Enzymatic biodegradation of chemosynthetic atactic P(3HB) enhanced by an amorphous non‐biodegradable polymer: blend of atactic P(3HB) with PMMA

Communication: The phase structure and biodegradability were investigated for a blend of chemosynthetic atactic poly((R,S)‐3‐hydroxybutyrate), a‐P(3HB), and poly(methyl methacrylate), PMMA. The thermal analysis indicated that amorphous a‐P(3HB)/PMMA blends with 20 wt.‐% and 40 wt.‐% PMMA shows sophisticated phase behavior and is partially miscible. The depolymerase of natural poly((R)‐3‐hydroxybutyrate) purified from Alcaligenes faecalis T1 did not degrade chemosynthesized a‐P(3HB) at all in the pure state, but it degraded a‐P(3HB) in some a‐P(3HB)/PMMA blends. The results suggested that enzymatic degradation of a‐P(3HB) can be enhanced by an amorphous non‐biodegradable polymer.     

Influence of multiple processing on selected properties of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)

The effect of multiple (up to 10 times) injection molding of processed poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P(3,4HB)) on its phase transition temperatures, degree of crystallinity, degradation temperature, mass flow rate, mechanical properties, dynamic mechanical properties, and Charpy's impact strength is presented. The studies have shown that the multiple injection lowers the degree of crystallinity and the thermal stability of P(3,4HB). The mass flow rate values increased with increasing the injection number. It was found that the multiple injections had no substantial effect on the tensile strength up to 10 injection cycles and the tensile strength at break, tensile strain at tensile strength, and tensile strain at break up to 6 injection cycles. The maximum value of storage modulus at 30 °C and impact strength were recorded for sample after 4 cycles of injection, while the values of storage modulus at 120 °C increased with increase of the injection cycles. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of PCL‐branched P(MMA‐co‐HEMA) to toughen electrospun PLLA fiber membrane

Electrospun biodegradable fiber mesh is a promising alternative scaffold for delivering progenitor cells for repairing damaged or diseased tissue, but its cripple mechanical stability has not met the requirement of tissue engineering yet. In this work, the well‐defined poly(ε‐caprolactone)‐branched poly(methyl methacrylate‐co‐hydroxyethylmethacrylate) (PCL‐PMH) has been successfully synthesized to toughen electrospun poly(l ‐lactide) (PLLA) fiber membrane. Characterization of the obtained nanofibrous meshes indicates that PCL‐PMH and PLLA can be well blended to make smooth fibers, and fibrous diameter vary little with blending PCL‐PMH. The aggregation state of two macromolecules is closely correlated with blend ratio, molecular structure, and molecular weight of PCL‐PMH, and only when PCL‐PMH and PLLA form good interfacial adhesion can PMH give full play to its potential for toughening the fiber membrane. The tensile strength and elongation at break of the blend are 6.20 MPa and 63.40% under the optimal conditions, respectively, and it also exhibits the representative feature of toughness materials. The blending fiber membrane is as no cytotoxic as original PLLA. This work will provide a new way for toughness of electrospun fiber membrane in practice.     

Mechanical properties, structure analysis and enzymatic degradation of uniaxially cold-drawn films of poly[(R)-3-hydroxybutyrate-co-4-hydroxybutyrate]

Poly[(R)-3-hydroxybutyrate-co-4-hydroxybutyrate] (P(3HB-co-4HB)) films were prepared by uniaxial cold-drawing from an amorphous preform at a temperature below, but close to the glass transition temperature. Molecular and highly-ordered structures and physical properties of cold-drawn films were investigated by tensile testing, wide-angle X-ray diffraction and small-angle X-ray scattering. Enzymatic degradation of P(3HB-co-4HB) films was performed using an extracellular polyhydroxybutyrate depolymerase purified from Ralstonia pickettii T1. Tensile strength, elongation to break and Young’s modulus of P(3HB-co-4HB) with cold-drawn ratio 1200% reached 290 MPa, 58% and 2.8 GPa, respectively. X-ray fibre diagrams of cold-drawn P(3HB-co-4HB) films showed a strong reflection on the equatorial line, indicating a planar zigzag conformation (β-form) together with 2₁ helix conformation (α-form). The β-form seems to contribute to the high tensile strength, and a new mechanism of generation of the β-form is proposed. The enzymatic degradation rate increased with increasing draw ratio, and increased greatly with increasing 4HB content.     

Studies on Macromolecular Complexing Agents. II. Effects of Polypropylene Oxide on the Copolymerization Reaction between Butadiene and Styrene

ABSTRACT

Ultra-high-molecular-weight poly[(R)-3-hydroxybutyrate](P(3HB)) was biosynthesized from glucose by a recombinant Escherichia coli XL-1 Blue (pSYL105) harboring Alcaligenes eutrophus PHB biosynthesis phbCAB genes. Six kinds of P(3HB) samples with differ-ent weight-average molecular weight (M_w ) from 1.1 × 10⁶ to 11 × 10⁶ measured by multi-angle laser light scattering were respectively produced at pH values of 7.0 to 6.5 in culture media. Solvent-cast P(3HB) films of high-molecular-weights over M_w of 3.3 × 10⁶ were stretched easily and reproducibly at 160°C to a draw ratio of 400-650%. Mechanical properties of the stretched P(3HB) films were markedly improved relative to those of solvent-cast film. The elongation to break, Young's modulus, and tensile- strength of stretched film (M_w = 11 × 10⁶) were 58%, 1.1 GPa, and 62 MPa, respectively. X-ray diffraction patterns indicated that the stretched film was highly oriented and had a high crystallinity over 80%. When the stretched film was annealed at 160°C for 2 hours, the mechanical properties were further improved (elongation to break = 67%, Young's modulus = 1.8 GPa and tensile strength = 77 MPa). The mechanical properties of the stretched-annealed film remained almost unchanged for 6 months at room temperature, suggesting that a high crystallinity of the stretched-annealed film avoids a progress of secondary crystallization.

     

Dual Recycling of Depolymerization Catalyst and Biodegradable Polyester that Markedly Outperforms Polyolefins

Chemically recyclable, circular polymers continue to attract increasing attention, but rendering both catalysts for depolymerization and high-performance polymers recyclable is a more sustainable yet challenging goal. Here we introduce a dual catalyst/polymer recycling system in that recyclable inorganic phosphomolybdic acid catalyzes selective depolymerization of high-ceiling-temperature biodegradable poly(δ-valerolactone) in bulk phase, which, upon reaching suitable molecular weight, exhibits outstanding mechanical performance with a high tensile strength of ≈66.6 MPa, fracture strain of ≈904 %, and toughness of ≈308 MJ m⁻³, and thus markedly outperforms commodity polyolefins, recovering its monomer in pure state and quantitative yield at only 100 °C. In sharp contrast, the uncatalyzed depolymerization not only requires a high temperature of >310 °C but is also low yielding and non-selective. Importantly, the recovered monomer can be repolymerized as is to reproduce the same polymer, thereby closing the circular loop, and the recycled catalyst can be reused repeatedly for depolymerization runs without loss of its catalytic activity and efficiency.     

Assessing the mechanical,phase inversion,and rheological properties of poly-[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyvalerate] (PHBV) blended with poly-(l-lactic acid) (PLA)

Poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly-(l-lactic acid) (PLA) have attracted much interest in recent years since they are biodegradable, thus can replace synthetic non-degradable materials. In this study, improvements of PHBV, mechanical, phase inversions, and rheological properties were investigated after blending with PLA in varying ratio’s. Three different blends of commercially available PLAs with 92–98% l-lactide units and one grade of PHB with 5% valerate content were blended using a micro-compounder at 175 °C. The composition of PHBV in blends ranged from 50% to 80%. With the addition of PLA, increases in the flexural strength and elastic modulus were observed for several blends, while minor to no changes were detected in the elongation at break and tensile strength as compared to pure PHBV material. Like many conventional plastics, the complex viscosity decreased with increasing rotational frequency due to decreasing entanglements and molecular weight. The complex viscosity with respect to time was very stable for the blends, but no improvements in the PHBV viscosity were observed with the addition of PLA at 170 °C. Three phase inversion models were used to predict the continuity of the blends, and the results showed both dual- and PLA-continuity phase for the blends. In summary, the mechanical results showed improvements in the tensile and flexural properties, while the rheological observation showed minor improvements in the complex viscosity for numerous concentrations.     

A preliminary study on the development and characterisation of enzymatically grafted P(3HB)-ethyl cellulose based novel composites

In the present study, a novel enzyme-based grafting of poly(3-hydroxybutyrate) [P(3HB)] onto the ethyl cellulose (EC) as a backbone polymer was developed under a mild and ecofriendly environment and laccase was used as a grafting tool. The resulting composites were characterised using various instrumental and imaging techniques. The high intensity of the 3,358 cm^?1 band in the FTIR spectra showed an increase of hydrogen–bonding interactions between P(3HB) and EC at that distinct wavelength region. The morphology was examined by scanning electron microscopy, which showed the well dispersed P(3HB) in the backbone polymer of EC. X-ray diffraction pattern for P(3HB) showed distinct peaks at 2-theta values of 28°, 32°, 34°, 39°, 46°, 57°, 64°, 78° and 84°. In comparison with those of neat P(3HB), the degree of crystallinity for P(3HB)-g-EC decreased. The tensile strength, elongations at break and Young’s modulus of P(3HB)-g-EC reached the highest levels in comparison to the film prepared with pure P(3HB) only, which was too brittle to measure any of the above said characteristics. Results obtained in the present study suggest P(3HB)-g-EC as a potential candidate for various biotechnological applications, such as tissue engineering and packaging.     

Blends of poly(3‐hydroxybutyrate)/4,4′‐thiodiphenol and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/ 4,4′‐thiodiphenol: Specific interaction and properties

The specific interaction between poly(3‐hydroxybutyrate) [P(3HB)] and 4,4′‐thiodiphenol (TDP) and between poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) and TDP was investigated by Fourier transform infrared (FTIR) spectroscopy. Interassociated hydrogen bonds were found between the polyester chains and the TDP molecules in the binary blends. The fractions of associated carbonyl groups, F_b 's, in the blends first increased and then decreased as the TDP content increased. The thermal and dynamic mechanical properties of P(3HB)–TDP and PHBV–TDP blends were investigated by differential scanning calorimetry and dynamic mechanical thermal analysis, respectively. Thermal analysis revealed that the P(3HB)–TDP blends possessed eutectic phase behavior. Furthermore, it was found that the thermal and dynamic mechanical properties of P(3HB) and PHBV were greatly modified through blending with TDP. Environmental degradability in river water was evaluated by a biochemical oxygen demand tester, and it was clarified that TDP lowered the degradation rate of P(3HB). The results suggest that TDP is effective in modifying the physical properties as well as the biodegradability of polyesters. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2891–2900, 2000     

Mechanical properties and enzymatic degradation of poly[(R)-3-hydroxybutyrate] fibers stretched after isothermal crystallization near Tg

Poly[(R)-3-hydroxybutyrate] (P(3HB)) fibers with high tensile strength were prepared by stretching the fibers after isothermal crystallization near the glass transition temperature. Two samples with different molecular weights (M_w = 0.7 × 10⁶ and 4.3 × 10⁶) were used to investigate the effect on tensile strength. Increasing the time for isothermal crystallization of P(3HB) fibers resulted in a decrease in the maximum draw ratio. But, the tensile strength of P(3HB) fibers increased remarkably when the isothermal crystallization time was prolonged to more than 24 h. The tensile strength of low-molecular-weight drawn fibers was higher than that of high-molecular-weight fibers. Therefore, it can be concluded that this procedure does not increase the tensile strength of the high-molecular-weight drawn fibers. This is because, in this drawing method, small crystal nuclei grow initially during the isothermal crystallization process. Then, the molecular chains between the small crystal nuclei that acted as the entanglement points are oriented by stretching. In the case of the high-molecular-weight fibers, because the molecular length between the entanglement points of the small crystal nuclei is too long, the molecular chains are not sufficiently oriented by the stretching process. However, in the case of the low-molecular-weight fibers, the molecular length is suitable for generating the extended chains. Based on the result of X-ray analysis of P(3HB) fibers stretched after isothermal crystallization, fibers have the oriented α-form crystal with 2₁ helix conformation and β-form with planar zigzag conformation. The enzymatic degradation of the stretched P(3HB) fibers was performed by using an extracellular PHB depolymerase purified from Ralstonia pickettii T1. The enzymatic erosion rate of β-form was faster than that of α-form in the P(3HB) fibers stretched after isothermal crystallization.     

Toughening of polylactide by melt blending with a biodegradable poly(ether)urethane elastomer

Melt blending of polylactide (PLA) and a biodegradable poly(ether)urethane (PU) elastomer has been performed in an effort to toughen the polylactide without compromising its biodegradability and biocompatibility. The miscibility, phase morphology, mechanical properties, and toughening mechanism of the blend were investigated. The blend was found by dynamic mechanical analysis to be a partially miscible system with shifted glass transition temperatures. The PU elastomer was dispersed in the PLA matrix with a domain size of sub-micrometer scale. The addition of PU elastomer not only accelerated the crystallization speed, but also decreased the crystallinity of the PLA. With an increase in PU content, the blend shows decreased tensile strength and modulus; however, the elongation at break and the impact strength were significantly increased, indicating the toughening effects of the PU elastomer on the PLA. The brittle fracture of neat PLA was gradually transformed into ductile fracture by the addition of PU elastomer. It was found that the PLA matrix demonstrates large area, plastic deformation (shear yielding) in the blend upon being subjected the tensile and impact tests, which is an important energy-dissipation process and leads to a toughened, biodegradable polymer blend.     

Mechanical Properties of Uniaxially Cold-Drawn Films of Poly[(R)-3-hydroxybutyrate] and Its Copolymers

Uniaxially oriented films of poly[(R)-3-hydroxybutyrate] (P(3HB)) and two kind of copolymers, poly[(R)-3-hydroxybutyrate-co-8%-[R]-3-hydroxyvalerate] (P(3HB-co-8%-3HV)), and poly[(R)-3-hydroxybutyrate-co-[R]-5%-3-hydroxyhexanoate] (P(3HB-co-5%-3HH)), were prepared by cold-drawing from amorphous preforms at temperatures near to the respective glass transition temperatures. Melt-quenched films in a rubber state could be stretched reproducibly to a draw ratio of 500%∼1800%, and subsequent annealing under tension led to improvement of the tensile strength and Young's modulus. Two-step drawing resulted in further improvement of the mechanical properties. The mechanical properties remained unchanged after storing for 6 months at room temperature, suggesting that high orientation and crystallinity suppress the secondary crystallization.     

Low cost bifunctional initiators for bidirectional living cationic polymerization of olefins. II. hyperbranched styrene–isobutylene–styrene triblocks with superior combination of properties

Both bifunctional initiators, the new low cost bBCB‐diCl [4,9‐dichloro,2,4,7,9‐tetramethyl‐tricyclo[6.2.0.0³⁶]deca‐1(8),2,6‐triene] and the universally used “hindered” HDCCl [1‐(tert‐butyl)‐3,5‐bis(2‐chloropropan‐2‐yl)benzene] induce the living bidirectional block copolymerization of isobutylene (IB) followed by styrene (St), and produce PSt‐b‐PIB‐b‐PSt (SIBS) triblocks. We discovered that the molecular weights of triblocks kept significantly increasing long after St conversion reached completion during syntheses. Results were explained by the formation of blends consisting of the expected linear SIBS plus hyperbranched SIBS, HB(SIBS)_n. The structure of high molecular weight (>10⁶ g/mol) HB(SIBS)_n was characterized by various techniques, and key properties of SIBS/HB(SIBS)_n blends were investigated. The mechanism of HB(SIBS)_n formation and the synthesis of SIBS/HB(SIBS)_n blends was elucidated. The properties of SIBS/HB(SIBS)_n blends are superior to those of SIBS. Thus, whereas SIBS exhibits ∼25 MPa tensile strength and ∼450% elongation, SIBS/HB(SIBS)_n blends exhibit 25–27 MPa tensile strength and >400% elongation; deformation under constant load of SIBS is ∼12%, whereas that of SIBS/HB(SIBS)_n is <1%; permanent set of SIBS is 1.3% whereas that of SIBS/HB(SIBS)_n is <0.5%. SIBS/HB(SIBS)_n blends also exhibit higher yield, yield strength, and toughness than SIBS. The microstructure/property relationship of HB(SIBS)_n is discussed and the reasons for enhanced properties of SIBS/HB(SIBS)_n blends are analyzed. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 705–713     

Biosynthesis and Characterization of Poly (3-hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-3-hydroxyvalerate-<Emphasis Type="Italic">co</Emphasis>-4-hydroxybutyrate) Terpolymer with Various Monomer Compositions by <Emphasis Type="Italic">Cupriavidus</Emphasis> sp. USMAA2-4

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-4-hydroxybutyrate) [P(3HB-co-3HV-co-4HB)] terpolymer was produced using Cupriavidus sp. USMAA2-4 via one-step cultivation process through combination of various carbon sources such as 1,4-butanediol or γ-butyrolactone with either 1-pentanol, valeric acid, or 1-propanol. Oleic acid was added to increase the biomass production. The composition of 3HV and 4HB monomers were greatly affected by the concentration of 1,4-butanediol and 1-pentanol. Terpolymers with 3HV and 4HB molar fractions ranging from 2 to 41 mol.% and 5 to 31 mol.%, respectively, were produced by varying the concentration of carbon precursors. The thermal and mechanical properties of the terpolymers containing different proportions of the constituent monomers were characterized using gel permeation chromatography (GPC), DSC, and tensile machine. GPC analysis showed that the molecular weights (M _w) of the terpolymer produced were within the range of 346 to 1,710 kDa. The monomer compositions of 3HV and 4HB were also found to have great influences on the thermal and mechanical properties of the terpolymer P(3HB-co-3HV-co-4HB) produced.     

Graphene oxide/epoxy composites with enhanced fracture toughness for liquid hydrogen storage

Graphene oxide (GO)/epoxy composites cured by aliphatic dibasic acids have been prepared. The influences of structure of aliphatic dibasic acid and loading of GO on curing process and mechanical properties of epoxy composites were studied. The results show that the reaction activities, gel time of corresponding epoxy-acid system and tensile strength of the formed epoxy resins decrease with the increase of the chain length of aliphatic dibasic acids. Both fracture toughness (>1.96 MPa⋅m^1/2) and elongations at break (>6%) increase with the increase of the chain length of aliphatic dibasic acids. The introduction of GO is helpful to increase the mechanical properties and the gas transmission coefficient of GO/epoxy composites. A maximum of tensile strength and elongations at break were obtained when the loading of GO is 0.6 wt%. The gas transmission coefficient of GO/epoxy composite increases with the increase of GO loading. The excellent mechanical properties and gas leakage resistance coefficient of the formed epoxy composites provides potential application in many fields where conventional brittle epoxy resins are inapplicable.     

Controlled drug release behavior of metformin hydrogen chloride from biodegradable films based on chitosan/poly(ethylene glycol) methyl ether blend

In this study, novel smart drug release films were prepared by blending chitosan with polyethylene glycol methyl ether (PEGME), also named as methoxy polyethylene glycol (mPEG), for controlled drug release applications. The polymeric films were characterized by Fourier transform infra-red for functional groups analysis, scanning electron microscopy for morphology and X-ray photoelectron spectroscopy for chemical and surface analysis followed by mechanical and thermal analysis. The mechanical properties showed that with the addition of PEGME (40%), the tensile strength and elongation break were increased up to 34.14 MPa and 26.40%, respectively as compared to the controlled sample (without PEGME). The developed biodegradable films were tested for Metformin hydrogen chloride release ability at a particular rate in phosphate buffer saline solution at pH 7.4. The results showed that chitosan/PEGME blends could be employed for controlled drug release and other biomedical applications.     

Processing of a Strong Biodegradable Poly[(R)‐3‐hydroxybutyrate] Fiber and a New Fiber Structure Revealed by Micro‐Beam X‐Ray Diffraction with Synchrotron Radiation

Summary: Biodegradable poly[(R)‐3‐hydroxybutyrate] (P(3HB)) fibers with high tensile strength of 1.32 GPa were processed from ultra‐high‐molecular‐weight P(3HB) by a method combining cold‐drawing and two‐step‐drawing procedures at room temperature. The distribution of molecular structures in a mono‐filament was analyzed by micro‐beam X‐ray diffraction with synchrotron radiation. It was revealed that the P(3HB) fiber has a new core‐sheath structure consistent with two types of molecular conformations: a 2₁ helix conformation in the sheath region and a planar zigzag conformation in the core region.

P(3HB) fiber processed by cold‐drawing in ice water and two‐step drawing at room temperature, and subsequently annealing at 50 °C.     

Antibacterial poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) fibrous membranes containing quaternary ammonium salts

In this study, antimicrobial membranes based on biodegradable material poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) [P(3HB‐4HB)] and quaternary ammonium salts (QASs) by two methods have been performed. Three QASs with varied alkyl chain lengths have been synthesized successfully and characterized by ¹H nuclear magnetic resonance and Fourier transform infrared. The synthesized QASs were blended with P(3HB‐4HB) and electrospun into composite fibrous membranes or casted into conventional membranes. Electrospun fibrous membranes with large surface areas are a superior type of antimicrobial biomaterials, and they exhibit preferable properties than solution casting membranes. Specifically, electrospun fibrous membranes are tougher and can inactivate both Gram‐positive Staphylococcus aureus and Gram‐negative Escherichia coli O157:H7 in a contact time of 30 min, whereas the solution casting membranes cannot. The length of alkyl chain in the quaternary ammonium groups on the modified P(3HB‐4HB) membranes is able to influence the antimicrobial activity. This type of antimicrobial material may have potential applications in biomaterial field. Copyright © 2016 John Wiley & Sons, Ltd.     

Compatibilizing effect of a graft copolymer on bacterial poly(3‐hydroxybutyrate)/poly(methyl methacrylate) blends

Blends of isotactic (natural) poly(3‐hydroxybutyrate) (PHB) and poly(methyl methacrylate) (PMMA) are partially miscible, and PHB in excess of 20 wt % segregates as a partially crystalline pure phase. Copolymers containing atactic PHB chains grafted onto a PMMA backbone are used to compatibilize phase‐separated PHB/PMMA blends. Two poly(methyl methacrylate‐g‐hydroxybutyrate) [P(MMA‐g‐HB)] copolymers with different grafting densities and the same length of the grafted chain have been investigated. The copolymer with higher grafting density, containing 67 mol % hydroxybutyrate units, has a beneficial effect on the mechanical properties of PHB/PMMA blends with 30–50% PHB content, which show a remarkable increase in ductility. The main effect of copolymer addition is the inhibition of PHB crystallization. No compatibilizing effect on PHB/PMMA blends with PHB contents higher than 50% is observed with various amounts of P(MMA‐g‐HB) copolymer. In these blends, the graft copolymer is not able to prevent PHB crystallization, and the ternary PHB/PMMA/P(MMA‐g‐HB) blends remain crystalline and brittle. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1390–1399, 2002     

Tribological and Mechanical Properties of Poly[(R)-3-hydroxybutyric acid] Grafted with Vinyl Compounds: Insight into Possible Application

Biodegradable graft copolymers were prepared by gamma radiation-induced graft polymerization of two vinyl monomers, vinyl acetate and vinyl alcohol, onto poly[(R)-3-hydroxybutyric acid]. Success of the grafting reaction was verified by Fourier-transform infrared and nuclear magnetic resonance spectroscopy. Thermal remolding was used to create membranes from the copolymers. We determined tribological and mechanical properties of the membranes obtained. The lowest elongation at break in tensile testing is seen for P(3HB) and the highest for P(3HB-g-VA). Up to 5 N or so, the highest scratch resistance is exhibited by P(3HB-g-VA). Piezoelectric behavior is seen for P(3HB-g-VA) while P(3HB-g-VAc) and plain P(3HB) showed no electric response. Explanation of the piezoelectric behavior in terms of molecular structures is provided.