Preparation of Monodisperse Poly(Methyl Methacrylate)/Polystyrene Composite Particles by Seeded Emulsion Polymerization Using a Sequential Flow Process

We develop a sequential flow process for the production of monodisperse poly (methyl methacrylate) (PMMA)/polystyrene (PS) composite particles through a soap-free emulsion polymerization of methyl methacrylate (MMA) using the first water-in-oil (W/O) slug flow and a subsequent seeded emulsion polymerization of styrene (St) using the second W/O slug flow. In this process, monodisperse PMMA seed particles are first formed in the dispersed aqueous phase of the first W/O slug flow. Subsequently, removal of the oil phase from the slug flow is achieved through a porous hydrophobic tubing, resulting in a single flow of the aqueous phase containing the seed particles. The aqueous phase is then mixed with an oil phase containing St monomer to form the second W/O slug flow. Finally, monodisperse PMMA/PS composite particles are obtained by a seeded emulsion polymerization of St using the second W/O slug flow. We compared the reaction performance between the slug flow and the batch processes in terms of particle diameter, monomer conversion, particle size distribution, and the number of particles in the system. We found that internal circulation flow within the slugs can enhance mass transfer efficiency between them during polymerization, which results in monodisperse PMMA/PS composite particles with a large particle diameter and a high monomer conversion in a short reaction time, compared to those prepared using the batch process. We believe that this sequential microflow process can be a versatile strategy to continuously produce monodisperse composite particles or core-shell particles in a short reaction time.

Preparation and characterization of self-crosslinking acrylic emulsion with different fluorocarbon chain lengths

Purpose Fluorine materials have received the keen attention of many researchers because of their water repellency and low surface free energy. The purpose of this paper is to prepare self-crosslinking fluorocarbon polyacrylate latexes containing different fluorocarbon chain lengths by semi-continuous seeded emulsion polymerization technology. Design/methodology/approach Methyl methacrylate (MMA), butyl acrylate (BA), hydroxypropyl methacrylate (HPMA) and fluorine-containing monomers were used as main monomers. The fluorine-containing monomers included hexafluorobutyl methacrylate (HFMA), dodecafluoroheptyl methacrylate (DFMA) and trifluorooctyl methacrylate (TFMA). Potassium persulfate (KPS) was used as thermal decomposition initiator, non-ionic surfactant alkyl alcohol polyoxyethylene (25) ether (DNS-2500) and anionic surfactant sodium dodecylbenzene sulfonate (SDBS) as mixed emulsifier. Findings Through optimizing the reaction conditions, the uniform and stable latex is gained. The polymer of structure was characterized by Fourier transform infrared spectroscopy (FTIR). Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and contact angle (CA) were tested on latex films. The particle size and distribution range of emulsion were tested with nano particle size analyzer. After comprehensively comparing the latexes and films prepared by HFMA, DFMA and TFMA, the performance of DFMA monomer modified is better. Originality/value The self-crosslinking acrylic emulsion is prepared via semi-continuous seeded emulsion polymerization, which methyl methacrylate (MMA), butyl acrylate (BA), hydroxypropyl methacrylate (HPMA) and fluorine-containing monomers were used as main monomers. The fluorine-containing monomers were composed of hexafluorobutyl methacrylate (HFMA), dodecafluoroheptyl methacrylate (DFMA) and trifluorooctyl methacrylate (TFMA). Potassium persulfate (KPS) was used as thermal decomposition initiator, non-ionic surfactant alkyl alcohol polyoxyethylene (25) ether (DNS-2500) and anionic surfactant sodium dodecylbenzene sulfonate (SDBS) as mixed emulsifier. There are two main innovations. One is that the self-crosslinking acrylic emulsion is prepared successfully. The other is that the effects of monomers containing different fluorocarbon chain lengths on polyacrylate, such as monomer conversion rate, coagulation rate, mechanical stability, chemical stability, emulsion particle size and storage stability, are studied in detail.

Novel Chemical Architectures Based on Beta-Cyclodextrin Derivatives Covalently Attached on Polymer Spheres

This study presents the synthesis and characterization of polymer derivatives of beta-cyclodextrin (BCD), obtained by chemical grafting onto spherical polymer particles (200 nm) presenting oxirane functional groups at their surface. The polymer spheres were synthesized by emulsion polymerization of styrene (ST) and hydroxyethyl methacrylate (HEMA), followed by the grafting on the surface of glycidyl methacrylate (GMA) by seeded emulsion polymerization. The BCD-polymer derivatives were obtained using two BCD derivatives with hydroxylic (BCD-OH) and amino groups (BCD-NH2). The degree of polymer covalent functionalization using the BCD-OH and BCD-NH2 derivatives were determined to be 4.27 and 19.19 weight %, respectively. The adsorption properties of the materials were evaluated using bisphenol A as a target molecule. The best fit for the adsorption kinetics was Lagergren’s model (both for Qe value and for R2) together with Weber’s intraparticle diffusion model in the case of ST-HEMA-GMA-BCD-NH2. The isothermal adsorption evaluation indicated that both systems follow a Langmuir type behavior and afforded a Qmax value of 148.37 mg g−1 and 37.09 mg g−1 for ST-HEMA-GMA-BCD-NH2 and ST-HEMA-GMA-BCD-OH, respectively. The BCD-modified polymers display a degradation temperature of over 400 °C which can be attributed to the existence of hydrogen bonds and BCD thermal degradation pathway in the presence of the polymers.

Styrene–Acrylic Emulsion with “Transition Layer” for Damping Coating: Synthesis and Characterization

In order to study the dynamic mechanical properties of styrene–acrylic latex with a core/shell structure, a variety of latexes were synthesized by semi-continuous seeded emulsion polymerization based on “particle design” with the same material. The latexes were characterized by rotary viscosimeter, dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), dynamic mechanical analysis (DMA), and universal testing machine. The effects of difference at the glass transition temperature (Tg) of core and shell and the introduction of the “transition layer” on the damping and mechanical properties of latex film were studied. The results indicate that as the Tg of core and shell gets closer, the better the compatibility of core and shell, from phase separation to phase continuity. Furthermore, the introduction of the “transition layer” can effectively improve the tensile strength and tan δ (max) of the latex film. The tensile strength and maximum loss factor (f = 1 Hz) of latex with the “transition layer” increased by 36.73% and 29.11% respectively compared with the latex without the “transition layer”. This work provides a reference for the design of emulsion for damping coating.

Crosslinking in Semi-Batch Seeded Emulsion Polymerization: Effect of Linear and Non-Linear Monomer Feeding Rate Profiles on Gel Formation

Waterborne latex is often called a product-of-process. Here, the effect of semi-batch monomer feed rate on the kinetics and gel formation in seeded emulsion polymerization was investigated for the copolymerization of n-butyl methacrylate (n-BMA) and ethylene glycol dimethacrylate (EGDMA). Strikingly, the gel fraction was observed to be significantly influenced by monomer feed rate, even while most of the experiments were performed under so-called starve-fed conditions. More flooded conditions from faster monomer feed rates, including seeded batch reactions, counterintuitively resulted in significantly higher gel fraction. Chain transfer to polymer was intentionally suppressed here via monomer selection so as to focus mechanistic insights to relate only to the influence of a divinyl monomer, as opposed to being clouded by contributions to topology from long chain branching. Simulations revealed that the dominant influence on this phenomenon was the sensitivity of primary intramolecular cyclization to the instantaneous unreacted monomer concentration, which is directly impacted by monomer feed rate. The rate constant for cyclization for these conditions was determined to be first order and 4000 s−1, approximately 4 times that typically observed for backbiting in acrylates. This concept has been explored previously for bulk and solution polymerizations, but not for emulsified reaction environments and especially for the very low mole fraction divinyl monomer. In addition, while gel fraction could be dramatically manipulated by variations in linear monomer feed rates, it could be markedly enhanced by leveraging non-linear feed profiles built from combination sequences of flooded and starved conditions. For a 2 h total feed time, a fully linear profile resulted in 30% gel while a corresponding non-linear profile with an early fast-feed segment resulted in 80% gel.

Well Defined Poly(Methyl Methacrylate)-Fe3O4/Poly(Vinyl Pivalate) Core–Shell Superparamagnetic Nanoparticles: Design and Evaluation of In Vitro Cytotoxicity Activity Against Cancer Cells

The objective of this work is to develop and characterize polymeric nanoparticles with core–shell morphology through miniemulsion polymerization combined with seeded emulsion polymerization, aiming at the application in the treatment of vascular tumors via intravascular embolization. The synthesis of the core–shell nanocomposites was divided into two main steps: (i) Formation of the core structure, consisting of poly(methyl methacrylate)/magnetic oxide coated with oleic acid (OM-OA) via miniemulsion and (ii) shell structure produced through seeded emulsion polymerization of vinyl pivalate. Nanocomposites containing about 8 wt.% of OM-OA showed high colloidal stability, mean diameter of 216.8 nm, spherical morphology, saturation magnetization (Ms) of 4.65 emu·g−1 (57.41 emu·g−1 of Fe3O4), preserved superparamagnetic behavior and glass transition temperature (Tg) of 111.8 °C. TEM micrographs confirmed the obtaining of uniformly dispersed magnetic nanoparticles in the PMMA and that the core–shell structure was obtained by seeded emulsion with Ms of 1.35 emu·g−1 (56.25 emu·g−1 of Fe3O4) and Tg of 114.7 °C. In vitro cytotoxicity assays against murine tumor of melanoma (B16F10) and human Keratinocytes (HaCaT) cell lines were carried out showing that the core–shell magnetic polymeric materials (a core, consisting of poly(methyl methacrylate)/Fe3O4 and, a shell, formed by poly(vinyl pivalate)) presented high cell viabilities for both murine melanoma tumor cell lines, B16F10, and human keratinocyte cells, HaCaT.

Preparation and characterization of self-cross-linking long fluorocarbon polyacrylate latex modified by silane cross-linker

Purpose Silane cross-linkers have been used to strengthen the mechanical stabilities and friction resistance of plastic products. Therefore, the effect of silane cross-linkers on latex has been studied through preparing modified self-cross-linking long fluorocarbon polyacrylate latex. In this paper, nonionic surfactant alcohol ether glycoside (AEG1000) and anionic polymerizable surfactant 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate (DNS-86) acted as mixed emulsifier and 3-(methacryloyloxy) propyltrimethoxysilane (KH-570) and bis (2-ethylhexyl) maleate (DOM) were used as functional monomers. Design/methodology/approach The modified acrylate polymer latex was synthesized through the semi-continuous seeded emulsion polymerization with methyl methacrylate (MMA), butyl acrylate (BA), dodecafluoroheptyl methacrylate (DFMA) and hydroxypropyl methacrylate (HPMA) as main monomers. Potassium persulfate (KPS) was applied to initiate polymerization reaction, nonionic surfactant AEG1000 and DNS-86 acted as emulsifier, KH-570 and DOM were used as functional monomers, respectively. Findings The optimum conditions of synthesizing the modified latex were the following. The mass ratio of monomers containing MMA, BA, DFMA, HPMA, KH-570 and DOM was 13.58:13.58:0.90:1.20:0.15:0.60, the usage of initiator KPS was 0.5% of the total weight of monomers and the amount of emulsifier was 7% of all monomers with AEG1000:DNS-86 = 1:1. The results indicated that the conversion of monomer was 99% and the coagulation was about 2.0%. Originality/value The resultant latex was modified silane cross-linker KH-570 and DOM, which positively affected the comprehensive properties of latex and its film. Apart from this, the novel mixed emulsifier was used to improve the size and distribution of latex particles and reduce environmental problems caused by the use of emulsifiers.