In-depth characterization of polyolefin plastomers/elastomers (ethylene/1-octene copolymers) through hyphenated chromatographic techniques.

The chemical composition distribution (CCD) of three single site made ethylene/1-octene copolymers was investigated through offline-hyphenation of solvent gradient interaction chromatography (SGIC) with 1H NMR. Thus, a clear, non-linear correlation between SGIC elution time and chemical composition was found under the specific measurement conditions applied here. The application of 1H NMR as detection allowed to determine the CCD with unprecedented accuracy. 2D-LC of the copolymers revealed the correlation between CCD and molar mass distribution (MMD) in a quantitative manner. Furthermore, this approach allowed a comparison between the response behavior of an evaporative light scattering detector (ELSD, semi-quantitative, commonly applied in SGIC) and that of an infrared (IR) detector (quantitative, commonly applied in SEC). As a result, it could be shown that ELSD results are close to IR results for the system investigated here, in other words, the often-criticized semi-quantitative response behavior of the ELSD is affecting results in an acceptable manner.

High performance liquid chromatography of polyolefin plastomers/elastomers (ethylene/1-octene copolymers) - Comparison of different solvent systems.

A series of ethylene/1-octene copolymers with different chemical composition was separated in six binary mobile phases using solvent gradients and a column packed with porous graphite Hypercarb™. It was found that the elution volumes of the samples were to a larger extent influenced by the choice of desorption promoting solvent (desorli: 1,2-dichlorobenzene vs. 1,2,4-trichlorobenzene) than by the choice of adsorption promoting solvent (2-ethyl-1-hexanol, 1-decanol, n-decane). Elution volumes increased with decreasing number of chlorine atoms in the desorlis as well as with increasing polarity of the adsorlis. The resolution of HPLC systems depended pronouncedly on the choice of solvent pair: While in the majority of the tested HPLC systems, the chromatograms of the polymer samples indicate a shoulder, in n-decane→TCB the samples eluted without indication of a shoulder. In addition to the influence of different solvents on the samples elution behavior, the response of the employed detector, an evaporative light scattering detector (ELSD), was investigated. Its response was found to depend pronouncedly on the nature of the used solvents. Overall, the solvent pair 1-decanol→TCB appears to be the optimal compromise between the considered parameters and thus the best choice for HPLC of ethylene/1-octene copolymers.

Selective chromatographic separation of polycarbonate according to hydroxyl end-groups using a porous graphitic carbon column.

Porous graphitic carbon (PGC) has shown unique separation efficiency in liquid chromatography for a wide range of substance classes. In the characterization of polymers PGC has particularly been used for analysis of polyolefins. Its retention mechanisms differ dramatically from those of silica-based stationary phases and therefore allow interesting applications. Due to its unprecedented retention mechanisms PGC does not only promise good separation performance for polyolefins but also for more polar polymers such as Polycarbonate (PC). In this study, we determined the critical conditions of PC on PGC using CHCl3/dichlorobenzene (DCB) and CHCl3/trichlorobenzene (TCB) as eluents achieving separations according to hydroxyl end-groups, which was confirmed by MALDI-TOF-MS analysis. As the content of TCB at the critical point was lower compared to that of DCB, it was concluded that TCB is a stronger desorption promoting eluent than DCB for the present system. The temperature influence on the critical point was then investigated revealing that with increasing temperature the content of desorption promoting eluent has to be raised in order to achieve critical conditions. Furthermore, a peak shifting over time was observed using TCB as desorption promoting eluent, which was attributed to irreversibly adsorbed PC on the column material. However, when a flow cell-IR detector was applied monitoring the eluted samples, a recovery rate close to 100% was found.

Estimation of critical conditions of polymers based on monitoring the polymer recovery.

Liquid chromatography at critical conditions (LCCC) is a very attractive chromatographic technique on the border between the size exclusion and liquid adsorption mode of the liquid chromatography. The strong interest in LCCC arises from the fact that it is well suited to analyze the block lengths in segmented copolymers or the heterogeneities with regard to end groups present, for example, in functionalized polymers e.g., telechelics. In this paper a new method for identification of the critical conditions of synthetic polymers is proposed, which requires only one polymer sample with higher molar mass. The method is based on monitoring the recovery of the polymer sample from a column. The composition of the mobile phase is modified until the polymer sample is fully recovered from the column. The corresponding composition of the mobile phase is composition corresponding to LCCC. This new method was applied for the determination of critical conditions for polyethylene, syndiotactic polypropylene and isotactic polypropylene. The results of the new method will be compared to those of classical approaches and advantages will be pointed out.

Separation of maleic anhydride grafted polypropylene using multidimensional high-temperature liquid chromatography.

Functionalization addresses a property gap of polyolefins and opens new perspectives due to improved surface properties in applications like composites (e.g., glass fiber reinforced polypropylene) and anti-corrosive coatings for metals. Various techniques have been developed to characterize functionalized polyolefins, yet no analytical approach addressing their chemical heterogeneity exists. Using High Temperature Size Exclusion Chromatography (HT-SEC) coupled to infrared spectroscopy we could show for two model samples of polypropylene grafted maleic anhydride (PP-g-MA), differing in their nominal MA content, that the grafting density increases with decreasing molar mass. Crystallization Analysis Fractionation (CRYSTAF) does not enable to separate these samples according to their composition to the extent required. Yet, when using High Temperature High Performance Liquid Chromatography (HT-HPLC), with either silica gel or Mica as stationary phase and a gradient mobile phase, a deformulation into a grafted and a non-grafted fraction could be achieved. This was confirmed by analyzing the eluted fractions by infrared spectroscopy. Hyphenating the separation according to composition with a separation according to molar mass (HT-HPLC x HT-SEC) enabled for the first time to reveal the bivariate distribution of PP-g-MA with regard to the molar mass and composition. Using on-line infrared detection quantitative information on the compositional and molar mass parameters of the individual fractions could be obtained.

Separation of bimodal high density polyethylene using multidimensional high temperature liquid chromatography.

High-temperature two-dimensional liquid chromatography (HT 2D-LC) using HT-HPLC as first dimension and HT-SEC as second dimension holds enormous potential to investigate the distribution according to molar mass and chemical composition of bimodal high density polyethylene (BiHDPE), as it avoids drawbacks of crystallization-based techniques. In this study, we have stepwise optimized the chromatographic parameters of 1D, comprising gradient slope and temperature, using model homo- and copolymers of ethylene with the aim to minimize the impact of molar mass on the compositional separation. Then the HT-HPLC was hyphenated to HT-SEC and optimum conditions for the volume of the sample transfer loop were probed with regard to the resolution of BiHDPE into the individual constituents HDPE and LLDPE. A particular important aspect was the use of infrared (IR) detection, and the demands it puts on the chromatographic aspects: We have shown that IR detection can be successfully applied in HT 2D-LC of BiHDPE, which is broadly distributed with regard to short chain branching and molar mass, only when the separation in 2D is optimized with regard to chromatographic resolution. As final result a bimodality is evident in the contour and the 3D surface plots as well as in both HPLC and SEC projections generated from HT 2D-LC.

Application of the evaporative light scattering detector to analytical problems in polymer science.

Over the last two decades the evaporative light scattering detector (ELSD) has found more and more use in liquid chromatography (LC) of synthetic polymers. The reason behind this is that it can be used for a significantly wider variety of analyte/solvent combinations. Although in many of the applications the ELSD has been used in a qualitative manner, it can also be used quantitatively. For quantitative interpretation of analyses it is, in the case of synthetic polymers, essential to know how parameters, which characterize a polymer sample (i.e., molar mass and chemical composition), as well as parameters, which are a consequence of the LC separation (i.e., composition and flow rate of the mobile phase, its composition), influence the response of the ELSD. This review gives a tabulated overview over applications of ELS detectors in polymer analysis. The influence of parameters arising from either the polymer side or the chromatographic separation is discussed in detail and, in addition, the influence of the ELS detector's running conditions, i.e. type and flow rate of gas and temperature of nebulizer and evaporator), will be reviewed. This information will prove valuable whenever the calibration of an ELSD for the quantitative analysis of synthetic polymers is attempted.

Study of the abnormal late co-elution phenomenon of low density polyethylene in size exclusion chromatography using high temperature size exclusion chromatography and high temperature asymmetrical flow field-flow fractionation.

The elution behaviour of linear and branched polyethylene samples in SEC was studied. For the branched samples an abnormal late co-elution of large and small macromolecules manifests itself as an abnormal re-increase of the molar mass and the radius of gyration values detected with multi angle light scattering at high elution volumes in SEC. The late co-elution of small and large macromolecules cannot be explained by the SEC mechanism alone. The influence of several experimental parameters on the late co-elution was studied. It was found that the type of SEC column and the flow rate have a significant influence. The late eluting part of the sample was fractionated and separated by HT-SEC- and HT-AF4-MALS. The different results of both methods have been discussed with the aim to find possible explanations for the late elution. The experiments indicate that especially large branched structures show an increased tendency for the phenomenon.

Characterization of branched ultrahigh molar mass polymers by asymmetrical flow field-flow fractionation and size exclusion chromatography.

The molar mass distribution (MMD) of synthetic polymers is frequently analyzed by size exclusion chromatography (SEC) coupled to multi angle light scattering (MALS) detection. For ultrahigh molar mass (UHM) or branched polymers this method is not sufficient, because shear degradation and abnormal elution effects falsify the calculated molar mass distribution and information on branching. High temperatures above 130 °C have to be applied for dissolution and separation of semi-crystalline materials like polyolefins which requires special hardware setups. Asymmetrical flow field-flow fractionation (AF4) offers the possibility to overcome some of the main problems of SEC due to the absence of an obstructing porous stationary phase. The SEC-separation mainly depends on the pore size distribution of the used column set. The analyte molecules can enter the pores of the stationary phase in dependence on their hydrodynamic volume. The archived separation is a result of the retention time of the analyte species inside SEC-column which depends on the accessibility of the pores, the residence time inside the pores and the diffusion ability of the analyte molecules. The elution order in SEC is typically from low to high hydrodynamic volume. On the contrary AF4 separates according to the diffusion coefficient of the analyte molecules as long as the chosen conditions support the normal FFF-separation mechanism. The separation takes place in an empty channel and is caused by a cross-flow field perpendicular to the solvent flow. The analyte molecules will arrange in different channel heights depending on the diffusion coefficients. The parabolic-shaped flow profile inside the channel leads to different elution velocities. The species with low hydrodynamic volume will elute first while the species with high hydrodynamic volume elute later. The AF4 can be performed at ambient or high temperature (AT-/HT-AF4). We have analyzed one low molar mass polyethylene sample and a number of narrow distributed polystyrene standards as reference materials with known structure by AT/HT-SEC and AT/HT-AF4. Low density polyethylenes as well as polypropylene and polybutadiene, containing high degrees of branching and high molar masses, have been analyzed with both methods. As in SEC the relationship between the radius of gyration (R(g)) or the molar mass and the elution volume is curved up towards high elution volumes, a correct calculation of the MMD and the molar mass average or branching ratio is not possible using the data from the SEC measurements. In contrast to SEC, AF4 allows the precise determination of the MMD, the molar mass averages as well as the degree of branching because the molar mass vs. elution volume curve and the conformation plot is not falsified in this technique. In addition, higher molar masses can be detected using HT-AF4 due to the absence of significant shear degradation in the channel. As a result the average molar masses obtained from AF4 are higher compared to SEC. The analysis time in AF4 is comparable to that of SEC but the adjustable cross-flow program allows the user to influence the separation efficiency which is not possible in SEC without a costly change of the whole column combination.

Optimisation of ambient and high temperature asymmetric flow field-flow fractionation with dual/multi-angle light scattering and infrared/refractive index detection.

Asymmetric flow field-flow fractionation (AF4) enables to analyse polymers with very high molar masses under mild conditions in comparison to size exclusion chromatography (SEC). Conventionally, membranes for AF4 are made from cellulose. Recently, a novel ceramic membrane has been developed which can withstand high temperatures above 130 degrees C and chlorinated organic solvents, thus making it possible to characterise semicrystalline polyolefins by HT-AF4. Two ceramic membranes and one cellulose membrane were compared with regard to their quality of molar mass separation and the loss of the polymer material through the pores. Separating polystyrene standards as model compounds at different cross-flow gradients the complex relationship between cross-flow velocity, separation efficiency, the molar mass and peak broadening could be elucidated in detail. Moreover, the dependence of signal quality and reproducibility on sample concentration and mass loading was investigated because the evaluation of the obtained fractograms substantially depends on the signal intensities. Finally, the performance of the whole system was tested at high temperature by separating PE reference materials of high molar mass.

Elution behavior of polyethylene in polar mobile phases on a non-polar sorbent.

Linear polyethylene standards in the range of 1-500 kg/mol, dissolved in 1,2,4-trichlorobenzene, were injected into a column packed with oligo(dimethylsiloxane) modified silica gel. Fifteen polar solvents (cyclohexanone, cyclohexylacetate, cyclohexanol, nonylalcohol, dimethylformamide, dimethyl sulfoxide, ethylene- and diethylene glycol monobutyl ether, benzylalcohol, hexylacetate, bis(2-ethyl-hexyl)phthalate, N,N-dimethylacetamide, propylene carbonate, dipropylene glycol and N-methyl-pyrrolidone) were evaluated as mobile phases. Depending on the type of mobile phase evaluated, different elution behaviors are observed for polyethylene: (1) polyethylene was eluted in the size exclusion mode, (2) polyethylene was eluted together with the sample solvent peak at constant elution volume, (3) polyethylene was partially or fully retained on the column. The retained polymer was easily removed from the column by injecting a small volume of trichlorobenzene. The use of ethylene glycol monobutyl ether as the mobile phase enabled separation of the polyethylene from polypropylene. In this case polypropylene is eluted in the size exclusion mode, while polyethylene is eluted at a constant elution volume or remains in the column.