Evidence for the preservation of the particle identity in miniemulsion polymerization

Landfester, Katharina; Bechthold, Nina; Förster, Stephan; Antonietti, Markus

doi:10.1002/(sici)1521-3927(19990201)20:2<81::aid-marc81>3.0.co;2-g

Cited by 174 publications

(159 citation statements)

References 10 publications

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“…ultrasound or high pressure homogenization) [18][19][20] to a two phase mixture of oil (in a polymerization process typically the monomer) and water ( 2). [21][22] The latter describes the growth of larger droplets on the 6 account of smaller ones by diffusion of oil caused by the higher Laplace pressure in the smaller droplets that is defined as the difference of pressure (∆P) between the inside of a droplet (…”

Section: Miniemulsion Polymerizationmentioning

confidence: 99%

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Surface Patterning with Colloidal Monolayers

Vogel

2012

Springer Theses

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This thesis focuses on the controlled assembly of monodisperse polymer colloids into ordered two-dimensional arrangements. These assemblies, commonly referred to as colloidal monolayers, are subsequently used as masks for the generation of arrays of complex metal nanostructures on solid substrates.The motivation of the research presented here is twofold. First, monolayer crystallization methods were developed to simplify the assembly of colloids and to produce more complex arrangements of colloids in a precise way. Second, various approaches to colloidal lithography are designed with the aim to include novel features or functions to arrays of metal nanostructures.The air/water interface was exploited for the crystallization of colloidal monolayer architectures as it combines a two-dimensional confinement with a high lateral mobility of the colloids that is beneficial for the creation of high long range order. A direct assembly of colloids is presented that provides a cheap, fast and conceptually simple methodology for the preparation of ordered colloidal monolayers. The produced two-dimensional crystals can be transformed into nonclose-packed architectures by a plasma-induced size reduction step, thus providing valuable masks for more sophisticated lithographic processes. Finally, the controlled co-assembly of binary colloidal crystals with defined stoichiometries on a Langmuir trough is introduced and characterized with respect to accessible configurations and size ratios.Several approaches to lithography are presented that aim at introducing different features to colloidal lithography. First, using metal-complex containing latex particles, the synthesis of which is described as well, symmetric arrays of metal nanoparticles can be created by controlled combustion of the organic material of the colloids. The process does not feature an inherent limit in nanoparticle size and is able to produce complex materials as will be demonstrated for FePt alloy particles. Precise control over both size and spacing of the particle array is presented.Second, two lithographic processes are introduced to create sophisticated nanoparticle dimer units consisting of two crescent shaped nanostructures in close proximity; essentially by using a single colloid as mask to generate two structures simultaneously. Strong coupling processes of the parental plasmon resonances of the two objects are observed that are accompanied by high near-field enhancements. A plasmon hybridization model is elaborated to explain all polarization dependent shifts of the resonance positions. Last, a technique to produce laterally patterned, ultra-flat substrates without surface topographies by embedding gold nanoparticles in a silicon dioxide matrix is applied to construct robust and re-usable sensing architectures and to introduce an approach for the nanoscale patterning of solid supported lipid bilayer membranes.

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Section: Miniemulsion Polymerizationmentioning

confidence: 99%

“…Each droplet acts as an individual entity during polymerization (nanoreactor concept). [21][22] Thus, the composition of the final latex particles resembles the composition of the monomer phase. As no diffusion takes place, the polymerization kinetics resembles the kinetics of a bulk radical polymerization.…”

Section: Miniemulsion Polymerizationmentioning

confidence: 99%

Surface Patterning with Colloidal Monolayers

Vogel

2012

Springer Theses

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“…The kinetics investigation of miniemulsion polymerization was mainly focused on single monomer system such as St [22][23][24] and BA [25] before. Here, miniemulsion copolymerization of St and BA with or without the synthesized dyes was performed under the same conditions with 40 mM SDS to water, and 1.5 wt% of APS and 0.2 wt% of the dye to the St and BA; and the covalently red P(St-BA-AHAQ), non-covalently red P(St-BA)/PHAQ, and colorless P(St-BA) latexes were prepared.…”

Section: Characteristics Of Miniemulsion Polymerizationmentioning

confidence: 99%

Preparation of covalently colored polymer latex through miniemulsion polymerization based on a polymerizable dye

Wang

Jin

et al. 2015

Designed Monomers and Polymers

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A polymerizable red dye 1-(6-acrylamidohexylamino) anthraquinone (AHAQ) was synthesized and used to prepare colored polymer latexes using styrene and butyl acrylate as main monomers. Influences of the initiator and surfactant amounts, oil/aqueous phase ratio, and AHAQ content on the polymerization process, the particle size, and surface tension of the resulted latex were investigated, and the migration resistance and light fastness of the red latex films were determined. Results showed that the polymerization was carried out smoothly, and the miniemulsion polymerization mechanism was confirmed by monitoring the dimensions of oil phase before and after polymerization. The latex particle size can be adjusted by varying the surfactant amount, and when AHAQ content was 0.2-1 wt% of total monomers, the encapsulation efficiency and dye conversion could be achieved to 98.7 and 96.3%, respectively. The UV-vis spectra of AHAQ and its corresponding covalently colored polymer indicated that the maximum absorption peak was the same, meaning that the chemical structure of chromophore in AHAQ maintains unchanged after undergoing polymerization. The migration resistance and light fastness of the covalently colored latex films were much better than that of the correspondingly non-covalently colored ones.

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“…63,[69][70] While the presence of either a sterical or electrostatic surfactant prevents these droplets from coalescence, the kinetic stabilization is accomplished by the suppression of Ostwald ripening by the addition of a costabilizer to the dispersed phase. [71][72] The negligible solubility of this compound in the continuous phase creates an osmotic pressure in the droplets, thus counteracting the Laplace pressure. As a result the net diffusion between the droplets is inhibited and therefore, stable droplets of the same composition as the dispersed phase prior to emulsification are obtained and can be classified as "nanoreactors".…”

Section: Microgel Synthesis In Miniemulsionsmentioning

confidence: 99%

Light-Sensitive Polymeric Nanoparticles Based on Photo-Cleavable Chromophores

Klinger

2013

Springer Theses

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This thesis focuses on the design, synthesis and characterization of novel photo-sensitive microgels and nanoparticles as potential materials for the loading and light-triggered release/accessibility of functional compounds. In order to realize this concept, different approaches to irradiation-dependent response mechanisms have been investigated.Novel light-cleavable divinyl functionalized monomeric crosslinkers based on o-nitrobenzyl derivatives were synthesized and used for the preparation of either PMMA or hydroxyl functionalized PHEMA microgels swellable and degradable in organic solvents. By the introduction of anionic MAA moieties into the PHEMA microgels, this concept was successfully transferred to double stimuli-responsive p(HEMA-co-MAA) hydrogel nanoparticles exhibiting a pH-dependent swelling and light-induced degradation behavior in aqueous media. This sensitivity to two orthogonal triggers is proposed to combine a pHinduced post-formation loading mechanism with a pH-and light-triggered release. In addition, a new class of enzyme-and light-sensitive PAAm microgels based on (meth-)acrylate functionalized dextrans as photo-and enzymatically degradable macromolecular crosslinkers was developed by introducing a photo-labile linker between the enzymatically degradable dextran chain and the polymerizable vinyl moieties. Here, the water solubility of the crosslinkers is assumed to enable an in situ loading approach of hydrophilic compounds.A different approach to the loading of microgels is based on photo-labile covalent microgel-drug conjugates. The first step to the realization of this concept was achieved by the development of a novel functional monomer consisting of a doxorubicin molecule covalently attached to a radically polymerizable methacrylate group via a photo-cleavable linker.Moreover, in order to enable the release of hydrophobic substances in aqueous media, hydrophobic nanoparticles consisting of a photo-resist polymer were designed to be degradable upon irradiation in water. Light-triggered conversion of the initial hydrophobic polymer into hydrophilic PMAA induced in situ particle dissolution and release of nile red.Since the introduction of a stimuli-responsive shell around a microgel is assumed to prevent leakage of embedded compounds, studies on non-stimuli-responsive shell formation around preformed microgel seed particles and the formation of microgel cores in polymeric shells were conducted to investigate potential synthetic pathways to this approach.In a last attempt, the surface of PHEMA and p(HEMA-co-MAA) microgels was functionalized with cinnamoyl groups in order to trigger the (reversible) particles interaction with each other by light-induced [2+2] cycloaddition reactions.

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Evidence for the preservation of the particle identity in miniemulsion polymerization

Cited by 174 publications

References 10 publications

Surface Patterning with Colloidal Monolayers

Surface Patterning with Colloidal Monolayers

Preparation of covalently colored polymer latex through miniemulsion polymerization based on a polymerizable dye

Light-Sensitive Polymeric Nanoparticles Based on Photo-Cleavable Chromophores

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