Research Article pubs.acs.org/journal/ascecg
High Molecular Weight Polyesters Derived from Biobased 1,5Pentanediol and a Variety of Aliphatic Diacids: Synthesis, Characterization, and Thermo-Mechanical Properties Jing Lu, Linbo Wu,* and Bo-Geng Li State Key Laboratory of Chemical Engineering at ZJU, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China S Supporting Information *
ABSTRACT: High molecular weight aliphatic polyesters were synthesized from biobased 1,5-pentanediol and aliphatic diacids with 4, 5, 6, 9, 10, or 12 carbon atoms via melt polycondensation. The poly(1,5-pentylene dicarboxylate)s were characterized with intrinsic viscosity, gel permeation chromatography (GPC), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), thermogravimetric analysis (TGA), and tensile testing. The effects of dicarboxylate chain length on crystalline structure and thermo-mechanical properties were investigated. All the polyesters had weight-average molecular weight over 100,000 g/mol or intrinsic viscosity over 1.05 dL/g except poly(1,5-pentylene adipate) (PPeA), which was less thermally stable than others. As semicrystalline polymers, they have a polyethylene-like crystal structure and crystallize rapidly except poly(1,5-pentylene succinate) (PPeS). As a whole, the crystallizability and melting temperature (Tm) increase with dicarboxylate chain length, and the “even−odd” effect exists to a certain extent. Among them, poly(1,5-pentylene azelate) (PPeAz), poly(1,5-pentylene sebacate) (PPeSe), and poly(1,5-pentylene dodecanedioate) (PPeDo) have Tm of 50−62 °C, good thermal stability, and exhibit comparable or even superior tensile properties in comparison with polyethylene and the well-known biodegradable copolyester, poly(butylene adipate-co-terephthalate) (PBAT). These biobased and potentially biodegradable polyesters appear to be promising materials for practical applications. KEYWORDS: Biobased polymers, Biodegradable polymers, Poly(1,5-pentylene dicarboxylate)s, Thermal property, Mechanical property
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INTRODUCTION Aliphatic polyesters are often characterized by desirable biodegradability. Some of them such as polylactide (PLA), poly(butylene succinate) (PBS), poly(butylene succinate-coadipate) (PBSA), poly(hydroxyalkanoate) (PHA), and poly(εcaprolactone) (PCL) have reasonably good thermo-mechanical properties and have been industrialized and applied to biomedical or disposable materials over decades. In the past decade, research and utilization of renewable biomass and development of a biorefinery industry have provided many new opportunities for synthesis of biobased monomers1 and polyesters.2−5 Succinic acid, 1,10-sebacic acid, and 2,5furandicarboxylic acid are important examples of biobased diacids, and 1,3-propanediol (PDO), 1,4-butanediol (BDO), 1,5-pentanediol (PeDO), and 1,6-hexanediol (HDO) are typical biobased diols. From them, researchers have synthesized some biobased polyesters or copolyesters with unique properties which have attracted much attention from both academia and industry. As biobased counterparts of petroleum-based polyester poly(ethylene terephthalate) (PET), for example, © 2017 American Chemical Society
poly(trimethylene terephthalate), has been industrialized to produce biobased elastic fiber,6 poly(ethylene 2,5-furandicarboxylate) also has attracted much attention because of its superior gas barrier properties.7 PeDO, an important feedstock for production of polyesters, polyols, polyurethanes, coatings, inks, perfumes, and plasticizers can be produced from petrochemicals such as glutaric acid or its esters. It was commercialized by BASF and Ube Industries, but the production and applications are still in small scale because of limited raw materials and high cost.8 PeDO can also be synthesized from biomass through hydrogenation of furfural followed by hydrogenolysis of tetrahydrofurfuryl alcohol.9,10 Furfural is an important chemical commercially manufactured via acid-catalyzed hydrolysis of semicellulose and then dehydration of xylose. With the development of a highperformance catalyst used for one-pot hydrogenation and Received: April 6, 2017 Revised: May 22, 2017 Published: May 28, 2017 6159
DOI: 10.1021/acssuschemeng.7b01050 ACS Sustainable Chem. Eng. 2017, 5, 6159−6166
Research Article
ACS Sustainable Chemistry & Engineering hydrogenolysis,10 biobased PeDO would be industrially produced from furfural at economical scale and low cost. PeDO has already been used to synthesize some polyesters via melt polycondensation. In 1957, Korshak et al.11 reported the synthesis of poly(1,5-pentylene adipate) (PPeA) and poly(1,5-pentylene grutarate) (PPeG) for the first time. Recently, several PeDO-based aliphatic polyesters including poly(1,5-pentylene succinate) (PPeS),12−15 PPeA,16 poly(1,5pentylene pimelate) (PPePi),17 aromatic polyesters such as poly(1,5-pentylene furanoate) (PPeF)14,15,18−20 and poly(pentylene diphthalate),21 and copolyesters14,15,22,23 have been synthesized and characterized. Also, PeD-derived copolycarbonates synthesized via nonphosgene process,24 poly(ester-carbonate)s25 synthesized via interesterification− polycondensation, and functional copolyesters synthesized via enzymatic catalysis and used for drug release26 were also reported. However, low molecular weight (Mn < 15,000 g/mol) was reported in most PeDO-based aliphatic polyesters.11,13−15,17 Greiner et al.16 synthesized high molecular weight PPeA (Mn = 43,000 g/mol) through long-time reaction. When succinic anhydride was used instead of succinic acid, mediium intrinsic viscosity PPeS (0.65 dL/g)12 was synthesized. Meanwhile, some medium to high molecular weight PeDObased copolyesters were synthesized by Greiner et al.,16 Tsai et al.,23 and Li et al.24 For aromatic polyester, only medium intrinsic viscosity (0.53 dL/g) was reported for PPeF.19 As PeDO is an odd-carbon diol monomer, aliphatic poly(1,5pentylene dicarboxylate)s could be odd−even or odd−odd polyesters and therefore may have thermo-mechanical properties different from the more common even−even aliphatic polyesters. However, suffering from low molecular weight, the mechanical properties were poor17 or not reported. On the other hand, there is still no report so far on polymers synthesized from biobased PeDO. On the basis of the above context, we aimed to synthesize high molecular weight linear polyesters from biobased PeDO and aliphatic dicarboxylic acids with different chain lengths (carbon number: 4, 5, 6, 9, 10, 12) via melt polycondensation in this study. Among them, poly(1,5pentylene azelate) (PPeAz), poly(1,5-pentylene sebacate) (PPeSe), and poly(1,5-pentylene dodecanedioate) (PPeDo) are reported for the first time. Three long chain diacids, namely, azelaic, sebacic, and dodecanedioic acids, were used in order to increase the melting temperature (Tm) of the polyesters because when short chain diacids such as succinic, glutaric, and adipic acids were used Tm is too low (800 758 ± 45 750 148 750
this study this study this study 2 36 37 38 39 40
a Tensile modulus. bTensile stress at yield. cTensile stress at break. dElongation at break. ePoly(butylene azelate), Mn = 37 000. fEcoflex FBX 407, injection specimens. gEcoflex FBX 7011, thermal compression specimens. hEcoflex F blend C1200, thermal compression specimens. iLinear low density polyethylene, injection specimens. jPoly(ε-caprolactone), Mn = 120 000, thermal compression specimens.
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DOI: 10.1021/acssuschemeng.7b01050 ACS Sustainable Chem. Eng. 2017, 5, 6159−6166
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ACS Sustainable Chemistry & Engineering polyesters having a Tm of 50−62 °C and exhibit good tensile properties at room temperature comparable to or even better than polyethylene and the well-known biodegradable copolyester PBAT. Because of potential biodegradability and superior mechanical properties, these polyesters appear to be promising substitutes of PE and PBAT for practical application.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.7b01050. Appearance of as-synthesized poly(1,5-pentylene dicarboxylate)s and specimens for tensile test (Figure S2-S1), details on assignments of 1H NMR (Table S2S1), FTIR spectra (Figure S2-S2) and their assignments, DSC thermograms (Figure S3-S1, Figure S3-S2), and decomposition temperatures (Table S3-S1). (PDF)
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Linbo Wu: 0000-0001-9964-6140 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work was supported by the National Key Research and Development Program (2016YFB0302402), National Nature Science Foundation of China (51373152), and 151 Talents Project of Zhejiang Province.
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