A series of uniform, macroporous poly(styrene-co-divinylbenzene) microspheres with diameters ranging from 6.6 0.6 to 8.6 0.2 mm was prepared in a multistep procedure involving precipitation polymerization synthesis of polystyrene seed particles, swelling of seed particles with plasticiser and porogen, and polymerization of styrene–divinylbenzene (S–DVB) inside the seed particles. Particles prepared with varying DVB feed ratios had comparable diameters (as evidenced by scanning electron microscopy) with specific surface areas increasing with DVB content from 11 to 467 m2 g1 (measured by nitrogen adsorption). Residual double bonds were converted into azide functionality (through HBr addition and bromo-azide substitution) or alkyne functionality (Br2 addition followed by double elimination) which allowed for CuAAC-click chemistry conjugation with reagents carrying the respective complimentary alkyne or azide functional groups including the fluorescent dye derivatives 7-nitro-4-(prop-2-ynylamino)benzofuran (NBD-alkyne) and Rhodamine B hexylazide synthesised for this purpose. Efficiency of chemical transformations was determined using a combination of CHN and IC elemental analyses, solid state NMR spectroscopy, FT-IR spectroscopy, Raman spectroscopy, and confocal scanning fluorescence microscopy. Although the respective second steps in each modification route (substitution and elimination) suffered from lower yields (35%), porous particles with azide loadings of up to 0.71 mmol g1 and alkyne loadings of up to 0.78 mmol g1 were prepared. Confocal laser scanning microscopy on Rhodamine B-labelled microspheres indicated functionalization throughout the particles featuring a core–shell structure with higher functionalization in the outer layer of particles. Results are expected to contribute to the development of advanced, well-defined, macroporous particles with high, chemically accessible surface areas

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UV-Irradiation of azide-functional microspheres for several minutes is shown to result in efficient crosslinking based on nitrene chemistry and to spare a controllable amount of azide functionality which is amenable to click-modification through CuAAC.

SynopsisIn the present article the kinetics of polymerization of vinyl acetate in suspension up to high conversion was studied. The molecular weight distribution and the side chain branching of polyvinyl acetate produced were examined with respect to micro and macro mixing as well as to reactor type. The following results were achieved: the time-activity curves of the polymerization can be described up to high conversions considering the exponential increase in viscosity of the polymerizing system and combining the viscosity with rate constants of the polymerization. The change of volume of the polymerizing system has no significant influence on kinetics. The narrowest molecular weight distribution of the poly(viny1 acetate) produced was achieved when polymerizing in the homogeneous continuous stirred tank reactor while the broadest molecular weight distribution was observed in the segregated continuous stirred tank reactor. The batch reactor and the flow tube reactor produce polymers with molecular weight distributions lying in between. Considering the side chain branching, another order was found. The batch reactor and the tube reactor show the lowest side chain branching, the homogeneous continuous stirred tank reactor shows a larger one and the segregated continuous stirred tank reactor shows the largest. Possible reasons for the different behavior of the different reactors are discussed. The degree of segregation was determined by experiments. EXPERIMENTALVinyl acetate (Hoechst AG, polymerization grade) used for the polymerization was rectified in a large column and stored at low temperature. Dicyclohexyl peroxidicarbonate (P1652, Peroxid Chemie) was used as initiator and 2,2-diphenyl-l-pikryl-hydrazyl (DPPH) (Fa. Fluka) was used for stopping the reaction after sampling. The dispersion agent utilized was partly saponified poly(viny1 acetate) (Mowioll8-88, Hoechst AG). Tertiary butanol (Bayer AG) was used as solvent for the polymerization in solution because this solvent has the smallest transfer constant of a poly(viny1 acetate) radical to a solvent molecule.Unless mentioned otherwise, the volume fraction of vinyl acetate to water was 0.12 to 0.25, and the initiator concentration was 0.5 wt % related to the monomer. For the polymerization in solution, 15 wt % monomer was solved in tertiary butanol and the same monomer to initiator ratio was chosen.For polymerization, a 1.5 1 thermostatic stirred tank reactor (ratio height/ diameter = 2.5) with a blade stirrer (stirrer diameter to reactor diameter 1:3, centrosymmetrically arranged one-third away from the bottom of the vessel) of 600 rpm for the polymerization in suspension was used. During the continuous process, feeding was put in through an injector at the bottom of the vessel. Outlet and sampling took place in the upper part of the reactor. All experiments were

Summary: This article presents a novel design of smart scale PTFE tubular reactor systems for continuous polymerization reactions. To optimize the flow pattern, CFD calculations and RTD experiments were done. These results led to an unique tube geometry combined with a specialized arrangement of static mixers. A comparison of heat transfer properties of two different types of tubular reactors shows the feasibility of using PTFE instead of stainless steel as reactor construction material. The versatility of the operation modes is demonstrated for emulsion copolymerization experiments with the same recipe but at the different modes.

We report a novel approach of seeded emulsion polymerization in which nanocrystals are used as seeds. Ultrasmall biocompatible polymer-coated nanocrystal with sizes between 15 and 110 nm could be prepared in a process that avoids any treatment with high shear forces or ultrasonication. The number of nanocrystals per seed, the size of the seeds, and the shell thickness can be independently adjusted. Single encapsulated nanocrystals in ultrasmall nanobeads as well as clusters of nanocrystals can be obtained. Polysorbat-80 was used as surfactant. It consists of poly(ethylene glycol) (PEG) chains, giving the particles outstanding biofunctional characteristics such as a minimization of unspecific interactions.

A new experimental method for the analysis of mass and energy transport and reactions on microparticles is presented. A chain of microdroplets from a vibrating orifice generator was injected into a quiescent gas phase. Linear Raman spectra from the microparticles and the surrounding gas were taken at different distances from the generator. Concentration changes were measured as a function of droplet lifetime. A period of time of up to 20 ms could be studied with a resolution of 10 μs. An argon-ion laser in a 90° scattering geometry was used for excitation. Spectra were taken through a modified double monochromator with a two-dimensional charge-coupled device (CCD) detector, one axis of which was used for spatial resolution. Profiles of gaseous components near the droplets could be measured with a resolution of 50 μm. The method has been applied to analysis of absorption, dissociation, and isomerization in the SO2–H2O system and to the investigation of the desorption process of CO2 from water droplets. Chemical components in gas and liquid phase could be separated. The detection limit in aqueous media was 1 mmol/L.

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