Search results for "Molar mass"

Polymers with Side-chain Mesogenic Units

1989

Liquid crystalline (LC) polymers are usually prepared by combining formanisotropic structural units (so-called mesogenic groups) and polymer chains (Figure 1). The mesogenic groups used for this purpose are rigid rod-like or disc-like units, which are known to favour LC phases in the case of low molar mass substances. There are two main ways of combining the mesogenic groups and polymer chains. The mesogenic groups can either be incorporated actually into the polymer chains (LC main-chain polymers, see Volume 5, Chapter 38) or they can be attached to flexible polymer chains as side groups (LC side-chain polymers).

Efficient Synthesis of High Molar Mass, First- to Fourth-Generation Distributed Dendronized Polymers by the Macromonomer Approach

2003

A homologous series of first- to fourth-generation (G1±G4) dendronized macromonomers, 5, 7, 10, and 12, was synthesized, and their poly- merization behavior under radical con- ditions investigated. These conditions were thermally induced radical poly- merization (TRP) and atom-transfer radical poymerization (ATRP). TRP was applied to all monomers and gave polymers PG1±PG4, whose molar masses range from several millions for PG1 to estimated several hundreds of thousands for PG2 and PG3, and to the oligomeric regime for PG4. ATRP was applied only to the G1 and G2 monomers 5 and 7. Kinetic studies on monomer 5 provide evidence that its polymerization proceeds in a control- led fashion. The hig…

Fluorescence Correlation Spectroscopy in Dilute Polymer Solutions: Effects of Molar Mass Dispersity and the Type of Fluorescent Labeling

2015

Fluorescence correlation spectroscopy (FCS) has become an important tool in polymer science. Among various other applications the method is often applied to measure the hydrodynamic radius and the degree of fluorescent labeling of polymers in dilute solutions. Here we show that such measurements can be strongly affected by the molar mass dispersity of the studied polymers and the way of labeling. As model systems we used polystyrene and poly(methyl methacrylate) synthesized by atom transfer radical polymerization or free-radical polymerization. Thus, the polymers were either end-labeled bearing one fluorophore per chain or side-labeled with a number of fluorophores per chain proportional to…

1996

An iterative, approximative procedure is presented, to calibrate the determination of molar masses of polymers with gel-permeation chromatography, additionally using viscometry, and transformations, according to Benoit's concept of universal calibration, even if only polymers with broad molar mass distribution are available. The calculated (intermediate) values of the average molar masses from each step of iteration converge to final values. With at least two fractions of the polymers to be analyzed, and with measured intrinsic viscosities of the fractions, a calibration curve of gel-permeation chromatography and Mark-Houwink's constants can be determined. Assumptions for the use of the cal…

1995

Supramolecular structures based on 4-(3,5-dioxo-1,2,4-triazolidin-4-yl) benzoic acid (U4A) units act as effective junction zones in functionalized polybutadienes, resulting in the formation of thermoplastic elastomers. The dynamics on a molecular scale of the phenyl rings have been probed by 2H-NMR. In the polymeric system, there are three spatially separated environments, which are reflected in the mobility of the polar units. Phenyl rings which are incorporated in the structures are either rigid or undergo 180° phenyl flips. The small fraction of free functional groups move isotropically and their mobility is coupled to the dynamics of the polybutadiene matrix. In two model compounds, whe…

Continuous polymer fractionation of polysaccharides using highly substituted trimethylsilylcellulose

1998

Trimethylsilylcellulose (TMSC) was prepared from commercial cellulose with a mixture of hexamethyldisilazane and chlorotrimethylsilane in the solvent system N,N-dimethylacetamide/lithium chloride. The soluble, highly silylated polymer (degree of substitution, DS 2.9) had a molar mass M, of 500 kg/mol and a molecular non-uniformity U = (M w /M n )- 1 of 2.9. In order to investigate the principal suitability of a continuous polymer fractionation for polysaccharides like cellulose derivatives and to obtain TMSC with different molecular weights and lower non-uniformity TMSC was fractionated by means of CPF (Continuous Polymer Fractionation), well-established in the field of synthetic polymers. …

Cellulose/Water:  Liquid/Gas and Liquid/Liquid Phase Equilibria and Their Consistent Modeling

2007

Liquid/liquid and liquid/gas equilibria were measured for the water/cellulose system at 80 °C using three different polymer samples. For these experiments we prepared cellulose films of approximately 20−25 μm in thickness and determined their equilibrium swelling in water. Thereafter the polymer concentration in the mixed phase was increased by means of a stepwise removal of the volatile component, and the equilibrium vapor pressures were measured using an automated combination of head space sampling and gas chromatography. Contrary to the usual behavior of polymers, the swelling of cellulose increases as its molar mass becomes larger. The Flory−Huggins interaction parameters calculated fro…

Viscosity-molecular weight relationship for cellulose solutions in either NMMO monohydrate or cuen

2010

The intrinsic viscosities, [η], of nine cellulose samples, with molar masses from 50 × 103 to 1 390 × 103 were determined in the solvents NMMO*H2O (N-methyl morpholin N-oxide hydrate) at 80°C and in cuen (copper II-ethlenediamine) at 25°C. The evaluation of these results with respect to the Kuhn–Mark–Houwink relations shows that the data for NMMO*H2O fall on the usual straight line in the double logarithmic plots only for M ≤ 158 103; the corresponding [η]/M relation reads log ([η]/mL g−1) = –1.465 + 0.735 log M. Beyond that molar mass [η] remains almost constant up to M ≈ 106 and increases again thereafter. In contrast to NMMO*H2O the cellulose solutions in cuen behave normal and the Kuhn–…

Molecular characterization of α , β -poly(asparthylhydrazide) a new synthetic polymer for biomedical applications

1999

Abstract α , β -Poly(asparthylhydrazide) (PAHy) is a new synthetic polymer that exhibits interesting properties and is a candidate for biomedical applications. In this article the characterization of PAHy polymer by multi-angle laser light scattering (MALS) and single-capillary viscometer (SCV) detectors on-line to a size exclusion chromatography (SEC) system is reported. The SEC–MALS–SCV system furnishes exhaustive and consistent characterization of the PAHy polymer. Further, it is possible to characterize the PAHy polymer through conventional SEC and universal calibration. The universal calibration method gives intrinsic viscosity and dispersity very close to those measured by the absolut…

Entanglement Transition in Hyperbranched Polyether-Polyols

2010

Are hyperbranched polymers capable of forming entanglements? This is the central issue of this contribution. Hyperbranched polyglycerol (hbPG) samples with different molecular weights (600-106 000 g · mol(-1) ), narrow polydispersities (1.2-1.8) and high degrees of branching (≈0.6) were prepared by anionic ring-opening polymerization. The viscoelastic properties of these polymers with respect to molecular architecture and molar mass were investigated. At low molecular weights "classical" scaling behavior between zero shear viscosity and molecular weight can be observed, whereas between 3 000 and 10 000 g · mol(-1) a plateau-like area is found. The results indicate entanglement dynamics when…