Synthesis of methylene butyrolactone polymers from itaconic acid

Trotta, Jacob T.; Jin, Mengyuan; Stawiasz, Katherine J.; Michaudel, Quentin; Chen, Wei‐Liang; Fors, Brett P.

doi:10.1002/pola.28654

Cited by 42 publications

(83 citation statements)

References 63 publications

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“…Unfortunately, conventional living polymerization techniques (e.g., anionic, ATRP, RAFT, etc.) give rise to statistical distributions and due to the low degrees of polymerization targeted for these branches (DP n = 4, 6, 8, and 15), minor disparities in branch lengths significantly influence the final properties, obscuring any structural trends . For these reasons, preparing oligomonomers of precise DP n ( Ð = 1) was of utmost importance and our recent development of a scalable separation strategy for the isolation of discrete oligomers utilizing automated silica gel chromatography proved to be key .…”

Section: Resultsmentioning

confidence: 99%

Scalable synthesis of an architectural library of well‐defined poly(acrylic acid) derivatives: Role of structure on dispersant performance

Lunn

Seo

Lee

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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The synthesis and systematic comparison of a comprehensive library of well‐defined polymer architectures based on poly(acrylic acid) is reported. Through the development of new synthetic methodologies, linear, single branched, precision‐branched comb, and star polymers were prepared and their performance as dispersants was evaluated. The ability to accurately control chain lengths and branch points allows the subtle interplay between structure and dispersant performance to be defined and affords critical insights into the design of improved polymeric additives for coating formulations. The general industrial relevance of ionic polymers and branched macromolecular architectures supports these design rules for a wide range of other applications and materials, including as additives for personal care products and in water treatment. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 716–725

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Section: Resultsmentioning

confidence: 99%

Scalable synthesis of an architectural library of well‐defined poly(acrylic acid) derivatives: Role of structure on dispersant performance

Lunn

Seo

Lee

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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“…[ 161 ] More recently, Fors and co‐workers synthesized MBL and γ,γ‐dimethyl‐α‐methylene‐γ‐butyrolactone (Me 2 MBL) from the β‐monoester methyl itaconate. [ 144 ] Using an excess of Grignard reagent in tetrahydrofuran (THF), they obtained Me 2 MBL with a 39% isolated yield under conditions similar to those of Santelli and co‐workers. By reacting methyl itaconate with 6 equivalents of reducing agent NaBH 4 in water/THF mixtures, they were able to obtain MBL with a 42% isolated yield.…”

Section: Production Of Biobased Acrylates and Analogsmentioning

confidence: 86%

“…[ 143 ] Recently, Fors and co‐workers reported the controlled reduction of IA into α‐methylene‐γ‐butyrolactone (MBL), thereby paving the way for its high‐scale production, which was not possible when it was obtained from tulipalin. [ 144 ] Gowda and Chen also developed a potentially industrially relevant process for the production of another methylene butyrolactone. [ 145 ] These biobased monomers could then be vinyl polymerized to yield high glass‐transition temperature ( T g ) analogs of poly(methyl methacrylate) (PMMA) (see Section 3.3).…”

Section: Production Of Biobased Acrylates and Analogsmentioning

confidence: 99%

“…RAFT polymerization can also be employed, as illustrated by Fors, who obtained well‐defined materials with MBL and Me 2 BL derived from IA. [ 144 ] Over the last decade, the Chen group issued a number of publications on MBL and γ‐MMBL polymerization using various initiators and/or catalytic systems, most of them being more active for γ‐MMBL. Hence, these studies are reviewed in the next paragraph.…”

Section: Polymerization Of (Meth)acrylic Monomers and Analogsmentioning

confidence: 99%

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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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“…[ 1–4 ] Itaconic acid is a bio‐derived vinyl monomer in radical polymerization. [ 5,6 ] It is synthesized via a microbial fermentation process of glucose by Aspergillus terreus or thermal isomerization of citric acid. [ 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.…”

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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Synthesis of methylene butyrolactone polymers from itaconic acid

Cited by 42 publications

References 63 publications

Scalable synthesis of an architectural library of well‐defined poly(acrylic acid) derivatives: Role of structure on dispersant performance

Scalable synthesis of an architectural library of well‐defined poly(acrylic acid) derivatives: Role of structure on dispersant performance

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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