Synthesis of multi-functional epoxides derived from limonene oxide and its application to the network polymers

Morinaga, Hisatoyo; Sakamoto, Mayu

doi:10.1016/j.tetlet.2017.05.021

Cited by 16 publications

(24 citation statements)

References 15 publications

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“…In contrast to bis‐ trans ‐LO, the reaction of bis‐LO and BPEI 600 yielded no network polymer regardless of the feed ratio due to the low reactivity of cis ‐LO moiety and the low content of multiple trans ‐LO species in a single molecule. The composition of bis‐LO may be statistically regarded as three types as shown in Scheme : both trans ‐LO (approximately 25%), one trans ‐LO and one cis ‐LO (approximately 50%), and both cis ‐LO (approximately 25%) . To investigate the effect of both trans ‐LO moieties in bis‐LO on the polymer yield, both trans ‐LO moieties ranging from 25 to 96% were tested, as shown in Table .…”

Section: Resultsmentioning

confidence: 99%

“…It is well known that the reactivity of nucleophilic attack to cis ‐limonene oxide ( cis ‐LO) by amines is much lower than that to trans ‐limonene oxide ( trans ‐LO) because of the high energetic boat‐like transition state . Recently, a crosslinking reaction of multifunctional epoxides derived from LO composed of cis and trans isomers with branched polyethyleneimine (BPEI) was reported . To the best of our knowledge, no reports on the effect of the difference between cis and trans isomers of LO on properties of resulting network polymers have been published.…”

Section: Introductionmentioning

confidence: 99%

“…15,16 Recently, a crosslinking reaction of multifunctional epoxides derived from LO composed of cis and trans isomers with branched polyethyleneimine (BPEI) was reported. 17 To the best of our knowledge, no reports on the effect of the difference between cis and trans isomers of LO on properties of resulting network polymers have been published. Herein, the synthesis of a bis-functional epoxide composed of trans-LO alone is reported, affording the corresponding network polymer with high performance, including tensile strength, adhesive strength, and heat resistance.…”

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confidence: 99%

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Crosslinking network of bio‐based bis‐functional epoxides derived from trans‐limonene oxide

Morinaga

Ogawa

Sakamoto

et al. 2019

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

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The thiol‐ene reaction between trans‐limonene oxide (trans‐LO) and ethane‐1,2‐dithiol in the presence of triethylborane affords a bio‐based bis‐functional epoxide (bis‐trans‐LO). The crosslinking reaction of bis‐trans‐LO with branched polyethyleneimine (BPEI; Mn = 600; BPEI600) at a feed ratio of bis‐trans‐LO/BPEI600 = 57/43 (wt/wt) yields the corresponding network polymer with Td10 (10% thermal decomposition temperature) of 304.7 °C in 98% yield. In contrast, negligible amounts of network polymer are obtained by the reaction of bis‐LO (bis‐functional epoxide derived from cis and trans‐LO) and BPEI600 regardless of the feed ratio. The mechanical strengths as measured by direct tensile tests of the network polymers derived from bis‐trans‐LO and BPEI600,1800 (Mn = 600 and 1800) were approximately 16 and 11 times higher than that of bis‐LO and BPEI1800, respectively. The tensile shear strengths of the metal‐to‐metal adhesive bonds induced by bis‐trans‐LO and BPEI600,1800 were 9.5 and 14.1 MPa, respectively. DMA revealed that the storage modulus of the network polymer derived from bis‐trans‐LO and BPEI1800 in the rubber region was higher than that of the material prepared from bis‐LO and BPEI1800, indicating higher crosslink density of the bis‐trans‐LO/BPEI1800 system. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2466–2473

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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Crosslinking network of bio‐based bis‐functional epoxides derived from trans‐limonene oxide

Morinaga

Ogawa

Sakamoto

et al. 2019

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

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“…Glycidyl esters of rosin acid oligomers have been cross‐linked with isophorone diamine and shown to lead to epoxy polymers with comparable properties to those obtained with BADGE 14 . Limonene Oxide (LO) has been dimerized with various dithiol compounds via a thiol‐ene reaction, and the resulting products have also been used as epoxy monomer 15–17 . The recent report that limonene can be catalytically epoxidized using oxygen 18 sparked our interest for the use of limonene dioxide (LDO) as biosourced epoxy monomer (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Trans‐limonenedioxide, a promisingbio‐basedepoxy monomer

Schutz

Kazemi

Mackenzie

et al. 2021

Journal of Polymer Science

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Vast quantities of the natural terpene (R)‐limonene can be collected from food waste. Epoxidation of its two double bonds provides limonene dioxide (LDO), a difunctional epoxy monomer. However, LDO is a mixture of four isomers, two of which (trans‐LDO) are actually difunctional while the others (cis‐LDO) have one epoxide group which is significantly less reactive, as revealed by Fourier transformed infrared spectroscopic analysis of formulations cross‐linked with polyethylene imine. These results are also confirmed when preparing epoxy formulations using respectively cis or trans isomers. From DFT calculations, the reactivity of each epoxide group of LDO has been assessed in model reactions with primary and secondary amines, in the presence of amine or alcohol hydrogen‐bond donors. The kinetics of cross‐linking has also been probed by differential scanning calorimetry. As measured by dynamic mechanical analysis, the resulting epoxy resins based on trans isomers have a storage modulus of ca 1GPa at room temperature and a glass transition temperature (Tg) of 70°C. These results demonstrate that trans LDO is a promising bio‐based epoxy monomer, which could be used as an alternative to petroleum‐based epoxy monomers.

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“…More surprisingly, to the best of our knowledge, only one recent paper described the use of limonene oxide for this application. In fact, Morinaga and Sakamoto [ 22 ] synthesized multifunctional limonene-based epoxides using di-, tri- or tetra-thiols and crosslinked them with branched polyethyleneimine. They observed that a large excess of amine groups was required to obtain satisfactory crosslinking at 100 °C.…”

Section: Introductionmentioning

confidence: 99%

Limonene-Based Epoxy: Anhydride Thermoset Reaction Study

et al. 2018

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The development of epoxy thermosets from renewable resources is of paramount importance in a sustainable development context. In this paper, a novel bio-based epoxy monomer derived from limonene was synthesized without epichlorohydrine and characterized. In fact, this paper depicts the synthesis of bis-limonene oxide (bis-LO). However, intern epoxy rings generally exhibit a poor reactivity and allow reaction with anhydride. Therefore, we used a reaction model with hexahydro-4-methylphthalic anhydride to compare reactivity of terminal and interepoxy functions. We also studied the influence of methyl group on intern epoxy functions. Furthermore, the influence of epoxy:anhydride stoichiometry and initiator amount was studied. These studies allow to propose an optimized formulation of bis-LO. Finally, a bis-LO-based thermoset was obtained and characterized.

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Synthesis of multi-functional epoxides derived from limonene oxide and its application to the network polymers

Cited by 16 publications

References 15 publications

Crosslinking network of bio‐based bis‐functional epoxides derived from trans‐limonene oxide

Crosslinking network of bio‐based bis‐functional epoxides derived from trans‐limonene oxide

Trans‐limonenedioxide, a promisingbio‐basedepoxy monomer

Limonene-Based Epoxy: Anhydride Thermoset Reaction Study

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