Long-chain branching (LCB) is known as a suitable method to increase the melt strength behavior of linear polypropylene (PP), which is a fundamental weakness of this material. This enables the modification of various properties of PP, which can then be used—in the case of PP recyclates—as a practical “upcycling” method. In this study, the effect of five different peroxides and their effectiveness in building LCB as well as the obtained mechanical properties were studied. A single screw extruder at different temperatures (180 and 240 °C) was used, and long-chain branched polypropylene (PP-LCB) was prepared via reactive extrusion by directly mixing the peroxides. The peroxides used were dimyristyl peroxydicarbonate (PODIC C126), tert-butylperoxy isopropylcarbonate (BIC), tert-Butylperoxy 2-ethylhexyl carbonate (BEC), tert-amylperoxy 2-ethylhexylcarbonate (AEC), and dilauroyl peroxide (LP), all with a concentration of 20 mmol/kg. The influence of the temperature on the competitive prevalent reactions of degradation and branching was documented via melt mass-flow rate (MFR), rheology measurements, and gel permeation chromatography (GPC). However, via extensional rheology, strain hardening could be observed in all cases and the mechanical properties could be maintained or even improved. Particularly, PODIC C126 and LP signaled a promising possibility for LCB in this study.
Ziegler‐Natta (ZN) based co‐polymerization processes for the production of linear low‐density polyethylene (LLDPE) generally give rise to a non‐uniform incorporation distribution of the comonomer. It has been shown that lowering the titanation temperature during catalyst synthesis can increase the evenness of this distribution. However, polymerization process parameters also affect the resulting incorporation distribution. To investigate these factors, a ZN system using a variety of comonomer‐types, at various ‐concentrations and polymerization temperatures is studied. The molecular properties of the polymer samples obtained are analyzed by high‐temperature size‐exclusion chromatography (HT‐SEC). It is shown that a more uniform incorporation distribution of the comonomer can be achieved by lowering either the polymerization temperature or the comonomer concentration, and that lowering both increases the effect.
The microstructure of linear low‐density polyethylene (LLDPE) is strongly influenced by short‐chain branches (SCBs) incorporated into the polymer backbone. Varying the number, distribution, and length of SCBs allows the properties of the resulting polymer to be tailored to meet specific requirements. Using Ziegler–Natta (ZN) catalysts for synthesis has disadvantages in terms of the comonomer incorporation distribution (CID) compared to, for instance, metallocene and post–metallocene catalysts. Nevertheless, ZN catalysts continue to be widely used, as many of the new generations of catalysts are more difficult to handle and cannot match the cheap cost of ZN catalysts. To improve this aspect of ZN catalysts, we investigated the influence of catalyst titanation temperature and polymerization process parameters on the CID. Our results show that it is possible to manipulate the process parameters of the present ZN catalyst system to yield a desired comonomer amount and CID in the polymer. Varying the titanation temperature clearly influenced the titanium content of the catalyst. Molecular‐weight distribution analysis and deconvolution results indicate that changes in the amounts of comonomer incorporated and in the CID are directly related to the catalyst's active site that produces the lowest‐molecular‐weight fraction.
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