ABSTRACT
Ansa-zirconocene complexes are widely employed as precatalysts for olefin polymerization. Their synthesis generally leads to mixtures of their rac and meso isomers, whose separation is often problematic. In this contribution, we report on the synthesis of a novel silyl-bridged bis(indenyl)-based metallocene, and on the separation of its rac and meso isomers by simple recrystallization from toluene. The two complexes, activated by methylaluminoxane (MAO), have been used as precatalysts in ethylene/1-hexene copolymerization. Regardless of the reaction conditions, the meso complex outperformed its rac congener. A similar trend was observed by performing the process in the presence of the silica-supported versions of the complexes. This is remarkable, since meso metallocenes generally display lower activities than their rac analogues. Furthermore, the meso isomer generates polymer products that are more in line with the targets for the preparation of a bimodal PE grade made of a lower-MW high-density (HDPE) fraction and a higher-MW linear low-density (LLDPE) fraction.
ABSTRACT
The rising demand for more and more specialized polyethylene represents a challenge for synthesis and analysis. The desired properties are dependent on the structure, but its elucidation is still intricate. For this purpose, we applied thermal analysis hyphenated to single photon ionization mass spectrometry (STA-SPI-MS). The melting and pyrolysis behavior of different types of polyethylene were tracked by DSC and mass loss. Crystallinity and melting point give hints about the branching but are also influenced by the molecular weight distribution. The evolving gas analysis patterns obtained by SPI-MS however, contain specific molecular information about the samples. Shifts in the summed spectra, which can be clearly observed with our technique, result from differently favored degradation reactions due to the respective structure. Pyrolysis gas chromatography mass spectrometry (Py-GC-EI-MS) was used to support the assignment of pyrolysis products. Principal component analysis was successfully applied to reduce the complexity of data and find suitable markers. The obtained grouping is based on the molecular fingerprint of the samples and is strongly influenced by short-chain branching. Short and medium alkenes and dienes have the strongest impact on the first four principal components. Thus, two marker ratios could be defined, which also give a comprehensible and robust grouping. Butene and pentene were the most abundant signals in our set of samples. With STA-PI-MS, a broad range of pyrolysis products can be measured at the same time, possibly extending the range for quantifiable short-chain branches to more than six carbon atoms for PE. Unfortunately, no clear trend between long-chain branching and any grouping was observed. The quite universal and soft single photon ionization enables access to many different compound classes and hence other polymers can be studied.
ABSTRACT
Rational characterization of most organometallic compounds is hampered by their high reactivity, in particular, toward oxygen and water. Mass spectrometry experiments require physical introduction of the sample in the ionization source. So, the main challenge is to transfer air-sensitive organometallic compounds from inert atmosphere to the ionization source. In this aim, we have developed an easy technique that allows the analysis of air-sensitive compounds using the atmospheric solid analysis probe (ASAP). This method consists of a glass capillary filled with the sample (solid or liquid) and sealed by a paraffin plug to maintain the inert sample until the ionization process. It is illustrated through the structural characterization of a new highly air-sensitive dinuclear zirconium complex supported by an original switchable stilbene platform.
ABSTRACT
Herein, we report the copper-catalyzed domino borylation/aldolisation of methyl 2-fluoroacrylate with carbonyl compounds followed by an elimination to give Morita-Baylis-Hillman (MBH) analogues. The optimal conditions described were shown to be compatible with a wide range of aldehydes and ketones. Unprecedented MBH adducts derived from ketones were efficiently synthesized.