Morphology of micron-sized monodispersed poly(butyl methacrylate)/polystyrene composite particles produced by seeded dispersion polymerization

In order to develop the seeded dispersion polymerization technique for the production of micron-sized monodispersed core/shell composite polymer particles the effect of polymerization temperature on the core/shell morphology was examined. Micron-sized monodispersed composite particles were produced by seeded dispersion polymerizations of styrene with about 1.4-μm-sized monodispersed poly(n-butyl methacrylate) (Pn-BMA) and poly(i-butyl methacrylate) (Pi-BMA) particles in a methanol/water (4/1, w/w) medium in the temperature range from 20 to 90 °C. The composite particles, PBMA/polystyrene (PS) (2/1, w/w), consisting of a PBMA core and a PS shell were produced with 2,2′-azobis(4-methoxy-2,4-dimethyl valeronitrile) initiator at 30 °C for Pn-BMA seed and with 2,2′-azobis(isobutyronitrile) initiator at 60 °C for Pi-BMA seed. The polymerization temperatures were a little above the glass-transition temperatures (T _g) of both Pn-BMA (20 °C) and Pi-BMA (40 °C). On the other hand, when the seeded dispersion polymerizations were carried out at much higher temperatures than the T _g of the seed polymers, composite particles having a polymeric oil-in-oil structure were produced. Received: 14 October 1998 Accepted in revised form: 2 June 1999     

Morphology control in polystyrene/poly(methyl methacrylate) composite latex particles

The effect of the presence of different amounts of block copolymers [polystyrene-block-poly(methyl methacrylate)] on the morphology of polystyrene/poly (methyl methacrylate) composite latex particles was investigated. The block copolymers were produced in situ by controlled radical polymerization (CRP) through the addition of the second monomer to a seed prepared by miniemulsion polymerization with a certain amount of a CRP agent. With an increase in the amounts of the block copolymers, the particle morphology changed from a hemisphere morphology (for a latex without block copolymers, i.e., without the use of a CRP agent during the polymerization) to clear core–shell morphologies as a result of decreasing polymer–polymer interfacial tension © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2484–2493, 2007     

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%.     

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.     

Preparation of micrometer-sized, monodisperse, hollow polystyrene/poly(ethylene glycol dimethacrylate) particles with a single hole in the shell

Micrometer-sized, monodisperse, hollow polystyrene (PS)/poly(ethylene glycol dimethacrylate) (PEGDM) composite particles with a single hole in the shell were prepared by seeded polymerization using (ethylene glycol dimethacrylate/xylene)-swollen PS particles in the presence of sodium dodecyl sulfate (SDS). Single holes were observed at SDS concentrations above 3 mM, much lower than in the PS/polydivinylbenzene (PDVB) system previously reported (above 45 mM). Phase separation inside droplets occurred at lower conversion in the PEGDM system than the PDVB system. Phase separation in the droplet at the early stage of the polymerization is an important factor for the formation of the single hole in the shell. Part CCCXIII of the series “Studies on Suspension and Emulsion.”     

Thermal degradation studies in poly(vinyl chloride)/poly(methyl methacrylate) blends

The miscibility, morphology, and thermal properties of poly(vinyl chloride) (PVC) blends with different concentrations of poly(methyl methacylate) (PMMA) have been studied. The interaction between the phases was studied by FTIR and by measuring the glass transition temperature (T_g) of the blends using differential scanning calorimetry. Distribution of the phases at different compositions was studied through scanning electron microscopy. The FTIR and SEM results show little interaction and gross phase separation. The thermogravimetric studies on these blends were carried out under inert atmosphere from ambient to 800 °C at different heating rates varying from 2.5 to 20 °C/min. The thermal decomposition temperatures of the first and second stage of degradation in PVC in the presence of PMMA were higher than the pure. The stabilization effect on PVC was found most significant with 10 wt% PMMA content in the PVC matrix. These results agree with the isothermal degradation studies using dehydrochlorination and UV-vis spectroscopic results carried out on these blends. Using multiple heating rate kinetics the activation energies of the degradation process in PVC and its blends have been reported.     

Synthesis of iron oxide/poly(methyl methacrylate) composite latex particles: Nucleation mechanism and morphology

A magnetic poly(methyl methacrylate) (PMMA) composite latex was prepared by soapless emulsion polymerization in the presence of ferrofluid, and the ferrofluid was prepared by means of a coprecipitation method. The effects of various polymerization parameters, such as the monomer concentration, ferrofluid content, and initiator concentration, on the conversion curve and particle size of the magnetic composite latex particles were examined in detail. The results showed that two nucleation mechanisms were involved according to the polymerization conditions. In the monomer‐rich and less ferrofluid system, self‐nucleation of PMMA was dominant over the entire course of emulsion polymerization. In the ferrofluid‐rich system, seeded emulsion polymerization was the main course to form the magnetic composite latex particles. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5695–5705, 2004     

Fracture surface morphology and phase relationships of polystyrene/poly(methyl methacrylate) systems. I. Low-molecular-weight polystyrene in poly(methyl methacrylate)

Samples of low-molecular-weight polystyrene (PS) in poly(methyl methacrylate) (PMMA) were prepared by first dissolving PS in methyl methacrylate monomer and then polymerizing the monomer. Forty-three specimens of varying number-average molecular weight (2100–49,000) and composition (5–40 wt %) of PS were prepared, and the surface morphology and phase relationships studied by scanning electron microscopy. Four distinct types of phase relationships were observed: (i) a single phase consisting of PS dissolved in PMMA; (ii) PS dispersed in PMMA; (iii) PMMA dispersed in PS; and (iv) regions of PS dispersed in PMMA coexisting with regions of PMMA dispersed in PS. Values of the size and population density of the dispersed particles are reported. Finally, the size and distribution of the dispersed particles and the various types of phase relationships are discussed in terms of the ternary polystyrene/poly(methyl methacrylate)/methyl methacrylate phase diagram.     

Effect of Nanoclay on the Phase Separation Behavior of Poly（methyl methacrylate）/Poly（vinyl acetate） Binary Polymer Blends

The effect of nanoclay on the phase-separation behavior of poly（methyl methacrylate）/poly（vinyl acetate）（PMMA/PVAc） blends has been mainly investigated by small-angle laser light scattering. It is found that the effect of clay on the thermodynamics and kinetics of phase-separation for PMMA/PVAc blends seems inconsistent. The kinetics phaseseparation rate decreases, while the thermodynamics parameters, cloud points Tc and delay time tD of isothermal phaseseparation also decrease, and the variation amplitude depends on the matrix composition. The affinity of clay to PMMA results in the composition difference between the border layer and the polymer matrix and further causes the concentration fluctuation at the early stage of phase separation to reduce Tc and tD. On the other hand, the decrease of phase-separation rate is caused by the mechanical barrier effect of clay on the macromolecular diffusion of blend matrix. Hence, such seemingly counterintuitive results on the thermodynamics and kinetics of phase-separation are attributed to different dominant factors.     

Preparation of micron-sized, monodispersed, “onion-like” multilayered poly(methyl methacrylate)/polysterene composite particles by reconstruction of morphology with the solvent-absorbing /releasing method

Micron-sized, monodispersed, “onion-like” multilayered poly(methyl methacrylate) (PMMA)/polystyrene (PS) (1/1, w/w) composite particles were prepared by the solvent-absorbing/releasing method (SARM). The viscosity within toluene-swollen composite particles, the release rate of toluene therefrom, the PMMA/PS ratio, and the kind of solvent had great influences on the reconstruction of the morphology of the PMMA/PS composite particles by the SARM. From these results, the conditions for the preparation of the multilayered composite particles by the SARM are clarified. Received: 28 September 2000 Accepted: 27 October 2000     

Colloidal stability of chitosan-modified poly(methyl methacrylate) latex particles

Experiments of coagulation kinetics were used to study the influence of the electrolyte concentration on the colloidal stability of cationic poly(methyl methacrylate) latex particles with various degrees of chitosan modification. For the chitosan-free latex products prepared by various levels of 2,2′ azobis(2-amidinopropane) dihydrochloride (V-50) at constant pH, the critical coagulation concentration (ccc) increases with increasing V-50 concentration, due to the enhanced particle surface charge density. On the other hand, the chitosan-modified latex products at constant pH do not exhibit very different values of ccc. This result is attributed to the counterbalance between two opposite effects related to the grafted chitosan, that is, the increased particle surface charge density and the enhanced shift of the particle's shear plane toward the aqueous phase with the chitosan content. The ccc of the latex products with various degrees of chitosan modification decreases significantly when the pH increases from 3 to 7. This is because the degree of ionization of the surface amino groups (the particle surface charge density) decreases with increasing pH. As a result, the stability of the colloidal system decreases significantly with increasing pH. The apparent Hamaker constant and diffuse potential were obtained from the coagulation kinetics data. These two parameters along with the zeta potential and particle size data for the latex samples taken immediately after the end of the coagulation experiments were also used to study the effect of ionic strength on the colloidal stability of the latex particles. Received: 10 October 1998 Accepted in revised form: 16 December 1998     

Molecular dynamics and phase behavior of polystyrene/poly(vinyl methyl ether) blend in the presence of nanosilica

The variation of phase morphology, critical temperature of demixing, and molecular dynamics for polystyrene/poly(vinyl methyl ether)(PS/PVME) blends induced by hydrophilic nanosilica(A200) or hydrophobic nanosilica(R974) was investigated. With the phase separation of blend matrix, A200 migrated into PVME-rich phase due to strong interaction between A200 and PVME, while R974 moved into PS-rich phase. The thermodynamic miscibility and concentration fluctuation during phase separation of blend matrix were remarkably retarded by A200 nanoparticles due to the surface adsorption of PVME on A200, verified by the correlation length ξ near the critical region from rheological measurement and the weakened increment of reversing heat capacity(ΔC_p) during glass transition via modulated differential scanning calorimetry(MDSC). The restricted chain diffusion induced by nanosilica still occurred despite no influence of A200 and R974 on the segmental dynamics of homogenous blend matrix. The interactions between nanosilica and polymer components could restrict the terminal relaxation of blend matrix and further manipulate their phase behavior.     

Morphology and mechanical properties of poly(ether-imide)-modified polycyanurates

A high temperature thermosetting bisphenol A dicyanate (BADCy) was modified with a novel thermoplastic poly(ether-imide) (PEI) at various compositions. Fourier transform infrared spectroscopy was used to measure the conversion of BADCy. Curing kinetics of the BADCy/PEI blend were studied by the dynamic differential scanning calorimeter method. Morphologies of PEI-modified polycyanurates were investigated by scanning electron microscopy (SEM). It was found that the phase structures of the blends changed dramatically with the PEI content and molecular weight. The tensile results showed that the mechanical properties could be correlated with the morphologies. The blend with cocontinuous morphology had the highest tensile strength and elongation at break while the blend with ribbon-like morphology had the lowest one despite PEI molecular weight.     

Effect of molecular weight on the morphology of polystyrene/poly(methyl methacrylate) composite particles prepared by the solvent evaporation method

The effect of molecular weight on the morphology of polystyrene (PS)/poly(methyl methacrylate) (PMMA) composite particles was investigated. PS/PMMA composite particles with different molecular weights (M*=MwPS+MwPMMA)/2 approximately 2x10(4)-1x10(6) g.mol(-1)) were prepared by the release of toluene (T) from PS/PMMA/T (1/1/24, w/w/w) droplets dispersed in an aqueous solution of polyoxyethylene nonylphenyl ether nonionic surfactant (Emulgen 911). As T evaporated, the spherical droplets phase separated, resulting in snowmanlike composite particles with Janus morphology. The nonspherical shape was closely related to the morphology, which depended on M*. The interfacial tension between the phase-separated PS and PMMA phases increased with an increase in M*, and this would allow the formation of the snowmanlike shape to decrease the interfacial area between the PS and the PMMA phases.     

Effect of dicarboxy terminated polystyrene on strengthening immiscible polystyrene/poly(methyl methacrylate) interface

The fracture toughness between polystyrene (PS)/poly(methyl methacrylate) (PMMA) reinforced with reactive polymers, poly(glycidyl methacrylate) (PGMA) and dicarboxy or monocarboxy terminated PS (dcPS and mcPS), was measured by the asymmetric fracture test. Molecular weight effect of mcPS, although the molecular weight distribution is rather polydisperse, on the maximum achievable fracture toughness, G_max qualitatively agreed with the results of the monodisperse case^4,5). In the case of dcPS with M_w ≅ 142 K, G_max reached ca. 170 J/m² which is nearly 8 times higher than that of mcPS of molecular weight of about 150K. From the mechanical point of view, dcPS with a degree of polymerization (N) greater than the ratio of chain breaking force to monomeric friction force (f_b/f_mono) is more effective in enhancing the interfacial adhesion than mcPS since it provides two stitches to the interface. It was also shown by Monte Carlo simulation on reactive polymer system that the di‐endfunctional polymers are more effective than mono‐endfunctional polymers in reinforcing the week interface between immiscible polymers.     

Preparation of micron-sized, monodisperse poly(methyl methacrylate)/polystyrene composite particles having a large number of dents on their surfaces by seeded dispersion polymerization in the presence of decalin

Seeded dispersion polymerization of styrene with 1.77-µm-sized, monodisperse poly(methyl methacrylate) seed particles was carried out in a methanol/water medium (8/2, w/w) in the presence of decalin droplets. The monodisperse poly(methyl methacrylate)/polystyrene composite particles produced had a large number of dents on their surfaces. The effects of the amount of decalin in the polymerization system on the number, the diameter, and the depth of the dents on the surface of the composite particles were clarified.     

Interactions between dextran-modified poly(methyl methacrylate) latex particles and concanavalin A

The electrostatic and affinity interactions between concanavalin A (Con A) and dextran-modified latex particles were investigated. The ratio of the initial number of dextran active sites to that of Con A molecules plays an important role in determining the structure of flocs formed during adsorption and, thereby, has an influence on the amount of adsorbed Con A and the subsequent elution yield. NaCl and d-glucose, used successively in the two-step desorption of Con A, were employed to study the relative importance of electrostatic and affinity interactions involved in the Con A adsorption process. A significant fraction of adsorbed Con A is attributed to the electrostatic interaction mechanism. The feasibility of using the dextran-modified latex products to purify Con A from Jack bean meal was demonstrated. Received: 22 February 2000 Accepted: 19 September 2000     

Real time laser interference microscopy for bar‐spread polystyrene/poly(methyl methacrylate) blends

We demonstrate that real‐time laser interference microscopy can be used to directly observe the dynamics of film formation and phase separation processes for a bar‐spread polystyrene/poly(methyl methacrylate) blend. The ability to dynamically image laser interference patterns allows compete drying curves and polymer content to be determined throughout the film formation process. The polymer content at which phase separation structure first is observed in the interference micrograph sequence is in good agreement with calculated spinodal curves. Morphology evolution proceeds from phase separation onward via coarsening and coalescence to arrive at the final domain structure. In comparison, spin coating the same polymer blend results in structure evolution being quenched further from equilibrium due to the faster drying rate. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 985–992