Search results for "Polymer fractionation"

Continuous fractionation and solution properties of PIB. I. Search for the best mixed solvent and first results of the continuous polymer fractionati…

1987

To adopt a recently developed method for large scale fractionation (CPF = continuous polymer fractionation, a special kind of counter current extraction) to polyisobutylene (PIB), a systematic search for the best mixed solvent was performed. For this purpose, the essential parts of the phase diagrams solvent/nonsolvent/PIB were determined for 21 mixed solvents by cloud-point measurements; with eight systems of special interest, the molecular weight distributions of the polymers contained in the coexisting phases were also studied. On the basis of these experiments and of considerations concerning additional criteria for the performance of the continuous counter current extraction, the mixed…

Theory-based improvements of continuous polymer fractionation demonstrated for poly(carbonate)

1992

For the first time, a quantitative theoretical analysis (liquid/liquid phase equilibria treated by means of the continuous thermodynamics) of the operating characteristics of continuous polymer fractionation (CPF) was performed. The results of these calculations were compared with data published for CPF of polyethylene. It turned out that the efficiency of the conventional CPF corresponds to approximately two theoretical plates only. For this reason, several improvements, suggested by theoretical considerations, were realized experimentally, for which purpose the system dichloromethane/diethylene glycol/bisphenol-A polycarbonate was chosen. The pulsating sieve-bottom column was replaced by …

CPF : Continuous polymer fractionation

1992

A method is presented by means of which it is possible to fractionate polymers according to their solubility on a technical scale. The CPF consists of a continuous counter-current extraction process in which a homogeneous mixture of a molecularly or/and chemically non-uniform high molecular weight product is divided into two portions of considerably lower non-uniformity. The principle of the CPF is described in general terms and examples are given for the fractionation of homopolymers.

Continuous fractionation and solution properties of PIB. II. CPF optimization

1987

The quality of polymer fractionation depends on the choice of the mixed solvent as well as on the particular conditions of operating the continuous countercurrent extraction. With a polyisobutylene (PIB) sample of medium molecular weight Mw = 98,400 g/mol and U = (Mw/Mn) − 1 = 1.4 plus the mixed solvents toluene/2-butanone (TOL/MEK) and n-heptane/2-butanone (HEP/MEK) (both giving comparably good fractionation in equilibrium experiments), possible ways to optimize the CPF were tested. The mixed solvent HEP/MEK turns out to be superior to TOL/MEK for kinetic reasons. Due to the larger gap between its density and that of the pure polymer, the coexisting phases can still move through the column…

Spherical and rod-like colloids with polymer-brush surfaces

2008

In this paper, we describe a strategy to overcome incompatibility of colloidal particles and polymer coils as well as immiscibility of spherical and rod-shaped nanoparticles. Two new types of model colloids are presented, colloidal nanospheres with hairy surfaces (spherical brushes) and polymacromonomers to represent cylindrical brushes. The spherical brushes are synthesized from polyorganosiloxane-μ-gels of diameter 20 nm by grafting onto anionically prepared polystyrene macromonomers of molecular weight M w=5000 g/mol. On average, each sphere has a surface layer of 200 polymer chains. Compatibility of spherical nanoparticles with polymer coils was probed by turbidity of as-cast films as w…

Synthesis and large scale fractionation of non-linear polymers: brushes and hyperbranched polymers

2002

Polymer brushes with poly(methyl methacrylate) (PMMA) backbone and polystyrene side chains were synthesized by radical polymerization of ω-methacryloyl-polystyrene macromonomers. Hyperbranched PMMA was obtained by means of self-condensing group transfer copolymerization of methyl methacrylate with an initiator-monomer containing a polymerizable methacryloyl moiety and an initiating silylketeneacetal function. Both non-linear products were fractionated using the method of continuous polymer fractionation, consisting in a particular type of continuous countercurrent extraction. The combination of methyl ethyl ketone (solvent) with acetone (AC) (precipitant) turned out to be suitable for the f…

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. …

The Efficiency of Polymer Fractionation at Lower Critical Solution Temperatures

1978

The efficiency of a single fractionation step (i.e. of the partition of a given polymer sample between the coexisting phases which form when its solution demixes) is governed by the variation of the mass ratio of the individual P-mers with chain length. These dependences have been measured for the system dimethoxymethane/diethylether/ polystyrene which exhibits lower critical solution temperatures by means of the Baker-Williams method and by means of g.p.c. Their comparison with the results of previous investigation on systems showing upper critical solution temperatures reveals no thermodynamic differences in the aptitude of upper and lower critical solution temperatures for fractionation …

Branched versus linear polyisoprene: Fractionation and phase behavior

2007

Abstract Branched polyisoprene (PI) was prepared from PI-macromonomers. Linear byproducts of the synthesized polymer were removed by means of inverse spin fractionation, using the solvent cyclohexane (CH) and the precipitant acetone (AC). A well-defined fraction (Mw = 17.5 kg/mol, Mw/Mn = 1.8) of the branched polyisoprene obtained in this manner was used to determine different phase diagrams with branched and/or linear PI in the mixed solvent CH/AC at 25 °C. For comparable molar masses of the polymers the two-phase area is smallest for the branched PI and slightly larger for the linear PI; in the case of the unfractionated original sample of the branched polymer one observes a pronounced pe…

1995

45 g of poly(acrylic acid) (PAA 500) with a trimodal molar mass distribution (Mw = 500 kg/mol, (Mw/Mn) −1 = 2.33) were fractionated by means of CPF (continuous polymer fractionation) in two steps using 1,4-dioxane as solvent. The counter-current extraction was performed in a glass column (length: 190 cm, diameter: 1.5 cm) filled with a network of wires, introducing the feed 75 cm from its upper end. The distribution of the highest molar mass fraction (Mw = 760 kg/mol) is unimodal and comparatively narrow ((Mw/Mn) −1 = 0.66). Indications exits that fractionation is not only taking place with respect to molar mass but also with respect to tacticity. Mit Hilfe der kontinuierlichen Polymerfrakt…