Dispersion Polymerization Of Methyl Methacrylate Research Articles

Dispersion Polymerization of Methyl Methacrylate Using Poly(vinyl acetate/vinyl propionate) Based Copolymers as Stabilizers in Supercritical Carbon Dioxide

Dispersion Polymerization of Methyl Methacrylate Using Poly(vinyl acetate/vinyl propionate) Based Copolymers as Stabilizers in Supercritical Carbon Dioxide

Exploiting the tuneable density of scCO2 to improve particle size control for dispersion polymerisations in the presence of poly(dimethyl siloxane) stabilisers

The dispersion polymerisation of methyl methacrylate (MMA) is a widely employed method for producing discrete, spherical PMMA particles from traditional solvents, which cover a broad particle size range. With environmental impact becoming an ever more widespread concern, there is increasing demand for greener solvents with advantageous characteristics. Supercritical carbon dioxide (scCO2) offers the potential of a greener solvent for dispersion polymerisations, with uniquely tuneable solvent properties and the ability to avoid energy and cost intensive drying steps. In this work, the tuneable density of scCO2 was exploited to influence the solubility of poly(dimethyl siloxane) stabilisers in the dispersion polymerisation of methyl methacrylate as a proof-of-concept. By varying the reactor pressure at the start of polymerisation, the final particle size was altered, without the need for cosolvent systems used in traditional solvents. Finally, this additional particle size control mechanism was exploited to achieve a PMMA particle size range far beyond what was previously attainable with this stabiliser. Thus, further enhancing the potential use of scCO2 as a green solvent for industrial polymer production.

RAFT Dispersion Polymerization of Methyl Methacrylate in Mineral Oil: High Glass Transition Temperature of the Core-Forming Block Constrains the Evolution of Copolymer Morphology

RAFT dispersion polymerization of a prototypical methacrylic monomer, methyl methacrylate (MMA), is performed in mineral oil using various poly(lauryl methacrylate) (PLMA) precursors prepared with a trithiocarbonate-based RAFT agent. GPC analysis indicated reasonably narrow molecular weight distributions (Mw/Mn ≤ 1.39) for all diblock copolymers, with 1H NMR studies indicating high MMA conversions (≥95%) for all syntheses. An efficient one-pot synthesis protocol enabled high blocking efficiencies to be achieved when targeting higher PMMA DPs. However, the relatively high glass transition temperature (Tg) of the corresponding core-forming PMMA block unexpectedly constrains the evolution in copolymer morphology during polymerization-induced self-assembly (PISA). More specifically, well-defined PLMA22–PMMAx spheres (x = 19–39) and relatively short worms (x = 69–97) can be obtained at 90 °C when using a PLMA22 precursor but targeting higher x values (x ≥ 108) invariably leads to colloidally unstable aggregates of spheres, rather than long worms or vesicles. Interestingly, similar constraints were observed when targeting higher solids, when using n-dodecane instead of mineral oil, or when employing an alternative steric stabilizer block. Raising the PISA synthesis temperature from 90 to 115 °C (i.e., from below to above the Tg of the final PMMA block) does not alleviate this unexpected problem. Moreover, only spherical nanoparticles can be obtained at 115 °C when targeting PMMA DPs between 50 and 400 with the same PLMA22 precursor. This suggests that nanoparticle formation may occur by a chain expulsion/insertion mechanism at this relatively high reaction temperature. PLMA22–PMMAx nanoparticles were characterized in terms of their particle size and morphology using dynamic light scattering (DLS), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). DLS and TEM studies of a 0.1% w/w dispersion of PLMA22–PMMA69 short worms indicated an irreversible worm-to-sphere transition on heating from 20 to 150 °C. Oscillatory rheology and TEM studies indicated that this thermal transition was only partially reversible for a 20% w/w dispersion of PLMA22–PMMA69 short worms.

Influence of structure and solubility of chain transfer agents on the RAFT control of dispersion polymerisation in scCO2.

Reversible addition–fragmentation chain transfer (RAFT) dispersion polymerisation of methyl methacrylate (MMA) is performed in supercritical carbon dioxide (scCO2) with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight. Kinetic studies of the polymerisation in scCO2 also confirm these data. By contrast, only poor control of MMA polymerisation is obtained in toluene solution, as would be expected for this CTA which is better suited for acrylates. In this regard, we select a range of CTAs and use them to determine the parameters that must be considered for good control in dispersion polymerisation in scCO2. A thorough investigation of the nucleation stage during the dispersion polymerisation reveals an unexpected “in situ two-stage” mechanism that strongly determines how the CTA works. Finally, using a novel computational solvation model, we identify a correlation between polymerisation control and degree of solubility of the CTAs. All of this ultimately gives rise to a simple, elegant and counterintuitive guideline to select the best CTA for RAFT dispersion polymerisation in scCO2.

Dispersion Polymerization of Methyl Methacrylate in Supercritical CO2: A Preliminary Evaluation of In Situ Incorporation of Copaiba Oil

In-situ dispersion polymerization of methyl methacrylate (MMA) in the presence of scCO2 is investigated as an alternative technique to load copaiba (Copaifera ssp.) oil in poly (methyl methacrylate...

Better RAFT Control is Better? Insights into the Preparation of Monodisperse Surface-Functional Polymeric Microspheres by Photoinitiated RAFT Dispersion Polymerization

Efficient synthesis of polymeric microspheres with high uniformity, well-defined surface functionality, and precise diameter and composition has long been a challenging goal in polymer science. Herein, we exploited photoinitiated reversible addition–fragmentation transfer (RAFT) dispersion polymerization of methyl methacrylate using poly(glycerol monomethacrylate)-based macromolecular chain transfer agents (macro-CTAs). We showed that the use of a binary mixture of macro-CTA and CTA with poor controllability was crucial for obtaining monodisperse poly(methyl methacrylate) (PMMA) microspheres. Evolution of PMMA microspheres during the polymerization was followed by scanning electron microscopy and 1H NMR spectroscopy, confirming a linear evolution of particle volume with monomer conversion. PMMA microspheres with better colloidal stability were obtained when increasing the amount of macro-CTA used in photoinitiated RAFT dispersion polymerization. Finally, a two-stage photoinitiated RAFT dispersion polymerization was also explored by adding additional monomers in the second stage. We demonstrated that the particle size of polymeric microspheres could be precisely controlled by adding different amounts of the monomer in the second stage. Moreover, polymeric microspheres composed of two polymers were also prepared by adding a different monomer in the second stage. This study not only optimizes reaction conditions for preparing monodisperse surface-functional polymeric microspheres but also provides mechanistic insights into photoinitiated RAFT dispersion polymerization.

Continuous-porous N-doped carbon network as high-performance electrode for lithium-ion batteries

Hierarchical porous N-doped carbon (NPC) is prepared by pyrolysis of poly(methyl methacrylate) (PMMA) particles decorated by graphene oxide (GO) and polypyrrole (PPy) as precursors and used as anode for lithium-ion batteries. The composite precursors with different diameter and composition (PMMA/GO/PPy-A and B) were conveniently prepared by dispersion polymerization of methyl methacrylate in the presence of graphene oxide as stabilizer in aqueous medium, followed by addition of pyrrole and its oxidative polymerization. After pyrolysis, the resulting NPC composites with hierarchically structured macro- and mesopores exhibit high surface area (289–398 m2/g) and different N-doping levels (7.46 and 4.22 wt% of nitrogen content). The NPC with the highest N-doping level (7.46 wt%) shows high reversible capacities of 831 mAh/g at 74.4 mA/g (C/5) after 50 cycles and excellent rate performances.

Raft approach to the copolymerisation of methyl methacrylate based polymeric micelles

In this study, copolymer micelles were synthesised via free radical RAFT bulk polymerisation and RAFT dispersion polymerisation of methyl methacrylate. 4-CPDB-PDMS was used as the macro- RAFT agent, leading to the formation of the micellar nanostructures. Copolymer micelles obtained from the bulk polymerisation were used as macro RAFT agents in the dispersion polymerisation of methyl methacrylate in hexane, at 70 o C. Characterisation of the various polymeric products was carried out using gel permeation chromatography (GPC), nuclear magnetic resonance spectroscopy(NMR), fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and dynamic light scattering (DLS) analyses. The results show that the molecular weights of the copolymers in the bulk are controlled. The block copolymers in the dispersion have broad polydispersity indices (PDI) and the kinetic study indicates a deviation from ‘pseudo first order’ kinetics at higher conversions. Keywords: RAF; polymerisation; methyl methacrylate; micelles

Improved Particle Size Control for the Dispersion Polymerization of Methyl methacrylate in Supercritical Carbon Dioxide

Dispersion polymerization is a well‐established method of producing polymer particles that are easily handled and processed. With careful choice of reaction conditions this technique can yield well defined, spherical particles for a wide range of applications. The use of supercritical carbon dioxide (scCO2) as a reaction medium offers a route to performing these syntheses without excessive use of volatile organic solvents and minimizes work‐up and disposal steps. However a significant drawback has been the fact that up till now the control of particle size and morphology from CO2 have been limited. This study presents control of particle size and morphology over an unprecedented range for a single stabilizer in scCO2 by coordinating a few simple parameters to tailor the conditions toward different sizes. Further, this study introduces the novel approach in scCO2 of using delayed monomer addition which allows considerable reduction of the batch‐to‐batch variability as well as reduced agglomeration between particles. image

Dispersion polymerization of methyl methacrylate with three types of comblike fluorinated stabilizers in supercritical carbon dioxide

ABSTRACTDispersion polymerizations of methyl methacrylate in supercritical carbon dioxide were conducted with three types of comblike fluorinate polymer stabilizers: poly(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10‐heptadecafluorodecyl methacrylate) (PHDFDMA), poly(3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl methacrylate) (PTDFOMA), and poly(2,2,3,3,3‐pentafluoropropyl methacrylate) (PPFPMA). The effect of the polymerization pressure was not significant on the mean diameters of the poly(methyl methacrylate) (PMMA) particles from 20 to 40 MPa. However, the coefficients of variation of the particle diameters produced at 20 MPa ( , where is the number‐basis mean particle diameter), where the heterogeneous phase was found before polymerization, were larger than those produced at 30 and 40 MPa, where the homogeneous phase was found. The mean size of the PMMA obtained with PTDFOMA and PPFPMA strongly depended on the stabilizer concentration compared with that obtained with PHDFDMA. Moreover, the mean size decreased as the carbon dioxide‐philic side chain length increased. As shown by the results of this study, the best stabilizer among the three types of stabilizers for producing PMMA particles was PHDFDMA. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43813.

Porous membranes from acid decorated block copolymer nano-objects via RAFT alcoholic dispersion polymerization

Acid decorated diblock copolymer nano-objects were prepared by polymerization-induced self-assembly via RAFT dispersion polymerization of methyl methacrylate. Spheres were used to prepare thin film membranes.

Dispersion polymerization of methyl methacrylate in supercritical carbon dioxide using vinyl terminated poly(dimethylsiloxane)

PMMA has applications on the medical, pharmaceutical and engineering areas. Different processes may be employed for its production. Here, MMA polymerization was performed by supercritical carbon dioxide dispersion. CO2 is inert, easily retrievable and separated from the product. The monomer is soluble in dense CO2, unlike PMMA, requiring a stabilizer to maintain the dispersion. Here, vinyl terminated PDMS was used as a dispersing agent. The reactions were conducted at 16MPa/80°C for 4h. Product characterization was performed by SEM, to evaluate the morphology at estimate the particle size, SEC, to determine the molar mass and polydispersion index, 1H NMR and FTIR spectroscopy, in order to verify the chemical structure of the product, and also gravimetric analyses, to determine the residual monomer. The results confirmed the adequacy of the process and of the stabilizer for PMMA particles production.

One‐pot synthesis of self‐stabilized and carboxyl‐functionalized fluorescent poly(methyl methacrylate) microspheres covalently dyed with tris(8‐hydroquinolinato)aluminium by dispersion polymerization

AbstractThe dispersion polymerization of methyl methacrylate (MMA) with fluorescent monomer tris[2‐((8‐hydroxyquinolin‐5‐yl)methoxy)ethyl methacrylate]aluminium (Al‐HQHEMA) was investigated to obtain fluorescent microspheres under varying conditions (such as composition of dispersion medium, and content of stabilizer polyvinylpyrrolidone (PVP) and Al‐HQHEMA) in methanol–water at 70 °C with 2,2′‐azoisobutyronitrile as the initiator. Fluorescent microspheres with particle size of 2.039 µm and uniformity of 0.171 were obtained under the following conditions: methanol–water, 7:3 (v/v); PVP, 15 wt% of MMA; Al‐HQHEMA solution, 1.5 mL. Maleic monoester of monomethoxyl poly(ethylene glycol) (Mal‐MPEG) was used as a comonomer to simultaneously incorporate carboxyl groups and PEG chains. With Mal‐MPEG, no aggregation was observed in the measurements of particle size and size distribution for the obtained microspheres after cleaning off PVP, indicating that self‐stabilized fluorescent microspheres were obtained. While without Mal‐MPEG, obvious aggregation was observed. The determination of surface carboxyl content using aqueous acid–base titration showed that most of the carboxyl groups of Mal‐MPEG were located on the surface of the microspheres. © 2015 Society of Chemical Industry

Synthesis of PMMA Microparticles with a Narrow Size Distribution by Photoinitiated RAFT Dispersion Polymerization with a Macromonomer as the Stabilizer

Macromonomers can serve as efficient and effective stabilizers for dispersion polymerization of monomers such as styrene and methyl methacrylate, but the size distributions of the polymer microparticles obtained tend to be broad. We are interested in functional microbeads which can be used for immunoassays, where the size distribution has to be very narrow. We report a photoinitiated RAFT dispersion polymerization of methyl methacrylate (MMA) in ethanol–water mixtures, with methoxy-poly(ethylene glycol) methacrylate (Mn = 2000 g/mol, EO45) as the reactive steric stabilizer. We identify reaction conditions where one can obtain PMMA microspheres with coefficient of variation in the particle diameter (CVd) less than 3%. Carboxy-functional PMMA microspheres were obtained by a two-stage (seeded) polymerization with methacrylic acid (MAA) added as a comonomer in the second stage. We show that the functional microspheres prepared in this way are effective substrates for the covalent attachment of proteins such as BSA and IgG immunoglobulins. In one set of experiments with a dye-labeled secondary antibody, we found that we could detect 104 IgGs per PMMA microbead.

Seeded dispersion polymerization of MMA using submicron PMMA particles as seed: a mechanistic study

Micron-size poly(methyl methacrylate) (PMMA) particles having a narrow particle size distribution were prepared by seeded dispersion polymerization of methyl methacrylate (MMA) using submicron PMMA particles as seed. The processes of particle aggregation and nucleation were controlled by the initial seed size, initial seed number, and initiator concentration, determining the formation of the mature particles and the number (N (final)) and size of the final particles. It was found that N (final) was equal to the number of particles produced in the absence of seed (N (ab initio)) when the initial number of seed particles (N (initial)) was less than N (ab initio). When N (initial) was greater than N (ab initio), N (final) was equal to k × N (initial), where the value of k was a function of seed size and initiator concentration. k increased with seed size and was less than 1 at high initiator concentrations (0.52 and 1.00 %), while at low initiator concentrations (0.23 and 0.30 %), a maximum value of k was found for a 198 nm seed size. k could be greater than unity in some cases.

Charge Generation in Low-Polarity Solvents: Poly(ionic liquid)-Functionalized Particles

We present a straightforward strategy for the synthesis of highly charged poly(ionic liquid)-functionalized particles in low-polarity solvents. A series of cationic liquid monomers consisting of a tetraalkyl ammonium cation and a fluorinated tetrakis[phenyl] borate anion linked, via a C3-alkyl chain, to a methacrylate unit were synthesized. The addition of this ionic monomer to a conventional dispersion polymerization of methyl methacrylate and methacrylic acid at 80 °C in a mixed dodecane/hexane solvent yielded spherical, highly monodisperse particles with mean diameters of between ~50 and 2500 nm with high electrophoretic mobility and stability in nonpolar solvents such as dodecane. The surface potential in dodecane could be adjusted in the range from 0 to 180 ± 9 mV by altering the ratio of ionic monomer to methacrylate monomers. The particles open up new opportunities for the electrostatic assembly of nanoparticles and organized structures in nonpolar environments.

Tracking the fate of seed particles in dispersion polymerization: Preparation and application of fluorescent polymer particles

AbstractThe mechanism of seeded dispersion polymerization of methyl methacrylate (MMA) was investigated by employing submicron fluorescent polymer particles as seed. These poly(methyl methacrylate) latex particles, containing fluorescent material, were synthesized by a two‐step miniemulsion polymerization process and then applied in the seeded dispersion polymerization of MMA. The seed particles were located by tracking the fluorescent signal in the micron‐size final particles. The analysis of the final particles showed that most of them contained more than two seed particles. On average, there were 3.7 seed particles in each final particle as obtained under the given conditions of the seeded dispersion polymerization. The location of the seed within the particles being well‐separated from each other was considered to indicate that the aggregation of the particles did not occur immediately, but took place after some particle growth had first taken place. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Determination of the Critical Chain Length of Oligomers in Dispersion Polymerization.

The critical chain length (jcrit) in dispersion polymerization is systematically investigated utilizing low molecular weight poly(methyl methacrylate) oligomers synthesized by catalytic chain transfer polymerization. The solubility of these oligomers in methanol/water media of different compositions and at different temperatures has been visually determined. The results show that the solubility of the oligomers increases with increasing methanol fraction and increasing temperature. The constructed solubility map allows for an estimate of jcrit as a function of these important polymerization parameters. Furthermore, it is found that the value of jcrit changes with the concentration of the oligomers in the methanol/water medium, an important consideration for understanding the nucleation stage of a dispersion polymerization. The obtained results have been successfully correlated to earlier data reported on the dispersion polymerization of methyl methacrylate.

Effect of molecular weight on the surface morphology of crosslinked polymer particles in the RITP-dispersion polymerization

The RITP (reverse iodine transfer polymerization)-dispersion polymerization of methyl methacrylate (MMA) was conducted and the molecular weight and SEM images of them were investigated to propose the mechanism of the formation of surface morphology in crosslinked polymers. The morphology of the crosslinked particles varied depending on the sorts and contents of the crosslinking agents and iodine. As the iodine content increased under the same content of the crosslinking agent, the average molecular weight of the polymers [uncrosslinked portion of the polymers] decreased and the surface roughness simultaneously reduced. On the other hand, as the contents of the crosslinking agent increased, the molecular weight of polymers reduced and the surface morphology changed from smooth to rough in the absence of iodine. On the other hand, was the molecular weight was barely changed and the solubility increased upon iodine. Thus the mechanism of the formation of crosslinked polymers in the RITP-dispersion polymerization was proposed as the following; when crosslinking agent and iodine were simultaneously involved, the low molecular weight of polymers were first formed due to the effect of iodine and then the crosslinking was taking place, resulting in that iodine was a critical factor in controlling the molecular weight, particle size, solubility and the surface morphology in the crosslinked polymer particles.

Experimental and theoretical study of the reaction locus during the dispersion polymerization of methyl methacrylate in a nonpolar hydrocarbon solvent at low temperature

AbstractThe dispersion polymerization of methyl methacrylate (MMA) has been studied in a nonpolar hydrocarbon solvent at low temperature using N,N‐dimethylaniline (DMA) and lauroyl peroxide (LPO) as redox initiation system. To explain the heterogeneous kinetic characteristics of the polymerization process, the reaction locus has been experimentally and theoretically investigated. The evolutions of monomer conversion, polymer molecular weight distribution (MWD), and particle morphology were measured throughout the polymerization. It was found that the significant preferences of LPO and DMA to accumulate in the polymer‐rich phase after the system phase separation are mainly responsible for both the uniformity of particle sizes and the broad polymer MWDs. It was observed that particle agglomeration and breakup mechanisms were enhanced under agitation, thus promoting the formation of broader particle size distributions. The observed kinetics and thermodynamics of the low‐temperature polymerization were also examined through a mathematical model where the distributions of initiators, solvent, and monomer between phases were considered. A good agreement between the experimental and theoretical results was observed and the model was used to estimate the conditions that promote bimodal MWDs. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers