Semibatch emulsion polymerization of methyl methacrylate using different polyurethane particles

Aqueous acrylic‐polyurethane (AC–PU) hybrid emulsions were prepared by semibatch emulsion polymerization of methyl methacrylate (MMA) in the presence of four polyurethane (PU) dispersions. The PU dispersions were synthesized with isophorone diisocyanate (IPDI), 1000 and 2000 molecular weight (MW) poly(neopentyl) adipate, 1000 MW polytetramethyleneetherglycol, butanediol (BD), and dimethylol propionic acid (DMPA). MMA was added in the monomer emulsion feed. We studied the effect of the use of different PU seed particles on the rate of polymerization, the particle size and distribution, the number of particles, and the average number of radicals per particle. The PU rigidity was controlled by varying the polyol chemical structure, the polyol MW (M_n), and by adding BD. The monomer feed rate was varied to study its influence on the process. It was observed that the PU particles that had been prepared with a higher MW polyol swelled better with MMA before the monomer‐starved conditions occurred. There seemed to be no significant discrepancies between the series with different PU seeds in the monomer‐starved conditions. The overall conversion depended on the monomer addition rate, and the polymerization rate acquired a constant value that was comparable to the value of the monomer addition rate. The instantaneous conversion increased slightly. The average particle size increased, and the total particle number in the reactor was constant and similar to the number of PU particles in the initial charge. The average number of radicals per particle increased. The differences between the system with a constant particle number and average number of radicals per particle and the system with a fixed radical concentration are discussed. The semibatch emulsion polymerization of MMA in the presence of PU particles studied was better compared to the system with a fixed radical concentration. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 844–858, 2005     

Synthesis of submicron-sized peanut-shaped poly(methyl methacrylate)/polystyrene particles by seeded soap-free emulsion polymerization

Submicron-sized peanut-shaped poly(methyl methacrylate)/polystyrene(PMMA/PS) particles were successfully synthesized by seeded soap-free emulsion polymerization of styrene on the spherical crosslinked PMMA seed particles.The obtained peanut-shaped particles showed a novel internal morphology:PS phase formed one domain which linked to the other domain having PMMA core encased by PS shell.     

Synthesis of Core-Shell Particles of Polystyrene and Poly(methyl methacrylate) Using Emulsion Photopolymerization

Summary: Submicron core-shell particles of polystyrene (PS) and polystyrene-co-poly(methyl methacrylate) (PS-co-PMMA) coated with PMMA were obtained by emulsion photopolymerization. The seeds of PS or PS-co-PMMA were prepared by emulsion polymerization with or without emulsifier and a ratio of functional monomer and crosslinker (SVBS/EDGMA) in order to obtain different surfaces for the subsequent coating with PMMA. At each stage, the evolution of the average particle size were monitored by using photon correlation spectroscopy (DLS) and the final polymer particles was analyzed via transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The core-shell morphology was identified as the increase of the average particle size in the second stage by DLS technique and by the direct observation by TEM of the differentiation between PS core and PMMA shell, and by the presence of two glass transition temperatures (T_g) as a consequence of the existence of two partially miscible phases.     

Ultrasonically initiated emulsion polymerization of methyl methacrylate

The ultrasonically initiated emulsion polymerization of methyl methacrylate (MMA) was investigated. Experimental results show that sodium dodecyl sulfonate (SDS) surfactant plays a very important role in obtaining a high polymer yield, because in the absence of SDS, monomer conversion is near zero. Thus, the surfactant serves as an initiator and as interfacial modifier in this system (MMA/H₂O), and the monomer conversion increases significantly with increasing SDS concentration. An increase in the reactor temperature also leads to an increase in the monomer conversion. An appropriate increase in the N₂ purging rate also leads to higher conversion. The conversion of MMA decreases with increasing monomer concentration because of the higher viscosity of the system. With the experimental results, optimized reaction conditions were obtained. Accordingly, a high monomer conversion of about 67% and a high molecular weight of several millions can be obtained in a period of about 30 min. Furthermore, transmission electron micrographs show that the latex particles prepared are nanosized, indicating a promising technique for preparing nanoscale latex particles with a small amount of surfactant. In conclusion, a promising technique for ultrasonically initiated emulsion polymerization has been successfully performed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3356–3364, 2001     

Synthesis and properties of soap-free poly(methyl methacrylate-ethyl acrylate-methacrylic acid) latex particles prepared by seeded emulsion polymerization

In order to obtain functional polymer latex particles with clean surface and with surface carboxyl groups, P(MMA-EA) seed particles with the diameter of 335 nm were first synthesized via soap-free batch emulsion polymerization of methyl methacrylate (MMA) and ethyl acrylate (EA), and then the seeded emulsion copolymerization of MMA, EA and MAA (methacrylic acid) onto the seed particles were performed in the absence of emulsifier. Influences of ingredients and conditions on polymerization, latex particle size (D_p) and its distribution were investigated. Results showed that most of the monomers polymerized onto the seed latex particles in the second step of polymerization by using drop-wise addition method, and D_p increased from 483 nm to 829 nm with the mass ratio of core/shell monomers [C]/[S] decreased from 1:2 to 1:15. It was found that D_p decreased with the increase of MAA and initiator amounts, and the size of the latex particles became uniform with the decrease of MAA amount and with the increase of [C]/[S] value.     

Synthesis of ZnO/polystyrene composites particles by Pickering emulsion polymerization

ZnO/polystyrene composite particles were synthesized by Pickering emulsion polymerization. ZnO nanoparticles were first prepared by reaction of zinc acetate and sodium hydroxide in ethanol medium. Then different amount of styrene monomer was emulsified in water in the presence of ZnO nanoparticles either by mechanical stirring or by sonication, followed by polymerization of styrene. Two kinds of initiators were used to start the polymerization, azobisisobutyronitrile (AIBN) and potassium persulfate (KPS). The X-ray diffraction pattern verified the crystal structure of ZnO and FT-IR spectra evidenced the existence of ZnO and polystyrene (PS) in ZnO/polystyrene composite particles. Different morphologies were observed for the composite particles when using different initiators. From TEM photographs, AIBN-initiated system produced mainly core-shell composite particles with PS as core and ZnO as shell, while KPS-initiated system showed both composite particles and pure PS particles. Two schemes of reaction mechanism were proposed to explain the morphologies accordingly. Both systems of composite particles showed good pH adjusting ability.     

聚甲基丙烯酸甲酯-氯化银复合纳米微球的制备及其摩擦学性能

采用原位种子乳液聚合法合成了聚甲基丙烯酸甲酯 氯化银(PMMA AgCl)核壳结构复合纳米微球,通过透射电镜(TEM),红外光谱(IR),热分析(TG DTA)和X射线粉末衍射(XRD)等测试手段对其结构及性能进行了表征.在四球试验机上对其摩擦学行为进行了考察,研究结果表明,PMMA AgCl核壳结构复合纳米微球用作润滑油添加剂具有良好的抗磨性能,能显著提高基础油的失效负荷.     

Poly(methyl methacrylate) composites prepared by in situ polymerization using organophillic nano-to-submicrometer zinc oxide particles

Nano- and submicrometer zinc(II) oxide particles were synthesized by the polyol method and were used for the preparation of ZnO/poly(methyl methacrylate) (ZnO/PMMA) composite materials by the chain polymerization of methyl methacrylate (MMA) in bulk. ZnO particles with an organophilic surface layer were homogeneously dispersed in the PMMA matrix. Very low concentrations (0.1 wt.%) of nano zinc oxide absorbed over 98% of UV light as determined by UV-vis spectroscopy. Nano zinc oxide (75 nm) increased the initial decomposition temperature of the PMMA matrix by 30-40 °C at concentrations of 0.1% and above. This was explained by the changes in the termination mechanism of MMA polymerization resulting in a reduced concentration of vinylidene chain ends. Nano ZnO also increased the MMA polymerization reaction rate and reduced the activation energy. Submicrometer ZnO showed lower UV absorption, thermal stabilization and no influence on the reaction kinetics indicating that average particle size is of vital importance for the properties of PMMA nanocomposites and for MMA polymerization.     

Connection of poly(methyl methacrylate) microgel particles dispersed in poly(vinyl alcohol) matrix by seed polymerization

Poly(methyl methacrylate) microgels covered with poly(hydroxyethyl methacrylate) thin layer was dispersed in poly(vinyl alcohol) matrix. Homogeneous and regular arrangement of the microgel particles was suggested by Bragg diffraction for the films prepared by varying the PVA/microgel ratio (from 6/4 to 3/7 (w/w)). It was proved that the regular arrangement and connection of the microgels by seeded polymerization in poly(vinyl alcohol) were possible. © 1996 John Wiley & Sons, Inc.     

Preparation of poly(methyl methacrylate)/CaCO3/SiO2 composite particles via emulsion polymerization

A novel method to prepare organic/inorganic composite particles, i.e. poly(methyl methacrylate)/CaCO₃/SiO₂ three-component composite particles, using emulsion polymerization of methyl methacrylate with sodium lauryl sulfate as a surfactant in an aqueous medium was reported. CaCO₃/SiO₂ two-component inorganic composite particles were obtained firstly by the reaction between Na₂CO₃ and CaCl₂ in porous silica (submicrometer size) aqueous sol and the specific surface area of the particles was measured by the Brunauer–Emmett–Teller (BET) method. The results show that the BET specific surface area of the CaCO₃/SiO₂ composite particle is much smaller than that of the silica particle, indicating that CaCO₃ particles were adsorbed by porous silica and that two-component inorganic composite particles were formed. Before copolymerization with methyl methacrylate, the inorganic composite particles were coated with a modifying agent through covalent attachment. The chemical structures of the poly(methyl methacrylate)/CaCO₃/SiO₂ composite particles obtained were characterized by Fourier transform IR spectroscopy and thermogravimetric analysis. The results show that the surface of the modified inorganic particles is grafted by the methyl methacrylate molecules and that the grafting percentage is about 15.2%.     

Fluorescent polymer particles by emulsion and miniemulsion polymerization

We describe the synthesis and characterization of latex particles labeled with a brightly fluorescent yellow dye (HY) based on the benzothioxanthene ring structure. Three dye derivatives were synthesized with different spacers connecting the HY nucleus to a methacrylate group. For one of the dyes (HY2CMA, r_A), we show that the reactivity ratios with styrene (r_A = 0.71, r_B = 0.25) and butyl methacrylate (r_A = 0.87, r_B = 0.14) should lead to random dye incorporation if the amount of dye in the feed is small. Seeded emulsion polymerization fails to lead to significant dye incorporation unless large amounts of nonionic surfactant are present. In contrast, miniemulsion polymerization worked well to yield latex particles of polystyrene, poly(butyl methacrylate), and poly(methyl methacrylate) with high monomer conversion and essentially quantitative dye incorporation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 766–778, 2003     

Poly(methyl methacrylate) encapsulation of calcium carbonate particles

Dispersed calcium carbonate particles are encapsulated with poly(methyl methacrylate). The optimum condition for the polymerization is investigated; and the encapsulated particles are characterized by spectrophotometric analysis, acid decomposition, thermal analysis, and microscopic observation. From the conversion comparison of the MMA monomer it is found that the optimum concentration of polymerization initiator is 1.58 × 10^?3 mol/L. The highest yield of encapsulation is obtained at 250 rpm with a concentration of 0.5 wt % surfactant (sodium dodecyl benzene sulfonate). A comparison of the Fourier transform IR spectra distinctly indicates the formation of PMMA on the surface of the calcium carbonate particles. The outcome of an acid decomposition test proves that the PMMA coating protects the particles. In addition, thermal analyses and microscopic observation characterize the PMMA on the surface of encapsulated particles. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4063–4073, 2004     

Thermal properties of poly(methyl methacrylate) prepared by emulsifier-free emulsion polymerization

Emulsifier-free emulsion polymerization of methyl methacrylate in the presence of potassium persulfate initiator, taken in several different concentrations, at various pH values was studied with the aim to obtain colloidal crystals. The thermal properties of poly(methyl methacrylate) prepared by emulsifier-free emulsion polymerization, as the starting material for fabrication of photonic crystals, were examined in relation to the synthesis conditions.     

The role of initiation in the synthesis of silica/poly(methyl methacrylate) nanocomposite latex particles through emulsion polymerization

Silica/poly(methyl methacrylate) nanocomposite latex particles have been synthesized by emulsion polymerization of methyl methacrylate using a nonionic surfactant: nonylphenol poly(oxyethylene) and three different initiators, namely: 2,2′-azobis(2-amidinopropane) dihydrochloride (AIBA), potassium persulfate (KPS) and azobis(isobutyronitrile) (AIBN), being cationic, anionic and nonionic, respectively. A silica sol with an average diameter of 68 nm was used as the seed. The polymerization reaction was conducted under alkaline conditions in order to evaluate the role of the surface charge of the hydrophilic silica on the coating reaction. AIBA was found to be adsorbed on the silica surface owing to electrostatic interactions of the amidine function of the cationic initiator with the silanolate groups of the oxide surface, while the anionic and the nonionic initiators did not adsorb on silica under the same conditions. Nonetheless, whatever the nature of the initiator, polymerization took place on the silica particles as evidenced by transmission electron microscopy. The extent of interaction between the inorganic surface and the polymer particles was quantified by means of ultracentrifugation and a material balance. As much as 65% by weight of the total polymer formed was found to be present at the silica surface using AIBA, while only 40% for KPS and 25% for AIBN was found to cover the silica particles under alkaline conditions. We demonstrate that by using a cationic initiator and by controlling the pH of the suspension it is possible to significantly decrease the amount of free polymer. Coating of the silica particles took place through a kind of in situ heterocoagulation mechanism. Received: 8 December 2000 Accepted: 22 February 2001     

Synthesis of Poly(methyl methacrylate) Nanosize Particles by Differential Microemulsion Polymerization

Poly(methyl methacrylate) nanosize particles were synthesized by a differential microemulsion polymerization process. Sodium dodecylsulfate and ammonium persulfate were used as the surfactant and initiator, respectively. The effects of reaction conditions on the particle size have been investigated. A particle size of less than 20 nm in diameter has been achieved with surfactant/monomer and surfactant/water weight ratios of 1:18 and 1:120, i.e. much milder conditions than those previously reported in the literature.

TEM image of nanoparticles prepared via differential microemulsion polymerization.     

Synthesis of high oil‐absorption resins of poly(methyl methacrylate‐butyl methacrylate) by suspended emulsion polymerization

The synthesis of high oil‐absorption resins by suspended emulsion polymerization process for the first time with butyl methacrylate (BMA) and short‐chain methyl methacrylate (MMA) as the monomers was studied. And the effects of different polymerization technological parameters, such as the comonomer, initiator, crosslinker, emulsifier, dispersant agent, and the agitation rate, on the oil absorbency of high oil‐absorption resins were discussed in detail. The optimum polymerization conditions were obtained. With the increasing contents of these factors, the oil absorbency increased first, and then decreased. The highest oil absorbency to toluene was 17.6 g/g. The particle morphology of the high oil‐absorption resins was observed by scanning electron microscopy (SEM). The resins were determined by FTIR spectrometry. Compared with the high oil‐absorption resins prepared by suspension polymerization process and emulsion polymerization process, the high oil‐absorption resins prepared by suspended emulsion polymerization process had the higher oil absorbency, faster oil‐adsorbing rate, better oil‐retention, and regeneration property. Copyright © 2010 John Wiley & Sons, Ltd.     

Polylactide hollow spheres fabricated by interfacial polymerization in an oil-in-water emulsion system

A one-step pathway has been adopted to fabricate biodegradable polylactide (PLA) hollow spheres by interfacial polymerization in an oil-in-water emulsion system. The mechanism of sphere formation is suggested with respect to interfacial cross-linking polymerization and subsequent precipitation of the unreacted PLA macromonomers onto the preformed shells. Their hollow nature and morphology were verified by transmission electron microscopy and scanning electron microscope characterizations.     

Synthesis of nano-ZnO/poly(methyl methacrylate) composite microsphere through emulsion polymerization and its UV-shielding property

Nano-ZnO/poly(methyl methacrylate)(PMMA) composite latex microspheres were synthesized by in-site emulsion polymerization. The interfacial compatibility between nano-ZnO particles and PMMA were improved by treating the surface of nano-ZnO particles hydrophobically using methacryloxypropyltrimethoxysilane (MPTMS). TEM indicated that nano-ZnO particles present in nanosphere and have been encapsulated in the PMMA phase. FT-IR confirmed that MPTMS reacted with the nano-ZnO particle and copolymerized with MMA. It was clearly found from SEM that ZnO nanoparticles can be homogeneously dispersed in the PVC matrix. The absorbance spectrum of the nanocomposite polymer suggested that increasing the amount of nano-ZnO in composite particles could enhance the UV-shielding properties of the polymers. The nano-ZnO/PMMA composite particle could eliminate aggregation of ZnO nanoparticle and improve its compatibility with organic polymer. This means that the composite particles can be widely applied in lots of fields.     

Reversible addition–fragmentation chain transfer polymerization of methyl methacrylate in emulsion

Theoretical simulations showed that for controlled/living radical polymerization in an emulsion system, some of the earliest born particles could be superswollen to a size close to 1 μm. We hypothesized that the superswelling of these particles would lead to colloidal instability. Under the guidance of the simulation results, reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of methyl methacrylate (MMA) was carried out. Experimental results showed that increasing the initiation rate, surfactant level, and targeted molecular weight could improve the colloidal stability of the RAFT polymerization of MMA in an emulsion. The experimental results were in full accord with the theoretical predictions. The poor control of the molecular weight and polydispersity index was found to have a close relationship with the colloidal instability. For the first time, we demonstrated that RAFT polymerization could successfully be implemented with little coagulum, good control of the molecular weight, and a low polydispersity index with the same process used for traditional emulsion polymerization but with higher surfactant levels and initiation rates. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44:2837–2847, 2006     

Preparation and characterization of poly(methyl methacrylate)/titanium oxide composite particles

Before polymerization, the introduction of double bonds onto the surface of the TiO₂ particles was achieved by the treatment of the TiO₂ particles with the silane-coupling agent. Via in-situ emulsion polymerization, the poly(methyl methacrylate) (PMMA)/titanium oxide (TiO₂) composite particles were prepared by graft polymerization of MMA from the surface of the modified TiO₂ particles. The structure of the obtained PMMA/TiO₂ composite particles was characterized using fourier transform infrared spectra (FT-IR), thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC) and size excluding chromatography (SEC). The morphology of the obtained PMMA/TiO₂ composite particles was observed by transmission electron microscope (TEM). The results of FT-IR and TGA measurements show that PMMA is successfully grafted from the surface of the TiO₂ particles and that the percentage of grafting and the grafting efficiency can reach 208.3% and 96.6%, respectively. At the same time, the TGA and DSC measurements indicate an enhancement of thermal stability. TEM images demonstrate a better dispersion of the TiO₂ particles in the composite latex. In addition, UV-visible absorption measurements show that the PMMA/TiO₂ composite particles can absorb over 95% UV light at 210–400 nm wavelength.