Dataset Information

Nano-Dispersed Ziegler-Natta Catalysts for 1 ?m-Sized Ultra-High Molecular Weight Polyethylene Particles.

ABSTRACT: A catalytic approach to synthesize microfine ultra-high molecular weight polyethylene (UHMWPE) particles was proposed based on the exploitation of nano-sized catalysts. By utilizing MgO nanoparticles as a core material, a Ziegler-Natta-type MgO/MgCl2/TiCl4 core-shell catalyst with the particle size in a nano-range scale was prepared in a simple preparation step. The organic modification of MgO surfaces prior to catalyzation prevented agglomeration and facilitated the full dispersion of catalyst particles at a primary particle level for the first time. The nano-dispersed catalysts successfully afforded a direct access to UHMWPE having the particle size in the range of 1-2 ?m at a reasonable activity. Extremely fine polymer particles yielded several advantages, especially at a significantly lower fusion temperature in compression molding.

SUBMITTER: Chammingkwan P

PROVIDER: S-EPMC6232879 | biostudies-literature | 2018

REPOSITORIES: biostudies-literature

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Nano-Dispersed Ziegler-Natta Catalysts for 1 μm-Sized Ultra-High Molecular Weight Polyethylene Particles.

Chammingkwan Patchanee P Bando Yusuke Y Terano Minoru M Taniike Toshiaki T

Frontiers in chemistry 20181030

A catalytic approach to synthesize microfine ultra-high molecular weight polyethylene (UHMWPE) particles was proposed based on the exploitation of nano-sized catalysts. By utilizing MgO nanoparticles as a core material, a Ziegler-Natta-type MgO/MgCl<sub>2</sub>/TiCl<sub>4</sub> core-shell catalyst with the particle size in a nano-range scale was prepared in a simple preparation step. The organic modification of MgO surfaces prior to catalyzation prevented agglomeration and facilitated the full d ...[more]

PMID: 30460228

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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

Nano-Dispersed Ziegler-Natta Catalysts for 1 ?m-Sized Ultra-High Molecular Weight Polyethylene Particles.

Publications

Nano-Dispersed Ziegler-Natta Catalysts for 1 μm-Sized Ultra-High Molecular Weight Polyethylene Particles.

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