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BACKGROUND: Preparative successive solution fractionation (SSF) is a powerful technique for obtaining narrow-dispersity fractions on a multi-gram scale of high-density polyethylene (HDPE). in a previous paper, the operative separation mechanisms during SSF of a broad HDPE in cyclohexanone were studied. Two mechanisms, and not only one as expected from the literature, contribute to the separation of HDPE molecules according to their molar mass (MM). The very low MM chains are separated by a solid-liquid (S-L) mechanism, while the longer chains are isolated by a liquid-liquid (L-L) phase separation. In the present paper, the influence of a poorer solvent, diphenyl ether, is reported. RESULTS: It is shown that the relative importance of the S-L mechanism with respect to the L-L one is altered by the use of this solvent. The L-L temperature range is increased in diphenyl ether while the S-L transition temperature remains unchanged. Consequently, the SSF efficiency is improved. Large amounts (on a gram scale) of narrow-dispersity fractions are isolated, mainly by the L-L mechanism. Polydispersities are about 1.5 (compared to 2.0 for cyclohexanone) and a broader MM range of closer molar mass distribution fractions is available. CONCLUSION: This work demonstrates that the use of diphenyl ether, a poorer solvent than cyclohexanone (always used as SSF solvent for polyethylene in the literature), leads to an improvement of SSF efficiency for an essentially linear HDPE. The differences of behaviour during the separation with cyclohexanone or diphenyl ether are explained by the establishment of a phase diagram. (C) 2009 Society of Chemical Industry

BACKGROUND: Preparative fractionation techniques are currently used in order to obtain large amounts of polyethylene fractions. Preparative successive solution fractionation (SSF) and temperature rising elution fractionation (TREF) are compared as regards obtaining, at a multi-gram scale, low-dispersity fractions of high-density polyethylene (HDPE). The operative separation mechanisms during a SSF of a broad HDPE, which are not yet totally elucidated, are also studied in this work. RESULTS: SSF and TREF approaches lead to the separation of HDPE macromolecules according to their molar masses. If very homogeneous fractions (dispersities from 1.1 to 1.3) are isolated in TREF at the lowest elution temperature, the collected mass is too low. At higher elution temperatures, the fractions have too broad a molar mass distribution (dispersities from 2.7 to 3.7). With the SSF procedure, dispersities are not as low as for the first TREF fractions. But, the relative weight fraction is better distributed between the different extraction temperatures. The molar mass distribution exhibits a dispersity of around 1.9. CONCLUSION: The SSF method is the most suitable way to obtain large gram amounts of low-dispersity (ca 2) HDPE fractions over a wide molar mass range. Complementary gram-scale rheological characterization is thus possible enabling a better comprehension of the SSF mechanism. Liquid-liquid demixing is the main mechanism in SSF, but its relative importance depends on polymer characteristics and solvent quality. (C) 2008 Society of Chemical Industry

We characterize sparsely and randomly branched polycarbonate and fractions thereof by a combination of solution and rheological techniques, and we compare the observations with the results of Monte Carlo simulations as well as tube-based modeling. On-line coupling of size exclusion chromatography with intrinsic viscosity (SEC-IV) yields values for the viscosity branching index g', which deviate significantly from linear behavior above approximately 0.3 branches per chain. The experimental g' also follows closely the predictions for the geometric branching factor g calculated by Monte Carlo simulations of the polymer structure across the entire molar mass distribution (g=g'). The Monte Carlo simulations provide an explicit description of the molecular architectures present and can therefore in principle be used to test models suitable for sparsely branched polymers. Experimental dynamic moduli of unfractionated and fractionated samples are compared with predictions of a tube-based model recently published in van Ruymbeke et al. [J. Non-Newt. Fluid Mech. 128, 7-22 (2005b)]. When the model is calibrated for polydisperse linear polycarbonate, discrepancies between the predicted and measured dynamic moduli are clearly observed at levels well below the detection limit of branching by the SEC-IV coupling method. The comparison between observed and predicted moduli is therefore a very sensitive method for the detection of sparse long chain branching in poorly and moderately entangled polymers, of which polycarbonate is a good example. (c) 2006 The Society of Rheology.

We have developed a sensitive method to detect very low levels of long chain branching in sparsely branched polymers and applied it to high-density polyethylene samples with broad molar mass distribution obtained by Ziegler-Natta, Phillips, and metallocene catalysis. We compare experimental dynamic moduli with predicted values. The predicted moduli, which are only valid for truly linear chains, are computed from a known molar mass distribution by the application of a modified time-dependent diffusion reptation model described in [van Ruymbeke et al., Macromolecules 35, 2689 (2002)]. Discrepancies between experimental and predicted moduli are observed at branching levels below the usual detection limit Of C-13 nuclear magnetic resonance (about I branch per 10000 carbon atoms). Our method is easier to implement and the results more clearcut than those obtained by the zero-shear viscosity method. The sensitivity is comparable with the activation energy spectrum method described in [Wood-Adams et al., Macromolecules 33, 7489 (2000)]. The use of our method is however not restricted to thermorheologically complex polymers. The interest of polymer fractionation is also demonstrated for the detection of extremely low levels of long chain branching. (c) 2005 The Society of Rheology.

Owing to their low polydispersity and their well controlled molecular architecture, 3-arms stars polystyrenes made by anionic synthesis are suitable models to study the solution proper-ties of long chain branched polymers. A fine characterization of such polymers by size exclusion chromatography-viscometry has shown that they often contain unwanted linear chains, leading to chromatograms presenting overlapping peaks. A mathematical procedure has been developed in order to deconvolute these chromatograms and has been validated, thanks to blends of polystyrene standards. It allows one to calculate the purity of the sample as well as the intrinsic viscosity and molar mass distribution of each component. For stars with three arms of the same length, branching parameters have also been calculated and a viscosity law has been established. (C) 2002 Elsevier Science Ltd. All rights reserved.

In this study we correlate parameters describing molecular structure (molar mass distribution, short chain branching content, intermolecular heterogeneity) of different ethylene-hexene Cr-catalyzed copolymers, with slow crack growth and rapid crack propagation resistances, respectively measured with Bent Strip and Charpy tests. The PTREF technique, coupled with classical techniques, was used. Two new indices were proposed to correlate mechanical properties and molecular structure. (C) 2001 John Wiley & Sons, Inc.

HTX, a poly(aryletherketone-co-sulfone), is characterized in solution in concentrated sulfuric acid. Upon dissolution in concentrated H2SO4, HTX is chemically modified by sulfonation of phenyl rings. The modification of the chemical structure is studied with a model compound by means of IR spectroscopy. The increase of the molar mass corresponding to a complete sulfonation is determined by means of mass spectrometry. Light scattering and F-19 NMR measurements are performed in order to obtain the weight- (M(w)BAR)s and number-average (M(n)BAR)s molar masses of sulfonated HTX samples. (M(w)BAR)s values allow the determination of the Mark-Houwink-Sakurada relationship for HTX in 99,5% H2SO4 at 25-degrees-C.

A new method for poly(ether ether ketone) (PEEK) molecular-mass characterization by room-temperature (r.t.) size (steric) exclusion chromatography (s.e.c.) based on a derivatization procedure that improves the polymer solubility is described. Upon dissolution in 99.5% sulfuric acid at room temperature, PEEK is chemically modified by sulfonation of phenyl rings without polymer degradation. As complete sulfonation is achieved, the reproducibility of the chemical modification is ensured as well as the increase of molecular mass. Sulfonated PEEK is soluble at room temperature in different solvents suitable for s.e.c. N-Methyl-2-pyrrolidine (NMP) is selected as PEEK s.e.c. solvent. Owing to the polyelectrolyte nature of sulfonated PEEK, a salt (0.1 M LiBr) is added to NMP. Various broad-dispersity PEEK standards are used to establish specific and universal calibrations. The viscosity laws of sulfonated PEEK in NMP + LiBr (0.1 M), in methanesulfonic acid (MSA) and in 99.5% H2SO4 are determined. As sulfonated PEEK is a hygroscopic polymer, some spectroscopic methods are developed to determine the absolute concentration of the standards in order to perform accurate viscometric experiments giving the Mark-Houwink-Sakurada parameters in NMP-salt and in MSA. The s.e.c. universal calibration curve is constructed with poly(methyl methacrylate) narrow-dispersity standards.

HTX, a poly(aryletherketone-co-sulfone), is characterized by size exclusion chromatography (SEC) at room temperature. As HTX is not soluble in any solvent compatible with the SEC instrumentation, a derivatization procedure is applied in order to prepare a modified copolymer with improved solubility properties. This derivatization consists in a sulfonation by concentrated sulfuric acid. The derivative polymer is soluble in N-methyl-2-pyrrolidone (NMP), a classical SEC solvent. Sulfonated HTX (HTXS) is a polyelectrolyte. Consequently, a salt is added to NMP to perform reliable viscometric and SEC analyses. The SEC method is standardized with the establishment of the universal calibration with poly(methyl methacrylate) standards and the determination of the Mark-Houwink-Sakurada relationship of HTXS in NMP-salt at 25-degrees-C. Finally, the reliability of the derivatization procedure and of the SEC method is confirmed by comparison with molecular masses from NMR.

Some poly(ether ether ketone) (PEEK) samples were analysed by light scattering (l.s.) before and after complete sulfonation. Afterwards, the average molecular masses and molecular-mass distribution of the same PEEK samples are determined by high-temperature size (steric) exclusion chromatography (s.e.c.) for unmodified PEEK and by room-temperature s.e.c. (r.t.s.e.c.) for totally sulfonated PEEK. From this work, it appears that l.s. and s.e.c. measurements using sulfonated or unsulfonated PEEK sample give identical results within the limit of the s.e.c. and l.s. accuracy. This verification assesses the reliability of the derivatization method used to perform r.t.s.e.c. It is also shown that number-average molecular masses ((M) over bar(n)) of fully fluoroarylketone-terminated PEEK determined by F-19 nuclear magnetic resonance experiments agree very well with (M) over bar(n) values from s.e.c. These results support the validity of both s.e.c. methods used in this work. Finally, a PEEK-carbon fibre composite is characterized. The fibre content is evaluated. The derivatization process is applied to the matrix and the molecular parameters are obtained by r.t.s.e.c.

Attempts have been made to determine the weight average molecular weight ( M W ), the radius of gyration ( R G ) and the second virial coefficient (A2) of five samples of poly(ether-ether-ketone) (PEEK) by light scattering (LS) in concentrated sulphuric acid. Account has been taken of the sulphonation of the polymer. Correlations between LS-molecular weights, melt viscosities and intrinsic viscosities in sulphuric acid or in a 50 50 phenol-trichlorobenzene mixture have been established. Gel permeation chromatography (g.p.c.) analyses at 115°C have been performed in this latter solvent and two calibration methods were compared.