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. 2026 May 27;6(4):1192–1199. doi: 10.1021/acspolymersau.6c00068

Biobased Carbohydrate-Based Linear Aliphatic Polyesters Containing Acetyl-Protected Sorbitol, Mannitol, and Xylitol: Synthesis and Their Thermal, Tensile Properties

Ayana Inoue †, Mohamed Mehawed Abdellatif †, Seiji Higashi ‡, Kousaku Tao ‡, Hiroshi Hirano ‡, Koichi Takada ‡, Makawun Sonkasettrin §, Panuwat Padungros §,*, Kotohiro Nomura †,*
PMCID: PMC13474338  PMID: 42602653

Abstract

Development of functional polymers from biorenewable resources has been considered as an important subject in terms of circular economy. High molecular weight biobased aliphatic polyesters (M n = 53900–65600 g/mol) consisting of bis­(undec-10-enoate) of acetyl-protected D-sorbitol, D-mannitol, and of D-xylitol have been prepared by acyclic diene metathesis (ADMET) polymerization using molybdenum–alkylidene catalyst in toluene; subsequent olefin hydrogenation gave the saturated polyesters without significant decreases in the M n values (M n = 55300–64900 g/mol). The resultant saturated polyesters containing sorbitol and xylitol were semicrystalline materials possessing melting temperature at 17.1 and 14.3 °C, respectively, whereas the polyester containing mannitol was amorphous. The mechanical properties (tensile stress and elongation at break) of the resultant polymer film containing sorbitol displayed a unique contrast to that containing the reported isosorbide-based polyester and showed unique elongation at break (1580%). The mechanical properties in the polymer films containing mannitol and xylitol were improved by preparing the composite materials with a small amount of cellulose nanofiber (1.0 wt %).

Keywords: biobased polyesters, sugar-based polyesters, sorbitol, xylitol, long aliphatic polyesters, tensile properties

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Introduction

The development of chemically recyclable functional polymers from renewable feedstocks has been an important subject in circular economy as well as in polymer chemistry, sustainable chemistry, and materials science. − Biobased long-chain aliphatic polyesters derived from plant oil (fatty acid esters) are recognized as promising materials − due to their rather facile chemical recyclability − compared to conventional petroleum-based polyolefins (polyethylene, polypropylene, etc.) by transesterification even under acid- and base-free conditions. −

It has been known that, in general, the physical properties of linear aliphatic polyesters of type [C­(O)­O­(CH2) x OC­(O)­(CH2) y ]n are influenced by the methylene chain length (called odd–even effect), ,− but such an effect was diminished by an increase in the number of the methylene units; the physical and chemical properties of the biobased long-chain linear aliphatic polyesters consisting of all fatty acid esters, exemplified in Chart (1), ,− thus reach those of polyethylene-like materials. In contrast, in biobased aliphatic polyesters, consisting of linear fatty acid esters and certain diols exemplified in Chart (2), it has been recognized recently that not only physical and chemical properties but also their mechanical properties in films and their crystallization characteristics are influenced by the monomer repeat units employed. ,− In particular, the “middle diol unit (segment)” plays an important role − for displaying unique properties through interpolymer communication (interaction). Recent studies also reveal that tensile properties [tensile stress (strength) and strain (elongation) at break] in the films are also influenced by their polymer chain length (M n values). , These properties – especially polyesters containing isosorbide (C18IS) or isomannide (C18IM, Chart ) – increased upon increase in the M n values (M n = >40000), attributable to enhanced interpolymer interactions arising from greater chain entanglement between polymers. Although carbohydrate-based linear aliphatic polyesters are expected to display promising properties through rather strong interpolymer interaction via hydrogen bonding, as far as we know, there have been no reports of synthesis of such high molar mass polymers. −

1. Selected Reports for Aliphatic Polyesters from Biorenewables.

1

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We herein report on synthesis of high molar mass biobased polyesters (M n = 55400–64900) derived from acetyl-protected sorbitol, mannitol, and xylitol (denoted as HP1–3, Chart ) by acyclic diene metathesis (ADMET) polymerization of the bis­(undec-10-enoate)­s using molybdenum–alkylidene catalysts and subsequent complete olefin hydrogenation. This study also reports that the middle diol segment (sugar alcohol units) plays a crucial role for exhibiting their thermal and tensile properties in film.

Results and Discussion

Synthesis of Acetyl-Protected Sorbitol-, Mannitol- and Xylitol-Based Monomers, and Polymers by Acyclic Diene Metathesis (ADMET) Polymerization and Subsequent Hydrogenation

Three monomers consisting of bis­(undec-10-enoate)­s of acetyl-protected D-sorbitol (M1), D-mannitol (M2), or D-xylitol (M3) have been chosen on this study because these sugar alcohols are readily commercially available from naturally abundant sugars and should be thus suited to start the project. These α,ω-nonconjugated diene monomers (M1–M3) could be isolated by direct reaction from 10-undecenoyl chloride (2.0 equiv) with these sugar alcohols shown in Scheme . Since the primary alcohols in these sugar alcohols are generally highly reactive compared to the secondary alcohols, the initial reaction thus gave a mixture of the desired diester and the corresponding monoester as the major product (Figures S1 and S2). Although direct isolation of the diesters containing hydroxy groups seemed challenging, the nonconjugated dienes of bis­(undec-10-enoate) derivatives (M1–M3) could be thus isolated after acetylation with acetic anhydride in pyridine, following the reported procedure for synthesis of sugar alcohol-based norbornene monomers for ring opening metathesis polymerization (ROMP). − The resulting monomers (M1–M3) could be isolated as pure forms after purification through column chromatography (yield 29–55%), and they were identified by NMR spectra including peak assignments through 2D NMR (HMBC and HSQC) spectra (Figures S3–S12, Supporting Information) and APCI-MS mass spectrometry.

1. Synthesis of Nonconjugated Diene Monomers Containing Acetyl-Protected D-Sorbitol (M1), D-Mannitol (M2), and D-Xylitol (M3) as the Diol Units.

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The molybdenum–alkylidene catalyst, Mo­(CHCMe2Ph)­(N-2,6-Me2C6H3)­[OC­(CH3)­(CF3)2] (Mo cat.), has been chosen for this study, not only because the catalyst afforded high molar mass isosorbide- and isomannide-based polymers (C18IS and C18IM, respectively, Chart ) but also because the molybdenum catalyst enabled ROMP to proceed of norbornene monomers containing acetyl-protected sugars (glucose, maltose) in a controlled (living) manner. , ADMET polymerizations of M1–M3 were thus conducted in toluene (1.0 mL) in the presence of Mo cat. (1.0 or 0.5 mol %) under reduced pressure followed by the reported procedure. In the drybox, a sealed reaction tube containing a toluene solution of prescribed monomer and Mo cat. was cooled by placing it into a chilled toluene bath (−30 °C), and the tube was then connected to a vacuum line with opening the valve for a while. The sealed tube was then stirred at room temperature (25 °C) under reduced pressure. The polymerization was carried out with freeze–degassing intervals – every 10 min for the first hour, every 30 min for the second hour, and every hour thereafter – for a total of 6 h. The reaction was terminated by addition of excess benzaldehyde. The time course experiments revealed that the M n value in the ADMET polymerization of M1 increased even after 3 h (run 1 vs runs 2–6, Table ), and all the other polymerization runs were, therefore, conducted for a total of 6 h. The results are summarized in Table .

1. Synthesis of Polyesters (P1–P3) by ADMET Polymerization .

run monomer Mo cat./ mol % M n / g·mol–1 M w/M n yield/%
1 M1 1.0 36800 2.29 85
2 M1 1.0 56100 1.77 71
3 M1 1.0 62900 2.01 74
4 M1 1.0 58900 2.30 88
5 M1 1.0 56400 2.26 81
6 M1 0.5 53900 1.74 74
7 M2 1.0 59000 2.25 83
8 M2 1.0 65600 2.27 83
9 M2 1.0 62300 2.53 88
10 M3 1.0 58900 1.80 77
11 M3 1.0 56200 2.43 66
12 M3 1.0 64100 2.12 88
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a

Conditions: Monomer 287 mg in 1.0 mL toluene, 25 °C for 6 h.

b

GPC data in THF vs polystyrene standards.

c

Isolated yield by precipitation as the cold methanol insoluble fraction.

d

Reaction: 3 h.

e

M n = 34300, M w/M n = 1.72 (Figure S31); measurement of absolute molar mass.

As summarized in Table , the resultant polymer from M1 (expressed as P1, Scheme ) possessed high molecular weights with unimodal molecular weight distributions (M n = 53900–62900, M w/M n = 1.74–2.30, runs 2–6, GPC traces are shown in Figure S25, Supporting Information; these M n values were estimated based on a calibration curve with polystyrene standards) with good reproducibility, and the polymerization in the presence of 0.5 mol % of Mo cat. (in place of 1.0 mol %) led to a decrease in the M n value (run 6). Similarly, the polymerizations of M2 and M3 gave the polymers which possess high molecular weights (P2, M n = 59000–65600; P3, M n = 56200–64100, their GPC traces are shown in Figures S26 and S27, respectively); observed difference in the M n values were probably due to the effect of viscosity (stirring) of the reaction mixture close to the final stage (maybe due to the degree of removal of ethylene remaining). Measurement of absolute molar mass (sample run 2) also confirmed that the resultant polymer possessed a high Mn value with unimodal molecular weight distribution (M n = 34300, M w/M n = 1.72, Figure S31).

2. Acyclic Diene Metathesis (ADMET) Polymerization of Nonconjugated Diene Monomers (M1–M3) Using Molybdenum-Alkylidene Catalyst (Mo cat.) and Subsequent Olefin Hydrogenation by RhCl­(PPh3)3 .

2

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The 1H NMR spectrum in the resultant polymers (P1, in CDCl3 at 25 °C, Figure S13) showed resonances characteristic of the internal olefinic protons with disappearance of those assigned to protons of the terminal olefins in M1 (Figure S3). The other resonances in M1 were unchanged even after the polymerization (P1), except protons ascribed to olefinic double bonds. Moreover, the 13C­{1H} NMR spectrum of P1 (P1, in CDCl3 at 25 °C, Figure S14) displays that resonances assigned to carbon of the internal olefins were observed with disappearance of resonances ascribed to those of terminal olefins, whereas the other resonances were unchanged by polymerization (Figure S4 vs Figure S14). The NMR spectra for the other polymers (P2, P3) showed similar spectral trends (Figures S15–S19). Taking into account these results, it is thus clear that the resultant polymers (P1–P3) were produced by ADMET polymerization. ,−

According to the previous report, olefin hydrogenations of the resultant polymers (P1–P3) were conducted in toluene in the presence of RhCl­(PPh3)3 (called Wilkinson catalyst) under 1.0 MPa of H2 at 50 °C for 20 h. The results are summarized in Table . Both 1H and 13C­{1H} NMR spectra of the hydrogenated polymers HP1 (in CDCl3 at 25 °C, Figures S19 and S20) did not show any resonances ascribed to protons/carbons of the internal olefins, whereas no significant changes of the other resonances were seen between P1 and HP1. The other hydrogenated polymers (HP2 and HP3) showed similar trends in the NMR spectra (Figures S21–S24). Moreover, it should be noted that no significant differences in the M n values were observed before (P1–P3) and after the hydrogenation (HP1–HP3), clearly demonstrating successful synthesis of the saturated polyesters.

2. Synthesis of Saturated Polyesters (HP1–HP3) by Olefin Hydrogenation .

  before hydrogenation
 after hydrogenation
run sample no. M n / g·mol–1 M w/M n T m (T g)/ °C M n / g·mol–1 M w/M n yield/% T m (T g)/ °C
13 P1 (run 2) 56100 1.77   52900 1.89 95  
14 P1 (run 3) 62900 2.01   60100 2.23 94  
15 P1 (run 5) 58900 2.30 (1.9) 55300 2.31 93 17.7
16 P2 (run 7) 59000 2.25   57200 2.22 87  
17 P2 (run 8) 65600 2.27   64900 2.38 93  
18 P2 (run 9) 62300 2.53 (−0.5) 61700 2.57 92 (5.9)
19 P3 (run 10) 58900 1.80   58200 1.88 90  
20 P3 (run 11) 56200 2.43   55400 2.42 95  
21 P3 (run 12) 64100 2.12 (−10.7) 63000 2.21 95 14.3
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a

Conditions: 150 mg of ADMET polymer, 2.0 mg of RhCl­(PPh3)3 cat., toluene 2.0 mL, H2 1.0 MPa, 50 °C, 12 h.

b

Run numbers are given in Table .

c

GPC data in THF vs polystyrene standards.

d

By DSC thermograms.

e

Isolated yield by precipitation as the methanol insoluble fraction.

f

M n = 34300, M w/M n = 1.72 (Figure S31, before hydrogenation, run 2) and M n = 32400, M w/M n = 1.77 (Figure S32, after hydrogenation, run 13); measurement of absolute molar mass.

As shown in Figure (left), DSC thermograms of the resultant unsaturated polymers (P1–P3) obtained by ADMET polymerization were amorphous with uniform compositions possessing sole glass transition temperatures (T g), and the T g values were dependent upon the alcohol employed. The T g value increased in the order: P3 (−10.7 °C) < P2 (−0.5 °C) < P1 (1.9 °C). In contrast, interestingly, as shown in Figure (right), the resultant saturated polymers (after olefin hydrogenation) containing acetyl-protected sorbitol (HP1) and xylitol (HP3) possess a melting temperature (semicrystalline), whereas the polymer containing mannitol (HP2) was amorphous, possessing a sole T g value (5.9 °C). In all cases, the resultant polymers possess uniform compositions (possessing a sole T g or T m value), and completion of the olefin hydrogenation could be confirmed by both the NMR spectra (Figures S9–S20) and the DSC thermograms (Figure ).

1.

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DSC thermograms for aliphatic polyesters containing sorbitol, mannitol and xylitol before and after olefin hydrogenation (P1–P3, HP1–HP3, respectively).

Attempted preparations of the polymer thin films of HP1–HP3 for tensile analysis revealed that only HP1 sample (M n = 55300, M w/M n = 2.31, run 15) could be deserved for preparation of dumbbell shaped test sheets by cutting the solvent cast films. It seemed, however, very challenging for preparation of films suitable for the analysis from HP2 (Figure S37, M n = 61700, M w/M n = 2.57, run 18) and HP3 (M n = 55400, M w/M n = 2.42, run 20). Their composite films with cellulose nanofiber [CNF, HP-NFBC (CNF modified with hydroxypropyl groups), Kusano Sakko Co.] were successfully prepared through the solvent cast method after sonication of the THF solution containing the polyester and 1.0 wt % CNF (used as thin fibers prepared by the freeze-dry method) for the homogeneous dispersion according to the reported method (the composite film prepared from HP2 is shown in Figure S37).

The tensile tests (stress/strain experiments), measurements of the prepared films were performed by using a universal testing instrument at an elongation rate of 20 mm/min under controlled conditions (23 °C, humidity 50 ± 10%). Further experimental details are described in the Experimental Section. The measurements were repeated at least 3 times (by using dumbbell shaped test sheets) to ensure the reproducibility, and the original data are shown in SI (Figures S33–S36). The representative results are summarized in Figure .

2.

2

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Tensile strength (stress) and strain (elongation) at break for polyester films (HP1) and the composite films for HP1–HP3 with 1.0 wt % cellulose nanofiber (speed 20 mm/min). These films were prepared by the solvent cast method, and details are described in the Experimental Section.

It was revealed that the solvent-cast film of HP1 containing sorbitol (M n = 55300, M w/M n = 2.31, run 15) showed notably high elongation at break (tensile strain at break, 1580%) compared to the isosorbide-based polyesters (C18IS in Chart ; elongation at break 436%, M n = 48200) reported previously, whereas HP1 showed significantly low tensile stress (strength) at break [0.30 MPa (HP1) vs 39.7 MPa (C18IS)]. These results clearly indicate that the tensile properties are affected by the middle diol unit (segment) employed. Moreover, the tensile stress (strength) in the composite films increased in the order HP3+CNF < HP1+CNF (0.21 MPa) < HP2+CNF (0.56 MPa). The composite film (HP1+CNF), however, did not show significant improvements in the tensile stress, whereas a decrease in the tensile strain (elongation) was observed, as observed in the composite films of C18IS. The tensile properties for HP2 and HP3 improved by preparation of composite films, although the composite film of HP3 still showed very low tensile stress (strength) along with remarkable elongation (1200%).

Concluding Remarks

We have shown that acyclic diene metathesis (ADMET) polymerization of bis­(undec-10-enoate)­s of acetyl-protected D-sorbitol (M1), D-mannitol (M2), and of D-xylitol (M3) using the molybdenum–alkylidene catalyst (Mo cat) afforded high molar mass polymers (P1–P3, M n = 53900–65600 g/mol) with uniform compositions as well as unimodal molecular weight distributions. As far as we know, this is the first report for synthesis of high molar mass carbohydrate-based linear polyesters. − The subsequent olefin hydrogenation catalyzed by RhCl­(PPh3)3 yielded saturated aliphatic polyesters without significant decreases in the M n values in all cases (Table , M n = 55300–64900 g/mol). The resultant polyesters consisting of acetyl-protected sorbitol (HP1) and xylitol (HP3) are semicrystalline polymers possessing melting temperature, whereas the resultant polyester consisting of D-mannitol (HP2) was amorphous, possessing a sole T g value.

The tensile analysis reveals that the resultant HP1 film showed unique elongation at break (1580%). The mechanical properties in the film (HP2, HP3) were improved by preparation of the composite films with cellulose nanofiber (CNF, 1.0 wt %). The results should present interesting data that the tensile behavior in the biobased aliphatic polyesters is strongly influenced by the middle diol (sugar alcohol) unit employed.

The presented synthetic methodology employed should provide a simple, straightforward method for preparation of polyesters containing sugars (carbohydrate-based linear polyesters). The ADMET polymerizations using Mo cat. should be suitable for the purpose for obtaining high molar mass polymers which should exhibit better entanglement between polymer chains (interpolymer interaction). The tensile results presented here demonstrate a unique contrast to those reported previously, especially C18IS and C18IM, strongly suggesting that these tensile properties are strongly influenced by the diol units employed. Since we recently demonstrated an improvement (modification) of the tensile property by placement of two diols by connecting with dicarboxylic acids (shown in Chart , trans-1,4-cyclohexane dicarboxylic acid, 2,5-furane dicarboxylic acid), the efforts through this study should contribute to the design and development of the advanced biobased polyesters for circular economy; further efforts will be introduced in the near future.

Experimental Section

General

Experimental procedures in this study were performed under a nitrogen atmosphere unless otherwise noted. Solvents of anhydrous grade (greater than 99.5%, Kanto Chemical Co., Inc.) were stored in a bottle containing molecular sieves in the drybox. Toluene for the polymerization was stored in the presence of Na–K alloy and was passed through an alumina short flush column under nitrogen flow in the vacuum atmosphere drybox. Molybdenum catalyst, Mo­(CHCMe2Ph)­(N-2,6-Me2C6H3)­[OC­(CH3)­(CF3)2]2 (Mo cat), was prepared according to the reported procedure. All chemicals of reagent grade were used as received.

Analyses of 1H and 13C­{1H} NMR spectra for identification of monomer and polymers were conducted using a Bruker AV500 spectrometer (500.13 MHz for 1H, 125.77 MHz for 13C­{1H}). Analyses of molecular weights and the distributions (M w, M n, M w/M n) in the resultant polymers were conducted by GPC in tetrahydrofuran at 40 °C, using columns filled with a spherical poly­(styrene-co-divinylbenzene) porous gel (MW < 102 to 2 × 107). A calibration curve using standard polystyrene samples with certified molecular weights was used for estimation of M n values in the resultant polymers. DSC (differential scanning calorimetric) analysis for thermal properties of the polymer samples was carried out using a Hitachi DSC 7020 analyzer under nitrogen atmosphere. Molecular weights of monomers (M1–M3) were measured through APCI (atmospheric pressure chemical ionization) mass spectrometry (Bruker MicroTOF IISDT1).

Tensile tests were conducted by using Shimadzu Universal Testing Instruments (Autograph AGS-10kNX) equipped with a load cell (500 N capacity) with speed of 20 mm/min under controlled atmosphere (23 °C, humidity 50 ± 10%). Dumbbell-shaped test specimens [overall length 25 mm (thickness 60–86 μm, shown in SI): width of parallel portion 3 mm, distance between grippers (or gripping distance) 10 mm] were prepared by cutting the solvent cast films (prepared from toluene solution on Petri dish, ϕ 50 mm on hot plate). According to our reported methodology, a THF solution (2.0 mL) of polymer sample (HP1–HP3, 150 mg) was mixed with a THF solution (3.0 mL) containing 1.0 wt % CNF, and the mixed solution was sonicated for 10 min; the solution was then poured into a PTFE dish (ϕ 50 mm) and dried over a hot plate to form the thin films.

Detailed experimental descriptions concerning syntheses of monomers (M1–M3) and polymers (P1–P3, HP1–HP3) including NMR spectra for identifications are shown in Supporting Information.

Supplementary Material

lg6c00068_si_001.pdf (2.2MB, pdf)

Acknowledgments

This project was partly supported by JST-CREST (Grant Number JPMJCR21L5) and JST SICORP (Grant Number JPMJSC19E2) for the International Collaboration (KN, PP).

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acspolymersau.6c00068.

  • (i) General procedure and synthetic procedures of monomers and polymers including NMR spectra, (ii) selected GPC traces and (iii) tensile analysis for the prepared films. (PDF)

KN designed the project (conceptualization, polymer design, methodology, supervision) including funding acquisition and project administration. KN and PP designed the project for collaboration. AI conducted all synthetic and analysis experiments, and MMA helped conduct research with AI and KN; SM helped synthesize related monomers under PP and exchanged efforts with KN, MMA. SH, KT and HH conducted measurements of tensile properties, and MMA helped with analysis. KT measured absolute molar mass in some polymer samples. KN, AI, MMA, SH, HH wrote the original manuscript, and KN revised the manuscript. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Japan Science and Technology Agency (JST), Core Research for Evolutional Science and Technology (CREST, Grant Number JPMJCR21L5)

The authors declare no competing financial interest.

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