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. 2023 Oct 4;12(10):1403–1408. doi: 10.1021/acsmacrolett.3c00481

Synthesis of High Molecular Weight Biobased Aliphatic Polyesters Exhibiting Tensile Properties Beyond Polyethylene

Mika Kojima †, Xiuxiu Wang †, Lance O’Hari P Go †, Ryoji Makino †, Yuichi Matsumoto †, Daisuke Shimoyama †, Mohamed Mehawed Abdellatif †, Joji Kadota ‡, Seiji Higashi ‡, Hiroshi Hirano ‡,*, Kotohiro Nomura †,*
PMCID: PMC10586459  PMID: 37793171

Abstract

graphic file with name mz3c00481_0005.jpg

Synthesis of high molecular weight polyesters prepared by acyclic diene metathesis (ADMET) polymerization of bis(undec-10-enoate) with isosorbide (M1), isomannide (M2), and 1,3-propanediol (M3) and the subsequent hydrogenation have been achieved by using a molybdenum-alkylidene catalyst. The resultant polymers (P1) prepared by the ADMET polymerization of M1 (in toluene at 25 °C) possessed high Mn values (Mn = 44400–49400 g/mol), and no significant differences in the Mn values and the PDI (Mw/Mn) values were observed in the samples after the hydrogenation. Both the tensile strength and the elongation at break in the hydrogenated polymers from M1 (HP1) increased upon increasing the molar mass, and the sample with an Mn value of 48200 exhibited better tensile properties (tensile strength of 39.7 MPa, elongation at break of 436%) than conventional polyethylene, polypropylene, as well as polyester containing C18 alkyl chains. The tensile properties were affected by the diol segment employed, whereas HP2 showed a similar property to HP1.

Aliphatic polyesters derived from plant resources are attracting considerable attention1−8 not only as an alternative of petroleum-based polymers but also in terms of their circular economy9−11 due to rather facile chemical recycling by the depolymerization (through transesterification, etc.)12−15 compared to conventional polyolefins. These polyesters would also provide a possibility as new promising materials with better mechanical properties through interpolymer interactions as well as better compatibility with biobased fibers (described below). An olefin metathesis route consisting of acyclic diene metathesis (ADMET) polymerization16−19 and the subsequent hydrogenation (Scheme 1) have been considered as the synthetic route due to the wide polymer scope (especially the polymer main chain, called the middle segment in Scheme 1) in addition to the condensation–polymerization route.7 In spite of the number of reports by ADMET polymerization in the presence of ruthenium-carbene catalysts,15,20−34 however, synthesis of the high molecular weight polymers still seems to be difficult.35 Two studies28,34 reported the synthesis of the high molar mass polyesters under bulk conditions (80–90 °C, G2, 16–20 h). However, polymerization at such high temperature led to catalyst decomposition which not only causes isomerization and undesired side reactions by formed radicals (metal particles)15,21,24 but also causes the separation of metals from the resultant polymers to be difficult. The method also faces the difficulty of stirring due to high viscosity.15

Scheme 1. Synthesis of Aliphatic Polyesters by Acyclic Diene Metathesis (ADMET) Polymerization.

Scheme 1

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Recently, the polymerization of M1 and M2 conducted in ionic liquid (IL, no vapor pressure) with continuous removal of ethylene byproduced afforded polymers with Mn value higher than 30000 (Scheme 1),15 whereas the polymerization conducted in toluene or CHCl3 (even under optimized conditions with careful removal of ethylene) afforded polymers of Mn values up to 15000.21,32 We thus herein communicate that the synthesis of high molar mass polymers (Mn = 44000–49400 g/mol), which exhibit better tensile properties than conventional polyethylene, has been achieved by using the molybdenum-alkylidene catalyst, Mo(CHCMe2Ph)(2,6-Me2C6H3)[OC(CH3)(CF3)2] (Mo cat.), even in toluene at 25 °C.36

Table 1 summarizes the selected results for ADMET polymerization of M1–M3 in toluene (at 25 °C) in the presence of the molybdenum-alkylidene catalyst (Mo cat.). Three monomers (M1–M3) have been chosen in this study because these are easily available from castor oil (undecenoate) and sugars (isosorbide, isomannide, and 1,3-propanediol). The Mo catalyst has been chosen because the catalyst showed unique characteristics especially for the synthesis of poly(9,9′-dialkyl-fluorene-2,7-vinylene)s in the ADMET polymerization.37,38 The experimental details and the additional polymerization results and selected NMR spectra for the identifications are shown in the Supporting Information (SI).

Table 1. ADMET Polymerization of M1–M3a.

runa monomer (μmol) cat. cat./mol % solvent (mL) temp/°C time/h yieldb/% Mnc/g·mol–1 Mw/Mnc
1d M1 (90.5) Mo 5.0 toluene (0.72) 25 6 99 16000 1.79
2d M1 (90.5) Mo 5.0 toluene (0.72) 25 8 91 20800 1.73
3 M1 (90.5) Mo 2.5 toluene (0.72) 25 6 90 25100 1.43
4d M1 (90.5) Mo 1.0 toluene (0.72) 25 6 88 34400 1.49
5 M1 (90.5) Mo 1.0 toluene (0.72) 25 6 84 31100 1.89
6 M1 (272) Mo 1.0 toluene (0.72) 25 6 88 46100 2.08
7d M1 (272) Mo 1.0 toluene (0.72) 25 6 91 46100 1.84
8 M1 (272) Mo 0.5 toluene (0.72) 25 3 93 22600 1.93
9 M1 (272) Mo 0.5 toluene (0.72) 25 6 90 48700 2.04
10 M1 (272) Mo 0.5 toluene (0.72) 25 6 84 47500 1.78
11 M1 (543) Mo 0.5 toluene (1.0) 25 6 90 44500 2.23
12 M1 (543) Mo 0.5 toluene (1.0) 25 6 95 44400 1.92
13 M1 (543) Mo 0.5 toluene (1.0) 25 6 91 49400 2.47
14e M2 (272) Mo 1.0 toluene (0.72) 25 6 87 34800 1.87
15 M3 (272) Mo 1.0 toluene (0.72) 25 6 99 67200 2.27
16 M1 (624) HG2 1.0 toluene (0.14) 50 5 71 7100 1.58
17 M1 (624) HG2 1.0 toluene (0.14) 50 12 86 8700 1.39
18 M1 (624) HG2 1.0 toluene (0.14) 50 24 88 14000 1.42
19f M1 (624) HG2 1.0 CHCl3 (0.14) 50 24 88 11000 1.21
20g M1 (624) HG2 1.0 [Bmim]PF6 (0.14) 50 16 89 32200 1.87
21g M1 (624) HG2 1.0 [Hmim]TFSI (0.14) 50 16 93 39200 1.95
22g M2 (624) HG2 1.0 [Hmim]TFSI (0.14) 50 16 92 26000 1.95
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a

Conditions: (runs 1–15) Mo(CHCMe2Ph)(N-2,6-Me2C6H3)[OC(CH3)(CF3)2]2 (Mo), toluene 0.72 or 1.0 mL, 25 °C, quenched by benzaldehyde (for termination through Wittig-type cleavage37,38) and (runs 16–18) HG2, toluene 0.14 mL, 50 °C (optimized conditions in ref (31)).

b

Isolated yield (as MeOH insoluble fraction).

c

GPC data in THF (at 40 °C) vs polystyrene standards.

d

4-Me3SiOC6H3CHO (runs 1, 24) or ferrocenecarboxaldehyde (run 7) was used instead of benzaldehyde.

e

Ethylene removal every 5 min (instead of 10 min) at the initial 30 min, see SI.

f

Cited from ref (31).

g

Cited from ref (15). RuCl2(IMesH2)(CH-2-OiPr-C6H4) [HG2; IMesH2 = 1,3-bis(2,4,6-trimethylphenyl) imidazolin-2-ylidene, Cy = cyclohexyl]. [Bmim]PF6: 1-n-butyl-3-methyl imidazolium hexafluorophosphate; [Hmim]TFSI: 1-n-hexyl-3-methyl imidazolium bis(trifluoromethanesulfonyl) imide.

It was revealed that the Mn value in the resultant polymer, expressed as P1, increased with a decrease in the amount of the Mo catalyst loaded [ex. Mn = 9500 g/mol (Mo 10 mol %, run S1 in Table S1, SI) < 16000 (5.0 mol %, run 1) < 31100 (run 5), 34400 (run 4, Mo 1.0 mol %); M1 90.5 μmol scale], whereas the Mn value was also affected by the time course (4–8 h, runs 1, 2, and S2). Note that the Mn values further increased when the polymerizations were conducted under rather high initial monomer concentration (rather a large reaction, M1 0.272 mmol scale) conditions [Mn = 46100 (runs 6 and 7, [M1]0 = 0.38 mmol/mL; [M1]0 = initial M1 concentration) vs 31100 (run 5, [M1]0 = 0.13 mmol/mL)], and the results are reproducible even terminated with different aldehydes (through Wittig-type cleavage between metal–alkylidene species with aldehyde,37,38 runs 6 and 7). Also note that the Mn values reached 47500–48700 g/mol when the polymerizations were conducted under low Mo loading (0.5 mol %), and the results were reproducible (runs 9, 10, and S4). The polymerizations of M1 under increased reaction scale (M1 0.543 mmol in 1.0 mL of toluene) also afforded high molar mass P1 (Mn = 49400, run 13), as reported previously,15−19,30,31,33 and careful removal of byproduced ethylene (especially at the beginning) is a prerequisite for the synthesis of high molar mass polymers in this condensation–polymerization (runs 11–12 and S6–8), probably due to increased viscosity under these rather high initial M1 concentration conditions (as demonstrated previously).15

Similarly, the Mn values in the resultant polymers from M2 (expressed as P2, Mn = 32200–36700, runs 14, S9, and S10) were higher than those prepared by the ruthenium catalyst in IL (Mn = 26000, run 22).15 The Mn values in P3 (Mn = 59900–67200, runs 15, S12, and S13) and polymers from bis(undec-10-enoate) with 1,3-propanediol (M3) were higher than those in P1 and P2. In contrast, the polymerizations of M1 by ruthenium catalysts (HG2, G2, shown in Scheme 1) in toluene (conducted under the same procedure) or CHCl331 afforded polymers with low Mn values (runs 16–19 and S14–S18), whereas improvements in the Mn values were seen when the reactions were conducted in IL (runs 20, 21, and S19). The results thus indicate that the molybdenum catalyst is effective for the synthesis of high molar mass polymers (even under rather simple reaction conditions compared with those conducted in IL).

The resultant polymers (P1–P2) were hydrogenated in the presence of RhCl(PPh3)3 in toluene (H2 1.0 MPa, 50 °C) according to a reported procedure for hydrogenation of ethylene/conjugated diene copolymers, poly(ethylene-co-isoprene)s39 and poly(ethylene-co-myrcene)s.40 As summarized in Table S2, no significant changes in the Mn values and the Mw/Mn values were observed in all cases; the resultant polymers (expressed as HP1 and HP2) were identified by NMR spectra (selected NMR spectra, GPC traces are shown in the SI).

Tensile property tests (stress/strain experiments) for the resultant hydrogenated polymers were conducted by using a universal testing instrument with an elongation rate of 10 mm/min (23 °C, humidity 50 ± 10%). The small dumbbell-shaped test specimens were prepared by cutting the polymer sheet (prepared by a hot press, the detailed procedures are described in SI),37 and at least three specimens of each polymer were tested (additional data are shown in SI). Samples (P1, HP1) of different (rather low) Mn values were prepared by using ruthenium catalysts,15,31 and the details are shown in Table S2. The polymer sheets prepared by the hot press method were chosen because these samples showed better tensile properties than those prepared through solvent cast methods (detailed comparisons are shown in the SI).41

Figure 1 summarizes the results for the effect of molecular weight on the tensile properties, and the additional results are shown in Figure S28. The results for tensile properties are summarized in Table 2. It should be noted that a rather significant increase in both tensile strength (stress) and the elongation at break (strain) were observed upon increasing the Mnvalues ofHP1. In particular, HP1 with the highest Mn value (Mn = 48200, hydrogenated sample of P1, run 13) exhibited a tensile strength of 39.7 MPa along with the elongation at break of 436%; a fairly good linear relationship between the tensile strength and the elongation at break was observed (in HP1 of Mn values higher than 25700, Figure S26).37 The value is indeed higher than a sample of high molar mass linear polyethylene (HDPE, Mn = 1.86 × 106, Mw/Mn = 3.44; tensile strength 30 MPa, elongation at break 180%) prepared for comparison.

Figure 1.

Figure 1

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(a) Effect of molecular weight (Mn value) on the tensile properties in HP1 (speed 10 mm/min, hot press film). (b) Expanded view of Figure 1(a). Data after hydrogenation for the preparation of the samples are shown in Table S2, SI. PE (polyethylene): Mn = 1.86 × 106 g/mol, Mw/Mn = 3.44 (see SI for synthesis).

Table 2. Summary of the Tensile Properties of Polyestersa.

sample Mnb/g·mol–1 Mw/Mnb tensile strength/MPa elongation at break/%
HP1 9400 1.61 6.2(±1.3) 8.0(±1.3)
HP1 25700 2.16 16.8(±1.8) 217(±35)
HP1 31800 2.23 20.6(±1.1) 245(±14)
HP1 40900 2.41 33.7(±2.2) 413(±13)
HP1 48200 2.56 39.7(±2.6) 436(±24)
HP2 23300 2.17 16.7(±0.7) 229(±22)
HP4 28700 3.42 8.79(±0.4) 165(±15)
P1 39600 1.89 18.17(±1.1) 513(±58)
P1 44500 2.23 19.85(±0.7) 507(±11)
P2 35900 1.52 15.14(±4.3) 535(±49)
P3 62200 2.36 13.99(±0.9) 251(±26)
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a

Details in stress/strain experiments including the sample preparations are described in SI.

b

GPC data in THF (at 40 °C) vs polystyrene standards.

It was revealed that HP2 showed similar tensile property to HP1 (Figure S27), whereas the hydrogenated polymer sample prepared by ADMET polymerization of bis(undec-10-enoate) with 1,4-cyclohexanedimethanol (expressed as HP4, Figure S27)15 was inferior to tensile strength and the elongation at break. Stress–strain curves for polymer samples before hydrogenation (P1–P3) are shown in Figure 2. P2 showed similar tensile property to that in P1, and P3 was inferior to elongation at break. The results suggest that the tensile properties are affected by the diol segment employed, and the polymer samples derived from isosorbide and isomannide showed better properties. It was revealed that elongation at breaks in both P1 and P2 samples before hydrogenation are apparently larger than those in HP1 and HP2, whereas HP1 and HP2 showed higher levels of tensile strengths compared to P1 and P2. Moreover, no significant differences in tensile strength and the elongation at break were observed in P1 with Mn values of 39600 and 44500, whereas the values were apparently low in the rather low molar mass sample [Mn = 28300, Mw/Mn = 1.75, prepared by HG2 in IL, 1.0 g scale in 0.3 mL of [Hmim]TFSI, 1.0 mol % of HG2, 50 °C, 6 h].15

Figure 2.

Figure 2

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Tensile properties in P1–P3 (samples before hydrogenation, speed 10 mm/min, hot press film).

Figure 3 shows plots of HP1 with different Mn values, and plots of PE-18,18, prepared from C18 dimethyl dicarboxylate and the corresponding diol by a condensation–polymerization with Ti(OiPr)4,10 commercially available samples including poly(ethylene terephthalate) (PET),42 high density polyethylene (HDPE),10,42 low density polyethylene (LDPE),42 polypropylene (PP),42 etc., are also shown for comparison.10,42 It is clear that the high molecular weight of HP1, presented in this communication, possesses higher tensile strength (stress) than the other polymer samples such as PP and PEs, whereas both the tensile strength and the elongation at break are affected by the Mn value. As described above, the sample before hydrogenation showed higher strain (elongation at break) with less stress (tensile strength), which is close to that of conventional HDPE.

Figure 3.

Figure 3

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Plots of tensile (fracture) strengths and strains (elongation at breaks) of HP1 with different Mn values. The plots of PE-18,18 (polyester-18,18),10 commercially available polyethylene terephthalate (PET), poly(lactic acid) (PLA), poly(ε-caprolactone) (PCL), high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), and polystyrene (PS).42 HDPE1* is a high molecular weight polyethylene sample (Mn = 1.86 × 106, Mw/Mn = 3.44) prepared in this study.

We have communicated a successful synthesis of high molar mass polyesters (HP1–HP3, ex. Mn = 48200) derived from plant resources, which exhibit tensile properties beyond conventional polyethylene and polypropylene (LDPE, HDPE, PP), prepared by ADMET polymerization using the molybdenum-alkylidene catalyst (in toluene at 25 °C). The effect of molecular weight on the tensile property in HP1 has been demonstrated.43 The results here should introduce a promising possibility of chemical recyclable15 biobased aliphatic polyesters not only as alternatives of conventional polyolefins but also as functional polymers suited to circular economy. Moreover, the mechanical property of HP1 was improved by the preparation of a composite with a small amount of cellulose nanofiber (CNF),42 whereas such an effect was not observed when the polyester containing a linear C9 alkyl was employed.36 More details including crystallinity (small-angle light scattering, SAXS analysis, etc.),43 the preparation of soluble network polymers that improve elongation breaks,36 and the fabrication with additives (CNF etc.)36,41 will be introduced in the near future.

Acknowledgments

This project was partly supported by JST-CREST (Grant Number JPMJCR21L5), JST SICORP (Grant Number JPMJSC19E2), Japan, and Tokyo Metropolitan Government Advanced Research (Grant Number R2-1). K.N. and H.H. express their thanks to Prof. Hiroki Takeshita (The University of Shiga Prefecture) for fruitful discussions. X.W. thanks the Tokyo Metropolitan government (Tokyo Human Resources Fund for City Diplomacy) for a predoctoral fellowship. L.G. also expresses his thanks to a MEXT (Japanese government, Ministry of Education, Culture, Sports, Science and Technology) fellowship for his predoctoral study.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsmacrolett.3c00481.

  • (i) General procedure, synthesis of polymers, (ii) additional polymerization, hydrogenation results, (iii) selected NMR spectra and GPC charts in the resultant polymers, and (iv) summary of tensile properties of the prepared film (PDF)

Author Contributions

§ Equal contribution as the first authors (M.K., X.W.).

The authors declare no competing financial interest.

Supplementary Material

mz3c00481_si_001.pdf (3.4MB, pdf)

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