Dataset Information

New Insight into Titanium-Magnesium Ziegler-Natta Catalysts Using Photoluminescence Spectroscopy.

ABSTRACT: This paper presents the results of study of titanium-magnesium catalysts often used in polymerization processes, by photoluminescence spectroscopy (PL) in combination with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The interaction of dibutyl phthalate (DBP) with MgCl2 was studied at DBPadded/Mg?=?0-1 (mol/mol). The luminescence spectra with excitation at 278 nm and the excitation spectra for main emission bands were recorded. It was shown that DBP adsorbed on magnesium chloride, both in the form of donor-acceptor complexes (D+A-) and in the form of molecular complexes. At DBPadded/Mg?<0.15, the formation of D+A- complexes occur predominantly; with an increase in DBPadded/Mg, the fraction of molecular complexes increases. Molecular complexes are destroyed during the treatment of the support by TiCl4. In this case, the structure of magnesium chloride is disordered and new coordination-unsaturated sites are formed. This work is a first attempt to apply PL spectroscopy in combination with DRIFTS spectroscopy to study titanium-magnesium Ziegler-Natta catalysts. The application of PL spectroscopy to such systems made it possible to detect interactions within and between donor molecules, which would be particularly challenging to achieve using other spectroscopic methods. Both spectroscopic methods provided crucial information about the existence of two types of complexes on the sample surface which is important for tuning the synthesis procedure of the titanium-magnesium catalysts for olefin polymerization.

SUBMITTER: Panchenko VN

PROVIDER: S-EPMC7577041 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

New Insight into Titanium-Magnesium Ziegler-Natta Catalysts Using Photoluminescence Spectroscopy.

Panchenko Valentina N VN Kostyukov Anton I AI Shabalin Anton Yu AY Paukshtis Evgeniy A EA Glazneva Tatiana S TS Kazarian Sergei G SG

Applied spectroscopy 20200618 10

This paper presents the results of study of titanium-magnesium catalysts often used in polymerization processes, by photoluminescence spectroscopy (PL) in combination with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The interaction of dibutyl phthalate (DBP) with MgCl<sub>2</sub> was studied at DBP<sub>added</sub>/Mg = 0-1 (mol/mol). The luminescence spectra with excitation at 278 nm and the excitation spectra for main emission bands were recorded. It was shown that DBP ...[more]

PMID: 32347103

Similar Datasets

Project description:Olefin polymerization using Ziegler-Natta catalysts (ZNCs) is an important industrial process. Despite this, fundamental insight into the inner working mechanisms of these catalysts remains scarce. Here, we focus on the low-? nuclei 25Mg and 35Cl for an in-depth solid-state NMR and density functional theory (DFT) study of the catalyst's MgCl2 support in binary adducts prepared by ball-milling. Besides the bare MgCl2 support and a MgCl2-TiCl4 adduct, samples containing donors that are part of the families of 2,2-dialkyl-1,3-dimethoxypropanes and phthalates used in fourth- and fifth-generation ZNCs are studied. DFT calculations indicate that the quadrupolar coupling parameters of the chlorines differ significantly between bulk and surface sites. As a result, the NMR visibility of the chlorine sites correlates with the particle size except for the adduct with 2,2-dimethyl-1,3-dimethoxypropane donor. The DFT calculations furthermore show that the surface sites are fairly insensitive to binding of different donor molecules, making it difficult to identify specific binding motives. The surface sites with large 35Cl NMR line widths can be observed using high radio frequency field strengths. For the 2,2-dimethyl-1,3-dimethoxypropane donor, we observe additional surface sites with intermediately high quadrupolar couplings, suggesting a different surface structure for this particular adduct compared to the other systems. For 25Mg, pronounced effects of donor binding on the quadrupole interaction parameters are observed, both computationally and experimentally. Again the adduct with the 2,2-dimethyl-1,3-dimethoxypropane donor shows a different behavior of the surface sites compared to the other adducts, which display more asymmetric coordinations of the surface Mg sites. Identifying specific binding motives by comparing 25Mg NMR results to DFT calculations also proves to be difficult, however. This is attributed to the existence of many defect structures caused by the ball-milling process. The existence of such defect structures both at the surface and in the interior of the MgCl2 particles is corroborated by NMR relaxation studies. Finally, we performed heteronuclear correlation experiments, which reveal interactions between the support and Mg-OH surface groups, but do not provide indications for donor-surface interactions.

Dataset Information

New Insight into Titanium-Magnesium Ziegler-Natta Catalysts Using Photoluminescence Spectroscopy.

Publications

New Insight into Titanium-Magnesium Ziegler-Natta Catalysts Using Photoluminescence Spectroscopy.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets