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Published on: February 7, 2017
Uracil as nucleating agent for bacterial poly[(3-hydroxybutyrate)-co-(3-hydroxyhexanoate)] copolymers
Pengju Pan1, Zhichao Liang, Nobuo Nakamura
1Department of Biomolecular Engineering, Tokyo Institute of Technology, 4259-B-55 Nagatsuta, Midori-ku, Yokohama 226-8501, Japan.
Uracil significantly enhances the crystallization rate and nucleation density of polyhydroxyalkanoates (PHAs) like poly(3-hydroxybutyrate) (PHB) and its copolymers. This pyrimidine derivative shows superior nucleation efficiency for PHBHHx compared to boron nitride.
Area of Science:
- Polymer Science and Engineering
- Materials Science
- Biomaterials
Background:
- Poly[(3-hydroxybutyrate)-co-(3-hydroxyhexanoate)] (PHBHHx) and poly(3-hydroxybutyrate) (PHB) are biodegradable polymers with potential applications in various fields.
- Efficient crystallization is crucial for tailoring the properties and processability of these polymers.
- Nucleating agents (NAs) are commonly used to accelerate crystallization and modify polymer morphology.
Purpose of the Study:
- To investigate the efficacy of uracil as a novel nucleating agent for PHBHHx copolymers and PHB homopolymer.
- To compare the nucleation performance of uracil with conventional nucleating agents like boron nitride (BN) and other pyrimidine derivatives (thymine, cytosine).
- To elucidate the effects of uracil on the crystallization kinetics, melting behavior, morphology, and crystalline structure of PHBHHx and PHB.
Main Methods:
- Differential Scanning Calorimetry (DSC) to analyze thermal properties and crystallization kinetics.
- Polarized Optical Microscopy (POM) for observing spherulite morphology.
- Wide-Angle X-ray Diffraction (WAXD) to determine crystalline structure.
- Synthesis of PHBHHx copolymers with varying 3-hydroxyhexanoate (HHx) content (5, 10, 18 mol-%) and PHB homopolymer.
Main Results:
- Uracil demonstrated comparable nucleation efficiency to BN for PHB, but significantly outperformed BN for PHBHHx copolymers.
- Incorporation of 1 wt.-% uracil enabled PHBHHx (0-10 mol-% HHx) to complete crystallization upon cooling at 10°C/min.
- Uracil significantly reduced crystallization half-times (t(1/2)) and increased nucleation density by 3-4 orders of magnitude, with enhanced rates at higher uracil concentrations.
- WAXD results indicated no discernible effect of uracil on the crystalline structure of PHBHHx.
Conclusions:
- Uracil is a highly effective nucleating agent for PHBHHx copolymers, offering superior performance compared to BN.
- The study proposes epitaxial nucleation as the likely mechanism for uracil-mediated nucleation in PHBHHx and PHB systems.
- Uracil holds promise for improving the processing and properties of biodegradable polyhydroxyalkanoates.
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