Shijia Ling; He Ren; Rui Zhang; Yue Liu; Boping Liu; Ruihua Cheng
Abstract
The chromium/vanadium bimetallic Phillips catalysts developed by our research group have been proved to be a promising process to produce bimodal polyethylene using a single-reactor process. The vanadium loading of CrV-1/1, CrV-1/2, and CrV-1/3 has a significant effect on the polymerization activity, ...
Read More
The chromium/vanadium bimetallic Phillips catalysts developed by our research group have been proved to be a promising process to produce bimodal polyethylene using a single-reactor process. The vanadium loading of CrV-1/1, CrV-1/2, and CrV-1/3 has a significant effect on the polymerization activity, product molecular weight (MW), as well as the molecular weight distribution (MWD). Due to the unstable and easy deactivation of vanadium active centers at atmospheric or low (0.4 MPa) reaction pressure [Macromol. React. Eng. 2015, 9, 462–472], the reaction is carried out at 1.0 MPa to strength the V active center on the activities of ethylene homopolymerization, ethylene/1-hexene copolymerization, and the H2 responds properties. The reaction carried out at higher pressure promotes the polymerization activities. With the same amount of cocatalyst, the highest activity of the three Cr-V bimetallic catalysts CrV-1/1, CrV-1/2 and CrV-1/3 decreases with the increase of vanadium loading. The Cr-V bimetallic catalysts require more cocatalyst than the single metal Cr cat. It was found two obvious peaks in the GPC curves of homopolyethylen and ethylene/1-hexene copolymer. It means that the higher reaction pressure benefits the promotion of the active center of catalyst for higher MW. By increasing the loading from 0.48 wt.% (CrV-1/1) to 0.96 wt.% (CrV-1/2), the molecular weight increases by nearly 30%. Besides, according to the deconvolutions of the GPC curves of homopolymers, ethylene/1-hexene copolymers, and the homopolymers with H2 modulation, the synergetic effect between Cr and V center is presented. As the vanadium loading increases, the active site accounted for the high molecular weight portion increases, and the Cr-V catalyst presents better hydrogen responds. When the partial pressure of hydrogen is 0.1 MPa, the molecular weight is reduced by nearly half. Specifically, the high molecular weight peak is weakened, while the low molecular weight peak is strengthened. The peak position does not change significantly. The higher vanadium content and the greater sensitivity of hydrogen modulation indicate that the vanadium active center has better hydrogen responds than the chromium active center does. The homopolymerization product of the Cr/V-1/1 catalysts exhibits higher tensile strength and elongation-at-break. The tensile properties of the copolymerized product of CrV-1/1 are further improved.
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 ...
Read More
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
Ting Fu; Ruihua Cheng; Xuelian He; Zhen Liu; Zhou Tian; Boping Liu
Abstract
Vanadium-modified (SiO2/MgO/MgCl2)•TiClx Ziegler-Natta catalysts were prepared through co-impregnation of water-soluble magnesium and vanadium salts under different pH values. Several key factors such as pH value of co-impregnation solution during catalyst preparation, catalyst performances including ...
Read More
Vanadium-modified (SiO2/MgO/MgCl2)•TiClx Ziegler-Natta catalysts were prepared through co-impregnation of water-soluble magnesium and vanadium salts under different pH values. Several key factors such as pH value of co-impregnation solution during catalyst preparation, catalyst performances including catalytic activity, ethylene/1-hexene copolymerization and hydrogen response were investigated. It is found that the components, structures and performance of the catalysts are obviously affected by changing the pH value (pH=5, 7 and 9) of co-impregnation solution. An appropriate pH value (pH=7) can maximize catalytic activity and hydrogen response, while lower pH value (pH=5) is beneficial to the 1-hexene incorporation. The GPC results show that the polymers obtained have high average molecular weight.
Catalysis
Qiaoqiao Sun; Ruihua Cheng; Zhen Liu; Xuelian He; Ning Zhao; Boping Liu
Abstract
Chromium-vanadium (Cr-V) bimetallic catalysts are prepared by the introduction of vanadium into the Phillips catalyst which is one of the most significant industrial ethylene polymerization catalysts for tuning the Phillips catalyst performances and improving polyethylene properties. In the present work, ...
Read More
Chromium-vanadium (Cr-V) bimetallic catalysts are prepared by the introduction of vanadium into the Phillips catalyst which is one of the most significant industrial ethylene polymerization catalysts for tuning the Phillips catalyst performances and improving polyethylene properties. In the present work, titanium species were introduced into the fluorine-modified chromium-vanadium bimetallic catalysts (Cr-V-F) and the prepared catalysts were systematically explored. The element content results of multi-component catalysts showed that a competitive inhibition interaction existed between chromium and vanadium, whereas chromium was more preferable to attach to the Ti-SiO2 than vanadium. In addition, ethylene homopolymerization and ethylene/1-hexene copolymerization were carried out and examined with different catalysts. The introduction of titanium into fluorine-modified bimetallic catalysts enhanced the molecular weight (MW) and broadened the molecular weight distribution (MWD) of polyethylene. The MW of the titanium- and fluorine-modified bimetallic catalysts (Cr-V-F/Ti) firstly rose up and then dropped down with the increasing of the Al/Cr molar ratio. The Cr-V-F/Ti catalysts showed slightly depressed hydrogen response and incorporation of 1-hexene. The short-chain branch distribution (SCBD) results, which were characterized by TREF/SSA, showed that the introduction of the titanium species increased the SCB content in low MW fractions and decreased the SCB content in the high Mw fractions of ethylene/1-hexene copolymers obtained from (Cr-V-F/3Ti)600 in contrast to that from (Cr-V-F)600.
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 ...
Read More
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
Ning Zhao; Ruihua Cheng; Qi Dong; Xuelian He; Zhen Liu; Shiliang Zhang; Minoru Terano; Boping Liu
Abstract
SiO2-supported silyl chromate catalyst is an important industrial catalyst for production of high grade HDPE pipe materials. The control of the short chain branch (SCB) distribution using this catalyst system is still a great challenge. In this work, ethylene and 1-hexene copolymers were synthesized ...
Read More
SiO2-supported silyl chromate catalyst is an important industrial catalyst for production of high grade HDPE pipe materials. The control of the short chain branch (SCB) distribution using this catalyst system is still a great challenge. In this work, ethylene and 1-hexene copolymers were synthesized using SiO2-supported silyl chromate catalyst combined with triisobutylaluminium (TIBA), triethylaluminium (TEA) and mixed TIBA/TEA at molar ratio 1:1 (TIBA/TEA/1:1) as three different Al-alkyl co-catalysts.The temperature rising elution fractionation (TREF) and successive self-nucleation and annealing (SSA, by DSC) methods were combined to analyze the short chain branch distribution (SCBD) of these ethylene/1-hexene copolymers. The results showed that different types of co-catalyst had a great influence on SCBD of ethylene/1-hexene copolymers. The copolymer produced with TIBA showed better SCBD than the copolymer produced with TEA, and the copolymer produced with TIBA/ TEA/1:1 showed a SCBD in between those with TIBA and TEA.
