Advanced Elasticity and Biodegradability of Poly(butanediol- hexanediol-isosorbitol-itaconate-sebacate) Copolyester Elastomer via the Decrystallization Effect of Isosorbide

Advanced Elasticity and Biodegradability of Poly(butanediol- hexanediol-isosorbitol-itaconate-sebacate) Copolyester Elastomer via the Decrystallization Effect of Isosorbide | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Advanced Elasticity and Biodegradability of Poly(butanediol- hexanediol-isosorbitol-itaconate-sebacate) Copolyester Elastomer via the Decrystallization Effect of Isosorbide Lisheng Tang, Yuanyuan Jin, Xiaoyan He, Ran Huang This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3849505/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The stability to against hydrolysis while maintaining excellent elasticity is a constant challenge in the development of biodegradable and environmental-friendly polyester elastomer. While monomers of longer chain can provide higher stability, the high crystallinity and rigidity impair their application in fabricating elastomer. This work reported a star-crosslinked Poly(butanediol-hexanediol-isosorbitol-itaconate-sebacate) (PBHIIS) elastomer synthesized by esterification and thermal curing. With the decrystallization effect of isosorbide as a large and rigid monomer, the original rigid Poly(butanediol-hexanediol-itaconate-sebacate) successfully transformed to be elastomer with lower T m and T g , much higher Elongation at break, and smaller tensile modulus, and biodegradability is also improved. The strategy is demonstrated to be efficient and may serve as a potential technique in the future development of biodegradable elastomers. Biodegradable Copolyester Elastomer PBHIIS Isosorbide Decrystallization Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1. Introduction Because of its special qualities, elastomers—a type of polymer with a low modulus and high elasticity—can rapidly return to their initial form following the removal of an external force. Because of these qualities, they are indispensable in both daily life and the economy [1–4]. Elastomers have been the subject of ongoing research and development to improve their strength, stability, aging resistance, and wear resistance in order to fulfill the ever-increasing performance requirements. However, these advantages make it harder to dispose of the waste products made from conventional elastomers, which pollutes the environment over time [5, 6]. However, the majority of elastomers are derived from poorly sustainable non-renewable fossil fuels. The creation of novel elastomers that are not dependent on fossil fuels has become highly demanded in recent times due to the immense strain imposed by carbon emissions. Bio-based elastomers are a great way to reduce carbon emissions and conserve resources in the elastomer sector since they may be made from natural plants directly or by synthesizing them from bio-based monomers produced from biomass resources. Due to excellent biodegradability, aliphatic polyester became a prominent area of research for environmentally-friendly products. Linear polyesters, such as poly(lactic acid) (PLA), polyglycolide acid (PGA), polycaprolactone (PCL), and their copolymers, have been extensively studied in the field of plastic for many years. And their industrial production is seeing tremendous growth [7–9]. Polyesters having a three-dimensional network have gained increasing interest, motivated by these linear polymers [10–11]. Like vulcanized rubber, the cross-linked network is formed by the incorporation of "star" monomers to create multi-branched chains, enabling the material to rapidly regain its shape when subjected to substantial deformation. Poly (glycerol sebacate) (PGS), polyoctyl citrate (POC), and their copolymers are the primary biodegradable polyester elastomers that have undergone substantial research. The pioneering work is the synthesis of PGS, an in-situ cross-linked polyester elastomer with a three-dimensional network structure and exceptional robustness, conducted by Langer et al. successfully synthesized in 2002 [10, 12]. In 2011, Zhang et al. firstly introduced chemically crosslinked polyester elastomer [13]. Subsequently, many other bio-based elastomers have been created [14, 15]. It is well known that monomers of longer chain are easier to be synthesized to be polyester with higher stability, due to the lower density of ester linkage. For example, PCL and PBS are commercially mature materials, which employ 4- or 6- carbon chain monomer [16], while Polyglycolide acid (PGA) with 2-carbon monomer is unstable to hydrolysis and its commercial application is very limited [17]. However on the other hand, when the goal of our research is to obtain elastomers, the high crystallinity and rigidity due to longer chains becomes a disadvantage. Hereby a technical difficulty arises, how to construct biodegradable polyester with decent stability, cross-linkage network, and sufficient elasticity? i.e. we probably need longer chain monomers, multi-functional "star" monomer, and some component to lower the crystallinity. In chemically crosslinked polyester elastomers, the glass transition temperature can be decreased and crystallization can be hindered by employing multicomponent copolymerization and including monomers with side groups, which in turn improves the elasticity [18, 19]. Particular monomers with side group, large volume and/or rigid segment can play a crucial role in decrystallization. Gao et al. [20] designed and synthesized biobased poly(1,4-butanediol/2,3-butanediol/succinic acid/Iconocarboxylic acid) co-polyesters (PBBSI) with varying 2,3-butanediol content. The co-polyesters underwent a transformation from stiff plastics to flexible elastomers due to the alteration in the amount of 2,3-butanediol. Hu et al. [21] synthesized the elastomer poly(2,3-butanediol-co-1,4-butanediol-co-succinate) (PBBS) by introducing 2,3-butanedioic acid into PBS, whose elasticity can be thereafter improved with the decrystallization effect. Butanedioic acid and succinic acid were employed to ensure the good compatibility of PBBS with PBS. In this work, we select butanediol, hexanediol and itaconate as “long chain” monomers to obtain a stable co-polyester, and take sebacate as the chemically crosslinking site [22]. Isosorbide, as a bulky, rigid, and food and environment safe monomer, is introduced to the copolyester Poly(butanediol-hexanediol-itaconate-sebacate) (PBHIS) to prepare the biodegradable elastomer as Poly(butanediol-hexanediol-isosorbitol-itaconate-sebacate) (PBHIIS). Linear chains of this two copolyesters are synthesized as so-called pre-PBHI(I)S, and a final thermal curing with initiator Benzoyl Peroxide (BPO) vulcanized the linear chains to be structural network. The scheme of this work is illustrated in Fig. 1 . The chemical structure, thermal and mechanical properties, and biodegradability of the final products were characterized. 2. Experimental 2.1 Reagents and materials Itaconic acid (analytic grade), hexylene glycol (analytic grade), and butanediol (analytic grade) are purchased from Shandong Yousuo Chemical Technology Co., Ltd, China; Isosorbide (analytic grade), sebacic acid (analytic grade), and Methylhydroquinone (analytic grade) are purchased from Shanghai Macklin Biochemical Co., Ltd. China; Stannous chloride (analytic grade), hydroquinone(analytic grade), Dichloromethane (analytic grade), Methanol (analytic grade), and Benzoyl peroxide (analytic grade) are purchased from Sino Pharm, China; p-toluenesulfonic acid (analytic grade) is purchased from Shanghai Lingfeng Chemical Reagent Co., Ltd, China; Deionized water was used in the whole process. 2.2 Synthesis of the prepolymer and PBHI(I)S elastomers A specific ratio (as shown in Table 1 ) of raw materials, such as sebacic acid, itaconic acid, hexanediol, butanediol, and isosorbitol, is measured and combined with a catalyst consisting of 0.1 wt.% stannous chloride and 0.1 wt.% p-toluenesulfonic acid. Additionally, polymerization inhibitors comprising of 0.05 wt.% methylhydroquinone and 0.02 wt.% hydroquinone are added. The resulting mixture is then placed in an oil bath and heated to a temperature of 140 ℃ to facilitate melting. Mechanical stirring and nitrogen environment for protection are employed during the entire esterification, while gradually raising the temperature. The reaction proceeds 1 hour each time the temperature increases by 10 ℃ within the range of 140 ℃ to 180 ℃, for a total duration of 5 hours. Subsequently, evacuate the system gradually raise the temperature while operating under lower pressure to facilitate the condensation reaction. Initially, the temperature is increased to 200 ℃ for a duration of 2 hours. Subsequently, it is further raised to 230 ℃ for another 2 hours. Finally, it is elevated to 260 ℃ for approximately 2 hours till the occurrence of climbing, which signifies the successful synthesis of prepolymers (pre-PBHIS or pre-PBHIIS). The prepolymer is subjected to repeated dissolution flocculation using a mixture of dichloromethane and methanol, which effectively eliminates some contaminants. Additionally, the majority of the solvent is eliminated through the process of rotary evaporation. Subsequently, the substance is introduced into a vacuum oven set at a temperature of 50 ℃, where it undergoes vacuum drying until the solvent is entirely eliminated. The initiator BPO of 1 wt.% is added into the prepolymers and subject it to a curing process at a temperature of 130 ℃ for a duration of 20 minutes. We prepared three sets of polyester elastomers with varying percentages of isosorbitol components. Table 1 displays the molar ratios of the three combinations of raw ingredients and the corresponding names of the polyester elastomers. Table 1 the molar ratios of the three combinations. Sebacic acid Itaconic acid Hexanediol Butanediol Isosorbide Product label 9 1 5 5 0 PBHIS 9 1 4 4 2 PBHIIS2 9 1 3 3 4 PBHIIS4 2.3 Characterization Gel Permeation Chromatography (GPC) analysis was carried out to determine the number-average molecular weight (Mn), weight-average molecular weight (Mw) and poly dispersity index (PDI) (PL-GPC220, Agilent Technologies, USA). Tetrahydrofuran was used as the eluent at a flow rate of 1 mL/min. The FTIR (ATR mode) were characterized on Nicolet iS 10 (Thermo Fisher Scientific, USA) with the scanning resolution of 4 cm − 1 over the wavelength range from 4000 to 650 cm − 1 for 32 times. Proton (1H) Nuclear Magnetic Resonance (NMR) spectra were measured at room temperature on a 600 MHz Bruker AV-600 spectrometer in methyl sulfoxide, using tetramethylsilane (TMS) as an internal standard. Mechanical properties were measured according to ISO37-2011 on a PT-1166Z Universal Testing Machine (Dongguan perfect-group Instrument, China) at a crosshead speed of 50 mm/min at room temperature. The size of the dumbbell spline is 35 mm in length, 2mm in width and 1mm in thickness. Differential scanning calorimetry (DSC) analysis was performed on DSC-3 (Mettler Toledo, Switzerland) under a nitrogen atmosphere. About 5–8 mg of the samples were placed into alumina crucibles and heated to 100°C at a heating rate of 10°C/min and kept for 5 min to eliminate previous thermal history, followed by cooling down to -50°C and finally heating to 100°C at a cooling/ heating rate of 10°C/min. The biodegradability of the PBH(I)S were characterized by composting according the EN ISO standard. [23] 3. Results and discussion 3.1 Chemical structure The molecular weight of pre-polymer significantly influences the structure and properties of the final cured product. Gel permeation chromatography was employed to examine the molecular weight of the prepolymers. The M n , M w , and PDI of pre-PBHI(I)S are summarized in Table 2 . Note that all the synthesis were undertaken with the identical device, procedure and operator, therefore the significant difference of molecular weight among PBHIS and PBHIIS mainly reflects the synthesizability of themselves. And it accords to our expectation that large and rigid isosorbide cause a harder chain formation with lower M n and M w , and subsequently it is reasonable that PBHIIS4 is even lower than PBHIIS2. Table 2 The M n , M w , and PDI of Pre-PBHI(I)S Mn Mw PDI PBHIS 50848 153935 3.03 PBHIIS2 18974 46432 2.45 PBHIIS4 27694 81012 2.93 Figure 2 . (a) shows the FTIR spectra of PBHIIS2 before and after curing, due to the presence of unsaturated itaconic acid, the peak of C = C stretching vibration is located at 1650 cm-1). Moreover, it can be seen from the figure that the intensity of the C = C peak located near 1650 cm − 1 of the cured PBHIIS2 decreases significantly, which indicates that the C = C on the molecular chain acts as a reaction site for cross-linking during the curing. Figure 2 (b) is the FTIR spectrum of various PBHI(I)S. The presence of an absorption peak representing ester carbonyl C = O near 1730 cm − 1 proves the occurrence of esterification, which results in the generation of ester bonds in the molecular structure. The peak of ether bond C-O-C near 1095 cm − 1 is enhanced significantly from PBHIS to PBHIIS4, which obviously agrees with the factor that only isosorbide contains C-O-C bond among all the monomers. The chemical structure of pre-PBHI(I)S was further characterized using NMR hydrogen spectroscopy. The 1 H NMR spectra of the prepolymers were normalized with the characteristic peak representing -CH2- on sebacic acid at δ = 1.23 ppm. The intensity of the tertiary hydrogen peaks representing isosorbide at δ = 4.70 ~ 4.78 ppm and near δ = 4.36 ~ 4.42 ppm in Fig. 3 was gradually enhanced, which indicated that the isosorbide component of raw material was increased, and the isosorbide segment in the synthesized molecular chain also increased. This further supports the above FTIR characterizations. 3.2 Thermal and mechanical property The DSC results of various PBHI(I)S are shown in Fig. 4 . The thermal properties such as T g (°C), T m (°C), ΔHm (J/g), T c (°C), and ΔH c (J/g) are summarized in Table 3 . The glass transition temperature of PBHIIS exhibited a progressive rise as the isosorbide concentration rose. This can be attributed to the incorporation of inflexible molecules, which hindered the relaxation within the polyester molecular chain. Nevertheless, the temperature at which PBHIIS crystallizes and the amount of heat released during crystallization gradually decreased as the content of isosorbitol increased. This suggests that the presence of the cyclic structure of isosorbitol hindered the orderly arrangement of polyester molecular chains, thereby diminishing the ability of PBHIIS to crystallize. The glass transition temperature (T g ), melting temperature (T m ), and crystallization temperature (T c ) of PBHIIS4 were lower than the temperature at which it was tested (25°C). Therefore, PBHIIS4 exhibits a high elasticity at room temperature. Table 3 Thermal properties of PBHI(I)S Tg (°C) Tm (°C) ΔHm (J/g) Tc (°C) ΔHc (J/g) PBHIS -38.78 50.84 65.98 36.52 69.35 PBHIIS2 -37.83 35.93 50.42 16.29 48.01 PBHIIS4 -37.50 24.53 37.83 -6.08 24.70 The mechanical properties of polyester elastomers were evaluated by tensile test, and the stress-strain curves of various PBHI(I)S are shown in Fig. 5 and the mechanical properties are summarized in Table 4 . The PBHIS exhibits a notable tensile strength of 12.5MPa and undergoes an obvious “necking” phenomenon during the tensile process, characterized by irreversible plastic deformation. The PBHIIS2 exhibits a crystallization temperature below room temperature, while its melting temperature surpasses room temperature. The polyester possesses excellent ductility due to the presence of a number of random molecular chains. Additionally, a small portion of crystals act as physical crosslinking agents, enhancing the material's strength and elongation at break. PBHIIS2 has both exceptional tensile strength and remarkable elongation at the point of fracture due to the presence of physical cross-linking and reinforcement from a limited number of crystals. The PBHIIS4 is a fully disordered polymer that does not form crystals at normal room temperature, and its stress-strain curves exhibit almost linear behavior. In the case of PBHIIS, the strength and modulus of the material declined dramatically as the amount of isosorbide rose. However, the elongation at break grew significantly, with PBHIIS4 even reaching an elongation at break of 846.8%. This suggests that both the composition of monomers with side groups and the specific type of monomers with side groups are important factors in determining the mechanical properties of copolyesters. In particular, isosorbide as monomer is an excellent option for improving the mechanical properties of polyester elastomers. Table 4 Mechanical behaviors of various PBHI(I)S. PBHIS PBHIIS2 PBHIIS4 Tensile strength 12.5MPa 6.32MPa 0.83MPa Elongation at break 73.3% 617.8% 846.8% Tensile Modulus 171.98MPa 12.83MPa 0.07MPa 3.4 Biodegradability Figure 6 shows the histogram of the degradation weight loss of PBHI(I)S with degradation time at 50°C and in a compost bin. From the degradation weight loss histograms, it can be seen that all the polyester elastomers synthesized in this work have excellent biodegradable properties, and almost all of them can be completely degraded in about 1 month. The degradation rate was relatively slow in the pre-composting stage probably due to factors such as microbial attachment, and the degradation occurred more and more rapidly as the polyester elastomers were gradually exposed to more degradable sites with the passage of time. The addition of isosorbide increases the hydrophilicity of PBHIIS, making it more susceptible to water and microbial "attack" and easier to degrade. The hydrolysable ester bonds in copolyester elastomers are responsible for their excellent biodegradability, and the degradation rate of copolyester elastomers can be modulated to a certain extent by the amount and type of monomers used in the synthesis system. 4. Conclusion Biodegradable polyester elastomers, PBHIIS, were successfully prepared from bio-based dibasic acids and diols by direct melt polycondensation and introducing the large and rigid monomer isosorbide to reduce the chemical and geometrical regularity of the molecular chain. By adjusting the molar ratios of the isosorbide monomer, it was found that, with the increase in the amount of the side group-containing monomers, the crystallization of the polyesters gradually weakened, the deformation of the polyesters in the tensile process shifted from mainly plastic to elastic deformation, and there was a tendency to accelerate the rate of the polyester's biodegradation. Comparing to PBHIS and PBHIIS2, the PBHIIS4 has a T m (24.53°C) close to room temperature, and a significant elongation at break of 846.8%, which is more than 11 times of the PBHIS. These findings certified that the isosorbide is a successful component in developing polyester elastomers and we hope it may serve as potential tool in the future research. Declarations Acknowledgments: This work is financially supported by the Postdoctoral Fellowships of Taizhou (282004), Taizhou Municipal Science and Technology Program (22gya19), the National Key Research and Development Program China (2022YFC2009500), Guangdong Provincial Science and Technology Program (2023A0505050146), the Medical Engineering Fund of Fudan University (yg2021-005, yg2022-008), and the RIZT Industrial Program (2022ZSS09, 2023CLG01, 2023CLG01PT). Declaration statement Competing interests: The authors declare no competing interests. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3849505","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":266296389,"identity":"1481b270-5c41-497c-bb09-b9206ca53e95","order_by":0,"name":"Lisheng Tang","email":"","orcid":"","institution":"Taizhou Institute of Zhejiang University","correspondingAuthor":false,"prefix":"","firstName":"Lisheng","middleName":"","lastName":"Tang","suffix":""},{"id":266296390,"identity":"df048c07-02d0-4eae-b855-208acbed3c14","order_by":1,"name":"Yuanyuan Jin","email":"","orcid":"","institution":"Taizhou Institute of Zhejiang 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06:14:11","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3849505/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3849505/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":49462215,"identity":"ebfa8a22-6f18-4f1a-bdf0-b9a081037e30","added_by":"auto","created_at":"2024-01-11 08:31:32","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":159007,"visible":true,"origin":"","legend":"\u003cp\u003eThe scheme of synthesis of pre-PBHI(I)S and curing vulcanization.\u003c/p\u003e","description":"","filename":"floatimage1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-3849505/v1/a3c41c43bf9b7860453392dc.jpeg"},{"id":49462214,"identity":"c24ced1f-e547-45d4-881d-f9f6111f7cfb","added_by":"auto","created_at":"2024-01-11 08:31:32","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":328240,"visible":true,"origin":"","legend":"\u003cp\u003eThe FTIR spectrum of PBHI(I)S (a) PBHIIS2 before and after the curing (b) various PBHI(I)S.\u003c/p\u003e","description":"","filename":"floatimage2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-3849505/v1/6d357b025dffeae95e553004.jpeg"},{"id":49462212,"identity":"6624df42-c6a3-4a6d-88ac-3d3dae8e66ff","added_by":"auto","created_at":"2024-01-11 08:31:32","extension":"jpeg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":238705,"visible":true,"origin":"","legend":"\u003cp\u003eThe \u003csup\u003e1\u003c/sup\u003eH NMR spectrum of various PBHI(I)S\u003c/p\u003e","description":"","filename":"floatimage3.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-3849505/v1/12140aa8362908e5cbb4dca3.jpeg"},{"id":49462426,"identity":"acdf4007-344e-42d3-9c07-4f1df64ff7f5","added_by":"auto","created_at":"2024-01-11 08:39:32","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":153164,"visible":true,"origin":"","legend":"\u003cp\u003eDSC cooling and heating scan of various PBHI(I)S.\u003c/p\u003e","description":"","filename":"floatimage4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-3849505/v1/d2cbd63f80e44a8f2a469afa.jpeg"},{"id":49462218,"identity":"530b2f6a-4a36-4cba-a5e8-a15ad4f8b8ef","added_by":"auto","created_at":"2024-01-11 08:31:32","extension":"jpeg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":145787,"visible":true,"origin":"","legend":"\u003cp\u003eTensile stress-strain curves of various PBHI(I)S.\u003c/p\u003e","description":"","filename":"floatimage5.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-3849505/v1/12d3b1917fccce75c5182b84.jpeg"},{"id":49462216,"identity":"24dfef3f-0728-487e-8b1d-6a10a095f124","added_by":"auto","created_at":"2024-01-11 08:31:32","extension":"jpeg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":168819,"visible":true,"origin":"","legend":"\u003cp\u003ethe degradation weight loss of PBHI(I)S\u003c/p\u003e","description":"","filename":"floatimage6.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-3849505/v1/b2b350d92bf341c4b47b1147.jpeg"},{"id":52599660,"identity":"2516d362-181f-4ae0-89d9-e62a1369d9fe","added_by":"auto","created_at":"2024-03-13 12:43:17","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":716318,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3849505/v1/741363ca-3bcb-4f7a-9537-b3bf668f9a12.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Advanced Elasticity and Biodegradability of Poly(butanediol- hexanediol-isosorbitol-itaconate-sebacate) Copolyester Elastomer via the Decrystallization Effect of Isosorbide","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eBecause of its special qualities, elastomers\u0026mdash;a type of polymer with a low modulus and high elasticity\u0026mdash;can rapidly return to their initial form following the removal of an external force. Because of these qualities, they are indispensable in both daily life and the economy [1\u0026ndash;4]. Elastomers have been the subject of ongoing research and development to improve their strength, stability, aging resistance, and wear resistance in order to fulfill the ever-increasing performance requirements. However, these advantages make it harder to dispose of the waste products made from conventional elastomers, which pollutes the environment over time [5, 6]. However, the majority of elastomers are derived from poorly sustainable non-renewable fossil fuels. The creation of novel elastomers that are not dependent on fossil fuels has become highly demanded in recent times due to the immense strain imposed by carbon emissions. Bio-based elastomers are a great way to reduce carbon emissions and conserve resources in the elastomer sector since they may be made from natural plants directly or by synthesizing them from bio-based monomers produced from biomass resources.\u003c/p\u003e \u003cp\u003eDue to excellent biodegradability, aliphatic polyester became a prominent area of research for environmentally-friendly products. Linear polyesters, such as poly(lactic acid) (PLA), polyglycolide acid (PGA), polycaprolactone (PCL), and their copolymers, have been extensively studied in the field of plastic for many years. And their industrial production is seeing tremendous growth [7\u0026ndash;9]. Polyesters having a three-dimensional network have gained increasing interest, motivated by these linear polymers [10\u0026ndash;11]. Like vulcanized rubber, the cross-linked network is formed by the incorporation of \"star\" monomers to create multi-branched chains, enabling the material to rapidly regain its shape when subjected to substantial deformation. Poly (glycerol sebacate) (PGS), polyoctyl citrate (POC), and their copolymers are the primary biodegradable polyester elastomers that have undergone substantial research. The pioneering work is the synthesis of PGS, an in-situ cross-linked polyester elastomer with a three-dimensional network structure and exceptional robustness, conducted by Langer et al. successfully synthesized in 2002 [10, 12]. In 2011, Zhang et al. firstly introduced chemically crosslinked polyester elastomer [13]. Subsequently, many other bio-based elastomers have been created [14, 15].\u003c/p\u003e \u003cp\u003eIt is well known that monomers of longer chain are easier to be synthesized to be polyester with higher stability, due to the lower density of ester linkage. For example, PCL and PBS are commercially mature materials, which employ 4- or 6- carbon chain monomer [16], while Polyglycolide acid (PGA) with 2-carbon monomer is unstable to hydrolysis and its commercial application is very limited [17]. However on the other hand, when the goal of our research is to obtain elastomers, the high crystallinity and rigidity due to longer chains becomes a disadvantage. Hereby a technical difficulty arises, how to construct biodegradable polyester with decent stability, cross-linkage network, and sufficient elasticity? i.e. we probably need longer chain monomers, multi-functional \"star\" monomer, and some component to lower the crystallinity.\u003c/p\u003e \u003cp\u003eIn chemically crosslinked polyester elastomers, the glass transition temperature can be decreased and crystallization can be hindered by employing multicomponent copolymerization and including monomers with side groups, which in turn improves the elasticity [18, 19]. Particular monomers with side group, large volume and/or rigid segment can play a crucial role in decrystallization. Gao et al. [20] designed and synthesized biobased poly(1,4-butanediol/2,3-butanediol/succinic acid/Iconocarboxylic acid) co-polyesters (PBBSI) with varying 2,3-butanediol content. The co-polyesters underwent a transformation from stiff plastics to flexible elastomers due to the alteration in the amount of 2,3-butanediol. Hu et al. [21] synthesized the elastomer poly(2,3-butanediol-co-1,4-butanediol-co-succinate) (PBBS) by introducing 2,3-butanedioic acid into PBS, whose elasticity can be thereafter improved with the decrystallization effect. Butanedioic acid and succinic acid were employed to ensure the good compatibility of PBBS with PBS.\u003c/p\u003e \u003cp\u003eIn this work, we select butanediol, hexanediol and itaconate as \u0026ldquo;long chain\u0026rdquo; monomers to obtain a stable co-polyester, and take sebacate as the chemically crosslinking site [22]. Isosorbide, as a bulky, rigid, and food and environment safe monomer, is introduced to the copolyester Poly(butanediol-hexanediol-itaconate-sebacate) (PBHIS) to prepare the biodegradable elastomer as Poly(butanediol-hexanediol-isosorbitol-itaconate-sebacate) (PBHIIS). Linear chains of this two copolyesters are synthesized as so-called pre-PBHI(I)S, and a final thermal curing with initiator Benzoyl Peroxide (BPO) vulcanized the linear chains to be structural network. The scheme of this work is illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The chemical structure, thermal and mechanical properties, and biodegradability of the final products were characterized.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Reagents and materials\u003c/h2\u003e \u003cp\u003eItaconic acid (analytic grade), hexylene glycol (analytic grade), and butanediol (analytic grade) are purchased from Shandong Yousuo Chemical Technology Co., Ltd, China; Isosorbide (analytic grade), sebacic acid (analytic grade), and Methylhydroquinone (analytic grade) are purchased from Shanghai Macklin Biochemical Co., Ltd. China; Stannous chloride (analytic grade), hydroquinone(analytic grade), Dichloromethane (analytic grade), Methanol (analytic grade), and Benzoyl peroxide (analytic grade) are purchased from Sino Pharm, China; p-toluenesulfonic acid (analytic grade) is purchased from Shanghai Lingfeng Chemical Reagent Co., Ltd, China; Deionized water was used in the whole process.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Synthesis of the prepolymer and PBHI(I)S elastomers\u003c/h2\u003e \u003cp\u003eA specific ratio (as shown in Table \u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) of raw materials, such as sebacic acid, itaconic acid, hexanediol, butanediol, and isosorbitol, is measured and combined with a catalyst consisting of 0.1 wt.% stannous chloride and 0.1 wt.% p-toluenesulfonic acid. Additionally, polymerization inhibitors comprising of 0.05 wt.% methylhydroquinone and 0.02 wt.% hydroquinone are added. The resulting mixture is then placed in an oil bath and heated to a temperature of 140 ℃ to facilitate melting. Mechanical stirring and nitrogen environment for protection are employed during the entire esterification, while gradually raising the temperature. The reaction proceeds 1 hour each time the temperature increases by 10 ℃ within the range of 140 ℃ to 180 ℃, for a total duration of 5 hours. Subsequently, evacuate the system gradually raise the temperature while operating under lower pressure to facilitate the condensation reaction. Initially, the temperature is increased to 200 ℃ for a duration of 2 hours. Subsequently, it is further raised to 230 ℃ for another 2 hours. Finally, it is elevated to 260 ℃ for approximately 2 hours till the occurrence of climbing, which signifies the successful synthesis of prepolymers (pre-PBHIS or pre-PBHIIS). The prepolymer is subjected to repeated dissolution flocculation using a mixture of dichloromethane and methanol, which effectively eliminates some contaminants. Additionally, the majority of the solvent is eliminated through the process of rotary evaporation. Subsequently, the substance is introduced into a vacuum oven set at a temperature of 50 ℃, where it undergoes vacuum drying until the solvent is entirely eliminated.\u003c/p\u003e \u003cp\u003eThe initiator BPO of 1 wt.% is added into the prepolymers and subject it to a curing process at a temperature of 130 ℃ for a duration of 20 minutes. We prepared three sets of polyester elastomers with varying percentages of isosorbitol components. Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e displays the molar ratios of the three combinations of raw ingredients and the corresponding names of the polyester elastomers.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003ethe molar ratios of the three combinations.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSebacic acid\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eItaconic acid\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eHexanediol\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eButanediol\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eIsosorbide\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eProduct label\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003ePBHIS\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003ePBHIIS2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003ePBHIIS4\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Characterization\u003c/h2\u003e \u003cp\u003eGel Permeation Chromatography (GPC) analysis was carried out to determine the number-average molecular weight (Mn), weight-average molecular weight (Mw) and poly dispersity index (PDI) (PL-GPC220, Agilent Technologies, USA). Tetrahydrofuran was used as the eluent at a flow rate of 1 mL/min.\u003c/p\u003e \u003cp\u003eThe FTIR (ATR mode) were characterized on Nicolet iS 10 (Thermo Fisher Scientific, USA) with the scanning resolution of 4 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e over the wavelength range from 4000 to 650 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for 32 times.\u003c/p\u003e \u003cp\u003eProton (1H) Nuclear Magnetic Resonance (NMR) spectra were measured at room temperature on a 600 MHz Bruker AV-600 spectrometer in methyl sulfoxide, using tetramethylsilane (TMS) as an internal standard.\u003c/p\u003e \u003cp\u003eMechanical properties were measured according to ISO37-2011 on a PT-1166Z Universal Testing Machine (Dongguan perfect-group Instrument, China) at a crosshead speed of 50 mm/min at room temperature. The size of the dumbbell spline is 35 mm in length, 2mm in width and 1mm in thickness.\u003c/p\u003e \u003cp\u003eDifferential scanning calorimetry (DSC) analysis was performed on DSC-3 (Mettler Toledo, Switzerland) under a nitrogen atmosphere. About 5\u0026ndash;8 mg of the samples were placed into alumina crucibles and heated to 100\u0026deg;C at a heating rate of 10\u0026deg;C/min and kept for 5 min to eliminate previous thermal history, followed by cooling down to -50\u0026deg;C and finally heating to 100\u0026deg;C at a cooling/ heating rate of 10\u0026deg;C/min.\u003c/p\u003e \u003cp\u003eThe biodegradability of the PBH(I)S were characterized by composting according the EN ISO standard. [23]\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Chemical structure\u003c/h2\u003e \u003cp\u003eThe molecular weight of pre-polymer significantly influences the structure and properties of the final cured product. Gel permeation chromatography was employed to examine the molecular weight of the prepolymers. The M\u003csub\u003en\u003c/sub\u003e, M\u003csub\u003ew\u003c/sub\u003e, and PDI of pre-PBHI(I)S are summarized in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. Note that all the synthesis were undertaken with the identical device, procedure and operator, therefore the significant difference of molecular weight among PBHIS and PBHIIS mainly reflects the synthesizability of themselves. And it accords to our expectation that large and rigid isosorbide cause a harder chain formation with lower M\u003csub\u003en\u003c/sub\u003e and M\u003csub\u003ew\u003c/sub\u003e, and subsequently it is reasonable that PBHIIS4 is even lower than PBHIIS2.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eThe M\u003csub\u003en\u003c/sub\u003e, M\u003csub\u003ew\u003c/sub\u003e, and PDI of Pre-PBHI(I)S\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMn\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMw\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003ePDI\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePBHIS\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e50848\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e153935\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e3.03\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePBHIIS2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e18974\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e46432\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.45\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePBHIIS4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e27694\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e81012\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.93\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. (a) shows the FTIR spectra of PBHIIS2 before and after curing, due to the presence of unsaturated itaconic acid, the peak of C\u0026thinsp;=\u0026thinsp;C stretching vibration is located at 1650 cm-1). Moreover, it can be seen from the figure that the intensity of the C\u0026thinsp;=\u0026thinsp;C peak located near 1650 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of the cured PBHIIS2 decreases significantly, which indicates that the C\u0026thinsp;=\u0026thinsp;C on the molecular chain acts as a reaction site for cross-linking during the curing. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(b) is the FTIR spectrum of various PBHI(I)S. The presence of an absorption peak representing ester carbonyl C\u0026thinsp;=\u0026thinsp;O near 1730 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e proves the occurrence of esterification, which results in the generation of ester bonds in the molecular structure. The peak of ether bond C-O-C near 1095 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is enhanced significantly from PBHIS to PBHIIS4, which obviously agrees with the factor that only isosorbide contains C-O-C bond among all the monomers.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe chemical structure of pre-PBHI(I)S was further characterized using NMR hydrogen spectroscopy. The \u003csup\u003e1\u003c/sup\u003eH NMR spectra of the prepolymers were normalized with the characteristic peak representing -CH2- on sebacic acid at δ\u0026thinsp;=\u0026thinsp;1.23 ppm. The intensity of the tertiary hydrogen peaks representing isosorbide at δ\u0026thinsp;=\u0026thinsp;4.70\u0026thinsp;~\u0026thinsp;4.78 ppm and near δ\u0026thinsp;=\u0026thinsp;4.36\u0026thinsp;~\u0026thinsp;4.42 ppm in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e was gradually enhanced, which indicated that the isosorbide component of raw material was increased, and the isosorbide segment in the synthesized molecular chain also increased. This further supports the above FTIR characterizations.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Thermal and mechanical property\u003c/h2\u003e \u003cp\u003eThe DSC results of various PBHI(I)S are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. The thermal properties such as T\u003csub\u003eg\u003c/sub\u003e (\u0026deg;C), T\u003csub\u003em\u003c/sub\u003e (\u0026deg;C), ΔHm (J/g), T\u003csub\u003ec\u003c/sub\u003e (\u0026deg;C), and ΔH\u003csub\u003ec\u003c/sub\u003e (J/g) are summarized in Table \u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. The glass transition temperature of PBHIIS exhibited a progressive rise as the isosorbide concentration rose. This can be attributed to the incorporation of inflexible molecules, which hindered the relaxation within the polyester molecular chain. Nevertheless, the temperature at which PBHIIS crystallizes and the amount of heat released during crystallization gradually decreased as the content of isosorbitol increased. This suggests that the presence of the cyclic structure of isosorbitol hindered the orderly arrangement of polyester molecular chains, thereby diminishing the ability of PBHIIS to crystallize. The glass transition temperature (T\u003csub\u003eg\u003c/sub\u003e), melting temperature (T\u003csub\u003em\u003c/sub\u003e), and crystallization temperature (T\u003csub\u003ec\u003c/sub\u003e) of PBHIIS4 were lower than the temperature at which it was tested (25\u0026deg;C). Therefore, PBHIIS4 exhibits a high elasticity at room temperature.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eThermal properties of PBHI(I)S\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTg (\u0026deg;C)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eTm (\u0026deg;C)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eΔHm (J/g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eTc (\u0026deg;C)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eΔHc (J/g)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePBHIS\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-38.78\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e50.84\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e65.98\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e36.52\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e69.35\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePBHIIS2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-37.83\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e35.93\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e50.42\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e16.29\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e48.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePBHIIS4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-37.50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e24.53\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e37.83\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-6.08\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e24.70\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe mechanical properties of polyester elastomers were evaluated by tensile test, and the stress-strain curves of various PBHI(I)S are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e and the mechanical properties are summarized in Table\u0026nbsp;\u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. The PBHIS exhibits a notable tensile strength of 12.5MPa and undergoes an obvious \u0026ldquo;necking\u0026rdquo; phenomenon during the tensile process, characterized by irreversible plastic deformation. The PBHIIS2 exhibits a crystallization temperature below room temperature, while its melting temperature surpasses room temperature. The polyester possesses excellent ductility due to the presence of a number of random molecular chains. Additionally, a small portion of crystals act as physical crosslinking agents, enhancing the material's strength and elongation at break. PBHIIS2 has both exceptional tensile strength and remarkable elongation at the point of fracture due to the presence of physical cross-linking and reinforcement from a limited number of crystals. The PBHIIS4 is a fully disordered polymer that does not form crystals at normal room temperature, and its stress-strain curves exhibit almost linear behavior. In the case of PBHIIS, the strength and modulus of the material declined dramatically as the amount of isosorbide rose. However, the elongation at break grew significantly, with PBHIIS4 even reaching an elongation at break of 846.8%. This suggests that both the composition of monomers with side groups and the specific type of monomers with side groups are important factors in determining the mechanical properties of copolyesters. In particular, isosorbide as monomer is an excellent option for improving the mechanical properties of polyester elastomers.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab4\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eMechanical behaviors of various PBHI(I)S.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePBHIS\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003ePBHIIS2\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003ePBHIIS4\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTensile strength\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e12.5MPa\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e6.32MPa\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.83MPa\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eElongation at break\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e73.3%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e617.8%\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e846.8%\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTensile Modulus\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e171.98MPa\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e12.83MPa\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.07MPa\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.4 Biodegradability\u003c/h2\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e shows the histogram of the degradation weight loss of PBHI(I)S with degradation time at 50\u0026deg;C and in a compost bin. From the degradation weight loss histograms, it can be seen that all the polyester elastomers synthesized in this work have excellent biodegradable properties, and almost all of them can be completely degraded in about 1 month. The degradation rate was relatively slow in the pre-composting stage probably due to factors such as microbial attachment, and the degradation occurred more and more rapidly as the polyester elastomers were gradually exposed to more degradable sites with the passage of time. The addition of isosorbide increases the hydrophilicity of PBHIIS, making it more susceptible to water and microbial \"attack\" and easier to degrade. The hydrolysable ester bonds in copolyester elastomers are responsible for their excellent biodegradability, and the degradation rate of copolyester elastomers can be modulated to a certain extent by the amount and type of monomers used in the synthesis system.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eBiodegradable polyester elastomers, PBHIIS, were successfully prepared from bio-based dibasic acids and diols by direct melt polycondensation and introducing the large and rigid monomer isosorbide to reduce the chemical and geometrical regularity of the molecular chain.\u003c/p\u003e \u003cp\u003eBy adjusting the molar ratios of the isosorbide monomer, it was found that, with the increase in the amount of the side group-containing monomers, the crystallization of the polyesters gradually weakened, the deformation of the polyesters in the tensile process shifted from mainly plastic to elastic deformation, and there was a tendency to accelerate the rate of the polyester's biodegradation. Comparing to PBHIS and PBHIIS2, the PBHIIS4 has a T\u003csub\u003em\u003c/sub\u003e (24.53\u0026deg;C) close to room temperature, and a significant elongation at break of 846.8%, which is more than 11 times of the PBHIS. These findings certified that the isosorbide is a successful component in developing polyester elastomers and we hope it may serve as potential tool in the future research.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgments:\u003c/strong\u003e This work is financially supported by the Postdoctoral\u0026nbsp;Fellowships\u0026nbsp;of Taizhou (282004), Taizhou Municipal Science and Technology Program (22gya19), the National Key Research and Development Program China (2022YFC2009500), Guangdong Provincial Science and Technology Program (2023A0505050146), the Medical Engineering Fund of Fudan University (yg2021-005, yg2022-008), and the RIZT Industrial Program (2022ZSS09, 2023CLG01, 2023CLG01PT).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eCompeting interests: The authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability statements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u0026bull; The main data generated or analysed to support the conclusion during this study are included in this published article.\u003c/p\u003e\n\u003cp\u003e\u0026bull; The full datasets generated and/or analysed during the current study are available from the corresponding author by request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor Contributions Statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eR.H. supervised and coordinated project; R.H. and L.T. designed research; L.T., Y.J. performed research; L.T., X.H. and Y.J. analyzed data; R.H., X.H. and L.T. acquired funding and resource; and R.H. and L.T. wrote paper.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eLiu S, Qiu J, Han L, Ma X, Chen W. 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European Polymer Journal, 2019, 116: 438-44.\u003c/li\u003e\n\u003cli\u003e Tang L, He X, Jin Y, Huang R, Biodegradable Poly(ethylene glycol-glycerol-itaconate-sebacate) Copolyester Elastomer with Significantly Reinforced Mechanical Properties by in-situ Construction of Bacterial Cellulose Interpenetrating Network, in publication.\u003c/li\u003e\n\u003cli\u003e Plastics - Determination of the degree of disintegration of plastic materials under defined composting conditions in a pilot-scale test, EN ISO 16929-2019.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Biodegradable, Copolyester Elastomer, PBHIIS, Isosorbide, Decrystallization","lastPublishedDoi":"10.21203/rs.3.rs-3849505/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3849505/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe stability to against hydrolysis while maintaining excellent elasticity is a constant challenge in the development of biodegradable and environmental-friendly polyester elastomer. While monomers of longer chain can provide higher stability, the high crystallinity and rigidity impair their application in fabricating elastomer. This work reported a star-crosslinked Poly(butanediol-hexanediol-isosorbitol-itaconate-sebacate) (PBHIIS) elastomer synthesized by esterification and thermal curing. With the decrystallization effect of isosorbide as a large and rigid monomer, the original rigid Poly(butanediol-hexanediol-itaconate-sebacate) successfully transformed to be elastomer with lower T\u003csub\u003em\u003c/sub\u003e and T\u003csub\u003eg\u003c/sub\u003e, much higher Elongation at break, and smaller tensile modulus, and biodegradability is also improved. The strategy is demonstrated to be efficient and may serve as a potential technique in the future development of biodegradable elastomers.\u003c/p\u003e","manuscriptTitle":"Advanced Elasticity and Biodegradability of Poly(butanediol- hexanediol-isosorbitol-itaconate-sebacate) Copolyester Elastomer via the Decrystallization Effect of Isosorbide","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-01-11 08:31:27","doi":"10.21203/rs.3.rs-3849505/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"9432abe5-0ad4-4898-982d-78916dcba755","owner":[],"postedDate":"January 11th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2024-04-04T06:08:42+00:00","versionOfRecord":[],"versionCreatedAt":"2024-01-11 08:31:27","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-3849505","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3849505","identity":"rs-3849505","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}