生物可降解聚（3-羟基丁酸酯-co-4-羟基丁酸酯）的基本性质及其改性的研究
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摘要
聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[P(3HB-co-4HB)]是一种在微生物体内合成的热塑性材料,具有良好的生物降解性和生物相容性,可应用于器官移植、药物释放、食品包装和农用薄膜等领域,但P(3HB-co-4HB)的热稳定性差和结晶速度慢等方面的不足在一定程度上限制了其应用。本论文首次系统地研究了P(3HB-co-4HB)中4HB含量对共聚酯各种基本性质影响,在此基础上,首次以笼型多聚倍半硅氧烷(POSS)为成核剂、与聚乳酸共混及加入生物可降解的增塑剂等方法改性,研究了改性物的热性能,结晶性能及力学性能。同时,本文还探讨了热处理过程中共聚物的分子量的变化,首次考察了热处理后分子量对P(3HB-co-4HB)共聚酯各项性能的影响。
研究表明,P(3HB-co-4HB)中4HB的含量对其基本性能有重要的影响。随着4HB含量的增加,共聚酯的熔融温度,玻璃化温度,储能模量均降低;屈服强度,断裂强度也降低,而屈服应变和断裂伸长率增加;其热稳定性和流动性得到改善。
研究表明,加入增塑剂可有效的改善P(3HB-co-4HB)的加工性能。增塑剂的加入能降低共聚酯的熔点、结晶温度和结晶焓下降。相同含量增塑剂对4HB含量较低的共混体系结晶性能影响较大,而对4HB含量较高的共混体的结晶性能影响较小。
研究表明,笼型倍半硅氧烷(POSS)作为成核剂可有效改善P(3HB-co-4HB)的结晶性能。对苯胺基POSS(OAPS)和异丁基POSS(OIBS)的进一步研究表明,由于与基体的作用不同,OAPS可使结晶峰变尖,球晶细化,在一定程度上提高聚合物的力学性能和热稳定性,改性效果优于OIBS。
研究表明,共聚酯与聚乳酸共混可以提高共聚酯的热稳定性。虽然聚乳酸与P(3HB-co-4HB)的相容性差,导致共混物的机械性能下降,但聚乳酸的加入可以提高共混物的结晶度和共混物的热稳定性。
研究表明,共聚酯的热处理解过程中的分子量的变化符合酯基的自由断裂模型,在适当的热处理时间内,共聚酯分子量的降低,共聚酯具有较好的加工性能,并保持较好的力学性能。
Poly(3-hydroxylbutyrate-co-4-hydroxylbutyrate)[P(3HB-co-4HB)] is a kind of thermoplastic copolymer, possessing the biodegradability and biocompatibility ,which can be used in a lots fields such as implant applications, controlled drug release, food package, agriculture films and so on. However, its application is limited to a certain extent for brittleness, thermal stability and slow crystalline rate. In this paper, the effect of 4HB content on the properties of P(3HB-co-4HB) is discussed for the first time in detail, and some plasticizer, nucleation agent and PLA are added or blended in order to improve the property of P(3HB-co-4HB). At the same time, the thermal, crystalline and mechanical properties of the modified production are investigated. At last, the time-dependent changes in molecular weights of melt samples are monitored and the effect of molecular weight on the properties of copolyester is first discussed. The results show as follow.
With the increase of 4HB unit content, the melting temperature, glass transit temperature, storage mould, yield strength and strength at break decrease. At the same time, elongation at yield and break increase. The thermal stability and liquidity can be improved with the increase of 4HB content.
The incorporation of plasticizer can reduce melting temperature, crystalline temperature and crystalline enthalpy of blends. At the same time, the effect of 20wt% TEC on crystalline property of copolymer with low 4HB content is bigger than that with high 4HB content.
POSS can improve the crystalline property of P(3HB-co-4HB) as a nucleation agent. Moreover, OAPS and OIBS were further investigated. The addition of AOPS can make the crystalline peak sharper, and increase the number of spherulite. ft can promote the mechanical property and thermal stability of blends. The effect of OAPS is better than that of OIBS.
It is revealed that the compatibility of P(3HB-co-4HB) with poly(lactic acid) (PLA) is poor. There are seriously phases separate on cross-section. And, incorporation of PLA can decrease the mechanical property and increase the thermal stability and.crystallinity of blends.
And the time-dependent changes in molecular weights during the thermal degradation followed the kinetic model of random chain scission at ester groups. According to the decrease of molecular weight, the melting temperature increase, and glass transit temperature decrease. At the same time, both tensile strength and elongation at break decrease together. The melting index of copolymer increase and extruded product become smooth, so the processing property is improved with the decrease of molecular weight.
研究表明,P(3HB-co-4HB)中4HB的含量对其基本性能有重要的影响。随着4HB含量的增加,共聚酯的熔融温度,玻璃化温度,储能模量均降低;屈服强度,断裂强度也降低,而屈服应变和断裂伸长率增加;其热稳定性和流动性得到改善。
研究表明,加入增塑剂可有效的改善P(3HB-co-4HB)的加工性能。增塑剂的加入能降低共聚酯的熔点、结晶温度和结晶焓下降。相同含量增塑剂对4HB含量较低的共混体系结晶性能影响较大,而对4HB含量较高的共混体的结晶性能影响较小。
研究表明,笼型倍半硅氧烷(POSS)作为成核剂可有效改善P(3HB-co-4HB)的结晶性能。对苯胺基POSS(OAPS)和异丁基POSS(OIBS)的进一步研究表明,由于与基体的作用不同,OAPS可使结晶峰变尖,球晶细化,在一定程度上提高聚合物的力学性能和热稳定性,改性效果优于OIBS。
研究表明,共聚酯与聚乳酸共混可以提高共聚酯的热稳定性。虽然聚乳酸与P(3HB-co-4HB)的相容性差,导致共混物的机械性能下降,但聚乳酸的加入可以提高共混物的结晶度和共混物的热稳定性。
研究表明,共聚酯的热处理解过程中的分子量的变化符合酯基的自由断裂模型,在适当的热处理时间内,共聚酯分子量的降低,共聚酯具有较好的加工性能,并保持较好的力学性能。
Poly(3-hydroxylbutyrate-co-4-hydroxylbutyrate)[P(3HB-co-4HB)] is a kind of thermoplastic copolymer, possessing the biodegradability and biocompatibility ,which can be used in a lots fields such as implant applications, controlled drug release, food package, agriculture films and so on. However, its application is limited to a certain extent for brittleness, thermal stability and slow crystalline rate. In this paper, the effect of 4HB content on the properties of P(3HB-co-4HB) is discussed for the first time in detail, and some plasticizer, nucleation agent and PLA are added or blended in order to improve the property of P(3HB-co-4HB). At the same time, the thermal, crystalline and mechanical properties of the modified production are investigated. At last, the time-dependent changes in molecular weights of melt samples are monitored and the effect of molecular weight on the properties of copolyester is first discussed. The results show as follow.
With the increase of 4HB unit content, the melting temperature, glass transit temperature, storage mould, yield strength and strength at break decrease. At the same time, elongation at yield and break increase. The thermal stability and liquidity can be improved with the increase of 4HB content.
The incorporation of plasticizer can reduce melting temperature, crystalline temperature and crystalline enthalpy of blends. At the same time, the effect of 20wt% TEC on crystalline property of copolymer with low 4HB content is bigger than that with high 4HB content.
POSS can improve the crystalline property of P(3HB-co-4HB) as a nucleation agent. Moreover, OAPS and OIBS were further investigated. The addition of AOPS can make the crystalline peak sharper, and increase the number of spherulite. ft can promote the mechanical property and thermal stability of blends. The effect of OAPS is better than that of OIBS.
It is revealed that the compatibility of P(3HB-co-4HB) with poly(lactic acid) (PLA) is poor. There are seriously phases separate on cross-section. And, incorporation of PLA can decrease the mechanical property and increase the thermal stability and.crystallinity of blends.
And the time-dependent changes in molecular weights during the thermal degradation followed the kinetic model of random chain scission at ester groups. According to the decrease of molecular weight, the melting temperature increase, and glass transit temperature decrease. At the same time, both tensile strength and elongation at break decrease together. The melting index of copolymer increase and extruded product become smooth, so the processing property is improved with the decrease of molecular weight.
引文
[1] Lemoigne M. Produit de deAshydratation et de polymeArisation de l'acide b-oxybutyrique[J]. Bull. Soc. Chim. Biol., 1926, 8: 770-82
[2] Williamson D H, Wilkinson J F. The isolation and estimation of the poly-b-hydroxybutyrate inclusions of Bacillus species[J]. J. Gen. Microbiol., 1958, 19: 198-209
[3] Macrae R M, Wilkinson J R. Poly-b-hydroxybutyrate metabolism in washed suspensions of Bacillus cereus and Bacillus megaterium[J]. J. Gen. Microbiol., 1958, 19: 210-22
[4] Doudoroff M, Stanier R Y. Role of poly-b-hydroxybutyric acid in the assimilation of organic carbon by bacteria[J]. Nature Biotechnology, 1959, 183: 1440-1442
[5] Wallen L L, Rohwedder W K. Poly-b-hydroxyalkanoate from activated sludge[J]. Environ. Sci. Technol., 1974, 8:576-9
[6] Lageveen R G, Huisman G W, Preusting H, et al. Formation of Polyesters by Pseudomonas-Oleovorans - Effect of Substrates on Formation and Composition of Poly-(R)-3-Hydroxyalkanoates and Poly-(R)-3-Hydroxyalkenoates[J]. Applied and Environmental Microbiology, 1988, 54(12): 2924-2932
[7] Anderson A J, Dawes E A. Occurrence, Metabolism, Metabolic Role, and Industrial Uses of Bacterial Polyhydroxyalkanoates[J]. Microbiol. Rev., 1990, 54(4): 450-472
[8] Rehm B H A, Sieinbuchel A. Biochemical and genetic analysis of PHA synthases and other proteins required for PHA synthesis[J]. Int. J. Biol. Macromol., 1999, 25(1-3): 3-19
[9] Slater S C, Voige W H, Dennis D E. Cloning and Expression in Escherichia-Coli of the Alcaligenes-Eutrophus H16 Poly-Beta-Hydroxybutyrate Biosynthetic-Pathway[J]. J. Bacteriol., 1988, 170(10): 4431-4436
[10] Peoples O P, Sinskey A J. Poly-Beta-Hydroxybutyrate (Phb) Biosynthesis in Alcaligenes-Eutrophus H16 - Identification and Characterization of the Phb Polymerase Gene (Phbc)[J]. J. Biol. Chem., 1989, 264(26): 15298-15303
[11] Peoples O P, Sinskey A J. Poly-Beta-Hydroxybutyrate Biosynthesis in Alcaligenes-Eutrophus H16 - Characterization of the Genes Encoding Beta-Ketothiolase and Acetoacetyl-Coa Reductase[J]. J. Biol. Chem., 1989, 264(26): 15293-15297
[12] Gerngross T U, Martin D P. Enzyme-Catalyzed Synthesis of Poly[(R)-(-)-3-Hydroxyburyrate] - Formation of Macroscopic Granules in-Vitro[J]. Proc. Natl. Acad. Sci. U. S. A., 1995, 92(14): 6279-6283
[13] Kunioka M, Kawaguchi Y, Doi Y. Production of Biodegradable Copolyesters of 3-Hydroxybutyrate and 4-Hydroxybutyrate by Alcaligenes-Eutrophus[J]. Appl. Microbiol. Biotechnol., 1989,30(6): 569-573
[14] Shah N N, Hanna M L, Taylor R T. Batch cultivation of Methylosinus trichosporium OB3b .5. Characterization of poly-beta-hydroxybutyrate production under methane-dependent growthconditions[J]. Biotechnology and Bioengineering, 1996,49(2): 161-171
[15] Nakayama K, Saito T, Fukui T, et al. Purification and Properties of Extracellular Poly(3-Hydroxybutyrate) Depolymerases from Pseudomonas-Lemoignei[J]. Biochimica Et Biophysica Acta, 1985, 827(1): 63-72
[16] Choi J I, Lee S Y. Efficient and economical recovery of poly(3-hydroxybutyrate) from recombinant Escherichia coli by simple digestion with chemicals[J]. Biotechnology and Bioengineering, 1999,62(5): 546-553
[17] Mittendorf V, Robertson E J, Leech R M, et al. Synthesis of medium-chain-length polyhydroxyalkanoates in Arabidopsis thaliana using intermediates of peroxisomal fatty acid beta-oxidation[J]. Proc. Natl. Acad. Sci. U. S. A., 1998, 95(23): 13397-13402
[18] Poirier Y, Somerville C, Schechtman L A, et al. Synthesis of High-Molecular-Weight Poly([R]-(-)-3-Hydroxybutyrate) in Transgenic Arabidopsis-Thaliana Plant-Cells[J]. Int. J. Biol. Macromol., 1995, 17(1): 7-12
[19] Matsumoto K, Nagao R, Murata T, et al. Enhancement of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) production in the transgenic Arabidopsis thaliana by the in vitro evolved highly active mutants of polyhydroxyalkanoate (PHA) synthase from Aeromonas caviae[J]. Biomacromolecules, 2005,6(4): 2126-2130
[20] Song C J, Zhao L X, Ono S, et al. Production of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) from cottonseed oil and valeric acid in batch culture of Ralstonia sp strain JC-64[J]. Appl. Biochem. Biotechnol., 2001, 94(2): 169-178
[21] Moore T, Adhikari R, Gunatillake P. Chemosynthesis of bioresorbable poly(γ-butyrolactone) by ring-opening polymerisation: A review[J]. Biomaterials, 2005, 26(18): 3771-3782
[22] Noda I, Green P R, Satkowski M M, et al. Preparation and properties of a novel class of polyhydroxyalkanoate copolymers[J]. Biomacromolecules, 2005, 6(2): 580-586
[23] Dekoning G J M, Scheeren A H C, Lemstra P J, et al. Crystallization Phenomena in Bacterial Poly[(R)-3-Hydroxybutyrate] .3. Toughening Via Texture Changes[J]. Polymer, 1994, 35(21): 4598-4605
[24] Mitomo H, Barham P J, Keller A. Temperature-Dependence of Mechanical-Properties of Poly(Beta-Hydroxybutyrate-Beta-Hydroxyvalerate)[J]. Polymer Communications, 1988, 29(4): 112-115
[25] Mitomo H, Doi Y. Lamellar thickening and cocrystallization of polyhydroxyalkanoates on annealing[J]. Int. J. Biol. Macromol., 1999, 25(1-3): 201-205
[26] Shimamura E, Kasuya K, Kobayashi G, et al. Physical-Properties and Biodegradability of Microbial Poly(3-Hydroxybutyrate-Co-3-Hydroxyhexanoate)[J]. Macromolecules, 1994, 27(3): 878-880
[27] Hassan M K, Abdel-Latif S A, El-Roudi O M, et al. Improvement in the mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) by preorientationfJ]. Journal of Applied Polymer Science, 2004, 94(6): 2257-2262
[28] Shimamura E, Scandola M, Doi Y. Microbial Synthesis and Characterization of Poly(3-Hydroxybutyrate-Co-3-Hydroxypropionate)[J]. Macromolecules, 1994, 27(16): 4429-4435
[29] Saito Y, Nakamura S, Hiramitsu M, et al. Microbial synthesis and properties of poly(3-hydroxybutyrate-co-4-hydroxybutyrate)[J]. Polymer International, 1996, 39(3): 169-174
[30] Barham P J, Keller A, Otun E L, et al. Crystallization and Morphology of a Bacterial Thermoplastic - Poly-3-Hydroxybutyrate[J]. Journal of Materials Science, 1984, 19(9): 2781-2794
[31] Bluhm T L, Hamer G K, Marchessault R H, et al. Isodimorphism in Bacterial Poly(Beta-Hydroxybutyrate-Co-Beta-Hydroxyvalerate)[J]. Macromolecules, 1986, 19(11): 2871-2876
[32] Bluhm T L, Hamer G K, Marchessault R H, et al. Morphology of a Novel Copolyester - Bacterial Poly(Beta-Hydroxybutyrate-Co-Beta-Hydroxyvalerate)[J]. Abstr. Pap. Am. Chem. Soc, 1986, 192:221-POLY
[33] Bluhm T L, Hamer G K, Marchessault R H. Analysis of Poly(Beta-Hydroxybutyrate-Co-Beta-Hydroxyvalerate) Using X-Ray-Diffraction, Nmr-Spectroscopy and Differential Scanning Calorimetry[J]. Acta Crystallogr. Sect. A, 1984, 40: C467-C467
[34] Man Ken C, Peter H F Y, Cheng C. Crystallization kinetics and melting behaviour of microbial poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)[J]. Polymer International, 2005, 54(7): 1055-1064
[35] [35] Chen C, Cheung M K, Yu P H F. Crystallization kinetics and melting behaviour of microbial poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)[J]. Polymer International, 2005, 54(7): 1055-1064
[36] Kunioka M, Tamaki A, Doi Y. Crystalline and thermal properties of bacterial copolyesters: Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and poly(3-hydroxybutyrate-co- 4-hydroxybutyrate)[J]. Macromolecules, 1989,22(2): 694-697
[37] Nakamura S, Doi Y, Scandola M. Microbial synthesis and characterization of poly(3-hydroxybutyrate-co-4-hydroxybutyrate)[J]. Macromolecules, 1992, 25(17): 4237-4241
[38] Abate R, Ballistreri A, Montaudo G, et al. Thermal degradation of microbial poly(4-hydroxybutyrate)[J]. Macromolecules, 1994, 27(2): 332-336
[39] Kang I K, Choi S H, Shin D S, et al. Surface modification of polyhydroxyalkanoate films and their interaction with human fibroblasts[J]. Int. J. Biol. Macromol., 2001, 28(3): 205-212
[40] Kim K J, Doi Y, Abe H. Effects of residual metal compounds and chain-end structure on thermal degradation of poly(3-hydroxybutyric acid)[J]. Polymer Degradation and Stability, 2006, 91(4): 769-777
[41] Tsuji H, Suzuyoshi K. Environmental degradation of biodegradable polyesters 1. Poly(ε-caprolactone), poly[(R)-3-hydroxybutyrate], and poly(L-lactide) films in controlled static seawater[J]. Polymer Degradation and Stability, 2002, 75(2): 347-355
[42] Iwata T, Doi Y, Nakayama S, et al. Structure and enzymatic degradation of poly(3-hydroxybutyrate) copolymer single crystals with an extracellular PHB depolymerase from Alcaligenes faecalis Tl[J]. Int. J. Biol. Macromol., 1999,25(1-3): 169-176
[43] Nojiri M, Saito T. Structure and function of poly(3-hydroxybutyrate) depolymerase from Alcaligenes faecalis T1[J]. J. Bacteriol., 1997, 179(22): 6965-6970
[44] Kasuya K-i, Doi Y, Yao T. Enzymatic degradation of poly[(R)-3-hydroxybutyrate] by Comamonas testosteroni ATSU of soil bacterium[J]. Polymer Degradation and Stability, 1994, 45(3): 379-386
[45] Mabrouk M M, Sabry S A. Degradation of poly (3-hydroxybutyrate) and its copolymer poly (3-hydroxybutyrate-co-3-hydroxyvalerate) by a marine Streptomyces sp SNG9[J]. Microbiol. Res., 2001, 156(4): 323-335
[46] Abe H, Doi Y. Structural effects on enzymatic degradabilities for poly[(R)-3-hydroxybutyric acid] and its copolymers[J]. Int. J. Biol. Macromol., 1999, 25(1-3): 185-192
[47] Abe H, Doi Y, Hori Y, et al. Physical properties and enzymatic degradability of Copolymers of (R)-3-hydroxybutyric acid and (S,S)-lactide[J]. Polymer, 1998, 39(1): 59-67
[48] Abe H, Doi Y, Aoki H, et al. Solid-state structures and enzymatic degradabilities for melt-crystallized films of Copolymers of (R)-3-hydroxybutyric acid with different hydroxyalkanoic acids[J]. Macromolecules, 1998,31(6): 1791-1797
[49] Mitomo H, Enjoji T, Watanabe Y, et al. Radiation-Induced Graft-Polymerization of Poly(3-Hydroxybutyrate) and Its Copolymer[J]. J. Macromol. Sci.-Pure Appl. Chem., 1995, A32(3): 429-442
[50] Kai W H, He Y, Inoue Y. Fast crystallization of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxy-valerate) with talc and boron nitride as nucleating agents[J]. Polymer International, 2005, 54(5): 780-789
[51] Liu W J, Yang H L, Wang Z, et al. Effect of nucleating agents on the crystallization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)[J]. Journal of Applied Polymer Science, 2002, 86(9): 2145-2152
[52] Chen L J, Wang M. Production and evaluation of biodegradable composites based on PHB-PHV copolymer[J]. Biomaterials, 2002,23(13): 2631-2639
[53] Galego N, Rozsa C, Sanchez R, et al. Characterization and application of poly(β-hydroxyalkanoates) family as composite biomaterials[J]. Polymer Testing, 2000, 19(5): 485-492
[54] Chen G X, Hao G J, Guo T Y, et al. Crystallization kinetics of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/ clay nanocomposites[J]. Journal of Applied Polymer Science, 2004, 93(2): 655-661
[55] Choi W M, Kim T W, Park O O, et al. Preparation and characterization of poly(hydroxybutyrate-co-hydroxyvalerate)-organoclay nanocomposites[J]. Journal of Applied Polymer Science, 2003, 90(2): 525-529
[56] Lim S T, Hyun Y H, Lee C H, et al. Preparation and characterization of microbial biodegradable poly(3-hydroxybutyrate)/organoclay nanocomposite[J]. Journal of Materials Science Letters, 2002, 22(4): 299-302
[57] Withey R E, Hay J N. The effect of seeding on the crystallisation of poly(hydroxybutyrate), and co-poly(hydroxybutyrate-co-valerate)[J]. Polymer, 1999,40(18): 5147-5152
[58] El-Hadi A, Schnabel R, Straube E, et al. Effect of melt processing on crystallization behavior and rheology of poly(3-hydroxybutyrate) (PHB) and its blends[J]. Macromol. Mater. Eng., 2002, 287(5): 363-372
[59] Weihua K, He Y, Asakawa N, et al. Effect of lignin particles as a nucleating agent on crystallization of poly(3-hydroxybutyrate)[J]. Journal of Applied Polymer Science, 2004, 94(6): 2466-2474
[60] Fernandes E G, Pietrini M, Chiellini E. Thermo-mechanical and morphological characterization of plasticized poly [(R)-3-hydroxybutyric acid][J]. Macromol. Symp., 2004, 218: 157-164
[61] Janigova I, Lacik I, Chodak I. Thermal degradation of plasticized poly(3-hydroxybutyrate) investigated by DSC[J]. Polymer Degradation and Stability, 2002, 77(1): 35-41
[62] Baltieri R C, Mei L H I, Bartoli J. Study of the influence of plasticizers on the thermal and mechanical properties of poly(3-hydroxybutyrate) compounds[J]. Macromol. Symp., 2003, 197:33-44
[63]Yoshie N,Nakasato K,Fujiwara M,et al.Effect of low molecular weight additives on enzymatic degradation of poly(3-hydroxybutyrate)[J].Polymer,2000,41(9):3227-3234
[64]Chan C H,Kummerlowe C,Kammer H W.Crystallization and melting behavior of poly (3-hydroxybutyrate)-based blends[J].Macromol.Chem.Phys.,2004,205(5):664-675
[65]Bibers I,Tupureina V,Dzene A,et al.Biodegradable materials from plasticized PHB biomass[J].Macromol.Symp.,2001,170:61-71
[66]Kunze C,Freier T,Kramer S,et al.Anti-inflammatory prodrugs as plasticizers for biodegradable implant materials based on poly(3-hydroxybutyrate)[J].J.Mater.Sci.-Mater.Med.,2002,13(11):1051-1055
[67]蔡志江.聚乙二醇共混改性聚羟基丁酸醋的研究[J].天津科技大学学报,2006,21(2):30-34
[68]Choi H J,Park S H,Yoon J S,et al.Rheological Study on Poly-D(-)(3-Hydroxybutyrate)and Its Blends with Poly(Ethylene Oxide)[J].Polym.Eng.Sci.,1995,35(20):1636-1642
[69]He Y,Asakawa N,Inoue Y.Biodegradable blends of high molecular weight poly(ethylene oxide)with poly(3-hydroxypropionic acid)and poly(3-hydroxybutyric acid):a miscibility study by DSC,DMTA and NMR spectroscopy[J].Polymer International,2000,49(6):609-617
[70]李荣群,安玉贤.聚β羟基丁酸酯/聚氧化乙烯共混体系力学性能研究[J].高分子学报,2001,(2):143-147
[71]钟明强,王亮梅,益小苏.聚β-羟基烷酸酯共混改性研究进展[J].功能高分子学报,2000,(4):476-480
[72]Xing P X,Ai X,Dong L S,et al.Miscibility and crystallization of poly(beta-hydroxybutyrate)/poly(vinyl acetate-co-vinyl alcohol)blends[J].Macromolecules,1998,31(20):6898-6907
[73]Urakami T,Imagawa S,Harada M,et al.Development of biodegradable plastic-poly-beta-hydroxybutyrate/polycaprolactone blend polymer[J].Kobunshi Ronbunshu,2000,57(5):263-270
[74]Ikejima T,lnoue Y.Crystallization behavior and environmental biodegradability of the blend films of poly(3-hydroxybutyric acid)with chitin and chitosan[J].Carbohydrate Polymers,2000,41(4):351-356
[75]Gassner F,Owen A J.Some properties of poly(3-hydroxybutyrate)-poly(3-hydroxyvalerate)blends[J].Polymer International,1996,39(3):215-219
[76]杨冬芝,胡平.聚β羟基丁酸酯和聚碳酸亚丙酯的共混体系研究[J].塑料,2006,35(4):24-29
[77]彭树文,董丽松.PHB/PPC共混体系及其增容研究的研究[J].新型高分子材料,2000,(2):1169-1174
[78]陈建海,陈志良,侯连兵.聚羟基丁酸酯缓释微球的制备和性能[J].功能高分子学报,2000,13(1):61-64
[79]陈建海,陈志良,许重远.地西泮-聚羟基丁酸酯-羟基戊酸酯共聚物缓释微球制备与性质[J].中国医学杂志,2000,35(4):242-246
[80]Abe H,Doi Y,Yamamoto Y.Controlled Release of Lastet,an Anticancer Drug,from Poly(3-Hydroxybutyrate)Microspheres Containing Acylglycerols[J].J.Macromol.Sci.-Pure Appl.Chem.,1992,29:229-235
[81]Akhtar S,Pouton C W,Notarianni L J.Crystallization behaviour and drug release from bacterial polyhydroxyalkanoates[J].Polymer,1992,33(1):117-126
[82]王常勇,赵强,范明.聚羟基丁酸酯泡沫材料与软骨细胞体外培养的实验研究[J].第一届全国组织工程会议论文集,1999:199-202
[83]Boeree N R,Dove J,Cooper J J,et al.Development of a degradable composite for orthopaedic use:mechanical evaluation of an hydroxyapatite-polyhydroxybutyrate composite material[J].Biomaterials,1993,14(10):793-796
[84]Doyle C,Tanner E T,Bonfield W.In vitro and in vivo evaluation of polyhydroxybutyrate and of polyhydroxybutyrate reinforced with hydroxyapatite[J].Biomaterials,1991,12(9):841-847
[1]Sudesh K,Abe H,Doi Y.Synthesis,structure and properties of polyhydroxyalkanoates:biological polyesters[J].Prog.Polym.Sci.,2000,25(10):1503-1555
[2]Dekoning G J M,Scheeren A H C,Lemstra P J,et al.Crystallization Phenomena in Bacterial Poly[(R)-3-Hydroxybutyrate].3.Toughening Via Texture Changes[J].Polymer,1994,35(21):4598-4605
[3]Dekoning G J M,Lemstra P J.Crystallization Phenomena in Bacterial Poly[(R)-3-Hydroxybutyrate].2.Embrittlement and Rejuvenation[J].Polymer,1993,34(19):4089-4094
[4]Dekoning G J M,Embrittlement and Rejuvenation of Bacterial Poly[(R)-3-Hydroxybutyrate].In Polymers from Agricultural Coproducts,Amer Chemical Soc:Washington,1994;Vol.575,pp 188-201.
[5]Ishida K,Wang Y,Inoue Y.Comonomer unit composition and thermal properties of poly(3-hydroxybutyrate-co-4-hydroxybutyrate)s biosynthesized by Raistonia eutropha[J].Biomacromolecules,2001,2(4):1285-1293
[6]He J D,Cheung M K,Yu P H,et al.Thermal analyses of poly(3-hydroxybutyrate),poly(3-hydroxybutyrate-co-3-hydroxyvalerate),and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)[J].Journal of Applied Polymer Science,2001,82(1):90-98
[7]Kunioka M,Tamaki A,Doi Y.Crystalline and thermal properties of bacterial copolyesters:Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)and poly(3-hydroxybutyrate-co-4-hydroxybutyrate)[J].Macromolecules,1989,22(2):694-697
[8]Kunioka M,Doi Y.Thermal degradation of microbial copolyesters.Poly(3hydroxybutyrate-co-3-hydroxyvalerate)and poly(3-hydroxybutyrate-co-4-hydroxybutyrate)[J].Macromolecules,1990,23(7):1933-1936
[1] Tobella L M, Bunster M, Pooley A, et al. Biosynthesis of poly-beta-hydroxyalkanoates by Sphingopyxis chilensis S37 and Wautersia sp PZK cultured in cellulose pulp mill effluents containing 2,4,6-trichlorophenol[J]. J. Ind. Microbiol. Biotechnol., 2005, 32(9): 397-401
[2] Thakor N, Trivedi U, Patel K. C. Biosynthesis of medium chain length poly(3-hydroxyalkanoates) (mcl-PHAs) by Comamonas testosteroni during cultivation on vegetable oils[J]. Bioresource Technology, 2005,96(17): 1843-1850
[3] Tavares L Z, da Silva E S, Pradella J G D. Production of poly (3-hydroxybutyrate) in an airlift bioreactor by Ralstonia eutropha[J]. Biochemical Engineering Journal, 2004, 18(1): 21-31
[4] Chen G-Q, Wu Q. The application of polyhydroxyalkanoates as tissue engineering materials[J]. Biomaterials, 2005, 26(33): 6565-6578
[5] Cheng G, Cai Z, Wang L. Biocompatibility and biodegradation of poly(hydroxybutyrate)/poly(ethylene glycol) b|end films[J]. Journal of Materials Science: Materials in Medicine, 2003, 14(12): 1073-1078
[6] Choi J S, Park W H. Effect of biodegradable plasticizers on thermal and mechanical properties of poly (3-hydroxybutyrate)[J]. Polym. Test, 2004, 23(4): 455-460
[1]Inoue Y,Yoshie N.Structure and physical properties of bacterially synthesized polyesters[J].Prog.Polym.Sci.,1992,17(4):571-610
[2]de Koning G J M,Lemstra P J.Crystallization phenomena in bacterial poly[(R)-3-hydroxybutyrate]:2.Embrittlement and rejuvenation[J].Polymer,1993,34(19):4089-4094
[3]El-Hadi A,Schnabel R,Straube E,et al.Correlation between degree of crystallinity,morphology,glass temperature,mechanical properties and biodegradation of poly (3-hydroxyalkanoate)PHAs and their blends[J].Polymer Testing,2002,21(6):665-674
[4]Abe H,Doi Y,Aoki H,et al.Physical-Properties and Enzymatic Degradability of Copolymers of(R)-3-Hydroxybutyric and 6-Hydroxyhexanoic Acids[J].Macromolecules,1995,28(23):7630-7637
[5]Bauer H,Owen A J.Some Structural and Mechanical-Properties of Bacterially Produced Poly-Beta-Hydroxybutyrate-Co-Beta-Hydroxyvalerate[J].Colloid Polym.Sci.,1988,266(3):241-247
[6]Liu W J,Yang H L,Wang Z,et al.Effect of nucleating agents on the crystallization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)[J].Journal of Applied Polymer Science,2002,86(9):2145-2152
[1] Park T G, Cohen S, Langer R, Poly(L-lactic acid)/Pluronic blends: characterization of phase separation behavior, degradation, and morphology and use as protein-releasing matrixes. In 1992; Vol. 25, pp 116-122.
[2] Zhang L, Xiong C, Deng X. Miscibility, crystallization and morphology of poly([beta]-hydroxybutyrate)/poly(d,l-lactide) blends[J]. Polymer, 1996, 37(2): 235-241
[3] [Zhang L L, Goh S H, Lee S Y, et al. Miscibility, melting and crystallization behavior of two bacterial polyester/poly(epichlorohydrin-co-ethylene oxide) blend systems[J]. Polymer, 2000, 41(4): 1429-1439
[4] Chun Y S, Kim W N. Thermal properties of poly(hydroxybutyrate-co-hydroxyvalerate) and poly(epsilon-caprolactone) blends[J]. Polymer, 2000, 41(6): 2305-2308
[5] Lianlai Z, S. H. Goh S. Y. Lee. Miscibility and phase behavior of poly(D,L-lactide)/poly(p-vinylphenol) blends[J]. 1998, 70(4): 811-816
[6] Henk Verhoogt B A R B D F J A R, The influence of thermal history on the properties of poly(3-hydroxybutyrate-co-12%-3-hydroxyvalerate). In 1996; Vol. 61, pp 87-96.
[7] Penning J P, St. John Manley R. Miscible Blends of Two Crystalline Polymers. 2. Crystallization Kinetics and Morphology in Blends of Poly(vinylidene fluoride) and Poly(1,4-butylene adipate)[J]. 1996,29(1): 84-90
[1]Janigova I,Lacik I,Chodak I.Thermal degradation of plasticized poly(3-hydroxybutyrate)investigated by DSC[J].Polymer Degradation and Stability,2002,77(1):35-41
[2]Chen C,Fei B,Peng S,et al.The kinetics of the thermal decomposition of poly(3-hydroxybutyrate)and maleated poly(3-hydroxybutyrate)[J].Journal of Applied Polymer Science,2002,84(9):1789-1796
[3]Chen C,Fei B,Peng S W,et al.The kinetics of the thermal decomposition of poly(3-hydroxybutyrate)and maleated poly(3-hydroxybutyrate)[J].Journal of Applied Polymer Science,2002,84(9):1789-1796
[4]Li S D,He J D,Yu P H,et al.Thermal degradation of poly(3-hydroxybutyrate)and poly(3-hydroxybutyrate-co-3-hydroxyvalerate)as studied by TG,TG-FTIR,and Py-GC/MS[J].Journal of Applied Polymer Science,2003,89(6):1530-1536
[5]Kunioka M,Doi Y.Then-hal degradation of microbial copolyesters.Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)and poly(3-hydroxybutyrate-co-4-hydroxybutyrate)[J].Macromolecules,1990,23(7):1933-1936
[6]Robelin-Souffache E,Rault J,Origin of the long period and crystallinity in quenched semicrystalline polymers.1.In 1989;Vol.22,pp 3581-3594.
[7]Toshio O.Effects of molecular weight on mechanical properties of polypropylene[J].1992,44(10):1869-1871
[2] Williamson D H, Wilkinson J F. The isolation and estimation of the poly-b-hydroxybutyrate inclusions of Bacillus species[J]. J. Gen. Microbiol., 1958, 19: 198-209
[3] Macrae R M, Wilkinson J R. Poly-b-hydroxybutyrate metabolism in washed suspensions of Bacillus cereus and Bacillus megaterium[J]. J. Gen. Microbiol., 1958, 19: 210-22
[4] Doudoroff M, Stanier R Y. Role of poly-b-hydroxybutyric acid in the assimilation of organic carbon by bacteria[J]. Nature Biotechnology, 1959, 183: 1440-1442
[5] Wallen L L, Rohwedder W K. Poly-b-hydroxyalkanoate from activated sludge[J]. Environ. Sci. Technol., 1974, 8:576-9
[6] Lageveen R G, Huisman G W, Preusting H, et al. Formation of Polyesters by Pseudomonas-Oleovorans - Effect of Substrates on Formation and Composition of Poly-(R)-3-Hydroxyalkanoates and Poly-(R)-3-Hydroxyalkenoates[J]. Applied and Environmental Microbiology, 1988, 54(12): 2924-2932
[7] Anderson A J, Dawes E A. Occurrence, Metabolism, Metabolic Role, and Industrial Uses of Bacterial Polyhydroxyalkanoates[J]. Microbiol. Rev., 1990, 54(4): 450-472
[8] Rehm B H A, Sieinbuchel A. Biochemical and genetic analysis of PHA synthases and other proteins required for PHA synthesis[J]. Int. J. Biol. Macromol., 1999, 25(1-3): 3-19
[9] Slater S C, Voige W H, Dennis D E. Cloning and Expression in Escherichia-Coli of the Alcaligenes-Eutrophus H16 Poly-Beta-Hydroxybutyrate Biosynthetic-Pathway[J]. J. Bacteriol., 1988, 170(10): 4431-4436
[10] Peoples O P, Sinskey A J. Poly-Beta-Hydroxybutyrate (Phb) Biosynthesis in Alcaligenes-Eutrophus H16 - Identification and Characterization of the Phb Polymerase Gene (Phbc)[J]. J. Biol. Chem., 1989, 264(26): 15298-15303
[11] Peoples O P, Sinskey A J. Poly-Beta-Hydroxybutyrate Biosynthesis in Alcaligenes-Eutrophus H16 - Characterization of the Genes Encoding Beta-Ketothiolase and Acetoacetyl-Coa Reductase[J]. J. Biol. Chem., 1989, 264(26): 15293-15297
[12] Gerngross T U, Martin D P. Enzyme-Catalyzed Synthesis of Poly[(R)-(-)-3-Hydroxyburyrate] - Formation of Macroscopic Granules in-Vitro[J]. Proc. Natl. Acad. Sci. U. S. A., 1995, 92(14): 6279-6283
[13] Kunioka M, Kawaguchi Y, Doi Y. Production of Biodegradable Copolyesters of 3-Hydroxybutyrate and 4-Hydroxybutyrate by Alcaligenes-Eutrophus[J]. Appl. Microbiol. Biotechnol., 1989,30(6): 569-573
[14] Shah N N, Hanna M L, Taylor R T. Batch cultivation of Methylosinus trichosporium OB3b .5. Characterization of poly-beta-hydroxybutyrate production under methane-dependent growthconditions[J]. Biotechnology and Bioengineering, 1996,49(2): 161-171
[15] Nakayama K, Saito T, Fukui T, et al. Purification and Properties of Extracellular Poly(3-Hydroxybutyrate) Depolymerases from Pseudomonas-Lemoignei[J]. Biochimica Et Biophysica Acta, 1985, 827(1): 63-72
[16] Choi J I, Lee S Y. Efficient and economical recovery of poly(3-hydroxybutyrate) from recombinant Escherichia coli by simple digestion with chemicals[J]. Biotechnology and Bioengineering, 1999,62(5): 546-553
[17] Mittendorf V, Robertson E J, Leech R M, et al. Synthesis of medium-chain-length polyhydroxyalkanoates in Arabidopsis thaliana using intermediates of peroxisomal fatty acid beta-oxidation[J]. Proc. Natl. Acad. Sci. U. S. A., 1998, 95(23): 13397-13402
[18] Poirier Y, Somerville C, Schechtman L A, et al. Synthesis of High-Molecular-Weight Poly([R]-(-)-3-Hydroxybutyrate) in Transgenic Arabidopsis-Thaliana Plant-Cells[J]. Int. J. Biol. Macromol., 1995, 17(1): 7-12
[19] Matsumoto K, Nagao R, Murata T, et al. Enhancement of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) production in the transgenic Arabidopsis thaliana by the in vitro evolved highly active mutants of polyhydroxyalkanoate (PHA) synthase from Aeromonas caviae[J]. Biomacromolecules, 2005,6(4): 2126-2130
[20] Song C J, Zhao L X, Ono S, et al. Production of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) from cottonseed oil and valeric acid in batch culture of Ralstonia sp strain JC-64[J]. Appl. Biochem. Biotechnol., 2001, 94(2): 169-178
[21] Moore T, Adhikari R, Gunatillake P. Chemosynthesis of bioresorbable poly(γ-butyrolactone) by ring-opening polymerisation: A review[J]. Biomaterials, 2005, 26(18): 3771-3782
[22] Noda I, Green P R, Satkowski M M, et al. Preparation and properties of a novel class of polyhydroxyalkanoate copolymers[J]. Biomacromolecules, 2005, 6(2): 580-586
[23] Dekoning G J M, Scheeren A H C, Lemstra P J, et al. Crystallization Phenomena in Bacterial Poly[(R)-3-Hydroxybutyrate] .3. Toughening Via Texture Changes[J]. Polymer, 1994, 35(21): 4598-4605
[24] Mitomo H, Barham P J, Keller A. Temperature-Dependence of Mechanical-Properties of Poly(Beta-Hydroxybutyrate-Beta-Hydroxyvalerate)[J]. Polymer Communications, 1988, 29(4): 112-115
[25] Mitomo H, Doi Y. Lamellar thickening and cocrystallization of polyhydroxyalkanoates on annealing[J]. Int. J. Biol. Macromol., 1999, 25(1-3): 201-205
[26] Shimamura E, Kasuya K, Kobayashi G, et al. Physical-Properties and Biodegradability of Microbial Poly(3-Hydroxybutyrate-Co-3-Hydroxyhexanoate)[J]. Macromolecules, 1994, 27(3): 878-880
[27] Hassan M K, Abdel-Latif S A, El-Roudi O M, et al. Improvement in the mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) by preorientationfJ]. Journal of Applied Polymer Science, 2004, 94(6): 2257-2262
[28] Shimamura E, Scandola M, Doi Y. Microbial Synthesis and Characterization of Poly(3-Hydroxybutyrate-Co-3-Hydroxypropionate)[J]. Macromolecules, 1994, 27(16): 4429-4435
[29] Saito Y, Nakamura S, Hiramitsu M, et al. Microbial synthesis and properties of poly(3-hydroxybutyrate-co-4-hydroxybutyrate)[J]. Polymer International, 1996, 39(3): 169-174
[30] Barham P J, Keller A, Otun E L, et al. Crystallization and Morphology of a Bacterial Thermoplastic - Poly-3-Hydroxybutyrate[J]. Journal of Materials Science, 1984, 19(9): 2781-2794
[31] Bluhm T L, Hamer G K, Marchessault R H, et al. Isodimorphism in Bacterial Poly(Beta-Hydroxybutyrate-Co-Beta-Hydroxyvalerate)[J]. Macromolecules, 1986, 19(11): 2871-2876
[32] Bluhm T L, Hamer G K, Marchessault R H, et al. Morphology of a Novel Copolyester - Bacterial Poly(Beta-Hydroxybutyrate-Co-Beta-Hydroxyvalerate)[J]. Abstr. Pap. Am. Chem. Soc, 1986, 192:221-POLY
[33] Bluhm T L, Hamer G K, Marchessault R H. Analysis of Poly(Beta-Hydroxybutyrate-Co-Beta-Hydroxyvalerate) Using X-Ray-Diffraction, Nmr-Spectroscopy and Differential Scanning Calorimetry[J]. Acta Crystallogr. Sect. A, 1984, 40: C467-C467
[34] Man Ken C, Peter H F Y, Cheng C. Crystallization kinetics and melting behaviour of microbial poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)[J]. Polymer International, 2005, 54(7): 1055-1064
[35] [35] Chen C, Cheung M K, Yu P H F. Crystallization kinetics and melting behaviour of microbial poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)[J]. Polymer International, 2005, 54(7): 1055-1064
[36] Kunioka M, Tamaki A, Doi Y. Crystalline and thermal properties of bacterial copolyesters: Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and poly(3-hydroxybutyrate-co- 4-hydroxybutyrate)[J]. Macromolecules, 1989,22(2): 694-697
[37] Nakamura S, Doi Y, Scandola M. Microbial synthesis and characterization of poly(3-hydroxybutyrate-co-4-hydroxybutyrate)[J]. Macromolecules, 1992, 25(17): 4237-4241
[38] Abate R, Ballistreri A, Montaudo G, et al. Thermal degradation of microbial poly(4-hydroxybutyrate)[J]. Macromolecules, 1994, 27(2): 332-336
[39] Kang I K, Choi S H, Shin D S, et al. Surface modification of polyhydroxyalkanoate films and their interaction with human fibroblasts[J]. Int. J. Biol. Macromol., 2001, 28(3): 205-212
[40] Kim K J, Doi Y, Abe H. Effects of residual metal compounds and chain-end structure on thermal degradation of poly(3-hydroxybutyric acid)[J]. Polymer Degradation and Stability, 2006, 91(4): 769-777
[41] Tsuji H, Suzuyoshi K. Environmental degradation of biodegradable polyesters 1. Poly(ε-caprolactone), poly[(R)-3-hydroxybutyrate], and poly(L-lactide) films in controlled static seawater[J]. Polymer Degradation and Stability, 2002, 75(2): 347-355
[42] Iwata T, Doi Y, Nakayama S, et al. Structure and enzymatic degradation of poly(3-hydroxybutyrate) copolymer single crystals with an extracellular PHB depolymerase from Alcaligenes faecalis Tl[J]. Int. J. Biol. Macromol., 1999,25(1-3): 169-176
[43] Nojiri M, Saito T. Structure and function of poly(3-hydroxybutyrate) depolymerase from Alcaligenes faecalis T1[J]. J. Bacteriol., 1997, 179(22): 6965-6970
[44] Kasuya K-i, Doi Y, Yao T. Enzymatic degradation of poly[(R)-3-hydroxybutyrate] by Comamonas testosteroni ATSU of soil bacterium[J]. Polymer Degradation and Stability, 1994, 45(3): 379-386
[45] Mabrouk M M, Sabry S A. Degradation of poly (3-hydroxybutyrate) and its copolymer poly (3-hydroxybutyrate-co-3-hydroxyvalerate) by a marine Streptomyces sp SNG9[J]. Microbiol. Res., 2001, 156(4): 323-335
[46] Abe H, Doi Y. Structural effects on enzymatic degradabilities for poly[(R)-3-hydroxybutyric acid] and its copolymers[J]. Int. J. Biol. Macromol., 1999, 25(1-3): 185-192
[47] Abe H, Doi Y, Hori Y, et al. Physical properties and enzymatic degradability of Copolymers of (R)-3-hydroxybutyric acid and (S,S)-lactide[J]. Polymer, 1998, 39(1): 59-67
[48] Abe H, Doi Y, Aoki H, et al. Solid-state structures and enzymatic degradabilities for melt-crystallized films of Copolymers of (R)-3-hydroxybutyric acid with different hydroxyalkanoic acids[J]. Macromolecules, 1998,31(6): 1791-1797
[49] Mitomo H, Enjoji T, Watanabe Y, et al. Radiation-Induced Graft-Polymerization of Poly(3-Hydroxybutyrate) and Its Copolymer[J]. J. Macromol. Sci.-Pure Appl. Chem., 1995, A32(3): 429-442
[50] Kai W H, He Y, Inoue Y. Fast crystallization of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxy-valerate) with talc and boron nitride as nucleating agents[J]. Polymer International, 2005, 54(5): 780-789
[51] Liu W J, Yang H L, Wang Z, et al. Effect of nucleating agents on the crystallization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)[J]. Journal of Applied Polymer Science, 2002, 86(9): 2145-2152
[52] Chen L J, Wang M. Production and evaluation of biodegradable composites based on PHB-PHV copolymer[J]. Biomaterials, 2002,23(13): 2631-2639
[53] Galego N, Rozsa C, Sanchez R, et al. Characterization and application of poly(β-hydroxyalkanoates) family as composite biomaterials[J]. Polymer Testing, 2000, 19(5): 485-492
[54] Chen G X, Hao G J, Guo T Y, et al. Crystallization kinetics of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/ clay nanocomposites[J]. Journal of Applied Polymer Science, 2004, 93(2): 655-661
[55] Choi W M, Kim T W, Park O O, et al. Preparation and characterization of poly(hydroxybutyrate-co-hydroxyvalerate)-organoclay nanocomposites[J]. Journal of Applied Polymer Science, 2003, 90(2): 525-529
[56] Lim S T, Hyun Y H, Lee C H, et al. Preparation and characterization of microbial biodegradable poly(3-hydroxybutyrate)/organoclay nanocomposite[J]. Journal of Materials Science Letters, 2002, 22(4): 299-302
[57] Withey R E, Hay J N. The effect of seeding on the crystallisation of poly(hydroxybutyrate), and co-poly(hydroxybutyrate-co-valerate)[J]. Polymer, 1999,40(18): 5147-5152
[58] El-Hadi A, Schnabel R, Straube E, et al. Effect of melt processing on crystallization behavior and rheology of poly(3-hydroxybutyrate) (PHB) and its blends[J]. Macromol. Mater. Eng., 2002, 287(5): 363-372
[59] Weihua K, He Y, Asakawa N, et al. Effect of lignin particles as a nucleating agent on crystallization of poly(3-hydroxybutyrate)[J]. Journal of Applied Polymer Science, 2004, 94(6): 2466-2474
[60] Fernandes E G, Pietrini M, Chiellini E. Thermo-mechanical and morphological characterization of plasticized poly [(R)-3-hydroxybutyric acid][J]. Macromol. Symp., 2004, 218: 157-164
[61] Janigova I, Lacik I, Chodak I. Thermal degradation of plasticized poly(3-hydroxybutyrate) investigated by DSC[J]. Polymer Degradation and Stability, 2002, 77(1): 35-41
[62] Baltieri R C, Mei L H I, Bartoli J. Study of the influence of plasticizers on the thermal and mechanical properties of poly(3-hydroxybutyrate) compounds[J]. Macromol. Symp., 2003, 197:33-44
[63]Yoshie N,Nakasato K,Fujiwara M,et al.Effect of low molecular weight additives on enzymatic degradation of poly(3-hydroxybutyrate)[J].Polymer,2000,41(9):3227-3234
[64]Chan C H,Kummerlowe C,Kammer H W.Crystallization and melting behavior of poly (3-hydroxybutyrate)-based blends[J].Macromol.Chem.Phys.,2004,205(5):664-675
[65]Bibers I,Tupureina V,Dzene A,et al.Biodegradable materials from plasticized PHB biomass[J].Macromol.Symp.,2001,170:61-71
[66]Kunze C,Freier T,Kramer S,et al.Anti-inflammatory prodrugs as plasticizers for biodegradable implant materials based on poly(3-hydroxybutyrate)[J].J.Mater.Sci.-Mater.Med.,2002,13(11):1051-1055
[67]蔡志江.聚乙二醇共混改性聚羟基丁酸醋的研究[J].天津科技大学学报,2006,21(2):30-34
[68]Choi H J,Park S H,Yoon J S,et al.Rheological Study on Poly-D(-)(3-Hydroxybutyrate)and Its Blends with Poly(Ethylene Oxide)[J].Polym.Eng.Sci.,1995,35(20):1636-1642
[69]He Y,Asakawa N,Inoue Y.Biodegradable blends of high molecular weight poly(ethylene oxide)with poly(3-hydroxypropionic acid)and poly(3-hydroxybutyric acid):a miscibility study by DSC,DMTA and NMR spectroscopy[J].Polymer International,2000,49(6):609-617
[70]李荣群,安玉贤.聚β羟基丁酸酯/聚氧化乙烯共混体系力学性能研究[J].高分子学报,2001,(2):143-147
[71]钟明强,王亮梅,益小苏.聚β-羟基烷酸酯共混改性研究进展[J].功能高分子学报,2000,(4):476-480
[72]Xing P X,Ai X,Dong L S,et al.Miscibility and crystallization of poly(beta-hydroxybutyrate)/poly(vinyl acetate-co-vinyl alcohol)blends[J].Macromolecules,1998,31(20):6898-6907
[73]Urakami T,Imagawa S,Harada M,et al.Development of biodegradable plastic-poly-beta-hydroxybutyrate/polycaprolactone blend polymer[J].Kobunshi Ronbunshu,2000,57(5):263-270
[74]Ikejima T,lnoue Y.Crystallization behavior and environmental biodegradability of the blend films of poly(3-hydroxybutyric acid)with chitin and chitosan[J].Carbohydrate Polymers,2000,41(4):351-356
[75]Gassner F,Owen A J.Some properties of poly(3-hydroxybutyrate)-poly(3-hydroxyvalerate)blends[J].Polymer International,1996,39(3):215-219
[76]杨冬芝,胡平.聚β羟基丁酸酯和聚碳酸亚丙酯的共混体系研究[J].塑料,2006,35(4):24-29
[77]彭树文,董丽松.PHB/PPC共混体系及其增容研究的研究[J].新型高分子材料,2000,(2):1169-1174
[78]陈建海,陈志良,侯连兵.聚羟基丁酸酯缓释微球的制备和性能[J].功能高分子学报,2000,13(1):61-64
[79]陈建海,陈志良,许重远.地西泮-聚羟基丁酸酯-羟基戊酸酯共聚物缓释微球制备与性质[J].中国医学杂志,2000,35(4):242-246
[80]Abe H,Doi Y,Yamamoto Y.Controlled Release of Lastet,an Anticancer Drug,from Poly(3-Hydroxybutyrate)Microspheres Containing Acylglycerols[J].J.Macromol.Sci.-Pure Appl.Chem.,1992,29:229-235
[81]Akhtar S,Pouton C W,Notarianni L J.Crystallization behaviour and drug release from bacterial polyhydroxyalkanoates[J].Polymer,1992,33(1):117-126
[82]王常勇,赵强,范明.聚羟基丁酸酯泡沫材料与软骨细胞体外培养的实验研究[J].第一届全国组织工程会议论文集,1999:199-202
[83]Boeree N R,Dove J,Cooper J J,et al.Development of a degradable composite for orthopaedic use:mechanical evaluation of an hydroxyapatite-polyhydroxybutyrate composite material[J].Biomaterials,1993,14(10):793-796
[84]Doyle C,Tanner E T,Bonfield W.In vitro and in vivo evaluation of polyhydroxybutyrate and of polyhydroxybutyrate reinforced with hydroxyapatite[J].Biomaterials,1991,12(9):841-847
[1]Sudesh K,Abe H,Doi Y.Synthesis,structure and properties of polyhydroxyalkanoates:biological polyesters[J].Prog.Polym.Sci.,2000,25(10):1503-1555
[2]Dekoning G J M,Scheeren A H C,Lemstra P J,et al.Crystallization Phenomena in Bacterial Poly[(R)-3-Hydroxybutyrate].3.Toughening Via Texture Changes[J].Polymer,1994,35(21):4598-4605
[3]Dekoning G J M,Lemstra P J.Crystallization Phenomena in Bacterial Poly[(R)-3-Hydroxybutyrate].2.Embrittlement and Rejuvenation[J].Polymer,1993,34(19):4089-4094
[4]Dekoning G J M,Embrittlement and Rejuvenation of Bacterial Poly[(R)-3-Hydroxybutyrate].In Polymers from Agricultural Coproducts,Amer Chemical Soc:Washington,1994;Vol.575,pp 188-201.
[5]Ishida K,Wang Y,Inoue Y.Comonomer unit composition and thermal properties of poly(3-hydroxybutyrate-co-4-hydroxybutyrate)s biosynthesized by Raistonia eutropha[J].Biomacromolecules,2001,2(4):1285-1293
[6]He J D,Cheung M K,Yu P H,et al.Thermal analyses of poly(3-hydroxybutyrate),poly(3-hydroxybutyrate-co-3-hydroxyvalerate),and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)[J].Journal of Applied Polymer Science,2001,82(1):90-98
[7]Kunioka M,Tamaki A,Doi Y.Crystalline and thermal properties of bacterial copolyesters:Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)and poly(3-hydroxybutyrate-co-4-hydroxybutyrate)[J].Macromolecules,1989,22(2):694-697
[8]Kunioka M,Doi Y.Thermal degradation of microbial copolyesters.Poly(3hydroxybutyrate-co-3-hydroxyvalerate)and poly(3-hydroxybutyrate-co-4-hydroxybutyrate)[J].Macromolecules,1990,23(7):1933-1936
[1] Tobella L M, Bunster M, Pooley A, et al. Biosynthesis of poly-beta-hydroxyalkanoates by Sphingopyxis chilensis S37 and Wautersia sp PZK cultured in cellulose pulp mill effluents containing 2,4,6-trichlorophenol[J]. J. Ind. Microbiol. Biotechnol., 2005, 32(9): 397-401
[2] Thakor N, Trivedi U, Patel K. C. Biosynthesis of medium chain length poly(3-hydroxyalkanoates) (mcl-PHAs) by Comamonas testosteroni during cultivation on vegetable oils[J]. Bioresource Technology, 2005,96(17): 1843-1850
[3] Tavares L Z, da Silva E S, Pradella J G D. Production of poly (3-hydroxybutyrate) in an airlift bioreactor by Ralstonia eutropha[J]. Biochemical Engineering Journal, 2004, 18(1): 21-31
[4] Chen G-Q, Wu Q. The application of polyhydroxyalkanoates as tissue engineering materials[J]. Biomaterials, 2005, 26(33): 6565-6578
[5] Cheng G, Cai Z, Wang L. Biocompatibility and biodegradation of poly(hydroxybutyrate)/poly(ethylene glycol) b|end films[J]. Journal of Materials Science: Materials in Medicine, 2003, 14(12): 1073-1078
[6] Choi J S, Park W H. Effect of biodegradable plasticizers on thermal and mechanical properties of poly (3-hydroxybutyrate)[J]. Polym. Test, 2004, 23(4): 455-460
[1]Inoue Y,Yoshie N.Structure and physical properties of bacterially synthesized polyesters[J].Prog.Polym.Sci.,1992,17(4):571-610
[2]de Koning G J M,Lemstra P J.Crystallization phenomena in bacterial poly[(R)-3-hydroxybutyrate]:2.Embrittlement and rejuvenation[J].Polymer,1993,34(19):4089-4094
[3]El-Hadi A,Schnabel R,Straube E,et al.Correlation between degree of crystallinity,morphology,glass temperature,mechanical properties and biodegradation of poly (3-hydroxyalkanoate)PHAs and their blends[J].Polymer Testing,2002,21(6):665-674
[4]Abe H,Doi Y,Aoki H,et al.Physical-Properties and Enzymatic Degradability of Copolymers of(R)-3-Hydroxybutyric and 6-Hydroxyhexanoic Acids[J].Macromolecules,1995,28(23):7630-7637
[5]Bauer H,Owen A J.Some Structural and Mechanical-Properties of Bacterially Produced Poly-Beta-Hydroxybutyrate-Co-Beta-Hydroxyvalerate[J].Colloid Polym.Sci.,1988,266(3):241-247
[6]Liu W J,Yang H L,Wang Z,et al.Effect of nucleating agents on the crystallization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)[J].Journal of Applied Polymer Science,2002,86(9):2145-2152
[1] Park T G, Cohen S, Langer R, Poly(L-lactic acid)/Pluronic blends: characterization of phase separation behavior, degradation, and morphology and use as protein-releasing matrixes. In 1992; Vol. 25, pp 116-122.
[2] Zhang L, Xiong C, Deng X. Miscibility, crystallization and morphology of poly([beta]-hydroxybutyrate)/poly(d,l-lactide) blends[J]. Polymer, 1996, 37(2): 235-241
[3] [Zhang L L, Goh S H, Lee S Y, et al. Miscibility, melting and crystallization behavior of two bacterial polyester/poly(epichlorohydrin-co-ethylene oxide) blend systems[J]. Polymer, 2000, 41(4): 1429-1439
[4] Chun Y S, Kim W N. Thermal properties of poly(hydroxybutyrate-co-hydroxyvalerate) and poly(epsilon-caprolactone) blends[J]. Polymer, 2000, 41(6): 2305-2308
[5] Lianlai Z, S. H. Goh S. Y. Lee. Miscibility and phase behavior of poly(D,L-lactide)/poly(p-vinylphenol) blends[J]. 1998, 70(4): 811-816
[6] Henk Verhoogt B A R B D F J A R, The influence of thermal history on the properties of poly(3-hydroxybutyrate-co-12%-3-hydroxyvalerate). In 1996; Vol. 61, pp 87-96.
[7] Penning J P, St. John Manley R. Miscible Blends of Two Crystalline Polymers. 2. Crystallization Kinetics and Morphology in Blends of Poly(vinylidene fluoride) and Poly(1,4-butylene adipate)[J]. 1996,29(1): 84-90
[1]Janigova I,Lacik I,Chodak I.Thermal degradation of plasticized poly(3-hydroxybutyrate)investigated by DSC[J].Polymer Degradation and Stability,2002,77(1):35-41
[2]Chen C,Fei B,Peng S,et al.The kinetics of the thermal decomposition of poly(3-hydroxybutyrate)and maleated poly(3-hydroxybutyrate)[J].Journal of Applied Polymer Science,2002,84(9):1789-1796
[3]Chen C,Fei B,Peng S W,et al.The kinetics of the thermal decomposition of poly(3-hydroxybutyrate)and maleated poly(3-hydroxybutyrate)[J].Journal of Applied Polymer Science,2002,84(9):1789-1796
[4]Li S D,He J D,Yu P H,et al.Thermal degradation of poly(3-hydroxybutyrate)and poly(3-hydroxybutyrate-co-3-hydroxyvalerate)as studied by TG,TG-FTIR,and Py-GC/MS[J].Journal of Applied Polymer Science,2003,89(6):1530-1536
[5]Kunioka M,Doi Y.Then-hal degradation of microbial copolyesters.Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)and poly(3-hydroxybutyrate-co-4-hydroxybutyrate)[J].Macromolecules,1990,23(7):1933-1936
[6]Robelin-Souffache E,Rault J,Origin of the long period and crystallinity in quenched semicrystalline polymers.1.In 1989;Vol.22,pp 3581-3594.
[7]Toshio O.Effects of molecular weight on mechanical properties of polypropylene[J].1992,44(10):1869-1871