Elastomers play an irreplaceable role in our society due to their unique properties. Natural rubber is directly obtained from plants and is widely used in tires, shoes, etc. Recently, modified natural rubbers are proposed to expand the application of natural rubber. However, these natural rubbers have a limited variety of molecular structures and may not be able to meet ever‐demanding applications. Traditional synthetic elastomers have a variety of molecular structures and their properties are used in various fields, but mainly originate from fossil resources. This review deals with bio‐based elastomers, and more specifically natural rubber and bio‐based synthetic elastomers. Based on reprocessability, bio‐based elastomers can also be divided into bio‐based chemically cross‐linked ones and thermoplastic ones. Compared to traditional fossil‐based elastomers, bio‐based ones may alleviate environmental pollution and promote the sustainable development of the elastomer industry.

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/sus2.45

Current trends in bio‐based elastomer materials

To prepare biobased polymers, particular attention must be paid to the obtention of the monomers from which they are derived. (Meth)acrylates and their analogs constitute such a class of monomers that have been extensively studied due to the wide range of polymers accessible from them. This review therefore aims to highlight the progresses made in the production and polymerization of (meth)acrylates and their analogs. Acrylic acid production from biomass is close to commercialization, as three different high-potential intermediates are identified: glycerol, lactic acid, and 3-hydroxypropionic acid. Biobased methacrylic acid is less common, but several promising options are available, such as the decarboxylation of itaconic acid or the dehydration of 2-hydroxyisobutyric acid. Itaconic acid is also a vinylic monomer of great interest, and polymers derived from it have already found commercial applications. Methylene butyrolactones are promising monomers, obtained from bioresources via three different intermediates: levulinic, succinic, or itaconic acid. Although expensive, methylene butyrolactones have a strong potential for the production of high-performance polymers. Finally, β-substituted acrylic monomers, such as cinnamic, fumaric, muconic, or crotonic acid, are also examined, as they provide an original access to biobased materials from various renewable raw materials, such as protein waste, lignin, or wastewater.

Production and Polymerization of Biobased Acrylates and Analogs.

In recent years, countries worldwide have engaged actively in the research and development of green and sustainable materials in the face of the increasing depletion of petroleum resources, the need to reduce material waste, and the environmental pollution caused by the various types of waste. In the tire industry, the key materials for the various components of tires are mostly dependent on petroleum resources. Development of green tires and green processing technologies using sustainable materials is an important development direction for the future of the tire industry, and many tire‐manufacturing companies have proposed their visions for the development of eco‐friendly tires. Rubber, cord fabric, and additives are the main materials used in tire manufacturing. This article summarizes the research status of the green materials that can meet the requirements of environmental friendliness and sustainability, replace traditional materials, and reduce petroleum resource consumption in existing tire production. These materials mainly include natural rubber or bio‐based synthetic rubber, green renewable cord fabrics, and green processing additives. The prospects for the application of these new green materials in tire manufacturing are also discussed.

Research progress on sustainability of key tire materials

Cementation anisotropy associated with microbially induced calcium-carbonate precipitation and its treatment effect on calcareous and quartz sands

In response to increasingly stringent requirements for the sustainability and environmental friendliness of the rubber industry, the application and development of bio-based elastomers have received extensive attention. In this work, we prepared a new type of bio-based elastomer poly(dibutyl itaconate-butadiene) copolymer (PDBIB) nanocomposite using carbon black and non-petroleum-based silica with a coupling agent. Using dynamic thermodynamic analysis (DMTA) and scanning electron microscope (SEM), we studied the effects of feed ratio on dynamic mechanical properties, micro morphology, and filler dispersion of PDBIB composites. Among them, silica-reinforced PDBIB60 (weight ratio of dibutyl itaconate to butadiene 40/60) and carbon black-reinforced PDBIB70 (weight ratio of dibutyl itaconate to butadiene 30/70) both showed excellent performance, such as tensile strength higher than 18 MPa and an elongation break higher than 400%. Compared with the widely used ESBR, the results showed that PDBIB had better rolling resistance and heat generation than ESBR. In addition, considering the development of green tires, we compared it with the solution polymerized styrene–butadiene rubber with better comprehensive performance, and analyzed the advantages of PDBIB and the areas to be improved. In summary, PDBIB prepared from bio-based monomers had superior performance and is of great significance for achieving sustainable development, providing a direction for the development of high-performance green tire and holding great potential to replace petroleum-derived elastomers.

https://www.mdpi.com/2227-9717/8/12/1527/pdf

Itaconate Based Elastomer as a Green Alternative to Styrene–Butadiene Rubber for Engineering Applications: Performance Comparison

Ester-functionalized styrene-butadiene rubber (dibutyl itaconate-styrene-butadiene rubber) (D-ESBR) was synthesized by low-temperature emulsion polymerization using dibutyl itaconate (DBI) as a modified monomer containing ester groups. Nonpetroleum-based silica with hydroxy groups was used as a filler to enhance the D-ESBR, which can provide excellent mechanical properties, low rolling resistance, and high wet skid resistance. During the preparation of the silica/D-ESBR nanocomposites, a hydrogen-bonding interface was formed between the hydroxy groups on the surface of silica and the ester groups in the D-ESBR macromolecules. As the content of ester groups in the D-ESBR increases, the dispersion of silica in the nanocomposites is gradually improved, which was verified by rubber process analyzer (RPA) and scanning electron microscopy (SEM). Overall mechanical properties of the silica/D-ESBR modified with 5 wt % DBI were improved and became superior to that of the non-modified nanocomposite. Compared with the non-modified silica/D-ESBR, the DBI modified silica/D-ESBR exhibited a lower tan δ value at 60 °C and comparable tan δ value at 0 °C, indicating that the DBI modified silica/D-ESBR had lower rolling resistance without sacrificing wet skid resistance.

https://www.mdpi.com/2073-4360/11/11/1820/pdf

Preparation and Performance of Silica/ESBR Nanocomposites Modified by Bio-Based Dibutyl Itaconate.

Green processing strategy to fabricate silica-filled biobased elastomers with excellent heat oil resistance

A novel elastomer poly(diethyl itaconate-co-butyl acrylate-co-ethyl acrylate-co-glycidyl methacrylate) (PDEBEG) was designed and synthesized by redox emulsion polymerization based on bio-based diethyl itaconate, butyl acrylate, ethyl acrylate, and glycidyl methacrylate. The PDEBEG has a number average molecular weight of more than 200,000 and the yield is up to 96%. It is easy to control the glass transition temperature of the PDEBEG, which is ranged from −25.2 to −0.8 °C, by adjusting the monomer ratio. We prepared PDEBEG/CB composites by mixing PDEBEG with carbon black N330 and studied the oil resistance of the composites. The results show that the tensile strength and the elongation at break of the composites with 10 wt% diethyl itaconate can reach up to 14.5 MPa and 305%, respectively. The mechanical properties and high-temperature oil resistance of the composites are superior to that of the commercially available acrylate rubber AR72LS.

Design, Preparation, and Evaluation of a Novel Elastomer with Bio-Based Diethyl Itaconate Aiming at High-Temperature Oil Resistance

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Papers

Itaconate Based Elastomer as a Green Alternative to Styrene–Butadiene Rubber for Engineering Applications: Performance Comparison

Preparation and Performance of Silica/ESBR Nanocomposites Modified by Bio-Based Dibutyl Itaconate.

Green processing strategy to fabricate silica-filled biobased elastomers with excellent heat oil resistance

Design, Preparation, and Evaluation of a Novel Elastomer with Bio-Based Diethyl Itaconate Aiming at High-Temperature Oil Resistance