Sadiqali Cheruthazhekatt

Comprehensive high temperature two-dimensional liquid chromatography combined with high temperature gradient chromatography-infrared spectroscopy for the analysis of impact polypropylene copolymers.

Impact polypropylene copolymers (IPC) are extremely complex materials that can only be effectively analysed by multidimensional analytical approaches. IPC consists of isotactic polypropylene (iPP) as the major phase, ethylene-propylene (EP) copolymers of various compositions and small amounts of polyethylene. The molecular heterogeneity of two IPC samples having different ethylene contents was studied by using a novel cross-fractionation technique, developed from a combination of various analytical separation methods into an effective characterisation tool for complex polyolefins. The initial step involves the fractionation of the sample into EP rubber, EP segmented copolymer, and iPP, by preparative temperature rising elution fractionation (TREF). The resulting fractions are still distributed with regards to chemical composition and molar mass. The separation with respect to these parameters is conducted by comprehensive HT 2D-LC. This is the first time that the individual components in all TREF fractions of an IPC are separated and analysed mutidimensionally, by both SEC-FTIR, high-temperature (HT) HPLC-FTIR, and HT 2D-LC. Molar mass analysis of the chemically homogeneous fractions from HT HPLC is accomplished by HT SEC in the second dimension of HT 2D-LC. The chemical composition of all species is determined by coupling FTIR spectroscopy to HT HPLC via an LC-transform interface. This novel approach reveals the capability of this hyphenated technique to determine the exact chemical composition of the individual components in the complex TREF fractions of IPCs. The HT HPLC-FTIR results confirm the separation mechanism in the given chromatographic system using a 1-decanol to TCB solvent gradient and a Hypercarb stationary phase. The components of differing chemical composition are separated according to the nature and length of the propylene/ethylene segments, with their arrangement in the chains strongly affecting their adsorption/desorption on the stationary phase. FTIR analysis provides information on the ethylene and propylene contents of the fractions as well as on the ethylene and propylene crystallinities.

Combination of TREF, high-temperature HPLC, FTIR and HPer DSC for the comprehensive analysis of complex polypropylene copolymers

AbstractA novel, powerful analytical technique, preparative temperature rising elution fractionation (prep TREF)/high-temperature (HT)-HPLC/Fourier transform infrared spectroscopy (FTIR)/high-performance differential scanning calorimetry (HPer DSC)), has been introduced to study the correlation between the polymer chain microstructure and the thermal behaviour of various components in a complex impact polypropylene copolymer (IPC). For the comprehensive analysis of this complex material, in a first step, prep TREF is used to produce less complex but still heterogeneous fractions. These chemically heterogeneous fractions are completely separated by using a highly selective chromatographic separation method—high-temperature solvent gradient HPLC. The detailed structural and thermal analysis of the HPLC fractions was conducted by offline coupling of HT-HPLC with FTIR spectroscopy and a novel DSC method—HPer DSC. Three chemically different components were identified in the mid-elution temperature TREF fractions. For the first component, identified as isotactic polypropylene homopolymer by FTIR, the macromolecular chain length is found to be an important factor affecting the melting and crystallisation behaviour. The second component relates to ethylene–propylene copolymer molecules with varying ethylene monomer distributions and propylene tacticity distributions. For the polyethylene component (last eluting component in all semi-crystalline TREF fractions), it was found that branching produced defects in the long crystallisable ethylene sequences that affected the thermal properties. The different species exhibit distinctively different melting and crystallisation behaviour, as documented by HPer DSC. Using this novel approach of hyphenated techniques, the chain structure and melting and crystallisation behaviour of different components in a complex copolymer were investigated systematically. Fractionation and analysis of complex ethylene -propylene copolymers by using HT-HPLC-FTIR and HT-HPLC-HPer DSC