Novel spherical Ziegler–Natta catalyst for polymerization and copolymerization. I. Spherical MgCl<sub>2</sub> support

Ye, Zhaoyang; Wang, Li; Li, Feng; Gu, Xue‐Ping; Chen, Haihua; Zhang, Puyu; Pan, Jie; Jiang, Shan; Feng, Linxian

doi:10.1002/pola.10398

Cited by 45 publications

(40 citation statements)

References 9 publications

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“…Board peak at 2 = 26 o was mira film which was used to cover the sample from the moisture in the environment. The crystalline structure of anhydrous MgCl2 was an -crystal type, which was generally obtained from ball milling [14]. The porous MgCl2 particles obtained from spray drying was more crystallographic disorder, evident from the absence of the sharp peak at 003 planes especially in the case of n-propanol and n-butanol solvent.…”

Section: Xrd Pattern Of Mgcl2 Particlesmentioning

confidence: 99%

Preparation of Porous Anhydrous MgCl2 Particles by Spray Drying Process

Rojanotaikul¹,

Ayudhya²,

Charoenchaidet³

et al. 2012

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Abstract. Polyethylene (PE) is indispensable materials in daily lives. To produce PE, the catalyst was needed in the reaction. Ziegler-Natta catalysts were mostly used which consisted of TiCl4 on the MgCl2 supports. Polyethylene particle was reported to replicate the shape of the catalyst particles or catalyst support particles. Therefore, the MgCl2 supports need to satisfy various requirements regarding particle morphology such as shape, particle size with uniform size distribution as well as the porosity. In this research, the preparation of MgCl2 particles from irregular shape of anhydrous MgCl2 by spray drying method was studied. The moisture was reported as the poison of the catalyst, so the unusual close loop spray drying under N2 conditions was used in this study. The different types of alcohol, ethanol, n-propanol and n-butanol as solvent which was used to dissolve MgCl2 before feeding through the spray drying on the particle properties were investigated. The amount of residual alcohol (alcoholic hydroxyl group content), morphology, specific surface area, porosity and crystallinity were determined by GC method, scanning electron microscope (SEM), N2 sorption analyzer and X-ray diffraction (XRD), respectively. The results revealed that spray drying process can produce the porous anhydrous MgCl 2 particles which have rough surface, higher porosity and lower crystallinity than original anhydrous MgCl2.

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Section: Xrd Pattern Of Mgcl2 Particlesmentioning

confidence: 99%

Preparation of Porous Anhydrous MgCl2 Particles by Spray Drying Process

Rojanotaikul¹,

Ayudhya²,

Charoenchaidet³

et al. 2012

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“…This may be due to brittle films of impregnated MgCl 2 caused by the high ethanol content. Therefore, the effect of [EtOH]/[MgCl 2 ] on morphology structure of MgCl 2 deposited on the SiO 2 surface is similar to that on the MgCl 2 -supported catalyst in terms of producing loose and breakable MgCl 2 structures with high ethanol content [1]. …”

Section: Resultsmentioning

confidence: 99%

“…Currently, the activation of MgCl 2 is usually done via the chemical route. The recrystallization of MgCl 2 in alcoholic hydrocarbon solution is the well-known method to make spherical catalysts [1,2,3]. However, in the synthesis of MgCl 2 supports via this method it is not easy to obtain compact and good catalyst morphology because it is difficult to control the alcohol content in MgCl 2 -ethanol complexes, which influences the porosity and strength of the catalyst particles and the subsequent polymer-particle morphology due to the replication phenomena [4,5,6,7].…”

Section: Introductionmentioning

confidence: 99%

Effect of EtOH/MgCl2 Molar Ratios on the Catalytic Properties of MgCl2-SiO2/TiCl4 Ziegler-Natta Catalyst for Ethylene Polymerization

2011

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MgCl2-SiO2/TiCl4 Ziegler-Natta catalysts for ethylene polymerization were prepared by impregnation of MgCl2 on SiO2 in heptane and further treatment with TiCl4. MgCl2·nEtOH adduct solutions were prepared with various EtOH/MgCl2 molar ratios for preparation of the MgCl2-supported and MgCl2-SiO2-supported catalysts in order to investigate the effect on polymerization performance of both catalyst systems. The catalytic activities for ethylene polymerization decreased markedly with increased molar ratios of [EtOH]/[MgCl2] for the MgCl2-supported catalysts, while for the bi-supported catalysts, the activities only decreased slightly. The MgCl2-SiO2-supported catalyst had relatively constant activity, independent of the [EtOH]/[MgCl2] ratio. The lower [EtOH]/[MgCl2] in MgCl2-supported catalyst exhibited better catalytic activity. However, for the MgCl2-SiO2-supported catalyst, MgCl2 can agglomerate on the SiO2 surface at low [EtOH]/[MgCl2] thus not being not suitable for TiCl4 loading. It was found that the optimized [EtOH]/[MgCl2] value for preparation of bi-supported catalysts having high activity and good spherical morphology with little agglomerated MgCl2 was 7. Morphological studies indicated that MgCl2-SiO2-supported catalysts have good morphology with spherical shapes that retain the morphology of SiO2. The BET measurement revealed that pore size is the key parameter dictating polymerization activity. The TGA profiles of the bi-supported catalyst also confirmed that it was more stable than the mono-supported catalyst, especially in the ethanol removal region.

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“…An electron-donor compound (Lewis base) is indispensable and the most important component for achieving isospecificity, as well as high activity of the catalyst [37]. The role of the electron donor is to influence the environment around the Ti.…”

Section: The Titanium Chloride Species Adsorbed On Mgcl 2 Support Witmentioning

confidence: 99%

An insight into the chain-propagation mechanism of propylene polymerization catalyzed by traditional Ti-based Ziegler–Natta catalysts in view of recently developed catalysts

Sun¹,

Wang²,

Dong³

et al. 2006

Designed Monomers and Polymers

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The propagation mechanism of 1-alkenes, especially propylene, for newly developed catalysts such as metallocene catalysts and bis(phenoxy-amine)zirconium-based catalysts and traditional Ti-based Ziegler-Natta catalysts, and the relationship between the structure of the catalyst and the structure of polyolefins produced, was reviewed. We believe that the propagation mechanism of 1-alkenes, especially propylene, for traditional Ti-based heterogeneous catalysts and the relationship between the structure of the catalyst and the structure of polyolefins produced is elucidated more explicitly with metallocene catalysts and bis(phenoxy-amine)zirconium-based catalysts as reference.

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Novel spherical Ziegler–Natta catalyst for polymerization and copolymerization. I. Spherical MgCl₂ support

Cited by 45 publications

References 9 publications

Preparation of Porous Anhydrous MgCl2 Particles by Spray Drying Process

Preparation of Porous Anhydrous MgCl2 Particles by Spray Drying Process

Effect of EtOH/MgCl2 Molar Ratios on the Catalytic Properties of MgCl2-SiO2/TiCl4 Ziegler-Natta Catalyst for Ethylene Polymerization

An insight into the chain-propagation mechanism of propylene polymerization catalyzed by traditional Ti-based Ziegler–Natta catalysts in view of recently developed catalysts

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Novel spherical Ziegler–Natta catalyst for polymerization and copolymerization. I. Spherical MgCl2 support

Cited by 45 publications

References 9 publications

Preparation of Porous Anhydrous MgCl2 Particles by Spray Drying Process

Preparation of Porous Anhydrous MgCl2 Particles by Spray Drying Process

Effect of EtOH/MgCl2 Molar Ratios on the Catalytic Properties of MgCl2-SiO2/TiCl4 Ziegler-Natta Catalyst for Ethylene Polymerization

An insight into the chain-propagation mechanism of propylene polymerization catalyzed by traditional Ti-based Ziegler–Natta catalysts in view of recently developed catalysts

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Novel spherical Ziegler–Natta catalyst for polymerization and copolymerization. I. Spherical MgCl₂ support