Surfactants from Itaconic Acid: Physicochemical Properties and Assessment of the Synthetic Strategies

Malferrari, Danilo; Armenise, N.; Decesari, Stefano; Galletti, Paola; Tagliavini, Emilio

doi:10.1021/acssuschemeng.5b00264

Cited by 24 publications

(15 citation statements)

References 44 publications

(69 reference statements)

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“…When the tertiary amines were used as a surfactant, the nanoparticles were destabilized by purging with inert gas at 60 °C or by increasing the pH value. [82] Another interesting functional group for the CO 2 /N 2 based stabilization/destabilization is the (N-amidino) dodecyl arylamide (DAm, Table 2, entry 32). When the neutral alkyl amine was used as hydrophobic core in PVF nanocapsules, the purge with CO 2 led to the formation of a hydrophilic core.…”

Section: Co 2 -Responsive Surfactantsmentioning

confidence: 99%

“…[81] Furthermore, renewable surfactants obtained from itaconic acids and fatty amines (Table 2, entry 31) were applied as CO 2 switchable surfactants. [82] Another interesting functional group for the CO 2 /N 2 based stabilization/destabilization is the (N-amidino) dodecyl arylamide (DAm, Table 2, entry 32). It was introduced as surfmer for PS NPs by Zhu and co-workers.…”

Section: Co 2 -Responsive Surfactantsmentioning

confidence: 99%

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Functional Colloidal Stabilization

Bijlard

Wald

Crespy

et al. 2016

Adv Materials Inter

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acids), and protective agents. The unifying concept and key property of colloidal stabilizers is to provide a significant repulsion between the individual dispersed particles, making the heterophase system kinetically stable, which is typically accomplished via electrostatic or steric stabilization.Functional colloid stabilization provides additional features in addition to simple repulsion via physisorbed molecules. In fact, it is surprising that the majority of artificial heterophase systems have overlooked the simple and efficient possibility of spatially resolved chemical modification. The utilization of surface-active functional stabilizers is a fast and flexible method to obtain colloidal particles with strongly improved interaction properties. This functionalization has proved extremely material-and time-efficient. Due to the self-assembling ability of the stabilizers, the functional groups allow for an exact positioning of chemical and physical interaction sites directly in the surface region of the colloidal particle.The purpose of this review is to highlight functional colloidal stabilization as defined above. Our main focus concentrates on reactive systems, especially heterophase polymerization in oil-in-water (o/w) and water-in-oil (w/o) emulsions; a waterin-oil emulsion is regarded as an inverse emulsion. We differentiate between various types of surfactants which can either adsorb or react to the dispersed material with one segment, while the second part of the amphiphile stabilizes the dispersion. The stability of emulsions can be obtained by either low or high mole cular weight surfactants. Additionally, we distinguish between surfactants from so-called protective colloids of higher mole cular weight without significant self-aggregation properties. Throughout this review, the literature on functional colloidal stabilizers was revised and classified according to molecular weight, preparation technique, chemical structure, and stimuli-responsive behavior. Certain aspects such as inorganic/organic hybrids, or bioconjugates with sequence-defined structures such as peptides and nucleotides, are not in the scope of the present review and will only be briefly described when relevant.The review is structured as follows: we start with a brief summary of conventional low molecular weight (Section 2.1) and polymeric surfactants (Section 2.2) which typically lack of additional function besides the colloid stabilization. Only some of these also industrially used surfactants carry, for example, olefins or hydroxyl-groups embedded in their chemical structure, but do not have additional handles to the colloids. After this Surfactants can stabilize colloids in dispersion; however, also additional chemical or physical functions can be added by the surfactant chemistry to the colloid. This review covers functional colloid stabilization whereby supplementary features in addition to simple repulsion via physisorbed mole cules are described. The utilization of surface-active functional stabilizers as a fast and flexibl...

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Section: Co 2 -Responsive Surfactantsmentioning

confidence: 99%

Section: Co 2 -Responsive Surfactantsmentioning

confidence: 99%

Functional Colloidal Stabilization

Bijlard

Wald

Crespy

et al. 2016

Adv Materials Inter

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“…[ 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. [ 12–18 ] Itaconic acid is one of the 12 most promising bio‐based chemicals suggested by US Department of Energy.…”

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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“…A major limitation that is sometimes encountered in this protocol comes from the poor solubility of some substrates, which prevented good results from being obtained. We found an environmentally sustainable solution to this issue by using a new ionic surfactant recently developed by our group . This amphiphilic compound allows the system to undergo micellar catalysis; furthermore, the catalytic system composed of Pd, base, water, and surfactant proved to be highly recyclable without significant loss of activity.…”

Section: Introductionmentioning

confidence: 99%

Multicomponent Cascade Synthesis of Biaryl‐Based Chalcones in Pure Water and in an Aqueous Micellar Environment

et al. 2016

Self Cite

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The challenging multicomponent cascade synthesis of biaryl‐based chalcones was carried out in pure water and in an aqueous micellar system. The first step of the protocol was a simple Pd‐catalysed, ligand‐free, and aerobic Suzuki–Miyaura reaction in aqueous medium. This proved to be extremely efficient for the coupling of aryl and heteroaryl bromides with different arylboronic acids. Subsequently, the resulting intermediates underwent an in‐situ aldol condensation reaction to give biaryl(hetero)chalcones in good to excellent yields. When the protocol was applied to highly lipophilic or less reactive reagents, micellar catalysis was required for good results. To achieve this, we successfully used a new surfactant obtained from renewable resources that we recently designed. Furthermore, using this additive, the catalytic system can be repeatedly recycled without significant loss of activity.

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Surfactants from Itaconic Acid: Physicochemical Properties and Assessment of the Synthetic Strategies

Cited by 24 publications

References 44 publications

Functional Colloidal Stabilization

Functional Colloidal Stabilization

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

Multicomponent Cascade Synthesis of Biaryl‐Based Chalcones in Pure Water and in an Aqueous Micellar Environment

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