Copolymerization of Biomass-Derived Carboxylic Acids for Biobased Acrylic Emulsions

Bohre, Ashish; Ali, Mohamed E.A.; Ocepek, Martin; Grilc, Miha; Zabret, Jožefa; Likozar, Blaž

doi:10.1021/acs.iecr.9b04057

Cited by 12 publications

(12 citation statements)

References 38 publications

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“…This type of polymer may be useful for tissue engineering since it is biodegradable and compatible with tissues such as ophthalmic, cardiac, and vascular [ 13 ]. Another study utilized chemically produced citric acid-derived aconitic acid that could be decarboxylated to produce methylacrylic acid (MAA) using a BaAl 12 O 19 catalyst to give a 51% yield [ 22 ]. MAA is useful in the production of biobased polymers [ 22 ].…”

Section: Industrial Applicationsmentioning

confidence: 99%

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Aconitic Acid Recovery from Renewable Feedstock and Review of Chemical and Biological Applications

Bruni

Klasson

2022

Foods

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Aconitic acid (propene-1,2,3-tricarboxylic acid) is the most prevalent 6-carbon organic acid that accumulates in sugarcane and sweet sorghum. As a top value-added chemical, aconitic acid may function as a chemical precursor or intermediate for high-value downstream industrial and biological applications. These downstream applications include use as a bio-based plasticizer, cross-linker, and the formation of valuable and multi-functional polyesters that have also been used in tissue engineering. Aconitic acid also plays various biological roles within cells as an intermediate in the tricarboxylic acid cycle and in conferring unique survival advantages to some plants as an antifeedant, antifungal, and means of storing fixed pools of carbon. Aconitic acid has also been reported as a fermentation inhibitor, anti-inflammatory, and a potential nematicide. Since aconitic acid can be sustainably sourced from renewable, inexpensive sources such as sugarcane, molasses, and sweet sorghum syrup, there is enormous potential to provide multiple streams of additional income to the sugar industry through downstream industrial and biological applications that we discuss in this review.

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Section: Industrial Applicationsmentioning

confidence: 99%

“…Another study utilized chemically produced citric acid-derived aconitic acid that could be decarboxylated to produce methylacrylic acid (MAA) using a BaAl 12 O 19 catalyst to give a 51% yield [ 22 ]. MAA is useful in the production of biobased polymers [ 22 ].…”

Section: Industrial Applicationsmentioning

confidence: 99%

Aconitic Acid Recovery from Renewable Feedstock and Review of Chemical and Biological Applications

Bruni

Klasson

2022

Foods

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“…In a subsequent work, they copolymerized the MAA derived from IA with styrene and butyl acrylate, which showed the same behavior as fossil‐based MAA, as expected, thus reporting the first example of polymerization of biobased MAA. [ 80 ] Avoiding expensive catalysts and corrosive alkalis are the main strengths of the work of these two research groups.…”

Section: Production Of Biobased Acrylates and Analogsmentioning

confidence: 99%

Production and Polymerization of Biobased Acrylates and Analogs

Fouilloux

Thomas

2021

Macromol. Rapid Commun.

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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.

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“…[ 7 ] Itaconic acid is considered as a renewable substitute to petroleum‐based acrylic acid and methacrylic acid and find applications in surfactants, [ 8,9 ] elastomers, [ 10,11 ] and so forth. [ 12–18 ] Itaconic acid is one of the 12 most promising bio‐based chemicals suggested by US Department of Energy. [ 19 ] The dialkyl esters of itaconic acid such as dimethyl itaconate (DMI), diethyl itaconate (DEI), and di( n ‐butyl) itaconate (DBI) ( Figure ) can be synthesized via one‐step simple esterification of itaconic acid with the corresponding alkyl alcohols (methanol, ethanol, and n ‐butanol).…”

Section: Figurementioning

confidence: 99%

Organocatalyzed Living Radical Polymerization of Itaconates and Self‐Assemblies of Rod−Coil Block Copolymers

Sarkar

Zheng

et al. 2020

Macromol. Rapid Commun.

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lengths and tend to behave as rod-like polymers. The rod-like conformation is of interest in fundamental and practical perspectives.Living radical polymerization, [22−25] also termed reversible−deactivation radical polymerization, was used for itaconates to synthesize well-defined polymers with predicted molar masses and narrow molar mass distributions. For example, atom transfer radical polymerization (ATRP) and reversible addition−fragmentation chain transfer (RAFT) polymerization of DMI, DBI, and dicyclohexyl itaconate successfully yielded polymers with low dispersity (Đ = M w /M n = 1.3−1.5), [26−28] where M n and M w are the number-and weight-average molar masses, respectively. Because the chain transfer to monomer is generally significant for itaconates at high temperatures, the Đ value tended to increase as the polymerization proceeded. [29,30] The polymerization was also slow because of their small propagation rate constants (due to the large steric hindrance) and typically ceased at moderate monomer conversions (up to 55%). [28] Nevertheless, these results elegantly opened up the use of the biorenewable itaconate monomers to yield structurally controlled polymers.Our research group developed an organocatalyzed living radical polymerization exploiting alkyl iodides (R-I) as initiating dormant species and organic molecules such as tetrabutylammonium iodide (BNI (A + Isalt)) as catalysts. [31−35] The polymer−iodide (polymer−I) dormant species and the catalyst (iodide anion I − in A + I − ) form a complex (polymer−I⋅⋅⋅I -), and the complex subsequently reversibly generates the propagating radical (polymer•) and A + I 2 • − (Scheme 1a). Because A + I 2 •− is not a stable radical, two A + I 2 •− species can undergo disproportionation to produce A + I − and A + I 3 − anions, which are stable species (Scheme 1b). A + I − acts as an activator, whereas A + I 3 acts as a deactivator (Scheme 1c). Polymer• can thus be deactivated by either A + I 2 •-(Scheme 1a) or A + I 3 -(Scheme 1c). This polymerization is termed as reversible complexation mediated polymerization (RCMP). RCMP is attractive for no use of special capping agents or metal catalysts, ease of operation, and applicability to a broad scope of monomers (i.e., methacrylates, acrylates, styrene, and acrylonitrile) and polymer designs. [36−39] The present work aimed to further expand the monomer scope of RCMP to itaconates, i.e., DMI, DEI, and DBI. The use of RCMP may enable the synthesis of those biorenewable polymers with controlled structures in a metal-free and sulfur-free condition. Organocatalyzed living radical polymerizations of itaconates are studied, yielding low-dispersity linear and star polymers (Đ = M w /M n = 1.28−1.46) up to M n = 20 000 and monomer conversion = 62%, where M n and M w are the number-and weight-average molar masses, respectively. The block polymerization with functional methacrylates, an acrylate, and styrene yields various rod−coil block copolymers. Linear A−B diblock, linear B−A−B triblock, and 3-arm star A−B diblock copol...

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Copolymerization of Biomass-Derived Carboxylic Acids for Biobased Acrylic Emulsions

Cited by 12 publications

References 38 publications

Aconitic Acid Recovery from Renewable Feedstock and Review of Chemical and Biological Applications

Aconitic Acid Recovery from Renewable Feedstock and Review of Chemical and Biological Applications

Production and Polymerization of Biobased Acrylates and Analogs

Organocatalyzed Living Radical Polymerization of Itaconates and Self‐Assemblies of Rod−Coil Block Copolymers

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