UV cured transparent films including non‐aqueous conductive microgels

UV cured transparent films containing non‐aqueous conductive microgels coated with poly(aniline)/dodecyl benzenesulfonic acid(DBSA) were obtained. The conductive microgels were prepared by interface polymerization of aniline/DBSA in the presence of non‐aqueous polymeric microgels. The electrical conductivity and the particle size of the prepared conductive microgel were 0.5 S/cm and 58 nm, respectively. The prepared conductive microgels were easily blended with a UV curable coating formulation, and then were cured to make highly optically transparent films. For the UV cured film containing about 35 wt% of the conductive microgels, a surface resistance in the range of 10⁷ to 10⁸ Ω/square was obtained. In a polar cosolvent, such as NMP and m‐cresol, the critical volume was shifted to the lower range, with a value of 10 wt%. The UV cured films containing the conductive microgels exhibited good electrical stability against the thermal aging and humidity. Copyright © 2002 John Wiley & Sons, Ltd.     

Preparation and characterization of poly (N-isopropylacrylamide)/polyvinylamine core-shell microgels

In this paper, well-defined temperature- and pH-sensitive core-shell microgels were synthesized by graft copolymerization in the absence of surfactant and stabilizer. The microgel particles consisted of poly (N-isopropylacrylamide (NIPAm)) core crosslinked with N, N′-methylene-bisacrylamide (MBA) and polyvinylamine (PVAm) shell. The effect of MBA content and NIPAm/PVAm ratio on microgel size was investigated. SEM showed that the microgels were spherical and had narrow particle-size distribution. TEM images of the microgels clearly displayed well-defined core-shell morphologies. Zeta-potential measurement further elucidated that the microgels possessed positively charged PVAm molecules on the microgel surface. Turbidity measurement and ¹H-nuclear magnetic resonance (NMR) experiments indicated that the VPTT of microgels was the same as the LCST of PNIPAm. ¹H-NMR experiments also inferred that the methyl proton of N-isopropylacrylamide appeared three peaks and responded to hydrogen-bonding interaction including polymer chain with water molecular, intramolecular interaction and intermolecular interaction, respectively.     

Poly(N-vinylcaprolactam-co-glycidyl methacrylate) aqueous microgels labeled with fluorescent LaF3:Eu nanoparticles

We describe the synthesis and properties of functional microgel particles based on poly(N-vinylcaprolactam-co-glycidyl methacrylate) (PVCL/PGMA) copolymer. A series of colloidally stable microgel particles with a range of glycidyl methacrylate content were prepared by surfactant-free heterophase polymerization in water. The microgel particles obtained had hydrodynamic radii between 250 and 350 nm and were fairly monodisperse in size; however, a broadening of the particle size distribution was observed for samples with a low GMA content. The PVCL/PGMA microgel particles exhibit thermally responsive reversible changes in diameter in water, and the swelling degree increased with the PVCL fraction in the copolymer structure. These microgels were then modified with photoluminescent europium-doped lanthanum fluoride nanoparticles (LaF3:Eu-AEP) through reaction of the 2-aminoethyl phosphate surface ligands with epoxy groups present in the microgel. These hybrid microgels were colloidally stable and thermally responsive in aqueous solution.     

The microgel formation by crosslinking reaction of primary polymer

The crosslinking reaction of primary polymers under the influence of potentials was studied by computer simulation. Under the predominant action of repulsive potential, macrogelation did not appear and the products remained as a sol (microgel). With increasing repulsive potential, the particle size descended and the final size distribution became narrow (Pw/Pn = 1·06; Pw, weight average degree of polymerization; Pn, number average degree of polymerization). By the simulation according to a diffusion limited aggregation model with distant repulsive potential and short distant weak attractive potential, round and dense particles were obtained. In the crosslinking reaction of partially quaternized poly (4-vinylpyridine) (q-P4VP), the size of the particles declined and the size distribution became narrow with the quaternization degree of q-P4VP. This result agrees with that of the simulation.     

Poly (N-isopropylacrylamide) microgel based assemblies for organic dye removal from water: microgel diameter effects

Poly (N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgel based assemblies (aggregates) were synthesized from microgels of various diameters via polymerization of the crosslinker N,N′-methylenebisacrylamide (BIS) in the presence of microgels in solution. We investigated the ability of the respective aggregates to remove the organic, azo dye molecule 4-(2-hydroxy-1-napthylazo) benzenesulfonic acid sodium salt (Orange II) from water at both room and elevated temperatures. The results from the microgel aggregates made from 1.1-μm-diameter [Parasuraman and Serpe. ACS Applied Materials & Interfaces, 2011] microgels were compared to aggregates synthesized from 321-nm and 1.43-μm-diameter microgels. Aggregates made from the same size microgels showed increased uptake efficiency as the concentration of BIS in the aggregates was increased, while for a given BIS concentration, the uptake efficiency increased with increasing microgel size in the aggregate. We attribute this to the “nature” of the aggregates; aggregates have void space between the microgels that can serve as reservoirs for Orange II uptake—the void spaces are hypothesized to increase with larger diameter microgels. By exploiting the thermoresponsive nature of the microgels, and microgel based aggregates, 85.3 % removal efficiencies can be achieved. Finally, all uptake trends for the aggregates, at room temperature, were fit with a Langmuir sorption isotherm model.     

Preparation and Characterization of pH-Sensitive Microgels of Poly((2-dimethylamino) ethyl methacrylate)

Summary: pH-sensitive microgels of poly((2-dimethylamino) ethyl methacrylate) (PDMAEMA) were prepared by dispersion polymerization of 2-dimethylamino ethyl methacrylate in a mixed solvent of water/ethanol. ¹HNMR, FTIR and SEM were used to confirm the chemical structure and morphological properties of the resulting microgels. Dynamic Light Scattering (DLS) was used to measure the hydrodynamic diameter of the particles. SEM micrographs showed that the microgel particles have a diameter of about 100–200 nm in dry state. Mean hydrodynamic diameter of the particles at their collapsed state at pH = 9.5 was found to be about 150 nm. DLS measurements at various pH values showed that the prepared microgels have a volume phase transition around pH = 8 at which the hydrodynamic diameter decreased from about 470 nm to around 150 nm corresponding to a 32 fold change in the mean volume of a microgel particle.     

Synthesis,characterization, and influence of synthesis parameters on particle sizes of a new microgel family

Poly(p‐nitrophenylacrylate‐co‐methacrylamide) and poly(p‐Nitrophenylacrylate‐co‐N,N′‐isopropylacrylamide) reactive microgels were synthesized by precipitation polymerization. The process was followed qualitatively by infrared spectroscopy (ATR‐FTIR) and microgels composition was determined by nuclear magnetic resonance (¹H NMR). Scanning electron microscopy of obtained colloidal particles showed strictly spherical morphologies with a moderate polydispersity. The average hydrodynamic particle diameter and particle size distributions were measured by quasi‐elastic light scattering and the particle size distributions obtained ranged from 100 to 600 nm. Several synthetic parameters affect the particle size of these materials and thus, indirectly, their properties and future applications. In this article, we report the influence of different polymerization reaction conditions in the final microgel dimensions. For example, we observed that the different solvent‐comonomer affinity induced a significant change in swollen particle size of the copolymeric microgels. On the other hand, the crosslinking density limited the particle sizes, but an excess of crosslinker content in the reaction mixture resulted in the opposite effect. Finally, we also studied the influence of initiator content in the mean particle size. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3833–3842, 2007     

An Analysis of Oxidative Changes and the Fatty Acid Profile in Stored Poultry Sausages with Liquid and Microencapsulated Fish Oil Additives

This study deals with the fatty acid profile and oxidative changes (TBARS) in vacuum-packed (VP) or modified-atmosphere-packed (MAP) finely-comminuted poultry sausages with liquid fish oil and microencapsulated fish oil (MC) additives. An analysis of omega-3 fatty acids (EPA and DHA) showed that their content in the samples with the fish oil additive decreased from the initial value of 0.22 g∙100 g⁻¹ of the product to 0.18 g∙100 g⁻¹ (MAP) and 0.17 g∙100 g⁻¹ (VP), respectively. After in vitro digestion, the total EPA and DHA content in the sample with microencapsulated oil amounted to 0.17 g∙100 g⁻¹ of the product. The TBARS values showed the VP samples with both forms of the fish oil additive had the lowest values on the first day of storage. Storage of the samples for 21 days caused a slight increase in the degree of lipid oxidation. The research indicated that the forms of the oil additive did not have a negative influence on the sensory features or the physicochemical properties of the sausages. The EPA and DHA levels in samples with liquid fish oil and those with oil microcapsules were sufficient for the sausage producer to declare high content of these fatty acids in accordance with the current EC regulation.     

Preparation and Swelling Properties of Poly(NIPAM) "Minigel" Particles Prepared by Inverse Suspension Polymerization

The characterization of temperature- and pH-sensitive poly-N-isopropylacrylamide (poly-NIPAM) microgel particles, produced by surfactant-free emulsion polymerization, has been extensively reported. In the work described here poly(NIPAM) gel particles, cross-linked with N-N'-methylenebisacrylamide (BA), have been produced using inverse suspension polymerization. These particles have been termed "minigels" here since they are somewhat larger than conventional microgels. Results suggest that minigel particles are formed as a dilute suspension, within the aqueous dispersed (droplet) phase. The hydrodynamic diameter of the minigel particles produced in this work is 相似文献   

Fluorine-containing pH-responsive core/shell microgel particles: preparation,characterization, and their applications in controlled drug release

A kind of novel fluorine-containing pH-responsive core/shell microgels poly(DMAEMA-co-HFMA)-g-PEG were prepared via surfactant-free emulsion polymerization using water as the solvent. The well-defined chemical structure of the copolymers was characterized by FTIR, ¹H-NMR, ¹⁹F-NMR, and elemental analysis. The microgel particles were studied by florescence probe technique, dynamic light scattering, and zeta potential measurement; the microgels displayed a significant pH-responsive behavior. Furthermore, the cytotoxicity assay indicated that the copolymer microgels had low toxicity, and 5-FU-loaded microgels offered a certain killing potency against cancer cells. In addition, the drug loading and in vitro drug release demonstrated that 5-FU was successfully incorporated into polymeric microgels, and the drug-loaded microgels showed a marked pH-dependent drug release behavior. This study suggests that the poly(DMAEMA-co-HFMA)-g-PEG microgels play an important role in the release mechanism stimulated by the change in the pH and have potential applications as a controlled drug release carrier.     

Non-covalent reconfigurable microgel colloidosomes with a well-defined bilayer shell

Microgels are extremely interfacially active and are widely used to stabilize emulsions. However, they are commonly used to stabilize oil-in-water emulsions due to their intrinsic hydrophilicity and initially dispersed in water. In addition, there have been no attempts to control microgel structural layers that are formed at the interface and as a result it limits applications of microgel in advanced materials. Here, we show that by introducing octanol into poly(N-isopropylacrylamide-co-methacrylic acid) (PNIPAM-co-MAA) microgels, octanol-swollen microgels can rapidly diffuse from the initially dispersed oil phase onto the water droplet surface. This facilitates the formation of microgel-laden interfacial layers with strong elastic responses and also generates stable inverse water-in-oil Pickering emulsions. These emulsions can be used as templates to produce microgel colloidosomes, herein termed ‘microgelsomes’, with shells that can be fine-tuned from a particle monolayer to a well-defined bilayer. The microgelsomes can then be used to encapsulate and/or anchor nanoparticles, proteins, vitamin C, bio-based nanocrystals or enzymes. Moreover, the programmed release of these substances can be achieved by using ethanol as a trigger to mediate shell permeability. Thus, these reconfigurable microgelsomes with a microgel-bilayer shell can respond to external stimuli and demonstrate tailored properties, which offers novel insights into microgels and promise wider application of Pickering emulsions stabilized by soft colloids.

Inverse W/O Pickering emulsions and reconfigurable microgelsomes with a well-defined bilayer structure are prepared from octanol-swollen PNIPAM-co-MAA microgels and the combination of binary microgels, which promise wider application of soft colloids.     

Microgel formation in emulsion copolymerization. I. Polymerization without seed latex

Microgel formation during emulsion copolymerization of methyl methacrylate and ethylene glycol dimethacrylate is investigated both experimentally and theoretically. It was found that the average crosslinking density is fairly high even from a very early stage of polymerization. The molecular weight distribution (MWD) development in emulsion crosslinking copolymerization is completely different from that in homogeneous polymerization. Because the maximum molecular weights allowed to exist is limited by the particle size, a comprehensive model for the MWD development in nonlinear emulsion polymerization must account for the size of polymerization locus properly. During the formation of microgels, a drastic change in the weight-average molecular weights, which is characteristic of gelation in homogeneous media, is not always required. In a typical microgel formation process where a large mole fraction of divinyl monomer is used, the average molecular weights may increase just linearly with conversion in which a sharp MWD shifts to higher molecular weights with the progress of polymerization. It is shown that the microgels formed in emulsion polymerization are characterized as intramolecularly crosslinked macromolecules that occupy a very large weight fraction in each polymer particle. © 1996 John Wiley & Sons, Inc.     

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.     

原子转移自由基聚合原位合成温敏性微球

以过硫酸钾为引发剂、丙酮-水[V(丙酮)∶V(水)＝4∶6]的混合溶剂为反应介质, 在少量二乙烯苯存在的条件下使苯乙烯(St)和对氯甲基苯乙烯(CMSt)进行无皂乳液共聚反应, 得到了粒径大小均匀的交联型聚苯乙烯(PSt)微球, 由X射线光电子能谱对表面组分测定发现: CMSt上的氯原子在聚合过程中富集于交联微球的表面. 以此交联型PSt微球为原子转移自由基聚合(ATRP)的引发剂, 在22 ℃下引发N-异丙基丙烯酰胺(NIPAAm)进行原位ATRP反应, 得到了表面原子转移自由基聚合接枝的交联聚苯乙烯(PNIPAAm-g-PSt)温敏性微球. 借助傅立叶变换红外光谱、差示扫描量热仪、扫描电子显微镜及激光光散射仪等对PNIPAAm-g-PSt的结构、相转变温度、形态及不同温度下的粒径变化进行了测定, 结果表明NIPAAm单体成功地原位ATRP接枝在交联PSt微球的表面, 接枝微球的球形更规整, 在水中的相转变温度约为32 ℃, 具有明显的温度敏感性.     

Zwitterionic microgel based anti(-bio)fouling smart membranes for tunable water filtration and molecular separation

Tunable gating polymeric nanostructured membrane with excellent water permeability and precise molecular separation is highly advantageous for smart nanofiltration application. Polymeric nanostructures such as microgels with functionalizable cross-linkable moieties can be an excellent choice to construct membranes with a thin separation layer, functionality, and tunable transport properties. In the present work, we prepared switchable anti(bio)fouling membranes using zwitterionically functionalized antibacterial thermoresponsive aqueous core-shell microgels with a thin separation layer for controlled filtration and separation applications. The microgels were synthesized using a one-step graft copolymerization of poly(N-isopropylacrylamide) and polyethyleneimine (PEI) followed by zwitterionization of free amine groups of PEI chains with 1,3-propane sultone. Microgel synthesis and zwitterionization were confirmed by spectroscopic and elemntal analysis. The obtained microgels were thoroughly characterized to analyze their thermoresponsive behavior, morphology, charge, and antibacterial properties. After that, characterizations were performed to elucidate the surface properties, water permeation, rejection, and flux recovery of the microgel membranes prepared by suction filtration over a track-etched support. It was observed that zwitterionic membrane provides better hydrophilicity, lower bovine serum albumin (BSA) adsorption, and desirable antimicrobial activity. The pure water permeability was directly related to the microgel layer thickness, applied pressure, and temperature of the feed solution. The novel nanostructured membrane leads to an excellent water permeance with a high gating ratio, high flux recovery rate with low irreversible fouling, better rejection for various dyes, and foulant. Most importantly, the long-term performance of the membrane is appreciable as the microgel layer remains intact and provides excellent separation up to a longer period. Owing to easy preparation and well control over thickness, the zwitterionic microgel membranes constitute unique and interactive membranes for various pressure-driven separation and purification applications.     

Fabrication of Phosphorus-Doped Cobalt Silicate with Improved Electrochemical Properties

The development of electrode materials for supercapacitors (SCs) is greatly desired, and this still poses an immense challenge for researchers. Cobalt silicate (Co₂SiO₄, denoted as CoSi) with a high theoretical capacity is deemed to be one of the sustainable electrode materials for SCs. However, its achieved electrochemical properties are still not satisfying. Herein, the phosphorus (P)-doped cobalt silicate, denoted as PCoSi, is synthesized by a calcining strategy. The PCoSi exhibits 1D nanobelts with a specific surface area of 46 m²∙g⁻¹, and it can significantly improve the electrochemical properties of CoSi. As a supercapacitor’s (SC’s) electrode, the specific capacitance of PCoSi attains 434 F∙g⁻¹ at 0.5 A∙g⁻¹, which is much higher than the value of CoSi (244 F∙g⁻¹ at 0.5 A∙g⁻¹). The synergy between the composition and structure endows PCoSi with attractive electrochemical properties. This work provides a novel strategy to improve the electrochemical performances of transition metal silicates.     

Facile Microfluidic Fabrication of Biocompatible Hydrogel Microspheres in a Novel Microfluidic Device

Poly(ethylene glycol) diacrylate (PEGDA) microgels with tuneable size and porosity find applications as extracellular matrix mimics for tissue-engineering scaffolds, biosensors, and drug carriers. Monodispersed PEGDA microgels were produced by modular droplet microfluidics using the dispersed phase with 49–99 wt% PEGDA, 1 wt% Darocur 2959, and 0–50 wt% water, while the continuous phase was 3.5 wt% silicone-based surfactant dissolved in silicone oil. Pure PEGDA droplets were fully cured within 60 s at the UV light intensity of 75 mW/cm². The droplets with higher water content required more time for curing. Due to oxygen inhibition, the polymerisation started in the droplet centre and advanced towards the edge, leading to a temporary solid core/liquid shell morphology, confirmed by tracking the Brownian motion of fluorescent latex nanoparticles within a droplet. A volumetric shrinkage during polymerisation was 1–4% for pure PEGDA droplets and 20–32% for the droplets containing 10–40 wt% water. The particle volume increased by 36–50% after swelling in deionised water. The surface smoothness and sphericity of the particles decreased with increasing water content in the dispersed phase. The porosity of swollen particles was controlled from 29.7% to 41.6% by changing the water content in the dispersed phase from 10 wt% to 40 wt%.     

Influence of polyelectrolyte multilayer adsorption on the temperature sensitivity of poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) (PNiPAM) microgels

The electrophoretic mobility and temperature-dependent particle size of poly(N-isopropylacrylamide) (PNiPAM) microgels after alternating adsorption of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(sodium 4-styrenesulfonate) (PSS) have been determined. First a PNiPAM-co-acrylic acid (AAc) shell was added to the PNiPAM microgel, then PDADMAC and PSS were adsorbed alternately. The studies of the electrophoretic mobility revealed charge reversal when a polyelectrolyte (PE) layer was adsorbed. Particle size measurements revealed a strong influence of polyelectrolyte adsorption on the temperature-dependent particle swelling. The strong influence of the adsorbed polyelectrolyte on the particle size is in contrast to polyelectrolyte multilayer adsorption on rigid particles.     

Preparation of Acrylic Microgels by Modified Microemulsion Polymerization and Phase Inversion

Semi‐transparent reactive microgel in nanosize has been prepared by modified microemulsion polymerization using a common emulsifier, crosslinking agent and functional monomer. The microgels are translucent reactive nanoparticles, with the size of 40–100 nm, consisting of inner‐crosslinked polymer up to 40%. FT‐IR proved the functional groups, such as epoxy and hydroxy, are on the surface of the microgel nanoparticles. Rheological detection demonstrated the apparent pseudoplasticity of the non‐aqueous microgel dispersion prepared by the phase transfering from the O/W microlatexes.     

Poly(N-isopropylacrylamide)-block-poly(acrylic acid) hydrogels: synthesis and rapid thermoresponsive properties

In this contribution, we reported the synthesis of poly(N-isopropylacrylamide)-block-poly(acrylic acid) (PNIPAAm-b-PAA) copolymer networks via sequential reversible addition-fragmentation chain transfer (RAFT) polymerization. The PNIPAAm-b-PAA block copolymer networks were characterized by means of Fourier transform infrared spectroscopy (FTIR) and small angle X-ray scattering (SAXS). The volume phase transition (VPT) temperatures of the PNIPAAm-b-PAA hydrogels were measured by means of micro-differential scanning calorimetry (micro-DSC). It was found that the block copolymer hydrogels displayed the VPT temperatures lower than the control PNIPAAm hydrogel. Compared to the control PNIPAAm hydrogel, the deswelling and reswelling properties of the block copolymer hydrogels were significantly improved. The improved thermoresponsive properties of the PNIPAAm-b-PAA hydrogels have been interpreted on the basis of the formation of the architecture of the block copolymer networks.