0000000000048322
AUTHOR
Katja Nilles
Synthesis and polymerization of active ester monomers based on 4-vinylbenzoic acid
Abstract Nine active ester monomers based on 4-vinylbenzoic acid have been synthesized. Under free radical polymerization conditions these monomers could successfully be polymerized yielding reactive polymers with molecular weights of around M n = 20.000–50.000 g/mol and molecular weight distributions M w / M n of around or below 2 in good yields. Polymer analogous reactions with amines have been investigated by time-resolved FT-IR spectroscopy and it was found that especially poly(pentafluorophenyl 4-vinylbenzoate) featured a significant reactivity, such that polymer analogous reactions proceeded quantitatively with amines within less than 5 min at 0 °C.
Covalently bonded layer-by-layer assembly of multifunctional thin films based on activated esters.
We demonstrate that chemically stable, multifunctional polymer thin films can be obtained using the layer-by-layer (LbL) deposition based on covalent bonds between adsorbing chains. Poly(pentafluorophenyl-4-vinylbenzoate) (P1) or poly(pentafluorophenylacrylate) (P2) polymers were assembled with poly(allyl amine) (PAAm) to yield LbL multilayer films through amide bond formation by the reaction between activated esters of P1 or P2 and amine groups in PAAm, which was quantitatively monitored by Fourier transform infrared spectroscopy (FT-IR). It was found that the difference in the solubility of P1 and P2 against ethanol, which was used as the solvent for PAAm, during the LbL deposition yields…
RAFT polymerization of activated 4-vinylbenzoates
The reversible addition fragmentation chain transfer (RAFT) polymerization of five active ester monomers based on 4-vinylbenzoic acid had been investigated. Pentafluorophenyl 4-vinylbenzoate could be polymerized under RAFT conditions yielding polymers with very good control over molecular weight and narrow molecular weight distributions. Following the synthesis of diblock copolymers consisting of polystyrene, polypentafluorostyrene, poly(4-octylstyrene), or poly(4-acetoxystyrene) as an inert block and poly(pentafluorophenyl 4-vinylbenzoate) as a reactive block was successfully performed. The diblock copolymer poly(pentafluoro styrene)-block-poly(pentafluorophenyl 4-vinylbenzoate) had been a…
Surface and bulk ordering in thin films of a symmetrical diblock copolymer
Amphiphilic diblock copolymers have the ability to adapt their surface's molecular composition to the hydrophilicity of their environment. In the case of about equal volume fractions of the two polymer blocks, the bulk of these polymers is known to develop a laminar ordering. We report here our investigation of the relationship between bulk ordering and surface morphology/chemical composition in thin films of such an amphiphilic diblock copolymer. Upon annealing in vacuum, the expected lamella ordering in the bulk of the film is observed and we find the morphology of the film surface to be defined by the thickness of the as-deposited film: If the as-deposited thickness matches the height of…
Precise structural investigation of symmetric diblock copolymer thin films with resonant soft X-ray reflectivity
Symmetric diblock copolymers are known to form lamellar structures in the bulk of an organic thin film. Polymer/polymer and polymer/substrate interfaces play a critical role in this application. Here, we report the investigation of multiple buried interfaces by using a novel technique resonant soft X-ray reflectivity which benefits from enhanced contrast between different polymers near the carbon K-edge. This allows us to obtain a precise interface structure. We also present an alternative method to determine optical constants of polymers by fitting X-ray reflectivity of polymers with known structural parameters at specific soft X-ray energies. This approach is compared with the way of obta…
Sequential conversion of orthogonally functionalized diblock copolymers based on pentafluorophenyl esters
Statistic and block copolymers exhibiting activated ester side groups were synthesized by reversible addition-fragmentation chain transfer polymerization in the presence of cumyl dithiobenzoate, benzyl dithiobenzoate, and 4-cyano-4-((thiobenzoyl)sulfanyl)pentanoic acid as chain transfer agents. Pentafluorophenyl methacrylate and pentafluorophenyl 4-vinylbenzoate were used to enable a sequential functionalization of the obtained copolymers by conversion of the activated esters with different amines. 1H NMR spectroscopy, 19F NMR spectroscopy, and FTIR spectroscopy showed the successful step-by-step conversion of the different activated esters by aniline followed by aliphatic amines, thereby r…
Non-chromatographic speciation of toxic arsenic in fish
Abstract A rapid, sensitive and economic method has been developed for the direct determination of toxic species of arsenic present in fish and mussel samples. As(III), As(V), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) were determined by hydride generation–atomic fluorescence spectrometry using a series of proportional equations without the need of a chromatographic previous separation. The method is based on the extraction of arsenic species from fish through sonication with HNO3 3 mol l−1 and 0.1% (m/v) Triton and washing of the solid phase with 0.1% (m/v) EDTA, followed by direct measurement of the corresponding hydrides in four different experimental conditions. The li…
Reactive nanorods based on activated esterpolymers: a versatile template-assisted approach for the fabrication of functional nanorods
A new route for the fabrication of polymeric nanorods with functional moieties via post-modification of reactive nanorods is described. To this end reactive nanorods with a homogenous and narrow size distribution were fabricated by utilizing an anodic aluminium oxide (AAO) template-assisted approach. The nanorods are based on activated pentafluorophenyl esters, to enable quantitative post-modification with amines under very mild reaction conditions yielding the corresponding functionalized amide. Post-modification with fluorescent dyes as well as the conversion into well-dispersed rod-shaped poly(N-isopropylacrylamide) (PNIPAM) hydrogels that exhibit a thermal-responsive phase transition wa…
Modular approach toward bioactive fiber meshes carrying oligosaccharides
A modular strategy toward (bio)functional nanofiber meshes by electrospinning is described. In contrast to commonly established, multistep protocols or complex spinning setups, a straightforward single-step procedure is investigated to obtain polymer nanofibers with pentafluorophenyl (Pfp)-activated esters on the surface. The aim was to electrospin, for the first time, poly(pentafluorophenyl methacrylate) (PPfpMA) and PPfpMA/poly(epsilon-caprolactone) (PCL) blends, resulting in reactive nanofibers with fiber surfaces that can be functionalized with suitable bioactive entities. While PPfpMA fibers are brittle the spinning of PCL/PPfpMA blends leads to improved mechanical stability of the obt…
Polymerization of an activated ester monomer based on 4-vinylsulfonic acid and its polymer analogous reaction
Homopolymers containing sulfonic ester side groups were synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization utilizing benzyl dithiobenzoate, cumyl dithiobenzoate, and 4-cyano-4-((thiobenzoyl)sulfanyl)pentanoic acid as chain transfer agents. Likewise diblock copolymers containing poly(styrene), poly(octylstyrene) and poly(pentafluorostyrene) as the second block were synthesized. Additionally, nitroxide mediated polymerization (NMP) was investigated for the synthesis of a homopolymer as well as for a diblock copolymer. Furthermore, the post-polymerization functionalization with various amines to yield the respective sulfonamides was conducted. The conversion …
Modular approach towards multi-functional surfaces with adjustable and dual-responsive wettability using a hybrid polymer toolbox
Poly(methylsilsesquioxane)-based hybrid polymers carrying orthogonally reactive moieties demonstrate an effective modular approach to creating multi-reactive surface coatings. By a sequential surface-analogous reaction different functions could be immobilized in a defined ratio, resulting in dual- or triple-functionalized surfaces.
Synthesis of polymeric 1-iminopyridinium ylides as photoreactive polymers
Two synthetic routes to polymeric 1-imino pyridinium ylides as new photoreactive polymeric architectures were investigated. In the first approach, polymerization of newly synthesized 1-imino pyridinium ylide containing monomers yielding their polymeric analogues was achieved by free radical polymerization. Alternatively, reactive precursor polymers were synthesized and converted into the respective 1-imino pyridinium ylide polymers by polymer analogous reactions on reactive precursor polymers. Quantitative conversion of the reactive groups was achieved with pentafluorophenyl ester containing polymers and newly synthesized photoreactive amines as well as by the reaction of poly(4-vinylbenzoy…