Search results for "Molar mass distribution"

1982

The molecular weight distribution (MWD) of a high polymer is calculated from a weakly perturbed Zimm-plot of the classical light scattering on dilute solutions of Gaussian polymer coils (theta state). A typical Zimm-plot is simulated corresponding to the measurements of high accuracy as would be obtained by using the laser photometer described by Hack and Meyerhoff. The accuracy as published by these authors for small dissymmetries is used. Two numerical methods for calculating the MWD are briefly described and tested, both using an empirical formula for the Laplace image of the calculated MWD.

Gamma radiation induced polymerization of vinyl monomers in dense CO2

2002

Abstract The dispersion polymerization of methyl methacrylate in dense carbon dioxide, initiated by γ-rays, utilizing different polysiloxanes as polymeric stabilizers, was investigated. The progress of the reaction, as a function of the irradiation dose, was also studied and the occurrence of a gel effect has been detected. For comparison, the dispersion polymerization has been carried out in supercritical conditions ( T =65°C and 38 MPa) in the presence of 2,2′-azobis(isobutyronitrile) (AIBN) as initiator. High molecular weight polymer (M w > 1000 kg/mol) with narrow molecular weight distribution has been obtained both with γ-rays and AIBN. The electron scanning micrographs show that regul…

1990

The anionic polymerization of tert-butyl acylate (tBuA) initiated by tert-butyl α-lithioisobutyrate was investigated in THF at 25°C. The individual oligomers were isolated and characterized by UV, IR and NMR spectroscopy. The distribution of products was determined in the range of reaction times 0,02 s ≤ t ≤ 1800 s. The oligomerization is extremely fast. Even after 0,02 s at -30°C, no residual monomer could be detected. After short reaction times the reaction mixture almost exclusively consists of linear oligomers of tBuA. This indicates that there is no termination reaction by Claisen condensation during polymerization. Nevertheless, the molecular weight distribution is rather broad (Mw/Mn…

Chain-extending of Hydroxytelechelic Polybutadiene: Synthesis and Characterization

2010

Extension of hydroxytelechelic polybutadiene oligomers ( 3200 g/mol) is performed in mild conditions, in order to avoid backbone modifications, using succinic anhydride or methylenedicyclohexyl diisocyanate. The two routes present significative extension of the initial oligomers. Extension through the anhydride route, in the presence of DCC and DMAP, leads to new hydroxytelechelic oligomers ( 8000 g/mol). Extension through the diisocyanate route, catalyzed by DBTL at 65°C leads to hydroxytelechelic oligomers of higher average molecular weight ( 20000 g/mol). New materials are characterized by FTIR/1H-NMR and changes in their Tg according to , are discussed. The influence of reaction time on…

Dichlorovanadium (IV) complexes with salen-type ligands for ethylene polymerization

2008

Vanadium complexes with tetradentate salen-type ligands were first time explored in ethylene polymerizations. The effects of the vanadium complex structure, the alkyl aluminum cocatalysts type (EtAlCl2, Et2AlCl, Et3Al, and MAO), and the polymerization conditions (Al/V molar ratio, temperature) on polyethylene yield were explored. It was found that EtAlCl2 in conjunction with investigated vanadium complexes produced the most efficient catalytic systems. It was shown, moreover, that the structural changes of the tetradentate salen ligand (type of bridge which bond donor nitrogen atoms and type of substituent on aryl rings) affected activity of the catalytic system. The complexes containing li…

Diffusiosmessungen an polymeren in lösung mittels tracer-technik

2007

A cell for measuring coefficients of diffusion and self-diffusion by tracer techniques is described. The cell consists of two Teflon disks and is of the rotational shearing type. The amount of polymer is minimal (about 0.1 ml. for both components). Labeled and unlabeled fractionated polymethacrylate of identical molecular weight distribution was used to determine diffusion coefficients in benzene and toluene. The classical optical measurement is impossible, for these solvents exhibit a refraction index very close to that of polymethacrylate. In acetone, where optical as well as tracer techniques are applicable, the measured diffusion coefficients of the two methods are in good agreement. Al…

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…

Synthesis, structural studies and reactivity of vanadium complexes with tridentate (OSO) ligand

2007

The direct reaction between [VCl(3)(thf)3] or [VO(OEt)3] and 2,2'-thiobis{4-(1,1,3,3-tetramethyl-butyl)phenol (tbopH(2)) leads to the formation of [V(2)(micro-tbop-kappa(3)O,S,O)2Cl(2)(CH(3)CN)(2)] (1).4CH(3)CN or [V(2)(micro-OEt)2(O)2(tbop-kappa(3)O,S,O)2] (2), respectively, in high yield. Compounds 1 and 2 were characterized by chemical and physical techniques including X-ray crystallography and variable temperature magnetic susceptibility studies (J = -29.1 cm(-1)) for 1. Complexes 1 and 2 were supported on MgCl2 and when activated with aluminium alkyls, were found to effectively polymerize ethene to produce polyethylene with a narrow molecular weight distribution M(w)/M(n) approximately…

Apparent and Real Distribution in GPC (Experiments with PMMA Samples)

1971

Abstract Molecular weight distribution curves obtained by GPC are broadened if concentration and flow rate are fixed in the usual range. Therefore, the apparent nonuniformity U app of the samples is larger than the real non-uniformity U = (Mw/Mn) −1. For a number of fractionated and unfractionated samples of polymethyl methacrylate we determined M n and M w by osmotic, light-scattering, and viscosity measurements. Thus, the real value of U can be compared to U app obtained by GPC at different concentrations and flow rates, υ. The excess nonuniformity U exc is evaluated as function of concentration c, polydispersity, molecular weight, and flow rate. For c = 0 and υ = 0, U exc is not far from…

The Fractal Approach to Secondary Mechanisms in SEC

2007

Abstract Size‐exclusion chromatography (SEC) is one of the most used experimental techniques to characterize polymers in solution; it has been applied to interpret the elution behaviour of many polymer‐solvent systems in five types of column packings. The experimental data have revealed that the classical universal calibration is not accomplished. Deviations from a unique curve are a consequence of two effects: entropic (exclusion by size) and enthalpic (binary and ternary interactions between solvent, polymer, and gel), which results in secondary mechanisms accompanying the main “ideal” SEC separation mechanism. Therefore, three approaches of building a calibration curve have been compared…