Isocyanate-Free Synthesis and Characterization of Renewable Poly

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Isocyanate-free synthesis and characterization of renewable poly(hydroxy)urethanes from syringaresinol Marine Janvier, Paul-Henri Ducrot, and Florent Allais ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b01271 • Publication Date (Web): 24 Aug 2017 Downloaded from http://pubs.acs.org on August 24, 2017

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ACS Sustainable Chemistry & Engineering

Isocyanate-free synthesis and characterization of renewable poly(hydroxy)urethanes from syringaresinol Marine Janvier,a,b Paul-Henri Ducrot,*b Florent Allais*a,c AUTHOR ADDRESS [a] Chaire ABI, AgroParisTech, CEBB 3 rue des Rouges Terres 51110 Pomacle, France ([email protected] ; [email protected]) [b] Institut Jean-Pierre Bourgin, INRA / AgroParisTech / CNRS / Université Paris-Saclay, Route de SaintCyr 78026 Versailles, France ([email protected] ; [email protected]) [c] UMR 782 GMPA, INRA / AgroParisTech / CNRS / Université Paris-Saclay, Avenue Lucien Brétignières 78850 Thiverval-Grignon, France ([email protected]) KEYWORDS chemo-enzymatic synthesis, renewable bisphenol, syringaresinol, biobased NIPU, thermoplastics, thermosets

ABSTRACT In a context of replacement of petro-sourced and toxic bisphenol-A (BPA), syringaresinol, a naturally occurring bisphenol deriving from sinapic acid, has been proposed as a greener and safer alternative. This work focuses on its applications for Non-Isocyanate PolyUrethanes (NIPUs) synthesis. A five-membered cyclic carbonate SYR-CC has been prepared by carbon dioxide addition to bis-epoxy monomer SYR-EPO derived from syringaresinol. Upon polyaddition of SYR-CC with different biosourced and petrosourced diamines, the resulting polyhydroxyurethanes were fully characterized by structural analyses

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(FT-IR, 1H NMR, HPLC-SEC), and thermal analyses (TGA, DSC). These thermoplastics തതതത = 5.4 kg.mol-1), excellent thermal stabilities (Td5% = 267-281 °C) displayed high molar mass (‫݊ܯ‬ and glass transition temperatures (Tg) ranging from 63 to 98 °C. Complementary, the coupling of SYR-CC with a triamine gave a thermoset material with interesting Tg (62 °C) and high thermal stability (Td5% = 225 °C).

INTRODUCTION Since the first examples of polyurethanes (PU) described in the 1940’s, the PU market has reached about 5% of the global polymer market, with an estimated global market of 14 Mt in 2010 (according to Research and Markets).1 The adaptable properties of PU materials offer a wide development in various fields such as thermoplastics, thermosets or elastomers, for foams, coatings, adhesives, or isolation materials.2,3 Despite their interesting properties, PUs suffer from a major drawback, namely the use of harmful isocyanates as monomers. Indeed, isocyanates are toxic compounds and their synthesis involves the use of very harmful phosgene. Moreover, several isocyanates are now listed in the restriction list of annex XVII of REACH.4 For the development of safer alternatives, an increasing interest emerged towards new strategies for non-isocyanate polyurethanes (NIPUs) synthesis. Thus the polymer community has been particularly interested in the ring opening polymerization of polyfunctional cyclic carbonates as a greener alternative.5–18 Cyclic carbonate monomers avoid both the use of isocyanate and the production of byproducts. Moreover, the addition of carbon dioxide to oxirane rings constitutes an easy and green access to cyclic carbonates.19,20 Nevertheless, the use of catalysts, such as metal salts19,21 or complexes,22,23 silica-supported amines,24 is necessary to achieve good yields. Recently, an efficient synthesis of


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cyclic carbonates under mild conditions in bulk under atmospheric pressure of CO2 was described, using a bifunctional quaternary phosphonium iodide as catalyst.25 In this alternative, poly(hydroxyl)urethanes are obtained via step growth polymerization of diamine and dicarbonate. The presence of pendant hydroxyl moiety, differing from classical PUs, offers a new range of properties : the resulting NIPUs generally display an increased polarity,5 higher glass transition temperature (Tg) due to interchain hydrogen bonds,26 better thermal stability, lower solubility in organic media and higher water uptake.27 Their major drawbacks are the lower reactivity of cyclic carbonate towards amine8 and generally the lower തതതതത degree of polymerization (‫ܲܦ‬ ௡ ). In addition to the replacement of isocyanate, the substitution of petro-based monomers by renewable synthons attracted the attention of the polymer community. Javni et al. described the curing of carbonated soybean oil with different diamines leading to thermoset NIPUs with Tg ranging from 0 to 40 °C.28 Bähr et al. studied soy- and linseed carbonated oil with high cyclic carbonate functionalities, exhibiting Tg values up to 60 °C upon curing.29 The authors also evaluated cyclic terpene (limonene) for NIPU application with similar Tg (62 °C).16 Similarly, Avérous’ team recently described a sebacic acid-based cyclic carbonate and its bulk catalyst-free polymerization with, however, lower molar mass than conventional PU (up to 22 kg.mol-1).30,31 These studies highlighted a better reactivity of terminal cyclic carbonates compared to internal ones.16,32 Most examples of such biobased NIPUs were based on vegetable oils, with high functionality and varied structures of triglycerides, leading to low Tg thermosets or thermoplastics with low തതതതത ‫ܲܦ‬௡ . Higher mechanical properties could be obtained by using more rigid aromatic biosourced compounds as a competitive alternative to bisphenol-A (BPA), a widespread monomer in polymer industry. In fact, high concern has been recently raised towards


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BPA toxicity. Due to its structure similar to estrogens, BPA is recognized as an endocrine disruptor, inducing a reduced fertility and potentially cancers.33,34 Recently, the use of BPA-based packaging for child products has been prohibited by the United-States Food and Drug Administration.35 Despite the excellent properties obtained for BPA-based materials, its toxicity has raised a demand for BPA-free products and therefore increased the research of a safer and greener alternative.36 In this context, an interesting alternative envisaged is the valorization of lignin, the main bioresource for aromatic compounds, highly abundant (30% of the organic carbon in the biosphere37) and available as a by-product of paper industry without competition with food production. Nevertheless, to the best of our knowledge, published works on biophenol-based NIPUs are very scarce. Creosol based bisphenols were glycidylated, -1 തതതത carbonated and cured with various diamines (‫ܯ‬ ௡ up to 30 kg.mol and Tg ranging from 44 to 90

°C).38 Vanilin was also studied as a biophenol precursor for cyclic carbonate synthesis but has not been engaged yet in the synthesis of NIPUs.39 Our teams recently developed some biosourced bisphenols as an alternative to bisphenol-A (BPA), describing firstly ferulic acid-based bis- and trisphenols as potential substitutes to BPA (for example isosorbide dihydroferulate IDF shown in Figure 1).40 Interestingly the endocrine activity assay showed no endocrine disruption for these phenols. These bis- and trisphenols were used to synthesize linear (thermoplastics) or crosslinked (thermoset) non-isocyanate polyurethanes with a wide range of Tg (17 – 72 °C).41 Unfortunately, the aliphatic chain of the ester moiety of IDF is flexible and provides lower mechanical properties to the resulting polymers compared to those obtained from BPA. Moreover IDF exhibits higher sensibility towards acido-basic treatments, due to the polyester nature of the polymers. Committed to offering a genuine renewable alternative to BPA (with comparable thermo-mechanical


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properties), we are now taking into consideration syringaresinol (SYR) (Figure 1), a naturally occuring bisphenol present in plants such as Syringa patula42 or Magnolia Thailandica43, as a promising candidate. Our team indeed recently reported on an efficient selective chemoenzymatic process for the synthesis of syringaresinol, resulting from the oxidative coupling of two molecules of sinapyl alcohol, obtained from syringaldehyde.44 With cis-fused tetrahydrofuranic moieties and two aromatic rings providing high stiffness (Figure 1), syringaresinol shows interesting structural similarities with BPA but revealed no endocrine disruption. SYR has been used as a precursor for the synthesis of novel α,ω-dienes monomers for ADMET polymerization45 and, when derived as diglycidyl ether (SYR-EPO), for the formulation of epoxy-amine resins46 with high mechanical properties almost competing with BPA. In this study, we explored the potential of syringaresinol as a precursor for the synthesis of new biobased aromatic NIPUs. Cyclic carbonate SYR-CC is readily obtained via carbonation of SYR-EPO. After polyaddition of different diamines with SYR-CC, the resulting NIPUs were structurally (FT-IR, 1H and

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C NMR, HPLC-SEC) and thermally (TGA, DSC) characterized.

NIPU thermosets obtained by coupling with triamine were characterized by FT-IR, TGA and DSC. The resulting syringaresinol-based thermoplastics and thermoset properties were compared with previously described IDF- and widely used BPA-based counterparts.


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OR OMe

OR

OR MeO

O

OMe

O O

O

O

O O

OR

O

MeO

OMe OR

MeO OR -OR =

OH

-OR =

O

-OR =

O

O

O

O O

bisphenol-A (BPA )

isosorbide diferulate (IDF)

syringaresinol (SYR )

diglycidyl ether of bisphenol-A (DGEBA)

diglycidyl ether of isosorbide diferulate (IDF-EPO )

diglycidyl ether of syringaresinol (SYR-EPO )

bisphenol-A biscyclocarbonate (BPA-CC )

isosorbide diferulate biscyclocarbonate ( IDF-CC)

syringaresinol biscyclocarbonate (SYR-CC )

Figure 1. General structures of studied bisphenols (BPA, IDF and SYR) and their corresponding epoxy and cyclic carbonate derivatives EXPERIMENTAL SECTION Material and Methods Syringaldehyde, malonic acid, aniline, pyridine, diisobutylaluminium hydride (DIBAL-H), Trametes versicolor laccase, ferulic acid, Pd/C, benzyltriethylammonium chloride (TEBAC), lithium bromide and tris(2-aminoethyl)amine (TREN) were purchased from Sigma-Aldrich; epichlorohydrin and decane diamine (DA10) were purchased from Acros Organics; isophorone diamine (IPDA) was purchased from Chemical Industry Co; furfurylamine, isosorbide and diglycidyl ether of bisphenol A were purchased from Alfa Aesar. All reagents were used as received. CO2 was purchased from Linde. Solvents were purchased from ThermoFisher Scientific, dimethylformamide was dried on a mBraun SPS 800 system. Deuterated chloroform (CDCl3) and dimethylsulfoxide (DMSO-d6) were purchased from Euriso-top.


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Evaporations were conducted under reduced pressure at temperature below 40 °C for usual solvent, and at 60 °C for dimethylformamide. Column chromatographies were carried out with an automated flash chromatography (PuriFlash 4100, Interchim) and pre-packed INTERCHIM PF-30SI-HP (30 µm silica gel) columns using a gradient of cyclohexane and ethyl acetate for the elution. Carbonations were made in a 100 mL Paar autoclave equipped with magnetic stirring. FT-IR analyses were performed on Cary 630 FT-IR with ATR. UV analyses were performed on Cary 60 UV-Vis from Agilent technologies, by dissolving the samples in acetonitrile. Melting points were measured on a Mettler Toledo MP50 Melting Point System at 2 °C.min-1. NMR analyses were recorded on a Bruker Fourier 300. 1H NMR spectra of samples were recorded in CDCl3 at 300 MHz, chemicals shifts were reported in parts per million (CDCl3, CHCl3 residual signal at δ = 7.26 ppm ; DMSO-d6, DMSO residual signal at δ = 2.50 ppm). 13C NMR spectra of samples were recorded at 75 MHz (CDCl3 signal at δ = 77.16 ppm; DMSO residual signal at δ = 39.52 ppm). HRMS were recorded by the PLANET platform at URCA on a Micromass GCTOF. Thermo-gravimetric analyses (TGA) were recorded on a Q500, from TA. About 10 mg of each sample was heated at 10 °C.min-1 from 30 to 800 °C under nitrogen flow (60 mL.min-1) or compressed air (20 mL.min-1). Differential scanning calorimetry (DSC) thermograms were obtained using a DSC TA Q20, under inert atmosphere (N2), with a calibration using indium, n-octadecane and n-octane standards. For each sample, about 10 mg were weighed in a pan which was then sealed and submitted to 3 heat/cool/heat cycles: heating from 30 °C to 250 °C at 10 °C.min-1, cooling from 250 °C to -50 °C at 20 °C.min-1. Glass transition temperatures (Tg) were determined at the inflexion value in the heat capacity jump. High pressure chromatography by Size Exclusion (HPLC-SEC) was performed at 70°C on an Infinity 1260 system from Agilent Technologies with a quadruple detection (IR, UV, MALS, viscosimetry) and two PL-gel 5mm


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mixed-D columns (300 mm x 7.5 mm) in DMF (flow rate 1 mL.min-1) using polyethylene glycol/polyethylene oxide (PEG/PEO) calibration and toluene as internal standard. Synthesis of monomers The syntheses of ethyl sinapate,46–49 sinapyl alcohol 1,44 syringaresinol (SYR),44 bis-epoxysyringaresinol (SYR-EPO),46 ethyl dihydroferulate, IDF,50 IDF-EPO,50 IDF-CC50 and difurfurylamine (DIFFA)46 have been carried out following procedures previously described in the literature. Detailed procedures are reminded in ESI. Carbonation procedure : A solution of epoxy precursor SYR-EPO (5.05 g, 9.52 mmol), lithium bromide (41 mg, 0.476 mmol, 0.05 eq) in DMF (20 mL) was sealed in a 100 mL autoclave. The system was stirred at 80 °C under 20 bar of carbon dioxide for 24 hours. The solvent was removed by distillation and the crude product was solublized in ethyl acetate (150 mL) and washed with water (3 x 60 mL) to remove DMF traces. The organic phase was dried over anhydrous MgSO4, filtered and concentrated to give SYR-CC as a white amorphous solid (4.75 g, 81 % crude yield).

SYR-CC (white amorphous solid, 81% yield): 1H NMR (300 MHz, DMSO-d6) δ 3.07 (m, 2H, Hβ, Hβ’), 3.78 (s, 12H, H5, H5’), 3.84 (dd, 2H, J = 3.3 and 9.1 Hz, Hɣ1, Hɣ1’), 3.98 (dd, 4H, J = 3.5 and 11.9 Hz, H6), 4.14 (dd, 4H, J = 2.5 and 11.9 Hz, H6’), 4.21 (m, 2H, Hɣ2, Hɣ2’), 4.58 (m, 4H, H8, H8’), 4.69 (m, 2H, Hα, Hα’), 4.98 (m, 2H, H7, H7’), 6.66 (s, 4H, H2, H2’). 13C NMR (75 MHz, DMSO-d6) δ 53.8 (Cβ, Cβ’), 56.0 (C5, C5’), 65.8 (C8, C8’), 71.4 and 71.5 (C6, C6’ and Cɣ, Cɣ’), 75.6 (C7, C7’), 85.1 (Cα, Cα’), 102.9 (C2, C2’), 135.2 (C4,


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C4’), 137.8 (C1, C1’), 152.6 (C3, C3’), 155.0 (C=O). m.p.: 63 °C. UV (nm, λmax): 270. FT-IR (neat, cm-1): νmax 2937 (C-Harom), 1786 (C=O) 1400-1600 (C=Carom), 1000-1300 (C-O-C). HRMS (TOF MS, ES+): m/z calcd for C30H34O14Na: 641.1841; found: 641.1838.

BPA-CC (white solid, 92% yield) : 1H NMR (300 MHz, DMSO-d6) δ 1.58 (s, 6H, H2), 4.16 (dd, 2H, J = 4.5 and 11.3 Hz, H7), 4.24 (dd, 2H, J = 2.7 and 11.3 Hz, H7’), 4.38 (dd, 2H, J = 5.9 and 8.4 Hz, H9), 4.62 (t, 2H, J = 8.4 Hz, H9’), 5.13 (m, 2H, H8), 6.85 (d, 4H, H4), 7.12 (d, 4H, H5). 13C NMR (75 MHz, DMSO-d6) δ 30.7 (C2), 41.3 (C1), 66.1 (C9), 67.4 (C7), 74.9 (C8), 114.1 (C4), 127.6 (C5), 143.3 (C3), 154.9 (C10), 155.8 (C6). m.p.: 166 °C. UV(nm, λmax): 275 . FT-IR (neat, cm-1): νmax 2980 (C-Harom), 1783 (C=Ocarbonate), 14001600 (C=Carom), 1000-1300 (C-O-C). HRMS (TOF MS, ES+): m/z calcd for C23H24O8Na: 451.1363; found: 451.1376. General procedures for NIPU syntheses The cyclic carbonate precursor SYR-CC was melted around 80 °C, and the adequate amount of diamine (DA10, DIFFA and IPDA) or triamine (TREN) was added. An equimolar ratio was chosen, considering that one five-membered ring cyclic carbonate reacts only once with a primary amine. The system was then manually homogenized, transferred to a rubbery mold and cured. In order to avoid freezing of the system and to ensure optimal conversion, a temperature program was established. For example, for SYR-CC, the oven temperature was gradually increased by 10 °C.h-1 from 80 to 160 °C, then maintained at 160 °C for 18 hours (temperature superior to the exothermic reaction peak observed in DSC scan). The different compositions and corresponding temperature programs are depicted in Table 1.


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Cyclic carbonate precursor

Curing agent

Temperature

(w%)

(w%)

Program

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BPA-CC (72) IPDA (28) 165 °C (5 h) 180 °C (18 h) BPA-CC (75) TREN (25) IDF-CC (80) IPDA (20) 80 °C (5h) 100 °C (10 h) IDF-CC (83) TREN (17) SYR-CC (78) DA10 (22) SYR-CC (73) DIFFA (27) 80 to 160 °C (10 °C.h-1) 160 °C (18 h) SYR-CC (78) IPDA (22) SYR-CC (81) TREN (19) Table 1. Composition and temperature program of the formulated thermoplastics RESULTS AND DISCUSSION Synthesis of bisphenol SYR and functionalisation to cyclic carbonate Syringaresinol (SYR) was prepared from syringaldehyde with a 62% overall yield via a 3-steps process (Scheme 1) including as key step the oxidative enzymatic dimerisation of sinapyl alcohol.44 The enzyme-catalyzed dimerization was carried out under mechanical stirring combined with O2 bubbling for a better efficiency of the enzyme. SYR was engaged in the following step without further purification. Functionalization of bisphenol SYR towards epoxy precursor SYR-EPO was carried out in epichlorohydrin with a catalytic amount of triethylbenzylammonium chloride as phase transfer catalyst. A basic treatment with sodium hydroxide gave SYR-EPO with a functionality of 2.0 according to 1H NMR spectrum.46 This bisepoxy was then carbonated in presence of a metallic salt catalyst (lithium bromide) under high pressure of carbon dioxide (ܲ஼ைమ = 20 bar) at 80 °C. A complete conversion of oxiran rings was observed within 20 hours, and SYR-CC was obtained with a high purity and a functionality of 2.0 according to 1H NMR spectrum.


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Scheme 1. Synthesis of dicarbonate from syringaresinol (SYR-CC) Similarly, IDF was obtained in a 3-step procedure from ferulic acid, then glycidylated and carbonated to obtain IDF-CC with a 48% overall yield.41 The same procedure was applied on commercially available DGEBA to obtain BPA-CC with a 92% yield. SYR-CC, IDF-CC and BPA-CC were fully characterized by 1H and

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C NMR, UV, FT-IR and HRMS (see

Experimental section and ESI). Synthesis of NIPU thermoplastics and thermosets in bulk For the preparation of NIPU thermoplastics (or thermosets), an equimolar ratio of dicarbonate and diamine (or triamine) was mixed, considering that one primary amine group will react with one cyclic carbonate (Figure 2). Different carbonates were chosen, allowing the comparison between oil-sourced widely used BPA-CC, flexible biobased IDF-CC and rigid biobased SYRCC. For the choice of diamine, petro-based cycloaliphatic IPDA was chosen as reference, aliphatic DA10 (from castor oil) and aromatic DIFFA (from furfural) were used to synthesize fully biosourced NIPUs. For the thermosets curing, triamine TREN was chosen.


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Polyaddition were carried out in bulk in the molten state, following a temperature program adapted to each cycliccarbonate. IDF-CC was cured at the lower temperature (100 °C), to both ensure the homogeneity of the reaction media and avoid degradation of the fragile ester bond. A higher temperature curing is known to reduce the viscosity of the system and enhance the conversion. Nevertheless, higher temperature was not applied on IDF-CC as transamidation and/or chain scission may occur.2 Inversely, for both SYR-CC and BPA-CC, more robust, a higher temperature program was chosen (160 °C and 180 °C, respectively).

Figure 2. Structures of cyclic carbonates (BPA-CC, IDF-CC, SYR-CC), amines (DA10, DIFFA, IPDA, TREN) and resulting NIPU Structural analysis of the polymers


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FT-IR analysis The structures of the linear and cross-linked prepared NIPUs were first confirmed through FT-IR (Figure 3). The conversion was monitored by observing the disappearance of the carbonate signal (νC=O,carbonate ≈ 1800 cm-1) and the appearance of that of the carbamate (νC=O,carbamate ≈ 1700 cm-1, νNH ≈ 3400 cm-1) (Figure 3, left). This simple analysis allows a qualitative estimation of the conversion, very useful to adjust the polymerization temperature. For example, the FT-IR analysis of BPA-CC polymerized at different temperature showed an improvement of the conversion at higher temperature (Figure 3, right): the cyclic carbonate peak (γC=O at 1783 cm-1) is more intense after polymerization at 100 °C than 180 °C.

Figure 3. FT-IR analyses of (left) syringaresinol-based NIPU (right) BPA-based NIPU at different temperatures


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NMR analyses For all the linear NIPU synthesized, NMR analyses were carried out in DMSOd6. The formation of urethane link was confirmed by

13

C NMR spectroscopy, with the

appearance of new peaks for the quaternary carbon of the carbonyl moiety (at 156.0 and 156.4 ppm for SYR-CC-based NIPU, when resonance of the carbonyl group of the starting carbonates was observed at 155.0 ppm). In 1H NMR spectra, the appearance of peaks between 7.1 and 7.7 ppm corresponds to the NH of the urethane moiety obtained by ring opening. The 1H NMR gives access to an estimated conversion, calculated with the integration of the signal at 4.98 ppm corresponding to the residual unreacted SYR-CC (proton of the tertiary carbon of the cyclic carbonate group). Conversions are depicted in Table 2. NMR analyses also provide information on the regioselectivity of the ring opening polyaddition. As depicted in Figure 4, the nucleophilic attack of the primary amine on cyclic carbonate moiety gives access to both primary and secondary alcohols. The signal of primary alcohol at 4.8-5.0 ppm and that of secondary OH at 3.38-3.57 ppm in the case of SYR-CC were attributed thanks to 2D NMR (COSY, HSQC and HMBC) and hydrogen-deuterium exchange. The ratio of primary and secondary hydroxyl groups (RI/II) can thus be defined by the alcohols signals integrations ratio, as described in literature, and results are summed up in Table 2. RI/II values show the preferential formation of secondary alcohol compared to primary. This observation is in accordance with the literature,7,9,51 which established that the presence of an electro-withdrawing group (PhOCH2-) promotes a selectivity toward secondary alcohol.


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NH 2

O OH R

O

H N

O

O

R

O

O

O

HO

R

Secondary alcohol ( δΟΗ ≈ 3.5 ppm)

H N

O

O

O

Primary alcohol (δ ΟΗ ≈ 4.9 ppm)

Figure 4. Regioselectivity of the addition of amine on cyclic carbonate The careful examination of 1H NMR spectra shows no evidence of unreacted amine, so that we could assess that residual cyclic carbonates are end-chain groups. This hypothesis allows the calculation of the degree of polymerization. For instance, in the case of the NIPU SYR-CC DA10, the 83% conversion would be equivalent to 10 opened carbonates for 2 closed end-ofchain cyclic carbonates, corresponding to a തതതതതത ‫ ݊ܲܦ‬of 5. For all the NIPUs synthesized, similar തതതതതത were obtained (between 5 and 7), except for the couple DIFFA SYR-CC which offered a ‫݊ܲܦ‬ തതതതതത of 9. higher ‫݊ܲܦ‬

primary OH

CH Cyclic carbonate

secondary OH

NIPU composition

δ (in

δ (in Integration

ppm) BPA-CC IPDA IDF-CC IPDA SYR-CC DA10 SYR-CC DIFFA SYR-CC IPDA

RI/II

δ (in

Integration

Integration

ppm)

Conv.*

തതതതതത ‫݊ܲܦ‬

(%)

ppm)

5.23

0.70

4.94

0.57

1.22

5.13

0.30

85

6

5.20

0.67

3.57

1.57

0.20

5.09

0.26

87

7

4.90

0.95

3.55

1.11

0.86

4.98

0.34

83

5

4.97

0.43

3.38

1.88

0.23

4.9

0.21

90

9

4.98

0.99

3.57

1.87

0.53

4.98

0.27

87

6


15


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ூ(ଵு

Page 16 of 37

)

* Conversion is calculated via the formula : 100 − ூ(ଵு೎೤೎೗೚ × 100 ೌೝ೚೘)

Table 2. RI/II, conversion and degree of polymerization estimated by 1H NMR Size Exclusion Chromatography NMR analyses were then completed with size-exclusion chromatography (SEC). For the SEC analyses, thermoplastic NIPUs obtained were solubilized in DMF, using toluene as a flow marker. The molecular weights were determined according to polyethylene glycol/polyethylene oxide (PEG/PEO) standards. The refractive index signal was used to create a calibration curve. The results are summed up in Table 3. For all the NIPU, high conversions were obtained (between 78 and 93%). In the case of IPDA, തതതതത the degree of polymerization was slightly inferior for IDF-CC (‫ܲܦ‬ ௡ = 3), but similar between തതതതത BPA-CC and SYR-CC (‫ܲܦ‬ ௡ = 5 − 6). In all cases, dispersity superior to 1.5 was obtained, as expected for polyaddition. In the case of BPA and SYR, higher dispersities were observed: these results seem to be correlated to the higher polymerization temperature. Indeed, polymerization of BPA-CC at lower temperature (100 °C instead of 160 °C) led to lower polydisperisty index (PDI 1.5 instead of 2.9). The differences of തതതതത ‫ܲܦ‬௡ values between NMR estimation and SEC are correlated to the choice of SEC calibration standard. Indeed, PEG does not have similar molecular weight than NIPUs, for a given hydrodynamic volume; the presence of hydrogen bonds in NIPU reduces the hydrodynamic radius compared to PEG.

NIPU Composition

Mrepeat unit (g.mol-1)

Conversion (%)

തതതത ࡹ ࢔ (kg.mol-1)

തതതതത ࡹ ࢝ (kg.mol-1)

തതതതതത ࡰࡼ࢔

PDI

BPA-CC IPDA

599

88

3.0

8.4

5

2.9

BPA-CC IPDA 100 °C

599

81

2.0

3.0

3

1.5

IDF-CC IPDA

873

88

3.0

4.5

3

1.5

SYR-CC

791

78

5.4

26.7

6

4.9

DA10


16

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


SYR-CC DIFFA

853

93

5.3

16.8

6

3.2

SYR-CC IPDA

789

90

4.6

13.4

6

2.9

Table 3. HPLC-SEC analyses of NIPU Thermal characterization of the polymers The structural analyses of NIPU were completed with thermal characterization (TGA and DSC), and Table 4 sums up these results. NIPU Composition

Td5% (°C) N22 air3

%wchar (%) N22 air3

Tg (°C)4

BPA-CC IPDA

276

274

2

0.20

79

BPA-CC TREN

254

243

2

0.32

63

IDF-CC IPDA

2641

2601

101

0.171

621

IDF-CC TREN

228

228

15

0.19

47

SYR-CC

280

261

19

0.48

62

SYR-CC DIFFA

267

247

28

0.18

73

SYR-CC IPDA

273

271

21

0.12

98

SYR-CC TREN

225

225

24

0.26

62

DA10

1

as described by Menard et al.41; 2 determined by TGA (10 °C.min-1, N2 flow); 3 determined by TGA (10 °C.min-1, air flow); 4 determined by DSC on the second heatcool-heat cycle (10 °C.min-1, N2 flow) Table 4. Thermal characterization of NIPU prepared from BPA-CC, IDF-CC and SYR-CC Thermogravimetric analyses Thermal stability was assessed by TGA under inert atmosphere (N2) and oxidative atmosphere (air). Thermograms are depicted in Figure 5. Td5% is defined as the temperature at which the thermoplastic lost 5%w of its initial mass; w%char corresponds to the relative amount of stable residue at high temperature (700 °C). The behavior of NIPU prepared under heating showed a one-step degradation under inert atmosphere (Figure 5, top) and a two-


17


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Page 18 of 37

steps process under oxidative atmosphere (Figure 5, bottom). Table 4 sums up the values of Td5% and w%char of the NIPU prepared. The thermoplastics prepared from syringaresinol displayed good thermal stability, with a range of Td5% from 267 to 280 °C. This stability is similar to the stability of both IDF- and BPA-based NIPUs. For the thermoset materials, similar Td5% were obtained for SYR-, IDF- and BPA-based resins (ranging from 225 to 254 °C). Concerning the high temperature char content w%char, the DIFFA containing NIPU offers the highest char content and the DA10 the lowest. This trend is in accordance with the structure of the amine: during the thermal degradation, aromatic moiety (e.g., furanic rings of DIFFA) is favorable to the charring mechanism, contrary to aliphatic chains. When comparing the NIPUS with regards to IPDA, BPA-CC exhibits the lowest char content (2%) whereas both IDF-CC and SYR-CC display the highest (10 and 21%, respectively). The same trend is observed for the thermosets obtained with TREN. These high char contents could be interesting in the case of flame retardant applications. Interestingly, the TGA analyses under air revealed quiet similar thermal stability for both IPDA and TREN. In the case of DA10 and DIFFA, the presence of air implies lower Td5% (about 20 °C lower). Moreover, thermal degradation under air was total with the different materials, allowing full incineration for products end-life.


18

Page 19 of 37

100

SYR-CC DA10 SYR-CC DIFFA SYR-CC IPDA IDF-CC IPDA BPA-CC IPDA SYR-CC TREN IDF-CC TREN BPA-CC TREN

90 80

%weight

70 60 50 40 30 20 10 0 100

200

300

400

500

600

700

800

T (°C) 100

SYR-CC DA10 SYR-CC DIFFA SYR-CC IPDA IDF-CC IPDA BPA-CC IPDA SYR-CC TREN IDF-CC TREN BPA-CC TREN

80

60 %weight

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


40

20

0 100

200

300

400

500

600

700

800

-20 T (°C)

Figure 5. TGA analyses of NIPU prepared from BPA-CC, IDF-CC, SYR-CC (top : under N2 ; bottom : under air) Differential Scanning Calorimetry Analyses To assess the glass transition temperatures (Tg) of the prepared NIPU, DSC analyses were carried out. DSC curves of prepared NIPUs are presented in ESI and results are summarized in Table 4. For a same cyclocarbonate precursor (SYR-CC), the choice of diamines offers a wide range of Tg, from 62 °C with flexible aliphatic


19


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Page 20 of 37

DA10 to 98 °C for more rigid cyclic IPDA. For the same amine used (IPDA), IDF-based linear NIPU offered the lowest Tg (62 °C) due to the flexibility of the aliphatic chain of the esters. The same trend was previously observed for epoxy-amine resins.46 Interestingly, in the case of NIPU thermoplasitcs, the rigidity of syringaresinol offered the highest Tg, 20 °C higher than BPA. For NIPU thermosets, IDF offered the lower Tg (47 °C) while SYR reached BPA value. Moreover, Miller et al.52 had already described a rise of Tg linked to the presence of methoxy groups on the aromatic monomer, due to an increase of conformational barriers for chain motion. Interestingly the same trend was observed in our study, showing higher Tg for SYR (two methoxy) compared to IDF (one methoxy). Unfortunately, both thermoplastics and thermosets prepared were too brittle for further mechanical analysis (by DMA). CONCLUSIONS A renewable aromatic cyclic carbonate (SYR-CC) was synthesized in excellent yield and purity from syringaresinol, a bisphenol readily obtained at the multigram scale via an efficient chemoenzymatic pathway from syringaldehyde. This non endocrine disruptive biosourced bisphenol was studied as an interesting genuine safe alternative to BPA. In this purpose, SYR-CC was polymerized in bulk with different diamines, providing fully biobased linear NIPUs, with high conversion and average molar mass (4.6-5.4 103 g.mol-1, corresponding to തതതതതത ‫ = ݊ܲܦ‬6). The polyhydroxyurethane structures were confirmed by FT-IR and NMR analyses. For the thermal characterization, SYR-CC was compared to two other bisphenols: IDF-CC from biosourced ferulic acid and widely used BPA-CC from oil. The analyses of SYR-CC NIPUs demonstrated tunable glass transition and degradation temperatures by varying the diamine nature (up to Tg = 98 °C and Td5% = 280 °C) competing with that of BPA (Tg = 79 °C and Td5% = 276 °C). The തതതതതത observed to obtain high mechanical stiffness of syringaresinol thus compensated for the low ‫݊ܲܦ‬


20

Page 21 of 37

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properties. In the case of DIFFA and DA10, the polymers were fully prepared from renewable feedstocks and could be envisaged as sustainable substitutes to conventional petro-based polyurethanes. Additionally, NIPU thermosets were obtained by coupling SYR-CC with the triamine TREN, showing thermal properties comparable to similar BPA-based resins.

In

addition to ADMET45 and epoxy amine resine46 applications, this study thus confirms the great potential of syringaresinol as a greener and safer alternative to BPA. To further explore the potentiality of syringaresinol in polymers, α,ω-diene derivatives of syringaresinol are currently investigated for thiol-ene coupling polymerization and results will be reported in due course. SUPPORTING INFORMATION Complementary procedures,

1

H and

13

C NMR spectra, FT-IR spectra, HPLC-SEC

chromatograms and DSC traces. This material is available free of charge via the internet at http://pubs.acs.org. ACKNOWLEDGMENTS The authors are grateful to the Region Champagne-Ardenne, the Conseil Départemental de la Marne and Reims Métropole for their financial support. BIBLIOGRAPHY (1)

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aromatics.

Green

Chem.

2015,

17

(9),

4512–4517

DOI:

10.1039/c5gc01104c.


29


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Page 30 of 37

For Table of Contents Use Only

Syringaresinol, a biosourced bisphenol, was derivatized into difunctional cyclic carbonate SYRCC and polymerized with polyamines for the synthesis of renewable linear and cross-linked NIPU.


30

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment

OR ACS Sustainable Chemistry & Engineering

Page 32 of 37

OMe

1 2 3 4 5 6 7 8 9 10 11 12 13= -OR 14 15 16= -OR 17 18 19 20 -OR = 21 22 23

OR

OR MeO

O

OMe

O O

O

O

O O

OR

O

MeO

OMe OR

MeO OR OH

O

O

O

O

O O

bisphenol-A (BPA)

isosorbide diferulate (IDF)

syringaresinol (SYR)

diglycidyl ether of bisphenol-A ( DGEBA)

diglycidyl ether of isosorbide diferulate ( IDF-EPO )

diglycidyl ether of syringaresinol ( SYR-EPO )

Plus Environment isosorbide diferulate

syringaresinol biscyclocarbonate (SYR-CC )

ACS Paragon bisphenol-A biscyclocarbonate ( BPA-CC )

biscyclocarbonate ( IDF-CC)

Page 33 of 37

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33




1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43


Page 34 of 37

Page 35 of 37

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NH 2

O OH O

H N

O

O

O

R O

O

R

H N

O O O HO

R Secondary alcohol ( !"# $ 3.5 ppm)

Primary alcohol (! "# $ 4.9 ppm)


#!!" +!" *!" )!" (!" '!" &!" %!" $!" #!" !" #!!"

Page 36 of 37

,-./01"23#!" ,-./01"24553" ,-./01"4623" 425/01"4623" 763/01"4623"

$!!"

%!!"

&!!"

'!!"

(!!"

)!!"

)(*+,-(

!("#$%&'(

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

!"#$%&'(


#!!" +!" *!" )!" (!" '!" &!" %!" $!" #!" !" #!!"

,-./01"23#!" ,-./01"24553" ,-./01"4623" 425/01"4623" 763/01"4623"

$!!"

%!!"

&!!"

'!!"

(!!"

)(*+,-(


)!!"

Page 37 of 37


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment

Isocyanate-Free Synthesis and Characterization of Renewable Poly

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