Preparation of monodisperse fluorescent core–shell polymer microspheres with functional groups in the shell layer by two‐stage distillation–precipitation polymerization

Monodisperse crosslinked core–shell micrometer‐sized microspheres bearing a brightly blue fluorescent dye, carbazole, and containing various functional groups in the shell layers were prepared by a two‐stage distillation–precipitation polymerization in acetonitrile in the absence of any stabilizer. Commercial divinylbenzene (DVB), containing 80 vol.% of DVB, was polymerized by distillation–precipitation in acetonitrile without any stabilizer using 2,2′‐azobisisobutyronitrile (AIBN) as the initiator for the first stage of polymerization which resulted in monodisperse polyDVB microspheres used as the core. Several functional monomers, including 2‐hydroxyethyl methacrylate and acrylonitrile together with N‐vinylcarbazole blue fluorescent comonomer, were incorporated into the shell layers with AIBN as initiator during the second stage of polymerization. The resultant core–shell polymer microspheres were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, UV‐visible spectroscopy and fluorescence spectroscopy. Copyright © 2006 Society of Chemical Industry     

Suspension copolymerization of styrene and divinylbenzene: Formation of beads

Suspension copolymerization of styrene and divinylbenzene (DVB) was carried out using benzoyl peroxide as initiator and magnesium hydroxide as suspending agent in water at 80°C under nitrogen atmosphere to produce styrene–DVB copolymer beads. These beads were characterized by infrared spectroscopy, thermal gravimetric analysis, and scanning electron microscopy. Porosity generated in styrene–DVB copolymer beads by incorporation of solvents in the polymerization system was confirmed by SEM micrograph, apparent density, swelling measurements, and Brunauer, Emmett, Teller surface area. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3559–3563, 2006     

Narrow‐disperse or monodisperse crosslinked and functional core–shell polymer particles prepared by two‐stage precipitation polymerization

Narrow‐disperse and monodisperse cross‐linked core–shell polymer particles containing different functional groups, such as esters, hydroxyls, chloromethyls, carboxylic acids, amides, cyanos, and glycidyls, in the shell layers in the micrometer size range were prepared by a two‐stage precipitation polymerization in the absence of any stabilizer. Commercial divinylbenzene (DVB), containing 80% DVB, was precipitation polymerized in acetonitrile without any stabilizer as the first‐stage polymerization and was used as the core. Several functional monomers, including methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2‐hydroxyethyl methacrylate, glycidyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, t‐butyl acrylate, i‐octyl acrylate, acrylic acid, acrylamide, acrylonitrile, styrene, and p‐chloromethyl styrene, were incorporated into the shells during the second‐stage polymerization. The resulting core–shell polymer particles were characterized with scanning electron microscopy and Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1776–1784, 2006     

Preparation and properties of poly(WPSF‐co‐butyl acrylate) copolymer emulsion with ultrasonic radiation II. Monomer conversion rate and characterization

A stable emulsion of poly(WPSF‐co‐butyl acrylate) based on butyl acrylate, waste polystyrene foam was synthesized through emulsion polymerization using sodium dodecyl sulfate and octyl phenyl polyoxyethylene ether as surfactant, ammonium persulfate and sodium hydrogen bisulfate as mixed redox initiator, under ultrasound irradiation in the absence of inert gas. The effects of various copolymerization conditions on the monomer conversion were reported. The copolymers were characterized by means of IR, ¹HNMR, and gel permeation chromatography. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Pilot‐scale development of core–shell polymer supports for the immobilization of recombinant lipase B from Candida antarctica and their application in the production of ethyl esters from residual fatty acids

A recombinant lipase B from Candida antarctica (LipB) in Pichia pastoris was synthesized through submerged fermentation using crude glycerin as substrate. The immobilization of this enzyme on the core–shell polymeric supports is an effective alternative for its application. The supports with distinct levels of hydrophobicity were produced through combined suspension and emulsion polymerization in pilot scale. Particles with distinct compositions were synthesized (PMMA/PMMA; PMMA‐co‐DVB/PMMA‐co‐DVB; and PS‐co‐DVB/PS‐co‐DVB) and employed on the immobilization of the produced lipase (LipB) and the commercial enzyme (CalB). The morphological properties (specific area, average pore diameter, specific volume of pores, and hydrophobicity level) and the influence of the polymerization conditions on the morphology of the supports were studied. The thermal stability of such biocatalysts was also investigated in the presence of calcium cation (Ca⁺²), maintained 100% of the activity after 3 h at 50°C when the PMMA‐co‐DVB/PMMA‐co‐DVB was employed. The synthesized enzyme and supports manufactured in pilot scale were employed successfully for production of esters using residual fatty acids as substrates, adding value to these raw materials and increasing the ranges of possible applications.     

Fabrication by photoinitiated polymerization and characterization of millimeter‐size poly(divinyl benzene) hollow foam shells

In this study, millimeter‐size compound droplets were prepared easily by a one‐step microfluidic method. We varied the diameter and wall thickness of the shells over a wide range by setting the flow rate. Poly(divinyl benzene) (PDVB) shells with a 3–4.8 mm diameter were fabricated through photopolymerization and supercritical drying. The gel point of photopolymerization was monitored by a rotational rheometer. Moreover, the influence of the oil‐soluble photoinitiator phenyl bis(2,4,6‐trimethyl benzoyl) phosphine oxide (BAPO) on the properties of the foam shell were investigated by transmission electron microscopy, scanning electron microscopy, and nitrogen sorption measurements. Significant differences in the mechanical properties and porous features were obtained for different BAPO concentrations. The surface areas of the foam shells decreased, and the densities of the foam shells increased with increasing BAPO concentration. In addition, the nonconcentricity and out‐of‐roundness values were mainly less than 7 and 3%, respectively, for most of the shells. The results indicate that the PDVB hollow foam shells are a promising inertial fusion energy target. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41625.     

Synthesis and properties of natural rubber modified with stearyl methacrylate and divinylbenzene by graft polymerization

The graft polymerizations of stearyl methacrylate (SMA) and divinylbenzene (DVB) onto natural rubber (NR) were carried out in a solution process using benzoyl peroxide (BPO) as an initiator in toluene or chloroform. The main products of the grafted NR include an uncrosslinked (sol) part [sol(SMA–NR–DVB): s‐SNRD] and a crosslinked (gel) part [gel(SMA–NR–DVB), g‐SNRD]. s‐SNRD was obtained by extraction using tetrahydrofuran. It was identified by IR and ¹H‐NMR spectroscopies. The glass transition temperature (T_g) and thermal properties of s‐SNRD and g‐SNRD were studied by DSC and TGA. The glass transition temperature and thermal decomposition temperature of s‐SNRD and g‐SNRD were higher than were those of NR. The light resistance and weatherability of s‐SNRD were measured with a Weather‐o‐Meter. The light resistance and weatherability of s‐SNRD are better than are those of NR. The effects of the initiator concentration, mol ratio of SMA to DVB, reaction time, temperature on grafting ratio, and crosslinking ratio were investigated. The highest grafting ratio and crosslinking ratio in the graft polymerization of SMA and DVB onto NR were obtained when the mol ratio of SMA to DVB and BPO were 4.0 and 2 wt %, at 80°C for 48 h, respectively. Following several studies on oil‐absorptive polymers in our laboratory, 9 the oil absorptivity of g‐SNRD was examined using crude oil. The oil absorptivity of g‐SNRD was 600% when the immersion time was 10 min. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2464–2470, 2001     

Synthesis and properties of high oil‐absorbent 4‐tert‐butylstyrene‐EPDM‐divinylbenzene graft terpolymer

The graft crosslinking polymerization of 4‐tert‐butylstyrene (tBS) and divinylbenzene (DVB) onto ethylene–propylene–diene (EPDM) was carried out in toluene by using benzoyl peroxide (BPO) as an initiator. The synthesized graft terpolymer, tBS‐EPDM‐DVB (PBED), was extracted with tetrahydrofuran (THF) into gel (called as PBED I) and sol, and then they were identified by infrared (IR) spectroscopy. The effects of solvent amount, molar ratio of DVB to tBS, EPDM content, initiator concentration, reaction temperature, and reaction time on the graft crosslinking polymerization were examined. Among them, solvent amount and molar ratio of DVB to tBS were the important factors for this reaction system. Maximum oil absorbency of PBED I was 84.0 g/g but its oil‐absorption kinetic rate was very low. Sol PBED can be reused as oil absorbent (named as PBED II) through photocrosslinking by ultraviolet light irradiation. Although the oil absorbencies of PBED II were lower than those of PBED I in most cases, their oil absorption kinetic rates were higher than oil absorbencies of PBED I. The highest value of oil absorbency of PBED II was 56.0 g/g. The thermal stability of PBED I was studied by TGA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2119–2129, 2002     

Extrusion of microcellular open‐cell LDPE‐based sheet foams

In this research, highly open‐cell low‐density polyethylene sheet foams are achieved with an annular die by applying various strategies for cell opening, i.e., (i) creation of a structural nonhomogeneity consisting of hard and soft regions with partial crosslinking, (ii) blending of a hard second‐phase material (i.e., polystyrene phase) into the low‐density polyethylene matrix, (iii) plasticization of the soft region with a secondary blowing agent, (iv) decrease of the cell wall thickness by increasing the cell density, and (v) decrease of the cell wall thickness by increasing the expansion ratio while cell walls are soft. Although the higher surface‐to‐volume ratio of the sheet foams compared with filament foams made it challenging to prevent gas loss, highly open‐cell (up to 99%) and microcellular (up to 3.5 × 10¹⁰ cells/cm³) foam sheets were successfully manufactured with high‐pressure annular dies using the cell‐opening strategies. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3376–3384, 2006     

Preparation and characterization of microcellular thin polycarbonate sheets

A new method was developed for the microcellular processing of polycarbonate (PC) thin sheets by compression molding above PC's glass‐transition temperature and below its melting temperature within a few minutes. The effects of the foaming time, foaming pressure, foaming temperature, and foaming agent active ratio on the cell size, cell density, and relative density were studied. The structures of the microcellular PC foam were controlled in the foaming process by carefully choosing the foaming parameters. In addition, the thermal, dynamic mechanical thermal, and electrical properties of the microcellular PC foam were investigated. A differential scanning calorimetry analysis showed that the microcellularly processed PC may have a plastication effect. The variation of the storage modulus, loss modulus, and tan δ under dynamic mechanical thermal analysis was in accord with the calorimetry analysis. The measurement of the electrical property demonstrated that the insulation ability of the microcellular PC thin sheet was obviously enhanced and the dielectric strength of the microcellular PC foam was decreased compared to the unfoamed PC. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1760–1766, 2006     

Effect of selected boroorganic compounds on thermal and heat properties of rigid polyurethane–polyisocyanurate foams

The effects of three selected borates {tri(hydroxypropyl), tri[(3‐chloro‐2‐hydroxy‐1‐propoxy)‐1‐methylethyl], tri[(3‐chloro‐2‐hydroxy‐1‐propoxy)propyl]} on the heat and thermal properties of rigid polyurethane–polyisocyanurate foams was studied. Increasing the amount of tri(hydroxypropyl) borate and tri[(3‐chloro‐2‐hydroxy‐1‐propoxy)propyl] borate in the foam composition from 0.1 to 0.4 chemical equivalents caused an increase in the softening point, the temperature of the first decrement of foam mass, the extrapolated temperature of the main decrement of the foam mass, and the temperature of the highest rate of the mass decrement. When tri[(3‐chloro‐2‐hydroxy‐1‐propoxy)‐1‐methylethyl] borate was added to the foam compositions, the softening point decreased but the temperatures characterizing their thermal resistance were higher in comparison with the standard foam. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 768–771, 2006     

Mechanical properties of a particle‐strengthened polyurethane foam

Quasi‐static compression tests have been performed on polyurethane foam specimens. The modulus of the foam exhibited a power‐law dependence with respect to density of the form: E* ∝ (ρ*)ⁿ, where n = 1.7. The modulus data are described well by a simple geometric model (based on the work of Gibson and Ashby) for a closed‐cell foam in which the stiffness of the foam is governed by the flexure of the cell struts and cell walls. The compressive strength of the foam is also found to follow a power‐law behavior with respect to foam density. In this instance, Euler buckling is used to explain the density dependence. The modulus of the foam was modified by addition of gas‐atomized, spherical, aluminum powder. Additions of 30 and 50 wt % Al measurably increased the foam modulus, but without a change in the density dependence. However, there was no observable increase in modulus with 5 and 10 wt % additions of the metal powder. Strength was also increased at high loading fractions of powder. The increase in modulus and strength could be predicted by combining the Gibson–Ashby model, referred to above, with a well‐known model describing the effect on modulus of a rigid dispersoid in a compliant matrix. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2724–2736, 1999     

Preparation and application of partially porous poly(styrene‐divinylbenzene) particles for lipase immobilization

Partially porous poly(styrene‐divinylbenzene) (PS‐DVB) particles in the micron size range were prepared by the method of multistep swelling and polymerization involving the use of polymeric porogens. Polystyrene (PS) seeds prepared by dispersion polymerization were expanded in particle size by absorbing styrene and initiator, and then polymerized to form polymeric porogen particles. The newly synthesized PS chains served as the porogens of the PS‐DVB particles, resulting from the copolymerization of styrene and divinylbenzene in the swollen polymeric porogen particles. PS‐DVB particles with a specific surface area of up to 34 m²/g and a pore volume of up to 0.15 cm³/g were obtained. The average pore diameter of PS‐DVB particles was in the range of 15–24 nm. An increasing amount of toluene used in the copolymerization step increased the pore volume and specific surface area. Lipase from Candida rugosa was immobilized on the prepared PS‐DVB by physical adsorption. The optimum temperature for enzymatic activity was increased and the thermal deactivation of enzyme in organic solvent was slowed down by the immobilization. However, compared with soluble enzyme, the immobilized lipase on PS‐DVB retained a less activity after the first stage deactivation, suggesting a possible change in the conformation of enzyme molecule by immobilization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 39–46, 2001     

Morphology development in polychloroprene–polystyrene latex interpenetrating polymer networks

Latex interpenetrating polymer networks (LIPNs) have been prepared using a crosslinked polychloroprene latex as the seed emulsion, followed by the in situ polymerization of styrene, typically with a 10% divinyl benzene crosslinker. Polychloroprene–crosslinked polystyrene (XPS) ratios ranging from 70/30 to 40/60 were used, with the second monomer being added as a single aliquot rather than by “starvation” routes. The majority of the work has been conducted using the water‐soluble persulfate initiator method, which entails lengthy (∼ 6 h) polymerizations. To follow the development of microstructure, polymerizations were also stopped at 0.5, 1, and thence hourly intervals up to 6 h, so that any effect of time on shell and domains could be seen by transmission electron microscopy (TEM). Parallel studies using azo‐bis(isobutyronitrile) (AIBN) as initiator at the same temperature were conducted. Products were also studied, after staining, by TEM. For the persulfate initiator, domain structures predominated for the 70/30 ratio, but polystyrene‐rich shells are found in all cases, with increasing thickness as the chloroprene/styrene ratio was reduced. The styrene‐rich products (i.e., 40/60 Neoprene/XPS ratio) appear to have larger unstained domains suggesting phase separation. For the AIBN‐initiated styrene polymerization, shells are less evident, and where they exist, are both thinner and less continuously developed. Domain sizes are somewhat larger. This relatively hydrophobic initiator has caused polymerization predominately in the interior of each latex particle. The particle size distribution of the seed neoprene latex is broad and bimodal. As the LIPNs form, the larger diameter component increases and little evidence for fresh nucleation, in the form of small diameter particles, is seen. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 629–638, 1999     

Properties of calcium carbonate filled and unfilled polystyrene foams prepared using supercritical carbon dioxide

Foaming behaviors of four polystyrenes (PSs) filled and unfilled with various amounts of CaCO₃ using supercritical carbon dioxide were investigated. The PSs include three general purpose grades with different molecular weights (different melt index) and one high impact grade. By adjusting foaming conditions, foam density was determined for each investigated sample. In general, the sample with a lower molecular weight (i.e. higher melt index) yielded a lower foam density for the three general purpose PSs. With the addition of CaCO₃ filler, foam density would increase. The inclusion of rubber in high impact PS was found to complicate its foaming behavior. A qualitative correlation between various types of filled/unfilled PSs and foam density was found in a certain range. An optimum foaming temperature range was required to obtain low foam density for each sample. The corresponding change in matrix modulus by employing various PSs and various filler contents apparently affected the resulting foam density. Although several factors were involved in foaming conditions, the addition of CaCO₃ filler played a significant role in reducing cell size and increasing cell density of the PSs foams investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2276–2284, 2006     

A flame‐retardant composite foam: foaming polyurethane in melamine formaldehyde foam skeleton

A composite foam, polyurethane–melamine formaldehyde (PU/MF) foam, was prepared through foaming PU resins in the three‐dimensional netlike skeleton of MF foam. The chemical structure, morphology, cell size and distribution, flame retardancy, thermal properties and mechanical properties of such composite foam were systematically investigated. It was found that the PU/MF foam possessed better fire retardancy than pristine PU foam and achieved self‐extinguishment. Moreover, no melt dripping occurred due to the contribution of the carbonized MF skeleton network. In order to further improve the flame retardancy of the composite foam, a small amount of a phosphorus flame retardant (ammonium polyphosphate) and a char‐forming agent (pentaerythritol) were incorporated into the foam, together with the nitrogen‐rich MF, thus constituting an intumescent flame‐retardant (IFR) system. Owing to the IFR system, the flame‐retardant PU/MF foam can generate a large bulk of expanded char acting as an efficient shielding layer to hold back the diffusion of heat and oxygen. As a result, the flame‐retardant PU/MF foam achieved a higher limiting oxygen index of 31.2% and exhibited immediate self‐extinguishment. It exhibited significantly reduced peak heat release rate and total heat release, as well as higher char residual ratio compared to PU foam. Furthermore, the composite foam also showed obviously improved mechanical performance in comparison with PU foam. Overall, the present investigation provided a new approach for fabricating a polymer composite foam with satisfactory flame retardancy and good comprehensive properties. © 2018 Society of Chemical Industry     

Synthesis and application of poly(butadiene-g-acrylonitrile–styrene) core–shell rubber particles for use in epoxy resin toughening. I. Synthesis of poly(butadiene-g-acrylonitrile–styrene)

Graft copolymers of acrylonitrile (AN)–styrene (ST) onto polybutadiene were prepared via emulsion polymerization method using a redox initiator system, cumene hydroperoxide–tetrasodium pyrophosphate–ferrous sulfate–dextrose. The effects of initiator, reaction temperature, reaction time, polymer/grafting monomer ratio, and monomer dropping frequency on the graft copolymerization reaction were investigated. Transmission electron micrographs confirmed that the synthesized particles had a core–shell shaped structure. The powdery core–shell shaped poly(butadiene-g-AN–ST) particles with various AN contents in their shells and with different shell thicknesses were prepared, which can be incorporated into brittle epoxy resin as impact modifier. © 1996 John Wiley & Sons, Inc.     

Reactive blending approach to modify spin‐coated epoxy film: Part II. Crosslinking kinetics

Kinetics of the reactive blending of epoxy with a four‐armed ?‐caprolactone‐based carboxylic acid end‐functionalized oligomer was analyzed with a model‐free approach. The employment of a dual catalyst system ensured high density of crosslinking in the blends and minimized phase separation even when comparatively high concentration of the oligomer was incorporated. The two reactions were examined separately before analysis of the dual‐catalyzed system. The apparent activation energy of the single‐catalyzed reactions could be seen to fall into three regimes. It is proposed that regime I is due to reaction control, the middle part (II) to mass transport, and the high conversion tail (III) to structural control. The results of a thermal analysis carried out on the crosslinked samples corresponded well with the findings of the kinetic analysis. The combined kinetic and thermal results can be used in optimization of the crosslinking process. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3689–3696, 2006     

Influence of a density mismatch on TMPTMA shells nonconcentricity

Some laser target designs require low‐density organic foam shells to study fusion on the French high‐power laser laser mega joule. Low‐density trimethylolpropane trimethacrylate foam shells composed of C, H, and O, 2 mm diameter, 100‐μm wall thickness, and 250 mg cm^?3 density are synthesized by a microencapsulation technique using a droplet generator. These shells have to reach a sphericity higher than 99.9% and a nonconcentricity (NC) lower than 1%. The wall thickness variation is one of the most difficult specifications to meet. An important factor in reducing this defect is the density matching between the three phases of the emulsion at polymerization temperature. The influence of a density mismatch between the internal water phase and the organic phase on the NC of TMPTMA foam shells was studied. The best NC results and yields of shells are obtained with a density gap between the internal water phase and the organic phase of 0.078 g cm^?3 at 60°C, with an average NC around 2%. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Gas holdup of rotating foam reactors measured by γ‐tomography—effect of solid foam pore size and liquid viscosity

Rotating foam reactors have already shown to give high mass transfer rates compared to stirred tank reactors. For a deeper insight into the hydrodynamics of these reactors, the hydrodynamics of rotating foam reactors were studied using γ‐ray tomography. The two‐phase flow through the foam block stirrer is mainly influenced by the solid foam pore size and the liquid viscosity. For low viscosity, the optimal foam block pore size was identified in the range between 10 and 20 pores per inch (ppi). With smaller pore size, the gas holdup inside the foam block strongly increases due to bubble entrapment. For higher viscosity, pore sizes larger than 10 ppi have to be used to achieve a sufficient liquid flow rate through the foam block to avoid a strong gradient over the reactor height. The effect of the hydrodynamics on the gas–liquid and liquid–solid mass transfer and the reactor performance are discussed. © 2012 American Institute of Chemical Engineers AIChE J, 59: 146–154, 2013