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Synthesis, Properties, and Biodegradation of Sequential Poly(Ester Amide)S Containing Γ-Aminobutyric Acid

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Synthesis, Properties, and Biodegradation of Sequential Poly(Ester Amide)S Containing Γ-Aminobutyric Acid International Journal of Molecular Sciences Article Synthesis, Properties, and Biodegradation of Sequential Poly(Ester Amide)s Containing γ-Aminobutyric Acid Yuushou Nakayama 1,* , Kazumasa Watanabe 1, Ryo Tanaka 1 , Takeshi Shiono 1 , Norioki Kawasaki 2, Naoko Yamano 2 and Atsuyoshi Nakayama 2 1 Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan; [email protected] (K.W.); [email protected] (R.T.); [email protected] (T.S.) 2 Biomedical Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan; [email protected] (N.K.); [email protected] (N.Y.); [email protected] (A.N.) * Correspondence: [email protected]; Tel.: +81-82-424-7746 Received: 30 April 2020; Accepted: 20 May 2020; Published: 23 May 2020 Abstract: Poly(ester amide)s are attracting attention because they potentially have excellent thermal and mechanical properties as well as biodegradability. In this study, we synthesized a series of novel poly(ester amide)s by introducing γ-aminobutyric acid (GABA) regularly into polyesters, and investigated their properties and biodegradabilities. GABA is the monomer unit of biodegradable polyamide 4 (PA4). The new poly(ester amide)s were synthesized from the reaction of ammonium tosylate derivatives of alkylene bis(γ-aminobutylate) and p-nitrophenyl esters of dicarboxylic acids. All the obtained polymers showed relatively high melting temperatures (Tm). Their thermal decomposition temperatures were improved in comparison with that of PA4 and higher enough than their Tm. The poly(ester amide)s exhibited higher biodegradability in seawater than the corresponding homopolyesters. Their biodegradabilities in activated sludge were also studied. Keywords: poly(ester amide)s; γ-aminobutyric acid; thermal properties; biodegradation; seawater; activated sludge 1. Introduction Biodegradable polymers are attracting attention due to recent environmental problems caused by wasted polymer materials [1–4]. Bacterial aliphatic polyesters such as poly(3-hydroxyalkanoate)s (PHAs) and synthetic polyesters such as poly(l-lactic acid) (PLLA), poly(glycolic acid) (PGA), poly("-caprolactone) (PCL), and poly(butylene succinate) (PBS) are representative biodegradable polymers. In recent years, marine pollution by microplastics has become a worldwide issue [5–7]. Therefore, the polymers biodegradable in seawater should be useful for the applications where the complete recovery of the materials is difficult. Among the so-called biodegradable polymers, ones degradable in seawater are limited. PHAs and PGA are the representative examples reported to be biodegradable in seawater [8–10]. In contrast, aromatic polyesters such as poly(ethylene terephthalate) (PET) are not recognized as biodegradable polymers, although some microorganisms were reported to degrade PET [11]. We have recently reported a series of aliphatic-aromatic copolyesters with periodic sequences, where the copolyesters with glycolate units, poly((ethylene diglycolate) terephthalate), exhibited biodegradability in seawater, while the corresponding copolyester with l-lactate was hardly degradable [12]. These results could be related to high and low biodegradability of PGA [13] and PLLA [10,14–16] in seawater, respectively. Int. J. Mol. Sci. 2020, 21, 3674; doi:10.3390/ijms21103674 www.mdpi.com/journal/ijms Int. J. Mol. Sci. 2020, 21, 3674 2 of 13 Int. J. Mol. Sci. 2020, 21, x FOR PEER REVIEW 2 of 14 OnOn the other hand,hand, polyamides polyamides (nylons) (nylons) such such as as polyamide polyamide 6 (6-nylon) 6 (6-nylon) are are also also widely widely used used for their for theirhigh waterhigh water absorption, absorption, crystallinity, crystallinity, chemical chemic resistance,al resistance, high melting high point,melting strength, point, strength, and flexibility and flexibilityderived from derived intra- from and intermolecularintra- and intermolecular hydrogen bond hydrogen of amide bond groups. of amide However, groups. the However, commercially the commerciallyavailable polyamides available are polyamides made from fossilare made resources from and fossil hardly resources biodegradable. and hardly In contrast, biodegradable. polyamide In contrast,4 (PA4) canpolyamide be obtained 4 (PA4) from can bio-based be obtainedγ-aminobutyric from bio-based acid γ-aminobutyric (GABA), which acid can (GABA), be produced which can by befermentation produced ofby glutamic fermentation acid [17 of]. glutamic PA4 is also acid reported [17]. PA4 to be is biodegradable also reported in variousto be biodegradable media including in variousseawater media [18–23 including]. However, seawater PA4 has [18–23]. a disadvantage However, of relativelyPA4 has lowa disadvantage thermal stability, of relatively which can low be thermalsomewhat stability, improved which by can end-group be somewhat modification improved [24]. by end-group modification [24]. Poly(esterPoly(ester amide)s amide)s are are polymers polymers having having both both ester ester and and amide amide bonds bonds in in their polymer main chainschains [25–34]. [25–34]. Poly(ester Poly(ester amide)s amide)s with with aliphatic aliphatic es esterter moieties moieties can can possess possess both both biodegradability biodegradability for for aliphaticaliphatic ester bondsbonds andand excellent excellent physical physical properties properties due due to theto the amide amide bonds. bonds. Poly(ester Poly(ester amide)s amide)s with withvarious various monomer monomer combinations combinations have been have synthesized been synthesized and investigated and investigated for their thermal, for their mechanical thermal, mechanicalproperties and properties degradability. and degradability. Bayer has commercialized Bayer has commercialized poly(ester amide) poly(ester (BAK 1095)amide) that (BAK consists 1095) of that1,4-butanediol, consists of adipic 1,4-butanediol, acid, and " -caprolactam,adipic acid, whichand ε possesses-caprolactam, complete which biodegradability possesses complete as well biodegradabilityas excellent thermal as well and mechanicalas excellent propertiesthermal and and mechanical processability properties [35]. Several and processability poly(ester amides) [35]. Severalcontaining poly(esterα-amino amides) acids have containing been studied α-amino due toacids their have enzymatic been stud degradabilityied due to [30 their,33,36 enzymatic]. degradabilityAs PA4 has [30,33,36]. been reported to be biodegradable in seawater [22,37], we expected that the poly(ester As PA4 has been reported to be biodegradable in seawater [22,37], we expected that the amide)s containing GABA units could also be the polymers biodegradable in seawater. In addition [38], poly(ester amide)s containing GABA units could also be the polymers biodegradable in seawater. In the copolymers with regular sequences such as alternating and periodic copolymers could have some addition [38], the copolymers with regular sequences such as alternating and periodic copolymers specific properties such as higher melting temperature (Tm) and/or glass-transition temperature (Tg) not could have some specific properties such as higher melting temperature (Tm) and/or glass-transition expected from those of the corresponding homopolymers [39], in comparison with the corresponding temperature (Tg) not expected from those of the corresponding homopolymers [39], in comparison random copolymers [12,25,34,38]. In this study, we synthesized a series of new sequential poly(ester with the corresponding random copolymers [12,25,34,38]. In this study, we synthesized a series of amide)s containing GABA unit and investigated their thermal properties and biodegradabilities in new sequential poly(ester amide)s containing GABA unit and investigated their thermal properties seawater and in activated sludge. and biodegradabilities in seawater and in activated sludge. 2. Results 2. Results 2.1. Synthesis of the Sequential Poly(Ester Amide)s 2.1. Synthesis of the Sequential Poly(Ester Amide)s In this study, the sequential poly(ester amide)s containing GABA unit were synthesized in In this study, the sequential poly(ester amide)s containing GABA unit were synthesized in a a similar procedure for those containing α-amino acids [30,40]. For this purpose, tosylates of similar procedure for those containing α-amino acids [30,40]. For this purpose, tosylates of alkylene alkylene bis(γ-aminobutyrate)s and p-nitrophenyl esters of dicarboxylic acids were prepared from the bis(γ-aminobutyrate)s and p-nitrophenyl esters of dicarboxylic acids were prepared from the reactions shown in Schemes1 and2, respectively. The 2:2:1 reaction of GABA, p-toluenesulfonic acid reactions shown in Schemes 1 and 2, respectively. The 2:2:1 reaction of GABA, p-toluenesulfonic acid monohydrate (TsOH H2O), and alkanediol in toluene gave the corresponding tosylates of alkylene monohydrate (TsOH·H· 2O), and alkanediol in toluene gave the corresponding tosylates of alkylene bis(γ-aminobutyrate)s, gEg-OTs (alkylene = ethylene), gPg-OTs (alkylene = trimethylene), and gBg-OTs bis(γ-aminobutyrate)s, gEg-OTs (alkylene = ethylene), gPg-OTs (alkylene = trimethylene), and gBg- (alkylene = tetramethylene) in good yields after recrystallization from ethanol. On the other hand, OTs (alkylene = tetramethylene) in good yields after recrystallization from ethanol. On the other the chloride derivatives of dicarboxylic acids
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