Bio-based polymer networks by thiol–ene photopolymerizations of allyl-etherified eugenol derivatives

Yoshimura, Tsubasa; Shimasaki, Toshiaki; Teramoto, Naozumi; Shibata, Mitsuhiro

doi:10.1016/j.eurpolymj.2014.11.013

Cited by 86 publications

(73 citation statements)

References 27 publications

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“…Moreover, eugenol exhibits several pharmacological properties, such as antibacterial and antioxidant properties, because of the presence of phenol groups, leading to its utilization in perfume, cosmetic and flavoring applications . So far numerous studies have used eugenol as a building block for the synthesis of bio‐based polymers, such as benzoxazine resins, allyl‐etherified eugenol, polyester resins, cyanate ester resins, bismaleimide, epoxy resins, methacrylated eugenol (ME), etc . Among them, ME, prepared by incorporation of a polymerizable methacrylate group to eugenol, shows promising potential for use as a co‐monomer replacement for styrene in VE resins because both methacrylate groups and allyl groups can participate in free radical polymerization.…”

Section: Introductionmentioning

confidence: 99%

High‐performance thermosets with tailored properties derived from methacrylated eugenol and epoxy‐based vinyl ester

Zhang

Thakur

et al. 2018

Polymer International

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A renewable chemical, eugenol, is methacrylated to produce methacrylated eugenol (ME) employing the Steglich esterification reaction without any solvent. The resulting ME is used as a low‐viscosity co‐monomer to replace styrene in a commercial epoxy‐based vinyl ester resin (VE). The volatility and viscosity of ME and styrene are compared. The effect of ME loading and temperature on the viscosity of the VE–ME resin is investigated. Moreover, the thermomechanical properties, curing extent and thermal stability of the fully cured VE–ME thermosets are systematically examined. The results indicate that ME is a monomer with low volatility and low viscosity, and therefore the incorporation of ME monomer in VE resins allows significant reduction of viscosity. Moreover, the viscosity of the VE–ME resin can be tailored by adjusting the ME loadings and processing temperature to meet commercial liquid molding technology requirements. The glass transition temperatures of VE–ME thermosets range from 139 to 199 °C. In addition, more than 95% of the monomer is incorporated and fixed in the crosslinked network structure of VE–ME thermosets. Overall, the developed ME monomer exhibits promising potential for replacing styrene as an effective low‐viscosity co‐monomer. The VE–ME resins show great advantages for use in polymer matrices for high‐performance fiber‐reinforced composites. This work is of great significance to the vinyl ester industry by providing detailed experimental support. © 2018 Society of Chemical Industry

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Section: Introductionmentioning

confidence: 99%

High‐performance thermosets with tailored properties derived from methacrylated eugenol and epoxy‐based vinyl ester

Zhang

Thakur

et al. 2018

Polymer International

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“…Reversely, the latter displayed higher elongation at break than the former, suggesting that S4P-based polymer network has a lower crosslinking density than pS4P-based polymer network does. Consequently, A3F-pS4P exhibited the highest tensile strength and modulus (9.48 and 406 MPa), whose values were much higher than those of the already reported AEG-pS4P (0.98 and 23.9 MPa) [44]. The difference in the mechanical properties should be caused by the fact that the allyl functionality of A3F (3) is higher than that of AEG (2), leading to a higher crosslinking density.…”

Section: Ft-ir Analysis For the Thiol-ene Polymerization Of A3a And A3fmentioning

confidence: 70%

“…6 and 8 (251.4 and 289.4°C), respectively, indicating that the amino acid moiety has a similar thermal stability to the saccharide moiety [43]. However the T 5 s were lower than that (343.9°C) of the polymer network prepared by the thiol-ene photoplymerization of S4P and allyl-etherified eugenol (AEG) [44], indicating that the amino acid moiety has lower thermal stability than eugenol moiety. Figure 11 shows typical stress-strain curves by a tensile mode for A3A-pS4P, A3A-S4P, A3F-pS4P and A3F-S4P.…”

Section: Ft-ir Analysis For the Thiol-ene Polymerization Of A3a And A3fmentioning

confidence: 98%

“…Ortiz et al [42] reported polymer networks prepared by thiol-ene photopolymerizations of allyl-etherified sucroses. We also reported trehalose-and eugenol-incorpolated polymer networks by thiol-ene photopolymerizations [43,44]. In the past studies, thiol-ene reactions have been applied to the modification of unsaturated amino acids [45] and to the synthesis of peptide-functionalized conjugates [46], but amino acid-based polymer network has not been prepared by use of thiolene polymerization to the best of our knowledge.…”

Section: T1 Introductionmentioning

confidence: 99%

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Amino acid-incorporated polymer network by thiol-ene polymerization

Yokose¹,

Shimasaki²,

Teramoto³

et al. 2015

Express Polym. Lett.

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Abstract. Triallyl L-alanine (A3A) and triallyl L-phenylalanine (A3F) were synthesized by reactions of L-alanine and L-phenylalanine with allyl bromide in the presence of sodium hydroxide, respectively. Thiol-ene thermal polymerization of A3A or A3F with pentaerythritol-based primary tetrathiol (pS4P) or pentaerythritol-based secondary tetrathiol (S4P) at allyl/SH 1/1 in the presence of 2,2"-azobis(isobutyronitrile) produced an amino acid-incorporated polymer network (A3A-pS4P, A3A-S4P or A3F-S4P). Although the thermally cured resins were homogeneous and flat films, the corresponding thiol-ene photopolymerization did not give a successful result. Degree of swelling for each thermally cured film in N,Ndimethylformamide was much higher than that in water. The glass transition and 5% weight loss temperatures (T g and T 5 ) of A3F-pS4P and A3F-S4P were higher than those of A3A-pS4P and A3A-S4P, respectively. Also, A3F-pS4P and A3F-S4P exhibited much higher tensile strengths and moduli than A3A-pS4P and A3A-S4P did, respectively. Consequently, A3F-pS4P displayed the highest T g (38.7°C), T 5 (282.0°C), tensile strength (9.5 MPa) and modulus (406 MPa) among all the thermally cured resins.

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“…It has been reported that polysulfides derived from thiol-ene polymerization present some limitations in their physical/mechanical properties, particularly those related to modulus and attainment of high glass transition temperature due to the flexible core of the commercially available thiol monomers [18,19].…”

Section: Introductionmentioning

confidence: 99%

Multifunctional allyl-terminated hyperbranched poly(ethyleneimine) as component of new thiol–ene/thiol–epoxy materials

Acebo

Fernández‐Francos

Ramis

et al. 2016

Reactive and Functional Polymers

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Tarragona, October 23 th 2015Dear Prof. Advincula:We send our revised manuscript entitled: Multifunctional allyl-terminated hyperbranched poly(ethylenimine) as component of new thiol-ene/thiol-epoxy materials, to be accepted for publication in Reactive and Functional Polymers.We have included practically all the suggestions and corrections made by the reviewers and some answers to their questions have been included in the answer to the reviewer comments file.Looking forward to hearing from you, I remain. We agree and we have performed changes in the paragraph orders.3) Can you know the reaction rate of each scheme in scheme 3? It is not possible to measure both reaction rates, but the first is predominant over the second. We have decided to remove the second mechanism of thiol-epoxy condensation in Scheme 3, since the first equation is much more favorable than the second one. This is because the ammonium salt is much more acidic than the thiol, and then the formation of the thioether alcohol should take place only by the first equation.4) Please discuss the basicity of imidazole and so on. This information of base is important in this study. If we look to the pKa of the ammonium and imidazolium cations we realize that amines are more basic than imidazole (pKa of alkyl ammonium is ~10, whereas pKa of imidazolium is ~7). However, the problem arises from the amount of PEIene in the formulation. When the proportion of PEIene is high it catalyzes the second step in which a base is needed and thiol-epoxy reaction takes place overlapped. On the contrary, when the proportion of PEIene is low, then the basicity of the reaction medium is not enough to reach a complete thiol-epoxy conversion and 1-methylimidazole should be added. 5) Can you get mobility of electron in photo induced polymerization?No, there is no electron mobility. As the radical is formed it reacts instantaneously accordingly to a "click" reaction.6) Can you get turn over number in Scheme 2.The number of cycles is the same than the number of reacting molecules. It is a polycondensation mechanism and not a polyaddition reaction. Thiol-ene is a "click" reaction that occurs in a quantitative way. 7)In scheme 3, left side is same. combine it and only right side should be different scheme. Detailed Response to ReviewersWe have suppressed the second mechanism as commented above.Reviewer #2: Authors synthesized an allyl terminated hyperbranched poly(ethyleneimine). The multifunctional macromonomer has been used as -ene component in thiol-ene/thiol-epoxy curing formulations.Authors need to address the followings to meet publication requirements:1. Please add captions for schemes and figures, respectively.We apologize, but we forgot to add the file with the figure and scheme captions to the manuscript 2. Formats of Table 1, Table 2 and Table 3 are not consistent with each other. Please correct them. It is true. They have been corrected.3. There is a lack of discussion on how authors' work in comparison to others. It is important for authors to address this. formula...

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Bio-based polymer networks by thiol–ene photopolymerizations of allyl-etherified eugenol derivatives

Cited by 86 publications

References 27 publications

High‐performance thermosets with tailored properties derived from methacrylated eugenol and epoxy‐based vinyl ester

High‐performance thermosets with tailored properties derived from methacrylated eugenol and epoxy‐based vinyl ester

Amino acid-incorporated polymer network by thiol-ene polymerization

Multifunctional allyl-terminated hyperbranched poly(ethyleneimine) as component of new thiol–ene/thiol–epoxy materials

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