Olefin polymerization and copolymerization
Tingting Yang; Ao Li; Yawei Qin; Jin-Yong Dong
Abstract
Polypropylene is one of the most widely used synthetic resins, which is mainly synthesized with Ziegler-Natta catalysts. In this paper, the functionalized Ziegler-Natta catalyst is applied to prepare high-performance polypropylene. A new way to synthesize functionalized Ziegler-Natta catalysts is to ...
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Polypropylene is one of the most widely used synthetic resins, which is mainly synthesized with Ziegler-Natta catalysts. In this paper, the functionalized Ziegler-Natta catalyst is applied to prepare high-performance polypropylene. A new way to synthesize functionalized Ziegler-Natta catalysts is to dope with inorganic nanoparticles. The MgCl2/TiCl4/BMMF catalysts doped with halloysite nanotubes were prepared and applied to synthesize polypropylene containing less than 200ppm halloysite nanotubes. It is found that doping nanotubes in Ziegler-Natta catalyst has little impact on the structure, composition and activity of the catalyst, and polypropylene with high isotactic degree and molecular weight was synthesized with the functionalized Ziegler-Natta catalyst. Halloysite nanotubes are found to be dispersed in polypropylene in the form of individual nanotube, forming percolated network in the polymer melt effectively. Moreover, the polypropylene containing halloysite nanotubes exhibited better mechanical and thermal resistance properties as compared with conventional polypropylene, and the thermo-oxidative properties of which do not deteriorate as the introduction of nanotubes. This research provides a facile way to relieve the contradiction between the high activity of catalyst and high content of nanoparticles during the preparation of polyolefin nanocomposites by in-situ polymerization, and a new idea to prepare polyolefin nanocomposites by in-situ polymerization.
Characterization
Masayoshi Saito; Hiroshi Kashimura; Takuo Kataoka; Masahide Murata; Yusuke Sakuda; Hiroyuki Yamada; Hideyuki Takahashi
Abstract
This report is on the characterization of active Ti center in heterogeneous Ziegler-Natta catalysts with Soft X-ray Emission Spectrometer (SXES). Since titanium in the catalyst has various chemical bonds, it is important to grasp the chemical bond state. The outermost shell electrons are very important ...
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This report is on the characterization of active Ti center in heterogeneous Ziegler-Natta catalysts with Soft X-ray Emission Spectrometer (SXES). Since titanium in the catalyst has various chemical bonds, it is important to grasp the chemical bond state. The outermost shell electrons are very important for understanding the chemical bond state. SXES is the only method that can easily observe outermost shell electrons with current analytical instruments. Here, a co-milled solid of MgCl2, TiCl4, and Phthalate was used as a catalyst precursor, and three types of catalysts with significantly different catalytic activity levels were synthesized by changing the subsequent preparation process. The correlation between catalytic activity and the signal shape of Lα,β emission, which is the outermost shell electron of Ti in SXES analysis, was investigated. Lα,β emission was detected as broad signal. It could be observed that the high active catalyst had relatively strong signal intensity at the high energy side. The shape changes were also checked when the catalyst solids were treated by triethylaluminium. By this treatment, the relative intensity of the high energy side signal was further enhanced, suggesting that triethylaluminium treatment induced the elimination of inactive Ti from the catalyst solid. By comparing with the solid 13C-NMR analyses data of the Ziegler-Natta catalyst described in our previous report, the high energy side signal of Ti Lα,β in SXES results implies the relationship with the NMR results for carbonyl function.
Catalysis
Masayoshi Saito; Toshiya Uozumi; Masahide Murata; Takuo Kataoka; Riichiro Chujo
Abstract
Ziegler-Natta catalyst for propylene polymerization, which TiCl4 and di-alkyl phthalate were supported on MgCl2, was analyzed by solid state 13C NMR. It was confirmed that the spin-lattice relaxation time (“relaxation time” hereafter) of carbonyl group in phthalate was shortened with ...
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Ziegler-Natta catalyst for propylene polymerization, which TiCl4 and di-alkyl phthalate were supported on MgCl2, was analyzed by solid state 13C NMR. It was confirmed that the spin-lattice relaxation time (“relaxation time” hereafter) of carbonyl group in phthalate was shortened with increasing measurement temperature as a general manner because of the enhancing of molecular mobility at high temperature. The degree of the relaxation period reduction with temperature was influenced by the alkyl group size in phthalate molecule; the larger alkyl group showed a greater shorting of the relaxation period. A short relaxation time should suggest a weak interaction between the phthalate molecule and the MgCl2 support surface. The change in catalytic performance was discussed by the active site formation mechanism involving the phthalate removal step.
Structure and property relationship
Shokoufeh Hakim; Mehdi Nekoomanesh; Ali Shahrokhinia
Abstract
Three polypropylene samples (1-3) were synthesized with a 4th generation Ziegler-Natta catalyst in the presence of cyclohexyldimethoxymethylsilane (donor c), dicyclopenthyldimethoxysilane (donor d) and diisopropyldimethoxysilane (donor p), respectively, as external electron donors. The physical properties ...
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Three polypropylene samples (1-3) were synthesized with a 4th generation Ziegler-Natta catalyst in the presence of cyclohexyldimethoxymethylsilane (donor c), dicyclopenthyldimethoxysilane (donor d) and diisopropyldimethoxysilane (donor p), respectively, as external electron donors. The physical properties of the synthesized polypropylenes were determined. For samples 1 to 3, Successive self-nucleation and annealing (SSA) and Fourier transform infrared spectroscopy (FT-IR) analyses indicated that the relative content of the fraction with high isotacticity and regularity in conformational structure decreased in contrast with the fraction of low isotacticity and low uniformity in stereo-defect distribution from sample 1 to 3. The results demonstrated that the longer the isotactic sequence length and the less uniform the stereo-defect distribution, the greater the conformational order. Deconvolution of the molecular weight distribution curves indicated that the stability of the active centers increased from samples 1 to 3, but the participation of stereo-specefic active centers in the polymerization decreased. DMA tests showed that samples 3 and 1 had the highest damping ability and storage modulus, respectively.
Catalysis
Liang Zhu; Xuelian He; Ruihua Cheng; Zhen Liu; Ning Zhao; Boping Liu
Abstract
SiO2/MgCl2 (ethoxide type)/TiCl4 Ziegler-Natta catalysts for use in ethylene polymerization and ethylene/1-hexene copolymerization have been prepared using silica with a supported layer of magnesium ethoxide (Mg(OEt)2) as a catalyst precursor, followed by treating with TiCl4 at different Ti/Mg ...
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SiO2/MgCl2 (ethoxide type)/TiCl4 Ziegler-Natta catalysts for use in ethylene polymerization and ethylene/1-hexene copolymerization have been prepared using silica with a supported layer of magnesium ethoxide (Mg(OEt)2) as a catalyst precursor, followed by treating with TiCl4 at different Ti/Mg molar ratios, which showed significant effects on the active centers and pore structures of the catalysts. The formation amount of β-MgCl2 carrier increased to a maximum with increasing the Ti/Mg molar ratio from 1.50 to 2.25, and then decreased with the further increasing of Ti/Mg molar to 2.50. When the Ti/Mg molar ratio reached 2.25, the catalyst showed the best performance of polymerization, which could be attributed to the most active centers, high surface area and loose surface structure, mainly owing to the high conversion of Mg(OEt)2 to β-MgCl2. The polymers obtained showed medium and high molecular weight (Mw) with medium molecular weight distribution (MWD). In contrast to the conventional Mg(OEt)2-based ZN catalysts, the sphericity of particles was easy to control in this bi-supported catalyst. Furthermore, the prepared catalysts exhibited rather high activity, good copolymerization ability and hydrogen response.
Catalysis
Hossein Bordbar; Ali Akbar Yousefi; Hossein Abedini
Abstract
Titanium (Ti) is the ninth most abundant element on earth. The titanium mineral ores are widely distributed in different parts of the world. The two main ores of titanium include rutile (TiO2) and ilmenite (FeO.TiO2). It is aimed to provide the readers with an insight to the main processes currently ...
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Titanium (Ti) is the ninth most abundant element on earth. The titanium mineral ores are widely distributed in different parts of the world. The two main ores of titanium include rutile (TiO2) and ilmenite (FeO.TiO2). It is aimed to provide the readers with an insight to the main processes currently employed to extract and recover titanium tetrachloride (TiCl4) from different titanium ores. Due to the crucial importance of TiCl4 catalyst in the synthesis and polymerization of polyolefins, the present work examines the literature and developments made in the processing of ilmenite and rutile ores for the extraction of TiCl4. The attention has been paid to the chlorination processes and the main parameters affecting the recovery of TiCl4. Different approaches developed to date are reviewed. Different processes, reaction mechanisms and conditions as well as the kinetic models developed for extraction and purification of TiCl4 in fluidized bed reactors are also reviewed. A literature survey on the combined fluidized bed reactor systems developed for achieving a high-grade synthetic rutile via selective chlorination of low-grade titanium ores having high metal oxides content such as magnesium oxide (MgO) and calcium oxide (CaO) is also reported. Different strategies adopted to avoid agglomeration process during the extraction process are discussed too.
Catalysis
Ting Fu; Ruihua Cheng; Xuelian He; Zhen Liu; Zhou Tian; Boping Liu
Abstract
A novel imido-modified SiO2-supported Ti/Mg Ziegler-Natta catalyst for ethylene and ethylene/1-hexene polymerization is investigated. The catalyst is prepared by modification of (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalysts via supporting vanadium species followed by reaction with p-tolyl isocyanate ...
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A novel imido-modified SiO2-supported Ti/Mg Ziegler-Natta catalyst for ethylene and ethylene/1-hexene polymerization is investigated. The catalyst is prepared by modification of (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalysts via supporting vanadium species followed by reaction with p-tolyl isocyanate as imido agents, to get the merits from both the SiO2-supported imido vanadium catalyst and the (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalyst. The effects of cocatalyst amount, hydrogen and dosage of 1-hexene on polymerization behavior and the microstructures of their polymers are systematically investigated. Compared with (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalysts and vanadium-modified (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalysts, the imido-modified SiO2-supported Ti/Mg catalysts show lower but more stable activity including homopolymerization, polymerization with hydrogen and copolymerization owing to imido ligands, indicating that p-Tolyl isocyanate was unfavorable to improving catalytic activity but benefited the stability, and the products of all catalysts show lower 1-hexene incorporation but much higher molecular weight (MW) with medium molecular weight distribution (MWD). The most unique feature of the novel catalysts is the excellent hydrogen response without lowering the polymerization activity, showing great potential for industrial application.
Characterization
Mostafa Ahmadi; Seyed Mohammad Mehdi Mortazavi; Saeid Ahmadjo; Majid Zahmati; Khosrow Valieghbal; Davoud Jafarifar; Reza Rashedi
Abstract
Ethylene / 1-butene copolymers at different comonomer levels were synthesized using Ziegler-Natta catalyst to evaluate the applicability of thermal fractionation methods in predicting chemical composition distribution (CCD). The continuous melting endotherms by DSC were converted to continuous CCD, and ...
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Ethylene / 1-butene copolymers at different comonomer levels were synthesized using Ziegler-Natta catalyst to evaluate the applicability of thermal fractionation methods in predicting chemical composition distribution (CCD). The continuous melting endotherms by DSC were converted to continuous CCD, and the average comonomer contents were compared with NMR results. DSC underestimated comonomer content specifically at higher levels and was more sensitive to the drawn baseline. The thermally fractionated melting endotherms by SSA method were deconvoluted and transformed into discrete CCDs. SSA method underestimated average comonomer content even more, however results were more reproducible. The main shortcoming of the thermal methods was the inability of short ethylene sequences in forming discernible lamella thicknesses at high comonomer levels. Calibration curves were created for converting the predicted comonomer contents into absolute values and used for studying industrial LLDPEs with different comonomer levels. It was shown that SSA provides more reliable results and correlates more reasonably to the measured densities.
Catalysis
Maria Marques; Renato Oliveira; Rafael Araujo; Bruno Amantes
Abstract
A fourth-generation Ziegler-Natta catalyst was prepared to synthesize polypropylene (PP), which was stabilized by in situpolymerization employing lignin as antioxidant. The antioxidant properties of lignin were compared with those of the commercial antioxidant Irganox 1010. The presence of lignin in ...
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A fourth-generation Ziegler-Natta catalyst was prepared to synthesize polypropylene (PP), which was stabilized by in situpolymerization employing lignin as antioxidant. The antioxidant properties of lignin were compared with those of the commercial antioxidant Irganox 1010. The presence of lignin in the reaction medium slightly decreased the catalytic activity of the reaction. The isotacticity index (I.I.) of PP synthesized with lignin (PP-lig) was not affected by the presence of the additive in the reaction medium. The thermal properties, characterized by differential scanning calorimetry, showed slightly decreased degree of crystallinity (Xc), but the melting temperature (Tm) and crystallization temperature (Tc) were not affected when compared with the neat polymer. Lignin showed good activity as a stabilizer by thermogravimetry. The initial temperature of degradation (Tonset) increased when compared to the pure PP and PP stabilized with the commercial antioxidant. The lower carbonyl index of the PP, evaluated by infrared spectroscopy (FTIR) after thermo-oxidative treatment, also revealed the stabilizing action of lignin.
