Effect of Middle Diol Repeat Units in Biobased Aliphatic Polyesters on Thermal and Tensile Properties

Abstract

Biobased aliphatic polyesters derived from multiple nonedible plant resources generally display rather facile chemical recyclability, and their physical and chemical properties are affected by the monomer design. The polyesters consisting of 10-undecenoic acid (derived from castor oil) not only with monomeric diols [(1R,2R)-1,2-cyclohexanedimethanol, (+)-2,3-O-isopropylidene-L-threitol (LTh), and 1,9-diethyl L-(+)-tartrate] but also with long-chain diols consisting of isomannide (IM) or LTh connected through trans-1,4-cyclohexane dicarboxylic acid or 2,5-furane dicarboxylic acid (M4–M7) were prepared by acyclic diene metathesis (ADMET) polymerization and subsequent tandem hydrogenation. The thermal properties of the resultant polymers were affected by the diol middle segment employed, whereas the polymers consisting of a diol unit of two LTh or IM connected with the dicarboxylic acid were amorphous. Tensile properties in the prepared polymer films were also affected by the middle diol repeat units. Polyesters consisting of 10-undecenoic acid and two IM connected through trans-1,4-cyclohexane dicarboxylic acid [expressed as P7 (prepared by ADMET polymerization), and HP7 (saturated polyester after hydrogenation)] showed promising tensile stress and strain (elongation) at break, with observation of the yield strength. The observed values [stress 26.9 MPa, strain 449% (P7); 35.7 MPa, 349% (HP7)], especially the tensile strength (stress) at break, were larger than those of the reported polyester films consisting of IM or isosorbide. In contrast, similar polyester films containing 2,5-furan dicarboxylic acid showed brittle fracture behavior without yielding.

Introduction

Biobased long-chain aliphatic polyesters (Figure ), derived from diverse nonedible plant resources such as plant oils, are increasingly recognized as promising sustainable materials − as alternatives to petroleum-based polymers in the circular economy because of their rather facile chemical recycling and upcycling − compared to conventional polyolefins. It is known that their physical, chemical, and mechanical properties can be tuned by manipulating the monomer architecture (repeat unit) ,− and molecular weight, especially through interpolymer communication such as entanglement of polymer chains, as seen in conventional polyesters. There have thus been many reports on the synthesis of biobased aliphatic polyesters consisting of long-chain fatty acid esters; ,− these polyesters would also provide a possibility of new composite materials due to their better compatibility with natural, biobased fibers (owing to the similar hydrophilic nature of the main chain compared to conventional polyolefins such as polyethylene and polypropylene).

1.

Selected reported biobased polyesters (those with tensile properties). ,−

Our laboratory has recently reported that the tensile properties [tensile strength and strain (elongation at break)] of films of polyesters consisting of castor oil and isosorbide (C₁₈IS) or isomannide (C₁₈IM), as shown in Figure (and Scheme ), are strongly affected by the molecular weight, due to better entanglement of the polymer chain (interpolymer interaction). Moreover, these polyesters, consisting of diols derived from sugars (C₁₈IS, C₁₈IM), displayed crystallization behaviors from those consisting of long-chain aliphatic diols (PE-4.18, PE-18.18, etc.), which displayed different crystallization behaviors similar to polyethylene. As described above, the mechanical properties can be modified by the monomer repeat units employed; thus, we are interested in exploring the effect of middle diol repeat units, including the expansion of the middle segment by placing two isomannide (IM) units through ester linkages (shown in Scheme ).

1. Chemically Recyclable Biobased Aliphatic Polyesters: Effect of Middle (Diol) Segment toward the Tensile Properties (This Study).

Results and Discussion

Synthesis of Monomers and Polymers by Acyclic Diene Metathesis (ADMET) Polymerization and Subsequent Hydrogenation

Three monomers (α,ω-nonconjugated dienes, M1–M3), diester of 10-undecenoic acid with (1R,2R)-1,2-cyclohexanedimethanol (M1), (+)-2,3-O-isopropylidene-L-threitol (M2), and 1,9-diethyl L-(+)-tartrate (M3) as middle segments (diol units), shown in Scheme , were chosen in this study. According to the reported procedures, ,,, these monomers are easily prepared in moderate to high yields (53–98%) by treating 10-undecanoyl chloride (2.0 equiv) and the corresponding diols in toluene in the presence of triethylamine (Scheme ). The resultant dienes (M1–M3) were identified using NMR spectroscopy and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). Detailed synthetic procedures and identifications, including NMR spectra, are summarized in Supporting Information (SI).

2. Synthesis of Monomers (M1–7) and Polymers (P1–7) by Acyclic Diene Metathesis (ADMET) Polymerization, and Subsequent One-Pot Tandem Hydrogenation (HP1–7).

Moreover, in this study, α,ω-nonconjugated diene monomers (M4–M7) consisting of 10-undecenoate with long-chain diol units (middle segment), consisting of isomannide (IM) or (+)-2,3-O-isopropylidene-L-threitol (LTh) connected through trans-1,4-cyclohexane dicarboxylic acid or 2,5-furane dicarboxylic acid (Schemes and ) were chosen to explore the effect of diol units on the properties of the materials. Similar to the syntheses of M1–M3, the reaction of LTh or IM with 1.0 equiv of 10-undecenoyl chloride afforded the corresponding monoester, and subsequent treatment with 0.5 equiv of trans-cyclohexane-1,4-dicarbonyl dichloride or 2,5-furandicarbonyl dichloride afforded the diesters (M4–7), α,ω-nonconjugated dienes, consisting of 10-undecenoate and two diols (LTh, IM) connected through dicarboxylic acids. These dienes (M4–7) were also identified by NMR spectroscopy and APCI-MS. Detailed synthetic procedures and the identification data, including NMR spectra, are summarized in SI.

Table summarizes the results of the synthesis of (unsaturated) polymers by acyclic diene metathesis (ADMET) polymerization of nonconjugated dienes (M1–7) in the presence of a ruthenium-carbene catalyst at 50 °C. The Hoveyda–Grubbs type catalyst, RuCl₂(IMesH₂)­(CH-2-O ⁱ Pr–C₆H₄) [HG2, IMesH₂ = 1,3-bis­(2,4,6-trimethylphenyl)­imidazolin-2-ylidene], was chosen because it afforded higher molecular weight polymers for the synthesis of isosorbide/isomannide-based polymers , (Scheme ); these polymerizations were conducted at 50 °C to avoid the rapid catalyst decomposition at higher temperatures. − These polymerizations were conducted in chloroform or in bulk at 50 °C for 24 h since the M_n value of poly­(M2), expressed as P2, after 3 h was rather low (run 4, M_n = 13,100) compared to that after 24 h (run 5, M_n = 21,400). As reported previously, ,, the reaction mixture was placed in a liquid nitrogen bath to remove ethylene gas formed by opening the valve connected to the vacuum line for a short period (1 min), and the valve was then closed, and the tube was placed into the oil bath to continue the reaction. The resultant polymers were obtained as methanol-insoluble precipitates (detailed procedures are given in SI).

1. ADMET Polymerization of α,ω-Diene Monomers (M1–M7) Using a Ruthenium-Carbene Catalyst (HG2)­ .

run	monomer	Ru/mol %	time/h	Mn	M w/Mn	yield/%
1	M1	1.0	24	18,700	1.81	75.0
2	M1	0.5	24	19,400	1.81	83.0
3	M1	0.5	24	34,900	1.69	88.0
4	M2	2.0	3	13,100	1.75	88.0
5	M2	2.0	24	21,400	1.73	82.0
6	M2	1.0	24	23,900	1.71	70.0
7	M2	0.5	24	34,700	2.06	85.0
8	M2	0.5	24	29,800	1.58	84.0
9	M3	2.0	24	20,100	1.88	71.0
10	M3	2.0	24	32,500	1.59	97.0
11	M4	0.5	24	21,700	2.08	90.0
12	M4	1.0	24	24,800	1.87	96.0
13	M4	0.5	24	28,500	1.78	96.0
14	M5	1.0	24	12,100	1.81	99.0
15	M5	0.5	24	14,200	1.90	98.0
16	M5	0.5	24	19,300	1.73	79.0
17	M6	1.0	24	13,000	1.76	99.0
18	M6	0.5	24	19,800	1.76	99.0
19	M7	2.0	24	15,000	1.56	99.0
20	M7	2.0	24	35,800	1.95	98.0
21	M7	1.0	24	39,300	2.13	98.0
22	M7	0.5	24	26,000	1.90	99.0

^aConditions: Monomer 0.65 mmol in chloroform 0.18 mL (M6–M7 in 0.54 mL), 50 °C under reduced pressure (details are described in SI).

^bGPC data in THF vs. polystyrene standards.

^cIsolated yield by precipitation, as the methanol-insoluble fraction.

^dBulk conditions (solvent-free).

As summarized in Table , under the optimized conditions, the polymerization gave rather high molar mass polymers (M_n = 28,500–39,300), except for the polymerizations of M5 (M_n = 19,300, run 16) and M6 (M_n = 19,800, run 18). The NMR spectra of the resultant polymers (expressed as P1–P7) showed resonances ascribed to the internal olefinic double bonds along with resonances ascribed to the middle segment without significant changes in their resonances before/after ADMET polymerization (NMR spectra of the resultant polymers are shown in SI). These NMR spectra strongly suggest that ADMET polymerization proceeded under these conditions. It was revealed that the M_n values in the resultant polymers (P1, P2, and P5), prepared by polymerization in chloroform, increased upon decreasing the ruthenium catalyst loading (runs 1, 2, 5–7,14,15). Similar increases in the M_n values with a reduction in Ru loading were observed in the bulk polymerization of M4 and M6 (runs 12,13,17,18), whereas the M_n value in the polymerization of M7 decreased upon further decrease (runs 20–22).

The resultant polymers, P1 and P2, possess melting temperatures (T _m), whereas the other resultant polymers (P3–P7) are amorphous, possessing a sole glass transition temperature (T _g), as summarized in Table (and Figure a; DSC thermograms for P1–3 are shown in Figure S50, SI). The T _g values of P6 and P7, which possessed two IM, were higher than those of P4 and P5, which possessed two LTh. The T _g values of the resultant polymers possessing trans-1,4-cyclohexane dicarboxylic acid units were higher than those possessing 2,5-furan dicarboxylic acid units (P4 vs P5, P6 vs P7).

2. Synthesis of Saturated Polyesters (HP1–HP7) by ADMET Polymerization and Tandem Hydrogenation Using a Ruthenium-Carbene Catalyst (HG2)­ .

	before hydrogenation				hydrogenation
run	sample no.	Mn	Mw /Mn	T m (T g)/°C	H2/MPa	time/h	Mn	Mw /Mn	yield/%	T m (T g)/°C
23	P1 (run 1)	34,900	1.69	–11.8	2.0	5	35,700	1.60	99.0	36.9
24	P2 (run 8)	29,800	1.58	3.9	1.0	24	26,500	1.57	73.0	36.8
25	P3 (run 10)	32,500	1.59	(−45.1)	2.0	5	37,400	1.61	71.0	–18.0
26	P4 (run 11)	21,700	2.08	(0.4)	1.0	24	18,400	2.10	99.0	(1.1)
27	P4 (run 12)	24,800	1.87		1.0	24	24,300	1.59	99.0
28	P5 (run 15)	14,200	1.90	(−16.9)	1.0	24	12,800	2.24	99.0	(−17.4)
29	P6 (run 18)	19,800	1.76	(39.0)	1.0	18	16,900	1.83	99.0	(40.9)
30	P6 (run 17)	13,000	1.76		2.0	18	13,900	1.70	99.0
31	P7 (run 20)	35,800	1.95	(27.7)	1.0	24	35,200	1.89	94.0	(34.9)
32	P7 (run 22)	26,000	1.90		1.0	24	25,000	1.90	84.0

^aConditions: addition of Al₂O₃ 1.0 wt %, 50 °C (details are described in SI).

^bRun number in Table .

^cGPC data in THF vs polystyrene standards.

^dBy DSC thermograms.

^eIsolated yield by precipitation, as the methanol-insoluble fraction.

^fNot measured.

2.

Selected DSC thermograms of polyesters: (a) samples before hydrogenation (after ADMET polymerization) and (b) samples after hydrogenation, prepared in this study. The detailed polymerization data are listed in Table . Additional DSC thermograms are listed in SI.

According to the reported procedure, , the resultant reaction mixture containing P1–P7 was transferred into the stainless-steel autoclave with a minimum amount of chloroform upon the addition of ca. 1 wt % Al₂O₃, and the solution was stirred under hydrogen (1.0 or 2.0 MPa) at 50 °C. The resultant solution was poured into methanol to collect the hydrogenated polymer as a precipitate. The ¹H- and ¹³C-NMR spectra of the resultant polymers (expressed as HP1–7) showed the disappearance of resonances ascribed to the olefinic protons/carbons from those of P1–7, with the remaining resonances (methylene and the middle segment) unchanged. No significant differences in both the M_n and PDI (M_w /M_n ) values were observed in the polymers before/after the reaction. These results clearly indicate that tandem hydrogenation afforded saturated polyesters without alteration of the middle segments (with exclusive olefin hydrogenation).

The resultant saturated polyesters, HP1–3, possess T _m values, whereas the other resultant polymers (HP4–7) are amorphous, with a sole T _g value (Figure b, DSC thermograms for HP1–3 are shown in Figure S50). As observed in P4–7, the T _g values of HP6 and HP7 were higher than those of HP4 and HP5, whereas the T _g values of the polyesters possessing trans-1,4-cyclohexane dicarboxylic acid units were higher than those possessing 2,5-furan dicarboxylic acid units (HP4 vs HP5, HP6 vs HP7).

Effect of Middle Segment (Diol Repeat Units) in Biobased Aliphatic Polyesters toward Tensile Properties

The tensile properties of the resultant amorphous polymer thin films (P4–7, HP4–7) were analyzed by conducting stress/strain experiments using a universal testing instrument with elongation rates of 10, 50, or 200 mm/min (23 °C, humidity 50 ± 10%). Test polymer sheets with a dumbbell shape [width 3 mm (grippers on both sides 10 mm), total length 25 mm, 0.1 mm thickness] were prepared using the hot press method. As reported previously, the tests were conducted at least three times to confirm reproducibility. The polyester samples of unsaturated P1–3 and saturated HP1–3 (prepared by olefin hydrogenation, described above) could not be analyzed due to difficulties in preparing the test films. The selected analysis data are summarized in Figures and , and additional data, including the confirmation of reproducibility, are shown in the SI (Figures S51–63).

3.

Tensile strength (stress) and strain (elongation at break) of the polymer films (P4–P7, HP4–7). These films were prepared by hot pressing at a speed of 10 mm/min [except for HP4 (50 mm/min) and P7 (M_n = 11,000; 200 mm/min)]. The details are described in the Supporting Information.

4.

Effect of molar mass on tensile properties [tensile strength (stress) and strain (elongation at break)] of polymer films (P7 and HP7). These films were prepared using a hot press. The details are described in the Supporting Information.

It should be noted that the tensile properties [both tensile stress (strength) and the strain (elongation) at break] are strongly affected by the nature of the middle diol segments employed, as shown in Figure . The polymer films of P4 (M_n = 21,700, T _g = 3.7 °C, Figure a) and HP4 (M_n = 18,400, T _g = 5.4 °C, Figure b), consisting of two LTh connected with 2,5-furan dicarboxylic acid units, showed a low yield strength (0.26, 0.20 MPa) upon initial elongation, and the stress decreased with further elongation. These films are likely to be in a certain rubbery state, probably due to their low T _g values compared to the measured temperature (23 °C). Similarly, the polymer films of P5 (M_n = 14,200, T _g = – 16.9 °C, Figure a) and HP5 (M_n = 12,800, T _g = – 17.4 °C, Figure b), consisting of LTh connected to the trans-1,4-cyclohexane dicarboxylic acid unit, showed a small initial increase in the tensile stress upon loading the test films. It seems likely that the observed facts are probably due to the low T _g values of these samples with poor interpolymer entanglement (shown as the strain), although the effect of molecular weight for the entanglement might also be considered with these low molar mass samples (P4,5 and HP4,5).

In contrast, the polyester films of P6 (M_n = 19,800, T _g = 39 °C) and HP6 (M_n = 16,900, T _g = 40.9 °C), consisting of two IM connected to 2,5-furan dicarboxylic acid units, showed brittle fracture behavior without yielding [stress 40.4 N/mm² (MPa), strain (elongation at break) 12.8% (P6); stress 31.5 MPa, strain 8.7% (HP6)]. Interestingly, no apparent differences in tensile properties were observed between the unsaturated (P6) and saturated polyester (HP6) films. Since the polyester films consisting of diesters of 10-undecenoic acid with IM [PIM (15.1 MPa, 535%, for stress, strain, respectively; M_n = 35,900), HPIM (16.7 MPa, 229%, M_n = 23,300)] or isosorbide in such low molecular weights [the saturated polyester of M_n = 25,700:16.8 MPa, 217%] showed both low tensile stress (strength) with larger strain (elongation at break), the observed difference can be thus explained as an effect of 2,5-furan dicarboxylic acid unit introduced (also by consideration of comparison with the properties in P7 and HP7, described below).

Note that, as shown in Figure a, the polymer film consisting of diesters of 10-undecenoic acid with two IM connected through the trans-1,4-cyclohexane dicarboxylic acid units (P7) showed moderate tensile strength and strain (elongation) at break. The tensile stress and strain in (amorphous) P7 were affected by the M_n value, and a similar phenomenon was previously observed in (semicrystalline) the polyester consisting of 10-undecenoic acid with isosorbide. Moreover, the tensile property (tensile strength with elongation at break) of the P7 film was higher than that of the (semicrystalline) PIM film possessing a rather high M_n value [P7 (stress 24.8 MPa, strain 607%, M_n = 28,100) vs PIM (15.1 MPa, 535%, M_n = 35,900)]. Also, considering the tensile property of P6, the observed increases in P7 could be explained by the introduction of a trans-1,4-cyclohexane dicarboxylic acid unit. As reported previously for a polyester film containing a diester with IM, isosorbide, the saturated polyester (HP7) showed higher tensile stress along with lower strain compared to the unsaturated polyester (P7). Note that the high molar mass HP7 sample (M_n = 35,200) showed a yield strength (stress 21.1 MPa, strain 5.8%) with large tensile strength and strain (35.7 MPa, 348%, respectively), probably due to the higher T _g value of HP7 than that of P7.

Figure shows the effect of molecular weight on the tensile properties of P7 and HP7. Measurements of the high-molecular-weight P7 and HP7 samples with different elongation rates (speed, 10 mm/min vs 200 mm/min) were also conducted for comparison, since, as described above, the high-molecular-weight HP7 sample showed yield strength. As shown in Figure a, the tensile stress (strength) in the P7 polymer films increased with an increase in the M_n values [M_n = 11,000 vs M_n = 35,800 (200 mm/min); M_n = 28,100 vs M_n = 35,800 (10 mm/min)]. The high molar mass P7 film (M_n = 35,800) showed a slight increase in stress at break with a decrease in strain [stress 30.6 MPa, strain 375% (200 mm/min) vs 26.9 MPa, 449% (10 mm/min)] with yield strength (13.7 MPa, 8.2%, respectively), when the analysis was conducted at a speed of 200 mm/min. The tensile strain (elongation) at break was also affected by the M_n value as well as by the speed of elongation [strain 449% (10 mm/min) vs 375% (200 mm/min)]. The saturated polyester film (HP7) showed a similar molecular weight dependence toward the tensile properties, whereas the yield strengths were observed in high molar mass films (M_n = 35,200) irrespective of the speed of elongation. The reason for the observation of yield strength in high molar mass HP7 is unclear, but it might be related to the higher T _g in HP7 than that in P7.

Concluding Remarks

We herein prepared polyesters consisting of a diester of 10-undecenoic acid with different diols, as summarized in Chart . These polymers were prepared by ADMET polymerization using a ruthenium-carbene catalyst and subsequent hydrogenation to afford unsaturated polyesters (P1–7) and saturated polyesters (HP1–7). It is clear that their thermal properties were greatly affected by the diol repeat units employed (Figure and Figure S50, SI). The polyesters (P4–P7, HP4–HP7), possessing two (+)-2,3-O-isopropylidene-L-threitol (LTh) or isomannide (IM) connected through 2,5-furan dicarboxylic acid (P4, P6, HP4, HP6) or trans-1,4-cyclohexane dicarboxylic acid (P5, P7, HP7, HP7) units, are amorphous and polyesters containing two IM units (P6,7, HP6,7) showed rather high T _g values than those containing two LTh units (P4,5, HP4,5).

1. Biobased Aliphatic Polyesters Containing Different Middle Diol Segments (Repeat Units) in This Study.

The tensile properties [tensile stress (strength) and strain (elongation) at break] of the prepared films (P4–P7, HP4–HP7) were affected by the middle diol repeat units. Polyester films in P6 and HP6, possessing two IM connected through a 2,5-furan dicarboxylic acid unit, showed brittle fracture behavior without yielding, and no apparent differences in their tensile properties were observed between unsaturated and saturated polyester polymer films. In contrast, the films in P7 and HP7, possessing two IM connected through trans-1,4-cyclohexane dicarboxylic acid units, showed unique tensile properties; the polymer films with high M_n values [M_n = 35,800 (P7), 35,200 (HP7)] showed promising tensile stress and strain at break, with the observation of yield strength. Noteworthily, the observed values [stress 26.9 MPa, strain 449% (P7); 35.7 MPa, 349% (HP7)], especially tensile strength (stress), are larger than those of the polyester films consisting of IM (PIM) or isosorbide (PIS, HPIS), shown in Chart , possessing similar molecular weights [stress 15.1 MPa, strain 535% (PIM, M_n = 35,900); stress 33.7 MPa, strain 413% (HPIS, M_n = 40,900)], as summarized in Figure . The tensile properties are also affected by the speed of elongation. Moreover, it is clear from Figure that these polymers, especially P7 and HP7, showed promising tensile properties in films compared to conventional polyethylene (HDPE, LDPE) and polypropylene (PP).

5.

Summary of tensile properties of reported polyester films (PIS, PIM, HPIS) and polyester films in this study (P6, P7, HP6, and HP7). The data for PP (polypropylene), HDPE (high-density polyethylene), and LDPE (low-density polyethylene) are also given for comparison (cited from ref ).

We believe that the results introduced as an effect of the middle diol segment (repeat units) on the tensile properties should provide important information for the design of biobased polyesters to fulfill the desired properties. These efforts should contribute to the development of chemically recyclable advanced polyesters directed toward a circular economy. Further research on this subject, including the synthesis of biobased poly­(ester amide)­s with promising tensile properties, will be introduced in the near future.

Experimental Section

General

All experiments were conducted under a nitrogen atmosphere in a drybox, unless otherwise specified. Anhydrous grade solvents (>99.5%, Kanto Chemical Co., Inc.) were stored in a dry box in the presence of molecular sieves. Ruthenium-carbene catalyst, RuCl₂(-IMesH₂)­(CH-2-O ⁱ Pr–C₆H₄) [(HG2), IMes = 1,3-bis­(2,4,6-trimethylphenyl)-imidazolin-2-ylidene, Aldrich Chemical Co.], purchased was used as received. All chemicals of reagent grades (Tokyo Chemical Industry, Co., Ltd., except t-cyclohexane-1,4-dicarbonyl dichloride from Kishida Chemical Co.) were used as received.

¹H and ¹³C­{¹H} NMR spectra were recorded on a Bruker AV500 spectrometer (500.13 MHz for ¹H; 125.77 MHz for ¹³C­{1H}). The molecular weights (M_w , M_n , number- or weight-average molecular weight) and the molecular weight distributions (M_w /M_n ) of the polymer samples were determined by using gel permeation chromatography (GPC) in THF at 40 °C using GPC columns of a spherical porous gel made of styrene/divinylbenzene copolymer (ranging from <10² to 2 × 10⁷ MW). The M_n values were estimated using calibration curves with polystyrene standard samples. The thermal properties of the polymers were analyzed by differential scanning calorimetry (DSC) data for the polymer samples measured using a Hitachi DSC 7020 analyzer (under N₂). Atmospheric pressure chemical ionization (APCI) mass spectrometry was performed on a Bruker MicroTOF IISDT1. Shimadzu Universal Testing Instruments (Autograph AGS-10kNX) equipped with a load cell (cell capacity 500 N) was used to perform stress/strain experiments at 23 °C (speed 10, 50, or 200 mm/min, humidity 50 ± 10%). At least three specimens were tested for the analysis of each polymer.

Extensive descriptions of the experimental methods, detailed syntheses of the monomers and polymers, and their identifications (including NMR spectra) are described in Supporting Information.

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.5c13539.

• General experimental procedures; additional ADMET polymerization results of α,ω-diene monomers and the synthesis of saturated polyesters (P1–P7, HP1–HP7) and polymers (P1-7, HP1-7), including selected NMR spectra, selected NMR spectra of monomers and polymers, selected GPC traces and additional DSC thermograms for polymer samples (P1–3, HP1–3), and additional data for tensile tests for the prepared polymer films (PDF)

K.N. designed the project (conceptualization, polymer design, methodology, supervision), including funding acquisition and project administration. K.I. conducted all the synthetic and analysis experiments, and G.M. conducted measurements of mechanical properties under the supervision of S.H., K.T., and H.H.; M.M.A. helped in the analysis. K.N. wrote the original manuscript with M.M.A., S.H., K.T., and H.H., and K.N. revised the manuscript. The manuscript was written through the contributions of all authors. All authors have given approval to the final version of the manuscript.

The results were partly introduced by K.N. in 12th Workshop on Fats and Oils as Renewable Feedstock for the Chemical Industry (Dortmund, Germany, June 2024), Canadian Chemical Engineering Conference (CSChE 2024, Toronto, Canada, October 2024), International Symposium on Engineering Plastics (Harbin, China, August 2025), and Pacifichem 2025 (Honolulu, Hawaii, USA, December 2025).

The authors declare no competing financial interest.