Comb-like copolymers of n-alkyl monoitaconates and styrene

Inciarte, Helen; Orozco, Margie; Fuenmayor, M.; López‐Carrasquero, Francisco; Oliva, Haydée

doi:10.1515/epoly.2006.6.1.714

Cited by 5 publications

(4 citation statements)

References 11 publications

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“…As far as polymer chemistry is concerned, mainly two different classes of polymers derived from itaconic have been intensively studied. The α,β-unsaturated double bonds, allows for radical polymerization reactions, which has been exploited in several homopolymers and co-polymers of itaconic acid with a range of applications [9][10][11][12][13]. As a second pathway, the two carboxylic acid groups allow for polycondensation reactions to obtain polyesters [14][15][16][17][18][19][20].…”

Section: Introductionmentioning

confidence: 99%

First Example of Unsaturated Poly(Ester Amide)s Derived From Itaconic Acid and Their Application as Bio-Based UV-Curing Polymers

et al. 2020

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Recently, itaconic acid has drawn considerable attention as a novel radical-curing building block for polyester resins. These bio-based materials have been used in thermal, as well as ultra violet (UV) curing applications, such as printing inks or coatings. Poly(ester amide)s from itaconic acid could be very interesting, as the amide group could alter the properties of the resins as well as cured materials. However, standard polycondensation reactions with diamines are not possible with itaconic acid as the amines preferably react via an aza-Michael addition at the α,β-unsaturated double bond. Therefore, alternative and more elaborate synthetic strategies have to be developed. Herein, we present two different synthetic strategies to poly(ester amide)s from itaconic acid that circumvent the addition reaction of the amines. This is in both cases done by a pre-reaction to form stable amide building blocks that are then reacted with itaconic acid or polyesters derived thereof. The structural composition and the properties of the resin are characterized, and the UV-curing reactivity is examined. All properties are compared to corresponding polyesters from itaconic acid.

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Section: Introductionmentioning

confidence: 99%

First Example of Unsaturated Poly(Ester Amide)s Derived From Itaconic Acid and Their Application as Bio-Based UV-Curing Polymers

et al. 2020

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“…In addition, for most procedures, an excess of the alcohol is necessary, resulting in tedious purification of the products, especially when more complex alcohols with higher boiling points are used. Therefore, these methods are not applicable on an industrial scale due to cumbersome recrystallization and/or purification by means of column chromatography. − …”

Section: Introductionmentioning

confidence: 99%

Selective Synthesis of Monoesters of Itaconic Acid with Broad Substrate Scope: Biobased Alternatives to Acrylic Acid?

Arnaud

Andreou

Köster

et al. 2019

ACS Sustainable Chem. Eng.

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Over the last few years, there has been an increasing interest to identify biobased alternatives to acrylic acid in UV-curing materials. In this respect, itaconic acid has drawn considerable attention, due to its structural similarity. However, the second acid group in the molecule limits its use in many applications, as undesired side reactions can occur. One solution is the use of monoesters of itaconic acid to mimic the properties of acrylic acid. However, to date, no general applicable and straightforward synthetic protocol has been reported. Herein, the synthesis of a variety of monoesters of itaconic acid is presented. The methodology tolerates a broad substrate scope, is highly efficient, and does not suffer from tedious purification steps; therefore it can be applied on large scale. In the next step, the monoesters were reacted with epoxidized soybean oil to produce biobased UV-curing oligomers. The influence of the different monoesters on the properties of the functionalized vegetable oils, such as viscosity as well as the reactivity toward UV-light induced radical cross-linking, was studied. In addition, these findings were compared with those of acrylated soybean oil. Despite the lower rate of polymerization of the itaconic acid-based oligomers, the double bond conversion was higher in some cases. In addition, the viscosity was found to be lower in comparison to that of the acrylic acid-derived compound, making these novel monoesters promising alternatives to the petrochemical-based acrylic acid.

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“…For example, di-n-butyl itaconate (DBI) can impart lower glass transition temperatures in copolymers and consequently similar related dialkyl itaconates have been polymerized via conventional free radical polymerization (FRP) [2,11,[18][19][20][21][22][23][24][25][26][27][28][29][30][31] and more recently via reversible de-activation radical polymerization (RDRP), also known as controlled radical polymerization (CRP), specifically reversible addition fragmentation chain transfer polymerization (RAFT) [32,33] and atom transfer radical polymerization (ATRP) [34,35]. In one case, NMP has been reported using TEMPO-based initiators but no molecular weight distributions were provided, ascribed to the styrene/DBI copolymers adsorbing onto the gel permeation chromatography (GPC) columns [36]. Itaconate esters with stiffer substituents like itaconic anhydride have been similarly polymerized by conventional radical polymerization [37][38][39] and controlled radical polymerizations like RAFT [40] and would be expected to behave similarly to copolymerizations of styrene with maleic anhydride to provide alternating monomer sequences in the chain.…”

Section: Introductionmentioning

confidence: 99%

Nitroxide-Mediated Copolymerization of Itaconate Esters with Styrene

et al. 2019

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Replacing petro-based materials with renewably sourced ones has clearly been applied to polymers, such as those derived from itaconic acid (IA) and its derivatives. Di-n-butyl itaconate (DBI) was (co)polymerized via nitroxide mediated polymerization (NMP) to impart elastomeric (rubber) properties. Homopolymerization of DBI by NMP was not possible, due to a stable adduct being formed. However, DBI/styrene (S) copolymerization by NMP at various initial molar feed compositions fDBI,0 was polymerizable at different reaction temperatures (70–110 °C) in 1,4 dioxane solution. DBI/S copolymerizations largely obeyed first order kinetics for initial DBI compositions of 10% to 80%. Number-average molecular weight (Mn) versus conversion for various DBI/S copolymerizations however showed significant deviations from the theoretical Mn as a result of chain transfer reactions (that are more likely to occur at high temperatures) and/or the poor reactivity of DBI via an NMP mechanism. In order to suppress possible intramolecular chain transfer reactions, the copolymerization was performed at 70 °C and for a longer time (72 h) with fDBI,0 = 50%–80%, and some slight improvements regarding the dispersity (Ð = 1.3–1.5), chain activity and conversion (~50%) were observed for the less DBI-rich compositions. The statistical copolymers produced showed a depression in Tg relative to poly(styrene) homopolymer, indicating the effect of DBI incorporation.

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Comb-like copolymers of n-alkyl monoitaconates and styrene

Cited by 5 publications

References 11 publications

First Example of Unsaturated Poly(Ester Amide)s Derived From Itaconic Acid and Their Application as Bio-Based UV-Curing Polymers

First Example of Unsaturated Poly(Ester Amide)s Derived From Itaconic Acid and Their Application as Bio-Based UV-Curing Polymers

Selective Synthesis of Monoesters of Itaconic Acid with Broad Substrate Scope: Biobased Alternatives to Acrylic Acid?

Nitroxide-Mediated Copolymerization of Itaconate Esters with Styrene

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