Effects of Geometric Structure in Unsaturated Aliphatic Polyesters on Their Biodegradability

Takenouchi, Shigenobu; Takasu, Akinori; Inai, Yoshihito; Hirabayashi, Tadamichi

doi:10.1295/polymj.33.746

Cited by 32 publications

(36 citation statements)

References 18 publications

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“…The signals of the -CH 2 protons belonging to this diol are seen at 3.7-4.3 ppm (b) and the -CH proton at 5.10 ppm (c). The signals between 6.5 and 7.0 ppm (a) correspond to the protons of the double bonds of FuA moieties [29]. As expected, the presented spectra exhibit distinct peaks for the saturated dicarboxylic acid moieties.…”

Section: Results and Discussion 31 Polycondensation Of Ups Based Onsupporting

confidence: 76%

Going greener: Synthesis of fully biobased unsaturated polyesters for styrene crosslinked resins with enhanced thermomechanical properties

Costa¹,

Fonseca²,

Moniz³

et al. 2017

Express Polym. Lett.

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Abstract. The main goal of this work was the development of fully biobased unsaturated polyesters (UPs) that upon crosslinking with unsaturated monomers (UM) could lead to greener unsaturated polyester resins (UPRs) with similar thermomechanical properties to commercial fossil based UPR. After the successful synthesis of the biobased UPs, those were crosslinked with styrene (Sty), the most commonly used monomer, and the influence of the chemical structure of the UPs on the thermomechanical characteristics of UPRs were evaluated. The properties were compared with those of a commercial resin (Resipur 9837 ® ). The BioUPRs presented high gel contents and contact angles that are similar to the commercial resin. The thermomechanical properties were evaluated by dynamic mechanical thermal analysis (DMTA) and it was found that the UPR synthesized using propylene glycol (PG), succinic acid (SuAc) and itaconic acid (ItAc) presented very close thermomechanical properties compared to the commercial resin.

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Section: Results and Discussion 31 Polycondensation Of Ups Based Onsupporting

confidence: 76%

Going greener: Synthesis of fully biobased unsaturated polyesters for styrene crosslinked resins with enhanced thermomechanical properties

Costa¹,

Fonseca²,

Moniz³

et al. 2017

Express Polym. Lett.

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“…6 Z-conformation rich unsaturated polyester (molar ratio Z/E = 81/19) could be prepared, but 100% Z-conformation was never obtained because of the C=C double bond of Z-configuration isomerized into E-configuration as a side reaction during polycondensation. To clarify geometric structure effects on their biodegradability, ring-opening copolymerization 1 H NMR spectra along reaction time for the isomerization of polymer P2a.…”

Section: Ring-opening Copolymerization Of Acid Anhydrides and Propylementioning

confidence: 99%

“…6 In the case of saturated polyesters, chain extension reaction is often employed to make up polyester having high molecular weight. 15,16 In order to obtain high molecular weight of unsaturated polyester samples, chain extension reaction of polymer P2a was also examined by using a Titanium(IV) isopropoxide as a catalyst at 80 • C. However it resulted in gelation of the polymer in parallel with the chain extension reaction.…”

Section: Ring-opening Copolymerization Of Acid Anhydrides and Propylementioning

confidence: 99%

“…In controlling the biodegradation rate of polyester, it is very helpful to make geometrical effects clear. In our previous paper, 6 it was shown that in comparison with saturated polyesters, the ef- † To whom correspondence should be addressed. ficient degradation was prevented by introducing Zconfiguration of C=C double bond in the unsaturated polyesters but introducing E-configuration did not affect so remarkably.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4][5][6] Tokiwa and Suzuki reported that a few unsaturated polyesters containing 2-butenediol unit could be hydrolyzed by lipase. 1 On the other hand, slightly cross-linked unsaturated polyesters, poly(hexamethylene fumarate) and poly(cis-2-butene fumarate), were hardly hydrolyzed by lipase.…”

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Effects of Geometrical Difference of Unsaturated Aliphatic Polyesters on Their Biodegradability II. Isomerization of Poly(maleic anhydride-co-propylene oxide) inthe Presence of Morpholine

Takenouchi

Takasu

Inai

et al. 2002

Polym J

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ABSTRACT:Ring-opening copolymerizations of succinic anhydride (SAn, 1) or maleic anhydride (MAn, 2) with propylene oxide (PO) were carried out by using magnesium diethoxide (Mg(OEt) 2 ) as a catalyst. The unsaturated polyester (P2a) was found to have only Z-configuration around a C=C double bond from its 1 H and 13 C NMR spectra. Isomerization reaction of P2a from Z-to E-configuration was performed in 1,2-dichloroethane with a catalytic amount of morpholine. Thus unsaturated polyesters, P2b-e, having the same molecular weight but the different ratio of Z-/E-configuration could be optionally prepared from one original polymer P2a by controlling isomerization reaction time. Biodegradability of these polyester samples was evaluated from their biochemical oxygen demand (BOD) values in the presence of an activated sludge. Polyester P2a was hardly degraded during measurement. However, polyesters P2b-e, partially containing E-configuration of the C=C double bond, degraded considerably faster than P2a itself. The biodegradability of saturated polyester P1 was also examined to compare with the P2-series.KEY WORDS Biodegradability / Unsaturated Polyester / Geometrical Isomer / Ring-Opening Copolymerization / Cyclic Acid Anhydride / Propylene Oxide / Synthetic polymeric materials have provided many advantages in our daily life for the last century, and become one of the most important materials. When once almost all of synthetic polymers are disposed after use, however, those cause serious environmental problems. Thus, biodegradable polymers have received much attention in recent years as one of the answer to solve the problems. In fact, biodegradable polymers, especially aliphatic polyesters, have been widely investigated by many scientists in the world.In spite of a large number of studies on biodegradability of polyesters, little attention has been given to unsaturated polyesters. 1-6 Tokiwa and Suzuki reported that a few unsaturated polyesters containing 2-butenediol unit could be hydrolyzed by lipase. 1 On the other hand, slightly cross-linked unsaturated polyesters, poly(hexamethylene fumarate) and poly(cis-2-butene fumarate), were hardly hydrolyzed by lipase.A carbon-carbon double bond in unsaturated polyesters has two geometrical isomers (Z-and Econfiguration), and such difference should affect their biodegradability. In controlling the biodegradation rate of polyester, it is very helpful to make geometrical effects clear. In our previous paper, 6 it was shown that in comparison with saturated polyesters, the ef- † To whom correspondence should be addressed. ficient degradation was prevented by introducing Zconfiguration of C=C double bond in the unsaturated polyesters but introducing E-configuration did not affect so remarkably. However, the variety of samples was limited because of the difficulty in preparation of samples having the same molecular weight and the different Z/E ratio. Although polycondensation method of unsaturated acid anhydrides with diol in the presence of acid as a catalyst was employed in prev...

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Reversible Transformation between Amorphous and Crystalline States of Unsaturated Polyesters by Cis–Trans Isomerization

et al. 2019

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An aliphatic polyester has been prepared from ethylene oxide and maleic anhydride that undergoes reversible transformation between amorphous (Tg=18 °C) and crystalline (Tm=124 °C) states through cis–trans isomerization of the C=C bonds in the polymer backbone without any change in either the molecular weight or dispersity of the polymer. A similar transformation was also observed in chiral unsaturated polyesters formed from enantiopure terminal epoxides, such as epichlorohydrin, phenyl glycidyl ether, and (2,3‐epoxypropyl)benzene. These unsaturated polyesters with 100 % E‐configuration in the crystalline state were prepared by quantitative isomerization of their Z‐configuration analogues in the presence of a catalytic amount of diethylamine, while in the presence of benzophenone, irradiation with 365 nm UV light resulted in the transformation of about 30 % trans‐alkene to cis‐maleate form, thereby affording amorphous polyesters.

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Effects of Geometric Structure in Unsaturated Aliphatic Polyesters on Their Biodegradability

Cited by 32 publications

References 18 publications

Going greener: Synthesis of fully biobased unsaturated polyesters for styrene crosslinked resins with enhanced thermomechanical properties

Going greener: Synthesis of fully biobased unsaturated polyesters for styrene crosslinked resins with enhanced thermomechanical properties

Effects of Geometrical Difference of Unsaturated Aliphatic Polyesters on Their Biodegradability II. Isomerization of Poly(maleic anhydride-co-propylene oxide) inthe Presence of Morpholine

Reversible Transformation between Amorphous and Crystalline States of Unsaturated Polyesters by Cis–Trans Isomerization

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