Cross-Linking of Polypropylene with Thiophene and Imidazole

In this work, two novel routes to synthesis cross-linked polypropylene (PP) are introduced by using two different precursors (2-thiophenemethyl amine (TMA) and 1-(3 aminopropyl) imidazole (API)), both cross-linked with 1,1′-(methylenedi-4,1-phenylene) bismaleimide (BM) at two different annealing temperature values (T = 50 °C and T = 150 °C). Both Diels–Alder (DA) and Michael addition reactions were successfully performed with TMA and API, respectively, albeit with different reactivity. Imidazole clearly shows a higher reactivity compared to thiophene. In addition, an increase in annealing temperature leads to a higher degree of cross-linking. The highest degree of cross-linking was obtained by the imidazole product after annealing at 150 °C (IMG1A150) as evident from the highest complex viscosity (|η*|) value of IMG1A150. A difference in rheology and thermal properties between the imidazole and thiophene cross-linked products was also observed. However, both products have superior melt properties and thermal stability compared with the starting material. They show processability at high temperatures. The melt flow behavior and de-cross-linking at higher temperatures can be tuned depending on the choice of imidazole or thiophene. This study shows an advance on the cross-linked PP processing and its product performances for further application on the commercial scale

Cross-Linking of Polypropylene via the Diels-Alder Reaction

In this work, the possibility of preparing cross-linked polypropylene (PP) via Diels–Alder (DA) chemistry is explored. The overall strategy involves reaction of maleated polypropylene (the starting material), furfuryl amine (FFA), and bismaleimide (BM) as the cross-linking agent. The occurrence of reversible cross-linking was studied by checking the presence of relevant peaks in FTIR spectra, i.e., CH out-of-plane bending vibrations of the furan ring’s peak (γCH) at an absorption band of 730–734 cm(−1), CH=CH of the BM aromatic ring’s stretching vibrations (υCH=CH) at an absorption band of 1510 cm(−1), and the DA adduct (C-O-C, δDAring) at an absorption band of 1186 cm(−1). In agreement with the spectroscopic characterization, the presence of a cross-linked network is also confirmed by rheology, namely the higher storage modulus (G′) compared with loss modulus (G″) value (G′ >> G″), as obtained via temperature sweep. Both the maleic anhydride (MA) content as well as the annealing temperature (50 °C and 120 °C) favor the DA reaction, while only partial de-cross-linking (retro DA) is observed at the higher temperature range of 150–200 °C. In addition, the products show higher mechanical robustness and thermal stability compared to the starting material

A Morphology-Based Model to Describe the Low-Temperature Impact Behaviour of Rubber-Toughened Polypropylene

The roles of the rubber particle size, the rubber particle size distribution and the constitutive behaviour of the isotactic polypropylene matrix have been studied by combining the Lazerri–Bucknall energy criterion for cavitation with the Van der Sanden–Meier–Tervoort ligament model adapted for impact conditions. It is concluded that an optimised morphology offers great potential to achieve enhanced mechanical properties with far less rubber and hence achieve a superior stiffness/toughness/processing balance

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