Continuous microfluidic reactors for polymer particles

This article provides an overview of our work in the area of the synthesis of polymer particles in continuous microfluidic reactors. The method includes (a) the generation of highly monodisperse monomer droplets in a microfluidic flow-focusing device and (b) in-situ solidification of these droplets by means of photopolymerization. We discuss the effect of monomer properties on the emulsification process, the effect of the polymerization rate on the production of high-quality particles, the role of the material of the microfluidic device in droplet formation, and the synthesis of particles with different shapes and compositions. We also demonstrate the production of highly ordered arrays of polymer particles achieved by photopolymerization of the dynamic lattices of monomer droplets in microfluidic channels. The article is concluded with a summary of future research directions in the production of polymer colloids in microfluidic reactors.     

Preparation of micron-size monodisperse polymer particles having highly crosslinked structures and vinyl groups by seeded polymerization of divinylbenzene using the dynamic swelling method

Micron-size monodisperse polystyrene/polydivinylbenzene (PS/PDVB) composite particles having highly crosslinked structures and vinyl groups were prepared as follows. First, 1.9 m-size monodisperse PS seed particles produced by dispersion polymerization were dispersed in ethanol/water (70/30, w/w) solution which dissolved divinylbenzene (DVB) monomer, benzoyl peroxide as an initiator and poly(vinyl alcohol) as a stabilizer. The PS seed particles were swollen with a large amount of DVB monomers to 4.3 m in diameter while keeping good monodispersity by the dynamic swelling method, where water was slowly added, continuously, with a micro feeder into the dispersion. And then, the seeded polymerization of the absorbed DVB was carried out.Part CXXXV of the series Studies on Suspension and Emulsion     

Aggregation phenomena in the suspension polymerization of VCM

In the suspension polymerization of VCM, insoluble polymer particles are formed inside the monomer droplets. The growth and aggregation of these particles are responsible for important polymer properties, such as porosity. It is well established that the most characteristic polymer particles, the primary particles, are of a narrow distribution with a size (diameter) ranging from 0.10–0.20 m. This work studied the formation of primary particles based on the aggregation phenomena that take place inside a monomer droplet. This was done by formulating a population balance equation, which was based on the following considerations: a) polymerization occurs in both the monomer and the polymer phases; b) there is continuous formation of the basic particles in the monomer phase; c) the growth of the polymer particles occurs as a result of both polymerization in the polymer phase and aggregation of the particles; d) the colloidal properties of the particles that are responsible for the aggregation phenomena were considered to be the net result of attraction and repulsion energies.It was shown that for particles carrying a constant charge it was not possible to predict the formation of primary particles of size 0.10–0.20 m. The particle size distribution had a mode diameter equal to the diameter of the basic particles. Consequently, the particle charge was allowed to vary in a way proportional to the particle radius raised to a power coefficient. For values of the coefficient greater than zero, i. e., when the particle charge increased during polymerization, the aggregation of the basic particles was efficient enough to result in the formation of large primary particles.     

Polymer particles with various shapes and morphologies produced in continuous microfluidic reactors

We report a novel approach to continuous and scalable production of core-shell droplets and polymer capsules in microfluidic devices. The described method is also useful in the synthesis of polymer particles with nonspherical shapes. We used capillary instability-driven break-up of a liquid jet formed by two immiscible fluids. Precise control of emulsification of each liquid allowed for the production of highly monodisperse core-shell droplets with a predetermined diameter of cores and thickness of shells. We also achieved control over the number of cores per droplet and the location of cores in the droplet. We carried out fast throughput photopolymerization of the monomeric shells and obtained polymer particles with various shapes and morphologies, including spheres, truncated spheres and, hemispheres, and single and multicore capsules.     

Preparation of monodisperse PMMA microspheres in nonpolar solvents by dispersion polymerization with a macromonomeric stabilizer

We discuss a dispersion polymerization procedure for preparing monodisperse and micron-sized poly(methyl methacrylate) (PMMA) particles in hexanes with methacryloxypropyl-terminated polydimethylsiloxane stabilizers. We investigate the effects of the stabilizer molecular weight, stabilizer concentration, and monomer concentration on the particle size and polydispersity. We find that a minimum molecular weight of 10 000 g/mol is necessary to synthesize colloidally stable PMMA dispersions. The particle polydispersity is minimal (=5%) for stabilizer to monomer weight ratios of 0.02 to 0.1, while PMMA particles prepared under conditions outside this range are polydisperse. The particle diameter can be varied from 0.4 to 1.5 µm by appropriate choices of stabilizer and monomer concentrations. Stable PMMA suspensions can be prepared at up to 26.3% solids. The dispersions are stable in most liquid aliphatics, and are monodisperse enough to form ordered domains at high concentration. This single-stage synthesis, requiring only commercially available materials, may be of interest to those seeking a simple way to prepare highly monodisperse non-aqueous dispersions in the micron size range.     

Preparation of colloidal crystals with polyhedral building blocks through post-polymerization

An alternative approach was adopted to prepare colloidal crystal with polyhedral building blocks. First, monodisperse polystyrene particles that contained about 30% wt of monomer were obtained by emulsifier-free emulsion polymerization at 38 °C. These monomer-containing particles were used to prepare colloidal crystal on the surface of dispersion, before the spherical particles in the colloidal crystals underwent deformation between two quartz plates at 75 °C for 40 min by interfacial tensions, and finally the deformed particles were frozen through post-polymerization.     

Microfluidics: from dynamic lattices to periodic arrays of polymer disks

We used coupling of flow and geometric confinement to assemble emulsion droplets in two-dimensional gliding lattices with a high degree of order and symmetry. Highly monodisperse discoid droplets with circular shapes were generated in a microfluidic flow-focusing device. Originally, close-packed lattices formed from these circular discoid droplets. Progressive confinement led to the gradual deformation of the circular disks: first, they elongated in the direction parallel to the direction of flow and then transformed into hexagons. Assembly driven by the combination of flow and confinement also allowed for the formation of lattices from droplets with a bimodal size distribution. We used photopolymerization of the monomer droplets to trap the lattice structure in the solid state and produce highly periodic arrays of solid polymer disks.     

Functional Polymer‐Opals from Core–Shell Colloids

Colloidal photonic crystals were prepared from monodisperse core–shell particles. The shell is hereby formed from a functional monomer, such as glycidylmethacrylate or different reactive ester monomers, which can perform chemical reactions and the core from a standard monomer, which yields highly monodisperse colloids. It was possible to crystallize the core–shell particles into artificial opals with excellent optical properties. Reactions on the functional surface of the colloids were carried out, which lead to a dramatic rise in the mechanical stability or to a functionalization of His‐tagged silicatein, which acts as nanoreactor to synthesize and immobilize gold nanoparticles from auric acid onto the core–shell colloids.

     

Microfluidic large-scale integration on a chip for mass production of monodisperse droplets and particles

In this study, we report the mass production of monodisperse emulsion droplets and particles using microfluidic large-scale integration on a chip. The production module comprises a glass microfluidic chip with planar microfabricated 16-256 droplet-formation units (DFUs) and a palm-sized stainless steel holder having several layers for supplying liquids into the inlets of the mounted chip. By using a module having 128 cross-junctions (i.e., 256 DFUs) arranged circularly on a 4 cm x 4 cm chip, we could produce droplets of photopolymerizable acrylate monomer at a throughput of 320.0 mL h(-1). The product was monodisperse, having a mean diameter of 96.4 microm, with a coefficient of variation (CV) of 1.3%. Subsequent UV polymerization off the module yielded monodisperse acrylic microspheres at a throughput of approximately 0.3 kg h(-1). Another module having 128 co-flow geometries could produce biphasic Janus droplets of black and white segments at 128.0 mL h(-1). The product had a mean diameter of 142.3 microm, with a CV of 3.3%. This co-flow module could also be applied in the mass production of homogeneous monomer droplets.     

Preparation of micron-size monodisperse polymer microspheres having chloromethyl group

Micron-size monodisperse polymer microspheres having chloromethyl groups thereon were prepared by two-step polymerization process as follows. First, micron-size monodisperse polystyrene particles were prepared by dispersion polymerization with 2,2-azobisisobutyronitrile as initiator in ethanol-water medium in the presence of poly(acrylic acid) as stabilizer under various conditions. Secondly, in the presence of the 1.9-m monodisperse polystyrene particles produced under the optimum conditions, seeded copolymerization for styrene and chloromethyl styrene was carried out. The seeded copolymerization proceeded smoothly without producing new particles, and it was confirmed by x-ray photoelectron spectroscopy that the chloromethyl group existed more at the surface of the produced microsphere than at that of film cast from the benzene solution in which the microspheres were dissolved.Part CVI of the series Studies on Suspension and Emulsion.     

Preparation of micron-size monodisperse polymer particles by seeded polymerization utilizing the dynamic monomer swelling method

Utilizing a new type of monomer swelling method, 6.1 m-size monodisperse polymer particles were prepared by seeded polymerization. 1.8 m-size monodisperse polystyrene (PS) seed particles (1.8 m in size) were prepared by dispersion polymerization in ethanol-water (80/20, v/v) medium in the presence of poly(acrylic acid) as stabilizer with 2,2-azobisisobutyronitrile as initiator. The PS seed dispersion was mixed with ethanol-water (60/40, v/v) solution dissolving styrene (S) monomer, benzoyl peroxide as initiator, and poly(vinyl alcohol) as stabilizer. By slow, continuous, dropwise addition of water with a micro feeder into the mixture, the PS particles absorbed the many S monomers, which were separated from the medium and swelled from 1.8 m to 8.4 m while keeping the monodispersity high. We named this procedure the dynamic swelling method. Then, the seeded polymerization of the absorbed S monomer was carried out in the presence of NaNO₂ as water-solube inhibitor.Part CXXII of the series Studies on Suspension and Emulsion.     

Synthesis of spherical microcapsules by photopolymerization in aerosols

 The preparation of polymer microcapsules of well defined size in the range of 10–50 μm with different shell thickness to core diameter ratios is described. An aerosol of monodisperse droplets of a homogeneous ternary liquid system which contained a hydrophobic component and a hydrophilic component dissolved in a high-volatile mutual solvent, was produced by dispersing with a vibrating-orifice aerosol generator. After the evaporation of the solvent in a nitrogen atmosphere the particles demix and form a two-phase droplet of core-shell type. These droplets were illuminated with UV light and polymerized to highly monodisperse microcapsules with a solid polymer shell and a liquid core. The properties of the resulting particles (size, size distribution, shell thickness, shape and surface characteristics) were investigated by scanning electron microscopy, Raman spectroscopy on single optically levitated particles, and confocal Raman micro spectroscopy. The microcapsules were highly monodisperse and have spherical shape. Received: 24 July 1996 Accepted: 29 August 1996     

Formation of multihollow structures in crosslinked composite polymer particles

Micron-size monodisperse polymer particles having multihollow structures were prepared as follows. First, micron-size monodisperse polystyrene/poly(styrene-divinylbenzene) (PS/P(S-DVB)) composite particles were produced by seeded copolymerization of S and DVB with 2,2-azobisisobutyronitrile as an initiator in the ethanol/water (76/24, weight ratio) medium in the presence of 2.37 m-size monodisperse PS seed particles produced by dispersion polymerization. The molar ratio of S/DVB was changed in the range of 1/110/1. The uncrosslinked polymer within the composite particles was extracted with toluene under reflux. For the highest DVB content (S/DVB=1/1, molar ratio), one large hollow was observed in a part of the composite particles after the extraction. For the middle DVB content (S/DVB=4/1, molar ratio), multihollow structure was observed in all the particles. For the lowest DVB content (S/DVB=10/1, molar ratio), fine multihollow structure was observed in all the particles.Part CXLIII of the series Studies on Suspension and Emulsion     

Preparation of poly(vinyl chloride) latexes by polymerization of stabilized monomer droplets

Poly(vinyl chloride) latexes have been prepared by polymerization in micron and submicron sized monomer droplets. Monomer emulsions with excellent long time stability were obtained by diffusional swelling of vinyl chloride monomer into preformed, stable polydisperse pre-emulsions of water-insoluble oils or monodisperse, oligomer styrene seed particles. It was found that the size and size distribution of the final latex particles were determined by those of the parent monomer emulsions. Except for the secondary particles formed during polymerization, the size and size distributions of the latex particles were found to be com-parable to those of the monomer emulsions employed, indicating a complete nucleation of the parent emulsion droplets. The extent of secondary particle formation was found to be very dependent upon the emulsifier concentration as well as on the type and amount of initiator used. © 1995 John Wiley & Sons, Inc.     

A predictive approach of the influence of the operating parameters on the size of polymer particles synthesized in a simplified microfluidic system

Monodisperse and size-controlled spherical polymer particles were synthesized by in situ photopolymerization of O/W monomer emulsions. Monomer droplets were produced without surfactant or pretreatment at a needle tip in a simplified axisymmetric microfluidic device. The effect of the viscosity of the continuous phase on the particle size was studied. The system operated in the dripping mode, at a low Reynolds number. A dimensionless master curve describes the particle diameter as a function of the needle inner diameter as well as velocity and viscosity ratios of continuous and dispersed phases. An empirical law predicts the particle size. The normalized particle diameter depends upon the ratio of the capillary numbers of continuous and dispersed phases with an exponent equal to -0.22.     

New method of producing mono-sized polymer gel particles using microchannel emulsification and UV irradiation

It has been established that the combination of microchannel (MC) emulsification and UV-induced gelation is quite effective in producing mono-sized gel particles from acryloyl-type monomer/polymer solutions. MC emulsification allows one to produce the monomer solution droplets with less than ca. 5% relative standard deviation. On the other hand, using UV-induced gelation technique, pre-gel droplets containing a photoinitiator gelate by irradiation of UV light for a few minutes without requiring heating and/or intermediate adding of reaction accelerator. Conveniently, the particle size is adjusted from a few m to ca. 100-m by changing the slit size of the MC plate. Furthermore, gel particles may contain a variety of materials, such as metals, pigments, dyes, oils, bubbles, or others, suggesting various potential industrial applications.     

Synthesis of micron-sized, monodisperse polymer particles of disc-like and polyhedral shapes by seeded dispersion polymerization

Micron-sized, monodisperse polymer particles having unique disc-like and polyhedral shapes were produced by seeded dispersion polymerization of various methacrylates with 1.57 m-sized polystyrene seed particles in the presence of saturated hydrocarbon droplets in methanol/water. Such nonspherical shapes were controllable by the polymerization conditions.Part CCLX of the series Studies on Suspension and Emulsion     

SAXS study of core-shell colloids

Polymeric core-shell systems were produced by a two-stage emulsion polymerization technique under fixed conditions: i) monodisperse seed latex with a sufficiently high particle number; ii) starved monomer-II addition; iii) water-soluble initiator; iv) incompatibility of core and shell polymer. From electron micrographs, it is not possible to determine where the second polymer is located within these two-stage emulsion polymers. The internal structure of the particles can be detected by small-angle x-ray scattering. The results indicate that; i) the emulsion polymerization process takes place in a small surface layer region of the seed particles, and ii) a small interfacial layer exists between the core and shell polymer.Part 6 of Polymerizations in the Presence of Seeds     

N‐Vinylcarbazole as Versatile Photoinaddimer of Photopolymerization under Household UV LED Bulb (392 nm)

N‐vinylcarbazole (NVK) can act simultaneously as a photoin itiator, an addi tive, and a mono­mer (photoinaddimer) of photopolymerization upon exposure to the household ultraviolet (UV) light‐emitting diode (LED) bulb (emission wavelength centered at 392 nm). Even though the light absorption spectrum of NVK exhibits weak overlapping with the emission spectrum of the UV LED, the active species (i.e., radicals and cations) can be generated from the interaction between NVK and diphenyliodonium hexafluorophosphate (Iod) under irradiation of this LED device, which is investigated by steady state photolysis and electron spin resonance spin‐trapping methods. Interestingly, the generated radicals and cations from the NVK/Iod system demonstrate high efficiency to initiate the free radical photopolymerization of (meth)acrylates and the cationic photopolymerization of epoxide and divinyl ether under the UV LED irradiation, and the one‐step simultaneous catonic/radical photopolymerization of expoxide/acrylate blend can lead to the formation of tack free polyacrylate/polyether‐based interpenetrated polymer network film within 10 min even when the polymerization process is exposed to the atmosphere highlighting the high efficiency of the system to reduce the oxygen inhibition effect. More interestingly, NVK/Iod system can also initiate the photopolymerization of NVK under the UV LED irradiation to produce polyvinylcarbazole, and NVK acts as both a photoinitiator and a monomer in the system.