Binuclear Titanium Catalysts Based on Methylene-Bridged Tridentate Salicylaldiminato Ligands for Ethylene Homo- and Copolymerization

Li, Tingcheng; Lan, Zhi‐An; Xie, Guangyong; Luo, Derong; Li, Long; Xiong, Shengwu; Zhang, Li; Ouyang, Lipeng; Zhang, Aiqing

doi:10.1007/s10562-017-1985-9

Cited by 14 publications

(11 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…More α-olefins were produced with more Fe complex added, which led to higher calculated activities for Ti complex. These results also fully agreed with the copolymerization behaviors of ethylene and α-olefin catalyzed solely by Ti complex [59].…”

Section: Resultssupporting

confidence: 83%

“…The Ti complex Ti 2 L 1 and Fe complex FeL a exhibited high catalytic activity for ethylene polymerization or oligomerization when used separately (Entries 1 and 2 of Table 1), which has been detailedly investigated in our previous works [58,59], and the binuclear titanium complexes still displayed very high activity when combined with bisiminopyridyl Fe complex in this tandem catalytic system. The effects of the reaction temperature, [Fe]/[Ti] molar ratios and catalyst structures upon the copolymerization activities and properties of the copolymers were investigated.…”

Section: Resultsmentioning

confidence: 67%

“…The methylene-bridged tridentate salicylaldiminato binuclear titanium complexes displayed extremely high activities for ethylene polymerization and ethylene/α-olefins copolymerization at atmospheric pressure in our previous research [59], thus may be excellent candidates as copolymerization catalysts of dual-function catalytic systems for ethylene in-situ copolymerization. Here we investigated the tandem catalytic behaviors of non-metallocene binuclear titanium complexes ( Ti 2 L 1 - Ti 2 L 3 ) and bisiminopyridyl iron complex ( FeL a ) with ethylene as the only feed, and the results were listed in Table 1.…”

Section: Resultsmentioning

confidence: 99%

“…All other chemicals are used as received from commercial sources. Fe complex FeL a and binuclear Ti complexes Ti 2 L 1 , Ti 2 L 2 and Ti 2 L 3 were prepared according to our previous works [58,59].…”

Section: Methodsmentioning

confidence: 99%

“…Recently we have successfully prepared LLDPE from ethylene in a single reactor using non-metallocene titanium complex as the copolymerization catalyst of a tandem dual-functional catalyst systems [57,58]. We have also designed and synthesized a number of non-metallocene binuclear titanium complexes which demonstrated excellent activity for ethylene (co)polymerization [59,60,61,62]. Here we used the non-metallocene binuclear titanium complexes for the first time as copolymerization catalysts of a tandem catalyst system and described the direct synthesis of LLDPE from ethylene in a single reactor though [Fe]/[Ti] tandem catalysis, which was shown in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Methylene-Bridged Tridentate Salicylaldiminato Binuclear Titanium Complexes as Copolymerization Catalysts for the Preparation of LLDPE through [Fe]/[Ti] Tandem Catalysis

Luo

et al. 2019

Polymers

Self Cite

View full text Add to dashboard Cite

A novel tandem catalysis system consisted of salicylaldiminato binuclear/mononuclear titanium and 2,6-bis(imino)pyridyl iron complexes was developed to catalyze ethylene in-situ copolymerization. Linear low-density polyethylene (LLDPE) with varying molecular weight and branching degree was successfully prepared with ethylene as the sole monomer feed. The polymerization conditions, including the reaction temperature, the Fi/Ti molar ratio, and the structures of bi- or mononuclear Ti complexes were found to greatly influence the catalytic performances and the properties of obtained polymers. The polymers were characterized by differential scanning calorimetry (DSC), high temperature gel permeation chromatography (GPC) and high temperature 13C NMR spectroscopy, and found to contain ethyl, butyl, as well as some longer branches. The binuclear titanium complexes demonstrated excellent catalytic activity (up to 8.95 × 106 g/molTi·h·atm) and showed a strong positive comonomer effect when combined with the bisiminopyridyl Fe complex. The branching degree can be tuned from 2.53 to 22.89/1000C by changing the reaction conditions or using different copolymerization pre-catalysts. The melting points, crystallinity and molecular weights of the products can also be modified accordingly. The binuclear complex Ti2L1 with methylthio sidearm showed higher capability for comonomer incorporation and produced polymers with higher branching degree and much higher molecular weight compared with the mononuclear analogue.

show abstract

Section: Resultssupporting

confidence: 83%

Section: Resultsmentioning

confidence: 67%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Methylene-Bridged Tridentate Salicylaldiminato Binuclear Titanium Complexes as Copolymerization Catalysts for the Preparation of LLDPE through [Fe]/[Ti] Tandem Catalysis

Luo

et al. 2019

Polymers

Self Cite

View full text Add to dashboard Cite

show abstract

Binuclear titanium complexes coordinated by rigid p‐phenylene linked bis‐β‐carbonylenamine: Synthesis, structure, ethylene polymerization and copolymerization with 1,5‐hexadiene

Wang

Qin

et al. 2020

Applied Organom Chemis

View full text Add to dashboard Cite

Binuclear complexes for olefin polymerization have attracted great attention due to their unique catalytic properties compared with their mononuclear counterparts. Here a series of p‐phenylene‐bridgedbis‐β‐carbonylenamine ligands and their binuclear Ti complexes Ti2L1–Ti2L3 were prepared and characterized by 1H NMR, 13C NMR, Fourier transform infrared spectroscopy, and elemental analysis. The binuclear complex Ti2L3 bearing an octylthio sidearm was further investigated by single‐crystalX‐ray diffraction, which revealed that the ligand was of β‐imino enol form, with one titanium atom ligated with six other atoms, forming a deformed octahedral configuration. Furthermore, the ligand in Ti2L3 adopted a cis configuration, which was different from the trans configuration of its m‐phenylene‐bridged derivatives. These binuclear complexes (Ti2L1–Ti2L3) could catalyze ethylene polymerization and copolymerization with 1,5‐hexadiene(1,5‐HD) efficiently under modified methylaluminoxane activation. Compared with the mononuclear complex TiL5, the binuclear catalysts were thermally more stable and showed higher activity for ethylene polymerization at higher temperatures. The activity of these titanium complexes for the copolymerization of ethylene with 1,5‐HD were over 106 g/mol Ti.h.atm, almost twice as high as for homopolymerization. Compared with the mononuclear analogue TiL5 and the m‐substituted binuclear derivative Ti2L4, binuclear catalyst Ti2L2 showed higher activity and insertion rate of the comonomer. The activity of Ti2L2 was two to three times higher than that of TiL5 and Ti2L4, indicating that p‐substituted binuclear catalysts generate clear bimetallic synergistic effect for the copolymerization of ethylene and 1,5‐HD. Meanwhile, 1,5‐HD takes 1,3‐cyclopentyl form in the polymer by 1,3‐insertion. The copolymer prepared by binuclear catalysts had higher molecular weight and wider molecular weight distribution than that prepared by the mononuclear catalyst.

show abstract

Binuclear Ti(IV) complex with new compartmental ligand 2,6‐(bis‐CF₃‐carbinol)‐4‐tert‐butylphenol as precatalysts for ethylene polymerization and its copolymerization with propylene and 5‐ethylidene‐norbornene

Тuskaev

Гагиева

Bogdanov

et al. 2021

Applied Organom Chemis

View full text Add to dashboard Cite

The coordination chemistry of a new compartmental ligand 2,6‐(bis‐CF3‐carbinol)‐4‐tert‐butylphenol with Ti(IV) and Zr(IV) has been studied. The structures of Al, Ti, and Zr complexes with the participation of this ligand were established by X‐ray diffraction. Upon activation with Et2AlCl or Et3Al2Cl3 and Bu2Mg, Ti(IV) complex exhibited moderate catalytic activity for ethylene polymerization. The obtained UHMWPE samples were processed into high‐strength (up to 2.7 GPa) and high‐modulus (up to 162 GPa) films through solid‐phase molding and orientation drawing. The mononuclear and binuclear Ti(IV) complexes catalyzed the ternary copolymerization of ethylene, propylene, and 5‐ethylidene‐norbornene. Tercopolymers with a content of propylene units up to 36 mol% and 5‐EBN up to 8.6 mol% were synthesized with a high activity (2.8–6.3 tons of copolymer/mol Ti h); the mechanical characteristics of elastomeric materials have been studied.

show abstract

Binuclear Titanium Catalysts Based on Methylene-Bridged Tridentate Salicylaldiminato Ligands for Ethylene Homo- and Copolymerization

Cited by 14 publications

References 55 publications

Methylene-Bridged Tridentate Salicylaldiminato Binuclear Titanium Complexes as Copolymerization Catalysts for the Preparation of LLDPE through [Fe]/[Ti] Tandem Catalysis

Methylene-Bridged Tridentate Salicylaldiminato Binuclear Titanium Complexes as Copolymerization Catalysts for the Preparation of LLDPE through [Fe]/[Ti] Tandem Catalysis

Binuclear titanium complexes coordinated by rigid p‐phenylene linked bis‐β‐carbonylenamine: Synthesis, structure, ethylene polymerization and copolymerization with 1,5‐hexadiene

Binuclear Ti(IV) complex with new compartmental ligand 2,6‐(bis‐CF₃‐carbinol)‐4‐tert‐butylphenol as precatalysts for ethylene polymerization and its copolymerization with propylene and 5‐ethylidene‐norbornene

Contact Info

Product

Resources

About

Binuclear Titanium Catalysts Based on Methylene-Bridged Tridentate Salicylaldiminato Ligands for Ethylene Homo- and Copolymerization

Cited by 14 publications

References 55 publications

Methylene-Bridged Tridentate Salicylaldiminato Binuclear Titanium Complexes as Copolymerization Catalysts for the Preparation of LLDPE through [Fe]/[Ti] Tandem Catalysis

Methylene-Bridged Tridentate Salicylaldiminato Binuclear Titanium Complexes as Copolymerization Catalysts for the Preparation of LLDPE through [Fe]/[Ti] Tandem Catalysis

Binuclear titanium complexes coordinated by rigid p‐phenylene linked bis‐β‐carbonylenamine: Synthesis, structure, ethylene polymerization and copolymerization with 1,5‐hexadiene

Binuclear Ti(IV) complex with new compartmental ligand 2,6‐(bis‐CF3‐carbinol)‐4‐tert‐butylphenol as precatalysts for ethylene polymerization and its copolymerization with propylene and 5‐ethylidene‐norbornene

Contact Info

Product

Resources

About

Binuclear Ti(IV) complex with new compartmental ligand 2,6‐(bis‐CF₃‐carbinol)‐4‐tert‐butylphenol as precatalysts for ethylene polymerization and its copolymerization with propylene and 5‐ethylidene‐norbornene