Simulation & Modeling
Yogeshwar N Thakare; Ajay V Kothari; Saurabh Shinde; Pooja Kadam; Natarajan Venkateswaran; Virendrakumar Gupta
Abstract
MgCl2 supported Ti catalyst is used in commercial propylene polymerization process. Morphology is a key performance determination parameter for polymer resins produced by commercial olefin polymerization process. Higher resin flowability and bulk density (greater than 0.38g/cc) are demonstrated by ‘good’ ...
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MgCl2 supported Ti catalyst is used in commercial propylene polymerization process. Morphology is a key performance determination parameter for polymer resins produced by commercial olefin polymerization process. Higher resin flowability and bulk density (greater than 0.38g/cc) are demonstrated by ‘good’ morphological resins (sphericity close to ‘1’). Polymer resin morphology is controlled by morphology of the catalyst used as well as polymerization conditions. The industrially accepted approaches to control polymer resin morphology are by controlling catalyst morphology through various approaches like pre-polymerization of the catalysts. Morphology of the catalyst is dependent on precursor (support) morphology and process parameters for making the catalyst. In this work, we have developed magnesium alkoxide precursor, a Ziegler-Natta catalyst using the precursor and studied its performance in gas phase propylene polymerization process. Further, morphology of different precursor and catalyst samples is evaluated and correlated it using a “computer vision” based approach. The approach involves modeling the circularity (as an analog of sphericity) of a catalyst and precursor particle. It is observed that the circularity of catalyst particles is lower than that of precursor, due to attrition in the process. It is also reflected in increase in particle size distribution span from 0.83 to 1.32 while synthesis of catalyst from precursor. This approach provides a tool to evaluate and screen the catalysts for using in polymerization.
Polymer processing
Parthiv M. Trivedi; Sandip Patil; Virendra K. Gupta
Abstract
Ultra-high molecular weight polyolefin (UHMWPO) has enormous potential applications due to their excellent mechanical properties such as tensile strength, flexural modulus, toughness and outstanding chemical resistance. But the processing of polyolefin, in particular, UHMWPO fibers cannot be processed ...
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Ultra-high molecular weight polyolefin (UHMWPO) has enormous potential applications due to their excellent mechanical properties such as tensile strength, flexural modulus, toughness and outstanding chemical resistance. But the processing of polyolefin, in particular, UHMWPO fibers cannot be processed by conventional methods due to its very high melt viscosity. In this work, we synthesized isotactic ultra-high molecular weight polypropylene (UHMWPP) resin and studied the processability of UHMWPP fibers using gel spinning and investigated physicomechanical properties. UHMWPP gel was made at various concentrations in decalin solvent at 150°C to produce consistent spinning dope solutions. The 7 wt.% concentration of UHMWPP was deemed best for fiber creation, compared to 3 wt.% and 5 wt.%. A rheological time sweep was done to ensure the gel's stability at 170°C before the spinning process. The UHMWPP's gelation and fiber formation were studied by tweaking the gel concentration and adjusting the processing temperature. The resulting UHMWPP monofilament had a measure of 220-250 denier. The hot stretched fibers were analyzed with the scanning electron microscope (SEM) to understand the surface morphology of the fibers. The crystal morphology of UHMWPP fibers was measured with wide-angle x-ray scattering (WAXS) and DSC. The X-ray measurement of hot stretched UHMWPP fibers showed crystalline peaks compared to those without stretched fibers.
Olefin polymerization and copolymerization
Hiren Bhajiwala; Virendrakumar Gupta
Abstract
Ultra-high molecular weight polyethylene (UHMWPE) was synthesized using Bi-supported SiO2/MgCl2/TiCl4 (Si-Mg-Ti) Ziegler-Natta catalyst in conjugation with triethyl aluminum (TEA). The impact of temperature and the presence of a chain-terminating agent were examined in the context of ethylene polymerization. ...
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Ultra-high molecular weight polyethylene (UHMWPE) was synthesized using Bi-supported SiO2/MgCl2/TiCl4 (Si-Mg-Ti) Ziegler-Natta catalyst in conjugation with triethyl aluminum (TEA). The impact of temperature and the presence of a chain-terminating agent were examined in the context of ethylene polymerization. The findings showed that as temperature decreases, the activity of the polymerization decreases, and the molecular weight of the polymer increases. Conversely, in the presence of a chain-terminating agent, the molecular weight of the polymer decreases. The introduction of Triethyl borate (TEB) and Tetraethoxy silane (TEOS) as an external donor has a pronounced effect on the catalyst activity, causing a significant decrease, while simultaneously leading to a substantial increase in the viscosity average molecular weight (Mv). Additionally, when a chain-terminating agent is added along with Triethyl borate (TEB) in the system, it results in a significant decrease in molecular weight, albeit with a slight increase in activity compared to a system without a donor. The crystallinity, particle size and bulk density of the polymer synthesized with and without external donor also investigated.
Olefin polymerization and copolymerization
Virendrakumar. Gupta; Hiren Manojkumar Bhajiwala
Abstract
The copolymerization of methyl acrylate (MA) and glycidyl methacrylate (GMA) with 1-hexene was carried out using activator regenerator by electron transfer atom transfer radical polymerization (ARGET ATRP) employing Cu(0)/CuBr2 as a catalyst, pentamethyl diethylenetriamine (PMDETA) as a ligand, and ethyl ...
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The copolymerization of methyl acrylate (MA) and glycidyl methacrylate (GMA) with 1-hexene was carried out using activator regenerator by electron transfer atom transfer radical polymerization (ARGET ATRP) employing Cu(0)/CuBr2 as a catalyst, pentamethyl diethylenetriamine (PMDETA) as a ligand, and ethyl 2-bromoisopropionate (EBriP) as the initiator, all at a reaction temperature of 70°C. This process resulted in the production of viscous and transparent copolymers, namely poly (methyl acrylate-co-1-hexene) or PMH and poly (glycidyl methacrylate-co- 1-hexene) or PGMH. For the MA/1-Hex copolymer, conversion rates ranged from a maximum of 31 wt.% to a minimum of 12 wt.%, while the GMA/1-hexene copolymer exhibited conversion rates ranging from a maximum of 42 wt.% to a minimum of 12 wt.%. It was observed that increasing the amount of 1-hexene during the synthesis led to a higher incorporation of 1-hexene content in both the MA and GMA polymer backbones, with a maximum of 15 wt.% and 18 wt.% of 1-hexene being incorporated into PMH and PGMH, respectively. The incorporation of 1-hexene was confirmed through Nuclear Magnetic Resonance (NMR) studies, including 1H, 13C, and DEPT 135 studies. Additionally, the copolymer PMH and PGMH exhibited monomodal molecular weight distribution curves when evaluated using the size exclusion chromatography (SEC) high-performance liquid chromatography (HPLC) technique, with polydispersity values in the range of 1.19-1.37 and 1.07-1.11, respectively. These findings indicate that the copolymerization process was well-controlled and followed a radical polymerization mechanism.
