Stepan Podzimek

Round Robin Test on the Molecular Characterization of Epoxy Resins by Liquid Chromatography

ABSTRACT This paper reports results acquired during the IUPAC Project No. 1999-021-1-400 Round Robin Test on the Molecular Characterization of Epoxy Resins by Liquid Chromatography. The results obtained by size exclusion chromatography (SEC) with column calibration are compared with those determined by SEC combined with a light scattering or a viscometric detector and absolute methods of molar mass determination. The influence of SEC experimental conditions on the obtained results is studied.

Estimation of conformational characteristics of bisphenol-A based poly(hydroxyethers)

Two samples of bisphenol-A based epoxy resins (poly(hydroxy ethers)) were fractionated by precipitation. The fractions were characterized by the weight-average molecular weight (1.3<Mw×10−3<40) and the intrinsic viscosity in tetrahydrofuran and chloroform. Theories based on the worm-like touched-bead model were used to treat the molecular-weight dependence of the intrinsic viscosity and to estimate the conformational characteristics (Kuhn statistical segment length lK, Flory characteristic ratio C∞, and steric factor σ). Low values of these characteristics indicating rather high flexibility of the chain are discussed.

Enhanced multiparametric hyaluronan degradation for production of molar-mass-defined fragments

Hyaluronic acid (HA) is known to serve as a dynamic mediator intervening in many physiological functions. Its specific effect has been repeatedly confirmed to be strongly influenced by the molecular size of hyaluronan fragments. However common technological approaches of HA fragments production have their limitations. In many cases, the final products do not meet the strict pharmaceutical requirements, specifically due to size polydispersity and reaction contaminants. We present novel methodology based on combination of unique incidental ability of the plant-derived protease papain to split the glycosidic bonds and an indispensable advantages of biocompatible macroporous material with incorporated ferrous ions serving as carrier for covalent papain fixation. This atypical and yet unpublished highly efficient multiparametric approach allows enhanced HA fragmentation for easily and safely producing molar-mass-defined HA fragments with narrow size distribution. Native polyacrylamide gel electrophoresis (PAGE) and size exclusion chromatography/multi-angle light scattering (SEC-MALS) confirmed the effectiveness of our multiparametric approach.

A Review of the Application of Liquid Chromatography to the Characterization of Epoxy Resins

Abstract This review covers selected literature in the field of liquid chromatographic characterization of epoxy resins, including a number of the authors original examples of the applications of various chromatographic techniques. Several derivatization reactions are presented that can be used for the identification of components with functional groups other than epoxy. Size exclusion chromatography (SEC) coupled with a multi-angle light scattering (MALS) detector is demonstrated as the most efficient method of the determination of molar mass distribution. The number average molar masses determined by SEC-MALS are compared with those measured by vapor phase osmometry.

Characterization of Molecular Structure of Emulsion Acrylic Microgels: Exploring the Impact of Molar Mass on Coating Properties of Self-Cross-Linkable Latexes

ABSTRACT Self-cross-linkable latexes of core–shell microgel particles were synthesized by the emulsion polymerization of acrylic monomers. The molar mass of copolymers forming the shell layer was gradually reduced by isooctyl 3-mercaptopropionate included in the synthesis of the shell layers. The molar mass distribution of latex particles was determined using size exclusion chromatography and asymmetric flow field-flow fractionation, respectively, both separation methods being coupled with a multiangle light scattering detector. The results confirmed theoretical predictions and described empirically the effects of molar mass of the shell layer copolymer on decreasing the minimum film-forming temperature and influencing the end-use properties of coatings. GRAPHICAL ABSTRACT

Investigation of the effect of molar mass on coating properties of self-crosslinking latexes based on acrylic microgels

Abstract The effect of reducing the molar mass of the shell layer of core–shell latex particles on film-forming and final coating properties of self-crosslinking latexes was investigated. Latex particles were prepared by the semi-continuous non-seeded emulsion polymerization of methyl methacrylate, butyl acrylate and methacrylic acid as main monomers. The particle core was slightly cross-linked (using a constant amount of allyl methacrylate as a comonomer) to prevent the copolymers forming the core phase from migration into the shell phase. For interfacial cross-linking, diacetone acrylamide was copolymerized into the shell layer of latex particles to provide sites for subsequent reaction with adipic acid dihydrazide. The molar mass of copolymers forming the shell layer was systematically varied by isooctyl 3-mercaptopropionate chain transfer agent included in the synthesis of each of the shell layers and the molar mass distribution was determined using size exclusion chromatography coupled with a multi-angle light scattering detection. Fundamental properties of latexes and cast films were systematically compared. These properties included minimum film-forming temperature, pendulum hardness, adhesion, impact resistance, stress–strain properties as well as the characterization of water absorption. The results confirmed theoretical predictions and described empirically the effects of reducing the molar mass of the shell layer copolymer on final properties of coating films.

Getting Closer to Absolute Molar Masses of Technical Lignins

Abstract Determination of molecular weight parameters of native and, in particular, technical lignins are based on size exclusion chromatography (SEC) approaches. However, no matter which approach is used, either conventional SEC with a refractive index detector and calibration with standards or multi‐angle light scattering (MALS) detection at 488 nm, 633 nm, 658 nm, or 690 nm, all variants can be severely erroneous. The lack of calibration standards with high structural similarity to lignin impairs the quality of the molar masses determined by conventional SEC, and the typical fluorescence of (technical) lignins renders the corresponding MALS data rather questionable. Application of MALS detection at 785 nm by using an infrared laser largely overcomes those problems and allows for a reliable and reproducible determination of the molar mass distributions of all types of lignins, which has been demonstrated in this study for various and structurally different analytes, such as kraft lignins, milled‐wood lignin, lignosulfonates, and biorefinery lignins. The topics of calibration, lignin fluorescence, and lignin UV absorption in connection with MALS detection are critically discussed in detail, and a reliable protocol is presented. Correction factors based on MALS measurements have been determined for commercially available calibration standards, such as pullulan and polystyrene sulfonate, so that now more reliable mass data can be obtained also if no MALS system is available and these conventional calibration standards have to be resorted to.

Application of A4F-MALS for the Characterization of Polymers Prepared by Emulsion Polymerization: Comparison of the Molecular Structure of Styrene-Acrylate and Methyl Methacrylate-Acrylate Copolymers

ABSTRACT In this paper, organic asymmetric flow field flow fractionation coupled to a multi-angle light scattering detector is presented as a very efficient tool for the characterization of copolymers prepared by emulsion polymerization. The molar mass distribution and the extent of branching of styrene–acrylate copolymers have been compared with corresponding copolymers of methyl methacrylate. It has been found that the presence of acrylate monomer results in the increase of molar mass and formation of branched macromolecules due to intermolecular chain transfer to polymer similarly as in case of methyl methacrylate–acrylate copolymers. However, the effect is far less pronounced. GRAPHICAL ABSTRACT