogels with initial monomer composition of NVCL and NMA of 75% and 25%, respectively, and using 4% of MBA showed Tc around 35°C at pH 7.4. In addition, DLS studies also confirmed this result since the particle sizes became much larger after surpassing the temperature of 35°C. Due to this founding, such nanogels might have potential application in controlled release. Nevertheless, further studies regarding the adjustment of Tc are still needed.

Defining Endocytic Pathways of Fucoidan-Coated PIBCA Nanoparticles from the Design of their Surface Architecture.

PurposeThis work investigated the endocytic pathways taken by poly(isobutylcyanoacrylate) (PIBCA) nanoparticles differing in their surface composition and architecture, assuming that this might determine their efficiency of intracellular drug delivery.MethodsNanoparticles (A0, A25, A100, R0, R25 ) were prepared by anionic or redox radical emulsion polymerization using mixtures of dextran and fucoidan (0, 25, 100 % in fucoidan). Cell uptake was evaluated by incubating J774A.1 macrophages with nanoparticles. Endocytic pathways were studied by incubating cells with endocytic pathway inhibitors (chlorpromazine, genistein, cytochalasin D, methyl-ß-cyclodextrin and nocodazole) and nanoparticle uptake was evaluated by flow cytometry and confocal microscopy.ResultsThe fucoidan-coated PIBCA nanoparticles A25 were internalized 3-fold more efficiently than R25 due to the different architecture of the fucoidan chains presented on the surface. Different fucoidan density and architecture led to different internalization pathway preferred by the cells. Large A100 nanoparticles with surface was covered with fucoidan chains in a loop and train configuration were internalized the most efficiently, 47-fold compared with A0, and 3-fold compared with R0 and R25 through non-endocytic energy-independent pathways and reached the cell cytoplasm.ConclusionInternalization pathways of PIBCA nanoparticles by J774A.1 macrophages could be determined by nanoparticle fucoidan surface composition and architecture. In turn, this influenced the extent of internalization and localization of accumulated nanoparticles within cells. The results are of interest for rationalizing the design of nanoparticles for potential cytoplamic drug delivery by controlling the nature of the nanoparticle surface.Graphical abstract Supplementary InformationThe online version contains supplementary material available at 10.1007/s11095-022-03202-4.

Dibutyl Itaconate and Lauryl Methacrylate Copolymers by Emulsion Polymerization for Development of Sustainable Pressure-Sensitive Adhesives.

Renewable polymers possess the potential to replace monomers from petrochemical sources. The design and development of polymeric materials from sustainable materials are a technological challenge. The main objectives of this study were to study the microstructure of copolymers based on itaconic acid (IA), di-n-butyl itaconate (DBI), and lauryl methacrylate (LMA); and to explore and to evaluate these copolymers as pressure-sensitive adhesives (PSA). The copolymer synthesis was carried out through batch emulsion radical polymerization, an environmentally friendly process. IA was used in a small fixed amount as a functional comonomer, and LMA was selected due to low glass transition temperature (Tg). The structure of synthesized copolymers was studied by FTIR, 1H-NMR, Soxhlet extraction, and molecular weight analyses by GPC. Furthermore, the viscoelastic and thermal properties of copolymer films were characterized by DMA, DSC, and TGA. The single Tg displayed by the poly(DBI-LMA-IA) terpolymers indicates that statistical random composition copolymers were obtained. Moreover, FTIR and NMR spectra confirm the chemical structure and composition. It was found that a cross-linked microstructure and higher molecular weight are observed with an increase of LMA in the feed led. The Tg and modulus (G′) of the copolymers film can be tuned with the ratio of DBI:LMA providing a platform for a wide range of applications as a biobased alternative to produce waterborne PSA.

Janus particles by simplified RAFT-based emulsion polymerization process for polymer coating

We describe a simplified method to synthesize film forming polymer Janus particles by phase separation during RAFT-based free radical emulsion polymerization. Fully crosslinked snowman- or football-shaped polystyrene Janus particles (PSJPs) were first produced in a one-step batch process using amphiphilic triblock macro-RAFT copolymers as stabilizers. Such particles were in turn employed as seeds in a continuous emulsion polymerization in which a monomer mixture of methyl methacrylate (MMA) and butyl acrylate (BA) (1/1 by weight) was constantly injected into the reaction in the presence of a water soluble initiator. The added monomers wetted seed particle surface and their polymerization led to formations of 93-nm film forming single- or two-headed Janus particles. The resulted latex was successfully used to disperse and encapsulate solid calcite extender.Graphical abstract

Dispersion Polymerization versus Emulsifier-Free Emulsion Polymerization for Nano-Object Fabrication: A Comprehensive Comparison.

Although the preparation of nano-objects by emulsifier-free controlled/living radical emulsion polymerization has drawn much attention, the morphologies of these formed objects are difficult to predict and to reproduce because of the much more complex nucleation mechanisms of emulsion polymerization compared to only one self-assembling nucleation mechanism of controlled radical dispersion polymerization. The present study compares dispersion polymerization with emulsifier-free emulsion polymerization in terms of nucleation mechanism, polymerization kinetics, and disappearance behavior of the macrochain transfer agent, gel permeation chromatograms curves of the obtained block copolymer as well as the structural and morphological differences between the produced nano-objects on the basis of published data. Moreover, the effects of the inherently heterogeneous nature of emulsion polymerization on the mechanism of reversible addition-fragmentation transfer polymerization and the nano-object morphology are examined, and efficient agitation and adequate solubility of the core-forming monomer in water are identified as the most crucial factors for the fabrication of nonspherical nano-objects.

“Chemical modification of guar by different synthetic vinyl monomers for enhancing oil recovery under severe sandstone reservoir conditions”

Nowadays more emphasis is given to biodegradable polymers owing to their distinct properties. Biopolymers are natural, inexpensive, available, and environmentally friendly substitutes that are planned to substitute HPAM for enhanced oil recovery (EOR). In this research, grafted guar with different vinyl monomers prepared through a free radical emulsion polymerization reaction to enhance the drawbacks of native guar gum. Structure characterization was conducted by various spectroscopic techniques including (FTIR) spectroscopy, atomic force microscope (AFM), nuclear magnetic resonance (1H NMR), and thermal analysis established by TGA analysis. Rheological characteristics were tested at severe reservoir conditions. Laboratory flooding experiments performed by sandstone packed model. It is indicated from the rheological analysis that the modified composites have more temperature resistance, salt tolerance, and improved viscosity properties than native gum. The flooding data assumed that the prepared GG-g-AM& MMA and GG-g-AM, MMA&TEVS are suitable for EOR techniques where they can withstand the severe reservoir condition and achieve a recovery factor up to (47.7%) from residual oil by using GG-g-AM& MMA and (55.5%) of residual oil by using GG-g-AM, MMA&TEVS while native guar achieves only (27.7%).

Impact of Poly (Styrene-Acrylic Acid) Latex Nanoparticles on Colorectal and Cervical Cancer Cells.

Polymer nanoparticles are a promising approach for cancer treatment and detection, due to their biocompatibility, biodegradability, targeting capabilities, capacity for drug loading and long blood circulation time. This study aims to evaluate the impact of poly (styrene–acrylic acid) latex particles on colorectal and cervical cancer cells for anti-tumor efficiency. Latex particles were synthesized by a surfactant-free radical emulsion polymerization process and the obtained polymer particles were characterized in terms of size, size distribution, morphology using scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and electrokinetic property (i.e., zeta potential). Human colorectal and cervical cancer, and normal cell lines, were then treated with different concentrations of poly (styrene–acrylic acid) latex particles. The cell morphology changes were pointed out using an optical microscope and the nanoparticles’ (NPs) cell cytotoxicity was evaluated using MTT assay. The obtained results showed that poly (styrene–acrylic acid) latex particles are effective against colorectal and cervical cancer cells if treated with an appropriate particle concentration for 48 h. In addition, it showed that normal cells are the least affected by this treatment. This indicates that these NPs are safe as a drug delivery carrier when used at a low concentration.

Incorporating redox-sensitive nanogels into bioabsorbable nanofibrous membrane to acquire ROS-balance capacity for skin regeneration

Facing the high incidence of skin diseases, it is urgent to develop functional materials with high bioactivity for wound healing, where reactive oxygen species (ROS) play an important role in the wound healing process mainly via adjustment of immune response and neovasculation. In this study, we developed a kind of bioabsorbable materials with ROS-mediation capacity for skin disease therapy. Firstly, redox-sensitive poly(N-isopropylacrylamide-acrylic acid) (PNA) nanogels were synthesized by radical emulsion polymerization method using a disulfide molecule as crosslinker. The resulting nanogels were then incorporated into the nanofibrous membrane of poly(l-lactic acid) (PLLA) via airbrushing approach to offer bioabsorbable membrane with redox-sensitive ROS-balance capacity. In vitro biological evaluation indicated that the PNA-contained bioabsorbable membrane improved cell adhesion and proliferation compared to the native PLLA membrane. In vivo study using mouse wound skin model demonstrated that PNA-doped nanofibrous membranes could promote the wound healing process, where the disulfide bonds in them were able to adjust the ROS level in the wound skin for mediation of redox potential to achieve higher wound healing efficacy.

Cross-Linking Strategies for Fluorine-Containing Polymer Coatings for Durable Resistant Water- and Oil-Repellency.

Functional coatings for application on surfaces are of growing interest. Especially in the textile industry, durable water and oil repellent finishes are of special demand for implementation in the outdoor sector, but also as safety-protection clothes against oil or chemicals. Such oil and chemical repellent textiles can be achieved by coating surfaces with fluoropolymers. As many concerns exist regarding (per)fluorinated polymers due to their high persistence and accumulation capacity in the environment, a durable and resistant coating is essential also during the washing processes of textiles. Within the present study, different strategies are examined for a durable resistant cross-linking of a novel fluoropolymer on the surface of fibers. The monomer 2-((1,1,2-trifluoro-2-(perfluoropropoxy)ethyl)thio)ethyl acrylate, whose fluorinated side-chain is degradable by treatment with ozone, was used for this purpose. The polymers were synthesized via free radical polymerization in emulsion, and different amounts of cross-linking reagents were copolymerized. The final polymer dispersions were applied to cellulose fibers and the cross-linking was induced thermally or by irradiation with UV-light. In order to investigate the cross-linking efficiency, tensile elongation studies were carried out. In addition, multiple washing processes of the fibers were performed and the polymer loss during washing, as well as the effects on oil and water repellency were investigated. The cross-linking strategy paves the way to a durable fluoropolymer-based functional coating and the polymers are expected to provide a promising and sustainable alternative to functional coatings.

Process Characterization of Polyvinyl Acetate Emulsions Applying Inline Photon Density Wave Spectroscopy at High Solid Contents.

The high solids semicontinuous emulsion polymerization of polyvinyl acetate using poly (vinyl alcohol-co-vinyl acetate) as protective colloid is investigated by optical spectroscopy. The suitability of Photon Density Wave (PDW) spectroscopy as inline Process Analytical Technology (PAT) for emulsion polymerization processes at high solid contents (>40% (w/w)) is studied and evaluated. Inline data on absorption and scattering in the dispersion is obtained in real-time. The radical polymerization of vinyl acetate to polyvinyl acetate using ascorbic acid and sodium persulfate as redox initiator system and poly (vinyl alcohol-co-vinyl acetate) as protective colloid is investigated. Starved–feed radical emulsion polymerization yielded particle sizes in the nanometer size regime. PDW spectroscopy is used to monitor the progress of polymerization by studying the absorption and scattering properties during the synthesis of dispersions with increasing monomer amount and correspondingly decreasing feed rate of protective colloid. Results are compared to particle sizes determined with offline dynamic light scattering (DLS) and static light scattering (SLS) during the synthesis.