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1 Introduction
With increasing global energy demand and ecological concerns related to the consumption of fossil-based feedstocks, there is a need to develop alternative fuels
from sustainable, non-food resources. The effective utilization of abundantly available, inexpensive residues of agricultural and forest biomass to produce liquid fuels
and biogenic materials can play a crucial role in addressing this concern [1]. The
production of polymers heavily depends upon non-renewable feedstocks. However,
due to the finite nature of fossil-based feedstocks, it is necessary to find alternative
sustainable feedstocks like lignocellulosic biomass. Presently, 8300 million metric
tons per year (Mt) of polymers are produced from fossil resources that utilized ~7%
fossil fuels worldwide [2].
The finite nature of fossil-based sources and their environmental impact have
driven the need to produce polymers from sustainable feedstocks [3]. The sustainable polymers have the capability to replace the conventional fossil-derived polymers. However the high production cost and inferior performance are the two main
obstacles that render its commercialization limited [4].
Biomass-derived vinyl monomers such as itaconic acid (IA), acrylic acid (AA),
methacrylic acid (MAA), styrene (ST), etc. are important substrates for sealing
materials, household plastics, adhesive resins, and textile fiber applications. The
vast majority of vinyl monomers in industries are derived from fossil fuels through
several commercial processes. Apart from the utilization of unsustainable feedstocks, low product yield, multiple steps, and formation of toxic side products are
the other major drawbacks associated with industrial processes.
To address these drawbacks, the production of vinyl monomers has been directed
towards sustainable bio-catalytic processes utilizing bio-based feedstocks. As a
result, several research articles and patents have appeared recently that have shown
the benefits of sustainable vinyl monomer production [5, 6].
Vinyl monomers are industrially important commodity chemicals, which are
widely used to produce polyesters, polyacrylates, polystyrene adhesives, protective
coatings, paints, resins, rubbers, and other copolymers [7]. The chemical structure
of vinyl monomers contains an active double bond that can be further functionalized
to yield versatile synthetic intermediates and polymers. In this chapter, recent biocatalytic transformation strategies applied to the production of vinyl monomers
from biomass-derived feedstocks are discussed. Focus is given to four important
vinyl monomers: IA, AA, MAA, and ST. Each of these is produced at over 26 million tons per annum from petroleum feedstock with current market prices of about
$2500 per metric (Fig. 1) [8].
2 Itaconic Acid
Itaconic acid (IA) is a versatile chemical derived from the fermentation of carbohydrate feedstocks [9, 10]. It is composed of unsaturated dicarboxylic acid functionalities that make it an attractive building block to produce several novel copolymers.
K. Avasthi et al.
1 Introduction
With increasing global energy demand and ecological concerns related to the consumption of fossil-based feedstocks, there is a need to develop alternative fuels
from sustainable, non-food resources. The effective utilization of abundantly available, inexpensive residues of agricultural and forest biomass to produce liquid fuels
and biogenic materials can play a crucial role in addressing this concern [1]. The
production of polymers heavily depends upon non-renewable feedstocks. However,
due to the finite nature of fossil-based feedstocks, it is necessary to find alternative
sustainable feedstocks like lignocellulosic biomass. Presently, 8300 million metric
tons per year (Mt) of polymers are produced from fossil resources that utilized ~7%
fossil fuels worldwide [2].
The finite nature of fossil-based sources and their environmental impact have
driven the need to produce polymers from sustainable feedstocks [3]. The sustainable polymers have the capability to replace the conventional fossil-derived polymers. However the high production cost and inferior performance are the two main
obstacles that render its commercialization limited [4].
Biomass-derived vinyl monomers such as itaconic acid (IA), acrylic acid (AA),
methacrylic acid (MAA), styrene (ST), etc. are important substrates for sealing
materials, household plastics, adhesive resins, and textile fiber applications. The
vast majority of vinyl monomers in industries are derived from fossil fuels through
several commercial processes. Apart from the utilization of unsustainable feedstocks, low product yield, multiple steps, and formation of toxic side products are
the other major drawbacks associated with industrial processes.
To address these drawbacks, the production of vinyl monomers has been directed
towards sustainable bio-catalytic processes utilizing bio-based feedstocks. As a
result, several research articles and patents have appeared recently that have shown
the benefits of sustainable vinyl monomer production [5, 6].
Vinyl monomers are industrially important commodity chemicals, which are
widely used to produce polyesters, polyacrylates, polystyrene adhesives, protective
coatings, paints, resins, rubbers, and other copolymers [7]. The chemical structure
of vinyl monomers contains an active double bond that can be further functionalized
to yield versatile synthetic intermediates and polymers. In this chapter, recent biocatalytic transformation strategies applied to the production of vinyl monomers
from biomass-derived feedstocks are discussed. Focus is given to four important
vinyl monomers: IA, AA, MAA, and ST. Each of these is produced at over 26 million tons per annum from petroleum feedstock with current market prices of about
$2500 per metric (Fig. 1) [8].
2 Itaconic Acid
Itaconic acid (IA) is a versatile chemical derived from the fermentation of carbohydrate feedstocks [9, 10]. It is composed of unsaturated dicarboxylic acid functionalities that make it an attractive building block to produce several novel copolymers.
K. Avasthi et al.