Butadiene Rubber: Synthesis, Microstructure, and Role of Catalysts

Abstract

Butadiene rubber (BR) is one of the most useful and second most produced rubber worldwide. Polymerization of 1,3-butadiene (BD) is a highly stereospecific reaction that offers a wide variety of BR with different microstructures and influences the fundamental properties of the rubber. Since the first successful polymerization of conjugated diene using the Ziegler–Natta–based catalyst (TiCl4 or TiCl3 with aluminum alkyls) in 1954, the research on producing synthetic rubber with an appropriate catalyst system has been accelerated. Subsequently, various research groups are actively engaged in designing active catalyst systems based on a suitable combination of transition metal complexes with alkyl-aluminum and successfully using them in BD polymerization. Although various scientific inventions have proven their significance for the production of high-quality BR, with the rising demands in improving the quality of the product, research on developing new catalyst systems with enhanced catalytic activity and high stereoselectivity is still in progress. The present review focuses on the synthesis of BR using various transition metal catalysts and discusses their microstructures. The catalysts based on new-generation metal complexes with phosphorus, nitrogen, and oxygen donor ligands (e.g., phosphines, imines, 1,10-phenanthroline, and imino-pyridines) have been introduced. The role that catalysts play in the production of BR with different microstructures (i.e., high-cis, high-trans or low-cis, low-trans polybutadiene) has also been described. The combination of catalyst (transition metal complex) and suitable co-catalyst (alkyl-aluminum) is the major factor influencing the reaction and microstructure of the resulting polymer. This report focuses on the effect of transition metal catalysts (i.e., lithium [Li], titanium [Ti], zirconium [Zr], iron [Fe], cobalt [Co], nickel [Ni], and neodymium [Nd]) on the activity and stereoselectivity of polymers such as 1,4-cis-, 1,4-trans-, and 1,2-vinyl-polybutadiene.

Industrially applied and relevant transformations of 1,3-butadiene using homogeneous catalysts

“…As representative products, polybutadiene rubber (PBR) has adjustable tough or elastic properties depending on the proportions of raw materials used in its preparation. 21,22 Meanwhile, styrene-butadiene rubber (SBR) is the most common material for making of automobile tires. [23][24][25] The powerful properties of these rubber polymers bring tires with performance-enhancing components in terms of rolling resistance and traction.…”

“…26,27 Simultaneously, numerous chemicals produced from 1,3-butadiene are also widely used to manufacture paper coatings, turf, carpets, gloves, wetsuits, toys and other consumer products. Considering there are already various reviews/books on industrial polymers based on 1,3-butadiene for readers to refer, [21][22][23][24][25][26][27] this review will not duplicate this section but center at industrial transformation examples and some promising progress in recent research to produce other bulk chemicals. Particularly, we will focus on the development of catalytic systems achieving transformations of 1,3-BD towards functionalized products with high atom economy and avoiding environmental pollution.…”

“…26,27 Simultaneously, numerous chemicals produced from 1,3-butadiene are also widely used to manufacture paper coatings, turf, carpets, gloves, wetsuits, toys and other consumer products. Considering that there are already various reviews/books on industrial polymers based on 1,3-butadiene for readers to refer to, 21–27 this review will not duplicate this section but center on industrial transformation examples and some promising progress in recent research to produce other bulk chemicals. In particular, we will focus on the development of catalytic systems achieving transformations of 1,3-BD towards functionalized products with high atom economy and avoiding environmental pollution.…”

Unlocking the Potential of 5-Hydroxy-2(5H)-furanone as a Platform for Bio-Based Four Carbon Chemicals

“…Owing to the abundance of hexose and pentose sugars in biomass, platform chemicals with six and five carbon atoms, like 5-hydroxymethylfurfural and furfural, have been extensively studied. − C4 platform chemicals have received less attention, despite a huge demand for oxygen- and nitrogen-containing C4 chemicals in industry. For example, more than 2 million tonnes of 1,4-butanediol (BDO) is produced each year for the manufacture of polymers. − Maleic anhydride is another C4 chemical widely used as a precursor for polymers and C4 derivatives such as γ-butyrolactone (GBL) and 2-pyrrolidone. , Apart from the microbial fermentation, synthesis of the C4 chemical from sugars found in biomass is challenging due to the low selectivity of the C–C bond cleavage step. − Consequently, a C4 platform chemical that can be catalytically produced from biomass in high yield and serve as a versatile precursor for value-added chemicals is highly desirable.…”

Experimental and computational studies of the production of 1,3-butadiene from 2,3-butanediol using SiO2-supported H3PO4 derivatives

“…1,3-Butadiene (BDE) is a prolific building block for the chemical industry, [1][2] widely used in polymerization processes to produce synthetic rubbers, elastomers, and polymer resins. [3][4][5] Polymers derived from BDE are ubiquitous in manufacturing materials, such as tires, which have a tremendous worldwide economic impact. Promoted by the diminishing availability of fossil fuels and the adverse environmental effects of non-renewable resources, new and efficient syntheses of BDE from renewable feedstocks have attracted considerable attention within the scientific community.…”