Abstract
Highly cis-1,4 selective (up to 98%) coordination–insertion polymerization of 1,3-butadiene (BD) has been achieved herein using acenaphthene-based α-diimine cobalt complexes. Due to the presence of intra-ligand π-π stacking interactions, the complexes revealed high thermostability, affording polybutadiene products in high yields. Moreover, all of the obtained polymers possessed a relatively narrow molecular weight distribution as well as high molecular weight (up to 92.2 × 104 Dalton). The molecular weights of the resultant polybutadienes could be finely tuned by varying polymerization parameters, including temperature, Al/Co ratio, etc. Moreover, the copolymerization of butadiene with polar monomer 2-(4-methoxyphenyl)-1,3-butadiene (2-MOPB) was also successfully realized to produce a type of polar cis-1,4 polybutadiene (cis-1,4 content: up to 98.1%) with a range of 2-MOPB content (0.46–1.83%). Water contact angle measurements indicated that the insertion of a polar monomer into a polymer chain could significantly improve the polymer’s surface property.
Highlights
Hydrocarbon polymers, which mainly include polyolefins and polydienes, have been widely used in modern human life because of their excellent chemical and physical properties in combination with their low cost, superior processability, and good recyclability [1,2,3]
Copolymerization with polar monomers to access functionalized hydrocarbon polymers is the most direct and economic strategy to solve the above issue; most catalytic systems have extremely high oxophilic active species that are able to be decomposed by heteroatoms due to their strong and irreversible coordination to the metal center
Owing to the low oxophilic nature of the metal centers and the properties of α-diimine coordination ligand that are able to be regulated exactly, a catalytic system that shows a high heteroatom tolerance and that can directly catalyze the copolymerization of olefins with polar comonomers, has created a new field aiming to access functionalized polyolefins, and colossal advances have been made this field in the past few years [9,10,11,12]
Summary
Hydrocarbon polymers, which mainly include polyolefins and polydienes, have been widely used in modern human life because of their excellent chemical and physical properties in combination with their low cost, superior processability, and good recyclability [1,2,3]. Copolymerization with polar monomers to access functionalized hydrocarbon polymers is the most direct and economic strategy to solve the above issue; most catalytic systems have extremely high oxophilic active species that are able to be decomposed by heteroatoms (such as N, O, S, or other polar groups) due to their strong and irreversible coordination to the metal center. Owing to the low oxophilic nature of the metal centers and the properties of α-diimine coordination ligand that are able to be regulated exactly, a catalytic system that shows a high heteroatom tolerance and that can directly catalyze the copolymerization of olefins with polar comonomers, has created a new field aiming to access functionalized polyolefins, and colossal advances have been made this field in the past few years [9,10,11,12]. A series copolymerizations of 1,3-butadiene with polar comonomer 2-(4-methoxyphenyl)-1,3-butadiene (2-MOPB) is conducted, and the corresponding catalytic performances and microstructures of the resulting copolymers are discussed
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