Search results for "Copolymer"

Nucleation phenomena in polymeric systems

1995

Materials formed from long flexible macromolecules differ from their small-molecule analogs, because corresponding collective length scales are distinctly larger and many dynamical phenomena are very much slower; in addition, the variation of chain length N yields a control parameter that leaves intermolecular forces invariant, but allows a stringent test of theories. These concepts are exemplified in a discussion of nucleation barriers for symmetrical polymer (A, B)-mixtures (chain lengths NA = NB = N) near the critical temperature Tc, and for symmetrical block copolymers near the (fluctuation-induced) first order transition between the disordered melt and the lamellar mesophase. While in …

Overcoming Steric Hindrance in Aryl‐Aryl Homocoupling via On‐Surface Copolymerization

2019

On-surface synthesis is a unique tool for growing low-dimensional carbon nanomaterials with precise structural control down to the atomic level. This novel approach relies on carefully designed precursor molecules, which are deposited on suitable substrates and activated to ultimately form the desired nanostructures. One of the most applied reactions to covalently interlink molecular precursors is dehalogenative aryl-aryl coupling. Despite the versatility of this approach, many unsuccessful attempts are also known, most of them associated to the poor capability of the activated precursors to couple to each other. Such failure is often related to the steric hindrance between reactants, which…

1980

Formation and behaviour of radiation induced free radicals in statistical copolymers from vinyl hydrosulfide and styrene (1:1, 1:4, and 1:10) were investigated by means of ESR spectroscopy. The corresponding homopolymers were also included in these studies. After γ-irradiation of the copolymers at 77 K and subsequent annealing to 293 K it was possible to detect thio radicals. Their relative yields were found to increase with increasing styrene content. Investigations regarding the thermal behaviour of the radiation induced radicals in the copolymers allowed the assumption of two mechanisms responsible for the formation of the thio radicals: First, the formation takes place via ion radicals …

Introducing a 1,1-diphenylethylene analogue for vinylpyridine: anionic copolymerisation of 3-(1-phenylvinyl)pyridine (m-PyPE)

2021

3-(1-Phenylvinyl)pyridine (m-PyPE), prepared by Wittig reaction from the readily available 3-benzoylpyridine, represents a structural analog of 1,1-diphenylethylene (DPE), one phenyl group being replaced by pyridine. The suitability of m-PyPE for the copolymerisation with vinylpyridine is reflected by the 13C NMR shifts of the β-carbon of 2-vinylpyridine (2-VP; 118.32 ppm) and m-PyPE (115.83 ppm, measured in CDCl3), which possess predictive character for carbanionic copolymerisation. In analogy to DPE and its manifold reported derivatives, carbanionic homopolymerisation of m-PyPE was not possible, due to its steric bulk. Copolymers of 2-VP and m-PyPE with varied composition have been synthe…

Real time optical immunosensing with flow-through porous alumina membranes

2014

Through the presentation of analytical data from bioassay experiments, measured by polarimetry, we demonstrate for the first time a real time immunoassay within a free standing macroporous alumina membrane. The 200 nm nominal pore diameter of the membrane enables flow-through, thereby providing an ideal fluidic platform for the targeted delivery of analytes to bioreceptors immobilized on the pore walls, enabling fast sensing response times and the use of small sample volumes (<100 mu L). For the immunoassay, the pore walls were first coated with the functional copolymer, copoly(DMA-NAS) using a novel coupling process, before immobilization of the allergen protein, beta-lactoglobulin, by spo…

Continuous spin fractionation and characterization by size-exclusion chromatography for styrene-butadiene block copolymers.

2005

Abstract Linear and star-shaped styrene–butadiene block copolymers synthesized by anionic polymerization of butadiene and styrene were fractionated by applying a newly developed large-scale fractionation technique, named continuous spin fractionation (CSF). Their molecular weight and polydispersity index ( d  =  M w / M n ) were measured with size-exclusion chromatography and static light scattering. For the linear triblock copolymer a fractionation via temperature variation turned out to be better suited than the usual isothermal procedure. The star-shaped polymer with the d value of 1.33 was fractionated in two CSF steps to get the targeted sample, which has a considerably more uniform st…

Free radical copolymerization of vinylidene fluoride and acrylic acid in supercritical carbon dioxide

2010

Critical Micelle Density for the Self-Assembly of Block Copolymer Surfactants in Supercritical Carbon Dioxide

1999

The parameters which influence the self-assembly of molecules in solution include the temperature and solvent quality, and this study illustrates the use of these variables to regulate the degree of association of block copolymer amphiphiles in highly compressible supercritical carbon dioxide. Small-angle neutron scattering (SANS) has been used to examine the association behavior of a block copolymer containing a CO2-phobic moiety, poly(vinyl acetate), and a CO2-philic block, poly(1,1-dihydroperfluoro-octylacrylate). By adjustment of the density of the medium through pressure and temperature profiling, the self-assembly can be reversibly controlled from unimers to core−shell spherical micel…

A combined small-angle neutron and X-ray scattering study of block copolymers micellisation in supercritical carbon dioxide

2003

Small angle neutron and X-ray scattering (SANS and SAXS) are used to investigate the monomer–aggregate transition of fluorocarbon–hydrocarbon diblock copolymers in supercritical carbon dioxide. SANS data are analyzed using a polydisperse sphere core–shell model. Synchrotron SAXS data have been collected by profiling the pressure at different temperatures, and critical micellization densities have been obtained for a series of diblock solutions. Finally pressure jump experiments, combined with synchrotron SAXS, have revealed two steps in the dynamics of the formation of the aggregates.

Dispersion Copolymerization of Vinyl Monomers in Supercritical Carbon Dioxide.

2003

The thermally initiated free-radical dispersion copolymerization of methyl methacrylate (MMA) and N,N-dimethylacrylamide (DMA) in supercritical carbon dioxide has been studied in the presence of polysiloxane surfactants. The formation of a stable latex seems to be related to the presence of at least one reactive end group in the surfactant macromolecule, thus suggesting that anchoring of the stabilizer to the surface of the growing polymer particles occurs through chemical grafting. In the case of a molar ratio of DMA to MMA lower than 0.40, microspherical copolymer particles with yields ranging from 81 to 97% were collected from batch polymerizations carried out at 65 °C and 23-28 MPa usin…