Towards the design of new electron donors for Ziegler–Natta catalyzed propylene polymerization using QSPR modeling

Ratanasak, Manussada; Rungrotmongkol, Thanyada; Saengsawang, Oraphan; Hannongbua, Supot; Parasuk, Vudhichai

doi:10.1016/j.polymer.2014.11.022

Cited by 22 publications

(28 citation statements)

References 30 publications

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“…Most of the works have been focused on ethylbenzoates [10,16,23e25], phthalates [26], succinates [18], alkoxysilanes [19,27], and 1,3-diethers [28e30]. Malonate compounds as internal electron donor have been reported to be very potent electron donors which show good activity and high isotacticity [31,32]. However, there have not been thorough studies on the role of this class of electron donors.…”

Section: Introductionmentioning

confidence: 99%

Roles of malonate donor on activity and stereoselectivity of Ziegler–Natta catalyzed propylene polymerization

Ratanasak

Parasuk

2015

Journal of Organometallic Chemistry

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Section: Introductionmentioning

confidence: 99%

Roles of malonate donor on activity and stereoselectivity of Ziegler–Natta catalyzed propylene polymerization

Ratanasak

Parasuk

2015

Journal of Organometallic Chemistry

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“…Lee et al [20] found the relationship between adsorption energies of 1,3-diether donors to the MgCl 2 surface and the isotacticity and the productivity of polypropylene. Moreover, Ratanasak et al [56] have studied the relation between the adsorption energies of various classes of electron donors to the catalyst surface and activities. They found that the activity of polypropylene production linearly varies with the adsorption energy.…”

Section: Adsorption Energies Of Five Salicylate Donorsmentioning

confidence: 99%

Roles of Salicylate Donors in Enhancement of Productivity and Isotacticity of Ziegler–Natta Catalyzed Propylene Polymerization

2020

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Roles of internal salicylate donors (SID) in enhancing activity and stereoselectivity of Ziegler–Natta catalyzed propylene (PP) polymerization were examined using DFT calculations. Five salicylate donors were studied. The chelate mode is the preferred adsorption mode. The linear relationship (R2 = 0.96) between calculated adsorption energies (Eads) of five SIDs and the experimental PP activities was observed. Thus, the SID with the strongest adsorption energy will provide the highest activity in agreement with our previous studies. Compared with diisobutyl phthalate (DIBP), which is the industrial electron donor, SID has stronger Eads. The insertion step, which involves the π-complex formation (∆Eπ) and the insertion activation or intrinsic activation energy (Ea) for PP polymerization was also examined. The relation between ln(activity) and apparent activation energy (Ea(app)), which is ∆Eπ + Ea for the primary(1,2)-re insertion with R2 = 0.99, was observed. The salicylate donor also has a lower Ea(app) than that of DIBP. This explains the better catalytic performance of SID. Our results also demonstrated that the size and the type of hydrocarbon substituents play a key role in controlling stereoselectivity and activity. In addition, we found a good relationship between Eads and both intrinsic (Ea) and apparent (Ea(app)) activation energies of five salicylate donors with R2 of 0.90 and 0.97, respectively.

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“…Most of the commercial catalysts used for polypropylene manufacture are modifications of the original Ziegler-Natta system. 3 The catalyst for the production of isotactic polypropylene with high activity and stereospecificity consists of the MgCl 2 -supported TiCl 4 (Lewis acids) catalyst in conjunction with alkylaluminum (AlR 3 ) cocatalyst and Lewis bases, which are normally referred to as electron donors. 4 Lewis acids were selected among (metallic or not) halogenated derivatives according to the two principal following criteria: (1) solubility in hydrocarbons (or chlorinated hydrocarbons) solvents without introducing any polar solvents and (2) inability to lead by itself to polymerization-active species when AlEt 3 is added.…”

Section: Introductionmentioning

confidence: 99%

“…The direct bonding between the electron donor and MgCl 2 support suggests that the internal donor has a higher impact on the polypropylene product properties than the external donor. 3 The internal donors prevent the coagulation of MgCl 2 particles during the milling process 14 and stabilize small primary crystallites of MgCl 2 , [15][16][17] resulting in an enhancement of the effective surface area, 14 and also control the amount and the distribution of TiCl 4 on the support surface. 4,16,[18][19][20] Additionally, the internal donor could prevent the formation of aspecific sites or transforms aspecific sites into highly stereoselective sites.…”

Section: Introductionmentioning

confidence: 99%

“…24 As the electron donors play a major role in the Ziegler-Natta catalyzed propylene polymerization, therefore the development of new electron donors becomes one of the key targets in designing new generation polypropylene catalysts. 3 In the early 1980s, the MgCl 2 -supported catalyst system with a new internal donor, alkyl phthalate, 25,26 and organic siloxane as the external donor was developed. 9 This catalyst is called the fourth-generation Ziegler-Natta catalyst, so far it is still widely used in the polypropylene industry.…”

Section: Introductionmentioning

confidence: 99%

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Propylene Polymerization over MgCl₂‐Supported Ziegler–Natta Catalysts Containing Tri‐Ether as the Internal Donor

et al. 2016

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1-Methoxy-2,2-bis(methoxymethyl)butane as a new internal donor was synthesized by the reaction of 1,1,1-tris(hydroxymethyl)propane with sodium hydride as the base and methyl iodide as the alkyl halide. The tri-ether compound was characterized by NMR and FTIR techniques. The MgCl 2 -supported titanium catalysts were incorporated with varying amounts of 1-methoxy-2,2-bis(methoxymethyl)butane as the internal donor (ID) and also without the internal donor were synthesized, and then the prepared catalysts were characterized. The concentration of titanium, magnesium, and chloride were determined by spectrophotometry and by complexometric and argentometric titration, respectively. The polymerization of propylene was carried out with the prepared catalysts in conjunction with triethylaluminum as a cocatalyst and hydrogen as a chain transfer agent, with and without cyclohexylmethyldimethoxysilane as the external donor. The effects of a new internal donor on MgCl 2 -supported Ziegler-Natta catalysts for propylene polymerization were investigated, and then these results were compared to the obtained polypropylenes results, which were obtained using the conventional Ziegler-Natta catalyst containing diisobutyl phthalate as the internal donor. The highest isotacticity, melting temperature, and crystallinity degree of polypropylene were obtained using Cat-D with an ID/Mg molar ratio equal to 0.44, and the highest catalytic activity is related to Cat-B with an ID/Mg molar ratio equal to 0.22. The Ziegler-Natta catalysts incorporated with various ID/Mg molar ratios of 1-methoxy-2,2-bis(methoxymethyl)butane were synthesized. The polymerization of propylene was carried out with the prepared catalysts. The highest catalytic activity is related to Cat-B with an ID/Mg molar ratio equal to 0.22. The catalyst with an optimum ID/Mg molar ratio equal to 0.44 is a favorable catalyst for polymerization of propylene. C

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Towards the design of new electron donors for Ziegler–Natta catalyzed propylene polymerization using QSPR modeling

Cited by 22 publications

References 30 publications

Roles of malonate donor on activity and stereoselectivity of Ziegler–Natta catalyzed propylene polymerization

Roles of malonate donor on activity and stereoselectivity of Ziegler–Natta catalyzed propylene polymerization

Roles of Salicylate Donors in Enhancement of Productivity and Isotacticity of Ziegler–Natta Catalyzed Propylene Polymerization

Propylene Polymerization over MgCl₂‐Supported Ziegler–Natta Catalysts Containing Tri‐Ether as the Internal Donor

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Towards the design of new electron donors for Ziegler–Natta catalyzed propylene polymerization using QSPR modeling

Cited by 22 publications

References 30 publications

Roles of malonate donor on activity and stereoselectivity of Ziegler–Natta catalyzed propylene polymerization

Roles of malonate donor on activity and stereoselectivity of Ziegler–Natta catalyzed propylene polymerization

Roles of Salicylate Donors in Enhancement of Productivity and Isotacticity of Ziegler–Natta Catalyzed Propylene Polymerization

Propylene Polymerization over MgCl2‐Supported Ziegler–Natta Catalysts Containing Tri‐Ether as the Internal Donor

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Propylene Polymerization over MgCl₂‐Supported Ziegler–Natta Catalysts Containing Tri‐Ether as the Internal Donor